Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Testing Manual
15
th
Edition of the Gardner-Sward Handbook
Joseph V. Koleske
Editor
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
Downloaded/printed by
Universidad Nacional de Colombia pursuant to License Agreement. No further reproductions authorized.
Paint and Coating
Testing Manual
Fifteenth Edition of the Gardner-Sward Handbook
Joseph V. Koleske, EDITOR
ASTM Stock Number, MNL17-2ND
ASTM International
100 Barr Harbor Drive
PO Box C700
West Conshohocken, PA 19428-2959
Printed in U.S.A.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
Downloaded/printed by
Universidad Nacional de Colombia pursuant to License Agreement. No further reproductions authorized.
ii
Library of Congress Cataloging-in-Publication Data
Paint and coating testing manual : 15th edition of the Gardner-Sward
handbook / Joseph V. Koleske [editor].
p. cm.
ASTM Stock Number: MNL17-2nd
ISBN 978-0-8031-7017-9
1. Paint materialsTesting. 2. Paint materialsAnalysis. I.
Koleske, J. V., 1930-
TP936.5.P34 2011
667'.60284dc23
2011034983
Copyright 2012 ASTM International, West Conshohocken, PA. All rights reserved. This material may not be reproduced
or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media,
without the written consent of the publisher.
Photocopy Rights
Authorization to photocopy items for internal, personal, or educational classroom use of specific clients is granted by
ASTM International provided that the appropriate fee is paid to ASTM International, 100 Barr Harbor Drive, PO Box
C700. West Conshohocken, PA 19428-2959, Tel: 610-832-9634; online: http://www.astm.org/copyright/
ASTM International is not responsible, as a body, for the statements and opinions advanced in the publication. ASTM
does not endorse any products represented in this publication.
Printed in Bridgeport, NJ
January, 2012
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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iii
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .viii
Part 1: Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chapter 1Regulation of Volatile Organic Compound Emissions from Paints and Coatings . . . . . . . . . . . . . . . . . . . . . 3
J. John Brezinski and Ronald K. Litton
Part 2: Naturally Occurring Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Chapter 2Bituminous Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Ben J. Carlozzo
Chapter 3Cellulose Esters of Organic Acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Jos S. de Wit and Deep Bhattacharya
Chapter 4Drying Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Joseph V. Koleske
Chapter 5 Driers and Metallic Soaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Marvin J. Schnall
Part 3: Synthetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Chapter 6Acrylic Polymers as Coatings Binders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
John M. Friel and Edwin Nungesser
Chapter 7Alkyds and Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Dan Nelson
Chapter 8Amino Resins (Reaction Products of Melamine, Urea, etc., with Formaldehyde and Alcohols). . . . . . . . . 72
William Jacobs
Chapter 9Ceramic Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Richard A. Eppler
Chapter 10Epoxy Resins in Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Michael J. Watkins
Chapter 11Phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
John D. Fisher
Chapter 12Polyamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Robert W. Kight
Chapter 13Polyurethane Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
Han X. Xiao and Joseph V. Koleske
Chapter 14Silicone Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
D. J. Petraitis
Chapter 15Vinyl Polymers for Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Joseph V. Koleske
Chapter 16Miscellaneous Materials and Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Joseph V. Koleske
Part 4: Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Chapter 17Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Peter Tan and Leonard G. Krauskopf
Part 5: Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
Chapter 18Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Stephen A. Yuhas, Jr. and Rey G. Montemayor
Part 6: Pigments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
Chapter 19White Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Juergen H. Braun
Chapter 20Black Pigments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
Frank R. Spinelli
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iv CONTENTS
Chapter 21Colored Organic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Paul Merchak
Chapter 22Inorganic Colored Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
Peter A. Lewis
Chapter 23Ceramic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Richard A. Eppler
Chapter 24Extender Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
Richard A. Eppler
Chapter 25Metallic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
Russell L. Ferguson
Chapter 26Effect Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
Paul J. Nowak
Chapter 27Measurement of Gonioapparent Colors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Allan B. J. Rodrigues
Chapter 28Protective Coatings and Inorganic Anti-Corrosion Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
Lucien Veleva
Chapter 29Oil Absorption of Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
Charles W. Glancy
Part 7: Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
Chapter 30Bactericides, Fungicides, and Algicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
Janet H. Woodward
Chapter 31Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
Elvira Stesikova and Heinz Plaumann
Chapter 32Coalescing Aids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Kevin W. McCreight
Chapter 33Thickeners and Rheology Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Gregory D. Shay
Part 8: Physical Characteristics of Liquid Paints and Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
Chapter 34Density and Specific Gravity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375
Raymond D. Brockhaus and Ben J. Carlozzo
Chapter 35Characterizing Particle Size and Size Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
George D. Mills
Chapter 36Rheology and Viscometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
Richard R. Eley
Chapter 37Surface Energetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
Gordon P. Bierwagen, Andrew Huovinen, and Bobbi Jo Merten
Chapter 38Solubility Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
Charles M. Hansen
Part 9: Films for Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
Chapter 39Cure: The Process and Its Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Thomas J. Miranda
Chapter 40Film Preparation for Coating Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
Robert D. Athey, Jr.
Chapter 41Measurement of Film Thickness. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
John Fletcher and Joseph Walker
Chapter 42Drying Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528
Thomas J. Sliva
Part 10: Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 533
Chapter 43Color and Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
Robert T. Marcus
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CONTENTS v
Chapter 44Gloss . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 558
Gabriele Kigle-Bckler and Harry K. Hammond III
Chapter 45Hiding Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
Leonard Schaeffer
Chapter 46Mass Color and Tinting Strength of Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
Joseph V. Koleske
Part 11: Physical and Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
Chapter 47Adhesion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
Gordon L. Nelson
Chapter 48Abrasion Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 615
Daniel K. Slawson
Chapter 49Dynamic Mechanical and Tensile Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
Loren W. Hill
Chapter 50Flexibility and Toughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
John Fletcher and Joseph Walker
Chapter 51 Understanding Osmotic Activity in Paint Films and Determining Cause by Systematic
Analysis of Blister Fluids and Blistered Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
George Mills
Chapter 52Stress Phenomena in Organic Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
Dan Y. Perera
Chapter 53Friction and Slip Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673
Joseph V. Koleske
Part 12: Environmental Resistance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
Chapter 54Prevention of Metal Corrosion with Protective Overlayers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
William H. Smyrl
Chapter 55Types of Metal Corrosion and Means of Corrosion Protective by Overlayers. . . . . . . . . . . . . . . . . . . . . . 697
Kenneth B. Tator and Cynthia L. OMalley
Chapter 56Accelerated Weathering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
Valerie S. Sherbondy
Chapter 57Chemical Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
Latoska N. Price
Chapter 58Water-Resistance Testing of Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
John Fletcher and Joseph Walker
Part 13: Specific Product Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 737
Chapter 59Aerospace and Aircraft Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 739
Charles R. Hegedus, Stephen J. Spadafora, Anthony T. Eng, David F. Pulley, and Donald J. Hirst
Chapter 60Architectural Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
Neal Rogers
Chapter 61Artists Paints. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765
Benjamin Gavett
Chapter 62Can Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
Joseph V. Koleske
Chapter 63Testing of Industrial Maintenance Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
Dwight G. Weldon
Chapter 64Pipeline Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 787
Alfred Siegmund
Chapter 65Sealants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 792
Saul Spindel
Chapter 66Pavement Marking Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 799
James R. Swisher
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vi CONTENTS
Chapter 67Water-Repellent Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
Victoria Scarborough and Thomas J. Sliva
Part 14: Analysis of Paint and Paint Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
Chapter 68Analysis of Paint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
Darlene Brezinski
Chapter 69The Analysis of Coatings Failures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
George D. Mills
Part 15: Instrumental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
Chapter 70Atomic Absorption, Emission, and Inductively Coupled Plasma Spectroscopy . . . . . . . . . . . . . . . . . . . . . 851
Dwight G. Weldon
Chapter 71Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856
Rolando C. Domingo and updated by Rey G. Montemayor
Chapter 72Electron Microscopy Overview with Coating Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 881
David R. Rothbard and John G. Sheehan
Chapter 73Infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 895
Dwight G. Weldon
Chapter 74Methods for Polymer Molecular Weight Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 908
Thomas M. Schmitt
Chapter 75Ultraviolet/Visible Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
George D. Mills
Chapter 76X-Ray Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920
A. Monroe Snider, Jr.,
Part 16: Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
Chapter 77Paint and Coating Specifications and Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 943
Joseph V. Koleske
Part 17: New Coating Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 949
Chapter 78Radiation Curing of Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
Joseph V. Koleske
Chapter 79Powder Coating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 957
Joseph V. Koleske
Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 962
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 965
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Preface
vii
For historical purposes, it is important to point out that
at a January 1967 meeting of ASTM Committee D01 held
in Washington, D.C., the American Society for Testing and
Materials (ASTM International) accepted ownership of the
Gardner-Sward Handbook from the Gardner Laboratory.
It was through this laboratory that Dr. Henry A. Gardner
published the previous twelve editions of the manual.
Acceptance of this ownership gave ASTM an assumed
responsibility for revising, editing, and publishing future
editions of this well-known, respected manual. The under-
taking was assigned to Committee D01 on Paint and
Related Coatings, Materials, and Applications. This com-
mittee established a permanent subcommittee, D01.19 on
Gardner-Sward Handbook, whose stated scope is delin-
eated below. The 13th edition was published in 1972 as the
Paint Testing Manual (STP 500) with Mr. G. G. Sward as
editor and contributor. It was updated, expanded, and pub-
lished in 1995 as the 14th edition, Paint and Coating Testing
Manual (MNL 17) with Dr. Joseph V. Koleske as editor and
contributor. The manual has served the industry well in the
past by providing useful information that cannot be readily
found elsewhere.
It has been about fifteen years since the 14th edition
was published. Interest in the manual has been strong
through the years. This new edition of the Paint and Coating
Testing Manual, the Fifteenth Edition of the Gardner-Sward
Handbook (MNL 17), has been updated and expanded.
The scope of the new edition is in keeping with the
stated scope of Subcommittee D01.19:
To provide technical, editorial, and general guid-
ance for the preparation of the Fourteenth and
subsequent editions of the Gardner-Sward Hand-
book. The handbook is intended for review of both
new and experienced paint technologists and the
past, present, and foreseeable trends in all kinds of
testing within the scope of Committee D01. It sup-
plements, but does not replace, the pertinent parts
of the Societys Book of Standards. It describes,
briefly and critically all Test Methods believed to
have significance in the world of paint technology,
whether or not these tests have been adopted offi-
cially by the Society.
Once again, in this new edition, ASTM standard test
methods, procedures, and other documents are described in
minimal detail, with the various volumes of the ASTM Book
of Standards remaining the primary source of such informa-
tion. An effort was made to include references in the absence
of ASTM documents concerning industrial, national, inter-
national, and other society test methods. The new edition
contains either new chapters, or the previous topics/chap-
ters in rewritten/revised form. In a few cases, the previous
edition was merely updated, attesting to either the quality
of the earlier writing, the lack of development in the area,
or the apparent waning of interest in the topic. A variety of
modern topics have been included. New chapters have been
added as, for example, Measurement of Gonioapparent
Colors, Surfactants, Powder Coating, and Coalescing
Aids. As in the previous edition, individual authors, experts
in their particular fields, were given a great deal of freedom
in expressing information about their topics, but all chapters
were subjected to peer review by two colleagues. Thus, style
and content presentation may widely vary, but efforts were
made to have understandable syntax and thus readers should
find the information useful and easy to read and put to use.
Manuals such at this one are prepared though a great
deal of effort by the various authors and through the able
assistance and behind-the-scenes concerted efforts of peo-
ple such as Ms. Kathy Dernoga and Ms. Monica Siperko of
ASTM International and Ms. Christine Urso, Ms. Barbara
Carbonaro, Ms. Theresa Fucito, Ms. Patricia Mayhew, and
Ms. Benita Hammer, of the American Institute of Physics, all
of whom ensured that the manual was uniform in style and
grammar and that manuscripts were submitted and pro-
cessed in a timely fashion. The real unsung and unnamed
contributors are the reviewers who gave encouragement to
the various authors through constructive criticism, editorial
information, and recommendations without deleteriously
attempting to alter manuscripts from the authors intent.
To all of these people, a heart-felt thank you. Your talents
have been utilized, you sacrificed much personal time, and
you were patient with the numerous delays encountered on
the road to making the manual a success.
Joseph V. Koleske
Editor
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viii
Introduction
PAST TO PRESENT
The previous edition of this manual, the 14th, described
in detail the changes that took place in the coating indus-
try from the early 1970s to the early- to mid-1990s. Pub-
lished in 1995, the 14th edition classified powder coating,
radiation-cured coatings, and higher-solids coatings as
new, with a potentially reasonable growth curve. It noted
that at the time, all liquid coatings were at higher solids
content (lower volatile organic solvent content) than in
the 1960s when Rule 66 came into being. Powder coat-
ing and radiation curing were sufficiently new enough
that chapters related to testing them were not included
in the manual. High-solids development still struggled
with the difficulties of decreasing molecular weight for
low viscosity purposes and achieving the low molecular
weight with functionality on all molecules that quality
coatings require. However, the solids level has increased
in solvent-based coatings and achievements have been
realized in decreasing volatile organic content (VOC).
Since that time, powder coating has exploded. Today
the technology is well established, has a significant share of
the coatings market, is internationally accepted, and has a
strong technical society that aids in future growth. To illus-
trate the widespread acceptance of powder coatings, one
merely needs to look at advertisements. Outdoor metal fur-
niture advertisements, for example, proudly include words
that imply quality and durabilitythat is to say, powder-
coated finishes.
Of course, such furniture certainly is not the only com-
mercial outlet for powder coatings. Applications include
lighting fixtures, tubing and aerosol cans, automobile and
bicycle wheels, rebars, store fixtures, agriculture and con-
struction materials, and on and on. Initially, colors and
color changeovers were considered to be a major obstacle
to powder coating development, but today a broad variety
of colors is available, including many metallic and special
effect finishes with abrasion resistance, brilliance, and
overall high quality. Powder coating provides quality, econ-
omy in manufacturing space, increased production, energy
usage reduction, and other facets important to product
development and sales in todays marketplace.
As with powder coating, radiation curing of coatings
with either ultraviolet or electron beam radiation is no
longer a new process. This technology also has been experi-
encing strong growth since the last edition of this manual.
It is the technology in which, through an in situ means, a
low viscosity liquid system is converted into a polymeric
film or coating directly on a substrate that can be varied
in naturei.e., metal, wood, plastic, composite structures,
etc. In effect, the originally liquid system is instantaneously
converted into the final high molecular weight, cross-linked
coating. Radiation curing of liquid systems is not limited
to coatings, and it is growing in the printing ink and adhe-
sive areas. It is considered to be green technology, is well
established in the marketplace, has garnered a significant
portion of the total coatings market, has a strong technical
society dedicated to it, and is internationally accepted.
Radiation-curing technology has many facets that will
ensure future growth. Harbourne
1
has pointed out that
over and above the usual advantages behind ultraviolet
radiation curing technologyenergy conservation, usage
efficiency, and environmental conservationits driving
force is the fact that the UV process has enabled produc-
tion and development of products that could not have been
achieved with earlier existing technologies. Such products
include flexible electronics for energy storage and circuit
development, polymeric solar cells, printable electronics,
medical devices, touch screens, optical films, and on and
on. In the area of solar energy, highly efficient organic
photovoltaic cells are being developed that are thinner and
lighter in weight with significantly decreased production
costs. Such cells are used in emergency power genera-
tion, lighting, and outdoor power generation. New smart
materials with self-healing properties will provide overall
cost savings through high value-added finishes on a variety
of substrates. Solvent-based, high-solids coating systems
continue to be developed. Such coatings have markedly
decreased volatile organic content and provide high quality
coatings and reduced environmental damage.
FUTURE
As described above, powder and radiation-cured coatings
have been experiencing excellent growth over the past
decade or so, with each technology growing on its own
merits. More recently, a combination of the two tech-
nologiesUVCurable Powder Coatingshas very good
growth potential. New opportunities for the combination
are due to the same benefits mentioned aboveeconomic,
environmental, process, energy savings, and increased
productivity.
2
The combination is meeting the less expen-
sive, more rapid, and high quality challenges required by
the demanding customers of today. The coatings are being
used on medium-density fiberboard, plastics and other heat
sensitive substrates, composites, and preassembled parts
including completed items. Preassembled items often con-
tain a number of different materials such as electronic com-
ponents, gaskets, rubber seals, and the like--all of which
are heat sensitive in nature. The ability to coat and cure
such combinations with systems based on the combined
technologies results in less thermal damage to the sensitive
materials and thus greater efficiency and productivity along
with cost savings.
Nanotechnology is a field of emerging technology that
may hold great promise in the future for the coatings, inks,
and adhesives industry and certainly for a broad variety of
other industries. Nanotechnology has broad implications
1
Harbourne, A. D. P., The Evolution of UV Photopolymerization
in Global Industrial Manufacturing Markets and the Promising
Outlook for the Future of the Technology, The 31st International
Congress on Imaging Science, Beijing, China, pp. 013015 (2010).
2
Schwarb, Ryan and Knoblauch, Michael, New Opportunities for
UV-Curable Powder Coatings, Coatings World, Volume 16, Num-
ber 5, pp 43-48 (May 2011).
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INTRODUCTION ix
for new products and there are multi- and interdisciplinary
efforts in progress. The technology deals with science on
the nano, or one billionth-size, scale. Nanometer particles
are 0.000000001 meter or 0.001 of a micrometer in size.
Within the technology, an assembler or molecular manu-
facturing technique is used to position molecules through
chemical reaction or interaction into new products or
existing products with enhanced properties. Although the
term nanotechnology was initially used to define efforts
conducted on a molecular scale, currently the term has
taken on a loose connotation for anything that is very small
where small means something that is most usually smaller
than a micrometer. Many examples of nanometer-designed
products exist and a few of these are given below.
Recently a plant was built of produce carbon nano-
tubes
3
. Such tubes in combination with aluminum result
in new lightweight, high strength composite materials
that have promise in the energy, electrical, and computer
industries. In another area, a multilayered, polymeric nano-
composite has been devised and it is thought to have the
potential to make a self-healing paint.
4
In this technology,
emulsion polymerization processes are used to develop a
polymeric product that is covered with a silica-based layer
of nanoparticles. Nanocomposite coatings for fabrics have
also been described
5
. These coatings improve gas barrier
properties as well as enhance mechanical characteristics.
Another area that is receiving attention is additives
for coating formulation. An additive that improves prop-
erties of water-based metal coatings has been described
6
.
Although the additive is not chemically described, it is said
to increase crosslink density and thereby various mechani-
cal properties of cured films. An additive to accelerate the
radiation-curing process is a small particle-sized version of
nepheline syenite that is prepared by a micronizing pro-
cess
7
. The micronized, ultra-fine form of this combination
mineralsoda feldspar, potash feldspar, and nepheline--is
said to enhance optical and physical performance in clear
industrial and wood coatings. Properties such as gloss,
3
Anon, Bayer MaterialScience Builds Carbon Nanotubes Plant,
Paint and Coatings Industry, Volume 25, Number 11, p. 12 (Nov.
2009).
4
Colver, Patrick J., Colard, Catheline A. L., and Bon, Stefan A. F.,
Multilayered Nanocomposite Polymer Colloids Using Emulsion
Polymerization Stabilized Solid Particles, J. American Chemical
Society, Volume 150, No. 50, pp. 1685016851 (2008).
5
Eberts, Kenneth, Ou, Runquing, and Shah, Kunal, Nanocompos-
ite Coatings for High-Performance Fabrics, Paint and Coatings In-
dustry, Volume 26, No. 4, pp. 3236 (April 2010).
6
Herold, Marc, Burgard, Detlef, Steingrover, Klaus, and Pilotek,
Steffen, A Nanoparticle-based Additive for the Improvement of
Water-Based Metal Coatings, Paint and Coatings Industry, Volume
16, Number 8, pp. 2427 (Aug. 2010).
7
Van Remortel, Scott P. and Ratcliff, Robert E., Ultrafne Neph-
eline Syenite as a Durable and Transparent Additive to Accelerate
Radiation Cure, Paint and Coating Industry, Volume 27, Number
3, pp. 2734 (Mar. 2011).
hardness, and scratch resistance are altered in a desir-
able manner. Cure rate via double bond conversion was
enhanced in the presence of these very small mineral par-
ticles.
TESTING
As listed in Table 1, ASTM International has developed
several documents that are useful in the area of nano-
technology. Although the documents are not necessarily
directly related to coatings and paints, they provide useful
background for investigators in this field and, as is appar-
ent, useful guides for laboratory efforts in the areas of ter-
minology, particle handling, effect of nanoparticles on red
blood cells, particle mobility through a graduated index,
and other areas. In the future, it is expected that this area
will further develop within ASTM International.
Joseph V. Koleske
Editor
TABLE 1ASTM Standard Documents Related
to Nanotechnology
ASTM
Designation
Document Title
E2456-06 Terminology Relating to Nanotechnology
E2490-09 Standard Guide for Measurement of
Particle Size Distribution of Nanomaterials
in Suspension by Photon Correlation
Spectroscopy (PCS)
E2524-08 Test Method for Analysis of Hemolytic
Properties of Nanoparticles
E2525-08 Test Method for Evaluation of the Effect of
Nanoparticulate Materials on the Formation
of Mouse Granulocyte-Macrophage Colonies
E2526-08 Test Method for Evaluation of Cytotoxicity
of Nanoparticulate Materials in Porcine
Kidney Cells and Human Hepatocarcinoma
Cells
E2530-06 Practice for Calibrating the Z-Magnification
of an Atomic Force Microscope at
Subnanometer Displacement Levels Using
Si(III) Monatomic Steps
E2535-07 Guide for Handling Unbound Engineered
Nanoscale Particles in Occupational Settings
E2578-07 Practice for Calculation of Mean Sizes/
Diameter and Standard Deviations of
Particle Size Distributions
E2676-09 Practice for Tangible Property Mobility
Index (MI)
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Part 1: Regulations
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3
INTRODUCTION
PRIOR TO THE 1960S, THE COATINGS INDUSTRY
enjoyed a somewhat predictable regulatory and economic
environment. The paint formulator selected solvents based
on evaporation rate, solubility parameter, density, flam-
mability, and, of course, cost. There was no apparent
need to consider the relative photochemical reactivity of
these materials, nor was there any appreciable incentive
to reduce the solvent content of commercially acceptable
coatings.
It was recognized that objectionable odors were
released from some paints and coatings. Further, air emis-
sions resulting from the evaporation of solvents during
high-temperature processing of oils and resins caused occa-
sional complaints from persons living near the coatings
plant. The prevailing view of this period was summarized
by Francis Scofield in his article in the 13th edition of the
Paint Testing Manual entitled Atmospheric Pollutants [1].
These nuisance types of pollution are a continu-
ing problem but, in general, can be dealt with
by dilution and dispersion of the objectionable
materials to bring the concentration below a level
that can be detected by the neighboring citizenry.
Fortunately, most of the materials used by the
paint industry are not toxic at concentrations
significantly below the range at which they can
be detected by the human nose, and sophisticated
analytical procedures are rarely needed to deal
with these nuisance problems.
Since the 1960s, societal concern about health and
the environment has increased appreciably. Actions taken
by federal and state legislative bodies have resulted in a
steady avalanche of new laws and associated regulations
that affect virtually all of the chemical industry. Some of
the federal laws administered by the U.S. Environmental
Protection Agency (EPA) that impact the coatings industry
are shown in Table 1. They are designed to control the emis-
sion of pollutants to air, to water, and to soil.
In addition, among the new federal standards admin-
istered by the Occupational Safety and Health Administra-
tion are those that require manufacturersincluding those
making paints and coatingsto evaluate the hazards of
products they make and to provide appropriate safety infor-
mation to employees and users through the Material Safety
Data Sheet (MSDS) and product labels:
Hazard Communication Standard (HCS), 1983
Occupational Exposure to Hazardous Chemicals in
Laboratories, 1990
The discussion in this section will focus on the Clean Air
Act and its amendments that, in the authors opinions, have
had (and will continue to have) the greatest impact on coat-
ings. However, it should be noted that regulatory activities in
specific regions of the United States (for example, the state
of California and the Ozone Transportation Commission
that includes 12 states in the U.S. Northeast plus the Dis-
trict of Columbia) have resulted in the development of
VOC emissions rulings (see section on Other Important
U.S. Regulatory Activities), which are more stringent than
those enacted through EPA. In addition, other regions of
the world are developing or have already enacted regula-
tions addressing the emissions of volatile organic com-
pounds.
THE CLEAN AIR ACT AND AMENDMENTS
Photochemical Smog
A precipitating factor influencing the basis for selection
of solvents for coatings in the 1960s and early 1970s was
the recognition that solvents emitted to the atmosphere
contributed to the growing smog problem, particularly in
Southern California. The frequency of smog conditions in
this area had increased steadily during the 1950s and 1960s
as the number of automobiles, trucks, buses, and airplanes
increased and as industrial development expanded with the
accompanying growth of petroleum and chemical process-
ing and power plant utilization.
Examples of Processes that Produce Hydrocarbons
Petroleum production, refining, transport
Internal combustion engines
Natural processesforests and plants (isoprene and
terpenes)
Surface coatings
The smog problem was (and still is) very acute in the
Los Angeles air basin, an area uniquely situated in a series
of plains that originate in the high mountains to the east.
The basin enjoys predominantly sunny days with cool,
moist air flowing with a light westerly wind most of the year.
These factors cause a nearly permanent temperature inver-
sion layer, trapping air emissions that combine to produce
persistent and eye-irritating smog in the basin. A summer
1
Regulation of Volatile Organic Compound
Emissions from Paints and Coatings
J. John Brezinski
1
and Ronald K. Litton
2
2
Solvents Technical Service, Inc., 1015 Laurelwood Drive, Kingsport, TN 37660-8516.
1
Deceased, formerly of Hurricane, WV.
MNL17-EB/Jan. 2012
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4 PAINT AND COATING TESTING MANUAL 15TH EDITION
period in Los Angeles revealed that the use of organic sol-
vents (for all purposes) accounted for about 18 % of the
organic gases. About one half of the organic solvent emitted
was attributed to the coatings industry, chiefly to the use in
paint and coatings [1].
Based on the results of laboratory studies in smog
chambers, in which a mixture of a solvent and nitrogen
oxide was exposed for 6 h to light approximately the inten-
sity of noon sunlight, the solvents could be classified as
low or high in photochemical reactivity related to the
amount of peroxides and ozone produced. These studies
formed the basis for the well-known Rule 66, an air pol-
lution control regulation passed by the Los Angeles Air
Pollution Control District. Rule 66 identifies an approved
solvent as one that contains less than 20 % by volume of
specific chemicals and is further limited to certain com-
binations of these chemicals. Thus, approved solvents can
contain no more than designated amounts of the combina-
tions shown in Table 2.
In effect, Rule 66 promoted the use of specific solvents
such as aliphatic and naphthenic hydrocarbons, alcohols,
esters, normal ketones, chlorinated hydrocarbons (except
trichloroethylene), and nitroparaffins. Rule 66, superseded
in 1976 by Rule 442, Usage of Solvents, by the California
South Coast Air Quality Management District, was subse-
quently adopted by various other state jurisdictions.
VOC Definition
The U.S. EPA was created in 1970 by Congress as part of a
plan to consolidate several federal environmental activities.
Studies directed by EPA laboratories in Research Triangle
Park, NC, of the photochemical reactivity of materials in
a laboratory smog chamber revealed that when organic
materials and nitrogen oxide were irradiated for periods
of up to 36 h, even those solvents considered acceptable
under Rule 66 reacted to form peroxides and ozone. Only
a few materials showed negligible photochemical reactivity,
among which were: methane, ethane, methylene chloride,
1,1,1-trichloroethane, and fluorinated compounds.
Since 1977, EPA has used the reactivity of ethane
(based on a series of smog chamber experiments) as the
benchmark for determining negligible reactivity. Com-
pounds deemed less reactive than, or equally reactive to,
ethane under the assumed conditions were classified as
negligible. In contrast, compounds more reactive than eth-
ane continued to be classified as reactive VOCs and were
subject to appropriate control regulations.
These studies, which were prompted in part by the
passage of the Clean Air Act of 1970, led to the conclusion
that most organic compounds emitted to the atmosphere
contribute to the formation of ozone. On this basis, EPA
adopted as a regulatory objective the limit of essentially all
volatile organic compounds emitted to the atmosphere from
all sources, including paint and coatings applications [2].
EPA Regulatory Definition of VOC
The regulatory definition of volatile organic compounds
(VOC) was revised by EPA as of November, 2004. A part of
this definition is as follows:
40 CFR Part 51 Section 51.100 Definitions
3
Volatile organic compounds (VOC) means any com-
pound of carbon, excluding carbon monoxide, carbon
dioxide, carbonic acid, metallic carbides or carbonates, and
ammonium carbonate, which participates in atmospheric
photochemical reactions
1. This includes any such organic compound other than
those which have been determined to have negligible
photochemical reactivity. The original list is: meth-
ane; ethane; methylene chloride (dichloromethane);
1,1,1-trichloroethane (methyl chloroform); 1,1,2-tri-
chloro-1,2,2-trifluoroethane (CFC-113); trichlorofluo-
romethane (CFC-11); dichlorodifluoromethane (CFC-
12); chlorodifluoromethane (CFC-22); trifluoromethane
(HFC-23); 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-
114); chloropentafluoroethane (CFC-115); 1,1,1-tri-
fluoro 2,2-dichloroethane (HCFC-123); 1,1,1,2-tetra-
fluoroethane (HF-134a); 1,1-dichloro 1-fluoroethane
TABLE 1Federal Environmental Laws
Administered by the U.S. Environmental
Protection Agency.
Law Abbreviation
Clean Air Act, 1970 CAA
Amendments of 1977 CAAA-77
Amendments of 1990 CAAA-90
Clean Water Act of 1972 CWA
Amendments of 1977
Safe Drinking Water Act, 1974 SDWA
Toxic Substances Control Act, 1975 TSCA
Resource Conservation and Recovery Act, 1980 RCRA
Comprehensive Environmental Response
Compensation and Liability Act, 1980
CERCLA
(Superfund)
Superfund Amendments and Reauthorization
Act, 1986
SARA
Title III, Emergency Planning and Community SARA, Title III Right-to-
Know, 1986
TABLE 2Rule 66: Limits of Solvent
Categories in Approved Mixtures.
a
5 % 8 % 20 %
Hydrocarbons, Aromatic Ethylbenzene, branched
alcohols, hydrocarbons ketones, toluene, or
Aldehydes, (W/8 C atoms) trichloroethane
esters, ethers or
ketones having
an olefinic or
Cycloolefinic
Unsaturation
a
Calculated as the percent by volume of the total solvent.
3
Code of Federal Regulations (CFR) Part 51; Requirements for
Preparation, Adoption and Submittal of Implementation Plans,
Federal Register, Volume 2, 1 July 2002, pp. 131136.
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CHAPTER 1 REGULATION OF VOLATILE ORGANIC COMPOUND EMISSIONS 5
(HCFC-141b); 1-chloro 1,1-difluoroethane (HCFC-
142b); 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124);
pentafluoroethane (HFC-125); 1,1,2,2-tetrafluoroeth-
ane (HFC-134); 1,1,1-trifluoroethane (HFC-143a);
1,1-difluoroethane (HFC-152a); parachlorobenzotri-
fluoride (PCBTF); cyclic, branched, or linear complete-
ly methylated siloxanes; acetone; perchloroethylene
(tetrachloroethylene); 3,3-dichloro-1,1,1,2,2-pentafluo-
ropropane (HCFC-225ca); 1,3-dichloro-1,1,2,2,3-penta-
fluoropropane (HCFC-225cb); 1,1,1,2,3,4,4,5,5,5-deca-
fluoropentane (HFC 43-10mee); difluoromethane
(HFC-32); ethylfluoride (HFC-161); 1,1,1,3,3,3-hexa-
fluoropropane (HFC-236fa); 1,1,2,2,3-pentafluo-
ropropane (HFC-245ca); 1,1,2,3,3-pentafluoropro-
pane (HFC-245ea); 1,1,1,2,3-pentafluoropropane
(HFC-245eb); 1,1,1,3,3-pentafluoropropane (HFC-
245fa); 1,1,1,2, 3,3-hexafluoropropane (HFC-236ea)
1,1,1,3,3-pentafluorobutane (HFC-365mfc); chlorofluo-
romethane (HCFC-31);1 chloro-1-fluoroethane (HCFC-
151a); 1,2-dichloro-1,1,2-trifluoroethane (HCFC-
123a); 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxy-butane
(C4F9OCH3);2-(difluoromethoxymethyl)-1,1,1,2,3,3,3-
heptafluoropropane ((CF3)2CFCF2O CH3); 1-ethoxy-
1,1,2,2,3,3,4,4,4-nonafluorobutane (C4F9OC2H5);2-
(ethoxydifluoromethyl)-1,1,1,2,3,3,3-heptafluoropro-
pane ((CF3)2CFCF2OC2H5); methyl acetate and per-
fluorocarbon compounds which fall into these classes:
i. Cyclic, branched, or linear, completely fuorinated
alkanes;
ii. Cyclic, branched, or linear, completely fuorinated
ethers with no unsaturations;
iii. Cyclic, branched, or linear, completely fuorinated
tertiary amines with no unsaturations; and
iv. Sulfur-containing perfuorocarbons with no un-
saturations and with sulfur bonds only to carbon
and fuorine.
2. For purposes of determining compliance with emis-
sions limitsVOC will be measured by the test meth-
ods in the approved State implementation plan (SIP) or
40 CFR part 60, Appendix A, as applicable. Where such
a method also measures compounds with negligible
photochemical reactivity, these negligibility-reactive
compounds may be excluded as VOC if the amount
of such compounds is accurately quantified and such
exclusion is approved by the enforcement authority.
3. As a precondition to excluding these compounds as VOC
or at any time thereafter, the enforcement authority may
require an owner or operator to provide monitoring or
testing methods and results demonstrating, to the sat-
isfaction of the enforcement authority, the amount of
negligibly-reactive compounds in the sources emissions.
4. For purposes of Federal enforcement for a specific
source, EPA shall use the test methods specified in the
applicable EPA-approved SIP in a permit issued pur-
suant to a program approved or promulgated under
title V of the Act, or under 40 CFR part 51, subpart I
or Appendix S, or under 40 CFR parts 52 or 60. EPA
will not be bound by any State determination as to
appropriate methods for testing or monitoring negli-
gibly-reactive compounds if such determination is not
reflected in any of the above provisions.
5. The following compound(s) are VOC for purposes of
all recordkeeping, emissions reporting, photochemical
dispersion modeling and inventory requirements which
apply to VOC and shall be uniquely identified in emis-
sion reports, but are not VOC for the purpose of VOC
emissions limitations or VOC content requirement:
t-butyl acetate
NoteThe category of VOC-exempt compounds can
be modified (i.e., add compounds to or delete them from
the list) by EPA. Since the development of the initial list,
numerous petitions requesting VOC exemption on spe-
cific compounds were submitted to EPA by various com-
panies and trade associations. The petitions submitted
requested that compound A be exempted from VOC control
based on its low reactivity relative to ethane. As a result of
those initiatives, several solvents were exempted by EPA.
This list includes:
Methyl Formate (2004)
t-Butyl Acetate (2004)
Propylene Carbonate (2009)
Dimethyl Carbonate (2009)
The majority of VOC exempt solvents in the initial list
were not useful in formulating coatings with good solubil-
ity and application characteristics. The delisting of ace-
tone, parachlorobenzotrifluoride, volatile methyl siloxanes
(VMS), and methyl acetate in the mid-late 90s (coupled
with the recent delisting of the 4 aforementioned solvents)
has provided coatings formulators with greater latitude in
developing lower VOC coatings.
States may also have their own list of VOC-exempt
compounds. Although state lists are often modeled after
EPA definition, users of coating products should confirm
that a solvent deemed VOC exempt by the agency is classi-
fied similarly by the respective state.
Metrics for Defining Negligible Photochemical
Reactivity
In an effort to define chemicals as having negligible pho-
tochemical reactivity (and, therefore, exempt from VOC
regulations) EPA designated ethane as the benchmark for
separating reactive from negligibly reactive compounds
under the assumed conditions. Prior to 1994, EPA had only
granted VOC exemptions based on the metric known as the
k
OH
value. This value represents the molar rate constant for
reactions between the given compound and the OH radical
in the air. If the k
OH
value of a compound is less than ethane,
the compound may be less reactive than ethane and may be
declared to be negligibly reactive.
In the mid-1990s, in response to a petition for VOC
exemption, EPA used another type of comparison to ethane
based on the ozone forming potential of other reactions
of the compound in addition to the initial reaction with
the OH radical. This method was based on the concept of
maximum incremental reactivity (MIR). The MIR values
are usually expressed either as grams of ozone formed per
mole of VOC (molar basis) or as grams of ozone formed
per gram of VOC (mass basis). Both metrics were used to
exempt two compounds in the 1990s.
Thus, since 1997, EPA has considered three different
metrics to compare the reactivity of a specific compound
to that of ethane:
1. the reaction rate constant with the hydroxyl radical
(known as k
OH
)
2. MIR expressed as reactivity per gram basis
3. MIR expressed as reactivity per mole basis
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6 PAINT AND COATING TESTING MANUAL 15TH EDITION
Even though much debate and critique has ensued on
the merits of a mass versus mole comparison, in Interim
Guidance on Control of Volatile Organic Compounds in
Ozone State Implementation Plans published on Septem-
ber 13, 2005 (70FR 54046), EPA stated:
A comparison to ethane on a mass basis strikes
the right balance between a threshold that is
low enough to capture compounds that signifi-
cantly affect ozone concentrations and a threshold
that is high enough to exempt compounds that
may usefully substitute for more highly reactive
compounds. . . . When reviewing compounds that
have been suggested for VOC exempt status, EPA
will continue to compare them to ethane using
k
OH
expressed on a molar basis and MIR values
expressed on a mass basis.
The MIR values (both by mole and mass) are developed
measures of photochemical reactivity derived from a com-
puter-based photochemical model. This concept, which dem-
onstrates that VOCs have different reactivity, i.e., different
ozone-forming potential, is now shaping revised ozone con-
trol strategies at both the federal and state levels (view section
on Alternative Concept for Controlling Ozone Formation).
VOC and Ozone Formation
The understanding of photochemical smog and its contri-
bution to the formation of ground level ozone has increased
dramatically since the days of Rule 66. Basically, VOCs react
with oxides of nitrogen (NO
X
) in the presence of heat and
sunlight to form ground level. However, the interrelationship
of VOCs and NO
X
in ozone formation is a complex series of
reactions. One suggested pathway is depicted below [3].
NO
2
+ Sunlight NO + O
O + O
2
O
3
O
3
+ NO NO
2
+ O
2
VOCs + Sunlight Radicals
NO + Radicals NO
2
Primary Sources of NO
x
: On-road mobile sources, electricity
generating units, and nonroad mobile sources.
Other articles have been published on factors affecting
photochemical ozone formation and the potential of a given
compound to contribute to ozone formation in the tropo-
sphere (lower atmosphere) [4,5].
In addition to the concentration of NO
2
and available
sunlight in the atmosphere, ozone formation is also affected
by temperature, humidity, as well as the concentration and
composition of other VOCs present in the atmosphere. Also,
substantial biogenic (natural) VOCs released from trees and
other green plants can impact ozone formation at ground
level.
Considerable interest has developed recently in the
consideration of individual solvent photochemical reactiv-
ity in state, federal, and international programs related to
air quality control (see section on New Concept for Con-
trolling Ozone Formation).
Other VOC Definitions
The U.S. EPA defines a category of VOC-exempt com-
pounds (as described in the section on EPA Regulatory
Definition of VOC). However, for many consumer products
(i.e., floor polishes, glass cleaners, automotive rubbing or
polishing compounds, etc.), EPA has determined that low
volatility compounds may also be exempted from regula-
tions as VOCs. These include solvents:
Having a vapor pressure (VP) < 0.1 mm Hg at 20C; or
Consisting of > 12 carbon atoms, if the VP is unknown;
or
Having a MP > 20C, and which does not sublime (i.e.,
does not change directly from solid into a gas without
melting), if the VP is unknown.
Currently, there is no explicit LVP (low vapor pressure)
exemption for products used in paints and coatings. Thus,
some LVP products are regulated as VOCs in coatings but
not when used in consumer products.
Lastly, a wide disparity in the definition of a VOC
exists across countries. A product classified as a non-VOC
in the Unites States does not automatically receive the
same classification in Europe. For example, the criteria for
the EU eco-labeling scheme is that a VOC is any organic
compound with, at normal conditions for pressure, a boil-
ing point (or initial boiling point) lower than or equal to
250C [refOfficial Journal 39 (L4), 6 January (1996)].
Thus, coalescing aids for latex paints with a boiling point
(BP) >250C would not be a VOC under the EU eco-
labeling definition. Other countries are becoming more
proactive in developing rules and definitions addressing
VOC issues.
The Ozone Standard
The Clean Air Act of 1970 targeted six criteria pollutants
for control: carbon monoxide, lead, nitrogen dioxide,
ozone, particulates, and sulfur dioxide. Criteria pollutants
are those for which criteria were issued by EPA. These
documents include national ambient air quality standards
(NAAQS) for each criteria pollutantlevels that protect
against adverse effects to health and to plants and materi-
als [6]. These criteria documents and standards were to be
reviewed every 5 years and if necessary, revised to assure
that the standards provided adequate health protection. Cri-
teria pollutants are measured using a network of monitors
nationwide. Standards for ozone and nitrogen oxides are:
Ozone: In July 1997, the U.S. EPA revised its NAAQS
for ground-level ozone and particulate matter. The com-
plete standards appeared in the July 18, 1997, edition of the
Federal Register (pp. 3865238896). The EPA began phasing
out and replacing the previous 1-hour standard (last revised
in 1979) with a new 8-hour standard. The new standard
would be 0.08 ppm measured over 8 hours, replacing the
old standard of 0.12 ppm measured over 1 h. In establishing
the 8-hour standard, the EPA defined the new standard as a
concentration based form, and it called for measuring the
3-year average of the annual 4th-highest daily maximum
8-hour ozone concentration.
On June 20, 2007, the EPA administrator signed pro-
posed revisions to the NAAQS for ozone. The end result of
the proposal was the 8-hour primary standard for O
3
set
at 0.075 ppm in the March, 2008 final rule.
On January 6, 2010, the EPA proposed to strengthen
the NAAQS for ozone. This provision proposed that the 8-h
primary standard for ozone be set at a lower level within
the range of 0.0600.070 ppm. This action would provide
increased protection for children and other at risk popu-
lations against the adverse health effects related to ozone
exposure. According to the publication Ozone Air Quality
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CHAPTER 1 REGULATION OF VOLATILE ORGANIC COMPOUND EMISSIONS 7
Standards: EPAs Proposed January 2010 Revisions (fol-
lowing public hearings and comments)a final rule was
scheduled to be issued by August 31, 2010.
The Clean Air Act requires that the EPA set a stan-
dard based on the need to protect public health with an
adequate margin of safety. For policy guidance, timelines,
recent actions, etc., on the new ozone standard, see the fol-
lowing: www.epa.gov/air/ozonepollution/.
NotePrimary standards set limits to protect public
health, including the health of sensitive populations such
as asthmatics, children, and the elderly.
The implementation of a new ozone standard is of vital
interest to the paint industry since the CAAA-90 specifically
identifies paint and coatings for various controls for VOC
emission reductions, one precursor for ozone formation.
Under the new standard, there could be additional ozone
nonattainment areas that will increase the need for compli-
ant coating technology.
Nitrogen Dioxide: The nitrogen dioxide concentration
in the atmosphere cannot exceed 0.053 ppm as the annual
arithmetic mean concentration. In 2010, the EPA supple-
mented the existing annual standard for NO
2
by establish-
ing new short-time standard based on the 3-year average
of the 98th percentile of the yearly distribution of 1-hour
daily maximum. EPA set the level of this new standard at
100 ppb. Final rule is listed at: http://www.regulations.gov.
As of February, 2010, there are no areas in the United
States that are designated as nonattainment of the NO
x
,
NAAQS. Although no change has occurred in NAAQS
for nitrogen dioxide, decreasing NO
x
emissions [various
nitrogen compounds like nitrogen dioxide (NO
2
) and nitric
oxide (NO)] are receiving more attention from the EPA in
an effort to minimize ground level ozone, which is formed
when NO
x
and VOCs react in the presence of heat and sun-
light. This is an important shift in strategy for controlling
ozone formation since it recognizes that in geographical
regions in which the ratio of VOCs to NO
x
is high (NO
x
-limited conditions), additional reductions in VOC emis-
sions will have a minimal impact on air quality.
CONTROL OF VOC EMISSIONS FROM COATINGS
The Clean Air Act addresses air pollution emanating from
both existing sources and that from future new plant con-
struction or significant modification of existing sources.
States with areas that did not comply with the ozone stan-
dard were given primary responsibility to develop appro-
priate regulations for existing sources to meet the time
schedule for compliance specified by Congress. The plan
outlines the measures that the state will take in order to
improve air quality.
The Federal EPA was assigned oversight responsibility
for the state programs that were described in State Imple-
mentation Plans (SIPs). The plan outlines the measures
that the state will take in order to improve air quality. No
SIP can mandate weaker pollution controls than those
established by the EPA. The SIP is reviewed by the EPA and
if deemed unacceptable, the EPA must prepare one for it.
For example, failure by a state to submit an adequate SIP
can result in restrictions on federal highway funds.
Control Technique Guidelines
In 1977, the Agency issued the first of a series of guidance
documents for the states related to various industrial coat-
ing operations or end-use categories. These documents,
called Control Technique Guidelines (CTG) Series, Control
of Volatile Organic Emissions from Stationary Sources,
include recommended VOC emission limits, based on the
EPAs assessment of Reasonably Available Control Technol-
ogy (RACT): the limits are expressed as pounds of VOC per
gallon of coating (minus water), as applied. The EPA has
defined RACT as the lowest emission limit that a source can
meet by the application of control technology that is rea-
sonably available considering technological and economic
feasibility.
The Clean Air Act Amendments of 1977 directed that
states had to revise their implementation plans for areas
out of compliance with the national ozone standard. The
revised SIPs were to include sufficient control of VOC
emissions from stationary sources (buildings, structures,
facilities, and installations), such controls to incorporate
the RACT limits for coatings operations for which a CTG
was published.
NoteCTGs are not federal regulations. However, they
do provide federally prescribed control measures to be
incorporated as a part of approved SIPs.
Under the CAAA-90, the EPA scheduled issuance of
CTG documents for 29 categories of VOC sources, which
covered a variety of surface coating operations. Section 183
of the amended act also requires that the EPA issue CTGs
for an additional number of surface coatings processes by
1993. In addition, the EPA planned to integrate HAP (Haz-
ardous Air Pollutant) rulemaking with VOC requirements
under 183 (e).
For the industry source categories, the approach to
reduce VOC emissions has been for applicators to either
adopt an alternate coating technology (high-solids, water-
borne, powder, UV cure), or install engineering controls
(carbon adsorption, incineration, etc.).
NEW SOURCE PERFORMANCE STANDARDS
The control of VOC emissions from new coatings plants
and from significant modifications of existing plants was
addressed by the EPA in a series of New Source Perfor-
mance Standards (NSPS), the first of which issued in 1980.
These mandatory standards, which apply uniformly to all
parts of the country, define the emission sources more
narrowly and impose a tighter level of emission control
than that for related existing sources. Facilities that are
constructed, modified, or reconstructed after the NPSP was
proposed by the EPA are subject to NSPS.
The VOC limits defined in the NSPS, expressed as
kilograms of VOC per liter of applied solids, are based on
the best demonstrated technology (BDT) for the specific
coating operation. The NSPS requirements can be found in
the Code of Federal Regulations at Title 40 (Protection of
Environment), Part 60 (Standards of Performance for New
Stationary Sources): http://ecfr.gpoaccess.gov/cgi/tZtext/
text-idx?sid=474f779beade290997e4611971d078f4&c=ecfr
&tpl=/ecfrbrowse/Title40/40tab_02.tpl.
The emission limits in both the CTG and NSPS docu-
ments, in the majority of cases, focus on restricting the
VOC content per unit of coating or of coating solids applied
in the operation, rather than placing a ceiling on individual
plant emissions. The responsibility for establishing emis-
sion limits for particular plants, if appropriate, was left to
the states [7].
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8 PAINT AND COATING TESTING MANUAL 15TH EDITION
DETERMINATION OF VOC CONTENT
EPA Federal Reference Method 24
The procedures specified by the federal EPA for testing paint
products for compliance with VOC limits are described in
Federal Reference Method 24: Determination of Volatile
Matter Content, Density, Volume Solids, and Weight Sol-
ids of Surface Coatings [8]. This standard employs several
ASTM test standards, including those shown in Table 3. In
addition, Reference Method 24A: Determination of Volatile
Matter Content and Density of Publication Rotogravure
Inks and Related Publication Rotogravure Coatings incor-
porates these ASTM standards. These two documents pro-
vide the framework for referencing these ASTM standards
in determining VOC levels under regulation.
Method D2369 is a key procedure of Federal Method
24. Since 1980, several important revisions have been made
in this standard to make it compatible with revisions in
Method 24, including the addition in 1990 of instructions
for testing multicomponent coatings and the deletion of
sections dealing with testing at shorter times. The revised
version of Federal Reference Method 24 is also included
in the ASTM Manual on Determination of Volatile Organic
Compound (VOC) Content in Paints, Inks, and Related Coat-
ing Products, 2nd ed., 1993 [9].
Substantial revisions were also made in ASTM D3960,
Practice for Determining Volatile Organic Compound
(VOC) Content of Paints and Related Coatings, a standard
developed in ASTM Subcommittee D01.21 to provide a
guide for the calculation of VOC and to establish a base for
the investigation in ASTM of the precision of VOC content
determination. The definitions and symbols used in D3960
are those adopted by the EPA and included in the Agency
document Procedures for Certifying Quantity of Volatile
Organic Compounds Emitted by Paint, Ink and Other Coat-
ings that was published in 1984 [10].
Studies and discussions in ASTM Subcommittee
D01.21 that led to the modification and improvements of
ASTM standards referenced in Federal Method 24 and in
ASTM Practice D3960 were conducted with the coopera-
tion of EPA personnel of the Office of Air Quality Standards
Development at Research Triangle Park, NC.
EPA Method 24 was designed to be used for measur-
ing the VOC content of all coatings that are intended for
either ambient or baking film conditions. However, that
method was not applicable to ultraviolet (UV) radiation-
cured coatings. Therefore, the method was subsequently
amended to incorporate ASTM Method D5403-93, which
does contain those procedures. The test methods in
D5403 determine the weight percent volatile content of
paint, coatings, and inks that are designed to be cured by
exposure to ultraviolet light or to a beam of accelerated
electrons. After radiation cure, the specimens are baked at
1105C for 60 min.
The general expression for calculating VOC content
[ASTM D5201-05a (2010) Standard Practice for Calculat-
ing Formulation Physical Constants of Paint (Physical
Constants of Paint and Coatings)] is available from ASTM
International at the following link: http://www.astm.org/
Standards/D5201.htm.
The expression VOC includes all organic emissions
from a coating, not just the solvent in a coating. These emis-
sions can include volatile additives, by-products of the cure
reaction, etc. Formulation VOC content may or may not
be an acceptable means for compliance, depending on the
specific wording of the applicable regulation. It would be
acceptable if the same VOC content is obtained when tested
using EPA Method 24.
The EPA would have preferred to limit VOC emissions
in the CTG on the basis of the unit volume of coating solids
applied. However, the general expression for calculating
VOC content in which VOC content is defined as mass per
unit volume of coating less water and less exempt solvent
was necessary as no acceptable consensus procedure was
available for determining the volume percent nonvolatile
content. In a presentation in Copenhagen in 1990, James
C. Berry of the U.S. EPA stated: Though certainly less than
ideal, the major attraction is that the expression permits the
determination of compliance from the analysis of a coating
sample obtained during a plant inspection. In the simplest
case, these units require only one volumetric and one gravi-
metric measurement [7].
The measurement of low VOC content waterborne
coatings (e.g., architectural) using EPA Reference Method
24 was found to be unreliable (confirmed by industry
round-robin lab trials). Studies demonstrated that the
error in VOC measurements in waterborne coatings was
inversely proportional to the VOC content of the coating
(i.e., the lower the VOC content, the poorer the precision
to be expected). As industry moved toward lower VOC
coatings for compliance purposes, it was prudent that a
more reliable test method be found that more accurately
quantified VOC content in waterborne coatings. After
much stakeholder corroboration, the following test was
developed: ASTM D6886-03 Speciation of the Volatile
Organic Compounds (VOCs) in Low VOC content Water-
borne Air-Dry Coatings by Gas Chromatography, ASTM
International. The method was designed primarily for the
analysis of waterborne coatings in which the material VOC
content is <5 wt %. Presently, ASTM D6686-03 is being
revised (ASTM WK24436) to include VOC analysis of a
wider range of materials.
OTHER VOC-RELATED METHODS AND STUDIES
ASTM development activity on other VOC-related stan-
dards continues to expand. Some standards have not been
approved as yet by the Federal EPA for use in demonstra-
tion of compliance with VOC emission control regulations.
Use of any of these standards to demonstrate compliance
should be coordinated with appropriate regulatory agen-
cies. Document summaries on all ASTM standard test
methods are located at: http://www.astm.org.
TABLE 3Clean Air Act
Amendments1990 major source
identification based on VOC I emissions;
limits for area classifications
Ozone Nonattainment
Area Classification
VOC Emission Limit,
tons/year
Marginal or moderate 100
Serious 50
Severe 25
Extreme 10
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CHAPTER 1 REGULATION OF VOLATILE ORGANIC COMPOUND EMISSIONS 9
Additional information on ASTM test methods and the
EPAs surface coating rules are available at: http://www.epa
.gov/ttn/atw/coat/common/coatingscalc.html.
Supplementary Information
Further information about the development, significance,
and limitations of these VOC-related ASTM standards as
well as about the use of ASTM standards for the demon-
stration of compliance with VOC emission control regula-
tions is available in the ASTM Manual on Determination
of Volatile Organic Compounds in Paints, Inks, and Related
Coating Products [9]. Attachments in the second edition of
this manual include the 1992 revision of Federal Reference
Number 24 and a publication from EPAs Emission Stan-
dards Division titled Procedure for Certifying Quantity
of Volatile Organic Compounds Emitted by Paint, Ink and
Other Coatings [10]. Included in the latter publication are
VOC Data Sheets, applicable to coatings as supplied by
the manufacturer and for coatings as applied by the user.
The form used for as supplied coatings is patterned after
a recommendation of the American Coatings Association
(ACA). Other resources include other chapters from the
Paint and Coating Testing Manual.
CLEAN AIR ACT AMENDMENTS OF 1990
The Clean Air Act Amendments of 1990 defined a compre-
hensive long-term approach to achieve and maintain a
healthy environment while supporting a strong and sustain-
able economic growth and sound energy policy.
4
A major
impetus for these amendments was the continued inability
of a number of heavily populated urban areas to meet the
requirements of the national ambient air quality standards
for ozone and carbon monoxide.
Among the specific issues addressed in the Act were:
control of ozone in the atmosphere; control of hazardous
air pollutants (HAPs); reduction of acid rain; and the pro-
tection of ozone in the stratosphere.
Features of the Act that have had a major impact on the
coatings industry include:
Title IOzone Control in the Atmosphere
Title I specifically directed the EPA to develop control tech-
nique guidelines and maximum achievable control tech-
nology (MACT) standards for aerospace coatings and for
shipbuilding coatings and repair. The EPA was also directed
to prepare new control technique guidelines for additional
coatings uses that included:
Auto body refinishing
Plastic parts (business machines)
Plastic parts (others)
Offset lithography
Wood furniture
In 1997, the Coatings and Consumers Product Group
of the U.S. EPA began the development of additional CTGs
for a series of new surface coatings and for some of the cat-
egories, national rules. This coordinated rule development
was an effort by the agency to ensure consistency in the
rule developments within the surface coatings industries
and composite operations (collectively known as the Coat-
ings and Composites Coordinated Rule (CCCR). Coupled
with this effort was the development of National Emission
Standards for Hazardous Air Pollutants (NESHAPs) under
section 112 of the CAA (see following section Title III
Air Toxics Program). The EPA involved a wide variety of
industry stakeholders in the rule-making process in order
to expedite the promulgation of rules and to make the pro-
cess more cost effective for both the agency and industry.
Extensive information on the current status of the Coatings
and Composite Coordinated Rule Development is available
at: http://www.epa.gov/ttn/uatw/coat/coat.html.
While coating formulators worked under established
CTG and SIP guidelines, the CAAA-1990 (Section 183e)
also required the EPA to conduct a study of the role of
VOC emissions from consumer and commercial products
(including that from aerosols) in ozone formation. This led
to the development of national rules addressing VOC emis-
sions from AIM (architectural and industrial maintenance)
coatings and consumer products. The national AIM rule
was finalized on Sept. 9, 1998. Details of the rule are avail-
able at: http://www.epa.gov/ttnatw01/183e/aim/aimpg.html.
This rule was directed at area sources, a collection of
similar emission units within a geographical area. There-
fore, engineering controls were generally not an option for
coatings applied to structures in the fields. Thus, it was
necessary that the applied coating meet the specified VOC
content in the rule. Several states, including California and
other northeastern states (OTC), have introduced rules reg-
ulating VOC emissions from AIM coatings. Typically, these
are more stringent than the existing EPA national AIM rule
(see subsequent section Other Important U.S. Regulatory
Activities).
National Rules for Consumer Products were promul-
gated in 1998. The regulation was designed to control
VOC emissions from household consumer products, such
as floor polishes, personal care, etc. Details of the rule are
available at: http://www.epa.gov/ttn/atw/183e/cp/cppg.html.
In the CAAA-90, ozone nonattainment areas were
placed in five classifications (marginal, moderate, serious,
severe, and extreme) based on the mid-1991 ozone level
and compliance with the national ozone standard by spe-
cific years is mandated in the law. In addition, a Northeast
Ozone Transport Region was created, consisting of all states
north of Virginia and east of Ohio.
Increasingly strict provisions, including further reduc-
tion of VOC emissions, were imposed on areas, the magni-
tude to be related to the severity of the ozone problem (i.e.,
the more severe the problem, the longer that Congress has
provided for an area to reach attainment). Depending on
the area classification, several or all of the following were
required:
Increased monitoring and more accurate VOC and NO
2
emission inventory
Revision of state implementation plans to incorporate
RACT limits from previous and future CTGs for all
major stationary sources
New source review and permits for new or modified
stationary sources
Reduced emission threshold levels for the definition
of major stationary sources, ranging between 10 tons/
year for severe classification areas to 100 for marginal
or moderate areas
Higher VOC emission offset requirements for new or
modified sources
4
U.S. EPA Offce of Air and Radiation, Implementation Principles
for the Clean Air Amendments of 1990.
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10 PAINT AND COATING TESTING MANUAL 15TH EDITION
However, with the ongoing transition in the ozone
standard, the agency had to designate and reclassify all
nonattainment areas in the United States with respect to
the latest standard. In the interim, the nonattainment area
must demonstrate to EPA that they are making reasonable
further progress toward improving their air quality.
Additional information as related to ozone compliance
can be accessed at: http://www.epa.gov/air/ozonepollution/
index.html.
Title IIIAir Toxics Program
Before 1990, the EPA listed and regulated only eight HAPs
as National Emission Standards for Hazardous Air Pollut-
ants (NESHAP) under 40 CFR Part 61. The listed HAPs
were based on risk findings and Risk-Based NESHAP
were then developed to reduce the emissions of the des-
ignated pollutants. By the late 1980s, total HAP emissions
remained largely uncontrolled.
Under Title III, the EPA is directed to evaluate and con-
trol the emission of air toxics (also known as hazardous air
pollutants-HAPs) from major sources of air pollution. HAPs
are materials known or suspected to cause cancer or other
serious health problems, or to cause environmental and
ecological effects. Originally 189 products and product cate-
gories (now 187) were identified in the Act, and the EPA has
the authority to delete or add additional products to this list.
Industry groups have petitioned the EPA to delist products
(see following note). A list of the materials included on the
HAP list can be found on the following website: http://www.
epa.gov/ttn/atw/allabout.html.
NoteThree petitions were submitted by the American
Chemistry Council (ACC) requesting that the EPA delist
MEK, EB glycol ether, and MIBK from the HAP list.
The EPA issued a final rule on November 29, 2004,
removing ethylene glycol monobutyl ether (EGBE) from
the Clean Air Act list of Hazardous Air Pollutants (HAPs).
Later, on December 15, 2005, EPA issued a final rule
removing Methyl Ethyl Ketone (MEK) from the list of Haz-
ardous Air Pollutants (HAPs) under section 112(b) of the
Clean Air Act.
In the Spring 2010 Semiannual Regulatory Agenda
(SAN 4849, Sequence 688Petition to Delist a Hazardous
Air Pollutant from Section 112 of the Clean Air Act: Methyl
Isobutyl Ketone (MIBK)), the EPA reported the following:
However, since the last submittal by the peti-
tioner, a 2-year MIBK bio-assay by the National
Toxicology Program (NTP) has been completed.
A draft report of this study was reviewed by the
NTP Board of Scientific Counselors Technical
Reports Review Subcommittee, which accepted
unanimously the conclusions in the report that
there is some evidence of carcinogenic activity of
MIBK. EPA has notified the petitioner that further
review of the petition will require that the peti-
tioner submit information regarding the relevance
of the NTP study and a risk characterization for
the human risk of cancer from MIBK exposures,
which would include the derivation of a cancer
unit risk estimate.
In a previous ruling (40 CFR Parts 63 and 302), low
molecular weight EO glycol ethers such as 2-ethylhexyl ether
have been excluded from the glycol ether category in the list
of HAPs established by Section 112(b)(1) of the CAAA-1990.
The control of emissions of hazardous air pollutants
was to be achieved through the promulgation of emission
standards for facilities within an industry group (or source
category) that emit these products. The initial list of cat-
egories of sources published by the EPA (57FR31576, July
16, 1992) included under Surface Coatings Processes those
processes for which CTG or national rules have been issued
or planned.
Under the technology-based approach, the EPA was
directed to develop MACT standards based on the best-per-
forming existing sources and the current status of control
technology. The MACT standards are based on emission
levels already achieved by the best performing facilities.
These emission levels define a baseline (often referred to
as the MACT floortypically the control achieved by the
best 12 % controlled of existing facilities in the source cat-
egory). Normally, the emission limit in a MACT standard is
expressed as a per cent reduction in emissions or a concen-
tration limit that regulated sources must achieve.
The legislation addresses the amount of HAPs emitted
into the airnot the amount that may be used at a specific
site. Thus, facility owners have flexibility in determining
the most effective method to comply with the regulations. It
should be noted that the standards do not apply to coatings
that contain < 1 wt. % HAP content (cumulative total) or
<0.1 wt. % (if the HAP is a carcinogen). Thus, coatings that
contain less than these de-minimis levels are considered to
be HAP-free.
MACT standards apply to sources that are major emit-
ters of HAPs. Major sources are defined as sources that
emit or have the potential to emit 10 tons per year of any
listed HAP, or 25 tons per year of a mixture of HAPs. New
sources must comply immediately upon startup and exist-
ing sources within three years.
The Act directs that the health impact and economic
factors be considered in defining appropriate MACT limits.
The EPA must insure that MACT compliance is protecting
public health and must establish residual risk standards
within 9 years after promulgation of each MACT standard.
If studies show excessive risk, EPA must enforce stricter
standards.
Further, by the end of 1995 sufficient categories and
sub-categories must be listed to ensure that 90 % of the area
sources that emit the 30 most hazardous air pollutants are
subjected to regulation. An area source is defined as any
area that is not a major source, including structure, build-
ing or installation that emits or may emit HAPs.
A draft timetable for regulating the categories of
sources of hazardous air pollutants was published by EPA
in 1992 (57FR44147, 24 Sept. 1992). The Act established a
schedule for promulgating MACT standards as follows:
1. By 11/15/92, not less than 40 categories.
2. By 11/15/94, 25 % of listed categories
3. By 11/15/97, another 25 % of listed categories
4. By 11/15/2000, all categories
EPAs published list of source categories contains
numerous surface coating operations. By the end of 1994
HAP emission standards were due for the following sur-
face coating processes: magnetic tapes, printing/publish-
ing, shipbuilding and ship repair, and wood furniture.
Once promulgated, each NESHAP is published as an
individual Subpart to Title 40 Code of Federal Regulations
(CFR) Part 63.
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CHAPTER 1 REGULATION OF VOLATILE ORGANIC COMPOUND EMISSIONS 11
The EPA was required under Section 112 to complete
promulgation of all MACT Standards by November 15, 2000.
If that date was not met, then individual facilities within
those categories must apply for case-by-case MACT deter-
minations by May 15, 2002. This provision became known
as the MACT Hammer, and was intended to assure that
the EPA would issue the designated NESHAPs on schedule.
Even though some NESHAPs were completed for sur-
face coating categories prior to 2000, the promulgation of
many of those standards was delayed. Additionally, the EPA
was unable to meet the required deadline (May 15, 2002)
for promulgating a NESHAP for any category of major
sources. As a result, the agency promulgated a regulation on
April 5, 2002, that would allow affected sources a pathway
(two-part application procedure) to satisfy the requirements
of Section 112(J). Environmental groups challenged the
regulation in court and a settlement was issued giving states
and industry guidance and new timelines on the permit-
ting necessary for the remaining MACT rules that were not
promulgated in the required time period. The status of the
NESHAPs affecting coating processes can be found at sev-
eral EPA websites: http://www.epa.gov/ttn/uatw/coat/coat.
html and http://www.epa.gov/ttn/atw/mactfnlalph.html.
In addition to the federal HAP program, many states
have their own air toxics program. These programs may
include compounds not on the federal HAP list. One exam-
ple is the California Air Toxics Hot Spot Information and
Assessment Act. Thus, coatings users need to aware of state
guidelines regulating air toxics as well.
Determination of HAP Content
The EPAs National Emission Standards for Hazardous Air
Pollutants (NESHAP) for surface coatings specify that EPA
Method 311 shall be used for determining the type/amount
of volatile HAPs used in a coating (40 CFR Part 63 Appen-
dix A). This method (gas chromatographic separation and
quantification) applies only to HAPs that are included in
the original coating as manufactured, not to those HAPs
(methanol and formaldehyde) that may form as the coating
cures.
This method is suitable for the determination of most
compounds designated as HAPs by the EPA. Styrene, ethyl
acrylate, and methyl methacrylate can be measured by
ASTM D4827-93 or ASTM 4747-87. Formaldehyde can be
measured by ASTM PS 9-94 or ASTM D1979-91. Toluene
Diisocyanate (TDI) can be measured by ASTM D3432-89.
Issues remain over the precision of Method 311, par-
ticularly at very low HAP levels. Since no specific condi-
tions (carrier gas, oven temperature, etc.) are given for the
analysis in the test method, one single methodology may
not be applicable for all HAPs in the formulation. There-
fore, prior information on the volatile composition of the
coating will aid in choosing the proper conditions for that
analysis and ensure greater accuracy in the measurements.
Certified Product Data Sheets (CPDS) from suppliers is one
source of such information.
Title VState Operating Permit Program
The state operating permit program is considered by the
EPA as a cornerstone of the CAAA-1990 amendments
designed to ensure that the ozone nonattainment areas
meet compliance deadlines. This program will impact
many previously unregulated coatings manufacturers and
users. The final rule for the operating permit program was
issued in 1992 (57FR32250, 21 July 1992codified at 40
CFR Part 70).
The operating permit program has been called the
air pollution equivalent of the NPDES permit program
of the Clean Water Act, under which operating permits are
required of sources that discharge pollutants to water. In
the program under Title V, all federal and state air pollution
rules and regulations will be consolidated under a single
document wherein the states are given authority to monitor
and enforce the regulations. Sufficient funds will be avail-
able to the states from a minimum annual fee of $25 per
ton (with the Consumer Price Index Adjustment) for each
regulated pollutant emitted the fee to be assessed against
all major sources.
Major sources required to have state operating permits
include those that have the potential to emit [i.e., the maxi-
mum capacity of a stationary source to emit any air pollutant
under its physical or operational design (taking into account
federally-enforceable emission restrictions)] 10 tons or more
per year of a single regulated hazardous air pollutant or
25 tons per year of a combination of hazardous air pollut-
ants. These pollutants include those materials for which a
national emission standard (NESHAP) has been established.
Under Title V of CAAA-90, and the final rule on operating
permit programs, the EPA is to approve (or disapprove)
state permit programs within one year of receipt; the major
sources must apply for the five-year permit within one year
of the EPAs approval of the state program, and all permits
must be issued and be legally binding by the end of 1997. In
addition, federal requirements specify that renewal applica-
tions must be filed 18 months before current permit expires;
state programs may stipulate a shorter time. Under the rule,
states have the option of exempting all non major sources,
with some exceptions, from requiring a permit for five years
after the state permit program is approved by the EPA.
The characterization of a major source in ozone
nonattainment areas is also based on the amount of vola-
tile organic compounds emitted annually. The threshold
amount is related to the area classification and sources in
ozone nonattainment areas that emit above the designated
amount of VOC shown in Table 3 are identified as major
sources. These limits vary between 10 tons/year for the
extreme classification to 100 tons/year for the marginal
or moderate classification. For ozone transport regions
(e.g., one is established in the Northeast), a threshold limit
of 50 tons/year of VOC emissions applies.
The earlier amendments of the CAA had also estab-
lished specific permitting requirements. Permits were
required for a variety of sources, including new major
sources of criteria pollutants, which must undergo a pre-
construction review and permitting process in accordance
to federal law and regulations. In nonattainment areas,
the process is called New Source Review (NSR). Several
rule requirements must currently be met before a new or
expanded facility can obtain a permit to operate in a nonat-
tainment area. The permit applicant must adopt the most
stringent pollution controls as well as certify that other
facilities under its control in the state are in compliance
with the air pollution control requirements. Thirdly, the
permit applicant must obtain sufficient surplus emission
reductions to offset their net emission increases. The
offset ratios for nonattainment areas are not a one-to-one
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12 PAINT AND COATING TESTING MANUAL 15TH EDITION
offset. The ratio is greater for areas with more severe ozone
problems. EPA guidance on the use of emission offsets is
available in 40 CFR Appendix S to Part 51.
In addition to the permitting requirements for major
sources in nonattainment areas, EPA wanted to assure
that areas (attainment) currently meeting the NAAQS
maintain a healthy level of air quality. An attainment area
is governed by the Prevention of Significant Deteriora-
tion (PSD) program, which requires the new source to
obtain a preconstruction permit. Now under the CAAA-90,
such sources must also obtain and maintain an operating
permit. Since attainment is pollutant specific, an area may
be nonattainment for one pollutant and attainment for
others.
The permitting process is quite detailed and often
requires the assistance of an environmental consultant
and/or attorney. The Minimum Operating Permit Applica-
tion Requirements are defined at 40 CFR 70.5. Likewise,
the Minimum Requirements for the Permit Content are
defined at 40 CFR70.6.
Title VIStratospheric Ozone Protection
The CAAA-1990 directs the EPA to protect the stratospheric
ozone layer. Scientists found that certain chemicals, partic-
ularly chlorofluorocarbons (CFCs), were causing destruc-
tion of the ozone layer in the stratosphere. The EPA was
directed to publish and periodically update a list of Class
I and Class II substances. Class I must include at least 15
CFCs, three halons, carbon tetrachloride, and 1,1,1 trichlo-
roethane. Class II must include at least 33 HCFCs. Other
substances found to have harmful effects on the strato-
spheric ozone layer could be added to either list, depending
on their ozone depleting potential. Class I ODS has a high
potential for ozone depletion, whereas the propensity for
ozone depletion for Class II ODS is lower. Once the sub-
stances are properly categorized, the production and use
of the substances in each class is reduced according to a
specific schedule in the Act.
The most significant feature of the program to pro-
tect ozone in the stratosphere was the staged phaseout of
1,1,1-trichloroethane (also known as methyl chloroform, or
MCF), a material widely used in coatings and classified as
a VOC-exempt solvent by the EPA. The rule specified a
time schedule for manufacturers to gradually reduce their
production of methyl chloroform and to completely phase
out the chemical by 2002. However, in March 1993, follow-
ing additional scientific findings, the EPA proposed rules
to accelerate the phaseout CFCs, methyl chloroform and
carbon tetrachloride to January 1, 1996. Additional rule
information on the accelerated phase out schedule for Class
I substances can be found at: http://www.epa.gov/ozone/
title6/phaseout/accfact.html.
In conjunction with Title VI of the CAAA-1990, an
international effort to protect the stratospheric ozone layer
was already in effect. A multinational agreement known as
the Montreal Protocol was originally signed in 1997 and
substantially amended in 1990 and 1992. In November of
1992, the parties of the Montreal protocol agreed to accel-
erate the phaseout of CFCs, methyl chloroform and carbon
tetrachloride to January 1, 1996, in developed countries.
Developing countries could continue to produce and pur-
chase CFCs and carbon tetrachloride for use until 2010 and
methyl chloroform until 2015. More information on this
protocol and phase out schedules can be located at: http://
www.unep.org/ozone/index.asp.
Section 612 of the CAA requires the EPA to establish a
program to determine acceptable substitutes for the ODS
listed in both Class I and II. On March 18, 1994, the EPA
published the Final Rulemaking (59FR 13044), which pro-
vides the process for administering the SNAP (Significant
New Alternatives Policy). Substitutes are reviewed on the
basis of ozone depletion potential, global warming poten-
tial, toxicity, flammability and exposure potential. Lists of
acceptable and unacceptable substitutes will be updated
periodically in the Federal Register. The present list of
substitutes for ozone-depleting substances is available at:
http://www.epa.gov/ozone/snap/lists
Title VIIEnforcement
In addition to the requirements for enhanced monitoring,
the EPA is granted broad new authority to impose penalties
and substantial fines for various actions, including: viola-
tions of the SIP; violation of some of the operating permit
provisions; and false statements in records, monitoring
data, and reports. Also included are provisions for field
citations by inspectors, which can lead to a substantial per-
day-per-violation fine against a facility.
Criminal penalties are also built into the CAAA-1990
as well. Any person who knowingly violates the act can
receive fines as well as imprisonment. This is true also if
an individual fails to file or maintain records as required
or negligently releases any air toxics that causes harm
danger.
OTHER IMPORTANT U.S. REGULATORY
ACTIVITIES
In the United States, other organizations besides the EPA
are developing more stringent VOC levels for paints and
coatings. The two primary ones are the South Coast Air
Quality Management District (SCAQMD) with a myriad of
regulations in effect; and the Ozone Transport Commission
(OTC), with regulations that affect 13 Northeastern and
Mid-Atlantic states.
In 1998, the SCAQMD passed AIM Coating Rule
1113, imposing severe VOC limits on AIM coatings sold
in its district. In most categories, the VOC limits for AIM
products were more stringent than the federal standards.
Subsequent revisions (enforcing even more stringent VOC
limits for AIM paints) were challenged by industry repre-
sentatives and trade associations. Current information on
Rule 1113 is available from the districts website: http://
www.aqmd.gov.
Outside of California, the OTC developed model rules
of control measures for a number of source categories,
including AIM. The AIM Model Rule was developed for the
OTC northeastern states based on Californias Suggested
Control Measure (SCM) for VOC limits for AIM coating
applications. More information on OTC AIM Coatings Rule
Development can be located at: http://www.otcair.org/.
In addition to the organizations listed above, another
regional cooperation for working together on regional air
problems was established in 1989 by the states of Illinois,
Indiana, Michigan, and Wisconsin. This was known as the
Lake Michigan Air Directors Consortium (LADCO). The
state of Ohio joined LADCO in 2004. See the following web-
site for further details: http://www.ladco.org/.
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CHAPTER 1 REGULATION OF VOLATILE ORGANIC COMPOUND EMISSIONS 13
ALTERNATIVE CONCEPT FOR CONTROLLING
OZONE FORMATION
Background
When the EPA developed its original VOC control policy
for ozone formation, its general approach was based upon
the control of total VOC emissions by mass, without distin-
guishing individual species of VOC (except those that were
deemed negligibly reactive). And, collected emission data
from earlier years appeared to confirm that this approach
was relatively successfully. Specifically, the EPA estimated
that emissions from man-made sources nationwide declined
by 54 % from 1970 to 2003 even though population, vehicle
miles traveled and gross domestic product rose 39 %, 155
% and 176 %, respectively [11].
Ongoing science led to a better understanding of how
ozone forms and the rate of ozone formation in the atmo-
sphere. Thus, questions were raised by various stakehold-
ers about the current VOC policy for ozone control. For
example, are other regulatory methods, such as a VOC reac-
tivity scale, more effective for controlling ozone formation?
And, if so, will and how does the EPA include a reactivity
option in its current VOC policy?
Historical Perspective on Reactivity Concept
The continued research on photochemical reactivity led
many to believe that a reactivity-based approach for reduc-
ing VOC emissions would be more effective (especially in
areas requiring more aggressive VOC control) than the cur-
rent mass-based approach. Reactivity is a measure of how
much a volatile organic compound contributes to the pho-
tochemical formation of ozone. It is a property of the com-
pound as well as the environment in which the compound
is formed. Therefore, the reactivity of a specific VOC varies
with ambient conditions, VOC:NOx ratios, the identity of
other VOCs in the atmosphere, and the time interval of
interest. Thus, assigning a value to the reactivity of a specific
VOC and developing a ranking scale or method for regula-
tory purposes would require an extensive research effort.
Research over the last several decades led to the ulti-
mate development of a concept known as incremental
reactivity which enables one to assess relative atmospheric
reactivity differences in VOCs. As early as 1952, it was
noted that different organic compounds vary in their poten-
tial to form ozone [12]. Subsequent work in the late 1970s
and early 1980s [13,14] led to the development of reactivity
scales. Correspondingly in the 1970s, the EPA recognized
the variability of the ozone-forming potential of different
VOCs and created an extensive two-class reactivity bin
(negligibly reactive and reactive).
In the late 1980s, Dr. William P.L. Carter at the Univer-
sity of California Riverside [15], funded by the California
Air Resources Board (CARB), investigated 18 methods of
ranking the reactivity of individual VOCs. Subsequently, Dr.
Carter and coworkers at Statewide Air Pollution Research
Center (SAPRC) and later continuing at the College of Engi-
neering Center for Environmental Research and Technol-
ogy (CE-CERT) at the University of California at Riverside
(UCR) studied further incremental reactivities using smog
chambers and computer modeling. Three scales were sug-
gested for further consideration:
1. Maximum Incremental Reactivity (MIR)
2. Maximum Ozone Incremental Reactivity (MOIR)
3. Equal Benefit Incremental Reactivity (EBIR)
Following further investigations, Dr. Carter con-
cluded that the MIR scale was the most appropriate for
regulatory purposes [16] and is now the most common
measure of incremental reactivity in the United States.
MIR is defined as a measure of the average ozone yield of
VOCs derived by adjusting the NO
x
emissions in 39 base
case urban scenarios to yield the highest incremental
reactivity of the base ROG mixture, where ROG is reac-
tive organic gas. Using this methodology, each VOC is
assigned an individual reactivity value. MIR values for
hundreds of organic compounds have been determined
and continue to be revised. IR values, including MIR
values for coating solvents, can be downloaded from Dr.
Carters website: http:/www.engr.ucr.edu/carter/SAPRC/
saprc07.pdf.
NoteFile is largerefer to Appendix BMechanism
and Reactivity Listings for Individual VOCs. This report is
a completely updated version of the SAPRC-99 chemical
mechanism, designated SAPRC-07 that provides updates to
MIR values and other ozone reactivity scales for over 1,100
types of VOCs.
Many other scientists [1720] and stakeholders have
been active in the past two decades in advancing the sci-
ence of the reactivity concept. One such effort has been the
work of R. G. Derwent [21,22] and coworkers in Europe
who created a reactivity scale known as POCP (Photo-
chemical Ozone Creation Potential). This scale incorpo-
rated the meteorological conditions prevalent in Europe.
In December 2008, Derwent reported in a presentation at
the Atmospheric Chemical Mechanisms Conference that
the two chemical mechanisms [SAPRC-07 and MCMv3.1
(Master Chemical Mechanism)] appear to have generated
consistent reactivity scales (MRI and POCP), respectively,
under California conditions.
NoteThe stated references [35,1222] are only
samples of the comprehensive literature available on
atmospheric chemistry. Refer to section Regulatory
Information for more guidance on locating information
on VOC reactivity.
A major contributor to the development of an improved
scientific basis for reactivity-related regulatory policies
has been RRWG (Reactivity Research Work Group) that
was sponsored by NARSTO (formerly known as the North
American Research on Tropospheric Ozone) http://www.
narsto.org.
The RRWG was organized in 1998 to bring together
multiple stakeholders (government, industry and aca-
demia) actively interested in assessing future policies ger-
mane to the reactivity of organic compounds emitted to
ambient air. Prior to its formation, the most advanced VOC
reactivity potential regulations had been implemented by
California for the purpose of controlling emissions from
automobiles.
The RRWG organized and continues to commission
research efforts on VOC reactivity under various environ-
mental scenarios. The ongoing research has not only led
to a significantly better understanding of VOC reactivity
under a variety of environmental conditions but has helped
address policy-relevant science issues. The recent progress
in atmospheric science as it relates to ozone formation has
encouraged all stakeholders and their belief that future
regulatory approaches using VOC reactivity metrics will be
realized.
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14 PAINT AND COATING TESTING MANUAL 15TH EDITION
AEROSOL COATINGS REGULATIONS (ARB)
On Sept. 13, 2005, the EPA approved California Air Resource
Boards (CARB) SIP for ozone control,
5
including a reactiv-
ity-based approach to reduce ozone formation from aerosol
coatings. This regulation mandates that formulators of aero-
sol products must meet reactivity-based limits and encour-
ages reductions of higher reactivity VOCs. In this regulation
(using the MIR concept) the product-weighted reactivity of
the volatiles are controlled rather than the total mass of VOC
that is emitted. Thus far, it appears that the implementation
and workability of this rule has not been problematic [23].
The details of the process by which CARB estimates ozone
equivalent VOC reductions are located at: http://www.arb.
ca.gov/regact/conspro/aerocoat/aerocoat.htm.
In late 2008, the EPA also approved a National (reactiv-
ity-based) Volatile Organic Compound Emission Standards
for Aerosol Coatings: http://www.epa.gov/EPA-AIR/2008/
March/Day-24/a5589.htm.
EPA and CARB believe that the new aerosol rules will
create additional incentives for formulators to use solvents
with relatively low contribution to ozone formation. By
doing so, it will be possible to achieve more ozone reduc-
tions than through traditional VOC mass-based regulations.
SHAPING FUTURE REACTIVITY POLICY
As the science of reactivity continues to evolve, policymak-
ers will be even better equipped for assessing the feasibility
of using reactivity-based standards. As stated in the Aero-
sol Coating section, the EPA has already been proactive in
employing reactivity-based regulations at both the state and
federal levels.
The EPA continues to review its Photochemical Reac-
tivity Policy. There are many pathways to update and/or
revise EPAs existing rule [24]. According to the NARSTO
Review Panel Final Report on February 25, 2009:
On September 13, 2005, U.S. EPA published in the
Federal Register a Notice of Interim Guidance on
SIP Development, in lieu of a more formal Advance
Notice of Public Policy (ANPR). The interim guid-
ance encourages States to consider recent scien-
tific information on the photochemical reactivity
of volatile organic compounds and summarizes
recent scientific findings but does not change
any existing rules. The guidance is available on
EPA website at: http://www.epa.gov/ttn/oarpg/t1/
memoranda/27601interimguidvoc.pdf and http://
www.epa.gov/ttncaaa1/t1/meta/m27601.html. It
encourages the states to incorporate reactivity
features into their individual State Implementa-
tion Plans.
The EPA believes that traditional mass-based VOC con-
trol measures continue to be effective tools for minimizing
VOC contributions to ozone nonattainment problems in
many situations. However, as demonstrated by the recent
aerosol rulings, the EPA also believes that it is possible to
use reactivity-based limits to exceed what is achievable with
mass-based limits in a specific source category. Is the aero-
sol coatings scenario viable for other source categories?
Given the current unified effort of all stakehold-
ers involved with reactivity science, it is believed that a
pathway forward on VOC reactivity and how it may be
incorporated into the development of ozone control will be
expanded. And, when evidence supports that a reactivity-
based regulation for a category is more effective than
mass-based in ozone reduction benefits, then the current
regulation should be reviewed for revision.
SCENARIO FOR THE NEXT DECADE
CAAA-1990 and the myriad of new federal and state regula-
tions associated with implementation of this comprehen-
sive law have had a major impact on the coatings industry.
And, challenges still remain for essentially all coating oper-
ations: the level of new or stricter VOC emission limits for
coating operations (both federal and state); and the time,
manpower, and cost associated with complying with the
many new regulations associated with the amendments.
Other issues such as NO
x
reduction strategy, global
harmonization of VOC definition, and the expanded use of
the incremental reactivity concept can potentially impact
coating formulators. Regardless of the regulatory issue,
coating formulators must remain informed about changing
environmental regulations.
The paint market will continue to globalize, which
will require increased monitoring of developments in VOC
reduction programs in other countries. Important to the
coating formulators will not only be regulations germane
to a specific region but other labeling initiatives (i.e., EU
Eco Label, Green-label certification, LEED, etc.), specifying
coatings with lower VOC content.
As in the decades of 1970 through 1990, the new
millennium will continue to offer opportunities for raw
material suppliers to develop and provide environmentally
acceptable materials to paint formulators. This, in turn,
will facilitate the development of new or modified coatings
with reduced VOC/HAP content. Continued attention to the
improvement of coating processes and to the use of abate-
ment equipment for emission control during the application
of coatings (when feasible) will be ongoing. Ultimately, the
challenge for the paint chemist is to develop cost-effective
products that are tailored to meet or exceed the perfor-
mance and environmental requirements of the customer.
FINDING REGULATORY INFORMATION
EPA Sources
Federal environmental regulations, including those promul-
gated under the CAA, are published in the Code of Federal
Regulations (CFR), a series of books that are generally avail-
able on the internet as well as in major libraries and law
libraries. These regulations as well as those of related state
and local codes are also obtainable from the associated
regulatory offices. Regulations of particular interest to the
coatings industry can be found in subchapters of the Code of
Federal Regulations (Table 4): http://www.epa.gov/ttn/.
Proposed regulations are published by the EPA in the
Federal Register. Typically, a public (written) comment
period of 30 to 90 days on the proposals is allowed, and
often a public hearing is scheduled at which oral comments
can be presented. The comments received are considered by
the Agency in the development of a final regulation that is
published in the Federal Register together with the regula-
tion compliance date.
5
70FR 53930, September 13, 2005: Final Rule: Revisions to the Califor-
nia State Implementation Plans and Revision to the Defnition of Vola-
tile Organic Compounds (VOC)Removal of VOC Exemptions For
Californias Aerosol Coatings Products Reactivity-Based Regulation.
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CHAPTER 1 REGULATION OF VOLATILE ORGANIC COMPOUND EMISSIONS 15
Questions relating to the interpretation, applicability,
and compliance to air quality regulations may be addressed
to the U.S. EPA regional offices or to the specific state
regulating body responsible for air quality control. The
EPA regional offices as well as satellite locations and labo-
ratories can be accessed at: http://www.epa.gov/epahome/
postal.htm.
The EPA maintains a comprehensive website with links
to current regulatory and technical information germane
to the CAA. The primary site for information on air quality
issues, ozone depletion, air toxics, etc., is EPAs Office of
Air and Radiation site, located at: http://www.epa.gov/oar/.
Other Sources
Among the industry trade organizations (list is not exhaus-
tive) that provide information to their membership about
pending regulations and guidance on compliance with final-
ized regulations are: America Chemistry Council (ACC),
American Coatings Association (ACA), RadTech Interna-
tional North America, Chemical Coaters Association Interna-
tional (CCAI), Electrocoat Association (ECA), Paint Research
Association (PRA), Steel Structures Painting Council (SSPC),
Powder Coating Institute (PCI), Reactivity Research Work
Group (RRWG), Chemical Specialty Products Association
(CSPA), and European Solvents Industry Group (ESIG).
Several coatings journals publish excerpts from regula-
tions and summary reviews. In addition, numerous univer-
sities have programs devoted to scientific advancements
in coatings technology related to changes in air quality
regulations.
Information regarding paint raw materials, coating
technology, equipment, and environmental issues impact-
ing the industry are also available through various trade
shows and websites devoted to paints and coatings. Another
valuable resource for environmental issues associated with
the coatings industry is raw material manufacturers, espe-
cially solvent producers.
Notethe websites in this chapter were accessed on
August 30, 2010.
References
[1] Scofield, F., in Paint Testing Manual, 13th ed., ASTM Interna-
tional, West Conshohocken, PA, 1972, p. 413.
[2] EPA Policy Statement, Recommended Policy on Control of
Volatile Organic Compounds, Fed. Regist., Vol. 42, No. 131,
1977, pp. 3531435316.
[3] Bergin, M. S., Russell, A. G., Carter, W. P. L., Croes, B. E., and
Seinfield, J. H., VOC Reactivity and Urban Ozone Control, in
Encyclopedia of Environmental Analysis and Remediation; Mey-
ers, R. A., Ed., Wiley & Sons, New York, 1998, pp. 33553381.
[4] Hare, C. H., Atmospheric Chemistry, VOC Regulations and
the New Exemptions, Paint and Coatings Industry, Vol. 13,
No. 10, 1997, pp. 202214.
[5] Dimitriades, B., Photochemical Smog and Solvents, Met.
Finish., Vol. 95, No. 5, 1997, pp. 5559.
[6] Glossary for Air Pollution Control of Industrial Coating
Operations, EPA-450/3-83-013R, Environmental Protection
Agency, Washington, DC, December 1983.
[7] Berry, J. C., and U.S. EPA, Control of Volatile Organic Com-
pound (VOC) Emissions from Painting Operations in the
United States, International Symposium on Paint and the
Environment, Copenhagen, 1214 Nov. 1990.
[8] Code of Federal Regulations, Vol. 40, Subchapter C., Part 60,
Appendix A; Amendments in a Rule published in the Fed. Reg-
ist., Vol. 57, No. 133, 10 July 1992, pp. 3065430656.
[9] Manual on Determination of Volatile Organic Compounds in
Paints, Inks, and Related Coating Products, ASTM Manual
Series, MNL 4, ASTM International, West Conshohocken, PA,
1989, 2nd ed., 1993.
[10] Environmental Protection Agency, Procedures for Certifying
Quantity of Volatile Organic Compounds Emitted by Paint,
Ink and Other Coatings, EPA-450/3-84-019, Washington, DC,
December 1984.
[11] Environmental Protection Agency, Latest Findings on
National Air Quality: 2002 Status and Trends, EPA 454/K-
03-001, August 2003; The Ozone Report Measuring Progress
through 2003, EPA 454/K-04-001, April 2004, Office of Air
Quality Planning and Standards, Research Triangle Park, NC.
[12] Haagen-Smit, A. J., Bradley, C. E., and Fox, M. M., Forma-
tion of Ozone in Los Angeles Smog, Proceedings of the Second
National Air Pollution Symposium, Discussions on Fundamen-
tal Chemistry and Physics of the Atmosphere, Pasadena, CA, May
56, 1952, National Air Pollution Symposium, Los Angeles, CA.
[13] Bufalini, J. J., Walter, T. A., and Bufalini, M. M., Ozone
Formation Potential of Organic Compounds, Environ. Sci.
Technol., Vol. 10, 1976, pp. 908912.
[14] Dodge, M. C., Combined Effects of Organic Reactivity and
NMHC/NO
x
Ratio on Photochemical Oxidant FormationA Mod-
eling Study, Atmos. Environ., Vol. 18, No. 8, 1989, pp. 16571665.
[15] Carter, W. P. L., Development of Ozone Reactivity Scales for
Volatile Organic Compounds, J. Air Waste Manage. Assoc.,
Vol. 44, 1994, pp. 881899.
[16] California Air Resources Board, Initial Statement of Reasons
for the Proposed Amendments to the Regulation for Reducing
Volatile Organic Compound Emissions from Aerosol Coating
Products, California Environmental Protection Agency Air
Resources Board, Sacramento, CA, Chap. IV, 2000, pp. 3041.
[17] Dimitriades, B. Scientific Basis for the VOC Reactivity Issues
raised by Section 183(e) of the Clean Air Act Amendments of
1990, J. Air Waste Manage. Assoc., Vol. 46, 1996, pp. 963970.
[18] Atkinson, A., Atmospheric Chemistry of VOCs and NO
x
,
Atmos. Environ., Vol. 34, 2000, pp. 20632101.
[19] Stockwell, W. R., Review of the Updated Maximum Incre-
mental Reactivity Scale of Dr. William P. L. Carter, Final
report to the California Air Resource Board, September 17,
1999, Contract No. 98401.
[20] Grosjean, D., Atmospheric Chemistry of Alcohols, J. Braz.
Chem. Soc., Vol. 8, No. 4, 1997, pp. 433442.
[21] Derwent, R. G., Jenkin, M. E., Saunders, S. M., and Pilling,
M. J., Characterization of the Reactivities of Volatile Organic
Compounds Using a Master Chemical Mechanism, J. Air
Waste Manage. Assoc., Vol. 51, 2001, pp. 699707.
[22] Derwent, R. G., Jenkin, M. E., Saunders, S. M., and Pilling,
M. J., Photochemical Ozone Creation Potentials for Organic
Compounds in Northwest Europe Calculated with a Master
Chemical Mechanism, Atmos. Environ., Vol. 32, Nos. 14, 15,
1998, pp. 24292441.
[23] Avery, R. J., Reactivity-Based VOC Control for Solvent Prod-
ucts: More Efficient Ozone Reduction Strategies, Environ.
Sci. Technol., Vol. 40, No. 16, 2000, pp. 48454850.
[24] Helms, T., Johnson, W., and Tong, S., EPA Photochemical
Reactivity PolicyOverview and Update, Paint and Powder,
January 2003, pp. 3542.
TABLE 4Code of Federal Regulations
Sub-chapter Topics
Sub-chapter Subject Parts
C Air programs 5087
New source performance standards 60
D Water programs 104149
I Solid waste 240281
J Superfund/right-to-know 300372
N Effluent guidelines and standards 401471
R Toxic substances control act 700799
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Part 2: Naturally Occurring Materials
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19
INTRODUCTION
General Overview
IN THE UNITED STATES, THE TERMS BITUMINOUS
and asphaltic are often used interchangeably. In Europe,
bitumen usually refers to the mixture of heavy hydrocar-
bons, free of inorganic impurities. Asphalt is often consid-
ered the impure form of the generic material [1]. For our
purposes, the ASTM definitions will be used.
ASTM Standard Terminology Relating to Roofing,
Waterproofing, and Bituminous Materials (D1079-09) [2]
defines bitumen as either (1) a class of amorphous, black
or dark colored, (solid, semi-solid, or viscous) cementitious
substances, natural or manufactured, composed principally
of high molecular weight hydrocarbons, soluble in carbon
disulfide, and found in asphalts, tars, pitches and asphalt-
ites; or, (2) a generic term used to denote any material com-
posed principally of bitumen.
Asphalt is similarly defined as a dark brown to
black cementitious material in which the predominating
constituents are bitumens which occur in nature or are
obtained in petroleum processing. While the term has
historically implied the natural deposits (the Trinidad
Lake asphalts on the Island of Trinidad or the Bermu-
dez Lake, Venezuela, asphalts), most asphalt used in the
United States today for coatings applications is from
petroleum processing [3].
History and Background of Bitumens
As one of mans oldest engineering materials, the adhesive
and waterproofing properties of bitumen have been known
since the earliest days of civilization. The area between
the Tigris and Euphrates rivers in Iraq, long believed to be
the cradle of civilization, contains the earliest deposits
of asphalt and liquid petroleum. Early historical and bibli-
cal accounts tell of the use of asphalt in shipbuilding and
foundation mortars. The Egyptians were known to have
used asphalt in the mummification process; in fact, the
part-Persian word for asphalt, mumiya, is believed to be
the origin of our word mummy [4].
The first asphalts produced in the United States were
derived from California crude oils in the late 19th century.
A straight run distillation, often without steam, was able to
produce a good-quality material suitable for paving work.
Most of this material was competing with foreign imports
from the Lake Trinidad region on the Isle of Trinidad off
the north coast of South America. In the early 20th century,
Mexican asphalt obtained from Mexican crude oil was used
extensively in the eastern United States and gained a repu-
tation as a high-grade standard paving bitumen.
Today, asphalts are found throughout the world in sev-
eral natural deposits of soft bituminous material or as hard
glassy, black bitumen associated with certain rock forma-
tions or impregnating various limestone or sandstone-type
formations. Additionally, asphalts are derived from colloi-
dally dispersed asphalt hydrocarbons in crude petroleum.
This leads to the classification of bitumens into the two
following classes: (1) natural asphalts (bitumens) and (2)
artificial or oil asphalts (petroleum asphalts)
The purity of bituminous materials is generally related
to the degree that they are soluble in certain organic sol-
vents. For years, the degree of solubility in carbon disul-
fide (CS
2
) has been a typical method for determining the
purity of natural asphalts. ASTM Standard Test Method for
Bitumen Content [D4-86(2004)] formalizes this procedure
with CS
2
solubility as the primary screening test. Most oil
asphalts are generally greater than 99 % soluble in CS
2
.
The natural asphalts can be further classified by the
geographical region of their origin, as well as the extent
to which impurities are present. For example, Trinidad,
refined, of approximately 50 %57 % bitumen; Cuban,
refined, of 80 %90 % purity; Bermudez, refined, of 85 %
92 % purity; and various rock asphalts, i.e., limestone,
sandstone, tar sands, etc., with varying degrees of bitumen
content.
A separate class of natural bitumens is the asphaltites.
These are also called the solid bitumens and are asphalts
without impurities (silts, clays, salts, etc.), although their
degree of CS
2
solubility varies. Examples of these materials
are Gilsonite, grahamite, glance pitch, or manjak, as well
as harder materials that show no softening point, such as
the pyrobitumens. The most important of these for coatings
applications is Gilsonite.
Artificial bitumens have been classified into the three
following major groups [5].
1. Oil or petroleum asphalts are soft to hard asphalts of
high solubility in carbon disulfide (more than 99 %)
and are classed as pure bitumens. They are obtained
from the vacuum or steam distillation of crude oils
containing high asphalt content. The distillation con-
centrates the colloidally dispersed asphalt into the still
bottoms or residuum and is often a solid material.
Precipitation methods are also used to recover asphalt
from raw lubricating oils. This de-asphalting operation
uses propane or other low-boiling hydrocarbons. The
2
Bituminous Coatings
Ben J. Carlozzo
1
1
DCA Coatings, Cleveland, OH
MNL17-EB/Jan. 2012
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20 PAINT AND COATING TESTING MANUAL 15TH EDITION
materials produced are the so-called asphaltic resins,
with the hard, high asphaltene asphalts as the precipi-
tate. Variations are made by controlling the propane
stream. Oxidized or blown asphalts are obtained by
blowing air at high temperatures through soft or liquid
petroleum residues. This procedure can take semi-
asphaltic materials of low purity and produce consid-
erable amounts of bitumen. The resulting material is
harder, with a higher softening point.
2. Cracked asphalts are also petroleum derivatives, but
are obtained from by-products in oil-cracking pro-
cesses. Residues are distilled to produce asphalt. They
are variable in composition and may contain a certain
amount of uncracked paraffinic material. These mate-
rials represent asphaltic hydrocarbons approximately
intermediate in aromaticity between oil asphalts and
the completely aromatic, highly condensed bitumens
found in coal tars, water-gas tars, coal carbonization
tars, and their pitches.
3. Coal tar, water-gas tars, and their pitches are derived
from tars. ASTM D1079 defines tar as a brown or
black bituminous material, liquid or semi-solid in
consistency, in which the predominating constitu-
ents are bitumens obtained . . . from the processing
of coal, petroleum, oil-shale, wood, or other organic
materials. The free carbon content, or other carbon
disulfide insoluble matter, distinguishes coal tar from
the asphaltites and oil asphalts. The latter are devoid
of free carbon. Coal tars and their products are not
included in the category of asphalt.
In the early 1960s, approximately 70 % of all oil
asphalts were consumed by the road-paving industries with
20 % used in roofing. The solid bitumens and asphaltites of
natural origin found their greatest consumption in lacquer,
paint, and electrical insulation. Today, the paving industry
is still the largest user of these materials, but the scope and
area of specialty coatings has broadened considerably. In
recent years, asphalts and other bitumens have become
increasingly important as the cost of other natural and
synthetic binders has continued to escalate. Their ability to
act as adhesives with excellent moisture vapor transmission
properties continues to result in new and varied uses.
Coating Types
The types of asphaltic or bituminous coatings available can
be classified, in a large part, by the industry of use. Indus-
tries considered are as follows:
1. The paints and coatings industry, where bituminous
coatings have been used to protect metal from the
effects of water and oxygen degradation.
2. The roofing industry, where asphaltic coatings are used
extensively to weatherproof buildings.
3. The construction industries, where concrete and mor-
tar are waterproofed.
4. The paving industry, where the adhesive properties of
asphalt as binder are put to good use in roads.
Specialty Paints and Coatings
Asphalt, coal tar, and other bitumens have been used in sev-
eral specialty areas in the paint and coatings industry. The
predominating use has been in the area of pipe coatings
and automotive under-body coatings, although contain-
ment coatings are fast becoming a sizable market.
In pipe coatings, the base bitumen forms an inter-
penetrating network with a thermosetting resin to form
an impervious barrier to groundwater and the effects of
catastrophic rusting. On deep buried pipes or those set in
concrete, the cost associated the use of an expensive binder
is offset by the replacement costs involved. The thermoset
resins most frequently used have been the epoxides. The
bitumens used in these coatings have generally been the
coal tars and pitches. This was primarily due to the compat-
ibility of these highly aromatic materials with epoxy resins
as well as the ease of working with a liquid material. The
final film hardness is derived from the cross-linked epoxy
network.
There has been a growing concern over the years with
the toxicity of highly aromatic systems. The result has been
that trade sales and light industrial coatings have moved
away from coal tar or its pitches. Recently, the asphaltites
and oil asphalts have been used in these types of coatings.
The trend has been to use softer asphalts. Some form of
compatibilizer has also been necessary to make these lower
aromatic-content systems stable.
In automotive under-body rust proofing, bituminous
coatings have found extensive use. These materials are
modified with rubbery materials to give flexible coatings
with excellent adhesion to metal parts. Many years ago, the
predominant bitumen in use had been coal tar. Today, with
the move away from highly aromatic products, petroleum
asphalts are generally used. To use the harder bitumens
such as asphaltites and petroleum asphalts, plasticizers are
incorporated to soften and liquefy the bitumen. Originally
these plasticizers were materials such as di-octyl phthalate
(DOP) or butyl benzyl phthalate commonly found in other
coatings applications. However, the toxicity of DOP has
limited its use and items such as di-isodecyl and di-isononyl
phthalates are being used instead. Aromatic processing oils
were also used for this purpose but their toxicity has also
limited their use. Natural and synthetic waxes are added to
prevent chipping from road debris.
Given the severe penalties associated with contamina-
tion of groundwater, chemical and moisture-resistant coat-
ings for containment dikes are being used more and more
in the chemical process industry. Most state and local regu-
lations require the use of a containment wall around every
storage tank that may potentially rupture and contaminate
the water table.
Coatings for this application have included coal tar
epoxies and other coal tar/organic resin blends. Gilsonite-
based resinous coatings have been widely used and, depend-
ing on the chemical nature of the contained material,
petroleum asphalt urethanes and epoxides are available.
Additional areas where bitumens have shown appli-
cability as specialty coatings have included the areas of
sealing soil to minimize water penetration (pond liners,
seepage control for levees and dams, and hazardous waste
containment) as well as sound deadening on sheet metal
and their use in binding other bituminous materials such as
coal or lignite for pelletization.
Roof Coatings
In roof coatings, bitumens have been important raw mate-
rials since the turn of the century. Today, many commercial
roofing systems use some form of asphalt or chemically
modified asphalt in their construction. The application of
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CHAPTER 2 BITUMINOUS COATINGS 21
an asphalt or polymer-modified hot melt asphaltic material,
followed by the application of a reinforcing membrane, is
the basic construction of a modern built-up roof.
In some markets, the current industry trend has been
away from the use of hot melt coatings, where a roof-
ing kettle that heats the materials up to 450F (232C) to
reach their application viscosity is required, and toward
cold-applied systems. Here, the asphalt is usually modified
with solvents, fillers, and thixotropes as well as various
additives to result in a formulation that can be applied at
ambient temperatures with good flow properties and that
which will subsequently dry or cure into a weatherproofing
membrane.
In these coatings, volatile solvents are varied to con-
trol cure times. In general, the solvents are either mineral
spirits or naphthas. While asbestos was long a preferred
additive for thixotropy and reinforcement, the hazards of
working with and removing old installations with asbestos-
containing materials have driven the products toward
asbestos-free roofing materials. This has led to the use of
cellulose, synthetic, and glass fibers as a partial replace-
ment for asbestos. Bentonite and attapulgite clays are then
used to obtain the required thixotropy. Today, the use of
asbestos has been almost entirely eliminated in roofing.
The asphalt portion of these coatings usually consists
of materials referred to as cutbacks. Various solvents are
used to cut (solubilize) the asphalt, depending on the cure
times required. The solvent predominantly used today is
mineral spirits with a flash point of 104F (40C). Faster
evaporating versions of these cutbacks have been used
as primers for better substrate adhesion. These materials
generally use faster aromatic solvents, including toluene,
xylene, and the aromatic naphthas. The asphalt content
varies from 30 % to 70 % by weight.
The preceding materials, while they can, in the strictest
sense, be considered coatings, are actually closer to adhe-
sives in performance; that is, these coatings are applied to
hold the reinforcing membranes together. Although the last
coat applied may be a flood coat of the adhesive coating,
the roof is usually not left this way. Weathering characteris-
tics are significantly improved when these roofs are gravel
surfaced. This graveled surface blocks harmful ultraviolet
(UV) radiation and serves to improve the fire resistance.
The most common roof gravels are river-washed crushed
stone, granite, and blast-furnace slag recovered from the
iron ore reduction process and composed of silicates and
aluminosilicates of lime [6]. Other materials, also avail-
able for this purpose, include a variety of small, synthetic,
colored roofing granules, similar to those used on shingles.
From 400 to 600 lb (181272 kg) of river-washed gravel
per 100 ft
2
(9.29 m
2
) of roof is used, or, if weight consid-
erations are important, 5060 lb (22.6827.2 kg) of the
smaller roofing granules can be used. The bituminous coat-
ing is then an adhesive for these gravels.
Due to weight limitations on existing roofs and costs
associated with roof tear-offs and subsequent reroofing,
current philosophy is to maintain the existing roof. When
physically possible, restoration instead of replacement is
very cost effective. This requires the use of coatings whose
purpose is to repair damage to the roof and re-establish
or maintain the weather-tight seal. After the repairs are
complete, a reflective coating may be applied to act as a UV
barrier and thermal reflector, or additional gravel added.
Several different types of coatings have been available for
each of these purposes.
Asphalt cutbacks and emulsions are the primary coat-
ing used for restoration. They are applied in heavy applica-
tions of 4080 mm thick. This allows the coating to cover
minor surface defects that are present on the old roof.
Splits and cracks can be repaired by using these materi-
als with either fiberglass or polyester reinforcements. A
final application gives a reasonably watertight monolithic
appearance.
Asphalt emulsions consist of two types. In one, the
water is dispersed in the asphalt external phase. In the
other, the asphalt is dispersed in a water external phase.
The first are called water-in-oil (W/O) emulsions. The lat-
ter are oil-in-water (O/W) emulsions. Roofing emulsions
are predominately water-in-oil emulsions. The oil-in-water
emulsions are more widely used in the paving industry and
will be discussed in more detail in that section.
The water-in-oil emulsions are produced from finely
powdered clays, which act as dispersants for the water.
Dispersing agents of this type show some affinity for water
or are sufficiently hygroscopic to hold water and bring it
into dispersion in the asphalt. The bentonite clays form
extremely colloidal gelatinous mixtures and pastes with
water and result in asphalt dispersions of very small par-
ticle size. These smooth buttery emulsions are very stable
and can be fibered for reinforcement and modified with
latex resins to obtain a degree of elasticity. Most com-
mercial products are unmodified and yield a final coating
possessing all the properties of a gelled asphalt after evapo-
ration of the water. Several books are available that offer
more detail in the area of emulsion technology [79].
Asphalt emulsions can be left untopcoated, but are
frequently coated with reflective topcoats to help control
rooftop temperatures. For several years, the major types of
coatings for this application have been solvent-borne alu-
minum pigmented bituminous coatings. A wide variety of
bitumens have been used, including asphalt, asphaltite, tar,
and pitch. Their viscosity has generally been low with mod-
erate levels of volatile solvents present. Most of the solvent-
based aluminum bitumen paints in use today are asphalt
vehicles made from petroleum asphalt cutbacks. Mineral
spirits have been the predominately used solvent. The pig-
ment used has been a leafing grade of aluminum paste. It
is reported that some early formulations used cumerone
indene resin to improve the leafing characteristics and
act as an anti-bronzing agent. Bronzing occurs when low
molecular weight residue migrates to the surface, staining
the aluminum surface weeks to months after the film has
cured, making it look brown and limiting its reflectivity. A
level of 2.0 lb (0.91 kg) of aluminum paste is typically used
per gallon in these coatings [10].
With the recent increase in environmental legislation
and an increased awareness of health issues, alternatives
to these solvent-borne coatings are beginning to find their
place in the market. Specifically, asphalt emulsions of vari-
ous solids are being used in conjunction with new alumi-
num pigment technology, which allows the manufacture of
relatively stable waterborne versions [11,12]. These materi-
als generally consist of petroleum asphalt emulsions that
use organophosphate-treated leafing-aluminum pastes. The
phosphate passivates the aluminum, giving it more stabil-
ity on storage. The solids of such coatings vary from 25 %
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22 PAINT AND COATING TESTING MANUAL 15TH EDITION
to 50 % by weight. Additional modification similar to other
emulsion systems is also used in these coatings.
Newer technologies to stabilize aluminum pigments
in water have recently been introduced. Chemically bound
chrome is used to passivate the aluminum [13]. While quite
expensive, these products are finding use in the automotive
industry. As their cost decreases, perhaps they will be avail-
able for the waterborne bituminous aluminum market.
Other technologies exist that are non-bituminous in
composition. These coatings include elastomeric latexes,
solvent and waterborne urethanes, epoxides, and alkyds.
These are usually pigmented with titanium dioxide (TiO
2
),
aluminum or the newer infrared reflective pigments, to give
thermally reflective coatings. These types will be discussed
elsewhere in this manual.
Waterproofing Membranes
Bitumen-modified waterproofing membranes are used
extensively in the construction industry. The most common
substrate is poured or precast concrete or mortared cinder
block. Pre-stressed concrete in the foundations, walls, and
roof decks of high-rise buildings is also a suitable candidate
for these membranes. In the home construction and repair
industries, cinder block foundations and concrete footers
are commonly waterproofed with bitumen-modified poly-
meric coatings.
The bitumen of interest in these markets has predomi-
nately been coal tar pitch and petroleum asphalts. Water-
proofing membranes are generally composed of bitumen
in an elastomeric polymer matrix. The aromatic polyure-
thanes are frequently used for this purpose.
In coating structural steel and steel reinforcement bars,
coal tar epoxies have been extensively used. Their composi-
tion and purpose is similar to that of pipe coatings used for
the prevention of underground corrosion. Their composi-
tion can be modified to conform to a particular steel coat-
ings application.
As in other markets, the use of aromatic coal tars is
slowly being replaced by safer soft petroleum asphalts.
Environmental issues aside, higher technology systems are
beginning to be seen. Other types of coatings for rebar in
the past five years have included fused epoxy powder coat-
ings systems and polyethylene dip-coated systems. While
much more expensive than bitumen-modified systems,
their improved performance have made them of interest.
Coatings for Paving
The paving industry is probably the oldest using bitumen
and its coatings. Asphalt cutbacks have also been known as
road oils. For years, these solvent cut materials were used
to seal roads as well as coat aggregates for application to the
road surface. Today, hot asphalt or cutback is used to prime
new paving as well as to repair damaged or worn areas.
Today, most road coating uses asphalt emulsions. These
are generally chemically stabilized emulsions. The emulsion
is prepared beforehand and mixed with aggregate on site and
is referred to as chip and seal. Hot asphalt is not required in
this application, making it much easier than the use of hot
mix paving, where the asphalt is heated to melting before
application. In paving, oil-in-water emulsions predominate.
The oil-in-water emulsions are formed from the action
of a chemical emulsifier, which can be anionic, cationic, or
nonionic in nature. The anionic and cationic emulsifiers
form an emulsion in which the dispersed phase shows a
definite charge. These emulsions are said to break upon
contact with a charged aggregate, yielding the exclusion of
one phase from the other. The speed of break can be modi-
fied, yielding rapid, medium, or slow-setting emulsions.
The cat-ionic versions are preferred because the coating
formed does not re-emulsify. With anionic emulsifiers,
break occurs when emulsions destabilize due to water loss
on drying. One disadvantage of this is the possibility of re-
emulsification in the early stages of cure. Once the coating
has dried, water is no longer a problem.
Paving sealers are used to protect new or old asphalt
driveways or parking lots. The sealers are generally coal tar
in nature due to good resistance to gas and oil. Asphalt seal-
ers can also be used, but must be latex or polymer modified
to improve solvent resistance.
Other types of bituminous coatings used in the paving
industry include slurry seals and microsurfacing, which
uses latex or polymer-modified asphalts with fine aggregate
filler as a surface treatment for repair of minor damage to
roads. Coal tar is not used in this application because the
resulting coating is too slippery. Tack coats consisting of
asphalt cutbacks are also used when one layer of asphalt
needs to be adhered to another.
IDENTIFICATION OF BITUMINOUS MATERIALS
This section will catalogue several test methods currently
available through ASTM for characterization of bituminous
paints and coatings. Many of these methods are familiar to
the coatings chemist as standard paint-related tests found
in Volumes 6.01 through 6.04 of the Annual Book of ASTM
Standards. Several others are under the jurisdiction of
Committee D8 on Roofing, Waterproofing, and Bituminous
Materials. These methods appear in Volume 4.04 of the
Annual Book of ASTM Standards.
Tests on Bituminous Materials
The following test methods are used to differentiate one
type of bitumen from another. They also can distinguish
mixtures of bitumens and their purity. As bitumens are con-
sidered pseudo-plastic materials, with no true melt point,
softening point and penetration are the two major tests
routinely performed to identify differences within grades
of the different bitumen classes. Viscosities at elevated tem-
peratures are also very important with several instruments
and their methods listed.
In earlier editions of this manual, several tests were
described that were in common use in 1972. Among the tests
described were the solubility of bitumens in carbon disulfide
(CS
2
) to identify the purity of a bitumen sample, since by
definition only CS
2
soluble matter is bitumen. Also listed
were tests to determine the presence of asphalt and tar in
suspected mixtures (the Oliensis Spot Test) and the charac-
teristics of bituminous samples dispersed in solvent. These
methods have since been incorporated into the Annual Book
of ASTM Standards and will not be described in detail.
It is important to point out that each industry that
uses bitumens has tended to develop its own series of com-
mon pertinent tests. Today most of those pertinent tests
have been incorporated as ASTM standards. In addition to
ASTM, other organizations have tried to compile these tests
for their members use. The Asphalt Institute, an interna-
tional nonprofit organization sponsored by members of the
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CHAPTER 2 BITUMINOUS COATINGS 23
petroleum asphalt industry, also publishes a handbook that
has evolved over the past 50 years as the standard refer-
ence work in the field of asphalt technology and construc-
tion, especially in the paving industry [14]. This reference
book cites both ASTM test methods and, where applicable,
American Association of State and Transportation Officials
(AASHTO) counterparts to these methods. A large part
of the manual is devoted to practical how-to information
about how to use asphalt, as well as comprehensive data on
asphalt technology, and is highly recommended.
Standard Specifications and Standard Test Methods
for Bituminous Materials
D4-86(2004) Standard Test Method for Bitumen Content
D5-06e1 Standard Test Method for Penetration of
Bituminous Materials
D36-06 Standard Test Method for Softening Point
of Bitumen (Ring-and-Ball apparatus)
D70-09e1 Standard Test Method for Specific Gravity
and Density of Semi-Solid Bituminous
Materials
D88-07 Standard Test Method For Saybolt Viscosity
D92-05a Standard Test Method For Flash and Fire
Points by Cleveland Open Cup
D95-05e1 Standard Test Method for Water Petroleum
Products and Bituminous Materials by
Distillation
D140/D140M-09 Standard Practice for Sampling Bituminous
Materials
D529-04 Standard Practice for Enclosed Carbon Arc
Exposures of Bituminous Materials
D1079-09 Standard Terminology Relating to Roofing,
Waterproofing and Bituminous Materials
D1669-07 Standard Practice for Preparation of
Test Panels for Accelerated and Outdoor
Weathering of Bituminous Coatings
D1670-04 Standard Test Method for Failure End Point
in Accelerated and Outdoor Weathering of
Bituminous Materials
D4798/
D4798M-09
Standard Practice for Accelerated
Weathering Test Conditions and Procedures
for Bituminous Materials (Xenon-Arc
Method)
D4799-08 Standard Practice for Accelerated
Weathering Test Conditions and Procedures
for Bituminous Materials (Fluorescent UV,
Water Spray, and Condensation Method)
D4989-90a(2008) Standard Test Method for Apparent
Viscosity (Flow) of Roofing Bitumens Using
the Parallel Plate Plastometer
E96/E96M-05 Standard Test Methods for Water Vapor
Transmission of Materials
E102/E102M-
93(2009)
Standard Test Method for Saybolt Furol
Viscosity of Bituminous Materials at High
Temperatures
E108-07a Standard Test Methods for Fire Tests of
Roof Coverings
Specifications and Test Methods for Asphalt
D71-94(2004) Standard Test Method for Relative Density
of Solid Pitch and Asphalt (Displacement
Method)
D312-00(2006) Standard Specification for Asphalt Used in
Roofing
D449-03(2008) Standard Specification for Asphalt Used in
Dampproofing and Waterproofing
D1370-00(2007) Standard Test Method for Contact
Compatibility Between Asphaltic Materials
(Oliensis Test)
D1856-09 Standard Test Method for Recovery of
Asphalt from Solution Abson Method
D2042-09 Standard Test Method for Solubility of
Asphalt Materials in Trichloroethylene
D2521-76(2008) Standard Specification for Asphalt Used in
Canal, Ditch, and Pond Lining
D2746-07 Standard Test Method for Staining
Tendency of Asphalt (Stain Index)
D3461-97(2007) Standard Test Method for Softening Point
of Asphalts and Pitches (Mettler Cup-and-
Ball Method)
D4402-06 Standard Test Method for Viscosity
Determination of Asphalt at Elevated
Temperatures Using a Rotational
Viscometer
Specifications and Test Methods for Coal Tar,
Pitches, and Highly Cracked Petroleum Products
D61-75(2004) Standard Test Method for
Softening Point of Pitches
(Cube-in-Water Method)
D450-07 Standard Specification
for Coal Tar Pitch Used in
Roofing, Dampproofing, and
Waterproofing
D2318-98(2008) Standard Test Method for
Quinoline-Insoluble (QI) Content
of Tar and Pitch
D2319/D2319M-98(2008)e1 Standard Test Method for
Softening Point of Pitch (Cube-in-
Air Method)
D2320-98(2008) Standard Test Method for Density
(Relative Density) of Solid Pitch
(Pycnometer Method)
D2415-98(2008) Standard Test Method for Ash in
Coal Tar and Pitch
D2416-84(2004) Standard Test Method for Coking
Value of Tar and Pitch (Modified
Conradson)
D2764-99(2004)e1 Standard Test Method for
Dimethylformamide-Insoluble
(DMF-I) Content of Tar and Pitch
D2962-97(2007) Standard Test Method for
Calculating Volume-Temperature
Correction for Coal-Tar Pitches
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24 PAINT AND COATING TESTING MANUAL 15TH EDITION
D3104-99(2005) Standard Test Method for
Softening Point of Pitches
(Mettler Softening Point Method)
D4072-98(2008) Standard Test Method for
Toluene-Insoluble (TI) Content of
Tar and Pitch
D4312-95a(2005) Standard Test Method for
Toluene-Insoluble (TI) Content of
Tar and Pitch (Short Method)
D4616-95(2008) Standard Test Method for
Microscopical Analysis by
Reflected Light and Determination
of Mesophase in a Pitch
D4715-98(2008)e1 Standard Test Method for Coking
Value of Tar and Pitch (Alcan)
D4746-98(2008) Standard Test Method for
Determination of Quinoline
Insoluble (QI) Content in Tar and
Pitch by Pressure Filtration
D4892-89(2009) Standard Test Method for Density
of Solid Pitch (Helium Pycnometer
Method)
D4893-94(2004) Standard Test Method for
Determination of Pitch Volatility
D5018-89(2009) Standard Test Method for
Shear Viscosity of Coal Tar and
Petroleum Pitches
TESTS AND SPECIFICATIONS FOR COATINGS
General Tests for Coatings
Several of the test methods familiar to the industrial paints
and coatings chemist can also be used to characterize the per-
formance and physical properties of bituminous coatings. The
following methods can be found in Volume 3.02 and Volumes
6.01 through 6.04 of the Annual Book of ASTM Standards.
Tests and Specifications
B117-07a Standard Test Method of Salt Spray (Fog)
Testing
D522-93a(2008) Standard Test Methods for Mandrel Bend
Test of Attached Organic Coatings
D562-01(2005) Standard Test Method for Consistency of
Paints Measuring Kreb Unit (KU) Viscosity
Using A Stormer-type Viscometer
D609-00(2006) Standard Practice for Preparation of
Cold-Rolled Steel Panels for Testing Paint,
Varnish, Conversion Coatings and Related
Coating Products
D610-08 Standard Test Method for Evaluating
Degree of Rusting on Painted Steel Surfaces
D662-93(2005) Standard Test Method for Evaluating
Degree of Erosion of Exterior Paints
D714-02(2009) Standard Test Method for Evaluating
Degree of Blistering of Paints
D1212-91(2007) Standard Test Method for Measurement of
Wet Film Thickness of Organic Coatings
D1474-98(2008) Standard Test Methods for the Indentation
Hardness of Organic Coatings
D1475-98(2008) Standard Test Method for Density of Paint,
Varnish, Lacquer, and Related Products
D1640-03(2009) Standard Test Methods for Drying, Curing,
or Film Formation of Organic Coatings at
Room Temperature
D1644-01(2006) Standard Test Methods for Nonvolatile
Content of Varnishes
D1654-08 Standard Test Method for Evaluation of
Painted or Coated Specimens Subjected to
Corrosive Environments
D1849-95(2008) Standard Test Method for Package Stability
of Paint
D2243-95(2008) Standard Test Method for Freeze-Thaw
Resistance of Water-Borne Coatings
D2247-02 Standard Practice for Testing Water
Resistance of Coatings in 100 % Relative
Humidity
D2369-07 Standard Test Methods for Volatile Content
of Coatings
D2370-98(2002) Standard Test Method for Tensile Properties
of Organic Coatings
D2832-92(2005) Standard Guide for Determining Volatile
and Nonvolatile Content of Paint and
Related Coatings
D3170-03(2007) Standard Test Method for Chipping
Resistance of Coatings
D3359-09 Standard Test Methods for Measuring
Adhesion by Tape Test
D3960-05 Standard Practice for Determining Volatile
Organic Compound (VOC) Content of Paints
and Related Coatings
G6-07 Standard Test Method for Abrasion
Resistance of Pipeline Coatings
Solvent-Thinned or Cut-Back Coatings
The following test methods relate specifically to solvent
thinned or cut-back bituminous coatings such as those used
for weatherproofing roofs or protecting metal structures
and appurtenances. Although volatile organic content of
coatings has become increasingly more important, leading
to the greater use of emulsified bitumen, the sealing and
waterproofing properties of straight asphalt have contin-
ued to make these types of coatings viable. This in turn has
made their test methods pertinent.
General
D402-08 Standard Test Method for Distillation of
Cut-Back Asphaltic (Bituminous) Products
D529-04 Standard Test Method for Enclosed
Carbon Arc Exposures for Bituminous
Materials
D3105-08 Standard Index of Methods for Testing
Elastomeric and Plastomeric Roofing and
Waterproofing Materials
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CHAPTER 2 BITUMINOUS COATINGS 25
Roof Coatings
D41-05 Standard Specification for Asphalt Primer
Used in Roofing and Waterproofing
D43-00(2006) Standard Specification for Creosote
Primer Used in Roofing, Dampproofing
and Waterproofing
D1227-95(2007) Standard Specification for Emulsified
Asphalt Used as a Protective Coating for
Built-Up Roofing
D2823-05 Standard Specification for Asphalt Roof
Coatings
D2824-06 Standard Specification for Aluminum-
Pigmented Roof Coatings, Non-Fibered,
Asbestos Fibered, and Fibered Without
Asbestos
D4479-07 Standard Specification for Asphalt Roof
Coatings-Asbestos Free
D5076-90(2006) Standard Test Method for Measuring
Voids in Roofing and Waterproofing
Membranes
Waterproofing Membranes
D41-05 Standard Specification for Asphalt Primer
Used in Roofing, Dampproofing and
Waterproofing
D43-00(2006) Standard for Creosote Primer Used
in Roofing, Dampproofing and
Waterproofing
D5076-90(2006) Standard Test Method for Measuring
Voids in Roofing and Waterproofing
Membranes
Paving Sealers
D3320-00(2004)e1 Standard Specification for Emulsified Coal
Tar Pitch (Mineral Colloid Type)
D3423-84(2003) Standard Practice for Application of
Emulsified Coal Tar Pitch (Mineral Colloid
Type)
D4866-88(2003)e1 Standard Performance Specification for
Coal Tar Pitch Emulsion Pavement Sealer
Mix Formulations Containing Mineral
Aggregates and Optional Polymeric
Admixtures
Specialty Coatings
D41-05 Standard Specification for Primer Used in
Roofing and Waterproofing
D43-00(2006) Standard Specification for Creosote Primer
Used in Roofing, Dampproofing and
Waterproofing
D1187-97(2002)e1 Standard Specification for Asphalt-Base
Emulsions for Use as Protective Coatings
for Metal
Emulsion Coatings
General
D529-04 Standard Test Method for Enclosed
Carbon Arc for Bituminous Materials
D1187-97(2002)e1 Standard Test Method for Asphalt-Base
Emulsion for Use as Protective Coatings
for Metal
D2939-03 Standard Test Method for Emulsified
Bitumens Used as Protective Coatings
Clay Stabilized Emulsions
D1227-95(2007) Standard Specification for Emulsified
Asphalt Used as a Protective Coating for
Roofing
D3320-00(2004)e1 Standard Specification for Emulsified Coal
Tar Pitch (Mineral Colloid Type)
Anionic Emulsions
D1227-95(2007) Standard Specification for Emulsified
Asphalt Used as a Protective Coating
for Roofing
Non-Ionic Emulsions
D1227-95(2007) Standard Specification for Emulsified
Asphalt Used as a Protective Coating for
Roofing
Cationic Emulsions
D1227-95(2007) Standard Specification for Emulsified
Asphalt Used as a Protective Coating for
Roofing
Resin Modified Bituminous Coatings
Synthetic Resins
D3468-99(2006)e1 Specification for Liquid-Applied Neoprene
and Chlorosulfonated Polyethylene Used
in Roofing and Waterproofing
WITHDRAWN SPECIFICATIONS AND
TEST METHODS
The following specifications and test methods have been
withdrawn by ASTM since the last printing of this book.
The dedicated researcher may wish to investigate archived
copies of these methods for the potential insight they bring
to testing bituminous based coatings in general and asphalt
in particular. D1328 is the only method for which an alter-
nate method was established. The others were withdrawn
the year specified.
D255-70 Method for Steam Distillation of
Bituminous Protective Coatings
Withdrawn 2000No Replacement
D466-42 Method of Testing Films Deposited from
Bituminous EmulsionsWithdrawn
1991No Replacement
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26 PAINT AND COATING TESTING MANUAL 15TH EDITION
D555-94(1999) Standard Guide for Testing Drying Oils
Withdrawn 2007No Replacement
D1328-86 Standard Test Method for Staining
Properties of AsphaltWithdrawn 1992
Replaced by D2746-97
D1540-82 Standard Test Method for Effect of
Chemical Agents on Organic Finishes
Used in the Transportation Industry
Withdrawn 1991No Replacement
D1542-60 Standard Test Method for Qualitative
Detection of Rosin in Varnishes
Withdrawn 1997No Replacement
D2569-97(2002) Standard Test Method for Distillation of
PitchWithdrawn 2006No Replacement
D2963-78 Standard Test Method for Testing Flow
Table Consistency of Clay-Stabilized
Asphalt EmulsionsWithdrawn 1997No
Replacement
D3805-85 Standard Practice for Application of
Aluminum-Pigmented Asphalt Roof
Coatings Withdrawn 1996No
Replacement
CONCLUSION
Bituminous coatings are still used extensively today. The
waterproofing and adhesive properties, coupled with the
relatively inexpensive costs for most bituminous materials,
continue to drive their many diverse industrial applica-
tions. The preceding information will give the reader an
understanding of the chemistry and uses of bituminous
coatings in industry and a realization that even several
thousand years after their discovery and first use the usage
of these bituminous raw materials as an engineering raw
material is still growing.
References
[1] Barth, E. J., Asphalt: Science and Technology, Gordon and
Breach Science Publishers, New York, 1962.
[2] ASTM, Standard D1079-09, Roofing Waterproofing, and
Bituminous Materials, Annual Book of ASTM Standards, Sec-
tion 4, Vol. 4, ASTM International, West Conshohocken, PA,
2001, p. 100.
[3] Barth, E. J., Asphalt: Science and Technology, Gordon and
Breach Science Publishers, New York, 1962, p. 3.
[4] Martin, O., Bitumen, Teere, Asphalte Peche, Vol. 11, 1960,
p. 285.
[5] Barth, E. J., Asphalt: Science and Technology, Gordon and
Breach Science Publishers, New York, 1962, pp. 79.
[6] Griffin, C. W., Manual of Built-Up Roof Systems, 2nd ed.,
McGraw-Hill Book Co., New York, 1982, pp. 141151.
[7] Barth, E. J., Asphalt: Science and Technology, Gordon and
Breach Science Publishers, New York, 1962, pp. 471558.
[8] Bennett, H., Bishop, J. L., and Wulfinghoff, M. F., Practical
Emulsions: Materials and Equipment, Vol. 1, Chemical Pub-
lishing Company, Inc., New York, 1968.
[9] Bennett, H., Bishop, J. L., and Wulfinghoff, M. F., Practical
Emulsions: Applications, Vol. 2, Chemical Publishing Com-
pany, Inc., New York, 1968.
[10] Edwards, J. D. and Wray, R. L., Aluminum Paint and Powder,
Reinhold Publishing Corp., New York, pp. 6469.
[11] Williams, J. E., Water Resistant Aluminum Particles and
Coating, U.S. Patent No. 4,565,716 (1986).
[12] Besold, R., Aluminum Flake in Waterborne Coatings: Antago-
nism or Reality, Proceedings of the 18th Annual Higher Solids
and Waterborne Coatings Symposium, New Orleans, LA, 1991.
[13] Chapman, D. P., Aluminum Pigment Technology for Water-
borne and Powder Coatings in the 1990s, Proceedings of the
18th Annual Higher Solids and Waterborne Coatings Sympo-
sium, New Orleans, LA, 1991.
[14] The Asphalt Institute, The Asphalt Handbook, Manual Series
No. 4 (MS-4), 7th edition, Lexington, KY, 2007, p. 788.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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27
INTRODUCTION
CELLULOSE ESTERS ARE BASED ON ONE OF THE
most abundant naturally occurring biopolymers, namely
cellulose. This polysaccharide represents a readily avail-
able, sustainable feedstock alternative to petroleum-based
materials. Although a broad variety of cellulose esters can
be made, this chapter only provides a general discussion on
the commercially available organic acid esters of cellulose:
cellulose acetate (CA), cellulose acetate propionate (CAP),
and cellulose acetate butyrate (CAB).
Cellulose esters are the reaction product of combining
organic acids and/or acid anhydrides with the hydroxyl
groups found on the anhydroglucose repeating units of a
cellulose molecule [1, 2]. In addition to esterification, sev-
eral subsequent processing steps are required in the manu-
facture of cellulose esters including hydrolysis to obtain
the desired residual hydroxyl level, filtration, precipitation,
washing, dewatering, drying, and screening. Details about
these and other manufacturing steps can be found at vari-
ous places in the three volumes of Ott, Spurlin, and Grafflin
[3]. The final product is a dry, free-flowing powder in most
instances, although other physical forms can be produced
when required.
Basic information about physical properties, solubility
properties in various solvents and monomers, and compat-
ibility properties of various cellulose esters is provided.
Typical uses as well as selected new uses for cellulose esters
are briefly discussed as a general guide to selecting these
polymeric materials for a variety of applications.
TYPES OF CELLULOSE ESTERS
Three types of cellulose esters are commercially available,
including CA, CAP, and CAB (Fig. 1). Table 1 shows the
types of commercially available cellulose esters. Cellulose
acetate butyrate is the most commonly used organic cel-
lulose ester for coating applications.
3
Many types have been
manufactured by varying acetyl/butyryl ratios, hydroxyl
content and molecular weight to meet the requirements of
the applications for which they were developed.
Cellulose acetates are the least soluble and least com-
patible of the cellulose esters, and they require strong
solvents for dissolution. They have high glass transition
temperatures and produce tough and hard films with excel-
lent chemical resistance. CAPs have improved compatibility
and solubility and are used in applications where low odor
is required. CAB esters are used as binders in protective and
decorative coatings for metal, wood, textiles, cloth, paper,
plastic, human nail care, printing inks, trucks and buses,
polarographic oxygen electrodes, solid rocket propellants,
and leather. They provide excellent color and color retention,
toughness, flexibility, flow control, as well as good weather
resistance. All three products are available with a range of
substituents and molecular weights that determine their sol-
ubility, compatibility, viscosity, and hardness. Recently, Yuan
et al. [4] have investigated the permeability characteristics
of cellulose acetate butyrate coating films and their impor-
tance as semipermeable membranes in osmotic drug deliv-
ery systems. Similar studies related to this end use include
the use of CAB as a matrix tableting and/or taste masking
material when combined with CA and hydroxypropyl cel-
lulose [57]. A novel technique for forming very thick but
wrinkle-free membranes that involves solvent-nonsolvent
mixtures has been described [8]. Table 1 contains a listing
of properties for commercial cellulose esters.
CAB esters are also useful as coatings additives where
they can provide a significant performance edge. Fre-
quently, these polymers are described as versatile problem
solvers because cellulose esters provide qualities such as
good flow and leveling, faster drying, sag resistance, viscos-
ity control, intercoat adhesion, and metal flake orientation.
Cellulose esters are typically supplied as dry, free-flow-
ing fine powders and they should be handled accordingly
since any free-falling powder can generate static electricity.
Proper precautions should be taken when handling the dry-
powder cellulose esters.
FACTORS AFFECTING PERFORMANCE OF
CELLULOSE ESTERS IN COATINGS
Performance attributes of cellulose esters are affected by
the chemical composition and the molecular weight of the
ester. The larger size and lower polarity of the propionyl or
butyryl group on the molecule alters the packing density of
the cellulose chains, causing them to spread farther apart
and lowering the attraction between the neighboring units.
In solution, these groups affect the configuration and con-
formation of the molecular chains and thus alter proper-
ties. The extent to which these factors occur depends on the
degree of substitution (DS) and the particular substituents.
DS is commonly used to quantify the number of hydroxyls
per anhydroglucose unit groups being replaced by acyl
3
Cellulose Esters of Organic Acids
Jos S. de Wit
1
and Deep Bhattacharya
2
1
Sr. Technical Associate, Eastman Chemical Company, Kingsport, TN.
2
Technical Associate, Eastman Chemical Company, Kingsport, TN.
3
Although not discussed in this chapter, other cellulose derivatives are in commercial use. For example, cellulose nitrate is used as a lacquer
in the furniture coating business and alkylene oxide derivatives of cellulose are used in thickening and other liquid fow altering areas (see
Chapter 33 of this Manual).
MNL17-EB/Jan. 2012
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28 PAINT AND COATING TESTING MANUAL 15TH EDITION
groups. The DS ranges from 0 (cellulose) to 3 (tri-esters).
CABs are the most commonly used cellulose esters in coat-
ings and are discussed in more detail below.
As the butyryl content increases, solubility, compatibil-
ity, flexibility, diluent tolerance, and moisture resistance are
increased. Lower butyryl levels are associated with increased
chemical and grease resistance, hardness, and melting range.
Most of the butyrates are manufactured with a hydroxyl
content best suited for general applications (about 1.5 %),
permitting good solubility, compatibility, and performance
in coatings applications. Most CABs are soluble in esters,
ke-tones, glycol ethers, glycol ether esters, blends of alco-
hols, and aromatic hydrocarbons, and they are quite
tolerant of diluents such as aromatic hydrocarbons and
alcohols. At levels around 5 %, solubility in lower molecular
weight alcohols occurs. At higher hydroxyl levels, reactivity
increases, providing cross-linking capability with amino
and isocyanate resins. However, in non-cross-linking sys-
tems, higher levels decrease moisture resistance due to
increased hydrophilicity.
When considering the hydroxyl functionality in the
stoichiometry of a cross-linkable coating system, the fol-
lowing calculations may be useful:
Fig. 1Repeating unit in cellulose esters; R
1
, R
2
, R
3
= acetyl,
butyryl, or H.
TABLE 1Typical properties
a
Eastman
Cellulose Ester
Viscosity
b
OH (%)
Melting
range (C) T
g
(C)
Wt/Vol
MW
n
c
Comments S Poise (Ib/gal) (kg/L)
Cellulose acetate butyrate
CAB-551-0.01 0.01 0.038 1.5 127142 85 9.67 1.16 16 000 Butyryl level: flexibility, solubility, &
compatibility
CAB-551-0.2 0.20 0.76 1.8 130140 101 9.67 1.16 30 000
CAB-553-0.4 0.30 1.14 4.8 150160 136 10.00 1.20 20 000
CAB-531-1 1.90 7.22 1.7 135150 115 9.75 1.17 40 000
CAB-500-5 5.00 19.00 1 165175 96 9.83 1.18 57 000
CAB-381-0.1 0.10 0.38 1.3 155165 123 10.00 1.20 20 000
CAB-381-0.5 0.50 1.90 1.3 155135 130 10.00 1.20 30 000
CAB-381-2 2.00 7.60 1.3 171184 133 10.00 1.20 40 000
CAB-381-2 BP 2.20 8.36 1.8 175185 130 10.00 1.20 40 000
CAB-381-20 20.00 76.00 1.8 195205 141 10.00 1.20 70 000
CAB-381-20 BP 16.00 60.80 0.8 185195 128 10.00 1.20 70 000
CAB-321-0.1 0.10 0.38 1.3 165175 127 10.00 1.20 12 000
CAB-171-15 15.00 57.00 1.1 230240 161 10.50 1.26 65 000
Cellulose acetate propionate
CAP-504-0.2 0.20 0.76 5.0 188210 159 10.53 1.26 15 000
CAP-482-0.5 0.40 1.52 2.6 188210 142 10.20 1.22 25 000
CAP-482-20 20.00 76.00 1.8 188210 147 10.20 1.22 75 000
Cellulose acetate
CA-398-3 3.00 11.40 3.5 230150 180 10.90 1.31 30 000 Viscosity
CA-398-6 6.00 22.80 3.5 230250 182 10.90 1.31 35 000
CA-398-10 10.00 38.00 3.5 230250 185 10.90 1.31 40 000
CA-398-30 30.00 114.00 3.5 230250 189 10.90 1.31 50 000
a
Properties reported here are typical of average lots. Eastman makes no representation that the material in any particular shipment will conform
exactly to the listed properties. All Eastman cellulose esters are filtered and in the form of fine, white, dry powder except CA-394-60S, an unfiltered
pellet form. Like most organic materials in powder form, these materials are capable of creating a dust explosion. Refer to NFPA. Pamphlets No 654,
Prevention of Fire and Dust Explosions in the Chemical, Dye, Pharmaceutical, and Plastics Industries.
b
ASTM D817 (Formula A) and D1343.
c
Number-average molecular weight values, MW
n
, are polystyrene-equivalent molecular weights determined using size exclusion chromatography.
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CHAPTER 3 CELLULOSE ESTERS OF ORGANIC ACIDS 29
Hydroxyl number = 33 wt % hydroxyl
Hydroxyl equivalent wt = 1700 wt % hydroxyl
In general, CABs are compatible with most acrylics,
polyesters, phenolics, ureas, and isocyanates. They are also
compatible with some epoxides and poly(vinyl acetates).
CABs are often incompatible with melamines, urea formal-
dehydes, and most alkyds.
The molecular weight (often related to as viscosity) of
cellulose esters also influences physical properties of the
esters as well as coatings formulated with them. Increas-
ing the molecular weight slightly lowers its solubility and
compatibility with other polymers, but it does not affect
hardness and density. Generally, toughness and flexibility
are improved as molecular weight is increased.
CELLULOSE ESTERS AS FILM FORMERS,
MODIFIERS, OR ADDITIVES
In some protective and decorative coatings, cellulose esters
serve as the primary film-forming polymer or as a modify-
ing copolymer to impart a specific property to the liquid
or solid coating. There are four characteristics that explain
the benefits cellulose esters bring to coatings when they are
used as additives.
1. Due to their rapid viscosity build, cellulose esters pre-
vent film distortion and craters, sags and runs, picture
framing, poor metal flake orientation, color separation
in multipigment systems, pigment flooding and float-
ing, inconsistent gloss control with matting agents, and
poor holdout.
2. Due to their Newtonian rheology, cellulose esters
improve flow and leveling, rheology control, reduc-
tion of surface defects such as pinholes and craters in
atomization, roll coat, and curtain coat applications.
3. Due to their high glass transition temperatures, cellu-
lose esters provide rapid dry-to-touch times and excel-
lent hardness development.
4. Due to their cellulose backbone, cellulose esters have
good UV stability and dimensional stability.
APPLICATIONS FOR CELLULOSE ESTERS IN
COATINGS
In the automotive industry, cellulose esters have been used
for decades in both original equipment manufacturer and
refinish basecoats, refinish primers, clear coats, and mono-
coats. They are often an integral component in enabling
the formulator to achieve desired color effects, particularly
through consistent metallic flake orientation. CAB used in the
basecoat of a basecoat/clear-coat system provides improved
flake alignment and resistance to redissolve from the topcoat
solvents. CAB is also used in pigment dispersions for automo-
tive applications to provide consistent tints and to achieve the
maximum color development from a given pigment.
In addition to automotive metal coatings, CAB lacquers
are especially useful on structural aluminum, aluminum
foil, stainless steel, chromium, brass, silver, and tin, where
protection of the metal surface and maintenance of the
metallic luster are desired. By appropriate selection of
modifying resins, butyrate lacquers may be formulated into
clear or pigmented coatings that have good adhesion to
metallic surfaces and that are resistant to salt-fog, oxygen,
and other tarnishing and corroding elements. CABs used
in metallic coil coatings reduce surface defects, improve
metallic and pearlescent flake alignment, as well as provid-
ing improved flow and leveling, better gloss consistency,
and purer white color value.
CAB has been used for many years in coatings for
various plastic materials. Portions of the surface of molded
plastic articles are frequently coated with a lacquer that
primarily serves a decorative purpose; for example, metallic
coatings on cell phones or casings for DVDs. CAB polymers
are effective as release coatings for silicone rubber molds
used in forming rigid polyurethane articles. The base
release coating not only protects the mold from attack by
the poly-urethane components, it also becomes an integral
part of the plastic article and serves as a tie coat for other
coatings on the molded article.
A major use of CAB is in wood coatings for furniture,
plywood paneling, particleboard, and hardboard, both in
thermoplastic and thermoset systems. It can be formulated
into coatings (often a butyrate/acrylic composition) that
are nonyellowing, possess good durability, stain resistance,
plasticizer migration resistance, depth of finish, color, and
color stability.
Crosslinking systems such as a CAB/urea-formaldehyde
composition is frequently used in coating kitchen cabinets,
and high quality furniture finishes exhibiting outstanding
toughness and chemical resistance can be prepared by
blending CAB with an isocyanate prepolymer.
TABLE 2Viscosities of selected CABs in various solvents
Additive wt % HDODA
a
TMPTA
b
DPGDA
c
TPGDA
d
Styrene
CAB-553-0.4 5 1550 1550 1190 40 000 NA
CAB-381-0.1 5 60 1670 113 180 NA
CAB-321-0.1 5 53 1420 93 128 NA
CAB-551-0.2 5 87 2080 136 204 30
CAB-551-0.01 5 29 661 40 57 7
Solus 2100 5 ... 424 30 44 ...
Solus 2100 20 56 1660 104 172 10
a
HDODAHexanediol diacrylate.
b
TMPTATrimethylolpropane triacrylate.
c
DPGDADipropyleneglycol diacrylate
d
TPGDATripropyleneglycol diacrylate.
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30 PAINT AND COATING TESTING MANUAL 15TH EDITION
Flexible cloth lacquers made from CAB 381 are used in
coating nonyellowing window shades and flame-resistant
artificial leathers. CAB is used with urethane elastomers to
coat fabrics used in the production of sportswear, rainwear,
footwear, hats, coats, handbags, luggage, and upholstery
for furniture and automobiles. Blending CAB with these
polymers increases hardness, reduces tack, raises blocking
point, improves slip, and reduces dirt pickup of the coating.
Other applications include paper and lacquer emul-
sions for leather topcoats. CAB is used worldwide in
topcoats for leather items such as automotive upholstery,
footwear, and furniture. These topcoats containing CAB are
tough and have good resistance to abrasion and plasticizer
migration.
Cellulose esters are used as additives in radiation cur-
ing (RC) systems as well. Here, they provide similar benefits
as in solvent-borne coatings, such as flow and leveling,
improved gloss control, adhesion, and reduction of surface
defects. CAB 551 types are used in overprint varnishes at
levels of 15 %. In applying RC coatings, CABs can reduce
or eliminate holes in curtain coatings and reduce spatter-
ing in high-speed roll coat applications. Most commonly,
the CAB is dissolved in a monomer and then added to the
formulation. The viscosities of certain CABs in a variety of
monomers are given in Table 2.
Cellulose esters are also used in graphic arts as thermo-
plastic and thermoset inks, including over print varnishes.
Guidance for selecting the appropriate cellulose ester is
provided in Table 3.
COMPLIANT COATINGS
Environmental legislation across the globe has resulted
in the paint industry attempting to move toward greener
and more eco-friendly lower volatile organic component
(VOC) products with similar performance attributes as
conventional coating formulations. Some approaches for
achieving low VOC include: (a) increasing the solids load-
ing in a solvent-based system [9]; (b) using UV curable
formulations [10]; (c) replacing solvent with water [9]; and
(d) using powder coatings. Applicability of conventional
cellulose esters has been limited in modern reduced VOC,
high solids coating systems because of their high solvent
demand.
To meet the increasing demand of sustainable solutions
for compliant coatings, a new class of cellulose-based addi-
tives has been introduced [11]. Solus Performance Addi-
tives are very similar to conventional cellulose esters, but
these compounds have very low viscosity and allow high
solids systems to be formulated.
TABLE 4ASTM standards used in testing
cellulose esters
ASTM Title
D706 Standard Classification System and Basis for
Specifications for Cellulose Acetate Molding and
Extrusion Compounds
D707 Standard Classification System and Basis for
Specification for Cellulose Acetate Butyrate Molding
and Extrusion Compounds
D817 Standard Test Methods of Testing Cellulose Acetate
Propionate and Cellulose Acetate Butyrate
D871 Standard Test Methods of Testing Cellulose Acetate
D1343 Standard Test Method for Viscosity of Cellulose
Derivatives by Ball-Drop Method
D1562 Standard Classification System and Basis for
Specification for Cellulose Acetate Propionate
Molding and Extrusion Compounds
D1695 Standard Terminology of Cellulose and Cellulose
Derivatives
D2929 Standard Test Method for Sulfur Content of Cellulosic
Materials by X-Ray Fluorescence
D4209 Standard Practice for Determining Volatile and
Nonvolatile Content of Cellulosics, Emulsions, Resin
Solutions, Shellac, and Varnishes
D5226 Standard Practice for Dissolving Polymer Materials
D5897 Standard Test Method for Determination of Percent
Hydroxyl on Cellulose Esters by Potentiometric
TitrationAlternative Method
E1899 Standard Test Method for Hydroxyl Groups Using
Reaction with p-Toluenesulfonyl Isocyanate (TSI) and
Potentiometric Titration with Tetrabutylammonium
Hydroxide
TESTING OF CELLULOSE ESTERS
Cellulose acetate is tested by the manufacturer in accor-
dance with ASTM Test Methods for Cellulose Acetates
(D871), and mixed esters Cellulose Acetate Propionate and
Cellulose Acetate Butyrate (D817), which cover color and
haze, combined acetyl, free acidity, heat stability, hydroxyl
content, intrinsic viscosity, moisture content, sulfur or sul-
fate content, and solution viscosity. Coatings manufactur-
ers usually restrict their testing to viscosity of the ester,
solubility and appearance, and color and haze. Viscosities
TABLE 3Selector guide for graphic arts applications
Technology Cellulose Ester Comments
Digital CAB551, CAP482 Solvent based and UV
Flexography CAP504, CAP482, CAB553, CAB551 Solvent selection will be limited by the chemical
resistance of the image roll
Gravure CAP482, CAP504, CAB381, CAB531, CAB553, CAB551,
CAB500, CA398
The inert image roll allows wide selection of resin and
solvents
Screen CAP482, CAB381, CAB531, CAB500, CA398 Viscosity is a benefit in these applications
OPV CAB551, CAB381 Flow and leveling and improved adhesion
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CHAPTER 3 CELLULOSE ESTERS OF ORGANIC ACIDS 31
are determined using the falling-ball method, according
to ASTM D1343 in the solution described as Formula A,
ASTM D817. Viscosities in poises are converted to ASTM
seconds equivalent to values obtained under ASTM D817.
In Eastman nomenclature for cellulose esters, the viscos-
ity of each individual ester is indicated in its product code.
For example, CAB 381-2 has a viscosity of 2 s, CAB 381-20
has a viscosity of 20 seconds, and CAB 531-1 has a viscos-
ity of 1 s. The above ASTM standard documents as well as
others related to the testing and terminology used for cel-
lulose esters are listed in Table 4. In addition to the listing
in Table 4, there are numerous other ASTM test methods
and documents that relate to the testing of cellulose esters
for fibers, for molding compounds, and for other solid-
state uses.
ACKNOWLEDGMENTS
The writers want to thank Joe Koleske for his valuable and
insightful feedback and editing.
References
[1] Heyne, E., and Whistler, R. L., Chemical Composition and
Properties of Guar Polysaccharides, J. Am. Chem. Soc., Vol.
70, 1948, pp. 22492252.
[2] Carson, J. F., and Maclay, W. D., Esters of Lima Bean Pod and
Corn Cob Hemicelluloses, J. Am. Chem. Soc., Vol. 70, 1948,
pp. 293295.
[3] Cellulose and Cellulose Derivatives, Ott, E., Spurlin, H. M., and
Grafflin, M. W., Eds., Interscience Publishers, Inc., London,
19541955, Part I, pp. 1510; Part II, pp. 5111056; Part III,
pp. 10571601.
[4] Yuan, J., Dunn, D., Clipse, N. M., and Newton, R. R. J., Jr.,
CAB Coating Films: Permeability Study on Cellulose Acetate
Butyrate Coating Films, Drug Delivery Technology, Vol. 8,
2008, pp. 4651.
[5] Roche, E. J., Masking and Sustained Release Coatings for
Pharmaceuticals, U.S. Patent No. 5,074,114 (1991).
[6] Chen, C. M., Chiao, C. S. L., and Suarez, J., Controlled Release
Tablet Formulation, U.S. Patent No. 5,458,887 (1994).
[7] Shanbhag, A., Barclay, B., Koziara, J., and Shivanand, P.,
Application of Cellulose Acetate Butyrate-Based Membrane
for Osmotic Drug Delivery, Cellulose, Vol. 14, 2007, pp. 6571.
[8] Hagihara, B., Fumihide, I., Sasaki, K., and Kamigawara, Y.,
Cellulose Acetate Coatings for the Polarographic Oxygen
Electrode, Anal. Biochem., Vol. 86, 1978, pp. 417431.
[9] Giordan, B., The Challenge of Solvent Substitution in Coat-
ings, Noise Health, Vol. 4, 2002, pp. 2529.
[10] Stropp, J. P., Wolff, U., Kernaghan, S., Loftier, H., Osterhold,
M., and Thomas, H., UV Curing Systems for Automotive
Refinish Applications, Prog. Org. Coat., Vol. 55, 2006, pp.
201205.
[11] www.eastman.com.
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32
NOTE: IT MUST BE POINTED OUT THAT FROM AN
ASTM standpoint, this chapter is mainly included for his-
torical purposes. In general, ASTM no longer deals with
the standard test methods and specifications for drying
oils in paints and coatings. This activity is dealt with by the
American Oil Chemists Society (AOCS) with research and
technology in the area reported in the Journal of the Ameri-
can Oil Chemists Society. Since the ASTM documents
listed in the previous edition of this manual are found in
the technical literature, this chapter provides a route to the
past, some information about recent activities in the area,
and information about AOCSs current role. As indicated,
many of the ASTM documents listed in the previous edition
of this chapter are no longer available from ASTM. Those
applicable ASTM standards that can be downloaded from
ASTM are so indicated. A listing of some AOCS documents
that refer to drying oils can be found in Table 5.
Drying oils represent a small portion of the huge fats
and oils industry.
2
Soybeans are the largest oilseed crop
with a U.S. farm value of about $12.5 billion in 2000/2001.
This oil accounts for about 90 % of U.S. oilseed production
with the remainder comprised of oils such as cottonseed,
sunflower seed, flaxseed, canola, linseed, and other oils.
Argentina and Brazil are also important soybean grow-
ers and processors. Drying oils are included in the oilseed
category. In regard to coatings, the industry is very mature
with relatively little growth expected. The paint and coating
industrys need for drying oils is in an overall decline along
with other end use markets, such as binders for hardboard,
sealants, plasticizers, linoleum, and core oils. Drying oils
used in paints and coatings are being replaced with oil-free,
synthetic, petroleum-derived oligomeric and polymeric
binders carried in a variety of media or in a neat manner.
The printing ink market is the only one expected to have
small growth in the area of drying oils.
However, because drying oils have certain desirable
attributes and represent a readily available renewable
resource, interest is being renewed in certain oils through
sponsorship by interested organizations and through new
opportunities for modified vegetable oils. In the United
States, the United Soybean Board is funding research
dealing with catalysts for radiation curing of epoxidized
soybean oil at Bowling Green State Universitys Center
for Photochemical Sciences [1,2]. Other investigators are
studying the use of soybean oil modifications in water-
borne paints, high solids coatings, and inks [3]. In Malaysia,
where palm oil is readily available, research is being con-
ducted at the School of Industrial Technology at Universiti
Sains Malaysis on epoxidized and acrylated derivatives of
palm oil [4,5]. Again, the studies deal with using the prod-
ucts in the rapidly growing radiation curing market [6].
Oilseed Growers LLC has members who have commercially
produced carambe oil in the United States since 1996 [7].
This oil is rich in mono unsaturated erucic acid, and it is
used as a food emulsifier, as an ingredient in industrial slip
agents, pour point depressants, lubricants, hair care, textile
softening, and other end uses.
The processing techniques as well as the chemistry of
drying oils have been well known for some time. However,
within the past few decades, computer control and robot-
ics, EPA and OSHA regulations in the United States and
similar concerns elsewhere, rising energy costs, and similar
developments have led to important improvements in the
processing field whereby fish or plant components are con-
verted into the final use-products. Lusas [8] has recently
detailed a great deal of the old and new chemistry, nomen-
clature, and processing technology regarding drying oils in
a detailed book chapter. The chapter also includes informa-
tion about other animal and vegetable fats, oils, and waxes
as well as edible uses for the oils and fats, industrial uses
of the oils, numerous historical references, sources, and
several analytical methods that have been adopted by the
American Oil Chemists Society (AOCS). This chapter and
the previous edition of the chapter [9] are very useful refer-
ences for those working in this field. Hutchinson [10] has
reviewed new and traditional uses, technology advances,
environmental factors, and development strategies for veg-
etable oils in surface coatings.
Most naturally occurring fatty oils have their double
bonds occurring in a cis configuration, and heating such
oils as in industrial processing causes a portion of the cis
configured double bonds to be converted into a trans con-
figuration. Infrared absorption spectroscopy or gas chro-
matography are the usual methods of determining trans
content, but Milosevic and Kocak [11] used attenuated total
reflection (ATR) Fourier transform infrared spectroscopy
[12] to analyze oils, such as soybean oil and sunflower oil,
that had been untreated and heated for various times at
elevated temperatures. A FatIR heated single-reflection ATR
accessory was used for the analysis. The studies demon-
strated that the technique could be used for routine analysis
of trans double bond content and thus permit investigation
4
Drying Oils
Joseph V. Koleske
1
1
1513 Brentwood Road, Charleston, WV 25314-2307.
2
Information about this industry is developed by the U.S. Departments of Agriculture and Commerce and can be found on websites such
as www.ers.usda.gov.
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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CHAPTER 4 DRYING OILS 33
of reaction kinetics and the optimization of reaction param-
eters. Larock et al. [13] have found that small amounts
of homogeneous transition metal catalysts will affect the
isomerization transformation of soybean oil to conjugated
oil under mild conditions. Their preliminary tests indicate
that the conjugated oils have exceptional drying properties
with good solvent resistance.
Although new studies are currently being conducted,
modified drying oil products have been known for some-
time. A variety of oils have been epoxidized [14, 15] and
many of these have been further reacted to form acrylates
for use in radiation curable coatings and inks [1619].
Recent investigations of seed oils include castor oil that
has been used in the preparation of a variety of oil-based
binders [20], blown soybean oil that has been used in com-
bination with acrylates such as 1,6-hexanediol diacrylate to
make novel coatings [21], epoxidized soybean oil that has
been used in cationic-initiated, thermally cured coatings
[22], soybean oil that has been used to make phosphate
ester polyols for use in novel coatings [23], the synergistic
effect between metallic driers and soybean oil-based coat-
ings [24], and a method for modifying cashew nut shell
liquid by ozonolysis to form products useful in adhesives
and other products [25]. A variety of drying oils have been
reacted with multifunctional isocyanates to form products
that have been termed urethane oils and are akin to
alkyds [26]. Neat or raw drying oils have been mixed with
polymerized drying oils to form homogenous admixtures
used by artists as a painting medium [27]. Coatings that
have controlled release of organic solvents, particularly
formaldehyde, and improved properties have been pre-
pared from drying oils, such as linseed oil, and waxes as
the main compositional components [28]. Adhesives with
substantially no or low volatile-organic-compound emis-
sions and based on drying oils have been prepared [29].
Novel thermal processes that do not involve solvent extrac-
tion or caustic refining, which produce soybean oil that is
low in phospholipids have been recently developed [30]. A
method for determination of the primary hydroxyl content
of soybean oil polyols by reaction with monoisocyanates,
such as phenyl isocyanate, has been recently reported [31].
Usually in the fats and oils industry, products that are
solid or semisolid at room temperature are referred to as
fats, and products liquid at room temperature are termed
oils. Often times the terms fats and oils are used inter-
changeably within the industry. In a general sense, fats are
usually of animal origin or are vegetable oils that have been
hardened by hydrogenation or some other process. Dry-
ing oils, except for fish oil, are of vegetable origin and are
extracted from seeds or plant tissue.
Chemically, drying oils are water-insoluble, unsatu-
rated glycerides of long chain fatty acids with the general-
ized structure:
CH
2
OOCR
a
|
CHOOCR
b
|
CH
2
OOCR
c
Generalized Triglyceride
where R
a
, R
b
, and R
c
are the same or different and represent
the hydrocarbon chain residues of fatty acids. In simple
terms, this means that most oils are mixed triglycerides.
The triglycerides are produced by the condensation reac-
tion that occurs between a glycerol molecule and three fatty
acid molecules:
HOCH
2
CH(OH) CH
2
OH + 3R
x
COOH
Glycerol Fatty Acid
R
x
COOCH
2
CH(OOCR
x
) CH
2
OOCR
x
+ 3H
2
O
Triglyceride or Drying Oil
where R
x
is any one of R
a
, R
b
, or R
c
. This reaction is revers-
ible and when the oils are heated they can transesterify
with R
a
, R
b
, and R
c
and thus are capable of changing their
positions in an intermolecular and an intramolecular sense.
Drying oils also contain saturated glycerides of fatty acids,
but these are usually present at relatively low levels and
they do not participate in drying or polymerization phe-
nomenon. Hydrolysis of drying oils results in separation
into glycerol and the fatty acid.
Drying oils can be classified in many ways, but one
principal way is to divide them into drying, semidrying,
and non-drying (an oxymoronic term) oils in accordance
with their iodine values, which is a measure of unsatura-
tion content. Although such classification has been rather
arbitrary, Rheineck and Austin [32] defined the classes as
given in Table 1.
The main fatty acids found in drying oils and their
chemical compositions are given in Table 2. The unsatu-
rated-component content of selected drying oils is given in
Table 3. Stearic (18-carbon) and palmitic (16-carbon) acids
are the most widely distributed saturated fatty acids found
in drying oils. Except for cottonseed oil, which contains
29% palmitic acid, the drying oils listed in Table 3 contain
less than about 10 % of any particular saturated fatty acid
residue. The degree of double bond unsaturation controls
the drying rate. The higher the degree of unsaturation or
iodine number (see below), the faster the drying or polym-
erization of the oil. The double bond position is also impor-
tant because conjugated bonds, which is the term used to
describe two carbon-carbon double bonds separated by
one carbon-carbon single bond, are more susceptible to
autoxidation [34].
Physical characteristics of some typical commercial
drying oils are given in Table 4. The oils are particularly
characterized by their iodine value, which is a measure of
the amount of unsaturation present, and saponification
number, which is an indication of fatty acid chain molecule
weight. Selected property requirement ranges or minimum
values for various drying oils. The following drying oils are
the most important members of this class of coating raw
materials.
Castor oil is obtained from beans of the plant Ricinus
communis. The oil differs from the other oils in that it is
TABLE 1Classification of drying oils by
iodine value
Oil Class Iodine Value
Drying oil >140
Semidrying oil 125140
Nondrying oil <125
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34 PAINT AND COATING TESTING MANUAL 15TH EDITION
made up of a very high percentage of the hydroxyl-contain-
ing ricinoleic acid residue. Although the fatty acid residues
in this oil contain on the average only a single double bond
and for this reason castor oil is essentially a nondrying oil,
it can be converted into a drying oil by a dehydration pro-
cess in which its hydroxyl group and an adjacent hydrogen
atom are removed as water to form a double bond conju-
gate to the previously existing double bond. The resultant
product is known as dehydrated castor oil, which has good
drying characteristics.
Cottonseed oil is obtained from the plant Gossypium
malvaceae. Although it is a drying oil, cottonseed oil is
seldom used as an oil in the paint and coating industry. Its
main use is as a source of fatty acids that are used in the
manufacture of alkyds.
Linseed oil, which is obtained from seed of the flax
plant Linum usitatissimum, is the most common and
widely used drying oil. In the Western Hemisphere, it is
the oldest known drying oil. Linseed oil has a high degree
of unsaturation, which imparts a short drying time, due to
its large percentages of linolenic and linoleic triglycerides.
It is marketed in a number of modifications, including
alkali-refined, acid-refined, boiled, blown, and polymer-
ized linseed oil [1]. Polymerized linseed oils of various acid
values and viscosities are available. The effect of water
and air on the thermal oligomerization of linoleic acid has
been investigated, and it was found that water inhibited the
reaction and continuous air flow enhanced dimerization
and trimerization [36].
Oiticica oil is obtained from the nuts of the tree Licana
rigida, which grows wild and is only grown in Brazil. It has
a very high licanic acid content, and the three conjugated
double bonds of this acid result in rapid drying characteris-
tics. When the price of linseed oil is too high, oiticica oil is
used as a substitute for linseed oil and is often used as an
alternative or supplement to tung oil.
Safflower oil is obtained from seed of the plant Cartha-
mus tinctorius. This semidrying oil has drying characteris-
tics between those of linseed and soybean oils. Because of
its low linolenic acid content, it has low residual unsatura-
tion after cure and very good antiyellowing characteristics.
Soybean oil is obtained from the seeds of the widely
grown plant Soja hispida. Its main use is in the preparation
of alkyds. It has a wide variety of uses other than as a drying
oil. In an epoxidized form, this oil is widely used as a reac-
tive plasticizer and as an acid scavenger. Both epoxidized
soybean and linseed oil have been reacted with acrylic acid
to form products with residual acrylate functionality and
markedly higher viscosity. These acrylated oils have been
used as components in radiation-cure coating systems that
are initiated with free radicals.
Although tall oil is classified as a drying oil, it is not a
triglyceride. The product is obtained as the major byprod-
uct of sulfate or Kraft pulping of pine and certain other
TABLE 2Main unsaturated fatty acids found in drying oils
Fatty Acid Number Carbon Atoms Number Double Bonds Structural Formula
Linolenic 18 3 HOOC(CH
2
)
7
CH=CHCH
2
CH=CHCH
2
CH=CHCH
2
CH
3
Linoleic 18 2 HOOC(CH
2
)
7
CH=CHCH
2
CH=CH(CH
2
)
4
CH
3
Oleic 18 1 HOOC(CH
2
)
7
CH=CH(CH
2
)
7
CH
3
Eleostearic 18 3 HOOC(CH
2
)
7
CH=CHCH=CHCH=CH(CH
2
)
3
CH
3
Licanic 18 3 HOOC(CH
2
)
2
CH(O)(CH
2
)
4
CH=CHCH=CHCH=CH(CH
2
)
3
CH
3
Ricinoleic 18 1 HOOC(CH
2
)
7
CH=CHCH
2
CH(OH)(CH
2
)
5
CH
3
TABLE 3Weight percentage of major unsaturated fatty acid residues in selected drying oils
[32,33] (remainder of oils is essentially all saturated fatty acid residues)
Drying Oil
Unsaturated Fatty Acid
Linolenic Linoleic Oleic Eleostearic Licanic Ricinoleic
Cottonseed ... 40 24 ... ... ...
Castor ... 3 7 ... ... 87
Linseed 52 16 22 ... ... ...
Oiticica ... ... 6 ... 78 ...
Safflower 1 75 13 ... ... ...
Soybean 9 51 25 ... ... ...
Sunflower
a
2 7552 3414 ... ... ...
Tall Oil 3 41 46 ... ... ...
Tung 3 4 8 80 ... ...
a
There is wide variation in reported values for sunflower oil.
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CHAPTER 4 DRYING OILS 35
softwoods such as spruce and hemlock that are pulped in
Scandinavian countries. Crude tall oil is an approximately
50/40/10 by weight mixture of fatty acids, rosin acids, and
unsaponifiable compounds, such as higher alcohols, waxes
and other hydrocarbons, and sterols.
Tung oil is obtained from seeds (fruit or nuts) of
the trees Aleurites fordii and Aleurites Montana, and it is
mainly produced in China and South America, though in
1966 production began in the United States (Mississippi).
Tung oil contains mainly eleostearic acid with smaller
amounts of linoleic, oleic, and palmitic fatty acids. This
relatively high viscosity and refractive index oil is rapid
drying and is used in varnishes and alkyds where water
resistance is of principal importance. Tung oil is also
known as wood oil, Chinese wood oil, chinawood oil, and
mu oil. Martyak et al. [37] have investigated the controlled
oxidative curing of tung oil with cobalt driers and anti-
skinning agents as the control agents. When the process
is properly controlled, improved through cure and other
properties are obtained.
Vernonia oil is a unique oil that contains an epoxy
group and an unsaturated group in each of three vernolic
acid resides that are attached to a triglyceride residue [38].
It is obtained from the weed termed Vernonia galamensis
and is being investigated as a potential industrial crop in
certain frost-free African countries. The oil has a relatively
low viscosity, 100 cPat85F, dual functionality, and a poten-
tial for derivitization into acrylates or other compounds. In
addition, it has utility without alteration and may function
as a reactive diluent or other additive.
Agave fiber has been treated with acid to form hydrox-
ylates that contain furfural [39]. These plant extracts have
been condensed with tannins from tamarind to form oligo-
mers that were added to various drying oils to form var-
nishes with improved mechanical characteristics.
Fish oils are the only nonvegetable oils in the drying oil
class. They are principally obtained from menhaden (Alosa
menhaden). These oils are semidrying in nature and contain
a significant amount of saturated fatty acid residues. In
addition to 16- and 18-carbon fatty acid residues, fish oils
contain 30 %40 % of arachidonic (20-carbon with four
double bonds), clupanodonic (22-carbon with five double
bonds), and nisinic (24-carbon with five double bonds) acid
residues. Because of the presence of acid residues with high
degrees of unsaturation, fish oils have a strong tendency to
yellow after cure due to residual unsaturation. Fish oils do
represent a source of the very long chain fatty acids that are
not present in vegetable oils. Currently, they are not widely
used in the coatings industry, and their use is often dictated
by relative price of linseed and soybean oils.
Although raw drying oils are used in coating formula-
tions, the oils are often further processed before use. Such
processing includes alkali-refining, dehydration, drier addi-
tion, heat polymerization that involves heating an oil to
selectively advance molecular weight and viscosity, and
oxidation or blowing wherein air is bubbled into heated oil
and oxygen is taken up with a resultant molecular weight
increase. Drying oils are also modified by reaction with
maleic anhydride, by copolymerizing with vinyl monomers
such as styrene, and by epoxidation.
Reaction with oxygen is the most important reaction
that drying oils undergo in the drying or polymerization
process [40, 41]. Oxidation can result in trans isomer for-
mation, cleavage of the carbon-carbon chain along with
formation of volatile byproducts, and polymerization.
These reactions can be catalyzed with metallic salts, such
as cobalt naphthenate (see next chapter), that promote free
radical formation by reaction with hydroperoxides and
other peroxides that are formed in the oxidation process
[42]. Farmer and Sutton [43] were the first to describe the
mechanism of auto-oxidation wherein they found that four
different monohydroperoxides were formed when oxygen
was reacted with the methyl ester of oleic acid. A different
reaction path was involved when linoleic esters were auto-
oxidized since two monohydroperoxides and one cyclic
diperoxide were formed. Polymerization is initiated by
reaction of oxygen with an unsaturated fatty acid residue
and free radical formation followed by chain propagation
in which free radicals react with oxygen to form peroxy rad-
icals, which in turn react with other unsaturation sites [44].
The polymerization is terminated by combination of vari-
ous free radicals that exist in the reaction mass. Availability
TABLE 4Physical characteristics of some typical drying oils [35]
Oil
Specific Gravity
25.5/25.5C Iodine Value, Wijs
Saponification
Value Acid Value
Refractive Index
25C
Cottonseed 0.919 105 192 1.0 1.465
Dehydrated Caster 0.931 135 190 5.0 1.481
Fish 0.925 158 187 4.0 1.485
Linseed 0.926 180 190 3.0 1.478
Oiticica 0.967 150 190 4.0 1.510
Safflower 0.922 145 192 2.0 1.474
Soybean 0.920 135 190 2.5 1.473
Sunflower 0.917 135 192 2.0 1.473
Tall oil ... 133 196 194.0 ...
Tung 0.915 170 192 0.2 1.517
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36 PAINT AND COATING TESTING MANUAL 15TH EDITION
of multiple double bonds in some of the molecules results
in a cross-linked polymeric network.
Solidification or polymerization of a drying oil, such
as linseed oil, can be thought of in the following manner.
When the drying oil is exposed to air, there is an induction
period during which oxygen is absorbed and it consumes
antioxidants present in the system. In this step, there is
very little apparent change in physical or chemical proper-
ties. This is followed by a period in which there is a marked
oxygen uptake and an appearance of peroxides that decom-
pose to form free radicals. The free radicals then initiate an
addition polymerization of the unsaturation and a cross-
linked network results. During the reaction, low molecular
weight cleavage products including carbon dioxide and
water are formed.
ASTM D1640 Standard Test Methods for Drying,
Curing, or Film Formation of Organic Coatings at Room
Temperature has procedures recommended for determina-
tion of the stages and rates of film formation in the drying
or curing of organic coatings that are to be used at room
temperature.
Included are methods for determining tack-free, dry-to-
touch, dry-hard, dry-through, print-free, and dry-to recoat
times. In one instance (Section 7.5.1) a particular procedure
is specified for drying oils. ASTM Standard Test Method for
Gel Time of Drying Oils (D1955) deals with determination of
the gel time of oiticica and tung oil. This simple test method,
which involves heating the oil in a test tube and observing
the time required for the oil to congeal around glass rod
relative to a standard of known behavior, can be used for
other oils that have conjugated double bond or other gell-
ing characteristics. ASTM Standard Guide for Testing Dry-
ing Oils (D555) is an overall guide to selection and use of
procedures for testing drying oils that are commonly used
in coatings. ASTM D1640 is an active standard; however,
ASTM D1955 and D555 have been withdrawn by ASTM but
may still (at time of writing) be downloaded from the ASTM
website. A number of other ASTM standards that were dedi-
cated to drying oils have been withdrawn and are no longer
available. However, as mentioned at the beginning of this
chapter, AOCS deals with this topic. Some of their standards
are listed in Table 5.
References
[1] Howell, C., UV Curing, Soybean Oil Research Continues,
Modern Paint & Coatings, Vol. 91, 2001, p. 41.
[2] Greissel, M., Soy-Based UV-Curable Coatings on the Hori-
zon, Industrial Paint & Powder, Vol. 17, 2001, p. 36.
[3] Anon, New Soybean Oil is a Gusher, Modern Paint & Coat-
ings, Vol. 92, 2002, p. 23.
[4] Kumar, R. N., Goh, T. J., Abusamah, A., and Rozman, H. D.,
Epoxy-ENR Hybrid System for Ultraviolet Cationic Curing
of Surface Coatings, Proceedings of RadCure 95 Conference
on Radiation CuringAsia, Guilin, China, November 2024,
1995, p. 370.
[5] Kumar, R. N., Abubakar, A., and Kong, W. C., UV Radiation
Curing of Surface Coatings Based on ENR-Cycloaliphatic
TABLE 5AOCS test methods for industrial oils and derivatives. See specific methods for
detailed scopes and methods
AOCS Official Method Title ScopeApplicable to
Tt 1a-64 (Reapproved 1997) Acetone Tolerance heat-bodied oils
Te 2a-64 (Reapproved 1997) Acid Value drying oils, epoxidized oils, fatty alcohols and esters
Tm 1a-64 (Revised 2003) Ash drying oils, fatty acidsnot applicable to boiled oils
Td 1a-64 (Revised 2000) Color Gardner 1963 (Glass standards) drying oils, fatty acids and oil derivatives similar
to standards
Th 1a-64 (Revised 2005) Diene Value all normal drying oils
Tn 1a-64 Flash and Fire Points,
Cleveland Open Cup Method
drying oils and fatty acids except those with flash
points below 149C (300F)
Tg 1-64 (Reapproved 1997) Iodine Value, Wijs Method normal industrial oils and derivatives
S 2-64 (Revised 2003) Methods for the Testing of Commercial
Fatty Acids
selection and use of procedures for testing drying
oils used in paint and related products
Ca 2c-25 (Reapproved 1997) Moisture and Volatile Matter Air Oven
Method
animal and vegetable fats but not to drying or
semidrying oils of the coconut group
Tc 1a-64 (Reapproved 1997) Nonvolatiles (Solids) Solutions of Drying
Oils, Hot Plate Method
solutions of natural and synthetic drying oils in
organic solvents
Cd 7-58 (Reapproved 1997) Polyunsaturated Acids, Ultraviolet
Spectrophotometric Method
various detailed isomers
Tp 1a-64 (Revised 2003) Refractive Index drying oils and all fatty acids
To 1b-64 (Revised 2003) Specific Gravity drying oils and derivatives
Ce 5b-89 (Reapproved 1997) Triglycerides in Vegetable Oils by HPCL vegetable oils containing triglycerides of long-
chain fatty acids
Tk1a-64 (Reapproved 1997) Unsaponifiable Material fatty acids, drying oils, and polymerized fatty acids
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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CHAPTER 4 DRYING OILS 37
Diepoxide-Glycidyl Methacrylate System by Cationic Photoini-
tiators-Optimization of Process Variables Through Response
Surface Methodology, J. Coat. Technol., Vol. 71, 1999, p. 79.
[6] Guthrie, J. T., Tait, J. G., and Sagar, A. G., UV-Curable Coat-
ings from Palm Oil and Derivatives, Journal of Surface Coat-
ings International Part B: Coatings Transactions, Vol. 83, 2000,
pp. 278284.
[7] U. S. Dept. of Agriculture, 1966, Crambe, Industrial Rape-
seed, and Tung Provide Valuable Oils, Economic Research
Service, Washington, D.C.
[8] Lusas, E. W., Animal and Vegetable Fats, Oils, and Waxes,
Kent and Riegels Handbook of Industrial Chemistry and Bio-
technology, 11th ed., Vol. 2, J. A. Kent, Ed., Springer, New
York, 2007, pp. 15991656.
[9] Lusas, E. W., Animal and Vegetable Fats, Oils, and Waxes,
Riegels Handbook of Industrial Chemistry, 10th ed., J. A. Kent,
Ed., Kluwer Academic/Plenum Publishers, New York, 2003,
pp. 243328.
[10] Hutchinson, G. H., Traditional and New Uses for Vegetable
Oils in the Surface Coatings and Allied Industries, Journal of
Surface Coatings International Part B: Coatings Transactions,
Vol. 85, 2002, pp. 18.
[11] Milosevic, V., and Kocak, A., Analyzing Trans Fats in Edible
Oils and Fats Using Single-Reflection ATR-FTIR, Am. Lab.
(Shelton, Conn.), Vol. 36, 2004, p. 30.
[12] Rules and Regulations, 2003, Federal Register, 68 (No. 133;
July 11).
[13] Larock, R. C., Dong, X., Chung, S., Reddy, Ch. K., and Ehlers,
L.E., J. Am. Oil Chem. Soc., Vol. 78, 2001, pp. 447453.
[14] Swern, D. and Findley, T. W., Epoxidized Oils, U.S. Patent
No.2, 569,502 (1951).
[15] Wahlroos, A. W., Method of Preparing Epoxidized Oils and
the Like, U.S. Patent No. 2,813,878 (1957).
[16] Nevin, C. S., Vicinal Acryloxy Hydroxy Long Chain Fatty
Compounds and Polymers Thereof, U.S. Patent No. 3,224,989
(1965); U.S. Patent No. 3, 256,225 (1966).
[17] Steinberg, I. V., Epoxy Adhesive Containing Acrylic Acid-
Epoxy Reaction Products and Photosensitizers, U.S. Patent
No. 3,450,613 (1969).
[18] Borden, G. W., Smith, O. W., and Trecker, D. J., Acrylated
Epoxidized Soybean Oil Amine Compositions and Method of
Curing Same, U.S. Patent No. 3, 876,518 (1975).
[19] Trecker, D. J., Borden, G. W., and Smith, O. W., Method for
Curing Ink and Coating Compositions of Acrylated Epoxi-
dized Soybean Oil Amine Compounds, U.S. Patent No. 4,
016,059 (1977).
[20] Kabasakai, O. S., Guner, F. S., Arsian, A., Ergan, A., Erciyes,
At. T., and Yagcl, Y., Use of Castor Oil in the Preparation of
Various Oil-Based Binders, J. Coat. Technol., Vol. 68, 1996
p. 57.
[21] Ni, P., Jones, F. N., and Fu, S., Novel Coatings Based on
Mixtures of Blown Soybean Oil and Acrylate Prepolymers, J.
Coat. Technol., Vol. 73, 2001, p. 57.
[22] Raghavachar, R., Sarnecki, G., Baghdachi, J., and Massingill,
J., Cationic, Thermally Cured Coatings Using Epoxidized
Soybean Oil, J. Coat. Technol., Vol. 72, 2000, p. 125.
[23] Zhong, B., Shaw, C., Rahim, M., and Massingill, J., Novel
Coatings from Soybean Oil Phosphate Ester Polyols, J. Coat.
Technol., Vol. 73, 2001, p. 53.
[24] Deffar, D., and Soucek, M. D., Synergistic Effect of Driers on
Soybean Oil-Based Ceramer Coatings, J. Coat. Technol., Vol.
73, 2001, p. 95.
[25] Khan, M. L., Tomkinson, J., and Salisbury, R. J., Method of
Modifying Components Present in Cashew Nut Shell Liquid,
U.S. Patent Application No. 20020004576 (pending).
[26] Guner, F. S., Gumusel, A., Calica, S., and Erclyes, A. T., Study
of Film Properties of Some Urethane Oils, J. Coat. Technol.
Vol. 74, 2002, p. 51.
[27] Fels, Jr., D. C., Painting Medium for Artists, U.S. Patent
No.6, 011,097 (2000).
[28] Noda, T., Kaga, Y., and Oshima, T., Natural Paint and Method
for Manufacturing the Same, U.S. Patent No. 6, 755,904
(2004).
[29] Ddamulira, R. K., Raidy, Jr., J. E., Wright, B. K., and Regis,
D.C., Low Emissions One-Part Adhesive, U.S. Patent No. 6,
706,789 (2004).
[30] Tysinger, J. E., Richmond, J. F., Dawson, R. B., and Farr,
W. E., Soybean Oil Process, U.S. Patent No. 6, 511,690
(2003).
[31] Ionescu, M., Petrovic, Z. S., and Wan, X., Primary Hydroxyl
Content of Soybean Polyols, J. Am. Oil Chem. Soc., Vol. 85,
2008, pp. 465473.
[32] Rheineck, A. E., and Austin, R. O., Film Forming Composi-
tions, R. R. Myers and J. S. Long, Eds., Marcel Dekker, Inc.,
New York, 1968, Vol. 1, No. 2.
[33] Gunstone, F. D., Chemistry and Biochemistry of Fatty Acids and
Their Glycerides, 2nd ed., Chapman and Hall, Ltd., London,
1967.
[34] Solomon, D. H., The Chemistry of Organic Film Formers,
Kreiger, New York, 1977.
[35] Gallagher, E. C., Drying Oils, Paint Testing Manual, G. G.
Sward, Ed., 13th ed., ASTM International, West Conshohock-
en, PA, 1972, p. 53.
[36] Tolvanen, P., Maki-Arvela, P., Eranen, K., Warna, J., Holm-
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Am. Oil Chem. Soc., Vol. 85, 2008, p. 567572.
[37] Martyak, N. M., Alford, D., Picker, R., and Dowsling, C., Con-
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2005, pp. 3641.
[38] Dirlikov, S., Islam, M. S., Frischinger, I., Lepkowski, T., and
Muturi, P., Increasing High-Solids with a Weed, Industrial
Finishing, Vol. 68, 1992, p. 17.
[39] Kumar, K. P. V., Sethuraman, M. G., and Madhulatha, W.,
Plant Extracts Can Improve Varnishes, European Coating
Journal, Vol. 9, 2004, pp. 7679.
[40] Harwood, H. J., Reaction of the Hydrocarbon Chain of Fatty
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99154.
[41] Fox, F. L., Oils for Organic Coatings, Federation Series on
Coatings Technology, W. R. Fuller, Ed., Federation of Societies
for Paint Technology, Philadelphia, 1965.
[42] Russell, G. A., Fundamental Processes of Autoxidation, J.
Chem. Educ., Vol. 36, 1959, p. 111.
[43] Farmer, E. H., and Sutton, D. A., Peroxidation in Relation to
Olefinic Structure, J. Chem. Soc., 1946, p. 10.
[44] Cowan, J. C., Drying Oils, Kirk-Othmer Encyclopedia of
Chemical Technology, 3rd ed., 1979, Vol. 8, pp. 130150.
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38
INTRODUCTION
METALLIC SOAPS ARE COMPOUNDS OF ALKALINE
metals or heavy metals and monobasic carboxylic acids
containing from 7 to 22 carbon atoms. The water-insoluble
metallic soaps are of particular interest to the coatings
industry, although potassium and lithium soaps have lim-
ited water solubility.
Basically, the known techniques for preparation of
metallic soaps are divided in two processesa fusion
process and a double decomposition process. The fusion
process involves reacting a metal oxide or hydroxide with
a fused fatty acid such as a triglyceride in the presence
of water [1]. The process yields the desired metallic soap
and glycerin. The double decomposition process involves
reacting an alkali soap that is comprised of an alkaline
metal salt or an ammonium salt of a fatty acid with an
inorganic metal salt. Both processes are usually carried out
in a batch mode; and, as a result, a product contaminated
with unreacted starting materials and by-products that
must be further purified is formed. To obtain a product
essentially free of contamination, a continuous process
[2] involving the double decomposition scheme has been
devised. An aqueous solution of the alkali soap and an
inorganic metal salt are separately fed onto a rotating
impeller surface whereon they are instantaneously mixed.
The resulting aqueous slurry is rapidly discharged and a
contamination-free metallic soap results. Recently, a pro-
cess for making basic zirconium carboxylates of branched-
chain, five- to ten-carbon, aliphatic monocarboxylic acids
has been described [3]. The compounds are useful as driers
for paints and inks.
The applications of metallic soaps in coatings include
their use as driers, catalysts, stabilizers, biocides, bodying
agents, and flatting agents. An overview of metallic soap
applications is presented in Table 1. An interesting particular
end-use for metallic soaps is in the formation of a thin metal-
lic oxide coating on a substrate [4]. A solution of the metallic
soap is applied by reverse roll coating and then baked in a
manner such that a thin, about 110 m, film of the metallic
oxide is formed. Although this chapter concentrates primar-
ily on metallic soaps used as driers, a brief review of bodying
and flatting applications for these materials is included.
METALLIC SOAPS AS BODYING AND
FLATTING AGENTS
Aluminum stearates, aluminum octoates, and calcium
linoleate pulp were at one time widely used as bodying and
pigment-suspending agents in solvent-based coatings. Their
advantages include fairly high efficiency and ease of incor-
poration. However, they have a number of deficiencies,
including sensitivity to variations in the formulation and in
the processing of paints, as well as adverse effects on film
hardness and resistance properties. As a result, they have
been replaced to a considerable extent by the bentonite clay
and organic wax derivatives [5].
Zinc and calcium stearates are used on occasion as
flatting additives in clear solvent-based coatings. However,
precipitated and fumed silicas are now more commonly
used for this purpose. Zinc stearate is also used to facilitate
sanding of primers and sealers for wood furniture finish-
ing [5].
THEORY OF OXIDATIVE DRYING AND FUNCTION
OF DRIERS [5,6]
It is generally accepted that vehicles based on unsaturated
oils, including alkyds and oleoresinous varnishes, dry by
oxidation according to the following steps:
1. Induction period.
2. Oxygen absorption.
3. Peroxide formation.
4. Peroxide decomposition to free radicals.
5. Free radicals promote reactions that cause cross-
linking.
The induction period occurs because most drying oils
contain natural antioxidants, the effects of which must
be overcome before the drying process can begin. Oxygen
is then absorbed from the air at the unsaturated sites on
the oil molecule, and, as the absorption continues, forms
peroxides. These peroxides then decompose to form free
radicals that act as catalysts to promote cross-linking of the
oil or alkyd molecules at the unsaturated sites, resulting in
dried films.
These same steps will occur in the absence of driers,
but driers are used to accelerate the drying or curing pro-
cess by means of the following mechanisms [5,6]:
1. Removal of natural antioxidants.
2. Acceleration of oxygen absorption.
3. Acceleration of peroxide decomposition.
Naturally occurring antioxidants may be considered as
negative catalysts for oxidation, whereas driers are positive
catalysts, counteracting the effects of the antioxidants.
The multivalent nature of the drier metal is considered
to be a key factor accelerating oxygen absorption in the
film. The drier metal is initially in a divalent state and is
5
Driers and Metallic Soaps
Marvin J. Schnall
1
1
Coatings Consultant, 620 Airport Rd., Suite 304, Chapel Hill, NC 27514.
MNL17-EB/Jan. 2012
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CHAPTER 5 DRIERS AND METALLIC SOAPS 39
converted to a trivalent state by the presence of oxygen in
the film. The metal then releases the oxygen to the film and
is converted back to the divalent form. This action acceler-
ates the process of oxygen absorption, peroxide formation,
and peroxide decomposition, which is responsible for oxi-
dative film drying.
DESCRIPTION OF DRIER METALS
The metals that act as catalysts to promote oxidation and
which may be used in driers are indicated below:
Cobalt
Manganese
Vanadium
Active or Primary
Lead
Calcium
Zirconium
Zinc
Iron
Rare Earth
Cerium
Aluminum
Auxiliary or Secondary
Cobalt and manganese, particularly cobalt, are the
most active drier metals. Cobalt promotes surface dry-
ing of films, while manganese affects both surface and
through drying. Vanadium has been mentioned in the
literature as an active drier but is seldom used in coat-
ing formulations. Driers based on these active metals
are often termed primary driers since they have inherent
catalytic action.
The auxiliary or secondary driers are seldom used alone,
but rather in combination with cobalt and/or manganese or
other metals. Their functions are to increase the efficiency
of the active drier metals and to increase film hardness. In
the past, lead was the most frequently employed auxiliary
drier, but it is presently out of favor due to toxicity and
other health considerations. Calcium and zirconium driers
are most frequently used as lead replacements. Zinc is used
primarily for improved film hardness and to prevent wrin-
kling of thick films. Iron driers are used mainly to improve
drying of baking systems when their dark color can be
tolerated. Rare earth and cerium driers are recommended
occasionally for improved through drying and as oxidation
catalysts for baking. Interest in aluminum compounds as
auxiliary driers has recently increased with the advent of
high-solids alkyds. Aluminum compounds are being recom-
mended to improve film hardness with these compounds,
but at times they may adversely affect viscosity stability and
promote gelation.
DESCRIPTION OF DRIER ACIDS
To perform their function, driers should be soluble in the
vehicles to which they are added. Solubility is achieved
by reacting the drier metals with organic acids to form
metallic soaps. The most commonly employed acids are as
follows:
Linoleates,
Rosinates,
Tallates,
Naphthenates,
Octoates (2-ethyl hexanoates),
Synthetic acids, and
Neodecanoates.
Chronologically, the linoleates, rosinates, and tallates
were the first types developed, followed by the naphthe-
nates and the octoates. A more recent development is the
synthetic acid type, which is proprietary but closely related
to the octoates. The synthetic acid and neodecanoate driers
can be prepared at higher metal concentrations than the
other types and are gradually replacing the older acids.
Water-dispersible driers may be prepared by adding
non-ionic surfactants to naphthenate or synthetic acid dri-
ers. However, proprietary cobalt and manganese drier com-
pounds are available that are purported to be more suitable
for water-based coatings.
Trade names of the various commercial drier types
available are listed in Table 2.
MISCELLANEOUS DRIERS
Restrictions on solvent emissions have stimulated the devel-
opment of both higher-solids and water-reducible coatings.
In the process of formulating these coatings, chemists
are experiencing difficulty obtaining satisfactory drying
properties with the conventional metallic soap driers.
Alternative drier compounds, including both organics and
proprietary metallic complexes, are currently being offered
[7]. Some typical examples are shown in Table 3. They are
usually recommended in combination with conventional
metallic soap driers for improved drying efficiency.
Another class of metallic compounds closely related to
driers is loss of dry inhibitors or feeder driers. These are
compounds designed to prevent loss of drying efficiency of
paints on aging resulting from the adsorption of driers by
TABLE 1Coatings applications of
metallicsoaps
Applications Metals Acids
Driers Cobalt, manganese,
lead, iron, rare earth,
cerium, zirconium,
zinc, calcium, barium,
bismuth, potassium,
vanadium, aluminum
Tallates, octoates,
naphthenares,
neodecanoates,
synthetic acids,
linoleates, rosinates
Catalysts Potassium, lithium,
cobalt, copper, tin,
zinc, manganese
Octoates,
naphthenates,
laurates,
neodecanoates
Stabilizers Barium, cadmium, tin,
zinc, calcium, lead
Proprietary, sulfates,
carbonates, stearates
Biocides Copper, tin, zinc,
mercury
Naphthenates,
octoates, phenyl
acetates, phenyl
oleates, laurates,
butyl oxides
Bodying
agents
Aluminum, calcium Stearates, octoates,
linoleates
Flatting
agents
Zinc, calcium Stearates
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40 PAINT AND COATING TESTING MANUAL 15TH EDITION
pigments, particularly carbon black and organic red pig-
ments. They function by dissolving gradually into the coat-
ing vehicle so that the metals are available over a period of
time rather than immediately. In this manner, they replace
the drier metals that have been absorbed by the pigments,
thereby maintaining satisfactory drying on prolonged stor-
age. Lead compounds, including litharge, were used formerly
but have been replaced by lead-free compounds based pri-
marily on less soluble forms of cobalt and other drier metals.
Commercially available feeder driers are listed in Table 4.
All are lead-free metal complexes except for the last item [8].
DRIER LEVELS IN COATINGS
Drier requirements for coatings are usually expressed in
terms of percent drier metal based on oxidizable vehicle
nonvolatile content. A typical calculation is as follows [9]:
Assume:
1. In a 1,000 g paint formulation, there are 300 g of
vehicle nonvolatiles.
2. Cobalt drier used is 12 % metal by weight.
3. Calcium drier used is 10 % metal by weight.
4. Required for optimum drying: 0.05 % cobalt plus 0.2 %
calcium (percent metal based on vehicle nonvolatiles).
per 1,000 g of paint:
cobalt metal required = 0.0005 300 g = 0.15 g
calcium metal required = 0.002 300 g = 0.6 g
The optimum levels of drier metal required will vary
depending on the type of polymeric system employed and
the conditions of drying. Typical metal concentrations for
a number of common vehicles are indicated in Table 5. A
guide to the selection of the proper ASTM test methods for
determining volatile and nonvolatile content of driers and
related products is ASTM D4140, Standard Guide for Deter-
mining Volatile and Nonvolatile Content of Driers, Drying
Oils, Naval Stores, and Solvents.
TESTING OF DRYING EFFICIENCY
The procedures used to determine the stages of film forma-
tion during the drying of coatings are described in ASTM
D1640, Test Methods for Drying, Curing, or Film Formation
of Organic Coatings at Room Temperature. With coatings
containing metallic driers, it is recommended that the paint
samples age overnight following the drier additions before
drying tests. The drying conditions, shown in Table 6, are
usually specified but are subject to agreement between the
purchaser and the seller.
The methods used to determine the various stages of
drying may be summarized as follows:
1. Set-To-Touch-Timeno transfer of the coating upon
lightly touching the film with the finger.
2. Dust-Free-Time(a) cotton fibers dropped on the film
can be removed by blowing lightly; (b) fine calcium
carbonate extender dropped on the film can be com-
pletely removed by blowing gently and wiping with a
cloth or brush.
3. Tack-Free-Timesa specified type of paper or alumi-
num foil will no longer adhere to the film when applied
under specific conditions.
TABLE 3Alternate drier compounds
Trade Name Company Composition
Active-8 R. T. Vanderbilt Co. 1,10-phenanthroline
Dri-RX Mooney Chemicals
Inc.
2,2-dipyridyl
Drymax Huls America 2,2-dipyridyl
Nutra ADR 10 % Huls America proprietary metal
complex
Nutra LTD 18 % Huls America proprietary metal
complex
TABLE 2Commercial drier types [3]
Type of Drier Trade Name Supplier
Synthetic acid Cem-All Mooney Chemical, division
of OMG
NuXtra Huls America
Troymax Troy Corp.
Octoate Hex-Cem Mooney Chemical, division
of OMG
Octoate Huls America
Neodecanoate Ten-Cem Mooney Chemical, division
of OMG
Naphthenate Nap-All Mooney Chemical, division
of OMG
Nuodex Huls America
Troykyd Troy Corp.
Tallates Lin-All Mooney Chemical, division
of OMG
Water
dispersible
Hydro-Cem Mooney Chemical, division
of OMG
Hydro-Cure Mooney Chemical, division
of OMG
Nuocure Huls America
Troykyd WD Troy Corp.
Calcicat Ultra adhesives
Aquacat Ultra adhesives
Magnacat Ultra adhesives
Zircat Ultra adhesives
TABLE 4Commercial feeder driers
Company Trade Name
Mooney Chemical, division
of OMG
Hex-Cem LFD
Mooney Chemical, division
of OMG
Hydroxy Ten-Cem Cobalt
Troy Corporation Troykyd Perma Dry
Huls America Nuact Cobalt 254
Huls America Nuact NOPB
Huls America Nuact Paste (lead-based)
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CHAPTER 5 DRIERS AND METALLIC SOAPS 41
4. Dry-To-Touch-Timethe film no longer adheres to the
finger when pressed firmly and does not rub up when
rubbed lightly.
5. Dry-Hard-Timea thumb print applied under specified
conditions is completely removed from the film when
polished lightly with a soft cloth.
6. Dry-Through-Timethe film is not distorted or detached
when the thumb is applied to it in a specified manner
and rotated through a 90 angle.
7. Dry-To-Recoata second coat or top coat can be
applied without development of lifting or loss of adhe-
sion of the first coat.
8. Print-Free-Timearmy duck or cheesecloth applied at a
pressure of 3.5 or 6.9 KPa no longer marks the film as
TABLE 5Typical drier recommendations, percent metal based on vehicle nonvaluable
Cobalt Manganese Zirconium Calcium Zinc 1,10-Phetanthroline 2,2-Dipyridyl, 30 %
Long oil alkyd-air dry 0.040.06 0.10.3
0.040.06 0.10.3
0.040.06 0.10.2 0.10.2
Medium oil alkyd-air dry 0.040.06 0.10.3
0.040.06 0.10.3
0.040.06 0.10.2 0.10.2
Short oil alkyd air-dry 0.040.06 0.10.3
0.040.06 0.10.3
0.040.06 0.10.2 0.10.2
Chain-stopped alkyd 0.05-0.08 0.2
0.050.08 0.1 0.1
Medium oil alkyd-bake 0.010.03 0.10.5
Oil-modified urethane 0.020.04 0.10.3
0.020.04 0.10.3
0.020.04 0.2
Linseed oil 0.02 0.02 0.10.2 0.10.2
0.020.04 0.10.3 0.10.15
0.020.04 0.10.3
Alkyd-oil house paint 0.020.03 0.020.03 0.020.03
0.020.03 0.020.03 0.020.03
0.020.04 0.020.04 0.10.2 0.10.2 0.10.15
Epoxy Ester 0.030.05 0.10.2
0.030.05 0.10.2
Acrylic modified alkyd 0.040.08 0.1 0.1
Oleoresinous varnish 0.020.06 0.2
Vinyltoluene alkyd 0.020.04 0.1
0.020.04 0.1
High solids alkyd 0.040.06 0.50.9 0.2
0.040.06 0.50.9 0.2
0.040.06 0.20.4 0.20.4
Water-based alkyds
(water dispersible driers)
0.040.06 0.10.3
0.040.06 0.10.3
0.050.1 0.150.3 0.150.2 0.150.3
TABLE 6Standard drying conditions
Condition Typical Value
Ambient temperature 23 2C
Relative humidity 50 5 %
Film thickness (dry) 12.5 to 45 m
Substrate Clean glass
Lighting No direct sunlight
Applicators Doctor blades
Coating viscosity Close to normal application
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42 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 7Typical requirements of liquid paint driers
a
Class Metal
Metal Concentration
%
Nonvolative
Matter, % Max
Typical Specific Gravity,
25/25C
Color Gardner
b
(Test
Method D1544)
G-H Viscosity (Test
Method D1545) Min Max Min Max
A Calcium 3.9 4.1 50 0.884
c
... 3 A
A Calcium 4.9 5.1 60 0.894 0.912 5 C
B Calcium 3.9 4.1 70 0.902 0.937 10 D
B Calcium 4.9 5.1 85 0.932 0.970 11 T
C Calcium 4.9 5.1 46 0.888 ... 2 A
D Calcium 3.9 4.1 66 0.890 0.918 9 B
E Calcium 3.9 4.1 63 0.905 0.930 8 G
E Calcium 5.9 6.1 76 0.922 0.960 5 N
F Calcium 3.9 4.1 50 0.850 0.884 3 A
F Calcium 4.9 4.1 60 0.900 0.936 4 B
F Calcium 5.9 6.1 74 0.873 0.948 6 N
F Calcium 7.9 8.1 70 0.958 ... 5 B
F Calcium 9.9 10.1 65 1.000 1.030 78 K
A Cerium 5.9 6.1 30 0.856 ... 8 A
B Cerium 5.9 6.1 57 0.925 ... 17 A1
A Cobalt 5.9 6.1 45 0.875 0.900 Blue/purple A
A Cobalt 11.8 12.2 90 1.008 1.060 Blue/purple J
B Cobalt 5.9 6.1 67 0.918 0.970 Blue/purple B
C Cobalt 11.8 12.2 65 0.984 ... Blue A
D Cobalt 5.9 6.1 72 0.912 0.956 Purple C
E Cobalt 4.9 5.1 60 0.926 ... Red/purple A
E Cobalt 5.9 6.1 71 0.945 0.960 Blue/purple I
F Cobalt 5.9 6.1 70 0.870 0.958 Blue/violet A
F Cobalt 11.8 12.2 80 1.014 1.040 Blue/violet J
A Iron 5.9 6.1 50 0.900 0.930 Dark brown A
B Iron 5.9 6.1 67 0.960 0.990 Dark brown M
F Iron 5.9 6.1 50 0.905 0.930 Brown A
F Iron 8.9 9.1 78 0.950 0.985 Brown M
F Iron 11.8 12.2 75 1.068 ... Brown A
A Lead 23.8 24.2 65 1.090 1.110 3 A
B Lead 23.8 24.2 67 1.125 1.160 11 B
C Lead 23.8 24.2 61 1.100 ... 2 B
D Lead 23.8 24.2 66 1.100 1.125 10 A2
E Lead 23.8 24.2 71 1.125 1.150 7 A
F Lead 23.8 24.2 67 1.080 1.140 10 A
F Lead 35.8 36.2 81 1.350 1.393 8 H
A Manganese 5.9 6.1 50 0.888 0.920 Red/brown A
B Manganese 5.9 6.1 66 0.930 0.965 17 D
C Manganese 5.9 6.1 50 0.870 ... 10 A
(Continued)
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CHAPTER 5 DRIERS AND METALLIC SOAPS 43
determined by photographic standards shown in ASTM
D2091, Test Method for Print Resistance of Lacquers.
In addition to the above subjective tests, a number of
mechanical drying time recorders are available. The instru-
ment referred to most frequently in recent literature is the
Byk-Gardner improved circular drying time recorder [10].
This functions by moving a Teflon stylus over the applied
film in a circular path. The pattern left in the film by the
stylus after a complete revolution is observed. Recorders
are available, which make complete revolutions in 1, 6, 12,
or 24 h. With the use of a plastic template, set-to-touch,
surface dry, and through-dry times may be noted.
Development of film hardness is also an important
criterion of drier efficiency. Tests used to measure hardness
include:
1. ASTM D3363, Test Method for Film Hardness by Pencil
Testa series of pencils varying in lead hardness from
6B (softest) through 6H (hardest) are pushed into the
film, and the hardest pencil that will not penetrate the
film is noted.
TABLE 7Typical requirements of liquid paint driers
a
D Manganese 5.9 6.1 72 0.942 0.972 Brown E
E Manganese 4.9 5.1 42 0.911 Brown E
E Manganese 5.9 6.1 69 0.942 0.965 Brown E
F Manganese 5.9 6.1 55 0.870 1.020 18 A
F Manganese 8.9 9.1 80 0.950 1.020 18 A
F Manganese 11.8 12.2 75 1.044 ... 16 C
A Nickel 9.9 10.1 70 1.032 ... Green A
A Rare earth
d
5.9 6.1 30 0.630 0.880 6 E
A Rare earth 11.8 12.2 55 0.977 ... Yellow/green C
B Rare earth 3.9 4.1 35 0.840 0.855 10 A
C Rare earth 5.9 6.1 35 0.876 ... 8 A5
A Zinc 7.9 8.1 50 0.880 0.906 6 G
A Zinc 17.8 18.2 90 1.068 1.130 7 Z
B Zinc 7.9 8.1 70 0.915 0.960 9 A
B Zinc 9.9 10.1 75 0.980 1.044 8 L
D Zinc 7.9 8.1 70 1.008 ... 11 D
E Zinc 7.9 8.1 42 0.946 ... 2 A
F Zinc 7.9 8.1 60 0.855 0.963 7 C
F Zinc 15.8 16.2 80 1.020 1.100 3 B
A Zirconium 5.9 6.1 30 0.860 0.864 2 A
A Zirconium 11.8 12.2 56 0.960 0.992 4 A
A Zirconium 17.8 18.2 55 1.070 1.074 3 A
A Zirconium 23.8 24.2 77 1.240 ... 2 J
C Zirconium 5.9 6.1 23 0.864 ... 2 A5
C Zirconium 11.8 12.2 46 0.976 ... 2 A
E Zirconium 5.9 6.1 31 0.864 ... 4 A
E Zirconium 11.8 12.2 55 0.975 1.020 4 A
F Zirconium 5.9 6.1 28 0.855 0.870 2 A5
F Zirconium 11.8 12.2 55 ... ... ... ...
F Zirconium 17.8 18.2 80 1.090 1.130 4 Z
F Zirconium 23.8 24.2 93 1.240 1.260 6 J
a
Source: National Paint and Coatings Association, Chemical Specialties Section, Raw Material Index, April 1978 edition per Gardner Method D1544
b
If off the scale, as observed by the unaided eye.
c
Only one drier was listed in this category.
d
The metal content represents total rare earth metals calculated as cerium but the drier contains cerium and lanthanum, as well as minor amounts of
other rare earth metals.
TABLE 7Typical requirements of liquid paint driers
a
(Continued)
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44 PAINT AND COATING TESTING MANUAL 15TH EDITION
2. ISO 1522 Paints and VarnishesPendulum Damping
Testeither a Knig or a Persoz pendulum hardness
tester is employed with the time, in seconds, noted for
the swing amplitude of the pendulum to decrease by a
specified degree when set into oscillation on the dried
film.
3. ASTM D1474, Test Methods for Indentation Hardness of
Organic Coatingseither a Knoop or a Pfund indenter
is applied to a film under a specified loading, and the
depth of indentation is measured with the aid of a
microscope. The depth is converted to either a Knoop
or a Pfund hardness number using the equations in the
standard.
SPECIFICATIONS FOR LIQUID PAINT DRIER
Drier specifications as described in ASTM D600, Speci-
fication for Liquid Paint Driers involve the following
classes:
Class A2-Ethyl hexanoic acids in petroleum spirits.
Class BNaphthenic acids in petroleum spirits.
Class CNeodecanoic acids in petroleum spirits.
Class DTall oil fatty acids in petroleum spirits.
Class EAny of the above, plus additives to make the
driers water dispersible.
Class FOther unidentified acids and acid blends.
A comprehensive table of liquid paint driers of the
above classes is given in ASTM D600. The typical proper-
ties of the driers listed and reproduced in Table 7 include
percent metal concentration, percent nonvolatile con-
tent, specific gravity, Gardner color, and Gardner-Holdt
viscosity.
TESTING OF LIQUID PAINT DRIERS
ASTM D564, Test Method for Liquid Paint Driers outlines
the test procedures employed, including both physical and
chemical tests. The physical tests include:
1. Appearancevisual observations may be made for clar-
ity and cleanness.
2. Coloraccording to ASTM D1544, Standard Test Meth-
od for Color of Transparent Liquids (Gardner color
scale, which employs the Gardner numerical color
scale). However, a number of driers, including cobalt,
manganese, nickel, and rare earth, do not fit into this
scale and are reported descriptively.
3. Nonvolatile ContentASTM D1644, Test Methods
for Nonvolatile Content of Varnishes, according to
method A or B. Method A involves heating samples
at 105C for 10 min, while method B specifies 150C
for 10 min.
4. Miscibility with OilOne volume of the drier sample is
mixed with 19 volumes of raw linseed oil. The mixture
is observed for any signs of separation or clouding over
a 24 h period.
5. StabilityThe drier sample is stored for 7 days at 25,
20, and 50C and examined for indications of clotting,
gelation, or precipitation.
6. Drying powerAs described in the section entitled
Testing of Drying Efficiency.
7. ViscosityAccording to ASTM D1545, Test Method
for Viscosity of Transparent Liquids by Bubble Time
Method. This involves comparing the time of travel of
bubbles in tubes of the sample versus Gardner-Holdt
standard tubes. The standards were formerly designat-
ed by letter but are now indicated directly in stokes. A
table in this test method indicates the conversion from
letters to stokes.
Chemical analysis is used to determine the metal con-
tent of liquid paint driers. The EDTA method is used for
most drier metals (Table 8). The liquid drier is dissolved
or digested in solvents and then treated with an excess of
standard EDTA solution (disodium salt of ethylenediamine
tetraacetic acid dihydrate). The excess of EDTA is then
titrated to an end point determined by a specified indica-
tor. This method is applicable to single metal driers only,
not to drier blends. An EDTA method is not yet available
for cerium, and an oxidimetric determination is specified
(ASTM D3970, Test Method for Cerium in Paint Driers by
Oxidimetric Determination). Table 8 outlines the ASTM
designations, indicators, and titrating solutions for analysis
of drier metals by EDTAtitration.
References
[1] Blachford, J., Manufacture of Metallic Soaps, U.S. Patent
No. 4,316,852 (1982).
[2] Yoshizawa, F., Kikuchi, F., Kojima, S., and Yuasa, K., Con-
tinuous Process for Preparing Metallic Soaps, U.S. Patent No.
5,175,322 (1992).
[3] Reyniers, S. L. E., and SJegers, K., U.S. Patent No. 5, 861,
523 (1999).
TABLE 8Metal analysis by EDTA titration
Metal ASTM Method Solvent Indicator Titrating Solution
Cobalt D2373 Glacial acetic acid PAN
a
Cupric sulfate
Lead D2374 Glacial acetic acid PAN
a
Cupric sulfate
Manganese D2375 Toluene-ethanol Eriochrome black-T Zinc chloride
Calcium or zinc D2613 Toluene-ethanol Eriochrome black-T
Iron D3869 Isopropanol Eriochrome black-T Zinc chloride
Zinc D3969 HSO-HO Xylenol orange Bismuth nitrate
Vanadium D3988 Isopropanol-HCL Xylenol orange Zinc chloride
Total rare earth D3989 Isopropanol-HCL Xylenol orange Zinc chloride
a
1(2-Pyridylazo)-2-Naphthenol.
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CHAPTER 5 DRIERS AND METALLIC SOAPS 45
[4] Makita, K., Moriguchi, Y., and Okuda, J., U.S. Patent No. 5,
510, 141 (1996).
[5] Schnall, M., Thickeners for Solvent-Based Coatings, Hand-
book of Coatings Additives, Chap. 3, Marcel Dekker, Inc., New
York, 1987, pp. 3334.
[6] Godbole, V. A., Use of Metallic Driers in Organic Coatings,
Paintindia, Vol. 6, No. 4, 1986, pp. 2932.
[7] Belletiere, S. J., and Mahoney, D. M., Multi-Metallic Com-
plexes: The Next Generation of Driers, J. Coat. Technol., Vol.
59, 1987, pp. 101108.
[8] Raw Materials Index, Chemical Specialties Section, National
Paint and Coatings Association, Washington, DC, March 1989,
pp. 211 and 2227.
[9] Hurley, R., Metal Soaps: Drier Stabilizers and Related Com-
pounds, Handbook of Coatings Additives, Chap. 13, Marcel
Dekker, Inc., New York, 1987, pp. 485509.
[10] Drying Time, Instrument Catalogue, Section 9, Byk-Gardner,
Inc., Silver Springs, MD, 1990.
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Part 3: Synthetic Materials
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49
6
Acrylic Polymers as Coatings Binders
John M. Friel
1
and Edwin Nungesser
2
INTRODUCTION
ACRYLIC POLYMERS, WHICH ARE USED AS COAT-
ings binders, are comprised chiefly of esters of acrylic and
methacrylic acid that are polymerized by addition polymer-
ization, usually using a free radical mechanism:
Interest in acrylic technology dates back to the 1920s
when Dr. Otto Rohm developed a practical process for
making acrylate esters from ethylene. Shortly afterwards,
his associate, Otto Haas, established the first commercial
production of methyl and ethyl acrylate in the United States
[1]. The first commercial use of an acrylic polymer was as
an adhesive-like interlayer for laminated safety glass. Prob-
ably the highest profile use of an acrylic began in 1936 with
the introduction of thermoplastic, transparent methacry-
late sheet. With the advent of World War II, methacrylate
sheet became invaluable as a tough, weather-resistant glaz-
ing material for military aircraft. Since it could be formed
easily and had excellent optical properties, the transparent
plastic was used for aircraft canopies, bomber noses, and
gun turrets [2].
Acrylic technology soon expanded into the coatings
industry in the form of acrylic solution polymers, followed
later by acrylic emulsions. The acrylics gained widespread
market acceptance as coatings binders due to such out-
standing properties as color stability, transparency, and
resistance to weathering and aging. The good weathering
resistance of acrylic polymers is primarily due to their resis-
tance to hydrolysis and their lack of absorption of ultravio-
let (UV) light, the high-energy portion of the light spectrum
most responsible for degradation.
Acrylic solution polymers (often referred to as acrylic
resins) are generally copolymers of acrylate and methac-
rylate esters prepared by direct solution polymerization
in a solvent that has a solubility parameter similar to that
of the polymer. Typical solvents include aromatics such as
toluene and xylene, as well as ketones and esters. Acrylic
resins are typically supplied at about 30 % to 50 % solids
by weight, with viscosities ranging from a few hundred to
a few thousand centipoise. In later years, 100 % solid-grade
versions became popular since they reduced the cost and
safety concerns associated with shipping resins containing
high solvent levels. The coatings manufacturer is then able
to dissolve the solid-grade acrylic in a wide range of sol-
vents, thereby having greater control over the formulation
ingredients.
A wide range of properties can be built into an acrylic
coatings binder by careful selection of the type and level of
the acrylic monomers used. Some of the important proper-
ties (such as tensile strength and elongation of cast films)
for several acrylic homopolymers can be found in Ref. [3].
Coatings for a wide range of applications can therefore
be custom designed. Some of the principal applications
for acrylic solution coatings include automotive finishing,
factory and farm implement coatings, general-purpose pig-
mented coatings, aerosol lacquers, and clear coatings for a
multitude of substrates. There are two types of acrylic solu-
tion polymers: (1) thermoplastic polymers, which harden
simply by loss of solvent through evaporation; and (2)
thermosetting polymers, which contain functional groups
that react with another functional material (i.e., melamine,
epoxy, isocyanate, etc.) to form a cross-linked network.
The advantages and disadvantages of each are discussed in
detail later in this chapter.
Acrylic emulsion polymers (often referred to as acrylic
latexes) have become one of the major binder types in use
in the coatings industry today. To form an emulsion poly-
mer, the acrylic monomers are emulsified and then polym-
erized as small droplets in a continuous water phase. The
droplets are typically stabilized by surfactants, and usually
no solvent is present. While acrylic emulsions are gener-
ally associated with quality architectural coatings, they are
also used to formulate industrial coatings. In fact, the use
of acrylic emulsions in industrial applications is expand-
ing at the expense of solvent-based systems because of the
industrys need to control organic emissions. Over the past
20 years, acrylic emulsion manufacturers have made great
strides in improving the properties of acrylic emulsions
so that they now offer performance similar to the solvent-
based coatings they are replacing.
When the first acrylic emulsion designed for use in
house paints was introduced in 1953, it had the low-odor,
quick-drying, and easy cleanup features of its water-based
competitors, styrene-butadiene and poly(vinyl acetate)
emulsions; but, in addition, it offered excellent exterior
1
Retired from The Dow Chemical Company, Research Laboratories, 727 Norristown Road, Spring House, PA 19477.
2
Scientist, Adhesives and Functional Polymers, The Dow Chemical Company, Research Laboratories, 727 Norristown Road, Spring House,
PA 19477.
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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50 PAINT AND COATING TESTING MANUAL 15TH EDITION
durability that allowed use in exterior paints. During the
past 40 years, it has been good exterior durability that
enabled acrylic emulsions to replace solvent alkyds as the
dominant binder in the exterior house paint market.
Acrylic Monomers
Virtually all of todays world-wide supply of acrylic acid is
based on the two-stage vapor-phase oxidation of propylene
via an acrolein intermediate:
Generally in the first step, propylene is oxidized to
acrolein in the presence of steam and air using a Mo-
Bi-based multicomponent mixed oxide catalyst. A fixed
bed tubular reactor is used to facilitate heat removal and
steam generation. In a similar second reactor, containing a
Mo-V mixed oxide catalyst, the acrolein is further oxidized
to acrylic acid. Acetic acid is a minor byproduct. The hot
reactor effluent is quenched in an absorber and the aque-
ous rundown is sent to a purification section where crude
acrylic acid is recovered either as a distilled overhead
material or as a bottoms material also containing heav-
ies. Crude acrylic acid can either be converted to glacial
acrylic acid (by removing minor levels of organic acid
and aldehyde impurities) or it can be converted to acry-
late esters, such as methyl, ethyl, butyl, or 2-ethylhexyl
acrylate, by reacting it with the appropriate alcohol in the
presence of a strong organic or mineral acid or acidic ion
exchange resin.
Older acrylic acid technology based on the liquid-
phase carbonylation of acetylene with nickel carbonyl in
the presence of water or an alcohol to yield either acrylic
acid or an acrylate ester (Reppe chemistry) is no longer
practiced due to cost and safety considerations. Niche
chemistries, e.g., the hydrolysis of acrylonitrile, are only
practiced commercially at small scale where cost is not a
determining factor.
Methacrylates
Several process technologies are currently used to produce
methacrylic acid and methyl methacrylate. The conven-
tional acetone cyanohydrin route to methyl methacrylate
(MMA) has been practiced commercially since 1937 with
only minor improvements to the process over the past 74
years. The basic technology remains virtually unchanged:
HCN (on-purpose from natural gas and ammonia or by-
product from acrylonitrile production) is reacted with
acetone to form acetone cyanohydrin:
The acetone cyanohydrin is hydrolyzed with sulfuric
acid to an a-sulfato-isobutyramide intermediate which rear-
ranges to methacrylamide sulfate:
The methacrylamide sulfate is then either reacted with
water to make methacrylic acid or, more commonly, it is
esterified with methanol to methyl methacrylate:
Mitsubishi Gas Chemical recently developed a new
route to MMA that also relies on acetone cyanohydrin as a
key chemical intermediate but utilizes a different reaction
pathway to methyl methacrylate: acetone cyanohydrin is
reacted with water in the presence of a manganese dioxide
catalyst to yield a-hydroxy isobutyramide. (The conven-
tional technology tries to minimize the water content of
the hydrolysis feed to minimize a-hydroxy isobutyramide
formation.) The a-hydroxy isobutyramide is transesterified
in the liquid phase with methyl formate to produce methyl-
a-hydroxyisobutyrate which is, in turn, dehydrated in the
vapor phase to methyl methacrylate. The transesterifi-
cation step also generates formamide which is thermally
decomposed to hydrogen cyanide which is recycled to the
front-end of the process. This process chemistry uses no
sulfuric acid and much of the HCN required to produce the
acetone cyanohydrin is recycled within the process.
Today, about 80 % of the worlds methyl methacry-
late production capacity is based on acetone cyanohydrin
chemistry.
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CHAPTER 6 ACRYLIC POLYMERS AS COATINGS BINDERS 51
Most of the rest of the worlds supply of methyl meth-
acrylate is produced via the conventional two-stage vapor-
phase oxidation of isobutylene (or t-butanol) using process
technology that is an analogue of the propylene oxidation
technology described above for acrylic acid:
The methacrylic acid is subsequently esterified to methyl
methacrylate.
ACRYLIC SOLUTION POLYMERS
Thermoplastic Resins
Thermoplastic acrylic resins are acrylic polymers that are
polymerized directly in a suitable solvent and form a film
solely by evaporation of the solvent. They do not need to
be oxidized or cross-linked to form a hard, resistant finish.
They are fast-drying lacquer materials, but they remain
permanently soluble.
Acrylic resins are usually supplied in strong solvents
such as toluene, xylene, or methyl ethyl ketone. They are
clear, colorless solutions and, if left unpigmented, will also
dry down to clear, colorless films. They are often used in
unpigmented form as protective finishes over vacuum met-
alized plastics and polished metals such as brass.
Acrylic resins generally make excellent grind media for
dispersing pigments. No external pigment wetting agents
are required to make finely dispersed pigment grinds for
high-gloss lacquers. Also, thermoplastic acrylic polymers
are quite unreactive and consequently are stable when
mixed with pigments, extenders, and colors. They do not
discolor powdered metals, such as aluminum.
Acrylics are a uniquely versatile family of polymers
since an infinite array of properties can be achieved by
carefully selecting combinations of the various acrylic
monomers. Each acrylic monomer brings to the polymer
its own individual performance characteristics based
on its molecular structure. This is particularly true for
polymer hardness as determined by the glass transition
temperature (Tg) of the monomers that make up the homo-
polymer (only one monomer) or copolymer (two or more
monomers). The Tg of a polymer is a softening point: it is
actually a temperature range where the polymer undergoes
a second-order transition. At temperatures below the Tg,
the polymer is a glass, but above the Tg the polymer is a
rubbery material. To approximate the Tg for a copolymer
composition, it is useful to utilize the relationship pro-
posed by Fox [4].
1
1
1
2
2
T
W
T
W
T
g g g
= +
(1)
where
W
1
and W
2
= the weight ratios of Monomers 1 and 2,
respectively,
Tg
1
and Tg
2
= the Tgs of the homopolymers of Mono-
mers 1 and 2 in degrees absolute.
Since thermoplastic acrylics are not cross-linked to
achieve a desired level of performance, the concept of Tg
and the ability to manipulate Tg as a means to control prop-
erties is crucial in designing polymers that meet the needs
of the coatings market. The marked difference in Tgs, and
consequently polymer characteristics of the acrylics, can
phenomenologically be explained by the free-volume theory
proposed by Fox and Flory [5] and later refined by several
others. The free-volume theory states that the Tg for any
given polymer occurs at that temperature where the frac-
tional free volume (i.e., unoccupied space contained within
the polymer) reaches some universally constant value that
remains unchanged as temperature decreases below Tg.
Above this temperature, the free volume increases, permit-
ting sufficient molecular motion so polymer flow can begin.
In Fig. 1, Rogers and Mandelkern have plotted specific vol-
ume versus temperature for a series of methacrylates as a
means of establishing the relationship of Tg to free volume
[6]. The arrows (f) in Fig. 1 indicate the temperature at
Fig. 1Specific volume-temperature relations for the poly-
(n-alkyl methacrylates). (Reprinted with permission from the
American Chemical Society. Copyright 1975.)
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52 PAINT AND COATING TESTING MANUAL 15TH EDITION
which there is an inflection in the specific volume curve
indicating a sudden increase in free volume (as temperature
increases). This is the Tg. From the graph, it can be calcu-
lated that, at Tg, free volume accounts for 15 % of the total
polymer volume [6]. Simha and Boyer have independently
calculated that at Tg, free volume accounts for 11 % of a
polymers total volume [7].
On a molecular level, the Tg differences for the acrylic
family of polymers can also be easily explained. The acry-
lates have an alpha-hydrogen atom next to the carbonyl
group, giving them more rotational freedom and hence
greater segmental chain motion than the methacrylates.
The methacrylates have a bulky methyl group substituted
for the alpha-hydrogen atom, which hinders molecular
rotation, thereby increasing chain stiffness. The methac-
rylates are therefore higher in Tg, harder, higher in tensile
strength, and lower in elongation than analogous acrylate
polymers.
Equally important to Tg and polymer hardness is
the length of the ester side chain of the monomer. As the
alcohol moiety of the ester side chain becomes larger, the
polymer chains are pushed further apart, creating addi-
tional free volume, thereby encouraging greater molecular
rotation. Consequently, the polymers become increasingly
soft (as the ester side chain becomes larger) until the effects
of side-chain crystallization causes additional hardening
effects. The large range of Tgs that exist for the acrylate
and methacrylate family of homopolymers can be found in
Ref. [8].
The second most important parameter governing the
film properties of a thermoplastic acrylic polymer is
molecular weight (MW). Most dry film properties for
thermoplastic acrylics improve with increasing MW up to
a MW of about 100 000 and then tend to level off. Tensile
strength, elongation, toughness, solvent resistance, and
exterior durability are all dependent on MW. This depen-
dence of strength, elongation, and resistance of the acrylic
polymer on MW is primarily due to the greater number of
chain entanglements (which act almost like cross-links),
anchoring the polymer chains at higher M W (i.e., longer
chain length).
However, the viscosity of a solution polymer is pro-
portional to the MW of a polymer according to the Mark-
Houwink equation [9].
= K MW
a
( ) (2)
where
= solution viscosity
K and a = constants derived experimentally for a specific
polymer/solvent combination (for polymethyl
methacrylate in toluene, K 10
5
= 7.1 and
a=0.73). The type MW used in determining the
constants should be specified.
As MW increases, the solution viscosity also increases,
thereby posing handling and application problems if the
MW becomes too high. For example, high spray solids
are desirable for acrylic lacquers because of economy and
emissions concerns. The lower the MW of the polymer, the
lower the viscosity at a given solids content, or conversely,
the higher the spray solids at spray viscosity. Consequently,
low MW is beneficial to solids and application con-
cerns,whereas high MW is needed for good film properties.
The obvious answer to the viscosity versus film
property dilemma is to reach an optimum balance by
producing an intermediate MW polymer. For this rea-
son, most thermoplastic acrylic solution polymers have
weight-average MWs in the 75 000 to 100 000 range. It is
also helpful to narrow the MW distribution, reducing the
amount of low-molecular-weight fractions, which have a
deleterious effect on resistance and strength properties,
while also minimizing high-molecular-weight portions,
which increase viscosity and cause application problems
such as cobwebbing of spray-applied acrylic automotive
lacquers.
Since the application and drying properties of an
acrylic resin are largely controlled by the physical charac-
teristics of the solvent contained in the resin, as well as by
the interaction of the polymer and solvent, it is essential to
carefully select the solvent in which the acrylic is dissolved
(see Chapter 18 entitled Solvents). To ensure good solubil-
ity of the polymer, it is important to match the solubility
parameter of the solvent to that of the polymer. The solubil-
ity parameter is an estimation of the polarity of a solvent or
polymer and is related to the intermolecular energy of the
molecule (see Chapter 38 entitled Solubility Parameters).
The solubility parameter concept was defined by Hilde-
brand [10] and applied to coatings by Burrell. Burrell has
published the solubility parameters for an extensive list of
solvents [11].
For polymers, the solubility parameter can be calcu-
lated by knowing the molecular structure of the repeating
unit according to Smalls method. Small has published a
table of molar attraction constants used to calculate poly-
mer solubility parameters [12].
Besides being helpful in estimating solubility, the solu-
bility parameter concept is helpful in predicting the resis-
tance of polymers to solvents or other organics. In general,
the more polar acrylic polymers will have the best resis-
tance to hydrophobic materials, such as gasoline, grease,
or oil. More hydrophobic acrylics (with low & values) will
have better resistance to polar materials, such as water and
alcohol.
The evaporation rate of the solvent or solvent mixture
must also be carefully chosen to accommodate the expected
application method and conditions. For spray applica-
tion, moderately fast evaporating solvents are needed to
avoid running and sagging of the low-viscosity paint. For
roller coating, a much higher viscosity coating would be
used; therefore, slower evaporating solvents are required
to avoid skinning on the roller and to allow for flow out of
roller pattern created during application of the paint. Since
thermoplastic acrylics dry by evaporation of solvent alone,
extremely slow-drying solvents, which retard development
of properties, should be avoided.
The majority of thermoplastic acrylic solution poly-
mers are designed for general-purpose industrial finishing
(i.e., metal furniture and product finishing) and have a
Tg of approximately 50C. This Tg is generally obtained
by copolymerizing combinations of methyl methacrylate
(MMA), butyl methacrylate (BMA), ethyl acrylate (EA),
butyl acrylate (BA), and ethylhexyl acrylate (EHA). While
many other acrylate and methacrylate monomers exist,
as indicated in Table 2, these few are the primary acrylic
monomers that are commercially available and that are,
therefore, the most economically feasible.
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CHAPTER 6 ACRYLIC POLYMERS AS COATINGS BINDERS 53
At a Tg of 50C, these acrylic polymers are intermedi -
ate in hardness, having a Tukon hardness of about 11 to
12 [see ASTM Test Methods for Indentation Hardness of
Organic Coatings (D1474)]. They are hard enough to dry
rapidly to a tack-free state that allows early handling of
the coated product and also hard enough to resist marring,
print [see ASTM Test Method for Print Resistance of Lac-
quers (D2091)], block [see ASTM Test Method for Block-
ing Resistance of Architectural Paints (D4946)], and dirt
pickup. Yet, they retain enough flexibility and elongation
to have some impact resistance [see ASTM Test Method
for Resistance of Organic Coatings to the Effects of Rapid
Deformation (Impact) (D2794)], and some can even be
post-fabricated, such as is done with coil coated stock to
produce aluminum gutters, trim pieces, etc.
Up to the mid-1950s, nitrocellulose lacquers were
the major automotive coating in use. Nitrocellulose fin-
ishes gave an excellent original appearance but had poor
durability, particularly gloss retention, and required fre-
quent polishing by the car owner for the finish to look
good. This problem was eliminated in 1956 when General
Motors adopted acrylic lacquers based on poly(methyl
methacrylate). The acrylic lacquers gave significantly bet-
ter durability and allowed for the use of the more modern
eye-catching metallic pigments [13]. The acrylic lacquers
generally contain external plasticizers, such as the phthal-
ates, which contribute to improved chip resistance and
cold crack resistance. No internal plasticizing monomer
(i.e., acrylates) is generally contained in automotive acrylic
lacquers, and consequently their Tg is approximately 105C,
with a Tukon hardness of about 22.
Since they are very hard and fairly high MW (i.e.,
100000), the thermoplastic solution polymers designed for
automotive use are not capable of the excellent molecular
flow that would be expected of softer/lower- molecular-
weight polymers. Consequently, the acrylic lacquers
require factory buffing and or baking to obtain the kind
of maximum gloss required for the new-car showroom.
This disadvantage was shared by the older nitrocellulose
lacquers.
Also, because of hardness and high MW, the spray sol-
ids percent is low. Since these lacquers are thermoplastic,
they are permanently subject to softening by strong sol-
vents, such as toluene or acetone, if for some reason they
would contact the automotive finish. Conversely, however,
the thermoplastic acrylic lacquers can be easily repaired by
an additional coat of paint which melts into the original
coat, leaving no two-coat effects or intercoat adhesion
problems.
Thermosetting Acrylic Resins
Thermosetting acrylic resins are compositionally very simi-
lar to the thermoplastic-type acrylics, with the exception
that they contain functional groups, such as carboxyl or
hydroxyl, that are capable of reacting with another poly-
meric or monomeric multifunctional material to produce
a three-dimensional network structure. As has already
been discussed, the mechanical properties of thermoplastic
acrylic polymers for coatings are generally improved by
increasing MW, but polymers with overly high MW pro-
duce solutions of unworkably high viscosity. An alternate
route to improved film properties is to use a thermosetting
acrylic polymer, converting linear, moderate-molecular-
weight polymer chains to an infinite MW structure. This
cross-linking reaction takes place after the coating has been
applied to the substrate, often by the application of heat,
hence the term thermosetting. To be truly cross-linked,
one of the reactive species must have at least two reactive
sites, while the other species has at least three reactive sites
per molecule or chain.
Thermosetting acrylic polymers offer the following
advantages over thermoplastic acrylics: (1) improved hard-
ness and toughness, (2) better resistance to softening at
elevated temperatures, (3) improved resistance to solvents,
stains, and detergents, and (4) lower applied MW, resulting
in lower solution viscosity and consequently higher applica-
tion solids.
Over the years, numerous chemical reactions utilizing
various functional groups have been devised as a means to
cross-link acrylic polymers. However, we will elaborate on
some of the more commercially significant thermosetting
acrylics, namely those cross-linked with nitrogen resins,
epoxies, and isocyanates.
ACID-FUNCTIONAL ACRYLICS CROSS-LINKED
WITHEPOXY RESINS
Possibly the most resistant acrylic enamels are based on
thermosetting acrylic solution polymers that contain acid
functionality and are reacted with an epoxy resin. Typically,
the epoxy resin is a condensation product of Bisphenol A
and epichlorohydrin (see Chapter 10, entitled Epoxy Res-
ins in Coatings).
The acrylic solution polymer is made acid functional
simply by incorporating acrylic or methacrylic acid into the
backbone; when cured under suitable conditions, it reacts
with the epoxide to form ester linkages between the two
polymers:
An alternative reactant to epoxies based on Bisphe-
nol A/epichlorohydrin is another acrylic polymer wherein
epoxide sites have been incorporated by polymerizing gly-
cidyl acrylate, glycidyl methacrylate, or allyl glycidyl ether
into the acrylic backbone. This approach is limited in use,
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54 PAINT AND COATING TESTING MANUAL 15TH EDITION
however, because both economics and performance favor
the Bisphenol A type epoxides. Also, in recent years, epoxy
manufacturers have developed many aliphatic epoxides in
an attempt to mimic the benefits of the workhorse Bisphe-
nol A based products (i.e., resistance properties) without
the accompanying disadvantages (i.e., poor resistance to
UV light).
The carboxyl-functional acrylic resins typically have a
MW in the 10000 to 50000 range and a carboxyl content of
5 % to 20 %. Some higher solids acrylics are lower in molec-
ular weight with higher acid content. The acid content of
the acrylic polymer determines the equivalent weight of
epoxy resin required to react with the acrylic to achieve a
thoroughly cross-linked system.
Styrene or vinyl toluene are often incorporated into the
acrylic polymer as honorary acrylic monomers because
their reaction kinetics with acrylic monomers are fairly good
and because they often improve alkali resistance and are
low in cost. The cross-linking reaction between the carboxyl
group on the acrylic polymer and the epoxy resin is fairly
sluggish and requires a base catalyst such as dodecyl trim-
ethyl ammonium chloride, or tri(dimethylaminomethyl)
phenol. In some instances, melamine-formaldehyde resins
are sufficiently basic to be used as catalyst and have the
additional advantage of entering into the cross-linking
reaction [13]. For improved package stability, however, it is
preferable to add the base catalyst to the other components
just prior to use. Even with catalyst, the baking or stoving
requirements for acid/epoxide systems are fairly high, with
15 to 30 min at 150 to 190C being typical. Of course, the
higher the bake temperature, the shorter the bake time
required for cure. To determine the optimum conditions
for a given system, it is best to cure that system at a vari-
ety of baking conditions and then measure properties to
determine the temperature and time required for maximum
performance.
The primary uses for acid-functional acrylics cross-
linked with epoxy resin are as appliance enamels and coat-
ings for interior metal furniture and equipment. Acrylic/
epoxy enamels fill the needs of the appliance industry pri-
marily because of their excellent alkali/detergent resistance
[see ASTM Practice for Detergent Resistance of Organic
Finishes (D2248-89)], which is critical to the performance
of washing machine coatings. Other properties that are
important to the appliance industry include: hardness,
scratch resistance, grease resistance, stain resistance, as
well as flexibility, impact resistance, and adhesion to metal.
Acrylic/epoxy enamels, on the whole, offer an excellent
balance of these important properties. Typical properties
for an enamel based on an acid-functional acrylic resin
cross-linked with a Bisphenol A based epoxy are shown in
Table 1.
The disadvantages associated with acrylic/epoxy coat-
ings are usually concerns brought about by the aromatic
nature of the Bisphenol A based epoxy cross-linker. Their
most significant limitation is poor resistance to UV light,
which restricts their use to interior applications. If used
outside, thearomatic Bisphenol A portion of the epoxy
would degrade rapidly, and early chalking would occur. In
some of the newer high-solids acrylic/epoxies, the epoxy
content is very high and can therefore cause discoloration
problems even indoors due to UV light. Where this is a
problem, an aliphatic epoxy can be substituted for at least
some of the Bisphenol A based epoxy to reduce sensitivity
to UV radiation (see Chapter 10 entitled Epoxy Resins in
Coatings).
ACRYLIC POLYMERS CROSS-LINKED
WITHAMINORESINS
Acrylic polymers containing acid or hydroxyl functional-
ity can be cross-linked with amino resins such as: urea,
melamine, and benzoguanamine formaldehyde conden-
sates (see Chapter 8 entitled Amino Resins) as follows:
TABLE 1Application properties for a white
enamel based on an acid functional acrylic
resin cross-linked with Bisphenol A based
epoxy (baked 39 minutes at approximately
180C) [14]. Reprinted with permission of
TheDow Chemical Company
Tukon hardness 16.2
Pencil hardness 2H
Solvent resistance, glass
Cellosolve acetate, 15 min 6B
Cellosolve acetate, 60 min 6B
Xylol, 15 min 5B
Stain resistance, cold-rolled steel
Mustard, 30 min no stain
Ink, 30 min trace
Print resistance, cold-rolled steel
82C, 30 min, 2 psi light print
Detergent resistance
a
1 % detergent, 74C, 200 h Few6
Optical properties, CRS (two coats)
Original 60 gloss 95.5
Gloss after 16 h at 178C 95.4
Original color 9.2
Color after 16 hr at 178C 13.0
Microknife adhesion, CRS H Value 22.8
Mandrel flexibility
b
1/2 in., 1/4 in., 1/4 in.
Cold-rolled steel 0-0-0
Bonderite 1000 0-0-0
Reverse impact, inch-lbs (joule)
Cold rolled steel 22 (2.48)
Bonderite 1000 15 (1.70)
Direct impact, inch-lbs (joule)
Cold-rolled steel 35+ (3.96+)
Bonderite 1000 50+ (5.65 +)
a
ASTM blister rating. A rating of 10 means no blistering, a rating of 0
means very large blisters, with intermediate ratings judged by ASTM
photo standards.
b
0=no cracks; 9=delamination.
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CHAPTER 6 ACRYLIC POLYMERS AS COATINGS BINDERS 55
AMINO RESIN NHCH
2
OR + ACRYLIC COOH
AMINO RESIN NHCH
2
OCO ACRYLIC + ROH
AMINO RESIN NHCH
2
OR + ACRYLIC OH
AMINO RESIN NHCH
2
O ACRYLIC + ROH
Reactions with amino resins containing an -NH-
CH
2
OH group are possible because this group differs from
a simple alcohol in that it is far more acidic and reactive.
Likewise, the methylol ether (when capped with alcohol)
is more reactive than a conventional dialkyl ether. The cur-
ing condition required for acid functional acrylics cross-
linked with amino resins is approximately 30 min at 150
C, while for an analogous hydroxyl functional acrylic, the
reaction is more facile, requiring 30 min at 125C with an
acid catalyst [15]. Since the acid-methylol reaction is rela-
tively slow, it allows significant self-condensation of the
amino resin [16]. This detracts from the overall toughness
and resistance properties.
The hydroxyl-functional acrylics are, therefore, favored
over acid-functional polymers and are most often used in
combination with a methylolated or butylated melamine-
formaldehyde or benzoguanamine-formaldehyde conden-
sate. Urea-formaldehyde condensates are less durable and
have been found to have lower gloss and poorer chemical
resistance. Hydroxyl functionality is incorporated into
the acrylic polymer by copolymerizing monomers such as
hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate
(HEMA). This type of combination produces cross-linked
acrylic/amino enamels with outstanding exterior durabil-
ity, good hardness, and mar resistance, as well as excellent
resistance to solvent attack. Acrylic/amino thermosetting
enamels were, therefore, very successful in replacing the
less durable alkyd/melamine systems in automotive top-
coat applications, and general industrial finishing. Over
the years, the automotive industry has relied heavily on
this type of thermosetting acrylic because it offers the
outstanding durability of acrylic lacquers but with better
resistance to solvents and elevated temperatures. It also
offers significantly higher application solids. Also, it does
not require factory buffing to achieve high gloss as do the
acrylic lacquer coatings.
Another reason that acrylic/amino resin technology
became so popular is because of the versatility of the
chemistry, whereby properties can be readily altered by
varying acrylic Tg, acrylic monomers, acrylic function-
ality level, and cross-linker type and level. This is very
important in general industrial finishing, where coatings
often must be custom tailored to the specific end use.
Ref. [17] briefly demonstrates the kinds of variation in
performance that can be obtained by a few manipulations
in composition.
An alternate approach to a thermosetting acrylic
polymer is to prepare an acrylic polymer that contains
functionality analogous to a melamine/formaldehyde con-
densate. Methylol or methylol ether groups can be attached
to an acrylic backbone, and the resulting polymer can self-
condensate, resulting in a cross-linked structure without
the need for an external cross-linking agent. Initially, an
acrylic polymer is made containing acrylamide (AM). The
polymerization is usually a conventional free-radical, solu-
tion polymerization carried out in alcohol or a combination
of alcohol and aromatic solvent. As in most thermosetting
acrylic polymers, mercaptan is usually included to control
molecular weight. After the polymerization is complete, the
polymer is treated with formaldehyde to convert it to the
methylol amide. An acid catalyst will bring about etherifica-
tion with the alcohol present, usually butanol. The conver-
sion proceeds as follows [18]:
POLYMER CO NH
2
+ HCHO
POLYMER CO NH CH
2
OH
POLYMER CO NH CH
2
OH + ROH
POLYMER CO NH CH
2
OR + H
2
O
As an alternative process, the AM monomer can be me-
thylolated before being polymerized. The finalized methy-
lolated amide acrylic polymers condense readily when acid
catalyzed at bake conditions of 30 min at 150C. The con-
densation process is a two-stage reaction [19]:
2 POLYMER CO NH CH
2
OH
POLYMER CO NH CH
2
O CH
2
NH
CO POLYMER + H
2
O
further heat POLYMER CO NH CH
2
NH
CO POLYMER + H
2
O
If the methylolated amide has been etherified by buta-
nol capping, instead of water as a by-product, a mixture of
butanol and dibutyl ether would be obtained. These types
of self-condensing acrylic resins will also react with amino
resins, but usually there is no justification for so doing
(i.e., no improvements in performance). The strength of the
methylol amide acrylics is that they have no glaring weak-
nesses and make very good general-purpose resins.
ISOCYANATE-REACTIVE ACRYLICS
Acrylic solution polymers that are cross-linked with iso-
cyanates (often referred to as acrylic urethanes) are unique
among the various cross-linking systems because they cure
under ambient conditionsthey dont require baking. The
isocyanate group (N=C=O) is extremely reactive and will
cross-link with any type of functionality having a labile
hydrogen atom. This includes amines, alcohols, ureas,
urethanes, carboxylic acids, and amides. Acrylic polymers
designed to be cross-linked with isocyanate resins generally
contain hydroxyl functionality incorporated by polymeriz-
ing hydroxyethyl acrylate (HEA) or hydroxyethyl methacry-
late (HEMA) into the acrylic backbone.
There are six basic types of curing mechanisms for ure-
thane coatings [see ASTM Terminology for Paint, Related
Coatings, Materials and Applications, Varnish, Lacquer,
and Related Products (D16-75)]. The two-package poly-
isocyanate/polyhydroxyl coatings make up Type V. Of this
class, acrylic urethanes based on weather-resistant hydroxyl
functional acrylics predominate. The hydroxyl functional
acrylic reacts with isocyanate resin as follows:
ACRYLIC OH + R N = C = O
R NH COO ACRYLIC
(a urethane)
The preferred isocyanates are usually aliphatic, such as
the adduct of hexamethylene diisocyanate (HMDI), because
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56 PAINT AND COATING TESTING MANUAL 15TH EDITION
of the poorer color and exterior durability associated with
the aromatic types of isocyanates. While the aromatic vari-
eties of isocyanate react faster than the aliphatic types, a
wide range of catalysts are available, which can be used to
speed up the cure of aliphatic isocyanates. A few such cata-
lysts include triethylene diamine, zinc naphthenate, and
dibutyl tin-dilaurate [20].
Acrylic solution polymers cross-linked with aliphatic
isocyanates are ideal for applications where a durable,
high-performance coating is required but where baking is
not feasible because of the size or temperature sensitivity
of the object to be coated. Acrylic urethanes are, therefore,
invaluable in the transportation industry where high-qual-
ity coatings are needed for aircraft, railroad cars, trucks,
buses, etc. Automobile refinishing, heavy equipment coat-
ings, and high-performance maintenance coatings are also
areas where acrylic urethanes are appropriate. The acrylic
urethanes combine the inherent UV resistance and exterior
durability of acrylics with the ambient cross-linking ability
of aliphatic isocyanates to produce hard, tough, chemical-
resistant, high-performance coatings. The major drawback
of acrylic urethanes is that they are a two-package system
and cannot be mixed until ready for application because
they are so reactive and have a short pot life.
Over the years, the hydroxyl-functional acrylics have
been improving in performance, and now the emphasis
is on higher solids content for lower VOCs. To meet more
stringent VOC regulations, lower-molecular-weight, higher-
solids hydroxyl functional acrylics have been developed.
Increasing the solids of the acrylic reduces solvent levels in
theformulated coating. To compensate for lower molecular
weight, one way to improve performance is to increase
hydroxyl content, which in turn requires higher levels of
isocyanate.
An alternative approach to reduced solvent or higher
solids is to modify the acrylic urethane with a reactive dilu-
ent which is fluid and acts like a solvent but then reacts
to form part of the cross-linked network [21]. One such
diluent is a low-molecular-weight, difunctional oxazolidine
which is nonreactive with isocyanates until ambient mois-
ture opens the ring, releasing both hydroxyl and amine
functionality [22].
This type of functionality has the advantage that it is
one package stable with isocyanates as long as moisture is
excluded from the paint. Because it has four reactive sites
per molecule, it increases cross-link density for maximum
performance, while it decreases solvent emissions.
ACRYLIC EMULSION POLYMERS
An acrylic emulsion is a two-phase system in which acrylic
polymer droplets are dispersed in an external water phase,
usually with the aid of an emulsifier (i.e., surfactant). Unlike
some polymer emulsions, such as alkyds or epoxides, which
are emulsified as preexisting resins, acrylic emulsions are
made by an emulsion polymerization process wherein the
monomer droplets are emulsified in water and then polym-
erized. A typical acrylic emulsion polymerization recipe is
given in Table 2 [23].
The physical chemistry of acrylic emulsion polymers is
much the same as for their solution polymer analogs, and
the film properties of the emulsions can be controlled by
manipulating polymer composition and MW just as with
acrylic solution polymers. However, the viscosity of an
emulsion is unaffected by polymer MW since solution prin-
ciples do not pertain to emulsions (the polymer is insoluble
in the continuous water phase). Therefore, for the best
possible physical properties, the MW of acrylic emulsions
is generally higher than that of acrylic solution polymers:
100 000 to 1 000 000 for an emulsion versus 75 000 to
100000 for a solution polymer.
The particle size of an emulsion is also very important
in determining performance and must be carefully con-
trolled. For example, the film-forming ability of an emul-
sion, as well as its pigment binding capability, is dependent
on particle size, with smaller particle size being better than
large particle size. Particle size does affect emulsion viscos-
ity, with large particle size generally being associated with
low viscosity.
Acrylic emulsion polymers (also known as acrylic
latexes) have long been a mainstay of the architectural
coatings market, particularly in exterior paints where their
outstanding durability is so important. However, in recent
years, clean air regulations have further strengthened the
position of acrylic emulsions, usually at the expense of
solvent alkyds. The use of acrylic emulsions in industrial
coatings applications has also grown as a result of solvent
emission restrictions. At the same time, the properties of
acrylic emulsion polymers in the industrial coatings market
has improved so that they now offer performance similar to
their solvent-borne counterparts.
Acrylic Emulsions for Architectural Coatings
Architectural coatings are generally considered to be coat-
ings intended for on-site application to residential, com-
mercial, or institutional buildings; they are also known as
trade sales coatings. Over the last 50 years, this market has
evolved from an entirely oil-based market to one dominated
by emulsions. There are three underlying reasons for the
takeover of the architectural coatings market by emulsion
polymers. The health, safety, air quality, and odor concerns
associated with the solvents in oil-based paints have moved
people toward water-based latex paints whenever there is
not a large penalty in performance. Also, latex paints are
more tolerant of a wide variety of application conditions
and can even be applied over damp substrates. Thirdly,
emulsion polymers, particularly quality acrylic emulsions,
have surpassed oil-based paints for long-term performance
and protection in most applications.
Although acrylic emulsions generally provide a supe-
rior level of performance, their cost is somewhat higher
than lower-performance emulsions such as vinyl acetates.
Therefore, in segments of the architectural coatings market
where performance is not critical, such as for interior flat
paints, acrylic emulsions are not a dominant binder. How-
ever, in segments where performance and durability are
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CHAPTER 6 ACRYLIC POLYMERS AS COATINGS BINDERS 57
essential, such as for exterior flat and gloss paints, acrylic
emulsions control a very large portion of the market both in
the United States and abroad.
INTERIOR COATINGS APPLICATIONS
The high-volume, interior-flat market is dominated by
vinyl acetate copolymers plasticized with a soft acrylate
monomer, usually butyl acrylate at about the 15 % weight
level. Interior flat paints are aimed primarily at broad wall
applications. Performance requirements for this market are
fairly modest, with decorative features such as color, sheen
level, and hiding being the more influential factors deter-
mining consumer preference. The one resistance property
demanded in this market is scrub resistance; in this regard,
vinyl/acrylics perform satisfactorily.
There is a premium segment of the interior flat market
occupied by all acrylic latexes, and one of the key features
which they offer is improved rheology and application char-
acteristics resulting from the better interaction of acrylic
latex particles with the new associative thickeners. Associa-
tive thickeners (also referred to as rheology modifiers) dra-
matically enhance flow, brushability, film build, and spatter
resistance compared to conventional hydroxyethyl cellulose
(HEC) thickeners.
Since interior flat paints contain a high pigment load-
ing to increase hiding and reduce cost, the acrylic polymers
used in this market tend to be fairly soft with good binding
capacity. Typically, they are copolymers of a hard methac-
rylate monomer such as MMA with a soft, commercially
available acrylate monomer such as EA, BA, or EHA. The
Tg is generally around 10C.
Interior gloss and semigloss paints have much more
demanding requirements than flat paints since they are
used for more diverse and challenging substrates such as
windows, cabinets, and doors. Acrylic emulsions play a
major role in this market, especially at the high-perfor-
mance end. They are tailored to the specific needs of this
market by optimizing the important variables contributing
to performance: composition, hardness, MW, and particle
size.
TABLE 2Copolymerization of ethyl acrylate, methyl methacrylate, and methacrylic acid [23].
Reprinted with permission of The Dow Chemical Company
Materials:
375.0 g Deionized water
5.1 g Surfactant
100.0 g Ethyl acrylate (15 ppm MEHQ)
100.0 g Methyl methacrylate (25 ppm MEHQ)
4.0 g Glacial methacrylic acid (100 ppm MEHQ)
4.0 mL Ferrous sulfate solution (0.15 %)
1.0g Ammonium persulfate in 5 mL of water
0.7 g Sodium formaldehyde sulfoxylate in 5 mL of water
5 drops t-butyl hydroperoxide (70 %)
Procedure:
In a beaker. stir the surfactant with the water until disolved and adjust the pH to 9.0 by adding 50 % sodium hydroxide solution.
Transfer this solution into the reaction flask, rinse the beaker with a small amount of deionized water, and the monomers and ferrous
sulfate, and stir 15 min with flow of nitrogen before adding the initiators. The maximum temperature of 77C is attained in 12 to 15
min after adding the initiators, then cool to room temperature, adjust to pH 9.5 with 28 % aqueous ammonia, and filter: the gums
amounted to 0.17 %.
The free acid (unneutralized) surfactant can also be used as an emulsifier for the above copolymerization. In this case, the period of
purging with nitrogen after charging the monomers should not exceed 15 min before the addition of initiators to avoid the formation
of polymer emulsion product with excessive viscosity. Filtration of the finished emulsion gave only 0.05 % gums. The properties of
these emulsions were:
Surface Form Sodium Salt Free Acid
Solids content, %Calculated 35.0 36.0
Found 34.3 35.6
pH at25C 5.6 1.8
Viscosity (Brookfield), cP 7.9
a
10.5
a
Partial size (light scattering), % 22.8
b
12.3
c
Minimum film-forming temperature, C 22
a
30
a
a
Emulsion adjusted to pH 9.5 before measurement.
b
Measurement at 2 % solids.
c
Measurement at 0.4 % solids.
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58 PAINT AND COATING TESTING MANUAL 15TH EDITION
Acrylic emulsions used in gloss and semigloss paints
are copolymers of acrylate and methacrylate monomers
and are usually harder than emulsions used in flat paints.
They generally have a Tg in the range of 20 to 50C. The
harder polymers are necessary to build in block and print
resistance, which are needed to keep doors and windows
from sticking and to prevent marring and film damage
associated with softer polymers. Since gloss and semigloss
paints are formulated at low pigment volume concentra-
tion (PVC) to obtain gloss, the pigment does not contribute
significantly to film hardness; it must all come from the
polymer.
Since these gloss and semigloss latexes are often used
over old oil-based enamels, adhesion to aged oil-based
paints is required. This may be accomplished by copoly-
merizing adhesion promoting functional monomers into
the acrylic polymer backbone. A major breakthrough in
latex adhesion technology came about with the develop-
ment of ureide functional acrylic monomers [24]. The adhe-
sion promoter particularly is needed to improve adhesion
and blister resistance when the paint film becomes wet,
as it might in a bathroom. Since the gloss paints are often
used in wet areas such as a bathroom, the water resistance
of the dry film is also an important property. To ensure
good water resistance, acrylic emulsions used in this mar-
ket often contain hydrophobic monomers such as styrene.
Since interior trim paints are so highly visible, overall
appearance properties are critical to the success of the paint
job, and features such as flow and leveling, gloss, and film
build are expected to be similar to oil-based enamels. This
level of outstanding appearance has been possible in recent
years with the introduction of associative thickeners. The
traditional thickener for latex paints has been HEC, which
thickens by a flocculation mechanism and usually produces
poor flow and gloss. Associative thickeners loosely bind to
the surface of the latex particles through hydrophobic inter-
actions, forming a network structure which accounts for
their thickening action. The degree of interaction between
the thickener and the latex particle is largely a result of the
surface chemistry of the emulsion particles. Smaller parti-
cle-size emulsions have greater surface area and therefore
have more interaction with associative thickeners. More
hydrophobic latexes have stronger association with the new
thickeners. Consequently, small-particle-size, hydrophobic
acrylic emulsions have been designed specifically for use
with associative thickeners. These newer acrylic emulsions
optimize thickener interaction and produce exceptional
flow and gloss. In fact, before these new emulsion/thick-
ener systems, truly high-gloss latex paints were out of the
question. They also improve brushability and film build,
while eliminating the problem of roller spatter. Overall,
the appearance properties of the newer small-particles-size
hydrophobic acrylics, when used in combination with asso-
ciative thickeners, rivals that of oil-based enamels.
EXTERIOR COATINGS APPLICATIONS
By far the most challenging application for any coating
is as an exterior paint required to protect a multitude of
substrates in diverse and extreme weather conditions. It
is in this demanding role that acrylic emulsions have met
virtually all requirements and impressed the industry by
their outstanding durability. One primary reason for their
success, as mentioned earlier for solution acrylics, is their
lack of absorption of ultraviolet light coupled with their
inherent hydrolysis resistance. Over the years, acrylic
emulsions have evolved from simple polymers troubled by
shortcomings, such as poor adhesion or low film build, to
sophisticated systems incorporating elements designed to
address essentially every major challenge experienced by
an exterior paint.
One of the toughest demands facing exterior flat house
paints is the need to withstand the freeze-thaw type of
expansion and contraction of dimensionally unstable sub-
strates such as pine or other soft woods. To avoid the grain
cracking that often occurs over this type of substrate, acrylic
emulsions designed for flat house paints are fairly soft,
with a Tg in the range of 10 to 15C. A coalescing solvent
is usually used in the formulation to assist film formation,
particularly at lower temperatures. When the coalescent
leaves, the acrylic paint film remains pliable and able to
withstand substrate swelling and freezing, unlike oil-based
house paints, which become harder and embrittle on expo-
sure as they continue to cross-link. The primary concern
with making the acrylic polymer too soft is that dirt pickup
would worsen. Since flat house paints contain a fairly high
pigment content (i.e., PVC = 40 to 60 %), dirt resistance is
enhanced by the pigment loading. Experience over many
years indicates that a Tg of 10 to 15C is the optimum range
to balance grain-crack resistance with dirt resistance.
For exterior flat house paints, the inclusion of an
effective adhesion promoter in the acrylic backbone is
crucial for good adhesion. The adhesion promoter greatly
improves blister resistance. Furthermore, the improved
adhesion enhances crack resistance over dimensionally
unstable wood substrates. Painting over a degraded chalky
surface is a common practice that can be a potential disas-
ter if sufficient adhesion is not obtained. The chalk acts
like a powdery barrier, preventing the emulsion binder
from penetrating to the real substrate and establishing an
adhesive bond. Studies have shown that smaller particle-
size acrylic emulsions are much more effective than larger
particle-size emulsions for filtering down through the chalk
and obtaining adequate adhesion. For this reason, many
exterior grade acrylic emulsions have been designed at a
fairly small particle size of about 100 nm [25].
Small-particle-size, large-surface-area emulsions, when
thickened with HEC, have poorer flow and film build than
larger-particle-size emulsions, which are less aggregated
by the flocculating mechanism of HEC. Therefore, 100-
nm emulsions that were designed to have improved chalk
adhesion sacrificed some of the flow and film build of large
particle-size (500 nm) emulsions. In an attempt to combine
these seemingly mutually exclusive properties, particle-size
distributions have been carefully controlled to ensure a
tailored mixture of small particles that give good adhesion
to chalky surfaces and large particles that help to improve
flow in formulations thickened with HEC. In the emulsion
form, the key benefit of these bimodal polymers is their
ability to be made at higher solids than unimodal latexes.
Because of efficient packing of small with large particle,
low emulsion viscosity can be obtained at higher emulsion
solids. This packing efficiency leads to improved film prop-
erties over unimodal latexes. At the optimized particle sizes
of large and small particles and optimized weight ratios,
efficient packing of bimodal particles allow for longer dry-
ing times, because of less voids in the system which reduce
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CHAPTER 6 ACRYLIC POLYMERS AS COATINGS BINDERS 59
the surface area from which water can evaporate. Addition-
ally, minimum film forming temperature (MFT) and water
adsorption can be reduced with an optimized bimodal
emulsion [26]. Compared to large-particle-size unimodal
emulsions, bimodal emulsions improved adhesion proper-
ties of latex paints.
Wide particle-size distribution acrylic emulsions do
not significantly address the low film build associated with
smaller-particle-size emulsions when thickened with HEC.
Film build is particularly important to an exterior paint
because the durability of the film is usually proportional
to the film thickness, i.e., how much paint is applied to
the substrate. This was addressed in 1980s by the Rohm
and Haas Co. with the introduction of a Multilobe acrylic
emulsion, shown in Fig. 2 [27]. This type of polymer has a
lobed morphology that is grown out during the polymeriza-
tion process; it does not result from particle aggregation.
The lobes of this polymer are about 350 nm, but it has
an effective hydrodynamic volume of about 1000 nm and
is, therefore, very effective at imparting high film build
in paints thickened with HEC. It also reduces the level of
thickener needed to achieve a given viscosity. Since in its
commercial form this technology also contains small par-
ticles, good adhesion characteristics are retained while film
build is optimized.
Other important aspects of weatherability are color
retention and resistance to chalking. These properties are
made worse by the catalytic degradation effects of TiO
2
on
the binder, so that high PVC flat paints are generally poorer
than low PVC gloss paints. However, the inherent durabil-
ity of the binder is still a controlling factor, and acrylic
polymers have excellent resistance to sunlight and erosion,
which contribute to their very good chalk resistance and
color retention. Among the common acrylic copolymer
compositions in use commercially, MMA/BA polymers are
better than MMA/EA polymers, and higher methacrylate
containing binders are better than acrylics containing
higher levels of acrylate monomers. Of course, the meth-
acrylate/acrylate levels are generally determined by the Tg
required to achieve the desired balance of crack resistance
and dirt pickup.
Exterior gloss and semigloss paints are required to
withstand similar tortures as their flat paint counterparts
and, in addition, must provide equally good dirt resistance
at much lower pigment loadings. Acrylic emulsions have
been designed that meet all of these challenges and perform
very well in environments as diverse as the tropical regions
of Asia and the Philippines to the Scandinavian regions of
Europe. Since the acrylic emulsion engineered for interior
gloss/semigloss paints are intended to be high-performance
systems capable of good adhesion even in wet areas, they
are often able to be used outside as well. Since exterior
gloss paints must have good dirt resistance at low PVC,
the acrylic emulsions used in these paints are harder than
those used in flat paints and generally have a Tg in the area
of 20 to 35C (Fig. 3). This Tg range can provide acceptable
dirt resistance while still having good grain-crack resis-
tance. The very hardest acrylic emulsions used for interior
gloss paints (i.e., above Tg 35C) would not be appropriate
outside, at least in areas subject to freezing, because they
would be more prone to grain crack.
Since brush marks are much more obvious in a
gloss paint than in a flat paint, good flow and leveling is
much more critical for a gloss paint than for a flat paint.
Consequently, older acrylic emulsions intended for semi-
gloss paints (there were no high-gloss latex paints until
about 1980) are of large particle size to have the best
Fig. 2Scanning Electron Micrograph of RHOPLEX
MULTILOBE Acrylic Emulsion Polymer. (Reprinted with
permission of The Dow Chemical Company [27].)
Fig. 3Atomic force microscope (AFM) images of a bimodal blend two emulsion polymers with different Tgs and particle size.
The images on the left and right are the same images. The image on the left is a topographic image and the image on the right
is a phase modulated image (allowing differentiation between soft and hard materials). Using the image on the right: The dark
particles represent polymers with a particle size of 128 nm and Tg of 37C. The light particles represent polymers with a particle
size of 217 nm and Tg of 11C. (Reprinted with permission of The Dow Chemical Company.)
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60 PAINT AND COATING TESTING MANUAL 15TH EDITION
possible flow with the prevailing thickener of the day, HEC.
The flow of these systems could best be described as fair,
but overall they have demonstrated an admirable balance
of properties and are still popular today. However, newer
acrylic emulsions intended for exterior gloss paint appli-
cations, particularly those generally referred to as acrylic
enamel vehicles, are small in particle size (i.e., 100 nm) to
take advantage of the excellent flow, gloss, and rheology
available by using associative thickeners.
Over the past 20 years, the decorative as well as pro-
tective capabilities of exterior gloss paints have improved
significantly to the point where acrylic emulsions are rap-
idly replacing alkyd enamels as the preferred coating for
exterior trim.
Use of Acrylic Polymers as Property Modifier for
Poly(Vinyl Acetate) Architectural Coatings
In some instances to achieve an acceptable balance between
cost and film properties, blending of a low level of acrylic
emulsion in a predominately poly(vinyl acetate) (PVA)
paint is required. Generally, 100 % PVA binders have poor
exterior paint performance properties including: adhesion,
water resistance, dirt pickup resistance, efflorescence and
alkali resistance. Blending of a small amount of acrylic
binder will upgrade the performance of PVA paint in these
properties. Also, block resistance is improved by modify-
ing the PVA binder with a small amount of acrylic binder.
Conversely, some properties such as scrub resistance may
be degraded in the blended paints.
Acrylic Emulsion Maintenance Coatings
Maintenance coatings differ substantially from decorative
coatings since they are used primarily for their protective
features, which prevent substrate deterioration by cor-
rosive elements. Maintenance coatings are generally used
to protect metal surfaces such as bridges, storage tanks,
and other industrial facilities, often in harsh chemical and
corrosive environments. The first acrylic latex binders for
corrosion-resistant maintenance coatings were introduced
commercially in 1964. They are similar in hardness and
composition to exterior flat house paint binders with the
exception that they are formulated with reactive pigments
and additives, which help prevent rusting. The surfactants
and other salt and pepper ingredients used in the polym-
erization of maintenance acrylic emulsions are carefully
selected so as to not aggravate corrosion.
These acrylic latex maintenance coatings had the usual
advantages in application of water-based paints over sol-
vent alkyd paints along with expected advantages in chalk
resistance, color retention, and other decorative qualities.
However, to the surprise of some segments of the main-
tenance industry, acrylic maintenance emulsions often
outperformed solvent alkyds for corrosion resistance and
overall metal protection. This is partly because the alkyds
continue to harden and eventually crack, leaving the sub-
strate exposed and subject to the elements. Acrylic emul-
sions do not continue to harden once the paint film is dry,
and they remain sufficiently pliable to expand and contract
with the substrate.
The one weakness of the acrylic latexes in the area of
maintenance coatings was their low Tg, which reflected a
lower hardness than the alkyd paints. This limitation was
removed by the development of aqueous gloss enamel bind-
ers. These hard latex binders used in interior and exterior
gloss paints were fine tuned to maximize corrosion resis-
tance and overall protection. Commercialized in the mid-
1980s, this new generation of maintenance vehicles has
proved very successful in extensive field tests, particularly
on bridges in the southeastern United States. The small
particle size of these binders fits perfectly with associative
thickener technology to give tight water-resistant films,
which are an improvement over HEC-thickened paints that
can have microscopic defects as a result of the flocculating
mechanism of HEC [28]. In addition to use in thermoplas-
tic maintenance coatings, acrylic latices have been devel-
oped to react with epoxy resins and iso-cyanates to allow
for thermo set two component coatings with increased
levels of toughness and chemical resistance.
Acrylic Emulsions for Traffic Coatings
The success or failure of a roadmarking paint will depend
on its ability to: (1) dry quickly enough to prevent dam-
age by traffic following the striping truck, (2) adhere to
the road surface (concrete or asphalt) during the expected
lifetime of the marking, and (3) retain a large percentage
of the glass beads applied to the surface of the marking for
driver visibility at night. Solvent paints based on short and
medium oil alkyds with and without modification with
chlorinated rubber resins have been used to meet these
performance needs, but these paints do not retain glass
beads for very long because the alkyd resins embrittle
upon exposure to the elements. Roadmarking paints based
on acrylic emulsions retain glass beads longer because
they remain pliable upon exterior exposure. Before the
1990s, however, waterborne roadmarking paints based
on acrylic emulsions did not dry fast enough, particularly
when water evaporation is retarded by high humidity and
low air flow, to viable low VOC replacement for solvent
alkyd paints.
Waterborne paints based on acrylic emulsions quickly
replaced solvent alkyd paints in the United States in the
1990s after the development of quick-setting acrylic emul-
sions. Quick-setting latex binders are stable as they are
supplied and formulated at high pH (around 10). When
paint films are applied, the pH drops rapidly from the
evaporation of ammonia and causes the film to set. This
quick-setting mechanism allows films that still retain sig-
nificant water contents to resist being picked up by tires
and smeared on road surfaces and being redispersed and
washed away by rain. This allows waterborne paints to
have sufficient dry speeds over a wide range of humidities,
temperatures, and wind speeds.
Formulations for waterborne roadmarking paint differ
substantially from those of typical exterior architectural
paints. In order to speed the drying process, the volume
solids of a waterborne traffic paint is ca. 60 %, thereby min-
imizing the amount of water. By way of contrast, an archi-
tectural paint would have a volume solids in the range of 35
to 40 %. Similarly, traffic paint PVCs are ca. 60 %, which
is higher than their exterior architectural analogs, which
have PVCs on the order of from 40 to 50 %. The acrylic
emulsions used to formulate traffic paints must have good
shear stability because the need for high solids necessitates
dispersing the pigments in the emulsion. This allows for
ca. 60 % PVC and 60 % volume solids paints with 50 %
weight solids emulsions with particles sizes ca. 200 nm.
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CHAPTER 6 ACRYLIC POLYMERS AS COATINGS BINDERS 61
Paints based on emulsions with significantly lower particle
sizes are too viscous and those with higher particle sizes
tend to cause hard sediment to form on storage.
White roadmarkings need to have some degree of dirt
pickup and black tire marking resistance to maintain a vis-
ible contrast with lighter road surfaces, like concrete and
some asphaltic roads. The high pigment content enhances
the hardness and whiteness retention of traffic paints, but
the polymer emulsions used in traffic paints are also fairly
hard (Tg range from 20 to 45C). Incorporation of styrene
as the hard monomer to replace MMA in a copolymer
with BA makes the composition more hydrophobic, which
enhances wet adhesion to road surfaces. However, it is gen-
erally more difficult to achieve viscosity stability with styre-
nated compositions. Additionally, the long term retention of
glass beads (in the dried coating) can be adversely affected
due to the poorer UV resistance of styrene.
Acrylic Emulsions for Industrial Coatings
NONREACTIVE EMULSIONS
Industrial coatings users, who have traditionally applied
solvent-based polymers, have recently been under pres-
sure to reduce volatile organic emissions. This is par-
ticularly true in California, which has historically been at
the forefront of clean air legislation. In many instances,
these coatings users have complied with the stricter envi-
ronmental legislation by switching over to water-based
systems. Acrylic producers have responded to the needs
of these coatings users by developing more sophisticated
emulsions capable of meeting the demanding performance
requirements of many different end users. Early emulsions
aimed at industrial coatings applications were offshoots
of architectural coatings technology and were often too
soft for industrial coatings uses. Also, high gloss was not
possible with these older emulsions. Like the newer gloss
enamel emulsions for trade sales use, however, latexes
aimed at industrial coatings applications have evolved
into hard, resistant binders that match the performance
of their solvent-based counterparts. Without this evolution
in performance, it is unlikely that industrial coatings users
would switch to latex coatings even with the more severe
emissions regulations.
Thermoplastic acrylic emulsions designed for indus-
trial coatings applications generally have to be harder and
faster drying than architectural emulsions and have better
corrosion and chemical resistance. The typical Tg range
for such acrylics is about 30 to 70
(1)
where
P
1
and P
2
= vapor pressure, g cm
2
s
2
,
T
1
and T
2
= respective temperatures, K,
H = molar heat of vaporization, calg
1
, and
R = gas constant, 1.99 calC
1
mol.
Vapor pressure values are useful to estimate normal
boiling points at 760 mm mercury and solubility para-
meters [1]. Sears and Darby have reported that the vapor
pressure of binary plasticizer blends may be expected to fall
between the values of the neat plasticizers, but cannot be
predicted from knowledge of the blend ratio and the neat
vapor pressures.
Ester Value
Esters are the largest group of materials that are commer-
cially useful as plasticizers. This is a result of reasonable
costs and broad utility in a wide range of polymers hav-
ing moderate to high polarity characteristics. Ester value
can be used to estimate the purity or ester content of the
plasticizer. ASTM D1617, Test Method for Ester Value of
Solvents and Thinners, or ASTM D1045, Test Methods for
Sampling and Testing Plasticizers Used in Plastics, may be
used for this determination. The methods involve saponifi-
cation of the ester in a known excess amount of KOH. The
excess amount of KOH is then determined by titration with
standard sulfuric acid. The amount of KOH consumed in
the saponification process is a measure of the ester content
of the plasticizer.
A gas chromatography method, ASTM D3465, Stan-
dard Test Method for Purity of Monomeric Plasticizers by
Gas Chromatography, may also be used to determine the
purity of monomeric plasticizers. The GC method does not
provide ester values. It is useful to characterize major
isomers present versus known standards and to ascertain
trace quantities of nonparent organic compounds. GC
instrumentation is costly and requires comparison of out-
put traces against a library of known materials that have
been characterized under a specific set of conditions using
specific GC instruments and columns.
Flash Point
Most plasticizers are high flash materials. Either ASTM
D92, Test Method for Flash and Fire Points by Cleveland
Open Cup Tester, or ASTM D93, Test Methods for Flash
Point by Pensky-Martens Closed Cup Tester, may be used.
Preference should be for the closed cup method; this
yields a more conservative number and is consistent with
Department of Transportation (DOT) regulations in the
United States. DOT has revised the definitions and clas-
sifications of hazardous materials, effective 1 Oct. 1993,
as follows:
Flash Point
Not Regulated 93C (200F)
Combustible 6192.5C (142199F)
Flammable 60.5C (141F)
The flash point is defined as the minimum tempera-
ture at which a liquid gives off vapor within a test vessel in
sufficient concentration to form an ignitable mixture with
air near the surface of the liquid as determined by ASTM
D56, Test Method for Flash Point by Tag Closed Cup Tester,
or ASTM D3278, Test Methods for Flash Point of Liquids
by Small Scale Closed-Cup Apparatus. In industry, all four
methods are used for flash point determination.
Flash point values are reported for commercially signif-
icant monomeric plasticizers in E. J. Wicksons Handbook
on PVC Formulating [7]. While not a very good analytical
tool, flash points will reflect presence of nonparent, low-
flashpoint contaminants.
Pour Point
Due to the high molecular weight and isomeric mixtures
of plasticizers, few have distinct freezing points. The
pour point can be useful information for handling plas-
ticizers during cold seasons. Method of measurement is
described in ASTM D97, Test Method for Pour Point of
Petroleum Products, and ASTM D5950, Standard Test
Method for Pour Point of Petroleum Products (Automatic
Tilt Method). Plasticizer pour point temperatures may
also be estimated from viscosity/temperature plots as the
temperature at which kinematic viscosity is 50,000 cSt.
Most plasticizers have pour points of less than 30C [7];
no known relationship exists between pour point and
plasticizer performance properties in polymers under low-
temperature conditions [9].
Refractive Index
The refractive index of a plasticizer is measured using
ASTM D1218, Test Method for Refractive Index and Refrac-
tive Dispersion of Hydrocarbon Liquids. Refractive index is
often thought of as a means of identifying the plasticizer.
This is an erroneous assumption. It may be used, how-
ever, to differentiate between classes of plasticizers, as, for
example, between phthalates and adipates [10]. When used
with other physical measurements, refractive index may be
used as a supplemental test. Refractive index can also be
used to check for product contamination, but it is only use-
ful to distinguish commercial materials having very widely
different refractive indices.
Residual Odor
Residual odor may be contributed by reaction by-products
from manufacturing or by residual raw ingredients, which
are often more volatile and odorous than the plasticizer.
When ASTM D1296, Test Method for Odor of Volatile Sol-
vents and Diluents, is used, tests at elevated temperatures
(about 150C) can be considered to improve detection. Since
odor is a subjective characteristic, generalizations for plasti-
cizers are limited to terms such as mild and characteristic.
ASTM D6165, Guide for Comparison, Detection, and Iden-
tification of Odors of Paints, Inks, and Related Materials, is
also useful for ascertaining and differentiating odors.
Sampling
To obtain representative samples of plasticizers for evalu-
ation, ASTM D1045, Methods for Sampling and Testing
Plasticizers Used in Plastics, may be followed. ASTM E300,
Standard Practice for Sampling of Industrial Chemicals,
can also be used.
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142 PAINT AND COATING TESTING MANUAL 15TH EDITION
Density and Specific Gravity
Density is an important characteristic for design engineer-
ing of plasticizer storage and building facilities. Specific
gravity is the density of the given reagent relative to that of
water at the specified temperature; it is generally used in the
characterization of plasticizers or as a means to detect gross
contamination. Specific gravity at 20/20C is measured with
ASTM D891, Test Methods for Specific Gravity, Apparent,
of Liquid Industrial Chemicals, and is commonly employed
in industry. Commercial plasticizers typically fall within
the range of 0.921.50 sp gr at 20/20C. ASTM D4052, Test
Method for Density and Relative Density of Liquids by Digi-
tal Density Meter, is the recommended procedure to measure
specific gravity of fluids that lie between 0.68 and 0.97; this
method is applicable to hydrocarbons that are commonly
used as plasticizer extenders. Another standard method used
in the paint and coatings industry is ASTM D1475, Density
of Liquid Coatings, Inks, and Related Products.
Viscosity
Viscosity measures the fluids resistance to flow; the thicker
the fluid, the higher its viscosity and the greater its resis-
tance to flow under gravity. In ASTM D445, Test Method
for Kinematic Viscosity of Transparent and Opaque Liquids
(and Calculation of Dynamic Viscosity), time is measured in
seconds for a fixed volume of the fluid to flow under gravity
through the capillary of a calibrated viscometer at constant
temperature. The kinematic viscosity of a plasticizer varies
as a log log function versus the log of absolute temperature
according to the following equation
loglog log A B T
(2)
where
= kinematic viscosity, centistokes,
T = temperature, degrees Kelvin, and
A and B = constants.
This reflects the tremendous influence of temperature
on viscosity and allows one to interpolate viscosity values
at specified temperatures. The kinematic viscosity (centi-
stokes) can be converted to its dynamic viscosity (centi-
poise) by multiplying by the true density of the fluid at the
specified temperature: dynamic viscosity, cP = kinematic
viscosity, cSt, times density.
Water
Residual water from manufacturing processes and mois-
ture absorbed from the atmosphere can affect the quality
and clarity of coatings. Water content can be measured
using ASTM D1364, Test Method for Water in Volatile Sol-
vents (Karl Fischer Reagent Titration Method). Plasticizers
are hydrophobic liquids and typically have a limited capac-
ity to take up water and/or be dissolved into water. Higher-
molecular-weight phthalates are practically insoluble in
water with solubilities in the 0.1 to 1.2 mg/L (ppm) range
with even less solubility in salt water [6].
Typical Properties
As shown in Table 1, commercial plasticizers fall into about
seven chemical family groups (eight if we were to add a mis-
cellaneous grouping). The major plasticizer types in use are
phthalates, trimellitates, and aliphatic dibasic esters such as
adipates. The families of esters are formed by reacting the
parent acid with monomeric alcohols ranging from C4H9OH
(butanol) to C
13
H
27
OH (tridecanol); the alcohol may also vary
in isomeric structure ranging from normal (un-branched)
to very specific and/or randomly branched structures. Two
alcohols have found wide usage in synthesis of commercial
plasticizers2-ethylhexanol and isononanola mixture of
randomly branched (primarily methyl branched) nonyl iso-
mers. Table 2 is a summary of typical properties of plasticiz-
ers derived from these two alcohols with the major parent
acidsphthalic, trimellitic, and adipic [11].
METHODS OF IDENTIFICATION
A plasticizer may initially be characterized by its functional
groups. While absolute identification is complicated with-
out sophisticated chemical or instrumental methods, it is
possible to identify the type of plasticizer by functional
groups or presence of elements associated only with the
plasticizer by the use of infrared analyses or wet chemistry.
Most plasticizers are a member of one of the following
families:
Plasticizer Type/Functional Group
Adipates
Chlorinated compounds
Epoxides (oxirane)
Phosphates
Phthalates
Polyesters
Trimellitates
Isolation of Plasticizers
Plasticizers may be separated from a lacquer or dried film
by solvent extraction if it is to be analyzed. The lacquer is
first dried to remove all solvents present. The dried solid
is then solvent extracted (in an appropriate apparatus)
with hot ethyl ether or another appropriate solvent that
will extract the plasticizers while leaving most of the res-
ins behind. The extractant is concentrated, and a small
amount of methyl or ethyl alcohol is added. This will cause
some of the dissolved resin to precipitate out. Next, filter
and concentrate the extractant. ASTM D494, Test Method
for Acetone Extraction of Phenolic Molded or Laminated
Products, may be applied.
Instrumental Methods
Modern instrumental analytical methods are able to
separate, identify, and quantify components in compos-
ite mixtures. Rapidly falling costs of such instruments
have enabled instrumental methods to be more widely
available. These include gas chromatography (GC), high-
performance liquid chromatography, infrared spectros-
copy (FTIR), and other emerging analytical instruments
such as supercritical fluid chromatography, GC/FTIR, and
GC/mass spectrometry.
Infrared Spectrophotometry
An infrared scan of the isolated plasticizer is by far the
best way to identify the functional groups in the molecule.
Mixtures of plasticizers can present problems due to mask-
ing effects. If one or more of the component plasticizers is
known and its IR scan available, subtracting it from the IR
scan of the mixture may aid in identification of the other
component. Other chromatographic techniques could be
used to separate the components before scanning.
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CHAPTER 17 PLASTICIZERS 143
Liquid Chromatography
Column chromatography involves distribution of sub-
stances between liquid (mobile phase) and substrate (solid
phase). Column and thin layer chromatography can be
used. Instrumental methods using high-performance liquid
chromatography with ultraviolet detection can be used for
separation, identification, and quantification of plasticizers
that possess a suitable chromophore.
Gas Chromatography
By comparing relative retention times and peak shapes with
known samples, a plasticizer or mixture can often be identi-
fied and quantified. When coupled with IR (i.e., GC/FTIR),
the IR spectrum of each chromatographic peak can assist in
the identification of functional groups and hence plasticizer
identity, ASTM D3465, Standard Test Method for Purity of
Monomeric Plasticizers by Gas Chromatography.
Qualitative Methods
For the detection of nitrogen, chlorine, sulphur, or phospho-
rus, the sample needs to be fused with metallic sodium. This
preparation should be carried out in a fume hood and caution
observed when handling metallic sodium. A small amount
(about 3 mm
3
) of metallic sodium is placed in a dry 6 in.
(15.24 cm) test tube. The test tube should be held vertically by
clamping it at the open end. The test tube is then heated until
a cloud of sodium vapor begins to form. Remove the flame
immediately. Add two to three drops of the plasticizer sample
directly to the sodium vapor. When the test tube is cold, care-
fully break off the end containing the sodium in a mortar.
Add several milliliters of alcohol to destroy unreacted sodium.
Add about 20 mL of distilled or de-ionized water, grind up the
sample, transfer to a beaker, bring to boil, and filter. The fil-
trate is then used for the chemical detection of the elements.
Sulfur
Add two to three drops of 10 % solution of lead acetate
to 2 mL of a 10 % solution of sodium hydroxide. Add this
mixture to 5 mL of the filtrate. A black precipitate of lead
sulphide indicates the presence of sulphur. Positive identi-
fication suggests that the sample is either a sulphonamide
or sulphate.
Nitrogen
Bring 2 mL of the filtrate to boil in a test tube. Add five
drops of a 10 % solution of NaOH and five drops of 10%
ferrous sulphate solution. When cold, add, drop wise, a
10 % solution of hydrochloric acid until the solution is
acidic and the precipitate of ferrous hydroxide has dis-
solved. Avoid using an excessive amount of acid. A blue
or green color or blue precipitate indicates presence of
nitrogen. A positive test suggests that the plasticizer could
be an amide.
Chlorine
Acidify 5 mL of the filtrate with several drops of dilute sulfu-
ric acid and bring it to boil. Cool and acidify with nitric acid.
Add several drops of a 10 % silver nitrate solution. A white
precipitate indicates the presence of a chlorinated compound.
Phosphorous
Boil 5 mL of the filtrate with 3 mL of concentrated nitric
acid for 1 min. Cool and add twice the volume of 10 %
ammonium molybdate solution. Heat to about 60C and
set aside to cool. A yellow precipitate indicates the pres-
ence of phosphorous. Phosphate plasticizers will result in
a positive test.
Phthalates
Add about 0.05 g of resorcinol and 0.05 g of phenol to
separate 6 in. (15.24 cm) test tubes. Add to each test tube
two to three drops of the isolated plasticizer and a drop of
concentrated sulfuric acid. Heat the contents in an oil bath
at 160C for several minutes. Cool and add 2 mL of distilled
water and 2 mL of 10 % sodium hydroxide solution and
stir. The presence of phthalate is indicated by a pronounced
TABLE 2Selected physical properties of plasticizers prepared with 2-ethylhexyl (2-EH) and
i-nonyl (iso-N) alcohols. Note: Health information about these and other plasticizers can be
found by searching the CAS number on the Internet.
Abbreviation
a
Adipate Phthalate Trimellitate
DOA DINA DOP DINP TOTM TINTM
CAS No. 103-23-1 33703-08-1 117-81-7 28553-12-0 3319-31-1 53894-23-8
Alkyl group 2-EH iso-N 2-EH iso-N 2-EH iso-N
Boiling point 214C at 5 mm Hg 406C 384C >400C 414C 300C at 4 mm Hg
Density, 25C 0.925 0.920 0.985 0.972 0.988 0.978
Flash point
b
181C, OC 180C, COC 207C, CC 221C, CC 263C, CC 280C, COC
Formula MW 371 399 391 419 547 589
Pour point, C <60 <60 47 54 44 46
Refractive Index,
n
D
20
1.447 1.449 1.486 1.486 1.486 1.485
Vapor pressure,
mm Hg at 200C
2.4 1.5 1.32 1.0 0.5 0.45
a
DOAdi(2-ethylhexyl)adipates; DINAdi(iso-nonyl)adipates; DOPdi(2-ethylhexyl)phthalate; DINPdi(iso-nonyl)phthalate; TOTMtri(2-ethylhexyl)
trimellitate; TINTMtri(iso-nonyl)trimellitate.
b
COC = Cleveland open cup; CC = closed cup; OC = open cup.
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144 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 3Plasticizers and their compatibility with coating resins. C = compatible, P = partially
compatible, and I = incompatible.
Plasticizer CA CAB CN EC PMMA PS VAc VB PVC VC/VAc
Phthalates
DOP I C C C C C I P C C
DIOP 1 C C C C C C P C C
DINP P C C C C C C P C C
DIDP P C C C P C P P C C
Trimellitates
TOTM P C C C P C P P C C
TINTM P C C C P C P P C C
Phosphates
TCP C C C C P C C C C C
TOP P P C C I C I C C C
Acyclic esters
DOA P C C C P C P P C C
DINA P C C C P C P P C C
DOZ P C C C P C P P C C
DOS P C C C P C P P C C
Epoxidized
Soybean oil I P C C I I I I C C
(2EH)tallate I C C C L L L C C C
Polyesters
Adipic/Diol P C C C P C P P C C
Phthalic/Diol P C C C P C P P C C
Resins
CA = Cellulose acetate
CAB = Cellulose acetate/butyrate
CN = Cellulose nitrate
EC = Ethyl cellulose
PMMA = Methyl methacrylate
PS = Polystyrene
VAc = Vinyl acetate
VB = Vinyl butyral; 19 wt % vinyl alcohol
PVC = Vinyl chloride
VC/VAc = Vinyl chloride/vinyl acetate copolymer: 90/10
PLASTICIZERS
Phthalates
DOP = di(2-ethylhexyl)
DIOP = di(isooctyl)
DINP = di(isononyl)
DIDP = di(isodecyl)
Trimellitates
TOTM = tris(2-ethylhexyl)
TINTM = tris(isononyl)
Acyclic Esters
DOA = di(2-ethylhexyl) adipate
DINA = di(isononyl) adipate
DOZ = di(2-ethylhexyl) azelate
DOS = di(2-ethylhexyl) sebacate
Note: Compatibility of plasticizers in specific polymers is a function of relative concentration (PHR), as well as the presence of other formulating reagents
and residuals present in polymers. The above ratings are based on plasticizer levels typically used in coatings applications (<40 PHR).
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CHAPTER 17 PLASTICIZERS 145
green fluorescence in the tube with resorcinol, and the tube
with phenol will be red.
PERFORMANCE PROPERTIES
Compatibility
Compatibility is the ability of two or more substances to
mix together without objectionable separation [12]. In the
case of plasticizers, it is primarily a measure of the solvency
or strength of positive interactions between the plasticizer
and the polymer that attract them together.
Solvency is the extent (or amount) of interaction of
plasticizer or solvent molecules at the surface of a poly-
mer particle; a solid solution results when the polymer
and plasticizerand possibly additional reagentsbecome
molecularly homogeneous. The degree to which a homoge-
neous solution, or miscibility, is stable is a function of the
plasticizer/polymer interactions when in the presence of
other reagents employed in the coating formulation; it must
be recognized that the presence of these additional reagents
can compete with the polymer/plasticizer interactions. The
rule of thumb like dissolves like applies, but more specific
knowledge is required to avoid results that appear to be
anomalous.
Dried polymeric coatings may be considered as
solid solutions; the limits of miscibility are impacted
by all of the reagents that become components of the
coatingthose intentionally added, as well as inadvertent
contaminates and/or degradation products formed in the
coating process. When plasticizers are employed, they
have a major effect on compatibility, primarily due to the
level, or concentration, used in the polymer. If we accept
the definition of a solution as a homogeneous mixture
of two or more types of molecules, then solvency is a
measure of a given solvent or plasticizer to homogenize
and interact with a given polymer. Quantification of
this interaction has been elusive; scales that have been
devised are capable of measuring only gross differences.
Observations of phase separation of plasticizer/polymer
have been more finite than that predicted in many cases;
while on the other hand, observations of symptoms (com-
patibility) are incapable of separating solvency from
other interfering mechanisms that are concurrent, such
as diffusibility.
Hansen publications [13, 14] define the total solubility
parameters of polymers, solvents, and other reagents as a
function of three component parameters:
T d p h
= + + ( ) , ( )
/ / 2 2 2 1 2 3 1 2
cal/cm
(3)
where
T
= total solubility parameter,
d
= dispersion parameter,
p
= polarity parameter, and
h
= hydrogen bonding parameter.
The location of polymers and other nonionic reagents
may be defined on this three-dimensional grid. Hansen
states that it may be assumed that the closer a plasticizer
lies to the center of the polymer solubility space of a poly-
mer, the more compatible it will be with the given polymer.
Many materials have been characterized in this fashion.
Exxon Chemical Company has developed a computerized
capability to define the location of various solvents and
plasticizers relative to that of various polymers; it is called
the CO-ACT
_
,
141 5
60 60
1
Sp.Gr
331 5 .
No statement of reference temperature is required,
since 60F is included in the definition. API grav-
ity applies specifically to crude petroleum and to
petroleum products such as hydrocarbon solvents.
Gravities are determined at 60F (15.56C) or are
converted to values at 60F by means of standard
tables. These tables are not applicable to nonhydro-
carbons nor to essentially pure hydrocarbons such
as the aromatics.
A brief discussion of these definitions may be useful.
In scientific terminology, mass is a measure of the quan-
tity of material in a body, and it is constant regardless of
geographical location, altitude, or atmospheric conditions
as long as no material is added or taken away. Weight is
the force with which a body is attracted to the earth, and it
varies from place to place with the acceleration of gravity.
When an equal-arm balance is used to compare an
object with standards of mass (weights), the effects of
variations in the acceleration of gravity are self-eliminating
and need not be taken into account, but the apparent mass
of the object is slightly different from the true mass because
of the buoyant effects of the surrounding air. Mass can then
be computed from apparent mass by applying a correction
for air buoyancy. When a spring balance is used, an addi-
tional correction accounting for the local value of the accel-
eration of gravity is required for the computation of mass.
For many commercial and industrial processes the sci-
entific distinction between mass, apparent mass, and weight
is of no practical consequence and is therefore ignored. The
term weight in general practice has been accepted as being
the value secured when an object is weighed in air. This
weight or weight in air is often converted to weight in
vacuo by the application of an air buoyancy correction,
and it is then considered synonymous with mass.
All of the definitions listed above are based on either
mass or weight in air, with the distinction being that
air buoyancy corrections have been applied in the former
case and not in the latter. Density and specific gravity are
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172 PAINT AND COATING TESTING MANUAL 15TH EDITION
based on mass and should be similarly constant. Apparent
density and apparent specific gravity are based on weight
in air, and therefore they are subject to change with atmo-
spheric conditions, locality, and altitude. These changes
may be negligible, depending on the accuracy required for
the particular application.
HYDROMETER METHODS
Hydrometer methods are the quickest, simplest means for
measuring density, specific gravity (relative density), and
API gravity, especially in the field. These methods are based
on the principle that the specific gravity of a liquid varies
directly with the depth of immersion of a body floating
in it. The floating body, called a hydrometer, is graduated
in units of density, specific gravity, or API gravity units.
Hydrometers are useful when accuracy to three decimal
places is adequate.
The sample is brought to the prescribed temperature,
and it is transferred to a clear glass or plastic cylinder,
which is at approximately the same temperature. The
appropriate hydrometer, having the scale of interest, is
lowered into the sample and is allowed to float freely and
settle. After temperature equilibrium has been reached, the
hydrometer scale is read. Note is made of the hydrometer
scale graduation nearest to the apparent intersection of the
horizontal plane surface of the liquid (Fig. 22). Tempera-
ture of the sample is read from a separate thermometer
or from a thermometer integrated into the design of the
hydrometer.
Detailed descriptions of test methods for the proper
use of hydrometers can be found in ASTM D891, (Method
A), Specific Gravity, Apparent, of Liquid Industrial
Chemicals [9]; ASTM D287, Method for API Gravity of
Crude Petroleum and Petroleum Products (Hydrometer
Method) [11]; and ASTM D1298, Method for Density, Rel-
ative Density (Specific Gravity), or API Gravity of Crude
Petroleum and Liquid Petroleum Products by Hydrom-
eter Method [11].
For hydrocarbon solvent naphthas, values can be
measured on a hydrometer at convenient temperatures,
the readings of density may then be reduced to 15C, and
readings of relative density (specific gravity) and API grav-
ity at 60F are obtained by means of international standard
tables. By means of these tables, values determined in any
one of the three systems of measurement are convertible
to equivalent values in either of the other two systems
so that measurements may be made in the units of local
convenience.
PYCNOMETER METHODS
Pycnometer methods for measuring specific gravity are
more accurate and precise than hydrometer methods. They
are used when accuracy to four or more decimal places is
required. ASTM D891, (Method B), Specific Gravity, Appar-
ent, of Liquid Industrial Chemicals [9], describes the gen-
eral test method for using a pycnometer.
A pycnometer is a tared vessel which is filled with
water and weighed. It is then filled with the sample and
weighed. Water, sample, and pycnometer are at a specified
temperature. The ratio of the weight of sample to weight of
water in air is the apparent specific gravity.
Bingham PycnometerA Bingham-type pycnometer
may be used when density or specific gravity needs to
be determined to five decimal places (Fig. 23). Its use is
described in ASTM D1217, Method for Density and Relative
Density (Specific Gravity) of Liquids by Bingham Pycnom-
eter [11].
Fig. 23Bingham-type pycnometer.
Fig. 22Hydrometer and meniscus detail.
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CHAPTER 18 SOLVENTS 173
The pycnometer is first carefully calibrated by deter-
mining the weight of freshly boiled and cooled distilled
water (distilled from alkaline permanganate through a tin
condenser) held by the pycnometer when equilibrated to
volume at the bath temperature to be used for the deter-
mination. The liquid sample is introduced into the tared,
clean, dry pycnometer, equilibrated to the desired tem-
perature, and weighted. The relative density (specific grav-
ity) or density is then calculated from this weight and the
previously determined weight of water required to fill the
pycnometer at the same temperature, both weights being
corrected for the buoyancy of air.
Lipkin Bicapillary PycnometerThe Lipkin bicapillary
pycnometer is another type that is capable of high accu-
racy and precision when density or specific gravity needs
to be determined to five decimal places [42]. Its use was
described in ASTM D941, Method for Density and Relative
Density (Specific Gravity) of Liquids by Lipkin Bicapillary
Pycnometer, but this test method was discontinued in 1993.
The liquid sample is drawn into the pycnometer and
weighed. It is then equilibrated at the test temperature,
and the positions of the liquid levels in the capillaries are
observed (Fig. 24). The density or relative density of the
sample is then calculated from its weight, a calibration
factor proportional to an equal volume of water, and a
term that corrects for the buoyancy of air. NOTE: This test
method has been discontinued and is included for histori-
cal purposes.
DIGITAL DENSITY METER
A rapid, direct-reading, instrumental method for measuring
density or specific gravity is by means of a digital density
meter. Its use is described in ASTM D4052, Method for
Density and Relative Density of Liquids by Digital Density
Meter [23]. A small amount of sample (several milliliters) is
introduced into a oscillating quartz tube in the instrument
at a preset temperature. Operation of the instrument is
based on the principle that the period of oscillation of the
quartz tube is affected by the density of the sample within
it. The instrument provides a digital readout of either den-
sity or specific gravity at the specified temperature.
CALCULATIONS AND CONVERSION TABLES
ASTM D1250, Guide for Petroleum Measurement Tables
[11], is a description of the tables that comprise Chapter
11, Section 1, of the API Manual of Petroleum Measurement
Standards [43]. These are distributed in three basic systems
of measurement:
2
(D
84
D
50
+ D
50
/D
16
), with D = di-
ameter, and 84, 50, and 16 signify the respective percentiles.
15
For whiteness and brightness, green light matters most because
the human eye is most sensitive in the green waveband.
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CHAPTER 19 WHITE PIGMENTS 191
particles closer to about 0.16 m, red light by particles of
about 0.23 m. This optically effective particle size is likely
to differ from the size measured by analysis.
Particle-size distributions of commercial TiO
2
pigments
are narrower than those of many so-called monodisperse
particulates (Fig. 6). Population statistics approach log-
normal character, that is, a logarithmic transform converts
the size distribution curve to normal or Gaussian proba-
bilities. Appropriately ground, pigment dispersions contain
less than 5 wt % of particles smaller than 0.10 m and larger
than 1.0 m. The mean particle size of pigment grades is tai-
lored to the required light-scattering performance. Pigment
grades composed of small particles are made for applica-
tions at low-pigment volume concentration.
The pronounced wavelength dependence of optimum
scattering results in a subtle color effect caused by white
pigments in colored coatings. Their color shifts toward
red if the white pigment is larger than optimal or toward
blue if the white pigment is smaller than optimal. This
undertone is visible only in gray and colored coatings
and in white at incomplete hiding. In gray coatings, the
effect can be quite obvious, sometimes objectionable,
sometimes desirable. Small-size TiO
2
grades with blue
undertone are used to make colors look cleaner, i.e., less
yellowish.
16
Large particles in a paint film are detrimental to gloss.
Thus, the coarse tail of the size distribution of TiO
2
pigments
impacts gloss performance [1]. Fig. 7 shows what particle
size range impacts which performance characteristic.
Paint grind gages reveal the presence of minute quan-
tities of grit, which are clumps composed of tens of thou-
sands of primary particles. Grind gages do not respond to
pigmentary particle sizes. For TiO
2
pigments, the presence
of grit has no detectable optical effects.
Particle size control is one of the manufacturing secrets
of the TiO
2
industry. Additives and process conditions dur-
ing crystallization and grinding operations are crucial to
particle size and product performance in both the chloride
and the sulfate processes.
PARTICLE SIZE ANALYSIS
An upfront warning: Particle-size analysis and the interpreta-
tion of analytical data calls for specialized expertise. Potential
pitfalls are so numerous that serious misinterpretation is
the rule rather than the exception, particularly in the inter-
pretation of electron micrographs.
Problems arise in several ways. Two definitions of par-
ticle, be it clump, agglomerate, aggregate, or crystallite, are
vitally important: (1) the particle of the analysis and (2) the
particle that matters within the intended application. The
analytical particle is almost never the same as the particle
in a paint film that interacts with light.
Dispersion is a true grinding operation that reduces
particle size. In spite of this, grinding must be an inte-
gral part of the analytical procedure. Otherwise, the
softest and largest clumps become valid members of
population statistics.
In the process of sample preparation, dispersive work
is often expended on minute samples. Such work can
add up to enormous energy concentrations that can
break crystallites, which cannot be broken en masse.
Sampling statistics is a frequent problem considering
small quantities or low concentrations of pigment in
samples.
In microscopy, transmission images bear little resem-
blance to ordinary visual perceptions based on observa-
tion of surfaces. Scanning micrographs, by contrast,
correspond to human vision. Differences become appar-
ent when comparing Figs. 3 and 4.
In light-scattering methods, the extreme refractive
index of TiO
2
affects computational interpretation.
No certified standards are available pertaining to the
size range of pigments.
Numerous methods have been applied to the size
analysis of pigments: Andreasan pipettes, disk centrifuges,
transmission electron microscopy, light-scattering measure-
ments, field flow fractionation, etc., have been used. They
are too complex and far too costly for routine analysis.
Lately two methods have advanced TiO
2
technology
because reproducible results can be obtained routinely:
x-ray sedimentation and the x-ray disk centrifuge. Both
methods are usually combined with ultrasonic dispersion.
X-ray sedimentation measures the Stokes diameters of
particles settling in water by gravity. Settling causes den-
sity differences in the suspension and these are detected
by absorption of x-rays. Brownian motion interferes with
settling and distorts the small end of the size distribution
curve of the particle population. The x-ray disk centrifuge
substitutes centrifugal force for gravity and this avoids mis-
representation of small particle fractions.
COMMODITY COMPOSITION
The TiO
2
in the pigment is its optically active ingredient. Other
components adapt it to its end use. The commercial products
have compositions that fall into one of three categories: (1)
uncoated pigments, (2) coated pigments, and (3) Slurries.
Uncoated pigments contain 98 % or more titanium
dioxide; some contain up to about 1 % aluminum oxide
(anhydrous), and other products contain less than about
0.5 % aluminum oxide with some other inorganic, anhy-
drous oxides. Organic additives and their decomposition
products may be present in concentrations of fractional
weight percentages. Uncoated pigments are used in plastics
Fig. 6Particle size distribution of TiO
2
pigment. From Braun, J.
H., Introduction to Pigments, Monograph in the Federation
Series on Coatings Technology, Federation of Societies for
Coating Technology, United States, 1993.
16
Because dirt is colored by iron and thus reddish gray, a reddish or
yellowish cast is perceived as dirty.
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192 PAINT AND COATING TESTING MANUAL 15TH EDITION
and paper. In coatings, wet-treated pigments are preferred
because they are easier to disperse into liquids of low or
moderate viscosity.
Minor constituents, either carried over from the ore
or added in the manufacturing process, can be important
in determining pigmentary properties because they can
control crystallite size. Sulfate pigments retain up to 0.3 %
niobium pentoxide and 0.3 % phosphorus pentoxide from
the ore. They also contain up to 0.2 % alumina, which is
added to compensate for the presence of niobium. Com-
pensation minimizes discoloration by the semiconductor
imbalance that pentavalent and trivalent cations can cause
in the rutile lattice.
Chloride process pigments contain practically no
unwanted impurities because the titanium tetrachloride
intermediate can be effectively purified. They contain about
1 % pyrogenic alumina that is added for improved process
control and for photochemical stability improvement.
Trace constituents are generally unimportant except
for transition metals, such as iron, chromium, vanadium,
etc., which degrade color by semiconductor mechanisms.
Besides inorganic constituents, most uncoated and
many coated pigments contain up to 0.5 % of an organic
grinding aid to improve flow in the fluid energy mill,
thereby achieving more uniform grinds. The grinding aids
are usually polyhydroxyl compounds (for example, trimeth-
ylol propane, triethanolamine, etc.) that can undergo some
pyrolytic degradation in the mill.
For use in coatings, i.e., to be dispersible by conven-
tional paint-making equipment, TiO
2
pigments are coated.
In aqueous suspension, hydrous aluminum oxides are pre-
cipitated onto the surfaces of pigment particles. Interior
grades contain a coating of up to 5 % hydrous alumina for
ease of dispersion. Durable grades have another coating
that usually consists of about 2 % silica and sometimes also
oxides of zirconium, boron, zinc, cerium, and tin, usually in
concentrations of less than 1 %.
Rutile pigments are made suitable for extreme expo-
sure by encapsulating individual particles in glassy silica
sheaths. Silica surface treatments on TiO
2
pigments were
once considered detrimental to gloss performance. Silica
on pigment, however, comes in two distinct modifications,
either fluffy or dense. Fluffy silica does indeed reduce
gloss and is precipitated onto pigments intended for dry-
hiding paints to increase oil absorption. Dense silica is
used to encapsulate the TiO
2
particle in a distinct shell
and thereby make the pigment durable in severe exposure.
Special high oil absorption products are made for
paints formulated for dry flat hiding, that is, above the criti-
cal pigment volume concentration. They contain fluffy coat-
ings, 515 % hydrous silica and 26 % hydrous alumina, for
better spacing and improved optical efficiency in vehicle-
starved formulations. The fluffy silica increases oil absorp-
tion and water demand by the pigment. Gloss is reduced.
Slurry products for coatings applications are usually
based on coated pigments. In addition to the coated prod-
uct, they contain organic dispersants and stabilizers. Pre-
dispersed pigments, sold as aqueous slurries, contain from
60 to almost 80 % titanium dioxide by weight. They are
stabilized with low concentrations of organic chemicals.
Odorless amines are added for pH control. Together
with preservatives, about 1 % of organic material is present.
Pigment loading in slurry products is limited by the concen-
tration at which the slurry becomes too thick to be pumped.
Slurries of lightly treated grades are available at higher sol-
ids contents than slurries of heavily treated, dry flat grades.
The slurries can be shear thickening. Effects can be severe.
The pigment industry describes its products and the
hydrous oxides they contain in terms of their analytical
equivalents, alumina (A1
2
O
3
), silica (SiO
2
), and water (H
2
O)
or moisture content. Such description does not imply
structure or chemical characteristics of the components
but reflects analytical results. The actual components of
pigment coatings are hydrous oxides: boehmite (-AlOOH),
diaspor (-AlOOH), hydrargillite -Al(OH)
3
, etc.
Product descriptions in terms of analytical results are
preferred because they can be verified. By contrast, the
precise structural analysis of colloidal coatings on pigment
surfaces is always difficult and often beyond the capabil-
ity of even the most sophisticated analytical techniques.
Results are usually ambiguous. But because coatings are
precipitated from aqueous solution, the alumina coatings
on coated TiO
2
pigments contain structural water, i.e., they
are hydrous.
Fig. 7TiO
2
aggregate size distribution [1].
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CHAPTER 19 WHITE PIGMENTS 193
Wet treatments have profound effects on dispersibil-
ity and durability. In dry hiding paints, they affect hiding
through oil absorption and spacing. Brightness is not usu-
ally affected. Process details of wet treatment are guarded
secrets of the TiO
2
industry. The patent literature provides
little guidance because the most and least effective pro-
cesses can be described by equally factual performance
claims.
ELEMENTAL ANALYSIS
Chemical analysis of pigments presents no particular prob-
lems. The quality of the data meets the requirements of
pigment and coatings technologies. For routine analyses,
conventional, wet analytical methods, for example, ASTM
D1394, Standard Test Methods for Chemical Analysis of
White Titanium Pigments, have been replaced by instru-
mental techniques for cost savings, not data quality. Alu-
minum and silicon contents are usually determined by
x-ray fluorescence techniques. Water content is analyzed as
weight loss of volatiles by thermogravimetric analysis.
PIGMENT SURFACE
Because pigment particles are so very small, their surfaces
are enormously large. 1 lb of untreated TiO
2
has a surface of
about 1 acre. Thus, surface characteristics have a profound
impact on a pigments interactions with all the other com-
ponents of paints. Furthermore, pigment surfaces are com-
plex composites reflecting the nature of the commodity.
The rutile component of most TiO
2
pigments contrib-
utes up to 10 m
2
/g of composite surface area. Inorganic
treatments with hydrous aluminas and silicas can more
than double the total surface area of a pigment. Most pig-
ment surfaces are composites of TiO, TiOH, AlO, and
AlOH groups. Many pigment surfaces include SiO and
SiOH units. Silica-encapsulated grades have few if any
TiO and TiOH surfaces.
The surface areas themselves are not homogeneous.
Usually they are composites to which TiO
2
contributes 010
m
2
/g TiO
2
and 510 m
2
/g pigment, hydrous aluminas with
about 200 m
2
/g Al
2
O
3
xH
2
O and 28 m
2
/g pigment, silicic
acid with about 150 m
2
/g SiO
2
xH
2
O and up to 10 m
2
/g
pigment, silica glass 510 m
2
/g SiO
2
, 510 m
2
/g pigment, etc.
The chemical and physical characteristics of the surface are
specific to the component. Granted, the components share
important similarities. They are all hydrophilic oxides with
high-energy surfaces.
Even the surfaces of titanium dioxide crystallites them-
selves are not just composed of titanium and oxygen ions.
In the sulfate process, while the rutile crystallites grow,
insoluble components accumulate on their surfaces. Those
components are either impurities present in the ore and not
removed in the purification process or additives designed
to control crystal structure and growth and to regulate
agglomeration. This fortuitous surface is not necessarily
suitable for a given end-use application; thus, crystallite
surfaces are modified by treatments.
The surfaces of TiO
2
pigments are readily wetted. They
are usually hydrophilic and disperse spontaneously into
water. The energy of wetting is high, aiding dispersion
into organic liquids. The ease of wetting of TiO
2
pigments
contrasts with wetting problems of organic color pigments,
most of which are hydrophobic and have a low negative
free energy of wetting. Water does not wet them without
the help of surfactants. Suitable organic solvents may wet
organic pigments but often only sluggishly.
Since unmodified pigments tend to cake and flow
poorly, they are treated with up to 0.5 % of a grinding aid,
usually organic polyhydroxyl compounds, to improve dry
flow. These organic materials remain on the pigment sur-
face. Silicone treatment can be used to make dry pigment
flow like sand, but the pigment becomes hydrophobic and
unsuitable for most coatings applications.
SURFACE ANALYSES
Surface analysis of pigments involves three interrelated
subjects: surface area, surface composition, and surface
chemistry. For data interpretation, sample density data are
also required. Methods and results tend to be more interest-
ing to the scientist than the practitioner.
Instrumental surface area determinations are now rou-
tine. Nitrogen adsorption is used widely. Reliability of results
is satisfactory. Data are affected by the composite character
of pigments and its response to sample preparation.
The modem methods of surface analysis, Microprobe,
ESCA, etc., have been used to study pigment surfaces and
have yielded interesting results and valuable insights. Costs
and technical complexity preclude their widespread and
routine use.
Surface adsorption by pigments has been explored
extensively by surface calorimetry and in terms of adsorp-
tion isotherms, etc. Ambiguities introduced by the compos-
ite character of the surfaces have their impacts.
The density of a pigment can be measured precisely and
quickly by a helium densitometer. However, for fine powders
of known composition, calculated densities are often more
reliable than measured values. Density calculation requires
knowledge of the pigment composition and the density data
for the pure component oxides. It is decisively important to
include in the calculation the total water content: absorbed
moisture plus the structural water of the hydrous oxides.
PIGMENT PACKING
Pigment particle packing density affects paint film perfor-
mance. This density is an inverse measure of interstitial
volume, a reflection of the way pigment particles aggregate
and agglomerate into either stringy assemblies that hay-
stack loosely or compact clumps that pack densely.
Effects of packing density on performance are pro-
found. Packing characteristics determine the critical pig-
ment volume concentration of a pigment. Through the
critical pigment volume concentration, pigment packing
affects virtually all characteristics of paint films [3]. Fluffy
pigments have a low critical pigment volume concentration;
particulates that pack densely have high critical pigment
volume concentrations. In effect, the critical pigment vol-
ume concentration itself is a measure of the interstitial vol-
ume of wetted pigment particles. Adsorption layers are also
involved, but in most instances their contribution is minor.
Practitioners of coatings technology have long been
aware of the importance of packing density. They used
oil absorption of a pigment as one of its most important
descriptors. Oil absorption is still used today because it
reveals so much about the pigment even though linseed oil
has lost its importance as a binder.
Oil absorption is primarily a measure of wet pack-
ing complicated by the involvement of adsorption layers,
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194 PAINT AND COATING TESTING MANUAL 15TH EDITION
dispersion work, and flocculation. The measure predates
the insights of Asbeck/Van Loo into structure and perfor-
mance of paint films.
17
Thus, the connection between oil
absorptionthe practical measureand the scientific con-
ceptcritical pigment volume concentrationsis unnec-
essarily convoluted. Oil absorption of different pigments
cannot be compared because the measure is based on
weights, not volumes. Critical pigment volume concentra-
tion, by contrast, is based on volumes and lends itself read-
ily to comparisons of particulates that differ in densities. At
its best, when oil absorptions of similar pigments of identi-
cal densities are measured by an experienced individual
who uses a standardized procedure to his personal end
point, oil absorption values become a reasonably precise
measure of the packing of pigment particles in oil.
For wetted particles, pigment packing is not affected
much by the nature of the liquidwater, oil, or solvent
provided the particles are not flocculated. In practice,
surfactants must be added or be present as a natural com-
ponent of the system as they are in raw linseed oil. Liquid
absorption values agree pretty well with each other if
they are based on relative volumes of a pigment in a vari-
ety of liquids. Incidentally, oil absorption values correlate
inversely with the bulk density of a given pigment. The
fluffier the pigment packs in air, the more loosely it packs
in liquids.
PACKING MEASURES
In spite of its many shortcomings, oil absorption is the
only measure of packing that is widely accepted. The test
is a titration of raw linseed oil into dry pigment powder to
an end point at which the mass cakes. Two procedures are
in common use: ASTM D281, Standard Test Method for
Oil Absorption of Pigments by Spatula Rub-out and ASTM
D1483, Standard Test Method for Oil Absorption of Pig-
ments by Gardner-Coleman Method.
Precision of oil absorption data is poor unless one
experienced individual makes all measurements in the data
set. For tests by different laboratories, the spatula method
has a coefficient of variation of 12 %, with 5.3 % for the
Gardner-Coleman method. Data obtained by two analysts
tend to differ because the end point of the titration is more
difficult to define than to reproduce.
CONTAMINANTS
Extraneous metal ions within rutile crystallites can degrade
pigment brightness. Nickel and chromium can be detri-
mental in concentrations as low as a few parts per million.
Semi-conductor mechanisms are involved. Substitution
of extraneous ions for Ti
4+
in the TiO
2
lattices discolors
the crystals usually toward gray or yellow. Impurities and
coproducts introduced by the treatment chemicals are far
less detrimental to brightness. Coproducts can, however,
affect specialized performance requirements. Certain ions
can, for example, inhibit cure of acid or base-catalyzed
coatings or cause film defects in electrocoatings.
Purity and brightness of TiO
2
crystallites are process
related. TiO
2
crystallites made by the chloride process are
purer and brighter than sulfate products. The coproduct
content of a pigment commodity is usually not a matter of
poor operating practice but set by complex compromises
between conflicting performance requirements.
TRACE ANALYSES
Trace impurities in pigments are analyzed by conventional
emission spectroscopic and x-ray fluorescence methods.
Results are considered reliable though not particularly
precise.
COLOR
Titanium dioxide is a virtually colorless dielectric with
some semiconductor characteristics due to small amounts
of contaminants. Rutile absorbs in the violet end of the
visible spectrum. Fig. 8 is a schematic representation of
the reflectances of white, gray, and black paints pigmented
with only TiO
2
, with TiO
2
and carbon black, and with only
carbon black, respectively. Absorption of far violet radiation
imparts a slight yellow hue to large crystals. The anatase
absorption edge is at a shorter wavelength than rutile,
shifted almost completely into ultraviolet wavelengths.
Thus, anatase crystals are slightly less yellow than rutile
crystals. All this does not matter much in coatings. For
high-purity pigment, dry powder color does not correlate
with end use color because most polymers contribute far
more yellowness than the pigment.
Pigment brightness matters less in most coatings
applications than one might presume. Most coatings, even
white ones, are toned, that is, their brightness is reduced
intentionally by addition of carbon black or color pigments.
Purity, thus brightness, is important only for white coatings
that are usually not toned: Coatings for light fixtures, many
coil coatings, most inks, and ink-similar paints.
Chloride process pigments are intrinsically brighter
and whiter than their sulfate counterparts. Typically, chlo-
ride process pigments average 99.5 % L*
18
lightness,
19
and
98.5 % sulfate pigments.
20
The difference between chloride
and sulfate pigments, an L lightness difference of 1 %, is
about ten times larger than the least visible difference.
TiO
2
particle size has a significant effect on the color
of tinted coatings and thin white films. Smaller particles
scatter blue light more efficiently. As a result, pigment of
a smaller average particle size will shade bluer both tinted
coatings and white coatings at incomplete hiding. Pigment
of a larger average particle size will shade redder in the
same systems. Most TiO
2
grades for coating applications
are neutral in this particle-size-related undertone. Products
intended for very low end-use concentrations are often blu-
ish. Red undertone pigments are not in demand.
COLOR MEASUREMENT
Color measurements of pigments are performed on dry
pressed pellets. Modem spectrophotometers provide data
with more than sufficient precision for most purposes of
pigment quality control. Most of these instruments can
17
Asbeck and Van Loo recognized that the characteristics of paint
flms involve volume rather than weight consideration, no small
matter when densities of paint flm components can range from
0.9 to 6 g/mL.
18
CIELAB (Commision International de lEclairage, 1978) metric
of lightness.
19
Brightness/lightness of a dry pressed pigment pellet.
20
In very frst approximation, a TiO
2
pigment with an L* lightness
of 98.5 % contains a three times higher concentration of colorant
impurities than a pigment of 99.5 % brightness: 1.5 %/0.5 % = 3.
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CHAPTER 19 WHITE PIGMENTS 195
report their results in any of several color coordinates. The
L*a*b* system
21
seems particularly well suited to describe
variations on the theme of white.
HAZARDS
TiO
2
pigment is a benign chemical. Its hazards, and the rela-
tive lack thereof, are detailed in Material Safety Data Sheets
that must accompany any United States shipment. TiO
2
pres-
ents no pronounced health hazards; it is neither corrosive
nor acutely toxic and does not appear to be a significant car-
cinogen nor embryo toxin in the workplace. As a dry powder,
TiO
2
can become a nuisance dust that may require control.
TiO
2
pigment cannot burn nor explode, either as a dry
powder or as aqueous slurry. Neither the dry pigment nor
the slurry is corrosive or reactive. The hazards of pigment
dispersions in organic liquids reflect the characteristics of
the dispersion liquids.
Pigment Performance
The TiO
2
industry sells light scattering for the price of TiO
2
because there is no better and cheaper way to achieve effec-
tive hiding by thin films that are white or light in color.
Thus, optical effectiveness is the primary performance
characteristic of the pigment. However, TiO
2
pigment is
well optimized and functions near its theoretical potential.
Between products developed for similar end use, light scat-
tering differences are too small to matter or to be measured.
Thus, secondary performance characteristics can be com-
mercially decisive.
HIDING AND OPACITY
Pigment sells by weight but scatters light, that is, functions,
by its volume. The particle size of TiO
2
for white pigment
applications was optimized for the scattering of visible
light, first experimentally, later confirmed by theory. Com-
mercial grades perform near theoretical potential. A rutile
particle of about 0.2 m diameter is optimal for green light,
the wavelengths of greatest sensitivity of the human eye.
Fig. 1 illustrates the relationship between scattering
power and particle diameter. The Mie theory can specify the
optimal diameter for the scattering of an electromagnetic
wave by a dielectric particle with great precision, but the
result is limited to single spheres. This complex and abstract
theory must be translated (1) from a sphere into a real par-
ticle of elongated, angular shape, (2) from a single, isolated
particle to assemblies of massive numbers, and (3) from
monosize particles to particle-size distributions. The task is
formidable, yet significant progress has already been made.
Fig. 9 is an illustration of the effects of pigment concen-
tration on hiding of a paint film. At first, hiding increases
in direct proportion to concentration. Then, the crowding of
pigment particles causes the increase to diminish, to reach
a maximum, and to decrease toward the critical pigment
volume concentration. Beyond the critical pigment volume
concentration, dry hiding, that is, light scattering at air/ pig-
ment interfaces, causes hiding to increase again.
Crowding of pigment particles diminishes light scatter-
ing substantially [4] (Fig. 10). Effects become apparent at
pigment volume concentrations above about 8 vol%. More
than half of a pigments scattering effectiveness can be lost
between 8 vol % and the critical pigment volume concen-
tration. A simple optical model explains the effects [5].
Improvements in pigment effectiveness achieved through
control of crowding are likely to be fairly insignificant [6].
The optics within paint films are quantified by the
Kubelka-Munk theory that combines for thin films the
effects of light scattering (usually by white pigment) and
light absorption (usually by color pigment). The model
serves exceedingly well in spite of some theoretical limi-
tations. Kubelka-Munk equations provide a basis or an
explanation for most performance measurements: hiding,
opacity, and tinting strength.
MEASUREMENTS OF LIGHT SCATTERING
Until recently, pigments and paint films were evaluated
by visual comparisons, for example, ASTM D332, Stan-
dard Test Method for Relative Tinting Strength of White
Pigments by Visual Observation. The eye was more sensi-
tive than available instruments, and the mathematics of
Kubelka-Munk was too complex for routine calculations.
Two developments make quantitative evaluation of pig-
ments more appropriate: (1) Optical instruments have
become more sensitive and more reliable than the eye, and
(2) the least of computers can calculate results on the spot.
Light scattering and light absorption of paint films
can be quantified independently using light reflectance
or transmission measurements of thin
22
films drawn over
black and white substrates. In addition, film thickness or
film weight and composition must be measured. ASTM
Fig. 8Reflectance of white, gray, and black paints. From
Braun, J. H., Introduction to Pigments, Monograph in the
Federation Series on Coatings Technology, Federation of
Societies for Coating Technology, United States, 1993.
21
CIELAB (Commision International de lEclairage, 1978) metric
of color.
22
Thin enough to show obvious contrast between regions drawn
over black and white backgrounds but thick enough to look uni-
form rather than mottled.
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196 PAINT AND COATING TESTING MANUAL 15TH EDITION
D2805, Standard Test Method for Hiding Power of Paints
by Reflectometry, describes such a test.
Relatively inexpensive and very reliable spectropho-
tometers can measure reflectances in any specific and
narrow wave band. By measurements, wave band-by-wave
band across the spectrum of visible light, applicability of
hiding power measurements is extended from black and
white to color. Paints of different hues can be compared
and results expressed separately for performances of white
and color pigments. Computer programs are available for
data evaluation.
Tinting strength tests, ASTM D2745, Standard Test
Method for Relative Tinting Strength of White Pigments
by Reflectance Measurement, measure the relative light
scattering of a white pigment by overwhelming the slight
intrinsic absorptions of binder and pigment with a mas-
sive absorption by a standardized addition of colorant.
Measured are thick films of infinite hiding.
23
The same test
serves for the evaluation of color pigment. Here, the slight
intrinsic scattering of the color pigment is overpowered
by the massive scattering from standardized addition of a
white pigment.
Absorption of light within the paint film increases the
hiding power of the film. The effect is quite pronounced,
and either pigment or binder can cause it. When caused
by TiO
2
pigment of low brightness, this low-purity product
can get undeserved credit for a hiding power advantage
over purer products. Also, off-color extenders and colored
polymers can boost hiding power incidentally or deliber-
ately. This hiding improvement comes at the expense of
brightness.
DISPERSIBILITY
To make paint, dry powder has to be distributed in liquid
composed of binder and solvent. The process is called dis-
persion or paint grinding. The ease with which a powder
can be dispersed in a liquid depends primarily on its par-
ticle size. As pigments go, TiO
2
at 0.2 m size is large and
easy to disperse, almost as easy as extenders, much easier
than most color pigments. For all but glossy coatings, TiO
2
can be stirred into liquids with high-speed agitators. High-
gloss finishes require more powerful equipment: media,
roll, or ball mills.
Dispersing a pigment involves four distinct stages dur-
ing which most of the energy of grinding converts to heat:
1. Liquid replaces air-solid interfaces with liquid-solid
interfaces. The ease of wetting depends on (a) energy
characteristics of the surface of the solid and (b) the
chemical affinity between solid and liquid. TiO
2
s
high-energy surface wets well. By contrast, the low-
energy surfaces of organic color pigments wet only
with difficulty.
2. Bonds between particles are broken. TiO
2
crystals are not
broken in ordinary mills. Bonds between crystals range
in strength from strong within aggregates to weak with-
in agglomerates. Weak aggregates can be broken in the
high-energy mills of pigment and plastics technologies,
not, though, by equipment common in coating technol-
ogy. Agglomerates break in high-speed dispersers.
3. Particles are distributed throughout the liquid. The more
viscous the liquid, the more power that is required to
mix and distribute materials and the more effective is
the grind.
Fig. 9Hiding power of paint films. From Braun, J. H., Introduction to Pigments, Monograph in the Federation Series on
Coatings Technology, Federation of Societies for Coating Technology, United States, 1993.
23
Suffciently thick that a further increase in thickness does not
affect refectance. Fig. 10Scattering coefficient of TiO
2
[4].
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CHAPTER 19 WHITE PIGMENTS 197
4. The distribution of particles has to be stabilized against
reversible flocculation. Nonaqueous systems flocculate
by Brownian motion and are stabilized against floc-
culation by surfactants that provide steric hindrance.
Aqueous dispersions flocculate by (1) electrostatic
attraction and by (2) Brownian collisions. They are
charge stabilized by ionic dispersants.
Rheology matters decisively. When grinding in a
shear-thickening rheology regime, dilatent grinding is
highly effective. By contrast, shear-thinning rheology of
the grind charge absorbs energy into reversible bonding,
wasting much of it as heat. High viscosity helps the energy
transfer from mill to particulate. Thus, other parameters
equal, grinding viscous is more effective than grinding
thin, and grinding well cooled is more effective than
grinding hot.
Flocculation degrades optical performance. White pig-
ments can lose only a moderate fraction of hiding, rarely as
much as 30 %. By contrast, color pigments can lose most
of their color. Excessive or inappropriate grinding does
not degrade TiO
2
. Optical performance does not improve
with grinding because most of the pigment is dispersed
very early in the grind cycle. A few parts per million of
undispersed grit, however, can degrade film fineness from
excellent to inadequate.
MEASUREMENT OF DISPERSIBILITY
This author knows of no reliable and useful measurement
of dispersibility. Granted, it is possible to use standard-
ized procedures to establish a ranking of pigment samples
against specific performance requirements. Such a ranking
cannot be quantified and does not translate from one appli-
cation to another. In one such scheme, paint is made by
a minutely standardized, low-shear dispersion procedure.
The paint is then tested for grit by one of several conven-
tional fineness gages.
The residual grit aspect of dispersion is usually evalu-
ated by fineness-of-dispersion gages, for example, ASTM
D1210, Standard Test Method for Fineness of Dispersion of
Pigment-Vehicle Systems by Hegman-Type Gage. The gages
are shallow, tapered channels that are precision machined
into steel blocks. A paint sample is scraped into the chan-
nel. The surface of the paint wedge is then examined to see
at what depth the diameters of largest agglomerates exceed
the depth of the channel. This point is visible as a transition
from smooth to streaked paint surface.
PIGMENT EFFECTS ON PAINT FILM DURABILITY
Durability is the continuance of decorative and protective
performance of paint films and their components under
the influence of weathering. Lack of weathering resistance
manifests itself as (1) oxidation of polymer ultimately to
carbon dioxide and water, (2) discoloration and fading of
color pigments, and (3) chalking of the TiO
2
with concomi-
tant erosion and gloss loss. Instability of substrates intro-
duces additional degradation effects.
For paint films with TiO
2
, concerns involve the weath-
ering resistance of the films themselves. Exposure to
sunlight, moisture, and oxygen changes the appearance
of paint films. Some films chalk and eventually erode to
their substrates; others discolor and fade well before chalk-
ing becomes a problem. Degradation of coatings occurs
because paint films are slowly oxidized by air. Sunlight
triggers the degradation reactions. In the dark, paint films
can last for centuries, even millennia. In light, durability
depends on binders, pigments, and the conditions of expo-
sure. High humidity, particularly condensation, aggravates
degradation.
Only the ultraviolet radiation (UV) portion of sunlight
causes degradation directly because it has energy content
sufficient to break chemical bonds. The degradation of
UV-A and UV-B radiation
24
is irreversible for polymers and
for all organic and some inorganic pigments. A few inor-
ganic pigments are thermodynamically stable. Titanium
dioxide is stable, but UV above 3.08 eV activates its catalytic
characteristics. In effect, the band gap of TiO
2
25
is within
the energy levels present in sunlight. All white pigments
share some of this attribute. Extenders are stable and inert.
Their band gaps are too large to be activated by the UV
components of sunlight.
Titanium dioxide affects the durability of paint films
in two distinct and opposing ways. (1) As a strong UV
absorber, TiO
2
protects the paint film, and (2) as a UV-acti-
vated oxidation catalyst, TiO
2
degrades binders [7].
Three characteristics of TiO
2
are functionally disparate
but are manifestations of a single fundamental character-
istic of dielectric matter: (1) its unique refractive index,
which makes TiO
2
the best white pigment, (2) its extreme
UV absorptivity, and (3) UV catalytic activity of the TiO
2
surface.
Radiation of more than 3.08 eV, water, and oxygen are
all essential for the TiO
2
-catalyzed degradation of binder.
Their reactions combine into a cycle that generates two free
radicals from each active UV photon [8].
H
2
O + O
2
+ h
(UV)
OH+ HO
2
(in presence of TiO
2
)
The hydroxyl and peroxyl free radicals are highly reactive
agents that oxidize and thus degrade essentially any organic
polymer:
2 HO + 2 HO
2
+ CH
4
CO
2
+ 4H
2
O
The chain of chalking events is cyclic with respect to TiO
2
,
and it can be disrupted by exclusion of either UV, water, or
oxygen.
DURABILITY CONTROL
The TiO
2
industry inhibits the catalytic activity of the TiO
2
surface and improves the weathering resistance of its
products by encapsulation in amorphous silica. The shell
that forms is a true silica glass precipitated from aqueous
solution by technology invented by DuPont in the 1960s [9].
Encapsulation of TiO
2
made it practical to paint automo-
biles in white and bright colors. Meanwhile, binders were
improved so that less effective deactivation of the TiO
2
s
24
UV-A is the UV wavelength region near to visible radiation or
light, UV-B is the medium UV region, and UV-C is the far (shortest
wavelength) UV light. Sunlight contains little UV-B and essentially
no UV-C.
25
The band gap is the forbidden energy gap between the valence
band and the conduction band of a semiconductor. In the language
of physics: UV radiation induces semiconductor characteristics in
TiO2; in the language of chemistry: UV radiation reduces color-
less TiO
2
to black Ti
2
O
3
.
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198 PAINT AND COATING TESTING MANUAL 15TH EDITION
catalytic activity suffices and provides satisfactory perfor-
mance of automotive finishes in temperate climates.
The SiO
2
glass prevents contact between the catalytic
surface of rutile and the organic vehicle and provides a sur-
face for recombination of free radicals. Fig. 11 is a depic-
tion of superdurable pigment particles. Their silica sheaths
are barely visible on the transmission electron micrograph.
The silica sheaths themselves, after the TiO
2
was dissolved
out, are shown in the transmission electron micrographs of
Fig. 12. Even the holes are visible through which the rutile
cores were dissolved.
Intermediate levels of weathering resistance are
attained by partial encapsulation of the rutile in silica and/
or alumina with or without zirconia and by bulky coatings
of hydrous aluminum and silicon oxides on rutile.
Alternate approaches to chalking control are less effec-
tive or cause performance problems in coating applica-
tions. They involve attempts to (1) recombine holes and
electrons at the TiO
2
surface by semiconductor mechanisms
whereby the products are slightly yellow and (2) prevent the
hydroxylation of the TiO
2
surface, i.e., interfere with one
step of the chalking sequence, causing products to be gritty.
DURABILITY TESTING
Durability of coatings can neither be measured nor be pre-
dicted quantitatively. The best state-of-the-art technology
can do is rank coatings. Costs per sample are exorbitant,
precision is poor, and the time lag is prohibitive for many
purposes. Years of outdoor or months of accelerated expo-
sure are required for the pigment and binder combinations
for which durability is important to yield useful informa-
tion, that is, for durable pigment in durable binder.
Testing is done by simulation of a real world. Paints
are made from experimental pigment and usually several
pigment standards. Panels are painted. They are exposed
where weathering is severe but is not necessarily represen-
tative of the intended application. Certain appearance char-
acteristics are regularly measured and often chalk, color,
gloss, etc., are noted. Finally, data are reduced, correlated,
and compared. Reproducibility is barely sufficient to tell an
interior grade pigment from a durable grade without test-
ing replicates. Experimental durability differences within
grades are not generally detectable [10].
Results from one binder system cannot be extrapolated
quantitatively to binders involving different polymer chem-
istry, nor can a single acceleration factor predict outdoor
performance from accelerated exposures [11]. Pigment
manufacturers supplement their exposure testing by sci-
ence-based analyses of the catalytic activity of the pigment.
PIGMENT EFFECTS ON GLOSS
Powders do not have a gloss; only surfaces can be glossy.
Within surfaces, particulates affect gloss, for example,
pigments in paint films. They are detrimental, particularly
to the dimension of gloss perceived by the human eye.
Naturally glossy surfaces occur on liquids and amorphous
solids.
26
Particulates in paint film, pigments, extenders,
and some additives reduce gloss because they roughen
the film surface. The more particulate there is in the film,
the lower its gloss. Clear paint films are glossy if they are
sufficiently thick. Thin films can telegraph the roughness
of the substrate to the surface of the paint film, reducing
its gloss.
Since the volume concentration of white pigments
in paint films must be much higher for hiding than the
concentration of color pigments and blacks, the burden of
improvement falls on TiO
2
producers. They have increased
gloss performance for grades that serve the automotive and
industrial markets.
Gloss matters are complicated because a fundamental
difference exists between the measured gloss that guides
Fig. 11Encapsulated TiO
2
pigment.
Fig. 12Silica shells from encapsulated pigment.
26
Single crystals are an exception, but their surfaces are generally
small. Glass is an amorphous solid. Polished surfaces are not natu-
ral. Incidentally, only liquids, amorphous solids, and single crys-
tals can be transparent.
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CHAPTER 19 WHITE PIGMENTS 199
coatings formulation and the perceived gloss that sells
automobiles [1]. These two operational definitions of gloss,
one based on instrumental measurement of an intensity of
image and the other on the human perception of a distinct-
ness of image, differ profoundly in substance. However,
they correlate well enough to guide quality control and
pigment development by incremental improvement. The
fundamental difference between measured and perceived
gloss can, however, misdirect the strategy of product
development, for example, a development strategy focus
on increasing refractive index. A mechanism by which
pigment causes the surface roughness that degrades gloss
explains [1] that pigments diminish gloss by an interplay
between the surface tension of the wet film with the com-
pressive strength of a particulate bed and a gel structure
that develops within the film while it cures. While the
film is fluid, surface tension maintains the surface at a
molecular smoothness that results in perfect intensity-
of-image gloss. As the film dries, the structure within the
wet film strengthens until it overcomes the surface tension
that maintains gloss. Shrinkage of the partially cured film
continues, but now shrinkage becomes uneven on a micro-
scopic scale because only the binder/solvent combination,
not the pigment, shrinks. Thus, micro-roughness develops
and diminishes gloss.
GLOSS MEASUREMENT
Gloss measurement has long been routine, and one tech-
nique is described in ASTM D523, Standard Test Method
for Specular Gloss. Many conventional gloss meters are on
the market. Most perform well for coatings pigmented with
white and color pigments.
27
They come with measuring
heads for three specular angles, generally 20, 60, and 85.
High-gloss surfaces are best measured at low (20 specu-
lar angle), medium glosses at medium angle, and matte
surfaces at grazing angle, 85. The selection of the proper
specular angle improves instrumental precision.
The conventional gloss meters measure the intensity
of light reflected by a surface, the intensity-of-image com-
ponent of gloss. The human eye, by contrast, perceives the
distinctness-of-image
28
component of gloss. Thus, haze and
so-called distinctness-of-image data are used to supplement
the conventional gloss measurements.
COMPATIBILITY
Usually, TiO
2
is used in combination with other pigments.
Interactions between pigments can occur and are detri-
mental to performance. Often, hiding is decreased, color
strength is lost, and chroma is reduced; occasionally, the
hue shifts slightly.
Most interaction problems involve surface chemistry.
The immediate cause of the problem is flocculation. Either
the white or one of the color pigments has flocculated.
Almost inevitably, the color pigment is at fault.
Most color pigments enter the market as toners, lakes,
or dispersions, that is, complex composites that can contain
more surfactants and modifiers than colorant. These addi-
tives are chemically reactive and can interact detrimentally
with the surfactants or additives of the paint formula. Dry
TiO
2
pigments,
29
by contrast, contain no surfactants and are
inert and chemically less complex with far fewer possibili-
ties of adverse interactions.
Chemical interactions between pigments are problems
of the past caused by reactive pigments. White lead, for
example, was incompatible with TiO
2
because UV exposure
could cause gross, though temporary, discoloration. Few
modern pigments are susceptible to these problems.
Problems between TiO
2
pigment and polymers or addi-
tives do, however, occur occasionally because many paint
films contain much higher concentrations of TiO
2
than of
additives or of color pigments. Components of TiO
2
pig-
ment can thus have significant leverage even if present in
relatively small concentrations on the pigment. Problems
are usually quite specific to the paint formula. Several such
problems have been recognized and are resolved through
specialized TiO
2
grades made, for example, for electrocoat-
ing primers and for acid-catalyzed paints.
Product Types
ASTM D476, Standard Classification for Dry Pigmentary
Titanium Dioxide Products, distinguishes four types of
TiO
2
pigments (Table 2)one anatase type and three rutile
types: interior, exterior, and pigment for paints formulated
above the critical pigment volume concentration. The stan-
dard was formulated in 1939 with two classes of pigments.
In the years since, the design of pigments has progressed
to where the coatings industry can now select the most
suitable pigment grade for a specific application from
far more than two or four TiO
2
types. Granted, a single
TiO
2
grade could serve diverse needs but would do so only
moderately well. Optimal performance in any application
demands specialized pigment grades that satisfy specific
requirements of optics, surface chemistry, and dispersion
technology. Some of these requirements can be met only
through compromise.
The diversity of products can be described in terms of
four specific performance dimensions such as durability,
gloss, dispersibility, and undertone. Then there are prod-
ucts aimed at specific applications such as enamel paints,
dry hiding paints, pigment slurries, acid-catalyzed coat-
ings, electrocoated primers, etc. Finally, pigment grades are
designed for the specific requirements of whole industries
such as coatings, plastics, paper, and ink.
These are the products designed to specific perfor-
mance dimensions in coatings.
Durability: InteriorExteriorSevere Exposure. Inte-
rior grades are unfit for exterior applications except
when used underneath top coatings that absorb
all radiation with wavelengths below 400 nm. All-
purpose pigments are exterior durable in appropriately
durable vehicles at moderate severity of exposure and
for moderate appearance requirements. Severe expo-
sure grades are intended for satisfactory performance
including high gloss at exceptionally severe conditions,
for example, at the horizontal position in the humid
subtropics. Durability must be manufactured into the
pigment surface.
Gloss: ConventionalFlashy. Conventional pigments
satisfy the gloss requirements of most architectural and
27
For coatings that contain fake pigments, the interpretation of
angle-dependent refectance measurements is complicated.
28
The distinctness-of-image instrument is really an intensity-of-
image meter sensitized toward distinctness of image.
29
Slurry grades do contain some organic surfactant.
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200 PAINT AND COATING TESTING MANUAL 15TH EDITION
trade-sales applications and of many industrial coat-
ings. High-gloss pigments are aimed at automotive and
some flashy industrial finishes. High-gloss applications
call for pigments of small agglomerate size and low oil
absorption.
Dispersibility: ConventionalLow Shear. Conventional
pigments are designed to be dispersed by equipment
developing moderate to high shear:
30
media mills, ball
mills, roller mills, and high-speed dissolvers at low
rates of throughput. Special pigments are available
for low-shear, high-rate dispersion by high-speed dis-
solvers and for stir-in with screening. Dispersibility is
promoted by surface treatments at some detriment to
gloss. Unlike many color pigments, TiO
2
pigments are
sufficiently dispersible to not require predispersion.
Undertone: NeutralBlue. In coatings applications,
the undertone of the pigment, blue, neutral, or red, is
rarely an issue. Thus, most coating grades have a neu-
tral undertone. Blue undertone pigments are preferred
in applications at very low pigment volume concen-
tration. Red undertone pigments do not appear to be
in demand. Undertone is affected by pigment volume
concentration and controlled by the size of the primary
TiO
2
particle, small for blue, intermediate for neutral,
and large for red.
There are also specific coatings applications addressed
by special product designs.
Grades intended for coatings below the critical pigment
volume concentration. Most TiO
2
pigments, convention-
al interior and exterior grades, conventional and high-
gloss products, conventional and low-shear dispersible
pigments, the neutral and blue undertone pigments,
are all suitable for applications below the critical pig-
ment volume concentration.
Grades intended for applications above the critical pig-
ment volume concentration. Heavily treated, low-gloss
products perform better in dry-hiding paints than
grades made for high and moderate gloss. In effect,
the pigment contains its own, exceptionally effective
ex tender.
Slurries intended for waterborne paints. Aqueous slur-
ries are suited only for waterborne applications. The
costs of dispersion operations are borne by pigment
manufacturers. For medium- and large-scale opera-
tions, savings from the elimination of a process step
outweigh the costs of slurry-handling facilities.
Other specialized grades are made as opportunities are
recognized and solutions developed.
Finally, specific products targeted for industries other
than coatings.
Plastics. Plastics are pigmented by products most of
which are optimized for performance at PVCs of less
than 1 vol %. Durability and dry-flow characteristics
can be important to the plastics industry. High-gloss
and low-shear dispersibility are usually not required.
Paper. The wet-end stage of papermaking uses aque-
ous slurries. Slurry handling and optics are important:
Low-shear dispersibility, high gloss, and durability are
irrelevant.
Ink. Inks require pigments that are high in gloss. Com-
patibility with a wide range of solvents and vehicles is
often an important factor.
Miscellaneous end uses. Pigmentary applications
(floor coverings, elastomers, roofing granules, fibers,
fabrics, sealants, food additives, etc.) and nonpigmen-
tary applications where pigment is used for its TiO
2
content (ceramics, welding rods, etc.) or as a low-cost,
mono-disperse particulate (for example, as catalyst
support).
Also, the same products can be packaged in different
ways, bag, semibulk, or bulk, or analyzed for special pur-
poses, for example, food additive purity. Each such product
may enter commerce under its own grade designation.
The wrong grade of TiO
2
pigment for any specific
application will still be inert, white, and will hide well. But,
the inappropriate pigment will fall short of expectations on
secondary performance characteristics such as durability,
gloss, or rheology. This is in marked contrast to most color
pigments, where a grade inappropriate to an application is
likely to fail grossly.
Matters of pigment classification are complicated by
interactions among requirements.
1. Certain requirements are mutually exclusive. For
example, aqueous pigment slurries are obviously suit-
able only for waterborne applications.
2. Some industry requirements overlap. Paper coatings
resemble dry hiding paints and are served by similar
products.
3. Optimal performance in one dimension can come at
the expense of performance in another dimension.
Flashy gloss can be attained only at the expense of pig-
ment characteristics that promote stir-in dispersibility.
4. Premium performance can require additional process
steps, increasing the cost of manufacture. Pigments
for severe exposure and grades for flashy finishes are
sold at a premium because they are more expensive
to make.
5. Identical performance objectives can be achieved by
different product designs.
TABLE 2Excerpt from ASTM D476: Specification for titanium dioxide pigments
Type 1 Type II Type III Type IV
Anatase Free Chalking Rutile Medium Chalk
Resistant
Rutile Medium Chalk Resistant Rutile Highly Chalk Resistant
Typical
application
White exterior house
paint, interior use
Low-medium PVC
enamels and lacquers
Medium-high PVC enamels;
alkyd and emulsion flat wall
paints
Highly chalk-resistant exterior
coatings requiring excellent
durability and gloss retention
TiO
2
, min.% 94 92 80 80
30
High shear within coatings technology. The plastics industry uses
several more powerful mills.
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CHAPTER 19 WHITE PIGMENTS 201
Nevertheless, I have attempted classification of state-
of-the-art products in terms of six performance param-
eters and intended applications: concentration, gloss level,
exposure, optics, slurry, and dispersion. Permutations of
these requirements make for 72 potential product niches
for coatings applications alone. Commercial products
occupy 14 of the niches. They are shown in Table 3. All
major manufacturers sell at least several of these prod-
ucts as specific grades or by equivalent subclassifications
within grades.
About two-thirds of the potential product niches
appear to serve no practical purpose. For example, aque-
ous pigment slurries are not suited for solvent-based
paints, and high-PVC paint films are not made to have
flashy gloss. Obviously, the multiplicity of grades creates
costs and incentives for the development of universal
grades. Lately some of these attempts have been partially
successful, and a few universal products have appeared
on the market. Conspicuously absent from this table are
anatase pigments. They and the extended TiO
2
grades
that used to dominate TiO
2
markets are no longer used in
coatings.
OTHER WHITE PIGMENTS
In coatings, only void hiding competes with TiO
2
. The clas-
sic white pigmentslithopone, zinc sulfide, zinc oxide, and
white leadare far less cost effective. White lead is also too
toxic. Pigmentary zinc oxide is still being used in paint, not
as a white pigment but as a mildewstat.
Extenderscolorless ground minerals and precipitated
particulatesare sometimes described as pigments and
are advocated as supplements for true white pigments.
31
Extenders are formulated into coatings to reduce costs by
replacing expensive polymer with cheaper mineral. Below
the critical pigment volume concentration, that is, in films
with excess polymer, extenders do not scatter light because
their refractive indices are too low. In films with excess
particulates (films above their critical pigment volume
concentration), extenders hide indirectly by creating pores.
Only in very porous films do extenders scatter light at the
particulate/air interface.
In colonial times, calcium carbonate (CaCO
3
) was used
as a white pigment. The pigment was made in situ by the
reaction of atmospheric carbon dioxide with whitewash,
a brushed-on slurry of calcium hydroxide. The pigment
was held together by minimal amounts of binder. Light was
scattered at the CaCO
3
/air interface. Because the service
life of the coating was minimal, whitewashing ceased when
wages increased with industrialization.
TABLE 3Commercial TiO
2
pigment grades
Product Type Intended PVC
a
Intended Gloss Intended Exposure Pigment Delivery Intended Dispersion
1 Low
b
Flashy
c
Indoors Dry High Shear
d
2 Low
b
Flashy
c
Indoors Slurry
e
Dispersed
3 Low
b
Flashy
c
Outdoors Dry High Shear
d
4 Low
b
Flashy
c
Outdoors Slurry
e
Dispersed
5 Low
b
Flashy
c
Extreme
f
Dry High Shear
d
6 Low
b
Flashy
c
Extreme
f
Slurry
e
Dispersed
7 Low
b
Discreet
g
Extreme
f
Dry Low Shear
h,i,j
8 Low
b
Discreet
g
Extreme
f
Slurry
e
Dispersed
9 Low
b
Discreet
g
Extreme
f
Dry Low Shear
h,i,j
10 Low
b
Discreet
g
Extreme
f
Slurry
e
Dispersed
11 Low
b
Discreet
g
Extreme
f
Dry Low Shear
h,i,j
12 Low
b
Discreet
g
Extreme
f
Slurry
e
Dispersed
13 High
k
Discreet
g
Indoors
l
Dry Low Shear
h,i,j
14 High
k
Discreet
g
Indoors
l
Slurry
e
Dispersed
a
Pigment volume concentration, pigments plus extenders, in the paint film.
b
Always below the critical pigment volume concentration.
c
Application for which gloss is maximized at direct or indirect expense.
d
Media mills and the like at moderate or low throughput, optimized mill base.
e
Aqueous slurries.
f
Including horizontal exposure to tropical and subtropical levels of ultraviolet radiation.
g
Gloss levels from flat through semi-gloss to high gloss but excluding extremely high gloss.
h
High shear is generally not required for less than extremes levels of gloss.
i
High speed dispersers and the like.
j
The film qualities of low-shear dispersion are generally not satisfactory for flashy finishes.
k
Above the critical particulate volume concentration.
l
Coatings above the critical pigment volume concentration are usually not suited for outdoors.
31
They do not impart black or white or a color to other materials,
thus they do not meet Websters defnition of a pigment.
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202 PAINT AND COATING TESTING MANUAL 15TH EDITION
Void Pigments
Air-filled voids in a paint film can either act as if they were
pigment particles or enhance the effectiveness of a true pig-
ment. Both mechanisms have been implemented in coatings.
Pigmentary and subpigmentary voids contribute to
hiding of all dry hiding paints films, that is, films starved
of binder. Somewhere above the critical pigment volume
concentration voids join into an interconnected network of
pores. The pores become stress concentrators that degrade
the mechanical qualities of the paint film. The network
conducts chemical contaminants into the paint film and
to the substrate, diminishing the chemical and protective
qualities of the film.
It is through the creation of pores that extenders con-
tribute to light scattering. This scattering comes at the
expense of film qualities. Problems can be avoided if the
voids are sealed and spherical.
Voids of pigmentary size scatter light like particles,
about as effectively as pigmentary zinc sulfide but not
nearly as well as TiO
2
pigment. Unlike interconnected pores
that degrade paint films, sealed spherical voids are not, per
se, detrimental to mechanical and chemical film qualities.
One commercial product, Rhopaque
, generated
pigment-sized air voids in paint films by evaporation of
droplets of an organic solvent emulsified in the paint. If the
voids are of subpigmentary size, small enough to lose their
individual optical identity, they do not scatter much light
but collectively decrease the refractive index of the matrix.
A composite refractive index of polymer and air takes the
place of the index of polymer alone. This decrease of matrix
refractive index has a potent effect on the scattering of any
true pigment present in the paint film.
A product composed of vesiculated and pigmented
polymer beads makes use of this effect. The product, Spin-
drift
where:
T
O) and imino (
aa SO
Berlin white
2 4
6 3 6
4 2 6 2 4 4
Fe NH Fe CN H SO FeNH Fe CN ( ) ( ) ( ) aClO
3
66
4 2 4 2
3 3 NaCl NH SO H O ( )
Differing grades of iron blue that offer varying depth of
hue, strength, oil absorption, and dispersion characteristics
exist. Chinese blue, for example, offers a greener undertone,
whereas bronze blue features a surface bronziness effect
that varies with a dependence on the viewing angle and film
thickness.
Iron blue offers good resistance to weak acids but
markedly poor resistance to even mild alkali; furthermore,
the pigment has a tendency to bleach out on storage, los-
ing almost all its color when incorporated into a paint for-
mulation that contains oxidizable vehicles such as linseed
oil. The pigment has only acceptable light fastness proper-
ties when used at masstone levels; extension of the paint
with a white, such as titanium dioxide, gives a weak blue
tint that will rapidly fade on exposure to the environment.
ULTRAMARINE BLUE
Pigment Blue 29, C. I. Number 77007, is a polysulfide of
sodium alumino silicate of unknown constitution. Going by
such varied common names as laundry blue, dolly blue, and
lapis lazuli, this pigment, which is made by the controlled
grinding of a mixture of calcined kaolin, soda ash, sulfur,
coal, and sodium sulfate, is Pigment Blue 29. Empirically
the product is Na
6
Al
6
Si
6
O
24
S
4
, and its major use is as a com-
ponent of laundry powders and detergent soaps. Metals such
as potassium, lithium, or silver may also be incorporated
into the structure. Less than 5 % of the production is used
in the coatings industry for interior emulsion paints that
require high alkali resistance and moderate light fastness.
Yellows
STRONTIUM YELLOW
Pigment Yellow 32, C. I. Number 77839, SrCrO
4
: Strontium
chromate is prepared by precipitating a suitably soluble
chromate with an appropriate strontium salt. Finding a
primary use in corrosion-inhibiting coatings, this pigment
has poor tint strength, low opacity, and unsatisfactory alkali
and acid resistance, which limits its more widespread use
in the coatings industry. Little of this pigment is now manu-
factured in the United States.
CHROME YELLOW
Pigment Yellow 34, C. I. Number 77600 and 77603, PbCrO
4
xPbSO
4
: A co-precipitate of lead sulfate and lead chromate,
Pigment Yellow 34 has the empirical formula PbCrO
4
x-
PbSO
4
. Various types exist that differ in the ratio of the
lead sulfate to lead chromate and as such are described
as medium chrome, primrose, and lemon chrome yellows.
Typically primrose chrome will contain 23 %30 % lead
sulfate in the solid solution of the co-precipitate, whereas a
medium chrome will contain 0 %6 % lead sulfate. During
manufacture, proprietary techniques are employed such
that the orthorhombic crystal form is produced almost
exclusively in preference to the unstable monoclinic form.
Many different grades of this type of pigment are avail-
able and they offer such improvements in properties as
better chemical resistance, decreased tendency to darken
on exposure, improved weathering, and as a silica-encapsu-
lated product to minimize solubility of the lead contained
within the pigment.
Primrose chrome exhibits a very green shade and offers
good light fastness, high opacity, and low rheology coupled
with economy of use. The coatings industry, closely followed
by the ink and plastics industry, is the largest consumer of
primrose chrome. Medium chrome is used widely in road-
marking paints in the United States where the law requires
a yellow marking line as opposed to white. Grades that
have been pre-darkened by the use of antimony during the
precipitation stage offer much increased stability to weath-
ering since these grades will not darken further on exposure
to sulfur in the atmosphere. Due to the concerns regarding
the toxicity of lead-based pigments and their persistence in
the environment, there has been a very significant move to
replace such pigments with organic equivalents that do not
contain lead [4]. The use of lead-based pigments, both yel-
lows and white, in architectural and decorative paints was
discontinued in the United States over 25 years ago.
ZINC CHROMATE
Pigment Yellow 36, C. I. Number 77955, 4ZnOK
2
O4CrO
3
3H
2
O: Also called zinc yellow, this pigment is identified as
Pigment Yellow 36, as opposed to the lithopone version
incorporating barium sulfate, which is Pigment Yellow 36:1
(C. I. No. 77956). It is a bright, green shade of yellow made
by the precipitation of hydrated zinc potassium chromate
from the reaction of sodium bichromate with zinc oxide
and potassium chloride. Used primarily in corrosion-
inhibiting coatings, its poor tinctorial strength and poor
resistance to acid and alkali severely limits this pigments
use elsewhere.
CADMIUM ZINC YELLOW
Pigment Yellow 35, C. I. Number 77205, CdSxZnS: Yet
another solid solution, cadmium zinc yellow is prepared
from a cadmium salt co-precipitated with zinc sulfide. Cal-
cination of this product gives pure cadmium zinc sulfide.
The hue of the pigment is readily altered by varying the
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CHAPTER 22 INORGANIC COLORED PIGMENTS 237
ratio of the two components of this solid solution. Levels of
zinc sulfide of 14 % to 21 % yield a green or primrose shade,
while 1 % to 7 % results in a redder shade that achieves a
golden hue. Incorporation of barium sulfate during manu-
facture produces a lithopone version, Pigment Yellow 35:1.
Cadmium zinc yellows offer bright, clean, opaque pig-
ments with excellent resistance to heat, light, and strong
solvents. Their poor fastness to mineral acids and marked
tendency to fade when used at low tint levels limits their use
within the coatings industry.
CADMIUM SULFIDE YELLOW
Pigment Yellow 37, C. I. Number 77199, CdS: Also known
as cadmium lemon yellow, this pigment is obtained by the
calcination of calcium sulfide. This color can be produced
with hues ranging from a green shade to a very red shade by
simply varying the calcination conditions. Offering excel-
lent stability to heat, light, acids, and alkali, this pigments
only major drawback is its tendency to fade in the presence
of moisture. A lithopone version exists, CdSxBaSO
4
. (C. I.
No. 77199.1), which is a primrose yellow shade.
IRON OXIDE YELLOWS
Pigment Yellow 42, C. I. Number 77492, FeO(OH) nH
2
O:
As with most of the commercially available iron oxides, this
pigment can also be obtained as the natural grade, Pigment
Yellow 43, also known as Mars yellow, or the synthetic
variant, Pigment Yellow 42, originally obtained from the
mineral goethite (hydrated iron oxide). Both opaque and
transparent grades are marketed.
The natural yellow oxides, FeOxH
2
O, will also contain
clay and various other minor minerals. Available under
several names, often related to the country of origin or the
pigments history, the natural yellow oxide is also called
Indian ochre, ocher, sienna, and limonite.
The synthetic oxide is produced by direct precipitation
using ammonium hydroxide and ferrous sulfate, via the
Penniman-Zoph process from scrap steel and a ferrous salt
to grow seed particles, or by the aniline process where nitro-
benzene is reacted with metallic iron to produce iron oxide
and aniline. The synthetic product has the empirical for-
mula Fe
2
O
3
xH
2
O, irrespective of the manufacturing process.
Iron oxide yellows are economical pigments with excel-
lent light fastness, weatherability, opacity, and flow proper-
ties. On the downside, they are dull in masstone and exhibit
only fair tinctorial strength and moderate baking stability
at best. It is their value in use that has resulted in their
widespread acceptance throughout the coatings industry.
BISMUTH VANADATE/MOLYBDATE YELLOW
Pigment Yellow 184, C. I. Number 771740, 4BiVO
4
3Bi
2
MoO
6
: The most modern of the inorganic pigments dis-
cussed in this section, Pigment Yellow 184, was introduced
into the marketplace in 1985. It is also know as bismuth
vanadate yellow and is manufactured by dissolving bismuth
nitrate, sodium vanadate, and sodium molybdate in nitric
acid followed by precipitation of a complex mixture of
the metals. The precipitate is calcined to give a poly crys-
talline product, 4BiVO
4
3Bi
2
MoO
6
. The product is a green
shade of yellow.
The pigment is used principally for brilliant solid
shades in both automotive and industrial coatings. It is
recommended for use in alkyd and acrylic paints, water-
based paints, nitrocellulose lacquers, and baking enamels.
The pigment has excellent weather fastness coupled with
good hiding power and gloss retention (light fastness).
Thermal stability is also good. The pigment has found use
in replacing lead-based pigments in such traditional colors
as school bus yellow as well as chrome and cadmium
pigments. Earlier grades suffered from the unusual phe-
nomenon where the color under shadows would darken
only to lighten again once the shadow was removed. This
photochromic effect has been investigated [5] and CIE
chromaticity diagrams were developed for changes of bis-
muth vanadate pigments under the influence of sunlight or
incandescent light. More stable grades of the pigment have
been introduced and these do not suffer this drawback.
Oranges
CHROME ORANGE
Pigment Orange 21, C. I. Number 77601, xPbCrO
4
yPbO:
A basic lead chromate also known as chrome orange, this
color is formed under alkaline conditions to give a product
of empirical formula xPbCrO
4
y PbO, shades varying from a
yellow to red shade dependant on the alkalinity maintained
during the reaction sequence [6].
As with all lead-containing pigments, the product will
darken on exposure to the atmosphere with the rate of
darkening dependant on the sulfur content of the air. The
pigment offers low cost, moderate light fastness, and finds
use in the protective coatings marketplace with some use
as a shading pigment for road traffic paints. Grades encap-
sulated within an amorphous silica structure that offer a
product that is environmentally safer due to the occlusion
of the lead within the silica shell [7].
CADMIUM ORANGE
Pigment Orange 20, C. I. Number 77202, CdSxCdSe: Cad-
mium orange, cadmium sulfoselenide orange, is a solid
solution produced by calcining cadmium selenide with cad-
mium sulfide at approximately 1000C (1800F). A change
in the ratio of the solid solution components gives pigments
that vary from bright yellow (PY 35) to bright red (PR 108).
Barium sulfate added or produced during the processing
will form the lithopone grade, Pigment Orange 20:1.
This pigment is used in industrial coatings, for color-
coding applications, in ceramics and where chemical and
heat resistance are principal end use requirements.
CADMIUM MERCURY ORANGE
Pigment Orange 23, C. I. Number 77201, CdSxHgS: This
pigment is a solid solution of mercury sulfide in cadmium
sulfide. Various hues can be obtained by controlling the
formation of the mixed crystal manufactured by precipitat-
ing the sulfides of cadmium and mercury from a solution of
their soluble salts. The final stage is calcination in an inert
atmosphere to give an extremely heat-stable pigment with
excellent chemical and weather resistance as well as sol-
vent fastness. Little of this pigment is manufactured in the
United States, and its use in paint and coatings is minimal
due to environmental concerns [8].
Greens
CHROME GREEN
Pigment Green 15, C. I. Number 77520, 77601, 77603: This
pigment, also known as Brunswick green, is merely a mix-
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238 PAINT AND COATING TESTING MANUAL 15TH EDITION
ture of a green shade chrome yellow (PY 34) and iron blue
(PB 27). As such, Pigment Green 15 offers a range of hues
with a light yellow shade to a deep dark shade, providing
good hiding, high tint strength, and moderate chemical
resistance at an economical price. It can be used for bake
enamels where the bake temperature does not exceed 148C
(300F), but is restricted to exterior and industrial coatings
applications as opposed to decorative finishes because of
its lead content.
CHROMIUM OXIDE GREEN
Pigment Green 17, C. I. Number 77288, Cr
2
O
3
: Chrome
oxide green is a pure, calcined chromium oxide, Cr
2
O
3
,
manufactured by reduction of sodium bichromate with
carbon or sulfur:
Na Cr O C CO Na CO Cr O
2 2 7 2 3 2 3
2
This pigment has a unique use in camouflage paints
because of its ability to reflect infrared light. Otherwise, the
product finds a use where its price can be justified by the
resultant excellent light and chemical resistance properties
the pigment features. Minor applications also exist in the
cosmetics industry and as a colorant for cement.
HYDRATED CHROMIUM OXIDE GREEN
Pigment Green 18, C. I. Number 77289, Cr
2
O(OH)
4
: Also
known as Viridian green or Guignets green, Pigment Green
18 is a hydrated chromic oxide of formula Cr
2
O
3
2H
2
O
from the hydrolysis of the product produced by calcining
sodium bichromate with boric acid. The pigment is an
intense, bright, blue shade of green with outstanding fast-
ness properties in both masstone and deep tints.
Browns
NATURAL IRON OXIDES
A natural product obtained from either iron oxide mines
operating principally to supply ore as feedstock for blast fur-
naces with a small off-take directed to the pigment industry
or pigment mines, which operate solely to supply pigment
grade ore. Typically the mined ore is slurried in an aqueous
suspension and washed through a series of stages to remove
sand and clay after which the slurry passes into a separator
tank, then through a Dorr bowl rake where the iron oxide
ore is separated and dried as a thin layer on a rotary drum
drier. The dried natural ore is pulverized and classified to
produce pigmentary iron oxide. Pigment Brown 7 is an iron
oxide brown that is available in shades ranging from light
red to deep purple brown. Empirically the product is Fe
2
O
3
.
Metallic brown is produced from calcined hematite (PR
102) and burnt sienna from calcined limonite (PY 43).
Pigment Brown 7:x is a ferrosoferric oxide derived
from ores containing 25 % manganese dioxide with a dis-
tinct composition as Fe
2
O
3
xMnO with varying proportions
of clay. Classical names include such as raw umber, burnt
umber, raw sienna, burnt sienna, and Turkish umber.
SYNTHETIC BROWN OXIDES
Pigment Brown 6, C. I. Number 77491, 77492, 77499:
Also known as brown magnetite iron oxide, Pigment
Brown 6 is produced by controlled oxidation of Pigment
Black 11. Chemically the product may be represented as
Fe
2
O
3
xFeOyH
2
O.
Pigment Brown 11 (C. I. No.77495) is magnesium fer-
rite from the calcination of a blend of ferric and magnesium
oxides, MgO Fe
2
O
3
.
The volume of all types of brown oxides used in coat-
ings is generally low, since most browns are achieved by
mixing yellow, red, and black pigments. As a class, these
pigments have good chemical resistance and high tint
strength and as such find some use in wood stains and
furniture finishes. Minor applications also exist in the
field of colorants for cosmetics and for the coloration of
cement.
References
[1] Wright, P., Thomas, D., and McKenna, M. F., Transparent
Iron Oxide Pigments for Automotive Applications, Inorg. Col-
ored Pigm., Vol. 18, No. 5, 2002, pp. 46, 4849.
[2] Wright, P., and McKenna, M. F., Using Transparent Iron
Oxide Pigments in Wood Finish Applications, Inorg. Colored
Pigm., Vol. 16, No. 11, 2000, pp. 4454.
[3] Pitzer, U., Lerch, K., and Baubaum, G., Transparent Iron
Oxide Pigments, Processes for Their Production and Their
Use, U.S. Patent No. 5,368,640 (1994).
[4] Gosselin, R. E., Smith, R. P., Hodge, H. C., and Braddock, J.
E., Clinical Toxicology of Commercial Products, 5th ed., Wil-
liams and Wilkins, Baltimore, 1984, p.VI 172.
[5] Tucks, A., and Beck, H. P., The Photochromic Effect of Bis-
muth Vanadate Pigments. Part I: Synthesis, Characterization,
and Lightfastness of Pigment Coatings, J. Solid State Chem.,
Vol. 178, No. 4, 2005, pp. 11451156.
[6] Raw Materials Data Handbook, J. M. Fetsko, Ed., Pigments,
National Printing Ink Research Institute, Lehigh University,
Bethlehem, PA, Vol. 4, 1983.
[7] Pigment Handbook, 2nd ed., P. A. Lewis, Ed., John Wiley,
New York, 1988; Vol. I; Coatings Technology Handbook,
D. Satas, Ed., Marcel Dekker, Inc., New York, 1991, p. 62.
[8] Anon, Golden Artist Colors, Pigment Identification Chart,
www.goldenpaints.com, then click Research/Support and
then Pigment Identification Chart.
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239
CERAMIC PIGMENTS ARE COMPLEX MIXTURES of
oxygen-containing materials that have been calcined at
high temperatures to form specific crystalline phases [1].
In most cases, oxide raw materials are carefully mixed and
then calcined in either batch kilns or continuous calciners
[2]. After calcination, they are ground to the necessary fine-
ness in mills. Micronizers and/or jet mills are used to break
agglomerates. The final production step involves careful
control of the color tone.
Because these pigments are formed at high tempera-
tures, they generally offer superb thermal stability and are
relatively inert. This results in excellent weathering and
light fastness properties. Most of these pigments have supe-
rior acid and alkali resistance. They are nonmigrating and
nonbleeding in nature and do not interact with polymer
systems [3].
The principal disadvantage of ceramic pigments is
their low tinting strength. In addition, some are relatively
high in cost. This is particularly true with cobalt-containing
pigments. Some of these pigments are difficult to dis-
perse. However, the recent development of easily dispersed
ceramic pigments should eliminate this problem. A final
concern is the inherent hardness of these pigments. Their
hardness can lead to processing system damage through
abrasion. When using ceramic pigments, processing sys-
tem components designed for use with abrasive materials
should be considered.
The major use of ceramic pigments is for applications
such as vinyl siding, automotive paints, coil coating, and
high-temperature systems where the product is thermally
cured and then placed in an outdoor setting.
CERAMIC PIGMENTS USED IN ORGANIC PAINTS
The major criterion used in selecting ceramic pigments
for organic paints is hardness. The pigments listed in
Table 1 and discussed below are those that can be used
in paint processing equipment without causing excessive
wear. Property attributes of the pigments are given in
Table2. All are compatible with most polymer systems, with
manganese-doped rutile especially useful when it is neces-
sary to avoid iron.
Nickel-doped rutile, which is often called sun yellow, is
produced from a mixture of various amounts of titanium
(IV) oxide, nickel (II) oxide, and antimony (V) oxide by
high-temperature calcination [1]. The result is formation
of a crystalline matrix of rutile that has the basic chemi-
cal formula (Ti,Ni,Sb)O
2
. The pigment is used for coloring
high-performance industrial coatings, wire coatings, vinyl
sidings, automotive and other exterior paints, as well as for
roofing, granules, porcelain enamels, and ceramic bodies.
Chrome-doped rutile is prepared from a mixture of
varying amounts of titanium (IV) oxide, chrome (III) oxide,
and antimony (V) oxide by high-temperature calcination
[1]. The resultant crystalline rutile matrix has the basic
chemical formula (Ti,Cr,Sb)O
2
. The orange-yellow pigment
is used for coloring the same systems as nickel-doped rutile.
Manganese-doped rutile is prepared from a mixture
of various amounts of titanium (IV) oxide, manganese (II)
oxide, and antimony (V) oxide by high-temperature calcina-
tion [1]. The resulting crystalline rutile matrix has the basic
chemical formula (Ti,Mn,Sb)O
2
. The brown pigment is used
for coloring the same systems as nickel-doped rutile.
Spinel brown pigments are an example of the 2-4
inverse spinels [4]. The basic pigment is prepared by a high-
temperature calcination of titanium (IV) oxide and iron (II)
oxide [1]. The resulting crystalline matrix of spinel is brown
in color and has the basic chemical formula Fe
2
TiO
4
. The
spinel phase permits extensive substitution, within defined
limits, with other compounds to provide a variety of shades
of brown. Modifiers used for substitution include Al
2
O
3
,
CoO, Cr
2
O
3
, Fe
2
O
3
, MnO, and ZnO. The pigments are used
for coloring high-performance industrial coatings, wire
coatings, vinyl sidings, and automotive and other high-
quality exterior paints.
Titanate green and blue-green pigments are also pro-
duced by high-temperature calcination of mixtures of
titanium (IV) oxide, cobalt (II) oxide, nickel (II) oxide, and
zinc (II) oxide to form a crystalline matrix of inverse spinel
[1]. The pigments have the basic chemical formula (Co, Ni,
Zn)
2
TiO
4
. The pigments are used for coloring the same sys-
tems as the spinel brown pigments.
Cobalt blue pigments are crystalline spinels formed by
high-temperature calcination of cobalt (II) oxide and alu-
minum (III) oxide in varying amounts [1]. The basic cobalt
blue pigment (CAS 68186-86-7) has the chemical structure
CoAl
2
O
4
. The lighter-colored cobalt blue is prepared by addi-
tion of zinc (II) oxide to the ingredients used for the basic
pigment. The chemical structure of the resultant material
(CAS 68186-87-8) is (Co,Zn)Al
2
O
4
. Blue-green shades are
produced by introduction of chromium (III) oxide, partially
replacing aluminum (III) oxide in the basic cobalt blue sys-
tem. It has the chemical formula Co(Al, Cr)
2
O
4
. In addition
to being used to color the same systems as the rutiles, the
cobalt blues are used in ceramic glazes.
Cobalt phosphate violet is prepared by high-temperature
calcination of cobalt (II) oxide and phosphorus (V) oxide
23
Ceramic Pigments
Richard A. Eppler
1
1
Eppler Associates, 400 Cedar Lane, Cheshire, CT 06410.
MNL17-EB/Jan. 2012
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240 PAINT AND COATING TESTING MANUAL 15TH EDITION
to form a crystalline phosphate [1]. It has the formula
Co
3
(PO
4
)2. It is used for coloring the same systems as the
spinels and in printing inks. Manganophosphate violet
is produced by a precipitation process from ammonium
salts of manganese (III) and phosphorus (V) [3]. This pig-
ment has the chemical formula NH
4
MnP
2
O
4
. It is used for
inks and other applications where heat stability is of less
importance.
One ceramic black is a jet black powder produced by
calcination of mixtures of copper (II) oxide and chromium
(III) oxide to form a crystalline spinel [1]. The basic jet
black has the formula CuCr
2
O
4
. A marginally stronger black
is produced by a high-temperature calcination of cobalt (II)
oxide, iron (III) oxide, and chromium (III) oxide in varying
amounts, also to form a spinel. The product has the chemi-
cal formula (Co, Fe)(Fe, Cr)
2
O
4
. The ceramic blacks are
used in the same systems as the above-described rutiles.
Like most pigments, ceramic pigments are manufac-
tured to have a suitable particle size for incorporation
into the coating, but when a paint manufacturer receives
them in bags of dry material, the particles generally
have agglomerated or have absorbed moisture [5]. They
are stuck together in groups by this layer of water or
absorbed air. Hence, in the dispersing process, these lay-
ers must be destroyed and the primary particles dispersed
in the paint.
There are a number of wetting and dispersing agents
that can be added to a paint [5]. Discussion of this topic will
TABLE 1Recommended ceramic pigments for use in organic paints
Ceramic Pigment Pigment Powder Color Color Index/Name CAS Number
Nickel-doped rutile Yellow 77788/Pigment Yellow 53 71077-18-4
Chrome-doped rutile Orange-yellow or maple 77310/Pigment Brown 24 68186-90-3
Manganese-doped rutile Brown 77899/Pigment Yellow 164 68412-38-4
Spinel brown Brown 77543/Pigment Black 12 68187-02-0
Titanate greens and bluegreens Green 77377/Pigment Green 50 68186-85-6
Cobalt blue Blue (basic) 77346/Pigment Blue 28 68186-86-7
Cobalt-zinc blue Blue (lighter than basic) 77347/Pigment Blue 72 68186-87-8
Cobalt chromite blue Blue-green 77343/Pigment Blue 36 68187-11-1
Cobalt phosphate violet Purple 77360/Pigment Violet 14134 13455-36-2
Manganophosphate violet Purple ... 10101-66-3
Ceramic black Jet black 77428/Pigment Black 28 68186-91-4
Ceramic black Jet black 66502/Pigment Black 27 68186-97-0
TABLE 2Properties of recommended ceramic pigments (see Table 1 for color and pigment
reference numbers)
Ceramic Pigment Heat Stability
Weathering
Properties Light Fastness
Acid/Alkali
Resistance
Hydrolytically
Stable
Nonmigrating/
Bleed
Nickel-doped rutile High Excellent Excellent Excellent Yes Yes
Chrome-doped rutile High
*
Excellent Excellent Excellent Yes Yes
Manganese-doped rutile High Excellent Excellent Excellent Yes Yes
Spinel brown High Excellent Excellent Good Yes Yes
Titanate greens and
bluegreens
High Excellent Excellent Excellent Yes Yes
Cobalt blue-basic High Excellent Excellent Excellent Yes Yes
Cobalt zinc blue High Excellent Excellent Excellent Yes Yes
Cobalt chromite blue High Excellent Excellent Excellent Yes Yes
Cobalt phosphate violet High Excellent Excellent Excellent No Yes
Manganophosphate violet High Excellent Excellent ...
a
No Yes
Ceramic jet black High Excellent Excellent Excellent Yes Yes
Ceramic Jet black-stronger High Excellent Excellent Excellent Yes Yes
a
Manganophosphate violet has good acid resistance, but poor alkali resistance.
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CHAPTER 23 CERAMIC PIGMENTS 241
be found elsewhere in this manual. However, one important
additional factor should be noted. Most ceramic pigment
manufacturers today offer a line of easily dispersed pig-
ments. These products are formulated with a proprietary dis-
persant. Adding the dispersant to the pigment itself promotes
optimum contact between the dispersant and the pigment.
TESTING OF CERAMIC PIGMENTS
Ceramic pigments are usually tested for two important
properties: particle size and tinting strength. Hardness is
essentially a property of the pigment crystal produced and
is insensitive to production details. Hence, handbook values
for the crystal are usually adequate for most purposes.
There are three aspects of particle size to be consid-
ered: (1) the particle-size distribution, (2) the concentra-
tion of coarse particles, and (3) the particle shape as it
affects the formulation of the paint. The measurement and
reporting of particle-size distribution of pigments in paints
is contained in ASTM Practice for Reporting Particle Size
Characteristics of Pigments (D1366) [6]. The practice cov-
ers measurements by microscopic techniques, sedimenta-
tion methods, turbidimetric methods, absorption, and
permeability methods.
The recent laser dispersion and electric sensing zone
techniques are not yet dealt with in this standard. The pro-
cedures described in ASTM Test Method for Particle Size
Distribution of Alumina or Quartz by Electric Sensing Zone
Techniques (C690) and ASTM Test Method for Determining
Particle Size Distribution of Alumina or Quartz by Laser
Light Scattering (C1070) should be applicable to ceramic
pigments [7].
Determination of the concentration of coarse particles
that may cause defects in a coating is covered by ASTM Test
Methods for Coarse Particles in Pigments (Dl85) [6].
The amount of pigment that may be added to a paint
formulation is a strong function of the shape of the pigment
particles. Higher loadings are possible for pseudo-spherical
particles than is possible with plate-like particles. This
property of a pigment is measured by determining the
oil absorption characteristics of the pigment as described
in ASTM Test Method for Oil Absorption of Pigments by
Spatula Rub-out (D281) [8].
Tinting strength is the other important characteristic
that needs to be evaluated. The determination of the color
of a pigment requires that it be dispersed into a medium
similar to that in which it is to be used. It is never accept-
able to imply application color from the color of a dry pig-
ment. The techniques for dispersing a pigment in a suitable
vehicle and then measuring the color in both masstone
and letdown are detailed in ASTM Test Method for Color
and Strength of Color Pigments with a Mechanical Muller
(D387) [8].
References
[1] DCMA Classification and Chemical Description of the Mixed
Metal Oxide Inorganic Colored Pigments, 2nd ed., Dry Color
Manufacturers Association, Arlington, VA, 1982.
[2] Eppler, R. A., Ceramic Colorants, Ullmanns Encyclopedia
of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Wein-
heim, Germany, Vol. A5, 1986.
[3] Product literature from Shepherd Color Company, Cincinnati,
OH.
[4] Muller, O., and Roy, R., The Major Ternary Structural Families,
Springer Verlag, Berlin, 1974.
[5] Handbook of Coatings Additives, L. J. Calbo, Ed., Marcel
Dekker, Inc., New York, 1987, pp. 511539.
[6] Part 6.03: Pigments, Drying Oils, Polymers, Resins, Naval
Ores, Cellulosic Esters, and Ink Vehicles, ASTM Annual Book
of Standards, ASTM International, West Conshohocken, PA,
2009.
[7] Part 15.02 Glass, Ceramic Whitewares, ASTM Annual Book
of Standards, ASTM International, West Conshohocken, PA,
2009.
[8] Part 6.01, Tests for Chemical, Physical, and Optical Proper-
ties, ASTM Annual Book of Standards, ASTM International,
West Conshohocken, PA, 2009.
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242
PREFACE
IN PREPARATION OF THIS CHAPTER, THE CONTENTS
of the 14th edition were drawn upon. The author acknowl-
edges the author of the 14th edition, Henry P. Ralston. The
current edition will review and update the topics addressed
by the previous author, introduce new technology that has
been developed, and include up-to-date references.
INTRODUCTION
Coating formulators use extender pigments to reduce the
raw material cost of a coating formulation and to improve
coating performance. Extender pigments are relatively
inexpensive compared to titanium dioxide or color pig-
ments and are easily incorporated into a coating. Most are
white or near-white inorganic minerals, beneficiated to
varying degrees, with a coarser particle size and lower oil
absorption (binder demand) than primary pigments.
Extender pigments include inexpensive fillers, such as
coarse calcium carbonate, which are used to reduce cost
by filling coating volume with minimal impact on perfor-
mance. Very fine particle size silicates, particularly certain
kaolins and ultrafine talcs, can enhance coating perfor-
mance and provide very favorable economics by effectively
separating the individual pigment particles, optimizing the
opacifying effect.
The industrial mineral extenderswollastonite, talc,
mica, kaolin, feldspar, and nepheline syeniteare used as
functional fillers, chosen for specific features that improve
coating performance, such as better durability, coating
stability, rheology, and dry film properties. These effects of
the silicates on coatings are a consequence of (a) the min-
erals structure, which influences the particle shape, (b) the
volume fraction of the mineral in the coating film, which is
affected by the particle shape and size, and (c) the minerals
compatibility with the binder matrix, which depends on the
particle physical and surface chemical properties.
Some of these properties are derived from the unique
platy particle shape of talc, kaolin, or mica, or the acicu-
lar particle shape of wollastonite. Platy extenders tend to
enhance the mechanical properties of the film by lateral
reinforcement. They also minimize internal stress by allow-
ing better stress dissipation along the plane of the pigment.
When oriented parallel to the substrate, they reduce the
porosity of the film, sealing it. Acicular particles reinforce
the film, by preventing cracking and increasing tensile
strength.
While extender pigments can vary in form and use, the
added value delivered to the coatings formulator remains
[13].
CALCIUM CARBONATE
Description
Calcium carbonate, also known as calcite, whiting, or
limestone, has the chemical formula CaCO
3
. It is produced
by dry or wet grinding of marble or calcite ores, or by pre-
cipitation via carbonization of slaked lime. Product from
ground limestone is dependent upon both the initial crude
mineral and the subsequent degree of processing or ben-
eficiation. The ore is crushed and milled; the dry ground
product is air classified to different particle-size fractions.
Wet ground product is milled as a slurry, undergoes flota-
tion to remove impurities, and is then filtered and dried.
The proximity of the supplier to the customer is a major
consideration, as transportation is a significant portion of
the cost of the material.
Precipitated calcium carbonate is produced by heat-
ing natural limestone to form calcium oxide, which is then
slaked in water and reacted with carbon dioxide to form a
low-solids slurry. The precipitate is vacuum filtered, dried,
and ground. Both particle shape and size of precipitated
grades can be carefully controlled by altering reaction con-
ditions to yield effective extender pigments.
Calcium carbonate is used primarily as an inexpen-
sive filler material. However, fine-particle-size precipitated
grades and fine-ground limestones may have some value
as an extender pigment to lower titania or color pigment
concentration [1,4,5].
Physical Properties
Calcium carbonate products are differentiated by physical
properties, such as particle size, brightness, residue, and, for
precipitated grades, oil absorption. Fine-particle-size prod-
ucts have an average particle size of from less than 1 to about
4 m with coarse-particle-size grades ranging up to about
15m. Most calcium carbonates are high in brightness, rang-
ing from 90 to 98, with a pH of 910. Ground carbonates have
low oil absorption, which correlates with low resin demand
in coatings. The finer grades may be modestly higher.
Coatings Performance
Calcium carbonate is widely used in water-based trade
sales architectural coatings since it is less expensive than
titanium dioxide, a primary pigment in paints and coat-
ings, and significantly lowers raw material cost. Fine-
particle-size calcium carbonate functions as an extender
by spacing titanium dioxide and maintaining or improv-
ing optical properties of the dry coating film at lower
titanium dioxide levels. Higher-oil-absorption (binder
demand) precipitated grades may contribute to opacity.
24
Extender Pigments
Richard A. Eppler
1
1
President/Owner, Eppler Associates, 400 Cedar Lane, Cheshire, CT 06410.
MNL17-EB/Jan. 2012
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CHAPTER 24 EXTENDER PIGMENTS 243
Finer-particle-size grades tend to develop high gloss and
high brightness, which can have a positive effect on the
color of the coating.
Coarser grades of calcium carbonate are primarily used
as fillers to reduce cost but also contribute to flatting and
enhance low sheen control. Some grades may cause frost-
ing and chalking in exterior applications.
KAOLIN
Description
Kaolin, also known as china clay, is an aluminum silicate
with the chemical formula Al
2
O
3
2SiO
2
2H
2
O, which is com-
mercially available in both hydrous and calcined (anhy-
drous) forms. Domestic deposits occur primarily along the
fall line in South Carolina and Georgia. It has a platy particle
shape with finer particles present as individual platelets and
coarse particles present as stacks of platelets or booklets.
The hydrous form is produced by air flotation or water
washing. Air-floated grades are crushed and ground to a
specific particle size and air-classified. This process is very
dependent on the initial ore deposit.
Water washing involves processing the mineral in an
aqueous slurry and separating particles of different size,
which can then be recombined to yield products with con-
trolled particle-size distribution. These products can also be
further beneficiated by bleaching, ozonation, high-intensity
magnetic separation, or chemical flotation to remove
impurities and improve color. Some grades are subjected
to a delaminating process that physically separates coarse
platelets from one another.
Water washing offers a more carefully controlled prod-
uct available in either slurry or dried form. Predispersed
spray-dried beads offer ease of handling and are suitable
for water-based coating systems. Pulverized acid grades are
recommended for solvent-based coatings.
Calcined (anhydrous) forms are produced by subject-
ing water washed and bleached kaolin to thermal treat-
ment. Low temperature calcination (650700C) removes
structural hydroxyl, forming amorphous metakaolin. Spe-
cific gravity is decreased, while hardness and porosity are
increased. When added to a coating, they promote trapping
of air pockets, improving the opacity of the coating, prob-
ably by lowering the refractive index of the matrix. Fully
calcined clays (10001150C) are transformed into mullite,
with increased hardness and specific gravity.
Physical Properties
Kaolins are also differentiated by properties such as particle
size, brightness, residue, and oil absorption. Because of
kaolins effect upon the optical properties of coatings, they
are offered in more varieties than are other functional fill-
ers. Hydrous kaolins have an average particle size ranging
from an extremely fine 0.2 up to 5 m depending on the
product. Dry brightness ranges from 85 % to 90 %, and most
water-washed grades are very low in residue. Acid grades
have a pH of 45, while predispersed grades are 67. Kaolins
are chemically inert. Water-washed grades are lower in
impurities such as soluble salts than are air-float grades.
Calcined grades range from below 1 to 2.5 m in aver-
age particle size and are usually higher in brightness and
hardness than hydrous grades. These grades have a more
irregular particle shape and higher oil absorption than the
hydrous grades.
Coatings Performance
Fine particle-size hydrous kaolins are commonly used
in latex and alkyd trade sales paint. Finer particle size
improves opacity and allows for cost reduction by extend-
ing/reducing the amount of titanium dioxide. Finer particle-
size products also develop higher gloss and are particularly
useful in enamels and semigloss formulations. Chemically
modified hydrous kaolins are effective in high-solids and
water-reducible industrial coatings.
Delaminated grades also develop good opacity, and the
platy particle shape improves barrier resistance and film
integrity. Delaminated grades or coarser hydrous grades
are more suitable for interior wall paints and exterior trade
sales formulations and exhibit more controlled chalking
and better overall durability. Air-floated grades are not used
significantly in coatings because the higher water-soluble
salt content can cause viscosity instability.
Calcined kaolins are widely used in interior latex and
alkyd trade sales flats to develop dry hiding and reduce
cost at lower titanium dioxide levels. Dry hiding is due to
the higher oil absorption (binder demand) of the calcined
grades, resulting in more air/pigment and air/binder inter-
faces in the dry paint film. These grades develop good flat-
ting, and the harder calcined particles also improve scrub
resistance in interior latex coatings [1,6,7].
TALC
Description
Talc (also known as soapstone) is a hydrated magnesium alu-
minum silicate with the chemical formula 3MgO4SiO
2
H
2
O.
Deposits are found domestically in New York, Vermont,
Montana, Texas, and California. Talc varies widely in purity
depending on its source and may also contain dolomite,
limestone, and silica, among others. Western talcs are highly
platy, while eastern talcs have an acicular particle shape, and
often contain substantial quantity of tremolite and other ser-
pentine minerals. Both dry and wet grinding techniques are
used in its beneficiation. Ore flotation processes are used to
produce high-quality products. Dry processing includes use
of jaw crushers, Raymond mills, and cyclones. Advanced
milling technologies eliminate oversized particles.
Physical Properties
Key properties for talc include composition, color, particle
size, water solubility, and oil absorption. Some grades are
available with an average particle size of 13 m, but most
are around 515 m. It is unique in its softness (Moh hard-
ness 12) and lubricity. Brightness ranges from 70 to 85
for inexpensive grades and 87 to 92 for premium grades.
Oil absorption depends on particle shape and size but
in general fits in between calcium carbonate and kaolin.
Slurry pH is basic at 910. Talcs are hydrophobic and
organophilic.
Coatings Performance
Talcs are used in many different types of coatings includ-
ing interior and exterior trade sales paints, primers, traf-
fic paints, and industrial coatings. Western platy talcs
develop good flatting and provide good chemical and water
resistance due to high-purity and low-soluble calcium.
These are best for sanding primers because of softness and
good sealing properties, while coarse grades help develop
surface roughness (tooth). Platy talcs have good flow
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244 PAINT AND COATING TESTING MANUAL 15TH EDITION
properties and improve barrier resistance and durability
in exterior trade sales paints and enamel hold-out in inte-
rior applications. Talcs also enhance durability of traffic
paints. Eastern acicular talcs have better color and develop
lower viscosity at high loadings due to lower oil absorption
[1,5,8].
SILICA
Description
Silica is a general term describing products with the chemi-
cal formula SiO
2
of which both natural and synthetic types
are available. Those most widely used in paint and coat-
ings are crystalline, microcrystalline, diatomaceous, pre-
cipitated, and fumed. They differ in method of production,
physical properties, and function.
Crystalline silica is produced by crushing, grinding, and
classifying quartz. Microcrystalline differs from crystalline
in that its deposits, found principally in Arkansas, have a
higher concentration of fine particles. It is produced in a
similar manner as crystalline, but the ore is finer in par-
ticle size. Both are decreasing in usage because of reported
health and safety issues related to crystalline silica.
Diatomaceous silica, also known as diatomaceous
earth or simply diatomite, consists of the skeletal remains
of single-celled aquatic plants called diatoms. Domestic
deposits are located in California, Nevada, and Washington.
The ore is crushed, milled, dried, and air-classified. Cal-
cined grades are processed in high-temperature rotary kilns
to remove organics and separated into selected particle size
ranges by air classification. These products have superior
color and are preferred for coatings applications.
Synthetic silicas are produced by a number of differ-
ing chemical and thermal processes. Precipitated silica is
produced by acidification of sodium silicate in water solu-
tion, to form aggregates of ultra-fine particles. Aggregate
size and degree of structuring are controlled by reaction
conditions. Fumed silica, produced via high temperature
hydrolysis of silicon tetrachloride with hydrogen, also
exists in aggregates of ultra-fine particles, and particle size
and surface area are also dependent on reaction conditions.
It is more expensive than precipitated silica to produce.
Physical Properties
The several silica products are the optimum solution for
chemical resistance in service. Since processing of crystal-
line silica is essentially a size reduction operation, particle
size and particle-size distribution are the primary means of
differentiating products. Crystalline silicas range from 2to
10 m average particle size. They are low in oil absorp-
tion, providing inertness and durability. Microcrystalline
grades are easier to disperse and are less abrasive than
crystalline grades. Brightness is from 85 % to 90 % and
pH from 6 to 7. Oil absorption is intermediate between
calcium carbonate and hydrous kaolins. These extenders
are translucent and do not contribute to hiding as do some
calcium carbonates and kaolin. Crystalline silica (quartz)
has been identified as a carcinogen, limiting its use in
some applications.
Diatomaceous silica is a very high oil absorption mate-
rial found in aggregates ranging in mean particle size of
2to 20 m. They often contain up to 30 % organic material.
Calcined grades are more porous and have a brightness of
87 % to 90 %.
The synthetic silicas are differentiated by surface area
and particle size. Surface area of precipitated types is about
60300 m
2
/g, while fumed silica ranges from 50 to 400 m
2
/g.
Ultimate particle size of the individual particles are less
than 0.1 m for both; however, precipitated grades may
develop larger aggregates. Fumed silica has a pH of 34,
and precipitated silica has a pH of 68. These grades are
often made hydrophobic by reaction with organofunctional
silanes to improve performance in coatings. They are essen-
tially amorphous so they will not cause silicosis.
Coatings Performance
Crystalline silica is used in trade sales, industrial coatings,
and primers. It is an inexpensive extender that contributes
to low sheen control, burnish resistance, and durability
with minimal impact on rheology in latex trade sales paints.
It is also used in powder coatings where its low binder
demand does not affect flow properties.
Diatomaceous silica is primarily used as an inexpen-
sive flatting agent in latex trade sales paints because of
its high binder demand. Precipitated silicas are used as
flatting agents in solvent-based industrial coatings. Fumed
grades, more expensive than precipitated because of high-
energy requirements during production, are used as rhe-
ology modifiers and flatting agents in industrial coatings
[1,3,5,9].
MICA
Description
Mica is a family of hydrous aluminum potassium silicates
of which one, muscovite, has the chemical formula K
2
O
3Al
2
O
3
6SiO
2
2H
2
O. Micas are best known for a very platy
particle shape and high aspect ratio. These are coarser in
particle size than most extenders. Higher-aspect-ratio micas
are produced by frictional wet grinding. Dry processing in
high-pressure air jets to both delaminate and reduce the
particles results in lower-aspect-ratio mica.
Physical Properties
Most coating grades of mica have an average particle size
of 5 to 50 m. Residue of 325 mesh varies from less than
1 to as high as 50 %, depending on the particle size of the
product. Brightness ranges from 65 % to 80 %, low com-
pared to other extenders, while pH is 78. Oil absorption is
higher than other hydrous minerals and is closer to coarse-
calcined kaolins.
Coatings Performance
Mica is best known for its very platy particle shape, which
forms layers parallel to the paint film. Mica reinforcement
increases durability and resistance to moisture penetration,
corrosion, checking, heat, and chemicals. It helps prevent
cracking in exterior architectural coatings and traffic paint.
It prevents cracking and sagging in textured coatings. Mica
provides good barrier resistance in primers and roof coat-
ings. Its platy particle shape, however, limits loading levels
due to rheology constraints [10].
WOLLASTONITE
Description
Wollastonite is a calcium metasilicate with the chemical
formula CaOSiO
2
of which the primary domestic source
is New York. It has an acicular particle shape, is white in
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CHAPTER 24 EXTENDER PIGMENTS 245
color, and is alkaline in pH. It is beneficiated by wet pro-
cessing and/or high-intensity magnetic separation. Powder
grades are milled in inpact mills to a low aspect ratio (3:1 to
5:1) and top particle sizes 325 mesh to 10 m. High aspect
ratio (HAR) grades are carefully attrition milled to yield
aspect ratios of 12:1 to 20:1. Needle lengths range from 200
to 20 m micrometers.
Both powder and HAR grades of wollastonite are avail-
able with organosilane treatments for compatibility with
organic coatings. They are blended wet, and then dried.
Properties
Typical coating grades range from 2 to 10 m in mean par-
ticle size. More important is the aspect ratio, as discussed
in the last paragraph. Brightness ranges from 80 % to 95 %,
and pH is 910. Wollastonite exhibits moderate hardness
for scrub resistance, and moderate oil absorption relative to
its non-spherical shape. Its acicular particle shape provides
some reinforcement in coatings; and the high pH is effec-
tive in buffering latex systems. Surface-modified grades
improve performance in industrial coatings by reducing
resin demand and improving bonding between the mineral
and resin.
Coatings Performance
In addition to their use for corrosion control, high white-
ness powder grades of wollastonite are used in archi-
tectural, industrial, and marine coatings to ensure film
integrity in service. HAR wollastonite grades are used
in asphalt coatings, coal tar coatings, texture coatings,
and block fillers for mechanical strength and durability.
Wollastonite is used in epoxy powder coatings due to its
low binder demand and water resistance. Adhesion, chip
resistance, and thermal stability are benefits of using wol-
lastonite. Coarser acicular grades are used in primers for a
micro-textured surface [11].
FELDSPAR AND NEPHELINE SYENITE
Description
Feldspars are the most widespread mineral group, compris-
ing about 60 % of the Earths crust. They are commonly
differentiated according to the dominant alkali, although
most contain both soda and potash. Commercial feldspars
are produced by flotation and magnetic separation fol-
lowed by milling. Air classification is used for the finest
grades.
Nepheline syenite is a rock composed of sodium and
potassium feldspars and nepheline. It can form only in a
geologic environment deficient in silica. In Canada, typical
nepheline syenite is approximately 25 % nepheline, 55 %
sodium feldspar, and 20 % potash feldspar, yielding a nomi-
nal chemical formula K
2
O3Na
2
O4.5Al
2
O
3
20SiO
2
. It is pro-
duced by crushing, dry magnetic separation, and milling.
Properties
Milled feldspars and nepheline syenite crystalize as angular
nodular particles, leading to low surface area, easy disper-
sion, and low vehicle demand. High loadings are possible.
The particles interlock to improve the durability of the
coating film, conferring crack resistance, high hardness,
abrasion, and scrub resistance. They have high brightness
(95 %98 %) and are relatively coarse in particle size (2 to
16 m).
Coatings Performance
The low binder demand of these materials make them par-
ticularly effective in exterior trade sales and architectural
coatings. Their very low tint strength make them useful
for deep-tone and pastel colors with minimum colorant.
They provide good tint retention and prevent checking and
cracking in exterior paints and also develop good scrub
resistance in interior latex paints. They are the closest
replacement for crystalline silica when toxicity concerns
are raised.
Nepheline syenite is often favored over feldspar
because it is silica-free. However, in acidic environments,
such as acid rain, the durability of coatings using feldspar
is superior [12].
BARIUM SULFATE
Description
Barium sulfate (BaSO
4
) is available as barytes, its naturally
occurring form, or as blanc fixe, a synthetic precipitate. Bary-
tes has a nodular particle shape with deposits found predom-
inantly in Nevada, Georgia, Missouri, Montana, Tennessee,
Illinois, and Washington. The ore is beneficiated by flotation
techniques and then wet ground to obtain the required par-
ticle size and bleached to improve color. Some higher quality
ores are dry ground and air classified. Blanc fixe is a very
white, fine-particle-size extender not as widely used in paints
and coatings as barytes. It is precipitated to a specific particle
size from solutions of barium salts and sodium sulfate. Blanc
fixe is also used to make lithopone (extended) grades of pig-
ments. Multistage washing and filtration removes soluble
impurities, and the products are then dried and ground.
Physical Properties
Barytes is best known for its high density and very low oil
absorption relative to other extenders. Particle size ranges
from about 1 to more than 10 m depending on the grade.
Brightness also varies from below 70 % to greater than 90 %
depending on the source and degree of beneficiation. Slurry
pH runs from 4 to 10. Blanc fixe is a more uniform product
with a 12 m average particle size and high brightness
(95%98 %).
Coatings Performance
Barytes is used in industrial and automotive primers and
undercoats. Its low oil absorption allows for high loadings
with less impact on rheology compared to higher binder
demand extenders. It helps develop a smooth surface with
minimal impact on the gloss of subsequent coats. Because
extenders are sold by weight, high density can be a dis-
advantage in trade sales coatings where more weight is
needed to fill a given volume. Higher density relative to
other pigments can increase settling and cause stability
problems. Blanc fixe has been used to develop dry hiding
as a partial replacement for titanium dioxide in trade sales
and industrial coatings [13].
OTHER
Sodium Aluminosilicates
Synthetic sodium aluminosilicates are produced by reacting
aluminum sulfate with sodium silicate to produce a struc-
tured extender. These have high brightness (92 %98 %)
and relatively coarse particle size of 56 m. Sodium
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246 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 1Physical properties of pigment extenders
Ground Calcium
Carbonate
Precipitated
Calcium Carbonate
Hydrous
Kaolin
Calcined
Kaolin Talc
Crystalline
Silica
Free moisture 0.5 0.5 1.0 0.5 0.20.5 0.3
Specific gravity 2.71 2.71 2.58 2.63 2.80 2.65
Brightness, %
Fine 9095 9798 8890 9095 7592 8590
Coarse 8590 ... 8588 ... 7092 8590
Average particle size
Fine, m
13 0.51.5 0.25 0.82.5 13 23
Coarse, m
512 ... ... ... 515 510
pH 9.5 910 47 45 910 67
+325 residue, % 0.011 <0.05 0.010.1 0.01 0.011 <14
Oil absorption, g/100 g 1020 3060 3050 50100 2555 2030
Refractive index 1.66 1.66 1.56 1.62 1.60 1.54
Wollastonite
Diatomaceous
Silica Precipitated Silica
Fumed
Silica Mica
Powder
Wollastonite HAR
Free moisture <1 <1.5 5 0.10 <1 <1
Specific gravity 2.30 2.20 2.20 2.82 2.90 2.90
Brightness, % 8790 96 white 6580 8095 8595
Average particle size
Fine, m
34 0.010.05 0.010.05 0.2 5 24 1 20
Coarse, m
510 ... ... 2 50 710 16 200
pH 910 68 34 78 1011 1011
+325 residue, % <13 0.01 0.01 <150 <0.1 <150
Oil absorption, g/100 g 90130 100300 100400 5674 2030 2030
Refractive index 1.46 1.46 1.46 1.60 1.63 1.63
Feldspar Nepheline Synite Barytes
Sodium
Alumino
Silicate Alumino Hydrate
Free Moisture <1 <1 <1 <1 <1
Specific gravity 2.62 2.61 4.40 2.12.3 2.42
Brightness, % 8084 8898 8095 9598 8699
Average particle size
Fine, m
... ... 14 24 0.053
Coarse, m
310 210 812 716 0.360
pH 59 10 410 710 10
+325 residue, % <0.56 <0.56 <1 <0.5 <0.5+50
Oil absorption, g/100 g 1020 2130 1015 75115 4153
Refractive index 1.53 1.53 1.64 1.53 1.57
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CHAPTER 24 EXTENDER PIGMENTS 247
aluminosilicates are used as partial replacements for tita-
nium dioxide in latex trade sales paints similar to calcined
kaolin but at higher cost; some of the highly structured
grades are used as flatting agents in latex paint [14].
Calcium Borosilicate
Synthetic calcium borosilicate is produced by melting
complex mixtures of alkaline earth silicates and borates,
followed by fritting and milling to produce a structured
extender with particle size 110 m microns and oil absorp-
tion 2545 [15].
Alumina Trihydrate
Alumina trihydrate (ATH) has the chemical structure
Al(OH)
3
and is produced from bauxite ore as an intermediate
in aluminum production. It is most commonly used as a
flame retardant and smoke suppressant in thermoplastic
and thermoset polymer applications. ATH has a brightness
ranging from 85 % to 98 % depending on the grade. Some
very fine particle size grades, less than 1 m, may be effec-
tive in spacing titanium dioxide in trade sales paints [14].
COMPARISON OF DIFFERENT EXTENDER
PIGMENTS
Physical Properties
Physical properties of the pigment extenders described
above are compared in Table 1. Calcium carbonates are
available in different particle size grades and are very white
in color and high in brightness. Low oil absorption enables
high loading levels with minimal influence on rheology.
TABLE 2Comparative properties of extender pigments in coatings
Calcium
Carbonate 5 m
Hydrous Kaolin
0.5 m
Hydrous Kaolin
4.8 m
Calcined Kaolin
1.8 m Talc 8 m
Silica 5 and
10 m
Hiding power Very low Very high Moderate Very high Moderate Moderate
Gloss Low Moderate Low Low Low Low
Enamel holdout Poor Excellent Very good Poor Fair Poor
Stain removal Poor Excellent Very good Poor Fair Fair
Abrasion resistance Fair Poor Poor Excellent Good Good
Adhesion Poor Very good Very good Fair Good Very good
Water spot resistance Poor Excellent Excellent Excellent Good Excellent
Chemical resistance Very poor Very good Very good Good Good Excellent
Viscosity Very low High Low High High-mod. Low
Stability Poor-v.good Excellent Excellent Very good Poor-v.good Excellent
Suspension Poor Excellent Very good Very good Very good Poor
Ease of brushing Fair Excellent Excellent Good Fair-Poor Good
Leveling Excellent Very good Very good Good Fair Very good
Wollastonite Feldspar
Nepheline
Syenite
Hiding Power Low Low Low
Gloss Low Low Low
Enamel Holdout Poor Poor Poor
Stain Removal Good Very good Very good
Abrasion Resistance Excellent Very good Very good
Adhesion Good Good Good
Water Spot Resistance Good Very good Very good
Chemical resistance Fair Excellent Excellent
Viscosity Low Low Low
Stability Excellent Excellent Excellent
Suspension Good Very good Very good
Ease of Brushing Fair Good Good
Leveling Fair Very good Very good
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248 PAINT AND COATING TESTING MANUAL 15TH EDITION
High pH makes these products appropriate for latex paints.
Surface-treated grades are available for solvent-based sys-
tems. Precipitated forms are higher in brightness, finer in
particle size, and have higher oil absorption approaching
that of calcined kaolins.
Hydrous kaolins are the finest particle size natu-
rally occurring extenders. Neutral predispersed grades are
available for latex systems, and acid grades are available
for solvent-based systems. These products have very low
residue, which improves gloss development. The calcined
grades have slightly better color and higher oil absorption
contributes to opacity.
Talcs are available in a wide variety of grades depending
on the source. These are more similar to calcium carbonate
in particle size, although brightness is somewhat deficient.
Platy particle shape is a key parameter, improving durability.
Crystalline silica has lower binder demand than kaolin
or talc. It improves coating stability and durability. There
is concern about its toxicity. Coarser grades are effective
flatting agents.
The high oil absorption of diatomaceous earth makes
it an effective flatting agent. Precipitated and fumed silica,
as more carefully controlled reaction products, are more
appropriate for industrial coatings applications where high
oil absorption is acceptable.
Mica is much coarser in particle size than most extend-
ers. Its platy particle shape improves durability. It also has
lower brightness and high residue, which limit the levels at
which it may be used.
Wollastonite has a unique acicular particle shape,
which provides superior stability and durability, with less
increase in oil absorption than platy talc or mica.
Feldspar, nepheline syenite, and barytes are coarser-
particle-size products. Feldspar and nepheline syenite find
use as replacements for crystalline silica when there are
toxicity concerns.
Comparative Performance in Coatings
Performance characteristics of the extenders previously
discussed are compared in Table 2. Coarse calcium car-
bonate filler does not provide significant improvement
in coatings performance and is primarily used to reduce
TABLE 3ASTM standards for extender
pigments
Standard Title
Specifications
D602 Specification for Barium Sulfate Pigments
D603
a
Specification for Aluminum Silicate Pigments
(Hydrous)
D604
a
Specification for Diatomaceous Pigment
D605 Specification for Magnesium Silicate Pigment
(Talc)
D607 Specification for Wet Ground Mica Pigments
D1199 Specification for Calcium Carbonate Pigments
(Anhydrous)
D3619
a
Specification for Aluminum Silicate Pigments
(Anhydrous)
D4288 Specification for Calcium Borosilicate Pigments
Analytical
D34 Guide for Chemical Analysis of White
Pigments
D715 Test Methods for Analysis of Barium Sulfate
Pigment
D716 Test Methods for Evaluating Mica Pigment
D717 Test Methods for Analysis of Magnesium
Silicate Pigment
D718 Test Methods for Analysis of Aluminum
Silicate Pigment
D719
a
Test Methods for Analysis of Diatomaceous
Silica Pigment
D4487 Test Methods for Analysis of Calcium
Borosilicate
D5381 Guide for X-ray Fluorescence (XRF)
Spectroscopy of Pigments and Extenders
Physical Properties
D153 Test Methods for Specific Gravity of Pigments
D185 Test Methods for Coarse Particles in Pigments,
Pastes, and Paints
D281 Test Method for Oil Absorption of Pigments by
Spatula Rub-out
D1208 Test Methods for Common Properties of
Certain Pigments
D1210 Test Method for Fineness of Dispersion of
Pigment-Vehicle Systems by Hegman-Type
Gauge
D1366 Practice for Reporting Particle Size
Characteristics of Pigments
D1483 Test Method for Oil Absorption of Pigments by
Gardner-Coleman Method
D2448 Test Method for Water-soluble Salts in
Pigments by Measuring the Specific Resistance
of the Leachate of the Pigment
TABLE 3ASTM standards for extender
pigments (Continued)
Standard Title
D3360
a
Test Method for Particle Size Distribution by
Hydrometer of the Common White Extender
Pigments
D4139 Guide for Determining Volatile and Non-
Volatile Content of Pigments
D5380 Test Method for Identification of Crystalline
Pigments and Extenders in Paint by X-ray
Diffraction
E70 Test Methods for pH of Aqueous Solutions
with the Glass Electrode
a
These ASTM Standards have been withdrawn; however, the
designations and titles have been included for historical purposes.
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CHAPTER 24 EXTENDER PIGMENTS 249
cost. Fine-particle-size hydrous kaolin helps develop hiding
power and gloss. These extenders develop good film proper-
ties, help maintain stability, and aid in coating application.
Calcined kaolin also contributes to opacity development
and is fairly good in maintaining film properties, rheol-
ogy, and application properties. Talc and mica are platy
materials that improve durability and develop good film
properties but may have a deleterious effect on rheology,
particularly at higher loadings. Crystalline silica is an
adequate filler, which improves durability, but it is toxic.
Amorphous silicas improve durability without the toxic
problem, but are limited in possible loading by very high
oil absorption. Wollastonite is an acicular material that
improves durability and film properties without the adverse
effect on oil absorption of platy materials. Feldspar and
nepheline syenite are fillers of low oil absorption, which
improves durability. They act very similar to crystalline
silica and can be used as replacements for it.
PERTINENT ASTM TEST STANDARDS
ASTM standards useful in evaluating extender pigments
are shown in Table 3. Standard specifications are useful for
categorizing extenders by mineral type and provide some
general test guidelines. Analytical standards are useful for
chemical analysis of extenders for identification purposes.
Standards for measurement of physical properties are
very useful in categorizing extenders and for predicting
suitability for a particular coatings application. Particle
size, oil absorption, fineness of dispersion, pH, and water-
soluble salt content are important parameters in determin-
ing the suitability of an extender for a particular coatings
application. Actual product specifications should always be
mutually agreed upon by supplier and user.
References
[1] Stoy, W. S., and Washabaugh, F. J., Fillers, Encyclopedia
of Polymer Science and Engineering, J. I. Kroschwitz, Ed.,
Wiley, New York, 1987, pp. 5373.
[2] Ciullo, P., and Robinson, S., Functional Silicate Fillers: Basic
Principles, Paint Coat. Ind., Vol. 18, No. 8, 2002, pp. 3036.
[3] Hare, C. H., and Beck, R., Extenders, Paint Coat. Ind., Vol.
17, No. 3, 2001, pp. 7484.
[4] Eppler, R. A., Glazes and Glass Colors, American Ceramic
Society, Westerville, OH, 2000.
[5] Katz, H. S., and Milewski, J. V., Handbook of Fillers and
Reinforcements for Plastics, Van Nostrand Reinhold, New
York, 1978.
[6] Ciullo, P., and Robinson, S., Kaolin Clay: Functional Optical
Additives, Paint Coat. Ind., Vol. 19, No. 8, 2003, pp. 4247.
[7] Dietz, P. F., The Effect of Fine-Particle-Size Extenders and
Entrapped Air on TiO
2
in Emulsion Paints, Paint Coat. Ind.,
Vol. 19, No. 9, 2003, pp. 2837.
[8] Grexa, R. W., North American Talc-Competition in Every
Direction, Ind. Miner., No. 237, 1987, pp. 5254; Johns-
Manville Technical Literature, Functional Fillers for Indus-
trial Applications, Johns-Manville, Denver, CO, January
1985.
[9] Fubini, B., Surface Chemistry and Quartz Hazard, Acta.
Ceram., Vol. 14, No. 1, 2002, pp. 1428.
[10] KMG Minerals Technical Literature, White Wet Ground
Muscovite Mica, KMG Minerals Inc, Kings Mountain, NC.
[11] Ciullo, P., and Robinson, S., Wollastonite: A Versatile Func-
tional Filler, Paint Coat. Ind., Vol. 18, No. 11, 2002, pp.
5054.
[12] Ciullo, P., and Robinson, S., Feldspar and Nepheline Syenite
Fillers with a Purpose, Paint Coat. Ind., Vol. 19, No. 10,
2003, pp. 122125.
[13] Sachtleben Technical Service Note, Blanc Fixe Micro, a
New, Multi-Purpose Barium Sulphate Extender, Sachtle-
ben Chemie GmbH, Duisburg-Homberg, Germany, 1982.
[14] Lewis, P. A., Pigment Handbook, 2nd ed., John Wiley and
Sons, New York, 1988, Vol. 1.
[15] ASTM D4288-02, 2007, Standard for Calcium Borosilicate
Pigments, ASTM International, West Conshohocken, PA.
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250
PREFACE
THIS CHAPTER IS BASED ON THE CONTENTS OF THE
14th edition. Careful consideration has been given to the
addition of new information, test methods, and technology,
thus providing the most up-to-date information available
on metallic pigments.
Metallic pigments, including aluminum zinc, gold,
bronze, nickel, and stainless steel, provide the paint and
coatings industry with a variety of aesthetic and functional
properties. These pigments, either in flake or powder form,
contribute to the metallic effects associated with automo-
tive topcoats; general industrial finishes; silver, gold, and
copper finishes; metallic ink systems; and many of the high-
performance primers for coatings systems. In addition to
providing metallic and polychromatic effects, they provide
functional anticorrosive benefits.
HISTORY AND MANUFACTURING METHODS
The origin of metallic coatings can be traced back to early
civilizations, who utilized thin gold sheets to overlay wood,
bone, or other materials. As the artisans molded these foil
sheets, the thin edges would break off into flakes. It was
soon discovered that by mixing these flakes in a resinous
polymeric material, a similar effect could be achieved. This
process was later continued, and by shredding the foil into
flakes, artisans were able to produce gold and later silver
and bronze metallic effects on ornamental objects. In the
middle of the 19th century, a mechanical stamping process,
along with newly developed smelting processes, made gold
and silver substitutes more readily available. Aluminum,
gold, bronze, and later stainless steel and nickel became
readily accepted substitutes.
Today, with only a few exceptions, most metallic pig-
ments utilize the hall wet-ball milling method [1]. This pro-
cess carries out the particle-size reduction in the presence
of a suitable lubricant and solvent, offering a safer produc-
tion method. Eliminating the explosive hazards associated
with mechanical stamping processes has allowed the pro-
duction of finer metallic flakes that finds widespread use
today. Stamping and dry-ball milling are still utilized in the
manufacture of gold bronze flakes.
The post-milling manufacture processes for metallic
flakes generally include a screening operation to remove
undesirable particles, along with tight controls on aes-
thetic properties. Color adjustments, along with polishing
and blending operations, are utilized in the final stages of
the manufacturing process. The metallic flake pigments
are available as a dry flake or in a wide range of solvents,
including aliphatic and aromatic solvents, alcohols, plasti-
cizers, water, and coalescing solvents.
Zinc powders have a similar but divergent history. Not
being sought after for aesthetic properties, they were first
used in the mid-1800s for anticorrosive functionality and
were referred to as blue powder. Zinc-gray coatings were
used extensively for industrial and marine environments by
the early 1900s. However, it was not until the late 1930s and
1940s that the industry gained a firm foothold. The manu-
facture of zinc dust is carried out by melting and vapor-
izing zinc metal followed by a controlled condensation of
the vapor in an inert atmosphere. The product is collected,
screened, classified, and packaged [2].
In addtion to zinc powders, there is one additional type
of metallic pigment not manufactured by the Hall wet ball
milling method. Physical vapor deposition (PVD) is a method
used to produce aluminum pigments with very unique char-
acteristics. High purity aluminum metal is vapor deposited,
in a vacuum chamber, onto a flexible web that is surface
treated with a release coating. The metal is deposited in a
very thin layer and subsequently removed by solubilizing the
release coating in a solvent bath. The metal is then collected,
sized, and concentrated for sale.
PROPERTIES
Metallic pigments share similar properties; however, each is
distinct enough to be considered separately.
Aluminum
Aluminum flakes should be differentiated based on their
manufacturing method, i.e., milled using the Hall process and
PVD using a vapor deposition process. All aluminum pig-
ments, however, are manufactured from aluminum metal
with a purity ranging from 99.3 % to 99.97 %, depending
on the grade being manufactured. Although amphoteric
in nature, the pigment exhibits a high degree of chemical
resistance. Aluminum pigments owe their aesthetic and
functional properties to the geometry of the particle, par-
ticle-size, and particle distribution. The pigment is a flake-
like particle (lamellar) and has either a round or irregular
perimeter. Once formulated into a coating, they orient
parallel to the substrate and film surface. This orientation
provides for exceptional barrier properties in the appro-
priate coating system. Metallic or polychromatic coatings
containing aluminum flake pigments, either by themselves
or in combination with transparent colors, offer a two-tone
quality often sought after. The two-tone, or flop, feature is
an important characteristic in many automotive top coats.
25
Metallic Pigments
Russell L. Ferguson
1
1
Vice President of Technical Functions, Silberline Manufacturing Co., Inc., R.D. 2, P.O. Box B, Tamaqua, PA 18252.
MNL17-EB/Jan. 2012
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CHAPTER 25 METALLIC PIGMENTS 251
There are two general types of milled aluminum pig-
ments: leafing and nonleafing. Leafing grades are manufac-
tured using a saturated fatty acid as the lubricant (typically
stearic acid); which allows the flakes to float at, or near, the
surface of a paint film. This continuous layer of flakes pro-
vides a solid silver color, unable to be tinted with other pig-
ments. The nonleafing grades utilize an unsaturated fatty
acid as the lubricant (typically oleic acid), which allows
the flakes to orient throughout the paint film. Nonleafing
pigmented coatings can be tinted with organic pigments to
offer a polychromatic appearance.
Milled aluminum flakes range in size from 0.1 to 2.0
m in thickness and 0.5 to 200 m in diameter. Generally,
aluminum flakes are supplied in a paste form with a typical
composition of 64 % aluminum metal, 1 % lubricant, and
35 % hydrocarbon solvent [3].
PVD-generated flakes have dramatically different physi-
cal properties than milled flakes. The flakes have very regular,
well-defined perimeters, exceptionally smooth surfaces, and
are very thin. The thickness of these flakes is measured in
angstroms with a typical mean thickness of 300 .
Gold Bronze
Gold bronze pigments are neither gold nor bronze, but are
typically manufactured from a composition of copper and
zinc alloy. By altering the copper-zinc ratios, four standard
gold bronze colors can be produced. The standard alloy
subdivisions are: (1) copper100 % copper, 0 % zinc; (2)
pale gold90 % copper, 10 % zinc; (3) rich pale gold85%
copper, 15 % zinc; and (4) rich gold70 % copper, 30 %
zinc. Further oxidative treatments can be utilized to pro-
duce special colored bronzes, varying from brown-golds
to oranges and reds. Additionally, blending of any of the
above-mentioned bronze powders will result in an almost
unlimited pallet of gold-bronze colors.
Gold-bronze pigments are flake-like particles (lamellar)
with an irregular perimeter. In a coating or ink application,
they orient parallel to the substrate and film surface [4].
Zinc Pigment
Zinc dust is the only metallic pigment that is not found in a
lamellar form. Produced through the condensation of zinc
vapor in an inert atmosphere, the zinc dust is a spherical
particle averaging about 8 m in diameter. Zinc dust is pre-
dominantly zinc metal (96 %97 %), with some zinc oxide
(3 %4 %), and traces of lead, cadmium, iron, and other
elements.
Stainless Steel Flake
Stainless steel is a composition of iron, chromium, nickel,
manganese, and molybdenum. There are three groups of
stainless steel alloys available: (1) martensitic, (2) fer-
ritic, and (3) austenitic, differentiated according to alloy
composition. Of the three groups, austenitic is the most
corrosion resistant and typically used to manufacture
stainless steel flake. Austenitic alloys owe their corrosion
resistance to higher levels of nickel and molybdenum.
Stainless steel pigment has a lamellar geometry and
will orient itself parallel in a coating system. Stainless
steel flake has a high degree of durability and will resist
tarnishing, abrasion, and chemical attack. Additionally,
stainless steel flake is able to maintain stability in water-
based systems.
Nickel
Nickel pigments can be found in either powder or flake-like
form. They are typically composed of nickel metal, with traces
of carbon, oxygen, sulfur, and iron. Nickel flake powders are
available dry, as a paste in mineral spirits, or as a paste in min-
eral oil. Nickel powders have good electrical conductivity [5].
METALLIC PIGMENT GRADE CLASSIFICATION
Aluminum Pigments
Aluminum pigments are more widely used than any other
metallic pigment and can be divided into a number of dif-
ferent categories. The grade classification is, in general,
determined by the intended use. Most of the following
categories contain a wide range of grades from very coarse
large flakes to very fine small flakes.
LEAFING GRADES (MILLED)
The standard grade category is composed of a series of
grades from very coarse flakes (having water coverage
from) to very fine flakes (having water coverage in the area
of 35,000 cm
2
/g). These grades are used, primarily, in trade
sales and maintenance coatings. Their leafing values are
traditionally 50 % minimum.
The ultra-leafing grades are characterized by very
high leafing values (in the area of 90 + %) and exceptional
brightness. Their uses include aerosol coatings and ink
applications.
NONLEAFING GRADES (MILLED)
The standard grades are represented by a full range of
products from very coarse, low-opacity to very fine, high-
opacity grades. They are used in diverse applications from
maintenance coatings to general industrial applications
and automotive refinish.
The automotive grades are distinguished from stan-
dard grades by possessing improved aesthetics, including
brighter, more sparkling appearances, with tighter control
on particle-size distribution. Many subcategories exist
under this heading, including specialized grades for base
coat/clear coat systems, circulation resistance, etc.
Plasticized and polymer-modified grades are repre-
sented by a full range of products designed for end-use
systems that cannot tolerate solvents (mineral spirits). The
primary end use is plastic and ink applications.
The dedusted grade category comprises dry aluminum
flakes held loosely together by Teflon bonds, resulting in a
nondusting product. These grades are used in some general
industrial coatings; however, the primary application is to
act as a sensitizer for slurry explosives.
The surface-treated grades include aluminum flakes
whose surface chemistry has been altered to allow for
improved aluminum flake performance. These grades are
used in powder coatings and some solvent-borne coatings
where improvements in flake orientation and performance
are desired.
The aqueous grade category consists of aluminum pig-
ments treated with various chemical components to stabi-
lize the flake for use in waterborne systems. Various levels
of inhibition and performance are available.
PHYSICAL VAPOR DEPOSITED (PVD)
The grade differentiation is based on percent solids, and the
solvent in which the metal is dispersed. The typical com-
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252 PAINT AND COATING TESTING MANUAL 15TH EDITION
position is 10 % metal flake, 90 % solvent, although metal
concentrations as high as 20 % are available. The types of
solvents used are almost limitless; however, ethyl acetate is
most common. The particle size of these flakes can also be
controlled; however, most grades fall within the 1217 m
median particle size range. Although most of these products
are used in solvent-borne coatings and ink systems, appropri-
ate inhibition permits use in waterborne applications.
Gold Bronze Pigments
These pigments are primarily used for coating and ink
applications. They can be divided into four categories,
based on alloy composition:
1. Coppercoppery-red color (100 % copper).
2. Pale goldreddish gold color (90 % copper, 10 % zinc).
3. Rich pale goldgold color (85 % copper, 15 % zinc).
4. Rich goldgreenish gold color (70 % copper, 30 % zinc).
Zinc Pigment
The zinc pigment, dust and flake, is used in coatings, pri-
marily for corrosion-resistant properties. The categories
available are:
1. Regular zinc dust78 m particle-size diameter.
2. Fine zinc dust56 m particle-size diameter.
3. Ultra-fine zinc dust34 m particle-size diameter.
4. Zinc flakeAvailable in several grades, based on par-
ticle-size.
Stainless Steel Flakes
These flakes are used in specialized coatings that require
good resistance to severe environmental conditions.
Nickel Powder and Flake
The powder and flake are used in coating and plastic
systems to provide electrical conductivity and corrosion-
resistance characteristics.
FORMULATION AND APPLICATION GUIDELINES
Formulation Considerations
Metallic flake pigments, by the nature of their geometry
and composition, are malleable and therefore somewhat
fragile. The dispersion of these flakes into a coating system
is critical in maintaining optimum aesthetic and functional
performance. The preferred dispersion process involves the
addition of vehicle or solvent to the metallic pigments, with
slow-speed mixing, to gently separate the flakes. Once a
thick, uniform slurry of metallic flakes, solvent, and vehicle
is achieved, the formulator can continue to let down to
final product composition. Severe dispersion techniques,
such as Cowles high-speed mixers, sand mills, etc., will
destroy the flake integrity, resulting in loss of aesthetic and
perhaps functional properties. Zinc pigment, which is not a
flake, can be dispersed using conventional paint dispersion
techniques.
Appropriate selection of vehicle, solvents, and additives
must also be considered when formulating with metallic
pigments. The leafing properties of aluminum and bronze
flakes can be detrimentally affected by such properties
as acid value of the resin; polar solvents, or solvents with
low-surface tension; moisture in the system; and additives,
including driers that are good wetting agents. Since most
milled metallic pigments contain mineral spirits, coating
system compatibility must be considered.
The current trend toward waterborne coatings also
poses problems in formulation. Dispersion of metallic pig-
ments is assisted by the correct selection of an appropriate
coalescing solvent. However, even good dispersion will not
guarantee good coating performance. Metallic waterborne
coatings have the potential for hydrogen gas generation.
This potential has been addressed by many manufacturers
through various inhibiting processes. While many inhibited
grades are available on the market today, performance may
vary in different aqueous systems. In addition to the poten-
tial for hydrogen gas generation, tarnishing and printabil-
ity have been addressed by manufacturers of gold bronze
flakes. Stainless steel flakes, because of the very nature of
their composition, can be used in waterborne coating for-
mulations without the possibility of gas generation.
The use of waterborne coatings is generally targeted
toward resolution of environmental issues, most notably
VOC reduction. There are other solutions to the VOC issue
such as the use of powder coating sytems. Specialized grades
of aluminum pigments have been developed to meet the
needs of these 100 % solids systems. These grades have
been surface-treated to allow for improved flake orienta-
tion, along with modified electrical conductivity. Applied
electrostatically, the surface-treated aluminum flake will
perform in a similar fashion to the powder coating resin.
PVD flakes, because of their high volatile contents, gener-
ally pose issues relating to their use in low VOC type systems.
However, appropriate solvent carriers help limit this concern.
PVD flakes, because of their exceptionally high aspect ratio
(diameter:thickness), along with their very high opacity or
coverage, require special attention when formulating. Typical
inks and coating systems have very high pigment-to-binder
ratios (from 2:1 up to as high as 8:1), thus very little resin is
employed to assist in flake orientation. At the same time, the
loading levels of the pigment are held at low levels because of
the exceptional hiding or opacity.
The application of metallic pigmented coatings and
inks will depend on the system being used. Traditional ink
application methods will apply to both leafing and non-
leafing metallic pigments. In the case of coating systems,
leafing metallic pigments can be applied by brush, roller,
or spray application. PVD and milled nonleafing grades,
however, must be applied using appropriate spray applica-
tion techniques. Improper application techniques can lead
to poor flake orientation, which will result in reduced aes-
thetic and functional properties.
Market Applications
Metallic pigments are widely used in the coating, ink, plas-
tic, and explosive markets. In the coating industry, metallic
pigments offer both functional and aesthetic properties.
Those pigments that are lamellar (aluminum, gold, bronze,
stainless steel, and nickel) are opaque and orient parallel
to substrate and coating film surface. Thus, they provide a
barrier to ultraviolet and infrared light, along with moisture
and oxygen penetration. Zinc pigment, while not a flake,
possesses superior corrosion protective properties for steel
or iron substrates. Because zinc is higher in the electromo-
tive series, it acts as the anode of a corrosion cell. The iron
or steel substrate is protected by the zinc because of the for-
mation of insoluble compounds with lower oxidation states.
The aesthetic benefits of metallic pigments are widely
known in the coatings industry. In the area of trade sales
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CHAPTER 25 METALLIC PIGMENTS 253
and maintenance coatings, aluminum pigments provide
very bright silvery finishes typically found in many roof
coatings, aerosol applications, and bridges. In general
industrial and automotive coatings, various polychromatic
and metallescent appearances are produced utilizing non-
leafing grades. The PVD aluminum flakes can also generate
a second surface image that is mirror like. These pigments are
useful in applications that require high specular reflectance.
In the ink and plastic industries, the primary benefits
derived are from aesthetic properties. Gold bronze flakes,
along with aluminum flakes, provide attractive polychro-
matic finishes.
The explosives industry utilizes aluminum flake pig-
ment as a sensitizer in slurry explosives.
Economics of Use
The extensive market for metallic pigments has mandated
their use in a wide range of systems for many years. Their
properties, both functional and aesthetic, along with the
traditional economic values associated with their proper-
ties, have established them as an important raw material
in the coating, ink, and plastic markets. The economics
of these pigments are dependent on a number of factors,
including cost of the raw material, degree of sophistica-
tion of the pigment, and the end product for which it is
intended.
TESTING
ASTM Test Methods
ASTM covers various specifications and test procedures for
metallic pigments. Included are:
D962Specification for Aluminum Powder and Paste
Pigments for Paint.
D480Test Method for Sampling and Testing of Flaked
Aluminum Powders and Pastes (includes tests for vola-
tile analysis; coarse particles; leafing properties; brush-
ing, smoothness, lustre properties; and easily extracted
fatty materials).
D95Test Method for Water in Petroleum Products
and Bituminous Materials by Distillation.
D185Test Methods for Coarse Particles in Pigments.
D235Specifications for Mineral Spirits (Petroleum
Spirits) (Hydrocarbon Dry-cleaning Solvent).
D267Specifications for Gold Bronze Powder.
D520Specification for Zinc Dust Pigment.
D521Test Methods for Chemical Analysis of Zinc
Dust (Metallic Zinc Powder).
D4017Test Method for Water in Paints and Paint
Materials by Karl Fischer Method.
Other Test Methods and Specifications
ASTM test methods cover many of the properties of metal-
lic pigments; however, there are additional test methods
and non-ASTM tests that further serve to characterize these
pigments. Included are:
Federal Specification: TT-P-320D Pigment, Aluminum
Powder and Paste for Paint
DIN 55923: Pigments; Aluminum Pigments and Alu-
minum Pigment Pastes for Paints; Technical Delivery
Specification
ISO 1247: Aluminum Pigments
BS 388: Specification for Aluminum Pigments
GOST5494: Aluminum Pigments
ACID SPOT TEST
This test is designed to determine the acid resistance of alu-
minum pigments in coating systems. A metallic pigmented
coating is tested by placing drops of a 10 % solution of
hydrochloric acid on the panel. Three rows of three drops
are placed on the panel and each row is removed after 1 h
intervals (Fig. 1). If the aluminum pigment is acid resistant,
no spotting will be apparent after the first or second hour,
with only slight spotting after 3 h. A nonacid-resistant alu-
minum will show definite spotting from the acid solution
after the first hour.
PARTICLE-SIZE ANALYSIS
One of the key elements in any metallic pigment is the
particle-size distribution. Instruments are available on the
market today to characterize, or fingerprint, metallic pig-
ments. Unfortunately, most of these instruments are inca-
pable of characterizing lamellar-shaped pigments; however,
their increased sophistication has allowed for a very close
approximation. In addition to providing a distribution of
the particles in a pigment, also provided are surface area,
average particle size, and percentages at various levels.
WATER COVERAGE
This test can be used to determine the particle-size thickness
and surface area of leafing and nonleafing metallic flake pig-
ments. This test has been fully described by Edwards and
Ray [6]. A dry metallic pigment is dusted onto a surface of
clean distilled water, which is contained in a shallow rect-
angular pan. The accurately weighed flake metallic pigment
is dusted onto the surface of the water and separated until
it is one flake thick. The coverage of metallic flake on the
water can then be measured, and total surface area can be
calculated based on the weight of the metallic flake pigment
used. The thickness of the metallic flake pigment can also
be calculated using simple density and volume calculations.
DEGRADATION TEST
This test is designed to determine the level of flake deterio-
ration in a coating system when subjected to severe stress.
Automotive coating systems are often circulated through
pumps, regulators, and long piping and tank systems to
keep all the components of the coating in suspension. Cir-
culation may have detrimental effects on the metallic flake
integrity, causing bending, curling, and even breakage of
the metallic flake. The loss in aesthetic properties due to
Fig. 1Testing paints for acid resistance.
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254 PAINT AND COATING TESTING MANUAL 15TH EDITION
flake deformation results in a darkening of the coating,
along with a change in the flop characteristic. This test is
designed to evaluate the capability of the metallic flake to
resist deformation under these stress conditions.
A metallic pigmented coating is placed into a water-
jacketed Waring blender. Using a standard cutting blade,
the blender is operated at high speeds for 5-15 min. The
metallic coating is a sprayed pre- and post-blender opera-
tion, and visual and instrumental comparisons are made.
The degree of flake deformation can be translated into
numerical data based on the brightness of the metallic coat-
ing (face and flop).
GASSING TEST
Aluminum and other metallic pigments, by their very
nature, will react with water to generate hydrogen gas.
Today, due to VOC regulations, more and more coating and
ink systems are moving toward waterborne technologies.
Metallic pigment manufacturers have developed technolo-
gies to inhibit the aluminum flake pigments, and this test
is designed to determine the gas generation potential and
stability characteristics of metallic flake pigmented aque-
ous coating systems. Approximately 200 mL/s of a metallic
pigmented coating is charged into an Erlenmeyer flask.
Attached to the flask is a glass condenser with Tygon tubing
coming out of the top and extending into an inverted buret
filled with water. The Erlenmeyer flask is suspended in a
hot oil bath, which accelerates the potential for hydrogen
gas evolution. This test is operated for seven days (168 h)
at a temperature of 52C. The acceleration of the environ-
mental conditions will allow for hydrogen gas generation,
which will pass out of the Erlenmeyer flask, through the
Tygon tubing, and into the inverted buret. The water in
the inverted buret is displaced by the hydrogen gas and
generation can be easily read through this displacement
(Fig. 2). The specifications for gas generation should be
designed around the metallic flake pigment and coating
system tested. The specification for gas generation should
not exceed the volume of the buret (typically 100 mL/s).
ELECTRICAL RESISTIVITY/CONDUCTIVITY
In waterborne coating systems, it is often useful to know
the conductivity or resistivity of the components of the sys-
tem. In order to measure metallic pigments, it is necessary
to disperse the metallic pigment in an isopropyl alcohol/
de-ionized water mixture. This mixture should be agitated
using an air mixer for at least 5 min, after which the metal-
lic pigment should be filtered out. The resultant filtrate can
be tested for resistivity/conductivity using a conductivity
meter (i.e., Jenway Conductivity Meter, Model 4010).
pH MEASUREMENT
In waterborne coatings and ink systems, it is often neces-
sary to know the pH of the components of the system.
The pH of metallic pigments can be evaluated by adding
the metallic pigment to a mixture of isopropyl alcohol/
de-ionized water. The slurry should be mixed using an air
mixer for at least 5 min. The metallic pigment should then
be filtered out, and the pH of the resultant filtrate can then
be evaluated.
AESTHETIC PROPERTIES
Metallic pigments are used for the aesthetic properties
they lend to coating systems. Every metallic pigment grade
offers its own unique appearance due to the properties of
the individual pigment. Visual and quantitative data can
be generated to provide numerical data describing aes-
thetic differences. It should be noted, however, that the
appearance of a metallic film is significantly impacted by
various application methods. Coating application plays a
definitive role in flake orientation, which is critical to opti-
mized metallic appearance. Many papers have been written
describing the mechanism and challenges of flake orienta-
tion in paint films [710]
The face-color, or head-on-brightness, attribute general-
ly refers to the amount of reflected light from a metallic
pigmented coating when viewed at approximately 20
to 25 off of specular [11].
The flop, flip/flop, or metallic travel angle refers to the
amount of reflected light when viewing a metallic
pigmented coating at an angle that is 70 to 110 off
of specular. Metallic travel is often referred to as the
degree in change of brightness going from the face
angle to the flop angle [12].
Seed level refers to the degree of protrusion of the
metallic flake through a coating film surface.
DOI (distinctness of image), closely related to gloss,
refers to the reflection of an image from a metallic
pigmented coating back to the observer. The clearer, or
more distinct, the reflected image, the higher the DOI
value. Typically, the finer the pigment, the higher the
level of DOI [13].
Patina is the packing appearance of the metallic flakes
in coating systems. A good patina is often described as
having a smooth velvety appearance, lacking individual
flake identity in the coating. If an observer sees only a
continuous metallic film without breaks, protrusion, or
individual flake identity, the metallic coating is consid-
ered to have a good patina. Many coating systems and
pigment parameters affect the patina of a coating sys-
tem. Typically, higher solids coatings, poor application
methods, coarse pigments, and poor flake orientation
contribute to poorer patina properties.
The color attributes from the face and flop angles
can be numerically measured. There are a number of
instruments available today that are capable of measur-
ing reflected light at different angles. All of them are
goniospectrophotometers and are capable of measuring Fig. 2Gas evolution test for metallic coatings.
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CHAPTER 25 METALLIC PIGMENTS 255
reflected light on metallic pigmented coatings at angles
from 10 off specular to 110 off specular. Measurement
techniques are described in ASTM E2194, Standard
Practice for Multiangle Color Measurement of Metallic
Flake Pigmented Materials.
PHYSICAL PROPERTIES
The aspect ratio of metallic flakes, which is a ratio of flake
thickness to median flake diameter, can be calculated
using data generated by the water coverage test, and parti-
cle size analysis. A mathematical calculation can be made
from the water coverage test to generate reliable informa-
tion on flake thickness, which can then be compared to
the median particle size, thus generating the aspect ratio.
Another physical property relating to flake brightness
is surface smoothness of the metal flake. Using Atomic
Force Microscopy, relative differences in flake smooth-
ness can be measured. This advanced technology offers
analytical information, which, when combined with
other physical information, can describe the aesthetic
property of the flake.
References
[1] Hall, E. J., U.S. Patent No. 1,501,499 (1924); U.S. Patent No.
1,545,253 (1925); U. S. Patent No. 1,569,484 (1926); U.S. Pat-
ent No. 2,002,891 (1935).
[2] Ruddick, D. H., Zinc Pigment, Pigments Handbook, Vol. I,
Properties and Economics, John Wiley and Sons, New York,
1988, pp. 811817.
[3] Ferguson, R. L., Aluminum Flake, Pigments Handbook, Vol.
I, Properties and Economics, John Wiley and Sons, New York,
1988, pp. 785801.
[4] Humphrey, S. A., and Laden, P. J., Gold Bronze Pigment,
Pigments Handbook, Vol. I, Properties and Economics, John
Wiley and Sons, New York, 1988, pp. 803810.
[5] Antonsen, D. H., Nickel Powders and Nickel Flake Powders,
Pigments Handbook, Vol. I, Properties and Economics, John
Wiley and Sons, New York, 1988, pp. 823827.
[6] Edwards, J. D., and Wray, R. I., Aluminum Paint and Powder,
Reinhold Publishing, New York, 1955, pp. 1822.
[7] Tachi, K., Okuda, C., and Suzuki, S., Mechanism of Alumi-
num Flake Orientation in Metallic Topcoats, J. Coat. Technol.,
Vol. 62 No. 782, 1990 pp. 4350
[8] Sung, L., Nadal, M. E., McKnight, M., Marx, E., Dutruc, R.,
and Laurenti, B., Effect of Aluminum Flake Orientation on
Coating Appearance, 79th Annual Meeting Technical Program
of the FSCT, November 5-7, 2001, Georgia World Congress
Center, Atlanta, GA, p. 453.
[9] Elmoursi, A., and Lee, H. Y., Droplet and Flake Size Dis-
tribution in Electrostatic Spraying of Metallic Paint, SAE
Technical Paper Series, International Congress and Exposition,
Detroit, Michigan, February 27-March 3, 1989.
[10] Inkpen, S. L., and Melcher, J. R., Dominant Mechanisms
for Color Differences in the Mechanical and the Electrostatic
Spraying of Metallic Paints, Ind. Eng. Chem. Res., Vol. 26, No.
8, 1987, pp. 16451653.
[11] Hare, C. H. and Fernald, M. G., Anti-Corrosive Barrier Fin-
ishes, Mod. Paint Coat., Vol. 74, No. 10, 1978 pp. 138151.
[12] Humphrey, S. A. and Laden, P. J., Stainless Steel Flake, Pig-
ment Handbook, Vol. I, Properties and Economics, 2nd ed.,
John Wiley and Sons, New York, 1988.
[13] Smith, A., Inorganic Primer Pigments, Federation Series on
Coatings Technology, Philadelphia, PA, 1988.
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256
EFFECT PIGMENTS ARE TYPICALLY DEFINED
as flake or platy structures that impart a directional light
reflectance, scattering, absorption, or optically variable
appearance to the substrate in or on which they are applied.
It will be shown that effect pigments are no longer lim-
ited in composition to inorganic materials and in fact can
have alternative geometries. The mechanisms, however, by
which all effect materials manipulate light, and thus color,
still revolve around three basic optical principles, reflec-
tion, interference, and diffraction. It should be noted
that while metallic flake pigments can also be considered
effect materials, the article will focus on structures that
manipulate light primarily through selective interference,
and more recently diffraction, rather than specular reflec-
tion only. It should be emphasized, however, that reflection
is still an integral parameter in the most recent technologies
developed.
WHY EFFECT PIGMENTS?
What is the driving force that has led to the development
of so many different types and complexities of effect mate-
rials? The answer to this question may be more closely
related to our human condition versus commercial reason-
ing. For centuries, man has made colors symbolic of the
events and materials found in nature. While solid colors
have regional differences in terms of significance [1], a few
colors and effects could arguably be considered universal.
For example, the sparkle and luster of precious metals have
always denoted value. Pearls and other precious stones
denote wealth, and silk gives the impression in our minds
eye of a specific tactile feel and thus a sense of luxury.
The natural forms of such materials have been pursued
throughout history requiring men oftentimes to go beyond
the boundaries of the known, risking their lives to acquire
such materials. So is it the rarity of a substance that triggers
the desire or is it a psychological drive that may be simply
stated as perception? After all, color and effect are merely
our individual interpretation of a small part of the vast
electromagnetic spectrum that encompasses and connects
all things. Color is not a tangible object. It is a vast and
complex interactive biological process whose preference is
not static but rather dynamic. So it is more likely that the
development of effect materials is a result of our ability to
relate, on a deep emotional level, to the symbolic represen-
tations that our culture and society has effected. They are
tools used to appeal to our changing moods and emotions
caused by our own physiological and psychological makeup
at the moment, to create preferences and associations that
we then link to the color-emotion response itself.
From a commercial standpoint, with the prominence
of branding, color and effect are often the living embodi-
ment of a brands values and personality [2]. They are
identifying factors that connect with the consumer, are rec-
ognizable, stand out from the competition, and trigger, on
a subliminal level, the buying decision [1]. Color and design
play a pivotal role in ensuring that the consumers percep-
tion of the brand is mirrored in the package or product.
Consumers make a brand purchase just as much as they
make a product purchase. The study of the importance of
color and effect on us as human beings is still largely not
well understood.
HISTORY
Many excellent reviews on effect pigments have been written
[35]. In contemporary terms, the most common effect pig-
ments are referred to as pearlescent (nacreous) or iridescent
pigments. Pearlescent pigments are high-refractive-index
materials that are coated onto thin transparent flakes that
usually are mica, but many other substrates have been inves-
tigated as, for example, silica flakes [6]. Various flake mate-
rials will be discussed in the ensuing text. The flakes reflect
incident light but allow a portion of the light to be transmit-
ted. Basically, they are an attempt to create the natural luster
effect seen in pearls or seashells [7]. These types of materials
hold by far the lions share of this specialized, rapidly grow-
ing and changing market, and they were described in detail
in the previous edition of this manual [8]. Pearlescent pig-
ments, interference pigments, and special-effect pigments
are all names used for effect pigments.
The origin of effect pigments has been customarily
attributed to the French rosary maker Jaquin, who isolated
the silvery substance (guanine/hypoxanthine) found inside
fish scales around the 15th century [9]. The widespread
commercial use of such material really had its start in the
early 20th century where it was used to simulate mother
of pearl by incorporation into early forms of plastic, cos-
metics, and even applied to automobiles [10]. Due to the
obvious difficulties of isolating large quantities of guanine,
synthetic mono-crystalline alternatives were developed in
the 1930s and included compounds such as mercurous
chloride, lead hydrogen phosphate, lead hydrogen arse-
nate, and basic lead carbonate. Due to the obvious toxicity
concerns, these materials have been replaced by bismuth
oxychloride [11], which is still commercially produced.
Despite many efforts to create natural pearl essence
synthetically, a method to create the necessary platelike
structure has never been found even though the internal
crystal structure has been duplicated. This inability to
26
Effect Pigments
Paul J. Nowak
1
1
Marketing Manager, Wacker Chemical Corporation, 3301 Sutton Rd., Adrian, MI 49221, www.wacker.com.
MNL17-EB/Jan. 2012
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CHAPTER 26 EFFECT PIGMENTS 257
synthesize a true pearl essence led to the multi-layer inor-
ganic synthetics. Most notably was the work by Linton of
E.I. DuPont and others that was carried out in the early
1960s. These efforts involved coating titanium dioxide, iron
oxide, or combinations thereof onto mica platelets via a
hydrothermal process [12]. In this instance, the failure of
the obvious synthetic approach to produce natural pearl
essence was responsible for the ultimately greater success
of creating a new type of color unknown in previously exist-
ing pigments. It is this initial work by Linton that is cred-
ited as the foundation on which most, if not all, successive
technologies have been based.
In the 40-plus years that have followed, numerous
variations of the Linton method have been duplicated
and improved upon. Additionally, postprocessing of stan-
dard oxide-coated mica-based pigments has provided a
means to create new color variants. A couple of examples,
which are historically important as well as commercially
important, are the DynaColors
[14] developed
through a joint project between Shiseido of Japan and
Merck GmbH/EMD Industries of Hawthorne, NY
3
, and
was introduced to the general industrial market in 1991. In
this instance, the TiO
2
coated onto mica was subjected to
a solid-state redox reaction using a rotary kiln in the pres-
ence of nitrogen, Fig. 1. The reduction of the TiO
2
allowed
for the creation of a dark color base, which not only greatly
improved opacity, but also when subsequent layers of TiO
2
or other oxides were deposited in varying thicknesses on
this surface, unique, highly chromatic, optically variable
colors were produced. By using such methods and varia-
tions of them, literally hundreds of colors based on metal
oxide combinations coated onto mica have been produced,
leading to an estimated global market of $600 million dol-
lars per year.
Since the early 1960s, the implementation of computer-
controlled manufacturing, improvements in particle size
classification methods (primarily the ability to selectively
remove large or fine particles), the availability of higher
purity precursors, and more advanced mica beneficiation
methods have pushed the envelope for this class of effect
materials. The result of these advancements has been
not only an improvement in the overall batch-to-batch
consistency, but also a tremendous improvement in the
purity and number of colors available. Some of the more
recent product lines introduced to the market using these
developments are the Ultra Colors
developed by Merck
GmbH and the Lumina Colors
min
2dn
2
1 m
(2)
TABLE 1Refractive index for materials
used in effect materials
Medium Refractive index, n
Vacuum, air 1.0
Water 1.33
Alumina 1.35
MgF
2
1.38
Plastics, paint 1.41.7
Mica 1.51.6
SiO
2
1.50
Synthetic mica 1.55
Guanine, hypoxanthine 1.85
Basic lead carbonate 2.09
Bismuth oxychloride 2.15
Fe
2
O
3
2.4
TiO
2
(anatase) 2.5
TiO
2
(rutile) 2.7
Fig. 2Effect of increasing refractive index on light.
Fig. 3Influence on substrate/surface smoothness on
reflectivity.
Fig. 4Diagram to determine the phase relationship between
interfering light rays.
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CHAPTER 26 EFFECT PIGMENTS 259
All colors in the achromatic spectrum whose wave-
lengths correspond to the equation will be cancelled out. If,
however, a wave crest meets a wave crest, the intensity of
light is amplified (constructive interference) and Eq (3) is
valid (m = 0,1,2,3...):
max
4n d
2
1 2m
(3)
All colors whose wavelengths correspond to this equation
will be amplified. The relative intensity of the reflection
maximum can be calculated using a simplified Fresnel
equation [18]. Since Eqs (2) and (3) are only valid for one
wavelength or its multitudes, a part of the visible spec-
trum will weaken or be deleted while another part will be
reflected optimally. This is called selective reflection [19]
and can be calculated by using Eq (4)
r n n n n (0 ) /
0
max 2
2
1
2
2
2
1
2
2
+
1
]
(4)
The color of the reflection maximum depends upon the
layer thickness of the material in which the light enters at
the interface g
1
, Fig. 3. The maximum shifts to larger wave-
lengths with increasing layer thickness. The numerator
indicates that the greater the difference in refractive indi-
ces, the greater the reflectance. The effect of the difference
is magnified by the exponents.
With increasing layer thickness a minimum is added
to the reflection maximum in the visible range and clear
color impressions on the order of the colors of the rainbow
result. For example, if we increase the optical path length
to 100 nm, the reflection maximum lies in the bluish-white
range, and if the product n
2
d, Fig. 3, is further increased to
140 nm, a reflection maximum of yellow-white results. By
increasing the optical thickness further, reflection colors
are produced that change continuously from white, yellow,
red, violet, blue, and green, each reflection color accom-
panied by its complementary transmission color. This pat-
tern of color is repeated with the colors of the second and
higher orders. The color series of higher orders follow in
the same manner by increasing optical path length. As the
layer thicknesses increase, maxima and minima follow each
other more quickly and become more difficult to resolve.
The colors in the various higher orders are extremely desir-
able as they typically differ in shade, brilliance, and level of
saturation [20], Fig. 7.
In interference, the reflection and transmission colors
vary with angle of incidence. The reflection maximum and
minimum shift to lower wavelengths as the angle of incidence
increases. The color shift is governed by the expressions
max
/ ( sin ) ( ) 4 2 1
1
2 2
d m n i
(5)
and
min
( sin ) ( ) 2 / 1
1
2 2
d m n i
(6)
in which i is the angle of incidence at the initial phase
boundary. Equations (5) and (6) reduce to Eqs (2) and (3) for
perpendicular incidence where i = 0. The radical in Eqs (5)
and (6) change more rapidly with i for smaller values of n
1
.
Thus a lower refractive index produces a greater color shift.
From the discussion above, it can be seen that through
the manipulation of the variables within the optical equa-
tions it should be possible to maximize the levels of reflec-
tion at the phase boundaries by using semi-transparent
metal layers. When light falls on a metal, we would expect
that it should be totally absorbed. It is exactly because of this
extremely strong absorption of metals that absorption does
not have an opportunity to occur! To understand this appar-
ent paradox, we need to examine the process of reflection.
In dealing with an insulating material, such as most
inorganic and organic substances, the percent reflectivity
R for a beam of light falling on the material at normal inci-
dence, or on leaving the material, is given by the equation:
R + 100( 1) /( 1)
2 2
n n
(7)
where n is the refractive index. A typical dielectric medium
with n = 1.5 gives R = 4 %; thus most of the light is transmit-
ted into the medium and only very little is reflected. When
light falls onto a metal, it is so intensely absorbed that it can
penetrate to a depth of only a few hundred atoms, typically
less than a single wavelength. Since the metal is a conduc-
tor of electricity, this absorbed light, which after all is an
electromagnetic wave, will induce alternating electrical
currents on the metal surface. These currents immediately
remit the light out of the metal, thus providing an extremely
strong reflection.
Mathematically, in Maxwells equations we need to
replace the refractive index n by the complex refractive index
N + n ik (8)
Fig. 5Phase shift of /2 of a sine wave.
Fig. 6Interaction of light rays with various phase lengths.
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260 PAINT AND COATING TESTING MANUAL 15TH EDITION
where i is the imaginary square root of negative one and k
is the attenuation index, coefficient of absorption, or extinc-
tion coefficient. Equation (7) now becomes
R +
1
]
+ +
1
]
100 1 1)
2 2 2 2
( ) / ( n k n k (9)
The percent reflectivity for silver, as an example, and
sodium D light, the values n = 0.18 and k = 3.6 give a
reflectivity of 95 %. The metallic luster thus turns out to be
no more than a high reflectivity. To show its high reflectiv-
ity the surface of a metal alloy or semiconductor must, of
course, be very smooth.
Multiple reflections between parallel surfaces of semi-
transparent metals are used in the FabryProt filter used
in the study of interferometery [21]. Through modification
of the geometric thickness or path length, the transmitted
beams can be made to constructively and destructively
interfere. With the usual air-dielectric interface, a reflec-
tivity of 4 % is generated, the intensity of these reflected
beams falls rapidly, and the resulting interference pattern
is shown in the top curve of Fig. 8. If the reflecting sur-
faces are metallized, the multiple reflections become more
effective and there is a drastic change in the transmission
pattern as shown in the second and third spectral curves of
Fig. 8. Therefore, using such a construction, it is possible to
resolve very closely spaced colors and significantly improve
the levels of saturation, especially at the higher orders of
interference. In addition, the spectral bands are separated
as well as magnified, resulting in extremely sharp color
changes at various angles of viewing, which is essentially a
change in the angle of incidence. Only until recently has it
been possible to construct such a material on a commercial
scale mainly due to the developments in manufacturing.
It is this ability to magnify and resolve color using such
a system that the Chromaflair
pigments produced by
Flex Products, a JDS Uniphase Company,
4
are based. They
provide not only very highly saturated interference colors
but also have a very sharp angle-dependent multiple-color
effect. Such materials are without a doubt the most intri-
cate and highly sophisticated effect pigments on the market
today (see Fig. 9).
Advances have been made recently with the more tra-
ditional interference effect materials as well. While they are
not as precisely constructed as the FabryProt filters, they
do share many of the same attributes, namely, the ability to
produce optically variable colors with strong angle depen-
dence and reasonably high saturation.
In these cases, multiple thin films of varying thickness
of high refractive index such as the traditional metal oxides
(optical stacks) are coated onto substrates or layers of low
refractive index. By varying the thickness of the dielectric
and the metal oxides, they also can produce relatively nar-
row transmission bands through constructive and destructive
interference. One example is the structure of Fig. 10, using
only dielectric (nonmetallic) layers as the substrate. Here,
each layer contributes to the development of color. The TiO
2
layer being a higher refractive index material does not sepa-
rate the light ray as far from the normal as the SiO
2
layer. Thus
Fig. 7The dependence of interference color on oxide layer thickness.
Fig. 8Intensity distribution from Fabry-Prot filter with
different reflectivities.
4
Flex Products, A JDS Uniphase Company, 1402 Mariner Way, San-
ta Rosa, CA 95407, www.fexprod.com.
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CHAPTER 26 EFFECT PIGMENTS 261
by varying the thickness of each layer, each can be tailored to
a specific thickness to reflect selectively, specific wavelengths
of light as previously discussed. Since there is very little
absorption in such a construction, essentially all of the light
not transmitted is reflected. Materials used for such dielectric
interference filters include MgF
2
, borosilicate glass, alumina,
or SiO
2
. The latter two materials are marketed under the trade
name of Xirallic
.
Using these principles, the extent of extinction and
enhancement of particular wavelengths is efficiently
increased although less so than with the FabryProt fil-
ter types. Through the manipulation of the composition
of materials and thicknesses of those materials optical
stacks, there has been created a totally new series of effect
pigments that exhibit highly saturated interference colors, a
high degree of reflectivity, with the potential for high color
dependence on viewing angle (color flop), Fig. 11.
DIFFRACTION
An alternate method of separating light into its various
components is by diffraction [22]. Diffraction is the bend-
ing of light waves around an object. The term diffraction is
used to describe the behavior of light when it departs from
rectilinear propagation. This happens when the edge of an
object produces an interrupted wave front and the light
then bends around the edge: The resulting color-producing
phenomena involve interference. While diffraction neces-
sarily involves interference, the reverse is not true [23].
Just as increasing the number of reflections in the
FabryProt etalon increases the sharpness of the interfer-
ence colors, so the same happens with a diffraction grating.
The diffraction grating can be defined as an optical compo-
nent made by a periodic assembly of reflecting or transmit-
ting obstacles (grooves) separated by a distance comparable
to the wavelength of light applied. Various shapes, such
as triangular symmetrical, triangular blazed, square-wave
with different top plateau sizes, and sinusoidal gratings can
be produced. Additionally a variety of groove frequencies,
blazed angles, and depth profiles can be produced. For a
given grating frequency, the depth, shape, and orientation
of the grooves determine the relative intensity of the vari-
ous interference orders through the process as previously
discussed, mainly constructive and destructive interference.
When light is incident on a grating, it is diffracted
into discrete wavelengths. The incident beam is separated
forming the zero order diffraction or specular reflection,
that is a mirror effect color of the incident light. First order
diffractions (negative first order and first order) surround
the zero order. Eventually other higher orders surround the
first orders depending on the groove frequency of the grat-
ing, Fig. 12.
The ability of a grating to diffract light is described by
the grating equation:
m d(sin sin ),
(10)
5
BASFAG Ludwigschafen, Germany, www.basf.com.
Fig. 10Color contribution from each layer of an optical
stack.
Fig. 11Dielectric substrate pigments principle of color flop.
Fig. 9Thin film interference pigment flake cross section
(Fabry-Prot filter type).
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262 PAINT AND COATING TESTING MANUAL 15TH EDITION
where and are the angles between incident light and
normal, and the diffracted beam and the normal to the
grating, respectively. The integer m is called the diffraction
order. For m = 0, = for all , where the wavelengths
are not separated, this is the specular reflection or zero
order.
The higher the groove frequency, the greater the angu-
lar separation between orders. The size of the grating will
improve definition of the various orders (resolving power)
as adjacent spectral lines are clearly separated. Finally, for
a given grating frequency, the orientation of the grooves,
the depth and shape, determine the relative intensity of the
various orders.
In nature, color by diffraction is relatively rare. How-
ever, one of the most outstanding natural diffraction grat-
ings is the gemstone opal, showing on a white or black
background, flashes of varied colors can be observed. This
was at one time thought to involve thin film interference,
but electron microscope photographs taken of an opal
reveal its secret, demonstrating a regular three-dimensional
array of equal-size spheres, Fig. 13. The actual composi-
tion of the spheres is amorphous silica (SiO
2
), containing
a small amount of water. These spheres are cemented
together with more amorphous silica containing a different
amount of water so that a small refractive index difference
exists between the spheres and the cement [24].
The theory of a three-dimensional diffraction grating
consisting of stacks of identical layers is well known from
the field of x-ray crystallography, Fig. 14, where Braggs law
applies, Eq (11). Reinforcement of diffracted waves occurs
when the angle of incidence for diffraction from a layer
equals the angle of reflection, and when the path difference
between the reflections from adjacent layers with a spac-
ing d is a whole number of wavelength. The condition for
reinforcement becomes
n nd 2 (sin ) (11)
In natural opals, the uniformly packed spheres provid-
ing diffraction occur in patches ranging from less than a
millimeter to more than a centimeter across. Within each
patch the color will vary with the angle of viewing, with
thelongest wavelength appearing at normal incidence with
I = 0 as in
n d n I 2
2 2 1/2
( sin )
(12)
Films of certain types of liquid crystals, organic com-
pounds with a structure intermediate between that of a
crystal and that of a liquid, can show a left-handed or
right-handed twisted structure resulting in layer gratings
with a repeat distance in the range of visible light. Such
substances are called cholesteric or chiral liquid crystals
(not superimposable on their mirror images). When a beam
of white light falls on a film of such a substance, a narrow
wavelength region will be reflected by diffraction accord-
ing to Braggs law. This is expressed in the form of Eq (13),
where n is the refractive index, p is the pitch distance in
nm, and = angle of viewing.
ref
npcos
(13)
An interesting and unique phenomenon occurs with
such substances. The light will be circularly polarized with
the sense of the polarization related to the handedness of
the twist of the structure. Both the opposite polarization
and all other wavelengths are transmitted through the
film. The diffracted light resembles that from an ordinary
diffraction grating except for the polarization. It should
be noted that the diffracted color does not depend on the
total film or layer thickness as it does with interference pig-
ments, but rather on the layer repeat distance within the
film. Similar to a typical diffraction grating the colors vary
Fig. 12Incident white light and resulting spectral distribution
from a diffraction grating.
Fig. 13Electron micrograph of a synthetic opal.
Fig. 14Schematic representation of diffraction in a three-
dimensional diffraction grating as in opals.
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CHAPTER 26 EFFECT PIGMENTS 263
with viewing angle [25]. One difference, however, is that in
diffuse light the interference phenomenon is still visible.
Closely related to the diffraction effect in opals is the
ability of small particles to selectively scatter light [26]. This
scattering of light will depend on whether the wavelength
of the light is large or small compared to the diameter of
the particle. In practice, two different theories are used to
describe the scattering or diffraction of light from a particle
[27]. They can be distinguished by a dimensionless size
parameter, (a).
( ) / a r 2
(14)
For very small values of (a), the Rayleigh theory of light is
valid. For larger values of (a), the Mie theory [28] of light
scattering is necessary. For very large values of (a), dif-
fraction, reflection, and refraction can be used to explain
scattering. In practice, Raleigh theory is normally only
employed to describe the interactions between gas mol-
ecules and light. However, it can be used up to an (a) value
of 0.5 without incurring great error. Raleighs theory can be
simply expressed by Eq(15),
I / I s o constant
4
/ , (15)
where Is is the intensity of scattered light and Io is the
initial light intensity. In general, the shorter wavelengths
are more efficiently scattered by very small particles. The
end result is that it is possible to create optically variable
color effects with such small particles. Good blue scatter-
ing can be observed from particles as large as 300 nm (still
smaller than the 400 nm wavelength of violet light) down
to particles just a few atoms or molecules in size, say 1
nm in diameter. The exact shade of blue depends in a very
complex way on the size of the scattering particles, the dis-
tribution of sizes, their arrangement, and even their shapes.
When the size of the particle approaches and then
becomes larger than the wavelength of light , the Mie
theory is used to explain the scattering. The scattering is
no longer predominantly blue, but sometimes shows differ-
ent colors, mostly red and green bands, but only at certain
angles. The Raleigh scattering effect is the basis for the
nanoparticle size TiO
2
type of effect pigments that produce
a soft opalescent highlight with a blue undertone [28].
In more recent times (within the past ten years), novel
approaches to using the physical principles behind generat-
ing color through interference and diffraction have resulted
in what are now considered state of the art effect pigment
chemistries. These developments have primarily revolved
around the development of novel substrates and methods
of manufacture building on the foundation of the original
layer substrate technology.
DEVELOPMENT OF NEW SUBSTRATES
Apart from naturally occurring muscovite mica, naturally
occurring phlogopite, sericite, and biotite have all been
used to create various pearlescent and iridescent pigments.
Each of these common materials has their various advan-
tages and disadvantages when it comes to physical proper-
ties [29]. However, of these, the most widely used type of
mica is muscovite, chemically defined as KAl
2
(AlSi
3
O
10
)
(OH)
2
. More specifically is a grade of muscovite mica that
originates from mineral deposits in India. It differs from
domestic sources in that it has improved optical clarity due
to a lower level of iron and manganese contaminates. The
bulk color is typically a pale pink, rather than beige or yel-
low. The improvement in the initial quality of the substrate
bulk color allows for the ability to create brighter, and
whiter, white pearlescent pigments and more chromatic iri-
descent pigments. The mica is ground as an aqueous paste
in a Muller or friction mill to delaminate it into very thin
platelets with smooth surfaces. As the mill rollers go over
the mica, it becomes thinner and smaller in particle-size,
increasing the aspect ratio (lateral diameter to thickness).
These mica flakes are then dried, sieved, and classified into
the desired starting particle-size distribution.
The optimum particle size distribution as measured by
laser diffraction methods falls between 1040 m. This is
the particle size at which maximum luster occurs. Smaller
particles <510 m act as light scatters due to insufficient
coating or inefficient parallel orientation. Particles larger
than 40 m give a coarse effect and reduce opacity. It
has been found that not only the particle size distribu-
tion but also the uniformity in thickness of each particle
is important. The wet grinding process while fairly good
with respect to delamination and creating smooth flat
flakes is by no means optimum. There is some unavoid-
able uneven delamination of the mica layers resulting in a
stair step type morphology on the surface. These steps
scatter light similar to the platelet edges, which, in turn,
reduces the direct light reflection from the coated pigment
surface, Fig. 15. Furthermore, multiple domains of thick-
nesses reduce the intensity of the interference chroma and
cause a desaturation of the reflected color. The fact that
most mica in use today is a naturally occurring mineral, it
inherently has variation in terms of purity, crystal structure,
and surface smoothness. Therefore, nearly all of the newer
substrate technologies that have been developed to date
optimize the prerequisite properties of the substrate that
are delineated in Table 2.
The importance of the initial substrate quality cannot be
overstated. Of particular interest in this respect is the develop-
ment of synthetic mica or fluoro-phlogopite, KMg
3
(AlSi
3
O
10
)
F
2
, by Topy Industries in conjunction with Nihon Koken
Kogyo (NKK)
6
of Japan in 1992, and commercialized in
Fig. 15Schematic cross section of synthetic versus mica
substrates.
6
Nihon Koken Kogyo Co., Ltd., 15-18 Kodenmacho, Nihonbashi
Chuoku, Tokyo, Japan, Tel: 81-3-3663-6721.
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264 PAINT AND COATING TESTING MANUAL 15TH EDITION
1995 under the trade name Ultamica
trade name.
The latest generation of effect pigments based on the
layer substrate principle has been the development of syn-
thetic substrates based on calcium-aluminum-borosilicate,
and SiO
2
flakes [32] by Merck KGaA. These synthetic sub-
strates are manufactured in a way similar to the web coating
device used for synthetic mica [33], see Fig. 17. The thick-
ness can be controlled so precisely as to impart an interfer-
ence color of its own. This, when combined with a layer
of metal oxide similar to other more common pearlescent
pigments, allows for the development of a series of opti-
cally variable pigments (OVPs) in which the color is view-
ing angle dependent. They generate their colors through
the optical principles of simple interference filters. The
materials have been commercialized under the trade name
Colorstream
. These newly
developed pigments are arguably the most commercially
TABLE 2Prerequisite properties of effect
pigment substrates
Number Property
1 Refractive index
2 Optical clarity
3 Surface smoothness
4 Uniform particle thickness
5 Aspect ratio
Fig. 16Synthetic mica manufacturing process and metal oxidecoated mica deposition process.
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CHAPTER 26 EFFECT PIGMENTS 265
important effect pigments to be introduced to the market
since the original metal oxide coated mica-based pigments.
DEVELOPMENTS IN MANUFACTURING
The standard hydrothermal process of depositing metal
oxides on the surface of a substrate has drawbacks (see
Fig. 18). While the improvement in surface smoothness of
substrates allows for a smoother oxide coating, the crys-
tallite growth is, from an optical standpoint, fairly rough,
and the aqueous method cannot be used for all possible
substrates or all metal oxide depositions. If we can gain
anything from the evolution of effect materials to date, it
is that where there have been limitations, there have been
methods found to overcome those limitations. Two of the
companies leading the way in this regard are Flex Products,
a JDS Uniphase Company of Santa Rosa, CA, and BASF of
Ludwigschafen, Germany.
The process by which these companies create lamel-
lar pigments with optically variable interference effects is
based on deposition of metal oxides on a platy substrate
by either chemical or vacuum vapor deposition. The idea
of creating effect pigments by vapor deposition was actu-
ally described in a patent by Greenstein in 1955 [35] but it
was not until the process was actually developed for other
applications by the Polaroid Corporation in 1979 [36] that
it was actually proven to be feasible.
The two methods, while similar in theory, differ quite
substantially in the means by which the deposition and the
resulting pigments are constructed. In the BASF system
first described in 1981 by Ostertag [37] (Fig. 19), a substrate
is introduced into a cylindrical reaction chamber with a
conical bottom and fluidized by the introduction of nitro-
gen. The fluidization results in a complete separation of the
substrate particles, so that all surfaces of the pigments are
free. Once the fluidization is complete, the various chemi-
cals are introduced in a vaporized form. If the reaction con-
ditions are properly adjusted, the formed nano-crystalline
oxide particles are packed close together on the surface of
the substrate building a smooth and optically homogenic
film. The coating time determines the thickness of the oxide
layer. Once the appropriate thickness has been reached, the
reactor is cooled and the particles sieved to remove any
agglomerates. In principle, a variety of different substrates
and coatings are possible using the chemical vacuum
deposition process. It especially allows materials that can-
not be handled in acidic aqueous media to be coated, i.e.,
aluminum or organic pigments. Due to this feature, com-
pletely new species of pigments can be manufactured. They
are currently supplied to the marketplace under the trade
names of Paliocrom
and Variacrom
, respectively.
The second method is based on vacuum vapor deposi-
tion, see Fig. 20, and it was first described by Optical Coat-
ings Laboratories, Inc., [38] and commercialized by Flex
Products. This class of effect pigments creates Color by
Fig. 19Effect pigments by CVD.
Fig. 17Manufacturing process of SiO
2
flakes.
Fig. 18Schematic cross section of mica versus synthetic
flake. Fig. 20Effect pigments by VVD.
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266 PAINT AND COATING TESTING MANUAL 15TH EDITION
Physics. The optical principles on which they create the
sharp, dramatic, optically variable interference colors are
based on FabryProt type light filters [39] and thin film
interference, which was previously discussed.
The pigment is comprised of three to five layers of
precisely controlled thickness that are deposited on a poly-
meric film. Large rolls of the polymer film, either soluble
or non-soluble, are passed through a vacuum chamber
containing an electron beam that vaporizes the deposition
material from a crucible. Running the film at a specific
speed through the chamber controls the thickness of the
various layers deposited. This method is, to date, the most
precise in terms of controlling thickness of the various lay-
ers deposited. The film is then brought in contact with a
chill roller and subsequently passed back and forth multiple
times in order to build the various layers. These layers are
comprised of an opaque reflective core (aluminum oxide)
followed by a layer of MgF
2
which has a low refractive
index, at quarter wave thickness, on top of which is depos-
ited a thin glass-like layer (SiO
2
), followed by a semi-trans-
parent layer of absorber metal oxide. The pigments can be
made in either a symmetrical or nonsymmetrical fashion.
In addition, many color combinations can be constructed
by varying the thickness of the various layers or composi-
tion of those layers. The thin film is stripped from the web
by passing it through a solvent bath where the pigment
particles are released, and due to their specific gravity
(2.04.0 gm/cm
3
), fall to the bottom of the tank, where they
are subsequently recovered, washed, and dried. The particle
size is adjusted by dispersing the material in a solvent and
ultrasonically agitating. Again the flakes are filtered, dried,
and if an even smaller particle size is required they can be
subjected to an air grind using an impact pulverizer with-
out readily destroying the color characteristics of the flakes.
The result is a pigment with high reflectivity, opacity (due
to the metallic core), and outstanding sharp color changes,
in a very narrow particle size distribution and a thickness
of 1 m (see Fig. 21).
The color is computer controlled to provide a running
color profile at a specific angle across the width and length
of the web. An average can be ascertained for the roll that
then makes it possible to modify the color at a later step in
the event that the color is slightly off by essentially adding a
lower or higher color. For example, if the average dominant
wavelength of a roll is 495 nm and the desired wavelength is
490 nm, the desired wavelength can be obtained by adding
some lower-wavelength material having an average value of
485 nm to achieve the 490 nm target. In addition, it is also
possible to blend batches after final sizing to get an even
more precise and consistent color match to standard [40].
DIFFRACTION
Another exciting development in effect pigment technology
arises from the development of color through diffraction
rather than thin film interference. There are many dem-
onstrations of diffractive optical effects in non-flake form,
notably linear diffractive gratings on plastic or metal foils
and holograms [41]. The major characteristic of colors by
diffraction is that they are only visible in direct light and
disappear when light is diffused. There is a strong color
change with viewing angle and the color reflection is irides-
cent in nature (see Fig. 22).
Three companies have introduced variants of such
technology to the marketplace. They are Flex Products of
Santa Rosa, CA
4
[42], Spectratek Technologies, Inc., of Los
Angeles, CA,
7
and Eckart GmbH
8
(Prismatic Metalure
).
Of particular commercial interest are the developments by
Flex Products, in which several limitations with respect to
particle size, color development, and aspect ratio have been
optimized or overcome.
The process by which these pigments are constructed
utilizes the vacuum vapor deposition (VVD) process as
mentioned above for the Chromaflair
line of colorants.
The pigments are produced under tolerances similar to
semiconductor chip technology. The particles are com-
prised of an embossed reflective core layer (usually alu-
minum) that provides the optical interference pattern of
a diffraction grating. This reflective optical layer is then
encapsulated by a dielectric layer (MgF
2
) that provides
the necessary rigidity and durability to the diffractive pig-
ment flakes. The line frequency of the diffractive structure
on the flakes is between 1400 and 2000 ln/mm such that
light corresponding to the range of visible wavelengths in
the first or higher order diffracted beams is substantially
Fig. 22Diffractive phenomenon with Spectraflair pigment
technology.
Fig. 21OVP manufacturing process.
7
Spectratek Technologies, Inc., 5405 Jandy Place, Los Angeles, CA
90066, www.spectratek.net.
8
Eckart America L.P., 830 East Erie St., Painesville, OH 44077,
www.eckartamerica.com.
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CHAPTER 26 EFFECT PIGMENTS 267
angularly separated from the same range of wavelengths in
higher order diffracted beams when illuminated at normal
incidence up to about 60 from normal incidence. Addition-
ally, the diffractive structure amplitude, which in a grating
is the depth of the grooves (160 nm or greater), is such that
the zero order diffracted beam is substantially suppressed
in intensity so that the intensity of the higher order beams
are enhanced over the desired range of wavelengths and/
or angles of incidence. The diffractive structure is a linear
sinusoidal grating that is constructed by depositing thin
films (two to three atoms in thickness) on a structured
surface substrate having a releasable intermediate coating
layer such that the appropriately sized flakes defoliate from
the substrate, replicating its shape. The recovery process
of the flakes is then similar to the FabryProt OVPs dis-
cussed previously. The result is a very smooth, optically
variable diffractive pigment with an average particle size
of 25 m and an overall thickness of 11.4 m, resulting in
an aspect ratio of approximately 25:1. The effect achieved
with direct illumination is that of the rainbow and in dif-
fuse light gives a liquid metal look. They are currently sold
under the trade name of Spectraflair
and manufactured by
Flex Products, a JDS Uniphase Company in Santa Rosa, CA.
UNSUPPORTED (NON-SUBSTRATE) EFFECT
MATERIALS
It has been shown that many developments in the substrate
layer principle have occurred since 1963 and have led to
several state of the art effect pigments being commercial-
ized. Another area of relatively recent commercial interest
is the development of effect pigments that provide color
by interference, diffraction, absorption, or a combination
thereof, without the use of a supporting material. Several
efforts in this regard have been concurrently developed
over the last several years along with the advances in novel
substrates and manufacturing. It has long been known that
various mono-crystalline platy materials could be used as
effect materials (e.g., bismuth oxychloride). Some relatively
recent developments of particular commercial interest are
synthetic platy micaceous iron oxide (BASF Corporation
GmbH), platy graphite (Ciba-Geigy of Hawthorne, NY
9
),
platy TiO
2
(EMD Industries, Hawthorne, NY, and Engel-
hard, Iselin, NJ), and nano-particle size TiO
2
(Dainichiseika
Color and Chemicals America, Inc., Clifton, NJ
10
).
An area of special interest is the development of effect
materials based on purely organic components rather
than inorganic materials. Iridescent film technology devel-
oped and commercialized by the Engelhard Corporation
uses thin film interference principles to manipulate light
through the use of alternating layers of polymers differing
in their respective refractive indices. The material is manu-
factured using a co-extrusion process whereby a specialized
dye at the extruder head is used to create the 172-plus alter-
nating polymer layers into a film that is then stretched, slit,
and chopped using cryogenic techniques to create a flake
that can be and is used as an effect material. Such polymers
or more commonly called glitters have been commercial-
ized for some time and have been developed in a variety of
colors. To date, it has not been made robust or thin enough
in its flake form for most industrial and high-performance
decorative applications. They are, however, prevalent in the
hobby, craft, graphic arts, and cosmetics industries.
Liquid crystal polymeric effect pigments (LCPs) have
been introduced to create yet another class of unique
effect materials. Through developments in the late 1990s
by Wacker-Chemie GmbH [43], these materials are quickly
becoming commercially important as a means to pro-
vide optically variable color effects with a high degree of
metallic luster, through the use of a cholesteric or twisted
nematic helical structure. They are in the chemical class
of modified polyacrylates. They are manufactured, Fig. 23,
by applying a solution comprised of nematic liquid crystal
monomers, or oligomers, a chiral additive that acts as the
template for the helical superstructure, and an appropriate
cross-linking agent to form a polymer web. A sheer stress
is applied to the resulting film to control the thickness and
also orient the molecules into offset layers of parallel rows,
each row having a slightly different molecular orientation.
It is then exposed to ultraviolet radiation to complete cross-
linking and to fix optical properties. Subsequently the cured
film is mechanically removed from the web and subjected
to an air impact pulverizer, wherein it is made to a specific
particle size distribution, air classified, and packaged.
The color is controlled by spectrophotometrically mon-
itoring various points across the web during the manufac-
turing process, and the process parameters are adjusted
automatically as required to provide a uniform, consistent
color. If required, additional blending of the flakes can be
done to further adjust color to standard.
The resulting cigar-shaped polymer platelets are
approximately 35 m in thickness and can have a longi-
tudinal diameter of between 40 and 200 m and a specific
gravity of 1.3 g/cm
3
. Light falling upon the cholesteric nem-
atic liquid crystal helix is split into two parts. Most of the
light is transmitted but a small amount of light is reflected.
The wavelength of the reflected light corresponds to the
pitch (the distance between two layers of the same molec-
ular orientation) of the cholesteric helix, Fig. 24. This deter-
mines the wavelength of light being reflected. If one thinks
of the molecule as a spring and by either increasing or
decreasing the ratio of the chiral additive to liquid crystal,
it is possible to arbitrarily tune the wavelength of reflection
by compressing or expanding the length of the spring. The
wavelength of reflected light changes continuously with the
9
Ciba-Geigy Corporation, Pigment Division, 7 Skyline Dr., Haw-
thorne, NY 10532, www.cibasc.com.
10
Dainichiseika Color and Chemicals America, Inc., 40 Webro Rd.,
Clifton, NJ 07012, Tel: 201-777-0200. Fig. 23Helicone liquid crystal production process.
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268 PAINT AND COATING TESTING MANUAL 15TH EDITION
viewing angle due to the reflective diffraction of light by
the edges of the rigid molecules comprising the helix. The
color transition effect is significantly softer and less sharp
than corresponding multi-layer inorganic materials based
on FabryProt interference filters, or diffraction gratings,
as discussed previously. Due to the sharp spectral reflection
bands, however, the mixing of various colors results in each
particle retaining its own individual color characteristics
since there is little overlap of the spectral bands and thus
little destructive interference. Such polymer flakes are also
not as dependent upon orientation, as there are no edges
to scatter the light, resulting in superior levels of chroma
at the diffuse angle. In addition, such chiral molecules can
reflect and transmit circularly polarized light based on the
handedness of the helix. This property also allows color
and effect to be seen in diffuse light. They are supplied
to the marketplace by Wacker-Chemie GmbH of Munich,
Germany, under the trade name of HELICONE
HC, which
describes the helical-conical molecular structure.
FUNCTIONALITY
The ability of flake type materials to impart barrier proper-
ties to coatings is well established [44,45]. Over the course
of the past 15 years numerous examples of functional effect
pigments based on the layer substrate principle have been
developed. In automotive and coil coatings, for example,
patented surface treatments have been applied to improve
humidity resistance for such high-performance applica-
tions [4648]. They have also been modified to provide
better adhesion, improved dispersion [49], and even han-
dling characteristics during the coating and plastics master
batch-manufacturing process (e.g., pre-wetted). Treatments
have also been applied to enhance the performance of the
matrix in which they are used. In cosmetics, for example,
where smoothness and feel when applied to the skin are
important, effect pigments have been developed that not
only improve these properties but also improve press and
payoff of the powders in which they are formulated. In
sunscreens, where ultraviolet radiation protection is para-
mount, effect pigments have been developed to enhance
ultraviolet-radiation-screening capabilities [5052] while
providing a soft lustrous glow to the skin and thus an
enhancing cosmetic effect.
Traditionally, for use in powder coatings, effect materi-
als needed to undergo a proprietary postproduction step
called bonding, whereby the pigment was essentially
encapsulated in the powder resin. This process improved
the transfer efficiency, facilitated the use of overspray as
reclaim, and improved flake orientation. Surface treatment
technologies have now been developed that can help elimi-
nate the need for this extra step in the process [53]. Such
materials are marketed under the trade names of Af flair
PC DB by EMD Chemical and Cyclo by the Engelhard
Corporation.
In agricultural applications such as seed coatings, effect
materials have provided not only an easy means of identi-
fication, but also a way to prevent premature germination
and retain moisture during storage through decreases in
diffusion. By incorporation into plastic horticultural film, it
is possible to modify, through transmission and reflection,
certain wavelengths of the electromagnetic spectrum which
are beneficial to plants while blocking others enhancing the
speed, and quality of growth [54].
The laser marking of plastics has become a rapidly
expanding process used by end-product manufacturers
due to its speed, permanence, and quality versus standard
printing methods. Metal oxide-coated effect pigments have
been found to enhance and broaden the types of polymers
that can be used in this regard [55]. They provide a means
to improve the contrast within the surface of the plastic by
acting as a heat sink and allow the oxide on the surface of
the pigment to be partially reduced to the black sub-oxides
of titanium and can both amplify as well as enhance the
dark coloring.
An area of significant commercial importance, espe-
cially with the newer generations of effect materials, is
security. This functional application can be described to
have differing levels of importance. For example, credit
Fig. 24Cholesteric liquid crystal-optical properties.
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CHAPTER 26 EFFECT PIGMENTS 269
cards and high-end luxury packaging may have a number
of effect materials combined in specific ratios to create a
brand color that is difficult to copy. The needs for brand
identification, and protection, is a rapidly expanding area
in which effect pigments are being used either in or on the
products they are protecting. It has been known for some
time that standard interference colors when printed onto
documents cannot be photocopied due to the angle depen-
dence of the color. Many of the newer technologies such
as Chromaflair
, Spectraflair
, Variochrom
, Helicone
,
and Color Stream
measurement. These were correlated to observations using
a logistic regression model. Measurements at d/8, 45,
and 95 correlated well with visual observations. Inclusion
of the d/8 measurement in the optimized combination is
not surprising considering the diffuse-directional light-
ing used in the observations. Interestingly, statistically
equivalent results were obtained with 25, 45, and 110
measurements.
Alman [4] measured lightness, hue and chroma of
36 metallic colors as a function of aspecular angle. The
experiment was done in 1980. Metallics of those days exhib-
ited a strong lightness flop, while chroma flop was small and
hue flop almost nonexistent. Using polynomial modeling of
lightness as a function of aspecular angle, he determined
the residual error for each model. Large residual errors
resulted from linear models, obviously unable to fit the
curvature of the lightness response. Quadratic models with
three appropriately chosen measurement angles dramati-
cally reduced the average residual variance. Three angles
of measurement requires attention to color data (e.g., L, a,
b) at each of these angles, making colorimetric analysis a
nine-dimensional problem. Further reduction in residual
variance with four angles was insufficient to justify the
increased complexity posed by twelve dimensions. Based
on this work, he recommended measurement of metallics
at aspecular angles of 15, 45, and 110. Rodrigues [8]
repeated this experiment with base coat/clear coat colors,
including 18 metallics and 16 interference pearl colors used
in automotive finishes of the late 1980s. The interference
pearl colors exhibited strong lightness and chroma flop and
some hue flop. These experiments confirmed 15, 45, and
110 as the optimum angles of measurement. ASTM E2194
[9], Standard Practice for Multiangle Color Measurement
of Metal Flake Pigmented Materials, standardized this
geometry for measurement of metallic colors, as shown
schematically in Fig. 5. The 15 angle is referred to as the
near-aspecular angle, 45 as the mid-aspecular angle, and
110 as the far-aspecular angle.
Visual assessments of gonioapparent matches typically
cover a wide range of aspecular angles, from very near
specular (e.g., aspecular angle of 15), all the way to far
from specular (e.g., aspecular angle of 110). Occasionally
specimens are an acceptable match at angles between 25
and 75, but visual and instrumental assessments find the
match unacceptable outside this angular range. An example
(Fig. 6) shows lightness as a function of aspecular angle for
a standard (dark curve) and a batch (lighter curve) paint
sprayed on aluminum panels. The curves are a reasonably
good match at angles between 20 and 75 and were judged
visually acceptable when judged at these angles. However,
they deviate below 20 and above 75 and the panels were
judged as an unacceptable overall match. Both paints con-
tained the same absorbing and flake pigments. However,
the standard was a low solids paint, while the batch was
a medium solids paint. Higher solids allowed for less film
shrinkage as the sprayed batch paint dried, resulting in
poorer flake orientation. Side-tone scattering of light caused
by poorer flake orientation was visually quite apparent
Fig. 5Diagram of aspecular angles.
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276 PAINT AND COATING TESTING MANUAL 15TH EDITION
with the batch being judged unacceptably lighter and bluer
at the far-aspecular angle and slightly lighter at the near-
aspecular angle.
Commercially available spectrophotometers often pro-
vide 25 and 75 aspecular measurements in addition to
the angles standardized by E2194. The German standard
DIN 6175-2 [10] recommends use of 25, 45, 75, and
110. E2194 allows for this variation in angles as shown in
Table 1. Angles other than the preferred angles but within
the acceptable range may be used for less critical color
matches. For example, surface imperfections (e.g., orange
peel) resulting from spray application of finishes can cause
light to be reflected off the surface in a direction slightly
away from the nominal specular direction. Measurement
at 25 may be chosen as the near-aspecular angle when less
sensitivity to application differences is desired. However,
in critical color matching applications, batches should be
resampled and re-sprayed to match surface texture of the
standard specimen and adjusted to an acceptable color
match at the standardized 15 near-aspecular angle.
E2194 also provides a ray-tracing procedure to deter-
mine the effective aspecular angle and sets tolerances for
the percentage of rays that may deviate from the expected
angle. The Society of Automotive Engineers standard J1545
[11], Instrumental Color Difference Measurement for
Exterior Finishes, Textiles, and Colored Trim, also recom-
mends the angles standardized in E2194.
Fig. 5 shows a uniplanar geometry, i.e., the illumina-
tion axis, the viewing axes, and the normal to the specimen
surface are all in the same plane. Some commercial instru-
ments provide annular or circumferential measurement
or illumination. Annular geometry provides measurement
(or illumination) distributed continuously and uniformly
throughout the 360 of azimuth of the measurement. Cir-
cumferential measurement (or illumination) is an approxi-
mation of annular, using a discrete number of sensors
(or illumination beams) distributed at uniform intervals
throughout the 360 of azimuth of the measurement. These
measurements minimize directional effects such as surface
irregularities or preferential flake orientation. For example,
when paint is sprayed on a vertical surface, the Earths
gravity may cause the flake to tilt rather than remaining
parallel to the surface as the paint dries. If two halves of
such a painted panel are viewed side-by-side, both in the
same orientation as when sprayed, they will appear as a
good color match, regardless of aspecular viewing angle.
However, if one half is rotated 180 in its own plane, the
flakes in the two halves are now tilted in opposite directions
and the two halves will no longer match. This is referred
to as the venetian-blind effect. Annular or circumferential
instruments will average out the directional effects of
tilted flake and measure the two halves as being the same.
They would be the appropriate instruments if the goal is
to neglect these effects. However, often in the presence of
the venetian-blind effect, these instruments will provide
measurements that do not agree with visual assessments.
If a measurement neglecting the rotational effect is desired,
it can be achieved with a uniplanar geometry by averag-
ing several measurements taken while rotating the panel
orientation with respect to the instrument after each read-
ing. Another drawback is that annular or circumferential
geometry requires symmetry. Either the illumination or the
viewing axis must be on the normal or else determination of
the aspecular angle is ambiguous. This limits the maximum
aspecular angle to something less than 90, short of the
110 recommendation for critical color matching.
MEASUREMENT OF COLORS CONTAINING
INTERFERENCE FLAKES
A commercial automotive color, Mystichrome, containing
Chromaflair
2
interference flake was measured on a gonio-
spectrophotometer. This measurement is shown in Fig. 7
with hue angle as a function of aspecular angle at several
different illumination angles. Unlike metallics, where color
Fig. 6L* gonio-curves on real metallic paints showing
relative effectiveness of different geometries.
2
Flex Products Inc., 1402 Mariner Way, Santa Rosa, CA 95407.
TABLE 1ASTM E2194 angles for metallic
color measurement
Aspecular Angle
Preferred angle
for Critical Color
Match Acceptable Range
Near-aspecular 15 1525
Mid-aspecular angle 45 45
Far-aspecular angle 110 70110
Fig. 7Hue shifts observed in strong interference colors.
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CHAPTER 27 MEASUREMENT OF GONIOAPPARENT COLORS 277
is a function of only aspecular angle, hue of colors contain-
ing interference flakes is also a strong function of illumina-
tion angle. Hue is also dependent on whether viewing is
in a positive or negative direction away from the specular.
Thus the hue at aspecular angle minus 15 is very different
from that at plus 15. It is only at aspecular angles greater
than about 55 that the hue shifts are seen to be indepen-
dent of illumination angle. Fig. 8 shows that chroma of this
coloralso has a strong dependency on angle of illumination
and aspecular angle, with the curves beginning to overlap
at an aspecular angle of about 45. The degree of color shift
and its dependence on illumination angle is obviously a
function of the particular flake used, its content in the color
and the types of other pigments in that color. The interfer-
ence flake by itself would exhibit a stronger color shift.
Fig.9 shows hue shifts for a Chromaflair
interference flake
in a clear paint containing no other pigments. It shifts from
blue-green, through purple to green-yellow when viewed
10 off specular as illumination angle is changed. Thus
manufacturers of these flakes must measure them at a wide
variety of illumination angles, each at multiple viewing
angles. ASTM E2539 [12], Standard Practice for Multi-
angle Color Measurement of Interference Pigments covers
the instrumental requirements and parameters needed to
make instrumental measurements of thin film interference
pigments. The Standard states that these pigments are
typically evaluated for color and appearance in a medium
such as paint or ink. The geometries specified for measur-
ing these pigments are shown in Tables 2 and 3.
The physics of light interference shows that the hue
shift in interference pigments occurs only from flake ori-
ented so as to act as specular reflectors of the illumination
source to the detector. A term to address this is color angle,
not used in E2539 but defined in E284. The discussion of
this term in E284 states flakes in a coating have an angular
distribution, and the interference effect will be exhibited in
a given measurement geometry only by the flakes that are
oriented so that they behave as specular reflectors. Color
angle is defined as half the angle between the illumination
and detection axes of the measurement geometry. Fig. 10
is an a*-b* plot of the measurements of Mystichrome. The
curves show loci of constant aspecular angles with chang-
ing illumination angle. The slightly curved spokes ema-
nating from a point close to the origin are loci of constant
color angle. Each spoke is at approximately the same hue
angle. This suggests that measurements at color angles
could be useful in characterizing the hue shift of interfer-
ence colors. Another potentially useful term in E284 is flake
Fig. 8Chroma shifts observed in strong interference colors.
Fig. 9A Chromaflair
;
and Mike Nofi, Flex Products Inc., and Larry Steenhoek,
DuPont, for discussions on interference flakes and gonio-
spectrophoto-metric measurements.
References
[1] ASTM Standard E284, Standard Terminology of Appear-
ance, Annual Book of ASTM Standards, Vol 06.01, ASTM
International, West Conshohocken, PA.
[2] Nowak, P. J., Paint and Coating Testing Manual, 15th. ed.,
ASTM International, West Conshohocken, PA.
[3] ASTM Standard E2175, Standard Practice for Specifying the
Geometry of Multiangle Spectrophotometers, Annual Book
of ASTM Standards, Vol 0.6.01, ASTM International, West
Conshohocken, PA.
[4] Alman, D. H., Directional Color Measurement of Metallic
Flake Finishes, Proceedings of the ISCC Williamsburg Con-
ference on Appearance, Vol. 53, Inter-Society Color Council,
Reston, VA, 1987, p. 53.
[5] Schmelzer, H., Farbmessungen und Rezeptberechnungen bei
Metallic-Automobil-lacken, Proceedings of the 18th FATIPEC
Congress, Vol. I(B), www.fatipec.com, Brussels, Belgium,
1986, p. 607.
[6] Venable, V. H., A Model for Interpreting Three-Angle Mea-
surements of Flake Finishes, Proceedings of the ISCC Wil-
liamsburg Conference on Appearance, Vol. 57, Inter-Society
Color Council, Reston, VA, 1987, p. 57.
[7] Saris, H. J. A., Gottenbos, R. J. B., and van Houwelingen, H.,
Correlation between Visual and Instrumental Color Differ-
ences of Metallic Paint Films, Color Res. Appl., Vol. 15, 1990,
pp. 200205.
[8] Rodrigues, A. B. J., Measurement of Metallic and Pearlescent
Colors, Die Farbe, Vol. 37, 1990, pp. 6578.
[9] ASTM Standard E2194, Standard Practice for Multiangle
Color Measurement of Metal Flake Pigmented Materials,
Annual Book of ASTM Standards, Vol 06.01, ASTM Interna-
tional, West Conshohocken, PA.
[10] DIN Standard 6175-2, Farbtoleranzen fr Automobillacki-
erungen. Teil 2: Effektlackierungen, Deutsches Institut fr
Normung, Beuth-Verlag GmbH, Berlin, 2001.
[11] SAE Standard J1545, Instrumental Color Difference Mea-
surement for Exterior Finishes, Textiles, and Colored Trim,
Society of Automotive Engineers, Warrendale, PA.
[12] ASTM Standard E2539, Standard Practice for Multiangle
Color Measurement of Interference Pigments, Annual Book
of ASTM Standards, Vol 0.6.01, ASTM International, West
Conshohocken, PA.
[13] Steenhoek, L. E., Standardization of Gonio Color Measure-
ment, Presentation to the AATCC/ISCC Symposium on Indus-
trial Color Challenges, AATCC, Research Triangle Park, NC,
February 22, 2007.
[14] CIE Technical Report Colorimetry, CIE 15:2004, 3rd ed., CIE
Central Bureau, Kegelgasse 27, A-1030 Vienna, Austria.
[15] Rodrigues, A. B. J., et al., Weighting Function for the Measure-
ment of Lightness Differences in Gonioapparent and Dark
Colors, Proceedings of the 9th Congress of AIC, SPIE 4421,
SPIE, Bellingham, WA, 658661.
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282
INTRODUCTION
COATINGS ARE IMPORTANT WIDELY USED PRODUCTS
that provide corrosion
2
protection of metals and other
substrates. Paints that contain anti-corrosion pigments
account for about 65 %70 % of all areas protected by anti-
corrosion coatings. Paint
3
provides a number of desirable
attributes including relatively low cost, simplicity of appli-
cation to simple and complex structures, aesthetic beauty,
ease of repair and restoration, as well as metal corrosion
protection that is markedly enhanced when anti-corrosion
pigments are present.
Coatings may be classified in various ways such as by
their end use, surface character, and so on. For example, an
end-use classification might include coatings for transporta-
tion vehicles and associated hardware, such as boats, ships,
piers, and other items subject to marine environments,
such as reactors, drums, piping, buildings, etc., exposed
to harsh industrial environments; pipeline coatings, archi-
tectural coatings; artists paints that have aesthetic, aging,
substrate nature needs; and many others. Each of these
classes has different requirements. Marine coatings must be
resistant to high humidity, chloride presence, and aqueous
immersion; pipeline coatings must be resistant to crude oil,
natural gas, water and aggressive aqueous solutions, and
solvents; and so on [15]. Each end use will have its own
particular requirements. Various chapters in this manual
deal with coatings for a variety of end uses.
The three main components of an organic paint are
pigment, binder, and volatile vehicle.
4
The pigment is an
insoluble, finely ground material that provides color and
opacity as well as corrosion resistance and water barrier
properties when particular pigments are used. The binder is
the polymeric, nonvolatile portion of a formulated coating.
It is the important ingredient that forms a film
5
as paint
dries, and it holds the pigment particles or other additives
in a separated, suspended state within the paint film. Bind-
ers are either polymeric in nature or are capable of reacting
and forming a thermoplastic or thermoset polymeric film
under specified conditions. They are comprised of oils,
epoxides, alkyds, polyesters, acrylics, vinyls, and the like.
The volatile vehicle dissolves or disperses the binder, and it
allows the coating to form in a thin, continuous film. In cer-
tain formulations, a curing agent
6
or hardener will be incor-
porated into the system. In the case of ultraviolet-radiation
curable coatings, the curing agent will be a photoinitiator
that effects rapid polymerization of combinations of mono-
meric and oligomeric species.
Completed coatings are comprised of one or more film
layers with the number of layers and their individual thick-
ness dependent on the particular end use involved and on
specifications. For example, a three-layer coating system
7
might be composed of a primer that is directly applied to
the substrate surface, a color coat or decorative layer, and
a clear topcoat that protects the color coat and provides
gloss. Appliances may have two coats, a primer and a col-
ored topcoat. Automobile body coatings usually have four
layersan electrodeposited primer, a primer-surfacer, a
color coat, and a topcoat. Powder coatings are often used as
single-layer coatings. The most important layer in the coat-
ing system is the primer since it is primarily responsible for
protection against metal corrosion. It must have excellent
wetting and adhesion to the metal surface and to the next
applied coating. Components of the primer, when used
as an anti-corrosion paint, are various corrosion inhibi-
tors
8
that are also known also as anti-corrosion pigments.
Primer coatings are sometimes named after a pigment, for
example, zinc-rich primer (ZRP), whose formability may
be examined as described in ASTM D4146, Standard Test
Method for Formability of Zinc-Rich Primer/Chromate
Complex Coatings on Steel.
28
Protective Coatings and Inorganic
Anti-Corrosion Pigments
Lucien Veleva
1
1
Research Professor, Center for Investigation and Advanced Study (CINVESTAV), Applied Physics Department, Carr. Ant. a Progreso, Km.6,
Cordemex, Merida, C.P.97310, Yucatan, Mexico; e-mail: veleva@mda.cinvestav.mx
2
Corrosion: The physical-chemical interaction of metal (alloy) with its environment that results in change of metal properties (up to its fnal
destruction) and characteristics of the environment; general characteristics of corrosion are described in Glossary of Corrosion-Related
Terms, NACE International, 1998.
3
Paint: A pigmented liquid or paste coating material, or a coating resulting from the application of such a material.
4
Vehicle: The liquid portion of a formulated coating material.
5
Film: A thin, not necessary visible, layer of material.
6
Curing agent/hardener: A chemical substance used for curing ingredients in a coating formulation.
7
Coating system: The complete number and types of coats applied to a substrate in a predetermined order. (When used in a broader sense,
surface preparation, pretreatments, dry flm thickness, and manner of application are included.)
8
Corrosion inhibitor: Chemical mixture comprised of a combination of substances that, when present in the proper concentration in the
corrosion system, prevents or reduces the rate of metal corrosion.
MNL17-EB/Jan. 2012
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 283
An organic coating system protects metal substrates
against corrosion by means of one or more of several
mechanisms:
Decreasing the rates of anodic (oxidation) and/or
cathodic (reduction) corrosion half-reactions that
occur on the metal/paint interface.
Introduction of high electrical resistance into the
circuit of the metal/electrolyte corrosion cell
9
that
is caused by the nonconductive organic film that is
applied on the metal substrate.
Acting as an effective physical barrier against the trans-
port of aggressive species, such as water, which is the
basis of the electrolyte/humidity conditions; oxygen,
which is the oxidizing agent; and various corrosion
ions (Cl
, SO
4
2
, etc.) to the metal surface. In general,
the anti-corrosion efficiency of an organic primer film
is a function of four factors:
The nature of the metal substrate, that is, its suscep-
tibility to oxidative corrosion.
The state of the metal/primer interfacefor exam-
ple, its electrical resistance and capacity, the nature
of ions or molecules present in this region, etc.
The composition of the primer film and efficiency of
the anti-corrosion pigments and any other inhibitors.
Corrosion aggressivity
10
of the environment and the
characteristic nature to which the coated metal is
exposed.
CERTAIN DEFECTS AND COATING APPLICATION
Although anti-corrosion pigments play an important role
in protecting metals from corrosion, those applying the
coating must make sure a number of considerations are
met to ensure the coating properly functions. Blistering
(Fig. 1) is probably the greatest cause of coating failure.
It can be identified by small- to medium-sized bubbles or
blisters that form under the paint film. These result in par-
tial or complete detachment of the coating from the metal
substrate. Blistering is caused by painting on a damp or
wet surface, which causes trapped moisture to expand the
paint film; painting in direct sunlight on a hot substrate,
which dries the paint surface too quickly and traps solvent
vapor in the film; painting during rain or in a very high
humidity environment, including heavy dew; by painting
over an insufficiently dried coating; or a low-quality paint
that is porous.
When blistering occurs, the efficiency of anti-corrosion
pigmented coatings is significantly diminished, and they
cannot prevent metal corrosion; in fact, the process may
well be accelerated. The corrosion products
11
formed in
delaminated areas are usually voluminous in nature and
exert pressure on the coating film. This pressure buildup
will lead to cracking
12
or the appearance of micro-fissures
and further loss of adhesion.
Blooming
13
and filiform corrosion
14
are failures that
result in coating damage. These failures usually occur in
coating areas that are defective or in areas that have low
mechanical strength and physicochemical degradation
(aging). Thus, from the corrosion protection standpoint,
good substrate adhesion of the various layers is needed.
Good adhesion will result in a surface with high ionic resis-
tance that inhibits formation of local anodes and cathodes
on the metal surface thus improving corrosion resistance.
Since 1979, it has been suggested that the coatings having
a critical resistance of less than 10
7
cm
2
are not protec-
tive. Therefore, it is highly recommended that the electric
resistance applied coatings, including any defective areas,
be measured. This will provide important information
for the analysis of degree of coating protection and fail-
ures. ASTM D5162, Standard Practice for Discontinuity
Testing of Nonconductive Protective Coating on Metallic
Substrates, is a practice for electrical detection of minute
discontinuities. Some corrosion failures in paint coatings
are shown in Fig. 2.
SURFACE PREPARATION
When the term coating system is used in a broad sense,
surface preparation, pretreatments, dry film thickness, and
manner of application are included. The protective effi-
ciency and life of a coating system are markedly dependent
on proper surface preparation, which may be costly but is
a needed portion of the paint application process. It has
been shown that over 80 % of all paint failures (peeling,
efflorescence, etc.) can be attributed to poor or improper
surface preparation (Fig. 3). Therefore, paint manufactur-
ers often make comments such as good paint deserves a
good surface or the quickest way to achieve paint failure
is inadequate surface pretreatment.
COATING CHARACTERIZATION METHODS
Investigation of the parameters that characterize coatings
can be carried out according to specific methodologies
established in international standards (ASTM, NACE, ISO,
Fig. 1Blistering of paint coating.
9
Corrosion cell/galvanic cell: The combination of different elec-
trodes (anode and cathode), connected in series, in contact with
an electrolyte (ionic conductor); see Glossary of Corrosion-Related
Terms, NACE International, 1998.
10
Corrosion aggressivity/corrosiveness: The tendency of an envi-
ronment to cause corrosion.
11
Corrosion products: The substances formed as a result of the
metal corrosion process. Usually they comprise a majority phase
of various oxides and hydrated oxides (hydroxides) and some-
times a minority phase of carbonates, chlorides, sulfdes, sulfates,
or other.
12
Cracking (of coating): Breaks in coatings that extend through to
the substrate.
13
Blooming/blushing: Whitening and loss of gloss of a coating,
caused by moisture.
14
Filiform corrosion: Corrosion that occurs under coating in the
form of randomly distributed threadlike flaments.
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284 PAINT AND COATING TESTING MANUAL 15TH EDITION
etc.). Several ASTM International documents are listed in
the references section. These and other standards can be
used to characterize, develop methods, and analyze coating
failures. To select an appropriate anti-corrosive coating for
an environment of interest, two tests are recommendeda
natural weathering or field test under actual conditions
and an accelerated laboratory test under selected, artificial
conditions that is carried out in a test chamber. Acceler-
ated laboratory tests provide rapid comparative results in a
short time because they usually use higher values of some
parameters (temperature, humidity, particular radiation,
and aggressive environment) than those encountered in real
or field conditions [68].
A new group has recently been investigating a method
termed accelerated test in natural conditions. Their
efforts may result in an improved correlation between
field testing and accelerated weathering. The black box
test, in which the resistance of materials to solar radiation
filtered through glass is evaluated, has been found to be
a useful tool [9]. Procedures that deal with the black box
test can be found in ASTM D4141, Standard Practice for
Conducting Black Box and Solar Concentrating Exposures
of Coatings; ASTM G24, Standard Practice for Conduction
Exposures to Daylight Filtered Through Glass; and other
standards.
INORGANIC ANTI-CORROSION PIGMENTS
Anti-corrosion pigments are coloring components of paint
that can influence and control the corrosion of metal sub-
strates by moderating the rate at which corrosion takes
place. Because of this moderating effect, these pigments are
also known as corrosion inhibitors. These coating compo-
nents are usually introduced into the primer layer.
A variety of metals such as aluminum, chromium,
lead, iron, and zinc are known as effective anti-corrosive
pigments, and they are introduced into the coating for-
mulation as finely ground metal or powdered metal oxide.
Oxides of lead, chromium, and iron (burnt sienna,
15
burnt
umber,
16
and Tuscan red
17
) have been extensively used in the
past. Currently, their usage is restricted because of toxicity
considerations and their effect on the environment. How-
ever, it should be pointed out that the inhibiting protection
provided by pigments such as red lead (also called minium,
Pb
3
O
4
or 2PbO PbO
2
), yellow zinc chromate (ZnCrO
4
), and
red zinc chromate (ZnCrO
4
+ Fe
2
O
3
) is very satisfactory.
Anti-corrosive primers based on such compounds have
been used for a long time to satisfactorily protect metal
structures exposed to a variety of hostile environments.
Zinc phosphate (ZP), barium metaborate, and stron-
tium chromate pigments are also common ingredients in
corrosion-inhibiting coatings. Thin wash-inhibiting prim-
ers are often formulated with chromate or phosphate pig-
ments that are introduced in a synthetic polymeric binder
such as a vinyl chloride copolymer. The variety of inorganic
corrosion-inhibiting pigments includes also lead carbonate,
strontium chromate, zinc oxide, and ZP.
Chromate-Based Compounds
Due to their excellent cost/efficiency ratio, chromates are
one of the most used chemicals in corrosion protection sys-
tems for metallic surfaces. These anti-corrosive pigments
are incorporated into paints in the form of solid, fine par-
ticulate materials that are dispersed throughout the paint
film. They function as inhibitors, affording protection by
an electrochemical mechanism. The chromate-containing,
corrosion-inhibiting pigments include the sparingly soluble
chromates of the alkaline earths, Ca, Sr, Ba, and Zn. They
provide a source of active, inhibiting Cr
6+
compounds that
act as very powerful, effective corrosion inhibitors.
Chromate-based compounds are used in primers
throughout industry as a component in corrosion pro-
tection systems for a range of metal substrateseven
substrates exposed to aggressive environments of high
chloride/chromate ratios. The oxo-anions of hexavalent
chromium uniquely inhibit the corrosion of many met-
als and alloys, and they have been particularly useful
for protecting the high-strength aluminum alloys against
corrosion. Chromates are excellent inhibitors of oxygen
reduction in near neutral and alkaline solutions. In these
environments, they can stifle corrosion by suppressing
the cathodic oxygen reduction that is the necessary partial
reaction of the corrosion process.
The inhibition mechanism appears to involve reduc-
tion of Cr
6+
to Cr
3+
at a metal surface and formation of
an irreversibly adsorbed Cr
3+
hydroxide surface layer of
near-monolayer thickness [10]. The results indicate that
the adsorbed Cr
3+
film formed by Cr
6+
reduction is a power-
ful inhibitor of oxygen reduction on surfaces of aluminum
and its alloys. This is due both to occupation of any active
chemisorption sites and to inhibition of electron transfer.
In the context of corrosion protection, Cr
6+
acts as a site-
directed irreversible inhibitor that migrates to active sites
Fig. 2Corrosion failures in protective paint coatings: (a) Area
of corrosion of a substrate and appearance of red rust on
steel. (b) Corrosion products (rust) forming on steel, where
the protective coating system has been damaged mechanically
(scratch).
15
Sienna: Natural yellow-brown color pigment, the mineral limo-
nite FeO (OH) nH
2
O, used in the production of oil paints. Along
with ochre and umber, one of the frst pigments used by humans for
painting. Chemically, burnt sienna (a warm mid-brown iron oxide
pigment) is formed by burning raw sienna.
16
Umber: Natural brown clay pigment that contains iron and man-
ganese oxides. The dark brown pigment burnt umber is made by
heating umber, and it is used for oil and water color paint.
17
Tuscan red: The mineral hematite (ferric oxide), it is the principle
coloring agent in red ochres, such as Indian red, Terra Pozzuoli,
Venetian red, etc. These pigments are basically hematite associated
with varying proportions of mineral impurities such as clay, chalk,
and silica.
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 285
for the oxygen reduction reaction. Here it is reduced to Cr
3+
and forms a permanent inhibiting monolayer. The Cr
3+
film
formed is nonconductive and inhibits further Cr
6+
reduc-
tion and outer-sphere redox processes. Evidence from older
and more recent studies indicate that inhibition of alumi-
num corrosion is derived from both inhibition of oxygen
reduction and inhibition of metal dissolution reactions
mainly due to a delay in the onset of pitting. Inhibition of
corrosion by chromates appears to be closely linked to their
ability to irreversibly adsorb onto metal and oxide surfaces.
Chromates can also inhibit corrosion by slowly leach-
ing from the protection system and migrating through
moisture on the substrate surface where reaction with
actively corroding sites takes place. This scheme results in
passivation and suppression of pitting and crevice corro-
sion [1113]. When present in even a very small concentra-
tion (as 10
4
M), the dichromate ions (CrO
4
2
) effectively
decrease the metastable pit nucleation rate and minimize
pit growth rates that occur as a consequence of aggressive
chloride ions attack. This has a large effect in the cathodic
region and no effect in the anodic region. These observa-
tions suggest and confirm that chromate or its reduction
product act as efficient cathodic inhibitors.
The distribution of SrCrO
4
, BaSO
4
, and TiO
2
in two
chromate-inhibited primers has been characterized using
electron microprobe analysis, Raman spectroscopy, x-ray
diffraction, and position annihilation lifetime spectroscopy
[14]. It was found that TiO
2
was evenly dispersed throughout
the primer, while BaSO
4
and SrCrO
4
appeared as larger par-
ticles or platelets with sizes on the order of several microns.
When immersed in solutions of pH 1, 3, 5, and 7, SrCrO
4
,
and possibly SrCr
2
O
7
, was observed to leach out of the
primers after water uptake by the primer and dissolution of
SrCrO
4
particles. The amount of chromate leached from the
primers was greatest for pH 1, followed by pH 3, 5, and 7.
Kendig and Buchheit [15] have published a critical
review that deals with the aqueous chemistry of chromium
and the origins of chromium toxicity.
Zinc-Rich Paints
Anti-corrosive zinc-rich paints provide corrosion protection
by two principal mechanisms:
a) Galvanic or sacrificial protection.
18
This is due to
the fact that the standard electrode potential
19
of
zinc (0.76 V) is more negative than that of iron
(0.44 V), therefore in a zinc-iron (steel) coupling,
zinc will take the role of sacrificial anode that cor-
rodes (oxidizes) preferentially to iron. In this man-
ner, zinc is protecting the steel (iron) surface from
corrosion. Since this occurs, it indicates that very
good electric contact between the zinc particles and
metal substrate had been achieved and maintained.
Due to the presence of coating defects (porosity),
it is understood that the zinc-rich coating acts as a
porous electrode.
b) Physical barrier protection. The physical barrier behav-
ior of ZRPs is reinforced by the nature and quantity
of zinc corrosion products. These products result in
formation of a dielectric layer on the steel surface;
moreover, these products are less voluminous than
steel products, and, as a consequence, they do not exert
a great deal of pressure on the organic coating.
Different ZRPs have been tested in industrial atmo-
spheres. For example, when primers based on silicate and
on epoxide (70 % and 79 % Zn powder, respectively) were
investigated, the results indicated that the primers based
on silicate provided better galvanic (sacrificial) protection
than the epoxy primer. It is thought that in the coating the
zinc particles are in electric contact with each other and
also with the metal substrate (Fig. 4). With the zinc particles
interconnected, sufficient galvanic (cathodic) protection is
available to protect the metal substrate. However, while the
zinc corrosion products are not as voluminous as with some
primer systems, they produce a number of blisters in the
paint coating [Fig. 4(a)]. Moreover, the migration paths for
anti-corrosion agents through the organic coating could be
achieved through the pore defects in the coating [Fig. 4(b)].
Zinc Oxide-Containing Systems
Powdered zinc oxide was introduced as an inhibitive, anti-
corrosion pigment for primer formulations in the past few
decades. Typically the pigment was used at 3357 mass %
of the primer composition. It contributed to successful
anti-corrosion protection of metallic structures exposed
to marine atmospheres, i.e., highly chloride-contaminated
environments. Various organic compounds such as epoxy
esters, galic acid (antioxidant) polyesters, polyurethanes,
and the like are used as the binder for zinc oxide coatings. It
should be noted that several physicochemical properties of
zinc-rich paints (specific gravity, oil absorption, and other
properties of a pigment inhibitor) may be affected due to
the pigment volume concentration (PVC) considerations.
More than 25 years of paint evaluation at the Kennedy
18
Sacrifcial protection: Reduction of corrosion of a metal in an
electrolyte (humidity) by galvanically coupling it to a more anodic
metal having more positive electrode potential.
19
Electrode potential: The potential of an electrode in an electrolyte
as measured against a reference electrode.
Fig. 3Peeling (a) and efflorescence (b) failures in paint coatings.
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286 PAINT AND COATING TESTING MANUAL 15TH EDITION
Space Center (marine-coastal test station) has identified the
fact that zinc-rich paints are the best choice for corrosion
protection of launching equipment and support equipment
in service on land.
During production of zinc pigments, some zinc may get
oxidized to ZnO when it comes in contact with oxygen and
eventually all zinc dust will contain at least traces of ZnO
as an impurity. The electrical properties of ZnO are interest-
ing and complex. ZnO acts an inhibitor to chloride-induced
corrosion, seals pores in primers, and improves the primers
barrier properties. Therefore, it has been interesting to
include ZnO in a Zn-rich primer and to study its effect on
corrosion-protection properties [16]. In the reported study,
the effect of spherical ZnO on anti-corrosion properties
was evaluated along with lamellar zinc. ZnO was added in
various weight fractions to an epoxy-based primer at 60 %
PVC. These coated panels were evaluated along with others
for conductance, packing density, and morphology. Corro-
sion resistance was measured after a 3,000 h exposure in a
salt spray. Open circuit potential (i.e., corrosion potential)
was measured in a 3.5 wt % NaCl salt solution. When Zn
and ZnO are mixed together, they quite likely formed ap-n
junction at their interface. At a contact established between
a metal and a semiconductor (known as a Schottky junc-
tion), electrons will flow from the material with the highest
Fermi level to that with the lowest Fermi level, creating a
positive charge in the semiconductor. This will allow elec-
tron transport in a controlled manner on the top surface
of the coating, which provides better cathodic protection
for the Zn-ZnO combinations rather than for Zn only. The
packing density was better at 15 wt % ZnO, which implies
that the compactness was enhancing junction formation.
The best corrosion protection was obtained with 15 wt %
of ZnO. Hence, ZnZnO p-n junction formation gives bet-
ter corrosion resistance properties than either cathodic or
barrier protection alone, and the combination would be the
best choice for single-coat metal primer.
Electrochemical behavior of epoxy anti-corrosion
paints based on zinc molybdenum phosphate and zinc oxide
pigments has been studied. The main investigative tool used
to describe the efficiency of epoxy-based anti-corrosion
primers was electrochemical impedance spectroscopy (EIS)
[17]. The film-forming material (binder) in these studies
was a solvent-borne, bisphenol A epoxide polyamide, and
several pigments were used with this binder. The main anti-
corrosion pigment used was micronized ZnO (average par-
ticle diameter 1 mm) at loading levels of 10 % and 30 % by
volume and with respect to the total pigment content. The
complementary pigments used were ferric oxide (Fe
2
O
3
) and
barium sulfate (BaSO
4
). Twenty percent by volume of the
resulting pigment mixture were replaced with zinc oxide.
The ferric oxide was used because its colloidal particles
are said to interact with metallic substrates and thereby
increase coverage. Steel-coated samples were exposed to
a 0.5M NaCl solution and during the test their corrosion
potential was monitored every 24 h. The results indicated
that addition of micronized ZnO to the base mixture had a
positive reinforcement effect on the protective properties of
the anti-corrosion primer. This was thought to be related to
the isoelectric point of ZnO particles (pH<9), which deter-
mines their positive surface charge and electrostatic attrac-
tion with the molybdate anion. In this case, the double-layer
capacitor formed has a very high charge. Moreover, this
strong attraction inhibits and saves ZnO particles from
rapid dissolution by hydroxide. These results also indicate
that there is an optimum concentration ratio of zinc molyb-
denum phosphate to zinc oxide that will ensure the good
anti-corrosion properties.
Zinc Phosphate
ZP is the most commercially successful non-toxic inhibitive
pigment used in paint formulations. Furthermore, the use
of phosphates does not represent an excessive cost, and
their application is even easier than other proposed alter-
natives for chromate pigments. This is the anti-corrosive
pigment most frequently used in paints [1821]. The mas-
sive use of nontoxic and environmentally acceptable ZPs
developed an immense pressure for regulations that pro-
hibited the use of red lead and chromated anti-corrosion
pigments. Experimental results suggest that ZP and all
phosphate-based pigments (zinc-aluminum polyphosphate,
ZP modified with organic corrosion inhibitor, etc.) exhibit
improved anti-corrosion efficiency when their concentra-
tion is increased [21].
The effect of ZP over the barrier properties of different
paints has been studied using a variety of techniques. The
investigations revealed that commercial ZP powder was a
mixture of the dihydrate and tetrahydrate species, however,
when it is blended with a polymeric binder, only the tetrahy-
drate form was detected. Incorporation of this pigment into a
paint led to a definite improvement of the barrier properties.
This was particularly apparent in the case of chlorinated rub-
ber polymers. The finding suggests that the nature of binder-
pigment interactions play an important role and should be
given consideration in studies of barrier properties [22].
To improve the protective action of environmentally
acceptable coatings, a second generation of materials
aimed at combining, in a synergistic manner, the corrosion
inhibition properties of phosphates and molybdates, called
phosphomolybdate pigments, has been developed. Zinc
molybdenum phosphate seems to be one good possibility,
and it is claimed to have equal or superior anti-corrosion
behavior when compared with chromate and ZP. From a
corrosion point of view, when zinc molybdenum phosphate
Fig. 4Schematic representation of corrosion in steel pro-
tected by zinc-rich paint (ZRP): model of blister (a) and corro-
sive attack through the coating pore (b).
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 287
pigment is added to a water-borne paint and applied as a
unique protective coating to a steel substrate, an interesting
combination for study exists [23]. Paint with PVCs of 27 %
and 10 % (v/v) of this pigment provided effective protec-
tion against weather conditions and improved properties
such as chalking (Fig. 5), gloss, and yellowing. Similarly,
the efficiency of zinc tripolyphosphonate (ZTPP) as an anti-
corrosion pigment has been evaluated [24]. Solvent-borne
paints containing BaSO
4
, talc, and TiO
2
together with 30 % or
10% v/v (by volume) of ZTPP, with respect to the total pigment
content, have been formulated. Two polymers were chosen
as film-forming materials: an alkyd and an epoxy-polyamide
(1:1) mixture. The results demonstrated that ZTPP inhibited
corrosion when incorporated into a paint film. It showed
excellent performance when employed with the alkyl resin.
It should be pointed out that even though the literature
reports indicate phosphate-based pigments to be environ-
mentally acceptable and ZP is classified as not hazard-
ous to human health under United States regulations,
according to other regulations of the United States and the
European Union, ZP is considered very toxic in an aquatic
environment. Therefore, ZP-based pigments should not
be qualified as environmentally friendly products. With
this information in mind, the aim of a reported study [25]
was to evaluate the anticorrosive performance of organic
epoxy coatings pigmented with the following non-toxic
pigments: ZP, zinc phosphomolybdate (ZPM), and zinc
calcium phosphomolybdate (ZCPM). All of these coatings
were compared with an epoxy coating pigmented with zinc
chromate (ZC). The analysis was based on coated steel
samples immersed in aqueous 0.01 mol/L sodium chloride
solutions and in accelerated tests conducted in a salt-spray
chamber. ZPM and ZCPM coatings performed best in the
total immersion test, but in the salt spray test, the corrosion
inhibitor performance of all three pigmented coatings was
similar. This suggested that only in the less aggressive test
is it possible to detect any difference between the coatings
when investigating the non-toxic pigments.
Zinc Ferrites
The synthesis of zinc ferrites (ZnFe
2
O
4
) with different
particle shapes for applications in anti-corrosion coatings
provides a new way of protecting metals against corrosion
[26]. One benefit obtained with these anti-corrosion pig-
ments is the fact that they do not contain any environmen-
tally harmful substances. They are synthesized through a
high-temperature process that is conducted from about
600 up to 1,100C from hematite (alfa-Fe
2
O
3
), goethite
(alfa-FeOOH), magnetite (Fe
3
O
4
), and specularite (Fe
2
O
3
)
entering into a solid phase reaction with zinc oxide (ZnO).
The formulated zinc ferrites particles have a rod-like, lamel-
lar, and/or isometric shape. The zinc ferrites were used to
prepare coatings with epoxy and with water-borne styrene-
acrylate binders that were subjected to post-application
tests for physical-mechanical and anti-corrosion properties.
All of the synthesized pigments had good anti-corrosion
efficiency in the binders studied. When compared with a
commercially available anti-corrosion pigment, their pro-
tective power in coatings was demonstrably stronger.
Magnesium-Rich Primer
When two metals are exposed to a corrosive environment
and placed in contact with each other, the more active
metal will preferentially corrode and thereby provide sac-
rificial protection for the nobler or less active metal. This
concept has been applied for many years by use of ZRPs for
the protection of steel. Investigations using other composi-
tions and metals, including manganese, have been made
[27]. Zinc dust and magnesium-powder as pigments have
been incorporated in epoxy-polyamide and butyl-titanate
binders, with PVC that ranged from 20 to 74. These pro-
tective coatings were applied to mild steel substrates and
immersed in an aqueous 3 wt % sodium chloride solution
and the corrosion currents were measured to characterize
corrosion performance. The results were found to be com-
parable indicating that magnesium-powder can be used an
alternative to Zn-powder for metal-rich primers.
The electrochemical behavior of Mg-rich primer on
aluminum alloys (specifically, AA2024 and AA7075) has
been studied with EIS, open circuit potential, and poten-
tiody-namic polarization [28,29]. Results showed that the
magnesium-rich primer provides sacrificial protection for
the aluminum substrate by means of a two-stage mecha-
nism. In a first stage, corrosion of aluminum is prevented
by cathodic polarization. Magnesium cathodically polarizes
aluminum and shifts its potential below the pitting corro-
sion potential. The consequence of this polarization can
be either the prevention of pit nucleation at the exposed
aluminum areas or the inhibition of pit growth in the
nucleated pits. During this stage, any defects on the surface
will become cathodic whereas the magnesium particles are
anodic. At the cathodic areas, reduction of hydrogen takes
place and possibly dissolved oxygen increases the pH above
the threshold for the precipitation of magnesium oxide.
This precipitation leads to the formation of a porous layer
that further inhibits corrosion by a barrier mechanism,
which is considered to be the second or later stage of the
protective mechanism. The typically high dissolution rate
of magnesium is significantly decreased by its incorpora-
tion into the polymer matrix.
Iron Oxides
The iron oxides represent an important category of inor-
ganic pigments in which iron is most often present in a
trivalent form. Oxides, or rather hydroxide-oxides, can be
used as pigments in paints [30]. Ferric oxide is usually
introduced in the total pigment formula because its col-
loidal particles are said to interact with metallic substrates
increasing its coverage. Yellow-goethite -FeOOH with
needle-shaped particles, red hematite alfa-Fe
2
O
3
with gran-
ular particles, and specularite Fe
2
O
3
with lamellar particles
Fig. 5Chalking of paint coating.
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288 PAINT AND COATING TESTING MANUAL 15TH EDITION
so called iron mica, have been tested. The main features
of the coatings containing these ferric pigments are the
improvement of light stability and the resistance to weather
conditions and ultraviolet radiation. The parallel-oriented
lamellar particles of specularite moreover reinforce a paint
film, improve its mechanical properties, and reduce inter-
nal tension.
Silicate-Based Pigments with Non-Isometric
Particles
Talc, Mg
3
(OH)
2
(Si
4
O
10
), is a hydrated magnesium sili-
cate that belongs to the group of silicates with a layered
structure. It consists of electrically neutral layers without
inserted cations, and this construction gives rise to qualities
such as softness, smoothness, and lubrication. Its particles
are disk-like, lamellar, or micro-fibrous. Talc is resistant to
acids, has a low electric conductivity, and has high coating
power. It positively influences the rheological properties
of liquid paint and improves adhesion, strength, and anti-
corrosion properties of the coating [29].
Wollastonite is a calcium meta-silicate, CaSiO
3
(struc-
tural formula: Ca
3
Si
3
O
9
). It forms columnar needle-like or
radial straw-like white crystals. It can be split into very
fine fibers whose length to width ratio is 5:1 to 10:1 and
can even exceed 20:1. Wollastonite is a chemically inert
substance with low moisture content as well as suitable
thermal and electrical properties. It belongs to a silicate
family that has chain-like structures (SiO
4
). Chain meta-
silicates (SiO
3
2
)
n
are created by sharing of SiO
4
tetrahe-
dron structures. The needle-shaped particles fit into each
other well and reinforce the coating, improve ductility,
have balancing effects, and facilitate creation of an even
coating thickness.
The most effective pigment series comprises iron mica
(silicate), muscovite mica [aluminum-potassium silicate,
(KF)
2
(Al
2
O
3
)
3
(SiO
2
)
6
(H
2
O)], and aluminum or glass flakes.
Graphite
Graphite is a key additive that provides a combination of
color, conductivity, and ultraviolet radiation stability in
coatings and other products. It is a high-purity, micro-
scopic form of carbon produced by thermal cracking of a
hydrocarbon raw material. The formation process consists
of atomizing a heavy aromatic fraction of petroleum distil-
late in a preheated furnace followed by cooling and col-
lecting the formed carbon black. The graphite lattice exists
in the hexagonal structure of carbon. Graphite is found
in a macrocrystalline (flaky), micro-crystalline, and even
crypto-crystalline (amorphous) form. Particulate graphite
(metalliferous) is rare. Unlike synthetic electrographite,
natural graphite with a lamellar structure is often contami-
nated with various admixtures of forms.
The industrially important properties of graphite
include excellent splitting capacity and plasticity, chemical
and thermal resistance, and high thermal and electric con-
ductivity. Graphite can be used in color coatings as a pig-
ment with high chemical, ultraviolet radiation resistance
and light stability. This pigment is also capable of arrang-
ing itself into barrier lamellar structures. Experimental
results have shown that the best anti-corrosion efficiency
is displayed by a pigment based on natural graphite due
to the coating of particles with a polyaniline (PANI) layer
[30]. The lamellar particles of graphite coated with the
conductive form of PANI contributes to modification of
conducting properties as well as to improved barrier and
anti-corrosion efficiency.
Titanium Dioxide (TiO
2
)
Titanium dioxide is an important white inorganic pigment
that is used to provide hiding in paint. It is also called tita-
nium white, Pigment White 6, or CI 77891. It is used as a
pigment and a thickener that increases the viscosity and
stability of the paint mixture and improves the suspension
of added ingredients. Titanium dioxide has excellent chemi-
cal stability, heat resistance, and low electron conductivity,
features that make it an excellent anti-corrosion pigment.
Titanium dioxide is used in a finely suspended state and in
a viscous medium to formulate paints. The medium may be
a solution of a polymeric compound in an organic solvent
or aqueous latex.
Titanium dioxide is a naturally formed mineral that is
well known in its different structural forms as rutile (tetrag-
onal), anatase (tetragonal), and brookite (orthorhombic).
The most stable and common form is the mineral rutile.
Titanium dioxide is considered as a mineral ultraviolet
(UV) radiation blocker because of its high refractive index,
its strong UV radiation absorbing capabilities, and its resis-
tance to discoloration under UV radiation. In addition, it
has strong photo-catalytic properties (Honda-Fujishima
effect) and oxidative potential. Because of these facts, TiO
2
can directly oxidize oxygen or organic materials when, for
example, it is added to anti-fouling paint. Incorporated into
exterior paint for buildings, TiO
2
can substantially reduce
airborne pollutants, such as volatile organic compounds
(VOCs) and nitrogen oxides, because it becomes increas-
ingly hydrophilic when exposed to UV radiation.
Titanium dioxide flocculation has a detrimental effect
on opacity and other paint properties. It has been estab-
lished that flocculation increases as a function of alkyd
emulsion particle size. Mathematical modeling work has
been used to compare theoretical light-scattering efficiency
of alkyd emulsion paints with the measured scattering coef-
ficients. An experimental proprietary flocculation-resistant
grade of titanium dioxide has been incorporated into alkyd
emulsion paints to demonstrate the beneficial effect on
opacity that occurs when the level of flocculation in alkyd
emulsion paints is reduced.
Titanates
An anti-corrosion pigment combination based on calcium
titanate (CaTiO
3
) with a perovskite
20
structure (Fig. 6)
has been synthesized from titanium dioxide (TiO
2
) and
calcium carbonate (CaCO
3
) in a high temperature reac-
tion [31]. From an ecological standpoint, the application
of a new anti-corrosion pigment for paints represents a
highly positive trend. The synthesized pigment was used
20
Perovskite structure: Any material with the same type of crystal
structure as calcium titanium oxide (CaTiO
3
), which is known as the
perovskite structure. The general chemical formula for perovskite
compounds is ABX
3
, where A and B are two cations of very differ-
ent sizes and X is an anion that bonds to both. The A atoms are
larger than the B atoms. The ideal cubic-symmetry structure has
the B cation in six-fold coordination, surrounded by an octahedron
of anions, and the A cation in 12-fold cuboctahedral coordination
(Fig. 6).
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 289
to prepare epoxy coatings with varying anti-corrosion
pigment concentrations. The coatings were tested for
physical-mechanical properties after exposure in corrosive
atmospheres. The results were compared with the same
titanium dioxide that served as a starting material for cal-
cium titanate preparation. It was found that CaTiO
3
is a
highly efficient anti-corrosion pigment for use in paints to
protect base metals from corrosion.
Inorganic Oxoanionic Inhibitors
Inorganic oxoanionic compounds are considered as envi-
ronmental safe materials. Common oxometallate anions
are the molybdates (MoO
4
2
), phosphates (PO
4
3
), tung-
states (WO
4
, WO
3
3
), silicates (SiO
3
2
), vanadates (VO
3
),
and borates (B
2
O
4
2
). With the exception, perhaps, of zinc,
the most common inorganic cationic inhibitors are, for
example, the rare earth cations, as La
3+
, Nd
3+
, Eu
3+
, Y
3+
,
Ce
3+
, Gd
3+
[32]. However, it should be pointed out that these
inhibitors have similar performance characteristics to those
of chromate-based inhibitors, and they should provide cor-
rosion inhibition over a wide pH range.
The use of rare earth salts of cerium and lanthanum
[Ce(NO
3
)
3
and La(NO
3
)
3
] and bis-sulphur silane (BTESPT)
as chromate substitutes for galvanized steel conversion
coatings has been proposed [33]. These compounds when
applied by immersion and subsequent curing result in films
that improve corrosion resistance and paint adherence. The
two-step pretreatments result in good corrosion protection;
however, the best performance was obtained with the lan-
thanum conversion coating. This was observed either on
un-coated and coated substrates. The silane (BTESPT) by
itself also shows some improved corrosion protection. The
presence of the sulphur atoms on the silane molecule seems
to play an important role in the deposition process. Thus,
it can be suggested the presence of an internal layer rich in
sulphur and zinc hydroxides/oxides together with the silane
helps improve corrosion resistance.
Phospho-Molybdate Pigments
Phospho-molybdates are considered second-generation
corrosion-inhibiting pigments that have been introduced
in solvent- and water-based paints. Anti-corrosive pig-
ments based on molybdate are recognized as effective
corrosion inhibitors for coatings and these pigments are
well established and have been commercially available
for over 20 years. As environmental constraints continue
to limit the use of many types of corrosion inhibitors and
paints based on heavy metals, molybdate pigments are
increasingly being specified for environmentally compliant
paint systems.
Ongoing research has led to the development of sec-
ond generation molybdate pigments, which are described
as phospho-molybdate pigments. These compounds are
believed to have exceptional corrosion-inhibiting activ-
ity. Recently completed testing, based on long-term out-
door exposure, indicates that they can provide better
performance than traditional chromate-based corrosion
inhibitors. In another development, phospho-molybdate
pigments have been used to formulate a water-based acrylic
coating system that was recently approved by the Florida
Department of Transportation for bridge coatings.
Ion-Exchange Pigments
Ion-exchange pigments (IEPs) are a relatively new class
of inhibitive pigments. They are one of the alternatives
that could be adopted as non-toxic anti-corrosive pig-
ments in paints. From a scientific viewpoint, they appear
to be very attractive candidates. These compounds are
inorganic oxides with a comparatively high surface area
and that are loaded with ionic corrosion inhibitors by
ion exchange with surface hydroxyl groups. As might be
expected, the oxides are chosen for their acidic or basic
properties to provide either cation or anion exchangers
thus, silica is used as a cation support and alumina for
an anion support. The corrosion-protection behavior of
these pigments is controlled by the rate of ion release
by the exchanger. The ion-exchange release mechanism
allows efficient use of a comparatively low loading of
inhibitive pigments.
Calcium-exchanged silica, AlZn-decavanadate hydro-
talcite (HT), and cerium (III) and calcium (II) cation
exchanged bentonites have been incorporated as pig-
ments in anti-corrosive paints. The other advantage of this
approach is that it allows use of otherwise highly soluble
inhibitors. With knowledge of process kinetics for ion
release within the primer, it is possible to control the acces-
sibility of inhibitors and therefore to control its diffusion
onto the metal surface. The inhibition mechanism is related
to the ion-exchange reaction. On exposure of paint films
to an aggressive environment, water uptake occurs and
exchange of calcium with hydrogen and ions and release of
calcium ions takes place.
HTs, as anion exchange compounds, are layered clay
materials and are used for a variety of industrial purposes.
In general, they consist of a host structure with a fixed
charge. Specifically, HTs are being synthesized with vana-
dates (HT/V), which have been shown to be excellent inhibi-
tors of Al corrosion [34]. The ion exchange characteristic of
HTs is used to release vanadates into an attacking electro-
lyte and stifle corrosion. In the case of HT/V, the host is a
mixed AlZn hydroxide that is positively charged. The posi-
tive charge originates from the substitution of Al
3+
on Zn
2+
sites within the structure. Within the host, there are open
channels or galleries that can accommodate anions and
solvent molecules [35]. Cations may also be incorporated
in the gallery provided that overall electro-neutrality is
Fig. 6Perovskite structure ABO
3
. The red spheres are oxygen
atoms, the deep blue are smaller (Ti
4+
) metal cations (B-site)
and the green/blue are the larger (Ca
2+
) metal cations (A-site).
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290 PAINT AND COATING TESTING MANUAL 15TH EDITION
maintained in the solid, but in the initial state, HT/V con-
tains inhibiting anions in the gallery. On contact with an
aggressive electrolyte containing chloride ions, an exchange
reaction will occur in which the inhibitor anion is released
and chloride is adsorbed into the HT gallery.
Experiments have shown that HT compounds dis-
persed as an additive in organic (epoxy) compounds led
to potent corrosion inhibition of an underlying aluminum
alloy substrate. Corrosion inhibition is derived from release
of a decavanadate from crystalline AlZn hydroxide-based
HT particles into electrolyte that has permeated the pore
space of the coating. Decavanadate release is accompa-
nied by uptake of chloride ion in an exchange reaction.
The exchange of the large decavanadate anion for smaller
chloride ion in the HT structure results in a predictable
change in crystal structure, which can be detected by x-ray
diffraction. The use of this additive also imparts the ability
to detect environmental changes in the coating that are a
prelude to substrate corrosion.
It was demonstrated that the anti-corrosion perfor-
mance of paint pigmented with calcium-exchanged silica
(Ca/Si) is at least equal to or better than that obtained with
paints containing ZP [36] and closely approaching that of
chromate while having better efficiency than iron oxide
[37]. The results suggested a film-forming mechanism for
calcium/silica coatings. Calcium, released from the silica
surface, migrates to the paint-metal interface where a thin,
inorganic layer is deposited. This layer is essentially imper-
meable to moisture/ions and hence prevents the corrosion
reaction from proceeding. The anticorrosive effect of Ca/Si
pigment can be described by considering two mechanisms:
the exchange of calcium ions for cations (H
+
, etc.) that are
penetrating the coating from the environment, neutralizing
the acid compounds and forming a protective layer con-
sisting of calcium and iron silicate on the substrate [38].
Combinations with other active anticorrosive pigments (ZP/
molybdate, for example) are generally possible and may be
advantageous.
Novel corrosion-inhibitor pigments consisting of
cerium (III) and calcium (II) cation-exchanged bentonites
have been shown to provide effective cut-edge corrosion
resistance in organic coated galvanized steel. The benton-
ite pigments were prepared from a naturally occurring
bentonite with a cation-exchange capacity of 0.7 milli-
equivalents/g. Cation exchange was carried out by repeated
washing with aqueous solutions of cerium (III) chloride
and calcium (II) chloride to produce bentonites contain-
ing 31,500 ppm exchangeable cerium (III) and 13,500 ppm
exchangeable calcium (II), respectively. The resulting ben-
tonite pigments were dispersed in a polyester-based primer
paint system to give a PVC of 19 %. For comparison, two
similar primer systems were prepared containing a com-
mercial calcium (II) exchanged silica pigment [Shieldex:
60,000 ppm calcium (II)] and a strontium chromate disper-
sion, both at a 19 % PVC. All primer systems have been
applied to the zinc surface of galvanized 0.7 mm gauge
sheet steel and over coated with an architectural polyes-
ter topcoat. The performance of the inhibitor pigments
was compared by measuring the rate of corrosion-driven
organic coating delamination from the cut edge of samples
during 1,000 h of salt-spray testing. The calcium (II) ben-
tonite pigment exhibited an anti-delamination performance
similar to that of strontium chromate but superior to that
of Shieldex. However, the cerium (III) bentonite pigment
was superior in performance to both strontium chromate
and Shieldex. Thus, the bentonite pigments represent
promising, environmentally friendly, ion-exchange corro-
sion inhibitors that exhibit good anti-delamination perfor-
mance in comparison with current commercial systems
[39]. A schematic representation of the macro-structure of
a bentonite clay is shown in Fig. 7.
Recent research, which focuses on the anti-corrosive
protection of IEPs in alkyd coatings applied on low carbon
steel specimens and formulated with anionic (vanadates-
HT, HT/V 10 %) as well as cationic (calcium/silica, Ca/Si
5 %15 %) ion-exchangeable pigments, has been reported
[40]. The investigation compared the anti-corrosion effi-
ciency of these IEPs with traditional ZC pigments. The
results revealed that the anticorrosive behavior of ZnCrO
4
(10 %) stands out above that of the two IEPs considered in
this study. The anti-corrosive performance of IEPs depends
on the medium in contact with the coating. The anionic
HT/V shows a tendency toward a better behavior in chloride
environments (salt fog test, 0.5M NaCl solution) while the
cat-ionic Ca/Si behaves well in non-chloride environments
[humidity condensation and SO
2
(0.2 L)]. Good behavior
was found for the Ca/Si pigment at the intermediate con-
centration of 10 %. The other two studied concentrations
(5 % and 15%) afford the coatings that are highly deficient
anticorrosive properties.
An electrochemical evaluation of the corrosion protec-
tion afforded by environmentally friendly coating systems
that were applied on hot-dip galvanized steel samples
has been reported [41]. The primers used polyphosphate
(26 % P
2
O
5
) and anti-corrosive IEPs (A1
2
O
3
, CaO, SiO
2
).
Two types of coating systems were studied. The first
series of metal samples was galvanized steel covered only
with primer, and the second series were complete coat-
ing systems consisting of primer and topcoat. The results
revealed that the pigments had a significant inhibitive
effect, and they acted as cathodic inhibitors. The pigment
action resulted in layer deposition on the metal surface
and in reducing the corrosion rate. The barrier properties
of the complete coatings (primer plus top coat) were not
critical. On the contrary, the presence of low barrier prop-
erties and therefore a limited water uptake caused the pig-
ment dissolution to induce the activation of the pigment
inhibitive action.
The few studies conducted with IEPs are inconclusive
about their anti-corrosive efficiency, and controversy sur-
rounds their functioning mechanisms, interchange capac-
ity, and anticorrosive performance.
Super Primers
The concept of a super primer is relatively new. When
bis-silanes (SiH
4
) are mixed with conventional primers or
binders, they have been shown to impart excellent corro-
sion protection [42]. The concept of super primers, i.e.,
primers for metals with the conversion coating built in,
has proven to be feasible. Such primers do not require
a chromate (or other) conversion treatment of the metal
and can be applied on any bare metal (Fig. 8). The VOCs
content in the primer is kept low by using water-dispersed
organic polymers. Because of the high concentration of
organo-functional silanes contained in a super primer, its
adhesion, both to the substrate and to primer overcoats,
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 291
is excellent. The corrosion resistance of the primer can
be further improved by adding corrosion-inhibiting pig-
ments such as micronized ZP into the formulation. A set
of super primers has been developed, and they have been
put through performance tests and characterized with a
variety of methods. An attempt to explain the mechanism
by which one of the coatings, the epoxy-acrylate-based
primer, deposited onto aluminum, protects the metal from
corrosion, is given (Fig. 9).
The corrosion-protection mechanism of the epoxy-
acrylate coating, which is self-assembled into layers after
it was deposited from a water-borne dispersion, is unique.
The chemistry of the coating facilitates leaching of the
ZP on demand when the coating is scribed and attacked
by an electrolyte. The chemistry of the coating allows the
ZP to act as chromate ions would act in a regular coating
when the coating is exposed to salt water. The chromate
ions are well known to leach out only on demand, as when
a polymer coating is exposed to a corrosive environment.
The extensive study of the epoxy-acrylate primer has
demonstrated that ZP pigment particles can in fact function
as active on demand corrosion inhibitors in this coating
that has been formed from a water-borne polymer disper-
sion. In this particular coating the ZP is able to leach out
only from the hydrophilic acrylate-silane-ZP layer, creating
a reservoir of saturated ZP in the surrounding salt solution.
At the same time, the hydrophobic epoxy layer protects
the acrylate containing layer and thereby the rest of the
coated metal.
Pigments for Smart Anti-Corrosion Coatings
Under certain conditions, the driving force of corrosion
produces protective oxide films, a process typically referred
to as metal passivity. In cases where passivity is difficult to
achieve, for example, as with aluminum alloys in neutral
sodium chloride solutions, it is conceivable that a smart
coating can be micro- or nano-engineered to use the energy
of the corrosion process to on demand generate a corro-
sion inhibitor for stopping or slowing corrosion at defects.
Work at Rockwell Scientific Company provides evidence
Fig. 7(a) Schematic representation of the macro-structure of a bentonite clay. The negatively charged layers, with exchangeable
compensating cations between them, are held together electrostatically. (b) Schematic illustration of the potential mode of
operation of a cation exchanged bentonite inhibitor pigment on a corroding galvanized surface. (c) Schematic illustration of the
negatively charged layers blocked by the numerous compensating cations between them [39].
Fig. 8Schematic of the superprimer coating system [42].
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292 PAINT AND COATING TESTING MANUAL 15TH EDITION
that anionic inhibitors for the oxygen reduction (cathodic)
reaction, when used as dopants for conducting PANI films,
inhibit corrosion of an aluminum (Al 2024-T3) substrate at
a scribe [43]. In effect, the scribe polarizes the PANI, caus-
ing it to release the inhibitor.
PANI ranks high among electrically conducting poly-
mers. Its high conductivity and chemical variability makes
it suitable for a number of applications. In the course of
polymerization, PANI has the ability to create thin conduct-
ing films with very good adhesion to various base materials
[44]. To prove the retention of its inhibiting properties in
a paint film, it was found advisable to apply this polymer
in organic binders, where it would function as an organic
corrosion inhibitor or an anti-corrosion pigment. There-
fore, the main objective of a reported study was evaluation
of the properties of organic coatings containing PANI and
PANI in combination with other anti-corrosive pigments
[45]. The adhesion, barrier, and anti-corrosion properties
of the coatings containing PANI and selected chemically
active pigments were studied as well as the combination
of PANI with zinc dust. Epoxides of the bisphenol A type
cured with a polyamine-based curing agent were used as
a binder. To examine the synergic effect of PANI and anti-
corrosion pigment in epoxy coatings, Zn
3
(PO
4
)
2
2H
2
O with
an acidic aqueous extract, Ca
3
(BO
3
)
2
with a basic aqueous
extract, and SrCrO
4
with a neutral aqueous extract were
tested. Comparison of the results of the corrosion tests
revealed that the PANI plus Zn
3
(PO
4
)
2
2H
2
O combination
increased the anti-corrosion efficiency of organic coatings.
Both these pigments utilize the acidic pH of the aqueous
extract, and this may lead to very high anti-corrosion effi-
ciency. The investigation of the total anti-corrosion effi-
ciency of coatings with the PANI plus Zn-dust combination
found that the PANI combination with a PVC of 5 % and
Zn-dust [PVC/critical PVC (CPVC) = 0.65] achieves high
anti-corrosion efficiency.
A new pigment for smart anticorrosive coatings, based
on modified zeolite, has been proposed as a pigment for
paints [46]. Alkyd paints were formulated by employing
different anti-corrosion pigments: (1) 30 % by volume
(v/v) of the modified zeolitic rock, (2) 10 % (v/v) of ZP, and
(3)a mixture of 10 % (v/v) ZP plus 20 % (v/v) of the modi-
fied zeolitic rock. In every case, percentages were referred
to the total pigment content. Titanium dioxide, zinc
oxide, and barium sulfate were incorporated to complete
the pigment formula. The PVC/CPVC ratio was 0.8. The
performance of the resulting anticorrosive paints was
assessed by accelerated tests in salt spray and humidity
chambers and by electrochemical measurements of cor-
rosion potential, ionic resistance, and polarization resis-
tance. It was demonstrated that the modified zeolite is
effective in protecting steel from corrosion when it is used
in combination with ZP. There exists a synergism between
the modified zeolite and ZP that allows the ZP content in
anticorrosive paints to be reduced.
A group of mixed oxides with the structure of spinel
and perovskite ZnAl, ZnFe, and CaTi inorganic pig-
ments in combination with a conducting PANI phosphate
layer were selected for the surface modification [30]. In
many applications of paints, it is convenient to formulate
a composite made up of inorganic particles (a pigment)
with a suitable chemical composition that is coated with a
functional layer of a conductive polymer. PANI has redox
properties that can be used in protection against corrosion.
When inorganic particles are suspended in the reaction
medium used for the oxidation of aniline, they become
coated with a thin (100 nm) layer of PANI. Such PANI
modified particles have been tested in an attempt to find
the potential synergetic effect and/or improvement of anti-
corrosion properties. The study reports the anti-corrosion
effects of various PANI-modified pigment particles in
paints. Included in the study was another interesting group
of functional pigments represented by iron oxides and sili-
cates with various structures and diverse particle shapes.
The last type of pigments included in the study was graph-
ite of both natural and synthetic origin. Uncoated pigments
and PANI powder have also been tested for comparison.
Considering all the groups of pigments, the pigments
coated with a PANI layer displayed the smallest corrosion
loss. It is obvious that the extract of the pigments contain-
ing PANI contributes, with its optimum conductivity, to
the passivation of the metal base. When testing paint films
that contained mixed metal oxides, the pigments alone
that is, those without PANI coatingdisplayed improved
corrosion resistance. The films based on iron oxides and
silicate pigments exhibit similar results with regard to both
PANI-coated pigments and pigments without coating. The
excellent results of anti-corrosion efficiency were detected
in the paint films that contained graphite-based pigments.
The PANI coating of the synthetic graphite and especially
of the natural form of graphite contributed to the marked
enhancement of the total anti-corrosion efficiency of the
paint film.
Needle-Shaped Anti-Corrosion Pigments
Use of synthesized, needle-shaped pigments in anti-
corrosion paints for protecting metals is a new concept.
The benefit of their use and method of synthesizing is
that they do not contain heavy metals and are acceptable
for the environment. The following pigments have been
synthesized from oxides or carbonates at high tempera-
tures: ZnFe
2
O
4
, MgFe
2
O
4
, CaFe
2
O
4
, MgO2ZnO8Fe
2
O
4
, and
CaO2ZnO8Fe
2
O
4
[47]. They were used to formulate epoxy
coatings with a PVC of 10 % for the synthesized pigment
and with the PVC/CPVC ratio of 0.3. The coatings were
tested for physical-mechanical properties and in corrosion
atmospheres. The test results revealed that all pigments
had high anti-corrosion efficiency comparable with that of
ZnAl phospho-molybdate.
Fig. 9Principle of the corrosion-inhibiting mechanism of the
acrylate-epoxy-silane superprimer containing the ZP pigments,
which protect the metal on-demand [42].
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 293
Spinel-Type
21
Pigments
Spinel pigments are oxides derived from the crystalline
structure of the natural mineral spinel, MgAl
2
O
4
. With
these XY
2
O
4
-type oxides, the ionic charges can be balanced
with three combinations of oxidation states: X
2+
B
2
3+
(typeI),
X
4+
B
2
2+
O
4
(type II), and X
6+
B
2
1+
O
4
(type III). The structure of
these oxides is determined by the grouping of voluminous
oxygen-containing anions in a face-centered-cubic arrange-
ment. Free cavities for the placement of cations are of two
types: octahedric (coordination number 6) and tetrahedric
(coordination number 4). In perovskite, the large ions, Ca
2+
and O
2
and the smaller cation of Ti
4+
located in one of the
void spaces create a closely packed structure. Lamellar
spinel-type pigments have been characterized as especially
appropriate for high barrier efficiency coatings because
they increase the diffusion path for water and oxygen. In
addition, it has been shown that in addition to pigment
particle shapes, their chemical compositions also plays
a role.
Spinel pigments containing Zn(II), Ca(II), Mg(II),
Sr(II), Fe(III), Al(III), and Ti(IV) cations have been syn-
thesized as potential candidates for replacing toxic anti-
corrosive pigments with pigments acceptable from the
point of view of environmental protection [48]. Combining
the cations in various oxide groups, the pigments were
applied to alkyd, styrene-acrylate, epoxides, and chlori-
nated rubber binders. The binder containing acid groups
gave aqueous extracts with better inhibitive properties than
the non-reactive binders. The chemical composition of the
synthesized pigments clearly shows that the compounds are
ecologically harmless.
The spinel-type oxides are useful in heat-resistant organic
coatings, and they are designed for applications where tem-
peratures in a range of 200500C are encountered [49].
Several inorganic pigments (salts) are produced by Kremer
Pigments Inc., as praseodym yellow (Zr,Pr)SiO
4
, zirconium
cerulean blue (Zr,V)SO
4
, spinel black (Fe,Mn)(Fe,Mn)
2
O
4
,
zinc-iron brown dark (metal oxide/hydroxide and 5 %7 %
of TiO
2
), all of them are not classified as hazardous pigments.
They are suitable for paints based on oil, acrylics, tempera,
watercolor/gouache, lime/silicate binder, etc.
Metal Flake Pigments
Metal flake coating compositions are well known in the
coating industry. In particular, metal flake coating compo-
sitions are widely used in automotive coatings to produce
unique aesthetic effects and to provide anti-corrosion pro-
tection of metal substrates. Aluminum pigment, typically
as an aluminum flake, is used in metallic decorative top-
coats whereas zinc pigment-flake is used as anti-corrosive
pigmentespecially in primers. Both metal powder pig-
ment flakes play the role of self-sacrifice anodes for rust
prevention and corrosion inhibition, due to the more nega-
tive electrode potential relative to that of iron (steel). The
flake-pigment is often used in the form of a pigment paste.
The paste is processed and dispersed in a polymeric vehicle
along with a conventional pigment to produce automotive
paint coatings that have various appearance effects, such
as silver metallic, gold metallic, blue metallic, and various
other colored metallics.
Both aluminum and zinc pigments react in aqueous
alkaline media (e.g., water-borne paints) with the evolution
of hydrogena process known as gassing [50]
2Al + 6H
2
O 2Al(OH)
3
+ 3H
2
Zn + 2H
2
O Zn(OH)
2
+ H
2
, or (OH)
; for
example, calcium phosphate Ca
5
(PO
4
)
3
(F, OH, Cl).
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 295
properties of primers is one of the important lines of
research in the field of organic coatings. Goals include
improved protection and increased service lifetime for the
coated substrates. The corrosion and degradation processes
in organic/metal systems is complex. The main experimen-
tal routes used to examine different exposure processes
are field testing and accelerated aging testing as in a salt
fog spray cabinet. Such testing routines must be given
serious planning because they are expensive to conduct.
Salt spray (fog) is an accelerated test carried out with an
aqueous 5 wt% sodium chloride solution, and it is one of
the most widely used evaluation techniques. The practice is
described in ASTM B117, Standard Practice for Operating
Salt Spray (Fog) Apparatus, which provides a controlled
corrosive environment for obtaining corrosion resistance
of coated metals. Even though a useful tool, this practice is
very subjective and does not give quantitative information
about the corrosion process and its interpretation.
For this reason, various electrochemical techniques
have been used to evaluate the corrosion protection per-
formance of organic coating/metal systems: (a) anodic and
cathodic polarization curves, (b) EIS, and (c) rapid testing
that consists of a combination of cathodic polarization and
EIS measurements (ac/dc/ac procedure). EIS has proven to
be a useful technique for the study of anti-corrosive primer
behavior, but to obtain good, meaningful results, long eval-
uation times of days, weeks, and even months are needed
The concept of inspection/monitoring is gaining impor-
tance for cost and environmental reasons. In addition to
the traditional approaches of basic visual assessment and
adhesion testing, new techniques for monitoring paint deg-
radation and the resulting corrosion are emergingthese
include the following:
Thin film electrochemical sensors embedded under
paint films.
Electrochemical sensors applied to the outer surface
of paint films.
Microwave techniques.
Thermography.
Color and fluorescence changes (smart coatings).
Fiber optic sensing.
Chemical sensors for detecting surface contamination
at the surface preparation stage.
SMART COATINGS
The use of smart materials for corrosion sensing purposes
relies on a material undergoing a transformation through
its interaction with a corrosive environment. It is such
transformations that can potentially be used for indicating
and detecting corrosion damage. Ideally the sensing func-
tion could be integrated with additional actuation and con-
trol functions designed to control corrosion damage.
Several initiatives have been launched on the front of
using smart coatings as corrosion sensors, but presently
the technologies reside mainly in the experimental labora-
tory domain. As such, they are futuristic in nature. Some
smart coating principles including those relevant to cor-
rosion sensing or that are potentially relevant include the
following:
Paint systems with color-changing compounds that
respond to pH changes that result from the corrosion
processes.
Changes of coating compounds from non-fluorescent
to fluorescent states when oxidation or complexation
with metal cations takes place.
Release of color dyes from incorporated dye-filled
microcapsules when coating damage occurs.
Use of pigments that absorb corrosive chemicals,
Use of pigments that release corrosion-inhibiting
chemicals on demand.
Piezo-electric thin film applications.
Fiber optics.
ENVIRONMENTALLY FRIENDLY PAINTS
AND PIGMENTS-INHIBITORS
Due to the restriction limits on the use of toxic pigments
(for example, those based on lead and heavy metals)
because of health and environmental considerations, paint
producers are searching for a new generation of pigments/
inhibitors that are more acceptable. Numerous investi-
gations have been performed in an attempt to evaluate
promising candidate replacement inhibitors. The need for
substitution of toxic pigments can be made on different
levelshumanistic, economic, or ecologic. The corrosion
inhibition characteristics of many inorganic compounds
have been examined for more than five decades with the
hope of identifying an equivalent to the excellent corrosion
inhibition of chromate pigments inhibitors.
As companies search for a system with equivalent or
better properties than the chromates, it is necessary to
consider raw material costs. New pigments are usually
more expensive than classical pigments. Although such
cost difficulties may exist, the use of organic coatings
remains as one of the most economical methods of obtain-
ing corrosion protection. This is related to the relatively
low application costs in comparison to protection methods
such as galvanizing, enamel coating, or the use of finer
materials. The true advantage of the use of paints lies in
their all-purpose and easy application onto the surface of
various materials.
For perhaps the past 20 years, a considerable effort
has been focused on developing non-chromate corrosion-
inhibiting compounds for protection of aluminum alloys.
A number of chromate alternatives have been considered,
including molybdates, phosphates, metaborates, zinc oxide
(ZnO), vanadates, and silicates [55]. The patent literature
suggests the use of sol-gel technology for generating an end-
less variety of non-chromate pigments. In addition to borate
salts, organic acid salts of barium have been considered
as corrosion inhibitors. Although barium-metaborate as it
exists at pH 10 provides very good inhibition of Aluminum
Fig. 11Schematic representation of the three states for
cathodic detachment of paint coating. The left part represents
the first stage, when anodic and cathodic sites are separated in
the exposed area; in the centerblocked defect, consequently
transporting oxygen (O
2
); and in the rightfinal situation.
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296 PAINT AND COATING TESTING MANUAL 15TH EDITION
2024, its ability to inhibit decreases with decreasing pH and
thus decreases as corrosion takes place.
To date, no single compound has demonstrated cor-
rosion/inhibitor potency that is comparable to chromate-
based inhibitors. A promising alternative is use of a
synergistic combination of two or more compounds,
organic and inorganic, as a coating system. The inhibitor
synergy is an additive phenomenon wherein the total inhi-
bition provided by the combination exceeds the arithmetic
sum of the individual components. However, because of
the known release of inorganic pigments from organic
matrices [56], and the unpredictable release kinetics of
organic additives from organic matrices, the investiga-
tions have emphasized use of inorganic compounds for the
replacement of chromates. Compared to chromated pig-
ments or zinc dust, modern, environmentally friendly pig-
ments in epoxy-ester primers have shown excellent results,
especially in salt spray tests. These systems include zinc
phospho-molybdate, ZP modified with organic corrosion
inhibitor, calcium hydrogen phosphate, zinc-aluminum
polyphosphate, etc. [21]. Reported results of the properties
of a wide variety of industrially employed fillers and pig-
ments contained in paints reveal that the formulation of
steel protecting coatings can be optimized. For example,
this can be accomplished by selecting the optimum filler
for an epoxy coating with barrier anticorrosive properties,
thickness of coatings, etc. [57].
The inorganic species considered as replacements of
chromate can be divided into the following categories [10].
(a) Reducible hypervalent transition metals (compounds
of Mo, V, Mn, Tc). The term hypervalent as used here
refers to the highest valence state of the oxoanion,
which is typically not thermodynamically stable in
aqueous media. Metals, such as Mn, Tc, Mo, and V, that
form oxometallates have soluble hypervalent oxoanions
that reduce to form insoluble oxides in the same way
as chromium. However, Mn, Cr, and Tc compounds
exhibit very broad ranges in pH around neutral where
their reduced oxides are stables, while V and Mo,
exhibit relatively narrow ranges in pH. On the other
hand, vanadium oxide is relatively more stable toward
high pH and the Mo oxide is more stable toward lower
pH values. However, as oxides, the elements of Mo and
V will never give the same stability as seen in analogous
Cr
3+
oxide. But, they should not be completely ruled out
as chromate replacements.
(b) Difficult-to-reduce transition metal oxides (Zr, Hf, Ta,
Ti, Y) and covalent oxides (oxides and mixed oxides
of Si, Ge, P, Te). Elements such as Nb, Hf, Ti, Zr, and
Ta form very stable oxides in their highest oxidation
state. Unfortunately, soluble and mobile precursors
of these oxides remain difficult to stabilize in aque-
ous media. It is difficult to imagine how such active
precursors could be retained in the resulting films in
a manner analogous to the retention of Cr
6+
in Cr con-
version coatings. Both the former group (a) and this
group (b) can be carried out using sol-gel methods.
(c) Precipitated coatings. These coatings include boehmite
[-AlO(OH)] and HT [Mg
6
Al
2
(CO
3
)(OH)
16
4(H
2
O)] coat-
ings, and rare-earth metal coatings. The mechanism
for the rare-earth inhibition seems to arise from the
alkaline precipitation of protective oxide films at active
cathodic sites formed on the metal surface. Cerium
(Ce) species appear to offer the most effective corro-
sion inhibition: Ce
3+
reversibly adsorbs on anodized
aluminum, but it acts at much different sites than the
Cr
6+
oxoanions.
In a broad examination of the literature in which the
substrate material is not specified, compounds identified
as having promising performance include barium metabo-
rate, vanadium-based compounds, rare-earth compounds,
molybdates, zinc-based compounds, calcium silicate, thio-
glycolates, calcium oxide, phosphate salts, calcium silicoflu-
oride, and benzotriazole among others. Additional studies
have been made studying synergistic effects achieved by
combining promising candidate inhibitors. The corrosion-
inhibition efficiency of 27 candidate compounds has been
studied and the inhibitors selected for continued testing
were: barium metaborate, cerium chloride, cerium oxalate,
lanthanum chloride, and sodium metavanadate. Sodium
meta-vanadate appeared to be a possible candidate as a
chromate replacement [34]. Zinc-molybdenum phosphate
could also be a good possibility as a replacement of heavy
metal compounds. It is thought that its anticorrosive pro-
tection efficiency is similar or superior of that of ZC or ZP.
While all coatings are important in that they protect a
wide variety of objects from the harshness of various envi-
ronments, they also provide us with aesthetic beauty. Stud-
ies such as many of those described in this chapter and that
are ongoing in many laboratories strongly suggest that new
solutions to environmentally and health-acceptable anti-
corrosion pigments and inhibitors will be found.
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Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
Downloaded/printed by
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 297
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[15] Kendig, M. W., and Buchheit, R. G., Corrosion Inhibition
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1, 2000, pp. 2732.
[20] del Amo, B., Veleva, L., Di Sarli, A. R., and Elsner, C. I.,
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50, No. 3, 2004, pp. 179192.
[21] Kalendova, A., Kalenda, P., and Vesel, D., Comparison of the
Efficiency of Organic Non-Metal Pigments with Zinc Powder
in Anticorrosion Paints, Prog. Org. Coat., Vol. 57, No. 1,2006,
pp. 110.
[22] Beiro, M., Collazo, A., Izquierdo, M., Novoa, X. R., and Perez,
C., Characterization of Barrier Properties of Organic Paints:
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No. 2, 2003, pp. 97106.
[23] del Amo, B., Di Sarli, A. R., Lecot, J., and Caprari, J. J., Pro-
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B-Coat Trans. (JOCCA), Vol. 86, No. B2, 2003, pp. 141143.
[24] Dey, M., Vetere, V. F., Romagnoly, R., and Amo, B. D., Zinc Tri-
polyphosphate: An Anticorrosive Pigment for Paints, Surf. Coat.
Int. Part B-Coat. Trans. (JOCCA), Vol. 86, No. B1, 2003, pp. 7985.
[25] Lima-Neto, P., Arajo, A. P., Arajo, W. S., and Correia, A. N.,
Study of the Anticorrosive Behaviour of Epoxy Binders Con-
taining Non-Toxic Inorganic Corrosion Inhibitor Pigments,
Prog. Org. Coat., Vol. 62, No. 3, 2008, pp. 344350.
[26] Kalendova, A. and Vesely, D., The Properties of ZnFe
2
O
4
as
an Anticorrosion Pigment Dependent upon the Structure of
Initial Fe
2
O
3
, Anti-Corros. Methods Mater., Vol. 55, No. 4,
2008, pp. 175190.
[27] Selvaraj, M., and Guruviah, S., Optimization of Metallic Pig-
ments in Coatings by an Electrochemical Techniques and an
Investigation of Manganese Powder as Pigment for Metal Rich
Primers, Prog. Org. Coat., Vol. 28, No. 4, 1996, pp. 271277.
[28] Simes, A. M., Battocchi, D., Tallman, D. E., and Bierwagen,
G. P., Assessment of the Corrosion Protection of Aluminium
Substrates by a Mg-Rich Primer: EIS, SVET and SECM
Study, Prog. Org. Coat., Vol. 63, No. 3, 2008, pp. 260266.
[29] Battocchi, D., Simes, A. M., Tallman, D. E., and Bierwagen,
G. P., Electrochemical Behaviour of a Mg-Rich Primer in the
Protection of Al Alloys, Corros. Sci., Vol. 48, No. 5, 2006, pp.
12921306.
[30] Kalendov, A., Veselm, D., Stejskal, J., and Trichov, M.,
Anticorrosion Properties of Inorganic Pigments Surface-
Modified with a Polyaniline Phosphate Layer, Prog. Org.
Coat., Vol. 63, No. 2, 2008, pp. 209221.
[31] Kalendova, A., Vesely, D., and Kalenda, P., Anticorrosion Pig-
ment Based on Calcium Titanate with a Perovskite Structure,
Pigm. Resin Tech., Vol. 36, No. 3, 2007, pp. 123133.
[32] Taylor, S. R., and Chambers, B. D., Identification and Char-
acterization of Nonchromate Corrosion Inhibitor Synergies
Using High-Throughput Methods, Corrosion (Houston), Vol.
64, No. 3, 2008, pp. 255270.
[33] Ferreira, M. G. S., Duarte, R. G., Montemor, M. F., and
Simes, A. M. P., Silanes and Rare Earth Salts as Chromate
Replacers for Pre-Treatments on Galvanized Steel, Electro-
chim. Acta, Vol. 49, No. 12, 2004, pp. 22912305.
[34] Cook, R. L., Jr., and Taylor, S. R., Pigment-Derived Inhibitors
for Aluminum Alloy 2024-T3, Corrosion (Houston), Vol. 56,
2000, pp. 321333.
[35] Buchheit, R. G., Guan, H., Mahajanam, S., and Wong, F.,
Active Corrosion Protection and Corrosion Sensing in Chro-
mate-Free Organic Coatings, Prog. Org. Coat., Vol. 47, Nos.
34, 2003, pp. 174182.
[36] Romanoli, R., Dey, M. C., and Amo, B. D., The Mechanism
of the Anticorrosive Action of Calcium-Exchanged Silica,
Surf. Coat. Int. Part B-Coat. Trans. (JOCCA), Vol. 86, No. B2,
2003, pp. 135141.
[37] Vasconcelos, L. W., Margarit, I. C. P., Mattos, O. R., Fragata,
F. L., and Sombra, A. S. B., Inhibitory Properties of Calcium
Exchanged Silica Epoxy Paintings, Corros. Sci., Vol. 43, No.
12, 2001, pp. 22912305.
[38] Goldie, B. P. F., Calcium Exchanged Silica Anti-Corrosion
PigmentA Review, J. Oil and Colour Chem. Assoc., Vol. 71,
No.9, 1988, pp. 257263.
[39] Bohm, S., McMurray, H. N., Powell, S. M., and Worsley, D. A.,
Novel Environment Friendly Corrosion Inhibitor Pigments
Based on Naturally Occurring Clay Minerals, Mater. Corros.,
Vol. 52, No. 12, 2001, pp. 896903.
[40] Chico, B., Simancas, J., Vega, J. M., Granizo, N., Das, I., de
la Fuente, D., and Morcillo, M., Anticorrosive Behaviour of
Alkyd Paints Formulated with Ion-Exchange Pigments, Prog.
Org. Coat.,Vol. 61, Nos. 24, 2008, pp. 283290.
[41] Deflorian, F., and Felhosi, I., Electrochemical Impedance
Study of Environmentally Friendly Pigments in Organic
Coatings, Corrosion (Houston), Vol. 59, No. 2, 2003, pp.
112120.
[42] Seth, A., van Ooij, W. J., Puomi, P., Yin, Z., Ashirgade, A.,
Bafna, S., and Shivane, C., Novel, One-Step, Chromate-Free
Coatings Containing Anticorrosion Pigments for MetalsAn
Overview and Mechanistic Study, Prog. Org. Coat., Vol. 58,
Nos. 23, 2007, pp. 136145.
[43] Kendig, M., Hon, M., and Warren, L., Smart Corrosion Inhib-
iting Coatings, Prog. Org. Coat., Vol. 47, Nos. 34, 2003, pp.
183189.
[44] Abu, Y. M. and Aoki, K., Corrosion Protection by Polyaniline-
Coated Latex Microspheres, J. Electroanal. Chem., Vol. 583,
No. 1, 2005,pp. 133139.
[45] Kalendov, A., Vesel, D., and Stejskal, J., Organic Coatings
Containing Polyaniline and Inorganic Pigments as Corrosion
Inhibitors,Prog. Org. Coat., Vol. 62, No. 1, 2008, pp. 105116.
[46] Dey, C., Romagnoli, R., and del Amo, B., A New Pigment for
Smart Anticorrosive Coatings,J. Coat. Tech. Res., Vol. 4, No.
2, 2007, pp. 167175.
[47] Kalendova, A., and Vesely, D., Needle-Shaped Anticorrosion
Pigments Based on the Ferrites of Zinc, Calcium and Magne-
sium, Anti-Corros. Methods Mater., Vol. 54, No. 1, 2007, pp.
315.
[48] Kalendov, A., Alkalizing and Neutralizing Effects of Anti-
corrosive Pigments Containing Zn, Mg, Ca, and Sr Cations,
Prog. Org. Coat., Vol. 38, Nos. 34, 2000, pp. 199206.
[49] Kalendov, A., Application of Spinel Pigments in Anticor-
rosive Heat-Resistant Coatings, Pigm. Resin Tech., Vol. 29,
No. 3, 2000.
[50] Mller, B., Corrosion Inhibition of Aluminum and Zinc Pig-
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15691582.
[51] Mller, B., and Fischer, S., Epoxy Ester Resins as Corrosion
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48, No. 9, 2006, pp. 24062416.
[52] Wissling, P., State-of-the-Art Technology in Aluminum Pig-
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(JOCCA), Vol. 82, No. 7, 1999, pp. 335347.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
Downloaded/printed by
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298 PAINT AND COATING TESTING MANUAL 15TH EDITION
[53] Kiehl, A., and Greiwe, K., Encapsulated Aluminum Pig-
ments, Prog. Org. Coat.,Vol. 37, Nos. 34, 1999, 179183.
[54] Karpov, A. S., Nuss, J., and Jansen, M., New Ceramic Pigments
on the Basis of Phosphate Apatities Containing Oxocuprate
Ions in the Hexogonal Channels, Max-Plank-Insitut fr Fest-
krperforschung, Stuttgart, Germany, 2003.
[55] Kendig, M., Cunningham, M., Jeanjaquet, S., and Hardwick,
D., Role of Corrosion Inhibiting Pigments on the Electro-
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J. Electrochem. Soc., Vol. 144, No. 11, 1997, pp. 37213727.
[56] Sinko, J., Challenges of Chromate Inhibitor Pigments
Replacement in Organic Coatings, Prog. Org. Coat., Vol. 42,
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[57] Kalendov, A., Vesely, D., and Kalenda, P., A Study of the
Effect of Pigments and Fillers on the Properties of Anticor-
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8394.
ASTM documents related to anti-corrosion
pigments and their use in coatings
D16 Standard Terminology for Paint, Related Coatings,
Materials, and Applications.
D34 Standard Guide for Chemical Analysis of White
Pigments.
D49 Standard Test Methods of Chemical Analysis of
Red Lead.
D50 Standard Test Methods for Chemical Analysis
of Yellow, Orange, Red, and Brown Pigments
Containing Iron and Manganese.
D81 Standard Specification for Basic Carbonate White
Lead Pigment.
D126 Standard Test Method for Analysis of Yellow,
Orange and Green Pigments Containing Lead
Chromate and Chromium Oxide Green.
D480 Standard Test Methods for Sampling and Testing of
Flaked Aluminum Powders and Pastes.
D610 Standard Practices for Evaluating Degree of Rusting
on Painted Steel Surfaces.
D660 Standard Test Method for Evaluating Degree of
Checking of Exterior Paints.
D661 Standard Test Method for Evaluating Degree of
Cracking of Exterior Paints.
D662 Standard Test Method for Evaluating Degree of
Erosion of Exterior Paints.
D714 Standard Test Method for Evaluating Degree of
Blistering of Paints.
D772 Standard Test Method for Evaluating Degree of
Flaking (Scaling) of Exterior Paints.
D822 Standard Practice for Filtered Open-Flame Carbon-
Arc Exposures of Paint and Related Coatings.
D870 Standard Practice for Testing Water Resistance of
Coatings Using Water Immersion.
D913 Standard Test Method for Evaluating Degree of
Resistance to Wear of Traffic Paint.
D964 Standard Specification for Metallic Copper Powder
for Use in Antifouling Paints.
D1014 Standard Practice for Conducting Exterior Exposure
Tests of Paints and Coatings on Metal Substrates.
D1301 Standard Test Methods for Chemical Analysis of
White Lead Pigments.
D1641 Standard Practice for Conducting Outdoor Exposure
Tests of Varnishes.
D1648 Standard Specification for Basic Lead Silicochromate
Pigment.
D1654 Standard Test Method for Evaluation of Painted
or Coated Specimens Subjected to Corrosive
Environments.
D1735 Standard Practice for Testing Water Resistance of
Coatings Using Water Fog Apparatus.
D1844 Standard Test Methods for Chemical Analysis of
Basic Lead Silicochromate.
D2092 Standard Guide for Preparation of Zinc-Coated
(Galvanized) Steel Surfaces for Painting, Historical
Standard.
D2200 Standard Practice for Use of Pictorial Surface
Preparation Standards and Guides for Painting Steel
Surfaces.
D2247 Standard Practice for Testing Water Resistance of
Coatings in 100 % Relative Humidity.
D2486 Standard Test Methods for Scrub Resistance of Wall
Paints.
D2803 Standard Guide for Testing Filiform Corrosion
Resistance of Organic Coatings on Metal.
D3003 Standard Test Method for Pressure Mottling and
Blocking Resistance of Organic Coatings on Metal
Substrates.
D3258 Standard Test Method for Porosity of White or Near
White Paint Films by Staining.
D3260 Standard Test Method for Acid and Mortar
Resistance of Factory-Applied Clear Coatings on
Extruded Aluminum Products.
D3276 Standard Guide for Painting Inspectors (Metal
Substrates).
D3322 Standard Practice for Testing Primers and Primer
Surfaces Over Preformed Meta.
D3359 Standard Test Methods for Measuring Adhesion by
Tape Test.
D3623 Standard Test Method for Testing Antifouling Panels
in Shallow Submergence.
D3723 Standard Test Method for Pigment Content of
Water-Emulsion Paints by Low-Temperature Ashing.
D3843 Standard Practice for Quality Assurance for
Protective Coatings Applied to Nuclear Facilities.
D3891 Standard Practice for Preparation of Glass Panels
for Testing Paint, Varnish, Lacquer, and Related
Products.
D4141 Standard Practice for Conducting Black Box and
Solar Concentrating Exposures of Coatings.
D4146 Standard Test Method for Formability of Zinc-Rich
Primer/Chromate Complex Coatings on Steel.
D4213 Standard Test Method for Scrub Resistance of Paints
by Abrasion Weight Loss.
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CHAPTER 28 PROTECTIVE COATINGS AND INORGANIC ANTI-CORROSION PIGMENTS 299
D4214 Standard Test Methods for Evaluating the Degree of
Chalking of Exterior Paint Films.
D4228 Standard Practice for Qualification of Coating
Applicators for Application of Coatings to Steel
Surfaces.
D4288 Standard Specification for Calcium Borosilicate
Pigments
D4417 Standard Test Methods for Field Measurement of
Surface Profile of Blast Cleaned Steel.
D4487 Standard Test Methods for Analysis of Calcium
Borosilicate
D4541 Standard Test Method for Pull-Off Strength of
Coatings Using Portable Adhesion Testers.
D4585 Standard Practice for Testing Water Resistance of
Coatings Using Controlled Condensation.
D4587 Standard Practice for Fluorescent UV-Condensation
Exposures of Paint and Related Coatings.
D4752 Standard Test Method for Measuring MEK
Resistance of Ethyl Silicate (Inorganic) Zinc-Rich
Primers by Solvent Rub.
D4797 Standard Test Methods for Chemical and
Gravimetric Analysis of White and Yellow
Thermoplastic Traffic Marking Containing Lead
Chromate and Titanium Dioxide.
D4828 Standard Test Methods for Practical Washability of
Organic Coatings.
D4938 Standard Test Method for Erosion Testing of
Antifouling Paints Using High Velocity Water.
D4939 Standard Test Method for Subjecting Marine
Antifouling Coating to Biofouling and Fluid Shear
Forces in Natural Seawater.
D5043 Standard Practice for Field Identification of
Coatings.
D5178 Standard Test Method for Mar Resistance of Organic
Coatings.
D5894 Standard Practice for Cyclic Salt Fog/UV Exposure of
Painted Metal (Alternating Exposures in a Fog/ Dry
Cabinet and a UV/Condensation Cabinet).
D6280 Specification for Zinc Phosphate Pigments.
D6442 Standard Test Method for Determination of
Copper Release Rate From Antifouling Coatings in
Substitute Ocean Water.
D6577 Standard Guide for Testing Industrial Protective
Coatings.
D6695 Standard Practice for Xenon-Arc Exposures of Paint
and Related Coatings.
D7087 Standard Test Method for An Imaging
Technique to Measure Rust Creepage at Scribe
on Coated Test Panels Subjected to Corrosive
Environments.
F1428 Standard Specification for Aluminum Particle-Filled
Basecoat/Organic or Inorganic Topcoat, Corrosion
Protective Coatings for Fasteners.
SSPC-PS
Guide
8.00
Guide to Topcoating Zinc Rich Primers.
G85 Standard Practice for Modified Salt Spray (Fog)
Testing.
G90 Standard Practice for Performing Accelerated
Outdoor Weathering of Nonmetallic Materials Using
Concentrated Natural Sunlight.
G113 Standard Terminology Relating to Natural and
Artificial Weathering Tests of Nonmetallic
Materials.
B117 Standard Practice for Operating Salt Spray (Fog)
Apparatus.
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300
MIXING A PIGMENT WITH LINSEED OIL AND MAK-
ing a paste is a preliminary test applied to pigments that
has been in use in a systematic manner for almost a century
and perhaps even longer in a less defined manner. This
proved to be a practical means to qualitatively characterize
the approximate color and texture of pigments quickly with
materials and tools readily at hand. The work of mixing
and the flow properties of the resulting paste provided an
estimate of the rheological impact of a new pigment under
consideration or a proposed pigment composition change.
Thus, valuable insight of the dispersion performance of a
pigment or formulation change in a mill base could be esti-
mated. Further extension of the test was found to be useful
in predicting the consistency of finished products. Mills [3]
indicated that if equal volumes of oil absorption paste
are mixed or thinned with equal volumes of thinners, the
paints prepared have equal resistance to flow, viscosity, or
consistency. While the application of oil absorption values
as a formulation tool originated many years ago in the age
of oil- and alkyd binder-based paints, the ability to use this
information to calculate the binding power index of latex
binders, latex porosity index of latex paints, and free binder
continues to demonstrate the value of pigment oil absorp-
tion data today to solve coatings formulation problems.
This is especially true for the field of interior and exterior
architectural paints.
If the oil absorption test is conducted in a quantita-
tive manner, the result is a measure of the oil needed to
wet the surface area of the pigment and to fill the voids in
and among the pigment particles. If this result is achieved,
profoundly important information is obtained of high value
to pigmented paint and coatings development. A number
of relatively simple test procedures have been developed to
measure oil absorption of pigments. The difficulty generally
to successfully applying these tests has been in two areas.
First, great care and effort is required to reach and interpret
the oil absorption end point. Secondly, one must obtain par-
ticle separation in the test to the same degree as achieved
with the formulation in the pigment dispersion manufac-
turing process to which oil absorption value is to be related.
Two ASTM pigment oil absorption test methods are
available, which cover two incorporation methods. The dif-
ferent methods result in different end points and therefore
different oil absorption values. Stieg [4] found that if the
oil absorption value is determined by the ASTM D281 (Test
Method for Oil Absorption of Pigments by Spatula Rub-
Out) and expressed on a volume basis, it is proportional
to the critical pigment volume concentration (CPVC) of
alkyd wall paints. Later he and others demonstrated the
extension of oil absorption values to calculate the CPVC of
pigment compositions to predict the performance of latex
paints and other calculated factors useful in formulating
these coatings. GardnerColeman oil absorption, ASTM
D1483 (Test Method for Oil Absorption of Pigments by
Gardner Coleman Method), values have been related to
pigment paste viscosities and found useful in estimating
consistencies by comparison to a reference standard pig-
ment behavior in the same dispersion machinery. A number
of non-ASTM methods for the determination of oil absorp-
tion values have been reported in the literature and a few
will be listed below.
MECHANISM
When the oil absorption test is performed, the surface of
each pigment particle is wet and saturated to a certain
extent with oil and thus is encased in an oil shell that has
been estimated to be as thick as eight molecules [4,5]. The
amount of oil needed depends on the specific pigment area,
which is a function of particle size, roughness, and porosity.
With temperature and humidity constant, the oil adsorp-
tion value depends on the duration and vigor of the rubbing
operation and on the affinity of the oil for the pigment.
As oil is added beyond the particle encasement stage, the
interstices between the oil-encased particles become filled
with oil. The amount of oil required for this stage of the
test is a function of the type of packing taken on by the par-
ticles [6]. Packing can range from rhombehedral to cubic.
In addition, the presence of aggregates, which are clusters
of pigment not broken up by the rubbing process, and
agglomerates, which are clusters of pigment formed after
the pigment has been wet, have an effect on the amount of
oil needed. Agglomeration is affected by the nature of the
oil, and linseed oil with an acid number of 3 1 and that
meets the specifications shown in Appendix A should be
used. More extended discussions of oil absorption theory
and practice can be found in the literature [711].
METHODS FOR DETERMINING OIL ABSORPTION
There are two ASTM methods for determining oil absorp-
tion that will be described briefly as well as related methods
tabulated and referenced in Table 1.
Spatula Rub-Out Method
This is the classical method and the following directions
summarize those of ASTM D281 [12], first published by
ASTM in 1928 and updated from time to time with the
29
Oil Absorption of Pigments
1
Charles W. Glancy
2
2
5916 Marina View Court, Prospect, KY 40059.
1
This chapter is an abridged and modifed version of the chapters with the same title found in the previous editions of this manual [1,2].
MNL17-EB/Jan. 2012
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CHAPTER 29 OIL ABSORPTION OF PIGMENTS 301
latest reapproval in 2007. It is approved for use by agencies
of the U.S. Department of Defense. In this test, linseed oil
is added in a dropwise manner to the pigment while it is
being thoroughly rubbed with a spatula until a stiff putty-
like paste is formed. It differs from the Gardner-Coleman
Method [13], which requires only gentle folding and stir-
ring, whereas the rub-out test requires a thorough rubbing
action of the pigment and oil with a steel spatula.
Raw linseed oil that meets the specifications in Appen-
dix A but with an acid number of 3 1 is slowly added in
a dropwise manner to a known amount of pigment. The
amount of pigment should be sufficient to require 1 mL
or more of oil. After the addition of each drop of oil, the
oil is incorporated into the pigment by working or rubbing
the two together with the spatula. The end point is taken
to be the point where sufficient oil has been incorporated
into the pigment to produce a very stiff, putty-like paste
that does not break up. The weight of oil is determined by
multiplying the volume of oil by its density (0.93 g/mL). The
oil absorption value is reported as the grams of oil used per
100 g of pigment. Various stages in the spatula rub-out test
are described in Fig. 1.
The test requires extreme care to obtain acceptable
precision. The method is very tedious yet requires close
attention to avoid over-shooting the end point. Test results
by a single operator are often considered satisfactory if
within 5 %, but comparisons between different opera-
tors is much more problematic. As reported in ASTM 281,
results by a single operator and between different opera-
tors in different laboratories that differ by more than
14.3 % and 38.0 %, respectively, are suspect at the 95 %
confidence level. Stieg has reported that lack of a clear
understanding of the end point accounts for the differ-
ences reported between operators [14]. He reported almost
perfect correlation between CPVC calculated from oil
absorption values and experimentally determined CPVC
values when the end point is determined by the very
least amount of oil that will cause the pigment mass to
cohere while not causing it to wet either the glass plate or
the spatula. Then the method is repeated with a slightly
smaller amount of oil to be sure that no lower oil value
can be obtained. A comprehensive study [7] of oil absorp-
tion measurement by the British Standards Institution
method found individual operator capable of accuracy of
about 3 %, but results between different operators were
of the same order of magnitude as reported in ASTM 281.
TABLE 1Various non-ASTM methods for determination of oil absorption values
Method Comment Ref.
Azam Method same as ASTM D281 except end point is where paste
just adheres to the spatula. See text.
[15]
Bessey-Lammiman An indirect method. Pore volume of a compressed pigment
wafer is determined. From this, an oil adsorption number is
calculated.
[9]
British Standards Institution BS EN ISO 787-5:1995 and
German Institute for Standardization DIN ISO 787-5
Method is similar to ASTM D281. A defined weight of pigment
or extender is placed on a glass plate. Linseed oil is slowly added
by burette to the sample and mixed in using a palette knife. The
volume of oil required to form a smooth paste-like mass is noted
and the oil absorption is expressed as milliliters or grams of oil
required per 100 g of sample.
...
Density End Point Assumes density of pigment and oil are additive. Can have void
volume errors associated with it.
[16]
National Lead Company Method is similar to ASTM D281 and Azam methods, but an
attempt is made to regulate rubbing pressure and contact area
of spatula and rubbing plate
[17]
Smith-Stead Pigment is added to oil in this method and a mechanical muller
is used to better define the rubbing effort.
[18]
Fig. 1[1]A, B, and C in the top photograph represent 1 g
of zinc oxide that has been mixed with increasing amounts
of linseed oil. Rub-out A (top left) is crumbly and breaks up
when an attempt is made to lift it with a spatula. Rub-out
B (top middle) is coherent and tends to form a roll when
deformed with the spatula. Rub-out C (top right) contains
too much oil and does not roll. It can be lifted as a sheet
and the mixture is beyond the end point. The bottom
two photographs are additional examples of the mixture
condition just before the end point is reached. A single drop
of oil will convert the crumblings into coherent masses.
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302 PAINT AND COATING TESTING MANUAL 15TH EDITION
The wider range between operators was attributed to the
difference in effort expended during the rubbing of the oil
into the pigment rather than end point determination, and
that the amount of effort that should be expended cannot
be rigidly defined. Clearly, where comparisons are to be
made between operators, extreme care must be exercised
to ensure that the same mixing effort and end point deter-
minations are made. Oil absorption values obtained by
this test and the GardnerColeman test are given in Table 2.
AZAM METHOD
The Azam Method [15] is essentially the same test as ASTM
D281 with the main difference being a more rigorously
defined end point. The end point is defined as the point
where the paste just adheres to the spatula and the paste
was termed a complete paste. Azam found that a com-
plete paste absorbed no more oil when immerse in oil, but
an incomplete paste would absorb oil in an amount suf-
ficient to make it a complete paste. The end point check was
made by immersing the rub-out mass in a known amount of
oil and then determining the change after two or three days.
Rowland-Stieg Simplification of ASTM D281
This modification [19] of the classical method reports oil
absorption volumetrically in terms of milliliter of oil per
milliliter of pigment. This simplified procedure eliminates
several sources of error and is the logical procedure where
the objective is to calculate the CPVC rather than to report
the oil absorption value. The abbreviation OA
V
was selected
to identify the volumetric oil absorption determined by this
procedure. The specified pigment sample size in grams
equal to 1.25 mL is calculated by multiplying the pigment
bulking value in pounds per gallon by the factor 0.15 (the
exact value is 0.15006). This provides a sample size of about
5 g for the majority of architectural paint pigment com-
positions. The measured volume of oil from the titration
multiplied by 0.80 (to express milliliter of oil per milliliter
of pigment) is OA
V
.
GardnerColeman Method
This method or some variation of it has been in use for
about three quarters of a century. The current method,
ASTM D1483 by GardnerColeman Method [13], has
been in use for over 45 years. In this test, a soft paste is
formed from the pigment by drop-wise addition of raw
linseed oil that meets the specification in Appendix A but
with an acid number of 3 1 from a burette to the gently
stirred pigment. As the oil is slowly added, the mixture
is continuously stirred and folded so the oil strikes dry
pigment as long as any remains. The mixture is not vig-
orously rubbed as in the rub-out method. Eventually the
mixture collects in small lumps that gradually coalesce.
The rate of oil addition is reduced as the end point is
reached. The amount of oil required to form a paste
is used to calculate the oil absorption value. The end
point for paste formation is taken to be the point when
the lumps of wet pigment form a single ball or when an
excess of oil smears the wall of a container (see Fig. 2).
This will take place within one or two drops of oil. It is
important that there is no rubbing or grinding when this
test is carried out. Although the current test calls for use
of a steel spatula with particular dimensions and a glass
flask for the test, variations of these tools have been used
[20,21].
Oil Absorption, A, is expressed as grams of oil per 100g
of pigment and is calculated as follows:
A
M
P
_
,
( . ) 0 93
100
(1)
where M is the mL of oil used, P is the amount of pigment
used in grams, and 0.93 is a constant that represents the
density of the linseed oil. Test results by a single operator
and between operators in different laboratories that differ
by more than 9.9 % and 15.3 %, respectively, are suspect.
Oil absorption values obtained by this method and the rub-
out method are given in Table 2.
Characterization of Dispersions at the Oil
Absorption Point
Examination of the dispersions (pastes) formed between
oil and pigment at the oil absorption point is a source of
considerable information. Large differences exist in such
TABLE 2Oil absorption values, grams
of oil/100 g of pigment, of some common
pigments [1]
Pigment
Gardner-
Coleman Test
Spatula Rub-out
Test
Barytes 13.5 ...
Basic carbonate of
white lead
18 13.0
Basic sulfate of white
lead
30 12.8
Blanc fixe 30 15.0
China clay 51 30.0
Gypsum 33.5 ...
Lithopone 33 21.5
Silica, crystalline 23 ...
Silica, amorphous 32 29.0
Talc 60 ...
Titanox 26 18.5
Whiting 32 17.5
Zinc oxide 52 19.5
Fig. 2[1]Critical states in the Gardner-Coleman test. Left
photograph is the oil/pigment mass just before the end point
where the mass retains its rigidity. The right photograph
is the mixture at the end point where the mass undergoes
slight flow and smears the glass.
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CHAPTER 29 OIL ABSORPTION OF PIGMENTS 303
pastes with some being long, stringy, and soft in character.
Others are tough and short, others have a high gloss, others
have a dull appearance, others are soft and easy to spread,
and still others are stiff and require a large pressure spread
or flatten. The amount of oil needed is not closely related
to these attributes, and one is led to the conclusion that
pigments with essentially the same oil absorption value can
yield pastes with markedly different character.
Daniel and Goldman [22] developed a scheme for
evaluating dispersion character by using the paste obtained
at the end of the spatula rub-out test. The amount of liquid
needed to wet the pigment and produce flow is determined.
From this information and the types of flow exhibited by the
pastes, dispersions are classed as good, fair, or poor. From
10 to 20 g of dispersion is worked with a fairly stiff steel
spatula in the test. The oil absorption value is called the wet
point. From this point, oil addition is continued until the
flow point is reached. In well-dispersed systems, the flow
point is the stage where a substantial portion of the paste
flows from a vertically held spatula without leaving jagged
flow edges. In poorly dispersed or flocculated systems, the
flow point is the stage where the paste drops from a verti-
cally held spatula. Cases intermediate to these two are dif-
ficult to define. At the instant when paste drops from the
spatula, it elongates at the edge. If a paste does not flow
after addition of 10 %20 % more liquid than is required for
the wet point, a portion of the diluted paste is placed on the
tip of a horizontally held spatula. The spatula is then tapped
near the handle with a finger. The tapping is gentle at first
and then more vigorous. The paste may then become glossy
and flow over the edge of the spatula, in which case it is pas-
sively dilatent, or it may tend to rise or otherwise decrease
the interface between it and the blade, in which case it is
flocculated. Characteristics of pastes tested in this manner
are given in Table 3. A test such as this can yield practical
rheological results without sophisticated testing equipment.
Plasticizer Absorption By Pigments
Although linseed oil is used to obtain the oil absorption
values, it is obvious that a variety of liquids can be absorbed
by pigments. Typical data for selected plasticizers as well as
raw linseed oil are given in Table 4.
CRITICAL PIGMENT VOLUME
For a long time, the paint industry formulated on a weight
basis. In 1926 Calbeck [23] concluded from a statistical
study of house-paint test results that the pigment/binder
system should contain at least 28 vol % pigment. Not long
after this, Wolff [24,25] related optimum performance of
exterior paints to their critical oil contents, and simple
graphical methods for determining this parameter were
devised [26]. When Elm [27] investigated this concept, he
confirmed Wolffs findings, but found it necessary to reverse
the point of reference so it expressed the critical composi-
tion in terms of pigment content as in the work of Calbeck.
Later Vannoy [28] studied the matter and concluded that
replacement of certain pigments by others on a volume
basis was the manner in which formulating should be
approached. From such studies, the relationship known as
the pigment volume concentration (PVC) came into use. It
is a simple percentage calculated in the following manner:
PVC
pigment volume
pigment volume vehicle so
+ llids volume
_
,
[ ] 100 (2)
Studies such as these led to the CPVC concept, and
its importance to paint formulation was established by
Asbeck and Van Loo [29] in 1949. They illustrated the CPVC
concept by relating marked changes in gloss, rust, blister-
ing, and permeability over a relatively narrow (36) PVC
range. Many other properties including dry hiding, scrub
resistance, stain holdout, enamel holdout, and film tensile
strength also transition over this range. The CPVC may be
defined as the PVC where there is just sufficient binder
present to fill the interstices between pigment particles at
the densest possible packing and wet the pigment surface
in the dry film. The packing characteristics of the pigments
determine the void volume to be filled with binder. The sur-
face characteristics of the pigments determine the amount
of vehicle that is tightly bound to the surface. Usually the
formulators task for both economic and performance
reasons is to define the highest CPVC possible for the raw
materials and pigment dispersion processes available. The
CPVC relationship is expressed in the following equation:
TABLE 3Characteristics of pastes from oil absorption studies [1]
Observation Point Good Dispersion Fair Dispersion Poor Dispersion
At wet point Shines without tapping or with
light tapping; dry and difficult
to knead
Shines when sharply tapped Remains dull even when
sharply tapped
At intermediate stage ... Flows only on tapping;
occasionally has a resistance to
suddenly applied pressure
Rises on tapping; has no
resistance to suddenly applied
pressure; has a high yield value
At flow point Flows without tapping; offers
resistance to suddenly applied
pressure
Falls with elongation at
breaking line; no resistance to
suddenly applied pressure; has
visible thixotropy
Falls without elongation at
breaking line
Gap between wet and flow
points
Very small ... Very large
CPVC
volume of pigment
volume of pigment vo
/
,
x
mL oil/mL pigment
latex binding power in x ddex (1 for solution binder) .0
(5)
The following CPVC equation was published by Ramig
[41] and is useful to calculate the CPVC of any latex formu-
lation from binding power index, density and oil absorption
of the pigment composition.
CPVC
BI 1
OA Dp (BI) 1
OA pigmen
( )( )
( ) ( )
00
00
tt oil absorption in grams/1 g of pigment 00
BBI binding power index
Dp density of pigmen
tt
CALCULATION OF FILM POROSITY INDEX
The porosity index is a numerical expression of film poros-
ity and can be calculated from the oil absorption CPVC
of a pigment composition [42]. The greatest value of the
porosity index concept is as a means to guide the optimiza-
tion of the dry hiding of interior flat paints, while minimiz-
ing to the extent possible the negative characteristics of
porosity driven paint properties. The porosity index is the
fraction of pigment air voids in a paint film not filled by
the formulation PVC binder volume divided by the binder
volume required by the pigmentation at CPVC. It is easily
calculated for solution binder systems by the equation
PI
CPVC(1 PVC)
PVC(1 CPVC)
PI porosity in
1
ddex
CPVC pigmentation CPVC calculated from ooil adsorption
PVC formulation PVC
(4)
(6)
(7)
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306 PAINT AND COATING TESTING MANUAL 15TH EDITION
This equation provides a way to balance or maintain
constant porosity related properties such as permeability,
stain or enamel hold-out, and dry hiding power when
making pigment or extender changes. For example, the
porosity index of an existing formulation can be calculated
from the PVC and the oil absorption determined CPVC. If
an extender pigment adjustment is made, the PVC change
necessary to maintain equal porosity index can be readily
calculated by using the oil absorption of the new pigment
mix after rearranging the equation and solving for the PVC
required. Frequently a new composition is tested in the
laboratory at the same PVC/CPVC (lambda) ratio as the
original with a 5 (or more) paint PVC ladder centered on
this PVC. Evaluating performance at the lambda ratio of
equal porosity index should more accurately provide a cen-
ter point for further testing.
The equation for latex systems is the same as for sol-
vent systems except that the binding power index, discussed
in the next section, is included to take the film-forming
capability of the latex into account. Stieg has published
several articles that discuss useful graphical methodologies
that may save considerable laboratory time when dealing
with pigment or latex substitutions with a need to balance
dry hiding and porosity-dependent performance proper-
ties [19,43]. Plotting the percent pigment, binder and air
on a volume basis on triangular co-ordinate graph paper
is a convenient means to obtain the porosity index and the
percent air volume or porosity of the composition [44]. The
porosity index is indicated at the point a line from the pig-
ment apex strikes the pigment-air axis, that also intercepts
the point that a line from the air apex to the formulation
PVC on the pigment-binder axis crosses the formulation
CPVC line. The CPVC line is the formulation CPVC line
running from the pigment-binder axis to the pigment-air
axis. With latex paints the CPVC line in this graph must be
the value determined experimentally (apparent CPVC) or
the PVC at zero porosity calculated from the latex porosity
equation below where LP= 0. The percent air in the coating
film may also be determined by reading from the intercept
point on the CPVC line horizontally to the pigment-air axis.
LP 1
CPVC(1 PVC)
PVC(1 CPVC)
( )
LP latex poro
x
ssity index
CPVC pigmentation CPVC calculate dd fromoil adsorption
PVC formulation PVC
x vvehicle volume fraction binding power inde xx
Because the binding power index is a primary latex
property that does not vary with pigmentation changes
[41], the porosity-dependent properties of two different
latex paints may be matched by formulating at a constant
latex porosity index using the binding power index and
the oil absorption CPVC of the pigment blends. The PVC
change required to match the latex porosity index of the
paints can be calculated by the relationship below:
CPVC 1 PVC
PVC 1 CPVC
CPVC 1 PVC
a a
a a
b b
x
( )
( )
( )
(
a
))
( )
( )
PVC 1 CPVC
b b
b
x
(9)
In the case where the same latex is being used and the
pigment composition is changed, the above equation may
be used omitting the binding power index term on both
sides of the equation. With the oil absorption CPVC values
of both pigment compositions determined, the PVC adjust-
ment to maintain equal latex porosity index in the new for-
mulation can be calculated. Since the binding poor index is
constant x is omitted, and the terms of the equation reverts
to the solvent binder form.
CALCULATION OF LATEX BINDING POWER INDEX
Berardi [45] developed the concept that a constant ratio
exists between oil absorption and latex polymer concen-
tration required at the CPVC. This relationship can be
expressed as
BI
V
V
o
l
(10)
V
o
= volume of oil required to bind 100 g of pigment as
determined by oil absorption; V
l
= volume of latex binder
required to bind 100 g of the same pigment as determined
by an experimentally determined CPVC.
Stieg [46] eventually concluded the vehicle fraction
factor x he had developed to adapt the porosity index (PI)
equation developed for solution paints to latex paints was
identical to Berardis binding power index. The formula he
developed to calculate the binding power index (x) of a latex
may be derived by rearranging the latex porosity equation
to solve for x when LP is zero. See Ref. [46] for a detailed
discussion of this subject.
latex porosity (LP) 1
CPVC(1 PVC)
PVC(1 CP
0
VVC)
( ) x (11)
For LP
PVC (1 CPVC)
CPVC 1 PVC
PVC ap
0
0
0
0
x
( ( ))
pparent CPVC PVC of zero porosity
CPVC CPVC
,
calculated fromoil absorption
vehicle f x rraction factor binding power index
(12)
PVC
0
may be determined by the detection of dry hiding
in a formulation with no or a low concentration of opaque
pigment. Schaller [47] published an excellent method for
determining the PVC at zero porosity with a PVC ladder
in a single extender pigment paint. He determined PVC
0
by the appearance of dry hiding by measuring the contrast
ratio. The method is precise and relatively easy to perform
and very suitable to determining the binding power index
of a latex. Schaller demonstrated in his paper that the PVC
0
,
the apparent CPVC, of latex paint systems is dependent
on the latex particle size and polymer modulus. It was
demonstrated that increasing latex particle size and the
polymer modulus detract from efficient filming and pack-
ing of the latex particles in the pigment matrix leading to
latex binders exhibiting a lower apparent CPVC value com-
pared to solution binders in the same pigment composition.
Coalescent solvent effective for the latex must be included
in the single pigment test to accurately access PVC
0
. In sys-
tems with high white hiding power pigment, the end point
must be determined by tinting a PVC ladder of the formu-
lations with a constant amount of lampblack colorant and
determining the break in apparent tintorial strength or
S-values calculated from the Kubelka-Munk relationship
assuming constant K-value. The Pierce-Holsworth or the
(8)
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CHAPTER 29 OIL ABSORPTION OF PIGMENTS 307
Cole methods discussed in a later section may be used for
determining CPVC of a formulation with a high concentra-
tion of opaque pigment.
Ramig [41] provided a proof of the equivalency of
Berardis binding power index and Stiegs vehicle fraction
factor x. In the referenced paper he demonstrated that the
CPVC in latex systems is more than a basic pigment char-
acteristic and also that the binding power index is a funda-
mental latex property that remains constant in any pigment
composition. Ramig derived another equation to determine
the binding power index in terms of oil absorption, pigment
density and PVC
0
.
BI
OA PVC Dp
1 PVC 1
PVC apparent
( )( ))
( )( )
0
0
0
00
CCPVC PVC of zero porosity
determined
,
experimentally
OA pigment oil a bbsorption in cc/1 g of pigment
density
00
D
p
of pigment
(13)
CALCULATION OF FREE BINDER
When making necessary formula adjustments in exterior
paints, a means to adjust either the pigment or vehicle
to maintain constant durability has long been desired.
In the days of linseed oil paints, the concept of free
binder was developed as a formulation principle [48,49]
that held that if a formulas oil content was adjusted up
or down with pigmentation changes to maintain equal
viscosity, equal free binder was maintained. Fortunately
the optimum viscosity for durability and brushing coin-
cided for oil-based paints. This approach was, of course,
not applicable to latex paints. Stieg defined an equation
[5052] below to express the free binder of a paint as the
excess vehicle above the amount required for the CPVC
of the formula pigmentation calculated as a percentage
of the total binder volume. This equation was derived
from one published by Dintenfass [53] on the theoreti-
cal relationship between the relative viscosity of a dis-
persion, as compared to that of its vehicle, as a function
of the volume occupied by its settled pigmentation. The
percent free binder present in any oil-based or soluble
binder-system is calculated by the following equation:
%
( )
Free Binder
CPVC PVC
CPVC
(1 )
CPVC Pigme
00
nntation CPVC calculated fromoil adsorption n
PVC Formulation PVC
The equation indicates that the higher the CPVC of the
pigmentation is increased by pigment composition adjust-
ments, the higher the PVC may be for a constant percentage
of free binder.
For latex paint systems the binding power index will be
less than 1.0 and this must be taken into account to calcu-
late the free binder. The following equation was derived in
Refs. [51,52] for latex paints:
% ( )
)
free binder 1 PVC
PVC(1 CPVC)
CPVC(
(1
x
000)
CPVC pigmentation CPVC calculated fromo iil adsorption
PVC formulation PVC
latex bi
_
,
1100)
(16)
The PPF and OA values are compared in Table 5. If val-
ues are ranked from highest to lowest, the values calculated
from the PPF are highest, those from GardnerColeman fall
next, and those from the spatula rub-out test are lowest.
Explanations for the difference based on conditions exist-
ing at the endpoint are tabulated in Table 6.
Cole Method for CPVC
The CPVC depends on pigment particle packing or ori-
entation [10,29], and Cole [54] noted that spherical par-
ticles might pack similarly in both liquid and dry films. To
demonstrate this, a dry-film method was developed. The
method is based on the fact that below the CPVC dry film
volume, V, is a sum of the pigment volume, V
p
, and binder
solids volume, V
b
V V V
p b
+
(17)
and that above the CPVC the volume of the voids must also
be considered with
V PV
p
(18)
where P is the relative pigment packing factor (the ratio of
bulk volume to true volume). Two graphical and calculation
methods were used to obtain CPVC.
(14)
(15)
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308 PAINT AND COATING TESTING MANUAL 15TH EDITION
Pierce-Holsworth Method for CPVC
This method [55] also used paint films, but it treated the
data in a different manner by introducing specific volume
concepts. The specific volume, v, of a dry paint film can be
expressed as:
v
V
W
V
W W
v f v f
p b
p p b b
+
+
(19)
where V is the dry film volume, v, v
p
, and v
b
are specific
volumes of the dry film, pigment, and binder, W, W
p
, and
W
b
are weights of dry film, pigment, and binder, and f
p
and
f
b
are weight fractions of pigment and binder, respectively.
Since the sum of f
p
and f
b
is unity, the expression can be
arranged to
v v v f v
p b p b
+ ( )
(20)
If v is plotted as a function of f
p
, a straight line of slope
(v
p
v
b
) and intercept of v
b
should result.
Above the CPVC, the volume of the film is given by
V Pv
p
W
p
(21)
where P is a packing factor. If both sides of this expression
are divided byW, the expression
v Pv f
p p
(22)
TABLE 5Comparison of pigment packing
factors, calculated and experimentally
determined oil absorption values [1]
Pigment PPF
Oil Absorption Values
Calculated
from PPF
Gardner
Coleman
Method
Spatula
Rub-out
Method
Carbon black,
medium
10 456 212 124
Chrome green 34 41 33 20
Chrome yellow 27 46 33 24
Iron oxide, light red 37 32 24 19
Lampblack 29 128 70 51
Magnesium silicate 39 50 27 25
Midori blue 33 104 87 51
Phthalocyanine blue 20 225 55 34
Silica, diatomaceous 24 131 105 65
Toluidine red toner B 25 199 62 48
Zinc oxide 27 45 19 12
TABLE 6Physical conditions that exist at the end points of pigment packing factor and oil
absorption test [1,10]
Parameter PPF Gardner-Coleman Spatula Rub-out
Dispersion Aggregates are completely
broken down.
Only a few of the largest
aggregates are broken down
and the interstices are filled
with oil.
More aggregates are broken
down than in the Gardner-
Coleman methods and the
interstices are filled with oil.
Electrokinetic equilibrium Agglomeration is complete
because of high system fluidity.
Agglomeration is incomplete
because of low system fluidity.
Agglomeration is incomplete
because of low system fluidity.
Pigment surface requirements Satisfied Not completely satisfied Substantially satisfied
Work of dispersion Defined and very high
(approaching maximum)
Undefined but low Undefined but relatively high
Work of packing Defined and very low
(approaching zero)
Undefined but low Undefined but relatively high
TABLE 7Comparison of the critical pigment volume concentration calculated by the Pierce-
Holsworth method [28] and comparison with results from physical property measurements [1]
Paint system
Critical Pigment Volume Concentration
PierceHolsworth
Method
Tensile Strength
Method
Elongation at Break
Results
Water Vapor
Permeability Results
Acrylic latex exterior House Paint A 47 47 42 46
Acrylic latex exterior House Paint B 41 42 41 42
Poly (vinyl Acetate) latex masonry paint 44 44 44 45
Acrylic exterior masonry paint (from
House Paint A above)
48 47 44 48
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CHAPTER 29 OIL ABSORPTION OF PIGMENTS 309
is obtained. If dry film specific volume, v, is plotted against
the weight fraction of pigment, f
p
, a straight line of slope
Pv
p
passing through the origin results. The intersection of
this line with the previously described straight line should
occur at a value of f
p
corresponding to the CPVC. Results
obtained by this method are presented in Table 7 along
with the CPVCs obtained by tensile strength, elongation,
and water vapor permeability. The good agreement is
apparent.
APPENDIX A
Properties of raw linseed oil from Table 1 ASTM D234a
Property Requirement ASTM Method
Specific gravity, 25/25C 0.9260.931 D1963
Acid value max 4.0 D1639
Saponification value 189.0195.0 D1962
Unsaponificable matter,
max, %
1.50 D1965
lodine value (Wijs), Min 177 D1959
Loss on heating at 150 to
110C, max %
0.2 D1960
Clarity Clear and
Transparent
At 65C
D2090
Color (Gardner), max 13 D1544
Foots, volumetric heated
oil, max, %
1.0 D1954
Foots, volumetric, chilled
oil, max, %
4.0 D1954
Gravimetric foots, max, % 0.25 D1966
Flash point, min, F 250 D93
a
ASTM D234-82 (Re-approved 1987). Unfortunately, ASTM D234
Standard Specification for Raw Linseed Oil was discontinued in
March 2007. The historical method will still be available from
ASTM.org.
REFERENCES
[1] Oil Absorption of Pigments, Paint Test Manual, 13th ed., G.
G. Sward, Ed., ASTM International, West Conshohocken, PA,
Chapter 3.5, 1972.
[2] Oil Absorption of Pigments, Paint Testing and Coatings Man-
ual, Gardner-Sward Handbook, 14th ed., Joseph V. Koleske,
Ed., ASTM International, West Conshohocken, PA, 1995,
Chap. 28.
[3] Mills, G., Pigment Surfaces, J. Oil and Colour Chemists
Assoc., Vol. 34, 1951, p. 497.
[4] Stieg, F. B. Jr., Color and CPVC, Off. Dig., Fed. of Paint and
Varnish Prod. Clubs, Vol. 28, 1956, p. 695.
[5] Long, J. S., Creative Imagination as it Applies to the Decora-
tive and Protective Industry, Off. Dig., Fed. of Paint and Var-
nish Prod. Clubs, Vol. 26, 1954, p. 989.
[6] Annual Book of ASTM Standards, Vol. 06.03, ASTM Interna-
tional, West Conshohocken, PA.
[7] Marsden, E., Oil Absorption: A New Assessment, Part II, J.
Oil and Colour Chemists Assoc., Vol. 42, No. 2, 1959, p. 119.
[8] Mill, C. C., and Bank, H. W., An Interpretation of the Oil
Absorption of Pigments, J. Oil and Colour Chemists Assoc.,
Vol. 32. 1949, p. 599.
[9] Bessey, G. E., and Lammiman, K. A., The Measurement and
Interpretation of Oil Absorption, Journal of the Oil and Colour
Chemists Association, Vol. 34, 1951, p. 519.
[10] Asbeck, W. K., Laiderman, D. D., and Van Loo, M., Oil
Absorption and Critical Pigment Volume Concentration, Offi-
cial Digest, Federation of Paint and Varnish Production Clubs,
Vol. 24, 1952, p. 156.
[11] Davidson, R. R., Whiting Dispersions, Particle Packing, and
Surface Adsorption, J. Oil and Colour Chemists Assoc., Vol.
43, 1960, p. 307.
[12] Annual Book of ASTM Standards, Vol. 06.03 ASTM Interna-
tional, West Conshohocken, PA.
[13] Gardner, H. A., and Coleman, R. E., Oil Absorption of Pig-
ments, Scientific Section Circular, No. 85, National Paint,
Varnish, and Lacquer Association, Washington, DC, 1920.
[14] Stieg, F. B. Jr., The Determination of CPVC by the OA Test,
Am. Paint J., Vol. 45, No. 4, 1958, p. 41.
[15] Azam, M., Oil Absorption of Pigments, Industrial and Engineer-
ing Chemistry, Ind. Eng. Chem., Analy. Ed., Vol. 14, 1942, p. 545.
[16] Bessey, G. E. and Lammiman, K. A., Oil Absorption of Pig-
ments and Extenders, J. Oil and Colour Chemists Assoc., Vol.
33, 1950, p. P411.
[17] Oil Absorption, Brochure No. TP-P-OA, National Lead Com-
pany, Titanium Division, New York, 10 April 1953.
[18] Smith, F. M., and Stead, D. M., Determination of Oil Absorp-
tion: A New Method, Journal of the Oil and Colour Chemists
Association, Vol. 37, 1954, p. 194.
[19] Rowland, H. R., and Stieg, F. B. Jr., Graphical Solutions to
CPVC Problems in Latex Paints, J. Coat. Technol., Vol. 54,
No.686, 1982, p. 51.
[20] Haugen, O. A., and Hentzen, H. D., Oil Absorption of Paint
Pigments, Chem. Metall. Eng., Vol. 29, 1923, p. 840.
[21] van Wullen-Scholton, W., Oil Absorption of Pigments, Far-
ben Zeitung, Vol. 344, 1929, p. 2940.
[22] Daniel, F. K., and Goldman, P., Evaluation of Dispersions by
a Novel Rheological Method, Ind. Eng. Chem., Anal. Ed., Vol.
18, 1946, p. 26.
[23] Calbeck, J. H., Application of the Statistical Method in Test-
ing Paints for Durability, Ind. Eng. Chem., Vol. 18, 1926,
p.1220.
[24] Wolff, H., Oil Absorption of Pigments, Farben Zeitung, Vol.
34, 1929, p. 2940.
[25] Wolff, H., The Critical Oil Content of Paints, Farben Zeitung,
Vol. 37, 1931, p. 374.
[26] Wolff, H., and Zeidler, G., Rapid Method for Determination
of Critical Oil Requirements, Paint and Varnish Prod. Manag.,
Vol. 12, No. 6, 1935, p. 7.
[27] Elm, A. C., Paint Durability as Affected by the Colloidal
Properties of the Liquid Paint, Ind. Eng. Chem., Vol. 26, 1934,
p.1245.
[28] Vannoy, W.G., Extenders in Exterior House Paints, Off. Dig.,
Fed. of Paint and Varnish Prod. Clubs, Vol. 33, 1961, p. 1215.
[29] Asbeck, W. K., and Van Loo, M., Critical Pigment Volume
Relationships, Ind. Eng. Chem., Vol. 41, 1949, p. 1470.
[30] Bierwagen, G. P., CPVC Calculations, J. Paint Technol., Vol.
44, No.574, 1972, pp. 4653.
[31] Farrokhpay, S., Morris, G., Fomasero, D., and Self, P., Titania
Pigment Particles Dispersion in Water-Based Paint Films, J.
Coat. Technol. Res., Vol. 3, No. 4, 2006, p. 275283.
[32] Deya, C., Romagnoli, R., and del Amo, B., A New Pigment for
Smart Anticorrosive Coatings, J. Coat. Technol. Res., Vol. 4,
No.2, 2007, p. 167175.
[33] Giudice, C. A., Benitez, J. C., and Pereyra, A. M., Influence
of Extender Type of Performance of Modified Lamellar Zinc
Primers, J. Coat. Technol. Res., Vol. 1, No. 4, 2004, p. 291304.
[34] Freeman, G. M., High Performance Pigments of Low Oil
Absorption, U.S. Patent No. 5,316,576 (1994).
[35] Hen, J., et al., Paints containing low sheen opacifying pig-
ments by flux. calcinations of kaolin clay, U.S. Patent No.
6,346,145 (2002).
[36] Philadelphia Paint and Varnish Production Club, Determi-
nation of CPVC by Calculation, Off. Dig., Fed. of Paint and
Varnish Prod. Clubs, Vol. 33, 1961, p. 1437.
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310 PAINT AND COATING TESTING MANUAL 15TH EDITION
[37] Philadelphia Paint and Varnish Production Club, Predicting
the Oil Absorption and the Critical Pigment Volume Concen-
tration of Multicomponent Pigment Systems, Off. Dig., Fed.
of Paint and Varnish Prod. Clubs, Vol. 31, 1959, p. 1490.
[38] European Coatings Handbook, U. Zorel, Ed., Vincentz Net-
work GmbH & Co. KG, Hanover, 2000.
[39] Stieg, F. B. Jr., Effect of Pigmentation on Modern Flat Wall
Paints, Off. Dig., Fed. of Paint and Varnish Prod. Clubs, Vol.
26, 1954, p. 81.
[40] Stieg, F. B. Jr., Particle Size As a Formulating Parameter, J.
Paint Technol., Vol. 39, No. 515, 1967, p. 703.
[41] Ramig, A., Jr., Latex Paints-CPVC, Formulation and Optimi-
zation, J. Paint Technol., 47, No. 602, 1975, pp. 6063.
[42] Stieg, F. B. Jr., and Ensminger, R. I., The Production and
Control of High Dry Hiding, Off. DIG., Vol. 33, No. 438, 1961,
p. 792806.
[43] Stieg, F. B. Jr., Latex Paints And the CPVC, J. Paint Technol.,
Vol. 41, No. 531, 1969, p. 243.
[44] Graystone, J. A., Coatings for Buildings, Paint and Surface
Coatings: Theory and Practice, 2nd ed., R. Lambourne and T.
A. Strivens, Eds., William Andrews Inc., Norwich, NY, 1999,
pp. 330410.
[45] Berardi, P., Parameters Affecting the CPVC of Resins in Aque-
ous Media, J. Paint Technol., Vol. 27, No. 7, 1963, p. 2435.
[46] Stieg, F. B. Jr., Particle Size Parameter and Latex Paints, J.
Paint Technol., Vol. 42, No. 545, 1970, p. 329.
[47] Schaller, E. J., Critical Pigment Volume Concentration of
Emulsion Based Paints, J. Paint Technol., Vol. 40, No. 525,
1968, p. 433.
[48] Vannoy, W. G., Current House Paints, Off. Dig., Fed. of Paint
and Varnish Prod. Clubs, Vol. 21, 1949, p. 235.
[49] Southard, W. A., Exposure of Exterior House Paints, Off.
Dig., Fed. of Paint and Varnish Prod. Clubs, Vol. 31, 1959,
p.646.
[50] Stieg, F. B. Jr., Are Conventional Trade Sales Formulating
Practices Wasteful?, J. Paint Technol., Vol. 48, No. 612, 1976,
p. 51.
[51] Stieg, F. B. Jr., The Free Binder Concept, Am. Paint J., Vol.
64, No.36, 1980, p. 58.
[52] Stieg, F. B. Jr., The Free Binder Concept II: A Correction,
Am. Paint J., Vol. 64, June 1980, p. 62.
[53] Dinenfass, L., Selective Polar Adsorption and Some Rheo-
logical Phenomena in Paint Systems, Journal of the Oil and
Colour Chemists Association, Vol. 41, 1958, p. 25.
[54] Cole, R. J., Determination of Critical Pigment Volume Con-
centration in Dry Surface Coating Films, J. Oil and Colour
Chemists Assoc., Vol. 45, 1962, p. 776.
[55] Pierce, P. E., and Holsworth, R. M., Determination of Critical
Pigment Volume Concentration By Measurement of Density
of Dry Paint Films, Off. Dig., Fed. of Paint and Varnish Prod.
Clubs, Vol. 37, 1965, p. 272.
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Part 7: Additives
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313
PREFACE
MANY BACTERIA, FUNGI, AND ALGAE CAN CAUSE
problems in the paint and coatings industry. These problems
arise during manufacturing, in-can, and post application.
To minimize or prevent the growth of these microorgan-
isms, the appropriate microbicide (algicide, bactericide,
and fungicide) must be effectively applied. Generally, the
microbicides are divided into two general categories: Those
used for in-can preservation and those used for dry-film
preservation. Knowing the groups of organisms against
which a microbicide will target is very important in select-
ing the best chemical to use. The organisms involved are
discussed in more detail elsewhere in this manual.
TECHNICAL TERMS
microbicidea substance that kills organisms; syn-
onym for biocide; the term is further defined (bac-
tericide, fungicide, algicide) to indicate the target
organisms.
microbiostata substance that prevents the growth of
microorganisms and their spores, but does not neces-
sarily kill them.
aerobesorganisms that grow in the presence of oxy-
gen, utilizing the oxygen as a terminal acceptor.
facultative anaerobesorganisms that grow in the
presence or absence of oxygen.
anaerobesorganisms that grow in the absence of
oxygen; oxygen can be toxic to these organisms.
efficacythe effect of a microbicide on the target
organism or group of organisms; can be measured in
percent kill compared to control, but should be defined
in the test method; the result is usually expressed as
the minimum inhibitory concentration (MIC) against a
specific organism.
spectrumdescribes the efficacy of a microbicide.
broad spectrummicrobicide is effective against
more than one group of organisms.
narrow spectrumdenotes activity against one group
or sub-group of organisms.
DESCRIPTION OF MICROBIAL PROBLEMS
In-can Preservation
Water-based paints are prone to contamination and spoilage
by bacteria and occasionally unicellular fungi (i.e., yeast)
and filamentous fungi. Bacterial growth requirements
include water, a carbon source, an energy source, oxygen
for aerobes, and other macroelements, such as nitrogen
and phosphorus. The majority of bacteria grow between 10
and 50C and pH range of 311. Paint formulations provide
an adequate supply of the minimal nutrients at the ideal pH
and temperature to maintain bacterial growth.
In-can contamination may originate from a number
of sources. The aqueous raw materials, such as defoam-
ers, surfactants, wetting agents, and pigment slurries, are
themselves susceptible to bacterial degradation. Powdered
materials, including starches, fillers/extenders, and pig-
ments may contain bacterial endospores and fungal spores
that can germinate under appropriate conditions. The most
common source of contamination is the process water.
Along with good housekeeping procedures, proper micro-
bicides must be used in the raw materials and water to
minimize bacterial contamination.
The problems commonly encountered in water-based
paints are shown in Table 1. These do not necessarily hap-
pen at the same time but develop as the microbial popula-
tion changes due to oxygen requirements. Because of the
initial oxygen-rich environment, aerobes and facultative
anaerobes will often initiate the degradation. They can
utilize a variety of paint components for nutrients. They
can produce enzymes, including proteases and glucanases.
The breakdown products resulting from numerous enzy-
matic activities act as nutrient sources for other bacteria.
As oxygen is depleted, the facultative anaerobes and strict
anaerobes will thrive. The metabolic processes produce
acids that can lower the pH; produce gasses, such as hydro-
gen (H
2
), carbon dioxide (CO
2
), and hydrogen sulfide (H
2
S),
which can cause bulging cans and odors; and produce
organic acids and other metabolic end products that cause
odors. Acids will also react with any calcium carbonate to
produce CO
2
. Anaerobes also produce cellulases. The cel-
lulases catalyze the breakdown of cellulose-based materials
such as thickeners. As the thickener is degraded, viscosity
is lost. More thorough discussions on these metabolic pro-
cesses can be found in Refs. [14].
To prevent these problems from occurring, the appro-
priate microbicide must be incorporated into the coating
formulation. In addition to being cost-effective, the micro-
bicide should be compatible with all coating components,
30
In preparation of this chapter, the contents of the 14th edition were drawn upon. The author acknowledges the author of
the 14th edition, Vanja King. The current edition will review and update the topics as addressed by the previous author,
introduce new technology that has been developed, and include up to date references.
Bactericides, Fungicides, and Algicides
Janet H. Woodward
1
1
Product Specialist, Biocide GroupPaper Technologies Division, Buckman Laboratories, Inc., 1256 N. McLean Blvd., Memphis, TN 38108.
MNL17-EB/Jan. 2012
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314 PAINT AND COATING TESTING MANUAL 15TH EDITION
be stable within a range of pH, temperature, and time
period, have no effect on rheology, impart no discoloration
or odors to the coatings, be water soluble in concentrations
used, and be environmentally acceptable [57].
Dry-Film Preservation
Microorganisms involved with dry-film problems include
bacteria, algae, and fungi. Bacterial growth requirements
are noted in the above paragraphs. In addition to sources
of carbon, nitrogen, and hydrogen, most fungi require a
relative humidity of 60 % or greater. All filamentous fungi
are aerobic whereas the unicellular yeast can be aerobic
or anaerobic. The ideal temperature range for fungi is
2035C. Although fungi can grow in alkaline conditions,
the ideal pH range is 4.56.5. Algae are photosynthetic;
they require light, carbon dioxide and water (i.e., moisture)
to produce energy. They survive in alkaline conditions and
temperatures of 1530C.
The most understood problem associated with dry-
film preservation is the defacement and discoloration of
the film itself when applied to surfaces such as interior
and exterior walls of buildings, bridges, and ships [4,
810]. Algae are more of a serious problem in temperate
and tropical regions and especially on masonry surfaces
because of the alkaline conditions [11,12]. Algal growth
may produce minor defacement; however, it will increase
moisture retention, which can lead to other problems
[10]. In hard, calcium-rich fresh water, algae can also
cause the precipitation of calcium carbonate onto sub-
merged surfaces, including antifouling paint [13]. Fungi
can produce mycelia and spores that will disfigure dry-
film. If the mycelia can grow through the coating, subse-
quent problems can include the film losing adhesion, the
initiation of corrosion, and the deterioration of wooden
structures. Table 2 lists problems in paint and coating film
preservation.
Studies [14,15] have indicated the succession of micro-
bial populations on dry-film as well as surfaces coated
with antifouling paint. Initial colonization is from bacteria
that produce extracellular capsular material. The resulting
conditioning of the surface allows for the subsequent
growth of fungi, algae, and other organisms. These studies
indicate the need for a dry-film preservative to be broad-
spectrum in its activity, i.e., it must be effective against
bacteria as well as fungi and/or algae. Other requirements
for a dry-film preservative include stability over a wide pH
range, temperature stability, low water solubility to pre-
vent or retard leaching, UV stability, long-lasting efficacy,
compatibility with the other materials in the formulation,
no discoloration or odors imparted, and environmental
acceptability[6,7].
GROUPS OF MICROORGANISMS RELATED TO
BIOCIDAL EFFICACY
It is important to know the activity of a particular micro-
bicide against the types of organisms encountered during
in-can or dry-film preservation. For this purpose, the most
important groups of microorganisms are:
Bacteria
Aerobic bacteria
Gram positive bacteria
endospore-forming bacteria
Gram negative bacteria
Facultative anaerobic bacteria
Gram negative bacteria
Anaerobic bacteria
Gram positive bacteria
endospore-forming bacteria
Gram negative bacteria
Oxygenic, photosynthetic
bacteria (Cyanobacteria, formerly called the blue-
green algae)
Fungi
Multicellular (molds)
Unicellular (yeasts)
TABLE 1Problems caused by contamination
of water-based paints and coatings
Type of Problem Common Cause
Viscosity Loss Cellulase enzymes from
bacteria or fungi catalyzing
degradation of cellulose
thickeners
pH changes Acids produced from
metabolic processes, typically
from anaerobic bacteria
Odors Organic acids and other
metabolic end products, such
as hydrogen sulfide from
anaerobic bacteria
Gassingbulging or exploding
cans
CO
2
or H
2
production from
anaerobic bacteria or yeast
Discoloration Colored pigmentary moieties
from bacterial and yeast
metabolism; sulfide from
sulfate-reducing bacteria
Foaming Degradation of antifoam
agents via bacteria
TABLE 2Problems in paint and coating film
preservation
Type of Problem Common Cause
Defacement/discoloration/dirt
entrapment
Algae and/or fungi; some
bacteria growing on film
Loss of adhesion Fungi growing under film
Deterioration of structure
(wooden)
Fungal enzymes catalyzing
the breakdown of cellulose,
hemicellulose, and
lignocellulose
Antifouling paint failures on
marine crafts, etc.
Bacteria, algae (including
diatoms), fungi, barnacles
Corrosion Bacteria, such as sulfate
reducers, and moisture from
fungi initiating corrosion
Destruction of cultural
material
Bacteria, algae, and fungi
growing on paintings, statues,
and buildings
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CHAPTER 30 BACTERICIDES, FUNGICIDES, AND ALGICIDES 315
Algae
Green algae
Brown algae
MODE OF ACTION OF MICROBICIDES: SPECTRUM
OF ACTIVITY
The spectrum of activity of a microbicide will describe
which organisms or group of organisms will be the targeted
by the biocide. Typically, microbicides are considered nar-
row spectrum, i.e., activity against one group or sub-group,
or broad spectrum, i.e., two or more groups of organism
will be affected. Thus, microbicides can be generally cat-
egorized as bactericides, fungicides, and algicides. Because
algae and fungi are eukaryotes, their overall cellular struc-
tures are different and somewhat more complex than the
prokaryotic bacterial cells. Thus, fungicides and algicides
are generally more toxic than bactericides.
Concentration will also affect a microbicides spectrum
of activity. At higher levels, some bactericides are effective
against fungi. The reverse is also true; some fungicides
at lower concentrations will act as bactericides. Another
aspect of concentration is the difference of a chemical being
microbiocidal (or biocidal) and microbiostatic (biostatic).
At low concentrations, some microbicides will be micro-
biostatic; instead of killing organisms, a microbiostat will
react with a physiological activity of a group of organisms
to prevent their growth.
Various microbicides used for in-can preservation
are listed in Table 3. These agents are incorporated into a
paint or coating formulation to prevent microbial contam-
ination of the final product; they are not added at elevated
concentrations to treat a contaminated component of the
formulation. Therefore, for any in-can preservative to be
effective, it is assumed that microbial contamination dur-
ing the manufacturing process has been kept to minimal
levels.
Common microbicides for dry-film preservation are
listed in Table 4; most anti-fouling agents are not specifi-
cally covered in this chapter. Dry-film preservation actives
differ from in-can actives because of two factors. Firstly, as
described above, dry-film contamination is typically caused
by fungi and algae rather than bacteria alone. Secondly,
dry-film preservatives have to be effective for extended peri-
ods of time; this can be years as compared with months for
in-can preservatives.
Table 5 lists some other microbicides used in paints
and coatings, especially during the manufacturing process.
As stated above, contamination of raw materials must be
kept to a minimum. The process water must also be kept as
clean as possible. Disinfection of process vessels and pipes
along with general good housekeeping procedures should
also help to decrease microbial contamination.
MODE OF ACTION OF SOME ANTIMICROBIAL
AGENTS
The following is used to give a general overview of the more
common modes of action of the microbial agents listed in
Tables 35.
Formaldehyde-Releasing Agents
Many microbicides are classified as formaldehyde-releas-
ing compounds. They are produced by reacting formal-
dehyde with amides (N-formals), with alcohols or glycols
(O-formals) or with amines or aminoalcohols (N,O- formals)
[7]. As implied by the category, some are biocidal due to
the release of formaldehyde. However, under application
conditions, certain microbicides in this category do not
rely on the release of formaldehyde for their specific mode
of action. The liberation of formaldehyde is also related
to pH; at alkaline pH, little or no formaldehyde will be
released.
Aldehydes including formaldehyde deactivate protein
by interacting with amine groups on the protein. Proteins
are found on the outer layers of microorganisms. Also,
all enzymes, i.e. catalysts for many metabolic reactions,
are protein. The deactivation of protein leads to disrup-
tion in cellular metabolism and transportation across cell
walls and membranes and ultimately leads to death of the
organism.
Formaldehyde can also be classified as an electrophilic
agent, i.e., a compound that reacts with the nucleophilic
components of a cell.
Agents that React with Nucleophilic Groups
Nucleophilic groups are described as those species that are
electron rich. The nucleophilic groups that are commonly
found in microorganisms are thiols (
(BASF),
Triton
(Rhone-Poulenc) sur-
factants are very effective additives having excellent inter-
facial properties and are used as emulsifiers, dispersants,
and wetting agents.
Due to increased environmental considerations, alkyl
phenol-free surfactants are getting more attention in the
industry and, in some applications, gain enough grounds
to replace alkyl phenol-containing additives. Alkyl phenol-
free surfactants are rather diverse and are based on EO-PO
block copolymers (Pluronic
surfactant
series), is another example of a unique surfactant chemistry
that found its applications as an effective wetting agent,
defoamer, and surface tension reducer [7].
The main distinction between ionic and nonionic sur-
factants is the charge and the molecular weight of their
molecules. The lack of ionic groups is primarily respon-
sible for lower water sensitivity of nonionic surfactants.
Because of their higher molecular weight, the water-
soluble segments of nonionic surfactants extend into the
water phase, forming a viscous barrier layer. This imparts
steric stabilization by inhibiting the approach of another
particle and preventing coagulation. Despite their unique
advantages, most of the time, nonionic surfactants are
used in combination with ionic amphiphiles. Such blends
enhance sheer, mechanical and electrolyte stability of the
paint in a wider pH range, electrolyte concentrations, and
temperature conditions. Thus, the presence of anionic
surfactant allows compensation for limited solubility of
nonionic surfactants at temperatures above their cloud
point. Nonionic surfactants, on the other hand, provide
additional stabilization to a dispersion when anionic sur-
factants experience electrolyte shock due to shrinking
double electric layer at elevated electrolyte concentra-
tions [8].
Hydrophobic Groups
Alkyl benzene and alkylated aromatics, paraffins, and ole-
fins (branched and linear), long-chain alcohols, alkylphenol
alkoxylates, fatty acids, and their derivatives are among
typical and most commonly occurring hydrophobic groups
of various amphiphilic molecules [1,6].
Fluorocarbon surfactants have similar molecular struc-
tures to the hydrocarbon molecules except all the carbon-
hydrogen bonds are replaced by carbon-fluoride bonds.
These surfactants exhibit extremely low surface tension, an
average 1020 mN/m lower than equivalent hydrocarbon
[1]. Because of the extremely hydrophobic nature of these
molecules, fluorocarbons have a very strong tendency to
preferentially adsorb on the interface, reducing the surface
tension down to 1522 mN/m, and provide spontaneous
spreading on low surface energy substrates. Despite their
unique surface activity and chemical stability, the wide use
of these surfactants is limited by their high cost and poor
compatibility. The latter could precipitate adhesion prob-
lems in the coatings.
Silicone-containing surfactants are another type of
nonhydrocarbon-based surfactant molecules. When func-
tionalized to produce water-soluble molecules, their surface
activity falls below hydrocarbons and above fluorocarbon-
based surfactants. Silicone surfactants effectively adsorb on
the interface, act as effective defoamers but do not exhibit
aggregation behavior such as micelle formation and solu-
bilization [5].
Polymerizable Surfactants
In recent years, with heightened demands for reduced
VOC and improved performance, polymerizable surfac-
tants have received much attention in both academic and
industrial circles [912]. The attraction of using polymeriz-
able surfactants for lattices is rationalized by the fact that
surfactant concentration in the aqueous media and on the
surface of a latex particle depends on many factors. These
include particle concentration, temperature, ionic strength,
pH, any of which could be changed during the storage and
application affecting the stability of the latex. During the
film formation and particle coalescence, the surface area of
the particles is significantly reduced, freeing a substantial
amount of surfactant to migrate toward remaining coating/
substrate and air/coating interfaces. This behavior affects
paint adhesion to the substrate and re-coating ability. This
could also adversely affect water resistance of the film and
its gloss.
It has been shown [912] that many surfactant-related
problems could be avoided or minimized by using polym-
erizable surfactants that become covalently bonded to the
latex particles during the emulsion polymerization. Several
types of ionic and nonionic reactive surfactants have been
introduced to the market. Most of them have ethylene and
propylene oxide blocks combined with a polymerizable
group like allyl (Reasoap surfactants, Clariants Emul-
sogen
) surfactant, diallyl
(Plurocoat RS surfactants), acrylic (Unichemas Max-
emul
(3)
Therefore, a surface active agent is a substance that, at
low solution concentrations, adsorbs on the interface and,
thereby, changes the amount of work required to expand
that interface, i.e., reducing surface tension. Specifically,
at the air/water interface, adsorption of the surfactant
is driven by unfavorable hydrophobic interactions. The
TABLE 1List of hydrophilic and lipophilic moieties of surfactant molecules
Hydrophilic Lipophilic
Ionic Sulfate OSO
3
Linear or branched C
6
C
20
Sulfonate SO
3
alkyl C
6
C
20
Carboxylate CO
2
Alkynebenzene
Quaternary ammonium R
4
N
+
Fluoroalkyl
Nonionic Alcohol CR
2
OH Poly(ethylene oxide) (OCH(CH
3
)CH
2
)
n
Na
+
38.7
CO
2
K
+
21.1
CO
2
Na
+
19.1
R
4
N
+
9.4
COO 2.4
COOH 2.1
OH 1.9
O 1.3
Lipophilic CH 0.475
CH
2
CH
3
=CH
(OCH
2
CH
2
)
n
0.33
(OCH(CH
3
)CH
2
)
n
0.15
TABLE 3Correlation between solubility of
a surfactant in water and its HLB value
HLB
No dispersability in water 14
Poor dispersion 46
Non-stable milky dispersion 57
Stable milky dispersion 710
Translucent emulsion 1012
Clear (micellar) solution >12
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324 PAINT AND COATING TESTING MANUAL 15TH EDITION
presence of hydrocarbon groups of the dissolved amphi-
philic molecule causes distortion of hydrogen bonding
network of water molecules and increase of the free
energy of the system. This is known as a hydrophobic
effect [17]. Once the surfactant is present in the solution,
substantially less work is required to bring a surfactant
molecule, rather than a water molecule, to the surface.
Hence, migration and preferential adsorption of a sur-
factant on the interface is a spontaneous process. As con-
centration of the surfactant in the solution increases, the
formation of an oriented and densely packed surfactant
monolayer with the hydrophobic tails extends away from
the water and the hydrophilic head groups submerge into
the water phase [Fig. 3(a)].
The surfactants adsorption at an interface is a dynamic
process that quickly establishes its equilibrium between
two phases: surfactant dissolved in the media and mol-
ecules adsorbed at an interface. Classical equations by
Gibbs and Langmuir describe quantitative relationships
between the equilibrium adsorption and major affecting
factors, such as interfacial surface tension and surfactant
concentration Thermodynamics of surfactant adsorption
from solution are reviewed in detail elsewhere [1,2,6,8,18].
The key property defining surfactant molecules is their
ability to adsorb on an interface and reduce interfacial
surface tension. The surfactants ability to reduce surface
tension of a solution depends on both its efficiency and
effectiveness [2]. Efficiency is related to the minimum con-
centration of the surfactant required to produce a given sur-
face tension reduction. Effectiveness of the surfactant is the
maximum reduction in surface tension that can be obtained
regardless the concentration. Efficient surface active agents
have relatively low molecular weight and, therefore, high
molecular mobility. Surfactants, which diffuse or migrate
rapidly, impart to the paint, by definition, low dynamic sur-
face tension and, therefore, reach equilibrium much faster
than higher molecular weight surfactants.
Micellization
Adsorption of a surfactant at the interface occurs over a
wide range of surfactant concentrations and is typically
complete above a well-defined concentration, called critical
micelle concentration (CMC). At the CMC, the interface is
near its maximum coverage and, to further minimize the
free energy of the system, the surfactant is forced to form
aggregates in the bulk. Thus, above the CMC, the system
consists of adsorbed surfactant monolayer at the air/water
interface [Fig. 3 (a)], free monomeric surfactant dissolved
in the bulk phase [Fig. 3(b)] and micelle aggregates in the
bulk phase [Fig. 3 (c)]. Dynamic equilibrium is quickly
established between all three states of surfactant existence
in the system.
The same mechanism, i.e., hydrophobic interaction,
that causes adsorption of amphiphilic molecules on an
interface, also leads to spontaneous association of such
molecules to form aggregates or micelles, when their con-
centration is sufficiently high [1,2,6,8]. Micelle formation
occurs over a fairly sharp, well-defined region called CMC.
Above the CMC, additional surfactant molecules form the
aggregates, whereas the concentration of unassociated sur-
factant remains fairly constant and equal to the CMC. Most
importantly, at much the same concentration, a rather dra-
matic change in concentration dependence can be observed
in common surfactant solution properties (Fig. 4). The
sudden change in solution properties is attributed to a sig-
nificant change in the nature of the solution and formation
of aggregates or micelles in solution.
According to Hartley [19], micelles are essentially
spherical aggregates with a diameter equal to approxi-
mately twice the length of the hydrocarbon chain. The
TABLE 4HLB ranges and surfactant
applications
HLB Range Application
46 Water-in-oil emulsion
79 Wetting agents
818 Oil-in-water emulsion
1315 Detergents
1018 Solubilizers
Fig. 3Schematic illustration of surfactant aggregates: Mono-
layer (a), monomeric state (b), micelle (c), inverted micelle (d),
liposome (e), and rod-like micelle (f).
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CHAPTER 31 SURFACTANTS 325
cluster of 50100 surfactant molecules, the core of the
micelle, is essentially hydrocarbon free of water or any
other polar solvent. The hydrophilic groups remain on the
surface of the micelle to allow for maximum interaction
with aqueous media. Counter ions are strongly or partially
bound to the polar head-groups, thereby reducing lateral
repulsive forces between those groups on the surface of the
micelle and stabilizing the entire aggregate.
The CMC value of a surfactant depends on many fac-
tors, including the experimental method of determining
this characteristic [18]. Thus, light scattering techniques
are sensitive to the weight average molecular weight and
particles size of the micelles. Surface tension and conduc-
tivity methods, on the other hand, depend on the number of
particles in the solution. Other major factors determining
CMC are the nature and structure of the hydrophobic and
hydrophilic groups, the nature of counter ion, temperature,
and the presence of electrolytes and additives [1,2].
The length of the hydrophobic group is one of the
major factors determining CMC. For the homologous series
of liner alkyl chains, the CMC decreases logarithmically
with increase of carbon number, according to the Klevens
equation [20]:
log (CMC)
min
A Bn
c (4)
where A and B are constants for a particular homologous
series and temperature, and n
c
is the number of carbons
in the hydrophobic alkyl chain. This equation predicts,
rather well, the behavior of linear single-chain surfactants.
However, CMC values deviate significantly when alkyl chain
branching, double bonds, or aromatic groups are intro-
duced into the hydrophobe moiety. In hydrocarbon surfac-
tants, chain branching increases the CMC value compared
to the straight chain surfactant [21]. Presence of a benzene
ring in the chain is equivalent to approximately 3.5 carbon
atoms [Eq(4)].
Varying the nature of the hydrophilic group from ionic
to nonionic has more impact on the CMC of the surfactant
than the exact nature of ionic group itself since a major
driving force for micelle formation is the entropy factor
[1,2]. For a C
12
hydrocarbon surfactant molecule, the CMC
of ionic surfactant occurs in the range of 1 10
3
mole/L,
while equivalent nonionic surfactant exhibits a CMC in the
range of 10
4
mole/L.
Since ionic surfactant micelles are formed and stabi-
lized by the interactions of water with the charged head
groups, an increase in degree of ion binding (or decrease
in electrostatic repulsion between ionic head groups)
decreases the CMC. For a given hydrophobic tail and
anionic head group, the CMC decreases in the order of
Li
+
> Na
+
> K
+
> Cs
+
> N(CH
3
)
4
+
> Ca
2+
= Mg
2+
. For the halide
series of cationic surfactants, the CMC decreases in the
order of F
> Cl
> Br
> I
.
Presence of electrolytes effectively shields the elec-
trostatic repulsions between ionic head groups, thereby
lowering the CMC and increasing aggregation number.
Temperature effect on the CMC of ionic surfactants is rela-
tively subtle, owing to the fact that its impact on bonding,
heat capacity, and volume is very weak. Nonionic surfac-
tants have more dramatic response to the temperature
changes, as elaborated in the discussion of the Krafft and
cloud points.
Other aggregates existing in surfactant solutions and
described in the literature include rod-like micelles [22]
[Fig. 3(f )], lamellar [23][Fig. 3(e)], and disk or cylindri-
cal aggregates [24]. As the surfactant concentration is
increased above CMC, the initially spherical micelles
become more distorted in shape and form cylindrical rods
and liquid crystals at much higher concentrations.
Solubilization
Solubilization is characterized by the dramatic increase
in the solubility of a lipophilic material in the presence of
a surfactant at the concentrations above the CMC. This
characteristic is frequently used to detect the onset of
micellization, even though the lipophilic material itself may
affect the value of the CMC [25]. The location of the solu-
bilized species in a micelle is determined primarily by the
chemical structure of the additive. In aqueous media, polar
molecules are solubilized in the polar surface of the micelle,
whereas non-polar additives are strongly associated with
the hydrophobic interior of the micelles. More complex
molecules containing both polar and non-polar regions
may partition between the polar and non-polar regions of
the micelles, producing more complex structures. Such
complex systems are believed to be stabilized via hydrogen
bonding or dipole-dipole interaction between the solute
matter and the surfactant [26,27].
Solubilization, similar to the adsorption micelliza-
tion, is a dynamic process. The average residence time of
solubilized molecules have been determined and depend
on many factors including temperature, the nature of the
solute and its concentration, type of surfactant, concentra-
tion, and CMC value [6]. Thus, solubilization increases with
increasing surfactant concentration in the region above
CMC level. Micelle solubilization capacity is proportional
to the length of hydrocarbon chain of the surfactant, which
controls CMC and micelle aggregation number. On the
other side, the solubilization is expected to decrease with
introduction of unsaturation, aromatic groups and hydro-
carbon chain branching in the surfactant molecules due to
weakened hydrogen bonding, and geometric and packing
constraints. Moreover, solubilization depends on the nature
of the additive that control its interactions with the sur-
factant molecules and its molecular size, which determine
packing requirements. However, the relationship between
the chemical structure of the additive and its ability to be
Fig. 4Schematic representation of the concentration de-
pendence of physical properties of micelle-forming surfactant
solutions.
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326 PAINT AND COATING TESTING MANUAL 15TH EDITION
solubilized by a surfactant solution is rather complex and
has not been quantified yet. Temperature has a combined
effect on the solubilization process. First, it affects the par-
ent process of micellization and may have impact on both
CMC value and aggregation number. Second, temperature
undoubtedly affects intermolecular interactions, such as
hydrogen bonding and hydrophobic interaction, between
solvent and solutes.
Cloud Point
Most nonionic surfactant solutions become visibly turbid
and cloudy upon heating. Cloud point is defined as a tem-
perature above which the phase separation of surfactant
solution occurs. Observed increase in turbidity is the result
of increase in aggregation number, augmentation of micelle
size, and their more efficient scattering of the light. On
the molecular level, more energetic thermal motions avail-
able at elevated temperatures weaken specific interactions
between surfactant and the media and cause dehydration of
the surfactant polar groups. Reduction or complete elimi-
nation of hydration shells around surfactant aggregates
diminishes or totally eliminates protection against inter-
molecular interactions. As the result, the micelle-micelle
interaction and their subsequent aggregation significantly
increase with temperature augmentation. This process
occurs in a narrow temperature range and is totally revers-
ible upon cooling.
Cloud point characteristics depend on the chemical
structure of the surfactant molecule. For poly(ethylene
oxide)(PEO) nonionic surfactants, the cloud point increases
with increasing EO content. For a given length of EO block
copolymer, the cloud point value decreases by increasing
the length of the hydrophobe, broadening the PEO chain
length distribution, and introducing branching in the
hydrophobe portion of the molecule. However, note that
the cloud point could also be affected by the presence of
electrolytes [28] and other polar and non-polar additives
[29,30] present in the formulation.
The cloud point phenomenon affects many processes
including solubilization, foaming, and dispersion. If appli-
cation temperature is above the cloud point of the sur-
factant solution, destabilization of dispersion, pigment
flocculation, phase separation, and defoaming may occur.
The latter could be a very desirable effect since surfactants
with cloud points near or below the application tempera-
ture are the most effective defoamers.
Krafft Temperature
Solubility of most solutes in water typically increases with
increases in temperature. However, for ionic surfactants
with low solubility, there is often a temperature at which
the solubility suddenly increases very dramatically. This
is known as Krafft point or Krafft temperature, T
k
, and is
defined as an intersection of the solubility and the CMC
curves (Fig. 5). Hence, the Krafft temperature is the point
at which surfactant solubility equals CMC. Below T
k
, sur-
factant is dissolved only in a single dispersed state and the
minimum achievable surface tension will correspond to the
concentration of maximum solubility and not the CMC.
Above T
k
, additional surfactant forms micelles and the solu-
bility rises sharply.
An abrupt increase of surfactant solubility in water
with temperature was first noted by Krafft and Wiglow and
had since been called Krafft point [31]. Originally, due
to coincidence of Krafft points and melting points of the
hydrocarbon chains, this phenomenon was interpreted as
the melting of the hydrocarbon chains of the surfactants.
However, current interpretation evolves around the transi-
tion between the dissolution of the surfactant to form ions
and dissolution to form micelles [2].
T
k
varies as a function of both the nature of the hydro-
phobic group and the character of the ionic interactions
between the surfactant and its counter ion. Krafft point is
critical for many applications since typical surfactant char-
acteristics such as surface tension reduction and micelle
formation cannot be achieved below T
k
. Because of their
different mechanism of solubilization, nonionic surfactants
do not exhibit a Krafft temperature. Characteristic temper-
ature/solubility relationship of nonionic surfactants relies
on the delicate balance of specific interactions promoting
solubility and thermal motions that destabilize the system.
As temperature increases, nonionic surfactants become less
soluble and form cloudy suspension (cloud point).
APPLICATIONS
Emulsifiers
The majority of water-based paints consist of aqueous
dispersions of water-insoluble polymers made by emulsion
polymerization, i.e., lattices. Emulsifiers used for latex
preparation are often a combination of both ionic and
nonionic surfactants [3,12]. Despite numerous advantages
of non-ionic surfactants, they do not completely replace
anionic emulsifiers, but rather used in combination for
several reasons. First, the presence of anionic surfactants
during the synthesis offsets the negative temperature
dependence of ethoxylated nonionic surfactants. As elabo-
rated in the discussion of the cloud point phenomenon,
temperature increase during the radical polymerization
may lead to a decrease in water solubility of the surfactants
and a possible phase inversion (from oil-in-water to water-
in-oil emulsion). In practice, emulsion polymerizations are
often carried out in semi-continuous processes, where the
presence of ionic surfactants and adequate reaction cooling
circumvent this problem, providing better control over the
kinetics and particle size of the resultant latex.
Another reason for using a combination of ionic and
nonionic emulsifiers is their enhanced electrolyte stability.
Anionic surfactants provide electrostatic stabilization to
the latex particles at low and moderate salt concentration.
Fig. 5The Krafft temperature T
k
is the point at which
surfactant solubility equals the CMC.
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CHAPTER 31 SURFACTANTS 327
However, evaporation of water during the storage leads to
higher electrolyte concentration and subsequent particle
coagulation due to higher ionic strength. Presence of non-
ionic surfactant provides additional steric stabilization to
the latex, preventing it from immediate coagulation upon
subtle change in the ionic strength.
Another advantage of using blends of both ionic and
nonionic surfactants for emulsification is the fact that
adsorption-desorption mechanism is dynamic and driven
by many factors including molecular weight of the surfac-
tants, affinity to the surface and media properties. Note-
worthy is the fact that nonionic surfactants have a stronger
driving force toward the adsorption, which is augmented by
the entropy factor. As the result, the ratio of nonionic/ionic
surfactants in the adsorbed layer is significantly higher
than their ratio in the bulk solution. It is the nonionic sur-
factant that is responsible for improved sheer and electro-
lyte stability of the resultant lattices.
Some common ionic surfactants used for emulsifica-
tion [32] are the sodium and potassium salts of naturally
occurring fatty acids, salts of sulfated linear alcohols, salts
of alkylbenzene sulfonates and alkylnaphthalene sulfonates,
and salts of alkylphosphates. Typical nonionic surfactants
may include polyethoxylated alkylphenols and straight-
chain alcohols or polyethoxylated polypropylene glycol
block co-polymers. Note that the length of the hydrophobic
part of the molecule (propylene oxide block, alcohol, or
alkylphenol) could be adjusted relative to the hydrophilic
part (ethoxylated block) for targeted HLB. While this list
is not exhaustive, the combinations of ionic and nonionic
surfactants are truly infinite. The primary guideline for
selecting the best combination of surfactants is not only
the stability of the latex particles, but mainly the applica-
tion performance of the final product. Since the presence
of surfactant in the final dry coating increases its water
sensitivity and inadvertently results in surfactant migration
to the coating/air and coating/substrate interfaces, the com-
promise often is necessary in emulsion polymer synthesis.
Wetting Agents
Wetting agents are, by definition, used to improve the
wetting of pigment particles and substrate surfaces. Wet-
ting phenomenon involves the displacement of air from a
solid surface by a liquid. It also leads to the reduction of
the inter-facial surface tension between solid and liquid
interfaces.
For a spontaneous wetting to occur, the spreading
coefficient of water at a solid surface, S
w/
s, must be positive
[1,8],
S
w/s s/a s/w w/a
( ) (5)
where
s/a
,
s/w
and
w/a
are the interfacial surface ten-
sions for the solid/air, solid/water and water/air interfaces,
respectively. The presence of surfactant molecules in the
system reduces both
s/w
and
w/a
surface tensions, providing
a positive value for the spreading coefficient and prompting
spontaneous wetting. Low surface tension of the surfac-
tant solution in the media (
w/a
) are usually an indication
of wetting effectiveness of the surfactant in a given paint
formulation.
Wetting is not an issue in the solvent-based paints
since their surface tension is usually low enough to spread
on any surface. Good wetting agent for a waterborne paint
formulation should be a surfactant with a strong ability to
adsorb on the interface and ability to reduce surface ten-
sion to that of conventional solvent-based coatings, i.e.,
2532 mN/m [3]. These requirements also imply that wet-
ting agents should be hydrophobic surfactants with limited
water solubility (HLB 7-9, Table 4). Upon paint applica-
tion and formation of two new interfaces (coating/air and
coating/substrate), the migration of surfactant molecules
to these new interfaces is a diffusion-controlled process
depending on surfactant availability in the bulk phase. This
latter condition is satisfied for surfactants with high CMC,
e.g., surfactants containing bulky or branched hydrophobic
groups such as Pluronic
WA and Surfynol
products.
Fast surfactant migration is possible for surfactants
exhibiting high diffusion coefficient [3]. Since the rate of
diffusion decreases with the size of the molecule according
to the StokesEinstein equation:
D k T/ R
B h
6
(6)
where k
B
is the Boltzmann constant, T is the absolute
temperature, is the viscosity of the solvent, and R
h
is
the hydro-dynamic radius of the molecule. Large size of
the surfactant molecule and corresponding large hydrody-
namic radius will prevent it from fast diffusion rendering
it a poor wetting agent. Therefore, lower molecular weight
surfactants are preferred to achieve more efficient wetting.
Dispersing Agents
Pigments provide various optical properties and special
effects, influencing corrosion resistance and mechani-
cal characteristics, adhesion and rheology, and imparting
mechanical strength and protective properties. The per-
formance of pigments, however, depends on many factors,
including their chemical structure, particle size, and degree
of dispersion. The latter is a function of pigment wetting
and stabilization and could be largely influenced by the
presence of dispersant agents or lack thereof.
Dispersing additives improve the incorporation of
pigments and fillers in a coating and ensure their stability
during manufacturing, storage, and application processes.
Dispersant agents coat suspended pigment particle to form
a barrier that, either by ionic repulsion or steric hindrance
or both, prevents particle-particle contacts and aggrega-
tion[33].
A surfactants unique ability to adsorb preferentially at
the interface is the essence of their application as pigment-
dispersant agents. In aqueous systems, the hydrophobic
groups of nonionic surfactants are adsorbed on the par-
ticle surface, with the hydrophilic groups extending into
the bulk of the aqueous media. This partitioning provides
not only the reduction of interfacial tension but also steric
stabilization around the particles. Such stabilization is
the result of steric hindrance created by the chains of the
surfactants solvated in the liquid phase. Additional charge
stabilization could be provided by ionic surfactants, which
adsorb to generate surface charge and repulsive forces,
preventing agglomeration of two or more particles with the
same charge. Better understanding of the stability char-
acteristics of the colloidal system is provided by the well-
known DLVO theory [34] that accounts for attractive van
der Waals and repulsive electrostatic forces in suspensions.
Both electrostatic and steric (entropic) stabilization may be
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328 PAINT AND COATING TESTING MANUAL 15TH EDITION
combined to achieve maximum stabilization effect in the
system. Such electrosteric stabilization is very common for
paint formulations.
Pigment dispersion process involves initial particle
wetting, particles separation, dispersion in the media,
and stabilization against flocculation. Improved pigment
dispersion is realized initially by modifying the surface of
the pigment. This is typically achieved by adsorbing a sur-
factant during pigment manufacturing without disclosing
particular details of surface treatment. Dispersant agents in
the paint formulation adsorb on the particles interface to
form loose assemblies and further prevent agglomeration.
Block or graft copolymers are proven to be very effective
dispersant agents that adsorb and anchor to the pigment
particle and further lower the interfacial surface tension.
The main distinction between dispersing and wetting
agents is that a dispersing agent must wet, anchor to the
surface of the pigment particle, and provide a connecting
link between the particle and the dispersion media. In order
to be an effective dispersing agent, a surfactant molecule
should meet a number of structural requirements that are
somewhat different from those of wetting agents. Thus, a
dispersing agent molecule must be long enough to provide
adequate wetting by adsorbing on the surface and provide
steric stabilization by protruding to the media. Effective
anchor groups should have high affinity to the pigment and
have little or no solubility in the media. Wetting agents typi-
cally have much shorter chain length and are not effective
dispersants.
Organic polyelectrolyte dispersants are the most com-
mon type of dispersants of inorganic pigments used in
waterborne paints [3]. Polymeric phosphates, polyacry-
lates, polyamines, and other polymers of relatively low
molecular weight have the advantage of providing sufficient
anchoring at the particle surface. This is favored by poly-
meric structure of the molecules and quick adsorption rate,
which is controlled by keeping the molecular weight of the
molecules relatively low.
Organic pigments are generally more hydrophobic
than inorganic pigments and require the use of various
types of ionic and nonionic surfactants for their disper-
sion. Alkylbenzene sulfonates and alkylphenol ethoxylates
with relatively long poly(ethylene oxide) chains of 2030
ethylene oxide units are the most commonly used disper-
sant agents. However, with the increased attention to the
perceived environmental effect of alkylphenol ethoxylate
surfactants and their slow biodegradation, they are gradu-
ally being replaced by linear and branched alkyl alcohol
ethoxylates. Unfortunately, even after matching the HLB
values of alkylphenol ethoxylate, fatty alcohol ethoxylate
are still lacking the benzene moiety that provides additional
electron donor-acceptor mechanism of interaction with pig-
ment surfaces.
Due to vast diversity of pigment structures, particle
size, and paint formulations designed for different applica-
tions, there is no universal wetting or pigment dispersant
agent that would work in every formulation. Preference is
given to a particular surfactant based on performance and
environmental considerations, cost, and availability.
Foaming and Antifoaming Agents
Foam is created when air is introduced into paint during
manufacturing or application. Complex paint formulations
include several vehicles that promote foam stabilization,
i.e., wetting agents, dispersants, and emulsifiers. These
surfactants stabilize the foam due to one or several mecha-
nism available to them including hydrogen bonding, ionic,
and van der Waals forces. Foaming is highly undesirable
and almost unavoidable. It reduces manufacturing effi-
ciency and causes film defects. This necessitates the use of
foam control agentssurface-active additives that prevent,
reduce, or eliminate foaming during manufacturing and
application.
Physically unstable foam composed of thin lamellae-
structured film of surfactant with water molecules trapped
inside. Foam stabilization mechanism is associated with
well-known MarangoniGibbs effect [3,18]. The thinning of
the foam lamellae leads to a surfactants concentration gra-
dient, which, in turn, establishes a surface tension gradient.
The surface transport of the surfactant molecules from
low to high surface tension region (Marangoni flow) will
eliminate the gradients, but will also pull water molecules
in the process, thus restoring the width of the lamella and
preventing it from complete drainage. Ionic surfactants
assist in foam stabilization by creating electrostatic repul-
sion between the two sides of the film. Additionally, they
provide high osmotic pressure due to the presence of high
concentration of counter ions. Since none of these mecha-
nisms are available in the absence of ions, nonionic surfac-
tants produce less foam and less stable foam, thus offering
a substantial benefit of utilizing nonionic surfactants in
coatings.
Foaming is resolved by creating inhomogeneities in the
surface tension of the foam lamellae to cause instability and
ruptures. Such effects can only be achieved if defoaming
additives have a very limited compatibility with the aque-
ous media. These molecules also must have a positive enter-
ing (E) and spreading coefficients (S) to enter the foam
lamellae and spread at the interface, and be able to adsorb
the surfactant and drastically reduce lamellae stability [18],
S =
f a/ f a
(7)
E =
f a/ f a
+ (8)
where
f
is a surface tension of the foaming medium (such
as aqueous),
a/f
is an interfacial tension between media
and antifoam, and
a
is the surface tension of the antifoam.
Typically, foam control agents are hydrophobic molecules
with low surface tension in the range of 2025 mN/m [3],
present in the small amounts, less than 5%.
In addition to quantitative calculations, the simple and
most straightforward method for defoamers evaluation is
simply to shake a measured amount of surfactant solution
in a graduated cylinder or other suitable container, under
controlled conditions (rpm, temperature, time, and con-
centration), and note the amount of the foam generated
and the rate of its disappearance. Defoaming effectiveness
is rated in comparison to the control solution with no
defoamer present [35].
There are two types of foamsmacrofoams and micro-
foams [36]. The former consists of polyhedral foam bubbles
that, once they rupture and dry, produce craters in the coat-
ing films. The latter is revealed by the existence of small
spherical air bubbles dispersed throughout the paint that
produce pinholes. Foam control agents are called antifoams
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CHAPTER 31 SURFACTANTS 329
if they prevent or retard foam formation, or defoamers
if they destroy already existing foam. All antifoams are
defoamers but not all defoamers are antifoam agents.
Defoamers generally fall into two main categories:
silicon-based and silicon-free organic defoamers. Silicon
defoamers are based on polydimethylsiloxane chemistries
and combine non-volatility with low surface tensions.
They proved to be outstanding universal defoamers, but
find limited application due to high cost and substantial
contribution to coating defects, such as fish eyes, poor
recoatability or loss of adhesion. Moreover, with the
increased general pollution of siloxanes in Nordic coun-
tries, less toxic non-silicon defoamers are promoted by
the manufacturers. For example, surfactants based on
propylene oxide (Pluronic
surfactants),
and fluorochemical backbones [37] are very effective
foam killers.
Unfortunately, there is no single universal defoaming
agent that would prevent foam formation in all systems.
Paints are very complex formulations and potentially any
constituent could affect either foam behavior or the effec-
tiveness of the defoamer [38].
Coalescent Agents
Coalescing agents aid film formation, improve leveling,
gloss, adhesion, and scrub resistance. Prior to the VOC
regulations, high-boiling solvents were used as coalescing
agents to provide better coalescence or fusion of polymer
particles by reducing the T
g
in polymer particles below
minimal film formation temperature (MFFT). Examples of
these additives include Union Carbides Carbitol
, carbitol
acetate, Butyl Cellosolve
surfactants EO-PO-EO or
PO-EO-PO of approximately 2,000 molecular weight and
50 % copolymer compositions also reduce T
g
of the PBMA
polymer by 3 and 8C, respectively [47].
Coating Defects
Most common coating problems could be attributed to one
of the two main causes: defects driven by surface tension
and pigment dispersion problems. The former includes cra-
tering, telegraphing, sinks and bumps, crawling, and bead-
ing. The latter manifests itself in flooding, floating, poor
color development, and insufficient gloss, which could be
solved, at least partially, by carefully selecting a dispersant
agent better suited for a particular application.
Surface-tension-driven defects are formed in the pres-
ence of and in the vicinity of surface tension gradients
caused by contaminants, such as oil, or by temperature and
surfactant concentration gradients across the surface of the
coating. An established surface tension gradient will cause
the material to flow from low to high surface tension area
until the driving force is diminished or the materials cure
and resist the flow.
Poor initial wetting of the substrate and subsequent
dewetting could yield crawling defects. Solution to this
problem involves a better cleaning of the substrate surface
or addition of wetting agents to the paint. Surfactants,
however, do not differentiate and could migrate to both
substrate/coating and coating/air interfaces. When used
in excess, surfactants could improve wettability of the
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330 PAINT AND COATING TESTING MANUAL 15TH EDITION
substrate but also weaken the adhesion and cause difficul-
ties during touch-up and re-coating applications.
CONCLUSIONS
In summary, it is important to emphasize that surfactants
remain to be the key paint additives. They enable water-
based paint technology to reduce paint surface tension, wet
the substrates, aid in film formation, disperse pigments,
and emulsify polymers. The term surfactant is used as a
general term for surface active agents. In paint applica-
tions, these include wetting agents, dispersants, emulsifiers,
coalescent agents, and defoamers. In addition to numerous
and frequently conflicting functions of surfactant additives
in paints and coatings, high paint performance standards
and growing environmental concerns are important practi-
cal considerations for paint formulators. Volumes of pub-
lications and decades of experience do not change the fact
that surfactants applications in coatings, although based
on strong scientific foundation, mainly rely on empirical
guidelines and remain to be an art. Where wetting agents
are used to improve surface wetting and assist pigment
dispersion, foam issues may arise and contribute to coating
defects. Likewise, anionic surfactants, useful for electro-
static stability of dispersions and freeze/thaw stability of
the lattices, yield excessive water sensitivity that shortens
the longevity of the coatings.
Because of the complex interactions of surfactant mol-
ecules with multi-component paint systems, it is practically
impossible to design universal additives, or accurately pre-
dict their impact on a particular formulation. As a result, a
particular choice of surfactant additives depends on many
factors including the nature of the coating formulation and
its intended use. However, it also represents a delicate balance
of desirable and undesirable properties for the final coating.
TRADEMARK NOTICE
Emulan, Pluracol and Lutensol are registered trademarks
of BASF.
Pluracoat is a trademark of BASF.
Triton, Carbitol and Cellosolve are registered trade-
marks of Union Carbide Corp.
Igepal is a registered trademark of Rhone-Poulenc Sur-
factants and Specialties.
Surfynol is a registered trademark of Air Products.
Tegopren is a registered trademark of Goldschmidt.
Reasoap is a trademark of Adeka.
Emulsogen is a registered trademark of Clariant.
Maxemul is a registered trademark of Unichema.
Eleminol is a trademark of Tomen.
Noigen and Hitenol are trademarks of Montello.
ACKNOWLEDGMENTS
The authors would like to thank BASF Corporation for per-
mission to publish this chapter, Lynn Koller for her edito-
rial contributions, and the entire staff BASF North America
Information Center for providing resources and access to
the materials cited in this manuscript.
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CHAPTER 31 SURFACTANTS 331
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2003, p. 88868889.
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332
LATEX PAINTS CONTAIN FINE DISPERSIONS OF
high molecular weight film-forming resins in water. Com-
mon film-forming resins include vinyl acetate-acrylic
co-polymers, vinyl acetate-ethylene copolymers, acrylic
copolymers, or styrene-acrylic copolymers although many
other types of systems are also commercially available. For-
mulations of latex paints are complicated by the presence
of pigments, surfactants, dispersants, biocides, defoamers,
thickeners, freeze-thaw stabilizers, and coalescing aids.
Paints must be formulated such that good stability and
excellent coating properties can be achieved over a wide
range of application conditions. Many important paint
properties, including scrub resistance, porosity, and gloss,
are linked to the quality of film formation that is achieved.
Film formation in latex paints is promoted by the addition
of coalescing aids, which enable the latex particles to con-
solidate and yield a continuous film.
HISTORY
Latex paints based on styrene and butadiene copolymer
were first commercialized in about 1946 and rapidly
developed wide acceptance in the marketplace [1]. Other
film-formers of this period included vinyl acetate, acry-
lates, styrene, and vinyl chloride copolymers [2]. Since
many of these latexes had relatively high glass transition
temperatures, it was understood early on that plasticiz-
ers, such as phthalates or phosphates, were required in
order to achieve good film formation. In a paper written
by Green in 1953, it was noted that plasticizers should
be liquids that are solvents for the film-forming resin
and exhibit low color, mild odor, non-flammability, and
minimal toxicity [3]. These comments were echoed in a
paper written by Sullivan in 1954, which also stated that
the primary function of the plasticizer is facilitation of
film formation through solvation of the resin in the paint
[4]. Subsequent work illustrated that overuse of plasticiz-
ers could lead to paint films with poor scrub resistance
and increased dirt pickup [5]. These issues arose from the
extremely low volatility of the plasticizers, which caused
them to persist to a significant degree after film formation
had occurred. In order to overcome the problems that had
been encountered with plasticizers, the concept of coalesc-
ing aids was introduced. Coalescing aids have higher
volatility than plasticizers, which enables them to facili-
tate film formation and then evaporate such that scrub
resistance and dirt pickup are not negatively impacted.
Early coalescing aids included hexylene glycol, ethylene
glycol monoethyl ether, diethylene glycol monoethyl ether
acetate, ethyleneglycol monobutyl ether acetate, and
diethylene glycol monobutyl ether acetate [5]. In 1963,
a patent was issued for 2,2,4-trimethyl-1,3-pentanediol
monoisobutyrate (Tex-anol Ester-Alcohol) [6], which
became the most widely used coalescing aid for latex
paints [7]. Coalescing aids that are currently used include
glycol ethers, ester-alcohols, glycol ether-esters, esters, and
glycols. These materials vary widely in evaporation rate
and hydrophobicity.
INTRODUCTION TO COALESCING AIDS
In relation to latex paints, coalescence may be defined as
the process by which latex particles come into contact with
one another and unite to form a continuous homogeneous
film. The process of coalescence is governed by the glass
transition temperature (T
g
) of the paint system (including
coalescing aids and other additives). T
g
may be defined
as the temperature at which the onset of cooperative seg-
mental backbone motion occurs in a polymer chain. In
other words, a polymer below its T
g
acts glassy since the
molecules have no short-range mobility, while a polymer
above its T
g
is rubbery and the molecules are free to
move. In order for film formation to occur, the polymer
molecules in the latex must have sufficient mobility to
interdiffuse across the boundaries between latex particles
under a range of application conditions (temperature and
humidity). A coalescing aid acts as a temporary plasticizer
to reduce the T
g
of the latex below that of the application
or drying temperature to enable good film formation. Fig. 1
provides a simplified illustration of the impact of a coalesc-
ing aid on the T
g
of a paint. In section A, it is seen that T
g
of
the paint is significantly higher than the desired minimum
application temperature. Under these conditions, the latex
particles cannot coalesce since the polymer molecules that
compose the latex are in the glassy state and do not have
sufficient mobility to enable film formation. Section B
illustrates the same paint after the addition of an appropri-
ate amount of a coalescing aid. The coalescing aid reduces
the T
g
of the paint below that of the minimum application
temperature and enables mobility of the polymer mol-
ecules in the latex such that particle coalescence can occur.
After application of the paint, the water and the coalesc-
ing aid begin to evaporate from the coating (section C).
Although Fig. 1 illustrates the evaporation of the water and
coalescing aid as discrete events, they actually evaporate
simultaneously (although the rate of evaporation of the
coalescing aid is generally much slower than that of the
water, as indicated). While the coalescing aid evaporates,
32
Coalescing Aids
Kevin W. McCreight
1
1
Group Leader, Specialty Coatings Application Development, Eastman Chemical Company Research Laboratories, Kingsport, TN 37662-5150.
MNL17-EB/Jan. 2012
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CHAPTER 32 COALESCING AIDS 333
the T
g
of the paint film increases and returns to approxi-
mately its uncoalesced value. As T
g
increases, the polymer
molecules become much less mobile and a well-coalesced
block resistant film is formed. Plasticizers may be added
to a paint formulation to enable film formation, but since
they tend to evaporate extremely slowly, they must be used
judiciously in order to prevent the coating from remaining
tacky, which may manifest itself as problems with block
resistance and dirt pickup.
AN OVERVIEW OF FILM FORMATION
There have been numerous studies on the mechanism of
film formation [819] and while there is some disagreement
as to the detailed driving forces for coalescence, there is
general agreement in a three-step depiction of the process.
Fig. 2 provides a general model of the stages that proceed as
a latex paint dries. Initially, water evaporates from the sys-
tem and the latex particles become more closely packed
also known as consolidation. As the coating continues to
dry, the particles begin to contact one another, deform, and
compact. This process is believed to be driven by capillary
pressures or van der Waals forces that occur in the inter-
stices between adjacent latex particles as drying proceeds.
[8,9] Coalescing aids facilitate compaction by reducing the
elastic modulus and yield strength of the particles. [10]
Finally, coalescence occurs by the diffusion of polymer
molecules across the latex particle boundaries and a strong,
continuous film is formed.
REQUIREMENTS FOR EFFECTIVE COALESCING
AIDS
Coalescing aids must meet several important criteria in
order to be considered for use in latex paints. The issue
of primary importance involves the compatibility of the
coalescent with not only the common film-forming resins,
but also all of the other paint components including pig-
ments, thickeners, surfactants, and freeze-thaw stabiliz-
ers. The coalescing aid must also efficiently reduce the T
g
of the system. Many coalescing aids are considered to be
volatile organic compounds (VOCs), and therefore selec-
tion of an efficient coalescent minimizes the amount of
VOC that must be added to a formulation in order to meet
minimum application temperature requirements. Evapora-
tion rate of coalescing aids is important since the majority
of the water needs to leave the paint system prior to the
coalescent, regardless of the conditions of temperature
and humidity. As a result, most coalescing aids tend to
have relatively low evaporation rates in order to ensure
that film formation can be achieved. Coalescing aids must
also exhibit reasonable hydrolytic stability under the rela-
tively high pH conditions that are common in latex paints.
Hydrolysis of a coalescing aid can lead to reductions in
coalescing efficiency and shelf stability. The water solubil-
ity (or insolubility) of a coalescing aid impacts the extent to
which it partitions between the latex and the water. It has
been found that relatively water insoluble coalescing aids
function very effectively since they partition largely to the
latex, which enhances their efficiency [20] Other important
properties for coalescing aids include a low freezing point
(so that the coalescent does not solidify at low application
temperatures), low odor, low color, reasonable cost, and
acceptable properties from a health, safety and environ-
mental (HSE) perspective.
PERFORMANCE EVALUATION OF
COALESCING AIDS
Coalescing Efficiency
One of the most important properties of a coalescing aid
is how efficiently the material can reduce the T
g
of a latex.
Since measurement of the impact of a coalescing aid
on the T
g
of a latex is not straightforward by use of dif-
ferential scanning calorimetry, a minimum film-forming
temperature (MFFT) instrument is used in accordance
with the ASTM Test Method for Minimum Film Formation
Temperature of Emulsion Vehicles (D2354, withdrawn in
2007 but still available). MFFT may be defined as the lowest
temperature at which a system can form a coherent film,
and generally has a value relatively close to T
g
. A MFFT
instrument consists of a stainless steel plate with a specified
temperature gradient along its length. By preparing mix-
tures of a latex and coalescing aid at various coalescent con-
centrations, a determination may be made as to the MFFT
of a system as a function of coalescent level. Fig. 3 provides
an illustration of a typical MFFT bar set with a temperature
gradient of 018C. Five coalescing aid/latex mixtures have
been drawn down on the bar under controlled conditions
of temperature and humidity, with coalescent concentra-
tion increasing from the front (near side) of the bar to the
back. The part of the film that appears to be white is not
coalesced since in that temperature range, the polymer
molecules have insufficient mobility to interdiffuse. The
Fig. 1Impact of coalescing aid on T
g
of a paint applied at the
minimum application temperature.
Fig. 2A simplified view of the film formation process.
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334 PAINT AND COATING TESTING MANUAL 15TH EDITION
point at which the film changes from white to clear is
designated as the MFFT for that particular blend. As more
coalescing aid is added to the latex, the MFFT of the sys-
tem decreases since the additional solvent allows sufficient
molecular mobility for lower temperature film formation.
From this type of test, a plot can be made of MFFT as a
function of coalescent concentration for a given latex and
coalescing aid combination. Fig. 4 demonstrates the impact
of three different coalescing aids in a typical latex with a
MFFT of about 15C. Coalescent A is more efficient than
coalescent B since at a given MFFT, a given quantity of A
yields a lower MFFT than an equivalent amount of B. If a
manufacturer specifies a minimum application tempera-
ture of 10C, in order to have a reasonable margin of safety,
a MFFT of 5C might be selected. From Fig. 4, it can be
seen that 3.2 parts per hundred parts of resin (phr) of A is
necessary while 4.7 phr of B is required. Coalescent C is
ineffective in conjunction with this latex since it provides
no reduction in MFFT regardless of the level of incorpora-
tion. An estimate of the overall efficiency of a coalescing aid
may be obtained by preparing blends of a given material
with a wide range of latex types and determining the total
amount of coalescent necessary to achieve a target MFFT.
Paints that contain high T
g
industrial maintenance type
latexes require a significantly higher quantity of coalescing
aid compared to the low T
g
latexes that are used for interior
flat paints. In addition to MFFT measurements, atomic
force microscopy (AFM) proves to be a useful technique
for observation and quantification of the extent of coales-
cence. Fig. 5 demonstrates the appearance of a high T
g
(~40C) acrylic latex with two different amounts of a typical
coalescing aid5 phr for A and 10 phr for B. The left side
of each image represents the height in the vertical direction
and gives a feel for surface roughness, while the right side
of the image provides phase contrast between the hard and
soft sections of the latex particles. Note that in A, there is
insufficient coalescing aid to form a homogeneous film,
while in B there is a marked decrease in surface roughness,
and the particle boundaries are less well-defined.
When considering coalescing efficiency, it is important
to consider the impact of substrate and substrate poros-
ity on paint performance. Since water soluble coalescents
partition predominantly to the water phase, it has been
suggested that porous substrates could absorb both the
water as well as some of the solubilized coalescent [21]. In
this case, the residual coalescing aid in the paint may be
insufficient to provide for adequate film formation, espe-
cially under adverse conditions (see illustration in Fig. 6).
Perera has examined the potential for selective penetration
Fig. 3Minimum film-forming temperature apparatus (tem-
perature range of 018C).
Fig. 4Impact of coalescing aid concentration on MFFT of a
typical latex.
Fig. 5AFM images of a high Tg acrylic latex with coalescent
levels of (A) 5 phr and (B) 10 phrthe height image is on the
left, and the phase image is on the right.
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CHAPTER 32 COALESCING AIDS 335
of paint components into common substrates by evaluating
paint T
g
and the concentration of coalescent and binder in
the substrate for several types of paint [22]. His work sug-
gested that penetration of the binder and coalescing aid
into porous substrates leads to increases in both the T
g
and
pigment volume concentration.
Evaporation Rate
The evaporation rate of a coalescing aid is measured relative
to a standard such as n-butyl acetate in accordance with the
ASTM Test Method for Evaporation Rates of Volatile Liq-
uids by Shell Thin-Film Evaporometer (D3539). As stated
previously, the evaporation rate of the coalescing aid needs
to be significantly slower than that of water regardless of
temperature and humidity conditions. Fig. 7 provides an
illustration of the variation in the evaporation rate of water
as a function of relative humidity at 25C. A coalescent with
a fast evaporation rate may not adequately coalesce a paint
under high humidity conditions, while a very slow evapo-
rating coalescent has the potential to remain in the coating
too long, which may result in poor hardness development,
blocking problems, and dirt pickup.
Hydrolytic Stability
Hydrolytic stability of a coalescing aid may be evaluated
by combining the material with a high pH latex (generally
above 9.0) and holding the system at elevated temperature
(usually 50C). The pH of the system is then monitored over
a period of four weeks. Dramatic reductions in pH are often
associated with hydrolysis of a coalescing aid, which can
negatively impact paint performance.
Water Solubility
Water solubility of a coalescing aid may be determined by
preparing a 50/50 v/v mixture of coalescent and distilled
water which is agitated. If separation occurs, samples can
be taken from each of the layers to be quantified using a
technique such as gas chromatography (GC). Alternative
measures of water solubility are the ASTM Test Method
for Partition Coefficient (N-Octanol/Water) Estimation
by Liquid Chromatography (E1147) and the ASTM Test
Method for Measurements of Aqueous Solubility (E1148).
In general, water insoluble coalescents function with maxi-
mum efficiency since the majority of the solvent partitions
to the latex particles where it can effectively act to reduce
the T
g
of the film former. The extent of partitioning may be
expressed by means of the distribution coefficient, which
is the ratio of the concentration of coalescent in the water
to its concentration in the latex. Distribution coefficients
may be determined experimentally by a centrifugation/GC
technique [20]. In addition, models have been developed
to predict partitioning behavior of coalescents [23]. There
is some data to suggest that hydrophobic coalescing aids
(which partition more extensively to the polymer) lead to an
increase in latex particle size while hydrophilic coalescents
can actually lead to slight reductions in particle size [24]. A
simple model for the location of a coalescing aid in a latex
paint has been developed by Mercurio [25]. As shown in
Fig. 8, the location of a coalescent in a paint system can
be characterized by location A (the interior of the latex
particle), B (the surface of the latex particle), C (the aque-
ous phase), or a combination. The most efficient coalescing
aids tend to reside in the AB region, which encompasses the
most critical region for film formation.
Odor
Although odor is becoming an increasingly important
property in paints, particularly for institutional use, it also
tends to be very subjective. Coalescing aids can contribute
to odor in latex paints, but the impact a single raw material
on the odor of a paint formulation is not easily quantified.
A paper has recently been published by researchers at the
Fig. 6Impact of using a water soluble coalescing aid in paint
applied over a porous substrate [21].
Fig. 7Effect of relative humidity on the evaporation rate of
water at 25C.
Fig. 8General schematic for coalescing aid distribution in a
latex paint (after Mercurio [25]).
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336 PAINT AND COATING TESTING MANUAL 15TH EDITION
Monell Chemical Senses Center that addresses the impact
of a common coalescing aid on odor perceptions in formu-
lated paints [26].
STRUCTURES AND PROPERTIES OF COMMON
COALESCING AIDS
Fig. 9 illustrates the names and structures of some of the
more widely used coalescing aids. The most common
coalescents are ester-alcohols and glycol ethers. Table 1
provides a summary of the evaporation rate, water solu-
bility, and partitioning behavior of these same coalescing
aids. The majority of these materials have slow evaporation
rates relative to n-butyl acetate (0.0020.006). In the case
of ethylene glycol monobutyl ether, the evaporation rate
is 0.06, which is close to the evaporation rate of water at
about 85 % relative humidity and 25C. Under hot, humid
conditions, a fast evaporating coalescing aid, such as ethyl-
ene glycol monobutyl ether, may evaporate at a comparable
rate to the water, which may leave insufficient coalescent
for complete film formation. An appropriate coalescing aid
should be selected so that (1) coalescence can be achieved
under the most adverse conditions of temperature, humid-
ity, and substrate and (2) the coalescing aid will evaporate
from the film at a rate that will allow adequate property
development. Coalescing aids are commonly blended to
provide an optimized evaporation rate for a given paint
and the associated application conditions. Table 1 dem-
onstrates that the majority of common coalescing aids
have relatively minimal water solubility and partition
predominantly to the latex particle and its surface (the AB
region). More hydrophilic glycol ethers, such as ethylene
glycol monobutyl ether and diethylene glycol monobutyl
ether, are completely water soluble and partition in the
BC region. Although these water soluble coalescing aids
may not provide optimum efficiency in systems applied to
porous substrates, they may improve freeze-thaw stability
and open time since they have a significant presence in the
aqueous phase of the paint [25].
GUIDELINES FOR INCORPORATING
COALESCING AIDS
Although a properly selected coalescing aid should be
compatible with the remainder of the paint components,
some care must be exercised during formulation to prepare
a paint with the expected performance properties. Most
hydrophobic coalescing aids can be successfully added
directly to the letdown, assuming the latex is relatively
stable. In contrast, certain highly hydrophilic coalescents,
such as ethylene glycol monobutyl ether, can shock or
destabilize the latex if added directly to the letdown. These
coalescents can be successfully incorporated by premix-
ing with some water prior to being added to the paint. In
some cases, a portion of the coalescent may be added to the
grind, where it may reduce surface tension and may func-
tion as a pigment dispersant.
INFLUENCE OF COALESCING AIDS ON
PAINT PROPERTIES
Coalescing aids have significant impact on the properties
of paints due to their function in film formation as well
as their interaction with other additives in the formula-
tion. Not surprisingly, coalescing aids have major effects
on properties that relate to the quality of film formation,
such as scrub resistance, gloss, color development, and
weathering.
Scrub Resistance
Scrub resistance of a coating may be evaluated according
to the ASTM Test Method for Scrub Resistance of Wall
Paints (D2486). This method simulates the resistance of
a paint to cleaning with an abrasive cleaner and a nylon
bristle brush. Scrub resistance is generally measured after
the paint is allowed to dry for at least a week, during
which time the majority of the coalescing aid evaporates
from the coating. In common architectural coating for-
Fig. 9Chemical names and structures of common coalescing
aids.
TABLE 1Physical properties and partitioning characteristics of common coalescing aids
Evaporation Rate (n-BuOAc=1) % Solubility in Water Partitioning Properties
a
2,2,4-trimethyl-1,3-pentanediol
monoisobutyrate
0.002 Insoluble AB
Ethylene glycol monobutyl ether 0.060 100 % BC
Ethylene glycol mono 2-ethylhexyl ether 0.003 0.2 % AB
Diethylene glycol monobutyl ether 0.003 100 % BC
Dipropylene glycol monobutyl ether 0.006 5 % ABC
Propylene glycol monophenyl ether 0.002 2 % AB
a
See Fig. 8 for description of partitioning designations.
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CHAPTER 32 COALESCING AIDS 337
mulations, paints with no coalescing aid have minimal
scrub resistance while the addition of increasing amounts
of coalescent increases scrub resistance up to a point. If
an excessive amount of coalescing aid is used, the latex
can be softened to the point that the scrub resistance of
the paint is reduced. Although plasticizers can aid in film
formation, their use in paints has the potential to reduce
scrub resistance since they evaporate extremely slowly,
which may cause the paint film to remain soft. Early block
resistance (hardness development) of a latex paint can also
be reduced by overuse of plasticizer or slow evaporating
coalescing aids.
Gloss
Gloss of a paint film is also related to the quality of film for-
mation. In general, smoother coating surfaces yield higher
gloss. Specular gloss is most commonly measured using
a glossmeter in accordance with the ASTM Test Method
for Specular Gloss (D523). A poorly coalesced film will
have lower gloss than a well-formed film. Proper choice of
coalescent is critical to the development of acceptable gloss
under harsh conditions (for example, low temperature and
high humidity). Under adverse conditions, a very volatile
coalescing aid may not allow development of good gloss
since the coalescent may evaporate before it can function
to enable film formation.
Color Development (Low Temperature
Coalescence)
Film formation may also be analyzed by comparing the
color obtained from a slightly tinted paint at two tem-
peratures (room temperature and 4.5C) by the ASTM Test
Method for Low Temperature Coalescence of Latex Paint
Films by Porosity Measurement (D3793). To achieve simi-
lar color development under two temperature conditions,
a coalescing aid must provide equivalent film formations
in both cases. If an insufficient amount of coalescent or a
coalescent that does not provide adequate film formation
under adverse temperature conditions is used, the color
may not match. This could be an issue if part of a room is
painted under a given set of environmental conditions, and
the rest of the room is painted at a later time and the tem-
perature and/or humidity have changed drastically.
Block Resistance
Block resistance testing provides insight as to the tendency
of two painted surfaces to stick together when they come
into contact with one another, such as in the case of doors
and windows. Testing is carried out in accordance with the
ASTM Test Method for Blocking Resistance of Architectural
Paints (D4946), which specifies that the painted surfaces
be placed face to face at 50C for a set period of time and
applied weight. The degree to which the painted surfaces
can be separated from one another to one another after
testing is referred to as the block resistance. The ASTM
method is sometimes referred to as a heated block test,
and in some cases variants such as the room temperature
block or wet block may also be reported, although under
different conditions of sample preparation, applied weight,
paint cure time, and temperature of the testing. If a paint
film is too soft or poorly coalesced when tested, block
resistance will be poor. Appropriate selection of coalescing
aids is critical when working with high T
g
latexes, which
may require significant amounts of coalescent and can
lead to a balancing act between achieving low temperature
coalescence and maintaining block resistance. Overuse of
slow-evaporating coalescents or plasticizer can lead to poor
block resistance, but appropriate choice of coalescent type
and level will yield complete film formation and excellent
block resistance.
Exterior Durability
Exterior durability of paints is impacted by the quality of
film formation as well as the composition of the latex. A
well-chosen coalescing aid will reduce the porosity of a
latex paint while increasing the film strength. Both of these
effects can increase the potential for a paint film to with-
stand the forces of wood expansion or contraction without
cracking and to minimize the water vapor transmission
that can lead to delamination of paint from a substrate.
Solvents or additives that remain in the paint film have the
potential to bloom to the surface and lead to dirt pickup.
As a result, it is important to select a coalescing aid with an
appropriate evaporation rate at a use level that will ensure
timely hardness development. Dirt collection on coated
exterior panels may be evaluated by the ASTM Test Method
for Quantifying Dirt Collection on Coated Exterior Panels
(D3719).
Rheology
Coalescing aids interact with associative thickeners and
different types of coalescent can significantly modify the
viscosity of a latex paint formulation. Relatively hydropho-
bic coalescing aids can interact with the hydrophobic modi-
fications present in associative thickeners, which increases
viscosity and effectively increases thickener efficiency [27].
In contrast, more water soluble coalescing aids can actually
interfere with the function of associative thickeners and
may lead to a reduction in the viscosity of a formulation. If
alternate coalescing aids are dropped into a formulation
as a direct substitute, there is a potential for the paint rheol-
ogy to be altered such that the application characteristics of
the paint change.
Freeze-thaw Stability
Architectural coatings are evaluated for freeze-thaw sta-
bility by cycling paint samples between room temperature
and 0C as outlined in the ASTM Test Method for Freeze-
Thaw Resistance of Waterborne Coatings (D2243). Freeze-
thaw stability is often achieved through use of completely
water soluble diols, such as ethylene glycol or propylene
glycol, which serve as freezing point depressants. Since
the most efficient coalescing aids tend to be relatively
hydrophobic, these materials do not improve and may
actually reduce freeze-thaw stability. Wegmann suggested
that the mechanism for this reduction in freeze-thaw sta-
bility stems from the coalescing aid increasing the solubil-
ity of the surfactant in the water, which destabilizes the
latex [28].
Wetting and Defoaming
Many coalescing aids effectively reduce the surface tension
of water. In latex paints, this property serves to aid in the
process of both pigment and substrate wetting [29]. It has
been reported that hydrophobic coalescing aids can be used
to activate silicone defoamers in aqueous systems [29].
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338 PAINT AND COATING TESTING MANUAL 15TH EDITION
IMPACT OF VOC REGULATIONS ON
COALESCING AIDS
VOC Regulations and Test Methods
Over the past 10 years, there have been significant changes
in the regulations governing the use of VOCs in architec-
tural and industrial maintenance (AIM) coating applica-
tions. In the United States, several regulatory bodies have
restrictions in place, including SCAQMD (South Coast Air
Quality Management District), OTC (Ozone Transport Com-
mission), CARB (California Air Resources Board), and the
U.S. EPA. Table 2 provides a summary of the historical,
current, and proposed regulations for these four organiza-
tions. From this table, it is evident that the usage of VOCs
has been and will continue to be curtailed by these new
regulations. The European Union (EU) is covered by the
Decopaint Directive 2004/42/CE of the European Parlia-
ment, which was issued on April 24, 2004. Annex II of
this directive outlines two sets of VOC limits for paints
and varnishes, one that was implemented on 1/1/2007,
and a more stringent standard that will come into force
as of 1/1/2010. The reader is cautioned that U.S. and EU
limits are not directly comparable, as both VOC defini-
tions and test methods are different. In the United States,
VOC is evaluated according to ASTM Standard Practice for
Determining Volatile Organic Compound Content of Paints
and Related Coatings (D3960), which is analogous to EPA
Federal Reference Method 24. At low VOC, EPA Method 24
has significant error [30], and a newer method is described
in the ASTM Test Method for Speciation of the Volatile
Organic Compounds in Low VOC Content Waterborne Air-
Dry Coatings by Gas Chromatography (D6886), although
this method has not yet been adopted for regulatory pur-
poses by the EPA. The European Union uses test meth-
ods from the International Standards Organization (ISO)
titled Paints and VarnishesDetermination of Volatile
Organic Compound Content Part 1: Difference Method (ISO
11890-1, for use with VOC contents above 15 % by weight)
and Part 2: Gas-Chromatographic Method (ISO 11890-2,
for use with VOC contents less than 15 % by weight). As
more restrictive rules are implemented, significant research
has been carried out in order to determine the most
effective approaches to maintain paint properties within
the guidelines of these regulations.
In addition to the changes observed with respect to
VOC limits in paints and coatings, there has begun to be
more interest in long-term emissions from painted sub-
strates, both from the regulatory and research perspectives.
Some recently published work focused on obtaining a
better understanding of the fate and availability of coalesc-
ing aids in latex paints. Corsi studied the partitioning
of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate in flat
and semi-gloss paints over aluminum, gypsum board, and
concrete substrates [31]. His work led to mass balances
of coalescing aid in the substrate, paint film, and air over
the period of about 1 year, which revealed that airborne
recovery of 2,2,4-trimethyl-1,3-pentanediol monoisobutyr-
ate ranged from <25 % to 90 % and was dependent on both
paint type and substrate type.
Reformulating to Reduce VOC
Regulations have led to the need for extensive reformula-
tion in the coatings industry, which has in turn spawned
a desire for new lower-VOC components for latex paints.
The main VOCs in latex paints are the freeze-thaw stabi-
lizer/open time additive and the coalescing aid. Several
approaches to meet lower-VOC limits have been espoused,
generally including a resin modification, a coalescing aid
modification, or both.
Low-VOC Coalescing Aids
From the perspective of VOC reduction through use of
alternative solvents, possible solutions involve more effi-
cient coalescents, low-VOC coalescing aids or plasticizers,
reactive coalescing aids, or elimination of the freeze-thaw
stabilizers. The premise for VOC reduction based on effi-
ciency stems from the fact that if less coalescent is required
to meet a target MFFT, VOC will be reduced accordingly.
Lower-volatility coalescents have been considered for use
in formulations based on the fact that the VOC contribu-
tions of very nonvolatile materials may be much less than
100 % according to EPA Federal Reference Method 24
(Determination of Volatile Matter Content, Water Content,
TABLE 2Summary of the progression of U.S. AIM VOC regulations (in grams per liter)
EPA CARB SCAQMD OTC
Product
Type
2002 2009 2000 2003 2010 2000 2002 2006 2002 2005
Flat 250 100 250 100 50 250 100 50
a
250 100
Non-flat 380 150 250 150 100 250 150 50 380 150
Non-flat
high gloss
380 250 250 250 150 250 150 50
b
380 250
Primer,
Sealer,
Undercoater
350 200 350 200 100 350 200 100 350 200
Industrial
Maintenance
450 340 340 340 250 420 250 100 450 340
a
Postponed until 2008.
b
Postponed until 2007.
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CHAPTER 32 COALESCING AIDS 339
Density, Volume Solids, and Weight Solids of Surface Coat-
ings). Some of these materials may be classified as having
nearly zero VOC contribution based on the U.S. definition.
Low-VOC coalescents often share similar chemistry with
conventional coalescing aids, but are less volatile since
they are higher molecular weight esters, glycol ethers, or
ester-alcohols. As described previously for plasticizers,
careful formulation is required when using low-volatility
coalescents in order to avoid issues with block resistance,
scrub resistance, and dirt pickup. The concept of a reactive
coalescing aids involves a coalescing aid acting to promote
film formation in the traditional manner and then cross-
linking to become a permanent part of the coating. One
approach to reactive coalescents involves esterification of
relatively nonvolatile unsaturated materials that can cross-
link through an oxidative cure mechanism [32]. The ben-
efits for this technology are twofold: VOC is reduced and
these products may be viewed as renewable, since many
of the unsaturated materials are of natural origin. Poten-
tial shortcomings for this approach include slow hardness
development due to the minimal crosslinking from the low
level of coalescent incorporation, the potential for color
development, and the fact that driers may be required to
promote cross-linking.
Reducing VOC through Resin Modification
Alternative technology based on resin modifications
includes reduction of latex T
g
to limit the coalescent
requirements, manipulation of latex composition or mor-
phology (core-shell or power feed processes) to reduce
coalescent requirements, or copolymerization of reactive
monomers that allow cross-linking subsequent to film
formation. By reducing T
g
of the base latex, the paint film
can form a film without using as much (or any) coalescent.
While this reduces VOC, it can also lead to a softer film that
is less durable and more prone to dirt pickup and blocking
problems, as demonstrated by Testa in a study compar-
ing the performance of coalesced versus coalescent-free
paints [33]. There has been extensive work on cross-linking
latex systems in which a functional monomer is polymer-
ized into the latex and which may or may not require use
of an additional crosslinker. These systems were initially
directed more extensively toward the industrial mainte-
nance market, but are beginning to gain some traction in
the architectural area, although cost considerations are
more significant in this market. Taylor and Winnick have
written a comprehensive review of the technologies in the
functional and thermoset latex field [1].
Currently, although there are many technologies under
examination from both the additive and resin standpoints,
it is clear that maintaining excellent paint properties while
meeting future VOC regulations will continue to be a sig-
nificant challenge.
ACKNOWLEDGMENTS
Special thanks are extended to Dr. Louis T. Germinario for
the AFM images and to Mr. Gary Robe and Mr. Jerry Mitch-
ell for allowing reproduction of the illustration in Fig. 6.
References
[1] Taylor, J. W., and Winnik, M. A., Functional Latex and Ther-
moset Latex Films, J. Coat. Tech. Res., Vol. 1, No. 3, 2004, p.
163.
[2] Parker, C. H., Fundamental Considerations in the Develop-
ment of Latex Paints, Off. Dig., Vol. 24, No. 333, 1952, p. 700.
[3] Green, R. B., Externally Plasticized Latices in Paints, Ind.
Eng. Chem., Vol. 45, No. 4, 1953, p, 726.
[4] Sullivan, W. M., Interior Wall Paints Based on Vinyl Acetate
Latex, Paint Varnish Prod., Vol. 44, No. 12, 1954, p. 23.
[5] Schwahn, C. O., and Sullivan, W. M., Effective Filming of
Polyvinyl Acetate Latex Paints, Off. Dig., Vol. 30, No. 405,
1958, p. 1122.
[6] Texanol
type spindle
viscometer can be used when operated at the higher speed
selections (20100 rpm) to give the appropriate shear rate.
However, the measurement readout is in cP rather than KU.
As discussed later in the next section, this same instrument
is also useful at lower speeds (0.3 or 0.5 rpm) for determi-
nation of low-shear viscosity and processes related to LSV.
The Rotothinner
CMC CMC
Ashland/Aqualon BLANOSE TM refined CMC CMC
Ashland/Aqualon CULMINAL
HPMC (MHPC) MHPC 400, MHPC 3000 P1R, MHPC 6000 R, MHPC 20000 R
Ashland/Aqualon CULMINAL
HPC HPC
Ashland/Aqualon NATROSOL
HEC 250 HHR, 250 H4R, 250 HR, 250 MHR, 250 MR, 250 KR, 250 GR
Ashland/Aqualon NATROSOL
VISCALEX
HPMC MK/MKS
DOW Chemical WALOCEL
na CVS-2, CVS-3
FMC Corporation FMC Biopolymer MCC Lattice NTC 80, AVICEL
Huber/Kelco CELFLOW
Xanthan Gum AR, ASX, ASX T, BT, CC, HP, HP-T, RD, S, ST, T
Huber/Kelco WHELAN GUM Welan Gum K1A96
ISP STABILEZE
MVE/Mah O6, QM
King Industries DISPARLON
ASE 330
OMG/Borchers BORCHI
GEL PN ASE A LA
Shin-Etsu METOLOSE
MC SM
Shin-Etsu METOLOSE
HPMC SH, SE
Shin-Etsu/SE Tylose TYLOSE
RHEOVIS
RHEOVIS
HEUR 1514, 1516, 1525, 1550, 3100, 3220, 3256, 3290, 3291, 3515, 3800
Cognis DSX
HASE DR-1, DR-72, DR-73, DR-110, DR-130, DR-300, DR-5500, RM-5, RM-6,
RM-7, RM-55, TT-615, TT-935, TT-935ER
Dow Chemical ACRYSOL
HEUR PUR 21
Lubrizol/Langer SOLTHIX HASE A100
Munzing TAFIGEL
HEUR PUR 40, PUR 41, PUR 45, PUR 50, PUR 55, PUR 60, PUR 61, PUR 80
Munzing TAFIGEL
GEL HEUR 013, 0024, 0434, 0435, 0620, 0621, 0622, 0625, 0626, L 75 N, L76, LW 44,
PW 25, WN 50 S
Shinetsu/SE Tylose TYLOSE HMHEC HX 4000 YP2, HX 8000 YP2
Rockwood/SCP OPTIFLO
HASE HV80
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362 PAINT AND COATING TESTING MANUAL 15TH EDITION
however, readily dispersible with conventional agitators.
For effective incorporation, pH must be carefully regulated.
If it is too high, excessively rapid hydration occurs, and if it
is too low, hydration times are long with loss in thickening
efficiency. The presence of salts (electrolytes) may cause
flocculation, rendering bentonite ineffective in highly ionic
environments. The bentonite and hectorite clays are often
organically treated with hydrophobic quaternary amines to
produce organoclay thickeners as discussed later.
HECTORITE CLAYSWELLING (NATURAL
AND SYNTHETIC)
Hectorite is a rare soft, greasy smectite clay mineral that
occurs with bentonite. Like bentonite, hectorite is derived
from volcanic ash and tuff but with relatively high glass
content. Hectorite is often associated with hot spring activ-
ity and is an alteration of the mineral clinoptilolite. This
smectite group mineral gets its name from a mining loca-
tion near Hector, California, and it is one of the two primary
swelling smectite clay thickeners, the other being bentonite,
Na
0
, 3(Mg,Li)
3
Si
4
O
10
(OH)
2
. Hectorite differs from bentonite
in that it contains lithium in its crystal lattice with absence
of aluminum. Of these two similar clays, natural hectorite
is a relatively more scarce mineral in nature. When it is
mined and purified it is an effective swelling thickener
similar to bentonite but is somewhat more efficient. To
compensate for its natural lack of abundance, synthetic
hectorite was commercially developed. This synthetic hec-
torite produces relatively clear solutions in water, is a more
efficient thickener for suspension than natural purified hec-
torite, and is also significantly more efficient than bentonite
as determined by measuring yield stress values [191193].
ATTAPULGITE CLAYSTRUCTURING
Attapulgite clay is the most commonly used inorganic
thickener in latex paints because it is economical and can
also function as an extender pigment [194196]. Attapulg-
ite is a magnesium aluminum phyllosilicate with formula
(Mg,Al)
2
Si
4
O
10
(OH)4(H
2
O) which occurs in a type of clay
soil common to the Southeastern United States. Attapulgite
was named after the town Attapulgus in Georgia where it
is very abundant, but the primary mineral in this clay is
palygorskite, which was originally discovered in the Ural
mountains and is given its name for the mining location
there. Attapulgite is not a single mineral, but is actually
a composite of smectite and predominately palygorskite.
Attapulgite clays found in the MeigsQuincy district of
Georgia are bundles of palygorskite clay particles sur-
rounded by a matrix of smectite clay, which is slightly
swellable. Georgian attapulgite clay particles consist of
a palygorskite core surrounded by smectite. Unlike pure
smectite, the palygorskite component is an acicular bristle-like
crystalline form that does not swell or expand. Attapulgite
in its natural form consists of lathe-shaped colloidal par-
ticles called spicules, which are typically less than 0.5
m in diameter. These particles form a crystal chain-like
structure in which the spicules attract each other, become
entangled, and result in entrapment and suspension of
solids. It does this by establishing a lattice structure of par-
ticles connected through hydrogen bonds.
In an aqueous environment, attapulgite is nonswelling
and essentially inert. Unlike bentonite, which is sensitive to
the presence of salts, attapulgite will form gel structures in
both fresh water and salt water systems. Taking advantage of
this characteristic, attapulgite is widely used in special salt
water drilling muds that are used for drilling through brine
formations. Coatings containing attapulgite clay thicken not
by swelling, but instead by the structured reflocculation of
the pigment particles into a colloidal interaction network
after shearing. In coating preparation, attapulgite clays can
be added as powders or as pregelled dispersions throughout
the formulation process. However, they are normally added
TABLE 7Inorganic thickeners for waterborne and solvent-borne coatings: their classification,
synonyms, composition, type of thickening, and where they are used
Inorganic Thickeners for Waterborne (WB) and Solvent-borne (SB) Coatings
Class Clay or Silica Synonyms Chemical Composition Type Primary Use
Smectite clays Bentonite Montmorillonite
a
aluminum phyllosilicate Swelling WB
Hectorite magnesium lithium phyllosilicate Swelling WB
Organoclays modified bentonite
and hectorite
smectite clays modified with quaternary
ammonium hydrophobes
Structuring SB/WB
mixed mineral
thixotropes
MMT composite of several different types of
clays and modified with QAH
Structuring SB/WB
Other clays Attapulgite Palygorskite
b
magnesium aluminum phyllosilicate Structuring WB
Sepiolite Meerschaumc
c
hydrated magnesium silicate Structuring WB
Synthetic silicas Precipitated Silica hydroxylated sodium silicate Structuring WB
Fumed Silica Pyrogentic Silica silicon dioxide Structuring WB
Hydrophobic
silicas
organo modified
silica
made from organo treatment of
precipitated or fumed silica
Structuring SB/WB
a
Depending on the reference, montmorillonite is the principal mineral in bentonite, or bentonite is the principal mineral in montmorillonite.
b
Palygorskite is the principal mineral in attapulgitealso some smectite present.
c
Meershaum (meaning sea foam) was the previous name for sepiolite.
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CHAPTER 33 THICKENERS AND RHEOLOGY MODIFIERS 363
in the grind using high-speed mixers for dispersion and
hydration. The thickening power of these clays is high, and
salts have little or no effect on viscosity. However, like many
other ITRMs, the amount of attapulgite clay required for
thickening is generally higher than for organic TRMs, and
the water demand is high (water is pulled from the aque-
ous phase to wet the particle surface, thereby increasing
effective coating solids). Attapulgite can be used for solvent-
borne systems with a cationic surfactant. Some advantages
of attapulgite clay are compatibility with a wide range of for-
mulations, use over a broad pH range, insensitivity to pres-
ence of salt, and resistance to attack by microorganisms.
SEPIOLITE CLAYSTRUCTURING
There are many specialty clays in nature, but only a few
have commercial significance for coatings. Sepiolite is
a light, porous, high-surface-area clay that was formerly
known as Meerschaum (sea froth) [197]. This is an unusual
form of non-swelling clay that functions as a thickener
in a manner similar to attapulgite. Sepiolite is relatively
rare with few commercial deposits, mostly located near
Madrid, Spain. This mineral is unique in that it has the
highest surface area of all the clay minerals. Chemically,
it is a hydrated magnesium silicate with chemical formula
(Si
12
Mg
8
O
30
(OH
2
)
4
8H
2
O) or Mg
4
Si
6
O
15
(OH)
2
6(H
2
O). Unlike
smectites, sepiolite is not a layered phyllosilicate but in-
stead is described as a quincunx of five talc sheets separated
by parallel open channels within its crystal structure. It has
a chain-like structure of needle particles rather than the
plate-like particles of many other clays. Although sepiolite
is a non-swelling clay, the needle particles have an excep-
tionally large surface area. This provides a high degree of
hydrogen bonding to produce structure in fluids includ-
ing waterborne and solvent-borne coatings. This structure
entraps the mobile phase liquid, thereby increasing viscos-
ity and suspension of the fluid. The structure is stable even
in high salt-content fluids.
ORGANOCLAYSSTRUCTURING
Many different grades of organoclays are available for both
solvent-borne and aqueous coatings [198202]. Although
these products differ in their chemical modification, the
mechanism for thickening and rheology control is sub-
stantially the same. Bentonite and hectorite clays are the
principal minerals used to prepare organoclays. Because
these clays initially are both hydrophilic and oleophobic in
their natural form, they must be modified for dispersion
in organic solvents. Only after a sophisticated purification
process followed by cation exchange with organic ammo-
nium bases is the surface rendered sufficiently organophilic
for use in nonaqueous media. As supplied, organoclay
thickeners are in the form of agglomerated platelet stacks.
Conventional organoclays require wetting and shear for
deagglomeration and the addition of a chemical polar acti-
vator for full rheological development. The chemical activa-
tor serves to disperse the organoclay and also carries water
into the hydrophobic organic solvent to insure full hydro-
gen bonding. Some newer products still require wetting
and shear but are functional without the chemical polar
activator. Although not essential, elevated temperatures
are preferred for efficient processing. High-performance
organoclays have recently been developed with greater
thixotropy and improved sag resistance. Special grades of
organoclays (organophilic clays) have also been designed
for aqueous coatings. Some of these depend on shear, wet-
ting, and hydration for full rheological performance, while
others are available in readily activated slurry form. The
efficiency of these products is generally independent of pH.
MIXED MINERAL THIXOTROPES (MMT)
Mixed mineral thixotropes (MMTs) are essentially non-
conventional organoclays [203]. The most widely used
thixotropes (mainly for solvent-borne systems) are organo-
clays, fumed silicas, and castor waxes. Although the base
materials for MMTs and organoclays are both clays, the
particle structure is significantly different than the laminar
organoclays that are based on the smectites (bentonite and
hectorite). MMTs differ by being made up of many different
types of clay minerals that are condensed to give particles
with multi-shaped architecture, including platelet-shaped,
ribbon-shaped, and pipe-shaped clays. This allows them to
be separated more easily than conventional organoclays.
Like organoclays, the surface of MMTs is covered with qua-
ternary ammonium compounds to render it hydrophobic.
In organic media, the platelets of MMTs interact with each
other by hydrogen bonding to form a three-dimensional
network producing thixotropy in coatings that is similar to
that of fumed silica. Two advantages of MMTs are the pos-
sibility to produce pregels at higher concentrations and the
reduced shear required for their dispersion.
Synthetic Silicas
Another class of inorganic thickeners are certain types of
synthetic amorphous hydrophilic and hydrophobic silicas
[204]. Both are widely used in solvent-borne coatings; how-
ever, excessive hydration generally limits the utility of the
hydrophilic silicas to aqueous media. Two forms of amor-
phous hydrophilic silica are commercially available and get
their names, precipitated silica and fumed silica, from
the respective manufacturing processes. A proposed thick-
ening mechanism for these silicas is based on hydrogen
bonding between the silica particles and with other coating
components to form a three-dimensional structure. High
water demand may also contribute to thickening with these
products.
PRECIPITATED SILICA
Precipitated silica is obtained in a wet process by the neu-
tralization of sodium silicate solution [205]. This results in
a polar, fully hydroxylated surface. Consequently, hydrogen
bonding is strong, and excellent thickening comparable
to that of fumed silica is obtained especially in nonpolar
media. However, because of the competition between
hydroxyls on the silica and those in the continuous phase,
precipitated silica tends to be less efficient than fumed
silica in polar media.
FUMED SILICA
Fumed silica (pyrogenic silica) is amorphous, non-porous,
low-density, high surface area silicon dioxide prepared by
vapor phase hydrolysis of silicon tetrachloride in a hydro-
gen-oxygen flame [206,207]. An optional process is the
vaporization of quartz sand in an electric arc. Particle size
of fumed silica is on the order of 550 nm with surface area
of 50600 m
2
/g. First discovered in a Degussa laboratory in
1941, this synthetic product gets its name from the smoke-
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364 PAINT AND COATING TESTING MANUAL 15TH EDITION
like appearance as it forms in the flame. In the fuming
process, the particles formed have a partially hydroxylated
surface containing hydroxyl, silanol, and siloxane groups.
The resulting particle surface is somewhat less polar than
that of precipitated silica. Fumed silicas primarily pro-
vide thickening through the formation extensive network
structures generated by hydrogen bonding via the silanol
groups, which can interact with a number of functionalities
including hydroxyl, carboxylic acids, carboxylic esters, and
other silanol groups. The structuring is accomplished by
the creation of relatively large silica particle chains, which
associate via interparticle hydrogen bonding. Because
fumed silicas have both hydrophilic (hydroxyl and silanol)
and hydrophobic (siloxane) functionality, they are effective
in producing thickening in both polar and non-polar media.
To take full advantage of their thickening potential, the
proper incorporation of the silica is very important. Like
some clay thickeners, suboptimal dispersion can impact
coating gloss. pH does have a significant effect on the thick-
ening efficiency of fumed silica in aqueous systems. To be
effective, pH must be below about pH 7.5. Above this pH,
electrostatic repulsion keeps the particles far enough apart
to inhibit hydrogen bonding. Some fumed silicas have very
small surface area, which results in very high thickening
efficiency even in non-polar media. Some performance
properties claimed for fumed silica are improved sag
resistance, crack resistance, film hardness, and dirt pick-
up resistance. To improve on incorporation into coatings,
aqueous fumed silica dispersions have been developed. This
liquid form provides advantages in handling, health, ease of
dispersion and speed of thickening equilibration. The liquid
form also has the potential to reduce VOCs since the disper-
sions are solvent free and surfactant free.
HYDROPHOBIC SILICA
In less-polar environments, the silica hydroxyls of precipi-
tated silica or the silanol groups of fumed silica are encour-
aged to interact with each other through hydrogen bonding
for development of the thickening network. To make pre-
cipitated silica and fumed silica particles more hydropho-
bic, they are often reacted with organophilic groups on
the silica surface to produce hydrophobic silica grades
[208,209]. The reactants are typically either organosilane
or organosiloxane compounds, which replace many of the
surface hydroxyl groups with the organic functionality.
Various patented processes are used and the following are
representative. Fumed silica can be reacted with chlorosi-
lanes in a fluidized bed reactor to produce hydrophobic
fumed silica. Precipitated silica can be hydrophobized
with alkylchlorosilanes or trimethylsilanol in precipitated
solution to produce hydrophobic precipitated silica. After
treatment, these products have few surface silanol groups
left for hydrogen bonding, and the amount of carbon incor-
porated onto the surface is typically on the order of 15%.
Hydrophobic silicas are generally superior to hydrophilic
silicas in water-reducible systems.
Compiled in Table 8 is a current list of commercial
suppliers of inorganic thickeners and rheology modifiers
used in waterborne and solvent-borne coatings. Some
close-up photomicrographs showing the diversity of par-
ticle shapes for four different inorganic thickeners are
shown in Fig. 13.
TABLE 8Commercial inorganic-based thickeners and rheology modifiers for WB and SB coatings
Company Trade Name Thickener Type Thickener Product Codes
Active Minerals Int. MIN-U-GEL
L 10 Smectite/Ca Bentonite
Rockwood/SCP GELWHITE
H15, H18, H20, H30 Hydrophobic fumed silica for Polar Systems
Wacker WACKER HDK
N20, N20P, T30, T30P, T40 Hydrophylic fumed silica for Non-Polar Systems
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CHAPTER 33 THICKENERS AND RHEOLOGY MODIFIERS 365
Thickener Blends
Often, one or more different thickener types are used in
coatings formulation to obtain a desired combination of
performance properties. This is usually not an issue when
conventional type thickeners are combined with other con-
ventional types. However, care must be taken when com-
bining thickeners with thickening mechanisms that may
compete with each other [210214]. One such combination
is a high molecular conventional hydrodynamic thicken-
ing polymer with a highly associative polymer which can,
on occasion, result in syneresis, loss of hiding, and loss of
gloss. However, the thickeners can often be made compat-
ible with the appropriate addition of surfactants and/or
optimum dispersant selection.
ORGANIC TRMs FOR SOLVENT-BORNE
COATINGS
Besides the inorganic products described above, a variety
of organic additives also function as thickeners, rheology
modifiers, and mainly thixotropes in solvent-borne systems
[215217]. These products are available in liquid paste and
powder form. Many require some dispersion and activation
for thickening, and the recommended process temperatures
often depend on the strength of the solvent present in the
coating formulation. Careful formulation procedures are
required to avoid seeding, false body, or loss in thicken-
ing efficiency. Among the many types of organic products
available for use as thickeners and flow control agents for
solvent-borne systems are castor oil derivatives, polyethyl-
ene glycol, polyamides, polymerized oil derivatives, organic
esters, complex polyolefins, and aramid pulp fibers, over-
based calcium sulfonate. Some of the materials that are
very effective are waxes with melting points. Among these
are the polyamides and polyethylene glycols. The waxes
are favored for their performance in many formulations.
Because of the number of products, their diverse nature,
and the fact that little information is available on many
due to their proprietary status, only a few of the principal
TRM types for solvent-borne will be discussedcastor oil
derivatives, polyamides, and overbased calcium sulfonate.
In Table 9, a list of commercial suppliers of organic thicken-
ers for solvent-borne coatings, the products of each, and the
chemical class type is compiled.
CASTOR OIL DERIVATIVES
(CASTOR WAXES)STRUCTURING
One of the main classes of thickeners for solvent-borne sys-
tems are castor oil wax derivatives [218,219]. As the name
implies, these products are produced by modification of
castor oil, including their sulfonation, hydrogenation, and
esterification with polyols. These materials provide thick-
ening by structure formation due to hydrogen bonding of
the pendent hydroxyl groups in the castor derivatives with
each other and also with the hydrophilic entities within
the solvent-borne binders. Often heat activation is recom-
mended for effective incorporation.
POLYAMIDESSTRUCTURING
Polyamides are another widely used TRM class for solvent-
borne coatings [220,221]. Polyamides are high molecular
weight polymeric waxy solids typically produced by the
reaction of diamines with dicarboxylic acids. The internal
segments of these polymers contain amide functionality
while the terminal ends usually do not. These polymers cre-
ate structure viscosity in coatings by swelling in the coating
solvents, which increases the effective volume and provides
chain entanglement. The structure formed is weakly associ-
ated and thus easily disrupted (shear thins) by mixing and
also for high-shear application processes such as spraying
and roll coating. Like some of the clays and silicas used as
thickeners, polyamides require high shear for incorpora-
tion. One issue with polyamides is migration to interfaces
in the coating films that can result in a blotchy appearance
on the surface or intercoat adhesion at the substrate.
OVERBASED CALCIUM SULFONATESTRUCTURING
Overbased calcium sulfonate gels are a complex matrix of
calcium carbonate in its calcite crystalline form stabilized
by sulfonate dispersants [222,223]. The dispersants typi-
cally used are alkyl benzene sulfonates. In the overbasing
process, calcium hydroxide is formed in situ to provide col-
loidal stability. In the preparation of this thickening com-
ponent, the calcium carbonate undergoes a change to its
calcite crystalline form, and the alkali-metal portion of the
sulfonate dispersant adsorbs onto the hydrophilic carbon-
ate particles with the hydrophobes extending into the con-
tinuous solution phase. The carbonate crystals interact with
the polar heads of the dispersant, producing ionic crystal
flocs to provide structure and colloidal stability. Additional
structure is generated through Van der Waals interactions
of dispersant hydrophobe tails with the nonpolar phase
components in the coating. Good suspension and anti-sag
properties are conferred to the coatings, and since they are
supplied in pre-gel form, they do not reduce coating gloss.
The structure is easily broken down with shear and reforms
rapidly after shear is removed. These thickeners do not
require heat for activation and are typically incorporated at
the pigment dispersion stage.
MODIFIED POLYUREASTRUCTURING
Modified ureas function by their selective insolubility,
which results in a controlled separation of fine needle-like
particles [224,225]. The mechanism of thickening is by
strong cohesive hydrogen bonding interactions of these
particles to form a three-dimensional network and by
association with binder molecules producing gel structure
and rheology modification. Solvent-borne coatings with
Fig. 13Photomicrographs of various dispersed thickeners
particles: A=clay, B=fumed silica, C=polyolefin, D=polyamide.
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366 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 9Other commercial thickeners for solvent-borne coatings: producers, product
trade names, product codes, and thickener type
Company Trade Name Thickener Type
OMG Borchers Borchi
Polyamide
Cognis Rilanit
Oxidized Polyethylene
Cray Valley Crayvallac
Modified Urea
Evonik/Degussa Aerosil
Oxidized Polyolefin
Elementis Post 4
Not Specified
Elementis Thixatrol
Polyamide
Elementis Thixin
Surfactant, Polyamide
Ferro Synpro
Aluminum Stearate
King Industries Disparlon
Overbased Sulfonate
Lubrizol Ircothix
Oxidized Polyolefin
Poly-Resyn Polythix
1
eed Density at C 0
(3)
If a Liquid A has the same density as water at T
1
when
determined by a buoyancy device, then the density can be
determined from a table of known density values estab-
lished for pure water over a range of temperatures.
When T
2
equals 4.0C, the relative density for pure water
equals the measured density. As temperature increases,
water expands. For a constant volume, the mass of water
must be decreased to fit into a given volume. Thus, waters
density value, Table 1, must decrease with increasing tem-
perature. Relative density is a ratio of two values carrying
the same units. Therefore, relative density is a dimension-
less number.
TABLE 1Density of water (g/cm
3
) at
various temperatures (C) [15]
Temperature, C Density, g/cm
3
15 0.999 127
16 0.998 971
17 0.998 772
18 0.998 623
19 0.998 433
20 0.998 231
21 0.998 020
22 0.997 798
23 0.997 566
24 0.997 324
25 0.997 072
26 0.996 811
27 0.996 540
28 0.996 260
29 0.995 972
30 0.995 684
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CHAPTER 34 DENSITY AND SPECIFIC GRAVITY 377
Specific gravity is an old term but still widely used
today, particularly when the density determination is of a
liquid such as paint; the term relative density is identical
and may be less misleading [4].
Apparent densityThis term refers to a density value
widely used for powders and macroscopic particulate sol-
ids, which are compacted by vibration, such as pigments
and extenders. Air is still present in the voids between the
particles and in pockets or voids at the irregular surface
of the macroscopic particles. This means the volume is
greater than just for the solids, and the density is smaller in
value than if the material was a liquid or compacted such
that no voids existed. Pigments used in paint are mechani-
cally worked with solvents and resins to fill in these voids.
The true density of the pigment, which is needed in paint
calculations, is that obtained without any of the air (void)
contribution.
Fundamental ConceptsMaterial, Objects,
Volumes, Masses, and WeightsWhat Really
is Density?
Density is more than just the mathematical numerical value
identified above. It also incorporates units of measure
which are, in turn, based upon more general and funda-
mental concepts. These units of measure assume a set of
definitions that will be explored in very general terms.
These units are crucial to understanding the dynamic
model of density and in allowing microscopic concepts to
be explored.
MaterialAnything (a physical entity) that exists for
a period of time, occupies space, and has mass. Mass is
a stable configuration of atoms individually loosely orga-
nized as elemental atoms or joined together chemically to
form molecules.
ObjectA collection of materials, homogeneous or
heterogeneous, localized to a portion of volume (space).
The material can be in any one of three states: solid, liquid,
or gaseous. The shape of the volume of space occupied by
the object plays a role in dealing with density but does not
define the object itself.
Volume is based upon measurement of distance in
three directions at right angles to each other as in Fig. 1.
The physical universe in which we live is often described
in three dimensions in terms of distance, which is a scalar
property. When dealing with three dimensions, the term
distance is described as length, width, and depth.
An object having all three is described as having vol-
ume. The mathematical value for volume is the product of
multiplication of the three scalar values. Volume can exist
without objects occupying that space. This condition is
called a vacuum. Vacuums volume and objects volume can
both be of very irregular and non-matching shapes, yet they
can equal in the scalar value of the volumes. Examples are
shown in Fig. 2.
PROBLEMS WITH VOLUME MEASUREMENTS
Customers often make use of material based on volume as
applied and want to purchase these products in contain-
ers recognized to hold standard volumes. Materials have
the property of responding to temperature changes with
expansion or contraction of their volume. Products that
experience wide temperature ranges during filling, ship-
ping, storage, or in use must also have extra unfilled volume
to accommodate expansion or the material forces leak and
material is lost. This problem is most severe with liquid
materials. Material suppliers use containers with larger
than exact volume required to allow for expansion. These
vessels must be marked in some way to indicate the volume
increments if they are to be used for filling by volume. Pro-
ducers seldom can or want to control temperature during
packaging. Temperature control devices will add expense
without making a difference in the materials performance.
Without temperature control, filling at a constant volume
will produce units of varying amounts of material. Use of
density overcomes these problems and permits correct vol-
umes to be filled out.
Weight and Mass
A fundamental attribute of a physical entity is mass. This is
one of the indefinable mechanics [4]. Two physical objects
exhibit an attraction for each other in proportion to the
quantity of mass in each object. The greater the mass, the
greater the attractive force. When the ratio of two masses is
grossly unequal, such as the planet Earth and an object on
Fig. 1Coordinated in three dimensions.
Fig. 2Examples of physical objects.
Fig. 3Moderate distance to large body center.
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378 PAINT AND COATING TESTING MANUAL 15TH EDITION
its surface, the larger mass is assumed to be constant and
the second object is described to have a weight relative
to this larger object. The mass of the planet is effectively
unchanging and thus constant. Our moon is also a very
large object, but smaller than Earth, thus its attraction to a
second object would be weaker than for Earth. Mass is the
unchanging, fundamental property.
But we are human, and we deal in the measurement of
weight, which is a force. While weight is a vector quantity
having both scale and direction, the direction portion is
taken for granted and weight is usually treated as only a
scalar value. Fig. 3 and 4 graphically depict this issue.
Weight, w, is defined as a force of gravity, F
g
, [4].
w F G
mm
R
mg
g
E
2
(4)
where:
G = a gravitational constant for Earth
= 6.670 10
11
Nm
2
/kgm
2
,
m
E
= mass of the Earth = 5.98 10
27
g,
R = the radius of the Earth = 6370 km,
m = mass of a second body (Newtons law) [5],
g
E
= 9.80 m/s
2
or 32.0 ft/s
2
,
g
Moon
= 5.333 ft/s
2
or 1 /6 that for Earth,
g
Distance from Earth
= 1.0 10
6
km= g
E
/[(1.0064 10
6
km)
2
/
(6370 km)
2
] = 0.004g
E
These values are given as constants in physics calcu-
lations but actually represent average values. In the real
world, the value of g varies from location to location for
a variety of reasons. Table 2 shows that variation present
in the value of g, the acceleration due to gravity, is greatly
influenced by the distance that point on the earth is to the
center of gravity of the earth. Mountains many miles above
sea level and deserts below sea level have an effect, not to
mention the varying densities of the composite materials
which make up earth itself [5].
Example 1: A gallon of paint produced in Galveston,
Texas, has a weight of 10.000 lb/gal. The product then finds
its way to Eagle City, Alaska. Here it has a gallon weight of
10.03 lb/gal. The difference is minor but real.
If the paint specification is a density in the range of
9.90 to 10.10 lb/gal, the +0.03 lb leaves only 0.07 lb for
testing errors before the material is identified as out of
specification. As environmental regulations on the vola-
tile organic content (VOC) increase in importance, these
minor differences will play a larger role and should not be
overlooked for their contributions to relationships such as
density.
The pull of gravity is not as strong at a mountaintop as
it is on the plain. The reason is because the mountaintop
is at a greater distance from the center of gravity than the
plain. A plumb line might not point exactly to the Earths
center of gravity, however, if it is attracted to a large deposit
of denser material beneath the earths crust that is not in
line with the Earths center of gravity [5].
Example 2: The weight of a gallon of paint in New York
City is recorded at 9.5 lb. The distance from the center of
the Earth is 6370 km at this location. At a distance of one
million kilometers from the earth, the same gallon of paint
would weigh 0.003 78 lb.
Has the amount of mass changed? No. Has the weight
changed? Yes, because of distance. Has the volume of the
material changed? Possibly. If the gallon container is sur-
rounded by air at 1 atm, the container shape is retained and
the material in it will not overflow. But, in the new loca-
tion, the fluid does not want to remain together. It forms
droplets and wants to float off in all directions. It has lost
the cohesiveness provided by gravity. Has the density of the
material changed? By definition, yes, drastically! By fact,
little. The same physics rules apply in both locations, but
the environment has changed and with it our appreciation
for the term mass.
Example 3: A 1.00 m
3
Styrofoam cube of material
is created on Earth in our atmosphere (air) at 20C and
1.0 atm. This is a heterogeneous material because it has
trapped air in the foam. Let us say it weighs 900 g on a bal-
ance on an open desktop.
Density
earth
= 900 g 1.00 m
3
= 900 g/m
3
Next, this cube is taken to the moon (gravitational factor=
1/6 Earth) and kept inside a building with 1.0 atm at 20C:
Density
moon
= (900 1/6 1.00 m
3
= 500 g 1.00 m
3
= 500 g/m
3
Next, the cube is taken out onto the moons open sur-
face, where there is no atmosphere (vacuum conditions).
Now, two things happen to this cube.
1. There is no air to displace when weighing the cube.
It can thus exhibit a heavier weight since there is no
buoyancy correction: 1 m
3
of air weighs 1.29 g on
Earth and 0.215 g on the Moon. So the weight would
be 150.215 g.
TABLE 2Values of g, the acceleration due
to gravity [5]
Place Value
a
Place Value
a
Cambridge,
Massachusetts
980.398 Denver,
Colorado
979.609
Eagle City, Alaska 982.183 Galveston,
Texas
979.272
Greenwich, England 981.188 Honolulu,
Hawaii
978.946
Madras, India 978.281 New Orleans,
Louisiana
979.324
Punta Delgada,
Azores
980.143 Reykjavik,
Iceland
982.273
a
Centimeters per second per second. Use of centimeters emphasizes the
differences that are occurring in the second through sixth numerical place.
Fig. 4Vast distance to large body center.
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CHAPTER 34 DENSITY AND SPECIFIC GRAVITY 379
2. The material can also lose the air entrapped in the
foam. This may be a slow process, but it can hap-
pen. Now the cube will appear to lose weight. Let us
say it loses 0.050 g by moon weight and now weighs
150.2150.050 g.
Density
vacuo,moon
= 150.165 g 1.00 m
3
= 150.165 g/m
3
Return the cube back into the building on the moon
with 1.0 atm and the weight might now be 149.95 g if the
foam structure is strong enough to retain the cubic shape
without crushing from the external pressure. Its density is
now 149.95 g/m
3
.
Density is a very simple, straightforward concept and
relationship. Still, as noted before, physical reality can and
does impact on it, adding subtle perturbations that should
be understood. What appears to be homogeneous may not
be. Physical reality is a source of variability, and affects
must be taken into consideration when arriving at results
we will share with one another.
Solids, Liquids, and GasesAs Concepts,
Under Ideal Conditions
Materials exist in one of three states: solids, liquids, or
gases. For an equal amount of weight, solids usually occupy
less volume than liquids, which occupy much less volume
than a gas. Solids also retain a shape and flow or distort
very slowly. Liquids take on the form of a containing vessel.
Gases have no shape and are bounded and shaped by their
container. Techniques exist to determine densities for all
three states.
SolidsFig. 5 is a depiction of a solid in which the
particles are atomic or molecular in scale. The distance
between particles is a regular, repeatable distance. Most
kinetic energy is gone. Only external pressure can shorten
the distance between particles. This shortening is called
compression and affects the ratio of weight present and
the actual volume occupied by that mass of material. If
the solid remains compressed after the external pressure is
released, the material is called inelastic. If it returns to the
original volume, it is elastic. Density of solids can depend
on the processing history.
LiquidsIn a liquid as depicted in Fig. 6, the particles
are molecular or atomic in scale. Distances between par-
ticles are not constant. Kinetic energy is greater than in
solids. External pressure can shorten the distance between
particles. Each material has a characteristic compressibil-
ity factor. All liquids behave elastically, flowing back and
filling in. The population of particles has a distribution
of kinetic energy values, with some being greater than the
surface energy. The portion of the population that has a
kinetic energy greater than the surface energy escapes, and
is called vapor.
For ideal conditions and conceptual materials, no
interactions occur between the materials, the testing con-
tainers, and the surrounding environment. The material
investigated is well behaved. When such materials are
mixed together, the weight of each material times the indi-
vidual materials density will add together as a linear sum.
For a majority of coatings this is a good approximation and
allows formulating programs to give useful density values
for the finished products. These include older solvent-borne
technologies, as well as waterborne latex formulations.
Exceptions to this rule are two component systems where
the separate ingredients begin to react with each other
forming various intermediates. Some of these will eventu-
ally be lost as VOCs. Densities measured of the different
parts can be useful for filling operations, but determining
the density of the mixed materials may not give reliable
numbers. Other exceptions involve highly ionic mixtures
in waterborne formulations. (Salts of amines, and acids
designed to improve water solubility as well as anionic
and cationic surfactants, are usually nonlinear additions,
although the small amounts used of the later can still allow
for close approximations to actual density.)
GasesIn a gas, as depicted in Fig. 7, the particles are
molecular or atomic in scale but more widely separated.
Distance between particles is irregular. Kinetic energy is
even higher than in liquids. External pressure can shorten
the distance between particles. Each material has a charac-
teristic compressibility factor.
Weighing solid or liquid material in a container or as a
solid object is an easy task. Instruments for this task keep
improving in accuracy, precision, ease of use, and lower
cost. For gas-phase material, vessels of accurately deter-
mined volume can be purchased and used. Materials of
Fig. 5Simple model of particles of matter in solid state.
Fig. 6Simple model of particles of matter in liquid state.
Fig. 7Simple model of particles of matter in gas state.
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380 PAINT AND COATING TESTING MANUAL 15TH EDITION
construction for durability and reuse are of concern. If the
temperature of testing is controlled within the tolerance of
the calibration of these vessels, expansion is not a concern.
Since gases are seldom incorporated into a paint system
(on purpose, although entrapped air manifested as foam
can throw off measurements and in most cases is removed
before the material is deemed finished), this topic will be
skipped.
Further Discussion of Liquids and Solids
For liquids, containers can be constructed to hold a known
volume. These vessels can be mass produced with adequate
accuracy to allow large numbers of users to have access.
These are called liquid pycnometers. Some are also called
Weight per Gallon Cups. Within the temperature range of
1C and 99C, the density of water can be determined. More
detail will be given in the section entitled Liquids. Devices
that can float in water can be calibrated to show a scale
calibrated directly in density. When these floats are used
along with a scale for weighing, the volume of material can
be determined [6,7].
Fig. 8 contains drawings of several pycnometers as
seen in a commercial scientific supplies catalog. The
catalog text descriptions for two pycnometers have been
included to inform you as to sizes, capacities, materials of
construction, etc. The features discussed identify attributes
of importance to the end user.
Liquids have other properties that can be used to test
for density. One of these is sound transmission. Replace-
ment of air with a liquid in a container will cause that
container to shift a tone impulse to higher frequencies.
The extent of the shift is related to the liquids density and
can provide a direct measurement with different degrees of
accuracy depending on the sophistication of the instrument.
For solids, the task is more complex. Two paths are
available. Either shape the solid into a known geometric
figure and calculate the volume or use the solid to displace
a material, such as a liquid or a gas, which has a known
density. The solid can be shaped by mechanical, thermal,
or chemical means. Mechanical means can be employed
to cut, carve, and shape, then weigh. Thermal shaping is
changing the solid into a liquid using heat to melt the solid,
pouring the liquid into a mold, cooling to form a solid, and
then weighing. Chemical shaping is dissolving the solid in a
carrier liquid (solvent), pouring the solution into an open
mold, and evaporating the solvent, leaving behind a solid
properly shaped to accommodate testing. The drawbacks
of this technique are:
Complete solvent removal is often difficult.
Chemical reshaping of solids can cause problems if the
original solid had small air pockets or if the solvent
used is trapped in these voids, thus actually chang-
ing the solid and affecting its apparent density. Solids
which demonstrate the latter behavior have a bulk
density different than their skeletal density.
The principle of buoyancy, discovered in the third cen-
tury by Archimedes, provides a means to determine volume
[5]. Determination of volume by displacement requires
acquiring a weight in air and a weight in a liquid of known
density at the testing temperature. Complete submersion of
the solid object or a representative portion of the material
in a liquid of known density is required while determin-
ing the materials apparent weight. The weight difference
is equal to the weight of the volume of liquid displaced.
Knowing the liquids density and the weight difference, the
volume for the tested portion can be calculated. The practi-
cal application of Archimedes Principle is used in the fol-
lowing discussions to describe the determination of specific
gravity of pigments and other solid ingredients in paint.
Solids, Liquids, and Gases as Concrete
Materials in a Physical WorldA Practical
Guide to Density
A vast variety of materials exist, and interactions are pos-
sible between any of the different types of materials. When
an attribute, like density, can be directly measured, it is pos-
sible to identify two types of these interactions.
The first is ideal behavior with respect to the attribute
under investigation and the amount of mass used. These
interactions are well behaved and produce predictable attri-
bute changes. The second type is non-ideal and means that
other interactions are taking place than just that of mass-to-
mass attraction. Materials are ideal if when mixed together
the sum of the weight fraction of each material multiplied
by the materials density equals the density determined for
the entire mixture. Materials are non-ideal if when mixed
together the sum of the weight fraction of each material
multiplied by the materials density does not equal the den-
sity determined for the entire mixture.
Some solids can exist with varying degrees of crystalline
domains incorporated into their solid form. As tempera-
tures cycle up and down in the surrounding environment of
Fig. 8Specific gravity testing pycnometers. (Courtesy of Sargent-Welch.)
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CHAPTER 34 DENSITY AND SPECIFIC GRAVITY 381
these solids, the solids will change density as these domains
increase or decrease and they move toward a thermody-
namically stable form of the solid.
Finally, as we alluded to earlier, materials can chemically
interact when mixed, producing or absorbing heat and gener-
ating an entirely new material with its own unique attributes.
These actions are not bad or good, but they basically exist
and must sometimes be taken into consideration when deal-
ing with mixtures such as liquid paints and solid coatings.
When a material (A) is homogeneous, the density is a
fixed value for a fixed temperature. When a material (B) is
heterogeneous, the density is also a fixed value for a fixed
temperature. When two different materials, homogeneous
or heterogeneous, are mixed together, they become a new,
heterogeneous material, and the resultant density is a new
fixed value for a fixed temperature. Depending on whether
the interactions are ideal or non-ideal, the density can be
predicted by calculation or a deviation in the density will
result. Paints are formulated as ideal mixtures, but they
dont always follow this assumption. The relationships
between these values are given below [8].
A A has A s density which is +
+
+
W W
W W
A A A A
A A
(5)
B + B has B s density which is
+
+
W W
W
B B B B
B
WW
B
(6)
A + B has a new density which may be =, >, or < that of A
or B and is:
W W
W W
A A B B
A B
+
+
(7)
where:
W = weight of component,
= density of the component.
Many important materials are available as complex
mixtures in todays world. These mixtures can be hetero-
geneous in terms of phase. Gasoline for the car and lawn
mower can contain butane dissolved into the heavier
hydrocarbons. Paints, inks, and cements contain liquids
and solids, with the liquid phase either neutral or reactive.
If the liquids role is neutral, it can be a solvent or carrier or
plasticizer. If the liquids role is reactive, it is called a binder,
reactive diluent, or catalyst.
Modern paints contain chemically reactive, low-
molecular-weight polymers that, when heated, produce a
crossed-linked solid and usually volatile by-products. When
chemical changes occur, the linear density addition model
is correct only by chance. Usually the volume is reduced
from chemical bonds forming, and as a result, the density
goes up.
Theoretical volume solids have been calculated for
years in the coating industry using the linear model. This
model has worked well for lacquers, varnishes, and other
systems where chemical reactions took place at low lev-
els and were of the oxygen uptake type, making the final
film heavier from oxygen addition. Modern paints react
internally, generate by-products of low molecular weight,
and actually lose weight during cross-linking and film
formation. But, because there has been no good way to
determine the volume of paint films that is repeatable and
reproducible, the practice of calculating volume solids is still
used in 2010. (Repeatable means in the same lab, with the
same instrument, time after time, and reproducible means
between different sites or labs using similar but physically
different instruments like balances, ovens, etc.)
Definitions Related to Density
and Specific Gravity
BULK DENSITY
=
Total weight of object including air or wat ter
Total volume occupied including air or wwater
(8)
SKELETAL DENSITY
=
Total weight of object less air or water
Tottal volume of actual material less air or wwater
(9)
Surface interactionsThese interactions involve wet-
ting of solid surfaces by liquids during liquid displacement
testing. In determining the volume of a material due to
displacement of a liquid, the liquid must come in close
contact with the material surface. When the liquid meets
or wets the surface without penetration into the bulk of the
material, the volume of liquid displaced is equal to the bulk
volume of the material being tested. When the liquid does
not contact and wet the surface, a thin layer of air exists
between solid and liquid. This also displaces liquid, mak-
ing the apparent volume of the material larger. In tests like
ASTM D2965, where the volume of paint film being tested
is very low, this error can be significant. Materials called
surfactants can be added to increase wetting, but they affect
the density of the liquid. Where surfactants cannot be used,
another liquid must be used.
PermeationWhen the liquid meets or wets the sur-
face with total penetration into the bulk of the material,
the volume of liquid displaced is equal to the skeletal
volume of the material being tested. If there are molecules
with low molecular weight left inside the bulk of the solid,
these can migrate out, leaving the testing liquid in its place.
These will change the bulk testing liquids density as they
accumulate.
MEASUREMENT SYSTEM UNITS, CONVERSIONS,
DENSITY, AND RELATIVE DENSITY
Todays world uses three systems of measurement [4]:
1. International System of Units (SI), previously referred
to as the metric system, based upon powers often.
This was called the MKS system, standing for meters
(distance), kilograms (force), and seconds (time). A
common form of this system uses millimeters, grams,
and seconds as the units. By universally accepted defi-
nition, 1.0000 g of distilled water occupies 1.0000 cm
3
(or 1.0000 ml) at 4.00C.
2. The British system uses the British yard (distance),
pound (force), and second (time).
3. The United States (U.S.) system uses the U.S. yard (dis-
tance), pound (force), and second (time).
The British and U.S. systems use the same basic linear
distance and force units, but, when measuring volumes, the
systems do not have equivalency. A British gallon of water
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382 PAINT AND COATING TESTING MANUAL 15TH EDITION
(volume) weighs 9.993 lb at 77F (25C), while a U.S. gal-
lon of water weighs 8.321 lb at 77F (25C) [7]. Conversion
between the three systems can be accomplished using the
following relationships:
2.54 cm = 1.00 in.
231 in.
3
= 1.00 U.S gallon
453.6 g = 1.00 lb
or
277.4 in.
3
= 1.00 British (Imperial) gallon
From SI to U.S.:
(2.54 cm/in.) in U.S. gal g lb
3
( . / )/ . / 231 453 6
3
=8.345 cm lb U.S. gal. g
3
/
(10)
(2.54 cm/in.) in British gal
3
( . . / )/ . 277 4 453 6
3
gg lb
=10.02 cm lb British gal g
3
/
/
(11)
These are conversion factors, which carry particular
units. They are used to convert density values for a material
at any temperature into a second set of units at that same
temperature. The 8.345 factor for converting to U.S. lb/gal
is sometimes confused with the 8.321 value for a U.S. gallon
of water at 25C (77F) [9].
Density (in the SI system) at any temperature = density
(in the U.S. system) 8.345 at the same temperature.
Example for pure water at 4C (39.2F):
1 000
1 000
1 000 8 345
3
.
.
( ) . . ( )
g
cm
SI conversion
88 345 4 .
lb
U.S. gallon
at C
(12)
For pure water at 25C (77F):
0 997 04
1 000
0 997 04 8 345
3
.
.
( ) . . (
g
cm
SI conversi oon
lb
U.S. gallon
at C
)
. 8 321 25
(13)
Note in these examples that the volume of space (container
internal volume) has not changed with temperature. But,
the amount of material which can fit into that volume has
changed with temperature! Using known volume devices
provides only density values. Temperature must be stated
as a significant variable.
LIQUIDS
Densities of LiquidsMethods of Determination
BUOYANCY-HYDROMETERS
Hydrometers are flotation devices that are calibrated using
water at various temperatures. When placed in clear liq-
uids, the relative density is read directly from the scale on
the hydrometer. The hydrometers range from low-cost, low-
precision versions, to expensive, high-precision devices.
Higher-grade hydrometers also have thermometers incor-
porated for temperature correction and greater indepen-
dence of reading liquids in an as-is condition. A balance or
a known volume device is not needed with this technique.
Simplicity is the advantage of this technique. Shown in
Figs. 9 and 10 are two types of hydrometers. The catalog
text has been included to explain ranges and features
unique to these devices.
ASTM methods using hydrometers are [10,11] Stan-
dard Test Method for Density, Relative Density (Specific
Gravity), or API Gravity of Crude Petroleum and Liquid
Petroleum Products by Hydrometer Method (D1298) and
Standard Test Method for Calculation of Volume and
Weight of Industrial Aromatic Hydrocarbons (D1555).
DISPLACEMENT-SUBMERSIONSPECIFIC GRAVITY
BALANCES
A specific gravity balance is similar to the hydrometer.
It is actually a balance that measures the counterweight
appliedto balance a plummet submerged in the liquid sam-
ple. The weight and volume of a mercury-filled elongated
glass bulb (plummet) is determined by comparison with
standards established by regulatory agencies and traceable
back to well-characterized standards, referred to as primary
standards, established by national scientific bureaus. The
plummet is attached to a balance and submerged into a
liquid to displace some of the liquids volume. The change
in weight is attributed to the weight of the displaced liq-
uid. The plummets volume is known, and it is related to
Fig. 9Hydrometersspecific gravity scaleplain design [6].
Fig. 10HydrometerSugar with Brix scale and enclosed thermometer [6].
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CHAPTER 34 DENSITY AND SPECIFIC GRAVITY 383
displacement of water. These are related back to water as a
calibration liquid, so they provide a relative density rather
than a true density. With this device, the sample does not
need to be clear because there are no markings on the plum-
met. The devices also allow the liquid to be at temperatures
other than 4.0C. This type of device is good for solvents and
low-volatility materials. Two balances are shown in Fig.11
and are from recent scientific lab supplier catalogs [12].
The catalog descriptions have been included because they
are concise statements about the devices, their operating
principles, ranges, and other relevant information.
ASTM method using submersion [13], Standard Test
Method for Specific Gravity (Relative Density) and Density
of Plastics by Displacement (D792).
DisplacementFluid External Media
This is a device where the sample-holding chamber is not
of a known, calibrated volume. A helium gas pycnometer
can be used to determine the volume of a liquid in a metal
or glass container. The pycnometers test chamber volume
is first established by determination of gas pressure differ-
ences in a sample chamber and after expansion into a con-
necting expansion chamber. Then an independent, empty
sample container is introduced into the gas pycnometer test
chamber and tested. The reduction in volume is allocated
to the empty sample container. The independent sample
containers weight is measured on an analytical balance.
The sample is added to the sample container and weighed.
The container and sample are tested again to establish
a new volume. The sample volume is (sample + con-
tainer volume) (container volume). The sample weight is
( sample+ container weight) (container weight). Density is
(sample weight/sample volume). The test is fairly fast. Con-
tainers of predetermined volume can be kept available to
help shorten testing time. Precision and accuracy are good.
The ASTM method for using a helium gas pycnometer
[14] is Standard Test Method for Percent Volume Nonvola-
tile Matter in Clear or Pigmented Coatings Using a Helium
Gas Pycnometer (D6093).
Displacement-Known Volume Devices-Fluid
Internal Media
These are devices of known, internal volume. They have
many names such as liquid pycnometers, U.S. standard
weight-per-gallon cups, U.S. mini weight-per-gallon cups,
British standard weight-per-gallon cups, featherweight
type weight cups, and Monk cup [7,9,15]. Liquid pyc-
nometers come in a variety of sizes, shapes, volumes, and
materials of construction. For precision, glass (inert, light
weight, and transparent) is usually used. For testing condi-
tions that require demanding repeated use, other materials
with reasonable inertness or resistance to chemical attack,
such as stainless steel, are used. To combine both the lighter
weight of glass and the ruggedness of metal, a feather-
weight construction of anodized, high-tensile aircraft alloy
is employed at a cost consistent with the use of special-
ized materials of construction. The Monk cup is a special
design (Fig. 12) and discussed under the topic of handling
entrapped air in samples.
Liquid pycnometers or weight-per-gallon cups are built
with a main body or container volume, a cap or lid with
a vent hole, and sometimes a tare weight object. The tare
weight is used as a counterweight for dual pan balances.
The weight read after correcting for the tare weight is attrib-
uted to the material contained in the vessel at a level which
reaches the top of the vent hole in the cap (see Fig. 13).
Both the vessel and a sample of the material to be
tested are equilibrated to room temperature or a constant
temperature bath temperature. Common temperatures for
Fig. 11Specific gravity balanceschain balance and Mohr
Westphal balance with catalog text instruction and comments
[11]. (Courtesy of Fisher Scientific.)
Fig. 12Monk cup (weight per gallon cup) (courtesy of C. J.
Monk and Journal of Oil and Color Chemists Association) [5].
See reference for a discussion of Parts A to M.
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384 PAINT AND COATING TESTING MANUAL 15TH EDITION
paint and solvent testing are 20C (68F) and 25C (77F)
because these are temperatures in the human comfort
range. Using temperatures greater than these would drive
off solvents. Moisture is not likely to condense out on sur-
faces from being too cool (weight gain drift during weigh-
ing), and volatile materials will not evaporate at a rate that
significantly affects the weight readings taken (weight loss
drift during weighing). Temperatures colder than these
are easily obtained, but are less comfortable for the tester.
However, any temperature can be used if the temperature is
noted and the vessel volume is corrected for that tempera-
ture. If the bath is used, the vessel exterior must be dried
off. This has to be done with minimum handling to prevent
temperature changes from heat exchange by hands or dry-
ing materials.
Next, a portion of the tempered sample is poured into
the vessel up to the top rim. The lid is carefully placed on
the vessel so that the excess liquid is forced up through the
vent hole in the lid without coming out around the lid lip.
The excess is carefully cleaned off the surface of the lid and
from around the lid lip. This is a cleaning, not merely a
wiping off. Wiping leaves residues, which affect the results
obtained. The sample-containing vessel is then carefully
weighed.
Afterwards, the vessel and lid are cleaned as soon as
possible and as well as possible to prevent buildup of resi-
dues, which will change the vessels volume. A verification
test should be performed at frequent intervals with distilled
water to catch inaccuracies from poor cleaning or damage
to the vessel surfaces. For improved accuracy, the vessel
can be calibrated using pure water at normal reading tem-
peratures. Divide the gram weight of water by the weight
determined by direct testing. This produces a correction
factor. This factor number is multiplied by the weight of
the gallon weight found for an unknown liquid or mixture.
If the determined density of water was less than expected,
a factor greater than 1.000 is generated. As a result, the
vessels volume is less than expected. Tracking the factor
value will alert the tester to problems arising from poor
cleaning or rough handling that can damage and alter the
testing vessel.
Sample sizes range from 10 to 84 ml. The combined
weight of the vessel, lid, and sample affect the type of bal-
ance that can be used to provide good repeatability and
reproducibility. The larger the size, the easier it is to get a
sample representative of the bulk material. But the larger
the size, the harder it is to remove entrapped air bubbles
from the sample introduced during sample collection or
preparation. For very volatile solvents, use of larger size
vessels offsets the weight drift seen during weighing.
The problem of entrapped air can be countered in two
ways:
1. The Monk cup is designed to pressurize the sample to
150 lb/in.
2
in a known volume of space. This pressure
compresses the entrapped air in the sample to such
an extent that occluded air bubbles are reduced to a
negligible volume. Entrapped air of up to 10 vol % can
be dealt with by this technique. The volume produced
is still larger than the true volume, and a density error
is still present. Entrapped air should not be accounted
for if the air escapes before use or the air is an artifact
of sample mixing before testing. The Monk cup is large
and heavy and requires use of non-analytical balances.
Fig. 12 is a schematic diagram and picture of a Monk
pressure weight-per-gallon cup.
2. An alternative technique is to mix a measured weight
of the unknown density material with the weight of a
known diluent from a full weight per gallon cup. The
blend is then placed back into the cup and weighed.
The following, enclosed in quotes, is copied directly
from the GARDCO mini catalog Number 9, including
the diagrams, with permission from GARDCO [7].
X
W B
W W
unknown lend wt per gallon
unknown diluen
+ (
tt cup weight lend wt per gallon
B
WB
W A B
+
10
10
)
( )
(14)
where A = W
diluent cup weight
.
Heavy-bodied materials which entrap air present a
problem in true weight per gallon (density) measurements.
Air entrapment causes the apparent volume of a material
to be greater than actual and density or weight-per-gallon
calculations are low and erroneous. The practice of mea-
surement under pressure does reduce the error but the
error is far from eliminated as the entrapped air is normally
not removed, but only compressed, as shown in Figs. 14
and 15.
Most materials that are difficult to evaluate can be
simply and accurately measured by the following depicted
procedure.
A measured weight of the unknown material is thor-
oughly blended with the weight of a known diluent from a
full weight per gallon cup. The blend is then placed in the
cup and the weight per gallon is determined. The value of
Fig. 13Mini weight per gallon cups [7].
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CHAPTER 34 DENSITY AND SPECIFIC GRAVITY 385
the unknown material is calculated from the formula given
above. The diluent liquid must be compatible with the
material containing the entrapped air and it must be thin
enough in viscosity to allow entrapped air to rise to the
blends surface and escape. In the case of particulate, such
as pigment, the liquid must be able to wet the particle
surfaces and displace air in pockets or depressions on the
surface.
ASTM methods using known volume devices are
[15,16] Standard Test Method for Density or Relative Den-
sity of Pure Liquid Chemicals (D3505) and Standard Test
Method for Density of Paint, Varnish, Lacquer, and Related
Products (D1475).
Sonic Frequency Shifts
Waves of air reaching a human ear are recognized as sound.
The pitch of a sound is related to how many waves reach our
ear per unit of time. This unit of time is referred to as fre-
quency. Waves are made by an object moving in the media:
air or liquids or even solids. The media touched by the wave
can pass this movement through itself. When a boundary
between two media of different densities is encountered by
the wave, two actions occur: (1) some waves are reflected
back; (2) a portion of the waves are passed into the new
media but with their frequency changed.
Changes in density also lead to changes in frequency.
This can be demonstrated by filling a matched set of water
glasses to different levels with water, then striking each
glass lightly to produce a sound. The higher the water
level is in the glass, the higher the tone. Just as the fre-
quency changes from an empty glass (air, less dense) to a
high frequency tone when filled with water (more dense),
thereplacement of liquids of differing densities also shifts
the frequency for glasses filled to the same level. This is the
principle for several digital density meters commercially
available today.
Measuring devices have been devised using a glass
tube, an oscillator, and a sensor. The oscillating frequency
of the tube changes when air is replaced with a liquid.
The instrument can use air and water to establish a set
of constants, called A and B, for the following relation-
ships [17]:
A T T d d
w a w a
( ) ( )
2 2
(15)
B T A d
a a
2
( )
(16)
where
T
w
= observed period of oscillation for cell con-
taining water,
T
a
= observed period of oscillation for cell con-
taining air,
d
w
= density of water at test temperature,
d
a
= density of air at test temperature,
t = test temperature expressed in degrees Kelvin,
p = test barometric pressure expressed in Torr,
d
a
(g/ml) = 0.001 293 (273 t) ( p 760)
d
w
(g/ml) = 0.997 04 at 25C (273+ 25 = 298K)
Constant A is used by the instruments computer to
calculate constants K
c
and K
cr
. Constant B is used by the
instruments computer to return the reading for air density.
Modern digital density instruments are equipped with
heating and cooling devices internal to the instrument, such
that the sample can be equilibrated within the instrument
in a matter of seconds. This leaves the pressure term, P, as
a visible variable. Pressure changes can occur over a period
of time due to weather changes.
The sample tube must be cleaned after each use. The
tubes condition needs monitoring to verify that it is at
original condition. Frequent calculation of the instrument
cell constant K
c
overcomes both of these problems.
For density values
K
A
d d
T T
c
w a
w a
1
2 2
(17)
d d K T T
w c a w material
+ ( )
2 2
(18)
For relative density values
K
d
T T
cr
a
w a
1 0000
2 2
.
(19)
d K T T
cr s w material
+ 1 0000
2 2
. ( )
(20)
where:
T
w
= observed period of oscillation for cell con-
taining water,
T
s
= observed period of oscillation for cell con-
taining sample,
K
c
= instrument constant for density,
K
cr
= instrument constant for density,
d
w
(g/ml) = 0.997 04 at 25C (273 + 25 =298K)
density of water at test temperature, and
t = test temperature expressed in degrees Kelvin.
Small process computer chips built into commercially
available instruments handle all the necessary calculations.
Small sample volumes (1.0 to 2.0 ml) are used so heteroge-
neous samples like paint must be well mixed. The samples
Fig. 14Liquid with entrapped air [7]. Figure provided by Paul
N. Gardner Co., Inc.
Fig. 15Diagram for mixing known- and unknown-density
materials [7]. Figure provided by Paul N. Gardner Co., Inc.
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386 PAINT AND COATING TESTING MANUAL 15TH EDITION
must be free of entrapped air. Small amounts of air cause
fluctuations in the readings. Use of dilution with a compat-
ible solvent (of known density) to thin the sample can be
used if the thinning does not cause pigment dropout. The
contribution of the thinner solvent can be calculated and
backed out.
The ASTM method using the digital density meter is
[17] Standard Test Method for Density and Relative Density
of Liquids by Digital Density Meter (D4052).
SOLIDS
Densities of SolidsMethods of Determination
With solids, determining the volume for a known weight
of the material is a challenge for several reasons. First, the
form is fixed and direct, accurately known volumes are the
exception rather than the rule. Second, solids are seldom
homogeneous in their density. Processing often introduces
voids or regions of differing degrees of crystallinity, both of
which affect density. For large objects, displacement tech-
niques as well as sonic shifts are useful. For powders and
small particles, displacement and density by mixing with
liquid diluent are the most common techniques. For thin
films, only displacement techniques are useful.
Direct Volume Measurement by Pycnometer
Pigments are insoluble, solid particles used to impart
color or light reflectance in paints. To provide more than
an apparent density, special steps must be taken. ASTM
Method for Specific Gravity of Pigments (D153) is a set
of three variations on the diluent pycnometer technique
described in Fig. 15. It uses a vacuum pump and vacuum
dessicator or bell jar to reduce the pressure on a sample
of solid pigment. Variation A places a weighed sample of
pigment in a dry, weighed glass pycnometer. White kero-
sene is then added to cover the pigment. The pycnometer
and sample is then placed in the dessicator or bell jar and
slowly evacuated to remove air entrapped on the irregular
surfaces of the pigment. This is a method to wet the pig-
ment surface and remove the contribution of entrapped
air in the pigment. After all bubbling stops, air is let back
into the jar and the pycnometer is filled to the top with
kerosene and weighed. Variation B evacuates the pycnom-
eter before the kerosene is added. Most of the kerosene is
added to the pycnometer while it is under vacuum. The
pycnometer is topped off with kerosene after returning
to normal pressure. Variation C uses a measuring burette
to add the kerosene so that volume of kerosene added is
known [9,18].
ASTM methods using a pycnometer are [18,19] Stan-
dard Test Methods for Specific Gravity of Pigments (D153)
and Standard Test Method for Density (Specific Gravity) of
Solid Pitch (D2320).
Displacement of Liquids
This was discussed in the section Solids, Liquids, and
Gasesas Concepts Under Ideal Conditions.
Density gradient column systems (Fig. 16) are another
form of submersion test methodology, inverted from the
plummets of the density balances. Here the fluid is the
calibrated, known test media, and the solid is the unknown.
A vertical column tank with black background is carefully
filled with a mixture of liquids in a very strict order to estab-
lish a heavy-to-light liquid density gradient. Measurements
are made by adding in both unknown solid materials such
as fibers, film pieces, powders, and glass particles and refer-
ence materials of known density. The particles will sink to
the level of their own density. Using the proper reference
materials, exact matches can be established within 0.0001g/ml.
There is a problem when the sample interacts with the fluids
and absorbs them or interacts in other chemical ways that
perturb the normal test action as with inert materials such
as glass or plastics. Powders with irregular surfaces can also
experience surface wetting problems and air pocket entrap-
ment. Densities can be determined from 0.79 to 2.89 g/ml
with this technique [26].
The test is of long duration, requiring a settling time
of usually several hours. Several caution notes are included
concerning thin film samples and their handling, which
could change the density. Potential users should review
ASTM D1505 to assess the applicability of this technique to
their own personal needs and use.
ASTM methods using displacement of liquid and gases
are [13,20,21] Standard Test Method for Specific Gravity
(Relative Density) and Density of Plastics by Displacement
(D792), Standard Test Method for Volume Nonvolatile Mat-
ter in Clear or Pigmented Coatings (D2697), and Standard
Test Method for Density of Plastics by the Density-Gradient
Technique (D1505).
DisplacementGases
Helium pycnometers have been available for a number of
years with many people expressing interest in using these
devices to determine the volume of solids of known weight.
These instruments are usually relatively expensive and only
recently have become sufficiently automated to reduce the
Fig. 16Density gradient column systems with text from
supplier catalog [6]. (Courtesy of Fisher Scientific.)
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CHAPTER 34 DENSITY AND SPECIFIC GRAVITY 387
intense manual labor required to do a good job. The main
problem is to provide a sufficient amount of free paint film
to test at a valid film thickness. Films that are too thick
can retain solvents. Films that are too thin are very hard
to handle. Free films develop static charge buildups, which
further complicate the testing procedure.
Dry powders are a second candidate for this technique.
Helium gas displacement eliminates the need for the vac-
uum pump and the kerosene used in ASTM Method D153,
Test Methods for Specific Gravity of Pigments, to replace the
air in the voids and available surface cavities. The drawback
is that the fine powder is easily blown around. The instru-
ment must be designed to eliminate powder travel and to
keep the fine particles from the valves and seals. Hopefully
most of these drawbacks have been addressed [14].
ASTM methods using Helium Pycnometry are [14,22]
Standard Test Method for Percent Volume Nonvolatile
Matter in Clear or Pigmented Coatings Using a Helium Gas
Pycnometer (D6093) and Standard Test Method for Density
of Solid Pitch (Helium Pycnometer Method) (D4892).
Sonic Frequency Shifts
The sonic frequency shift, principle and equations, has
been discussed previously. Use of the sonic technique is lim-
ited to continuous objects that can be cut and shaped. Pow-
ders and small particles can be suspended in liquids and
tested using the equipment discussed previously and using
the equations noted earlier under Sonic Frequency Shifts.
When the instrument uses solids instead of liquids, several
considerations change. A glass tube is no longer used. The
solid specimen must be cut into a rectangle with a smooth
surface. Surface flaws will introduce errors in the readings.
A sonic sensing head is attached to the solid specimen
(approximately 75 mm in thickness), and measures the
velocity of sound transmitted through the specimen. Solid
specimens require a minimum conditioning time period
under controlled temperature and humidity conditions
before testing. A calibration curve can be established using
materials of known density. The published use is limited
to polyethylene plastics. Alternative methods are probably
cheaper or less time/labor consuming.
ASTM method using ultrasound [23] The Standard
Method for Density of Polyethylene by the Ultrasound Tech-
nique (D4883).
Apparent Density
Many pigments or powders are tested without regard to
the air entrapment on the particle surfaces or in the voids
between where the particles touch. These materials are
placed in a graduated transparent container, and a vibra-
tor is touched to the container wall. The particles pack
down and a weight is taken. This is referred to as apparent
density.
ASTM methods based on apparent density include [24
26] Test Methods for Methylcellulose (D1347), Standard
Test Methods for Sodium Carboxymethylcellulose (D1439),
and Standard Test Methods for Hydroxypropyl Methylcel-
lulose (D2363).
PAINT VOLUME SOLIDS
Paint is a mixture of materials that is designed to protect
and beautify a substrate. When paint is sold, it is sold by
volume as gallons or liters. What the consumer wants is the
most coverage for the money. Commercial painters and orig-
inal equipment manufacturers paint surfaces to a minimum
thickness called hiding. They know the square footage or
square meter surface area they need to cover. With the thick-
ness for hiding known, a volume of solids needed for paint-
ing a house or an automobile can be calculated. Government
regulators would like to know the volume of volatile organic
material included in a gallon of paint. A ratio of volume
volatiles to volume solids would be a measure to compare
paint products in terms of pollution contribution.
Theoretical Calculations of Paint Volume Solids
For many paint systems in commercial use today, a straight
calculation of solids content can be performed with good
results using the densities and weight percent content of
materials that contribute solids to the final product. For
many other systems, however, this calculated answer does
not account for additional reaction by-products or provide
information about how the density of the material has
changed when cross-linking occurs. For these systems an
analytically tested answer is needed. For the last revision of
this book, the major document in force by the U.S. Environ-
mental Protection Agency (EPA) was Reference Method 24:
Guidelines of Testing for VOCs at 110C for 1.00 Hour Bake
[1]. This was the document to which all methods develop-
ment related to VOCs relied. In the last 1520 years, several
ASTM test methods have been developed to address the
concerns associated with how and when a VOC is occur-
ring, be it the slight amount of solvent introduced via a
minor additive, or a reaction product of a catalyzed system.
All of the methods referenced in this manual that deal with
paint and coatings raw materials and finished products
reference EPA Method 24. These analytical methods are
appropriate regardless of whether the composition of the
coating is a known or an unknown.
Analytical Determination of Paint
Volume Solids
Standard Test Method for Volume Nonvolatile Matter in
Clear or Pigmented Coatings (D2697) [20] is commonly
used. The test is based on displacement of liquids, usu-
ally water or kerosene. Perhaps a more reliable test is
Standard Test Method for Percent Volume Nonvolatile
Matter in Clear or Pigmented Coatings Using a Helium
Gas Pycnometer (D6093) based on volume determina-
tion by gas (helium) displacement [14]. The helium is a
pervasive gas that behaves closely to an ideal gas. Where
paint surfaces are hard to wet with water, the helium has
no problem getting very close to the paint surface and dis-
placing air residing at the surface. The test chambers are
usually from 5.0 to 30 cm
3
in volume. The paint sample is
introduced as a free film or attached to a carrier such as a
metal disk or aluminum foil. When the film is a free film,
static charges can build up and cause sample loading and
handling problems. The test instrument is not inexpensive,
but it is highly automated and minimizes the human labor
required to about 5 min per test. The fact that the test
specimen is a solid film is very beneficial in the case of
reactive systems, which are not chemically the same before
and after cure. This may be the only means to ascertain the
reactive elements (by difference), which should be included
in VOC determinations.
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388 PAINT AND COATING TESTING MANUAL 15TH EDITION
CRITICAL PIGMENT VOLUMES
The pigment volume concentration is a physical prop-
erty of paint that can help indicate its performance. The
definition of Pigment Volume Concentration (PVC) is the
ratio of the pigment volume divided by the pigment volume
plus resin solids (and sometimes additive solids) volumes.
The reader is directed to chapter 28 of this book where this
concept is discussed in greater detail.
Pertinent to our discussion is a volume concentration of
pigment known as the Critical Pigment Volume Concentra-
tion (the CPVC or cPVC). At this ratio, several things hap-
pen to the properties of the paint. At this point, there is just
enough resin or binder to completely fill the spaces between
all the pigment particles. As the PVC increases past the
cPVC, the dried paint film will contain voids. The porosity
will increase, the moisture vapor transmission will increase,
the stain resistance will decrease, the wet hiding will
decrease, but the dry hiding will increase. As the paint dries,
a condition will exist where the paint has too much pigment
and too little polymer such that the internal voids created
will entrap air or solvent in the vapor phase [1]. Paint com-
panies actually take advantage of one of these properties to
make inexpensive paints that can still hide in the dry state.
By formulating above the cPVC, the coating can contain
much less pigment, while still performing sufficiently well
enough for noncritical applications (ceiling paints and the
interior low-performance application). For our discussion
it is enough to say that a solid is created that has a higher
apparent volume than really exists (see Fig. 17).
If a volume solids test is used that uses strictly liquids
to determine displacement solids, they may be unable to
penetrate into the void areas. A larger volume of water will
be displaced and the apparent weight loss will be greater in
water. The bottom line is that all the tests that rely on an
accurate determination of specific gravity will be in error.
It is exactly in this situation where the ability to accurately
determine the volume solids of a paint film, such as the
Standard Test Method for Percent Volume Nonvolatile
Matter in Clear or Pigmented Coatings Using a Helium Gas
Pycnometer (D6093), really shows its worth.
References
[1] Manual on Determination of Volatile Organic Compounds,
MNL4, J. J. Brezinski, Ed., ASTM International, West Con-
shohocken, PA, 1989, pp. 113.
[2] ASTM D16-03, 2005, Standard Terminology for Paint, Relat-
ed Coatings, Materials, and Applications, Vol. 06.01, ASTM
International, West Conshohocken, PA, pp. 18.
[3] Lee, G. L., Principles of Chemistry-A Structural Approach,
International Textbook Co., Scranton, PA, 1970, Gases, p. 40,
Solids and Liquids, pp. 6488.
[4] Sears, F. W., and Zemansky, M. W., University Physics, 3rd ed.,
Part 1, Addison-Wesley Publishing Co., Palo Alto, CA, 1963,
pp. 102107.
[5] The Book of Popular Science, Vol. 2, Grolier Society Inc., New
York, 1966, pp. 3032, 317318.
[6] Sargent-Welch Catalog, 1992, pp. 39, 104, 149, 752, 756.
[7] Gardco New Paint Testing Instruments, Mini-Catalog No. 9,
Paul N. Gardner Co., Inc., Pompano Beach, FL, 1992, pp.
3638, 231239.
[8] ASTM D5201-05a, 2009, Standard Practice for Calculating
Formulation Physical Constants of Paints and Coatings, Vol.
06.01, ASTM International, West Conshohocken, PA, pp.643-
648.
[9] Paint Testing Manual, 1972, ASTM STP 500, G. G. Sward, Ed.,
ASTM International, West Conshohocken, PA, pp.165172.
[10] ASTM D1298-99 (2005), 2009, Standard Test Method for
Density, Relative Density (Specific Gravity), or API Grav-
ity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method, Vol. 05.01, ASTM International, West
Conshohocken, PA, 2009, pp. 544549.
[11] ASTM D1555-04a, 2009, Standard Test Method for Calcula-
tion of Volume and Weight of Industrial Aromatic Hydrocar-
bons, Vol. 06.04, ASTM International, West Conshohocken,
PA, pp. 301308.
[12] Fisher Scientific Catalog, 1992, pp. 14481449.
[13] ASTM D792-09, 2009, Standard Test Method for Specific
Gravity (Relative Density) and Density of Plastics by Displace-
ment, Vol. 08.01, ASTM International, West Conshohocken,
PA, pp. 164169.
[14] ASTM D6093-97 (2003), 2009, Standard Test Method for
Percent Volume Nonvolatile Matter in Clear or Pigmented
Coatings Using a Helium Gas Pycnometer, Vol. 06.01, ASTM
International, West Conshohocken, PA, pp. 705707.
[15] ASTM D3505-96 (2006), 2009, Standard Test Method for Den-
sity or Relative Density of Pure Liquid Chemicals, Vol. 06.04,
ASTM International, West Conshohocken, PA, pp.372383.
[16] ASTM D1475-98 (2008), 2009, Standard Test Method for
Density of Paint, Varnish, Lacquer, and Related Products,
Vol. 06.01, ASTM International, West Conshohocken, PA,
pp.152155.
[17] ASTM D4052-96 (2002)e1, 2009, Standard Test Method for
Density and Relative Density of Liquids by Digital Density
Meter, Vol. 05.02, ASTM International, West Conshohocken,
PA, pp. 266270.
[18] ASTM D153-84 (2004), 2009, Standard Test Method for Spe-
cific Gravity of Pigments, Vol. 06.03, ASTM International,
West Conshohocken, PA, pp. 2933.
[19] ASTM D2320-98 (2008), 2009, Standard Test Method for
Density (Specific Gravity) of Solid Pitch, Vol. 05.01, ASTM
International, West Conshohocken, PA, pp. 880882.
[20] ASTM D2697-03 (2008), 2009, Standard Test Method for
Volume Nonvolatile Matter in Clear or Pigmented Coatings,
Vol. 06.01, ASTM International, West Conshohocken, PA,
pp. 339341.
[21] ASTM D1505-03, 2009, Standard Test Method for Density of
Plastics by the Density Gradient Technique, Vol. 08.01, ASTM
International, West Conshohocken, PA, pp. 329335.
[22] ASTM D4892-89, 2009, Standard Test Method for Density of
Solid Pitch by Helium Pycnometer Method, Vol. 05.02, ASTM
International, West Conshohocken, PA, pp. 842844.
[23] ASTM D4883-08, 2009, Standard Test Method for Density of
Polyethylene by the Ultrasound Technique, Vol. 08.02, ASTM
International, West Conshohocken, PA, pp. 678681.
[24] ASTM D1347-98, 1992, Test Method for Methylcellulose,
Vol. 06.02, ASTM International, West Conshohocken, PA, pp.
226231. Note: This method was withdrawn in 2003 and now
can be found in the historical archives of ASTM.
[25] ASTM D1493-03 (2008), 2009, Standard Test Methods for
Sodium Carboxymethylcellulose, Vol. 06.03, ASTM Interna-
tional, West Conshohocken, PA, pp. 248256.
[26] ASTM D2363-79 (2006), 2009, Standard Test Methods for
Hydroxypropyl Methylcellulose, Vol. 06.03, ASTM Interna-
tional, West Conshohocken, PA, pp. 346355.
Fig. 17Pigment volume relationships.
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389
INTRODUCTION
CHARACTERIZING THE SHAPE, SIZE AND SIZE-
distribution of particles that go into liquid paint or coating
formulations as well as dry formulated powdered coatings
are very important. These materials may vary from being
ground mineral fillers to crystalline epoxy cross-linkers and
catalysists used in finished powdered paint products. There
is a significant effect on the coatings density, mechanical
strength, electrical, thermal as well as sound and small mol-
ecule transmission properties as a function of the included
average particle size and shape.
An example of the importance of particle size is the
inclusion of crystalline dicyandiamide (dicy) as a cross-
linker in fusion bonded epoxy (FBE) powder coatings or
the blowing agent in fire resistive paints. Dicy is not
stable after melting and decomposes to gaseous products if
not consumed in a curing reaction with epoxy. The use of
the standard commercial particle size dicy in FBE formu-
lations leads to an unusual type of coating failure. In this
case, to remedy the problem, a separate step is performed
on the standard commercial-sized powdered dicy used in
FBE coatings to produce a micronized powdered dicy. If
micronized dicy is not used, it cannot be fully incorpo-
rated into the un-cured FBE matrix during the short time in
the extrusion process. This leads to very small regions of the
crystalline dicy cross-linker remaining after cure. Because
of its slight water solubility, tiny osmotic blisters are formed
causing the coating failure. This same material, dicy, is
used as a blowing agent in the formulation of intumesant
paints. In this case the dicy particle size incorporated into
the paint dictates the foam density produced on heating
and decomposition. This impacts the thermal transfer value
of the fire resistive paint.
Particle-size measurements associated with the paint
and coatings industry has broadened in scope considerably
over the past few decades. Not only must we evaluate the
size, shape, and size distribution of the pigments, fillers, and
emulsified resin particles used in the formulation of the coat-
ing system, but major efforts are now put forth to address
environmental and applicators health problems that are spe-
cific to particle size, nature, and morphology. Environmental
and economic concerns have been a substantial driving force
in the development of powder coating technology, which
requires monitoring finished powder size and size distribu-
tion to ensure consistent application parameters.
We have learned that the size, shape, and nature of
dust particles in the air we breathe during the manufacture,
application, and abrasive removal of paints are of utmost
concern to our health. Airborne dusts of silica and asbestos,
as well as lead- and chromium-laden paint debris generated
during abrasive blasting, are serious health threats. In an
effort to protect the general public, government regula-
tions now address the monitoring of small reparable dust
particles of less than 10 m (R10 particles) during the
abrasive removal of certain coatings.
In the production of electronic microcircuits, chips,
and semiconductors, photo-resist coatings are applied to
silicon wafers with line-to-line resolution of fractions of a
micron. Dust particles, which are a fraction of this size, if
allowed to contaminate the coated surface, will cause the
production of defective chips. Dust has forced the devel-
opment of more sophisticated clean-room technology in
recent years. The reject rate of produced microchips caused
by defects in the coating as a result of ultra-small particles
of dust is a major problem.
As technology advances in the evaluation of smaller-
size particle systems, materials used to standardize and
calibrate the measuring/monitoring equipment must be
developed. The necessity for standard traceable test mate-
rials, i.e., from the National Institute of Standards and
Technology (NIST), formerly National Bureau of Standards
(NBS), which are required to ensure the reliability of the
measurements, has led to secondary industries that pro-
duce these standards from various materials.
Due to pressing global concerns with solvents emis-
sions as well as the associated economic benefits, powder
coatings as a class have grown at a very fast rate over the
past 30 years. Many properties impacting the production,
delivery, application, and film-forming characteristics are
related to the average particle size of the manufactured
powder coating. Often, of equal importance, is the amount
of very small particles present. These fines impact flu-
idization and electrostatic application characteristics of the
powder coating.
With the exception of physically sieving a powder sam-
ple using different sized screens, particle size analysis usu-
ally employs laboratory instruments. These lab instruments
employ various physical principles. Current technology
instrumentation has the ability to determine particle size as
small as 0.003 m utilizing Quasi Elastic Light Scattering
35
Characterizing Particle Size and
Size Distribution
George D. Mills
1
1
Ph. D., President, George Mills & Associates International, Inc., Foley, AL 36535.
MNL17-EB/Jan. 2012
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390 PAINT AND COATING TESTING MANUAL 15TH EDITION
to 1200 m using electrical resistance zone sensing. These
technologies are addressed later.
Particle characterization methodologies currently
employed include:
Physically sieving using various screens having differ-
ent size openings;
Sedimentation (using centrifugal and gravity forces);
Surface area determination (employing both gasses
and liquids surface adsorption);
Individual particle sensing (light blocking and electri-
cal resistance);
Direct microscope measurements (static and dynamic
image microscopy, visual light microscopes and elec-
tron microscopes);
Light attenuation and scattering;
Liquid paint draw-down gage.
There are currently emerging techniques that employ
the physical principle of ultrasonics. The specific instru-
mental techniques include Acoustic Attenuation Spectros-
copy having a measurable size range of 0.05 to10 m. With
this technique concentrated colloids, emulsions, and sus-
pensions can be analyzed. When the transmission of light
through the sample is required to affect the particle size
analysis, the sample must be diluted considerably. Unfortu-
nately, some of these particle systems are not stable at these
dilutions. The use of ultrasonic waves of a range of frequen-
cies directed through the dispersed medium and accurately
measuring the attenuation at each frequency allows col-
lecting an attenuation spectrum that can be converted
to a particle size distribution as well as a measure of the
concentration of the dispersed phase. This has been made
possible by the recent development of ultrasonic transducer
and advancements in digital signal processing [1].
Another developing technique using ultrasonics is Elec-
troacoustic Spectroscopy (Electrokinetic Sonic Amplitude)
having a measurable size range of 0.1 to 10 m. Single Fre-
quency Colloid Vibration Current and Electrokinetic Sonic
Amplitude have a measurable size range of 10 nm to more
than 10 m. A major benefit is the ability to accept samples
as concentrated as slurries [2].
Although an understanding of the relationships of
powder properties to product application characteristics
and performance is important, quality assurance/quality
control (QA/QC) requirements demand high-speed, on-line
(real-time) monitoring. This demand for rapid, accurate
analysis of particle characteristics has been a driving force
in the development of current instrumentation. The avail-
ability of low-cost computers and pertinent software as
well as highly reliable and stable energy power sources and
detectors have allowed the development of fast, accurate,
broad spectrum, and in-process instrumentation. The
development of robust solid-state laser diodes has allowed
the replacement of bulky gas lasers, which required optical
table stability. Further, the development of fiber optics, as
well as the technology associated with its ease of alignment,
has assisted in downsizing the footprint of some current
generation instrumentation.
A major objective of this chapter is to provide an under-
standing of many of the various methodologies available for
evaluating particle size, shape, and distribution. The hiding
power and light transmission characteristics of coatings are
greatly affected by the particle size of included pigments
and fillers. Tensile strength of the cured system, water and
gas vapor transmission coefficients, chemical resistance,
and interface anticorrosive activity are only a few areas
impacted by the size, shape, nature, and size distribution of
the pigments and fillers formulated into the coating.
This chapter will allow an educated choice of tech-
nologies based on the size-dependent measurement most
related to the desired property of importance. An apprecia-
tion of the mathematics involved will aid in determining
and understanding the limitations and potential errors
inherent in the measurement.
History of Particle-Size Analysis
The earliest reported particle sizing was about 150 B.C. in
Greek and Roman mining manuals using sieves made of
leather, woven hair, and planks. The Germans introduced
wire-woven screens in the 15th century. Microscopes
were reportedly used in the 1700s for size analysis. Auto-
mated machinery was developed in the 1800s for weaving
metal-wire sieve fabric. In the late 1800s to early 1900s,
standards were developed defining sieve sizes. The first
apparatus of record used for classification of pigment par-
ticles into different sizes was reported by Thompson [3] in
1910. Oden proposed the use of gravity sedimentation as
early as 1916 [4,5].
Energy sources of various wavelengths, employing
many different configurations, have been used to measure
particle size. Visible light photometry was reported by Stutz
and Pfund [6] in 1927. Gamble and Barnett [7] employed
radiation in the near-infrared region. Atherton and Peters
reported using light-scattering techniques in 1953 [8]. The
electron microscope found use in the 1940s for character-
izing very small particles as well as to define the corre-
sponding surface topography. After the laser light source
was invented, light scattering technologies were expanded.
The development of better diode array detectors opened the
way for developing the fast light-scattering and blocking
instruments now widely used since the 1990s. The recent
advancements in transducer technology and digital data
collection are opening the way for the instruments using
ultrasonics mentioned above.
The latest technology since 2010 includes laser diffrac-
tion spectrometry, ultrasonic extinction, and photon cross
correlation spectrometry. There have been improvements in
image analyses, both static and dynamic. These technolo-
gies allow a particle size measurement range of 1 nm to
10 mm [9].
Importance of Particle-Size Analysis
As the physical properties of paints, coatings, and polymers
in general are impacted by the size, shape, and size distri-
bution of the fillers included in the formulation, it is imper-
ative that characterization of the pigment and filler system
be correlated with the physical properties of the coating.
Because of the early importance of zinc oxide as a pig-
ment in oil-based paints and its existence in multi forms
and shapes, this material was studied in the 1920s and
1930s. Bunce [10] found that as the average diameter of
zinc oxide in paint increased from 0.19 to 0.31 m, the
elongation of the film increased and the load at the break-
ing point decreased (Fig. 1). Eide [11] showed that coarse
acicular zinc oxide imparted greater durability to a paint
than did round zinc oxide. In related studies, Morris [12]
and Nelson [13] found evidence that acicular asbestine of
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 391
a wide distribution of sizes favorably influenced the dura-
bility of paints, and a review by Jacobsen [14] cites many
examples of the significance of particle size and shape of
pigments and extenders on the optical and physio-chemical
properties of coating systems.
Many surface properties are impacted by the pigments
and fillers particle size and nature of which gloss is one
of the most prevalent. While the larger-size particles can
protrude through the surface of the coating, causing a
surface roughness related to the size of included particles,
extremely fine particles can affect gloss by adsorbing
binder to a point that the gloss is decreased due to a lack
of available binder at the coating surface. The oil adsorp-
tion of the pigment is a function of its surface area and
increases as the average particle size decreases. ASTM
D1483 presents a standard test method for determining
the oil absorption of a pigment [15]. The critical pigment
volume concentration (CPVC) exists at a pigment loading
such that there are just enough binder solids to completely
wet out the included filler and pigment particles. Coatings
formulated above the CPVC cannot be glossy. Abrasion
resistance of the coating may be increased by the addition
of hard fillers such as silica. The relationship between par-
ticle dimensions and film properties is depicted in Fig. 2.
The National Paint, Varnish, and Lacquer Association
has published a Pigment Index that gives information on
the particle size of many of the pigments available on the
American market [16].
Other coating properties impacted by variations in
particle size and shape include the efficiency of contained
ultraviolet (UV) blockers and absorbers such as carbon
black pigments. The use of acicular (needle-like) pigments
such as Wollastonite (asbestos free) is popular in many
types of coatings. The tensile and compressive strength of
coatings also can be modified by judicial choice of particle
size and shape, and gas vapor and molecular water vapor
transmission of a coating can be altered with the proper
choice of pigment loading, shape, and size.
The coalescent and film-forming characteristics of
emulsion binders are impacted by the particle size of the
dispersed resin particles. Cold touch-up, brush ability,
and mechanical stability during pigment dispersion are a
function of properties that are related, in part, to polymer
particle size. Surfactant demand and effectiveness are a
function of polymer particle size (as well as other binder
variables). Because of the importance (dependence) of
many coating properties on the small finite size of the
pigment, fillers, catalysts, and polymers formulated into
the coating, the demand for rapid, accurate analysis of
particle characteristics has led to the refinement of many
techniques.
CONSIDERATIONS IN SAMPLING TECHNIQUES
Normally, when a particle-size determination is made, one
will not work with the total collection of particles compris-
ing the bulk sample. A representative collection of par-
ticles is usually chosen. This sample is then reduced in size
a few more times until only a few milligrams remain for
the actual instrumental testing. The assumption is usually
made that the fraction actually evaluated is, in fact, identi-
cal in particle size, size distribution, shape, and nature to
the total of the bulk material. This, essentially, is never true.
This sample test fraction, which usually does not exactly
represent the bulk, can be a major source of error, intro-
ducing considerable bias and distortion to the results. The
reliability of any measurement depends on the degree of
representativeness of the test sample. Thus, the sampling
technique is often more important than the actual particle-
size measurement.
Theoretical Considerations of Variance
inSampling
To obtain a representative sample, the sampling process is
usually divided into several steps during which a conscious
effort is made to reduce bias. The bulk material is usu-
ally obtained in huge, ton lots. The first sample reduction
Fig. 1Stress-strain curves of some paint films. These illustrate the effect of the particle size of zinc oxide on the strength
of paint films.
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392 PAINT AND COATING TESTING MANUAL 15TH EDITION
provides the gross sample, which is on the order of kilo-
grams. This sample is then reduced to the laboratory
sample, which is on the order of grams. The actual evalu-
ation sample introduced to the instrument is on the order
of milligrams. The reduction process, almost always, will
introduce some bias, depending on the actual spread in
the distribution. This bias will diminish as the consistency
approaches unity, i.e., all particles approach being identi-
cal. The bias exists because the physical forces acting on the
particles in a collection are not the same, but are, in fact,
size dependent. The fines act differently in a pile than will
the coarse particles. Their angle of repose is different, often
resulting in particle stratification and some segregation.
There are some established rules that must be followed
to minimize this bias. The perfect sample is one in which
the differences seen between the evaluated characteristics
and those that actually exist in the bulk can be ascribed
to the expected number variations described by statistics.
For a sand (A) and sugar (B) mix, the probability that the
number fraction, p, of (A) in the bulk actually is represented
by the number fraction (pi) in the sample is computed
from the number of actual particles in the bulk (N) and the
reduced sample (n) [17]. The equation is as follows:
Var( )
( )
p
p p
n
n
N
i
j
(
,
\
,
(
1
1
(1)
Theoretically, the expected deviation (i.e., standard devia-
tion),
i
, is the square root of the variation. Since the use of
the weight fraction is often more convenient, the equation
for variance is given by
Var( )
( )
[ ( ) ] P
P P
w
Pw P w
w
W
i B A
+
j
(
,
\
,
(
1
1 1
(2)
where the weight fraction in the sample and bulk are P; and
P, respectively, W and w are the bulk weight and sample
weight, respectively, and w
A
and w
B
are the weights of indi-
vidual grains of A and B, respectively.
Even with the perfect sample, there is a finite prob-
ability that the measured sample will deviate from the
actual bulk by some predictable value. To minimize this
guaranteed deviation, a minimum sample size is required.
One may calculate the minimum sample size required to
yield values within preset statistical limits [18]. The equa-
tion relating the minimum sample weight of a gross sample
is given by
M w d
s
1
2
1 2 10
2 3 3
[ / ][ / ]
(3)
where:
M
s
= the limiting weight in grams,
= the powder density in g/cm
3
,
2
= the variance of the tolerated sampling error,
w
,
,
]
]
]
]
18
1 2
g(
p
)
/
(4)
where:
D = diameter of sphere,
= medium viscosity,
v = velocity of fall under influence of gravity,
g = gravitational constant,
p
= sphere density, and
= medium density.
Most often, the particles are not exactly spherical.
Because of this, it is difficult to relate a particles dimensions
directly to the observed settling rate. The usual procedure is
to use Stokes equation to determine the values for d from
the sedimentation distance and its corresponding time. The
value so determined is then the Stokes diameter of the
particle. The definition then becomes the diameter of a
sphere that has the same density and free falling velocity (in
Fig. 6Ro-tap testing sieve shaker. (Courtesy of W. S. Tyler Co.)
http://www.wstyler.com/html/ro_tap.html.
Fig. 7Diagram of the Allen-Bradley sonic sifter. (Courtesy of Allen-
Bradley Co.)
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396 PAINT AND COATING TESTING MANUAL 15TH EDITION
a given fluid) as the particle being investigated (within the
range of Stokes law).
This practice avoids the problem of variations in free
fall velocities caused by shapes that differ from being a
sphere. The assumption holds and permits useful compari-
sons of the size distributions when similar types of materials
are evaluated. The size distribution of particles of different
shapes may be compared provided that the phenomenon
being studied is dependent on its behavior in the fluid.
While the concept of the Stokes diameter is useful, it
is necessary to appreciate its limitations. One should not
equate the Stokes diameter to a sphere of equal volume
or other related quantity. Two types of errors may be intro-
duced. In the first case, errors arise when the particles
movements depart from Stokes law and, in the second case,
errors are introduced by the experimental technique itself.
Departure from Stokes law can occur when flow condi-
tions are not met. Stokes equation is valid under laminar
flow only. Consequently, there is an upper limit to the size
of a particle that can be evaluated in a given liquid. Large
particles can experience too high a velocity in the liquid and
create turbulent flow. Vortexes in the liquid in the vicinity
of other particles also introduce errors. Laminar flow is
determined by the Reynolds number experienced by the
particle/ fluid system at the fall rate. The Reynolds number,
Re, is defined as
Re = vd/ (5)
where v is the velocity in the fluid, d is the diameter in cen-
timeters, is density of the particle in grams per milliliter,
and is the viscosity in poise. According to British Stan-
dard (B.S.) 3406 [27], the value of Re cannot exceed 0.2 if
the introduced error from Stokes law deviation is to be less
than 5 %. This would imply that the upper limit of particle
size would depend on both the viscosity and density of the
fluid. For water, this value would place an upper limit of
about 60 m. However, as might be anticipated from the
Reynolds equation, this limit may be stretched somewhat
when using either more dense or more viscous liquid media
than water.
Another problem arises when the concentration of par-
ticles is too great. The Stokes equation assumes single par-
ticles having no influence from the wall of the vessel or other
particles in close proximity. Wall effects are minimized by
employing properly sized vessels. While some investigators
have recommended that the volume concentration should
be kept less than 0.05 %, others recommend concentrations
of up to about 0.5 to 1 % by volume. Certain investigators
feel that this compromise introduces systematic errors and
renders the method inappropriate as an absolute measure,
although it is suitable as a routine control method. The floc-
culating nature of the powder in the test fluid will impact
the maximum concentration that can be used. B.S. 3406
recommends a concentration of 1 % by volume, although
it cautions that, under certain circumstances, a small inter-
ference may occur. Because of the potential introduction of
systematic errors at higher concentrations, efforts to refine
the technique so that reduced concentrations are used are
underway. Precision with differentials no more than 4 %
are usually expected.
Another problem that must be addressed is the tem-
perature stability of the liquid. Not only is there a change
in the liquid viscosity, but thermally produced convection
currents grossly impact the sedimentation process. Because
of the difficulty in maintaining thermostatic control over
the long periods required for gravitational settling, there is
usually a lower particle-size limit of about 2 m when water
is used as the suspending liquid.
GRAVITY SEDIMENTATION
The analysis of particles by sedimentation is possible
because of Stokes law, which states that the time of fall
of a particle through a viscous medium is proportional
to the particles density (the difference between it and the
medium) and its diameter. Of course, if the density of the
medium were greater than the particle, the particle would
float. Another requirement is that all of the particles must
have a common density. This rules out mixtures of different
minerals and pigments having different densities since they
cannot be determined together.
Because of the time required for sedimentation to
occur, the simple gravimetric method and the photometric
method appear to be limited to pigments of sizes above
0.5 to 1.0 m. Cadle [28] and Orr and Dallavalle [29] have
reviewed the many variations of the method. Gravity set-
tling was first proposed by Oden [30,31]. Calbeck and
Harner [32] were among the first to use the technique for
paint pigments; Jacobsen and Sullivan [33] brought the
method to a higher degree of refinement by using an ana-
lytical balance with one of the pans replaced with a cup
submerged in the suspension.
Hydrometer Method. The density of a dispersion is pro-
portional to the concentration of the dispersed material,
and methods for particle-size analysis based on the use of
Fig. 8Alpine air-jet sieve. (Courtesy of Gilson, Inc.)
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 397
the hydrometer have been developed. One such method is
ASTM Method for Particle-Size Analysis of Soils (D422).
Another, developed in large part by Bauer [34], is Techni-
cal Association of the Pulp and Paper Industry Method
T649sm, Determination of Particle Size of Clay. Included
in the method is a nomograph by Casagrande [35] to aid
in the calculations. The same nomograph is found in Test
Method for Particle Size Distribution by Hydrometer of the
Common White Extender Pigments (D3360) [36].
Radioactivity Method. Connor and Hardwick [37] report
on this method for determining the height of the sedimen-
tation. The radioactivity is either induced in the specimen
or is used as an external probe. The technique avoids dis-
turbing the suspension by periodic sampling and can be
used with both gravity and centrifugal sedimentation.
CENTRIFUGAL SEDIMENTATION
The centrifuge is used to provide an accelerating force for
sedimentation analysis. Configurations exist using rotating
disks with see-through ports as well as holders of small
see-through cells.
Disk Centrifuge. The technique for the disk centrifuge
was developed by Atherton et al. [38]. The apparatus might
be considered to be a direct descendant of the single cell
centrifuge of Donoghue [39] and the scratch start technique
of Marshall [40]. The range is from 0.01 to 0.5 m.
The apparatus consists of a centrifuge unit, a sam-
pling unit, and an electronic control unit [41]. The rotor
of the centrifuge is a cell (hollow disk) of plastic or glass
that rotates on a horizontal axis (Fig. 9). The back wall is
attached to the shaft of the rotor. The front wall has a hole
in the middle that serves as an access port. The inside diam-
eter of the standard cell is 10 cm, and the width is 1 cm. In
operation, the cell takes liquid up to a minimum radius of
2.3 cm. The speed ranges from 500 to 8000 rpm.
The sampling unit (Fig. 10) consists of a probe con-
nected to collection flask and a clock motor. The probe is
an L-shape thin-wall steel tube arranged to rotate about
the axis of one arm. The other arm terminates in a sharp
bevel for scooping up the contents of the cell in a manner
analogous to that of an inside cutter in a lathe. The center
of rotation of the probe lies below the center of the rotor.
To make a test, an appropriate volume of spin fluid,
typically a 4 % sucrose solution, is transferred to the rotat-
ing cell. After swirling stops (20 to 30 s), the specimen
usually 0.5 ml of a 0.5 % dispersionis expelled from a
syringe against the back wall near the center of rotation.
The specimen flows outward over the wall unit it reaches
the free surface of the spin fluid, where it forms a band
about 1 mm thick. The spin fluid and the dispersion do not
mix because of the higher density of the former. Thus, zero
time for the measurement is defined rather accurately.
After the desired time, spin fluid is withdrawn from
the cell with the probe, which is driven by a clock motor at
1 rpm. With the pickup end of the probe in the 12 oclock
position, the motor is started automatically. All but 5 ml of
the spin fluid is removed for measurement of the under-
sized fraction of the dispersed powder.
The development of detector systems must consider the
action on a transmitted light beam. Light-scattering theory
dictates that when light of intensity I
0
attempts to pass
through a dilute suspension (i.e., no multiple scattering) of
particles, it is lost or extinguished to an extent that I
t
makes
it through. Mathematically [42,43], the transmitted light is
given by
I
t
= I
0
exp(
ext
L) (6)
where L is the length through the suspension, and
ext
is
the attenuation coefficient (turbidity). The value of
ext
is
related to the number concentration of particles, N per unit
volume, by
ext
= NC
ext
(7)
where C
ext
is the extinction cross section of the particles.
The extinction efficiency of a particle of cross-sectional
Area A is conveniently expressed as
A = C
ext
/Q
ext
(8)
This yields the relationship
ext
= Nd
2
Q
ext
/4 (9)
Fig. 9Diagram illustrating the principle of the disk centrifuge. (Courtesy of Joyce, Loebl & Company, Ltd.)
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398 PAINT AND COATING TESTING MANUAL 15TH EDITION
Photo extinction detectors on modern turbidity instruments
essentially determine
ext
. The internal calculation of Q
ext
requires knowledge of the particle refractive index, size,
shape, orientation, state of polarization, and wavelength
of the scattered light as well as the refractive index of the
suspending liquid. Using Mie theory [44,45], size may be
deduced. Oppenheimer [45] has pointed out that a source of
potential error is that the refractive index of the suspending
liquid and particles must be known for each wavelength.
Rotating Cell Holder Centrifuge. Real time monitoring is
provided on some instruments and is advantageous when
irregular measurements force an abort. One such instru-
ment can perform centrifugal as well as gravity analysis
using the same on-board computers. With ten different
rotor speeds switchable from 300 to 10,000 rpm, an acceler-
ating potential of up to 9000 g is available. Particles as small
as 0.01 m are reported to be measurable.
The instrument uses two small, transparent rectangular
cells (Fig. 11) mounted opposite each other on the balanced
rotor. While they counterbalance each other, one serves as
a reference for the suspension liquid, and the other holds
the particle suspension system under analysis. Three photo-
cells in the top monitor three opposite light-emitting diodes
(LED) on the back side of the rotor. This allows real-time
monitoring of the reference cell, the sample cell, and the
rotor speed (Fig. 12). Data are displayed in real time on a
built-in computer monitor as well as printed out on tape
after the analysis for a permanent record. Graphs are pre-
sented indicating the absorbance versus time, frequency
distribution, and cumulative distribution (either percent
undersize or percent oversize).
Particle Size from Surface Area Employing
Both Gasses and Liquids
It is often useful to use the approximation of size from
surfaces to evaluate other parameters derivable from the
volume function, such as specific surface area and density.
The basic equations that describe a spheres surface area
and volume are given by
Area of a sphere = D
2
(10)
Volume of a sphere = D
3
/6 (11)
These relationships allow determination of the mean
particle diameter if the specific surface (area) is known.
Particle-size characterizations that employ surface area
techniques in the size determination yield average diame-
ters. The surface area of a powder may be determined from
gas adsorption experiments. By assuming uniform-size
non-porous and spherical particles, the mean particle size
may be determined from the surface area data. The spe-
cific surface obtained equals the determined surface area
divided by the product of the particle volume and density.
With appropriate units conversion
D = 6/[A] (12)
where:
D = particle diameter, m,
= particle density, g/cm
3
, and
A = specific surface area, m
2
/g.
Any shape other than a sphere, either regular or
irregular, has a greater ratio of surface to volume, and
consequently the particles will be smaller than calculated.
Cracks, crevices, and pores are other factors leading to an
increase in specific surface area and to a corresponding
decrease in calculated particle size.
Perfectly spherical particles are seldom encountered
in mineral pigments and fillers used in paint and coating
applications since these particles result from shatter-
ing by crushers and high-speed pulverizers. Crystalline
materials fracture along crystal planes, while some pig-
ments are acicular (like needles). With the many shapes
Fig. 10Relationship of disk and probe of disk centrifuge sampling. (Courtesy of Joyce Loebl & Company, Ltd.)
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 399
Fig. 11Reference cells used in a centrifuge. (Courtesy of Horiba Instruments, Inc.). www.horiba.com/us/en/scientific/products/particle-
characterization/particle-size-analysis/.
Fig. 12A modern instrument for determining particle size in real time.
of particles to be evaluated and characterized, instru-
ments that operate on different principles see different
values of the size-dependent variable being monitored.
As a result, a sample characterized by one machine may
yield a somewhat different value when evaluated using
a different technique. For this reason, the practitioner
must be aware of the size-dependent variable to which his
machine is sensitive.
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400 PAINT AND COATING TESTING MANUAL 15TH EDITION
Methods [46] for determining specific surface include
adsorption of gases by the pigment, adsorption of solutes
from solutions by the pigment, and permeability of pressed
pigment particles to gases or liquids.
Adsorption of Gases
This method is based on determining the number of gas
molecules that will adsorb as a monomolecular layer on
the surface of the particles. Knowing the area occupied by
one molecule and the number of molecules, the specific
surface area of a specimen of pigment may be calculated
from
= nNA (13)
where:
= specific surface area in cm
2
,
n = number of moles of gas per gram of pigment,
N = Avogadros number, 6.02 10
23
, and
A = area covered by each molecule.
Knowing the specific surface, the surface mean diam-
eter may be calculated.
Brunauer-Emmett-Teller (BET) Method. The general
procedure for this method [47,48] includes introducing
the specimen into an enclosed space of known volume
followed by degassing with heat and evacuation. A known
amount of gas is admitted to the system, and its pressure is
determined. The gas is then compressed to a new volume,
and the corresponding pressure is determined. The pro-
cedure is repeated until enough data for the preparation
are obtained. By means of the BET equations, the surface
area is found, and from it the average particle size may be
calculated.
Continuous Flow Method. This method makes use of
the BET equation, but the adsorbed gas is determined by
concentration measurements in a continuous flow system
[49]. Nitrogen gas is adsorbed by the specimen at liquid
nitrogen temperature from a stream of nitrogen and helium
gas and is later eluted by warming the specimen. The
amount of nitrogen liberated is estimated by thermal con-
ductivity. For detecting changes in the amount of adsorbed
nitrogen, Beresford et al. [50] used the Perkin-Elmer-Shell
sorptometer with conductivity bridge and potentiometric
recorder.
Gravimetric Method. In addition to the volumetric
methods, a gravimetric method using balances patterned
after that of McBain and Bahr [51] can be used. The proce-
dure is much simpler but requires care as the apparatus is
very fragile and the changes in weight are very small.
An essential part (Fig. 13) of the gravimetric method
is a fused silica spring balance from which a small glass
bucket for the specimen is hung. The balance assembly
is located in a glass housing connected to a source of gas
and to a manometer for determining the pressure. The
bucket is hung on the balance, the housing is closed,
and the specimen is degassed by evacuation. The zero
point of the balance is recorded. Gas is admitted to the
housing, and the change in weight of the specimen is
determined by noting the change in the elongation of the
balance with a traveling microscope. Details are set forth
in Ref. 17.
ADSORPTION OF NONGASEOUS MOLECULES
Adsorption of molecular species other than typical gaseous
molecules is possible also. These include the adsorption of
solvents and surfactants in special cases.
Adsorption of Solutes onto Pigments. This method
depends on the adsorption of solute molecules onto a
particle when it is wet out by a solution containing the
dissolved surface active solute [52]. The process requires
that the adsorbent be thermodynamically more active
than the solvent and the kinetics be such that wet-out
times be reasonable. Typical systems used are stearic
acid in benzene, dyes in benzene, and wetting agents
in water. The amount adsorbed will asymptotically
approach a constant value with time. At this value it is
assumed that the surface of the particles is covered with
a mono-molecular layer of solute. The area occupied by
a single molecule of solute may be obtained from tests
made with solids of known areas. The amount adsorbed
is obtained by analysis of the solution before and after
adsorption.
A disadvantage of the method is uncertainty about the
size and orientation of certain types of molecules. On the
other hand, the method is rapid and easy to perform. For
this reason it is suited to routine tests where its reliability
has been established.
Soap Titration of Emulsion Particles. Maron et al. [53]
determined surface area and particle size of a synthetic
latex by titrating with a soap until the critical micelle con-
centration of the soap in the solution was attained. From
the effective molecular surface area of the adsorbed soap
and the amount adsorbed, surface area and particle size
are calculated. The method is calibrated with electron
micrographs. Brodnyan and Brown [54] also studied the
technique.
Fig. 13The components of a basic gravimetric adsorption
apparatus.
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 401
Permeation Through Packed Powders
In this method, a gas, usually air, is forced through a com-
pacted bed of the pigment. The rate of flow is a function of
voids (pore space), pressure drop through the bed, specific
surface of the pigment, and viscosity of the gas. Knowledge
of all the other factors allows calculation of the specific
surface area and, from it, the mean surface diameter. The
method is fairly simple and is suitable for routine determi-
nations of spherical or near-spherical particles.
Gooden-Smith Method. Using air as the gas, Gooden
and Smith [55] designed a permeation method with two
special features: (1) the weight of specimen used in grams
is numerically equal to its density and (2) every specimen
is packed to the same volume (Fig. 14). Together with a
graphic calculator, these features greatly simplify the test
and make it attractive for routine testing or research in the
particle-size range 0.2 to 50 m.
Hutto-Davis Method. The principal differences between
this and the preceding method are: (1) the weight of the
powder used to make the compacted pellet is calculated
to give a definite porosity, and (2) the volume of air is kept
constant for all plugs.
Hutto and Davis [56] modified the apparatus of Car-
man and Malherbe [57] by providing an improved manom-
eter, better control of the volume of air, and an improved
press for preparing the specimen. They also designed a
nomograph for calculating specific surface and surface
area. The apparatus consists of: (1) a U-tube with legs of
unequal length and closed at each end with a sintered glass
disk, (2) a manometer, (3) a capillary specimen tube, and
(4) a leveling bulb containing mercury.
To provide the constant volume of air, the U-tube is
inverted and filled through the stopcock at the bend. Then,
with a capillary eyedropper, a weight of mercury equivalent
to 1 ml is removed, leaving an equal volume of air after
which the stopcock is closed and sealed. The mercury
does not pass through the sintered glass disk at the pres-
sure used in the test. To make a test, a plug of pigment is
formed inside the specimen tube using the special press.
The weight of the specimen is a function of its density and
the desired porosity of the plug (usually about 0.5). With
the leveling bulb in the lower position, the specimen tube
is attached to the side arm of the apparatus, and a vacuum
is applied by opening the stopcock at the upper right-hand
corner. The vacuum is adjusted, and simultaneously the
stopcock is closed, timing is started, and the leveling bulb
is raised to its upper position, which forces the 1 ml of air
into the system. The timing is stopped when the manometer
returns to zero. The stopcock is then opened, and the bulb
is returned to its lower position for another run.
Individual Particle Sensing by Light Blocking
and Electrical Resistance
In this technology, individual particles are separated from
each other by a diluted suspension in either air (by fluidiza-
tion followed by entrainment in a flowing stream) or a con-
stantly stirred conductive solution. The particles are then
forced to pass through the sensing zone. In one air-fluidized
instrument, the time of flight between two precisely placed
laser light sources and detectors is used to calculate size.
In another, the attenuated light as detected by a photo-
diode is used to calculate a size. In the liquid suspension
instrument, a change in the established electrical resistiv-
ity through an electrolyte circuit is measured as a particle
passes through a small orifice.
TIME OF FLIGHT FROM LIGHT BLOCKAGE
An instrument based on aerodynamic time-of-flight (TOF)
technology was developed by Dahneke [58]. The measure-
ment range is reported to be from 0.2 to 200 m, with 150
channels per decade and a count rate of up to 100,000
particles per second. Output may be reported in either geo-
metric or aerodynamic diameter. In this instrument, a gas
(usually air for pigment particles) is used to break down
agglomerate material and entrain them in a controlled flow;
a specially designed pulse-jet dispenser is used where a
Fig. 14Gooden-Smith apparatus for surface area. (Courtesy of Official Digest.)
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402 PAINT AND COATING TESTING MANUAL 15TH EDITION
controlled flow of air is directed down onto a sample placed
into a small cup (Fig. 15). Depending on the nature of the
sample, the operator sets the computer values for particle
count rate, flow pressure, and pulse pressure. The disperser
flow pressure controlling the carrier gas usually remains
constant. The disperser pulse pressure determines the num-
ber of particles fed through the analyzer.
Measurements are made over 2 s intervals to ensure
that the minimum count rate is met. Should the count
rate fall below the predetermined count rate, the pressure
is increased. Should the count rate exceed the maximum
allowed, the pressure is dropped by a factor of 2, thus
maintaining the number of counts between the allowed
maximum and minimum.
The particles are deaggregated to primary size and
fed into the injection tube of the sonic nozzle suspended
as single particles in the air stream moving at about 6 L
per minute. There is no operator involvement during the 1
to 5 min determination. Two laser beams set at a discrete
distance apart and directed onto two photomultipliers
make up the sensing zone (Fig. 16). As the particle passes
through the set of laser beams, light that is attenuated and
scattered is monitored by the detectors. Signal analysis
using cross-correlation techniques give the particles TOF
with a resolution of 25 ns. The technique is reported to be
able to discriminate between particles with only a 10 % size
difference. Attachments to the instrument also allow the
investigation of sprayed aerosol droplets as well.
ELECTRICAL RESISTANCE
According to the Coulter principle [59,60], when a particle
suspended in an electrically conductive liquid enters a con-
stricted path between electrodes, it changes the pathway
electrical resistance between the electrodes. This change
produces a fluctuation in the applied voltage that, under
proper conditions, is inversely proportional to the vol-
ume of the particle. When the dispersion is made to pass
through a hole small enough to pass the particles one by
one, the resultant series of voltage fluctuations may be elec-
tronically amplified, scaled, and counted [61].
A functional diagram is shown in Fig. 17. The beaker
and tube contain the suspension. When the stopcock is
opened, a controlled vacuum starts flow of the suspension
from the beaker into the tube and also unbalances the mer-
cury in the manometer. The stopcock is then closed, and
the mercury siphon continues the flow of the suspension.
Electrical contacts in the manometer start and stop the
counting of the particles. The volume of the manometer
tube between the contacts determines the volume of the
Fig. 15A diagram of the operation of the dry-powder pulse jet disperser. (Courtesy of Amherst Process Instruments, Inc.)
Fig. 16Schematic of the aerosol beam generator and detection
mechanism. (Courtesy of Amherst Process Instruments, Inc.)
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 403
specimen. This ranges from 0.02 to 5 ml. A fresh volume is
drawn for each count. A typical count requires from 3 to 30
s, depending on the size of the hole and the volume between
the contacts in the manometer. The Coulter counter was
found to be useful by Princen et al. [62] for particle-size
determination of emulsified oil systems.
The principle utilized to determine individual particle
size is the electrical resistance of the particle as it is forced
to pass through a small hole in a glass envelope through
which an electrical potential exists.
Direct Microscopic Measurement Using Visual
Light Microscopes and Electron Microscopes
Microscopes, both optical and electron as well as auto-
mated image analyzers, are used to measure particle size
directly. Optical techniques suffer somewhat from an
inability to focus on the edge of a particle at very high
magnifications due to a depth of field problem. The lower
limit is set by its resolving power and the upper limit by its
depth of focus. The microscope is especially useful for mea-
surement of plate-like and needle-shape particles that do
not obey Stokes law, on which the sedimentation methods
are based. Disadvantages of the method are that it is slow
and laborious. Hence, it is used chiefly for the calibration
of the more rapid relative methods. ASTM Practice for Par-
ticle-Size Analysis of Particulate Substances in the Range of
0.2 to 75 m by Optical Microscopy (E20) and a paper by
Loveland [63] are good references. Dark field illumination
can use the detecting power of the microscope rather than
the resolving power for sizes below the resolving power of
the optical microscope.
Green [64] was the first investigator to systematize
the use of the microscope for direct measurement. He
dispersed the pigment in a medium on a microscope slide,
photographed the dispersion at a known magnification,
and projected the image on a screen to increase the magni-
fication for measurement. Dunn [65] bypassed the photo-
micrograph by projecting the image of the particles directly
from the slide on the screen.
Ideally, the pigment should be dispersed in the medium
in which it is used, but this is rarely done. Green used tur-
pentine, Allen [66] recommended a viscous vehicle, and
Eide [67] used fused resins. Gehman and Morris [68] milled
the pigment in rubber, dissolved the mix in a solvent, and
applied the suspension to the slide.
Microscopes equipped with view-through linear scales,
circles or ellipses in graduated sizes, may be used as a direct
measurement method [69]. The comparison scale may
be a micrometer eyepiece, an eyepiece reticule, or a scale
engraved on the microscope side.
The use of the electron microscope for particle charac-
terization is now a routine practice. The resolving power is
many times that of the light microscope and may be used in
scanning as well as transmission mode. With state-of-the-
art surface analysis tools such as energy dispersive x-ray
(EDX) built into the scanning electron microscope (SEM)
equipment, elemental analysis of a single-pigment particle
within the coating matrix can be done conveniently while
the coating sample is in the instrument.
ARRAY METHOD USING OPTICAL MICROSCOPE
The array method of particle sizing lends itself to systems
of monodispersed spheres, as in Fig. 18 (from Duke [69]).
These are highly uniform with respect to diameter. When
placed on a flat plate, the spheres tend to align themselves
into hexagonal arrays. These are characterized by straight
rows of the particles. Because of this, the rows can be mea-
sured, and the diameter of the particles may be derived by
dividing by the number in the row.
TRANSMISSION ELECTRON MICROSCOPY
Transmission electron microscopy (TEM) is useful for the
measurement of latex microspheres of 200 nm and larger
[70,71]. The procedure usually utilizes the magnifica-
tion factor of the microscope in the size determination
from photomicrographs. Because this factor is not always
dependable, photographs are sometimes made against a
replica diffraction grating of known spacing. Fig. 19 shows
100-nm latex microspheres on a 2160-line/mm grating.
Sources of error include uncertainty in the accuracy of the
line spacing, the roughness of the lines, and the line thick-
ness relative to the size of the particles. Duke [72] has used
an internal standard of NIST traceable materials, as shown
in Fig. 20, and reports accurate sizing to as small as 50 nm.
Chromatography: Angstrom Particle Sizing
The separation of angstrom-sized particles may be affected
by the use of hydrodynamic chromatography. In this
Fig. 17The Coulter principle: A fluctuation in current flow
occurs when a particle partially blocks the small opening between
the electrodes. The size of the particle is related to the amount of
change in current flow.
Fig. 18Microphotograph of 10 micron particles in array. (Photo
compliments of Thermo Fisher Scientific Inc.)
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404 PAINT AND COATING TESTING MANUAL 15TH EDITION
technique, the mixture of very small particles is allowed to
transgress a long capillary tube in which the liquid medium
is flowing in laminar flow. It is well known that fluids,
both gasses and liquids, will experience a pressure drop as
a function of distance traveled and of the diameter of the
tubing that occurs because the fluid in actual contact with
the wall of the tube does not flow and is stationary. For
noncompressible fluids (i.e., liquids), this variation in flow
velocity from wall to center of tube may be used to separate
particles of differing size.
For laminar flow, the velocity of flow through the
cross section of the tube increases from the wall to the
center, essentially in concentric layers [73]. This may be
represented by the vectorial diagram in Fig. 21 of the flow
velocity profile. The actual velocity of flow of one of the
concentric circular layers will be a function of its dis-
tance from the wall of the tube. The flow velocity gradient
is given by
V
P P R
r R
r
L
( )
[ ( / ) ]
0
2
2
4
1
L
(14)
where:
V
r
= liquid velocity at radius, r,
(P
0
P
L
) = pressure drop for the distance, L,
R = inside radius of capillary,
R = effective radius of liquid at V
r
,
= viscosity of fluid in flow, and
L = length of capillary.
Because the larger particles tend to have statistically
more volume in the fluid away from the wall, the larger
particles are under a greater influence of the faster-moving
fluid away from the wall more so than the smaller particles,
which can physically fit in the slower-moving layer nearer
the wall. Thus, the larger particles advance faster than the
smaller ones affecting the separation.
Light Attenuation and Scattering Techniques
Spectrophotometric Techniques. Gamble and Barnett [74]
developed a method for measuring particle-size distribution
by the scattering of light in the near infrared. The pigment
is dispersed in low concentration and placed in a transmis-
sion cell for spectrophotometric measurement. From the
shape of the spectrophotometric curve, the relative size and
size distribution characteristics of an unknown pigment are
obtained in terms of calibrated samples (Fig. 22).
Bailey [75] also developed a spectral transmission
method using infrared wavelengths from 0.4 to 2 m. The
spectrophotometric curve was related to size by graphic
comparison with specimens of known sizes.
Atherton and Peters [76] measured light scattering by
polydispersed system of spherical particles. The size distri-
bution curves for the materials compared favorably with
direct measurement with the electron microscope.
Leobel [77] used a spectrophotometer to obtain the
effect of wavelength on turbidity in the determination of the
size of latex particles. The sizes of particles used for calibra-
tion were determined from electron micrographs.
LIGHT-SCATTERING TECHNIQUES
When solid particles pass through a light beam, the light
will interact with the particles in one or more ways. It can
Fig. 19Microphotograph of 100-nm latex spheres against a 2160-
line/mm grating. (Photo compliments of Thermo Fisher Scientific Inc.)
Fig. 21Vectorial representation of the velocity of a fluid (gasses
and liquids) in laminar flow. The velocity at the wall of a pipe is zero
and a maximum at the center in the absence of turbulent flow. The
rate of increase in velocity toward the center is a function of the fluid
viscosity in the absence of turbulent flow. (Drawing compliments of
George Mills, Jr. Building Design Solutions, LLC.)
Fig. 20TEM 450 nm particles with 100 nm microspheres on a
smooth substrate with NBS SRM 1691 as an internal standard.
(Courtesy of Thermo Fisher Scientific Inc.)
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 405
either be reflected, refracted, diffracted, or adsorbed and
reradiated. This is shown schematically in Fig. 23. The
scattered radiation will present a pattern that is depen-
dent on the shape and size distribution of the particles.
By evaluating the scattered radiation detected at different
locations relative to the beam direction and in different
positions, much can be learned about the scattering media.
Fig.24 depicts some of the angular intensities of scattered
light produced by particles of various sizes. With low-cost
computers and stable detectors, instruments have been
developed that can monitor this scattered radiation, giving
fast and reliable data.
Angular-dependence techniques, which include detec-
tion and manipulation of signals from front (reflection) as
well as side and rear (diffraction), have been integrated into
a single instrument. Angular-dependence, light-scattering
techniques have been widely studied for information con-
cerning the sizes of both pigmentary and nonpigmentary
particles. In the latter class, polymeric organic materials
from molecular to latex sizes have been included. Debye
and Bueche [78] described how to characterize the optical
inhomogeneities related to size from information concern-
ing the way a system scatters light.
Angular-dependence techniques include the work of
Brice et al. [79], who designed a photoelectric photom-
eter for measurement of molecular weight by applying the
Debye theory.
Aughey and Baum [80] note that particles in the size
range of large molecules produce variations in the intensity
of light scattered at large angles to the illuminating beam.
Progressively larger particles produce significant variation
in the light scattered at small angles. The light source is
a well-defined monochromatic beam. The cell containing
the dispersion is stationary, and the photoelectric tube
travels around the cell in an arc that covered a useful
range from 0.05 to 140. Scattered light reaches the tube
through a small aperture in the housing for the tube. The
radii of the optical inhomogeneities range from 0.1 to
100m. Modern diode array detectors are now available to
do similar tasks without the movement.
Diffraction of Laser Light. Instruments using diffraction
of single-wave-length laser light have been made possible
by the development of low-cost, highly stable lasers and
diode array detector technology. By fluidizing the particles
in a stream of air, they are directed through a cell being
illuminated by a laser source. The HeNe laser, emitting a
coherent beam of 632.8 nm wavelength, is often used. To
increase the cross-sectional area of the beam, expanders are
often employed (Fig. 25).
The diffraction pattern that is seen by the detector is
a pattern of rings varying in darkness depending on the
size distribution of the passing particles. On-board com-
puters use both the Fraunhofer diffraction and Mie scat-
tering theories to calculate the particle-size distribution
Fig. 22Particle size may be determined from the scattering of
radiation in the near infrared region of the spectrum.
Fig. 23Possible interactions when light strikes a particle. (Drawing
compliments of George Mills, Jr. Building DesignSolutions, LLC.)
Fig. 24Angular intensity of scattered light after striking a particle.
(Drawing compliments of George Mills, Jr. Building Design Solutions,
LLC.)
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406 PAINT AND COATING TESTING MANUAL 15TH EDITION
Fig. 25Schematic layout for the large-particle system. (Courtesy of Horbia Instruments, Inc.)
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 407
of the sample. These methods allow the determination
of size distribution based on the intensity distribution of
the diffracted laser beam. Since the intensity pattern is a
function of the actual particle size, mixtures of particles
having different densities may be measured together, unlike
those relying on Stokes law. The instrument is reported to
address 0.1 to 200 m particles.
Total Light Scattering. Instruments capable of moni-
toring light from all sides can effectively measure par-
ticles even smaller than the usual limit of 0.1 m. This
limit is imposed because of the physics relating the wave-
length of the incident radiation and the interacting par-
ticles. By taking advantage of a set of detectors located
strategically around the scattering cell, data relating
to even very small particles less than 0.1 m are deter-
mined. As the size of the particle decreases, the intensity
of the scattered light obscures critical differences in the
angular distribution. In practice, this difficulty in treat-
ment of data leads to the so-called laser-diffraction mea-
surement barrier.
Since there is an increase in both the side and rear scat-
tering with very small particles, it is possible to take advan-
tage of the phenomenon. Fig. 26 is an instrument diagram
with an arrangement of detectors that allow a single instru-
ment to measure a broad range of sizes. Light irradiating
the particles is scattered at various angles. For relatively
large particles, light is scattered in the forward direction,
while, for smaller particles, the light tends to be scattered in
all directions. By arranging a lens system and manipulating
data from the detectors, the particle-size distribution is cal-
culated from the Mie theory. Since the size of the particles
measured is a function of the wavelength of the impinging
radiation, the instrument uses a beam of filtered blue light
to expand the range.
X-RAY SCATTERING
The Debye-Scherrer small angle x-ray scattering technique
for observing interference effects related to particle size is
well known [81]. Some generalizations on the use of the
technique were addressed by Debye [82].
Yudowitch [83] and Danielson et al. [84] both employed
the diffraction peak procedure for the determination of
latex particle size. For control they used a latex whose size
had been determined under the electron microscope.
Particles that are perfect spheres can be described by a
single value representing the spheres diameter. Calibrated
microscopes are useful in reading such values directly from
the reticule. They have some utility with spherical resin
particles and with visual measurement of standardized
test materials. Classification of most powders, on the other
hand, must address particles of various shapes and sizes
together as a collection.
A particle-size determination utilizes some size-depen-
dent property that can be measured and then relates
Fig. 26Schematic layout for a system measuring both large and small particles. (Courtesy of Horiba Instruments, Inc.) www.horiba.com/us/
en/scientific/products/particle-characterization/particle.
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408 PAINT AND COATING TESTING MANUAL 15TH EDITION
this property to a linear dimension. The measurement
derives either from individual particles or as a prop-
erty of the collection of particles that is often expressed
as a diameter of sorts. Measurement of a single indi-
vidual particle may have its size expressed in differ-
ent diameters depending on the direction and method
of view. Particle characterization may involve deter-
mining the rate of a particles travel through a fluid
(either under the influence of gravity or while being subjected
to angular acceleration due to rotation), its actual surface
area, its ability to pass through a screen of square or round
holes of differing size, or its ability to scatter light of various
wavelengths in various directions. For the new technology
employing ultrasonics, the interference of sound transmis-
sion through a liquid is used to correlate a size distribution.
It is convenient to use the term equivalent diameters
when comparing sizes. The value so determined for a given
collection of irregular particles will vary somewhat depend-
ing on the technique used (i.e., the size-dependent variable
being measured). The definition of some of these diameters
is presented in Table 2 along with their mathematical rep-
resentation. Table 3 lists some of the methods, the nominal
particle-size range, and the size measured. The methods
available for determining particle size take advantage of
many different characteristics of the powder particle.
Definitions of Particle Size and Shape
Particle shapes are everything but spherical for pigments
and fillers that are produced, essentially, by crushing and
shattering. As the sizes get smaller, the actual particle shape
plays an increasingly important role in its use in a coating
as well as on the physical laws employed for its character-
ization. From the diagram in Fig. 5, the same particle may
be defined in a number of ways [85]. Some of these include
the following:
Martins Diameter. The distance between opposite sides
of a particle measured on a line bisecting the projected
area. To ensure statistical significance, all measurements
are made in the same direction regardless of particle ori-
entation.
Ferets Diameter. The distance between parallel tangents
on opposite sides of the particle profile. Again, to ensure
statistical significance, all measurements are made in the
same direction regardless of particle orientation. Note:
TABLE 2Definitions of particle size
Symbol Name Definition Formula
d
v
Volume diameter Diameter of a sphere having the same volume as the particle
V =
6
d
v
3
d
s
Surface diameter Diameter of a sphere having the same surface as the particle
S = d
s
2
d
S
v Surface volume
diameter
Diameter of a sphere having the same external surface-to-volume ratio
as a sphere
d =
d
d
sv
v
3
s
2
d
d
Drag diameter Diameter of a sphere having the same resistance to motion as the
particle in a fluid of the same viscosity and at the same velocity (d
d
approximates to d
s
when Re is small)
F = C A
v
2
D D pf
2
where C
0
A = f(d
d
)
F
d
= 3d
d
v Re < 0.2
d
f
Free-falling diameter Diameter of a sphere having the same density and the same free-falling
speed as the the particle in a fluid of the same density and viscosity
dst Stokes diameter The free-falling diameter of a particle in the laminar flow region (Re
<0.2)
d
d
d
st
v
d
2
3
=
d
a
Projected area
diameter
Diameter of a circle having the same area as the particle resting in a
stable position
A d
a
=
4
2
d
P
Projected area
diameter
Diameter of a circle having the same area as the projected area of the
particle in random orientation
Mean value for all possible
orientations d
P
= d
s
for convex
particles
d
c
Perimeter diameter Diameter of a circle having the same perimeter as the projected outline
of the particle
d
A
Sieve diameter The width of the minimum square aperture through which the particle
will pass
d
F
Ferers diameter The mean value of the distance between pairs of parallel tangents to
the projected outline of the particle
d
M
Martins diameter The mean chord length of the projected outline of the particle
d
R
Unrolled diameter The mean chord length through the center of gravity of the particle
E d d d
R
( ) =
R
0
2
R
1
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 409
Both Martins and Ferets diameters are generally used for
particle-size analysis by optical and electron microscopy.
Equivalent Circle Diameter. The diameter of the circle
having an area equal to the projected area of the particle in
random orientation. This diameter is usually determined
subjectively and measured by ocular micrometers called
graticules.
Equivalent Spherical Diameter (E.S.D.). This often
affords a more useful measure, particularly where indus-
trial processing is involved. This diameter is determined,
in effect, by measuring the behavior of the irregular
particle in a certain circumstance and relating that to the
behavior of a sphere of otherwise identical properties.
Sedimentation (Stokes) E.S.D. The diameter of a sphere
of the same density as the particle and having the identical
free-fall velocity of the particle.
Volume E.S.D. The diameter of a sphere having the
same volume as the particle.
Drawdown Techniques for Texture
and Oversize
During the manufacturing of paints and coatings, there
is a need for rapid, on-the-floor testing to determine
whether a dispersion has reached its maximum grind. The
grind gages were developed to provide quick, on-the-spot
answers. Some of the tests could be done in the factory
at the disperser during the grinding stage of production.
Actually, during the production of paints and pigmented
coatings, the pigments are not ground but are only wet out
and dispersed to their primary size. This primary size is
the smallest possible size supplied from the producer.
TABLE 3Comparison of particle-sizing
methods
Nominal
Range, m
Size Determined
Gas Permeability
Gas Adsorption
Brownian Motion
0.140
0.00550
0.013
Mean
Mean
Mean
Sieving
Dry >10 Passing through
Wet 274 minimum opening
Microscope
Optical 0.5500 Martins, Ferets, or
equivalent circle
diameter
Electron 0.00215
Zone sensing
Resistivity 0.05500 Volume or area
Optical 1500
Elutriation
Laminar flow 375 Equivalent spherical
diameter (E.S.D.)
Cyclone 850
Centrifugal classification 0.550 E.S.D.
Mercury intrusion 0.01200 E.S.D.
Centrifugal
sedimentation
E.S.D.
Mass accumulation 0.0525
Photo extinction 0.5100
X-ray 0.015
Gravity sedimentation E.S.D.
Pipettes and
hydrometers
1100
Photo extinction 0.05100
X-ray 0.160
Hydrodynamic
chromatography
Packed column 0.032 E.S.D.
Capillary column 0.160
Cascade impactor 0.0530 Aerodynamic
diameter
Fig. 27Hegman fineness-of-dispersion gage. (Compliments of
Lynn Shirey.)
Fig. 28ASTM dispersion gage and scraper.
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410 PAINT AND COATING TESTING MANUAL 15TH EDITION
THIN-FILM DRAWDOWN FOR OVERSIZE PARTICLES
This test [86] is suited particularly for detecting oversize
particles that adversely affect the gloss of high-gloss indus-
trial enamels. A 2-mL wet film of the enamel is spread on
a glass plate with a Bird applicator blade. Inspection of the
film is best made in a dimly lit room with the operator fac-
ing a light source such as a window or under a fluorescent
light with a grid that can be reflected from the wet paint
sample. With the eye focused on the silhouetted image of
the window sash or the reflected pattern from the light or
ceiling, extremely fine particles may be detected and com-
pared with a visual standard. They appear as a roughness
to the wet surface.
A variation of this approach is to illuminate the speci-
men at grazing incidence with a spotlight and view the film
through a magnifier parallel to the specimen. Still another
version is the use of wedge-shape or step-wise multithick-
ness films.
FINENESS-OF-DISPERSION GAGES
Drawdown tests for the detection of oversize particles led
to development of fineness-of-dispersion gages, or, as first
called, fineness-of-grind gages. The gage is a steel block
in which is cut a wedge-shape channel, tapering usually
from 4 mils at the deep end to zero at the other end,
though other depths and different widths and lengths of
the channel are available. Some gages have twin channels.
An excess of the sample is placed in the deep end of the
channel, and the excess is drawn to the shallow end with a
scraper. At some point along the channel, coarse particles
or agglomerates become visible. The results are interpreted
by reference to standard reference patterns. The addition
of slow-evaporating solvents may be required to thin down
the system to allow more time for reading the gage without
experiencing volume loss by evaporation.
Fig. 29Typical pattern produced by a dispersion gage.
Fig. 30The roller particle-size analyzer.
Fig. 31Felvation. Fractionating powders into different sizes by a
combination of fluidization, elutriation, and sieving. (Courtesy of
Chemical and Engineering News.)
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CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 411
St. Louis Gage. This [87], the first of the dispersion
gages, was designed to facilitate the use of the North Stan-
dards. The channel is 2 in. (51 cm) long and 0.005 in. (0.13
mm) deep at the deep end. The sample and the selected
North Standard are placed side by side in the deep end,
drawn by a scraper toward the shallow end, and compared.
Hegman Gage. The Hegman gage [88,89] (Fig. 27) made
the North standards and the St. Louis gage obsolete. It is
essentially a St. Louis gage with the addition of a scale to
show the depth of the channel or the distance from the
deep end. Instead of evaluating the dispersion in terms
of the North standards, the distance from the deep end is
reported. The finer the dispersion, the greater the distance.
This is the reverse of the North standards, where the finer
the dispersion, the lower is the number of the standard.
ASTM Gage. The gage specified in ASTM Test Method
for Fineness of Dispersion of Pigment-Vehicle Systems
(D1210) is almost identical to the Hegman. The steel block
(Fig. 28) is about 180 mm long, 63.35 mm wide, and 12.7
mm thick. The channel is 100 m deep at the heel. The
gage is calibrated according to depth in steps of 10 m
along one edge and to the corresponding nearest 0.1 mil
along the other. The dimensions of the scraper are shown
in the diagram.
Experience has shown that the speed of drawdowns
and the angle at which the scraper is held have no impor-
tant effect on the results. However, the time lapse between
the drawdown and reading, as well as operator technique,
are important [87]. Readings should be made within 10 s
after completion of the drawdown, especially for disper-
sions with a rating of seven or better due to the volume
loss from solvent evaporation. Good practice suggests
three drawdowns using fresh material each time. The first
drawdown allows accommodation to the light source and a
rough estimate of the dispersion pattern and the end point.
Subsequent readings may then be made within 3 or 4 s.
ASTM directs viewing the drawdown with the line of vision
at a right angle to the long dimension of the channel and
at an angle between 20 and 30 with the face of the gage
in a light that renders the pattern readily visible. Diffuse
subdued light is preferred.
Elimination of operator variance is aided by the use of
six standard patterns. Fig. 29 illustrates reading of the end
points, and the scales show the depth of the channel. This
scale appears to have some advantage over both the North
and the Hegman scales as it is related directly to the dimen-
sions of the oversize particles. Other scales in use include
the FSCT (Federation of Societies for Coatings Technology)
scale, which divides the distance into ten parts.
Constant Depth Gage. The channels in this gage are of
constant depth rather than tapered as in the gages previ-
ously described. The gage most often used has four chan-
nels, 1/2 in. (1.3 cm) wide and 6 in. (15 cm) long, having
depths of 0.002 (0.005 cm), 0.0015 (0.0038 cm), 0.0010
(0.0025 cm), and 0.0005 in. (0.004 cm), equivalent to Heg-
man values of 4, 5, 6, and 7, respectively. Other depths
can be supplied. The advantage of this type of gage is the
long path available for inspection, a condition that should
minimize the influence of bubbles and foreign matter on
the ratings.
NPIRI Grindometer. Printing ink films are much thin-
ner than those of paints or coatings. Relatively fine particles
in the latter would be considered relatively coarse in the
ink. Because of this, the printing ink range is addressed
with a gage designed by the National Printing Ink Research
Institute (NPIRI) called the Grindometer [90,91]. The chan-
nel of this gage is only 0.001 in. deep at the deep end, is 1 in.
(2.54 cm) wide, and the scale is graduated in steps of 0.0001
in. (0.000 25 cm) [92].
X-RAY MICRORADIOGRAPHY TECHNIQUE
This technique detects undispersed clumps of pigment
(inorganic types only) in paint. It uses low-energy x-rays
[93] to resolve oversize material in the range of 1 m or
less, which is below the range detectable with fineness-of-
dispersion gages.
A thin film of paint is spread over the surface of photo-
graphic-sensitized, fine-grain film. The specimen is exposed
to x-rays and the film developed after removal of the paint.
The film is enlarged optically to reveal silhouettes of the
oversize materials on a photographic negative. Determina-
tion of size may be made following the methods used for
light and electron microscopy.
Separation and Collection: Particle Size
by Elutriation
This approach is primarily a means for separating or frac-
tionating a quantity of pigment into portions according
to particle size rather than providing a value of the sizes
separated. Size determinations may then be made on the
separated fractions. The technique has utility in evaluat-
ing the influence of pigment and filler particle size on the
properties of the formulated product. After standardizing
operating conditions for a material and measuring sizes by
an independent method, approximate size distribution may
be estimated for additional material.
Roller Particle-Size Analyzer. This device [94] uses elu-
triation by air to separate pigments into sizes. The glass
U-tube at the bottom of Fig. 30 is charged with the speci-
men of pigment. Air under pressure is admitted through
a nozzle that extends to the bottom of the tube. The other
arm of the tube is connected to the metal settling tube.
By proper selection of size of nozzle, size of settling tube,
and velocity of the air, separation into desired fractions is
obtained. The fractions are collected in paper extraction
thimbles connected with a gooseneck to the settling tube.
During the separating, the U-tube and the settling tube are
vibrated vigorously. Using 25-g charges, the average time
required for separations ranges from 62 min for particles
up to 5 m in diameter to 11 min for particles from 40 to
80 m in diameter.
Felvation. This method [95] combines elutriating and
sieving for fractionating fine powders. The basic apparatus
(Fig. 31) consists of a column about 4 in. (10 cm) in diam-
eter and 24 in. (61 cm) in height. The specimen is placed
in the narrow tube at the right. Fluid is introduced and
allowed to pass through at a relatively low rate. The powder
soon becomes fluidized in the conical base of the column.
The flow of the liquid is increased gradually. The smaller
particles reach the sieve and pass through it. The throttling
action of the sieve increases the flow through it. Hence,
particles that have passed through do not fall back and clog
the screen. Eventually, particles just larger than the sieve
openings reach the sieve, but they do not block the screen
as they reduce the flow around them and then tend to fall
from the sieve.
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412 PAINT AND COATING TESTING MANUAL 15TH EDITION
The sieve functions only as a gage. It does not support
the powder. Highly accurate electroformed sieves are used,
but, because of their small size [1 in. (2.5 cm) in diameter],
their cost is reasonable. Besides being economical, the
method is rapid. Complete fractionations can be run in a
period as short as 10 min.
THE ROLE OF PARTICLE-SIZE REFERENCE
TEST MATERIAL
Carefully prepared particles of known size and composi-
tion have become an important part of testing for emul-
sions, powders, film, and processes. When properly used,
reference particles are an important factor in demonstrat-
ing compliance with standards such as ISO-9000, U.S.
Food and Drug Administration (FDA) Good Manufacturing
Practices, and various military specifications [96]. In the
past two decades, the need for instrument calibration has
prompted the establishment of several businesses special-
izing in the production and supply of reference particles,
which are available in assortment of materials of various
sizes, densities, and grades.
A brief discussion of some typical applications will
illustrate the usefulness of these test reference particles.
They are used for instrument calibration, filter checking,
flow tracing, and evaluation of processes such as blending,
cleaning, and spraying, to name a few.
Instrument calibration and checking covers two broad
classes: (1) particle-size analyzers and (2) particle contami-
nation analyzers. Both types of instruments are calibrated
or controlled by spherical particle-size standards, primarily
polystyrene microspheres, which are normally measured
and calibrated by methods traceable to the National Insti-
tute of Standards and Technology (NIST). The spherical
calibration particles have fairly predictable instrument
responses and are available as aqueous suspensions of
highly uniform particles in discrete sizes (diameters) from
0.02 to 2000 m. In addition to polystyrene spheres, which
may be nonfluorescent or may contain various fluorescent
dyes, calibration spheres are composed of silica and glass.
Nonspherical materials such as alumina, quartz, and vari-
ous milled powders are available as experimental materials
or controls.
Particle-size spectrometers are used to measure the
particle-size distribution of powders, suspensions, emul-
sions, and aerosols. Other than composition, particle-size
distribution is probably the most important variable in
product quality and performance. The major class of
instruments, particle counters, is used to measure trace
amounts of particle contamination in air, water, chemicals,
beverages, and medicines. A recent variation of the par-
ticle counter can measure particle contamination on flat
surfaces, such as silicon wafers, and a variety of optical
and electronic parts. These instruments, as well as optical
and electron microscopes, require calibration and refer-
ence particles to assure both the quality and traceability of
measurements.
In addition to instrument evaluation and calibration,
reference particles are used to verify retention ratings and
pore-size distribution of air and liquid filter media. Using
aerosol particle generators and precision particle counters
up and down stream, high-efficiency particulate air (HEPA)
filters can be certified for use in ultraclean manufacturing
operations for rigorous contamination control. Polystyrene
spheres with approximately a 0.25-m diameter are fre-
quently used for this purpose.
Another broad class of reference particle application
is their use in validating processes, such as for cleaning,
blending, dispersing, separation, and spraying. Fluorescent
particles, which have bright and distinctive colors that can
be contrasted with other background materials, are fre-
quently used to follow the flow or direction of a process.
Other materials such as pollens, ground walnut shells,
refractory powders, or other materials of the desired par-
ticle size and specific gravity are available as model systems
for evaluating processes.
In conclusion, reference particles are a key ingredient
of modern testing methods, and their use should be con-
sidered at an early stage in any QA/QC program as quality
management programs require the regular and timely eval-
uation and standardization of particle-sizing equipment.
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Downloaded/printed by
Universidad Nacional de Colombia pursuant to License Agreement. No further reproductions authorized.
CHAPTER 35 CHARACTERIZING PARTICLE SIZE AND SIZE DISTRIBUTION 413
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414 PAINT AND COATING TESTING MANUAL 15TH EDITION
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neous Solid, J. Appl. Phys.,Vol. 20, 1949, p. 518.
[79] Brice, B. A., Halwer, M., and Speiser, R., Photoelectric
Light-Scattering Photometer for Determining High Molecular
Weights, J. Opt. Soc. Am., Vol. 40, 1950, p. 768.
[80] Aughey, W. H., and Baum, F. J., Angular Dependence Light
ScatteringA High Resolution Recording Instrument for
the Angular Range 0.05-140, J. Opt. Soc. Am., Vol. 44, 1954,
p. 833.
[81] Marculaitis, W. J., Particle Size and Particle Size Distribution
of Pigments by Small Angle X-Ray Scattering, J. Colloid Sci,
Vol. 12, 1957, p. 581.
[82] Debye, P., Light Scattering as a Tool, Official Digest, Federa-
tion of Paint and Varnish Production Clubs, Vol. 36, 1964, p. 518.
[83] Yudowitch, K. L., Latex Particle Size from X-ray Diffraction
Peaks, J. Appl. Phys., Vol. 22, 1951, p. 214.
[84] Danielson, W. E., Shenfil, L., and Du Mond, J. W. M., Latex
Particle Size Determination Using Diffraction Peaks Obtained
With the Point Focusing X-Ray Monochromator, J. Appl.
Phys., Vol. 23, 1952, p. 860.
[85] HORIBA: PARTICLE SIZING SEMINAR, Notes and Work-
book, Horiba Instruments, Inc., Irvine, CA, 1992, p. 5. www.
horiba.com/us/en/scientific/products/particle-characteriza-
tion/particle-size-analysis/.
[86] Pigments Division, duPont Co., White Pigments for Paint, Sec-
tion 2, 1956, p. 11.
[87] St. Louis Paint and Varnish Production Club, Effects of
Wetting Agents upon Pigment Dispersion, Scientific Section
Circular, National Paint, Varnish, and Lacquer Association,
No. 471, 1934, p. 429.
[88] Fasig, E. W., The Hegman (Sherwin-Williams) Fineness
Gage, Drugs, Oils, and Paints, Vol. 54, 1938, p. 438.
[89] Purdy, J. M., The Hegmen Fineness Gage, Paint, Oil, and
Chemical Review, Vol. 109, 1946, p. 14.
[90] Doubleday, D., and Barkman, A., Reading the Hegman Grind
Gage, Official Digest, Federation of Paint and Varnish Produc-
tion Clubs, Vol. 22, 1950, p. 598.
[91] National Printing Ink Research Institute, The NPIRI Produc-
tion Grindometer, Project Report 12, 1949.
[92] Walker, W. C., and Zettlemoyuer, A. C., Fundamentals of Grin-
dometers, American Ink Maker, Vol. 28, No. 7, 1950, p. 31.
[93] Venuto, L. J., and Hess, W. M., A New Look at Carbon Black,
American Ink Maker, Vol. 45, No. 10, 1967, p. 42.
[94] Roller, P. S., Measurement of Particle Size with an Accurate
Air Analyzer, Proceedings, ASTM International, West Con-
shohocken, PA, Vol. 32, Part II, 1932, p. 607.
[95] Anonymous, Felvation Speeds Powder Fractionation, Chem.
Eng. News, 6 March 1967, p. 50.
[96] Private communication with Stan Duke, Duke Scientific
Corp., Palo Alto, CA, 1993.
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415
36
NOMENCLATURE
Fluidity integral
Rate of decay of roughness amplitude, s
1
Time constant characteristic of a critical shear rate, s
Dimensionless shear strain
Shear strain rate, s
1
w
Wall shear rate in tube flow, s
1
Phase shift; thickness of adsorbed polymer layer
Extensional (Hencky) strain, dimensionless
Extensional (Hencky) strain rate, s
1
Coefficient of viscosity
0
Zero-shear viscosity
d
Dispersion viscosity
e
Extensional viscosity
l
Liquid-phase viscosity
Relative viscosity
d
/
l
Dynamic viscosity
[] Intrinsic viscosity (limiting viscosity number)
Angle of inclination with respect to the vertical
Wavelength of coating surface striations; elastic stress
relaxation time constant
Kinematic viscosity
Ratio of circumference of a circle to its diameter
Density
Surface tension
Shear stress; generalized stress
0
Stress imposed at zero time; Yield stress
e
Tensile stress
s
Tangential surface shear stress
w
Wall shear stress
Viscosity-kinetic time constant for drying, wicking, or
thixotropy
Volume fraction of internal (dispersed) phase of a
dispersion
e
Effective volume fraction for a dispersion
Plateau modulus
G*
Complex shear modulus
G Storage modulus
G Loss modulus
K
Consistency in power law model; constant in viscosity-
molecular weight equation
L
Capillary tube length
M
w
Weight-average polymer molecular weight
M
c
Critical (entanglement) polymer molecular weight
P
Pressure
Q
Volumetric flow rate
R
Capillary tube radius; particle radius; air bubble radius
T
Absolute temperature
T
g
Glass transition temperature
a
Curvature parameter in Eq (15); amplitude of coating
surface striations
a
0
Time-zero amplitude of coating surface striations
e
Base of the natural logarithmic scale 2.71828
f
Frequency, hertz
g
Gravitational acceleration
h
Film thickness
k
Boltzmanns constant; general rate constant
l
Length
m
Kinetic energy correction term for capillary tube flow,
Eqs (74) and (75)
n
Power law exponent
t
Time
v
Velocity
x
Coordinate parallel to substrate
y
Coordinate normal to substrate
INTRODUCTION
THIS ARTICLE PRESENTS A BRIEF REVIEW OF
principles and methods of rheological analysis for the coat-
ings industry. However, the information and methodology
discussed applies equally well to the characterization of
coatings, adhesives, inks, and sealants. These products
share a common task, in that they are applied to a sub-
Rheology and Viscometry
1
Richard R. Eley
2
1
Portions of this article are excerpted, by permission, from Rheology in Coatings, Principles and Methods, by R. R. Eley, in Encyclopedia of
Analytical Chemistry (2000), John Wiley & Sons Ltd., Chichester.
2
Senior Scientist, AkzoNobel Packaging Coatings, Strongsville Research Center, 16651 Sprague Road, Strongsville, OH 44136.
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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416 PAINT AND COATING TESTING MANUAL 15TH EDITION
strateand must functionas a thin film. The process of
application and film formation obviously requires not only
a large total deformation, but also a high degree of control
of flow, in order to achieve success. Flow cannot be con-
trolled unless it is properly measured. Typical industrial
viscosity test methods have several faults: (1) the methods
do not closely relate to actual industrial processes, (2) the
test devices are unsuitable for non-Newtonian fluids, (3)
the result is usually a single point, and (4) in general, such
measurements do not correlate well to performance. The
objective for the applied rheologist, therefore, is to develop
methods of rheological characterization that
1. yield accurate data for complex fluids and
2. can be specifically related to the critical processes that
paints must undergo. To meet the latter goal requires
characterization methods that cover a wide range of
stresses and time scales.
Though all other properties be acceptable, a coating will
usually not meet with success if the rheology is not. Experi-
enced formulators say that more than half the cost of new
product development is consumed in getting the rheology
right. Furthermore, minor changes in a raw material or
process can create significant and unexpected variability in
product rheology, and such problems naturally require urgent
solution. For these reasons and others, rheological analysis is
a vital and cost-effective tool for the coatings industry.
The performance of coatings is governed by viscosity
variations over a span of several orders of magnitude in
shear rate or shear stress (at least four to as many as eight),
if processes ranging from coating application, to leveling
and sagging, to pigment settling are considered. To char-
acterize fluid rheology over such a broad range of stress
and deformation requires a research-quality rheometer.
In order to take advantage of the capabilities built into the
sophisticated rheological instrumentation now available,
more than a passing knowledge of the subject of rheology
is required. This chapter is therefore tutorial in style, aim-
ing to provide the novice an entry point to the discipline.
Certain concepts are discussed at some length because of
their importance or complexity. One of these is viscoelastic-
ity. It is worth the time because (a) a number of commercial
instruments are capable of viscoelastic characterization of
materials and (b) it is established that viscoelasticity exerts
control over coating processes when present.
Finally, in the words of Professor Ken Walters, rheol-
ogy is a difficult subject. This is certainly true, as it com-
bines several disciplines under one banner: mathematics,
physics, physical chemistry, colloid and polymer science,
fluid mechanics, etc. In addition, the experimental meth-
ods used are often complex and highly specialized. Fur-
thermore, rheology requires mastery of concepts peculiar
to the science, with which most persons have had limited
opportunity to become familiar in the normal course of a
technical education. Nevertheless, it is quite possible for
the nonspecialist to acquire a useful working knowledge of
the principles and practice of rheology, which may be used
profitably to understand the link between formulation and
performance of coatings.
DEFINITIONS OF BASIC TERMS
Rheology
The term rheology derives from the Greek , which
means to flow. Rheology is defined classically as the
study of the deformation and flow of matter, and may be
defined operationally as the study of the response of cer-
tain materials to stress. In order to quantify the deforma-
tion and flow behavior of materials, three basic terms must
be defined. The first two of these relate to the measurement
of the deformation (strain and strain rate) and the third to
the measurement of the force required to deform a mate-
rial (stress).
Deformation (Strain)
A deformation (or strain) is a change in shape and/or volume
of a material in response to an applied stress. There are two
principal types of deformation: reversible (elastic, rubber-
band-like), and irreversible (inelastic or viscous). Irrevers-
ible deformation is the definition of flow. Rheologically
interesting materials display a third type, in which either
or both viscous and elastic response to stress can be seen,
depending on the rate or the duration of stress applied.
During the lifetime of a coating the deformation his-
tory may be complex (see Table 1), the most important
deformation types being simple shear and extension. For
purposes of definition, we will limit our discussion to
simple shear. Simple shear deformation is analogous to the
spreading of a deck of playing cards, each card representing
a thin volume element (or shear plane) displaced relative to
its neighbor (Fig. 1). If a force F is applied to the uppermost
volume element (thickness dy), the material will deform by
the displacement of adjacent volume elements by a distance
dx. The total thickness is y, and the total displacement is
x. The shear strain is the ratio of the net displacement x
to the distance of separation of the confining surfaces y,
x
y
(1)
Strain Rate
Unlike solids (e.g., rubber band), liquids cannot support a
constant deformation or strain. Thus, in order to measure
the viscosity or resistance to flow of a fluid, we do not
measure the deformation (strain), but, instead, the rate of
deformation (strain rate). The strain rate is the change in
strain per unit time, or the time derivative of the strain,
symbolized
x
t
x/ y
t
x/ t
y
v
y
( ) ( )
(2)
For the case of simple shear deformation the strain rate
is termed the shear rate. The dimensionality of is LT
1
L
1
(e.g., cm s
1
cm
1
). Unit cancellation leaves reciprocal
time (s
1
) as the unit of shear rate. It is conceptually helpful,
however, to remember that, as shown by Eq (2), the shear
rate is actually a velocity gradient (v/y, change in velocity
per unit gap between shearing surfaces).
Stress
Force applied to a material creates a state of stress within
the material. Stress can be expressed in units of force per
unit area (e.g., dyn cm
2
), or, equivalently, energy per unit
volume (e.g., erg cm
3
). In terms of Fig. 1, the shear stress
is the force F necessary to maintain steady shearing
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 417
motion against the resistance of the confined fluid, divided
by the area of the shear face A,
F
A
(3)
The stress is determined both by the magnitude of the
applied force and by the area over which it is applied. Stress
can therefore be thought of as a kind of force intensity or
the concentratedness of the force. Consider the analogy of
a bowling ball placed on a mattress. It sinks deep into the
mattress because the area over which its weight is applied
is relatively small. However, if a two-foot square board were
placed under the ball first it would barely sink at all. The
depth to which the ball sinks into the mattress depends on
the area over which the force is applied. The smaller the
area of contact of the weight with the mattress, the higher
the stress, and the greater the resulting strainthe deeper
the weight sinks.
Viscosity
The viscosity of a fluid characterizes its resistance to flow.
The resistance to flow is, in turn, a measure of the friction
between the flow units of the fluid (e.g., molecules), and
may also be a measure of the forces of interaction between
the flow units. Thus, a viscous fluid (one reluctant to
flow) may be so because of high molecular weight (as in
motor oil) or be of relatively low molecular weight, but
having strong inter-molecular interactions (e.g., hydrogen
bonds, as between sugar molecules in honey).
The interaction of molecules in flow dissipates
energy, chiefly as frictional heat. Flow, therefore, is a
process that costs energy, of which the viscosity is a mea-
sure. For the case of shear deformation, the viscosity is
calculated as the ratio of shear stress to shear rate. The
viscosity, following from the discussion above, is there-
fore the energy per unit volume dissipated to attain a unit
velocity gradient,
(4)
Modulus
Materials comply with an applied stress by deforming or
undergoing strain. For ideal Hookean materials, the strain
will be proportional to the applied stress. The modulus is Fig. 1Diagram for term definitions for simple shear.
TABLE 1Rheological components of coating processes
Process Deformation Type or Attribute Rheological Property
Roll coating Squeezing flow Biaxial extensional viscosity
Stretching flow Uniaxial extensional viscosity
Shearing flow Shear viscosity
High strain rates High-shear viscosity
Large accelerations
Elasticity (G)
Large decelerations
G recovery
Surface area transients Dynamic surface tension
Spray High shear rate High-shear viscosity
Large accelerations
Elasticity (G)
High-strain-rate extensional deformation Extensional viscosity/elasticity
Surface area transients Dynamic surface tension
Brushing/rolling Medium shear rate Shear viscosity
Stretching flow Extensional viscosity/elasticity
Surface area transients Dynamic surface tension
Leveling/sagging Slow shear flow Low shear stress viscosity
Surface-stress driven Dynamic surface tension
Transient (nonequilibrium process) Structure recovery kinetics
Curtain coating Stretching flow Extensional viscosity/elasticity
Surface area transients Dynamic surface tension
Shear (pumping, extrusion) Shear viscosity
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418 PAINT AND COATING TESTING MANUAL 15TH EDITION
the proportionality constant between the stress and strain,
as in
G
(5)
where the shear modulus G is equal to the ratio of the shear
stress to the shear strain. Most polymeric materials and
coatings systems, in the solid state, are non-Hookean, i.e.,
the modulus is not a material constant, but will depend on
both rate and extent of deformation.
Units
Various systems of units for rheological variables may be
encountered in the literature. Until recently, the most com-
mon system of units for rheological terms was the cgs (cen-
timeter-gram-second), or small metric system. However,
international convention now specifies Systme Internatio-
nale (SI) units as the standard. The SI system is based on
the large metric, or MKS (meter-kilogram-second) units,
with some additional named units. The units associated
with the above defined variables according to the various
units systems are given in Table 2.
GENERAL CLASSIFICATION OF FLUID BEHAVIOR
Newtonian Fluids
Isaac Newton postulated that the force resisting motion of
liquids is proportional to the rate at which one attempts to
separate the parts of the liquid. In terms of our defined
quantities, this would be expressed as a proportionality of
stress to rate of strain:
(6)
or
= (7)
where is the constant of proportionality, and is termed the
coefficient of viscosity or simply the viscosity.
Equation (7) is the simplest example of a constitutive
equation, an expression that allows one to predict the flow
properties of a material in response to an applied stress.
Fluids that obey Eq (7) over a range of shear rate are said to
be Newtonian over that range. The viscosity of Newtonian
fluids is a material constant (like the density or heat capac-
ity) and depends only on the thermodynamic variables of
temperature, pressure, and concentration. If the viscosity of
a Newtonian fluid is measured at any arbitrary shear rate
or shear stress, the viscosity under all deformation condi-
tions is known.
Non-Newtonian Fluids
Fluids of commerce comprise a wide variety of materials,
with a wide range of consistencies. In general, polymer
solutions, emulsions, colloidal dispersions, and other sus-
pensions of particulate solids will be non-Newtonian. For
non-Newtonian materials, the viscosity is no longer a mate-
rial constant, but is now a material functionin this case,
a function of the shear rate (or shear stress). For non-
Newtonian fluids, a viscosity measured at a single shear
rate is not an adequate representation of the rheology of
the system.
TYPES OF NON-NEWTONIAN BEHAVIOR
In the following sections, the various types of non-New-
tonian behavior will be outlined. At the same time, some
mathematical expressions that are commonly used to
describe non-Newtonian flow will be introduced. Math-
ematical models are useful for summarizing flow behav-
ior quantitatively. To be sure, materials can be evaluated
merely by qualitative comparison of flow curves (e.g., by
visual inspection), but the mathematical analysis of flow
has value. For one thing, the model constants may have
physical significance. For example, some models contain a
yield stress term as a fitted parameter (see Plastic (Yield)
Behavior). The magnitude of this parameter may be
coupled to sag or leveling performance [1]. A later section
of this chapter, Leveling, gives examples of how leveling
can be predicted for non-Newtonian fluids using constants
from models discussed below. Furthermore, the values of
model parameters may be related to formulation variables,
allowing one, in principle, to optimize rheology by adjust-
ing composition in a rational way.
It should be understood that the models about to be
discussed are idealizations, and therefore are limited in
their ability to represent the behavior of real materials. The
models are able to describe real behavior at least over a
limited range of stress or strain rate. Thus, a second use of
mathematical models of flow is to make predictions of flow
behavior, bearing in mind that it is risky to extrapolate the
models beyond their range of validity.
As mentioned above, the simplest flow model is the
Newtonian expression, which has only one constant, the
coefficient of viscosity . To describe more complicated
behavior we will have to add additional coefficients and
terms, the physical significance of which will be given when
possible.
Shear-Dependent Viscosity
Materials for which the viscosity falls with increasing shear
rate
3
are designated shear thinning. Simple shear thinning
without either time dependence (see Time-Dependent
Fluids) or a yield stress (see Plastic (Yield) Behavior)
is termed pseudoplastic behavior. An increase of viscosity
with increasing rate of shear is called shear thickening. The
term dilatancy (see under Shear Thickening Fluids) is
often applied to shear thickening behavior, although this
strictly refers to shear thickening accompanied by a volume
TABLE 2Units in various systems
Variable cgs MKS SI
Strain Dimensionless Dimensionless Dimensionless
Strain rate s
1
s
1
s
1
Stress dyne cm
2
Newton(N) m
2
Pascal (Pa)
(=1 Nm
2
)
Viscosity Poise (P) ... Pas (=10 P)
Centipoise (cP)
(= 0.01 P)
mPas (=10
3
Pas=1 cP)
Modulus dyne cm
2
Nm
2
Pa
3
Any defnitions or descriptions of shear rate-dependent behavior
may likewise be stated in terms of shear stress dependence.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 419
increase, as the term implies. Fig. 2 shows curves illustrat-
ing viscosity-shear rate relationships for Newtonian and
some non-Newtonian fuids.
Equation (4) describes Newtonian behavior, for which
the viscosity is a material constant and independent of
shear rate (contour N, Fig. 2). More complicated viscosity-
shear rate behavior requires a more complex expression to
model it. The first level of complexity is to add a yield stress
term
0
(see Plastic (Yield) Behavior) to the Newtonian
model, resulting in the Bingham equation [2]
0 p
(8)
Equation (8) says that above the yield stress the shear stress
(minus the yield stress) is directly proportional to shear
rate.
4
It is a common misconception that this corresponds
to Newtonian behavior above the yield stress. Fig. 2, curve
B shows that the Bingham model displays power-law-like
behavior, but deviates from the power law (curve PL) at
higher shear rate, approaching the so-called plastic viscos-
ity
p
as a limit. Casson [3] obtained an equation similar
to Binghams except each term appears as the square root,
1/2
0
1/2 1/2 1/2
(9)
The Casson model is not empirical, but was theoretically
derived, specifically for systems whose primary flow units
are rigid rods. Cassons equation is reputed to hold for
a variety of paint systems, particularly as modified by
Asbeck[4]
1/2 1/2
0
1/2 1/2
(10)
which is somewhat surprising since few paints utilize rod-
shaped particles as fllers or pigments. In fact, this authors
experience is that the Casson model does not represent
paint fow as well as certain other models (see below). Cohu
and Magnin [5] showed that if the exponent 1/2 is replaced
by 1/n the Casson form is able to describe paint rheology
over several decades of shear rate. In Eqs (9) and (10),
(sometimes called the Casson viscosity) is not actually an
infnite-shear viscosity, but represents a limiting viscosity
that is approached at high shear rate. The value obtained
for the Casson viscosity will vary with the maximum
experimental shear rate. As with all such models, the user
must be aware that the constants resulting from a Casson
analysis do not necessarily represent true physical proper-
ties because the analysis is merely a process of curve-ftting.
For example, a fnite yield value will usually be obtained by
Casson analysis even when the material clearly does not
exhibit yield behavior.
The next complication we will introduce is to let the
exponent of the shear rate in the Newtonian law take values
other than unity. In other words, the shear stress now will
depend on some power of the shear rate
= K
n
(11)
Eq (11) is known as the power law or OstwalddeWaele
model. Here, K is a constant sometimes called the con-
sistency,
5
, which has replaced the coefficient of viscosity
. This substitution of K for is necessary because the
exponent n can be other than unity, in which case K will not
have proper viscosity units associated with it. The power
law exponent n has been termed the flow index. Its value
characterizes the dependence of viscosity on shear rate, i.e.,
whether the viscosity rises or falls with increasing shear. A
value of n < 1 corresponds to shear thinning behavior and n
> 1 to shear thickening (Fig. 2 curves PL). Dividing Eq (11)
through by
.
yields a form of the power law that relates the
viscosity to the shear rate
=
1
K
n
(12)
If n = 1 in Eqs (11) and (12), the power law reduces to the
Newtonian law.
The next complication consists in adding a yield stress
term to the power law expression
0
= K
n
(13)
giving an expression known as the HerschelBulkley equa-
tion. This model describes power law behavior above the
yield point (curve HB, Fig. 2).
Fig. 3 shows a generalized equilibrium flow curve [6,7].
This figure represents the general features of the shear rate
dependence of viscosity for non-Newtonian fluids (log-log
axes). The term equilibrium means that time-dependence
has been removed experimentally by measuring the equi-
librium viscosity. Fig. 3 consists of four main segments: a
low shear rate Newtonian regime, region I; a power-law
shear thinning regime, region II; a high-shear Newtonian
regime, region III; and a possible shear-thickening regime,
region IV. The figure is explained in detail below (see Shear
Thinning Fluids). The chief limitation of the power law
models is that they are valid only over a limited range,
namely, the linear portion of region II in Fig. 3. Power law
models cannot account for the upper or lower Newtonian
regions and, in fact, predict infinite viscosity at zero shear
rate and zero viscosity at infinite shear rate, both unrealis-
tic limiting behaviors. Nevertheless, the power law models
are found to be useful within their limitations, particularly
Fig. 2Viscosity-shear rate curves for simple flow models. Symbols
represent the following fluid models: N = Newtonian; B = Bingham
(
p
= plastic viscosity); HB = Herschel-Bulkley; PL = power law (n =
exponent).
4
In the Bingham expression and in other models incorporating a
yield stress term, it is important to note that the equations describe
fow behavior only when >
0
. When
0
, = 0 (i.e., = ), and
there is no fow.
5
Mathematically, K corresponds (in numerical magnitude but
not dimensionally) to the viscosity at unit shear rate (1 reciprocal
second).
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420 PAINT AND COATING TESTING MANUAL 15TH EDITION
for engineering-type calculations. The Herschel-Bulkley
equation has been found to be superior to a number of
other models in describing the flow behavior of a wide
variety of coatings materials over a useful range of defor-
mation conditions [8].
In order to account for the behavior outside region II in
Fig. 3, more elaborate models are required. A simple exten-
sion of the power law model is to add an upper Newtonian
limiting viscosity,
= +
1
K
n
(14)
This expression is known as the Sisko model [9] and
includes regions II and III of Fig. 3.
Of several proposed models encompassing regions I, II,
and III inclusively, two in particular have found wide accep-
tance and utility in the literature. These are the Cross and
Carreau models. Hieber et al. [10] wrote a general form of
which the Cross and Carreau models are special cases (here
modified to include Region III):
= +
1 /
0
1 ( [ ] )
(
a n) a
(15)
Here,
0
is the first Newtonian plateau viscosity and a is
a constant that determines the curvature of the transition
region between the lower Newtonian regime and the power
law regime. The value of a can be a measure of the molecu-
lar weight distribution of a polymer [10] or the particle-size
distribution of a colloidal dispersion. Setting a = 1 n in the
above expression yields the Cross equation, while setting
a = 2 gives the Carreau-B model. The parameter n has the
identical meaning as in the simple power law model [Eqs
(11) and (12)], i.e., it is the slope of the power law regime in
a log-log plot of shear stress versus shear rate. The constant
has the dimension of time and is actually a time constant
representing a characteristic time of the system. This time
constant may be related to, for example, the diffusional or
rotational relaxation time of the flow units (be they colloi-
dal particles or polymer chains) or to the time for rupture
of particle flocs or aggregates under shear. The transition
from the initial Newtonian plateau (region I) to the shear
thinning regime (region II) in Fig. 3 is governed by the
value of , in an inverse sense: increasing decreases the
shear rate of the onset of shear thinning and vice versa. In
other words, defines a characteristic shear rate of transi-
tion,
.
tr
[1113]
tr
=
1
(16)
The constant will be related to the time constant for
Brownian diffusion of the primary flow units of a fluid.
StokesSmoluchowskiEinstein theory gives the value of
for a dilute particulate dispersion as
=
6
3
d
k T
B
(17)
where is the viscosity of the continuous phase, d is the
particle diameter, k
B
the Boltzmann constant, and T abso-
lute temperature. For a typical aqueous latex dispersion, d
= 250 nm, = 0.05 P, for which (at 25C) =0.36 s, corre-
sponding to
.
tr
=2.8 s
1
.
When the experimental shear rate equals 1/, the shear-
ordering effect begins to dominate the randomizing effects
of Brownian motion, and onset of shear thinning is seen
[14] (see Shear-Thinning Fluids). This event corresponds
approximately to point c in Fig. 3. Equations (16) and (17)
tell how to control the transition from Newtonian to shear
thinning behavior. Any change that increases the value
of (such as increasing the effective particle size or the
continuous-phase viscosity, or lowering the temperature)
will move the shear thinning transition to lower shear
rates. Decreasing extends Newtonian behavior to higher
shear rates. While Eq (17) is strictly valid only for very
dilute dispersions, it still provides qualitative guidelines for
manipulating the rheology of dispersions. For concentrated
dispersions, should be taken as the viscosity of the disper-
sion [1517].
It follows from the above discussion that the broader
the size distribution of the flow units, the wider the
Fig. 4Dilute suspension of glass microspheres in a polymer solution
confined between glass plates with small plate separation: (a) just
after loading, particles are randomly distributed; [(b)(d)] after being
sheared in a side-to-side direction at both increasing duration and
shear rate. (By permission from J. Michel, R. Patzold, and R. Donis,
Rheologica Acta, Vol. 16, 1977, p. 317. Cited in Ref. [20].)
Fig. 3Generalized equilibrium flow curve:
0
= zero-shear viscosity
(random structure, maximum disorder);
= high-shear limiting
viscosity (maximum order). Region I is the first Newtonian plateau.
Region II is the power law regime. Region III is the second Newtonian
plateau. Region IV the shear-thickening regime (adapted from Ref.
[6]).
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 421
spectrum of relaxation times and the more gradual the
transition from region I to II (corresponding to a smaller
value of a). The shear rate of transition is fixed by (a
mean relaxation time), while a represents the distribution
of relaxation times.
Shear-Thinning Fluids
The term pseudoplastic has been applied to fluids that
decrease in viscosity with increasing shear rate (or shear
stress) and implies shear-thinning behavior without yield
stress. However, the term is passing out of use in favor of
the more general description shear thinning. Particulate dis-
persions, polymer colloids, and polymer solutions can dis-
play this behavior above a certain concentration threshold.
Viscosity is a measure of the dissipation of energy
or the energy cost to flow. Shear thinning behavior,
therefore, implies that an increase of shear rate causes a
structural change in the fluid that allows it to flow more
efficiently and consequently with less energy dissipation.
The mechanism
6
involves a shear-induced increase in
order, or anisotropy, within the system. Thermal (Brown-
ian) motion tends to keep systems disordered (of random
order). Shear forces work against this, tending to impose
orderliness. If shear rates are low, the randomizing forces
win out and the micro-structure and hence the viscosity
do not change for small increases of shear rate (point a to
b in Fig. 3). Because of Brownian motion, the microstruc-
ture is no less random anywhere in region I than at zero
shear rate, and therefore the viscosity is equal to
0
, the
zero-shear value. As the shear rate approaches a critical
magnitude (see Shear-Dependent Viscosity), the competi-
tion of thermal randomizing and shear ordering starts to
favor ordering (point c in Fig. 3). In the case of polymers in
solution, randomly coiled polymer chains tend to stretch in
the direction of shear, partially uncoil, and align in more or
less parallel fashion, at 45 to the shear gradient. In the case
of a dispersion, the particles tend to line up like strings of
pearls (Fig. 4) and eventually in ordered planes perpendic-
ular to the shear gradient, according to Hoffman [1820].
The result is a steadily decreasing viscosity with increasing
shear rate as the degree of order increases. Ultimately, if the
shear rate is high enough, the maximum amount of shear
ordering possible is attained and the viscosity once again
becomes independent of shear rate (Newtonian region III).
Fig. 3 shows the overall way in which viscosity varies
with shear rate for systems such as those described above.
Region I is the low-shear Newtonian regime (where Brown-
ian motion controls structure). Region II is the shear-thin-
ning segment of the flow curve (where shear forces control
the structure). Here, the viscosity decreases exponentially
with shear rate, hence, it is often referred to as the power
law regime. Region III is the high-shear Newtonian
regime. Here, the maximum degree of shear ordering has
been attainedthus, the viscosity is once again indepen-
dent of shear rate. The high-shear limiting Newtonian
viscosity is usually given the symbol
. Fig. 5 superposes
the micrographs of Fig. 4 on the non-Newtonian flow curve
of Fig. 3, illustrating the microstructural state associated
with each of the regions I, II, and III. Thus, in region I,
the particles are isotropically (randomly) distributed due
to Brownian motion. In region II there is a progressively
increasing degree of order, culminating in a completely
ordered micro-structure in region III.
Region IV is a shear-thickening region that is occasion-
ally seen, especially with concentrated dispersions. In actu-
ality, shear thickening in dispersions may occur at virtually
any shear rate, depending on dispersion concentration [21],
so that one or more of the other regimes are obliterated.
That is, the equilibrium flow curve may consist of regions I
to IV; I, II, and IV only; I and IV only; or IV only.
Note, once again, that structural order and viscous dis-
sipation are inversely related. An increase in order means
decreasing viscosity (Region II), while a decrease in order
results in an increase in viscosity (Region IV) [22]. It fol-
lows that, for Newtonian behavior, no change must occur
in structural ordering with shear. If the disperse system
is unstable, i.e., tending to flocculate, the dotted curve
may be followed (Fig. 6) instead of displaying a low-shear
Newtonian regime [7]. Some systems may possess an
apparent yield stress (see Plastic (Yield) Behavior). (See
6
The following discussion applies strictly to stable systems, i.e.,
those in which the net force between fow units is repulsive and
which therefore do not focculate. The shear-thinning mechanism
for unstable systems (net interparticle force attractive) is discussed
in the subsection entitled Mechanism of Thixotropy.
Fig. 5Figs. 4(a)4(d) superimposed on the equilibrium flow curve
(Fig. 3) to illustrate the progression from random microstructure
in region I through increasing degree of order in region II, to
completely ordered microstructure in region III.
Fig. 6Flow curve seen for unstable (flocculating) dispersions is
indicated by the ascending curve going toward infinite viscosity at
low shear rate.
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422 PAINT AND COATING TESTING MANUAL 15TH EDITION
Dispersion Rheology for additional discussion of particu-
late system rheology.)
As a general statement, the range of accurate measure-
ment of most laboratory viscometers (for typical coatings
fluids) is in the power law region. It may require extraor-
dinary methods or special instrumentation to characterize
fluid behavior in regions I or III.
SHEAR-THICKENING FLUIDS
We have seen above that shear thinning involves a shear-
induced increase in order of a system. This allows the
elements of a fluid to move or flow with minimum expen-
diture of energy. Conversely, shear thickening implies that
shear has caused a decrease in order of a system. The
resulting disordered system dissipates more energy dur-
ing flow and hence is more viscous. An example of this is
provided by the catastrophic increase in viscosity observed
by Hoffman [19], which he attributed to the buckling or
log-jamming of ordered, layered arrays of particles. Hoff-
man has recently reviewed the differing viewpoints on the
mechanism of shear thickening [23].
A frequently encountered type of shear thickening
behavior is dilatancy. Properly, dilatant behavior is shear
thickening accompanied by an increase in volume of the
fluid. It is most commonly observed in relatively concen-
trated disperse systems. In a dilatant system, the disperse
phase particles are minimally lubricated by the liquid
continuous phase. Furthermore, at rest, the particles of the
disperse phase are in a random close-packed structure for
which the interstitial volume is relatively minimal as well
(Fig. 7). If the dispersion moves only slowly, adequate time
exists for the meager liquid phase to flow sufficiently to
maintain the dispersed phase in a wetted or lubricated
state, and the system is able to maintain its close-packed
structure. Faster or more forceful motion causes a liquid-
starved condition because the interstitial volume increases
as the system is deformed or made to flow (Fig. 7). Conse-
quently, there is no longer enough liquid to lubricate the
system. The particles are, therefore, incompletely wetted
and forced flow would ultimately create microscopic voids,
leading to fracture of the material. The surface of a dilat-
ant material may appear dry when stressed due to the
withdrawal of surface liquid into the increased interstitial
volume. This can be seen when walking on wet sand on the
beach. The resistance to deformation of the material can
increase tremendously with increased deformation rate due
to these effects.
During the course of a pigment grind operation, a
fairly sudden maximum in viscosity is often seen and is
an indication that a good grind (i.e., to primary particles)
has been achieved. In fact, the surge in viscosity and power
draw result from the grind having become dilatant. Dilat-
ancy is desirable here because it facilitates energy transfer
throughout the grind. Thus, dilatancy is frequently an indi-
cator of the achievement of a stable dispersion of primary
particles. In general, dilatant systems are not also thixo-
tropic, and therefore will flow under even very low stresses.
For this reason, coating systems in a dilatant state may
suffer from rapid settling and be difficult to redisperse. For
most coating operations, dilatancy is undesirable. Pumping
of dilatant dispersions may result in high back-pressure in
lines, excessive wear of system components, high power
consumption, and loss of metering. In industrial rollcoat-
ing, dilatancy shortens coating lifetime on the roll, causing
dry edges and loss of film thickness control.
Dilatancy is very sensitive to dilution and can be dra-
matically reduced or eliminated by a small reduction in sol-
ids. Also, addition of polymeric flocculants or electrolyte, or
of a particulate phase of different particle size, or warming
can alleviate undesirable dilatancy. Flow curve measure-
ment is an excellent way to quantify the degree of reduction
of dilatancy achieved by these measures.
Time-Dependent Fluids
Time-dependent fluids are those whose viscosity is a func-
tion of time, as well as shear rate (or shear stress). The
most common such behavior encountered in coatings is
time-dependent shear thinning or thixotropy [24]. Barnes
has written a comprehensive review of the subject of thix-
otropy [25]. At constant shear rate and temperature, the
viscosity of thixotropic fluids will fall, eventually reach-
ing a constant value representing equilibrium between
structure breakdown and restructuring processes. If the
shear rate is changed, the viscosity will approach a new
equilibrium value at a characteristic rate. This behavior
is illustrated in Fig. 8, showing the way viscosity changes
for a time- dependent system when the imposed shear rate
(or shear stress) is changed in steps. Initially, the shear
Fig. 7Dilatant behavior is volume expansion under shear. Random
close-packed structure gives way to less-efficient packing with
necessary volume dilation.
Fig. 8Time-dependent fluid behavior. At
.
= 0, viscosity is high
(or infinite). Imposing
.
> 0 causes viscosity to fall exponentially,
reaching new equilibrium value. Subsequent changes in
.
result in
re-equilibration of structure, hence viscosity.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 423
rate is zero, and the viscosity is very high or infinite for
a thixotropic system. If a shear rate greater than zero is
imposed (
.
1
), the viscosity drops exponentially, ultimately
reaching a constant value. Increasing the shear rate to
.
2
decreases the viscosity further to a new equilibrium value.
A decrease of the shear rate to
.
3
results in an exponential
rise of viscosity to a higher equilibrium value. If, instead of
a multiple steady-shear experiment, just described, we were
to carry out a shear rate (or shear stress) ramp experiment
[Fig. 9A], the time dependence would result in a loop [Fig.
9B]. The explanation of the loop is given below, but has
to do with the fact that in a ramp experiment the equilib-
rium structure is never attained. The circuit in Fig. 9(b) is
called a thixotropic loop. Roughly bisecting the loop is the
equilibrium-structure curve generated from the equilib-
rium viscosity data of Fig. 8. The analogous time-dependent
behavior for shear thickening materials has been called
rheopexy (a rather rare phenomenon). The preferred term
now for the latter is antithixotropy.
Thixotropic Index Test
We emphasize that the most important characteristic of
thixotropic behavior is not shear thinning alone, but time
dependence. The relatively slow change of viscosity pro-
vides a means of control of flow behavior and is the reason
thixotropy is formulated into coatings. Hence, it is impor-
tant to correctly characterize the time-dependent aspect
of the behavior. For this reason, the so-called thixotropic
index test is of limited benefit for characterization of such
systems.
We will digress for a moment to discuss the thixotropic
index test since it is very widespread in practice. This mis-
named test determines the ratio of viscosities measured
at arbitrary high- and low-shear conditions. ASTM Test
Method D2196 specifies taking the ratio of viscosities
measured on the Brookfield Synchro-Lectric viscometer
at two speeds, representing a tenfold speed ratio. Since
only equilibrium viscosities are measured, the test yields
no information about time dependence and should be
called the shear-thinning index instead (it is so termed in
ASTM D2196). Its value, like many quality-control tests, is
in its simplicity and quick-and-easy character, requiring
no interpretation. As long as a given coating formulation
changes little, so that the hidden kinetic factor would be
expected to change little, the thix index can reveal when
something has gone awry (i.e., can be useful as a gross indi-
cator whether a formulation error has occurred). However,
it is always possible that the recovery kinetics of the system
might change, and this would go completely unnoticed if
the thix index were the only test used to evaluate the rhe-
ology. Below, we will present test methods which can be
almost as simple as the thix index, but which give more use-
ful, relevant, and complete information about thixotropic
systems.
Mechanism of Thixotropy
Thixotropy is formally defined as an isothermal, reversible
sol-gel (fluid-solid) transformation [26]. As stated, it is
experienced as a viscosity which is both time- and shear-
dependent. Its origin is the breakdown under shear of inter-
nal fluid structure to smaller flow units, or the reassembly
of structure from smaller units when shear is relaxed.
The mechanism of shear thinning in thixotropic (time-
dependent) systems is different from that in pseudoplas-
tic (time-independent) systems. In pseudoplastic systems,
shear thinning is the consequence of order externally
imposed by shear [14]. In thixotropic systems, an internally
imposed, viscosifying structure exists at rest, and the vis-
cosity falls because of the collapse of that structure under
shear. (Flocculated systems possess extra mechanisms of
energy dissipation [27]; therefore, their viscosity will be
higher than that of a deflocculated dispersion of the same
composition.) A further important difference between
the two is in the amount of time the structure requires
to respond to changes in shear rate. In the case of time-
independent systems, rapid structural equilibration quickly
accommodates to changes in shear rate. The accommoda-
tion process essentially is particle diffusion, which is rapid
for submicron particles (see Shear-Dependent Viscosity).
The viscosity (a measure of structure) thus always keeps
up with changes in shear rate for such systems. For
thixotropic systems, the rate of structural reorganization
is slower than the experimental rate of change of shear
rate (
.
) or slow with respect to the time of observation
at constant shear rate. In a shear rate ramp experiment
(see below), the structural breakdown always lags behind
the ever-increasing shear rate, so that the viscosity on the
up ramp will be higher than the equilibrium viscosity
at a given shear rate. On the down side of the ramp, the
rebuilding of structure lags behind the rate of reduction of
Fig. 9(A) Shear rate or shear stress ramp experiment. Shear rate or stress increases linearly (or logarithmically) to pre-selected maximum over
a selected sweep time period, resulting in a given acceleration gradient (
.
) or stress rate (
0
=
T
K
m
(19)
where K is the vane geometric constant given by
K
D H
D
= +
3
2
1
3
j
(
,
\
,
(
(20)
Fig. 12Experimental curves of G (elastic modulus, ) and
G (viscous modulus, O) versus time for a viscoelastic step-shear
experiment.
7
For this reason, yield stress values cited in the literature
are meaningless unless the exact experimental methodology is
provided.
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426 PAINT AND COATING TESTING MANUAL 15TH EDITION
where D is the rotor diameter and H the vane height.
Using a controlled-stress rheometer, measurement of
the yield stress using the vaned rotor is straightforward.
The torque is ramped slowly and the stress at which a finite
displacement is detected is reported as the yield stress.
Practical Aspects of Yield Behavior
Some of the practical consequences of yield behavior occur
in the processing of pigment dispersions, for example.
Dispersions with high yield stresses may be difficult to
dispense accurately or reproducibly via automatic meter-
ing systems. Pumps may actually refuse to move or such
materials may cavitate while being pumped; solenoid valves
may freeze. Coatings with significant yield stresses may
exhibit poor leveling [1] since, as the shear stress decreases
during the course of the leveling process, the material effec-
tively becomes immobile when the dynamic yield stress is
reached.
On the other hand, a small yield stress can be of great
value in inhibiting settling of particulate suspensions.
The shear stress exerted on the surrounding medium by a
spherical particle falling under the influence of gravity may
be calculated using the following relationships:
= =
Force of gravity on particle
Surface a
F
A
g
rrea of particle
F R g A R
g p l
= =
4
3
4
3 2
( ) ;
g p l
R
g =
3
( )
where R is the particle radius,
p
is the particle density,
l
is the liquid density, and g is gravitational acceleration. For
a titanium dioxide particle of radius 0.2 mm and density 4
gcm
3
, the shear stress acting on the particle due to gravity
is about 0.2 dyne/cm
2
. To prevent settling of such a particle,
the surrounding medium need only resist with an oppos-
ing stress of greater than 0.2 dyne/cm
2
. Even this, alas, is
impossible for a Newtonian liquid, be it water or honey
since it will flow under all stresses no matter how small
(it is only a question of how slowly). A pigment particle
will inevitably settle out of such a fluid, especially for vis-
cosities of practical magnitudes. However, if the suspending
medium possesses a yield stress equal to or greater than the
particle shear stress, the particle thinks it is suspended in
a solid and will remain suspended indefinitely. This argu-
ment assumes more or less ideal yield behavior, which, as
described above, may rarely be encountered. A medium
with a measured yield stress of apparently sufficient
magnitude may or may not permit the particle to settle
over long periods of time due to the possibility of viscous
flow below the apparent yield point. In addition, ambient
vibration can break the structure locally around a particle,
leading to settling even where the measured yield stress
appears adequate. Therefore, to ensure practical stability,
one should build in a higher yield value than that calculated
from the above.
Elastic Liquids (Viscoelasticity)
In ideal viscous flow, all input energy is converted either
to heat or energy of motion. None is stored (i.e., none is
converted into potential energy). Therefore, viscous flow
results in irreversible deformation. Newtonian liquids show
essentially ideal viscous (also called inelastic) behavior
over a wide range of deformation rate. For ideal elastic
(Hookean) substances, all the energy of deformation is
stored, similar to a stretched rubber band. Consequently,
elastic deformation is not permanent, but is in fact com-
pletely reversible. Real materials can display a mixture of
elastic and viscous character, in varying degrees. Hence, the
term viscoelastic is applied to such materials. Not all non-
Newtonian fluids have significant elastic properties, but
many do. Significant elasticity in fluids generally indicates
the presence of some association network or microstruc-
ture. That is, elementary flow units are linked together in
some fashion such that the structural relaxation time (see
below) is measurably long. This structure, and particularly
the destruction and rebuilding process that occurs during
and after coating application, can have great consequences
for application and film formation processes. An example
of this is the influence of elasticity on leveling of an applied
coating [41] (see also Massouda [42], Glass [43], and Cohu
and Magnin [44]).
As the term implies, viscoelasticity refers to a material
response, which is a combination of viscous and elastic
behavior. Viscous flow superimposed on elastic strain
results in the relaxation, or gradual disappearance, of
stress within the strained object. This is manifested as an
imperfect, or fading, stress memory. Fig. 13 illustrates the
material response to an applied elongational stress for a
material with permanent stress memory (e.g., rubber band)
and one with fading stress memory (e.g., bouncing putty).
The Viscoelastic Parameters and Their
Measurement
A convenient way of experimental characterization of visco-
elastic materials is by alternating the direction of strain (or
stress). Most often, a sinusoidal deformation is employed
(Fig. 14). The strain amplitude must be kept small so that
the material response remains in the linear viscoelastic
regime, where stress and strain are linearly related.
8
For
perfectly elastic behavior (Hookean spring), the stress
and strain are in phase with each other. That is, upon
8
This is a requirement because the equations used are valid only
for linear viscoelasticity.
Fig. 13Viscoelastic stress-memory loss: stretch-force experiment.
Rubber band is cross-linked polymer, does not relax stress (
E
) when
stretched. Viscoelastic material can accommodate to strain by
molecular motion (viscous flow), allowing elastic stress to decay.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 427
deformation, the maximum stress and maximum strain
occur at the same instant in time. However, if there is any
viscous (energy-loss) component in the material response,
the stress and strain maxima will not be coincident but will
be out of phase. This happens because viscous flow con-
tinually relieves the stress within the material, causing the
stress to reach a maximum and die away before the strain
maximum. That is, as the rate of strain decreases near the
maximum (or minimum) of the strain sine wave, stress
relaxation catches up and overtakes the stress-building
effect of the strain. Thus, the maximum in the stress must
occur before the maximum in strain, and will do so ear-
lier in the deformation cycle the more rapid is the viscous
relaxation. The separation of the stress and strain maxima
is called the phase shift (or phase angle, the angular part of
a complete cycle in degrees or radians represented by the
phase shift). The phase shift is often given the symbol .
The faster the viscous stress-relaxation process, the earlier
in the cycle the stress maximum will occur, i.e., the larger
the phase shift will be. The limiting value of the phase angle
for purely viscous liquids is 90 (see Fig. 14). This is because
for sinusoidal deformation the maximum strain rate (maxi-
mum slope of the strain sine wave) occurs 90 ahead of the
maximum strain, and for Newtonian liquids the stress is
proportional to strain rate. Therefore, the maximum stress
must occur at the maximum strain rate, which corresponds
to a phase shift of 90.
The derivation of viscoelastic parameters from a sinu-
soidal shear experiment begins with the calculation of the
complex shear modulus G*. This is simply the ratio of the
maximum stress,
0
, to the maximum strain,
0
(G* =
0
/
0
).
From G* may be separated G the modulus of elasticity
(storage modulus) and G, the viscous modulus (loss modu-
lus). Fig. 15 demonstrates the geometric relationship of G*
to its in-phase and out-of-phase components G and G,
governed by the phase angle . It is obvious from geometry
that when is zero, G* = G, and when =90, G* = G. The
physical meaning is that when = 0, the measured modu-
lus is comprised solely of an elastic response, and when
= 90, the modulus is due entirely to a viscous response.
This follows from the discussion of the phase shift, above.
By trigonometry, G = G*cos and G = G*sin . Alternately
stated, G is the component of the complex shear modulus,
which is in phase with the strain. G therefore represents
the elastic part of viscoelastic behavior. The viscous compo-
nent (G), on the other hand, is derived from the part of the
modulus which is out of phase with the strain but in phase
with the strain rate.
Consider a dynamic test in which a sinusoidally vary-
ing strain is applied to a viscoelastic material. The angular
frequency of the deformation is given by = 2f, where f is
the frequency of oscillation (s
1
) and is in rad/s. Now, the
amplitude of the strain with time is given by
=
0
cos t
(21)
which describes a cosine wave of maximum amplitude
0
and period 1/. The strain rate experienced by the material
is then
=
0
sin t
(22)
The oscillating strain produces a stress response
= + )
0
cos( t
(23)
where is the phase shift, advancing the phase of the stress
relative to the strain. Eq (23) may be equivalently written
[45]
* cos cos sin sin =
0 0
t t
(24)
which describes a complex stress where, by complex plane
relationships analogous to Fig. 15,
0
cos is the stress
component in-phase with strain and
0
sin the stress com-
ponent that is out-of-phase with the strain (but in-phase
with the strain rate). We therefore can define a dynamic
viscosity as the quotient of the stress in-phase with the
strain rate, divided by the strain rate
= = = =
0
0
0
0
sin sin *sin
G G
(25)
The above expression is obtained using the relationships
0
(strain-rate amplitude) =
0
and G*=
0
/
0
.
The magnitudes of G and G reveal the relative impor-
tance of viscous and elastic behavior in the mechanical
response of a material. In Fig. 15, again by trigonometry,
the tangent of the phase angle equals the ratio G/G. Thus,
tan quantifies the balance of energy storage and loss mea-
sured under particular conditions of temperature, pressure,
and frequency or rate of deformation. For solids, tan as
Fig. 14Stress response to oscillatory strain for ideal viscous and
elastic bodies. Stress is in phase with the strain for an elastic solid; the
stress leads the strain by phase shift =90 for an ideal viscous liquid.
Fig. 15Viscoelastic relationships in the complex plane.
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428 PAINT AND COATING TESTING MANUAL 15TH EDITION
a function of frequency can be useful to predict the likeli-
hood of brittle or ductile failure of a polymer or the sound
absorption or vibration damping properties. For liquids,
tan can monitor the progress of fluid restructuring in
thixotropic recovery. The latter may be useful in computing
sag resistance, for when tan S becomes less than unity the
system has essentially become immobilized (i.e., reached a
dynamic yield point). When tan > 1, viscous flow (i.e., a
steady-state viscosity) is possible. When tan < 1, however,
the material is more elastic than viscous (i.e., a percolating
network extends throughout the bulk, and it is essentially
an elastic solid).
Viscoelastic Models
It turns out that viscoelasticity can be rather realistically
modeled by simple mechanical analogues. These are use-
ful not only as an aid to conceptualization of viscoelastic
behavior, but also in helping to understand the elementary
mathematics of viscoelasticity. As we have said, viscoelas-
ticity is a combination of two idealized behaviors: Hookean
elasticity and Newtonian viscosity. The mechanical ana-
logue of Hookean behavior is a spring of force constant G,
and that of Newtonian flow is a dashpot (a piston-in-cylinder
filled with a fluid of viscosity ). These elements are com-
bined in various ways to model viscoelastic mechanical
response.
To build our first model we will connect a spring and
dashpot in series (Fig. 16), an arrangement known as the
Maxwell model. To imagine what response the model
has, let us apply a constant stress
0
to one end, the other
being fixed. By the way, our dashpot is considered to be
infinitely long so that the piston never runs out of travel.
This being the case, one can see that an equilibrium strain
would never be reached but rather the dashpot would
continually move as long as the stress is applied. Since the
model can flow without limit, this is obviously a model
for viscoelastic liquids (sometimes called elasticovis-
cous). We have just described what is known as a creep
experiment, in which a sudden stress
0
is applied, and
the evolution of the strain, or deformation, is followed
with time. The creep of a Maxwell liquid is not very inter-
esting, however. The strain-time curve consists merely of
a straight line with intercept equal to
0
/G and slope of
0
/ [Eq (28)].
We will use the Maxwell model to illustrate how equa-
tions describing viscoelastic behavior may be derived. Just
as the stress is the same in every part of a stretched string,
so is the stress the same on both elements for the Maxwell
model, and also, therefore, the rate of change of stress is
identical as well
total clastic viscous
= = = ( )
0
(26)
and
T E V
= =
(27)
Furthermore, the total strain is clearly the sum of the
strains undergone by the two elements
T E V
E V
= = = +
G
t
(28)
The expression on the right follows from the definition of
the modulus (G = /), Eq (4), and the fact that =
.
t
. It is
also true that
T E V
E V
= = = +
G
(29)
An alternative to the creep method that is particularly use-
ful for viscoelastic solids is to apply a sudden deformation
and follow the decay of stress with time. This is similar
to the experiment depicted in Fig. 13 and is known as
stress relaxation. Sudden imposition of a strain
0
results
in instantaneous lengthening of the spring. The dashpot
experiences, in turn, an initial stress
0
from the extended
spring, causing a gradual movement of the dashpots piston,
resulting in relaxation of the stress. By manipulation of
the above equations, we can arrive at a quantitative way of
describing this relaxation process.
Since the strain
0
in a stress-relaxation experiment is
constant, the total strain rate
.
T
= 0. Therefore, from Eq (29)
V E
= =
G
d dt
G
/
(30)
rearranging
d G
dt
V
=
(31)
Integrating Eq (31) from time 0 to time t results in the Max-
well stress relaxation expression
=
0
e
Gt /
(32)
Fig. 17 illustrates the decay of stress in a constant strain
or stress relaxation experiment for the Maxwell model,
described by Eq (32). Note that the quantity /G has the
Fig. 16Maxwell model for viscoelastic liquid behavior. G is force
constant (modulus) of spring, is the viscosity of the dashpot fluid,
and
0
is the applied stress.
Fig. 17Stress relaxation experiment. A fixed strain is imposed,
creating an initial elastic stress
0
, which relaxes viscously with time
constant (=/G). is the time at which the stress has decayed to
0
/e.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 429
dimension of time. We will assign to this quantity the sym-
bol and refer to as the stress-relaxation time constant.
It can be seen from Eq (32) that when t = /G, =
0
/e.
Therefore, represents the time required for the stress to
fall to 1 /e of its initial value (Fig. 17) and gives a convenient
way of quantifying the rate of decay of stress in viscoelastic
materials.
The time constant, , could also be called the stress
memory time constant since it is related to the time it takes
for a viscoelastic material to forget its initial elastic stress
level when subjected to a constant strain. As such, deter-
mines the role that viscoelasticity plays in an industrial
process. That is, elastic materials generate an elastic extra
stress when deformed, which can result, among other
things, in the stabilization of fluid structures that would
ordinarily collapse too quickly to be of consequence. These
include, for example, liquid fibers and webs, which result in
roller spatter [46], and the formation of ribs on rollcoating
[47]. The latter effects are particularly sensitive to exten-
sional viscoelasticity [48] (see Extensional Rheology.) The
magnitude of the undesirable effect will depend on the rate
at which the elastic extra stress decays or relaxes, as we
will see below.
In modern rheometers, sinusoidal oscillation is a com-
mon method of viscoelastic characterization. (Creep is also
available as a viscoelastic test mode for controlled-stress
instruments and stress relaxation for controlled-rate instru-
mentssee below.) Equations derived for the Maxwell
model [49,50] show how the viscoelastic time constant
may be obtained from the oscillatory data
= =
+
G
G
1
2 2
(33)
and
G
G
=
+
2 2
2 2
1
(34)
from which
tan
= =
G
G
1
(35)
where G
=
0
1
G
e
t
( )
/
(36)
KelvinVoigt stress relaxation
=
0
G
(37)
and
tan = (38)
These equations describe an exponentially increasing strain
at constant stress [see Fig. 19 and Eq (36)] and a nonrelax-
ing stress at constant strain [Eq (37)], respectively.
The Maxwell and Voigt models, by themselves, are
too simple to accurately describe most real viscoelastic
materials. However, a Maxwell element connected in series
with a KelvinVoigt element turns out to model the linear
viscoelasticity of many real systems rather well. Fig. 20
shows such an arrangement, known as the Burgers model.
For completeness (and also because an error in the Burgers
stress-relaxation expression has crept into the literature),
equations describing creep and stress relaxation behavior
for the Burgers model are given:
Burgers creep
= + +
0
2
0
2
0
1
1
1
G
t
G
e
t
( )
/
(39)
Burgers stress relaxation
=
0 2 0 1
2
G e G
t
+
/
(40)
where
1
=
1
/G
1
and
2
=
2
/G
2
. The creep and stress relax-
ation behavior for the Burgers model are shown in Figs.21
and 22. Modern rheometers of the type known as con-
trolled stress (see Rotational Instruments) are capable
of performing creep measurements. Viscoelastic constants
Fig. 19Kelvin-Voigt creep experiment. At constant applied
stress
0
the strain increases exponentially with time constant
(/G).
Fig. 18Kelvin-Voigt model. Symbol definitions same as Fig. 16.
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430 PAINT AND COATING TESTING MANUAL 15TH EDITION
can then be extracted from the data by analysis according
to one or more of the above models.
Viscoelasticity and Industrial Processes
The role of viscoelasticity in an industrial process depends
on the rate (or frequency) of deformation. Put another way,
the response of a viscoelastic material depends on how long
a stress is applied (1/), relative to the time required for any
elastic extra stress to decay. This suggests taking a ratio
of the stress relaxation time to the time (duration) of the
process stress, t
De
t
=
(41)
This ratio is a defined rheological term known as the
Deborah number, De. It is named for the Biblical prophet-
ess Deborah, who prophesied that the mountains flow
before the Lord [51]. This is a perfectly accurate statement
(long before being verified by the science of geology) of
the fact that, on Gods time scale, rock formations can be
observed to undergo permanent deformation, or flow. In
other words, if the stress time scale, t, greatly exceeds the
relaxation time, (De 1), the material will respond as
a viscous fluid (because elastic stress has time to decay).
Conversely, if De 1, the stress duration is too brief to pro-
vide an opportunity for viscous relaxation, and the material
behaves as if an elastic solid. Thus, the Deborah number
quantifies the proportion of elastic to viscous control of
a process. This is one reason why a determination of the
viscoelastic properties of paints and coatings is important.
Keunings and Bousfield [41] give the following expres-
sion for the effect on leveling rate a of elastic extra stress,
through the relaxation time constant
=
=
Newt
Newt
1
(42)
where
Newt
is the leveling rate in the absence of viscoelastic
relaxation. Since the Newtonian leveling rate is always posi-
tive, elasticity ( > 0) always retards leveling, in the above
expression. Eq (42) can be adapted to the situation of a
typical paint, and the influence of elastic-stress relaxation
is seen in Table 4.
To be sure, real materials may not exhibit simple expo-
nential stress decay (i.e., a single relaxation time), but rather
may possess a spectrum of relaxation times. However, the
mechanical response will be dominated by a mean relax-
ation time (or sometimes the longest relaxation time [41]),
obtained from experiments such as described in foregoing
sections. Simple viscoelastic dispersions can show Max-
wellian behavior with a single relaxation time [52,53].
One of the reasons that associative thickeners (ATs)
have been so successful in being able to thicken paints with-
out at the same time adversely affecting flow and leveling
is no doubt due in part to their low elasticity. Even though
ATs generate a three-dimensional network structure within
the fluid,
9
they often have negligible G values, in contrast
to typical cellulosic thickeners, for example. This is believed
to be due to the extreme lability of the micellar junctions
of the associative network, resulting in very short network
relaxation times [52,54]. Thus, the decay of elastic stress in
ATs is so rapid that such stresses are virtually unobserved
(De 1).
As stated before, the process consequences of visco-
elasticity are due in part to the stabilization of otherwise
unstable liquid structures by the elastic extra stress.
Thus, liquid fibers and webs, which would ordinarily
collapse by surface tension, are stabilized, producing, for
example, excessive rollcoat spatter (or misting) and rib-
bing, and inhibiting atomization of sprayed materials.
The importance of viscoelasticity for a particular process
Fig. 20Burgers model. Symbol definitions same as Fig. 16.
Subscript 1 refers to the Voigt element; subscript 2 to the Maxwell
element.
Fig. 22Burgers model stress relaxation. Imposition of constant
strain
0
causes stress which decays exponentially, governed by the
relaxation time
2
(=
2
/G
2
). Voigt element contributes unrelaxed
stress
=
0
G
1
.
Fig. 21Burgers creep experiment. Under constant applied stress
0
, the Burgers model undergoes instantaneous deformation of
magnitude
0
/G
2
. The next segment of the curve is retarded spring
motion where strain increases exponentially with time. Finally, the
spring is fully extended and viscous flow occurs with a constant strain
rate d/dt.
9
See Chapter 33Thickeners and Rheology Modifers.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 431
is gauged using the Deborah number, by the ratio of the
stress-relaxation time constant to the time duration of the
process stress. Of course, both the magnitude and lifetime
of the elastic stress will be important, for together they will
govern the degree of stabilization.
The analysis of the industrial problem of viscoelastic
effects is complicated by the fact that many processes, par-
ticularly of coatings application, involve strain magnitudes
beyond the range of linear viscoelasticity. Approaches to
nonlinear viscoelasticity exist, but are beyond the scope of
this chapter. Quantitative prediction of viscoelastic effects
would require the use of a model for the fluid behavior, or
viscoelastic constitutive equation, also outside the scope
of this presentation. However, it is often possible to build
experimental correlations between coating elasticity and
performance problems, so that guidance may be provided
for formulation efforts to solve them.
For most modern coatings, in particular, the origin
of elasticity is likely to be an associated structure built up
from a dispersed phase rather than polymeric entangle-
ment. Such particulate flocs are generally shear-sensitive
and are reduced or destroyed by high-shear application
processes. The elastic modulus G will be seen to decrease
with increasing strain and strain rate outside the linear
regime. Thus, in most cases, G is a measure of structure
that has its greatest effect at low strain and strain rate
(unless the elastic character is due to polymeric entangle-
ment). Therefore, under most conditions of application,
structure (and elasticity) is destroyed and must rebuild in
the applied film. Herein, it is seen that thixotropy and vis-
coelasticity are kindred phenomena for disperse systems.
EXTENSIONAL RHEOLOGY
In addition to simple shear, the other important mode of
deformation that is important for coatings is extensional
(or elongational) deformation. Extensional or stretching
deformation causes an increase in length and decrease in
cross section of an object. In a simple shear field, particles
or polymer coils (i.e., the flow units) rotate with a velocity
e
e
=
(43)
The strain in extension is usually defined as a Hencky
strain, = l/l
0
, where l
0
is the original length and l the
increase in length under tensile stress
e
. The Hencky strain
rate is then the time derivative of the strain or
= =
In 1
l
dl
dt
d l
dt
( )
(44)
Extensional Viscosity in Coatings Processes
Many coatings processes involve stretching (elongational)
flows (Table 1) and when coatings can support large exten-
sional stresses (i.e., possess high extensional viscosity)
performance can be dominated by such flows. As men-
tioned, the viscosity of a Newtonian liquid in extension is
three times that measured in shear. For non-Newtonian
fluids, the Trouton ratio [(
)/(
)] can be as much as
10
4
. Furthermore, whereas the shear viscosity is usually
a decreasing function of shear rate, extensional viscosity
frequently displays strong extensional strain rate thicken-
ing. For example, Lu [55] observed that polyacrylamide
thickeners in latex paint systems showed extensional
thickening behavior, whereas hydroxyethyl cellulose-type
thickeners did not. Coatings application processes are
generally high strain rate, so it is clear that
e
can pos-
sibly dominate the mechanical response, generally leading
to detrimental consequences. Extensional stresses can
stabilize liquid webs and fibers, such as form in direct
rollcoating, allowing them to grow large instead of dissi-
pating. This can result in heavy ribbing and misting (roll
spatter) [56]. On the other hand, the breakup of a liquid
jet to form atomized droplets in spray application is sup-
pressed by a high extensional viscosity because the liquid
fibers formed intermediary to droplet formation are inhib-
ited from disintegration. J. E. Glass has been the chief
proponent of the study of extensional viscosity in relation
to paint performance, correlating it to roller spatter [46]
and the performance of sprayed coatings [57]. Massouda
did a clever and, unfortunately, largely overlooked study
of the relationship of extensional stress measurements to
viscoelastic relaxation kinetics and thence to spattering of
paints [42].
Extensional Viscosity Measurement
There have been, unfortunately, few commercial instru-
ments suitable for extensional measurement on coatings.
The Spin-Line Rheometer (SLR) formerly offered by TA
Instruments, utilizing the fiber-spinning geometry, and
the Rheometrics (now part of TA Instruments) RFX rhe-
ometer, using opposed-nozzle flow to measure extensional
forces, are no longer commercially available. However,
the recent introduction by Thermo Electron Corporation
of the CaBER Rheometer (Capillary Breakup Extensional
Rheometer) provides a promising method of extensional
rheometry that is appropriate for paints, adhesives, inks,
gels, and polymer solutions. With the necessary electro-
mechanical design and fabrication resources, one might
attempt to build a simple extensional rheometer, perhaps
patterned after that of Gupta [58]. The relatively simple
technique of convergent flow analysis was used by Lu for
measuring extensional properties of latex paints [55]. An
overview of extensional rheometry has been published by
James and Walters [59].
TABLE 4Leveling rate dependence on
Maxwell relaxation time, . = da/dt, where
a = roughness amplitude, and t
1/2
= time for
a0.5a
0
(initial amplitude).
, s
0.0 0.1 1 10 50 100
, s
1 34.5 7.75 0.972 0.0997 0.02 0.01
t
1/2
0.02 0.09 0.67 6.95 34.7 69.3
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432 PAINT AND COATING TESTING MANUAL 15TH EDITION
POLYMER MELT AND SOLUTION RHEOLOGY
High-polymer solution rheology is a subject of relatively
little interest with respect to coatings due to the shift from
solvent-borne to environmentally compliant technologies,
such as waterborne, higher solids, and powder coatings.
The polymers used for high solids and powder coatings are
little more than oligomers in order to achieve necessary
flow for satisfactory processing and film formation. Even
the polymers used in solvent-borne varnishes and paints are
below the entanglement molecular weight M
c
, hence both
their neat and solution rheology are Newtonian. Similarly,
powder coating melts are Newtonian until near gelation
[60]. The viscosity of polymer solutions below M
c
is propor-
tional to the weight-average molecular weight, M
w
0
= KM M M
w w c
( ) <
(45)
where K is a constant dependent on chain flexibility (T
g
),
polymer-solvent interaction, temperature, etc. If M
w
> M
c
,
the motion of entangling polymers becomes much more
complex, and the viscosity now depends on M
w
raised to the
power of approximately 3.4 [61]
0
3 4
= KM M M
w w c
.
( ) >
(46)
The viscosity of polymermelts follows a similar relation-
ship. It should be noted that polymers having highly polar
or hydrogen-bonding functionalities (such as commonly
used in high-solids formulations) can show nonlinear
dependence of viscosity on molecular weight even below M
c
due to transient intermolecular associations [62].
The sole use of high-polymer binders in coatings today
is where they exist as a separate phase dispersed in a liquid
carrier medium
10
. Such materials are known as polymer
latexes, or latex dispersions Because the latex polymer is
segregated from, and therefore non-interacting with, the
solvent, the rheology of latexes is much simpler than for
the same high polymer in the solution state. The rheology
of polymer dispersions will be discussed below.
DISPERSION RHEOLOGY
Dispersions of solids in liquids, for example, titanium
dioxide particles dispersed in a liquid medium, play a cen-
tral role in the manufacture and performance of coatings.
Fully dispersed, stable dispersions favor the attainment
of optimum intrinsic properties, improved process ability
and workability, improved storage stability (shelf-life), and
can provide higher solids at application viscosity. Rheol-
ogy is particularly useful for dispersion characterization
because of its sensitivity to the microstructure. Both stabil-
ity and quality of dispersions can be evaluated. Dispersion
rheology has two broad aspects: (1) The dependence of
viscosity on the concentration of the dispersed phase, and
(2) the dependence of viscosity on shear stress and shear
rate (discussed in Classes Of Non-Newtonian Behavior).
A third important aspect is the viscoelastic properties of
dispersions, that will not be discussed here. Factors that
determine the foregoing properties include particle shape,
rigidity, particle size and size distribution, and interparticle
forces, both attractive and repulsive. All these elements
combine to determine the microstructure of the dispersion,
its response to stresses, and hence its rheology.
A dispersion (or suspension) consists of a suspended or
dispersed discontinuous phase contained within a continu-
ous phase. As an example, this might be a system in which a
fine particle size solid is wetted by and thoroughly mixed in
a liquid. However, the dispersed phase may be a liquid (an
emulsion), a solid (suspension), or gaseous (a foam) as well.
The dividing line of terminology between dispersions and
suspensions is essentially one of particle size. Dispersions
are generally of colloidal dimension, about 10 nm to 1 m.
Due to their small size and mass, colloidal particles are
very slow settling or nonsettling because Brownian motion
effectively keeps them randomly suspended. Suspensions
above 1 m generally exhibit rapid settling because Brown-
ian forces are ineffective with such massive particles, and
also because Van der Waals attractive forces increase in
proportion to particle size.
Addition of a particulate phase to a liquid increases
its viscosity in proportion to the volume fraction of the
dispersed phase. is the fraction of the total volume of the
dispersion occupied by the dispersed material (a dimen-
sionless number),
volume of particles
volume of dispersion
(47)
A convenient way of expressing the effect of a dispersed
phase on the viscosity of a liquid is by normalizing the
dispersion viscosity to the pure-liquid viscosity. This ratio
is termed the relative viscosity
r
and is also dimensionless
r
d
l
(48)
The contribution of a single particle to the viscosity of a
dispersion is characterized by its intrinsic viscosity (or lim-
iting viscosity number) [], a function of particle shape and
deformability. [] is obtained as the slope of a plot of
r
1
(formerly known as the specific viscosity) versus
[ ] lim
0
1
r
(49)
It is reasonable that the viscosity of a liquid will be aug-
mented by a factor equal to the product of the particle
intrinsic viscosity and the concentration of particles
r
+ 1 [ ]
(50)
Einstein [56] was the first to calculate the intrinsic viscos-
ity for noninteracting rigid spheres in a Newtonian liquid,
obtaining the number 2.5
r
+ 1 2 5 .
(51)
The intrinsic viscosities of other particle shapes (e.g., pro-
late and oblate spheroidsdiscs and rods) have been calcu-
lated [63] and are always greater than 2.5. This means that
any deviation from spherical particle shape will increase
the viscosity of a dispersion. Equation (51) is valid only in
the very dilute regime ( < 0.05), where the flow around a
10
Some high-molecular-weight, water-soluble polymers are used as
thickeners. However, they are used at low levels, and their effects
on rheology are mainly colloidal/osmotic rather than as solution
polymers.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 433
single particle is not affected by the presence of other par-
ticles. At higher concentrations, the motion of particles is
perturbed by interactions with other particles. These inter-
actions are accounted for by higher-order terms in , as,
for example, by Batchelor [64], who extended the rigorous
treatment to somewhat higher volume fractions by using a
second-order expression in
r
k + + 1 2 5
2
.
(52)
The value of k is of the order of 5. Fig. 23 illustrates the
typical dependence of
r
on for actual dispersions (using
data of Eilers [65]) and shows curves corresponding to the
predictions of Einsteins and Batchelors equations. It can
be seen that Batchelors equation predicts a finite viscosity
at = 1, which is not realistic. Also in Fig. 23, it is seen that
r
rises toward infinity at a volume fraction considerably
less than unity. The volume fraction
m
corresponding to
r
is called the maximum volume fraction, or maximum
packing fraction. At =
m
, the density of particle packing
is such that the dispersion can no longer flow. The value
of
m
will be system-dependent (also shear dependent)
and will be determined by particle shape, particle-size dis-
tribution, the ionic strength of the medium, the degree of
particle flocculation, and the manner in which the particles
arrange themselves (pack) in three-dimensional space.
Numerous models have been proposed containing
m
[15,66,67]. Probably the most successful in fitting a variety
of data is the KriegerDougherty equation [68]
r
m
m
j
(
,
\
,
(
1
[ ]
(53)
Fig. 23 shows the fit of the KriegerDougherty model to
data of Eilers [65] using a value of [] close to the Einstein
value. The maximum packing fraction will have differ-
ent, unique values at low and high shear rates because
the strength of the shear field determines how efficiently
particles are able to pack together. Reviews of the rheology
of polymer colloids are recommended for further reading
[6,14,69].
It should be noted here that although the dispersion
rheology is controlled by the disperse-phase volume frac-
tion , the effect of the particle phase on the rheology may
be greater than expected solely on the basis of the volume of
material added to make up the dispersion. This is because
the disperse-phase volume may be augmented by various
effects tending to increase the effective particle radius. It is
the hydrodynamically effective particle volume that deter-
mines the rheology. Thus, the rheological behavior will be
found to scale with the effective volume fraction
eff
, rather
than with the formulated volume fraction .
There are two mechanisms that can cause
eff
to be
greater than . In the first, the effective particle radius
increases as a consequence of various methods of disper-
sion stabilization. For example, adsorption of a polymeric
stabilizer onto the surface of a particle adds the thickness of
the stabilizer layer to the particle radius. By steric-osmotic
interactions between stabilizer layers, the close approach
and flocculation of particles is prevented, resulting in steric
stabilization. If the thickness of the steric stabilizing layer
on the particle is , the effective volume fraction is [69]
eff
+
j
(
,
\
,
(
,
,
,
]
]
]
]
1
3
R
(54)
where R is the original particle radius. Quantitative vis-
cometric methods have been developed for inferring the
adsorbed-layer thickness [69,70].
The effective particle radius and hence the effective
volume fraction
eff
can also be increased by the effects of
particle electrical charge. Aqueous dispersions are often
stabilized by association of repulsive electrical charge
with the particle, known as electrostatic stabilization. The
charge may be due to adsorption of ions, anionic or cationic
surfactants or polyelectrolytes, or, in the case of polymer
colloids, to the presence of ionizable groups which are part
of the polymer molecules. (In the case of functionalized
polymer latexes, such groups tend to migrate to the particle
surface.) The surface ionic charge surrounds the particle
with an electrical field, which propagates into the aqueous
phase a distance inversely proportional to the ionic strength
of the medium. In the presence of dissolved counterions,
an ionic atmosphere envelops the charged particle. These
phenomena are the origin of the so-called electroviscous
effects, which have to do with the way the electrical field
surrounding the particle affects the effective volume frac-
tion or collision cross section, and also the nature of the
hydrodynamic interaction between particle and surround-
ing liquid [63,71]. The rheology of a dispersion can be
greatly altered as a consequence of these effects, as the solu-
tion ionic strength or pH are varied. In a study by Krieger
and Eguiluz, in a dispersion of uniform polystyrene latex
spheres ( = 0.4) the
r
decreased from 10
6
to 10 as the
result of increasing the concentration of electrolyte by two
orders of magnitude [72]. In that study, the low-electrolyte
latexes exhibited apparent yield stress behavior, a conse-
quence of the increase of the effective volume fraction of
the latex particles due to the expansion of the repulsive
electrostatic field. The effect is so great that the particles
Fig. 23Dispersion relative viscosity data of Eilers, together with
best-fit curves for the Einstein model, Batchelor model, and the
Krieger-Dougherty model.
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434 PAINT AND COATING TESTING MANUAL 15TH EDITION
become locked into crystalline arrays that can diffract
light, producing striking iridescent colors. As the electrolyte
concentration is increased, the counterion cloud both
shrinks the electrostatic field and shields particle fields
from each other. Consequently, the viscosity drops dramati-
cally (remember that the volume change depends on the
cube of the radius change).
A second mechanism by which
eff
can exceed is floc-
culation. When particles form flocs, the liquid phase con-
tained within the interstices of the floc is not free-draining,
but effectively becomes part of the floc. Thus the volume of
a flocculated phase is augmented by the volume of trapped
interstitial liquid. Consequently, the disperse-phase volume
fraction is higher than for the deflocculated system.
Dispersions can exhibit the full range of rheologi-
cal behavior mentioned previously, including Newtonian,
shear-dependent, time-dependent, plastic, and elastic
behavior. A dispersion of noninteracting spherical particles
will be Newtonian up to about = 0.2 [15]. Above this
concentration, onset of non-Newtonian character begins
due to particle interactions and hydrodynamic factors.
Mechanisms for these effects are discussed in the section
Shear-Thinning Fluids.
RHEOLOGY AND FILM FORMATION
In the next two sections two coating flows, sagging and
leveling, are discussed. These two flows occur early in
the film formation phase in an applied coating layer. In
sagging flow, gravity acts on the wet coating layer on a
vertical substrate, causing drainage downward, which can
lead to unsightly dripmarks. In leveling flow, surface ten-
sion attempts to level out any nonuniformities in surface
height. Oftentimes good leveling and acceptable sagging
are in opposition. Acceptable appearance of a paint layer
will be dependent on proper rheological control of these
flows.
In discussing how coating rheology influences these
flows, there is an important point to be made: Both sag-
ging and leveling are driven by specific shear stresses,
which can be calculated from the forces acting (gravity and
surface tension, respectively) and the geometry of the film.
However, the shear rates over which these processes occur
can vary widely depending on the coatings viscosity at the
acting shear stress. The shear rate is a dependent variable,
for real processes. The appropriate independent variable to
best differentiate the performance of paints according to
their rheology is the shear stress. For this reason (and oth-
ers), it is preferable to plot flow curves as viscosity versus
shear stress, as opposed to viscosity versus shear rate, which
is the more common practice. To do otherwise is wrong
in principle and will result in incorrect relative ranking of
paints by their rheology with respect to their rates of sag-
ging, leveling, pigment settling, or to their ease of applica-
tion. This issue is key to using rheological data correctly in
the interpretation of flow curves.
Viscosity versus shear rate plots are in fact an incor-
rect representation of the flow properties of paints with
respect to specific coating processes, which are governed
not by shear rate but by shear stress. Plotting with shear
stress as the independent variable, as in Fig. 24, permits a
direct comparison of paints at the shear stress specific to
a particular process. Viscosity is a nonlinear function of
the shear stress, and each part of the sometimes complex
curve has a role to play in various coating processes. Fur-
thermore, because of geometrical and process variables,
the shear stress for a given process may not be constant
for the duration of the process. The process stresses illus-
trated by dashed lines in Fig. 24 are for (a) application
by brush or roller, (b) surface tension-driven leveling of
surface roughness, and (c) gravity-driven sagging of 3-,
6-, and 12-mil wet films. Gravitational settling of pigment
particles occurs at even lower stresses. The point is that,
for a given process, the shear stress acting on a coating
layer is independent of the rheology (for a given geometry,
density, surface tension). The shear rate for the process,
however, is dependent on the rheology, and will vary with
the viscosity of a particular coating at the process shear
stress. Fig. 25 shows the same two paints as in Fig. 24, but
this time with the viscosity plotted as a function of shear
rate. Note that the constant-shear-stress dashed lines now
slant to the left, and shear rates for the processes identified
in Fig. 24 are shifted to the left for the higher viscosities.
The constant-shear-stress lines cut the flow curves at the
shear rate of the process for that paint. It can be seen for
the two paints that shear rates for some process stresses
are shifted nearly two decades (100-fold). Clearly, the
assumption that processes such as leveling and sagging
occur at a constant shear rate (say, 1 s
1
) can be wrong by
orders of magnitude.
Fig. 25 also shows that if one were to predict compara-
tive paint performance from viscosities at constant shear
rate, the viscosity ratios would be several times smaller
than the correct ratios measured at the true process shear
stress. Table 5 shows viscosities at selected shear stresses
and at approximately corresponding shear rate values from
Fig. 24Log-log plot of viscosity versus shear stress for two paints:
= Paint 05; = Paint 07. Stress-Map plot showing shear stresses
calculated for specific coating processes, indicated as dashed vertical
lines, with calculated stresses, in dyne- cm
2
, attached. Process
stresses indicated are for brush/roller application; initial leveling
of sinusoidal striations of wavelength 0.1 cm and same when 50 %
leveled; sagging stresses at 3, 6, and 12 wet-mils film thickness. (From
Eley, R. R., Rheology Reviews 2005, 173-240, K. Walters and D. M.
Binding, Eds., British Society of Rheology (2005). Used by permission
of British Society of Rheology.)
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 435
Fig. 25. Crossover rheological behavior, as in Figs. 24 and
25, is very common among paints and can often lead to a
failure of lab-bench measures of rheology to correlate to
paint performance.
SAGGING
A coating layer on a nonhorizontal surface will experience a
tangential shear stress due to gravity, given by
g
gh cos
(55)
where is the liquid density, g is the gravitational accel-
eration, and h is the uniform layer depth. is the angle of
inclination of the substrate to the vertical. For a vertical
substrate,
g
= gh (Fig. 26).
The shear stress on any layer within a coating will be
equal to the load from the outer layers. For a vertical sur-
face
g
g h y ( )
(56)
is the shear stress acting on a layer a distance y from the
substrate, due to the weight of the outer layer of thickness
h y (Fig. 26).
Coating layers having a yield stress
0
(see Plastic
(Yield) Behavior) will not sag unless the gravitational shear
stress exceeds the yield value. The shear plane where yield
occurs will therefore be at y (for ideal yield behavior) when
the following expression is satisfied
0
g h y ( )
(57)
Since only layers deeper than y experience sufficient stress
to flow, it follows that the layer h y (from y to the free
surface) is solid and slides as a solid sheet over the fluid
inner layers. For a coating with a large yield stress, the
load necessary to cause yield and flow is correspondingly
greater. Therefore, the yield plane moves deeper into the
coating layer, leading to a phenomenon known as slump-
ing. Slumping, therefore, is diagnostic of the presence of
a significant yield stress. Fig. 27 illustrates the effect of a
yield stress on sagging, leading to plug flow (slumping).
Croll [73] showed direct evidence of plug flow in a sagging
coating possessing a yield stress.
Fig. 26Sagging driven by gravitational shear stress. Gravity acts
in the x-direction, film thickness coordinate is y, wet film thickness
is h. Shear stress is maximum at the substrate surface, due to the
weight of outer layers of coating.
Fig. 25Log-log plot of viscosity versus shear rate for two paints:
=Paint 05; = Paint 07. Shown also are the same dashed lines
representing constant process shear stresses as in Fig. 24, now
leaning leftward. As consequence of the leftward slant, ratios of
the viscosities of the two paints at an arbitrary shear rate are much
smaller than those at roughly similar shear stress in Fig. 24. See Table
4. (From Eley, R. R., Rheology Reviews 2005, 173240, K. Walters
and D. M. Binding, Eds., British Society of Rheology (2005). Used by
permission of British Society of Rheology.)
TABLE 5Viscosity ratios at constant shear
stress versus constant shear rate for Paints 05
and 07. (From Eley, R. R., Rheology Reviews
DCMP48 2005, 173240, K. Walters and D.
M. Binding, Eds., British Society of Rheology
(2005). Used by permission of British Society
of Rheology.)
Viscosity, Poise
Shear
stress
=8dyncm
2
Shear
rate
=0.01 s
1
Shear
stress
=80dyncm
2
Shear
rate
=1.0 s
1
Paint 05 210 410 26.7 42.6
Paint 07 8000 2526 1445 259
Viscosity
ratio
38 6.2 54 6.1
Fig. 27Slumping (plug flow), caused by the presence of a yield
stress,
0
. Coating layer of thickness h-y will slump or slide
downward as a solid sheet over liquid sublayer if
0
g(h-y).
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436 PAINT AND COATING TESTING MANUAL 15TH EDITION
Wu [74] gives sagging velocity expressions for various
types of non-Newtonian behavior. The surface velocity of a
sagging Newtonian liquid is
=
gh
2
2
(58)
Sagging transmits substrate imperfections to the coating
surface and amplifies them [75]. This is because any sur-
face irregularity necessarily results in fluctuations in the
local coating thickness normal to gravity and therefore in
the local sagging shear stress. Furthermore, any local varia-
tions in film thickness due to application or to substrate
features (e.g., a hole or a corner) can produce local accel-
erations of sagging in which thicker elements overtake thin-
ner elements. This is a self-accelerating process, leading to
drips, tears, runs, or curtaining [76]. Such undesired
flows can be minimized by proper characterization and
control of rheology [77].
The sagging of a coating is similar to the problem of
drainage of a liquid layer from an inclined surface. The
difference between the two is that, in sagging, the coating
layer is assumed infinite in extent; hence, sagging causes no
change in the local coating thickness, on a flat substrate. If
this assumption is not correct, then gravitational flow will
result in thinning of the coating layer at the top and thick-
ening at the bottom of a finite substrate. The distinction
between the two processes may be useful for those desiring
to calculate, for example, the degree of wedging on a dip-
coated part as against simply calculating a sag length or
sagging velocity. Again, in the case of sagging, h is assumed
constant and a sagging distance x may be calculated,
whereas for drainage the thickness h varies with distance x
down the substrate. The equations describing the flow are
otherwise identical and interchangeable. By a derivation
similar to that of Wu [74,78] for sagging, the expressions
below, describing drainage, can be obtained.
For a Newtonian liquid, the thickness at time t at a
distance x down from the upper edge of the liquid layer is
given by
h
x
pt
=
cos
(59)
The angle is as defined above. Most coatings are non-
Newtonian, however, which will have great impact on the
drainage behavior. For example, shear-thinning fluids will
drain to a much more uniform film thickness than Newto-
nian fluids. The gravity drainage of a power law fluid (see
Shear-Dependent Viscosity) is given by
h
n
n
x
t
K
g
n n
=
+1
1
j
(
,
\
,
(
j
(
,
\
,
(
,
,
]
]
]
j
(
,
+ /( )
cos
\\
,
(
+ 1 1 /( ) n
(60)
In the above, K is the consistency term and n the exponent
in the power law expression (see Shear-Dependent Viscos-
ity). Here we see a practical application of mathematical
flow models. The parameters obtained from fitting the
power law to an experimental flow curve can be inserted
into the above equation and the sagging behavior of a
coating formula can be calculated and graphed. For shear-
thinning fluids with yield stress, the drainage equation is
h
n
n
x
t
K
g
n n
=
+1
1
j
(
,
\
,
(
j
(
,
\
,
(
,
,
]
]
]
j
(
,
+ /( )
cos
\\
,
(
+ 1 1 /( ) n
g
+
0
(61)
The constants n, K, and
0
are obtained by fitting the Her-
schelBulkley flow model to the experimental flow curve
(see Shear-Dependent Viscosity).
As with leveling, a realistic description of sagging must
include not only non-Newtonian effects, but also effects of
drying, geometry of the applied film, and the instantaneous
rheological state of the applied film. Croll has published a
review, analysis, and experimental study of sagging which
examines these effects [73]. Eley and Schwartz [79] have
used numerical simulation to analyze in detail the effect of
rheology and substrate shape on the variation of film thick-
ness in a drainage flow.
Measures of Sagging
A number of laboratory methods for evaluating sagging
have been used, some of which measure some rheologi-
cal property related to sagging behavior [80] and some of
which measure sagging directly. Among the latter is ASTM
D4400, in which a drawdown blade with multiple slots of
graduated depths spreads paint stripes of graduated thick-
nesses over a nonabsorbent substrate (Leneta drawdown
bar and sag chart). The chart is suspended vertically and
the paint stripes allowed to flow under gravity. Sag is rated
according to the thickest stripe that does not show sag (Fig.
28). A similar but somewhat simpler test involves the use of
a wire device that scribes two lines, of 1/8 and 1/4 in. (0.32
and 0.64 cm) width across a 3-wet-mil paint stripe, which
is then hung vertically, and sagging is visually evaluated on
the dry paint film.
11
The method is illustrated in Patton [81].
Another device that has apparently met with some success
is the so-called sagging balance [82], which uses an elec-
tronic balance to measure the shift in mass accompanying
drainage of a coating applied to an inclined plate.
Sagging is, of course, driven by gravitational shear
stress. The magnitude of the sagging shear stress depends
solely on the wet film thickness and density [Eq (55)].
The resulting shear rate of sagging is determined by the
rheology profile of the paint in question. It is imprecise
to attempt to predict sagging from viscosity measure-
Fig. 28Sagging evaluated by Leneta drawdown blade. Sagging is
rated by the thickest paint stripe that does not show sag.
11
Federal Test Method 4493, September 1965.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 437
ments at an arbitrary sagging shear rate and may lead
to incorrect estimates of relative sagging. The proper way
to predict relative sagging tendency is to plot viscosity
as a function of shear stress rather than shear rate as in
Fig. 24. Shear stress levels corresponding to the pertinent
wet film thickness can be calculated, and the magnitude
of the viscosity controlling sagging, determined from the
graph. Fig. 29 compares two paints in this manner, with
indicated gravitational shear stress levels corresponding
to a wet film thickness of 12 mils. The dashed lines in Fig.
29 indicate the approximate shear stress of the Stormer
paddle viscometer for the two paints. At the Stormer shear
stress (approximately like hand stirring), the viscosity of A
is higher than B (12 vs. 7.5 P). This difference is easily felt
when hand stirring the two paints. However, at the sag-
ging shear stress of about 40 dyncm
2
paint B is over 60%
higher in viscosity, and should therefore sag less than A,
which is observed experimentally.
LEVELING
The mechanics of coating application generally cause the
applied coating layer to be initially rough and consequently
of varying thickness. Uniform film thickness is desired both
for reasons of appearance (color and hiding uniformity)
and for substrate protection (necessary minimum film
thickness). The process of smoothing of the initial rough
surface is called leveling. Adequate leveling is of obvious
critical importance to the success of a protective or decora-
tive coating. Hence, a large number of studies of the subject
have been published (e.g., Refs. [1,41,8391]), but the role
of rheology and other factors in the leveling of paint films
is not fully understood. One might expect leveling to cor-
relate reasonably well to low-shear viscosity. However, fac-
tors such as viscoelasticity, time dependence, volatilization,
wicking, and surface tension gradient flows make leveling a
complex process. The leveling and film formation of a paint
layer is so complex that, in the opinion of this author, only
computer modeling has the potential to provide a wholly
satisfactory method of analysis and prediction (see, for
example, Eley and Schwartz [79,87]). However, such model-
ing capability is not readily available to most practitioners,
so we will review some of the analytical models of leveling.
These can provide at least a qualitative understanding of
the role of rheology and other factors in leveling.
The mechanism of leveling is illustrated in Fig. 30
for a liquid without surface tension gradient (/x = 0),
having a sinusoidal surface profile. The sum of all surface
tension vectors in the curved surface produces a net force
downward at the peaks and upward in the valleys, the
liquid-air interface acting as if it were a stretched elastic
membrane. Forces due to liquid surface curvature are
called capillary forces and result in capillary pressure varia-
tions within the liquid layer (P/x 0). Thus, leveling is
driven primarily by capillary pressure gradients due to local
surface curvature, under conditions of uniform surface ten-
sion. Liquid is pumped from the peaks into the valleys,
ultimately producing a level surface. For thin films, gravity
is of negligible effect on leveling unless a critical roughness
wavelength is exceeded. For a typical paint, the critical
wavelength is of the order of 1 cm [93].
The quantitative prediction of leveling from physical
properties requires the use of some mathematical model
of the process. Smith et al. [1] derived such a model by a
linear lubrication approximation-type analysis, assuming a
uniform sinusoidal surface profile. (The Los Angeles Paint
Club obtained a similar equation in 1953 [94] for surface
roughness approximated by semicircular arcs.) Orchard
later [95] developed a complicated expression for the level-
ing of a more realistic, arbitrarily rough surface profile in
terms of a Fourier series. However, the expression simpli-
fies considerably when the coating thickness is assumed to
be small relative to the roughness wavelength. Assuming a
single sinusoidal wavelength (which is a reasonable approx-
imation since the leveling behavior will be dominated by
the longest wavelength), the Orchard equation is
In =
a
a
h t
t
0
4 3
4
16
3
(62)
for constant surface tension and viscosity . The equation
says that the ratio of the surface wave amplitude a at time
Fig. 30Surface tension-driven leveling. Curvature of liquid surface
creates capillary overpressures and underpressures P. There is no
surface tension gradient along the film coordinate (/x = 0).
Pressure is not uniform, however (P/x 0), and drives fluid flow
toward leveling of surface height variations.
Fig. 29Illustration of how to obtain the viscosity governing sagging
from flow curve data. The gravitational shear stress driving sagging
is indicated for a 6-mil wet film thickness. This stress intercepts the
flow curves for paints A and B at the viscosities resisting drainage
flow. B is higher than A at sagging stress and so would sag less.
Stormer
+
j
(
,
\
,
(
j
(
,
\ 1
0
1
1
1
2 1
2
=
,,
(
+
+
( )
( )
3
2 1
n n
n n
h
t
(63)
This expression contains the power law coefficients, K
and n, all other terms retaining the same definitions as
above. Note that the leveling rate increases as the power
law exponent, n, decreases (i.e., as the paint becomes more
shear thinning). As expected, the leveling rate decreases
with increasing K (consistency). Lu [55] found the Murphy
equation valid for correlating the change of brushmark
amplitude with time for systems where the leveling was
clearly dominated by the viscosity. However, the Murphy
equation still assumes that viscosity depends only on shear
rate and that surface tension does not change during the
leveling process. In reality, viscosity and surface tension will
both change due to evaporation of the volatile phase of the
coating or to wicking. The Murphy equation may be modi-
fied to take account of time-dependent viscosity increase by
including a time-integral expression for the viscosity
a a
n
n
n n n n n
n
( )/ ( )/
( )
+
+
j
(
,
\
,
(
1
0
1 1
3
1
2 1
2
=
nn
n n
t
h
t
dt
( )
( )
2 1
0
1
+
j
(
,
\
,
(
(64)
where (t) is some time function of viscosity relating
effects of thixotropy, drying, wicking, etc. The effect of
time-dependent viscosity on leveling is dramatic, as shown
in Fig. 31. Here, for two different paints, the decay of
surface amplitude is calculated using Eq (63) and (64),
together with an experimentally determined expression for
the increase of viscosity with time due to drying. Camina
[84] reported that the viscosity of a drying paint increases
exponentially in the initial stages. Therefore, an expression
such as the following would fit drying-viscosity data
( ) ( ) t e
kt
= 0
(65)
where (0) is the viscosity before drying has begun, k a dry-
ing rate constant, and t the time. Such an expression can
be inserted into Eq (64) in place of (t) and integrated
12
to
calculate the leveling curve for a paint whose viscosity is
increasing with time due to solvent loss.
Quach [93] has discussed and summarized the short-
comings of various laboratory methods of leveling evalu-
ation. As noted by Quach, much work on leveling has
been done without adequately taking into account the
numerous interacting subprocesses whose final result
is the dried film profile. An additional important factor
dealt with experimentally and theoretically is the influ-
ence of surface tension gradient-driven flows (Marangoni
flows) [86,97,98]. Surface tension gradients may arise
due to a number of causes during film formation and can
have consequences for the course of film leveling, among
other things. Figure 32 illustrates the mechanism of sur-
face tension gradient-driven flow, which can result in the
deleveling of an initially level liquid layer. Local surface
tension gradients can develop due to differential solvent
evaporation or to temperature gradients (or other causes).
This results in a surface flow from regions of low surface
tension toward regions of high, in an attempt to reach sur-
face equilibrium. The moving surface drags subsurface
liquid along, creating a bulk flow. This is the Marangoni
effect. In the case of differential evaporation, the driving
force for Marangoni flow is a shear stress
s
tangent to the
film surface, given by
s
S
S
x x
= =
[ ]
[ ]
(66)
where y/ [S] is the dependence of surface tension on sol-
vent concentration and [S]/x is the solvent concentration
gradient (x is the coordinate along the substrate). Hence,
the surface tension gradient /x drives the flow. For the
case where Marangoni flow is driven by thermal surface
tension gradients, replace [S] by T in the above. If sur-
Fig. 31Calculated brushmark leveling for two paints, with and
without effects of drying. Curves calculated using Eqs (64) and (65):
Paint A, with drying; Paint A, without drying; Paint B,
with drying; Paint B, without drying.
12
Provided that the viscosity during drying is measured at unit
shear rate, K in Eq (63) becomes in Eq (64).
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 439
face tension gradients persist until the film is incapable
of reflow, an appearance defect will result. Overdiep [86]
demonstrated (for solvent-based paints) that Marangoni
flows initially enhance the leveling rate, but can produce
a rebound effect that ultimately worsens film roughness.
Wilson [98] recently modeled this behavior by a linear
perturbation analysis. Other authors have discussed the
importance of Marangoni flows for waterborne, cosolvent-
containing coatings [87,99].
The role of viscoelasticity in leveling has been a subject
of some debate, with some authors concluding that elastic-
ity enhances leveling [100] and some that it retards leveling
[41,101]. The evident link between elasticity and the under-
lying structural rheology for coatings (see Viscoelasticity
and Industrial Processes) suggests the presence of a gel-like
structure of some sort in systems possessing significant
elasticity. Such a structure would be expected to inhibit
flow at low stress levels so that coatings that exhibit elastic-
ity should also show poorer leveling. The leveling behavior
of viscoelastic systems has been modeled by Keunings and
Bousfield [41], where the presence of viscoelastic relaxation
shown to retard leveling. The leveling rate as a function of
the Newtonian leveling rate
Newt
was shown to be
=
+
Newt
Newt
1
(67)
where = rate of change of roughness amplitude (s
1
), and
is the elastic stress-memory time constant (or relaxation
time) (see Viscoelastic Models). In Eq (67), the Newtonian
leveling rate is always positive, hence elastic extra stress
( > 0) always retards leveling. Interestingly, if surface
tension gradients are present,
Newt
may actually become
negative (i.e., deleveling). In such cases, late-developing
elasticity will be of benefit by retarding the de-leveling.
Table 4 shows the results of a calculation similar to that of
Keunings adapted for the case of a typical paint. It is seen
that, for =100 s, the leveling rate dramatically decreases
and the leveling half-time increases (by a factor of 3,500),
relative to the Newtonian ( = 0) values.
Measures of Leveling
Visual evaluation of leveling is common practice. However,
it is generally agreed that visual rating is subjective, and
leveling rankings are often found to be operator-dependent.
Numerous objective methods and standards have been
published. Quach [93] discussed aspects of both scientific
and laboratory practical studies of leveling. For the latter,
special drawdown blades have been used such as the NYPC
leveling test blade (ASTM D2801: now withdrawnno
longer an ASTM method), which has five pairs of notches
over a range of depths. Leveling is judged by the flowing
together of adjacent paint stripes. This method has been
criticized by Quach and others [29] because the paint pass-
ing through the notches experiences a varying shear rate
with notch depth, resulting in a different shear history for
each stripe, and because the shear rate achieved is unreal-
istically low. The latter test has been superseded by ASTM
D4062, based on a grooved drawdown rod. In this method,
the paint is presheared, simulating brushing shear rates,
by ejection from a syringe and 15-gauge needle prior to
drawdown. The leveling quality is then estimated by visual
comparison of the dried film with plastic leveling standards
viewed against oblique lighting.
Kornum [102] gives a good discussion of issues of
measurement under test conditions approximating real
paint processes, including leveling. Dodge [29] also empha-
sizes that the best rheological test for leveling should most
closely simulate the application experience of the paint.
This means (1) the paint should experience shear rates/
stresses of similar magnitude and duration to those of the
application process, (2) the shear rate/stress should then
be step-changed to values representative of the leveling
process, and (3) the change of viscosity with time should
then be followed under the latter conditions. This proto-
col is essentially identical to the step-shear method of
characterizing thixotropic recovery described in Thixot-
ropy Test Methods. This kind of procedure is most easily
accomplished by employing a rheometer capable of job
streaming or linked methods. However, the foregoing
method still suffers from the limitation that the effect of
drying on viscosity during the leveling period is neglected.
Fig. 31 demonstrates that this can be a very significant
effect. Paints A and B were commercial formulas which
differed markedly in leveling performance. The increase of
viscosity with time during drying of a film of typical applied
thickness was measured for both and found to obey Eq
(65). The latter expression was then inserted into Eq (64)
as the time-integral function for viscosity (as described in
the previous section) and the leveling curves in Fig. 31 were
calculated. There are two curves for each paint, one show-
ing how the paint levels without the effect of drying, and
one calculated taking the increase of viscosity due to drying
into account. The effect of drying is most dramatic on Paint
B, where the reduction of surface roughness achieved after
3 min decreases from 50 % to 10 %.
It is established that leveling shear stress decays expo-
nentially as leveling progresses [80]. A controlled-stress rhe-
ometer with programmable logarithmic stress ramps offers
the ability to simulate the variation of viscosity with real-
istic shear-stress decay using variable ramp times. Leveling
efficiency might then be judged by numerically integrating
the fluidity over the leveling period
=
0
t
1
dt
(68)
Fig. 32Deleveling by Marangoni (surface tension gradient-driven)
flow. Surface tension gradient (/x 0) drives surface flow,
resulting in bulk flow and de-leveling of initially level surface.
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440 PAINT AND COATING TESTING MANUAL 15TH EDITION
The leveling might be expected to be logarithmically related
to the fluidity integral [103].
A very promising method for direct observation of
paint leveling has been described by Klarskov [88]. It is
an optical interferometric method that is simple but quite
precise for real-time surface profile measurement, having
a vertical resolution of a fraction of a micron. At present,
unfortunately, there is no commercial instrument based on
Klarskovs method.
RHEOLOGY INSTRUMENTATION
A great number of instruments have been devised to mea-
sure viscosity or consistency in the industrial laboratory.
However, a number of them have serious design limitations
that make them generally poorly suited for measurements
of non-Newtonian fluids. The importance of this issue
becomes apparent when it is realized that the majority of
coatings and coatings components are non-Newtonian, yet
many laboratories continue to use methods that are not
suited for such materials. The problem with many familiar
laboratory viscometers is that the flow field (trajectories of
fluid elements or streamlines) is complex and not subject
to mathematical analysis. The result is that an accurate
stress or strain rate cannot be calculated. Therefore, the
true (absolute) viscosity cannot be known. Furthermore,
the nonuniformity of the shear field causes the viscosity to
vary within the test specimen for non-Newtonian materi-
als. For complex flow fields, such an error cannot be cor-
rected. The measurement error will be in proportion to the
degree of deviation from Newtonian character. A second
important deficiency of most simple viscometers is a lack
of temperature, which can contribute a very significant
measurement error. Nevertheless, such instruments have
been in use throughout the industry for decades and no
doubt will continue to be used for the foreseeable future.
The approximate measurement given is somehow related
by the practitioner to something believed relevant to the
performance. One suspects that when the result is contra-
dictory, as is probably often the case, it is either ignored or
worked around. We shall refer to this type of device as
a Q/C (quality control) instrument or a qualitative vis-
cometer. It should be emphasized that these instruments
are accurate for Newtonian or near-Newtonian materials
and are generally useful as Q/C test devices even when the
measurement is approximate. However, the practitioner
should be alert to situations where their deficiencies can
be of significance.
In years past, many coating fluids were nearly New-
tonian, which accounts in part for the success of Q/C-type
instruments. As alluded to before, it is very easy to charac-
terize a Newtonian fluid. Virtually any type of flow measure-
ment device may be used to obtain accurate information on
the viscosity of such a material provided the device used is
calibrated with known standard fluids and the temperature
is controlled. It is not even necessary to know the shear
rate of the measurement since Newtonian fluid viscosity
is independent of the shear rate. Consequently, Newtonian
viscosity measured by any test is valid for all process con-
ditions (except turbulent flow). Even instruments which
measure viscosity according to some arbitrary scale may be
used since they may be calibrated in absolute units using
Newtonian standard fluids.
A requirement for an instrument to measure non-
Newtonian fluids properly is that the flow field within the
test fluid be viscometric, defined as everywhere indistin-
guishable from steady simple shear [104]. Instruments
which measure under such well-controlled conditions we
will call research instruments. Nonviscometric flows such
as tube flow can be used for non-Newtonian fluids when
necessary corrections are applied.
Q/C INSTRUMENTS
These are of three types of Q/C instruments, which are as
follows: (1) efflux devices, (2) rotational devices, and (3)
obstructed-flow devices (following Barnes et al. [105]).
Efflux Devices (Orifice Flow)
Efflux devices, or orifice cups, come in a variety of types,
but share one principle: measuring viscosity by flow from
a reservoir or cup through a restriction of some type. In
most cases, the restriction is simply a hole in the bottom of
the reservoir, but in some it is a short tube. These devices
have the advantages of low cost, ease of cleaning, durabil-
ity, and simplicity in the measurement, which is simply the
time to empty (in whatever manner empty is defined).
However, they also have a number of limitations. The first
is that the flow is never viscometric. Even when the fluid
exits via a short capillary tube, the length-to-diameter ratio
is too small for proper tube flow to develop, so that the flow
is dominated by entrance effects. In fact, the orifice cups
have been described as poor capillary viscometers. Since
substantial shear stress is not developed in the exit hole,
orifice cups are not suitable for very thin liquids because
a significant fraction of energy is dissipated not in viscous
flow, but rather to accelerate the fluid. In other words, mea-
surements on low viscosity fluids are subject to significant
fluid inertia errors. Thus, for the Ford No. 4 Cup (ASTM
Method D1200), liquids with an efflux time of less than
20 s should not be used. The flow in efflux cups is stress-
driven, controlled by the hydrostatic head, i.e., the fluid
height in the cup. The pressure varies as the liquid drains;
consequently, the shear stress and flow rate vary during the
test. The viscosity of shear-thinning liquids, therefore, will
increase in the course of the test, and in extreme cases such
materials may not fully drain from the cup. Because the
flow field is complex, the shear rate cannot be calculated,
and from the previous argument will depend on the viscos-
ity-shear stress relationship for non-Newtonian materials.
For the above reasons, it must be concluded that orifice
cups are really only suitable for viscosity measurements of
Newtonian liquids of moderate viscosity. Non-Newtonian
liquids should not be tested unless they are nearly Newto-
nian within the shear rate range of the test. Materials with
possible yield stress (meaning any thixotropic materials)
should not be tested with efflux devices. A final caution for
these devices is that, unless the temperature of the cup is
controlled by means of a water jacket, large errors are likely
to result. Even if the test liquid is thermostatted in a water
bath prior to test, it can rapidly change in temperature and
viscosity when placed in a cup that is at the temperature of
the room. Fig. 33 shows data for replicate measurements
on a Ford #4 cup with and without temperature control.
Obviously, the errors in the data taken with the standard
cup would hide the real batch-to-batch differences of the
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 441
product. A good Q/C test should reveal, not obscure, prod-
uct variability.
Rotational Devices
STORMER
VISCOMETER
The widely-used Stormer Viscometer
13
was one of the earli-
est controlled-stress rotational viscometers [106]. Rotors of
various geometries are available, but the paddle rotors,
in which two small vanes are attached in offset fashion to
a rotating shaft, are used exclusively for the measurement
of the consistency of paints. During a measurement (in
the original device), the rotation is driven by a free-falling
weight attached to a string and pulley arrangement, the
string being wound around a drum. The shear stress is
varied by use of different weights. A counter tallies up the
number of revolutions as the weight falls. After the first ten
revolutions, the time required for the next 100 is measured.
(Stroboscopic timers are available.) The apparent viscosity
is calculated from a plot of applied torque versus rotor rpm.
The measurement can also be made in terms of the weight,
W, required to achieve a rotational speed of 200 rpm. The
viscosity is obtained according to an arbitrary scale called
Krebs units (KU). A conversion table of W versus KU is
supplied. Electronic versions of the device are available
(see below), which operate at constant speed rather than
at constant stress. This difference may produce slightly
different results as compared to the nonelectronic versions
of the instrument, unless care is taken to reproduce the
same conditions of measurement. As with any viscometer
whose flow field is complex, an absolute viscosity (i.e., in
engineering units of Poise or Pascal seconds) cannot be
calculated with the Stormer for non-Newtonian fluids. The
Stormer viscometer is specified in a number of standard
test methods.
14
For its purpose, i.e., to measure the in-can feel of
paint, the Stormer is a very good viscometerthat is, the
Stormer measures by stirring the paint, as the consumer
would. Thus, the instrument satisfies the criterion of
measuring under conditions closely approximating those
of a relevant process. This justifies the use of an arbitrary
measurement scale, in this case, and makes the Stormer a
useful component of the paint laboratory. The only caveat
would be not to violate the above-mentioned principle by
attempting to use Stormer data to predict paint perfor-
mance for a process that is far removed from the flow kine-
matics of the instrument.
THOMAS-STORMER
=
( )
s l
gd
U
2
18
(69)
where g is gravitational acceleration. This deceptively
simple method has several drawbacks, however. For one,
the Stokes solution is only valid for low Reynolds numbers
(viscous forces controlling, rather than fluid inertia, i.e.,
slow flow), and for low-viscosity fluids the ball density must
be small enough to produce appropriately slow rates of fall.
For another, a wall correction may be needed to account for
the interference of the container wall with the flow field of
the ball and hence its falling rate. Perhaps the greatest dif-
ficulty, however, is the fact that the flow field around a mov-
ing sphere is complex, and when the fluid is non-Newtonian
the complexity becomes mathematically intractable. There-
fore, for non-Newtonian fluids, the falling-ball apparatus
will not yield absolute viscosity, and the results would not
be expected to correspond with those from an instrument
having viscometric flow geometry. A solution to the above
problems is provided by a relatively new instrument called
the falling needle viscometer (see below).
Rising-Bubble Viscometers
If certain flow field assumptions are made for a rising air
bubble in a liquid, the viscosity of the liquid can be calcu-
lated from [49]
=
1
3
gR
2
(70)
where is the liquid density, R is the radius of the air
bubble, and v is the rising velocity. However, the calcula-
tion is only approximate because the air bubble shape often
deviates from the assumed sphericity due to buoyancy.
Furthermore, if the liquid phase were non-Newtonian, sig-
nificant errors would result for which there is no correction
available.
The Gardner-Holdt bubble tubes provide a rapid means
of estimating the kinematic viscosity (see Capillary Vis-
cometers) of transparent liquids such as varnishes and
resins using the rising bubble principle. These consist
of a series of sealed glass tubes containing mineral oils
comprising a range of standard viscosities. The test liquid
is placed into a similar tube (ensuring the contained air
bubble is the same volume) and thermostatted in a water
bath. The test material and a rack containing the standard
tubes are inverted, and the viscosity of the test specimen is
identified according to the letter (or sometimes number)
designation of the standard tube whose rate of bubble rise
is nearest the same. Interpolation between the standards is
sometimes done. Bubble tubes are disposable, easy to use,
and the results can be converted to kinematic viscosity by
means of tables. Bubble tubes can also be used to measure
resin color. For process resins nearing the gelation point,
the bubble can display a pointed tail, or pronounced
inverted teardrop shape, an indication of the onset of vis-
coelasticity. As a reference for the use of the Gardner-Holdt
method, see ASTM D1545.
16
RESEARCH RHEOMETERS/VISCOMETERS
Research-quality rheometers are mainly of two types:
rotational rheometers and efflux rheometers. Rotational
rheometers employ steady (uniform) shear, oscillatory
shear, and transient (time-dependent) shear experiments of
various types. Efflux rheometers extrude the fluid through
a small-gap orifice, which can be a capillary tube, a slit, or
an annulus (concentric cylindrical-walled tube). The flow
in these devices is well-defined and data can be obtained
in absolute or engineering units for non-Newtonian fluids.
Summaries of instrumentation and methods are found in
Refs. [107109]. Although dated, Van Wazers book is still
a useful source [49]. Appendix A lists vendors of research
rheometers and viscometers.
Rotational Instruments
CONTROLLED STRESS AND CONTROLLED RATE
There are two basic types of rotational viscometers, which
work in the following ways: (1) apply a controlled rotation
rate and measure the opposing viscous torque or (2) apply
a controlled torque and measure the resulting rate of rota-
tion. In the first case, which may be termed controlled-
strain or controlled strain rate, the applied angular
velocity is the independent variable and the viscous drag
torque the dependent or measured variable. In the second
case, termed controlled-stress, the applied torque is the
independent variable and the measured angular velocity
the dependent variable. Examples of controlled strain rate
instruments include the Wells-Brookfield Cone and Plate
Viscometer, the Haake RotoVisco 1, and the TA Instruments
ARES. Instruments of the controlled-stress type include the
TA Instruments ARG2, the Reologica Stresstech HR, the
Thermo Haake Rheostress 600, and the Physica MCR-series
rheom-eters. See Appendix for a list of instrumentation
vendors.
The choice between the two types of instruments
depends on the material under test and the intended experi-
ments. In terms of performance, controlled-stress (CS)
instruments can measure much lower angular velocities
than can controlled-strain-rate (CR) instruments, but CS
instruments tend to be more limited at the high angular
velocity and oscillation frequency end. Both CS and CR
16
Additional standard test methods using bubble tubes are ASTM
D803, D1131, and D1725 and Federal Test Method 4271 (141-a).
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 443
instruments have inertia issues affecting the accuracy at
high frequencies or for rapid accelerations. In the case of
CS, the issue is measurement system inertia and is correct-
able; for CR the problem is torque measurement system
resonance and is not correctable. CS is well suited to mea-
suring long relaxation times because of the stability of the
applied torque [110].
CR instruments impose a shear-rate sweep while mea-
suring the drag-torque response of materials. Structured
fluids tend to be shear-sensitive (more precisely, strain-
sensitive). Consequently, as strain increases exponentially
under a linear strain-rate sweep protocol, fluid structure
tends to collapse rapidly, with the result that relatively few
data points are obtained to provide information on struc-
ture. In contrast, CS devices use linear (and logarithmic)
rates of stress increase, an intrinsically gentler mode
of deforming materials, which allows materials to obey
their own rules of stress-strain response, thus resolving
the maximum amount of information. CS instruments are
especially useful for characterizing structured fluids, such
as paint, printing ink, adhesives, ceramic slips, coal slur-
ries, cement, pigment and colorant dispersions, drilling
muds, medicines, foodstuffs, cleaners, personal care prod-
ucts and cosmetics, solder pastes, etc. This is particularly
true where materials exhibit yield behavior. CS instruments
can, in principle, directly measure the stress at the onset of
yield (see Plastic (Yield) Behavior), avoiding errors associ-
ated with extrapolation or curve-fitting methods (see Yield
Stress Test Methods).
CS and CR instruments each do their own version
of a transient experiment: creep for CS and stress relax-
ation for CR. The stable torque and high strain resolution
capabilities of CS mean creep experiments can be used to
probe very slow relaxation processes. A modified creep
methoda programmed series of small torque incre-
mentscan be used for determining the first Newtonian
plateau down to very low shear rates, e.g., region I of the
equilibrium flow curve (see Shear-Thinning Fluids). A
limiting factor in the accuracy of such methods, however,
is the ability to minimize or correct for spurious air bear-
ing torque.
INERTIA CORRECTION
It can be particularly important for rotational rheometers
of the controlled-stress type to correct the data for inertia
error. If the test fluid is low in viscosity, and/or the test rotor
has a large moment of inertia, and/or the acceleration is too
high (short ramp time), a significant portion of the applied
torque is dissipated not viscously, but in the acceleration of
the rotor. A correction for this error has been published by
Krieger [111]. Some commercial controlled-stress instru-
ments now feature on-line inertia correction.
Brookfield Viscometers
BROOKFIELD SYNCHRO-LECTRIC
The Brookfield Synchro-Lectric viscometer utilizes a set of
spindles or disks as the rotor/sensor, which are rotated in
the test fluid at selected rpm, so that the apparent viscos-
ity may be measured at several shear rates to obtain a flow
curve. Its advantages include low cost, simplicity of use,
ease of cleaning, and durability. The instrument is in wide
use throughout the industry and is the basis for ASTM
D2196 and a number of other ASTM test methods.
17
It is
included here in the list of research quality viscometers
because the viscosity can be reported in absolute units over
a range of shear rate, although often it is not (see below).
Its limitations include the latter fact, plus that temperature
control is not integral to the instrument. The Synchro-
Lectric is available with digital output, automatic viscosity
calculation, and computer-interfaced versions with analysis
and graphing software.
Brookfield spindle viscometer measurements suffer
from the use of arbitrary or nonfundamental units in
reporting the result. Even though the viscosity is reported
in absolute units (cP or mPas), the shear rate is not. Thus,
both the spindle speed (rpm) and the spindle identity
must be reported along with the measured viscosity. The
measured viscosity can be different at the same rpm if a
different size spindle is used. Without knowing the actual
shear rate of measurement, an absolute flow curve can-
not be constructed from the results. The true flow curve is
desirable for several reasons, among them the possibility
of comparison with results from other instruments, the
quantitative description of the sample rheology by use of
mathematical flow models and the subsequent application
of such models to predict paint performance (see Leveling
and Sagging for example). Methods for calculation of the
corrected shear rate for Brookfield RVT spindles were given
by Williams [112] and also Pierce [113]. Smith [85] has
given a simplified method. (See also Ref. [22], pp. 2831.)
Some of the foregoing issues are at least partially resolved
with certain accessories available from Brookfield. These
include options that have small-gap bob-in-cup geometry
and temperature control, e.g., the small-sample adapter.
WELLS-BROOKFIELD CONE AND PLATE
VISCOMETER
Brookfield also offers an instrument possessing a well-
defined geometry and good temperature controlthe
Wells-Brookfield cone and plate viscometer. Its operation
and appearance are very similar to the Synchro-Lectric,
except the lower end has been modified to mount a cone
and plate geometry with integral temperature control via a
water jacket. Because the true shear rate can be calculated
from the cone geometry and rpm, the viscosity of non-New-
tonian materials can be measured in absolute units and an
equilibrium flow curve determined. This instrument, there-
fore, is recommended over the standard Synchro-Lectric
for routine viscosity measurement.
BROOKFIELD DV SERIES RHEOMETERS
The DV series of viscometers is basically an enhanced spin-
dle-disk system offering programmability, a range of rota-
tion speeds and computer interface and control capability.
BROOKFIELD CAP 2000 VISCOMETER
The Brookfield CAP 2000 multispeed digital cone-plate vis-
cometer is similar to the ICI cone and plate viscometer, but
represents an improvement in that it is capable of variable
shear rate measurement (10 to 12,000 s
1
). It also provides
a digital display of viscosity and temperature as well as a
17
These include ASTM D115, D816, D1076, D1084, D1286, D1337,
D1338, D1417, D1439, D1638, D1824, D2364, D2393, D2556, and
D2669 and Federal Test Method 4287.
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444 PAINT AND COATING TESTING MANUAL 15TH EDITION
data interface to a personal computer or data logger with
applications software.
ICI CONE AND PLATE VISCOMETER
The ICI cone and plate viscometer is a relatively high shear
rate instrument capable of absolute viscosity measurement.
It is normally sold in a room-temperature, single-speed
configuration. Temperature control is integral to the instru-
ment, but there is no provision for control of solvent loss
from the sample. This can be improvised, if desired. A high-
temperature version is available, which is useful for resin
melt viscosity measurement. The chief use of the instru-
ment has been the measurement of viscosity at a shear rate
of 10,000 s
1
(at 50 Hz alternating current) or 12,000 s
1
(at 60 Hz ac) for the prediction of brushability. (See ASTM
method D4287, titled High-shear viscosity using a cone
and plate viscometer.)
FALLING-NEEDLE VISCOMETER
This is an obstructed-flow device that utilizes a long,
slender rod or needle as the falling object. In so doing,
it overcomes the objections to the falling ball viscometer
while retaining the latters simplicity of operation and
relatively low cost [114]. The needle is hollow (allowing
a wide range of needle densities) with hemispherically
capped ends. End effects due to the finite needle length
are mathematically correctable. This geometry produces
a well-behaved flow field known as annular-ducted flow,
with the central tube (needle) moving at a constant (ter-
minal) velocity. Because of the well-defined flow field the
true velocity gradient between the needle and container
wall can be obtained, and the instrument therefore is suit-
able for measurements of non-Newtonian fluids [115]. The
falling-needle viscometer may be useful for determination
of very low shear stress or shear rate behavior of non-
Newtonian fluids, for example the zero-shear viscosity
(region I of Fig. 3) and measurement of yield stresses
[116].
18
Fig. 34 compares first- and second-run flow curves
of a semigloss paint, obtained on a rotational rheometer,
with data points obtained from the Irvine-Park Falling
Needle Viscometer (FNV). The agreement is quite good
with the up curve of the second run, indicating that the
FNV experiment imposes enough shear on the sample
during the measurement that the results correspond to a
pre-sheared system rather than to a previously unsheared
system. This was found to be a consistent result for several
paints. For highly thixotropic paints, the result was in
between the first- and second-run flow curves.
CAPILLARY VISCOMETERS
Capillary tube flow is a classical viscometric method that is
useful for coatings in two main ways. Capillary viscometry
is the method of choice for measurement of intrinsic viscos-
ity (ASTM Method D446 and D2162) (see also Dispersion
Rheology) and also for the measurement of very high shear
rate rheological properties (see below).
For fluid flowing through a tube, the shear stress at the
tube wall is
w
PR
L
=
2
(71)
where P is the decrease in pressure occurring over tube
length L of radius R. The shear rate at the tube wall for a
Newtonian fluid is given by
w
Q
R
=
4
3
(72)
where Q is the volumetric flow rate (cm
3
s
1
). The viscos-
ity is then
= =
w
w
R P
LQ
3
8
(73)
which is the well-known Hagen-Poiseuille equation. For
pressure-driven capillary flow, particularly for high-shear
measurements, a correction to Eq (73) is required because
the fluid undergoes a large acceleration as it enters the
capillary. Therefore, the acceleration of the fluid accounts
for part of the energy loss represented by the pressure drop
P. As a result, the calculated viscosity will be too high and
a subtractive term or kinetic energy correction is necessary
=
R P
LQ
m Q
L
4
8 8
(74)
where = fluid density and m is a constant equal to unity
for Newtonian fluids. For non-Newtonian fluids obeying
the power law (see Shear-Thinning Fluids), m is calcu-
lated from
m
n
n n
=
+1
+2 +3
3 3
4 5
2
( )
( )( )
(75)
where n is the power law exponent. Various additional cor-
rections for capillary flow are described in van Wazer [49].
The pressure head P can be created two ways: By
pressurizing the delivery vessel or by relying on a gravita-
tional hydrostatic head to drive the flow through the capil-
lary. In the latter case, the density of the fluid becomes an
important part of the measurement because the rate of flow
will depend both on the fluids viscosity and on the magni-
tude of P, which now depends on the fluid density and
on the height of the fluid above the capillary, h (P = gh).
Fig. 34Comparison of Falling Needle Viscometer
=
(76)
That is, the kinematic viscosity is equal to the shear vis-
cosity divided by the density. The viscosity obtained from
gravity-driven capillary flow is in units of stokes (stoke =
Pgcm
3
). The absolute shear viscosity can then be calcu-
lated from = .
The velocity profile in tube flow is parabolic in shape
for Newtonian liquids [as can be proven by integration of
Eq (72)], with the maximum shear rate at the walls and
zero shear rate in the tube center. For non-Newtonian fluids
the velocity profile is nonparabolic and of complex shape.
Because the shear rate in tube flow is nonuniform, the
viscosity of non-Newtonian materials will vary across the
diameter of the tube. Non-Newtonian fluid measurements
may be made accurately only if the Weissenberg-Rabinow-
itsch correction is applied [117], which corrects for the
variations in viscosity across the capillary arising from the
nonuniform shear field
=
a
a
w
d
d
1
1
4
1
,
]
]
]
(log )
(log )
(77)
where
a
is the uncorrected apparent viscosity.
19
The second
term inside the brackets is obtained by calculating the slope
of a log-log plot of the measured viscosity versus wall shear
stress.
Tube flow is inappropriate for materials with yield
behavior. Reviews by Schoff [108,109] describe the applica-
tion of capillary viscometry to coatings.
HIGH-SHEAR CAPILLARY RHEOMETRY
It has been claimed by some that the measurement of very
high shear rate viscosity is not necessary because it may
be estimated from moderate-shear data. This is true to an
extent, especially if one can obtain an adequate description
of the general flow curve by use of one of the flow models
containing the high-shear limiting Newtonian viscosity
(e.g., the Sisko, Cross, or Carreau models). If a good enough
fit to experimental data is obtained, the latter models can
be extrapolated to predict viscosity beyond the experimen-
tal range of shear rate, with caution. The simple power-law
models should not be used for estimation of high-shear
viscosity since they predict unrealistic high-shear behavior
(see Shear-Dependent Viscosity). However, under the best
of circumstances, data should be extrapolated no further
than about a decade of shear rate. This means that, in gen-
eral, shear rates of only about 10
5
s
1
can be reached, even
by extrapolation methods. It should be pointed out here
that the onset of shear thickening (region IV, Fig. 3) cannot
be predicted by extrapolation, yet it can cause disastrous
consequences in high-shear application processes. In any
case, for precise comparisons of materials, extrapolation
will be unsatisfactory. There are several industrial processes
which involve shear rates of 10
5
to 10
6
s
1
. These include
airless spray and reverse rollcoating, for example. It will
be difficult to resolve performance problems of coatings
exposed to such high shear without direct experimental
measurement under the appropriate deformation condi-
tions. Such severe conditions of shear can cause a funda-
mental change in a material, such as gross coagulation of
an emulsion, with a possible deleterious effect on rheology
and hence on postapplication film formation behavior. It
is recommended, therefore, to characterize by high-shear
rheometry materials that must be exposed to high-shear
processing.
There are some commercial high-shear viscometers
which use small-gap bob-in-cup geometry. Problems with
this geometry include poor temperature control due to vis-
cous heating and a tendency toward flow-field instabilities.
Capillary viscometry has some advantages in both regards.
The very short residence time in the capillary at high flow
rates minimizes temperature rise, and, for length-to-diam-
eter (L/D) ratios of 50 or greater, entrance effects are negli-
gible and the flow field will be essentially uniform.
By use of short, small-diameter capillaries and high
pressures, shear rates of approximately 10
6
s
1
are achiev-
able for fluids in the range of viscosities typical of paints
[118]. At this writing, however, we are unaware of any com-
mercial capillary rheometers suitable for high-shear rate
measurement of coatings fluids other than the Paar-Physica
HVA-6.
Rank Pulse Shearometer
This instrument is a relatively inexpensive and simple
viscoelastometer. A fixed-frequency acoustic wave pulse is
passed through a test sample and the signal detected by a
receiving transducer. The propagation velocity is mea-
sured from the signal transit time and used to calculate the
shear elastic modulus according to
G =
2
(78)
The signal wave is of high frequency but very small ampli-
tude (10
4
rad), so that weak gels are not disturbed (the
induced strain will likely be within the linear viscoelastic
regime). Because of the high frequency used, the measured
shear modulus corresponds to the plateau modulus G
(see
Viscoelastic Models). This gives a useful measure of the
gel strength of even weak gels and has an advantage in
this regard over instruments which subject the sample to
uncontrolled shear upon closure.
RHEOMETRY
Rheometry is the experimental aspect of rheology. A rhe-
ometer is an instrument that measures some rheological
property, or material function, such as the viscosity as a
function of shear rate or shear stress. Normally, a curve will
be produced representing the functional dependence of the
measured property. A viscometer, in contrast, will generally
measure viscosity at a single (sometimes even unknown)
value of the shear rate (or shear stress), or perhaps over
a limited range of values. These types of devices are typi-
cally found in the industrial quality control or formulation
laboratory, and have been discussed in earlier sections. This
19
The apparent viscosity is simply the quotient of the apparent (or
experimentally measured) shear stress and the apparent shear rate.
The true values of the foregoing, however, may be different from
the apparent, as for example for fow felds where the shear rate
varies across the feld and must be corrected for non-Newtonian
effects, or where inertia errors are involved.
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446 PAINT AND COATING TESTING MANUAL 15TH EDITION
section will focus on techniques for the use of rotational
rheometers to characterize fluids with complex rheological
properties.
Rotational Rheometry
Simple shear deformation was defined previously for a
fluid confined between a stationary surface and a mov-
ing surface that are in parallel, rectilinear motion (i.e., a
sliding plate rheometer). There are, however, very few
rheometric instruments that utilize this test geometry. This
is due to the fact that it is not a practical geometry, because
either the experiment must be rather short in duration or
one of the shear faces must be very long. This predicament
is solved by using rotational motion to shear a material
between, say, a fixed plate and a rotating disk. The major-
ity of commercial rheometers operate in this way, using a
variety of rotating fixtures or geometries, mainly:
20
1. cone and plate
2. parallel plate
3. concentric cylinder (bob and cup).
Detailed descriptions of these standard geometries can be
found in the referenced monographs [22,45,107,119].
There are three principal rheometric techniques typi-
cally used for rotational rheometers, discussed below.
1. Steady shear (large strain)
a. Equilibrium viscosity measurement
b. Non-equilibrium viscosity measurement
c. Normal stress measurement.
2. Creep (medium strain)
3. Oscillation (small strain).
Steady Simple Shear (Equilibrium Flow)
Steady simple shear involves a uniform flow field in which
the shear rates and stresses are independent of position.
Not all rheometer test geometries meet this criterion
exactly, but they do generally satisfy the requirements of
viscometric flow, defined by Dealy [120] as a flow field that
is everywhere indistinguishable from steady simple shear.
Viscometric flow is a necessary requirement in order to
properly measure the viscoelastic material functions.
Some rotational rheometers utilize steady-shear equi-
librium viscosity measurements to characterize flow behav-
ior by means of a series of shear rate steps. If, for example,
a constant torque is applied to a specimen until a constant
shear rate is observed (after inertial and structural relax-
ation effects have equilibrated with time), the system is
undergoing steady simple shear and the steady-state viscosity
or equilibrium viscosity can be measured. (Even with thixo-
tropic materials, one should generally be able to observe a
steady-state viscosity value eventually.) An equilibrium flow
curve (as in Fig. 3) can be generated in this way.
Time-Dependent Materials: Nonequilibrium
Flow Curve
As mentioned, one can construct a curve of equilibrium
viscosity versus shear rate or shear stress by a series of
step-equilibrium experiments. However, the nonequilib-
rium flow curve is less time-consuming experimentally
and perhaps more informative with regard to the process-
ability of time-dependent materials. The nonequilibrium
flow curve is obtained by recording the viscosity while
either the angular velocity or the torque is ramped
i.e., increased with time (usually followed by a decreasing
torque or velocity ramp) [Fig. 9A]. Time-dependent effects
such as hysteresis can be seen in this way [Figs. 9B and
24]. The collapse of structure can be seen, but which is
lost in an equilibrium measurement. Fig. 24 (solid circles)
shows a flow curve for a structured fluid, measured by a
stress-ramp procedure, with the upper curve correspond-
ing to the increasing-stress ramp and the lower curve the
decreasing-stress ramp.
SHEAR HISTORY EFFECTS: SAMPLE MOUNTING AND
CONDITIONING
A great many industrial and commercial fluids possess
time-dependent rheology, usually thixotropy, but occasion-
ally anti-thixotropy (see Time-Dependent Fluids). Time-
dependent materials pose a special set of challenges to the
experimentalist, and it is easy to make mistakes in char-
acterizing them. For time-independent systems, the pre-
experiment shear history is of no consequence. In contrast,
the shear history of time-dependent materials prior to the
experiment can greatly influence the results.
Both the degree of deformation in mounting a sample
and the time lapse since mounting will determine the rheo-
logical state of a time-dependent material, and hence the
experimental result. Failure to take account of this issue often
leads to poor repeatability of data on such systems. Some
approaches to the control of the shear history problem are:
1. Controlling the rate of closure of the platens in a paral-
lel plate or cone-plate experiment (e.g., exponentially
decreasing closure rate)
2. Allowing a rest time for the sample after mounting
(limited by evaporation and productivity issues)
3. Giving a controlled shear history to the sample, e.g.,
preshearing the specimen for a set period, then initiat-
ing the experiment immediately on cessation of shear.
(An up-down ramp cannot be applied in this case, since
the sample would begin to recover in an uncontrolled
way concurrent with the initial low-shear ramp onset.
Instead, a series of step reductions from high shear
can be applied, with the time delay between steps
being varied, in order to simulate the effects of varying
degrees of structural recovery [121].
Method (1) reduces the strain rate (but not the strain)
that the sample experiences as the instrument gap closes,
but will be limited in its effectiveness because practical
rates of closure (and the coupled deformation) are likely
to be significant in terms of their effect on the specimens
structural integrity. Furthermore, depending on the geom-
etry (e.g., cone and plate) the strain may not be uniform.
Method (2) is limited by the time one can afford to wait
for structure recovery. It is not uncommon for a material
to require hours in order to regain its rest-state condi-
tion. The use of an arbitrary rest time is a compromise that
provides a practical (if not ideal) method of characterizing
thixotropic materials. Method (3) is somewhat arbitrary,
too, in that it is not known a priori at what shear stress or
shear rate or for how long a material must be precondi-
tioned in order to achieve adequate or consistent structural
breakdown. Whatever the method chosen, it is important to
20
Another principal test geometry used in steady shear fow is tube
fow or capillary rheometry. Its use is somewhat limited outside of
the characterization of polymer melts, and will not be further dis-
cussed here.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 447
adhere strictly to a constant protocol if results are wanted
on a comparable basis.
RAMP METHODS
Many rotational rheometers are able to apply a time-
based ramp of torque or angular velocity for purposes of
flow curve measurement. Some allow a choice of a linear
time-based ramp or one that is logarithmic with time. The
latter method spaces the data points very close together in
the beginning of the ramp, which increases the amount of
information obtained at low shear rates and stresses. For
time-dependent systems, it is important to keep both the
pre-experiment shear history and the experimental protocol
constant, in order to assure valid comparison of materials.
This means keeping the following experimental settings the
same for a given series of experiments:
1. Sample preconditioning
2. Choice of linear or log time-based ramp
3. Ramp duration
4. Initial and maximum shear stress (or shear rate)
5. Duration of any hold-time at ramp maximum.
TRANSIENT METHODS
Transient methods are non-steady state, i.e., the stresses,
strains and material properties are not at equilibrium, and it
is their behavior as a function of time that is being studied, as
they move toward equilibrium. Transient methods include:
1. Step shear stress (creep and recovery)
2. Step shear strain (stress relaxation)
3. Step shear rate (thixotropic recovery)
4. Startup of flow. The first two methods have been briefly
discussed in the section on Elastic Liquids. The third
method was described in the Time-Dependent Fluids
section. The last method will not be discussed here. For
more detail on creep methods see Ref. [122].
Oscillatory Shear
If, instead of applying a stress (or, interchangeably, strain)
21
in a constant direction, the direction of the strain under-
goes cyclic reversal, then the specimen is subjected to
oscillatory deformation, sometimes also referred to as a
dynamic test. Most commercial rheometers are capable of
oscillatory shear using a variety of test geometries. Oscil-
latory testing is normally done in the linear viscoelastic
regime (LVER), where the stress and strain are related by a
linear differential equation. The usual practice is to employ
sinusoidal variation of strain or stress. Testing modes in
oscillation include:
1. Torque sweep or strain sweep at constant frequency
2. Frequency sweep at constant strain
3. Time or temperature sweep at constant frequency and
strain.
Oscillation is a convenient way of characterizing
medium to short time-scale response of viscoelastic mate-
rials. The employment of small strains (below the critical
strain limit of the LVER) at low frequencies is a reason-
able simulation of the physical state of a newly applied
coating layer in the process of film formation. Hence,
the low-frequency linear viscoelastic properties of coat-
ings are of interest in understanding this phase of coating
performance, especially if measured subsequent to a high-
shear, high-strain experience.
TORQUE SWEEP/STRAIN SWEEP
Torque sweep on a controlled-stress rheometer or strain
sweep on a controlled-strain-rate rheometer are used to
determine the strain-sensitivity of the viscoelastic param-
eters, and thus determine the critical strain
cr
, which is the
strain limit of linear viscoelastic response. Above the criti-
cal strain, the fluid microstructure responsible for elastic
response begins to break down. The elastic modulus G is a
sensitive indicator (more so than the dynamic viscosity) of
the breakdown of structure, and is often used to determine
the critical strain. The experiment is done by applying a
constant frequency (e.g., 1 Hz) while increasing the torque
gradually, so that the strain amplitude steadily increases. G
will be constant within the linear viscoelastic regime. The
critical strain is sometimes arbitrarily chosen as the point
where G has fallen by 10 % (Fig. 35). The strain is then
held constant at the critical value for subsequent frequency
sweep experiments, ensuring that the deformation remains
within the linear regime. It should be noted, however, that
the critical strain is not a single value for a given material
but will decrease as the oscillation frequency decreases,
a consequence of the superposition of viscous and elastic
deformation responses in a viscoelastic material.
Polymeric systems can have quite large critical strains
(>10 %), while
cr
for colloidal systems can be quite small
(<10 %). The critical strain value is a measure of the brit-
tleness or ductility of the microstructure, and an indica-
tor of the relative length scale of the forces responsible for
the elastic behavior. Difficulty is often encountered in find-
ing the linear regime for thixotropic materials composed of
flocculated or associated particles, because the structure is
rather brittle, attractive forces are short-range, and the
critical strain is consequently small.
FREQUENCY SWEEP
In a frequency sweep experiment, the oscillation frequency
is steadily increased, while the strain is held constant
below the critical value. Typically, the frequency is swept
logarithmically with time, so that the discrete frequency
points are linear on a log axis. A typical plot of viscoelastic
Fig. 35Illustration of torque-sweep (strain-sweep) data and the
location of the critical strain
cr
for oscillatory shear testing.
21
Note that it is immaterial whether the independent variable is
the stress or the strain, for oscillatory linear viscoelastic measure-
ments. Wherever the discussion mentions stress, one may equally
well read strain.
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448 PAINT AND COATING TESTING MANUAL 15TH EDITION
functions for a frequency sweep experiment is shown in
Fig. 36. G and G normally increase with frequency while
decreases with frequency, trends which can be under-
stood by examination of the mechanical models response.
As pointed out in Elastic Liquids, values for the visco-
elastic functions can be obtained from frequency-sweep
data, e.g., the frequency
c
where G and G cross equals
the inverse of the relaxation time (Maxwell model). A gel
is distinguished by having a nearly constant value of G
with frequency.
TIME OR TEMPERATURE SWEEP
A time sweep at constant frequency is used to character-
ize recovery of structure after shear, e.g., for a thixotropic
material (see Time-Dependent Fluids). Emulsion stability
can be indicated by temperature sweep experiments at con-
stant frequency [123]. An oscillatory temperature sweep is
an excellent way to characterize the chemical advancement
of thermosetting polymers, a technique used in a subdis-
cipline known as chemorheology (study of the rheology of
chemically reacting systems) [60,124].
EXPERIMENTAL PROTOCOL
Similar to the discussion of shear-history effects above, the
rheological state of a specimen is of concern, with an eye
to obtaining repeatable results. Consequently, the following
series of experimental steps is recommended:
1. Specimen should be prior-sheared in steady shear at
an arbitrary high shear rate or stress value, to put the
specimen in a low-structure state;
2. A constant-frequency small-strain oscillatory time-
sweep step should be immediately begun, following
the structural recovery to a constant-property state, if
possible;
3. Once the specimen has recovered to equilibrium prop-
erties, either of two experiments can be done:
a. Oscillatory frequency-sweep experiment, or
b. Steady-shear flow curve ramp experiment.
The above protocol is a logical sequence that permits tests
to be done on a specimen that is in a repeatable rheologi-
cal state.
APPENDIX
List of Rheometer/Viscometer Suppliers
Anton Paar USA Inc.
10215 Timber Ridge Drive
Ashland, VA 23005
Ph: 804-550-1051
Fax: 804-550-1057
E-mail: info.us@anton-paar.com
www.anton-paar.com
Brookfield Engineering Laboratories, Inc.
11 Commerce Boulevard
Middleboro, MA 02346
Ph: 508-946-6200 or 800-628-8139
Fax: 508-946-6262
E-mail: sales@brookfieldengineering.com
www.brookfieldengineering.com
BYK-Gardner USA 9104
Guilford Road
Columbia, MD 21046
Ph: 301-483-6500
Fax: 301-483-6555
www.byk.com/instruments/
E-mail: info.BYK.GardnerUSA@altana.com
Cannon Instrument Company
P.O. Box 16
2138 High Tech Road
State College, PA 16804-0016
Ph: 800-676-6232
Fax: 814-353-8000
E-mail: sales@cannoninstrument.com
www.cannoninstrument.com
Malvern Instruments, Inc.
117 Flanders Road
Westborough, MA 01581-1042
Ph: 508-768-6400
FAX: 508-768-6403
E-mail: info@malvernusa.com
www.malvern.com
Reologica Instruments, Inc.
231 Crosswicks Road
Bordentown, NJ 08505
Ph: 609-298-2522
Fax: 609-298-2795
E-mail: info@reologicainstruments.com
www.reologicainstruments.com
Stony Brook Scientific
1055 West Germantown Pike
Norristown, PA 19403
Ph: 610-635-1740/888-889-7764
Fax: 610-635-1780
E-mail: info@stonybrooksci.com
www.stonybrooksci.com
TA Instruments, Inc.
109 Lukens Drive
New Castle, DE 19720
Ph: 302-427-4000
Fax: 302-427-4001
E-mail: info@tainstruments.com
www.tainst.com
Fig. 36Typical dependence of the viscoelastic parameters on
frequency in a frequency-sweep experiment. Crossover frequency
c
is indicated.
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 449
Thermo Scientific
(Haake Rheometers/Viscometers)
Ph: 800-258-0830
www.thermo.com
Thomas Scientific
99 High Hill Road
P.O. Box 99
Swedesboro, NJ 08085-0099
Ph: 856-467-2000
Fax: 800-345-5232
E-mail: value@thomassci.com
www.thomassci.com
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Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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CHAPTER 36 RHEOLOGY AND VISCOMETRY 451
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452
Nomenclature
a = Integration limit, distance from surface into bulk
of material, Eqs (3) and (6)
a = Subscript for advancing contact angle
A = Surface area
A = Subscript indicating adhesion, Eqs (12), (13), (31),
and (32)
b = Variable in Eq (25), the difference in maximum and
minimum diameters in elliptical orifice
c = Constant in Eq (33)
c = Surfactant concentration
c
i
= Concentration of species i
c
i0
= Concentration of species i in the bulk
C = Subscript indicating cohesion, Eqs (11) and (13)
D = Diffusion coefficient
E = Surface elasticity
f = Correction factor, Eq (22)
f = Fractional surface area, Eq (15)
F = Pull-off force, Eq (31)
g = Acceleration of gravity
G = Gibbs free energy
h = Variable defined in Eq (9)
h = Height in capillary rise measurements
h = Width of falling film in curtain coating, Eqs
(36)(38)
i = Index identifying species i
j = flux of adsorbing and desorbing species
k =
Wave number = 2/ ( = wavelength, see below),
Eq (27)
l = Subscript indicating liquid phase
l = Length of capillary pore path in Eq (23)
n = Normal vector to surface, Eq (3)
n = Exponent in Eq (4)
n = Most probable number of drops from breakup of
charged drop, Eq (31)
n
i
= Number of moles of component i, Eq (2)
p = Pressure
p = Pressure tensor in the bulk phase, Eq (3)
p
T
= Tangential pressure tensor, Eq (3)
P = Perimeter length
Q = Liquid flux, volume/second
q = Charge on drop
r = Variable in Eq (25), sum of maximum and minimum
radii in elliptical orifice
r = Radius
r = Roughness ratio, Eq (14)
r = Subscript for receding contact angle
r = Average pore size in rate of penetration into
powder measurements, Eq (34)
R = Ring radius in Du Nouy ring surface tension
measurement
R = Diameter of probing tip in direct force AFM
measurements, Eqs (31) and (32)
R
1
, R
2
= Principal radii of curvature
s = Subscript indicating solid phase
S = Entropy
S = Subscript indicating spreading, Eq (13)
T = Temperature
T
c
= Critical temperature
u = Velocity, Eqs (26) and (26a)
x = Distance from surface in Eq (6)
v = Index indicating vapor phase
v = Velocity, Eq (25)
V = Volume
W = Weight
W = Work, Eqs (11)(13)
Y = Subscript for Youngs contact angle
f
= Final film thickness in dip coating
= Difference
= Dielectric constant
= Viscosity
= Contact angle
= Wavelength
i
= Chemical potential of species i
= 3.141 59
= Density
= Frequency
0 = Subscript indicating zeroth or bulk phase, or
reference value
INTRODUCTION
SURFACES ACT AND PERFORM DIFFERENTLY FROM
the bulk material because they have two distinct properties
that do not exist in the bulk. First, the unbalanced forces
on molecules or atoms at the surface cause it to have excess
free energy when compared to the bulk [1] (i.e., they are
in a higher state of potential energy). This excess energy
per unit area is the thermodynamic cost of forming a new
surface; it has the units of energy/area or force/length. The
latter units are those of tension, and the surface excess free
energy is often known as surface tension and can be mea-
sured for liquids as such. (A more detailed discussion of
this excess free energy identified with a surface, including
the thermodynamic definition of surface tension, is given
below.) Second, there is a preferred direction normal to the
surface that can be defined in the mechanical definition [2]
of surface tension. This directional effect of surfaces can be
observed in molecular directionality in adsorption phenom-
ena, surface area minimization by surface tension effects,
and molecular ordering in Langmuir-Blodgett films depos-
ited from ordered mono-molecular layers (monolayers).
Since the first version of this chapter was published
in 1995, there has been a significant increase in the atten-
tion given to surface and interfacial effects, including those
in organic coating systems [3]. Much of this interest has
been due to the increasing importance of science at the
nanoscale. When one approaches nanometer dimensions,
surface effects begin to predominate, and careful consid-
eration must be given to surface energetics [4]. For this
reason, we have revised and updated this chapter into its
present form. Much of what was stated in the first ver-
sion remains true, but more recent research has yielded
additional knowledge regarding the science of surfaces.
Scanning tunneling microscopy, atomic force microscopy
[5], and a broad range of new characterization tools that
greatly enhance our capabilities to characterize and visual-
ize surfaces at nm dimensions have become everyday tools
for scientists and engineers working in many fields.
Surfaces occur only when the energetic cost of creat-
ing an interface between two dissimilar materials or phases
is satisfied. Thus, there are no stable interfaces between
gases, nor among phases in a material above its critical
point. However, surfaces can occur between gas and liquid
(g/l), liquid and liquid (l/l), gas and solid (g/s), liquid and
solid (l/s), and solid and solid (s/s) phases. An example of
a g/l interface is the surface of an open, unfrozen body of
water. Because a liquid surface cannot support a stress,
its surface energy phenomena can be analyzed directly by
equilibrium thermodynamics. For a solid, object history
will affect the properties of the surface. As a result, surface
energy and surface stress must both be considered in ana-
lyzing the properties of an interface [6]. Even though this is
well known, there has not been as much concern given to
the surface history of solids when determining their surface
properties as is necessary [7].
Surface effects relative to bulk properties become more
important as the surface area to volume ratio for materials
becomes larger. In the simplest case, a sphere, this ratio is
given by
A
V
r
r
r
= =
4
4
3
3
2
3
,
,
,
]
]
]
]
]
(1)
In the most general case, one can estimate that the sur-
face to volume ratio for any object shape always scales
as the reciprocal of some characteristic linear dimension
of the object. Surface effects thus increase in importance
as the size of the object being considered becomes smaller.
Statistical thermodynamics and molecular dynamics con-
siderations indicate that the range of surface effects as two
to five molecular diameters [8]. Simple arguments concern-
ing the dimensions of a [solid polymer 1/polymer 2] inter-
face give similar estimates [9]. An interesting feature of this
type of analysis of surface effects and their ranges is that
the distance of propagation of surface effects into the bulk
from a polymer adsorbed at an interface can be quite large
in atomic dimensions. In effect, the interface pins one end
of the polymer, removing one of its degrees of freedom, and
thus making it a location of different thermo-mechanical
properties than the bulk of the polymer. This is of excep-
tional importance when analyzing the adhesion of poly-
meric films to bulk substrates. The strength of the adhesive
bond can be influenced by these directionality effects and
can be even more important if the substrate is a plastic
(polymer), since the ordering effects propagate on both
sides of the interface [10]. The directionality and ordering
of surrounding polymeric bulk media near an interface can
extend unexpectedly large distances. Many of the properties
of self-ordering systems have these effects as their origin.
This will be commented upon further in the discussion of
surface effects in pigment dispersion and emulsions.
Anyone dealing with coatings must realize that surface
effects are very important in all stages of coating prepara-
tion, application, and utilization. Coatings are thin films
with high surface-to-volume ratios. Pigments also have
large surface-to-volume ratios, and their surfaces are
often chemically reactive or catalyze reactions [11]. Latex
polymers also occur in fine particulate form, and their use
and stability depends on surface-dominated effects. Foam-
ing, cratering, and other coating defects develop through
surface-mediated events [12,13]. The wetting, coverage and
adhesion of a coating to a substrate is strongly affected by
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454 PAINT AND COATING TESTING MANUAL 15TH EDITION
surface effects. Adsorption at surfaces of particulate materi-
als in a coating, be they pigments or polymer particles, is
controlled by the energetics of the interface between the
particles and the suspending liquid.
SURFACE THERMODYNAMICSBASICS
Liquid Surfaces
To understand surface energetics in coatings, one must
first understand the basic thermodynamics of surfaces and
interfaces. However, when the system under consideration
contains a surface, the definition of the Gibbs free energy is
modified. The defining equation for liquids is
dG SdT Vdp dn dA
i i i
= + + +
(2)
where G, T, S, V, p,
i
, and n
i
are the thermodynamic quan-
tities Gibbs free energy, temperature, entropy, volume, pres-
sure, chemical potential of component i, and the number
of moles of component i, respectively, and and A are the
surface tension and surface area. The other equations of
thermodynamics can be similarly modified. As can be seen,
the energetic cost of expanding a liquid surface is the dA
term. Again, the use of is valid only for liquid interfaces;
it cannot be considered a thermodynamic quantity for solid
surfaces because they store energy as surface stress and are
thus not in true equilibrium [7]. Many references discuss
this equation in detail (see Ref. [4], for example) Another
equation for is the mechanical definition given in Ref. [2],
also discussed by Adamson [1] and reviewed by Burshtein
[14] and Navascues [15] as
=
+
p p n
T
a
a
d
( )
(3)
where +a and a are distances in either direction from the
surface such that molecules at these positions are in the
bulk phases, p and p
T
are the bulk and tangential pressure
tensors, respectively, and n is the normal vector to the sur-
face; this is shown schematically in Fig. 1. The direction of
n is the preferred direction of a surface referred to above.
Even if it is not commonly included in introductory discus-
sions of surface phenomena, it is important to consider
Eq (3) when considering the thermodynamics of surfaces
because it is the relationship between the bulk mechanical
properties of the system and the almost discontinuous
behavior of the system properties at an interface. A more
recent discussion of this manner of expressing surface ten-
sion is given by Davis [16]. This expression also describes
the directionality that an interface possesses and is very
crucial to modern theories of capillarity [17].
In general, the surface tension, , of pure liquids
decreases with increasing temperature. An approximate
form of this temperature dependence is [16,18]
=
0
1
T
T
c
n
j
(
,
\
,
(
(4)
where
0
is the surface tension at T = 0, T
c
is the critical tem-
perature of the material, and n is an empirical exponent,
~11/9 for organic liquids.
The other important thermodynamic relation for sur-
faces is the Gibbs equation. In multi-component systems,
one must consider the effects of materials absorbing at the
interface. When these are properly taken into account, the
Gibbs equation (at constant T and p) gives
d d
i i i
=
(5)
where i is the surface excess concentration for component
i [4,19]. This equation gives the relationship between the
surface tension of a fluid interface and the amounts of sur-
face active materials (hereafter referred to as surfactants) in
the solution (component i). The surface excess concentra-
tion i is the difference between the actual and bulk con-
centrations, c
i
and c
i0
, of component i and can be calculated
in a manner analogous to Eq (3) as
i i i
a
a
c c dx =
+
0
( )
(6)
where x is again the direction normal to the interface and
+a and a are locations equidistant from the interface in
the bulk of the material. Fig. 2 expresses this schematically
for a single surfactant. In adsorption of materials to an
interface, the local concentration in the neighborhood of
the interface can be much higher (by factors of up to 10
8
or greatersee Ref. [1], Chapter 3 for further details or for
a more recent version, see Ref. [20]) than that in the bulk.
Fig. 1Schematic of local pressure changes at surface giving
surface tension.
Fig. 2Schematic of surface excess concentration as calculated
as difference for bulk concentration.
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CHAPTER 37 SURFACE ENERGETICS 455
The net energy of the system is minimized by the surfac-
tant molecules adsorbing and orienting at the interface to
reduce interactions between unlike molecular components.
The terms often used to describe the compositional differ-
ences in surfactants are polar/nonpolar or hydrophobic/
hydrophilic. Materials that act as surfactants are those that
have a distinct separation of properties between different
sections of their molecules, the classic example being soaps,
with an alkyl nonpolar group and a [carboxylat+metal ion]
polar group.
In concentrated systems of surface-active materials,
especially those of low inherent solubility in the liquid
phase, there exists a certain concentration where the addi-
tion of further surfactant no longer depresses the surface
tension, as the surface is saturated, and the molecules of
the surfactant begin to form self-ordered structures, or
micelles, in the bulk liquid [21]. Micelles are aggregates
of surfactant molecules that form in solution to minimize
the total system energy. In water, they orient with the
hydrophobic portion of the molecule directed toward the
interior of the micelle, and in non-aqueous systems they
have the hydrophilic end in the interior. At the surfactant
concentration where micelles just begin to form, many of
the solution properties also undergo rapid change; this
breakpoint in surfactant solution properties is known as
the critical micelle concentration (CMC) (Fig. 3). The CMC
is a unique concentration for a surfactant/solvent com-
bination at a specified temperature. The book by Rosen
[22] gives an expanded discussion of surfactant behavior,
and Tanfords book [23] provides further description of
micellar behavior in aqueous systems. These texts also
describe the complex aggregates that form in surfactant/
solvent mixtures, including membrane-like structures and
liquidcrystals.
Micellar effects and the more general case of self
organization in materials has become a very important
part of recent studies in materials science. Much of what
is considered under what is termed Soft Matter concerns
itself with colloidal and surfactant behavior involving self-
organized matter [3,4,9,24,25]. This still-evolving area of
materials science appears to be very pertinent to the science
of organic coatings [3].
As Gibbs first noted, the presence of a material adsorb-
ing preferentially at an interface imparts elasticity to the
surface, as it will tend to resist expansion and contraction.
This surface elasticity is given by
E
d
d A
d
d
= =
ln ln
(7)
where A is the surface area. This elasticity is the resistance
to disturbance of a film by the presence of a surfactant.
The effects of this surface elasticity have been reviewed
with respect to liquid films and liquid threads [26]. Recent
reviews of surface elasticity discuss this effect in surfactant
solutions [25,27], furthermore, an examination in coat-
ing application processes emphasizes the importance of
dynamic effects in such processes [28]. Surface elasticity
measurements have been used to characterize the proper-
ties of monomolecular layers at surfaces [29]. If a soluble
surfactant diffuses to the surface (see below, Dynamic
Properties of Liquid Surfaces), it will reduce the surface
elasticity, effectively short circuiting the surface tension
changes by surface replenishment [3032]. In these cases,
Eq (7) should be modified to read
E
d d
h dc d
=
+
/ ln
/ /
( )
( ) ( ) ,
]
]
1 2
(8)
where c is the surfactant concentration and h is given by
the relationship
h
D
= 2
(9)
where D is the surfactant diffusion coefficient, and is
the frequency of the surface motion [31]. Surface elasticity
effects are a major consideration in foam stability [33] and
where there are rapid surface area changes and creation of
new surfaces [34].
Liquid/Solid Interfaces: Wetting and Contact
Angles
When a liquid comes into contact with a solid, a three-
phase contact, or wetting, line develops between the liquid,
solid, and vapor. Three interfaces are generated; thermody-
namic equilibrium exists when the total interfacial energy,
the excess energy attributed to the solid-liquid, solid-vapor,
and liquid-solid interfaces, is minimized. The liquid-vapor
interface forms a characteristic angle tangent to the solid
surface as a result [35]. This contact angle is often used to
determine the surface excess energy, or surface tension, of
the solid-vapor interface through Youngs equilibrium equa-
tion [4,36]:
sv sl lv
= + cos
(10)
Here,
sl
,
sv
, and
lv
represent the solid-liquid, solid-vapor,
and liquid-vapor surface tensions, respectively, and the
contact angle is measured between the solid-liquid and
liquid-vapor interfaces. The equation is applicable to any
solid surface when
sl
and
lv
are known and is measur-
able; issues such as roughness and chemical heterogene-
ity will be revisited later [24,37]. Often
sl
is unknown;
here, two measurements using different liquids of known
lv
gives two equations with two unknowns and
sv
is
Fig. 3Schematic of physical property changes in surfactant
solution at critical micelle concentration (CMC).
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456 PAINT AND COATING TESTING MANUAL 15TH EDITION
solved algebraically. Fig. 4 shows the measured contact
angle between the three phases. Further derivations and
applications of Youngs equation are discussed in the review
by Churaev and Sobolev [38]. The case where the sub-
strate is an immiscible liquid is discussed in Chapter 13
of Ref. [4].
A contact angle describes the wetting behavior of a liq-
uid for a given solid. Complete wetting, or a contact angle
of zero, occurs when the liquid spreads spontaneously over
the substrate. In this case
lv
is lower, or more favorable,
than
sv
and the liquid displaces the air in contact with the
solid surface. Any contact angle greater than zero causes
the liquid to not wet the solid, or to bead up and form a
sessile drop. From Youngs equation the relation between
sv
and
sl
determines the shape of the drop such that the
contact angle is less than 90 when
sv
>
sl
and 90 when
sv
<
sl
. Fig. 5 lists the possible scenarios for wetting. The work
of spreading, W
S
, is a measure with which a liquid favors
spontaneously wetting a solid. This value is the difference
between the work of adhesion, W
A
, and work of cohesion,
W
C
, for the solid-liquid interface [39].
W
C sl
= 2
(11)
W
A sv sl lv
= +
(12)
W W W
S A C sv sl lv
= = + ( )
(13)
A positive spreading coefficient indicates the liquid pos-
sesses sufficient excess energy in the liquid to spread
spontaneously under equilibrium conditions, whereas a
finite contact angle is formed for W
S
less than zero [40,41].
The surface energy of a substrate is the determining
factor in the degree of wetting that occurs. Polarity, which
often describes affinity to water, has also been discussed as
a basis for predicting extent of wetting and is dependent
on the nature of the substrate [42]. Low surface energy,
hydrophobic solids such as hydrocarbons or fluorocarbons
are not easily wet and form high contact angles with most
pure solvents or solutions; poly(tetrafluoroethylene), or
Teflon
gh
r
=
2 cos
(21)
where p is the density difference between the liquid and
air, g is the acceleration of gravity, h is the height of the
capillary rise, and the rest of the terms are defined above.
This equation allows one to measure the surface tension
from a simple measurement of the height of the rise of the
liquid in a capillary of known radius and contact angle with
the test liquid. This method is shown schematically in Fig.
8. As a measurement technique, it has remained largely
unchanged since its inception, with only the addition of
computer-aided analysis of the instrument.
Drop Weight
The weight of a drop when it is formed slowly is the weight
just to exceed the force of surface tension times the radius
of the capillary tip from which it is formed, with a cor-
rection factor required for the formation of small satellite
drops. Thus, one has
W rf = 2
(22)
where W is the weight of the drop and f is the correction
factor, which is discussed in Adamson [1]. This method is
simple to use and accurate if precautions are taken for clean-
liness and very slow flow rates of the liquid in the formation
of drops. The method is shown schematically in Fig.9. The
simplicity of this measurement, and easy availability of the
equipment, results in it being a popular technique. Refer-
ence [79] provides a review of this technique.
Du Nouy Ring
Applying Eq (13) to the case where the object is a ring being
pulled from the surface of a liquid, one has
W W R = +
ring
4
(23)
where W is the total weight sensed by a balance, W
ring
is the
ring weight, and R is the ring radius as shown in Fig. 10.
However, this formula requires a correction to be accurate
and holds only for a zero contact angle between the ring
and test liquid. Again, see Adamson [1] for further details.
The force measured by the balance is that force just at
detachment of the ring and so involves motion of the sen-
sor; the method is thus not an appropriate technique to
use in studying solutions. In general, this method is infre-
quently used, compared to the other options available.
Fig. 9Schematic of drop weight method of measuring
surface tension. (Image duplicated from Fig. 1 of Ref. 79). A
Critical Review: Surface and Interfacial Tension Measurement
by the Drop Weight Method, Boon-Beng, L., Ravindra, P.,
Chan, E.-S., Chem. Eng. Comm, Vol. 195, 2008, pp. 889924,
reprinted by permission of the publication (Taylor & Francis
Group, http://www.informaworld.com).
Fig. 10Schematic of Du Nouy ring method of measuring
surface tension.
Fig. 8Schematic of capillary rise method of measuring
surface tension.
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460 PAINT AND COATING TESTING MANUAL 15TH EDITION
Wilhelmy Plate
If one uses a thin plate instead of a ring and measures the
force exerted on the plate just touching the surface of a
liquid, one has
W W = +
plate
P
(24a)
where P is the perimeter of the plate. If the liquid does not
perfectly wet the plate, the expression
W W = +
plate
P cos
(24b)
must be used as illustrated in Fig. 11. The perimeter of
the plate may be determined in practice as an experimen-
tal constant from measurements with liquids of known
surface tension. Again cleanliness is most crucial, and a
roughened platinum plate cleaned in a Bunsen burner
flame is often used to create a clean plate that is wet by
most liquids. Because there is no motion of the plate in
the measurement, this method can be used to measure
dynamic as well as static values of . This technique may be
used as well with a rod [80] or cone [81] instead of a plate
and may also be used to measure the contact angle of a liq-
uid of known surface tension against a specific plate, fiber,
or cone-shaped substrate (see later in this chapter under
Contact Angle Measurements). Also, the method does not
require corrections as with the drop weight or the Du Nouy
ring methods.
Sessile or Pendant Drop Shape Methods
If the shape of a sessile or pendant drop is measured pho-
tographically or by a digital camera, a solution of Eq (18)
for the specific shape of the drop in the presence of a
gravitational field can be used with the measurements of
the drop profile to back calculate the surface tension of the
drop. Fig. 12 gives a schematic of the method. This method
works well at liquidair or liquidliquid interfaces and can
also be used to make dynamic measurements if the camera
response is continuous and rapid [82]. A variation of the
drop-shape method of measurement is used wherein the
drop is deformed by a centrifugal field or an electrical field.
The spinning drop shape method allows very small interfa-
cial tensions to be measured between two liquids [83].
Maximum Bubble Pressure Methods
A bubble created by forcing a gas through the end of a
capillary in a liquid and the maximum pressure on the
resultant bubble can be used to measure surface tension
by Eq (19). This measurement procedure is illustrated in
Fig.13. However, this is another measurement that requires
correction, in this case for the nonspherical shape of the
bubble. With rapid formation of the bubbles and accurate
differential pressure measurements, the technique may be
used to make dynamic measurements [84]. If capillaries of
two different radii are used simultaneously and the pres-
sure difference between the bubbles formed and the two
capillaries is measured, a rapid, accurate measurement of
surface tension can be made and has been used as a process
monitor in emulsion polymerization [85]. This is known as
the differential bubble pressure method and is illustrated
in Fig. 14. This technique has been improved by the use of
computers with the ADSA/ ABSA technique [86,87].
Dynamic Surface Tension Methods
When confronted with situations where fresh surfaces
are formed, flow is occurring, or there are polymer solu-
tions with long equilibrium times, it becomes necessary
Fig. 11Schematic of Wilhelmy plate method of measuring
surface tension.
Fig. 12Schematic of sessile and pendant drop methods of
measuring surface tension.
Fig. 13Schematic of maximum bubble pressure method of
measuring surface tension.
Fig. 14Schematic of differential bubble pressure method of
measuring surface tension.
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CHAPTER 37 SURFACE ENERGETICS 461
to consider dynamic surface tension. As previously men-
tioned, bubble pressure, drop-shape methods, and the
Wilhelmy plate method can be used for static as well as
dynamic measurements. These methods are appropriate
only for relatively slow changes in , and they will be dis-
cussed briefly below with literature references that discuss
their use in characterizing (t) effects. In addition to the
already mentioned methods, other techniques have been
developed to measure for short-time scales and fresh,
rapidly changing surfaces.
Oscillating Jet
The mechanical instability of a liquid jet leaving an ellipti-
cal orifice causes the stream to oscillate about a circular
shape and eventually break up into droplets, as illustrated
in Fig. 15. The oscillations are periodic, and measurement
of their wavelength can be used to determine as given by
app
=
+
+
4 1
37
24
6 1
5
3
2
2
2
2
2 2
2
b
r
r
r
j
(
,
\
,
(
j
(
,
\
,,
(
(25)
where is the liquid density, is the velocity of the jet, is
the wavelength of the oscillation, r is the sum of the mini-
mum and maximum radii, and b is their difference [1]. This
dynamic measurement of has been considered by Vijian
and Ponter [88], who give references to the earlier work of
Ray-leigh, Bohr, Sutherland, Hansen, and others.
Falling Curtain
In an analysis of curtain coating, Brown [89] observed
that the angle in the falling curtain formed by the break
around a small, non-wettable obstacle could be used to
measure surface tension as
sin
=
2
Qu
(26a)
where Q is the mass flow rate per unit orifice slit length
in the curtain and u is the velocity of the liquid. This can
enable one to calculate the dynamic surface tension in the
falling film at the point where the obstacle intersects the
falling curtain if the velocity u is greater than the bursting
velocity of the falling sheet. A schematic of this method is
given in Fig. 16. This has been considered further by Van
Havenburgh and Joos [90]. Antoniades et al. [91] reconsid-
ered the work of Brown and suggested that Eq (26), when
derived correctly, should be written as
sin
2
2
=
Qu
(26b)
and give experimental evidence for this corrected equation.
Capillary Waves
The properties of capillary waves, small wavelength waves
on the surface of a liquid with the dominant restoring
force being surface tension, can be studied to provide a
measurement of surface tension, surface elasticity, and
other dynamic surface properties. For clean surfaces of an
inviscid liquid, Kelvin [92] determined that on a liquid of
density, , waves of frequency, , and wave number k, the
surface tension is given for small wavelengths.
=
2
3
k
(27)
The situation for interfaces in real systems, viscous liquids
with surfactants present, has been studied in detail [15,17],
and the use of mechanically generated capillary waves
for studying interfaces has been reviewed by Hansen and
Ahmad [93]. The capillary waves generated by temperature
fluctuations at a surface can be measured by laser-light
scattering techniques, and these data can be used to gener-
ate very accurate values of surface and interfacial tensions
[94]. Capillary wave studies can be used to study the time
dependence of in some detail and are probably the most
accurate and complete of the methods for measuring all
dynamic surface properties.
The Falling Meniscus Method
The measurement of the height of a column of liquid in a
tube with a small opening on top can be used to measure
the dynamic surface tension of aqueous systems. The height
measurement versus time may be analyzed to calculate the
surface tension as a function of time. This is discussed in
further detail, together with a full description of the experi-
mental apparatus and analytical equations, by Defay and
Hommeln [95].
Modified Static Surface Tension Measurements
Maximum Bubble Pressure
If one can monitor the time response of pressure to the
time-dependent surface tension, one can use the maximum
bubble pressure technique described above to measure
dynamic surface tension [84]. The equipment required for
such measurements is the same as the static maximum
bubble technique plus instrumentation for time-dependent
measurement of the bubble pressure. Various authors have
examined the theoretical and experimental aspects of these
methods [96,97].
Fig. 15Schematic of oscillating jet method of measuring
surface tension.
Fig. 16Schematic of falling film method of measuring
surface tension.
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462 PAINT AND COATING TESTING MANUAL 15TH EDITION
Wilhelmy Plate
If a time-recording balance is used to monitor the force
of surface tension pulling on the immersed plate, the
Wilhelmy plate technique can be used for characterizing
dynamic surface tension. As discussed above, the method is
not useful for short times, but for slowly varying (t) values.
The method is used considerably with Langmuir film bal-
ances and has been applied to various other problems [98].
Other Methods
If a sensing technique that can be time resolved is coupled
to a specific static surface tension measurement, (t) data
can be acquired. Reference [82] discusses this for drop-
shape methods, and Jho and Burke [99] present a modifica-
tion of the drop weight technique for (t) characterization.
Reference [29] discusses the general issue of characterizing
surfactant effects in dynamic systems.
CONTACT ANGLE MEASUREMENTS
Introduction
Contact angle measurement remains the most common
method for determining
sv
or wettability. Arguments sug-
gest, however, that
Y
is difficult to obtain for a variety of
reasons. Surface roughness results in contact angle hyster-
esis, as mentioned earlier, in which
a
gives the closer fit to
Y
. A rigid, physically smooth, and chemically homogeneous
surface should be used in order to get the best approxima-
tion. Other assumptions include: the use of pure liquids
to eliminate preferential adsorption effects, physical and
chemical reactions do not occur between phases,
lv
is
higher than
sv
such that a drop forms on the surface, and
that
sv
is constant and independent of the liquid used. The
review by Kwok and Neumann [61] includes further details
on contact angle measurement techniques and their inter-
pretations.
In addition to the common contact angle measure-
ments, a partial list of practiced solid surface tension
measurement techniques not discussed here includes:
solidification front techniques, sedimentation techniques,
gradient theory, film flotation, Lifshitz theory of van der
Waals forces, and theory of molecular interactions. All
approaches share in common the assumed validity of
Youngs equilibrium equation. References relevant to these
solid surface tension determining techniques are given
in the review by Tavana and Neumann [63]. Recent work
has also been done to determine contact angles at high
temperatures [100] and under flow conditions [101]. This
chapter includes information on direct/indirect sessile drop
methods, Wilhelmy plate, capillary rise, rate of penetration,
ADSA-P, and atomic force microscopy (AFM).
Direct Measurement of Contact Angle
by Sessile Drop
The common contact angle measurement is also known as
the sessile drop measurement and refers to optical tech-
niques for determining contact angles [102]. These include
contact angle goniometry of the drop profile using a pho-
tograph or digital video image, see Fig. 17. The drop must
be small enough that gravitational forces have insignificant
effects on the drop shape; therefore, magnification is neces-
sary either using a digital image or goniometer-fitted micro-
scope. Once the contact angle is known, Eq (10) can be used
to calculate the surface tension of the solid if desired. Often
experimentation with two different liquids is necessary to
obtain two equations with two unknowns and solve for
sv
algebraically.
The contact angle measured by this method is referred
to as the equilibrium angle,
e
, which lies between
a
and
r
but nearer to the former and is not necessarily equal to
Y
. It may be desirable to know the values for
a
and
r
; this
is accomplished by slowly adding or removing liquid from
the sessile drop until the maximum and minimum contact
angles are recorded, respectively [63]. Differences of 5 to
20 are common between the two angles. The method was
first performed by Zisman and co-workers using a thin plat-
inum wire to add liquid and a fine glass capillary to remove
liquid [63]. Later, Good and co-workers [103] applied the
technique using micrometer syringes.
Two similar techniques for measuring the contact
angle are the captive bubble method and the tilting plate
method [104]. The captive bubble method places a drop of
air on the solid surface in a liquid environment instead of
vice versa. The same contact angle is measured as before,
however, it is now nearer to
r
. Although this method devi-
ates from the simplicity of a liquid drop on a surface, it
assures one that the saturated vapor pressure of the liquid
and the solid-vapor interface are in equilibrium [63]. The
tilting plate method suspends a plate or cylinder of the solid
material in a bath of liquid with known
lv
. The solid is then
tilted until the capillary rise on the plate is zero, such that
the liquid-vapor interface is flat at the contact line. A simple
goniometer scale gives the contact angle to be the plates
displacement from the position normal to the liquid. Plac-
ing a sessile drop on the tilted plate at this position gives
a good approximation of
a
and
r
. Considerations must be
taken when choosing the liquid used in this method as it
requires appreciable quantities.
Contact angle measurements are considered to be
dynamic when there is a time dependency. For example,
a
and
r
are found through dynamic techniques in which
the drop volume is steadily increased or decreased, respec-
tively. The key factor is that the contact line is not static; the
review by Blake [105] contains theoretical information on
dynamic contact angles, velocity of the wetting line, and the
models that describe them.
Measurement of Sessile Drop Dimensions
Using the same drop preparation as the direct measure-
ment, the contact angle may be calculated through trigono-
metric equations by measuring drop diameter and height,
volume, or mass (only if the liquid is of known density to
obtain drop volume). Reference [62] further explains the
methods and derives the necessary equations. The tech-
nique assumes that the drop is a section of a sphere of
Fig. 17Schematic of contact angle goniometer.
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CHAPTER 37 SURFACE ENERGETICS 463
radius, r, such that the surface tension is satisfied by the
Laplace equation
p r = 2/
(28)
where p is the difference in pressure across the liquid-
vapor interface. Error is commonly associated surface
heterogeneities, leading to variations in the diameter and
contact angle along the drop perimeter.
Wilhelmy Plate
The equation for Wilhelmy plate method is adjusted to give
the contact angle of a solid if the liquid surface tension is
known. Eqs (29a) and (29b) both satisfy the solution of this
method.
cos / = W P
(29a)
sin / = 1 2
2
gh
sl
( )
(29b)
As before, the surface tension of the solid is determined
from the Young equation using this contact angle. This
is the static Wilhelmy plate method; information on the
dynamic method is given above and by Erbil [62].
Capillary Rise Method
The capillary rise method is also used to determine contact
angles:
cos / = rgh
sl
2
(30)
Automated Curve-Fitting Approaches
In an effort to enhance the reliability of contact angle mea-
surements, curve-fitting programs have been developed
to analyze the profile of a sessile drop by transferring the
image to a computer for digitizatiion and analysis [58]. The
first such approach ADSA-P by Neumann and co-workers
[106,107]; adjustments have consistently been made to
improve its applicability as a high-accuracy technique.
Assuming that the profile is both Laplacian and axisymmet-
ric, an integration of the Laplace equation gives the contact
angle [104]. The method is used as a low-rate dynamic
technique to measure the advancing and receding contact
angles [61]. A similar approach, the automated polynomial
fitting, was proposed using a polynomial fitting of the drop
profile. This technique has similar accuracy to ADSA-P but
is applicable to non-axisymmetric systems also [108].
Direct Force Measurement by AFM
Drelich et al. [109] have reviewed the use of AFM in
determining the surface tension of a solid. Although this
technique is very sensitive to experimental conditions and
requires extensive setup and calibration, it is applicable to
microscopic surfaces that are too small for regular sessile
drop techniques [104]. Corrections must also be made for
the elastic deformation of the materials. The theory for this
technique is based on the work of adhesion between two
materials, being the solid surface of interest and the instru-
ment probe. The pull-off (adhesion) force, F, is measured
directly in this experiment as a function of W
A
F RW
A
= 2
(31)
where R is the diameter of the probing tip. The coefficient
2 assumes the particles in contact are perfectly rigid. Once
W
A
is known, the Young equation can be combined with Eq
(12) to obtain the Young-Dupre equation [37]:
cos / = W
A lv
1
(32)
Similarly the surface tension can be solved using a con-
stant, c, generally 1.5 or 2 depending on the model chosen;
more details can be found in Ref. [109].
sv
F c R = /2
(33)
Rate of Penetration into Powder
The rate of penetration relation is utilized when it is desir-
able to know the amount of time it will take for a liquid
to wet a porous medium; examples include enhanced oil
recovery operations, the movement of water through geo-
logical systems, or absorption in the clean-up of spilled
liquids [110]. In this dynamic contact angle measurement,
the liquid enters the powder at a given velocity, , and sub-
sequently wets the surfaces by capillary forces as a function
of
lv
and as shown in the Washburn equation [111]:
cos / = 4 l r
lv
(34)
Here, is the viscosity of the penetrating liquid, l is the length
of the capillary path in the powder, and r is the average pore
size; the equation assumes inertial and gravitational effects
to be negligible. Often the technique is used to find the
lv
of the wetting liquid that minimizes the rate of penetration.
Refer to Lavi and Marmur [110] or Subrahman-yam et al.
[112] for more information on this method.
SOME SPECIFIC APPLICATIONS OF SURFACE
ENERGETICS TO ORGANIC COATINGS
Coatings Application and Defects
Flow phenomena, and their control, at surfaces are very
important to coatings film application technology [12,113].
It is such an important consideration that there have been
several books written on this topic since the first version
of this chapter [12,114,115]. The creation of uniform thin
films at high speeds involves many problems that are
determined by a combination of the application geometry,
the velocity of the substrate relative to the liquid coating,
the physical properties of the liquid coating, especially the
energetics of the surface of the liquid coating, the surface
of the substrate, and the new liquid/solid and gas/liquid
interfaces created in the application processes. Analysis of
several application techniques is given below to illustrate
the importance of the use of concepts discussed in the prior
portion of this chapter.
Dip Coating
Dip coating is a coating method in which a sheet of mate-
rial is constantly withdrawn vertically from a coating liquid
bath at constant velocity, producing a constant film thick-
ness coating adhering to the sheet, which is usually then
dried or cured to produce the final coating on the sheet (see
Fig. 18). This problem was originally analyzed by Landau
and Levich [116], and its solution has been given in the
most commonly used form by Probstein [117]. Only the
solution of the problem will be given here, but it is repre-
sentative of the problems identified by chemical engineers
as coating flows. In these cases, the geometry of the coating
device, the relative velocity, , of the object to be coated, and
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464 PAINT AND COATING TESTING MANUAL 15TH EDITION
the physical properties of the coating fluid (surface tension,
; viscosity, ; density, ; and acceleration of gravity, g) fix
the solution to the coating flow problem. In this case, the
limiting film thickness,
f
, at large distances from the coat-
ing bath surface, is given by
f
g
= 0 946
2 3
1 6
.
( )
/
/
(35)
This solution is derived from the physical effects of surface
tension, as described above, plus the Navier-Stokes equa-
tion fluid mechanics. These authors assume Newtonian
viscosity behavior of the liquid, i.e., the viscosity, , is inde-
pendent of shear rate, time-independent surface tension,
and an absence of surface tension gradient-driven flows
(Marangoni flows), with the appropriate boundary condi-
tions determined by the coating process. This solution can
be used by the coating designer and user to establish a first
order estimate of the film thickness of the liquid film by
the properties of the coating and the velocity of sheet with-
drawal. Further analyses of the dip coating processes are
given in more recent monographs [3,12,118].
Curtain Coating
As described above in the section on measurement of
dynamic surface tension, analysis of the curtain coating
process has yielded a measurement method for dynamic
surface tension. In the analyses of this problem, Brown
[89] and Ha-venburgh and Joos [96] both modeled curtain
coating by a falling liquid film held in place by two vertical
wires (see Fig. 19). The flux Q of falling liquid is
Q v h =
0 0
(36)
where
0
is the velocity of the falling film and h
0
is the width
of the falling film at time zero at the slot through which the
liquid exits. The velocity of the falling film at a position x
from the slot is given by
v v
2
0
2
= +2gx
(37)
where g is the acceleration of gravity. Since the flux of mate-
rial is constant through the slot, we know that
Q v h hv = =
0 0
(38)
and therefore
h x
Q
v gx
( ) =
+
0
2
2
(39)
This equation gives the user a description of the thickness
of liquid film as a function of distance from the slot of the
curtain coater. This can also be used to estimate the surface
tension at a given position x by the following relation [96]:
( )
( )
x
h x v
=
0
2
2
(40)
These equations give the application engineer a reasonably
complete description of the curtain coating process. Stokes
and Evans [3] and Guthoff [119] give more recent descrip-
tions with a discussion of multilayered curtain coating
processes. Fig. 20 illustrates the system discussed in these
references. Miamoto and Katagari [120] give an extensive
discussion of curtain coating stability with respect to the
falling film and and give the following criteria for stability
Qv > 2
(41)
Electrostatic Spray
The application of surface energetics to the problem of
charged liquid droplets was first done by Rayleigh [121]. In
this study, the electrical repulsion forces between charges
on a drop are equated to the surface tension forces hold-
ing a drop together to give the following equation as an
estimate of the upper limit on the charge that can be held
on a drop
q r = 16
2
(42)
where is the dielectric constant of the drop and r is the
drop radius. This can be used to gain an estimate of the
drop size in electrostatic spray of liquid paints. Further sta-
bility analysis of this problem indicates that if a drop at this
charge limit breaks up, the total energy of the system will be
minimized if it does so into n droplets, where n is given by
n
q
r
=
2
0
2
4
(43)
where r
0
is the radius of the original drop [122]. This charge
limit has been studied and verified experimentally by sev-
eral workers [123,124] and also applied to problems of
spray painting [125]. All of this work further illustrates the
importance and extensive applications of surface energet-
ics to coatings use. A computer simulation of electrostatic
spray processes has been used to predict spray patterns on
planar substrates [126].
Powder Coating
An environmentally friendly process that often yields high-
performance coating films is the powder coating process.
This process is one of the fastest growing in terms of mar-
ket for recently introduced application methods for organic
coatings [127]. The process can be described by many of the
variables that describe liquid electrostatic painting for both
Fig. 18Schematic of dip coating process.
Fig. 19Schematic of curtain coater.
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CHAPTER 37 SURFACE ENERGETICS 465
electrostatic spray powder coating and electrostatic fluid-
ized bed coating [128,129].
Coating Defects
There are many ways in which surface energetics are
involved in coating defects, and these are discussed in many
references (for example, see Ref. [12]). There is indeed,
a whole book devoted to this topic [12]. Surface defects
occur by either imperfect coating applications or distor-
tions of the film during the film formation process [130].
The control and prevention of defects in organic coating
films requires a knowledge of surface energetics and film
formation processes. Cratering occurs, for example, when
a suface active impurity with a lower surface tension than
the bulk coating spreads over the surface of a wet film dis-
placing or thinning the coating film. The leveling process
occurs because of the Laplace pressure at sites of curvature,
such as brushmarks, in coatings. Bubbles stabilized by sur-
factant adsorption can be carried into films during appli-
cation and cause subsequent imperfections. Any thinning
or non-uniformity in film is a potential site for corrosion
attack on the underlying substrate, especially in purely bar-
rier coatings [131].
Cleaning and Pretreatment of Substrates
forCoating
A very important step in the total process of creating a
high-performance organic coating/substrate system is the
cleaning and pretreatment of the substrate prior to the
coating application step. The processing time and costs
of the cleaning step often exceed that of the coating and
curing steps, indicating the importance often assigned to
this part of the coating process by many users. The specific
purpose of cleaning and pretreating substrate surfaces is to
control and/or modify the surface energy of the substrate
so that a coating may be successfully applied to the sub-
strate and that the coating will subsequently adhere prop-
erly to the substrate and provide the performance desired.
Cleaning, as a general rule, involves the removal of sub-
stances foreign to the substrate by a surfactant/detergent
Fig. 20Schematic of multiple layer (A) curtain coater and (B) slide coater. (Image duplicated from Figs. 4.2 and 4.3 of Ref. 119).
Reprinted with permission of John Wiley & Sons, Inc.
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466 PAINT AND COATING TESTING MANUAL 15TH EDITION
solution, followed with rinsing by a solvent that leaves the
substrate surface clean of contaminants. This may have to
be preceded by a mechanical sandblasting, grinding, sand-
ing, scrubbing, etc., to remove thick layers of mil scale,
rust, scum, and other built-up material on what is the real
substrate. Vapor or organic solvent degreasing/cleaning is
also often used to yield a clean surface for coating. These
mechanical cleaning steps, along with the cleaning and
rinsing of the surface with low surface tension solutions
that leave no residue, are best done just before the coat-
ing step lest recontamination occur while waiting for the
coating step. The goal of all these cleaning procedures is to
insure a uniform surface that has a uniform contact angle,
usually and desirably zero, for wetting by the coating, and
to insure the interface created is the coating liquid/sub-
strate interface only. The mechanical sanding, polishing,
etc., will also contribute to a lower contact angle by the
surface roughness effect discussed above. Oil, dirt, rust,
or other contaminants will give poor and incomplete wet-
ting and poor adhesion of the coating at the contaminated
sites. Complete wetting is further assisted by insuring the
surface tension of the coating liquid is low so that all air is
displaced by the coating and the contact angle between the
liquid coating and the substrate is zero, or near to it. The
surface tension of the liquid coating is best lowered by the
polymer of the system or by surfactant additives to the liq-
uid system. Attempts to control the surface tension by the
solvent can cause problems in having the surface tension
increase as the solvent evaporates. As mentioned above,
control of surface defects in coating processes is often
achieved by proper cleaning and handling of the objects/
substrates coated in the process [12].
Substrate pretreatment is usually performed just after
the cleaning discussed above and is done to further insure
complete wetting and adhesion of the coating, as well as,
in the case of metallic substrates, to deposit a corrosion
inhibitive layer [132]. In the case of plastic substrates, the
pretreatment may be corona or flame modification to oxi-
dize the surface layer and lower the contact angle to near
zero. Metal pretreatments often involve the deposition or
creation of a rough-surfaced crystalline layer of metallic
phosphates, which give an easily wetted surface.
Standard Surface Phenomena Testing Methods
ASTM International is a source of testing methods and
procedure documents (www.ASTM.org). Table 1 contains a
listing of several ASTM documents that are related to sur-
face technology and may be useful to those investigating in
this area of science. In addition to this listing, other ASTM
methods exist that may be pertinent and can be found at the
above indicated web site.
SUMMARY
The concepts of surface energy, surface tension, and wet-
ting and contact angle phenomena are of exceptional
importance to the science and technology of organic coat-
ing; these are topics that are ongoing. Their understand-
ing is vital for the proper formulation and application of
coating. Many of the features of the final organic coating/
substrate system are controlled by proper understanding of
the surfaces of the liquid coating and the substrate, as well
as creation of a proper coating/substrate interface. Both
the static and dynamic aspects of liquid surface properties
should be considered and the dynamic aspects properly
accounted for in coating production and application. These
concepts have been reviewed, and references to further
reading in this important area of organic coatings science
have been given.
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TABLE 1ASTM standards used in testing
surface phenomena (partial listing)
Designation ASTM Title
C813 Hydrophobic Contamination on Glass by Contact
Angle Measurements
D971 Interfacial Tension of Oil Against Water by the
Ring Method
D2578 Wetting Tension of Polyethylene and
Polypropylene Films
D3825 Dynamic Surface Tension by the Fast-Bubble
Technique
D5725 Surface Wettability and Absorbency of Sheeted
Materials Using an Automated Contact Angle
Tester
D5946 Corona-Treated Polymer Films Using Water
Contact Angle Measurement
D7334 Surface Wettability of Coatings, Substrates
and Pigments by Advancing Contact Angle
Measurement
D7490 Measurement of the Surface Tension of Solid
Coatings, Substrates and Pigments Using
Contact Angle Measurements
D7541 Standard Practice for Estimating Critical Surface
Tensions
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CHAPTER 37 SURFACE ENERGETICS 467
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CHAPTER 37 SURFACE ENERGETICS 469
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470
NOMENCLATURE
c = Dispersion cohesion energy from Figs. 2 and 3
D = Dispersion cohesion (solubility) parameterin tables
and computer printouts
DM = Dipole momentDebyes
E
d
= Dispersion cohesion energy
E
p
= Polar cohesion energy
E
h
= Hydrogen bonding cohesion energy
E
V
= Energy of vaporization (=) cohesion energy
G
M
= Molar free energy of mixing
H = Hydrogen bonding cohesion (solubility) parameter
in tables and computer printouts
H
v
= Molar heat of vaporization
H
M
= Molar heat of mixing
P = Polar cohesion (solubility) parameterin tables and
computer printouts
R = Gas constant (1.987 cal/mole K)
R
s
= Distance in Hansen space
R
O
= Radius of interaction sphere in Hansen space
RED = Relative energy difference, R
S
/R
0
S
M
= Molar entropy of mixing
T = Absolute temperature
T
b
= (Normal) boiling point
T
c
= Critical temperature
V
M
= Molar volume
T = Lydersen critical temperature group contribution
= Thermal expansion coefficient
d
= Dispersion cohesion (solubility) parameter
h
= Hydrogen bonding cohesion (solubility) parameter
p
= Polar cohesion (solubility) parameter
T
= Total cohesion (solubility) parameter
i
= Volume fraction of component i
X = Polymer-liquid interaction parameter (Flory-
Huggins)
INTRODUCTION
SOLUBILITY PARAMETERS ARE USED IN THE COAT-
ings industry to select solvents. Liquids with similar solubil-
ity parameters will be miscible, and polymers will dissolve
in solvents whose solubility parameters are not too differ-
ent from their own. The basic principle is like dissolves
like. Solubility parameters help put numbers into this
simple qualitative idea.
The solubility parameter approach has been used for
many years to select solvents for coating materials. The
lack of total success has stimulated research. The skill with
which solvents can be optimally selected with respect to
cost, solvency, workplace environment, external environ-
ment, evaporation rate, flash point, etc., has improved
over the years as a result of a series of improvements in
the solubility parameter concept and widespread use of
computer techniques. Most, if not all, commercial suppliers
of solvents have computer programs to help with solvent
selection. One can now easily predict how to dissolve a
given polymer in a mixture of two solvents, neither of which
can dissolve the polymer by itself.
This contribution to the paint testing manual unfor-
tunately cannot include discussion of all of the significant
efforts leading to our present state of knowledge of the
solubility parameter. An attempt is made to outline devel-
opments, provide some background for a basic understand-
ing, and give examples of uses in practice. The key is to
determine which affinities the important components in a
system have for each other. For coatings, this means affini-
ties of solvents, polymers, pigment surfaces, additives, and
substrates.
It is noteworthy that the concepts presented here have
developed toward not just predicting solubility, which
requires high affinity between solvent and solute, but to
predict affinities between different polymers leading to
compatibility, and affinities to surfaces to improve pig-
ment dispersion and adhesion. Attempts are also being
made to extend these developments, largely attributable
to the coatings industry, to understand affinities and
phenomena for a large number of other materials not
specifically related to coatings. In these applications, the
solubility parameter has become a tool, using well-defined
liquids as energy probes, to measure the similarity, or lack
of same, of key components. Materials with widely dif-
ferent chemical structures may be very close in affinities.
Only those materials that interact differently with differ-
ent solvents can be characterized in this manner. Many
inorganic materials, such as fillers, do not interact dif-
ferently with these energy probes since their energies are
(presumed to be) very much higher. Changing their surface
energies by various treatments can lead to a surface that
can be characterized. It is also known that the surfaces of
such materials are covered with water. The extent to which
this is bound will influence practical performance, i.e.,
how easily can it be replaced?
Solubility parameters are cohesion energy parameters
since they derive from the energy required to convert a liq-
uid to a gas. The energy of vaporization is a direct measure
of the total (cohesive) energy holding the liquids molecules
38
Solubility Parameters
Charles M. Hansen
1
1
Jens Bornoes Vej 16, 2970 Hoersholm, Denmark.
MNL17-EB/Jan. 2012
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CHAPTER 38 SOLUBILITY PARAMETERS 471
together. All types of bonds holding the liquid together
are broken by evaporation, which has led to the concepts
described in more detail below. The term cohesion energy
parameter is more appropriately used when referring to
surface phenomena.
HILDEBRAND PARAMETERS
The term solubility parameter was first used by Hildebrand
and Scott [1,2]. The solubility parameter is the square root
of the cohesive energy density
j
(
,
\
,
(
( ) ( / )
/
/
/
c e d
E
V
v
M
1 2
1 2
3 1 2
cal cm or MPAA
1/2
(1)
where V
M
is the molar volume and E
V
is the (measurable)
energy of vaporization [see Eq (14)]. The solubility param-
eter is an important quantity in predicting solubility rela-
tions, as can be seen from the following brief introduction.
Thermodynamics requires that the free energy of mix-
ing must be zero or negative for the solution process to
occur spontaneously. The free energy change for the solu-
tion process is given by the relation
G H T S
M M M
(2)
where G
M
is the free energy of mixing, H
M
is the heat
of mixing, T is the absolute temperature, and S
M
is the
entropy change in the mixing process.
The heat of mixing, H
M
, is given by Hildebrand and
Scott as
H E V
M M
M
1 2 1 2
2
( )
(3)
where the s are volume fractions and V
M
is the aver-
age molar volume of the solvent. It is important to note
that the solubility parameter, or rather the difference in
solubility parameters for the solvent-solute combination,
is important in determining the solubility. It is clear that
a match in solubility parameters leads to a zero heat of
mixing, and the entropy change should ensure solution.
The maximum difference in solubility parameters that can
be tolerated where solution still occurs is found by setting
the free energy change equal to zero in Eq (2). It is, in fact,
the entropy change that dictates how closely the solubility
parameters must match each other. It can also be seen that
solvents with smaller molecular volumes promote lower
heats of mixing, which, in turn, means that smaller solvent
molecules will be thermodynamically better than larger
ones when their solubility parameters are equal. A practi-
cal aspect of this effect is that solvents with relatively low
molecular volumes, such as methanol and acetone, can dis-
solve a polymer at larger solubility parameter differences
than expected from comparisons with other solvents with
larger molecular volumes. The converse is also true. Larger
molecular species may not dissolve even though solubility
parameter considerations might predict this. This can be a
difficulty with plasticizers.
A first impression ADD of the Hildebrand approach is
that negative heats of mixing are not possible. Likewise,
the approach is limited to regular solutions as defined by
Hildebrand and Scott [2] and does not account for asso-
ciation between molecules, such as polar and hydrogen
bonding interactions would require. The latter problem
seems to have been largely solved with the use of multi-
component solubility parameters. Patterson and co-workers
have cleared up many questions in polymer solution ther-
modynamics [3-8]. One of the more important matters was
to clearly show that negative heats of mixing are allowed
by the solubility parameter theory, thus eliminating one of
the major mental stumbling blocks for further use of this
concept.
A more detailed description of the theory presented by
Hildebrand and the succession of research reports which
have attempted to improve on it can be found in Bartons
extensive handbook [9]. The slightly older excellent con-
tribution of Gardon and Teas [10] is also a good source,
particularly for coatings and adhesion phenomena. The
approach of Burrell [11], who divided solvents into hydro-
gen bonding classes, has found numerous practical appli-
cations, and the approach of Blanks and Prausnitz [12],
who divided the solubility parameter into two components,
nonpolar and polar, are worthy of mention, however, in
that these have found wide use and greatly influenced the
authors earlier activities, respectively.
It can be seen from Eq (2) that the entropy change can
be considered beneficial to mixing. When multiplied by the
temperature, this will work in the direction of promoting a
more negative free energy of mixing. Higher temperatures
will also promote this more negative free energy change.
The entropy changes associated with polymer solutions will
be smaller than those associated with liquid-liquid miscibil-
ity, for example, since the monomers are already bound
into the configuration dictated by the polymer they make
up. They are no longer free in the sense of a liquid solvent
and cannot mix freely to contribute to a larger entropy
change. This is one reason polymer-polymer miscibility
is difficult to achieve. The free energy criterion dictates
that the polymer solubility parameters match extremely
well since there is little help from the entropy contribution
when progressively larger molecules are involved. However,
polymer-polymer miscibility can be promoted by introduc-
tion of suitable co-polymers or co-monomers that interact
specifically within the system.
HANSEN SOLUBILITY PARAMETERS
A widely used solubility parameter approach to predicting
polymer solubility is that proposed by the author. The basis
of these so-called Hansen solubility parameters is that the
total energy of vaporization of a liquid consists of several
individual parts [1317]. Needless to say, without the work
of Hildebrand and Scott [1,2] and others not specifically
referenced here such as Scatchard, this postulate could
never have been made. The total cohesive energy, E
t
, can
be measured by evaporating the liquid, i.e., breaking all the
cohesive bonds. It should also be noted that these cohesive
energies arise from interactions of a given solvent molecule
with another of its own kind. The basis of the approach is,
therefore, very simple, and it is surprising that so many
different applications have been possible over the past 40
years. A number of applications are discussed below. A
lucid discussion by Barton [18] enumerates typical situa-
tions where problems occur when using solubility param-
eters. These are most often where the environment causes
the solvent molecules to interact with or within themselves
differently than when they make up their own environment,
i.e., as pure liquids.
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472 PAINT AND COATING TESTING MANUAL 15TH EDITION
Materials having similar (Hansen) solubility param-
eters have high affinity for each other. The extent of the
similarity in a given situation determines the extent of the
interaction. The same cannot be said of the total or Hilde-
brand solubility parameter [1,2]. Ethanol and nitrometh-
ane, for example, have similar total solubility parameters
(26.1 versus 25.1 MPa
1/2
, respectively), but their affinities
are quite different. Ethanol is water soluble, while nitro-
methane is not. Indeed, mixtures of nitroparaffins and
alcohols were demonstrated in many cases to provide
synergistic mixtures of two nonsolvents that dissolved
polymers [13].
There are three major types of interaction in common
organic materials. The most general are the nonpolar
interactions, which derive from atomic forces. These have
also been called dispersion interactions in the literature.
Since molecules are built up from atoms, all molecules will
contain this type of attractive force. For the saturated ali-
phatic hydrocarbons, for example, these are essentially the
only cohesive interactions, and the energy of vaporization is
assumed to be the same as the dispersion cohesive energy,
E
d
. Finding the dispersion cohesive energy as the cohesion
energy of the homomorph, or hydrocarbon counterpart, is
the starting point for the calculation of the three Hansen
parameters for a given liquid.
The permanent dipole-permanent dipole interactions
cause a second type of cohesion energy, the polar cohesive
energy, E
p
. These are inherently molecular interactions
and are found in most molecules to one extent or another.
The dipole moment is the primary parameter in calculating
these interactions. A molecule can be primarily polar in
character without being water soluble, so there is misuse
of the term polar in the general literature. The polar solu-
bility parameters referred to here are well-defined, experi-
mentally verified, and can be estimated from molecular
parameters as described below. As noted above, the polar
solvents include those with relatively high total solubility
parameters, which are not particularly water soluble such
as nitroparaffins, propylene carbonate, tri-n-butyl phos-
phate, and the like. Induced dipoles have not specifically
been treated by Hansen, but are recognized as a potentially
important factor, particularly for solvents with zero dipole
moments.
The third major cohesive energy source is hydrogen
bonding, E
h
. Hydrogen bonding is a molecular interaction
and resembles the polar interactions in this respect. The
basis of this type of cohesive energy is attraction among
molecules because of the hydrogen bonds. In this perhaps
oversimplified approach, the hydrogen bonding parameter
has been used to more or less collect the energies from
interactions not included in the other two parameters.
Alcohols, glycols, carboxylic acids, and other hydrophilic
materials have high hydrogen bonding parameters. Other
researchers have divided this parameter into separate
parts, for example, acid and base cohesion parameters, to
allow both positive and negative heats of mixing. These
approaches will not be dealt with here, but can be found
described in Bartons Handbook [9] and elsewhere [1921].
The most extensive division of the cohesive energy has
been done by Karger et al. [22], who developed a system
with five parameters: dispersion, orientation, induction,
proton donor, and proton acceptor. The Hansen hydrogen-
bonding parameter may be termed an electron interchange
parameter as well. As a single parameter, it has remarkably
accounted well for the experience of the author and keeps
the number of parameters to a level, which allows ready
practical usage.
It is clear that there are other sources of cohesion
energy in various types of molecules arising, for example,
from induced dipoles, metallic bonds, electrostatic interac-
tions, or whatever type of separate energy can be defined.
Hansen stopped with the three major types found in
organic molecules. It was and is recognized that additional
parameters could be assigned to separate energy types.
The description of organometallic compounds could be an
intriguing study, for example. This would presumably par-
allel similar characterizations of surface-active materials,
where each separate part of the molecule requires separate
characterization for completeness. The Hansen parameters
have mainly been used in connection with solubility rela-
tions, mostly, but not exclusively, in the coatings industry,
but their use is now spreading to other industries.
Solubility and swelling have been used to confirm the
solubility parameter assignments of many of the liquids.
These have then been used to derive group contribution
methods and suitable equations based on molecular prop-
erties to arrive at estimates of the three parameters for
additional liquids. The goal of a prediction is to determine
similarity or not of the cohesion energy density parameters.
The strength of a particular type of hydrogen bond or other
bond, for example, is important only to the extent that it
influences the cohesive energy density.
Hansen parameters do have direct application in other
scientific disciplines of interest to the coatings industry,
such as surface science, where they have been used to
characterize the wettability of various surfaces and adsorp-
tion properties of pigment surfaces [10,14,16,2325]. Many
other applications of widely different character have been
discussed by Barton [9] and Gardon [26]. Surface char-
acterizations have not been given the attention deserved
in terms of a unified similarity-of-energy approach. The
author can certify that thinking in terms of similarity of
energy, whether surface energy or cohesive energy, can lead
to rapid decisions and plans of action in critical situations
where data are lacking. In other words, the everyday indus-
trial crisis situation can often be reduced in scope by appro-
priate systematic approaches based on similarity of energy.
The basic equation that governs the assignment of Han-
sen parameters is that the total cohesion energy, E
t
, must
be the sum of the individual energies that make it up
+ + E E E E
t d p h
(4)
Dividing this by the molar volume gives the square of the
total (or Hildebrand) solubility parameter as sum of the
squares of the Hansen D, P, and H components.
+
+
E
V
E
V
E
V
E
V
t
M
d
M
p
M
h
M
(5)
t d p h
D P H + + + +
2 2 2 2 2 2
( ) computer printouts
(6)
METHODS AND PROBLEMS IN THE
DETERMINATION OF PARTIAL
SOLUBILITY PARAMETERS
The best method to calculate Hansen solubility param-
eters depends to a great extent on what data are available.
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CHAPTER 38 SOLUBILITY PARAMETERS 473
Hansen originally adopted an essentially experimental
procedure and established numbers for 90 liquids based
on solubility data for 32 polymers [13]. This procedure
involved calculation of the nonpolar parameter according
to the procedure outlined by Blanks and Prausnitz [12].
This calculational procedure is still in use and is considered
to be the most reliable and consistent for this parameter. It
is outlined below. The division of the remaining cohesive
energy between the polar and hydrogen bonding interac-
tions was done by trial and error to fit experimental poly-
mer solubility data. A key to parameter assignments in this
initial trial and error approach was that mixtures of two
nonsolvents could be systematically found to synergistically
(but predictably) dissolve given polymers. This meant that
these had parameters placing them on opposite sides of
the solubility region, a spheroid, from each other. Having
a large number of such predictably synergistic systems as
a basis, reasonably accurate divisions into the three energy
types were possible.
Using the experimentally established, approximate,
p
and
h
parameters, Skaarup [15] found that the Bttcher
equation could be used to calculate the polar parameter
quite well, and this led to a revision of the earlier values
to those now in wide use for these same liquids. These
values were also consistent with the experimental solu-
bility data for 32 polymers available at that time and Eq
(6). Furthermore, Skaarup developed the equation for the
solubility parameter distance, R
s
, between two materi-
als based on their respective partial solubility parameter
components
R
s d d p p h h
+ + 4
1 2
2
1 2
2
1 2
2
( ) ( ) ( ) (7)
This equation was developed from plots of experimen-
tal data where the constant 4 was found convenient and
correctly represented the solubility data as a sphere encom-
passing the good solvents. When the scale for the dispersion
parameter is doubled compared with the other two param-
eters, essentially spherical rather than spheroidal regions
of solubility are found. This greatly aids two-dimensional
plotting and visualization. There are, of course, bound-
ary regions where deviations can occur. These are most
frequently found to involve the larger molecular species
being less-effective solvents compared with the smaller
counterparts that define the solubility sphere. Likewise,
smaller molecular species, such as acetone and methanol,
often appear as outliers in that they dissolve a polymer
even though they have solubility parameters placing them
at a distance greater than the solubility sphere radius, R
0
.
This dependence on molar volume is inherent in the theory
developed by Hildebrand and Scatchard as discussed
above. Smaller molar volume favors lower heats of mixing,
which in turn promotes solubility. Such smaller molecular
volume species, which dissolve better than predicted by
comparisons based on solubility parameters alone, should
not necessarily be considered outliers. This statement is
justified by Eq (3), where it can be seen that the molar vol-
ume and the square of the solubility parameter difference
are weighted equally in estimating the heat of mixing in the
Hildebrand theory.
The molar volume is frequently used as a fourth param-
eter to describe molecular size effects. These are especially
important in correlating diffusion phenomena with the sol-
ubility parameter, for example. The author has preferred to
retain the three well-defined, partial solubility parameters
with a separate, fourth, molar volume parameter, rather
than to multiply the solubility parameters by the molar
volume raised to some power to redefine them. In response
to a reviewer request stating that molar volumes calculated
by software that is generally available do not agree with
those found by the author, it can be said that the approach
of dividing the molecular weight by the density was the way
the molar volume was found when the ideas for this chapter
emerged over 40 years ago. The author has seen no reason
to diverge from this practice. When densities are not known
or cannot be found in standard reference works, recourse
can be taken to comparison with related compounds or
other suitable procedure for determining the density. There
are various types of free volume, which can be a cause of
some difference in estimations depending on the assump-
tions made, but a deeper discussion at this point appears to
be beyond the scope of this chapter.
The exact reason for the constant 4 in Eq (7) is dis-
cussed below. It is currently considered both as an experi-
mental result related to the entropy changes in the systems
described and as a theoretically well-defined constant.
The author has also found in unpublished studies that
values close to 5 could represent solubility data equally
well for a few cases studied. The differences in solubility
parameters between the solvent and solute in the polar
and hydrogen bonding parameters are larger by a factor
of two than is tolerated when nonpolar solvents dissolve
the same polymer. This factor of 2 is squared to give 4 in
Eq (7). The term specific interactions is often applied
to the molecular polar and molecular hydrogen bonding
(electron interchange) interactions implying that these are
especially beneficial to achieving a solution since larger
differences in the characteristic parameters are allowed
with a successful result.
Another way to view this is as follows. It is assumed
that the (center-of-the-sphere) partial solubility param-
eters assigned by computer optimization techniques to
polymers using Eq (7) are the theoretically correct ones. A
solvent with parameters corresponding to the center is to
be changed in quality. If the nonpolar parameter difference
only is changed by one unit, the effect on R
s
is four units.
If the polar or hydrogen bonding parameter difference is
changed by one unit, the effect on R
s
is also one unit. The
entropy changes associated with the polar and hydrogen
interactions have reduced the total (free energy change)
effect by a factor of 4 and are thus four times larger than
those associated with the nonpolar interactions.
The discussion above follows from the fact that the
boundaries of the regions of solubility are characterized
by a free energy change of zero for the solution process.
The Flory-Huggins limiting chi parameter, , of about 0.5
is also characteristic for the boundary of the solubility
region. Patterson [6,27], in particular, has been instrumen-
tal in showing the relations between the chi parameter and
solubility parameters. Pattersons work led to the develop-
ments reported in the next section. This is strictly valid
only for the interactions described by this theory. So-called
theta solvents will also be located in boundary regions on
solubility parameter plots with these same restrictions.
Much polymer research has focused on these boundary
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474 PAINT AND COATING TESTING MANUAL 15TH EDITION
regions only, for the above reasons and because relatively
small changes in temperature, molecular weight, solvent
quality, etc., give large easily measurable changes in other
quantities.
The approach of computer optimizing solubility data
to spheres, which is currently in use, still seems most favor-
able, at least until an improvement is offered by an improved
theory. Plotting experimental solubility data defines bound-
aries of solubility, which in fact are fixed by the free energy
of mixing being experimentally equal to zero.
Equation (7) is readily used on a computer (or on a
hand calculator), and supplementary relations allow easier
scanning of large sets of data. It is obvious that solubility,
or high affinity, requires that R
s
be less than R
0
. The ratio
R
s
/R
0
has been called the RED number, reflecting the rela-
tive energy difference. A RED number of 0 is found for no
energy difference. RED numbers less than 1.0 indicate
high affinity, RED equal to or close to 1.0 is a boundary
condition, and progressively higher RED numbers indicate
progressively lower affinities. Scanning a sizeable computer
output for RED numbers less than 1.0, for example, rapidly
allows location of the most interesting liquids for a given
application.
The revised set of parameters for the 90 solvents was
the basis for group contribution procedures developed by
(most notably) Van Krevelen [28] and Beerbower [17,29],
who also used Fedors, work [30]. These various develop-
ments have been summarized by Barton [9], although
Beerbowers latest values have only appeared in the NASA
document [29]. Table 1 is an expanded table of Beerbower
group contributions, which was distributed among those
who were in contact with Beerbower in the late 1970s.
Beerbower also developed a simple equation for the polar
parameter [17], which involved only the dipole moment
and the square root of the molar volume. This is also given
below and has been found quite reliable by Koehnen and
Smolders [31]. This equation has also been found reli-
able by the author as well, giving results generally consis-
tent with Eq (6), which, again, is the basis of the whole
approach. Koehnen and Smolders also give correlation
coefficients for other calculation procedures to arrive at the
individual Hansen parameters.
A sizeable number of liquids have now been assigned
Hansen parameters using the procedures described here.
Many of these have not been published. Exxon Chemical
Corporation [32,33] has indicated a computer program
with data for over 500 solvents and plasticizers, 450
resins and polymers, and 500 pesticides. The authors
files contain the three parameters for about 1200 liquids,
although several of them appear with two or three sets of
possible values awaiting experimental confirmation. In
some cases, this is due to questionable physical data, for
example, for latent heats of vaporization or wide varia-
tions in reported dipole moments. Another reason for
this is that some liquids are chameleonic [34] as defined
by Hoy in that they adopt configurations depending
on their environment. Hoy [34] cites the formation of
cyclic structures for glycol ethers with (nominally) linear
structure. The formation of hydrogen bonded tetramers
of alcohols in a fluoropolymer has also been cited [35].
The term compound formation can be found in the
older literature, particularly where mixtures with water
were involved, and structured species were postulated to
explain phenomena based on specific interactions among
the components of the mixtures. Barton has recently
discussed some of these situations and points out that
Hildebrand or Hansen parameters must be used with
particular caution where the extent of donor-acceptor
interactions, and in particular hydrogen bonding within
a compound, is very different from that between com-
pounds [18]. Amines and water, for example, are known
to associate. Pure component data cannot be expected to
predict the behavior in such cases.
Still another reason for difficulties is the large variation
of dipole moments reported for the same liquid. The dipole
moment for some liquids depends on their environment, as
discussed below. A given solvent can be listed with different
values in files to keep these phenomena in mind.
Large data sources greatly enhance searching for
similar materials and locating new solvents for a polymer
based on limited data, for example. Unfortunately, different
authors have used different group contribution techniques,
and there is a proliferation of different Hansen parameters
for the same chemicals in the literature. This would seem
to be an unfortunate situation, but may ultimately provide
benefits. In particular, partial solubility parameter values
found in Hoys extensive tables [9,36] are not compatible
with the customary Hansen parameters reported here. Hoy
has provided an excellent source of total solubility param-
eters. He independently arrived at the same type division
of cohesion energies as Hansen, although the methods of
calculation are quite different.
Many solvent suppliers have also presented tables of
solvent properties and/or use computer techniques to get
these in their technical service. Partial solubility param-
eters not taken directly from earlier well-documented
sources should be used with caution. In particular it can
be noted that the Hoy dispersion parameter is consistently
lower than that found by Hansen. Hoy subtracts estimated
values of the polar and hydrogen bonding energies from the
total energy to find the dispersion energy. This allows for
more calculation error and underestimates the dispersion
energy since the Hoy procedure does not appear to fully
separate the polar and hydrogen bonding energies. The Van
Krevelen dispersion parameters appear too low. The author
has not attempted these calculations, being completely
dedicated to the full procedure described here, but values
estimated independently based on the Van Krevelen disper-
sion parameters are clearly low. A comparison with related
compounds, or similarity principle, gives better results
than those found from the Van Krevelen dispersion group
contributions.
In the following, calculation procedures and experi-
ence are presented according to the procedures found most
reliable for the experimental and/or physical data available
for a given liquid.
RECENT DEVELOPMENTSTHEORY
A new understanding of the Hansen solubility parameter
approach has developed since the publishing of the 14th
edition of the Gardner-Sward Handbook [37,38]. Chapter
2 in Ref. [38] and also Chapter 2 in Ref. [39] include a
comparison of the HSP approach with different theories of
polymer solution behavior. These include those developed
or modified by Huggins, Flory, Hildebrand, Prigogine, and
Patterson [6,27,3842].
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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CHAPTER 38 SOLUBILITY PARAMETERS 475
For those familiar with the widely used Flory inter-
action coefficient,
12
it can be shown [38,39] that there
is a relation between this and the RED number given by
Eq (8).
12
corresponds to
c
(RED)
2
(8)
c
is usually taken as being near 1/2 for the interaction
of typical solvents with polymers of very large molecular
weight. Unfortunately,
12
does not explicitly take account
of hydrogen bonding. Equation (8) is therefore only indica-
tive of a relation had the Flory approach included polar and
hydrogen bonding interactions explicitly.
TABLE 1Group contributions to partial solubility parameters
Functional
Group
Molar Volume, V
(cm
3
/mol)
London parameter, V
2
D
(cal/mol) Polar parameter, V
2
P
Electron transfer
parameter, V
2
H
(cal/mol)
Total parameter,
V
2
(cal/mol)
Aliphatic Aromatic
e
Alkane Cyclo Aromatic Alkane Cyclo Aromatic Aliphatic Aromatic Aliphatic Aromatic
CH
3
F
2
twid
d
40.0 48.0 0 0 0 700250
a
? 500250
a
0 0 1,700 1,360
e
F
3
triplet
d
66.0 78.0 0 0 0 ? ? ? 0 0 1,650 1,315
e
Cl 24.0 28.0 400100 ? 1,300100 1,250100 1,450100 800 100 10020
a
Same 2,760 2,200
e
Cl
2
twin
d
52.0 60.0 3,650160 ? 3,100175
a
800150 ? 400150
a
16510
a
18010
a
4,600 3,670
e
CL
3
triple
d
81.9 73.9 4,750300
a
? ? 300100 ? ? 350250
a
? 5,400 4,300
e
Br 30.0 34.0 1,050300
a
1,500175 1,650140 1,250100 1700150 800 100 500100 500 100 3,700 2,960
e
Br
2
twin
d
62.0 70.0 4,300300
a
? 3,500300
a
800250
a
? 400150
a
825200
a
800250
a
5,900 4,700
e
Br
3
triplet
d
97.2 109.2 5,800400
a
? ? 350150
a
? ? 1,500300
a
? 7,650 6,100
e
I 31.5 35.5 2,350250
a
2 200250
a
2,000250
a
1,250100 1,350100 575+100 1,000200
a
1,000200
a
4,550 3,600
e
I
2
twin
d
66.6 74.6 5,500300
a
? 4,200300
a
800250
a
? 400150
a
1,650250
a
1,800200
a
8,000 6,400
e
I
3
triplet
d
111.0 123.0 ? ? ? ? ? ? ? ? 11,700 9,3 50
e
O ether 3.8 Same 0 0 0 500150 600150 450150 45025 1,200100 800 (1,650150)
>CO ketone 10.8 Same ...
c
2,350400 2,8001352 25,0007%)/V 1,000300 950300 800250
b
400125
a
4,150 Same
CHO (23.2) (31.4) 950300 ? 350275 2,100200 3,000500 2,750200 1,000200 750150 (4,050) Same
COOester 18.0 Same ...
c
? ... (56,00012%)/V ? (338,00012%)/V 1,250150 475100
a
4,300 Same
COOH 28.5 Same 3,350300 3,550250 3,600400 500150 30050 750350 2,750250 2,850250
a
6,600 Same
OH 10.0 Same 1,770450 1,370500 1,870600 700200 1,100300 800150 4,650400 4,650500 7,120 Same
(OH)
2
twin
or adjacent
26.0 Same 0 ? ? 1,500100 ? ? 9,000 600 9,300600 10,440 Same
CN 24.0 Same 1,600850
a
? 0 4,000800
a
? 3,750300
a
500200
b
40012
a
4,450 Same
NO
2
24.0 32.0 3,000600 ? 2,550125 3,600600 ? 1750100 40050
b
35050
a
7,000 (4,400)
NH
2
amine 19.2 Same 1,050300 1,050450
a
150150
a
600 200 600350
a
800 200 1,350200 2250200
b
3,000 Same
>NH
2
amine 4.5 Same 1,150225 ? ? 10050 ? ? 750200 ? 2,000 Same
NH
2
amide (6.7) Same ? ? ? ? ? ? 2,700550
a
? (5,850) Same
PO
4
28.0 Same ...
c
? ? (810010%)/V ? ? 3,000500 ? (7,000) Same
a
Based on very limited data. Limits shown are roughly 95 % confidence; in many cases, values are for information only and not to be used for computation.
b
Includes unpublished infrared data.
c
Use formula in V
2
p
column in calculation, with V for total compound.
d
Twin and triplet values apply to halogens on the same C atom, except that V
2
p
also includes those on adjacent C atoms.
e
These values apply to halogens attached directly to the ring and also to halogen attached to aliphatic double-bonded C atoms.
f
From R. F. Fedors
25
.
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476 PAINT AND COATING TESTING MANUAL 15TH EDITION
It is instructive to arrange Eq (8) in the form given in
Eq (9):
(RED)
2
= (R
s
/R
o
)
2
corresponds to
12
/
c
(9)
(R
s
)
2
corresponds to
12
, both being interaction parameters.
These are respectively divided by the corresponding limit-
ing or critical values that allow solubility to find (RED)
2
.
These limiting values are (R
o
)
2
in the Hansen system and
c
in the Huggins-Flory approach. Thus R
s
greater than R
o
indicates nonsolubility just as values of
12
greater than c
have the same function. Values of R
s
and
12
that are less
than zero are not allowed (even though one finds many
measured values of the latter in the literature which are
negative).
The coefficient 4 in Eq (7) has been found correct
for all practical purposes in over 1,000 correlations using
Hansen solubility parameters. The coefficient 4 in front
of the difference in the nonpolar interactions shows that
the specific interactions described by the differences in
the polar and hydrogen bonding parameters are only 0.25
times as significant as the differences in the nonpolar term.
This factor (0.25) is predicted theoretically by the Prigogine
corresponding states theory of polymer solutions for the
importance of specific interactions relative to the atomic/
nonpolar interactions [3842]. This same factor can also be
traced back to still earlier approaches (Lorentz-Berthelot
mixtures) studying affinities among gases, for example [42].
The Hansen approach and the (first term in the) Prigogine
approach are in agreement with each other. The so-called
geometric mean to estimate the interaction between two
unlike species is used in both of these, and the coefficient 4
experimentally confirms that this type of mean is also valid
for hydrogen bonding interactions. The coefficient 4 must
be used to differentiate the behavior of the atomic (non-
polar, dispersion, or London) type forces from that of the
molecular dipolar and molecular hydrogen bonding forces.
The Hansen approach cannot be considered empirical. The
Huggins-Flory and subsequent new Flory approaches
seem inadequate for other than strictly nonpolar systems
since hydrogen bonding is not included. The pioneering
Hildebrand solubility parameter approach did not treat
specific interactions either, although it led the author to
develop the Hansen approach that does. The Prigogine
approach is too difficult to use and lacks specific consider-
ation of hydrogen bonding as well. This leaves the Hansen
approach as the only proven, reliable, and generally useful
means to systematically study the common types of interac-
tions involved in systems with hydrogen bonding and with
permanent dipoles. It is not in conflict with the other theo-
ries. It extends them in a general way to applications with
polar and hydrogen bonding.
Panayiotou has recently used a statistical thermody-
namica approach to calculate the HSP that is reported
in Chapter 3 in Ref. [39]. Expanding on earlier work, he
first calculates the hydrogen bonding solubility parameter.
After this the other HSP and the total solubility parameter
are calculated. There is also a new large set of group con-
tributions to help those not fully competent in statistical
thermodynamics. The values for all the parameters for
about 50 liquids calculated by Panayiotou are in amaz-
ingly good agreement with those reported by Hansen over
40 years ago [1316]. There is also exceptionally good
agreement for a number of the common polymers. These
results, coupled with the agreement, or perhaps better,
lack of disagreement, with the other theories of polymer
solutions, appear to confirm that the three-parameter
approach based on a division of the cohesion energy is
fundamentally sound.
CALCULATION OF THE DISPERSION SOLUBILITY
PARAMETER,
d
The
d
parameter is calculated according to the procedures
outlined by Blanks and Prausnitz [12]. Figs. 1 and 2, or 3,
can be used to find this parameter depending on whether
the molecule of interest is aliphatic, cycloaliphatic, or aro-
matic. These figures have been inspired by Barton [9], who
converted earlier data to SI units. All three of these figures
have been straight line extrapolated into a higher range
of molar volumes than that reported by Barton. Energies
found with these extrapolations have also provided consis-
tent results. The solubility parameters in SI units, MPa
1/2
,
are 2.0455 times larger than those in the older centimeter,
gram, second system, (cal/cc)
1/2
, which still finds extensive
use in the United States, for example.
The figure for the aliphatic liquids gives the disper-
sion cohesive energy, E
d
, whereas the other two figures
directly report the dispersion cohesive energy density, c.
The latter is much simpler to use since one needs only
take the square root of the value found from the figure to
find the respective partial solubility parameter. Barton also
presented a similar figure for the aliphatic solvents, but
it is inconsistent with the energy figure and in error. Its
use is not recommended. When substituted cycloaliphat-
ics or substituted aromatics are considered, simultaneous
consideration of the two separate parts of the molecules is
required. The dispersion energies are evaluated for each of
the types of molecules involved, and a weighted average for
the molecule of interest based on numbers of significant
atoms is taken. For example, hexyl benzene would be the
arithmetic average of the dispersion energies for an ali-
phatic and an aromatic liquid, each with the given molar
volume of hexyl benzene. Liquids such as chlorobenzene,
toluene, and ring compounds with alkyl substitutions with
only two or three carbon atoms have been considered as
cyclic compounds only. Such weighting has been found
necessary to satisfy Eq (6).
The author has directly used these figures to find the
cohesion energy for nonpolar molecules. This introduces
a small but unaccountable error since, for example, E
D
,
for an aromatic compound such as toluene, is not equal
to the total cohesion energy E
t
. In practice (so far) this
has not led to any apparent problems. The error becomes
less significant as the polar and hydrogen bonding effects
increase.
The critical temperature, T
c
, is required to use the
dispersion energy figures. If the critical temperature can-
not be found, it must be estimated. A table of the Lydersen
group contributions, T, [43] as given by Hoy [36] for
calculation of the critical temperature, is included here as
Table 2. In some cases, the desired groups may not be in
the table, which means some educated guessing is required.
The end result does not appear too sensitive to these situa-
tions. The normal boiling temperature, T
b
, is also required
in this calculation. This is not always available, either, and
must be estimated by similarity, group contribution, or
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CHAPTER 38 SOLUBILITY PARAMETERS 477
other technique. The Lydersen group contribution method
involves the use of Eqs (10) and (11),
T T
b c T T
/ . + ( )
0 567
2
(10)
T T T
r c
/
(11)
where T has been taken as 298.15 K.
The dispersion parameter is an atomic force parameter.
The size of the atom is important. It has been found that
corrections are required for atoms significantly larger than
carbon, such as chlorine, sulfur, bromine, etc., but not for
oxygen or nitrogen, which have a similar size. The carbon
atom in hydrocarbons is the basis of the dispersion parame-
ter in its present form. These corrections are applied by first
finding the dispersion cohesive energy from the appropriate
figure. This requires multiplication by the molar volume
for the cyclic compounds using data from the figures here
since these figures give the cohesive energy densities. The
dispersion cohesive energy is then increased by adding on
the correction factor. This correction factor for chlorine,
bromine, and sulfur has been taken as 1,650 J/mol for each
of these atoms in the molecule. Dividing by the molar vol-
ume and then taking the square root gives the (large atom
corrected) dispersion solubility parameter.
The need for these corrections has been confirmed
many times, both for interpretation of experimental data
Fig. 2Cohesive energy density for cycloalkanes as a function
of molar volume and reduced temperature.
Fig. 3Cohesive energy density for aromatic hydrocarbons as
a function of molar volume and reduced temperature.
Fig. 1Energy of vaporization for straight chain hydrocarbons as a function of molar volume and reduced temperature.
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478 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 2Lydersen group constants
Group
Aliphatic,
T
Cyclic,
T
T
P
Aliphatic,
P
Cyclic,
P
CH
3
0.020 ... 0.0226 0.227 ...
CH
2
0.020 0.013 0.0200 0.227 0.184
>CH 0.012 0.012 0.0131 0.210 0.192
>C< 0.000 0.007 0.210 0.210 0.154
CH
2
0.018 ... 0.0192 0.198 ...
N 0.060 ... 0.0539 0.36 ...
NCO ... ... 0.0539 ... ...
HCON< ... ... 0.0546 ... ...
CONH ... ... 0.0843 ... ...
CON< ... ... 0.0729 ... ...
CONH
2
... ... 0.0897 ... ...
OCONH ... ... 0.0938 ... ...
S 0.015 0.008 0.0318 0.27 0.24
SH 0.015 ... ... ... ...
CI 1 0.017 ... 0.0311 0.320 ...
CI 2 ... ... 0.0317 ... ...
Cl
2
twin ... ... 0.0521 ... ...
CI aromatic ... ... 0.0245 ... ...
Br 0.010 ... 0.0392 0.50 ...
Br aromatic ... ... 0.0313 ... ...
F 0.018 ... 0.006 0.224 ...
I 0.012 ... ... 0.83 ...
Conjugation ... ... 0.0035 ... ...
c is double bond ... ... 0.0010 ... ...
trans double bond ... ... 0.0020 ... ...
4 Member ring ... ... 0.0118 ... ...
5 Member ring ... ... 0.003 ... ...
6 Member ring ... ... 0.0035 ... ...
7 Member ring ... ... 0.0069 ... ...
Ortho ... ... 0.0015 ... ...
Meta ... ... 0.0010 ... ...
Para ... ... 0.0060 ... ...
Bicycloheptyl ... ... 0.0034 ... ...
Tricyclodecane ... ... 0.0095 ... ...
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CHAPTER 38 SOLUBILITY PARAMETERS 479
and to allow Eq (6) to balance. Research is definitely needed
in this area. The impact of these corrections is, of course,
larger for the smaller molecular species. The taking of
square roots of the larger numbers involved with the larger
molecular species reduces the errors involved in these cases
since the corrections themselves are relatively small.
It can be seen from the dispersion parameters of the
cyclic compounds that the ring also has an effect similar to
increasing the effective size of the interacting species. The
dispersion energies are larger for cycloaliphatic compounds
than for their aliphatic counterparts, and they are higher
for aromatic compounds than for the corresponding cyclo-
aliphatics. Similar effects also appear with the ester group.
This group appears to act as if it were, in effect, an entity
that is larger than the corresponding compound contain-
ing only carbon (i.e., its homomorph), and it has a higher
dispersion solubility parameter without any special need
for corrections.
The careful evaluation of the dispersion cohesive
energy may not have major impact on the value of the
dispersion solubility parameter itself because of the taking
of square roots. Larger problems arise because of Eq (4).
Energy assigned to the dispersion portion cannot be reused
when finding the other partial parameters using Eq (4) [or
Eq (6)]. This is one reason why group contributions are
recommended for the polar and hydrogen bonding compo-
nents in some cases below. The author has not used older
tables of group contributions for the dispersion parameter.
These were found to be not as reliable as the longer pro-
cedure discussed above when data are available. Frequent
use has been made of simple comparisons of similarity to
molecules whose dispersion parameters have already been
established. The group contributions for the dispersion
solubility parameter presented by Panayiotou in Chapter 3
in Ref. [39] appear to be a good third alternative, however.
CALCULATION OF THE POLAR SOLUBILITY
PARAMETER,
p
The earliest assignments of a polar solubility parameter
were given by Blanks and Prausnitz [12]. These parameters
were in fact the combined polar and hydrogen bonding
parameters as used by Hansen and cannot be considered
polar in the current context. The first Hansen polar param-
eters [13] were reassigned new values by Skaarup accord-
ing to the Bttcher equation [15]. This equation requires
the molar volume, the dipole moment (DM), the refractive
index, and the dielectric constant. These are not available
for many compounds, and the calculation is somewhat
more difficult than using the much simpler equation devel-
oped by Beerbower [17]
p
M
V
37 4
1 2
.
( )
( )
/
DM
(12)
The constant 37.4 gives this parameter in SI units.
Equation (12) has been consistently used by the author
over the past few years, particularly in view of its reported
reliability [31]. This reported reliability appears to be cor-
rect. The molar volume must be known or estimated in
one way or another. This leaves only the dipole moment
to be found or estimated. Standard reference works have
tables of dipole moments, with the most extensive listing
still being McClellan [44]. Other data sources also have this
parameter as well as other relevant parameters and data
such as latent heats and critical temperatures. The so-called
DIPPR database has been found useful for many com-
pounds of reasonably common usage, but many interesting
compounds are not included in DIPPR. This abbreviation is
for Design Institute for Physical Property Research,
2
Proj-
ect 801 of the American Institute of Chemical Engineers
at the Pennsylvania State University [45]. When no dipole
moment is available, similarity with other compounds,
group contributions, or experimental data can be used to
estimate the polar solubility parameter.
It must be noted that the fact of zero dipole moment
in symmetrical molecules is not basis enough to assign a
zero polar solubility parameter. An outstanding example of
variations of this kind can be found with carbon disulfide.
The reported dipole moments are mostly 0 for gas phase
measurements, supplemented by 0.08 in hexane, 0.4 in
carbon tetrachloride, 0.49 in chlorobenzene, and 1.21 in
nitrobenzene.
There is a clear increase with increasing solubility
parameter of the media. The latter and highest value has
been found experimentally most fitting for correlating per-
meation through a fluoropolymer film used for chemical
protective clothing [46]. Many fluoropolymers have con-
siderable polarity. The lower dipole moments seem to fit in
other instances. Diethylether has also presented problems
as an outlier in terms of dissolving or not, or rapid perme-
ation or not. Here the reported dipole moments [44] vary
from 0.74 to 2.0 with a preferred value of 1.17, and with
1.79 in chloroform. Choosing a given value seems rather
arbitrary. The chameleonic cyclic forms of the linear glycol
ethers would also seem to provide for a basis of altered
dipole moments in various media [34].
When Eq (12) cannot be used, the polar solubility
parameter has been found using the Beerbower table of
group contributions, by similarity to related compounds,
and/or by subtraction of the dispersion and hydrogen
bonding cohesive energies from the total cohesive energy.
The question in each case is: Which data are available and
judged most reliable? New group contributions have also
been developed from related compounds where their dipole
moments are available. These new polar group contribu-
tions then become supplementary to the Beerbower table.
For large molecules, especially those with long hydro-
carbon chains, the accurate calculation of the relatively
small polar (and hydrogen bonding) contributions present
special difficulties. The latent heats are not generally avail-
able with sufficient accuracy to allow subtraction of two
large numbers from each other to find a very small one. In
such cases the similarity and group contribution methods
are thought best. Unfortunately, latent heats found in a
widely used handbook [47] are not clearly reported as to
the reference temperature. There is an indication that these
are 25C data, but checking indicated many of the data
were identical with boiling point data reported elsewhere in
the literature. A more recent edition of this handbook has
a completely different and less voluminous section for the
latent heat of evaporation [48]. Again, even moderate varia-
tions in reported heats of vaporization can cause severe
2
Design Institute for Physical Property Research, Department of
Chemical Engineering, 167 Fenske Laboratory, The Pennsylvania
State University, University Park, PA 16802.
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480 PAINT AND COATING TESTING MANUAL 15TH EDITION
problems in calculating the polar (or hydrogen bonding)
parameter when Eqs (4) or (6) are strictly adhered to.
CALCULATION OF THE HYDROGEN BONDING
SOLUBILITY PARAMETER,
h
In the earliest work, the hydrogen bonding parameter was
almost always found from the subtraction of the polar and
dispersion energies of vaporization from the total energy of
vaporization. This is still widely used where the required
data are available and reliable. At this stage, however, the
group contribution techniques are considered reasonably
reliable for most of the required calculations and, in fact,
more reliable than estimating several of the other param-
eters to ultimately arrive at the subtraction step just men-
tioned. Therefore, in the absence of reliable latent heat and
dipole moment data, group contributions are judged to be
the best alternative. Similarity to related compounds can
also be used, of course, and the result of such a procedure
should be essentially the same as for using group contribu-
tions. The work of Panayiotou in Chapter 3 of Ref. [39],
discussed above, also provides an alternative method to
arrive at the hydrogen bonding parameter.
SUPPLEMENTARY CALCULATIONS
AND PROCEDURES
The procedures listed above are those most frequently used
by the author in calculating the three partial solubility
parameters for liquids where some data are available. There
are a number of other calculations and procedures that are
also helpful. Latent heat data at 25C have consistently been
found from latent heats at another temperature using the
relation given by Fishtine [49].
,
]
]
]
H T
H T
T T
T T
T
v
v
c
c
r
( )
( )
.
1
2
1
2
0 38
1
1
1 TT
T
T
r
r
r 2
0 38
1
2
0 38
1
1
,
,
]
]
]
,
]
]
]
. .
(13)
This is done even if the melting point of the compounding
being considered is higher than 25C. The result is consis-
tent with all the other parameters, and to date no problems
with particularly faulty predictions have been noted in this
respect, i.e., it appears as if the predictions are not signifi-
cantly in error. When the latent heat is given in cal/mole,
the above equation is used to estimate the latent heat at
25C. RT equal to 592 cal/mole is then subtracted from this
according to Eq (14) to find the total cohesion energy, E
V
,
in cgs units at this temperature:
E E H RT
v t v
(14)
Only limited attempts have been made to calculate
solubility parameters at a higher temperature. Solubil-
ity parameter correlations of phenomena at higher tem-
peratures have generally been found satisfactory when the
established 25C parameters have been used. Recalculation
to higher temperatures is possible, but has not been found
necessary. In this direct but approximate approach, it is
assumed that the parameters all demonstrate the same
temperature dependence, which, of course, is not the case.
It might be noted in this connection that the hydrogen
bonding parameter, in particular, is the most sensitive to
temperature. As the temperature is increased, more and
more hydrogen bonds are progressively broken, and this
parameter will decrease more rapidly than the others.
The gas phase dipole moment is not temperature
dependent, although the volume of the fluid does change
with temperature, which will change its cohesive energy
density. Beerbower has suggested relations to predict the
changes of the partial solubility parameters with tempera-
ture [17]. The coefficient of thermal expansion, , appears
in all of these relations. These are
d
dT
d
d
( )
.
1 25
(15)
d p
dT
p
( )
.
0 5
(16)
d p
dT
H
( )
( . . )
1 22 10 0 5
3
(17)
A computer program has been developed by the
author to assign the three Hansen parameters for sol-
vents based on experimental data alone. This has been
used in several cases where the parameters for the given
liquids were desired with a high degree of accuracy. The
procedure is to enter solvent quality, good or bad, into
the program for a reasonably large number of polymers
where the solubility parameters and appropriate radius of
interaction for the polymers are known. The program then
locates that set of
d
,
p
, and
h
parameters for the solvent
that best satisfies the requirements of a location within
the spheres of the appropriate polymers where solvent
quality is good and outside of the appropriate spheres
where it is bad.
An additional aid in estimating the Hansen parameters
for many compounds is that these parameters can be found
by interpolation or extrapolation, especially for homolo-
gous series. The first member may not necessarily be a
straight line extrapolation, but comparisons with related
compounds should always be made where possible to
confirm assignments. Plotting the parameters reported in
Table 3 for homologous series among the esters, nitroparaf-
fins, ketones, alcohols, and glycol ethers will aid in finding
the parameters for related compounds.
Table 3 contains Hansen solubility parameters for a
large number of liquids and plasticizers. These are given in
SI units. Over 800 HSP values can be found in Refs. [38,39].
SOLUBILITY PARAMETERS FOR POLYMERS
The solubility parameters for numerous polymers and film
formers are given in Table 4. Suppliers and trademarks are
given in Table 5. These data are based on solubility determi-
nations unless otherwise noted. There are four parameters,
the three describing the nonpolar, polar, and hydrogen
bonding interactions as for the liquids, and the fourth, R
0
,
a radius of interaction for the type of interaction described.
Most of these are taken from a report [50] from the Scan-
dinavian Paint and Printing Ink Research Institute. (This
institute unfortunately no longer exists.) Additional values
have been contributed according to the notes in the table to
indicate the types of data, which have been correlated with
these techniques. Barton [51] has also provided solubility
parameters for many polymers in a handbook. Additional
values are also found in Refs. [38,39].
Experimental determination of polymer solubility
parameters involves trying to dissolve the polymer at a
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CHAPTER 38 SOLUBILITY PARAMETERS 481
TABLE 3Hansen solubility parameters for selected liquids (solvents in alphabetical order)
No. Solvent Dispersion Polar Hydrogen Bonding Molar Volume
1 Acetaldehyde 14.7 12.5 7.9 56.6
2 Acetic acid 14.5 8.0 13.5 57.1
3 Acetic anhydride 16.0 11.7 10.2 94.5
4 Acetone
a
15.5 10.4 7.0 74.0
5 Acetonitrile 15.3 18.0 6.1 52.6
6 Acetophenone
a
19.6 8.6 3.7 117.4
7 Acrylonitrile 16.0 12.8 6.8 67.1
8 Allyl alcohol 16.2 10.8 16.8 68.4
9 Amyl acetate 15.8 3.3 6.1 148.0
10 Aniline 19.4 5.1 10.2 91.5
11 Anisole 17.8 4.1 6.7 119.1
12 Benzaldehyde 19.4 7.4 5.3 101.5
13 Benzene
a
18.4 0.0 2.0 89.4
14 1.3-Benzenediol 18.0 8.4 21.0 87.5
15 Benzoic acid 18.2 6.9 9.8 113.1
16 Benzonitrile 17.4 9.0 3.3 102.6
17 Benzyl alcohol 18.4 6.3 13.7 103.6
18 Benzyl butyl phthalate 19.0 11.2 3.1 306.0
19 Benzyl chloride 18.8 7.1 2.6 115.0
20 Biphenyl 19.7 1.0 2.0 155.1
21 Bromobenzene 20.5 5.5 4.1 105.3
22 Bromochloromethane 17.3 5.7 3.5 65.0
23 Bromoform 21.4 4.1 6.1 87.5
24 1-Bromonaphtalene 20.3 3.1 4.1 140.0
25 Bromotrifluoromethane 9.6 2.4 0.0 97.0
26 Butane 14.1 0.0 0.0 101.4
27 1.3-Butanediol 16.6 10.0 21.5 89.9
28 l-Butanol
a
16.0 5.7 15.8 91.5
29 2-Butanol 15.8 5.7 14.5 92.0
30 Butyl acetate
a
15.8 3.7 6.3 132.5
31 Sec-butyl acetate 15.0 3.7 7.6 133.6
32 Butyl acrylate 15.6 6.2 4.9 143.8
33 Butylamine 16.2 4.5 8.0 99.0
34 Butyl lactate 15.8 6.5 10.2 149.0
35 Butyraldehyde 15.6 10.1 6.2 90.5
36 Butyric acid 14.9 4.1 10.6 110.0
37 Gamma butyrolactone
a
19.0 16.6 7.4 76.8
38 Butyronitrile 15.3 12.4 5.1 87.3
39 Carbon disulfide 20.5 0.0 0.6 60.0
40 Carbon tetrachloride
a
17.8 0.0 0.6 97.1
41 Chlorobenzene
a
19.0 4.3 2.0 102.1
42 1-Chlorobutane 16.2 5.5 2.0 104.5
43 Chlorodifluoromethane 12.3 6.3 5.7 72.9
44 Chloroform
a
17.8 3.1 5.7 80.7
45 3-Chloro-l-propanol 17.5 5.7 14.7 84.2
46 m-cresol 18.0 5.1 12.9 104.7
47 Cyclohexane 16.8 0.0 0.2 108.7
48 Cyclohexanol
a
17.4 4.1 13.5 106.0
49 Cyclohexanone 17.8 8.4 5.1 104.0
50 Cyclohexylamine 17.2 3.1 6.5 113.8
51 Cyclohexylchloride 17.3 5.5 2.0 118.6
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482 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 3(Continued)
No. Solvent Dispersion Polar Hydrogen Bonding Molar Volume
52 Cis-decahydronaphthalene 18.8 0.0 0.0 156.9
53 Trans-decahydronaphthalene 18.0 0.0 0.0 156.9
54 Decane 15.7 0.0 0.0 195.9
55 1-Decanol 16.0 4.7 10.0 191.8
56 Diacetone alcohol
a
15.8 8.2 10.8 124.2
57 Dibenzyl ether 19.6 3.4 5.2 197.4
58 Dibutyl phthalate 17.8 8.6 4.1 266.0
59 Dibutyl sebacate 13.9 4.5 4.1 339.0
60 o-dichlorobenzene
a
19.2 6.3 3.3 112.8
61 2.2-Dichlorodiethyl ether 18.8 9.0 5.7 117.2
62 Dichlorodifluoromethane 12.3 2.0 0.0 92.3
63 1.1-Dichloroethane 16.5 7.8 3.0 84.2
64 1.1-Dichloroethylene 16.4 52 24 79.9
65 Di-(2-chloro-isopropyl) ether 19.0 8.2 5.1 146.0
66 Dichloromonofluoromethane 15.8 3.1 5.7 75.4
67 1.2-Dichlorotetrafluoroethane 12.6 1.8 0.0 117.6
68 Di-iso-butyl carbinol 14.9 3.1 10.8 177.8
69 Diethanolamine 17.2 10.8 21.2 95.9
70 Diethylamine 14.9 2.3 6.1 103.2
71 2-(Diethylamino) ethanol 14.9 5.8 12.0 133.2
72 Para-diethy l benzene 18.0 0.0 0.6 156.9
73 Diethyl carbonate 15.1 6.3 3.5 121.0
74 Diethylene glycol
a
16.6 12.0 20.7 94.9
75 Diethylene glycol butyl ether acetate 16.0 4.1 8.2 208.2
76 Diethylene glycol hexyl ether 16.0 6.0 10.0 204.3
77 Diethylene glycol monobutyl ether 16.0 7.0 10.6 170.6
78 Diethylene glycol monoethyl ether 16.1 9.2 12.2 130.9
79 Diethylene glycol monomethyl ether 16.2 7.8 12.6 118.0
80 Diethylenetriamine 16.7 13.3 14.3 108.0
81 Diethyl ether
a
14.5 2.9 5.1 104.8
82 Diethyl ketone 15.8 7.6 4.7 106,4
83 Diethyl phthalate 17.6 9.6 4.5 198.0
84 Diethyl sulfate 15.7 14.7 7.1 131.5
85 Diethyl sulfide 16.8 3.1 2.0 107.4
86 Di(isobutyl) ketone 16.0 3.7 4.1 177.1
87 Di(2-methoxyethyl) ether 15.7 6.1 6.5 142.0
88 N,N-dimethylacetamide 16.8 11.5 10.2 92.5
89 Dimethylformamide
a
17.4 13.7 11.3 77.0
90 1,1-Di methyl hydrazine 15.3 5.9 11.0 76.0
91 Dimethyl phthalate 18.6 10.8 4.9 163.0
92 Dimethyl sulfone 19.0 19.4 12.3 75.0
93 Dimethyl sulfoxide
a
18.4 16.4 10.2 71.3
94 Dioctyl phthalate 16.6 7.0 3.1 377.0
95 1,4-Dioxane
a
19.0 1.8 7.4 85.7
96 Dipropylamine 15.3 1.4 4.1 136.9
97 Dipropylene glycol
a
16.5 10.6 17.7 130.9
98 Dipropyiene glycol methyl ether 15.5 5.7 11.2 157.4,
99 Dodecane 16.0 0.0 0.0 228.6
100 Eicosane 16.5 0.0 0.0 359.8
101 Epichlorohydrin 18.9 7.6 6.6 78.4
102 Ethanethiol 15.7 6.5 7.1 74.3
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CHAPTER 38 SOLUBILITY PARAMETERS 483
TABLE 3(Continued)
No. Solvent Dispersion Polar Hydrogen Bonding Molar Volume
103 Ethanol
a
15.8 8.8 19.4 58.5
104 Ethanolamine
a
17.0 15.5 21.2 59.8
105 Ethyl acetate
a
15.8 5.3 7.2 98.5
106 Ethyl acrylate 15.5 7.1 5.5 108.8
107 Ediyl amyl ketone 16.2 4.5 4.1 156.0
108 Ethylbenzene 17.8 0.6 1.4 123.1
109 Ethyl bromide 16.5 8.4 2.3 74.6
110 2-Ethyl-l-butanol 15.8 4.3 13.5 123.2
111 Ethyl butyl ketone 16.2 5.0 4.1 139.0
112 Ethyl chloride 15.7 6.1 2.9 70.0
113 Ethyl chloroformate 15.5 10.0 6.7 95.6
114 Ethyl cinnamate 18.4 8.2 4.1 166.8
115 Ethylene carbonate 19.4 21.7 5.1 66.0
116 Ethylene cyanohydrin 17.2 18.8 17.6 68.3
117 Ethylenediamine 16.6 8.8 17.0 67.3
118 Ethylene dibromide 19.2 3.5 8.6 87.0
119 Ethylene dichloride
a
19.0 7.4 4.1 79.4
120 Ethylene glycol
a
17.0 11.0 26.0 55.8
121 Ethylene glycol butyl ether acetate 15.3 4.5 8.8 171.2
122 Ethylene glycol monobutyl ether
a
16.0 5.1 12.3 131.6
123 Ethylene glycol monoethyl ether
a
16.2 9.2 14.3 97.8
124 Ethylene glycol monoethyl ether acetate 15.9 4.7 10.6 136.1
125 Ethylene glycol monomethyl ether
a
16.2 9.2 16.4 79.1
126 Ethylene glycol monomethyl ether acetate 15.9 5.5 11.6 121.6
127 Ethyl formate 15.5 8.4 8.4 80.2
128 2-Ethyl hexanol 15.9 3.3 11.8 156.6
129 Ethyl lactate 16.0 7.6 12.5 115.0
130 Formamide
a
17.2 26.2 19.0 39.8
131 Formic acid 14.3 11.9 16.6 37.8
132 Furan 17.8 1.8 5.3 72.5
133 Furfural 18.6 14.9 5.1 83.2
134 Furfuryl alcohol 17.4 7.6 15.1 86.5
135 Glycerol 17.4 12.1 29.3 73.3
136 Heptane 15.3 0.0 0.0 147.4
137 Hexadecane 16.3 0.0 0.0 294.1
138 Hexamethylphosphoramide 18.5 8.6 11.3 175.7
139 Hexane
a
14.9 0.0 0.0 131.6
140 Hexylene glycol 15.7 8.4 17.8 123.0
141 Isoamyl acetate 15.3 3.1 7.0 148.8
142 Isobutyl acetate 15.1 3.7 6.3 133.5
143 Isobutyl alcohol 15.1 5.7 15.9 92.8
144 Isobutyl isobutyrate 15.1 2.9 5.9 163.0
145 Isooctyl alcohol 14.4 7.3 12.9 156.6
146 Isopentane 13.7 0.0 0.0 117.4
147 Isophorone
a
16.6 8.2 7.4 150.5
148 Isopropyl palmitate 14.3 3.9 3.7 330.0
149 Mesitylene 18.0 0.0 0.6 139.8
150 Mesityl oxide 16.4 6.1 6.1 115.6
151 Methacrylonitrile 15.8 15.1 5.4 83.9
152 Methanol
a
15.1 12.3 22.3 40.7
153 o-Methoxyphenol 18.0 8.2 13.3 109.5
Continued
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484 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 3(Continued)
No. Solvent Dispersion Polar Hydrogen Bonding Molar Volume
154 Methyl acetate 15.5 7.2 7.6 79.7
155 Methyl acrylate 15.3 6.7 9.4 90.3
156 Methylal 15.0 1.8 8.6 169.4
157 Methyl amyl acetate 15.2 3.1 6.8 167.4
158 Methyl butyl ketone 15.3 6.1 4.1 123.6
159 Methyl chloride 15.3 6.1 3.9 55.4
160 Methylcyclohexane 16.0 0.0 1.0 128.3
161 Methylene dichloride
a
18.2 6.3 6.1 63.9
162 Methylene diiodide 17.8 3.9 5.5 80.5
163 Methyl ethyl ketone 16.0 9.0 5.1 90.1
164 Methyl isoamyl ketone 16.0 5.7 4.1 142.8
165 Methyl isobutyl carbinol 15.4 3.3 12.3 127.2
166 Methyl isobutyl ketone
a
15.3 6.1 4.1 125.8
167 Methyl methacrylate 15.8 6.5 54 106.1
168 1-Methylnaphthalene 20.6 0.8 4.7 138.8
169 Methyl oleate 14.5 3.9 3.7 340.0
170 2-Methyl-1-propanol 15.1 5.7 15.9 92.8
171 Methyl-2-pyrrolidone
a
18.0 12.3 7.2 96.5
172 Methyl salicylate 18.1 8.0 13.9 129.6
173 Morpholine 18.8 4.9 9.2 87.1
174 Naphtha.high-flash 17.9 0.7 1.8 181.8
175 Naphthalene 19.2 2.0 5.9 111.5
176 Nitrobenzene
a
20.0 8.6 4.1 102.7
177 Nitroethane
a
16.0 15.5 4.5 71.5
178 Nitromethane
a
15.8 18.8 5.1 54.3
179 1-Nitropropane 16.6 12.3 5.5 88.4
180 2-Nitropropane
a
16.2 12.1 4.1 86.9
181 Nonane 15.7 0.0 0.0 179.7
182 Nonyl phenol 16.5 4.1 9.2 231.0
183 Nonyl phenoxy ethanol 16.7 10.2 8.4 275.0
184 Octane 15.5 0.0 0.0 163.5
185 Octanoic acid 15.1 3.3 8.2 159.0
186 1-Octanol 16.0 5.0 11.9 157.7
187 2-Octanol 16.1 4.9 11.0 159.1
188 Oleic acid 16.0 28 6.2 317.0
189 Oleyl alcohol 16.0 2.6 8.0 316.0
190 Pentane 14.5 0.0 0.0 116.2
191 2.4-Pentanedione 17.1 9.0 4.1 103.1
192 1-Pentanol 15.9 5.9 13.9 108.6
193 Perfluoro(dimethylcyclohexane) 12.4 0.0 0.0 217.4
194 Perfluoroheptane 12.0 0.0 0.0 227.3
195 Perfluoromethylcyclohexane 12.4 0.0 0.0 196.0
196 Phenol 18.0 5.9 14.9 87.5
197 Bis-(m-phenoxyphenyl) ether 19.6 3.1 5.1 373.0
198 1-Propanol 16.0 6.8 17.4 75.2
199 2-Propanol 15.8 6.1 16.4 76.8
200 Propionitrile 15.3 14.3 5.5 70.9
201 Propylamine 16.9 4.9 8.6 83.0
202 Propyl chloride 16.0 7.8 2.0 88.1
203 Propylene carbonate
a
20.0 18.0 4.1 85.0
204 Propylene glycol
a
16.8 9.4 23.3 73.6
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CHAPTER 38 SOLUBILITY PARAMETERS 485
given concentration, usually 10 % by weight, in a selection
of solvents intended to maximize information regarding all
types of interaction. Whenever possible, the author uses a
set of parameters indicated with an
a
in Table 3. The yes
or no solubility data can be plotted by hand or processed
by computer to yield a spherical characterization as
described above. Teas [52] has developed a triangular plot-
ting technique, which helps visualization of three param-
eters on a plain sheet of paper. Examples are found in Refs.
[9,10] as well.
Swelling, weight gain, solvent resistance, and surface
attack have also been used as a primary data to character-
ize polymers. The weighted-averaging of the respective
Hansen solubility parameters for the test liquids should be
done with caution. Many polymers have polar and hydro-
gen bonding parameters higher than any liquids, for which
TABLE 3(Continued)
No. Solvent Dispersion Polar Hydrogen Bonding Molar Volume
205 Propylene glycol monobutyl ether 15.3 4.5 9.2 132.0
206 Propylene glycol monoethyl ether 15.7 6.5 10.5 115,6
207 Propylene glycol monoisobutyl ether 15.1 4.7 9.8 132.2
208 Propylene glycol monomethyl ether 15.6 6.3 11.6 93.8
209 Propylene glycol monophenyl ether 17.4 5.3 11.5 143.2
210 Propylene glycol monopropyl ether 15.8 7.0 9.2 130.3
211 Pyridine 19.0 8.8 5.9 80.9
212 2-Pyrolidone 19.4 17.4 11.3 76.4
213 Quinoline 19.4 5.6 5.7 118.0
214 Stearic acid 16.3 3.3 5.5 326.0
215 Styrene 18.6 1.0 4.1 115.6
216 Succinic anhydride 18.6 19.2 16.6 66.8
217 1.1.2.2-Tetrabromoethane 22.6 5.1 8.2 116.8
218 1.1.2.2-Tetrachloroethane 18.8 5.1 9.4 105.2
219 Tetrachloroethylene 18.3 5.7 0.0 101.2
220 Tetraethylorthosilicate 13.9 4.3 0.6 224.0
221 Tetrahydrofuran
a
16.8 5.7 8.0 81.7
222 Tetrahydronaphthalene 19.6 2.0 2.9 136.0
223 Tetramethylurea 16.7 8.2 11.0 120.4
224 Toluene
a
18.0 1.4 2.0 106.8
225 Tributyl phosphate 16.3 6.3 4.3 345.0
226 Trichlorobiphenyl 19.2 5.3 4.1 187.0
227 1.1.1-Trichloroethane 16.8 4.3 2.0 99.3
228 Trichloroethylene
a
18.0 3.1 5.3 90.2
229 Trichlorofluoromethane 15.3 2.0 0.0 92.8
230 1.1.2-Trichlorotrifluoroethane 14.7 1.6 0.0 119.2
231 Tricresyl phosphate 19.0 12.3 4.5 316.0
232 Tridecyl alcohol 16.2 3.1 9.0 242.0
233 Triethanolamine 17.3 22.4 23.3 133.2
234 Triethylamine 17.8 0.4 1.0 138.6
235 Triethyleneglycol 16.0 12.5 18.6 114.0
236 Triethylene glycol monooleyl ether 16.0 3.1 8.4 418.5
237 Triethylphosphate 16.7 11.4 9.2 171.0
238 Trifluoroacetic acid 15.6 9.9 11.6 74.2
239 Trimethylbenzene 18.0 1.0 1.0 137.3
240 2.2.2,4-Trimethylpentane 14.1 0.0 0.0 166.1
241 2.2.4-Trimethyl-1.3-pentanediol M.I. butyral 15.1 6.1 9.8 227.4
242 Trimethyl phosphate 16.7 15.9 10.2 115.8
243 Water 15.5 16.0 42.3 18.0
244 Xylene 17.6 1.0 3.1 123.3
245 o-xylene 17.8 1.0 3.1 121.2
a
Indicates use in authors standard set of test solvents.
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486 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 4Solubility parameters for polymers
D P H R
Cellulose acetobutyrate
Cell it BP-300
a
16.6 12.0 6.7 10.2
Cellulose acetate
Cellidora A
a
18.2 12.4 10.8 7.4
Cethyl cellulose
Ethocel HE 10 ind
b
17.9 4.3 3.9 5.9
Ethocel Std 20 ind
b
20.1 6.9 5.9 9.9
Epoxy
Araldite DY 025 14.0 7.4 9.4 13.7
Epikote 828 21.3 14.2 6.1 17.7
Epikote 1001 18.1 11.4 9.0 9.1
Epikote 1004 17.4 10.5 9.0 7.9
Epikote 1007 21.0 11.1 13.4 11.7
Epikote 1009 18.9 9.6 10.7 7.8
Phenoxy PKHH 23.4 7.2 14.8 14.9
Epoxy curing agents
Versamid 100 23.8 5.3 16.2 16.1
Versamid 115 20.3 6.6 14.1 9.6
Versamid 125 24.9 3.1 18.7 20.3
Versamid 140 26.9 2.4 18.5 24.0
Polyurethane
Desmophen 651 17.7 10.6 11.6 9.5
Desmophen 800 19.1 12.2 9.9 8.0
Desmophen 850 21.1 14.6 12.0 16.2
Desmophen 1100 16.0 13.1 9.2 11.4
Desmophen 1150 20.6 7.8 11.6 13.1
Desmophen 1200 19.4 7.4 6.0 9.8
Desmophen 1700 17.9 9.6 5.9 8.2
Desmolac 4200 18.7 9.6 9.9 8.2
Macrynal SM 510N 19.9 8.1 6.0 9.8
Phenolic resins
Super Beckacite 1001
a
22.7 6.4 8.2 19.4
Phenodur 373 U
a
19.3 11.4 14.3 12.4
Hydrocarbon resins
Piccolyte S-100
a
16.14 0.4 2.8 8.4
Piccopale 110
a
17.2 1.2 3.5 6.4
Piccoumarone 450 L
a
19.0 5.4 5.6 9.4
Styrene-butadiene elastomer (SBR)
Polysar 5630
a
17.2 3.3 2.6 6.4
TABLE 4(Continued)
D P H R
Acrylonitrile-butadiene elastomer
Hycar 1052
a
18.2 8.6 4.1 9.4
Polybutadiene
Buna Hls B-10
a
17.1 2.2 3.3 6.4
Polyisoprene
Cariflex IR 305
a
16.2 1.4 0.8 9.4
Polyisobutylene
Lutonal IC/1203
a
14.2 2.5 4.6 12.4
Lutonal I60 16.9 2.5 4.0 7.2
Polyvinylbutyl ether 17.4 4.3 8.4 7.4
Lignin powder
a
19.7 14.3 14.7 11.4
Modaflow Multiflow 16.1 3.7 7.9 8.9
Polyvinylchloride
Vipla KR
a
17.2 7.4 8.2 3.4
Chlorparaffin
Cereclor 70 20.0 8.3 6.8 9.8
Chlorparaffin 40 17.0 7.6 7.9 11.9
Chlorinated rubber
Pergut S 5 17.4 9.5 3.8 10.0
Allopren R 10 17.4 4.3 3.9 6.1
Chlorinated polypropylene
Parlon P 10
a
19.8 6.2 5.3 10.4
Chlorosulfonated polyethylene
Hypalon 20
b
18.1 3.4 4.9 3.6
Hypalon 30
b
18.2 4.7 2.0 5.0
Cyclized rubber
Alpex
b
19.9 0.0 0.0 9.4
Nitrocellulose
1/2-sec-Nitrocellulose H 23
a
15.1 14.4 8.6 11.2
Rosin derivatives
Cellolyn 102
a
21.2 0.9 8.3 15.4
Pentalyn 255
a
17.2 9.2 14.0 10.4
Pentalyn 830
a
19.6 5.7 10.7 11.4
Ester Gum 8L
a
19.2 4.6 7.6 10.4
Polyamide
Versamid 930
a
17.0 1.9 14.9 7.4
Versamid 961 18.9 9.6 11.1 6.2
Versamid 965 20.4 0.4 14.0 12.9
Isocyanate
Desmodur L 17.5 11.3 5.9 8.5
Demodur N
a
17.6 10.0 3.7 9.3
Suprasec F-5100
a
19.7 12.9 12.8 11.4
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CHAPTER 38 SOLUBILITY PARAMETERS 487
TABLE 4(Continued)
D P H R
Polyvinylbutyral
Mowithal B 30 H 18.6 12.9 10.3 8.3
Mowithal B 60 H 20.2 11.2 13.2 11.2
Butvar B 76
a
18.2 4.3 12.7 10.4
Polyacrylate
Lucite 2042
a
17.2 9.4 3.9 10.4
Lucite 2044 16.2 6.8 5.7 9.1
Plexigum MB 319 18.6 10.8 4.1 11.5
Plexigum M 527 18.4 9.4 6.5 10.7
PMMA
a
18.2 10.3 7.7 8.4
Polyvinylacetate
Mowilith 50
a
20.5 11.0 9.4 13.4
Polystyrene
Polystyren LG
a
20.8 5.6 4.2 12.4
Vinylchloride/copolymers
Laroflex MP 45 18.4 8.4 5.8 9.0
Vilit MB 30 20.0 8.3 6.7 9.4
Vilit MC 31 20.0 8.3 6.7 9.4
Vilit MC 39 18.4 7.6 6.7 6.8
Vinylite VAGD 17.1 10.4 6.5 7.5
Vinylite VAGH 16.5 10.9 6.4 7.7
Vinylite VMCA 17.7 11.1 6.9 8.7
Vinylite VMCC 17.6 11.1 6.8 8.8
Vinylite VMCH 17.6 11.1 6.4 8.6
Vinylite VYHH 17.4 10.2 5.9 7.8
Vinylite VYLF 18.1 10.3 4.2 8.3
Alkyds and polyesters
Alftalat AC 366 18.6 10.0 5.0 10.4
Alftalat AM 756 23.0 2.2 4.2 16.9
Alftalat AN 896 22.9 15.2 7.6 18.1
Alftalat AN 950 22.6 13.8 8.1 17.1
Alftalat AT 316 20.5 9.3 9.1 12.4
Alftalat AT 576 19.2 5.3 6.3 11.9
Alkydal F 261 HS 23.6 1.0 7.6 19.0
Alkydal F 41 20.6 4.6 5.5 12.6
Duroftal T 354 17.3 4.2 7.9 9.3
Dynapol L 812 22.6 13.1 5.8 16.8
Dynapol L 850 20.0 6.2 7.0 9.5
Plexal C-34
a
18.1 9.0 4.8 10.4
Soalkyd 1935-EGAX 18.0 11.6 8.5 9.0
Vesturit BL 908 18.8 12.0 6.0 11.5
Vesturit BL 915 17.7 13.0 7.6 11.5
TABLE 4(Continued)
D P H R
Amino resins
BE 370 20.7 6.1 12.7 14.8
Beetle 681 22.2 0.4 10.1 18.4
Cymel 300
a
19.9 8.3 10.4 14.4
Cymel 325 25.5 15.2 9.5 22.2
Dynomin MM 9 18.8 14.0 12.3 10.5
Dynomin UM 15 19.9 15.8 13.4 11.7
Soamin M 60 15.9 8.1 6.5 10.6
Synresen A 560 22.1 5.0 11.3 15.5
Plastopal H
a
20.3 8.1 14.6 12.4
Uformite MX-61 22.7 2.8 5.4 16.2
Acrylate resins
Uracron 15 19.2 7.7 5.7 10.6
Paraloid P 400 19.2 9.6 9.3 12.2
Paraloid P 410 19.6 9.1 6.8 12.2
Paraloid experimental resin QR
954
18.4 9.8 10.0 12.4
Silicone resins
Baysilon UD 125 19.4 9.9 10.1 6.9
Wacker 190 F 16.6 1.9 8.0 8.0
Additional Special Data
DEN 438 (Dow epoxy novolak) 20.3 15.4 5.3 15.1
DEN 444 (Dow epoxy novolak) 19.5 11.6 9.3 10.0
Zink silicate (CR)-Chemical
resistance
23.5 17.5 16.8 15.6
2-Comp epoxy (CR)Chemical
resistance
18.4 9.4 10.1 7.0
Polyvinylidine fluoride 17.0 12.1 10.2 4.1
Coal tar pitch 18.7 7.5 8.9 5.8
PA6 polyamide chemical
resistance
17.0 3.4 10.6 5.1
PA66 polyamide solubility 17.4 9.8 14.6 5.1
PA11 polyamide chemical
resistance
17.0 4.4 10.6 5.1
Cellophane swelling 16.1 18.5 14.5 9.3
EVOHsolubility (ethylenevinyl
alcohol)
20.5 10.5 12.3 7.3
Note: D = dispersion; P = permanent dipoles; H = hydrogen bonding;
R = interation radius.
a
Taken from Hansen, C. M., Solubility in the Coatings Industry,
Frg och Lack, Vol. 17, No. 4, 1971, pp. 6977.
b
Calculated from solubility data in Polymer Handbook, 2nd Ed., John
Wiley & Sons Inc., New York, 1975.
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488 PAINT AND COATING TESTING MANUAL 15TH EDITION
reason any average will be too low. This is discussed in
more detail in Refs. [38,39].
APPLICATIONS
There are many applications documented in the literature
where solubility parameters have aided in selection of
solvents, understanding and controlling processes, and, in
general, offered guidance where affinities among materials
are of prime importance. In all of the examples below the
technical aspects only are discussed. It is clear that worker
safety and environmental impact must also be considered
in any solvent usage. Discussion of these aspects is beyond
the scope of this report.
To find the optimum solvent for a polymer using solu-
bility parameters, it is most desirable to have the solubility
parameters for the polymer. Matching the parameters of an
already existing solvent or combination of solvents can be
done, but does not necessarily optimize the new situation.
The optimum depends on what is desired of the system. A
solvent with highest possible affinity for the polymer is both
expensive and probably not necessary.
Most coatings applications involve solvents safely
within the solubility limit with a maximum of cheaper
hydrocarbon solvent. Some safety is advised because tem-
perature changes, potential variations in production, etc.,
can lead to a situation where solvent quality changes in an
adverse manner. Balance of solvent quality on evaporation
of mixed solvents is also necessary. Here again computer
approaches are possible.
An oxygenated solvent frequently added to hydrocar-
bon solvent and that has been cost effective in increasing
the very important hydrogen bonding solubility parameters
has been n-butanol. The mixture of equal parts xylene and
n-butanol can be used in conjunction with many poly-
mers, but a third solvent, such as a ketone or ester, is often
included in small amounts to increase the polar parameter/
solvency of the mixture. Glycol ethers can also be added to
hydrocarbon solvents with advantage, and the polar and
hydrogen bonding parameters are higher than had n-buta-
nol been added to the same concentration. There are many
possibilities, and a solubility parameter approach is particu-
larly valuable in quickly limiting the number of candidates.
Coalescing solvents in water-reducible coatings are
often those with somewhat higher hydrogen bonding
parameters than the polymer, which also means they are
water soluble or have considerable water solubility. The
distribution between the water phase and the dispersed
polymer phase depends on the relative affinities for water
and the polymer. Solvents that are not particularly water
soluble will preferentially be found in the polymer phase.
Such coalescing solvents may be preferred for applications
to porous substrates, making certain they are where they
are needed. Otherwise a water-soluble coalescing solvent
would tend to follow the aqueous phase penetrating the
substrate and not be available to do its job in the film itself.
When water evaporates, the solvent must dissolve to
some extent in the polymer to promote coalescence. This
can be determined and adjusted by either increasing or
decreasing the affinity for the polymer.
Amines are frequently added in water-reducible coat-
ings to neutralize acid groups in polymers, thus providing a
water-solubilizing amine salt. Amine in excess of that required
TABLE 5List of suppliers and trademarks
for paint binders and polymers
Suppliers Trademarks
Bayer (D) Cellit, Desmophen, Desmolac,
Pergut, Cellidora, Desmodur,
Baysilon Alkydal
Hercules (USA) Piccolyte, Cellolyn, Pentalyn,
Ester Gum, Parlon
Ciba-Geigy Araldite
Shell (D) Epikote, Cariflex
Union Carbide (USA) Vinylite, Phenoxy
Hoechst (D) Macrynal, Phenodur, Alpex,
Mowithal, Alftalat, Mowilith
Reichhold (CH) Super Beckasite, Uformite
Polymer Corp. (CAN) Polysar
Goodrich (USA) Hycar
Huls (D) Vilit, Vesturit, Buna Huls
BASF (D) Lutonal, Laroflex, Plastopal,
Polystyren
Monsanto (USA) Modaflow, Multiflow, Butvar
Montecatini Edison (I) Vipla
ICI (GB) Cereclor, Allopren, Suprasec
Du Pont (USA) Lucite
Hagedorn (D) 1/2-sec. nitrocellulose H 23
Rhm (D) Plexigum
Rohm and Haas (USA) Paraloid
Dynamit Nobel (D) Dynapol
SOAB (S) Soamin
BIP Chemicals (GB) Beetle
Dyno Cyanamid (N) Dynomin
DSM Resins (S) Uracron
Reichhold Chemie (CH) Super Beckasite, Uformite
Wacker (D) Wacker
Dow Chemical (CH) Ethocel
Cray Valley Prod. (GB) Versamid
W. Biesterfeld (D) Chlorparaffin
Synres (NL) Synresen
American Cyanamide (USA) Cymel
Polyplex (DK) Plexal
Pennsylvania Industrial
Chemical Corp. (USA)
Piccopal, Piccoumarone
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CHAPTER 38 SOLUBILITY PARAMETERS 489
for total neutralization acts like a solvent. Such amine salts
have been characterized separately to demonstrate that they
have higher solubility parameters than either (acetic) acid
or organic bases [53]. These salts are hydrophilic and have
very little affinity for coatings polymers, which means they
are to be found in a stabilizing role in interfaces in the aque-
ous phase, still being attached to the polymer. Electrostatic
repulsion contributes to stability as well.
Surface active agents, whether nonionic or ionic, are
also to be found where the affinities of the respective parts
of their molecules dictate their placement. The hydrophilic
end with a high hydrogen bonding parameter will be in the
aqueous phase, and the hydrophobic end will seek out an
environment where energy differences are lowest.
Increases in temperature lead to lower hydrogen bond-
ing parameters, especially. For this reason, solvents with
high hydrogen bonding parameters, such as glycols, gly-
col ethers, and alcohols, become better solvents for most
polymers at higher temperatures. This can markedly affect
hot-room stability in water-reducible coatings, for example,
since more of the solvent will partition to the polymer
phase, which swells, becomes more fluid, and has altered
affinities for stabilizing surface active agents, for example.
They may dissolve too readily in the dispersed polymer.
Carefully controlled, these temperature effects are an
advantage in water-reducible, oven-cured coatings, leading
to higher film integrity.
A simple approach to many practical problems is to
make a two-dimensional plot of polar versus hydrogen bond-
ing parameters with a circle (or estimated circle) for the
polymer in question. One can plot the points for potential
solvents and quickly arrive at a starting composition for an
experiment. This can subsequently be adjusted if necessary.
It should also be kept in mind that cyclic solvents generally
have higher nonpolar parameters than aliphatic solvents.
A long list of applications, in coatings and elsewhere,
was provided as early as 1975 in a review article by Barton
[54]. Many applications are given in Table 6 and in the
present discussion to give an idea of what can be studied
systematically using this concept. More recent references
and varied applications can be found in Refs. [9,10,38,39].
Beerbower [55] has given many of the more theoretical
applications for solubility parameters including correla-
tions of the Rehbinder effect of crushing strength of alu-
minum oxide under various liquids, the work of adhesion
for liquids on mercury, the Joffe effect of the consequences
of immersion in various liquids on the fracture strength of
soda-lime glass, and correlations of friction on polyethylene
treated with fuming sulfuric acid H
2
SO
4
+ SO
3
[55].
Direct and practical applications of solubility param-
eters in coatings have included their use as an aid in the
selection of solvents and solvent blends for many years.
Most solvent suppliers and frequent solvent users have com-
puter programs for this purpose, although as noted above,
such programs are not an absolute necessity. Reformulation
to meet environmental requirements is especially important
in this respect since one can quickly evaluate which of the
alternatives is most likely to meet the given requirements.
This includes reducing amounts of volatile organic solvent,
worker safety, or other environmental concern. Optimum
formulation in such cases often involves mixtures.
The main thing to remember in solvent selection using
solubility parameters is that the resultant values for mix-
tures can be estimated from volume fraction averages for
each solubility parameter component. Solvent quality can
be adjusted by the RED number concept or graphically as
described above.
A computer search for nearest neighbors for a given
single solvent has been used many times to locate alter-
nates. A similar application is to predict which other sol-
vents will probably be aggressive to a chemically resistant
coating where very limited data have indicated a single
solvent or two are somewhat aggressive. A nearest neighbor
search involves calculation of the quantity R
s
for a whole
TABLE 6Examples of the use of the
solubility parameter
Activity coefficients
Aerosol formulation
Biological materials and compatibility
Chromatography
Coal solvent extraction
Compressed gases
Cosmetics
Cryogenic solvents
Dispersion
Dyes
Emulsions
Gas-Liquid solubility
Grease removal
Membrane permeability and swelling
Paint film appearance
Pharmaceutical
Pigments
Plasticizers, polymers, resins
Plasticization
Polymer and plasticizer compatibility
Printing ink
Reaction rate of radical polymerization
Resistance of plastics to solvents
Rubber blends
Solid surface characterizationorganic and inorganic
Solid surface modification
Solvent extraction
Solvent formulation, environmental aspects
Surface tension
Urea-water solutions
Vaporization of plasticizers
Viscosity of polymer systems
Water-based polymer systems, coalescents
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490 PAINT AND COATING TESTING MANUAL 15TH EDITION
database, for example, and then arranging the printout in
RED number order with the potentially most aggressive
at the top of the list. Solvents with RED less than 1.0 are
good and easily recognized.
In many cases a marginal solvent is desired, in which
case RED numbers just under 1.0 will be sought. Marginal
solvent quality will ensure that polymer adsorbed onto pig-
ment surfaces has little reason to dissolve away from that
surface where it is desired as a stabilizing factor in the prod-
uct. The solvent in this case should have a RED number for
the pigment surface greater than 1.0 to aid in the planned
affinity approach to pigment dispersion stability. A sketch of
the optimum relations is given in Fig. 4, where the marginal
solvent is Number 1. Solvent 2 would probably be too expen-
sive and, in addition, will probably dissolve the polymer too
well. In special applications this extended polymer chain
configuration is desirable, but a solid anchor to the pigment
surface is required. A good anchor has high affinity for the
pigment surface and marginal or no affinity for the solvent.
Solvent 3 would adsorb onto the pigment surface preferen-
tially, and pigment dispersion stability will be poor. Pigments
have been characterized by long-time suspension studies
where some solvents will suspend the fines for days, months,
or years, while others of similar viscosity yield rapid settling.
The suspending solvents are the good ones and can be used
to define a sphere for surface wetting/adsorption. Details of
such characterizations are given in Refs. [38,39].
In other cases, better matches between solvent and
polymer solubility parameters are required. This is true
when two polymers are mixed and one of them precipi-
tates. This is most likely the polymer with larger molecular
weight, and it must be dissolved better. Lower RED num-
bers with respect to this polymer are desired, while still
maintaining affinity for the other polymer. Miscible blends
of two polymers have been found using a solvent mixture
composed exclusively of nonsolvents. This is demonstrated
schematically in Fig. 5, where it can be seen that different
percentage blends of solvents 1 and 2 will have different
relative affinities for the polymers. No other alternative the-
ory of polymer solution thermodynamics can duplicate this
predictive ability. Polymer miscibility is enhanced by larger
overlapping solubility regions for the polymers as sketched
in Fig. 6. Polymers A and B should be compatible, while C
will not be. Such a systematic analysis allows modification
of a given polymer to provide more overlap and enhanced
compatibility. The advantages of a copolymer containing
the monomers of A or B and C should also be evident. Such
a copolymer will essentially couple the system together.
Van Dyk et al. [56] have correlated the inherent vis-
cosity of polymer solutions with the solubility parameter.
This is interesting in that the solubility parameter is a
thermodynamic consideration, while the viscosity is a
kinetic phenomenon. Solvents with higher affinities give
greater polymer chain extension in solution, and the inher-
ent viscositythe solution viscosity divided by the solvent
viscosity at polymer concentrations approaching zerois
an expression reflecting polymer chain extension in solu-
tion. Higher intrinsic viscosities were found for solvents
with solubility parameters nearest the polymer solubility
parameters. As stated above, this approach may not always
be advisable since many polymers have polar and hydrogen
bonding parameters higher than the test liquids that have
been used.
The use of supercritical gases as solvents has become
more common in recent years. Space limitations prevent
going into the details of these developments. It should be
noted, however, that when a gas is compressed, its cohe-
sive energy density increases. This means that nonpolar
gases with their low nonpolar solubility parameters can
begin to dissolve given organic materials, which otherwise
have solubility parameters that are too high. Increasing
Fig. 4Solubility parameter relations for optimum pigment
dispersion stability.
Fig. 5Solubility relations for polymer mixtures can be
quickly evaluated to ensure solution stability. Even mixtures
of nonsolvents can be systematically used to regulate solution
behavior.
Fig. 6Schematic representation showing expected miscibil-
ity of polymers A and B with each other but not with poly-
merC.
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CHAPTER 38 SOLUBILITY PARAMETERS 491
the nonpolar solubility parameter of the gas by increasing
the pressure causes a closer match with the corresponding
parameter for potential solutes. Similar behavior is found
for polar gases such as carbon dioxide. The prevailing pres-
sure and temperature conditions determine its cohesive
energy density and changes in pressure or temperature
change solubility relations for this reason. Whereas non-
polar gases are most suitably used for relatively nonpolar
solutes, carbon dioxideand in principle other polar
gasesare most suitably used in connection with more
polar solutes. The solubility parameters for carbon dioxide
have been reported [57] based on the room temperature
solubility of the gas in different liquids (
d
,
p
,
h
equal to
15.3, 6.9, 4.1). These parameters resemble those of a higher
ketone, but are subject to revision when larger data sets
are processed. The
d
,
p
,
h
parameters for carbon dioxide
have been revised to 15.7, 6.3, and 5.7 based on a correla-
tion with a perfect data fit and R
0
equal to only 3.3, using
a much larger data set collected by Williams and reported
in Chapter 10 of Ref. [39]. The HSP are also reported in
this reference at higher temperatures and pressures. The
p
parameter experimentally confirms the presence of sizeable
values for compounds with zero dipole moments, and the
h
parameter emphasizes the need to use terminology electron
exchange for this parameter, traditionally called the hydro-
gen bonding parameter, since there is no hydrogen atom.
Chapter 3 in Ref. [39] has a plot of the HSP for water at
temperatures above the normal boiling point.
Pigment wetting/suspension characteristics have been
presented earlier [10,14,16]. Mixtures of nonsuspending
solvents could also be found which, when admixed, pro-
vided predictably higher affinity and suspension of pigment
particles for prolonged periods of time. An exceptionally
clear demonstration of pigment adsorption properties is
given in Ref. [10] where a triangular plot of the three partial
parameters shows the clearly different adsorption proper-
ties of untreated zinc oxide powder and organic phosphate
surface-treated zinc oxide powder. This triangular approach
to plotting was developed by Teas [52].
Other surface characterizations have also been given
for surfaces such as coatings and metal substrates [23,24].
These characterizations have been of the type sketched in
Fig. 7. Such cohesive energy plots can lead to systematic
modifications of systems to improve adhesion. It might
be added parenthetically that equal information can be
obtained from plots of the cosine of the contact angle ver-
sus the solubility parameter as for plots of these same data
versus liquid surface tension [23]. The energy information
obtained in these types of studies, the critical surface ten-
sion, corresponds to the condition of RED equal to 1.0, with
a solubility parameter approach, that is, marginal affinity.
The list of applications has recently been expanded to
include correlations of the breakthrough times for common
types of chemical protective clothing such as butyl rubber,
nitrile rubber, plasticized polyvinyl chloride, neoprene,
Viton rubber, polyvinyl alcohol, etc. [58]. Fig. 8 shows
the importance of combined use of the RED number and
molecular volume in correlating 3 h breakthrough times for
a fluoropolymer chemical protective product [59]. Mono-
mers with terminal double bonds diffuse more rapidly than
comparisons with non-double-bonded molecules of similar
size and solubility parameter would have predicted. The
smaller cross section at the end of the molecule reminds
one of a nail, and the preferred direction and relative rapid-
ity of transport become easily understandable.
In addition it should be noted that even biological
materials, some of which have interest for coatings applica-
tions and use, have been assigned Hansen solubility param-
eters [60]. These include keratin (which relates to skin
permeation), fat, sucrose, blood serum and zein (which are
proteins), urea, lignin (wood penetration), and chlorophyll
(which closely resembles lignin) [57,60]. The characteriza-
tion of other biological materials is also possible, of course,
with the assignment of HSP to DNA being one of the most
recent results [39].
Even inorganic salts have been characterized by solu-
bility parameters [61]. The practice of dissolving polymers
in solutions of organic liquids and inorganic salts can
thus be explained by the solubility parameter. A solubility
parameter correlation of the chemical resistance of an inor-
ganic zinc silicate coating is reported in Table 4. Finally, it
might be noted that Hildebrand presented a chapter on the
solubility parameters of metals [1]. Unfortunately, we do
not often coat metal, but rather metal oxides, for which no
solubility parameter work has been reported.
Examples in addition to the above are discussed in a
larger context in Refs. [38,39]. The material in the follow-
ing section has not been discussed in Ref. [38], but rather
in Refs. [39,62]. Inclusion here is justified by the presence
of solvents and additives in coatings, which may produce
these catastrophic effects in rigid polymeric systems.
HANSEN SOLUBILITY PARAMETERS AND
ENVIRONMENTAL STRESS CRACKING (ESC)
The Hansen solubility parameter approach allows system-
atic analysis of environmental stress cracking situations
[62]. One can locate those liquids that are most likely to
cause the problem based on limited experimental data for
a reasonable number of different solvents. The state of the
stress in a polymer is clearly important. Tensile stress is
required for the phenomena to occur. Higher stress levels
lead more easily to cracking. Test solvents to evaluate the
stress level present in given polymers can be systemati-
cally located. However, it is clearly not just solubility rela-
tions that control the phenomena. The size and shape of
the environmental challenge chemical are also important.
These relate to the rate of uptake (diffusion coefficient).
These factors collectively control how rapidly a challenge
Fig. 7Schematic diagrams showing surface energy/contact
angle characterizations using the Hansen solubility parameters
(cohesion energy parameters).
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492 PAINT AND COATING TESTING MANUAL 15TH EDITION
chemical can absorb into the surface of a polymeric mate-
rial, this being a requirement for the cracking to occur. The
absorbed chemical changes the local stress-bearing proper-
ties, and cracking can occur in unfavorable situations. The
times required may vary from seconds to years, depending
on the situation. Stress relaxation caused by the plasticiz-
ing effect of absorbed liquid can reduce the risk of ESC,
but can cause other problems, such as excessive softening
of the polymer. ESC phenomena in polymers are not fully
understood, but progress toward this goal is being made as
discussed in the following.
In general, those solvents causing cracking of a given
polymer will be taken up in lesser amounts at equilibrium
absorption than those amounts which will fully dissolve
the polymer. In terms of the Hansen approach, this means
that there will be the usual spherical characterization
for polymer solubility. Essentially concentric to this, but
with a larger radius, is another spherical characterization
encompassing both the true solvents at RED numbers less
than about 0.8, and the cracking solvents at RED numbers
typically between about 0.8 and 1.0. Fig. 9 shows these rela-
tions for a COC type (Cyclo-olefinic Copolymer) polymer.
The basis for this correlation was to consider as aggressive
(RED < 1) both those solvents that truly dissolve the poly-
mer as well as those that cause cracking. This type of plot
can be made for other polymers.
The above discussion is for exposure to a pure liquid.
It is also known that aqueous solutions can leave smaller
amounts of aggressive chemicals when the water has
evaporated. In this case almost any solvent, either good or
swelling only, will be a potential problem in this respect.
The small amount acts like a concentrated solvent, but only
at the surface. Solution can not occur, other than at the
Fig. 8Effects of molecular size (molar volume) and affinity (RED number) on the breakthrough time of Challenge 5100 [59].
Fig. 9Hansen solubility parameters correlate both solubility
(inner sphere) and solubility plus environmental stress
cracking (outer sphere). The liquids that crack the polymer
without application of external stress have Hansen solubility
parameters placing them in the clear shell in the figure.
From Ref. [62]. Reprinted with permission from Industrial
and Engineering Chemistry Research, Vol. 40, No. 1, 2001,
pp. 2125. Copyright 2001, American Chemical Society.
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CHAPTER 38 SOLUBILITY PARAMETERS 493
surface, because of the limited amount of solvent, but the
stress situation at the surface is altered unfavorably, thus
allowing cracks to form. There are also examples of ESC
where there was no measurable weight gain of the liquids
causing the failure. Crack initiation by the rotation of seg-
ments of polymers at the surface exposed to these liquids is
thought to be the reason. The rotation is driven by the HSP
of the liquid resembling the HSP of a buried or partially
buried polymer segment, thus reducing the free energy of
the system by rotation to surroundings of similar (cohe-
sion) energy. Higher energy segments of polymers are most
often buried just beneath the surface, if this is possible.
The polymer segments in contact with air are most often
those of lower energy, again, to keep the free energy at a
minimum [39].
CONCLUSIONS
The background and many uses of the solubility parameter
concept have been described in detail. Tables of solubil-
ity parameters for many liquids and polymers have been
presented. Systematic use of solubility, swelling, or per-
meation data for polymers allows their characterization
by these same cohesive energy parameters. Surfaces can
also be characterized using these same parameters. This
provides data for optimizing solvent selection, improving
compatibility, and enhancing pigment dispersion and adhe-
sion. When all of the materials involved in a given product
and application can be characterized with the same energy
parameters, the possibility exists to predict interactions
among them, even in complicated situations. Methods for
estimating the three Hansen solubility parameters have
been given with as much detail as has been possible to
ensure their more uniform use in the future. It has not been
possible to deal with all the primarily theoretical problems
with the solubility parameter concept. Some of these are
dealt with in the literature cited, most notably in Refs.
[6,9,10,18,26,38,39].
A simple approach is described to understand affinities
in such varied materials as gases, liquids, polymers, bio-
logical materials, surfaces, organic and inorganic coatings,
inorganic salts, and metals. An appeal made to the scientific
community earlier [37] to expand research on this seem-
ingly universal approach appears to have been responded to
by Panayiotou in Chapter 3 of Ref. [39]. Statistical thermo-
dynamics calculations of the
d
,
p
, and
h
parameters, start-
ing with the hydrogen bonding parameter, and extending
to the other parameters, have shown amazing agreement
with the values reported by the author 40 years ago [1316].
Information related to the Hansen solubility parameters
is continually being updated on the website www.hansen-
solubility. com.
References
[1] Hildebrand, J., and Scott, R. L., The Solubility of Nonelectro-
lytes, 3rd ed., Reinhold, New York, 1950.
[2] Hildebrand, J., and Scott, R. L., Regular Solutions, Prentice-
Hall Inc., Englewood Cliffs, NJ, 1962.
[3] Patterson, D., and Delmas, G., New Aspects of Polymer Solu-
tion Thermodynamics, Off. Dig. Fed. Soc. Paint Technol., Vol.
34, No. 450, 1962, pp. 677692.
[4] Delmas, D., Patterson, D., and Somcynsky, T., Thermody-
namics of Polyisobutylene-n-Alkane Systems, J. Polym. Sci.,
Vol. 57, 1962, pp. 7998.
[5] Bhattacharyya, S. N., Patterson, D., and Somcynsky, T., The
Principle of Corresponding States and the Excess Functions
of n-Alkane Mixtures, Physica (Amsterdam), Vol. 30, 1964,
pp. 12761292.
[6] Patterson, D., Role of Free Volume Changes in Polymer Solu-
tion Thermodynamics, J. Polym. Set, Part C: Polym. Symp.,
Vol. 16, 1968, pp. 33793389.
[7] Patterson, D. D., Introduction to Thermodynamics of Poly-
mer Solubility, J. Paint Technol., Vol. 41, No. 536, 1969, pp.
489493.
[8] Biros, J., Zeman, L., and Patterson, D., Prediction of the C
Parameter by the Solubility Parameter and Corresponding States
Theories, Macromolecules, Vol. 4, No. 1, 1971, pp. 3035.
[9] Barton, A. F. M., Handbook of Solubility Parameters and Other
Cohesion Parameters, CRC Press Inc., Boca Raton, FL, 1983.
[10] Gardon, J. L., and Teas, J. P., Solubility Parameters, Trea-
tise on Coatings, Vol. 2, Characterization of Coatings: Physical
Techniques, Part II, R. R. Myers and J. S. Long, Eds., Marcel
Dekker, New York, 1976, Chap. 8.
[11] Burrell, H., Solubility Parameters for Film Formers, Off.
Dig. Fed. Soc. Paint Technol., Vol. 27, No. 369, 1972, pp.
726758; Burrell, H., A Solvent Formulating Chart, Off.
Dig. Fed. Soc. Paint Technol., Vol. 29, No. 394, 1957, pp.
11591173; Burrell, H., The Use of the Solubility Parameter
Concept in the United States, VI Federation dAssociations
de Techniciens des Industries des Peintures, Vernis, Emaux et
Encres dImprimerie de lEurope Continentale, Congress Book,
1962, pp. 2130.
[12] Blanks, R. F., and Prausnitz, J. M., Thermodynamics of
Polymer Solubility in Polar and Nonpolar Systems, Ind. Eng.
Chem. Fundam., Vol. 3, No. 1, 1964, pp. 18.
[13] Hansen, C. M., The Three Dimensional Solubility Param-
eterKey to Paint Component Affinities I, J. Paint Technol.,
Vol. 39, No. 505, 1967, pp. 104117.
[14] Hansen, C. M., The Three Dimensional Solubility Param-
eterKey to Paint Component Affinities II, J. Paint Technol.,
Vol. 39, No. 511, 1967, pp. 505510.
[15] Hansen, C. M., and Skaarup, K., The Three Dimensional
Solubility ParameterKey to Paint Component Affinities III,
J. Paint Technol., Vol. 39, No. 511, 1967, pp. 511514.
[16] Hansen, C. M., 1967, The Three Dimensional Solubility
Parameter and Solvent Diffusion Coefficient, Ph.D. thesis
Danish Technical Press, Copenhagen.
[17] Hansen, C. M., and Beerbower, A., Solubility Parameters,
Kirk-Othmer Encyclopedia of Chemical Technology, Supple-
ment Volume, 2nd ed., A. Standen, Ed., Interscience, New
York, 1971, pp. 889910.
[18] Barton, A. F. M., Applications of Solubility Parameters
and Other Cohesion Energy Parameters in Polymer Science
and Technology, Pure Appl. Chem., Vol. 57, No. 7, 1985,
pp. 905912.
[19] Srensen, P., Application of the Acid/Base Concept Describ-
ing the Interaction between Pigments, Binders, and Solvents,
J. Paint Technol., Vol. 47, No. 602, 1975, pp. 3139.
[20] Van Dyk, J. W., Fourth Chemical Congress of America, New
York, 2530 Aug. 1991.
[21] Anonymous (Note: This was in fact Van Dyk, J. W., but this
does not appear on the bulletin), Using Dimethyl Sulfoxide
(DMSO) in Industrial Formulations, Report No. 102, Gay-
lord Chemical Corp., Slidell, LA, 1992.
[22] Karger, B. L., Snyder, L. R., and Eon, C., Expanded Solubil-
ity Parameter Treatment for Classification and Use of Chro-
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No. 14, 1978, pp. 21262136.
[23] Hansen, C. M., and Wallstrm, E., On the Use of Cohesion
Parameters to Characterize Surfaces, J. Adhes., Vol. 15, 1983,
pp. 275286.
[24] Hansen, C. M., Characterization of Surfaces by Spreading
Liquids, J. Paint Technol., Vol. 42, No. 550, 1970, pp. 660
664; Hansen, C. M., Surface Dewetting and Coatings Perfor-
mance, J. Paint Technol., Vol. 44, No. 570, 1972, pp. 5760.
[25] Hansen, C. M., and Pierce, P. E., Surface Effects in Coatings
Processes, Ind. Eng. Chem. Prod. Res. Dev., Vol. 13, No. 4,
1974, pp. 218225.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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494 PAINT AND COATING TESTING MANUAL 15TH EDITION
[26] Gardon, J. L., Critical Review of Concepts Common to Cohe-
sive Energy Density, Surface Tension, Tensile Strength, Heat
of Mixing, Interfacial Tension and Butt Joint Strength, J. Col-
loid Interface Set, Vol. 59, No. 3, 1977, pp. 582596.
[27] Flory, P. J., Principles of Polymer Chemistry, Cornell University
Press, New York, 1953.
[28] van Krevelen, D. W., and Hoftyzer, P. J., Properties of Polymers:
Their Estimation and Correlation with Chemical Structure, 2nd
ed., Elsevier, Amsterdam, 1976.
[29] Beerbower, A., Environmental Capability of Liquids, Inter-
disciplinary Approach to Liquid Lubricant Technology, NASA
Publication SP-318, 1973, pp. 365431.
[30] Fedors, R. F., A Method for Estimating Both the Solubility
Parameters and Molar Volumes of Liquids, Polym. Eng. Sci.,
Vol. 14, No. 2, 1974, pp. 147154.
[31] Koenhen, D. N., and Smolders, C. A., The Determination of
Solubility Parameters of Solvents and Polymers by Means of
Correlation with Other Physical Quantities, J. Appl. Polym.
Sci., Vol. 19, 1975, pp. 11631179.
[32] Anonymous, Co-ActA Dynamic Program for Solvent Selec-
tion, Brochure, Exxon Chemical International, Inc., 1989.
[33] Dante, M. F., Bittar, A. D., and Caillault, J. J., Program Cal-
culates Solvent Properties and Solubility Parameters, Mod.
Paint and Coat., Vol. 79, No. 9, 1989, pp. 4651.
[34] Hoy, K. L., New Values of the Solubility Parameters from
Vapor Pressure Data, J. Am. Oil Chem. Soc., Vol. 42, No. 541,
1970, pp. 76118.
[35] Myers, M. M., and Abu-Isa, I. A., Elastomer Solvent Inter-
actions III-Effects of Methanol Mixtures on Fluorocarbon
Elastomers, J. Appl. Polym. Sci., Vol. 32, 1986, pp. 35153539.
[36] Hoy, K. L., Tables of Solubility Parameters, Union Carbide
Corp., Research and Development Dept., South Charleston,
WV, 1985.
[37] Hansen, C. M., Solubility Parameters in Paint Testing Manu-
al, Manual 17, J. V. Koleske, Ed., American Society for Testing
and Materials, Philadelphia, 1995, pp. 383404.
[38] Hansen, C. M., Hansen Solubility ParametersA Users Hand-
book, CRC Press, Boca Raton, FL, 1999/2000.
[39] Hansen, C. M., Hansen Solubility ParametersA Users Hand-
book, 2nd, Ed., CRC Press, Boca Raton, FL, 2007.
[40] Hansen, C. M., PolymeroplselighedPrigogines Teori om
Korresponderende Tilstande og Hansen Oplselighedspar-
ameterteori Bekrfter Hinanden (Polymer Solubility
Prigogines Corresponding States Theory and Hansen Solubil-
ity Parameter Theory Confirm Each Other), Dansk Kemi, Vol.
78, No. 9, 1997, pp. 46.
[41] Prigogine, I. (with the collaboration of A. Bellemans, and A.
Mathot), The Molecular Theory of Solutions, North-Holland,
Amsterdam, 1957, Chaps. 16 and 17.
[42] Rowlinson, J. S., Liquids and Liquid Mixtures, Butterworths
Scientific Publications, London, 1959, pp. 254257 and 313
318.
[43] Reid, R. C., and Sherwood, T. K., Properties of Gases and Liq-
uids, McGraw-Hill, New York, 1958 (Lydersen Method, see
also Ref [31]).
[44] McLellan, A. L., Tables of Experimental Dipole Moments, W. H.
Freeman, San Francisco, 1963.
[45] Tables of Physical and Thermodynamic Properties of Pure Com-
pounds, American Institute of Chemical Engineers Design
Institute for Physical Property Research, Project 801, Data
Compilation, R. P. Danner and T. E. Daubert, Project Supervi-
sors, DIPPR Data Compilation Project, Department of Chemi-
cal Engineering, Pennsylvania State University, University
Park, PA.
[46] Hansen, C. M., Selection of Chemicals for Permeation Test-
ing Based on New Solubility Parameter Models for Challenge
5100 and Challenge 5200, Contract No. DTCG50-89-P-0333,
U.S. Coast Guard, June 1989, Danish Isotope Centre, Copen-
hagen.
[47] CRC Handbook of Chemistry and Physics, 65th ed., R. C.
Weast, Ed., CRC Press Inc., Boca Raton, FL, 1988-1989,
pp. C-672C-683.
[48] Majer, V., Enthalpy of Vaporization of Organic Compounds,
Handbook of Chemistry and Physics, 72nd ed., D. R. Lide, Ed.,
CRC Press Inc., Boca Raton, 19911992, pp. 6-1006-107.
[49] Fishtine, S. H., Reliable Latent Heats of Vaporization, Ind.
Eng. Chem., Vol. 55, No. 4, 1963, pp. 2028; IECHAD, Vol. 55,
No. 5, pp. 5560; IECHAD, Vol. 55, No. 6, pp. 4756.
[50] Saarnak, A., Hansen, C. M., and Wallstrm, E., Solubility
Parameters, Characterization of Paints and Polymers, Report
from Scandinavian Paint and Printing Ink Research Institute,
January 1990.
[51] Barton, A. F. M., Handbook of Polymer-Liquid Interaction
Parameters and Solubility Parameters, CRC Press, Inc., Boca
Raton, FL, 1990.
[52] Teas, J. P., Graphic Analysis of Resin Solubilities, J. Paint
Technol., Vol. 40, No. 516, 1968, pp. 1925.
[53] Hansen, C. M., Some Aspects of Acid/Base Interactions,
(Einige Aspekte der Sure/Base-Wechselwirkung) (in Ger-
man) Farbe und Lack, Vol. 83, No. 7, 1977, pp. 595598.
[54] Barton, A. F. M., Solubility Parameters, Chem. Rev. (Wash-
ington, D.C.), Vol. 75, No. 6, 1975, pp. 731753.
[55] Beerbower, A., Boundary LubricationScientific and Techni-
cal Applications Forecast, AD747336, Office of the Chief of
Research and Development, Department of the Army, Wash-
ington, DC, 1972.
[56] Van Dyk, J. W., Frisch, H. L., and Wu, D. T., Solubility, Sol-
vency, Solubility Parameters, Ind. Eng. Chem. Prod. Res. Dev.,
Vol. 24, No. 3, 1985, pp. 473478.
[57] Hansen, C. M., 25 Years with Solubility Parameters (25
rmed Oplselighedsparametrene) (in Danish), Dansk Kemi,
Vol. 73, No. 8, 1992, pp. 1822.
[58] Hansen, C. M., and Hansen, K. M., Solubility Parameter Pre-
diction of the Barrier Properties of Chemical Protective Cloth-
ing, Performance of Protective Clothing: Second Symposium,
ASTM STP 989, S. Z. Mansdorf, R. Sager, and A. P. Nielsen,
Eds., American Society for Testing and Materials, Philadel-
phia, 1988, pp. 197208.
[59] Hansen, C. M., Billing, C. B., and Bentz, A. P., Selection and
Use of Molecular Parameters to Predict Permeation Through
Fluoropolymer-Based Protective Clothing Materials, The
Performance of Protective Clothing; Fourth Volume, ASTM STP
1133, J. P. McBriarty and N. W. Henry, Eds., American Society
for Testing and Materials, Philadelphia, 1992, pp. 894907.
[60] Hansen, C. M., The Affinities of Organic Solvents in Biologi-
cal Systems, J. Am. Ind. Hyg. Assoc., Vol. 49, No. 6, 1988, pp.
301308.
[61] Hansen, C. M., The Universality of the Solubility Parameter,
Ind. Eng. Chem. Res., Vol. 8, No. 1, 1969, pp. 211.
[62] Hansen, C. M., and Just, L., Prediction of Environmental
Stress Cracking in Plastics with Hansen Solubility Param-
eters, Ind. Eng. Chem. Res., Vol. 40, No. 1, 2001, pp. 2125.
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Part 9: Films for Testing
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497
INTRODUCTION
AMONG THE MOST CRITICAL AND OFTEN MIS-
understood properties of a coating are cure and the mea-
surement of cure. If ASTM standard technology [1] is
examined, one will find no listing for the word cure. Cure
is something that can have different meanings for different
people. In the coating and paint field of study, cure is usu-
ally thought of as the chemical reaction between functional
groups that results in cross-linking of a system by one or
more of a variety of schemes including polymerization of
monomers, rearrangement, condensation or elimination,
reaction with adventitious moisture or oxygen, as well as
others. However, the word can be taken to mean much
more and should include the drying of a lacquer as when
thermoplastic coatings are applied, the solidification and/
or crystallization of polyolefins or other hot-melt applied
coatings, the drying of latexes or emulsions that can form
films through the high-pressure compacting forces of sur-
face tension, as well as of other ways of forming a coherent,
useful thin film with good mechanical, electrical, or other
properties. This chapter will mainly be concerned with
cross-linked systems and cure will be taken to mean reac-
tions that result in a thermoset or network-formed coating
[2], unless otherwise indicated.
The desired and often optimum chemical and physi-
cal properties of a coating are dependent on proper
curing conditionstime, temperature, and humidity.
For example, if a thermosetable, acrylic polymer-based
lacquer is applied to a substrate and solvent is allowed
to evaporate under ambient conditions, the resulting film
might have cracks, low gloss, and be hard and brittle.
Yet, the same system could result in a coherent, useful
film if the solvent were evaporated under controlled tem-
peratures for specific times. The film might still be brittle
and have poor chemical resistance, but such factors may
not be important in certain instances. However, strength
properties will be markedly improved as a cross-linking
agent is added, and the system is allowed to react under
proper temperature conditions for an appropriate length
of time. The resulting coating will be glossy, hard, tough,
and chemical resistant. The time and temperature rela-
tionship and the interaction of these parameters has been
reported by Neag and Prime [3] in the case of powder
coating cure.
Concept of Cure
Polymer is a word meaning many (poly) units (mers)
wherein the units are monomers or single-unit mers. Thus,
polymers are high molecular weight molecules that are
comprised of monomers that may be the same or different,
though if the monomers comprising the polymer are differ-
ent, the polymer is referred to as a copolymer. Polymers
are formed by a variety of polymerization mechanisms
including addition (such as the polyacrylates, polyvinyls,
etc.), cationic (as polyepoxides), condensation (as polyes-
ters), coordination (as polyolefins), ring opening (as Nylon
6 and polylactones), and rearrangement (as polyurethanes).
These compounds known as polymers range from high
to low molecular weight in nature. High molecular weight
polymers can form coating films with high gloss and good
mechanical properties; however, to achieve such useful
properties, the applied solids must be low due to the high
viscosities involved when such large-size molecules are
used. In the coatings arena, usually low molecular weight
polymers or oligomers comprising a relatively small num-
ber of chain units that either have one or more functional
groups or a co-unit that has functional or polyfunctional
groups on as many of the oligomer molecules as possible.
If used alone, the oligomers would have poor mechanical
and chemical properties and would either be sticky masses
(glass transition temperature, Tg, below room temperature)
or rock hard chunks (Tg above room temperature). To
transform these oligomers into useful materials with good
mechanical and other properties, it is necessary to build or
increase molecular weight. This transformation is accom-
plished by the addition of a cross-linking agent to the coat-
ing formulation wherein said compound will react with the
functional groups on the oligomers and then cure the liquid
system into a film comprised of extremely high molecular
weight molecules.
2
It should be clear from the above that thermoplastic
coatings are soluble in particular compounds we term
solvents and, in addition, if heated will liquefy with the
viscosity dependent on the molecular weight. In contrast,
thermoset coatings are insoluble but will often swell in
particular compounds and if heated may soften but will
thermally degrade rather than liquefy.
Of course, additives [4] that will markedly improve
the path to achieving a coating with designed gloss, good
39
Cure: The Process and Its Measurement
Thomas J. Miranda
1
1
Senior Consultant, Consolidated Research Inc., 16731 Brick Road, Granger, IN 46530.
2
The concept of molecular weight becomes lost when one discussed cross-linked systems. Dr. Herman Mark described the rubber in an
automobile tire after vulcanizing or cross-linking as one gigantic molecule. Although the defnition may be a bit ambitious, since defects
and the laws of probability exist, it is a good model to keep in mind when thinking about cross-linked chemicals. Thus, a chemical coating
can be thought of as a huge molecule with an extremely high molecular weight that is incapable of being dissolved.
MNL17-EB/Jan. 2012
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498 PAINT AND COATING TESTING MANUAL 15TH EDITION
mechanical and chemical properties, as well as rapid cure
are very important to the cure process. Accelerators, cata-
lysts, or other additives insure that cure or cross-linking will
be effected in an acceptable time. For example, in radiation
cure [5], monomeric and/or oligomeric molecules are com-
bined into a very fluid formulation and ultraviolet radiation-
activated cationic or free-radical initiator additives known as
photoinitiators cause the molecules to react in an extremely
rapid manner at coating line speeds of even several hundred
feet per minute. When an electron beam is used to effect
cure of such systems, photoinitiators are not required,
though flow-control additives would be used. With radiation
activation, cure is achieved in the snap of a finger.
When less-energetic reactions than those used in radia-
tion curing are involved, the cure process will be relatively
slow, say on the order of minutes at an elevated tempera-
ture. Examples of such a cure system might be the acid-
catalyzed, aminoplast cross-linking of hydroxyl-functional
oligomers to form thermoset films or the controlled evapo-
ration of solvent or other diluent from lacquers or latexes
to form thermoplastic films. In the case of powder coatings,
the coating material is in a dry form and thermal energy is
used to melt the powder particles and time at a temperature
is required to allow the particles to flow into a continuous
coating. If a cross-linking agent is present in the powder
coating, the cure system must be orchestrated in such a
manner that liquefaction and flow take place before signifi-
cant network formation occurs. Very slow reactions occur
in thermoset systems that cure by reaction of adventitious
oxygen with unsaturation in the oligomeric molecules.
Many details regarding coating film formation [6] and
the preparation of films for coating tests [7] can be found
elsewhere.
CURING MECHANISMS
Lacquers
Lacquers consist of thermoplastic polymers that are dis-
solved in a solvent. When the coating is applied, the solvent
evaporates under controlled conditions and a thermoplastic
film is formed. This is the type coating used in certain high
quality furniture finishes. A number of years ago, many
automobiles were coated in this manner, but today such
coatings are thermoset in nature.
Emulsions and Latexes
Another means of forming a thermoplastic film is film for-
mation from an aqueous-based emulsion or latex. In this
instance, a polymer such as a vinyl acetate-acrylic copoly-
mer latex is formulated with colorants and additives, cast,
and the water carrier is evaporated with a coherent film
resulting. In such systems, the water is not a solvent but a
dispersing medium. Microscopically, the polymer appears
as tiny ball bearings suspended in water with surface active
agents present to keep the polymer particles dispersed and
free from settling. As the water evaporates, hydrodynamic
pressure causes the small spheres to crowd closer and
closer until capillary action forces the particles to fuse and
form a continuous film. If the polymer is too hard in nature,
a poorly adherent, brittle film is formed. Often, this is the
reason paint manufacturers recommend that water-based
latex paints not be applied at low temperatures. To facilitate
fusion and continuity, small amounts of a coalescing sol-
vent such as diethylene glycol monobutyl ether are added to
decrease the glass transition temperature. As described, the
curing results in a thermoplastic coating. If desired, these
systems can be made into thermoset films by incorporating
a functional group into the latex molecules and employing
a cross-linking agent.
Oxidative Cross-linking
Oxidative cross-linking takes place in systems that contain
reactive, unsaturated double bonds as are found in unsatur-
ated fatty acids, drying oils such as linseed, soy, tung, and
tall oil (see Chapters 4 and 5 for a discussion of drying
oils and driers), as well as certain alkyds and oleoresin-
ous varnishes. This vehicle is formulated with a suitable
solvent, a drier (often termed a siccative) such as cobalt,
manganese, or zirconium salts in the form of naphthenates,
octanoates, or the like, and other ingredients. Curing takes
place through adventitious oxygen interacting with the
molecular unsaturation.
The coating film is applied by brushing, spraying, or
other means and solvent is removed by evaporation. The
resultant liquid or tacky film then undergoes an induction
period in which natural antioxidants inherent in the start-
ing materials are overcome as oxygen is absorbed from the
atmosphere. This is followed by hydroperoxide formation
on carbon atoms alpha to double bonds. This is followed by
peroxide decomposition and formation of free radicals that
initiate cross-link formation at the unsaturated sites with
the result formation of a cross-linked thermoset film [8,9].
A simplified reaction scheme in which R and R are alkyl
groups is shown below [10].
The starting materials are converted into polymer accord-
ing to the following scheme:
Termination by coupling increases the molecular sizesay,
doubling if the joined chains are the same in sizeand
eventually a network or cross-linked system is formed.
If properly formulated, the final product has the desired
chemical and physical characteristics.
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CHAPTER 39 CURE: THE PROCESS AND ITS MEASUREMENT 499
Reactive Cross-linking
In this type of cure system, a reactive intermediate is
added to a functionalized polymer or oligomer and a fur-
ther chemical reaction is initiated by heating alone or in
the presence of a catalyst or by some other means. The
functionality on the polymer molecules often is hydroxy in
nature. The reactive intermediate is often an amino com-
pound such as hexa(methoxymethyl)melamine.
MELAMINE
Melamine-formaldehyde condensates are often used to
cure a reactive polymer. Melamine is 2,4,6-triamino-
1,3,5-triazine, a compound prepared by condensing three
molecules of dicyandiamide. Melamine, in turn, can be
condensed with up to six molecules of formaldehyde and
6 molecules of methanol to form hexa(methoxymethyl)
melamine (HMMA) (see Chapter 8) or an oligomeric phe-
nolic compound (see Chapter 11).
Alcohols other than methanol can be used as the hydroxyl-
capping groups. Examples of commonly used alcohols are
isobutanol and butanol.
In practice, these compounds can be reacted with a
functionalized polymer such as an acrylic or an alkyd that
contain either acid or hydroxyl groups, which will react
with the melamine compound to liberate an alcohol by-
product with the multifunctional nature of the melamine
compound leading to a cross-linked coating film. This
cure system is briefly indicated by the following reaction
scheme:
wherein A is the residue from HMMA and P represents the
hydroxyl functionalized polymer that is being cross-linked.
Note that after the above reaction, the residue A still has
five functional groups that can react with other hydroxyl
groups on the same polymer molecule or on other poly-
mer molecules to set up the network. In addition to the
by-product methanol, it is possible for formaldehyde to be
a by-product. Narayan and coworkers [11] have addressed
various aspects of the cure and properties of polyesters
cured with HMMA. Numerous other articles can be found
in the literature.
UREA COMPOUNDS
A scheme similar to that described above for HMMA and
other melamine compounds is also applicable to ureafor-
maldehyde (UF) compounds. To form the UF compounds,
urea is reacted with formaldehyde and the product is end
capped with alkyl alcoholsusually methyl, isopropyl, or
butyl alcohols. A full reacted urea intermediate in which
methanol has been used as the capping agent has the fol-
lowing structure:
This multifunctional compound is capable of reacting with
hydroxyl groups to produce cross-links with by-products
such as alcohol, water, and formaldehyde.
Note that in the above examples, neither the
melamines, ureas, or most polymers would form a good
coating if used alone. The polymers act as flexibilizers
and/or tougheners for the hard, brittle cross-linking
agents.
EPOXIDES
Epoxides represent a ring-opening-mechanism form of
curing coatings. Aromatic epoxides are produced by the
reaction of epichlorohydrin and bisphenol A, with the
latter compound a condensation product of acetone and
phenol. Aliphatic epoxides are prepared by the peroxida-
tion of unsaturated linear or cyclic olefins. A typical epox-
ide used in coatings, is the diglycidylether of bisphenol A,
which is described below and wherein Z is a phenylene
group.
The epoxide groups can react with active hydrogen atoms
such as those found on amine, hydroxyl, and carboxylic
acid groups. Aromatic epoxides react very rapidly with
amines and hydroxyl groups and cycloaliphatic epoxides
react very rapidly with cations derived from acid function-
ality or hydroxyl groups. Opening an epoxide ring results
in linkage to the donating compound an formation of a
secondary hydroxyl group that may undergo further reac-
tion. Thus, the above described epoxide may be consid-
ered as tetrafunctional when it is in the presence of active
hydrogen atoms and as a result will rapidly lead to a highly
cross-linked, cured coating. Under the proper conditions,
the formed hydroxyl group can react with another epoxide
group or with a melamine-formaldehyde compound to pro-
duce coatings with improved properties such as hardness,
toughness, chemical resistance, and/or solvent resistance in
the cured film.
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500 PAINT AND COATING TESTING MANUAL 15TH EDITION
URETHANES
Urethane linkages represent a rearrangement mechanism
for the formation of cross-links and cure in polymeric
systems. Urethanes are the reaction product of a hydroxyl
group and an isocyanate group that undergo a rearrange-
ment with the formation of a urethane linkage as described
in the following.
This reaction is used in the manufacture of a broad range of
products from insulation and seating foams, reaction injec-
tion moldings, in high-performance coatings, and other end
uses. The isocyanate used in coatings and many other end
uses is usually a di- or tri-functional compound that will
lead to cross-linked systems. Monofunctional isocyanates
are used to end-cap hydroxyl compound in the preparation
of intermediates or to impart particular, desirable char-
acteristics for certain end uses. Included are isocyanates
such as iso-phorone diisocyanate, 4,4-diphenylmethane
diisocyanate, 4,4-dicyclohexylmethane diisocyanate, tri-
mers of hexam-ethylene diisocyanate, and others. The
higher molecular weight isocyanates are preferred when
practical, since they have a lower vapor pressure than their
lower molecular weight counterparts and thus provide for
improved working conditions. As would be expected, satu-
rated epoxides have better weathering characteristics than
aromatic epoxide coatings.
Isocyanates are used to cross-link a variety of polymers
containing hydroxyl or amine functionality. In the case of
amine functionality, the reactions are very rapid and result
in the formation of urea cross-links. The reactions with
hydroxyl functionality are usually catalyzed and proceed at
easily controllable rates. Among the coating systems cured
isocyanates or that contain urethane linkages are a variety
of acrylic polymers and copolymers; polyesters; poly ether,
polyester, and polylactone polyols; polyols capped with iso-
cyanates and cured with adventitious moisture, urethane
acrylates cured with ultraviolet or electron beam radiation,
as well as others.
PHENOLICS
Phenolic compounds used in coatings are the condensation
reaction products of phenol or substituted phenols and
formaldehyde. Two main types of phenolics are made with
the type depending on the catalyst used and the reaction
conditions. When an acid is used as the catalyst, a thermo-
plastic, soluble novolac phenolic is obtained. Under basic
conditions, the product obtained is a resole phenolic that
is thermoset in character and is cross-linked in the final
stages of the reaction. A phenol-formaldehyde condensate
(P-F) may have the following structure:
Hydroxyl-containing oligomers such as the alkyds can
be cross-linked through reaction of the hydroxy-methyl
function of the P-F with an hydroxyl group on the alkyd
with the elimination of water.
CURE MEASUREMENT
Complete or essentially complete cure development is a
very important factor in meeting coating specifications and/
or in determining the ultimate performance characteristics
of any particular coating. Therefore, it is very important for
the developer and the user of coatings to know how the cur-
ing process takes place and whether or not the final coating
is adequately cured. As cross-links develop and molecular
weight increases in a coating, performance characteristics
such as adhesion, solvent resistance, toughness, hardness,
gloss, and the like approach an optimum value, which is
near a set, desired, or specification value. Coatings that
are undercured will tend to be soft (lack hardness), have
poor solvent resistance, and probably have poor adhesion.
Overcured coatings may be hard and brittle, take on a dark,
undesirable color, have low gloss, or not meet other criteria.
Cure measurement can be determined by simple,
qualitative testing or through analytical techniques that
require sophisticated instrumentation. Often simple test-
ing can be used to give an investigator a quick benchmark
and tell if they are on the correct developmental track.
Then sophisticated techniques can be used to completely
understand the coating system and the coatings ultimate
properties. Finally, investigators attempt to correlate simple
and sophisticated tests so performance features may be
confidently determined during production, which is often
taking place at high line speeds, with relatively simple test-
ing. Also important is being aware that coating properties
may change after leaving a thermal curing oven, a radiation
source, or other curing device and properties after a length
of aging time should be considered. Methods for measuring
degree of cross-linking and the distance between cross-links
can be found in Chapter 46.
Rapid test methods are desirable because of time con-
straints and cost, but sometimes they do not tell the true
story. Yet, they do provide much useful information. It
should be kept in mind that one is attempting to ascertain
a molecular process, cross-linking (unless thermoplastics
are involved), and its relationship to coating performance.
Most thermoplastic coatings cure or dry by simple
evaporation of solvent. This is true for nitrocellulose, cellu-
lose acetate, and solvent soluble acrylic lacquers wherein
no cross-linking takes place. To measure cure of such
systems, the time for either a print-free or tack-free condi-
tion is determined. As the evaporation process takes place,
the nature of the coating goes from tacky to set-to-touch
to tack free. On further drying, the coating becomes print
free wherein a thumb print will not be visible on the coat-
ing surface. At times the effect of a twisted thumb print
under moderate hand pressure will be observed. Another
testing method involves dropping cotton linters or cotton
balls onto the surface and noting the time after which they
do not adhere to the coating. Thermoplastic or thermoset
coatings on metal substrates can be quickly tested with
a hand-held, fairly new nickel (U.S.A. five-cent piece) by
applying a quick, rapid, gouging scratch with the edge
of the coin to the coating and observing the results. One
quickly finds out if the coating is tough and adherent, since
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CHAPTER 39 CURE: THE PROCESS AND ITS MEASUREMENT 501
the hard, sharp coin edge will have a marked effect on the
coating.
Solvent Rubs
A convenient, often-used method for determining cross-
linking involves solvent rubs. A cloth soaked with a solvent
such as methyl ethyl ketone (MEK) or acetone is rubbed
vigorously back and forth on the film, and then the film
is examined after a specific number of rubs. If the film
is removed, softened, or loses gloss, it is considered inad-
equately cross-linked or it is considered nonresistant to
solvent. Often, the number of back-and-forth double rubs
that the film does pass is reported. Thermoplastic coat-
ing are not expected to pass the test. The tests involved
include ASTM D5402, Practice for Assessing the Solvent
Resistance of Organic Coatings Using Solvent Rubs, and
ASTM D4752, Test Method for Measuring MEK Resistance
of Ethyl Silicate (Inorganic) Zinc-Rich Primers by Solvent
Rubs. Related tests include ASTM D5109, Test Methods for
Copper-Clad Thermosetting Laminates for Printed Wiring
Boards; ASTM D1676, Test Methods for Film-Insulated
Magnet Wire; and ASTM D2671, Test Methods for Heat-
Shrinkable Tubing for Electrical Use.
One difficulty associated with this test is that the indi-
vidual testing the coating is not standardized. One person
may exert more pressure than another and this can have
a bearing on the final result. However, even with this defi-
ciency, the test does provide useful information when the
number of double rubs passed is reported.
Hardness
Hardness and scratch resistance provide another method
for obtaining information about the degree of cross-linking
and cure. There are a variety of tests that provide informa-
tion about this characteristic. The topic is discussed in
detail in another chapter in this manual.
PENCIL HARDNESS
A very simple, but complex, test for measuring the hard-
ness of coatings is pencil hardness, which is carried out
according to ASTM D3363, Test Method for Film Hardness
by Pencil Hardness. The test originated with manufactur-
ers of pencils who tried to develop a consistent means for
checking the quality of pencils. Along the development
way, someone suggested scratching a paint film, and it was
noticed that the different hardness of pencils were able to
penetrate the coating down to the substrate or to scratch
the coating to different degrees.
The test was later used by coating technologists and
currently is widely used in the industry to determine coat-
ing hardness. In this technique, a number of pencils of
known hardness, usually from a specified manufacturer,
are used. The pencil is trimmed so that 5 mm of lead is
exposed. The lead diameter is 1.8 mm and is sharpened
by rubbing it perpendicular to the surface of No. 400
carbide abrasive paper. The sharpened pencil is held at
a 45 angle to the coating and pushed along the surface
with hand pressure to attempt peeling away the coating.
The pencil that fails to scratch or cut through the coating
is considered the Pencil Hardness Value. The method
is simple, the equipment is low in cost, and results are
quickly obtained. However, values obtained can be opera-
tor dependent as well as dependent on the method of
sharpening the lead point, variances of lead hardness from
different pencil lots, and different manufacturers. Yet, as
mentioned above, the test is widely used and does provide
useful information.
KNOOP AND PFUND HARDNESS
The Knoop hardness test, described in ASTM D1474 Test
Methods for Indentation Hardness of Organic Coatings,
is a useful test in which a spherical, pyramidal, or coni-
cal indentor is pressed into the film to cause indentation
with the depth of penetration a measure of hardness. In
the test, a 25 g load is applied for 18 s and the length of
the indention line is measured with a microscope. The
Knoop hardness number (KHN) is calculated from the
expression[12]
where L is the applied load in kilograms, A
p
is the projected
indentation area in square millimeters, l is the length in
millimeters of the long diagonal of the indentation mark,
and C
p
is an instrument constant. Because of the thinness of
most coating films, this method is more useful for plastics,
since it required almost a 75 % indentation into the film
and can be influenced by substrate considerations. A more
generalized formula than the above can be found in the
referenced ASTM Test Method.
The Pfund Hardness Number (PFN) is obtained in an
analogous manner by using a hemispherical quartz or sap-
phire indenter that is pressed into the film. PFN is calcu-
lated from the expression
where L is the applied load in kilograms, A is the area of
the projected indentation in square millimeters, and d is the
diameter of the projected indentation in millimeters.
SWARD HARDNESS
Sward hardness depends on the change in surface prop-
erties and the viscoelastic nature of a film. This method,
which was discontinued in 1990, is used for automotive fin-
ishes and consists of a rocker containing two spirit-bubble
indicators. The method is described in ASTM D2134, Test
Method for Determining the Hardness of Organic Coat-
ings with a Sward-Type Rocker and in ASTM D4366, Test
Methods for Hardness of Organic Coatings by Pendulum
Damping Tests. The pendulum is rocked and the number
of swings are recorded and a reading is taken at the point
where the swing distance is equal to half the original value.
As cure increases, the Sward number increases. The value
of a Sward test is that a number that can be compared
to that of other coatings is obtained. This test must be
conducted under very clean conditions as lint and surface
imperfection can interfere with the results. Temperature
control is another important factor. The difficulty with this
test is that it only measures cross-link density or cure to
a point. Then, it cannot detect further cure or over cure,
since a plot of Sward numbers as a function of time or cure
tends to reach a limiting value. A comparison [13] of hard-
ness values obtained by different test methods is shown in
Table 1.
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502 PAINT AND COATING TESTING MANUAL 15TH EDITION
IMPACT RESISTANCE
Tests that measure the impact resistance of a coating can
be used to correlate with cure. An undercured coating
may exhibit a low impact value, but as cross-link density
increases, impact values improve. Of course, overcured
coating may be brittle and have a low impact value. ASTM
D2794, Test Method for Resistance of Organic Coatings
to the Effects of Rapid Deformation (Impact), is a widely
used test. It consists of placing a flat coated panel under
a weighted spherical ball assembly and then dropping the
weighted ball onto the panel from different heights. The
cylinder in which the ball assembly is mounted is cali-
brated such that an operator can directly read the impact
resistance in inch-pounds. The measurements are carried
out by dropping the ball directly on the coated surface
or on the reverse side with the results being reported as
direct or reverse impact, respectively. The impact causes
a dimple to form in the test panel, and it is examined
visually or with a ten-power lens to determine the extent
of cracking or other failure. This is a simple test that is
widely recognized in the coatings industry, and it gives
useful information about the performance characteristics
of the coating.
Related tests include ASTM D5420, Test Method for
Impact Resistance of Flat, Rigid Plastic Specimen by
Means of a Striker Impacted by a Falling Weight (Gardner
Impact); ASTM D950, Test Method for Impact Strength
of Adhesive Bonds; and ASTM D2137, Test Methods for
Brittleness Point of Flexible Polymers and Coated Fabrics.
In addition to these methods, certain industries, such as
the automotive industry, often develop their own in-house
test methods and these will vary from manufacturer to
manufacturer.
Thermal Analysis
Thermal analysis is an important analytical tool for deter-
mining the response of materials to changes in temperature
and is useful in determining cure of coatings. The technique
can be used to monitor the glass transition temperature, Tg,
of a coating and this property can be related to cross-link
density. For example, if a number of paint films that are
cured at various times and/or temperatures are evaluated,
thermal analysis can be used to determine the change in
Tg as a function of a bake schedule or, for that matter, of
formulation composition. From such studies, optimum
cure cycles can be determined to ensure quality finishes
are produced.
Thermal analysis devices have several modes for deter-
mining Tg and these include Differential Scanning Calo-
rimetry (DSC), Thermomechanical Analysis (TMA), and
Dynamic Mechanical Analysis (DMA). The glass transition
temperature is a second-order transition, and it represents
a temperature where segmental motion occurs in a poly-
mer chain. This motion also causes a volume change in the
polymer. Comparative changes of cross-linking measured
by Sward hardness, evaporative rate analysis, and DSC
indicated that the changes can be followed to high levels of
cross-linking, but Sward measurements reached a limiting
value while Tg continued to increase [14]. The importance
of using the correct window of time and temperature when
curing powder coatings has been described in the litera-
ture [15].
When DSC is used, a plot of endotherm/exotherm as a
function of temperature is obtained at a set rate of tempera-
ture increase. As Tg is reached, there is an abrupt change in
the endotherm that appears on the plot. Similarly, Tg can
be measured using a plot of change in expansion as a func-
tion of temperature with the TMA method. In this method,
a specimen is placed under a quartz probe and then heated.
As the film expands, a plot is obtained in which a change in
slope occurs. The intersection of the tangents of the expan-
sion cure yields the Tg value. In the penetration mode,
a depression occurs at Tg. Further details about thermal
analysis can be found in the literature [1619].
DYNAMIC MECHANICAL ANALYSIS
Another method for obtaining Tg is to use dynamic
mechanical analysis in which a coating film is fixed to the
ends of a tuning fork and the fork is driven over a frequency
range and at different temperatures to provide a plot of
damping as a function of temperature. Tg, being a second
order transition, is a function of both temperature and of
frequency. Information from both variables can be used to
obtain information about the film [20].
TORSION PENDULUM
The torsion pendulum provides another way to obtain Tg as
well as other dynamic properties such as the real and the
imaginary shear modulus. A coating film is either imbibed
into an inert substrate or used in a neat form (often dif-
ficult for this technique) and suspended between jaws and
a counterbalanced disk that is used to apply a twisting
torque to the specimen. The applied shear force then freely
decays. A difficulty is that many coating films do not have
the strength to support even the light stress of the counter-
balanced disk, especially when the glass transition region is
approached. This is why the coating is usually imbibed into
an inert substrate such as fiberglass. If the sample is held
at a constant temperature for a period of time, changes in
cross-link density are reflected in modulus and damping
changes. Details of the method and ways to construct a tor-
sion pendulum can be found in the literature [21,22].
Impedance Measurements
Meyers [23] investigated the drying behavior of latex sys-
tems using ultrasonic impedance measurements. In his
TABLE 1Hardness test comparisons [13]
Sample KHN Sward
a
Pencil (Brands)
A B C D E
1 3.09 24 5B 6B 5B 6B 4B
2 4.33 28 4B 6B 6B 6B 4B
3 2.77 24 5B 6B 5B 4B 3B
4 2.61 22 3B 4B 5B 4B 3B
5 5.81 38 2B 2B 2B 2B HB
10 25.7 54 H H H H 2H
12 39.1 40 3H 2H 2H 4H 3H
14 40 8H 9H 7H 7H 9H
a
Note how the values differ in this investigationespecially between the
different brands of pencils and the limiting values of Sward Hardness.
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CHAPTER 39 CURE: THE PROCESS AND ITS MEASUREMENT 503
studies, a latex coating was cast onto a quartz crystal and
ultrasonic energy was beamed at an eleven degree angle at
the underside of the coating, reflected to a detector that
measured the attenuation of the initial beam as absorbed
by the drying coatings. As water evaporated, there were
changes in impedance that could be correlated to curing in
the sense of drying.
EVAPORATIVE RATE ANALYSIS
A novel method for studying cure is Evaporative Rate
Analysis (ERA), which was developed by Anderson and co-
workers [24]. This methodology was applied to determine
the cleanliness of the surface of spacecraft. It was reasoned
that if a radioactive C
14
liquid were placed on a clean sur-
face, the evaporation would be retarded due to cleanliness.
In fact, the opposite was true. Nevertheless, this technique
was developed to measure the degree of cleanliness. If a
small amount of diethyl succinate-C
14
is deposited on a
surface and a controlled sweep of nitrogen is applied over
the surface, the rate of evaporation can be monitored using
a Geiger counter. The principle is that on a clean surface,
there is no interaction between the solvent and a clean
substrate and as a result normal evaporation takes place.
If, however, the surface contains a contaminant, then the
radioactive liquid will interact with the surface contami-
nant and retard the rate of evaporation of the radioactive
component. Plots that relate cleanliness to evaporation rate
can be prepared.
The investigators applied this technique to the cure
of organic coatings. They demonstrated that in an under-
cured surface, solvent retention increased and this led to
longer residence times for the radioactive substance on the
under-cured surface. By preparing coated panels having
different cure times or temperatures, and then measuring
the ERA of each panel, a plot of retention as a function of
bake schedule was obtained. The method was applied to
the cure of a variety of coatings by many coating technolo-
gists [14,24].
Other instruments are useful for determining the
cross-linking of coatings including the Vibrating Needle
Curometer that is used for liquid systems such as adhesive
and sealants. The instrument drives a vibrating needle at a
fixed frequency into the sealant or adhesive, and the damp-
ing amplitude is measured as a function of gel and cure
time [25]. Products that can be monitored for cure with this
technique include coatings, adhesive, foams, and sealants.
Recent Information
Readers are referred to other chapters in this manual for
related cure-measuring techniques. The information pro-
vided in this chapter is also applicable to radiation-cured
and powder coatings, since the performance of these coat-
ings depends on proper extent of cross-linking consistent
with the design of the polymers used [5,15].
In addition there have been recent advances in ana-
lytical techniques that provide coating chemists with
better tools to understand the process of cross-linking
[26]. Analytical techniques for measuring key polymer
properties are reviewed in polymer chemistry texts [27
29]. A recent application of space technology in which a
technique known as Near Infrared Thermal Processing
is being used to cure a wide range of coatings, printing
inks, and adhesives [30]. The technique involves high
energy sources that radiate near the infrared spectrum
(more than 90 % of the energy emitted is below 2 m)
and allow markedly higher rates of cure than infrared
or hot air systems. The systems have high process effi-
ciencies and reliability. The importance of cure and its
characterization is apparent from the recent April 2006
two-part, virtual-learning course offered about this topic
by the Federation of Societies for Coating Technology and
presented by Dr. T. Provder.
References
[1] ASTM D16-10, Standard Terminology for Paint, Relat-
ed Coatings, Materials, and Applications, Annual Book
of ASTM Standards, Vol. 06.01, ASTM International, West
Conshohocken, PA, 2010.
[2] Gotro, J., and Prime, R. B., Thermosets, Encyclopedia of
Polymer Science and Technology, 3rd ed., J. Kroschwitz, ed.,
John Wiley & Sons, NY, 2004.
[3] Neag, C. M., and Prime, R. B., The Application of Time-Tem-
perature Superposition Techniques to Powder Coating Cure,
J. Coat. Technol., Vol. 63, No. 797, 1990, p. 37.
[4] Koleske, J. V., Springate, R., and Brezinski, D., 2006 Addi-
tives Guide, Paint and Coating Industry, Vol. 22, No. 5, 2006,
p. 40.
[5] Koleske, J. V., Radiation Curing of Coatings, ASTM Manual
45, ASTM International, West Conshohocken, PA, 2002.
[6] Wicks, Z. W., Jr., Film Formation, Federation Series on Coat-
ing Technology, Federation of Societies for Coatings Technol-
ogy, Philadelphia, PA, June 1986, p. 19.
[7] Athey, R. D., Jr., Film Preparation for Coating Tests, Paint
and Coating Testing Manual, Chapter 37, ASTM Manual
Series MNL. 17, 14th ed., J. V. Koleske, ed., ASTM, West Con-
shohocken, PA, 1995.
[8] Hurley, R., Metal Soaps: Drier Stabilizers and Related Com-
pounds, Handbook of Coating Additives, Marcel Dekker, Inc.,
New York, 1987, Chap. 13, p. 485.
[9] Godbole, V. A., Use of Metallic Driers in Organic Coatings,
Paint India, April 1986, p. 28.
[10] Swaraj, P., Surface Coatings: Science and Technology, 2nd ed.,
John Wiley & Sons, New York, 1996, pp. 452453.
[11] Narayan, R., Chattopadhyay, D. K., Sreedhar, B., and Raju,
K. V. S. N., Cure, Viscoelastic and Mechanical Properties of
Hydroxylated Polyester Melamine High Solids Coatings, J.
Mater. Sci., Vol. 37, No. 22, 2002, pp. 49114918.
[12] Swaraj, P., Surface Coatings: Science and Technology, 2nd ed.,
John Wiley & Sons, New York, 1996, p. 485.
[13] Sato, K., Prog. Org. Coat., Vol. 8, No. 1, 1980, p. 12.
[14] Miranda, T. J., J. Paint Technol., Vol. 43, No. 553, 1971, p. 51.
[15] Anon., EDC Industrial Quality Control Applications Series,
Guide to Product Cure Optimization, EDC, Inc., www.edc.com,
1998.
[16] Seymour, R. B., and Carraher, C. E., Jr., Polymer Chemistry,
An Introduction, 5th ed., Marcel Dekker, New York, 2000,
p. 117.
[17] Stevens, M. P., Polymer Chemistry, An Introduction, 3rd ed.,
Oxford University press, 1999, p. 169.
[18] Miranda, T. J., Mechanical Behavior of Materials, Volume III,
The Society of Materials Science, Japan, 1972, p. 392.
[19] Lambourne, R., Ed., Paint and Surface Coatings, Ellis Hor-
wood Ltd., 1987, p. 607.
[20] Nielsen, L. E., Mechanical Properties of Polymers, Reinhold
Publish Corp., New York, 1962, p. 274.
[21] Allcock, H. R., and Lampe, F. W., Contemporary Polymer Chem-
istry, 2nd ed., Prentice Hall, Englewood, NJ, 1990, p. 427.
[22] Myers, R. R., J. Polym. Set, Part C: Polym. Symp., Vol. 35, No.
3, 1971.
[23] Anderson, J. L., Root, D. E., and Green, G., J. Paint Technol.,
Vol. 40, No. 320, 1968.
[24] Rossi, A. G., and Paolini, A., J. Paint Technol., Vol. 40, No.
328, 1968.
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504 PAINT AND COATING TESTING MANUAL 15TH EDITION
[25] Scott, K. W., Adhesive Age, Vol. 34, No. 11, 1991, p. 22.
[26] Taylor, J. W., and Winnik, J., JCT Res., Vol. 1, No. 3, 2004,
p.163.
[27] Fried, J. R., Polymer Science and Technology, 2nd ed., Prentice
Hall Professional Technical Reference, Upper Saddle River,
NJ, 2003.
[28] Allcock, H. R., Lampe, F. W., and Mark, J. E., Contemporary
Polymer Chemistry, 3rd ed., Pearson Education, Inc., Upper
Saddle River, NJ, 2003.
[29] Carraher, C. E., Jr., Polymer Chemistry, An Introduction, 6th
ed., Marcel Dekker, 2003.
[30] Bar, K., One, twocured!, http://www.beckers-bic.com, Oct. 2006.
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505
THE PERFORMANCE OF A COATING FILM IN A TEST
is likely to be dependent on the physical form of the film.
For instance, film thickness is an important factor in physi-
cal and appearance measurements (until the coating gets
too thick), so there must be some control of the film thick-
ness. Appearance is also related to how smooth the film sur-
face is, and care to make the film appropriately will ensure
that the appearance measurements are germane to the end
use. The substrate used as the carrier for the test film, even
temporarily, may affect the property measurements, as well.
The primary concern in making films for tests is that
the film prepared be homogeneous and consistent with
previous or future films for the same test. The jargon of
the trade calls the art of making films casting, but many
film formation methods are used to form the film, and each
method has its own set of advantages and drawbacks.
TEST REQUIREMENTS OF FILMS
Test requirements come in two classes, appearance (aes-
thetics) and physical properties. Choice of application
method for the film may affect the appearance in some
cases. For instance, the multicolor paints must be applied
by dip or spray techniques for laboratory testing or the
appearance does not give the desired mottle of nearly
circular spots. Roller, brush, or even drawdown bar will
cause these spots to become streaks. Choice of applica-
tion method for appearance includes drying technique,
as some films require special drying conditions to attain
their desired special appearance. Examples include leafing
aluminum flake metallic-look paints, hammer tones, and
wrinkle finishes.
Choice of application method driven by physical prop-
erty testing is also necessary. Think carefully of the three
kinds of stresses (tensile, compression, shear) and recog-
nize that all are blended in a hardness or adhesion evalu-
ation by indenter, pencil, mandrel bend, or dart impact
test on a coating. Recognizing these stress combinations
can make one aware of film preparation needs. In cases
where adhesion is stronger than cohesion of the film, one
should be able to distinguish between adhesive failure and
cohesive failure. Film preparation should not conflict with
these objectives.
The physical properties to be tested in specific ASTM
methods have a significance and use section in the
method to ascribe the relation of the test value to some in
use performance criterion. The preparation of the test film
should thus correspond to the standard field application of
the material, as well.
Another portion of film influence on the test is film
thickness. The presentation by the Technical Committee
from Toronto in the 1990 National FSCT Meeting and Paint
Show [1] dealt with hardness measurements in films of
varying thickness. However, the control of film thickness
was not as straightforward as might have been thought.
Hardness values turned out to be dependent on film thick-
ness along with other equally important variables [2].
Fluid rheology, concentration, and other factors govern
the amount of coating left after the application process.
Knowing the process variables associated with a film-
casting technique are essential to getting what is needed
for the ultimate test and results therefrom. Certain other
properties of the film (opacity, permeability, erosion rate by
some attacking mode, etc.) will depend on the thickness of
the film. So, understanding thickness control in the casting
process is crucial to obtaining meaningful results in terms
of meeting specifications in reproducibility.
In instances where fluid or gas permeation resistance
or corrosion barrier properties are to be tested, a pinhole,
holiday, or mud-crack in the film is a fatal flaw. The film
preparation technique must eliminate (as much as possible)
any such fatal flaw, or the test method should prescribe
what is to be done (for example, replications) in cases
where an unseen fatal flaw is detected by the test.
FILM CASTING TECHNIQUES
Free Films
Free films, that is, films not applied permanently to a sub-
strate, are used for a wide variety of tests and accordingly
vary in thickness and size. The most common castings of
free films are used for permeation or strength and elonga-
tion testing. They can also be used for cold flex tests or
moisture/ solvent absorption studies related to permeation.
Free film thickness can be measured as described in ASTM
D1005, Test Method for Measurement of Dry-Film Thick-
ness of Organic Coatings Using Micrometers.
Probably the most common free film castings are laid
down on a nonstick surface, such as the silicone-coated
papers (available through Leneta and other suppliers),
Teflon
TV or Tef-
lon
l
= density of liquid,
f
= density of dry lm,
G = clearance of drawdown barmils, and
S = weight fraction of solids in liquid.
Grenko [3] makes the point that these relationships are only
true for drawdown blades having substantial flat surface
between the leading edge of the bar and the trailing edge.
The Byk-Gardner information [18] suggests the following
expectations for cast films of varying thickness:
15 to 100 m
50 %
100 to 300 m
60 %
300 to 500 m
80 %
over 500 m
90 %
The hand-held drawdown bars are covered in an ASTM
specification, Method E in ASTM D832, Standard Practice
for Rubber Conditioning for Low Temperature Testing.
A wide variety of drawdown bars are commercially
available, and your local machine shop can make special
orders of any design, if needed. Table 1 lists a few of the
available types of drawdown bars, with commercial sources
of some suppliers. Some rectangular design devices have
differing gap depths on the sides so one may choose the
film thickness needed for casting (see Figs. 4 and 5).
Stainless steel or aluminum are the preferred materi-
als of construction, as corrosion can damage the region
of the drawbar controlling thickness of applied film. Good
laboratory practice dictates immediate cleaning of the paint
contact surfaces after every usage to minimize the threat of
corrosion or other damage. A caution on marking the draw
down bars, as some manufacturers label them not with the
gap spacing, but a number half the gap spacing since that is
the expected wet film thickness to be obtained.
TABLE 1Drawdown bars for film casting
Type Design Details Supplier
a
Reference
Bird knife Permanent fixed gap Byk-Gardner 3
Two-path applicator Bar has two cuts of different depth machined into top
and bottom
P. N. Gardner 20
Eight-path applicator Stainless-steel square tube with eight different depth cuts
in each of top and bottom edges
P. N. Gardner 20
Gardner Microm applicator (also
Hercules-Gardner adjustable [3])
Micrometers on each side lower or raise blade of U
shaped device
P. N. Gardner 20
Universal blade applicator Blade forms U shape with sides having slots and thumb
screws to raise or lower
P. N. Gardner 20
Dow latex film applicator U-shaped blade with wider cut for larger gap so second
cast film
Byk-Gardner 3
a
There may be many other suppliers, but only one is cited herein as a space-savings technique.
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CHAPTER 40 FILM PREPARATION FOR COATING TESTS 509
Some drawdown bars have film thickness adjustment
choices by micrometers or other techniques (see Table 1
and Fig. 6). When these are used, the settings should be
checked with feeler gages to make certain user wear has not
made them inaccurate. These also require dismantling and
cleaning after every use. If oil is used to inhibit corrosion
and make the mechanics move smoothly, make sure they
are rigorously cleaned of oil prior to usage.
Several drawdown bars have gradations of cuts into the
wet-film thickness controlling surfaces. For instance, the
Erichsen suppliers offer the Kruse Multi Clearance applica-
tor, having six to ten adjacent film strips of 10 to 200 m
in thickness for assessment of color yield, opacity, etc. (see
Fig. 7) [19]. A similar device, the Leneta TG19 Logicator,
is intended for hiding power and spreading rate measure-
ments. It is available from Gardner [20] and has eight
gates ranging from 2.65 to 10.4 mil in depth.
There are motorized film application devices specified
in Method C of ASTM D823, Standard Practices for Pro-
ducing Films of Uniform Thickness of Paint, Varnish, and
Related Products on Test Panels. The Model 509/1 Film
Applicator from Erichsen [19] may be fitted with any sort
of drawdown bar or blade (see Fig. 8). Speed of the motion
of the applicator may be preset, so the variation among
several samples may be minimized.
Two devices Grenko [3] included with drawdown bars
are more like bulk coating devices, as they do not require
putting down a puddle of coating before applying the blade.
Indeed, these devices contain the coating and apply it to a
stack of sheets, one sheet at a time as the sheets are pulled
out from underneath the device. One such device is the
Parks Film-O-Graph cylinder. One puts the cylinder on a
stack of Leneta charts or metal panels, fills the cylinder
with the coating, and pulls each sheet from underneath the
cylinder. A portion of the rim edge of the cylinder is milled
out to act as the gate to allow coating at a desired thickness.
One may even use it for very viscous coatings (even putty)
by forcing the fluid through the tube with a loose-fitting
plug from the top and wiping the bottom of the tube over
the substrate to be coated.
The second of the devices discussed was the Parks
Rapid coater. Paper sheets were stacked in the bottom of
a box with their ends out of a side slot at the bottom. The
box was then filled with coating fluid, and each sheet was
withdrawn individually. Grenko [3] noted that this was not
a precision device, but it was adequate for some purposes.
Grenko [3] also described the flat Parks Film-O-Graph,
which used a flat plate with spring clips to hold shims along
the sides of the sheet of substrate. One poured the coating
onto the substrate between the shims and used a bar such
as a ruler or other straight edge to doctor off the excess
and make the coating as thick as the shims. Bending of
the scraper bar by the very slightest amount would make
very thin films almost impossible, but for thick films (for
example, roof coatings), this technique worked well.
Some applicators are meant only for the wet film tests.
Two especially useful applicators for these are the sag test
devices and the wet hiding test devices. The latter, most
frequently the Pfund Cryptometers (available from Erich-
sen [19] and Byk-Gardner [20]), have black or white glass
(ceramic) beds over which a transparent wedged cover
levels the coating film (see Fig. 9). Although these devices
are quite hard, care in cleaning will assure they do not get
scratched. They must be stored carefully, wrapped, and
covered.
The sag test film casters in effect drawdown several
narrow films in gradations of film thickness. Many are
simply slotted U-shaped drawdown bars with variations in
slot depth from 1 to 6 mil, 3 to 12 mil, and 14 to 60 mil.
Fig. 5Multiple clearance applicatorEight film thickness
choices are available on one device. (Courtesy of Byk-Gardner
Inc.)
Fig. 4Applicator frame/step gap applicatorTwo film
thickness choices are available with this device. (Courtesy of
Byk-Gardner Inc.)
Fig. 6Fllm casting knifeMicrometers adjust the blade
clearance. (Courtesy of Byk-Gardner Inc.)
Fig. 7Multiple gap drawdown barSix or eight gaps are
machined along the same edge for casting side-by-side films
for comparison. (Courtesy of Erichsen GMBH & Co.)
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510 PAINT AND COATING TESTING MANUAL 15TH EDITION
However, the New York Paint Club Technical Committee
designed a special leveling test blade that had double
slots for each depth with a wide space between each set
of double slots [21]. Their slots are 1, 2, 4, 8 and 16 mil in
depth (see Fig. 10).
How a paint film drips or sags depends on the rheo-
logical characteristics, and the thickness of the coating that
first sags may be related to the gravity-applied shear stress
by the outer elements furthest away from the substrate on
that film. Other rheological factors (high shear viscosity,
ca. 10 000 s
1
, for instance) are also important in sag and
leveling. Sag test devices complying with ASTM D3730,
Standard Guide for Testing High-Performance Interior
Architectural Wall Coatings, and several federal specifica-
tions as well as the New York leveling test blades are avail-
able from Gardner [20] and Byk-Gardner [18].
Wire-Wound Rods
For very thin films, the wire-wound rods are quite useful
for quickly and easily applying films. The wire-wound rods
are simple rods of 12- or 16-in. (30- to 40-cm) length, of 1/4,
3/8, or 1/2 in. (0.63, 0.45, or 1.27 cm) diameter, with a spiral
wind of wire tight about 75 % to 80 % of the rod. Table 2
shows a selection of the wet film thickness that is obtained
from the rods with different wire diameter.
The film laid down with a wire-wound rod is almost
exactly a tenth the thickness of the wire winding. Strictly
speaking, as the film has the rod depart, there are ridges
in the film in the direction of travel of the rod. However,
these collapse to make a quite smooth film unless there is
rheological inhibition in the formulation or the coating is
very fast drying. This technique is quite effective to simulate
paper or can coating end products. There are industrial
production systems that employ wire-wound rods to meter
coatings onto roll substrates, as well.
Fig. 8Electrically driven drawdown deviceFour speeds may
be chosen to control drawdown rate. (Courtesy of Erichsen
GMBH & Co.)
Fig. 9Pfund crytometerThe white style shown is for black/
dark paints, while a similar black style is used for white/light
paints. (Courtesy of Byk-Gardner Inc.)
Fig. 10New York paint club leveling test bladeThe slotted
blades are for assessment of sag and leveling. (Courtesy of
Byk-Gardner Inc.)
TABLE 2Selected coating thickness
obtained from various wire-wound rods
Wire Wet Film Thickness
Size Diameter (in.) Mils Micrometers
2.5 0.0025 0.25 6.4
3 0.003 0.3 7.6
3.5 0.0035 0.35 8.9
4 0.004 0.4 10.2
4.5 0.0045 0.45 11.4
5 0.005 0.5 12.7
5.5 0.0055 0.55 14.0
6 0.006 0.6 15.2
10 0.01 1.0 25.4
20 0.02 2.0 50.8
30 0.03 3.0 76.2
40 0.04 4.0 101.6
50 0.05 5.0 127.0
60 0.06 6.0 152.4
70 0.07 7.0 177.8
80 0.08 8.0 203.2
90 0.09 9.0 228.6
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CHAPTER 40 FILM PREPARATION FOR COATING TESTS 511
A similar device called the spiral-film applicator is
available from Erichsen [19]. It is a wire-wound rod with a
perpendicular handle (see Fig. 11). It is available to apply
a film thickness of from 10 to 200 m in widths of 80, 150,
or 220 mm. Byk-Gardner offers a handle that attaches to
the ends of the wire-wound rod for lab film preparation as
well [18]. The Accu-Lab
100
( ) ( )
The CIE had defined perfect white as the perfect reflect-
ing diffuser, the ideal reflecting surface that neither
absorbs nor transmits light, but reflects all of it. Most
textbooks, Practice E308, and Ref. [15] provide examples
of the use of these equations. Because the fundamental
process is integration, for which summation is an approx-
imation, the process is usually referred to as tristimulus
integration.
If a large number of sets of reflectance data are to be
integrated for the same illuminant and observer, it is con-
venient to combine quantities such as S x ( ) ( ) by multiply-
ing them together and normalizing the products so that
k = 1. The resulting tristimulus weighting factors can then
be stored and used by multiplying them by whatever func-
tion R() is desired. The CIE has not tabulated or recom-
mended specific sets of tristimulus weighting functions, but
a substantial number can be found in Practice E308. They
may be used for wavelength intervals of 10 or 20 nm. For
closer intervals, such as 5 or 1 nm, the tables in Practice
E308, Ref. [15], or Refs. [16,18] should be used. For the
wavelength intervals of 10 or 20 nm, the raw spectral data
acquired by the instrument are affected by the spectral
bandpass error. This error is introduced because the spec-
tral bandpass must be of significant bandwidth to allow
sufficient energy to reach the detector. However, the spec-
tral data being reported has a theoretical zero bandwidth.
ASTM developed a Practice for Rectification of Spectro-
photometric Bandpass Differences (E2729). This Practice
outlines the methods that can be used to deconvolve, at
least in part, the spectral bandpass error of raw spectral
data acquired by abridged spectrophotometry.
Chromaticity Coordinates and Diagram
An important use of the CIE tristimulus values X, Y, and Z
is the calculation of coordinates describing the chromatic-
ity of a color, that is, its hue and chroma, ignoring its lumi-
nance or lightness. The CIE chromaticity coordinates x, y,
and z are computed from the tristimulus values X, Y, and Z
by dividing each of these by the sum X+Y+Z. Thus
x
X
X Y Z
+ +
y
Y
X Y Z
+ +
z
Z
X Y Z
+ +
Since x + y + z = 1, only two chromaticity coordinates
need be given; usually they are x and y. These chromaticity
coordinates can be plotted to yield the 1931 CIE x, y chro-
maticity diagram, shown in Fig. 9, or the 1964 CIEx
10
,y
10
diagram for the Supplementary Standard Observer; the two
are quite similar.
Features of the chromaticity diagrams include: (1) the
locations of the spectrum colors around the horseshoe-
shaped spectrum locus, from 400 nm (violet) at the lower
left to 700 nm (red) at the right; (2) the straight line along
which purples lie joining these two ends of the spectrum
locus; and (3) the location of whites (illuminant points)
near the middle of the diagram. As an alternative to the
three tristimulus values, colors can be specified by the chro-
maticity coordinates x and y together with the luminance
Y (or their equivalents in the 1964 system). These can be
arranged in a three-dimensional color space.
Other Features of the CIE System
Dominant Wavelength, Complementary Wavelength,
and Purity
Dominant wavelength is defined as the wavelength along
the spectrum locus at the end of a line drawn from the
white point (usually Illuminant C) through the sample
point to the spectrum locus. For purple colors where the
line would end at the purple locus, it is extended back
through the white point to the spectrum locus, and the
wavelength at that point is designated as the complemen-
tary wavelength of the sample. The fractional distance from
the white point to the sample point relative to the distance
to the spectrum or purple locus is called the (excitation)
purity of the sample. Dominant wavelength correlates well
with the hue of the sample, but purity does not correlate
well with any perceived quantity and is rarely used today.
Fig. 9The CIE 1931 x, y chromaticity diagram showing the various
features described in the text.
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544 PAINT AND COATING TESTING MANUAL 15TH EDITION
Blackbody Locus, Color Temperature, and Correlated
Color Temperature
When a metal, such as a lamp filament, is heated, it first
radiates heat in the infrared region, then light with a chro-
maticity at the red corner of the diagram. As it gets hotter,
the chromaticity shifts through the oranges and yellows.
The line along which these chromaticities lie for perfect
absorbers and emitters of radiation is called the blackbody
locus and is shown in Fig. 9. If the metal did not melt, its
color would continue along this locus through white to light
blue at infinitely high temperature. The temperature of a
perfect blackbody can be correlated with its chromaticity
and is called the color temperature of the body. It is mea-
sured in kelvins, K; the color temperature of Illuminant A
is, for example, 2856 K. Many light sources, including the
phases of daylight and fluorescent lamps, have chromatici-
ties that are close to, but not on, the blackbody locus. In
that case, the color temperature closest to the chromaticity
of the source is used and called its correlated color tem-
perature. An example is Standard Illuminant D65, with a
correlated color temperature of 6500 K.
Uniform Color Spaces
From almost the beginning of the CIE system, it was rec-
ognized that distances in the CIE space did not correlate
well with visual estimates of the magnitudes of color differ-
ences. Many proposals have been made for deriving quanti-
ties that are more uniformly visually spaced. In 1976, the
CIE recommended two more nearly uniform color spaces
that, although not perfect, have been widely used. Here we
describe the one that is most widely used in the paint and
related industries and mention briefly the second, more
useful, when colored lights are considered. The equations
for these two spaces, known by official acronyms CIELAB
and CIELUV, are found in Refs. [1,6,15] and in the Practice
E308.
CIE 1976 L* ,a*, b* (CIELAB) Space
CIELAB is an opponent-type color space, with a lightness
axis L*, a redness (positive values)-greenness (negative)
axis a*, and a yellowness (positive)-blueness (negative) axis
b*, all mutually perpendicular, as illustrated in Fig. 5. The
transformations from Y to L*, from X and Y to a*, and from
Z and Y to b* are all nonlinear, using cube-root functions.
The equations for these transformations are
L* = 116(Y/Y
n
)
1/3
16
a* = 500[(X/X
n
)
1/3
(Y/Y
n
)
1/3
]
b* = 200[(Y/Y
n
)
1/3
(Z/Z
n
)
1/3
]
X
X
Y
Y
Z
Z
n n n
, , 0.008856
where X
n
, Y
n
, and Z
n
are the tristimulus values of the illumi-
nant or white point. See Practice for Calculation of Color
Tolerances and Color Differences from Instrumentally Mea-
sured Color Coordinates (D2244) for alternate equations
when X/X
n
,Y/Y
n
, Z/Z
n
< 0.008856.
Because CIELAB does not have tristimulus values or
chromaticity coordinates as defined for the 1931 and 1964
CIE systems in Chromaticity Coordinates and Diagram, it
does not have a chromaticity diagram.
An alternative set of CIELAB coordinates results in an
LCH cylindrical color space. L remains the same but a*
and b* are combined to give a chroma C* and a hue angle
h (measured in degrees)
C a b h b a
* * * * *
( ); ( / ) +
2 2 1
tan
These correlate well with visual judgments of lightness,
chroma, and hue, respectively. Perhaps the widest use of
CIELAB is in the calculation of color differences (see Color
Difference Calculations).
CIE 1976 L*,u*,v* (CIELUV) Space
The CIELUV space has a chromaticity diagram with coor-
dinates u and v, which are linear transformations of x and
y, respectively. The linearity is important for the additive
mixing of colored lights (see Additive Mixing of Lights). For
the three-dimensional CIELUV space, these are combined
with the (nonlinear) L* transformation to give opponent-
type axes u* and v*, whose meanings are the same as those
of CIELAB a* and b*, respectively. An alternative set of hue
angle and chroma coordinates, like those in CIELAB, and
a color-difference equation, much less widely used than the
CIELAB equation, are also part of this system.
COLOR ORDER SYSTEMS
A color order system is a rational method or plan of order-
ing and specifying all producible object or display colors, or
all within a limited domain, by means of a set of physical
standards selected and displayed so as to represent ade-
quately the whole set of such colors under consideration.
In this section the major color order systems, which have
physical exemplifications or atlases illustrating underlying
systems, are briefly discussed. References [19, 20] provide
useful general coverage.
Munsell System
Dating from the early 1900s, the Munsell system is accepted
by most users as the standard for equal visual spacing. It is
described in the Practice for Specifying Color by the Mun-
sell System (D1535). Its color solid is like that of Fig. 4 with
the sole exception that lightness is called value in the Mun-
sell system. Munsell Hue is designated by position around
the hue circle in a notation combining letters designating
five major hues (red, yellow, green, blue, purple) and their
pairs (R, YR, Y, GY, G, BG, B, PB, P, RP) with numbers
from 1 to 10. Munsell Value, to which CIE lightness L*
is a good approximation, runs from zero for black to 10
for white. Munsell Chroma, which expresses the degree of
departure of the color from the gray of the same lightness,
starts at zero and is open-ended. To describe a color in the
Munsell system, the hue, value, and chroma are noted in a
prescribed sequence, as for example, 8R 4/10. This designa-
tion indicates that the hue is red (toward yellow-red, i.e., an
orange color), the value is 4, and the chroma is 10.
In 1943, the underlying Munsell system was defined
in colorimetric terms [21], and since 1968 the chips in the
glossy editions of the Munsell Book of Color have been pro-
duced to match these specifications. Fig. 10 shows contours
of equal Munsell Hue and Chroma at value 5 on the 1931
CIEx,y chromaticity diagram.
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CHAPTER 43 COLOR AND LIGHT 545
The Munsell Book of Color [22], which is available in
the United States, exemplifies the Munsell system.
ISCC-NBS System
In the 1950s the Inter-Society Color Council (ISCC) and
the National Bureau of Standards (NBS) developed the
ISCC-NBS Method of Designating Colors [23] based on the
Munsell system but grouping similar colors to produce a
smaller number (267) of categories. These are designated
by descriptive color names, for example, dark reddish
orange for the group containing 8R 4 /10.
Universal Color Language
The Munsell system and the ISCC-NBS system are both
parts of a Universal Color Language [23], a six-level sys-
tem for describing color to any desired degree of accuracy.
Level 1 consists of the use of 13 hue and neutral names.
At this level, the color with Munsell notation 8R 4/10
would be described as orange. In Level 2, which has 29
categories, intermediate hue names are added. Here the
color would be described as reddish orange. Level 3 is the
ISCC-NBS system, and Level 4 is the Munsell system as
used in the Munsell Book of Color; designations at these
levels are given above. Level 5 uses interpolated Munsell
notations based on visual comparison of the color with
Munsell Book chips. With practice it is possible to inter-
polate accurately to 1/10 value step, 1/4 chroma step, and
from 1 hue step at chroma /2 to 1/4 hue step at chroma
near /10 and above. Thus, at this level the color might be
designated very accurately as 8.25 R 4.1/9.75. The final
stage, Level 6, of the Universal Color Language is based on
the results of color measurement, expressed as CIE chro-
maticity coordinates x,y, and Luminance Y. Now the color
might be specified with greatest accuracy as x = 0.527,y =
0.343, Y= 12.5.
DIN System
The DIN Color System is the official German Standard
Color System [24]. Its coordinates are hue (for which domi-
nant wavelength is used), saturation (like chroma except
representing difference from black instead of from gray of
the same lightness), and relative darkness. From time to
time, atlases of DIN samples have been available in glossy
and matte finish and in transparent films. In the former
Fig. 10Lines of constant Munsell Hue and closed curves of constant Munsell Chroma, at Munsell Value 5 plotted on the CIE 1931 chromatic-
ity diagram.
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546 PAINT AND COATING TESTING MANUAL 15TH EDITION
two, chips are arranged on pages of constant hue, similar to
the Munsell arrangement.
NCS
Developed in the late 1960s and 1970s, the Natural Color
System (NCS) [25] is the national standard color order
system in Sweden and several other European countries.
It is based on an entirely different principle from that of
the other systems discussed, namely the resemblances of
colors to six imaginary elementary colors, unique red, yel-
low, green, and blue, and black and white. The four hues
are placed 90 apart on the hue circle. This does not lead to
visually equal hue spacing. Two opponent-type axes result,
perpendicular to the black-white lightness axis. The third
variable of the system is chromaticness.
In terms of resemblances, hue is defined as the resem-
blance of a color to the two nearest chromatic elementary
colors. For example, orange might be said to have 80 %
resemblance to red and 20 % to yellow; its hue notation
would be Y80R. Chromaticness is the resemblance of the
color to the (imaginary) color of the same hue having the
maximum possible chromatic content. Lightness is not an
explicit variable in the system; the third resemblance can
be to either white or black. Scales of resemblances to white,
black, and the aforementioned maximally chromatic color
are chosen so that these three add to 100 %, so only one of
the resemblances to white or black need be specified. For
the notation, resemblance to black has been selected, so
that the three variables of the system are blackness, chro-
maticness, and hue. The complete NCS notation for the
orange sample considered above in the Munsell system is
approximately 3070 Y80R.
In the NCS atlas, pages of constant hue notation con-
tain chips arranged on a grid in the form of an equilateral
triangle. The corner points of the NCS triangles are imagi-
nary elementary colors.
OSA-UCS System
The Optical Society of American Uniform Color Scales
(OSA-USC) system [26,27] was developed by a committee
of the OSA between 1947 and 1976. Although the com-
mittee concluded that no perfectly equally visually spaced
system can exist because color space itself is not Euclidean,
it attempted to achieve the best possible compromise and is
generally thought to have succeeded. The axes of the color
solid are lightness, L (with both positive and negative values
around zero at middle gray) and two opponent axes, j (from
the French jaune for yellow), with positive values toward
yellow and negative values toward purple-blue, and g (for
greenness), with blue-greens at the positive end and pinks
at the negative end.
The OSA-UCS system in described in Practice for
Specifying Color by Using the Optical Society of America
Uniform Color Scales System (E1360). The 558 samples
of the OSA atlas are arranged in a rhombohedral lattice in
which each sample, except those at the edges, has 12 near-
est neighbors.
COLORCURVE SYSTEM [28]
This new color order system was introduced in the United
States in 1989. It is based on a color space similar to CIE
1964 tristimulus space [29]. Aim points are laid out accord-
ing to additive mixing (see Additive Mixing of Lights) of
CIE 1964 tristimulus values X
10
, Y
10
, Z
10
for Illuminant D65,
starting from eight specified CIELAB points. The CIELAB
lightness axis L (designated only as L) is retained, but coor-
dinates along the CIELAB-type opponent axes are replaced
by a simple numbering system, giving the sample location
in terms of the number of lattice steps between it and the
neutral axis in the directions of two adjacent major axes
directed toward reds, yellows, greens, and blues. A typi-
cal Colorcurve notation would be L40 R1Y3 representing
at lightness level 40 the lattice point one step away from
neutral toward the reds and three steps toward the yellows.
This is an orange, only slightly different from the sample
discussed above.
Another feature of the Colorcurve system is that
spectral reflectances are furnished for the aim points.
These can be additively mixed like tristimulus values to
obtain the spectral curve corresponding to any Colorcurve
notation; this can be the basis for computer colorant for-
mulation (see Instrumental and Computer-Aided Color
Matching) to provide a match with minimum metam-
erism to the surrounding Colorcurve samples. Practice
for Specifying and Matching Color Using the Colorcurve
System (E1541) describes the system in more detail,
including a tabulation of spectral reflectances, tristimu-
lus values, and CIELAB coordinates for the sample aim
points.
3
The Colorcurve atlas [30] contains about 2,200
painted samples.
Color Collections
For each of the color order systems described above, atlas
samples consist of painted chips individually matched to
the specified aim points with a mean accuracy of about
one CIELAB unit. A number of color collections have
been produced by coating paint on paper, printing, mold-
ing plastic chips, and dying textiles. A colorist may be
required to match these collections. Painted samples are
probably the easiest to match because of the similarity of
pigments and resins. Plastic samples can present problems
because they are often translucent. However, many of the
pigments used in plastics are similar to paints and may be
fairly easy to match. Printed samples are often very dif-
ficult to match. Most are at incomplete hiding and have
high chromas because they are printed over white (possi-
bly fluorescent) paper. It may be impossible to achieve the
high chromas in a conventional paint system at complete
(or nearly so) hiding. The color reproducibility achieved
by printing is usually significantly lower than can be
achieved with a paint system. Textile samples are made by
dying fabric. It may not be possible to match the spectral
curve of a dyed fabric with the pigments used in a paint
system.
Single-Number Color Scales
Occasions arise in which the colors of samples vary along a
single direction in color space. In such a case the color can
be described adequately by a single scale value. Three cases
are of interest: whiteness, yellowness, and series ranging
from colorless to highly colored as the concentration of a
colored component increases.
3
E1541 was withdrawn in 2007 after production of the Colorcurve
atlas and related materials ceased. This section is included for his-
torical purposes.
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CHAPTER 43 COLOR AND LIGHT 547
Whiteness and Tint Indices
Whiteness scales start at the point corresponding to an
ideal white, which may be the perfect reflecting diffuser
(see Calculation of Tristimulus Values) or some other
industry standard, often assigned a whiteness of 100.
Practice for Calculating Yellowness and Whiteness
Indices from Instrumentally Measured Color Coordinates
(E313) extends the equations recommended by the CIE [15]
to Illuminants C and D50. The equation for the whiteness
index is
WI = Y + (WI,x)(x
n
x) + (WI,y)(y
n
y)
where:
Y,x,y = the luminance factor and the chromaticity coor-
dinates of the specimen,
x
n
and y
n
= the chromaticity coordinates for the CIE
standard illuminant and source used, and WI,x and WI,y =
numerical coefficients.
The whiteness index is valid only for specimens with 40
< WI < (5Y280).
E313 also includes a tint index
T= (T,x)(x
n
x) (T,y)(y
n
y)
where the symbols have meanings analogous to those for
the whiteness index.
The tint index is valid only for specimens with 3 < T
< +3.
Values for all the coefficients, except those measured
for the specimen, are given in Table 3.
Yellowness Indices
Yellowness indices show the departure of a specimen from
achromatic toward yellow. The yellowness index described
in Practice E313 is calculated using the equation
YI
C X C Z
Y
X Z
100( )
Values for all the coefficients, except those measured for the
specimen, are given in Table 4.
This equation supercedes the one given in the ASTM
Test Method for Yellowness Index of Plastics (D1925),
which has been withdrawn.
Scales for Liquids
When only a limited range of color is involved, for example,
in the testing of the color of oil, clear varnish, lacquer, or
solvents used in the paint industry, simple methods are used
consisting of comparison of the specimen with standard
colored solutions or glasses ranging from colorless to highly
colored. A standardized series of these colors is used to pro-
vide a specialized color scale. The color is often a measure
of concentration of an ingredient. One difficulty in the use
of these special color scales is that the color of the specimen
may not match that of the standard; this can make rating on
a single-number scale difficult. Nevertheless, their simplicity,
low cost, and adaptability to special situations has resulted
in wide use of single-number scales for certain applications.
Scales useful to the paint industry are shown in Table 5.
Test Method D6045 is an instrumental version of Test
Methods D1500 and D156. Practice E313 can be used to
determine the whiteness and yellowness indices of trans-
parent liquids. A number of single-number color scales
were compared by Johnston [31].
INDUSTRIAL COLOR MEASUREMENT
Instruments Using the Eye as Detector
The eye is the ultimate arbiter in color evaluation because,
of course, it is the means for making the final judgment
on the acceptability of a color. The first color-measuring
instruments used the eye as a detector. This practice is still
followed when use of a simple color comparator suffices, as
in many of the test methods for single-number color scales
described in the preceding paragraph. But there are many
factors, such as fatigue, poor color memory, and subjectivity,
as well as the perceptual phenomena described earlier under
TABLE 3Coefficients for the Equations for CIE Whiteness Index and Tint
CIE Standard Illuminant and Observer
Value C, 1931 D
50
, 1931 D
65
, 1931 C, 1964 D
50
, 1964 D
64
, 1964
x 0.3101 0.3457 0.3127 0.3104 0.3477 0.3138
y
n
0.3161 0.3585 0.3290 0.3191 0.3595 0.3310
WI,x 800 800 800 800 800 800
WI,y 1700 1700 1700 1700 1700 1700
T,x 1000 1000 1000 900 900 900
T,y 650 650 650 650 650 650
TABLE 4Coefficients of the Equation for Yellowness Index
CIE Standard Illuminant and Observer
Value C, 1931 D
65
, 1931 C, 1964 D
64
, 1964
C
X
1.2769 1.2985 1.2871 1.3013
C 1.0592 1.1335 1.0781 1.1498
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548 PAINT AND COATING TESTING MANUAL 15TH EDITION
Perception, that make the eye at least suspect for close
color evaluation work. Therefore, the use of the eye as a
detector has been almost entirely replaced by the use of
two types of photoelectric instruments developed since the
1940s for color measurement.
Spectrophotometers
Spectrophotometers provide the spectral reflectances (or
transmittances) required for the calculation of CIE tris-
timulus values and derived color coordinates, which were
described earlier under Colorimetry and the CIE System
and in Practice E308.
When radiation strikes a sample, it may be reflected,
absorbed, or transmitted. Each of these can be measured
by most spectrophotometers. All spectrophotometers con-
sist of a light source, a monochromator, arrangements for
illuminating and viewing the sample, a photodetector, and
an output device. In modern instruments, the latter consists
of a computer that processes the signals from the detector
and provides for the calculation of tristimulus values and a
wide variety of other color-related quantities. Each of these
components is described briefly.
The Illuminator
The illuminator is that part of a spectrophotometer that
provides the illuminating beam on the specimen, includ-
ing the source, occasionally a monochromator or spectral
filters, a diffuser such as an integrating sphere, if used, and
associated optics. In most cases the exact nature of the light
source in a spectrophotometer is of little importance as long
as it has adequate power and stability at all wavelengths in
the visible spectrum. Incandescent lamps or xenon flash
tubes are widely used. When fluorescent samples are mea-
sured (see Fluorescence), the source must illuminate the
sample directly and may be filtered to simulate a standard
source, such as CIE daylight D65. Most color measuring
spectrophotometers are designed with these features. Prac-
tice E991 provides more information on the measurement
of fluorescent samples.
Illuminating and Viewing Geometry
In most spectrophotometers, the geometry of sample illu-
mination and viewing follows CIE recommendations [15].
Two standard geometries are widely used. In hemispheri-
cal geometry, light from the source usually illuminates the
white interior of a hollow, approximately spherical cavity
called an integrating sphere, and the diffused light from
the sphere illuminates the sample from all angles in the
hemisphere bounded by its surface. The sample is viewed
at an angle near the normal or perpendicular to its surface.
If the sample is glossy, the specular or mirror reflection
from its surface will result in a portion of the wall of the
integrating sphere also being viewed. The user is given
the option of making this part of the sphere white, thus
including the specular component, or black, excluding it
(Fig. 11).
In bidirectional geometry, illuminating and viewing
are at angles along the normal to the sample surface (desig-
nated 0) and 45 from the normal, or the reverse (Fig. 12).
The use of bidirectional geometry with the specimen illu-
minated by white light is recommended when fluorescent
samples are measured. Hemispherical and bidirectional
geometries are described in the Guide for Selection of
Geometric Conditions for Measurement of Reflection and
Transmission Properties of Materials (E179) and in Prac-
tice E1164, as well as by the CIE [15].
In typical 45/0 or 0/45 geometry, several illuminating
or viewing beams, distributed around the azimuth at 45 to
the normal, may be used. When a specimen exhibits direc-
tionality, that is, its reflectance changes when it is rotated in
its own plane, the use of an instrument with multiple beams
provides data that average over the directionality, giving a
single number characteristic of the average properties of
the specimen. If it is desired to measure the directionality,
an instrument with one illuminating (or viewing) beam, or
two 180 apart in azimuth, should be used and measure-
ments made at several different specimen orientations.
TABLE 5ASTM standards on scales for
liquids
Designation Title
D156 Test Method for Saybolt Color of Petroleum
Products (Saybolt Chromometer Method)
D365 Guide for Soluble Nitrocellulose Base Solutions
D1209 Test Method for Color of Clear Liquids
(Platinum-Cobalt Scale)
D1500 Test Method for ASTM Color of Petroleum
Products (ASTM Color Scale)
D1544 Test Method for Color of Transparent Liquids
(Gardner Color Scale)
D1686 Test Method for Color of Solid Aromatic
Hydrocarbons and Related Materials in the
Molten State (Platinum Cobalt Scale)
D5386 Test Method for Color of Liquids Using
Tristimulus Colorimetry
D6045 Test Method for Color of Petroleum Products
by the Automatic Tristimulus Method
D6166 Test Method for Color of Naval Stores and
Related Products (Instrumental Determination
of Gardner Color)
Fig. 11A representation of the CIE hemispherical geometry.
Light illuminates the integrating sphere to diffusely illuminate the
sample. The receiver is placed slightly off of the normal so that the
specular reflection can be either included or excluded during the
measurement.
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CHAPTER 43 COLOR AND LIGHT 549
For the measurement of specimens exhibiting gonio-
appearance, in which the reflectance changes when the
illuminating or viewing angles are changed, the use of
special instruments capable of measuring at different com-
binations of these angles is required. Several such multi-
angle instruments, known as goniospectrophotometers, are
commercially available (Fig. 13). See the earlier section on
Gonioappearance.
The Receiver
The receiver converts the light reflected or transmitted by
the specimen into an electrical signal and includes all the
optics necessary to focus the light onto a photodetector.
The optics in the receiver direct the light to the spectral
analyzer in which a narrow (typically 10 to 20 nm) band of
wavelengths is selected from the full spectrum of the inci-
dent light. The spectral analyzers in modern instruments
usually use holographic diffraction gratings or interference
filters to isolate the narrow wavelength range. Spectral
light is received by the photodetector, usually a silicon
photodiode. The photo-detector may consist of an array of
diodes, each positioned permanently to receive light of a
given wavelength, thus eliminating the need for a spectrum
scanning device. The electrical signal from the detector is
usually amplified, digitized, and entered in an interfaced
computer. In addition to Practice E1164, the following
ASTM test methods cover the operation of modern spectro-
photometers: Test Method E1331, Test Method E1348, and
Test Method E1349.
Spectroradiometers
Instruments closely related to spectrophotometers but
made to measure light incident from external sources are
known as spectroradiometers. They could be used in the
paint industry when, for example, the specimen must be
sensed remotely after being illuminated externally to the
instrument. Methods for making such measurements are
described in Test Method for Obtaining Colorimetric Data
From a Visual Display Unit by Spectroradiometry (E1336),
Practice for Obtaining Spectroradiometric Data from Radi-
ant Sources for Colorimetry (E1341), and Practice for
Obtaining Colorimetric Data from a Visual Display Unit
Using Colorimeters (E1455).
Obtaining Tristimulus Values from Spectral Data
The first step in utilizing spectral data is the calculation of
CIE tristimulus values, as described earlier under Calcula-
tion of Tristimulus Values. This step is performed automati-
cally as part of the measurement sequence in all modern
spectrophotometers designed for color measurement. It is
usual that the spectral bandpass of the monochromator and
the measurement interval are selected to be the same. For
highest accuracy, the correct set of tristimulus weighting
factors, corresponding to the instrument bandpass, selected
from among those added to the Practice E308 in 1994
(Table 6), must be used in calculating tristimulus values. In
addition, the user must select the standard illuminant and
the standard observer used.
Spectrocolorimeters
Some spectrophotometers are designed so that the mea-
sured spectral reflectances or transmittances cannot be
accessed for examination; only the resulting tristimulus
values and other color coordinates can be printed out. Such
instruments are designated spectrocolorimeters.
Tristimulus (Filter) Colorimeters
Among the earliest photoelectric color-measuring instru-
ments were those in which the source-filter-photodetector
combinations duplicate the tristimulus functions of the
Standard Observer and a CIE Standard Illuminant, usually
Illuminant C [32]. How well their filters are designed and
matched to the spectral characteristics of the source and
of the detector determines how accurately the instrument
performs. Today a high degree of accuracy is attained in the
resulting tristimulus values.
Because of their ease of operation, good precision,
and relatively low cost, tristimulus (filter) colorimeters
had found wide application for industrial control. They are
used primarily as color-difference meters to evaluate the
difference in color between a production specimen and a
standard of similar spectral character. This last limitation
is important for most colorimeters. Because of their design,
Fig. 12A representation of the CIE 45/0 bidirectional viewing.
Light illuminates the sample from an angle of 45 and the receiver
views the light reflected from the sample along its normal. The posi-
tions of the illuminator and receiver can be reversed to obtain the
0/45 illuminating/viewing geometry. For non-directional specimens,
the two measurements will be equivalent.
Fig. 13A representation of a multiangle instrument (goniospec-
trophotometer) for measuring materials containing metallic flake
pigments. One illuminating angle and three viewing angles are suf-
ficient for these materials. To characterize interference pigments, at
least two illuminating angles are required.
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550 PAINT AND COATING TESTING MANUAL 15TH EDITION
most colorimeters provide colorimetric data for only one
combination of illuminant and observer and therefore can-
not detect metamerism. When specimens are metameric,
a colorimeter can give incorrect data on the differences
among them. Filter colorimeters should not be used to eval-
uate pairs of specimens that may be metameric. This limita-
tion should be clearly understood. As a result of improved
technology and lower costs, most tristimulus colorimeters
have been replaced by spectrophotometers.
The use of colorimeters is described in Test Method
E1347.
Selection and Calibration of Instruments
The potential user of color-measuring instrumentation must
carefully consider the selection of the proper instrument(s),
depending on his samples and measurement needs. Guide
E179 and Practice E805 address this topic. They should be
consulted, if possible, before the purchase of a new instrument.
The user of any color-measuring instrument must give
regular attention to its calibration. Appropriate calibration
standards, available from instrument manufacturers and,
in some cases, national standardizing laboratories, should
be obtained, maintained in good condition, and used at fre-
quent intervals in an established routine [33]. A collabora-
tive reference program [34] is available by means of which
a users instrument performance can be compared to that
obtained for the same samples by the color community as a
whole and by national standardizing laboratories.
With proper calibration and maintenance, modern
color-measuring instruments are capable of a repeatability
and reproducibility far greater than the repeatability with
which the samples themselves can normally be prepared for
industrial measurement. Thus, special care must be taken
to establish a highly reproducible method of paint sample
preparation and to establish by careful measurement and
periodic verification the uncertainties associated with this
step in the measurement process. ASTM standards perti-
nent to this topic are shown in Table 6.
The following two subsections apply mainly to spectro-
photometers.
Precision
The modern age of computer-interfaced color measur-
ing spectrophotometers began in the mid-1970s. By then
it had been clearly demonstrated that such instruments
could surpass the eye in the precision of color measure-
ment. In 1981 the short-term repeatability of instru-
mental color measurement was reported to be about 0.1
CIELAB unit of color difference [35] (see Color Difference
Calculations). By 2002 instrument manufacturers were
specifying the short-term repeatability for top-of-the-line
benchtop instruments to be in the neighborhood of 0.01
CIELAB units. In 1979 the average reproducibility within
a group of similar instruments was reported to be about
0.2 CIELAB units [36]. By 2002 instrument manufacturers
were specifying the inter-instrument agreement for top-of-
the-line benchtop instruments as less than 0.10. It should
be noted that the very low repeatability and reproducibility
numbers can only be achieved with stable standards at
a tightly controlled temperature. Note that 0.5 CIELAB
unit is approximately the smallest difference that can be
detected visually. Repeatability and reproducibility values
are published in the Precision and Bias section of Practice
E1164 and Practice for Calculation of Color Tolerances
and Color Differences from Instrumentally Measured Color
Coordinates (D2244).
Bias
This quantity, the difference between a measured result for
a standard sample and the result when it is measured in a
reference laboratory, is difficult to quantify for color mea-
surement where there are no absolute values. It is usual to
accept the results obtained in a national standardizing labo-
ratory as the reference. On this basis, when instruments are
selected to minimize differences in measuring geometry
and are properly calibrated and used, the average bias for
a group of standard samples can be as low as 0.5 CIELAB
unit [37]. In addition, the differences between the two sets
of measurements can be utilized effectively to model and
correct the systematic spectrophotometric errors leading to
the bias [38].
Commercial Instruments
Specific information about instruments published in a
manual such as this would almost certainly become obso-
lete by the time the manuscript is printed. For this reason,
detailed information on suppliers and their instrumenta-
tion is not included. Such information, including types
of instruments manufactured, their design features and
performance characteristics, can best be found by first
consulting buyers guides [39,40] that are revised annually.
Another useful source of information is the lists of exhibi-
tors at paint shows, such as the descriptions published
annually in the JCT Coating Tech. An additional source of
information on commercial instruments is the internet.
TABLE 6Standards pertinent to calibration
and maintenance of color-measuring
instruments
Designation Title
D3964 Practice for Selection of Coating Specimens
and Their Preparation for Appearance
Measurements
D5531 Guide for Preparation, Maintenance, and
Distribution of Physical Product Standards for
Color and Geometric Appearance of Coatings
E1164 Practice for Obtaining Spectrometric Data for
Object-Color Evaluation
E1331 Test Method for Reflectance Factor and Color
by Spectrophotometry Using Hemispherical
Geometry
E1345 Practice for Reducing the Effect of Variability
of Color Measurement by Use of Multiple
Measurements
E1348 Test Method for Transmittance and Color
by Spectrophotometry Using Hemispherical
Geometry
E1349 Test Method for Reflectance Factor and Color by
Spectrophotometry Using Bidirectional (45:0
or 0:45) Geometry
E2214 Practice for Specifying and Verifying the
Performance of Color-Measuring Instruments
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CHAPTER 43 COLOR AND LIGHT 551
Most color instrument suppliers maintain internet sites
with current information on their products and services.
Registered users can also obtain product updates and sup-
port. In contacting suppliers of instrumentation, the user
might request that they send literature, measure samples
sent them, or have a representative visit the user to dem-
onstrate the instrument. Another procedure is to negotiate
a rental-purchase contract. While some suppliers are reluc-
tant to negotiate such contracts, the procedure provides
users the opportunity to evaluate the instrument with their
own operators at their own facilities.
1. Portable instruments. In earlier times, production
samples had to be taken to a quality-control labora-
tory for evaluation. This procedure is still desirable
in some instances to permit control of such variables
as ambient light, temperature and humidity, and
atmospheric contamination. However, time can be
saved by making measurements on the production
floor using portable instruments. Many manufactur-
ers now supply portable spectrophotometers and
colorimeters that provide small size and light weight.
Some portable instruments perform nearly as well
as benchtop instruments. In many, the precision is
good, but limitations related to measurement geom-
etry may increase bias. If very small illuminated and
viewed areas are used, there may be an advantage in
that smaller portions of samples can be measured,
but averaging of multiple measurements (see Practice
E1345) may be required to obtain representative val-
ues for nonuniform samples.
2. Multiangle Evaluation. Several manufacturers now
supply instruments with multiangle geometry for
the measurement of gonioapparent samples, such as
those containing metal flake or pearlescent pigments.
For research in this field, a goniospectrophotometer
is required. For quality control, however, use of one
angle of illumination with several angles of view, or
several angles of illumination with one angle of view,
may suffice.
3. Location and Type of Use. For continuous processes,
online instrumentation is finding greater use. In addi-
tion, color measurement and computer-aided color
matching (see Instrumental and Computer-Aided Color
Matching) are used extensively at point-of-purchase
locations such as retail paint stores.
COLOR DIFFERENCE EVALUATION FOR
COLOR CONTROL
The color control of industrial paint products is generally
aided by color measurement, as described in the last sec-
tion. The instruments provide color coordinates of sample
and standard from which accurate measures of color differ-
ence may be derived. These data can also be used to estab-
lish color tolerances. Of course, color differences may also
be judged visually, and several ASTM standards address
this topic: Practice for Visual Appraisal of Colors and Color
Differences of Diffusely-Illuminated Opaque Materials
(D1729), Test Method for Evaluation of Visual Color Differ-
ence With a Gray Scale (D2616), and Guide for Selection,
Evaluation, and Training of Observers (E1499). This guide
also describes materials and methods for the testing and
evaluation of the observers color vision.
Color-Difference Calculations
In the 1931 and 1964 CIE systems, equal distances in differ-
ent parts of color space do not represent equally perceived
color differences. Although many proposals for more uni-
form color spaces have been made, an ideal uniform space
has not been and may not ever be devised. Sets of color
coordinates can be derived from tristimulus values that
correlate better with perceived color differences than do the
original CIE tristimulus values.
Modifications of CIE tristimulus values have been
proposed for more uniform color spaces. Those proposed
by Hunter [32], MacAdam [41-43], and the CIE [15] had
been widely use in the paint industry. The color-difference
equation based on the CIE 1976 L*a*b* (CIELAB) space
discussed earlier in Uniform Color Spaces and color-
difference equations based on that equation perform sig-
nificantly better than the Hunter and MacAdam equations
when compared to experienced visual color judgments. As
a result, the Hunter and MacAdam equations can no longer
be recommended.
The total CIELAB color difference, E
ab
*
, is given by
+ + E L a b
ab
* * * * /
[( ) ( ) ( ) ]
2 2 2 1 2
where
L L L
* * *
TRIAL STANDARD
a a a
* * *
TRIAL STANDARD
b b b
* * *
TRIAL STANDARD
It is convenient to express E
ab
*
in terms of differences in
the Munsell-type coordinates hue, chroma, and lightness,
but the hue angle h defined earlier in Uniform Color Spaces
does not have the same dimensions and scaling as chroma
C* and lightness L*. Instead of using h, it is necessary to
define CIELAB hue difference H* to combine with C*
and L*
( )
( )
( )
,
,
]
]
]
H E C L
ab ab ab
* * * *
/
2 2 2
1 2
Then
( )
( )
( )
,
,
]
]
]
E H C L
ab ab ab
* * * *
/
2 2 2
1 2
This method of computing H
ab
*
loses the information about
the sign of the hue difference (positive or negative) and can
be unstable for pairs of colors near the neutral axis. Alterna-
tive equations for determining H
ab
*
and its sign have been
proposed [44] that corrects both problems
( )
,
]
]
H s C C a a b b
ab ab B ab S B S B S
*
,
*
,
* * * * *
/
2
1 2
where
s a b a b S
S B B S
> 1 1 if , else
* * * *
in which the subscript B indicates the trial and the sub-
script S indicates the standard. The unit of CIELAB color
difference is two to three times the just perceptible color
difference.
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552 PAINT AND COATING TESTING MANUAL 15TH EDITION
In the use of color differences, it is important to exam-
ine the components of the color difference, such as L*, a*
and b*, or L*, C*
ab
, and H*
ab
, as well as E*
ab
itself.
The magnitudes and signs of these components can provide
valuable information on remedial action needed to bring
a production batch on shade. For near-neutral and pastel
colors, there are advantages to using the L*, *a, and *b
forms of the color-difference equation.
The interpretation of measured color differences
becomes more complex when the specimens are gonioap-
parent and measurements are made at several combina-
tions of illuminating and viewing angles. The quantitative
meaning of color differences as the angles change has not
yet been thoroughly studied.
Since the adoption of the CIELAB equations, a number
of new color-difference equations have been developed.
One of these, known as the CMC (l:c) equation [45,46], is
a modification of CIELAB that has improved uniformity
of visual perception of its color differences. The CMC (l:c)
equation has found widespread use in the coatings industry.
The CMC (l:c) equation modifies the L*, C*, and H*
components of the CIELAB color difference
j
(
,
,
\
,
(
(
+
j
(
,
,
\
E l c cf
L
l S
C
c S
L C
CMC
( : )
* *
2
,,
(
(
+
j
(
,
,
\
,
(
(
2 2
H
S
H
*
S
L
L
L
+
0.040975
0.01765
for L
*
*
*
( ) 1
16
S
L
< 0 511 16 .
*
for L
S
C
C
C
+
0.0638
1 + (0.0131
*
*
)
. 0 638
S S T f f
H C
+ ( ) 1
where
f
C
C
( )
( )
+
*
*
/
4
4
1 2
1900
T h = 0.56 + abs 0.2 cos( + 168 ) if 1644 < < 345 h
else
T = 0.36 + abs|0.4*cos(h + 35)|
in which abs indicates the absolute, i.e., positive value, of
the term inside the brackets.
The parameters l and c are to compensate for system-
atic bias or parameteric effects such as texture and sample
separation. The most common values for l:c are 2:1. The
parameter cf is a commercial factor [47] used to adjust the
total volume of the tolerance region so that accept/reject
decisions can be made on the basis of a unit value of the
tolerance.
In 2001 the CIE recommended an improved color-dif-
ference equation, CIEDE2000, based on the CIELAB color
space [48]. This equation has been shown to outperform
the CMC (l:c) equation [49]. CIEDE2000 is calculated from
L = L*
a = (1 + G) a*
b = b*
C a b + ( ) (
2 2
)
If b 0, then h = 180 (180/) arctan(a/b) 90 sign(b)
If b = 0, then h = 90 sign((a)
2
) 90 sign(a)
where sign is a function that returns the sign of the argument
and arctan is the inverse tangent function returning angles in
units of radians
G
C
C
+
j
(
,
,
\
,
(
(
0.5* 1
25
7
7 7
( *)
( *)
where C
*
is the arithmetic mean of the CIELAB C* values
for the pair of specimens (standard and batch).
L = L
B
L
S
C = C
B
C
S
( )
( )
( )
,
]
]
H s C C a a b b
2
S B S B S
where
s = 1 if a
S
b
B
> a
B*
b
S
, else s = 1
j
(
,
\
,
(
+
j
(
,
\
,
(
+
E
L
K S
C
K S
H
K
L L C C H
00
2
2 2
j
(
,
\
,
(
+
j
(
,
\
,
(
S
R
C H
K S K S
E
H
r
C C H H
2
00
E
00
2
The factors K
L
, K
C
and K
H
are correction terms for variation
in perceived color-difference due to the viewing conditions.
To obtain color-differences similar to CMC (2:1), set K
L
= 2
and K
C
= K
H
= 1.
S
L
L
L
+
( )
+
( )
1
50
20 50
2
2
0.015
,
]
]
]
30
275
25
2
exp
h
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CHAPTER 43 COLOR AND LIGHT 553
T = 1 [0.17 * cos(h 30)] + [0.24 * cos(2h)]
+ [0.32*cos(3h + 6)] [0.20*cos(4h 63)]
where h is the arithmetic mean of the CIELAB L values
for the pair of specimens (standard and batch). All angles
are in degrees. Take care calculating the mean hue-angle if
the color-difference pair has samples in different quadrants.
For example, a color-difference pair has hue angles of 30
and 300. The mean hue-angle for this example is 345. To
determine the mean correctly, calculate the absolute differ-
ence of the hue angles. If the absolute difference is larger
than 180 then add 360 to the smaller hue angle and divide
that sum by 2.
Color Tolerance
A valuable means of recording the experience gained in
the production of a given color is through the use of color
tolerances, expressed as numerical limits to E* and its
components or as color-tolerance charts. Because no color
space is entirely uniform, industrial color tolerances are
often based on acceptability, not perceptibility, consider-
ations between buyer and seller. General color differences
should be used only as a guide until enough experience has
been accumulated for each color to allow specification of a
firm tolerance limit.
Tolerance Charts
Color-tolerance charts are usually enlarged sections of a
nearly visually equally spaced diagram, such as the CIELAB
a*,b* diagram. A color-tolerance chart is set up with the
coordinates of the standard at the center, and the differ-
ences a* and b* of production batches are entered as
they are made (Fig. 14(a)). The process is described in Prac-
tice for Establishing Color and Gloss Tolerance (D3134). As
experience is gained, it should be possible to draw a toler-
ance-limit curve enclosing most, if not all, of the acceptable
batches and excluding most, if not all, of the unacceptable
batches. Because no known diagram is perfectly visually
uniform or if there is a preferred direction for the batches
relative to a standard, then the tolerance limit figure may
not be a circle or an ellipse and may not be centered on the
location of the standard.
Lightness differences between the standard and batch
must also be taken into account. This can be done by use
of a separate tolerance for L*, but better practice is to
use a second chart (Fig. 14(b)), in which L* is plotted
against either a* or b*, depending on the data. The
batch readings should fall within the tolerance figure on
both charts.
It must be emphasized that the final criterion for
acceptance of a color is always its visual appearance,
to which instrumental measurements, color differences,
and tolerance charts provide only clues. Instrument mal-
functions, miscalibrations, miscalculations, and operator
errors can be revealed only by use of confirming visual
observations.
Indices of Metamerism
Another important use of color-difference equations is to
quantify indices of metamerism as an aid in reducing this
defect between standard and batch. The CIE [15,50] has
recommended that indices of metamerism be calculated
as the color differences between two samples that match
under a standard illuminant or to a standard observer
when measured for a test illuminant or a test observer. For
illuminant metamerism, the standard illuminant is usually
daylight. The second observer is selected by the user and
is usually incandescent light. Often a third illuminant is
specified, which is usually a fluorescent lamp. For observer
metamerism, the standard observer is either the CIE 1931
or 1964 observer. To determine the index of metamerism,
a corresponding second standard deviate observer is pro-
vided [50] based on the range of normal color vision found
in the human population.
COLOR MIXING
Additive Mixing of Lights
When a white card is illuminated, its apparent color is the
color of the incident light; a red light, for example, makes
it appear red. Three colored lights (red, green, and blue),
if carefully chosen, would, when placed to overlap on the
same area of the card, produce white again (Fig. 15). In
this area, the reflected lights from the three sources add
together. These three lights are called the additive prima-
ries. By adjusting the intensities of each of the three lights,
a wide range of colors can be produced.
The procedure just described can provide an analytical
tool for color measurement. If an adjacent spot on the white
card is illuminated by light of an unknown color, it could
be matched visually, in principle, with the three-light com-
bination by adjusting their intensities. This is the basis for
color matching by addition of lights. The additive principle
is used to produce the colors in television and computer
monitors [51].
The analytical device described above is also a simple
version of the visual colorimeter used to generate the tri-
stimulus values of the spectrum colors that form the basis
for the CIE Standard Observers (see CIE Standard Observ-
ers). At each wavelength, the total light reflected is the
sum of the power reflected from each of the three primary
lights. Since tristimulus values are obtained by adding
such sums across the spectrum, they too are produced by
additive mixing. It is not necessary to know the spectral
nature of the additive primaries to predict the resulting
colors.
Subtractive Mixing in Transparent Films
Now consider the light falling on a white card after passing
through a film that contains three transparent colorants,
yellow, cyan (blue-green), and magenta (red-purple). This
might be the situation with a free-standing transparent
plastic film, for example. If the three colorants are ideally
chosen, all the light would be absorbed when all three colo-
rants are present, and the result would be black (Fig. 16).
These three colorants are called the subtractive primaries.
If varying quantities of them were combined in subtrac-
tive mixing, a wide variety of colors could be produced.
However, these mixture colors cannot be predicted from
the colors of the primaries alone, as in the additive mix-
ing described above. One must also know their spectral
character and compute, wavelength by wavelength, how
much light is removed by each primary through absorp-
tion, using the well-known Beers law relationship. From
what is not absorbed, tristimulus values can be calculated
in the usual way.
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554 PAINT AND COATING TESTING MANUAL 15TH EDITION
Pigment Mixing
Pigments are added to paints to produce a wide variety
of colors. The pigmentation is chosen to control the
three components of colorhue, lightness, and chroma.
Four pigments are needed to control the components.
Generally two pigments are used to control the hue, one
(a black or umber) to control the chroma and usually
a white to control the lightness. The white pigment is
also used as an opacifier. Mixing of colors using pig-
ments is more complex than simple subtractive mixing
in transparent films because of the scattering of light
caused by the pigments. Again, it is necessary to know
the spectral character of all the colorants present. The
Beers law calculation of the transparent case is replaced
by the Kubelka-Munk relation: For opaque films, as is
often the case in the paint industry, there are simple
equations relating the reflectance R() of the film at each
wavelength to the ratio of two constants describing what
happens to the light in the film
K S R R ( ) / ( ) [ ( )] / ( ) 1 2
2
R K S K S K S ( ) ( ) / ( ) [ ( ) / ( )] [ ( ) / ( )] + +
1 2
2
1 2 /
in which K() is the Kubelka-Munk absorption coefficient,
and S() is the Kubelka-Munk scattering coefficient. Here,
R() must be expressed as a decimal instead of the usual
percentage. The quantities K() and S() refer to the mix-
ture of pigments in the paint film. These are calculated by
adding the separate contributions of each pigment, using
its K() and S() weighted by its concentration C in the
mixture
K
S
C K C K
C S
( )
( )
[ ( )] [ ( )] ...
[ ( )]
MIXTURE
MIXTURE
+ +
1 1 2 2
1 1
++ + [ ( )] ... C S
2 2
in which there are as many terms as there are pigments
used. These equations form the basis for computer color
Fig. 14Color tolerance charts plotted in the CIELAB system: (a) chromaticity tolerance figure on a a*, b* diagram; (b) lightness tolerance
figure on a L*, a* diagram. In this case, a plot of L* versus b* would have served as well. (Based on ASTM D3134.)
Fig. 15Representation of the additive mixing of colored lights
showing the additive primaries red, green, and blue forming the
mixture colors yellow, cyan, and magenta where the primaries over-
lap in pairs and white where all three overlap.
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CHAPTER 43 COLOR AND LIGHT 555
matching described in the next section. The equations for
dealing with translucent films are more complex [52].
COLOR MATCHING
One of the major objectives of industrial coloring is to
match the color a customer wants. Whether this is done
visually or with the aid of instruments and computers is
often a matter of work load and economics. Therefore, we
address both visual and instrumental matching. In either
case, a major objective of color matching in paint systems
is the formulation of a nonmetameric match to a given
paint sample. The difference in spectral character of the
samples of a metameric pair is the property determining
their metamerism, and achieving a nonmetameric match
places several requirements on the formulation.
First, the same pigments must be used. This requires
identification of the pigments in the sample to be
matched. Second, the pigments must be used in the same
resin system since the spectral properties of pigments
can depend upon the choice of binder. Finally, the same
degree of dispersion must be achieved since the absorp-
tion and scattering properties of pigments that determine
their spectral character change with degree of dispersion.
This usually means that the same method of dispersion
must be used.
Visual Color Matching
The selection of visual color matchers should be made with
great care, and reference should be made to Guide E1499
for details of how to make the selection, test the color
vision of the candidates, and train them in making visual
judgments.
Beyond this there is no substitute for the experience of
the visual color matcher. He or she must learn the skill by
practice. This should include becoming familiar with one
of the better color order systems and atlases and learning
how to use it, coupled with knowledge of the behavior of
the paint system and pigments available, to predict the col-
ors that result from mixing them under carefully controlled
conditions. Careful record keeping to document the results
is essential. Visual methods of recognizing and controlling
metamerism have been described [53,54]. These require no
more than knowledge of the behavior in mixtures of the
pigments used and a good color matching booth (see Color
Matching Booths).
Instrumental and Computer-Aided
Color Matching
The importance of eliminating metamerism dictates that
the instrument of choice is clearly a spectrophotometer.
Display of the spectral curves of samples, and the computer-
aided color-matching operations that lead to spectral curve
shapes minimizing metamerism, cannot be achieved by
the use of other types of instruments. The spectrophotom-
eter can also be used in a simple but powerful method of
organic pigment identification [55] based on extraction of
the pigments into solution followed by spectrophotometry.
This can be an important aid to selecting the same pigmen-
tation for the match as was used in the standard.
Many modern color-measuring spectrophotometers
can be obtained with computer software for color match-
ing. Most of these systems work very well, but it must be
emphasized that the investment in building up the database
that is essential for their use, and in taking all the steps nec-
essary to bring the coloring process under precise control,
is not a small one.
The details of how computer color matching works are
beyond the scope of this chapter. In summary, most systems
call for measurement of the sample to put its spectral data
into the computer. These data are usually matched at each
of 16 or 31 wavelengths across the spectrum by Kubelka-
Munk-type calculations [56] using stored values of K() and
S() for the useful pigments in the product line. The results
are the pigment concentrations in the formulation. Several
formulations arising from mixing different pigments are
usually produced. Additional calculations of metamerism
indices and pigment costs allow the selection of the most
suitable results.
Computer color matching has been discussed in a book
[57], and some textbooks [1,2,5,58,59] provide useful sum-
maries. The underlying Kubelka-Munk theory, applied to
paint systems, has been the subject of a number of articles
[56,60-65] directed to paint colorists. More complex theory
appears to be needed only in special cases, such as match-
ing automotive paints containing metal flake or pearlescent
pigments. The development of such theories is still in its
early stages.
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rd
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magenta forming the mixture colors green, blue, and red where the
primaries are mixed in pairs and black where all three are mixed
together.
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556 PAINT AND COATING TESTING MANUAL 15TH EDITION
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Downloaded/printed by
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CHAPTER 43 COLOR AND LIGHT 557
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[62] Billmeyer, F. W., Jr., and Abrams, R. L., Predicting Reflec-
tance and Color of Paint Films by Kubelka-Munk Analysis, J.
Paint Technol. Vol. 45, No. 579, 1973; Part I, pp. 2330; Part
II, pp. 3138.
[63] Mudgett, P. S., and Richards, L. W, Kubelka-Munk Scat-
tering and Absorption Coefficients for Use with Glossy,
Opaque Objects, J. Paint Technol., Vol. 45, No. 586, 1973,
pp. 4353.
[64] Phillips, D. G., and Billmeyer, F. W., Jr., Predicting Reflec-
tance and Color of Paint Films by Kubelka-Munk Analysis. IV
Kubelka-Munk Scattering Coefficient, J. Coat. Technol., Vol.
48, No. 616, 1976, pp. 3036.
[65] Rich, D. C., Computer-Aided Design and Manufacturing of
the Color of Decorative and Protective Coatings, J. Coat.
Technol., Vol. 67, No. 840, 1995, pp. 5360.
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558
THE APPEARANCE OF THE SURFACE OF AN OBJECT
or material can be described by its color and gloss char-
acteristics. Like color, gloss can be subdivided into several
aspects depending on viewing conditions. In 1937, Hunter
identified five aspects of gloss [1] and the functions of
reflectance by which they could be evaluated. Later studies
by Lex [2] expanded Hunters gloss terms and divided them
into two groups. One group is based on visual observation
with the eye focused on the surface of the material (Fig. 1).
For the other group, the eye is focused on the image of the
object reflected by the material (Fig. 2). However, investiga-
tions have shown that no single objective measurement of
gloss will provide perfect correlation with the integrated
subjective appraisal of glossiness that the eye so quickly
renders. For this reason, the gloss evaluation requirement
of an object or material should first be examined and the
most useful gloss measurement aspects then selected.
ASPECTS OF GLOSS AND THEIR DEFINITION
The simple term gloss is defined in ASTM E284, Ter-
minology of Appearance [3] as angular selectivity of
reflectance, involving surface-reflected light, responsible
for the degree to which reflected highlights or images of
objects may be seen as superimposed on a surface. To
indicate specific types of angular selectivity, such as those
involving specular gloss (see below), sheen, or haze, and to
illustrate the difference between an evaluation where the
focus is on the surface and one where the focus is on the
reflected image, the complexity of the phenomenon gloss
is illustrated inFig. 3.
By focusing on the reflected image of an object, an
observer obtains information on the image forming capa-
bilities of the surface. A reflected light source may appear
brilliant or diffuse depending on the specular gloss of the
surface. The outline of a reflected object may appear dis-
tinct or blurred depending on the distinctness-of-image.
A halo surrounding the image of the reflected object is an
indication of haze. Focusing on the surface of an object
provides information on the size, depth, and shape of sur-
face structures contributing to such things as waviness or
directionality of brush marks.
Specular Gloss
Specular gloss is defined in ASTM E284 [3] as the ratio
of flux reflected in specular direction to incident flux for
a specified angle of incidence and source and receptor
angular apertures (Fig. 4). This aspect of gloss has been
measured most frequently because it is the one for which
an instrument is most easily constructed. In practice the
divergence angles of source and receptor are precisely spec-
ified in ASTM Test Method for Specular Gloss [4], D523, as
are the directional angles of incidence and reflection. Toler-
ances are specified for all angles. For simplicity, glossmeter
geometries are identified by reference to the incidence
angles, most frequently 20, 60, and 85. However, the
associated source and receptor aperture angles and their
tolerances play a vital role in determining the reproduc-
ibility of instrument readings. The measurement result is
dependent on the amount of light reflected in the specular
direction and the refractive index of the surface. ASTM
D523 Test Method for Specular Gloss [4] lists the gloss
values in dependence of the refractive index. A polished
glass with a refractive index of n = 1.550 has a maximum
20 gloss value of 95.4. If the refractive index changes to
n=1.510, the 20 gloss value will decrease to 84.7. There-
fore, gloss readings of materials with different refractive
indices, such as 1 and 2 K clear coat systems, will not corre-
late with the visual perception (Fig. 5). As long as the refrac-
tive index of the material does not change, a glossmeter will
give objective measurementresults.
Sheen
Sheen is defined in ASTM E284 [3] as the specular gloss
at a large angle of incidence for an otherwise matte speci-
men. The usual angle for sheen measurement is 85; from
the perpendicular to the specimen. This is about the maxi-
mum angle that can be used without encountering diffi-
culty in positioning the optics to illuminate and view the
specimen at near-grazing angles.
Haze
Haze of opaque products is called reflection haze, while
haze of transparent products is encountered as near-for-
ward scattering in transmission that is designated trans-
mission haze. ASTM E284 [3] defines haze in reflection as
percent of reflected light scattered by a specimen having
a glossy surface so that its direction deviates more than a
specified angle from the direction of specular reflection.
Distinctness-of-Image
This aspect of gloss is also referred to as image clarity.
ASTM E284 [3] defines distinctness-of-image gloss as the
44
Gloss
Gabriele Kigle-Bckler
1
and Harry K. Hammond III
2
1
Marketing Manager, BYK-Gardner GmbH, Lausitzerstrasse 8, 82538 Geretsried, Germany.
2
Consulting scientist, BYK-Gardner USA, 9104 Guilford Road, Columbia, MD 21046.
MNL17-EB/Jan. 2012
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CHAPTER 44 GLOSS 559
aspect of gloss characterized by the sharpness of images
of objects produced by reflection at a surface. During
visual observation, the sharpness of the light-dark edge of a
reflected object can be observed.
Waviness
One obvious type of waviness is designated orange peel.
ASTM E284 [3] defines orange peel as the appearance of
irregularity of a surface resembling the skin of an orange.
A surface may be described as exhibiting orange peel when
it has many small imperfections that are perceived as a
pattern of both highlighted and non-highlighted areas. This
pattern is interpreted by an observer as a three-dimensional
structure of peaks and troughs.
Directionality
ASTM E284 [3] defines directionality, perceived as the
degree to which the appearance of a surface changes as
the surface is rotated in its own plane, under fixed con-
ditions of illumination and viewing. A surface exhibits
directionality when specular gloss measurements are a
function of the direction for which measurements are
made. When paint is applied by brushing in one direc-
tion, the brush marks can cause the surface to have a
directional characteristic. Metallic materials frequently
exhibit directionality when the surface is polished in one
direction.
VISUAL GLOSS EVALUATION
Early investigations of gloss were carried out by observing
differences in the characteristics of images reflected in the
surfaces of specimens. In 1932, the Detroit Paint and Var-
nish Production Club [5] reported on investigations carried
out with their distinctness-of-image gloss comparator. In
1936, Hunter [6] reported an investigation where reflected
images of a target pattern were observed.
Only in comparatively recent times has there been
a major effort to investigate visual scaling of gloss and
to endeavor to develop correlation between visual and
instrumental measurements. ODonnell did a doctoral
thesis on visual gloss scaling at Rensselear Polytechnic
Institute, Troy, New York. Results were first presented,
in part, at an ASTM Symposium in 1984 [7] and more
fully in a journal article in 1987 [8]. In 1997, the DFO
(Deutsche Forschungsgesellschaft fr Oberflachenbe-
handlung) started a research project to investigate which
of the physically measurable parameters influence the
visual assessment of gloss. The conclusion of this study
was that the visual perception is influenced by scattered
light reducing the contrast and microstructures distort-
ing an objects outlines, which results in a lower sharp-
ness. Specular gloss measurement is dependent on the
refractive index of the material and the curvature of the
sample. Therefore, the visual assessment of gloss requires
Fig. 2Observer focuses on the illuminated surface of object.
Fig. 3Block diagram depicting relationships of various appearance characteristics.
Fig. 1Observer focuses on the image of reflected object.
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560 PAINT AND COATING TESTING MANUAL 15TH EDITION
a multi-dimensional description [9]. At about the same
time the ASTM committee E12 on Color and Appear-
ance started a new subcommittee, E12.14, on Multidi-
mensional Characterization of Appearance. The scope of
this subcommittee is to develop standards for visual and
instrumental assessment of appearance that address the
multiple dimensions of appearance. In the first step the
committee has conducted several round robin experi-
ments to judge distinctness of image both visually and
instrumentally [10].
Development of a Documentary Standard
In 1990, ASTM Committee D-1 on Paint and Related Coat-
ings and Materials published ASTM D4449, Method for
Visual Evaluation of Gloss Differences Between Surfaces
of Similar Appearance [11], for making visual evaluations
of gloss between surfaces of similar appearance. It uses
two types of light sources. One source consists of a tubular
fluorescent desk lamp modified by placing a matte-black
reflecting material behind the tubes and a coarse wire-mesh
screen in front. The directions of illumination and view can
be adjusted to be 20, 60, or 85 as desired for comparing
specimens having high gloss, intermediate gloss, or sheen.
The other light source is a clear-bulb incandescent lamp.
Light from the selected source illuminates the specimens
at the chosen angle. The sharpness of reflected images per-
mits a subjective comparison of the relative gloss of similar
surfaces.
Use of Landolt Rings to Visually Analyze
Distinctness of Image
Landolt rings have been used by ophthamologists to eval-
uate visual acuity for nearly a hundred years [12]. The test
consists of locating the gaps in a graduated series of sizes
of incomplete rings whose radial thickness and gap are
equal to one fifth the diameter of the ring. For gloss evalu-
ation of trans-illuminated rings, reflections are viewed on
a Mylar polyester film. Rings have different sizes and dif-
ferent gap orientations. An image-gloss scale is associated
with the different sizes of rings. An image-gloss scale
ranging from 10 to 100 in steps of 10 was established
for 11 sizes of rings from the largest to the smallest.
The development of the scale is not documented, but it
ostensibility took place in the General Motors Automo-
tive Division about January 1977. Visual observers select
the smallest size of ring for which they can call the gap
orientation correctly. The visual judgment is influenced
by the loss of contrast and sharpness of the outlines. The
numerical size of the rings is used as an inverse index of
distinctness-of-image gloss (Fig. 6). ASTM has not pub-
lished a method for visually evaluating distinctness-of-
image gloss by using Landolt rings, but equipment for this
purpose is available.
3
Visual Evaluation of Orange Peel
The automotive industry established a physical standard for
orange peel consisting of ten high-gloss panels with various
degrees of orange peel structure.
4
The panels are visually
ranked from 1 to 10 with Panel Number 1 depicting very
pronounced orange peel and Panel Number 10 illustrating
no orange peel. The visual observer can use these panels as
a supportive tool to evaluate degree of orange peel.
In order to understand this visual ranking it is impor-
tant to realize that our visual impression is influenced by
the structure size and the observing distance (Figs. 79)
INSTRUMENTAL MEASUREMENT TECHNIQUES
Specular Gloss Measurement
The design of many gloss meters is based on the precise
measurement of the specular component of reflected light
[13]. A light source, simulating CIE illuminant C, is placed
at the focal point of a collimating lens. The axis of the
collimated beam is set to the desired angle of illumina-
tion. A receptor lens with an aperture in the focal plane
followed by an illumination detector completes the basic
optical design (Figs. 10 and 11). The size of the receptor
aperture and the size of the source image in that aper-
ture are the elements that complete the optics and that
Fig. 4Reflected light flux distribution from a semigloss
surface is depicted by a broken curve. Three lines are shown
proceeding from the specimen surface. The center one depicts
the specular direction, the image of a ray reflected from a
mirror-like surface. The two other rays represent the range
of angles passing through the aperture (AP) to the detector
(shown as a rectangle).
Fig. 5Specular gloss is dependent on the refractive index of
the material: The 1 K and 2 K clear coat system look the same.
Due to the difference in refractive index the 2 K clear coat
system has a lower specular gloss value than the 1 K clear coat
system.
3
Apparatus for evaluating distinctness of image using Landolt
rings, available from Paul N. Gardner Co., Pompano Beach, FL.
4
Set of orange-peel panels can be obtained from Advanced Coatings
Technology, 273 Industrial Dr., Hillsdale, MI 49242.
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CHAPTER 44 GLOSS 561
determine the high, low, and intermediate gloss scale read-
ings.The specular angle largely determines the magnitude
of the reflected light. However, the tolerances assigned
to the source and receptor apertures are what determine
the accuracy and reproducibility of measurements made
with instruments having the same angles of illumination
andview.
Periodic calibration or verification of instrument per-
formance requires the use of calibrated gloss standards.
For permanence they should be made of glass or ceramic
material. ASTM D523 recommends the use of a primary
standard of polished black glass of known refractive index
for which the Fresnel (specular) reflectance [14] has been
computed for the angle of incidence of the geometry
for which the instrument is designed. Since about 1990,
national standardizing laboratories have preferred a pri-
mary reference standard made of a wedge of clear quartz.
Polished black glass working standards can be calibrated
by direct comparison of their reflectances with that of a
quartz wedge.
A single measurement geometry, such as 60, may not
provide instrument readings of gloss that correlate well
with visual observations when comparing different gloss
levels. This is why ASTM D523 [4] provides for measure-
ment at three different angles of incidence, namely 20,
60, and 85 (Fig. 12). Each of the three geometries uses the
same source aperture, but a different receptor aperture. The
choice of geometry depends on whether one is: (1)making
a general evaluation of gloss, (2) comparing high-gloss
finishes, or (3) evaluating low-gloss specimens for sheen.
ASTM D523 [4] states that the 60 geometry is used for
intercomparing most specimens and for determining when
the 20 or 85 geometry may be more applicable. The 20
geometry is advantageous for comparing specimens having
60 gloss values higher than 70. The 85 geometry is used
for comparing specimens for sheen or near-grazing shini-
ness. It is most frequently applied when specimens have 60
gloss values lower than 10.
The ASTM documentary gloss standard originally pub-
lished in 1939 contained only the 60 geometry [15]. The
desirability of using an auxiliary geometry of 85 for sheen
evaluation was recognized shortly afterward. However, the
use of another geometry with smaller angles of incidence
and view, such as 20, and a smaller receptor aperture to
provide improved differentiation of high-gloss finishes was
not published until 1947 [16]. The three geometries, 20,
60, and 85, were originally published as separate ASTM
standards. In 1953, ASTM D523 was revised to incorporate
all three geometries, and it still does.
Meanwhile, the Paint Committee of the International
Organization for Standardization, ISO TC-35, was inves-
tigating gloss measurements with various commercial
instruments prior to drafting an international standard. A
paper documenting what the committee had been doing
was published in 1976 by the Chairman of the Gloss Task
Group, Dr. Ulrich Zorll [17]. In 1978, the ISO Paint Com-
mittee published ISO 2813, essentially an international
version of ASTM D523 [18]. In keeping with the usual ISO
procedure, the standard was made available in English,
French, and German.
Instrument manufacturers report that measurement
precision, reproducibility, and data handling capabilities of
gloss meters have been improved markedly in recent years.
New instruments have been designed that are smaller, more
portable, and more convenient to use. Data storage and
analysis are frequently included as well as the capability
of electronically transferring data to a personal computer
[19,20].
Goniophotometry
Gonio means angle, and a photometer measures radi-
ance; so a goniophotometer is an instrument for measur-
ing the angular distribution of reflected or transmitted
light intensity. This type of instrument is often used in
the research laboratory to investigate the distribution of
light flux (Fig. 13). A goniophotometer with appropriate
apertures can also be used to provide gloss data for a wide
variety of angles and apertures. When goniophotometric
measurements are desired, reference should be made to
ASTM E167, Practice for Goniophotometry of Objects and
Materials [21]. Analysis of goniophotometric curves was
treated by Nimeroff [22].
Fig. 7Appearance changes with structure size.
Fig. 6Landolt Rings. Broken rings of various sizes are used
to provide a scale for visual evaluation of the distinctness of
surface-reflected images.
3
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562 PAINT AND COATING TESTING MANUAL 15TH EDITION
Measurement of Reflection Haze
Haze is a gloss parameter that causes a high-gloss sur-
face to appear milky and lighter, thereby losing contrast.
When visually evaluating the reflected image of a hazy
object, one observes halos around distinct reflection
outlines caused by scattered light. Haze can result from
various material or process parameters such as degree of
dispersion, flocculation, incompatibility of raw materi-
als (pigment-additive-resin), or from poor application
procedures.
Haze is most often associated with high-gloss surfaces
when small amounts of reflected light are scattered in a
region 1 to 4 from the direction of specular reflection.
Therefore, it is useful to place apertures several degrees
wide on each side of the specular receptor aperture
(Fig. 14). ASTM E430, Test Methods for Measurement of
Gloss of High Gloss Surfaces by Goniophotometry [23],
describes two methods for evaluating reflection haze, one
at 20 and another at 30. The instrument using a 30 angle
is no longer commercially available.
5
Since about 1992, a
20 laboratory gloss meter
6
was equipped with auxiliary
apertures for haze evaluation, thus permitting measure-
ment of 20 specular gloss and haze with the same instru-
ment (Fig. 15).
Fig. 9At a 40 cm observing distance structures with a
wave length size of 35 mm can be best seen. While at a
3mobserving distance structures with a wave length size
of1015 mm can be best seen: Typical orange peel.
Fig. 8Contrast sensitivity of our eyes is highest at three periods per cycle. Therefore, our visual assessment is dependent on the
observing distance.
Fig. 10Schematic diagram of a gloss meter. Source is on
the left, detector on the right. Lenses are used to provide
beam control. Source aperture is designated AP1, receptor
apertureAP2.
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CHAPTER 44 GLOSS 563
Measurement of Distinctness-of-Image
A variety of different technologies is commercially avail-
able to measure Distinctness of Image (DOI) [2428]. The
two most-often used principles are: (1) evaluation of the
steepness of the reflection indicatrix or (2) measurement of
contrast in dependence of the structure elements.
ASTM E430 [23] describes the design of an instru-
ment based on the evaluation of the reflection indicatrix
(Fig. 16). The instrument illuminates the specimen at a
30 angle and measures the light reflected at 0.3 from the
specular angle with an aperture of 0.3 width. This instru-
ment
7
is no longer commercially available.
Based on the DFO research project the visual percep-
tion of DOI is influenced by loss of contrast and micro-
structures distorting outlines. Therefore, in 1999 a new
measurement technology
8
[29] was developed to measure
light scattering caused by structure sizes smaller than
0.1 mm. This new measurement parameter was named
Dullness. A light emitting diode light source and a CCD
detector are used to detect the reflected image of the source
aperture (Fig. 17).
In Fig. 18 two different surfaces are compared. Surface
A is a polished black glass standard without dullness. In
this case the camera will detect a perfectly sharp image
no light scattering outside the aperture. Surface B shows
some light scattering, which results in a lighter image out-
side the aperture. The dullness measurement determines
the amount of light scattering within and outside the
aperture in a defined range. The dullness value is a ratio of
these two values. Therefore, this measurement parameter
is independent of the refractive index. In addition, an adap-
tive filter is used to separate between the inner and outer
image, which minimizes the influence of curvature.
Microstructures larger than 0.1 mm also influence
our impression of DOI. They are in the wavelength range
of 0.11 mm and can be objectively detected with the
same measurement principle as used for orange peel
measurement.
Measurement of Waviness (Orange Peel)
The phenomenon of waviness is most observable on a
glossy surface, a critical appearance phenomenon in the
automotive industry. Waviness has been evaluated by
visual means and by use of a profilometer. The correlation
between pro-filometry measurements and visual percep-
tion is satisfactory for surfaces with similar optical prop-
erties. The operation of a profilometer, however, is very
time consuming and limited to laboratory use. When the
eye of an observer is focused on a painted surface, vari-
ous types of waviness can be identified that involve size,
structure, and shape. Variations in process or material
parameters can cause differences in surface structure. For
example, poor flow or leveling properties of a coating will
usually cause a long wave structure often called orange
peel. Changes in substrate roughness, on the other hand,
will exhibit a short wave structure of higher frequency.
Because waviness is often caused on the production line,
it is important to control it there.
After considerable research, an instrument was
introduced in 1992 to provide an objective evaluation of
waviness with structure sizes between 0.3 and 12 mm
[30]. In 1999 the measurement principle of this instru-
ment was further developed to increase the resolution
and expand the measurement range from 0.1 to 30 mm
(Fig. 19).
A diode laser source is used to illuminate the speci-
men at 60. The reflected light intensity is evaluated at the
specular angle. During the measurement the instrument is
moved along the surface for a distance of about 10 cm. The
intensity of the reflected light is a maximum when coming
from a concave structure element. The detector receives
less light from a convex structure element. The human eye
cannot resolve the actual heights of the structural elements
of a painted surface, but the contrast between light and
dark areas provides an impression of depth. The contrast
of a surface structure can be expressed by use of the statis-
tical parameter variance. The final measurement results
Fig. 11Photograph of a modern miniature glossmeter
5
(cour-
tesy of BYK-Gardner).
Fig. 12Diagram depicting the positions of source and
receptor for the three geometries of ASTM D523.
5
Apparatus designated micro-TRI-gloss, available from BYK-
Gardner USA, Columbia, MD.
7
Apparatus designated Dorigon, Hunter Associates Laboratory,
Inc. VA.
8
Apparatus designated wave-scan available from BYK-Gardner
USA, Columbia, MD.
6
Apparatus designated haze-gloss, available from BYK-Gardner
USA, Columbia, MD.
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564 PAINT AND COATING TESTING MANUAL 15TH EDITION
Fig. 13Schematic diagram of a goniophotometer.
Fig. 14Schematic diagram of an instrument for reflection
haze measurement.
Fig. 15Photograph of a haze-and-gloss-measuring instru-
ment.
6
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CHAPTER 44 GLOSS 565
Fig. 17Schematic diagram of an instrument for dullness
measurement.
Fig. 16Schematic diagram of an instrument for DOI
measurement.
7
Fig. 18Surface A without dullness; Surface B with dullness.
Fig. 19Photograph of an orange-peel-measuring instrument.
8
Fig. 20Structure spectrum helps to understand appearance
of surface finishes
Fig. 21Original surface with high amount of long-, short-
and microstructures: Equivalent to the color gray.
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566 PAINT AND COATING TESTING MANUAL 15TH EDITION
are divided into five wave length ranges (WaWe) using
electronic filtering procedures. As a final result a structure
spectrum is obtained for structure sizes between 0.1 and 30
mm (Fig. 20).
In order to get a complete picture of the surface
appearance, this new instrument also includes the mea-
surement principle for dullness. The combination of two
measurement principles in one instrument simulates the
visual perception at different distances and permits catego-
rizing structure sizes with their causes.
Changes in Structure Spectrum Compared to
Changes in Color Measurement
For better understanding of how various structure sizes
influence the visual perception, changes in the structure
spectrum can be compared to color measurement. The
visible spectrum of color measurement is between 400
and 700 nm (blue red). For simplicity three colors can
be allocated to three structure sizes: Long waves cor-
respond to the color red, short waves correspond to the
color green, and micro-structures (DOI) correspond to the
color blue.
The ideal surface would be perfectly smooth, i.e., no
waves. In colorimetric terms we would be dealing with
Fig. 22Structure spectrums of original surface and first improvement step: reduction of longer waves.
Fig. 23Surface appearance is dominated by short waves after
longer waves were reduced: Surface appears dull.
Fig. 24Structure spectrum with reduced short waves by, e.g., sanding primer surfacer.
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CHAPTER 44 GLOSS 567
the color black (no waves = no color). In the following
example a coating with severe waviness is to be improved
whereas the main target is to reduce the longer waves.
The original surface has a high amount of long, short,
and microstructures corresponding to the color gray
(Fig. 21).
The structure spectrum of the original surface is shown
in Fig. 22. A reduction of the longer waves can be achieved
by optimizing the basecoat/clearcoat application (e.g.,
higher clear coat film thickness).
As a result the new look will be dominated by the
shorter waves, which would be equivalent to a blue/green
color (Fig. 23). In practice dominance in shorter waves can
be caused by, e.g., a poor-quality primer.
This high amount of shorter waves can be reduced
by, e.g., sanding the primer. In our example the shortened
microstructures were reduced below the amount of longer
waves (Fig. 24).
In color measurement the color red would be domi-
nating the look. And the same is true in appearance
measurement: The very low levels of shorter waves will
make the surface very brilliant with a high DOI and con-
sequently the small amounts of long waves will be very
obvious (Fig.25).
It is important to realize that the impression of gloss
is a multi-dimensional phenomenon. By changing the ratio
of different structure sizes, the visual appearance can be
dramatically changed. The structure spectrum is like the
fingerprint of a surface and can be compared to the spectral
curve of colorimetry. Currently the correlation of the dif-
ferent wavelength ranges to the visual perception is under
investigation. The goal is to obtain a measurement system
for appearance similar to the L*, a*, b* system of color
measurement [31].
References
[1] Hunter, R. S., Methods of Determining Gloss, J. Res. Natl.
Bur. Stand., Vol. 18, No. 77, 1937, p. 281.
[2] Lex, K., Die erweiterte Glanzmessung und die Messung von
Oberflaechenstrukturen, Pruftechnik bei Lackherstellung und
Lackverarbeitung, Vincentz Verlag, Hannover, Germany, 1992,
pp. 7074.
[3] ASTM Standard E284, 1994, Standard Terminology of
Appearance, Annual Book of ASTM Standards, Vol. 06.01,
ASTM International, West Conshohocken, PA.
[4] ASTM Standard D523, 1994, Standard Test Method for
Specular Gloss, Annual Book of ASTM Standards, Vol. 06.01,
ASTM International, West Conshohocken, PA.
[5] The Detroit Club, Accurate Gloss Measurement by a Practical
Means, Scientific Section Circular, No. 423, National Paint,
Varnish, and Lacquer Association (NAPVA), 1932.
[6] Hunter, R. S., Gloss Investigations Using Reflected Images
of a Target Pattern, J. Res. Natl. Bur. Stand., Vol. 16, 1936,
pp. 359366.
[7] ODonnell, F. X. D. and Billmeyer, F. W., Jr., Psychometric
Scaling of Gloss, Review and Evaluation of Appearance:
Measurements and Techniques, ASTM STP 914, ASTM Interna-
tional, West Conshohocken, PA, 1986, pp. 1432.
[8] Billmeyer, F. W., Jr., and ODonnell, F. X. D., Visual Gloss
Scaling and Multidimensional Scaling Analysis of Painted
Specimens, Color Res. Appl., Vol. 12, No. 6, 1987, pp. 315326.
[9] Schneider, M., and Schuhmacher, M., Untersuchung zur
Entstehung des visuellen Glanzein-druckes aus den Eigen-
schaften der Lackoberflche [Correlation between visual
assessment and phyisically measurable gloss parameters],
DFO research report, March 1999.
[10] Tannenbaum P. M., New Routes to surface Appearance
assessmentthe ASTM E12.14 Approach, 4th Wave-Scan
User Meeting by BYK-Gardner GmbH, Geretsried, Germany,
September 1998.
[11] ASTM Standard D4449, 1994, Standard Test Method for
Visual Evaluation of Gloss Differences Between Surfaces of
Similar Appearance, Annual Book of ASTM Standards, Vol.
06.01, ASTM International, West Conshohocken, PA.
[12] Landolt, E., Nouveaux Opto-types pour la determination de
lacuite visuelle, Archives dOphthalmologie, Vol. 19, 1899, pp.
465471.
[13] Horst Schene, Untersuchungen ber den optischphsiologischen
Eindruch der Oberflchenstruktur von Lackfilmen, Springer
Verlag, Berlin, 1990.
[14] Fresnel, A., Calcul des Tientes que Polarisation Developpe
dan Lames Cristallesees, Annal Chemie et Physic, Vol. 17,
1821, p. 312.
[15] Hunter, R. S., and Judd, D. B., Development of a Method of
Classifying Paints According to Gloss, ASTM Bull, No. 97,
1939, p. 11.
[16] Horning, S. C., and Morse, M. P., The Measurement of Gloss
of Paint Panels, Official Digest, Federation of Paint and Var-
nish Production Clubs, ODFPA, Vol. 19, 1947, pp. 153160.
[17] Zorll, U., Progress towards International Agreement on Gloss
Measurement of Paint Films, Journal of the Oil and Color
Chemists Association, Vol. 59, 1976, pp. 439442.
[18] ISO 2813, Paints and VarnishesMeasurement of Specular
Gloss of Non-Metallic Paint Films at 20, 60 and 85, Interna-
tional Organization for Standardization.
[19] New Product, The Micro-Gloss Family, Color Res. Appl., Vol.
15, No. 4, August 1990, p. 242.
[20] Paint Red Book, Communication Channels, Inc., 6255 Barfield
Road, Atlanta, GA 30328.
[21] ASTM Standard E167, 1994, Standard Practice for Gonio-
photometry of Objects and Materials, Annual Book of ASTM
Standards, Vol. 06.01, ASTM International, West Conshohock-
en, PA.
[22] Nimeroff, I., Analysis of Goniophotometric Reflection
Curves, J. Res. Natl. Bur. Stand., Vol. 48, No. 5, pp.
441448.
[23] ASTM Standard E430, Standard Test Methods for Measure-
ment of Gloss of High-Gloss Surfaces by Abridged Goniopho-
tometry, Annual Book of ASTM Standards, Vol. 06.01, ASTM
International, West Conshohocken, PA, 1994.
[24] Czepluch, W., Visuelle und messtechnische Oberflaechen-
charakterisierung durch Glanz, Industrie-Lack, Vol. 58, No.
4, 1990, pp. 149153.
[25] International Standard ISO 10 215, Anodized aluminum and
its alloysVisual method of image clarity of anodic oxidation
coatings.
[26] Loof, H., Goniophotometry with the Zeiss GP 2, Journal of
Paint Technology, Vol. 38, No. 501, 1966, pp. 632639.
[27] Matsuta, M., Kito, K., and Kubota, T., New Portable Orange
Peel Meter for Paint Coatings, Williamsburg Conference, Feb.
8-11, 1987, pp. 2528.
Fig. 25Very brilliant surface with a low amount of short
waves makes long waves very apparent.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
Downloaded/printed by
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568 PAINT AND COATING TESTING MANUAL 15TH EDITION
[28] Ladstaedter, E., and Gessner, N., Die quantitative Erfassung
von Reflexionsvermoegen, Verlaufsqualitaet und Glanzschlei-
er mit dem Gonioreflektometer GR-COMP, Farbe Lack, 1985,
Nr. 11, 1979, pp. 920924.
[29] Lex, K., and Hentschel, G., Neues Verfahren zur Glanz- und
Verlaufsstrukturbewertung, Berichtsband-Nr. 41: Jubilum-
stagung 50 Jahre DFO, 14./15. September 1999, Dsseldorf,
pp. 7380.
[30] New Product, Wave-Scan for the Measurement of Surface
Structure, Color Res. Appl., Vol. 18, No. 1, 1993, p. 69.
[31] Hentschel G., Weiterentwickelte wave-scan Technologie:
Neue Mglichkeiten der Glanzund Verlaufsmessung, Auto-
motive Circle International Conference: Die Ganzheitliche
Qualittssicherung bei der Karrosserielackierung, 19./20.
February 2001, Bad Nauheim, pp. 67113.
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569
45
CONCEPTS, RELATIONSHIPS, TERMINOLOGY
Opacity
WHEN LIGHT ENTERS A PAINT FILM, SOME OR ALL
of it is absorbed or reflected by the film before reaching
the substrate, thereby hiding the substrate to a lesser or
greater degree. The light that reaches the substrate is
partly absorbed by it and partly reflected back in confor-
mance with the substrates visual pattern. Reflection from
the substrate eventually emerges from the film carrying
the substrate reflectivity information perceived as visibil-
ity or lack thereof, and referred to as hiding. Opacity may
be qualitatively defined as the property of a paint film
that enables it to prevent the passage of light and thereby
to hide the substrate on which it has been applied. Note
that opacity is a film property, whereas hiding power is
a property of the whole paint. Hiding is a more general
term used frequently to refer to either opacity or hiding
power (HP).
Light Absorption
If most of the light is absorbed by the film before reach-
ing the substrate, the film is dark in color and hides the
substrate well, in which case hiding has been produced by
light absorption.
Light Scattering
If most of the light entering the film is reflected back and
reemerges without having reached the substrate, the film
is white or light in color and hides the substrate well. The
reflection mechanism of the film involves multiple internal
refractions and reflections that scatter the light to produce
a net reversal in its direction. Hiding in this case is pro-
duced by light scattering.
Incomplete Hiding
In all cases, the light-absorbing and light-scattering proper-
ties of the film act together to produce its opacity. If the
film is low in both light-absorption and light-scattering
ability, much of the light reaches the substrate. Such a film,
therefore, hides poorly and is characterized as being low
in opacity.
Test Substrates
An opacity test substrate generally has an ordered pattern
of contrasting colors or shades, usually black and white,
although black and gray and gray and white are also used.
Juxtaposition of contrasting areas permits both visual
observation and photometric measurement of film opacity.
Sealed paperboard charts are the most commonly used sub-
strates of this description. For photometric measurements
only, individual black glass and white glass panels are
sometimes employed to take advantage of their excellent
planarity. Clear plastic can also be used as an opacity test
substrate by placing it over black-and-white backgrounds.
Black and white painted metal panels are commercially
available for use with powder coatings. Standard black-
and-white opacity test substrates are defined in paint tech-
nology as having CIE-Y reflectances of 0.01 (1 %) maximum
and 0.80 (80 %), respectively.
2
White test areas are seldom
exactly 80 %, but equations are available for correction
of photometric values to that and any other standard
(see KubelkaMunk Equations for Correcting Reflectance
and CR
n
Measurements to a Standard White Substrate
Reflectance).
CR
The extent to which a paint film obscures or hides the
contrasting features of the test substrate on which it is
uniformly applied is the measure of its opacity. This is
expressed photometrically as the ratio of the luminous
(CIE-Y) reflectance over the darker, to that over the lighter,
area of the substrate, which is referred to as the CR (CR).
The Y-reflectance is employed because this CIE parameter
is designed to match the sensitivity of the human eye. The
CR and the reflectance are expressed as a percentage or as
a decimal fraction, the latter to be assumed unless other-
wise indicated. A CR value of unity indicates that too little
light has reached the substrate for the substrate reflectance
characteristics to have a measurable effect on the emergent
light flux; thus, there is complete absence of contrast, or
complete hiding. Lesser CR values define intermediate
levels of contrast, or incomplete hiding. The CR of a given
paint film varies with substrate reflectances, and therefore
has significance only with respect to a known substrate
and primarily to a standard black-and-white substrate as
defined in Test Subtrates. In practice, the white area of a
commercially available black-and-white substrate normally
deviates somewhat from the ideal reflectance of 80 %,
whereas the black area is normally 1 % or less, which has
no measurable effect on test results, and is therefore treated
mathematically as having zero reflectance. Conventional
symbols used in this connection are as follows:
W = the reflectance of the white area of the test
substrate,
Hiding Power
Leonard Schaeffer
1
The Leneta Company, 15 Whitney Road, Mahwah, NJ 07430. (Author deceased 2002.)
2
CIE = Commission Internationale dEclairage. Refectances are measured with specular (mirror) refection excluded.
MNL17-EB/Jan. 2012
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570 PAINT AND COATING TESTING MANUAL 15TH EDITION
R
w
= the reflectance of the paint film over a white area
of reflectance W,
R
0
= the reflectance of the paint film over the black
area,
C
w
= R
0
/R
w
, the CR of the applied paint film,
C
0.80
= R
0
/R
0.80
, the CR when W = 0.80, and
C = C
0.80
, the abbreviation sometimes used in
equations.
In careful HP measurements, if the white substrate
reflectance deviates more than 0.01 from the standard
value of 0.80, one of the following correction equations
3
is
employed. Correction equations
3
for normalizing CR values
to a standard white substrate reflectance are given in Cal-
culation of Hiding Power from Tinting Data.
C f R R W
WR R
R W
w 0 80 0
0 0
0
1 0 80
0 80 0
.
( , , )
( . )
( . ) .
+ 880 1
0
R WR
w
( )
(1)
1 0 80
0 80 0
0
C f C R W
WC R
C
w
w
( , , )
( . )
.
ww
W WR ( . ) . ( ) 0 80 0 80 1
0
+
(2)
Visual Observations of Contrast
Although intermediate levels of contrast cannot be directly
quantified by visual means, the eye is qualitatively very
sensitive to contrast variations. It can identify equalities or
nearly complete absence of contrast with considerable pre-
cision, which is the basis for the original, as well as several
current, HP methods to be described. Indeed, such visual
observations are the basic criteria of what constitutes hid-
ing and HP, to which all instrumental hiding measurements
trace their validity.
Film Thickness
This is usually expressed in thousandths of an inch (mils)
or in micrometres (m). A liquid paint usually contains a
substantial quantity of volatiles, so that its dry film thick-
ness (DFT) is substantially less than the original wet film
thickness (WFT). The WFT of architectural paints applied
in the field are typically in the neighborhood of 3 to 4 mils
(75 to 100 m). With other coating types, it might be as
low as 1 mil (25 m) or as high as 60 mils (1500 m). With
volatile-free liquid coatings, the WFT and DFT are the same
except for a possible small increase in density during cur-
ing. With powder coatings, for which film formation and
curing are concurrent, the term WFT is inapplicable and
DFT redundant, so that it is appropriate to refer simply to
film thickness.
SR
When paint is applied, whether for test purposes or in actual
usage, the area covered per unit quantity of paint is called
the spreading rate (SR) for that particular application.
When the quantity of coating is expressed volumetrically,
as is usual with liquid paints, the SR is usually expressed
in square feet per gallon (ft
2
/gal) or square metres per litre
(m
2
/L). When the quantity is expressed gravimetrically, the
SR is usually expressed in square feet per pound (ft
2
/lb) or
square metres per kilogram (m
2
/kg). SR is inversely related
to the film thickness; thus, for a given paint, the lower the
SR, the higher the film thickness and film opacity.
SR and Film Thickness Relationships
Let
H = SR of the coating (equivalent to SR),
4
T = wet film thickness (equivalent to WFT),
4
D = coating density (prior to loss of volatiles),
t = DFT (exclusive of air)
5
(equivalent to DFT),
d = dry film density (displacement density),
5
N = Nonvolatile fraction by weight (equivalent to
nonvolatile fraction by weight (NVW)), and
N
v
= nonvolatile fraction by volume (equivalent to
nonvolatile fraction by volume (NVV)).
U.S. UNITS
H T (ft /gal) (mil) = 1604.2
2
(3)
H t (ft /gal) (
2
mmil) = 1604.2ND d (4)
(ft /lb) (mil) = 1604
2
H T ..2 lb/gal) D( (5)
(ft /lb) (mil) = 1604.2
2
H t N d((lb/gal) (6)
METRIC UNITS
6
H L T ( ( m / ) m) = 1000
2
(7)
H L T ( ( m / ) m) = 100
2
00 (8)
m /kg) m) = 1000 (kg/L)
2
H T D ( (
(9)
m /kg)
2
H( m) = 1000 (kg/L) t N d (
(10)
U.S.METRIC UNIT CONVERSIONS
H H ( ( ft /gal) = m /L) 40.746
2 2
(11)
H H ( ( ft /lb) =
2
mm /kg) 4.8882
2
(12)
(mil) = ( m) 25.4 T T
(13)
lb/g D( aal) = kg/gal) 8.3454 D(
(14)
DRY VERSUS WET FILM RELATIONSHIPS
7
ND N d
v
=
(15)
t N T
v
(16)
T td ND (17)
DEFINITION OF HP
Qualitatively, HP is the property of a paint that is mani-
fested as opacity in its films. Quantitatively, it is the SR at
3
Derived from Eq (41) by equating to W = 0.80.
4
Note that WFT and SR, when the latter is expressed by volume,
are inverse ways of stating the same information.
5
Refers to flms containing no air or hypothetically compressed to
exclude air.
6
The following metric notations are identities: kg/L = g/mL = g/
cm
3
= g/cc.
7
These are applicable to both common and metric units since the
units all cancel.
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CHAPTER 45 HIDING POWER 571
which the film opacity is just sufficient to give complete
hiding over the specified standard black-and-white sub-
strate (see Test Substrates). The complete hiding point
is determined visually in some test procedures and photo-
metrically in others.
Visual HP End-Point
In the visual determination of HP, the operator increases
the film thickness gradually and records the amount of
paint applied at the supposedly exact point of complete
hiding. In practice, instead of perceiving such a point, a
range of uncertainty is reached beyond which, when hid-
ing seems unquestionably complete, it also seems that the
true end-point has been exceeded. To resolve this dilemma
and to obtain repeatable results, the operator chooses an
end-point at which it seems that only a negligible increase
in film thickness is required to completely obscure the con-
trasting features of the substrate. This so-called complete
hiding end-point is therefore more accurately described as
just short of complete hiding.
8
Photometric HP End-Point
Uncertainty as to the end-point also exists when measur-
ing HP photometrically. A curve of film thickness versus
CR approaches CR = 1 asymptotically, so in theory there
is no point at which the contrast is completely obscured.
Thus in practice the CR end-point for HP measurements
must be less than unity. A CR value of 0.98 is generally
accepted in paint technology as representing the point
of photometric complete hiding because it is in fact very
close to being visually complete, and a higher CR end-
point could not be identified with as much precision.
The concept of 98 % as the CR for complete hiding was
originally based on the WeberFechner law, from which it
can be deduced that differences of 2 % in reflectance (with
moderate illumination) are imperceptible to the human
eye [1]. Actually, this level of contrast, though slight, is
definitely visible.
THE ROLE OF PIGMENTS IN HP
Binders and Pigments
A typical paint binder, by itself, forms a transparent and
virtually colorless film that neither absorbs nor scatters
light to any appreciable degree and therefore makes no
contribution to the HP of the coating of which it is a part.
This task resides entirely in the pigment constituent of
the paint. Pigments are fine-particle-size, insoluble, and
usually crystalline solids that when dispersed in paint
vehicles contribute to the various properties of the mix-
ture, among which are the optical properties of color and
HP. Pigments that absorb light strongly over the entire
visible spectrum are black; those that are optically selec-
tive, absorbing strongly in parts of the visible spectrum
and poorly in other parts, are colored, viz. blue, red, yel-
low, etc., corresponding to the spectral region of nonab-
sorption. Those that absorb poorly over the entire visible
spectrum are white.
White Pigments
When dispersed in a paint binder, some white pigments
scatter light strongly and thereby contribute to hiding,
while others scatter very poorly and make little, if any, con-
tribution. On that basis, white pigments are classified as
hiding pigments or as extenders. White hiding pigments in
a paint formulation are sometimes called prime pigments
as distinguished from the nonhiding extender types.
The latter are also referred to as inerts in view of their
apparent passivity with regard to both light absorption and
scattering. The difference in scattering behavior between
hiding and extender pigments is a function of their refrac-
tive indices.
Refractive Index
Most pigments are crystalline in nature. If a single crystal
of white pigment were grown sufficiently large, it would be
perceived as shiny and transparent like glass, and objects
observed through it would look bent and distorted as when
observed through a glass prism. This is due to the change in
direction, referred to as refraction, that occurs when light
passes between media in which it has different velocities, as
illustrated in Fig. 1. The relationship between the angles in
this figure is expressed by Snells law of refraction
n = sin i/sin r (18)
in which i and r are the angles of incidence and refraction,
respectively, and n is a constant referred to as the refractive
index, which is the ratio of the velocity of light in the inci-
dent to that in the refraction medium. If the large pigment
crystal postulated previously is pulverized and dispersed in
a paint film, each small particle will refract incident light
in the same way as described for the large one. Light will
also be partially reflected at the surface, and both refrac-
tions and reflections will occur within the pigment particle
itself. This activity, endlessly repeated with a multitude of
pigment particles as illustrated in Fig. 2 (Ref. [2], p. 1),
results in the scattering of the original incident light with
concomitant film opacity and paint HP. The greater the dif-
ference between the refractive indices of the pigment and
the surrounding medium, the greater the amount of light
scattering that will occur. Refractive indices are reported
in Tables 1 and 2 with respect to a vacuum as the medium
of incidence. Values with respect to air are practically the
8
It has been proposed to use E of a uniform color space as the
HP endpoint instead of CR. This is a valid and feasible concept,
although to the writers knowledge it has not yet been employed in
a published test method.
Fig. 1Bending of a light ray by refraction toward the normal
as it enters a medium of lower light velocity (higher refractive
index).
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572 PAINT AND COATING TESTING MANUAL 15TH EDITION
same. Since white pigments are crystalline in nature, they
usually possess different refractive indices along the dif-
ferent crystal axes. Their indices also vary somewhat with
the wavelength of the light, generally being higher at the
blue (short wavelength) end of the spectrum than at the red
(long wavelength) end. Tables 1 and 2 give average values
[1,3].
White Hiding Pigments
A rough indication of the relative HP of a white pigment
can be calculated from its refractive index using the
Fresnell equation of reflectivity (Ref. [2], p. 1)
F
n n
n n
m
m
%
( )
( )
=
+
2
2
100 (19)
where F is the Fresnell reflectivity, n is the refractive index
of the pigment, and n
m
is the refractive index of the medium
in which it is dispersed. Since the refractive index of a
paint binder is, in general, very close to 1.5, Eq (19) can be
rewritten as
F
n
n
1.5
1.5
%
( )
( )
+
2
2
100 (20)
Tables 1 and 2 illustrate the use of this equation and
the general principle that the higher the refractive index of
a pigment the greater its HP. The relative HP values shown
therein indicate the magnitude of variation related to index
of refraction. Other factors can also affect HP substantially,
as discussed in Factors Affecting White HP.
Extender Pigments
Pigments in this category have low refractive indices in
the neighborhood of 1.5. In the form of a powder, with the
surrounding medium being air with a refractive index of
1.0, the difference in the two indices produces substantial
light scattering, so that extender pigments look white. But
dispersed in paint binders, which like themselves typically
have a value of about 1.5, they scatter light very poorly and
are virtually transparent. This is indicated by the low HP
values listed for them in Table 2 as compared with the white
hiding pigments in Table 1. Although extender pigments
are also referred to as inerts, the latter term is somewhat
of a misnomer. They have an indirect but strong influence
on light scattering and HP through phenomena referred to
as crowding and dry hiding. They also have important
effects on other physical properties of paints such as con-
sistency and gloss.
Colored Pigments
If a pigment absorbs some wavelengths of light more
strongly than others, it reflects back a higher proportion of
the weakly absorbed wavelengths and is perceived as hav-
ing the color of the latter (e.g., red, blue, yellow, etc.). Light
absorption of this nature is referred to as selective. Colored
pigments can vary greatly in HP depending on their light
absorption and light-scattering abilities. With regard to
light scattering, as with white pigments this is a function
of the refractive index or, more specifically, the difference
in refractive index between the pigment and surrounding
medium. Refractive indices of colored pigments vary widely
with wavelength, ranging from 1.3 to 2.7. These variations
cause such phenomena as bronzing, dichroism, color
TABLE 2Refractive index and relative HP of
some extender pigments
Pigment Refractive Index Relative HP F %
a
Barium sulfate 1.64 0.20
Calcium sulfate 1.59 0.08
Calcium carbonate 1.57 0.05
Magnesium silicate 1.57 0.05
Aluminum silicate 1.55 0.03
Silica 1.55 0.03
a
Calculated from Eq (20).
TABLE 1Refractive index and relative HP of
some white hiding pigments
Pigment
Refractive
Index
Relative
HP F %
a
Titanium dioxide (rutile) 2.76 8.8
Titanium dioxide (anatase) 2.55 6.7
Zirconium oxide 2.40 5.3
Zinc sulfide 2.37 5.0
Antimony oxide 2.19 3.5
Zinc oxide 2.02 2.2
White lead carbonate 2.01 2.1
White lead sulfate 1.93 1.6
Lithopone 1.84 1.0
a
Calculated from Eq (20).
Fig. 2Light-scattering behavior of a pigmented film.
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CHAPTER 45 HIDING POWER 573
change with film thickness, and differences in undertone
upon dilution with white pigments (Ref. [4], p. 22).
EARLY VISUAL HP METHODS
Brushouts
The earliest methods for determining HP employed the
practical procedure of brushing the paint uniformly onto
combination black-and-white test substrates, increasing
the amount of paint in small increments until reaching the
point of essentially complete hiding at which the amount
of visual contrast was considered negligible. The quantity
of paint was determined by weighing the container and
brush in grams before and after painting. The correspond-
ing SR is the HP by definition and was calculated from the
equation
SR(ft /gal) =
test area(ft ) paint densit
2
2
yy(lb/gal) 454
weight of paint (g)
(21)
For single-pigment paints, the value calculated from Eq-(21)
can be converted to pigment HP using the equation
SR (ft /lb) =
SR (ft /gal)
pigme
pigment
2 pigment
2
nnt concentration(lb/gal)
(22)
Variants of these equations provide for the use of metric
instead of U.S., units.
Early Test Substrates
Originally in the study of HP, test surfaces were prepared in
individual laboratories by painting black stripes on white-
painted panels. In response to the need for standardized
test surfaces, studies were made on oil cloth and linoleum
having printed checkerboard-type designs [5]. The Gard-
ner Contrast HP Board was a two-square-foot area glass
checkerboard with black and white squares painted on the
underside of a thin piece of glass (Fig. 3). The first formal-
ized ASTM method used a linoleum checkerboard surface
in the brushout test procedure described in Brushouts.
The Gardner glass board was used in the same way. Since
the complete hiding end point in those early methods was
determined when the paint was freshly applied and still
wet, the resultant HP value pertained only to the wet HP of
the paint, not to the dry. This was not a problem in the earli-
est days of HP measurement, when typical paints contained
relatively little volatile constituent and the opacity of the
film therefore did not change markedly while drying. But,
with the advent of modern paint formulations containing
substantial amounts of volatiles, the composition and with
it the opacity of the dry paint film could be substantially
different than that of the initially applied film. The need
to measure dry HP therefore became of paramount impor-
tance. As a practical problem in this connection, expensive
linoleum and glass test surfaces had to be cleaned for reuse
after each test, which made it very difficult to use them for
the study of dry HP. This problem was partly overcome with
the introduction of paper test charts circa 1931 that were
printed in various designs such as checkerboard, concentric
diamond-shaped bands, spirals, crescents, etc., and with
various degrees of contrast such as black-white, black-gray,
gray-white, and a graded series of stripes from black to
white. After printing, a coat of nitrocellulose lacquer or
other suitable clear sealer was applied. Many of those chart
types became and continue to be commercially available.
Contrast Design and Visual Sensitivity
Kraemer and Schupp [6] evaluated contrast surfaces in a
variety of designs prepared on glossy photographic paper.
These included the customary checkerboard design, a
design of narrow 15-mm-wide bands, another with much
broader bands, and one with dark half circles on a light
background. The results seemed to favor a narrow band
design subsequently employed by the Krebs Pigment Co.
in preparing the diamond stripe gray-and-white contrast
charts illustrated in Fig. 4. The test area of that chart was
1 ft
2
(0.0929 m
2
). The use of a gray-and-white contrast
Fig. 3Gardner contrast HP board. Fig. 4Krebs diamond-stripe HP chart.
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574 PAINT AND COATING TESTING MANUAL 15TH EDITION
combination was based on the idea that this is more rep-
resentative than black and white of the degree of contrast
encountered by paints in actual use.
Relative Dry HPKrebs Method
Although the introduction of paper test charts as replace-
ments for linoleum or glass made dry HP measurements
easier, they were still not easy enough. The problem was
that it required the preparation of a considerable number
of paint-outs at various SRs to obtain one that after dry-
ing could be identified with confidence as representing
the complete hiding end-point. One solution to this
problem was to determine comparative or relative dry
HP. In the Krebs Pigment Co. method, their square-foot
gray-and-white diamond stripe chart was used for that
purpose in the following manner: A partial hiding ladder
of six to eight brushout standards is made by applying a
standard paint at SRs ranging from 400 to 800 ft
2
/gal (10
to 20 m
2
/L) and allowing the brushouts to dry. The SRs
are precontrolled approximately by syringing specified
volumes of paint onto each chart and then determined
accurately by weight measurements and calculation as
described in Brushouts. A single test paint panel is like-
wise prepared at an intermediate SR. After drying, that
panel is compared with the standard panels to determine
the two that bracket it in contrast. Then, by visual inter-
polation, a fairly precise estimate is made of the SR of
the standard paint required to match the contrast of the
test paint panel. The relative dry HP of the test paint is
the percent ratio of its SR to that of the standard paint at
equal visual contrast, thus
%Relative Hiding Power =
SR
SR
Test Paint
Stdd. Paint
100 (23)
Pfund Cryptometers
ALL BLACK
Introduced in 1919, this was one of the first laboratory
instruments made for determining HP [7]. Referring to Fig.
5, A is a plate of black glass whose upper surface is optically
flat; B is a transverse groove 10 mm wide and about 2 mm
deep. Beginning at the left edge of the groove is a millime-
ter scale etched in the upper surface of Plate A. C is a plate
of clear glass whose lower surface is optically flat. D is a
steel shim cemented to C so that a wedge of paint may be
formed between the plates. This wedge abruptly becomes
infinitely thick at B, and so long as hiding is not complete,
the line of demarcation is visible. Sliding the wedge to the
left eventually causes the line to disappear. The WFT at the
point of complete hiding is determined from the scale read-
ing at the toe of the wedge and the thickness of the shim
at the heel, from which the HP in ft
2
/gal or m
2
/L can be
calculated using Eq (3) or Eq (7). Dark-colored paints can-
not be measured using this instrument because of the lack
of contrast with the black glass background. Nelson and
Norris of the New Jersey Zinc Co. used this cryptometer to
determine HP of colored pigments with results as shown in
Table 3. The pastes were prepared by rubbing the colors in
No. 0000 lithograph varnish. The rubbing was regulated to
represent the maximum development usually obtained in
practice. In addition to the regular black glass instrument,
Fig. 5Diagram of early model of Pfund cryptometer.
TABLE 3HP (m
2
/kg) of some colored
pigments measured with a Pfund
cryptometer
a
(Nelson and Norris)
Black Glass White Glass
Lampblack ... 105
Carbon black ... 41
Chromic oxide 29 ...
Prussian blue 72 ...
Chinese blue 106 ...
Blue toner 51 ...
Light green 129 ...
Medium green 187 ...
Deep green 88 ...
Light green 101 ...
Medium green 167 ...
Deep green 181 ...
Light green 62 ...
Medium green 98 ...
Light green 154 ...
Medium green 202 ...
Deep green 150 ...
Green toner 91 ...
Green toner dark 130 ...
Chrome yellow 23 27
Hansa yellow 31 34
Lt. chrome orange 44 56
Med. chrome orange 17 20
Dk. chrome orange 29 ...
Lithol toner 66 ...
Lithol toner 75 ...
Maroon toner 65 ...
Madder lake 36 ...
Toluidine toner 137 ...
Light para toner 224 ...
Deep para toner 160 ...
Light para toner 41 ...
Deep para toner 35 ...
a
Multiply by 4.9 to obtain HP in ft
2
/lb.
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CHAPTER 45 HIDING POWER 575
they used one specially made with white glass for several
measurements.
BLACK AND WHITE
Pfund [8] introduced the black-and-white cryptometer in
1930. It eliminated the well, making cleaning easier, and
worked for use with paints of any color because of the
black-and-white instead of all-black background. Referring
to 6, the black glass B and the white glass W are fused along
line LM. Longitudinal grooves catch the overflow of paint.
The wedge is moved to the right to make the line disappear,
then to the left to make it reappear. The position of the plate
is reversed and the observations repeated. From the mean
of all readings, the hiding is calculated as with the all-black
cryptometer (see All Black). Comparison of results for
white paints shows that the two cryptometer types (all-
black and black-and-white) yield the same values within
experimental error (Ref. [4], p. 22).
ROTARY TYPE
The rotary cryptometer was a short-lived device designed
to overcome the jerky movement of the top plate of the
regular cryptometer [9]. The wedge of the cryptometers
of Fig. 5 and 6 was replaced with a circular glass plate
mounted in a metal frame (Fig. 7). The thickness of the
film was read on a scale located on the bottom plate. While
the movement of the plate was much smoother with this
instrument, it was found that bubbles often obscured the
end-point.
ASSESSMENT OF CRYPTOMETERS (REF. [4], P. 25)
The cryptometer is a simple instrument requiring only small
quantities of paint, and determinations are quickly made.
However, reading the end-point is difficult, and the mean of
a number of determinations is therefore advisable.
Most users can repeat their own results, but agree-
ment among different users is not satisfactory although it
is improved by the use of a standard paint [10]. Another
major disadvantage of cryptometers is that they measure
only wet HP. One study [11] reported that cryptometers
were satisfactory with low-opacity but not high-opacity
paints. Consideration of its advantages and disadvantages
suggests that the cryptometer is better suited for control
work than for specification requirements. The crypto-
meters shown in Fig. 5 and 6 continue to be commercially
available.
Hallet Hidimeter
Along with the Pfund cryptometer, the Hallet hidimeter
[12] was one of the very early devices for evaluating HP.
The objective of a regular microscope is replaced by a long
tube fitted with a plain ground glass objective; the eyepiece
is replaced with a small hole. The principle of the device is
the light-diffusing property of ground glass. If a contrast
substrate is viewed through a plate of ground glass, the
contrast boundaries become more blurred as the distance
between plate and substrate increases. If a liquid paint
sample is sandwiched between them, it blurs the boundary
further, and the distance required to make the boundary
disappear decreases. Since that distance is the thickness of
the intervening paint film, it is a measure of the HP of the
paint. This measurement is essentially comparative because
it cannot be translated into regular HP units.
EARLY PHOTOMETRIC HP METHODS
Pfund Precision Cryptometer
In this device (Fig. 8) a photoelectric cell is used to measure
the reflectance of paint contained in a wedge-shaped layer
[13]. The base plate consists of black-and-white areas B
and W, whose boundary is parallel to the length of the plate
instead of perpendicular as with the visual cryptometer.
The photoelectric device is shifted until a position is found
where the reflectance of the paint over the black area is
98% of that over the white area. The film thickness and HP
Fig. 6Pfund black-and-white cryptometer.
Fig. 7Rotary cryptometer.
Fig. 8Pfund precision cryptometer. Uses a photoelectric cell
instead of the eye to measure reflectance.
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576 PAINT AND COATING TESTING MANUAL 15TH EDITION
calculations are the same as with the visual cryptometers
described in Pfund Cryptometers.
This cryptometer eliminates the uncertainties of the
visual type, as there is no sliding of the top plate over the
base plate and no need to estimate visually the appearance
and disappearance of an indistinct line. However, it retains
the disadvantage of permitting only wet hiding measure-
ments and has therefore been superseded by other photo-
metric devices and methods that permit the measurement
of dry HP.
Hanstock Method
Hanstock [14] studied the relationship of light transmission
through free paint films to opacity and HP on a black-and-
white substrate. For his transmission work, he employed
a flicker photometer and found that paint films were per-
fectly diffusing and that films having the same degree of
light transmission had approximately equal opacity. He fur-
ther showed the correspondence between refractive index,
the Fresnel relationship, and HP.
The problem with the transmission concept is that
modern paints have so much opacity it is difficult to accu-
rately measure the transmission of films of commercial
thickness. Moreover, HP is concerned in practice with paint
in intimate contact with opaque surfaces and not as a free
film. Consequently, measurement of light transmission
through paint films is done today only for very specialized
research.
Use of the Fell Equation
An empirical relationship between SR and CR was found by
Fell and reported by Sawyer [15] in the following form
log(CR 10) = SR + m b (24)
where m and b are experimental constants.
Since the graph for this equation is a straight line, it
is a simple matter after determining m and b from mea-
surements at two CR levels to find the SR required for any
desired CR. This procedure was adapted by Marchese and
Zimmerman to determine the HP of paints at a CR of 0.98,
and the method was used for many years by the Titanium
Pigment Co. (Ref. [4], p. 24). Experience has shown that
reasonably satisfactory results can be obtained if the equa-
tion is used for interpolation between points close to the
desired CR. But, as pointed out by Switzer [16], extrapo-
lation of results can lead to serious errors. He further
pointed out that the Fell equation method allows only a
single estimate of HP from at least two test applications,
thus requiring a considerable effort to obtain an estimate
of intralaboratory precision.
New York Paint Club (NYPC) Method
This method employed doctor blades to apply films at sev-
eral thicknesses on black-and-white cardboard HP charts.
After the films had dried, reflectance, weight, and area mea-
surements were made from which CRs and corresponding
WFT were calculated. CR values (rather than log 10 CR as
in the Fell equation) were plotted against reciprocal film
thickness and the HP calculated from the WFT at 0.98 CR.
If the white area of the chart deviated appreciably from the
standard reflectance of 0.80, the CR was corrected using
Eq (1) or Eq (2). The Club reported that most of the effort
in this method was to determine film thicknesses. To mini-
mize that effort they modified the method by casting films
on black and white glass plates and determined thicknesses
with an interchemical WFT gage in accordance with ASTM
Test Methods for Measurement of Wet Film Thickness of
Organic Coatings (D1212). Any error in film thickness, of
course, carries over to the HP value. According to Mitton,
the revised method sacrifices accuracy and precision for
speed [17]. In addition, graphical averaging makes it bur-
densome to estimate the precision with which the HP has
been determined for the same reason pointed out in Use
of the Fell Equation in connection with the Fell equation
method.
Van EykenAnderson Method
The method proposed by Van Eyken and Anderson [18]
uses CRs and film thicknesses in the same way as the
NYPC method described in New York Paint Club (NYPC)
Method Section, except that films of different thicknesses
are applied in a single operation by using a doctor blade
having seven clearances. A die is used to prepare uniform
area punch-outs of the paper charts to determine SR by the
basic weight-area-density-NVW calculation (see Eq (26)).
The defects of this method are that the small areas used for
reflectance and weighing make the achievement of good
precision difficult (Ref. [4], p. 31), and there is no provision
for correcting CR if the white substrate reflectance differs
from 0.80.
Federal Test Method for Dry Opacity
This is Method 4121 of U.S. Federal Test Method Standard
No. 141. It is a passfail test calling for a minimum dry film
CR at a specified WFT. Black-and-white HP charts are used
as the test substrate. For routine testing, the paint may be
applied either by brush or doctor blade. For referee tests,
application is by doctor blade only. The density and the
nonvolatile content of the paint are also required. Several
drawdowns are made to bracket the specified WFT. The
weight of dry paint film is determined for a measured area
on each drawdown and the WFT is then calculated from
the equation
WFT(mils) =
61 g)
(in.) g/mL)
2
M
A N D
(
(
(25)
where
M = the dry film weight,
N = the fractional nonvolatile content of paint by
weight,
A = the film area, and
D = the density of the paint.
The CR of each chart is measured and plotted against
the corresponding WFT. From a smooth curve drawn
through the points, the CR at the specified WFT is obtained.
If this is equal to or greater than the specified CR, then the
requirement for dry opacity has been met.
GENERAL HP METHODOLOGY
Film Application
The objective is to determine the SR at a specified level of
dry film opacity, which is usually full hiding as perceived
visually or corresponding to the CR: C = R
0
/R
0.80
= 0.98. The
basic experimental procedure is to apply a uniform film on
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CHAPTER 45 HIDING POWER 577
a suitable test substrate, to observe its opacity either visually
or photometrically, and to determine its SR. Since it is not
possible to apply a film with precision at a predetermined
dry opacity, several such applications need to be made
over a range of SRs and their results plotted graphically or
otherwise interpolated to the desired HP end-point. This
laborious procedure is exemplified in the visual methods
discussed in Brushouts and Relative Dry HPKrebs
Method and in the CR (CR) methods discussed in Van
EykenAnderson Method and Federal Test Method for Dry
Opacity. The Fell equation and NYPC methods (Use of the
Fell Equation and New York Paint Club (NYPC) Method)
attempt to reduce the workload to only two SR determi-
nations by plotting SR against CR or log CR and finding
the hiding end-point graphically on the basis of perceived
empirical straight-line relationships. Kubelka-Munk (K-M)
theory (see K-M Two-Constant Theory) shows how the
end-point can be calculated with just one SR determination.
SR (or Film Thickness) Determination
In both visual and photometric HP methods, the proce-
dures for observing film opacity are well-defined and can
be performed with dispatch. The experimental task most
demanding on the operators time and ingenuity is to
determine the SR or film thickness of the applied coating
with good precision. Although gages are available to mea-
sure WFT and DFT directly and quickly, the most accurate
procedure, by far, is to determine the weight of applied
paint film on a measured test area and then to calculate
the SR or film thickness as described in Brushouts and
Federal Test Method for Dry Opacity. The equations in
both of those methods contain mixed metric and com-
mon units. When the units are all metric, the equations
are simpler. Letting M = dry film weight and A = the film
area and using the symbolism in SR and Film Thickness
Relationships:
H
A N D
M
(m /L) =
(cm) (kg/L)
10 g)
2
2
(
(26)
T
M
A N D
( m) =
10 g)
(cm) (kg/L)
4
2
(
(27)
See Metric Units for equations interrelating SR, WFT, and
DFT. See U.S.Metric Unit Conversion for conversions
between metric and U.S. units.
If the volatiles have a relatively low evaporation rate
as with most architectural coatings, the film might be
weighed rapidly before appreciable loss of volatiles, in
which case Eqs (26) and (27) would still apply but with M
as the wet film weight and N as unity. The disadvantage of
this procedure is that it demands very skillful and speedy
manipulation to minimize loss of volatiles before weighing.
For that same reason, it is not applicable at all to coatings
containing fast-evaporating solvents.
With powder coatings, for which the SR is normally
expressed on a weight basis, Eq (26) becomes
H
A N
M
(m /kg) =
(cm)
10 g)
2
2
(
(28)
Assuming negligible volatile content, the value of N in
this equation can be taken as unity.
Photometric Measurements
The CIE-Y reflectance is measured because this function
defines the human eyes quantitative response to the lumi-
nous character of light across the visual spectrum. This
is valid for chromatic, as well as achromatic colors, as
reported by Tough [19], who found good correlation in a
large series of colored paints between visual HP measure-
ments and CR values based on CIE-Y measurements with
a spectrophotometer. The end-point of 0.98 CR is effective
with colors, although it appears that other end-points, for
example CIELAB color difference: E = 1.5, would make
some difference in the relative HP of various colored
paints [20]. However, the simplicity of the 0.98 end-point
and its history of validity and general agreement among
various workers make it the best choice regardless of color
(Ref. [4], p. 31). CIE-Y measurements can be made with
the green filter of a tristimulus colorimeter or with a spec-
trophotometer. When properly standardized, results with
the two instrument types should be the same. As a precau-
tion, there should be coordination between correspondent
laboratories with regard to instrumentation. In all cases,
reflectance measurements must be made excluding sur-
face reflection, which is implicit for instruments designed
with 0/45 geometry and optional with most other instru-
ment types.
CURRENTLY USED TEST SUBSTRATES
The substrate is generally the major factor affecting the spe-
cific experimental details of a test procedure. It is selected
or specified on the basis of its adaptability to the type of
coating being tested and for its perceived advantages in the
required or preferred test procedure.
Paperboard Charts
Substrates of this type are described in Relative Dry HP
Krebs Method. Their employment with baking finishes is
limited because of distortion and discoloration at high tem-
peratures, but they are used widely with air-dried coatings
for general HP observations. Black-and-white charts can be
used for precision photometric HP measurements by tak-
ing appropriate steps to allow for weight variations in the
substrate due to humidity and inherent random variations
in the area weight of paper. These steps include the use of
unpainted control charts and the averaging of multiple test
results. Charts with combinations of gray and black, gray
and white, and gradations of gray on a white background
are used in visual HP tests to obtain what are considered to
be more practical HP measurements.
Clear Plastic Film
Polyester is the preferred chemical type. Because of heat
distortion, its use is generally confined to air-dried coat-
ings. After the film has dried, a square of convenient size is
cut and the area measured. Values of R
0
and R
w
are read by
placing the painted plastic film alternately on a black and
a white background with the underside moistened with a
suitable liquid (e.g., mineral spirits or dibutyl phthalate) to
remove the air interface and establish good optical contact.
The dry film weight is determined as the difference in the
weight of the painted and unpainted substrate by stripping
off the paint film with a strong solvent.
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578 PAINT AND COATING TESTING MANUAL 15TH EDITION
Glass Panels
Individual black and white glass panels are used to take
advantage of the superior levelness of glass for casting of
uniform films and because the hard, smooth surface per-
mits rapid WFT measurements with an ASTM-type of WFT
gage (New York Paint Club (NYPC) Method). The same
information is obtained less rapidly, but with much better
precision by scraping off and weighing a defined area of dry
film and calculating as described in SR (or Film Thickness)
Determination. In some tests, CRs are calculated on the
questionable assumption that separate film applications on
black and white glass panels are identical in film thickness.
Painted Metal Panels
Panels of this type are generally used with coatings that
are applied by spraying and cured by baking. The weight
of the applied film is determined by weighing the panel
before the coating is applied and again after drying. The
SR or film thickness is then calculated as described in SR
(or Film Thickness) Determination. If desired, the DFT can
be determined without weighing, though with considerably
less precision, by direct measurement with a magnetic or
an eddy current thickness gage. Black-and-white panels
are used for CR measurements or for visual observation of
opacity. Mitton has described the use of all-black panels for
measuring the HP of baking enamels [21].
K-M TWO-CONSTANT THEORY
Introduction
The light that enters a paint film is subjected to scattering
and absorption as described in The Role of Pigments in
HP, and whatever is not absorbed by the film or substrate
eventually re-emerges as reflected light. In 1931 Kubelka
and Munk [22] published equations defining the optical
behavior of a translucent material in terms of two constants
referred to as coefficients of scattering and absorption.
Steele [23] in 1935 showed how these equations were adapt-
able to the measuring of paper opacity, and Judd et al. [24]
in 1937 did the same in connection with coatings. Kubelka
[25] in 1948 rearranged the original equations into new and
simplified forms from which Switzer [26] in 1952 devel-
oped equations designed specifically for the study of HP by
expressing the film thickness (or SR) as a function of the CR.
Using these equations and their derivatives, the CR of a coat-
ing can be calculated for any SR (or vice versa) from mea-
surements made at only one and its photometric HP thereby
determined by a single test application. This is in contrast
with the more laborious procedure of obtaining CR values
at two or more SRs for interpolation or extrapolation to the
HP end-point. The calculations appear formidable, but are
readily accomplished with a suitably programmed com-
puter. Graphs and tables are also available for this purpose,
although not as convenient and accurate as a computer. The
experimental steps are straightforward, and, as with most
HP methods, the most difficult and time-consuming opera-
tion is to determine the experimental SR (or film thickness)
with sufficient precision. How that is accomplished is the
essential difference between various K-M-based methods.
Equation Symbols
The symbols used here are based on ASTM Test Method for
HP of Paints by Reflectometry
(D2805-2003) as follows:
G = the substrate luminous reflectance (CIE-Y)
For a white substrate G = W.
For a standard white substrate G = W = 0.80.
For a black substrate G = B.
For a standard black substrate G = B 1 0.
R
G
= the luminous reflectance of a film applied
over a substrate of reflectance G.
R = reflectivitya property of the paintthe
limiting reflectance of the paint film as
it is increased in thickness. Also defined as
the reflectance at complete hiding as
evidenced by R
0
= R
w
over a black-and-white
substrate of uniform film thickness.
C
w
= the CR of a film applied at uniform thickness
over a black-and-white substrate; thus,
C
w
= R
0
/R
w
,
C
0.80
= the CR over a standard black-and-white
substrate, thus C
0.80
= R
0
/R
0.80
.
C = abbreviation for C
0.80
; the two are used
interchangeably, thus C = C
0.80
= R
0
/R
0.80
.
T = the film thickness in any stated unit, e.g.,
m, mils.
H = the SR in any stated unit, e.g., m
2
/L,
ft
2
/gal, m
2
/kg, ft
2
/lb, cm
2
/g.
S = the scattering coefficient, a measure of the
ability of the paint to scatter light, expressed
in units reciprocal to T or the same as H.
K = the absorption coefficienta measure of
the ability of the paint to absorb light,
expressed in the same unit(s) as S.
e = 2.718 28 the exponential base for natural
logarithms.
P = scattering powera measure of the ability
of a film to scatter light. A unitless film
constant defined mathematically by
the relationships: P = ST or P = S/H.
Subscripts
x = an experimentally determined value, e.g.,
T
x
, H
x
, P
x
.
c = a value calculated for a specified CR C, e.g.,
P
c
, H
c
.
0.98 = a value calculated for C = 0.98, e.g.,
H
0.98
, T
0.98
.
H = indicates a value pertaining to a SR e.g.,
C
H
, P
H
, S
H
.
T = indicates a value pertaining to a film
thickness, e.g., C
T
, S
T
.
a and b = simplifying functions of R, defined by
a R R +
1 2 1 / ( / )
(29)
b R R
1 2 1 / ( / )
(30)
From these definitions are derived the additional rela-
tionships
b a (
2 1 2
1)
/
(31)
R a b a a
(
2 1 2
1)
/
(32)
Note that R
j
(
,
\
,
(
( , ) coth
2
2
1
1
(33)
and the converse of Eq (31)
P f U R
b
U b
U b b
U
b
+
j
(
,
\
,
(
j
(
,
\
( , ) coth
1
2
1
1
ln
,,
( (34)
in which
ln = designation for natural logarithms, viz.,
log
e
x = ln x,
coth = designation for hyperbolic co-tangents,
defined by coth x
e
e
x
x
2
2
1
1
and
coth
1
= designation for inverse hyperbolic
cotangents, defined by
coth
1
x
x
x
1
2
1
1
ln
Values of natural logarithms and hyperbolic functions
are available in published tables and in calculators. Since
the tangent function is frequently provided without the
cotangent, the relationships between the two are stated
here as follows
coth x = 1/tanh x, coth
1
x = tanh
1
1/x
Original K-M Equations
The original equations are as follows:
For nonopaque films
R f ST R G
G R GR e
G R
G
R R ST
+
( , , )
/ ( )
( / )
1 1
1
+
( / )
( / )
1
1
R G e
R R ST
(35)
For opaque films
R f K S K S K S K S
+ + ( / ) / ( / / )
/
1 2
2 2 1 2
(36)
whose converse and more useful form is
K S f R R R / ( ) ( ) /
1 2
2
(37)
Functional forms are shown in this discussion along with
the corresponding explicit forms for a clearer perception of
the variables. Sometimes the functional form will be used
by itself for both brevity and clarity.
Eq (35) shows the reflectance of a paint film in terms
of two basic optical characteristics of the paint: the scat-
tering coefficient S, and reflectivity R
and the function U of Eq (33), Eq (35) can be rewritten in
the much abbreviated form
R f U R G f P R G
G a U
a U G
G
+
( , , ) ( , , )
( ) 1
(38)
Since film thickness T and SR H are reciprocally inter-
dependent (see Eqs (6) and (7)), it follows that P =S
T
T = S
H
/H,
with the scattering coefficient (S
T
or S
H
) being expressed in
a unit reciprocal to that of T (e.g., mil
1
, m
1
) or in the
same SR units as H (e.g., ft
2
/gal, m
2
/L, ft
2
/lb, m
2
/kg, cm
2
/g).
A clarifying concept in which SR units are mandatory is to
consider scattering as an entity quantifiable in area units,
with the scattering coefficient as the amount of scattering
per unit quantity of coating or coating ingredient, and scat-
tering power as the amount of scattering per unit area of
film. SR units have the further advantage over film thick-
ness and reciprocal film thickness of being directly relat-
able to gravimetric, as well as volumetric quantities. Thus,
for understandability, convenience, and standardization,
it is preferable to use SR units for scattering coefficients
and HP and more specifically the metric SR units m
2
/L and
m
2
/kg. These are translatable into film thicknesses and U.S.
units using the conversion equations in U.S.Metric Unit
Conversions. Equations for the numerical conversion of
scattering coefficients expressed in various units to stan-
dardized metric SR units are given in Table 4.
General K-M HP Method
The experimental procedure, in brief, is to determine the
reflectivity R
. If not, calculate
a f R R W Rw
R W R
WR
w
w
+
+
\
,
(
(
j
(
,
,
( , , )
0
0
0
1
2
(39)
and from Eq (32)
R a a
( )
2
1 2
1
/
The preceding two equations may be programmed
sequentially to give
R f R R W
w
( )
0
, ,
(40)
DETERMINATION OF R
0
AND H
X
This requires the application of a uniform film at a SR (or
film thickness) such that the CR C
w
is within the range of
0.96 to 0.985. These limits are established because too low
a CR requires excessive extrapolation to the C = 0.98 end-
point, and higher CR values become increasingly insensitive
to SR (or film thickness) variations. If the initial application
is outside that range, the application is repeated at a higher
or lower film thickness, as required.
The film may be applied on a black-and-white or an
all-black substrate. If black-and-white, then the test appli-
cation can be the same one used for determining R
in
Determination of Reflectivity R
(41)
Having obtained a film within the specified CR range,
R
0
is recorded and H
x
is determined by a suitable method.
Various techniques for determining the SR are available, but
the most precise is a weight-area-density-NVW method as
discussed in SR (or Film Thickness) Determination, using
applicable Eqs (26) and (27). The dry film weight M in those
equations is usually obtained as the difference in the weight
of the test area before and after application of the paint.
Sometimes, as with black glass, it is obtained by removing a
known area of film and weighing it directly. Such weighings
can be performed on an analytical balance with great accu-
racy. The density D and nonvolatile N of the paint must, of
course, also be determined if not already known.
With considerably less precision, the thickness of the
dry film can be measured using a caliper or electronic gage
on a metal panel, from which the SR can be calculated
using one of the following relationships
H
ND
t d
(m /L) =
1000
( m)
2
(42)
or
H
N
t d
(m /kg) =
2
1000
( m) (kg/L)
(43)
where
N = the nonvolatile fraction by weight NVW of
the test paint,
D = the density of a liquid paint,
d = the density of the dry or cured film, and
t = the thickness of the dry or cured film.
CALCULATION OF H
0.98
Having determined R
0
0
0
1 1 1
2
1
coth ln
1
RR R
R R
0
0
1
j
(
,
,
\
,
(
(
/
(44)
(b) The scattering coefficient S of the paint is calcu-
lated from S = P
x
H
x
.
(c) The scattering power P
c
of a paint film at the CR
C = 0.98 is calculated from
U f C R a
C
C C
0
2
1 2
1
1 60
1
+
j
(
,
\
,
(
,
,
,
]
]
]
]
( , )
.
/
++
1
1 60
C
C .
(45)
and Eq (34)
P f U R
( , )
which are solved sequentially to give
P f C R
c
( , ) (45)
(d) The HP H
0.98
is then calculated from H
c
= S/P
c
where
C = 0.98.
CR AT A SPECIFIED SR
Although this is not HP as such, it is frequently used as an
alternative HP criterion. After Step (b) of Calculation of
H
0.98
, calculate the scattering power P at the specified SR H
from: P
H
= S/H, then calculate the CR C
H
from Eq (33)
U f P R
H H
( , )
(46)
and
C f U R
a U
a U a U
H H
+
+
( , )
.
( )[ . ( )]
0 80
1 0 80
(47)
which together give
C f PH R
H
( , ) (48)
Judd Graph (Information Included for
Historical Purposes)
Prior to the availability of modern computers, K-M equa-
tions were much too complex for a practicable HP test
method. Judd [24], therefore, laboriously worked out a
general solution to Eq (35) in the form of a graph repro-
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CHAPTER 45 HIDING POWER 581
duced in Fig. 9. The graph relates the four variables R
0
,
C
0.80
, R
are
determined at the graph point corresponding to C
0.80
and R
0
,
and the scattering coefficient of the paint calculated from
S = P
x
H
x
. The value of P
0.98
is located at the intersection of
the R
.
The Judd graph is also useful for depicting the basic
optical properties of paints. It shows that paints with high
S values are lighter over black backgrounds than paints
of the same reflectivity with low S values. Also, if their S
values and film thicknesses are the same, paints with high
reflectivity are poorer in hiding than paints of low reflectiv-
ity. The latter fact may be demonstrated as follows: Sup-
pose a portion of paint for which R
), in which fac-
tor A
c
= 1604.2/P
c
. Values of factor A
c
are given in this table
for C = 0.98, 0.95, and 0.93, for all values of R
from 0.08
to 0.98 (8 to 98 %). The C value of most interest for HP
calculations is 0.98, representing full photometric hiding as
defined in Section Photometric HP End-Point. If desired, P
c
is easily calculated from factor A
c
.
The graph and table are typically used as follows: After
determining R
and R
0
experimentally, the index graph is con-
sulted in order to select the appropriate expanded graph on
which the scattering power P
x
of the experimental paint film
is to be found. Factor A
0.98
is determined from the table for the
measured value of R
( )
A
The preceding simple relationship holds when S is
expressed in reciprocal mils and HP is expressed in ft
2
/gal.
If the SR in m
2
/L is determined instead of the film thick-
ness, then after determining P
x
and R
)
2
/2R
.
From Scattering Coefficient and Scattering Power, S
and K can be considered as concentrations of scattering
and absorption per unit weight or volume. The K value
of a black tinter is determined by adding a measured ratio
to the standard paint sufficient to reduce the reflectivity to
about 0.40. The K value of the tinted paint is its initial K
value plus the tinter contribution, thus
K
2
= K
1
+ XK
t
(49a)
from which
XK
t
= K
2
K
1
(49b)
and dividing through (b) by the common value of S
XK
t
/S = K
2
/S K
1
/S (49c)
in which
K
t
= the absorption coefficient of the tinter,
X = the ratio of tinter to paint,
K
1
= the initial K value of the paint,
K
2
= the K value of the paint after tinting, and
S = the scattering coefficinet of the paint.
The ratios K
2
/S and K
1
/S are calculated from measured
values of R
)
2
/2R). If the standard paint is an untinted
white with a reflectivity no lower than 0.93, then its absorp-
TABLE 6White pigmentsHP and scattering coefficient values
a
Lead Carbonate Zinc Oxide Zinc Sulfide Anatase TiO
2
Rutile TiO
2
R
of the
test paint having thus been determined, its HP H
0.98
can be
calculated as in Calculation of H
0.98
(c) and (d) without the
tedious requirement of measuring the SR.
Experimental evidence for the validity of this proce-
dure is given by Mitton and Jacobsen [32], who, equating
the tinting strength of a white pigment with its scattering
coefficient, measured S (cm
2
/g) for a number of white pig-
ments by direct HP measurement and by the tinting proce-
dure. As shown in Fig. 13, the correlation between the two
methods is very close. If this simplified method is to work,
the K value of the black tinter must be the same in any paint
being tested. Also, the tinter must not change the degree of
dispersion of the white pigment so as to cause a change in
its S value. These conditions are not always met, so that it
is safest to apply the method only under favorable circum-
stances, when interaction of tinter and paint are known to
be negligible.
Determination of Relative HP of Untinted White
Paints from Tinting Data
For this purpose there is no need to determine the K value
of the tinter as in Calculation of HP from Tinting Data.
An equal ratio of black tinter is added to comparison paints
A and B, sufficient to reduce their R
( , , , )
( )( )
(
0
0
1
(51a)
C f R R W G
WR GR
R W G GR WR
G w
w
+
( , , , )
( )
( ) (
0
0 0
0 0
1
1 ))
(51b)
C f C R W G
WC GR
C W G G WR
G w
w
w
+
( , , , )
( )
( ) ( )
0
0
0
1
1
(51c)
Fig. 13Scattering coefficients determined by tinting and by
HP tests.
TABLE 7Scattering coefficient of a 20 %
PVC TiO
2
-alkyd paint film versus crystal size
of pigment.
S, m
1
Mean Crystal Size, m
0.76 0.24
0.73 0.20
0.64 0.16
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586 PAINT AND COATING TESTING MANUAL 15TH EDITION
where
R
0
= reflectance of the coating over the black
area
W = measured white substrate reflectance
R
w
= measured reflectance of the coating over
the white substrate
C
w
= measured CR
G = standard white substrate reflectance
Nominal:0.80
R
G
= normalize reflectance of the coating over
the white substrate
C
G
= normalized CR
FACTORS AFFECTING WHITE HP
As shown in Table 1 and Table 6, rutile titanium dioxide is
by far the most effective of the white hiding pigments in
producing light scattering and HP, which is true on a cost
as well as a weight basis. This fact has effectively eliminated
the use of other white hiding pigments except for special
properties or considerations. The important variables that
determine the scattering and hiding efficiency of a titanium
dioxide pigment in a paint are: (1) its mean crystal and
particle size, (2) the state of pigment dispersion, (3) its con-
centration in the paint film, and (4) film porosity.
Crystal and Particle Size
By decreasing the particle size of the pigment, the number
of particles and surfaces for light reflection and refraction
increase, and the light-scattering ability of a given quantity
of pigment will, therefore, tend to be enhanced. However, if
the particle size is too small in relation to the wavelength of
light, the wave front passes around rather than through it,
so there is no light scattering, and the dispersion is trans-
parent. Obviously, there is some intermediate optimum size
related to the wavelength of light at which maximum scat-
tering efficiency is obtained. The wavelength of the visible
spectrum ranges from approximately 0.4 to 0.7 m, peaking
in luminosity at 0.55 m. The mean crystal size for maxi-
mum opacity ranges from approximately 0.20 to 0.30 m
depending on both the PVC and the fraction of the pigment
consisting of single crystals. Commercial grades of titanium
dioxide developed for high-gloss finishes exhibit a single-
crystal content of about 20 % and have a mean crystal size
between 0.22 and 0.24 m. The adverse effect of a lesser
crystal size in such formulations is shown in Table 7 [33].
Pigment Dispersion
The process of obtaining a satisfactory dispersion involves
the wetting of the pigment by the dispersion medium to
displace air, breakdown of larger particles by milling, and
stabilization after the dispersion has been obtained. With
alkyd media, standard grades of titanium dioxide disperse
easily and develop full hiding with very little milling. Thus,
the main reason for milling alkyd dispersions is to reduce
or eliminate oversize particles that affect the appearance
of the film. With latex paints, milling can have an impor-
tant effect on opacity depending on the grade of pigment
employed [33], but the appearance factor is also an impor-
tant consideration, particularly with semigloss and gloss
finishes.
A major factor affecting the efficiency of TiO
2
in the
completed formulation is the phenomenon referred to as
flocculation, which is the formation of large particle groups
or floccules due to weak forces of cohesion. Floccules are
easily broken down but can spontaneously and quickly
recur in the wet paint or drying paint film. Despite their
weak bonding, floccules have the optical effect of increas-
ing the mean particle size, thereby decreasing the scattering
efficiency of the pigment. An auxiliary phenomenon related
to increased particle size is the preferential scattering of
longer wavelengths. Balfour and Hird took advantage of
this phenomenon to quantify pigment flocculation by mea-
suring backscattered infrared radiation (wavelength 25 m)
from a dried paint film to obtain what they refer to as a
flocculation gradient [34,35].
Pigment Concentration
In Refractive Index, it was pointed out that a very large
single crystal of a white hiding pigment is actually trans-
parent. Without undertaking a theoretical analysis, it is to
be expected that as the concentration of pigment increases
and its particles become more crowded, they approach the
optical condition of a very large particle with resultant loss
of scattering efficiency and HP. The crowding effect was
studied by Stieg [3638], whose results were used by Mitton
(Ref. [4], pp. 3435) to draw curves of HP H
0.98
versus PVC
for pure rutile and anatase titanium dioxide in alkyd enam-
els. These are shown in Fig. 14, in which HP is expressed
in ft
2
/lb of nonvolatile matter. If the paint is formulated at
50 % nonvolatile by volume, the HP results would be half
that shown in Fig. 14, but the shape of the curves would be
unchanged. Note the maximums in the curves at 25 to 30
% PVC, above which HP actually begins to decrease with
increasing concentration of pigment. When calculated in
terms of ft
2
/lb of pigment, the results appear as shown in
Fig. 15, clearly indicating the drastic decrease in TiO
2
effi-
ciency due to crowding.
Stieg [36] found empirically that the relationship
between TiO
2
HP and PVC, as shown in Fig. 15, could be
expressed by the equations
rutile: (ft /lb) = 370 410(PVC)
0.98
2 1/3
H
(52)
anatasse: (ft /lb) = 290 330(PVC)
0.98
2 1/3
H
(53)
The PVC values in these equations are decimal frac-
tions. Expressed in metric units, the equations become:
Fig. 14HP H
0.98
(ft
2
/gal) of solids at various PVC levels.
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CHAPTER 45 HIDING POWER 587
rutile:
0.98
2 1/3
(m /kg) = 75.7 839(PVC) H
(54)
anataase:
0.98
2 1/3
(m /kg) = 59.3 67.5(PVC) H
(55)
The question has been studied [36,39] of whether
extenders added to a gloss or semigloss paint film might
tend to increase the spacing of the TiO
2
pigment and
thereby its scattering efficiency. The physical picture that
emerges is of large particle-size extenders acting as massive
intrusions having no effect on the original TiO
2
spacing, and
of fine particle-size extenders dispersing uniformly so as to
increase TiO
2
spacing, but no differently in this respect than
an equal volume of binder. Consequently, when binder is
replaced by an equal volume of large particle-size extender,
TiO
2
efficiency decreases, whereas with small particle-size
extenders, TiO
2
efficiency has been found to remain essen-
tially the same and in no case improved.
Film Porosity
The preceding relationships pertain to pigment concentra-
tions at which there is sufficient binder to wet the pigment
completely and form a continuous phase, which means
below the critical pigment volume concentration (CPVC).
Above the CPVC, the dried film becomes porous, containing
entrapped air that increases pigment-scattering efficiency
by effectively lowering the refractive index of the surround-
ing medium. The air itself, as particulate matter in contact
with the higher refractive index binder, contributes to light
scattering. Thus, if the curves of Fig. 14 were extended to
a sufficiently high PVC, the HP of the film would begin to
rise again due to the opacification effect of film porosity.
Obviously this is an extremely impractical use of expensive
titanium dioxide with no relation to actual formulation
practice. However, porosity does in practice make a major
contribution to HP in the important interior flat wall paint
sector. In paints of that type, inexpensive inert white pig-
ments are included in the formulation, along with titanium
dioxide for the esthetic purpose of producing a flat finish
and to contribute HP by means of porosity. Stieg and Ens-
minger [38] showed that with paints over the CPVC that
contain both TiO
2
and extender, HP is in a straight-line
relationship with the Porosity Index (P.I.), with the slope
of the line depending on the percentage of prime pigment
and the nature of the extender. The P.I. is calculated from
the equation
P.I. = 1
CPVC(1 PVC)
PVC(1 CPVC)
(56)
The low-cost HP obtained from porosity is unfortunately
accompanied by a deterioration in the quality of the film as
manifested by poor scrub, soil, and stain resistance. This is
due to an insufficiency of binder, resulting in an air phase
continuum that gives ready capillary access to staining
materials.
MICROVOIDS FOR WHITE HP
Through the use of encapsulated preformed microvoids, it
has been found possible to obtain some of the HP benefit
of entrapped air while avoiding or minimizing the deleteri-
ous effect of film porosity. The microvoids are supplied as
a water dispersion of hollow beads having a plastic outer
shell and water-filled core. Incorporated into a latex paint,
the water in the core evaporates during the drying of the
film and is replaced by air that functions as light-scattering
particulates shielded from staining penetrants by the sur-
rounding plastic shell. Because the microvoids alone are not
able to produce the desired level of opacity in a film of nor-
mal thickness, the inclusion of titanium dioxide pigments
in the paint formulation along with microvoids is essential.
One widely used microvoid bead product is referred to as
opaque polymer and employs a shell of thermoplastic
polystyrene. Another type is a vesiculated bead in which
titanium dioxide and water-filled vesicles are associated
in a cross-linked polyester/styrene matrix. By using such
products to partially replace titanium dioxide pigment,
raw-material cost savings have been demonstrated with no
loss in film integrity or HP [35,40].
FORMAL HP METHODS
ASTM Methods
ASTM D344: TEST METHOD FOR RELATIVE HIDING
POWER OF PAINTS BY THE VISUAL EVALUATION OF
BRUSHOUTS
This is essentially the same as the Krebs Method described
in Relative Dry HPKrebs Method, differing only in
requiring black-and-white instead of gray-and-white charts
and in permitting checkerboard or other suitable contrast
designs as well as the diamond-stripe pattern. Modern
charts are 0.1 m
2
in area (1.076 ft
2
) instead of 1 ft
2
as speci-
fied originally. Provision is made for reporting results in
m
2
/L as well as ft
2
/gal.
ASTM D2805: TEST METHOD FOR HIDING POWER
OF PAINTS BY REFLECTOMETRY
This was adopted in 1969 and is actually a combination of
two earlier methods, ASTM D1738 and ASTM D2614, that
differed only in technique. It conforms with the general
K-M method described in General K-M HP Method but is
Fig. 15HP H
0.98
(ft
2
/lb) of pigment at various PVC levels.
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588 PAINT AND COATING TESTING MANUAL 15TH EDITION
designed specifically for air-dried coatings. Originally it pro-
vided for the use of either black glass or charts for determin-
ing H
x
and R
0
. In later versions, black glass is mandatory.
R
), S = P
x
H
x
, P
c
= f(C;R
), H
c
= P
c
/S for C = 0.98.
Earlier versions of ASTM D2805 and its predecessor
standards included or referenced the Mitton tables and
graphs described in Mitton Graph and Table [27], for solv-
ing the K-M equations. The method can be adjusted by
appropriate experimental modifications to the measure-
ment of baked enamels on black-painted metal panels as
discussed in Painted Metal Panels, or to other types of
coatings and test substrates.
ASTM D5007: TEST METHOD FOR WET-TO-DRY
HIDING CHANGE
This test method is concerned with determination of the
change in hading power of an architectural coating dur-
ing drying by visual evaluation of the wet and dry coating
films. It is a rapid visual test designed to measure percent
change in HP during drying. The paint is drawn down on
a black-and-white test chart using a special multinotch
applicator (Fig. 16) having eight notches with clearances
in geometric progression ranging from 67 to 264 m (2.65
to 10.4 mils). The clearance corresponding to an agreed
visual endpoint (Visual HP End-Point) is estimated imme-
diately after application and again after drying. The ratio of
the two clearances multiplied by 100 gives the percentage
change in HP:
CLEARANCE
WET ENDPOINT
CLEARANCE
DRY ENDPOINT
WWFT
WET ENDPOINT
WFT
DRY ENDPOINT
SPREADING R
AATE
DRY ENDPOINT
SPREADING RATE
WET ENDPOINT
(57)
The equation assumes that, for any one drawdown, the
ratio of clearance to WFT for the several notches does not
deviate appreciably. On that basis, WFT variations due to
application technique or paint rheology would not affect
the final test result. This is not a precision test, but provides
significant information of a practical nature with minimal
effort.
ASTM D5150: TEST METHOD FOR HIDING
POWER OF ARCHITECTURAL PAINTS APPLIED
BY ROLLER
This is a visual comparison method designed for use with
interior wall finishes and intended to provide practical
information from tests performed on a convenient labora-
tory scale. The test substrate is a large, sealed paper test
chart (Fig. 17), with a series of stripes numbered 1 through
6 on a white background. The stripes range in shade from
very light gray to black and were selected so that the color
difference
E
ab
between each successive stripe and the white
surround is in a geometric progression from 2 to 64 CIELAB
units. The dimensions of the test area are 24 by 36 in. = 6 ft
2
(610 by 914 mm = 5575 cm
2
), sufficiently large to simulate
practical application of paints with a roller. The paint is
applied at a specified, controlled SR, and the HP is reported
as the stripe number of the darkest stripe perceived as
being completely obscured. The concept of this test is that
in practical applications the levelness of the paint film and,
hence, its effective opacity are affected by the rheological
properties of the paint. Thus, in practice paints tend to have
lower HP than indicated by more customary test methods
in which films are applied with maximum uniformity using
a blade-type applicator. Relative practical HP among paints
can be influenced for that same reason.
ASTM D6441: TEST METHOD FOR MEASURING THE
HIDING POWER OF POWDER COATINGS
This standard conforms with the power coating industry
practice of reporting HP in terms of film thickness rather
than SR. A wedge shape film providing a range of film
thicknesses is applied by electrostatic spraying on black
and white painted metal panels. After curing, film thick-
nesses are measured with an electronic film thickness gage
and reluctances measured with a small aperture (e.g. 4 mm)
Fig. 16Multi-notch applicator for ASTM D5007.
Fig. 17Large gray scale chart (6 ft
2
, 5575 cm
2
) for roller
application tests per ASTM D5150.
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CHAPTER 45 HIDING POWER 589
spectrophotometer. Method A reports the CR at a specified
film thickness, and Method B the film thickness at a speci-
fied CR.
Federal Test Method Std. 141
METHOD 4121, CR AT A SPECIFIED SR
This passfail test was previously described in some detail
in Federal Test Method for Dry Opacity. Paint films are
applied on black-and-white charts by brush or drawdown,
and SRs are determined by a typical weight-area-density
procedure, discussed in SR (or Film Thickness) Determina-
tion. CR values are plotted at several SRs to obtain graphi-
cally the CR at a specified SR. For the test paint to pass, the
CR at the specified SR must have a specified minimum value.
ISO (International Standardization
Organization) Methods
ISO 2814, CR (CR) AT A NOMINAL SR (SR) OF 20 m
2
/L
ON BLACK-AND-WHITE CHARTS OR POLYESTER
FILM
A paint film is applied with a 100-m clearance applica-
tor to give a nominal WFT of 50 m, corresponding to a
SR of 20 m
2
/L. Black and white substrate reflectance are
measured and the CR calculated without a determination
of actual SR. Films cast on clear polyester film are mea-
sured, as described in Clear Plastic Film, by placing the
film alternately on black and white glass. Because different
paints and application techniques with the same applicator
give films differing significantly in thickness, the method
is satisfactory only as a rough guide for paints of the same
type and color evaluated by one operator.
ISO 6504-1, KUBELKA-MUNK METHOD FOR
WHITE AND LIGHT-COLORED PAINTS
This is in accordance with the general K-M HP method
described in General K-M HP Method section. It calls for
an all-black substrate, which can be glass or polyester film
over black glass. The Mitton graph and table described in
Mitton Graph and Table [27] are included, which makes it
very similar to early versions of ASTM D2805.
ISO 6504-3, DETERMINATION OF CR (OPACITY)
OF LIGHT-COLORED PAINTS AT A FIXED SR
This method is analogous to ISO 2814, but the SR is deter-
mined precisely by a weight-area-density procedure at
several film thicknesses. Substrates are clear polyester film
in Method A and black and white charts in Method B. The
CRs and SRs are plotted graphically and the CR at 210 m
2
/L
is reported. The CIE-Y reflectance of the white substrate is
specified to be 80 2 %.
British Standards Institute, BSI 3900
Part D4. Comparison of CR of Paints of the Same Type and
ColorThis method is technically identical with ISO 2814
(11.c).
Part D6. CR at 20 m
2
/L Using Polyester FilmThis
method is technically identical with ISO 3906-1980 (11.c).
Part D7. True HP (SR at C = 0.98) by the Kubelka-Munk
MethodThis method is technically identical with ISO
6504-1 (11.c) and in accordance with early versions of
ASTM D2805 and the general K-M HP method described in
General K-M-HP Method section.
Canadian General Standards Board, (CGSB)
1-GP-71
METHOD 14.1, VISUAL HIDING AT A SPECIFIED SR
The test substrates are black-and-white or black-and-gray
checkerboard charts with an area of 0.1 m
2
. The appropri-
ate chart is specified according to a list of CGSB color
numbers, with black-and-gray being used for lighter col-
ors. The paint is applied by brush or drawdown. In brush
application the SR is controlled accurately by weighing
container and brush before and after application, with a
specified volume being delivered to the chart surface by
syringe. With drawdowns, presumably identical applica-
tions are made on glass and charts and the WFT deter-
mined on glass by means of an Interchemical (ASTM
D1212) WFT gage. For the test paint to pass, the dry paint
film is required to completely obscure the contrast pattern
of the chart.
METHOD 14.2, SR DETERMINED AT FULL VISUAL
HIDING (FOR QUICK-DRYING COATINGS)
Successive thin coats are applied by spraying onto black-
and-gray or black-and-white charts until visual hiding of
the dry film is complete. The SR is calculated from the
difference in weight of the coated and uncoated chart. This
can be expressed in m
2
/kg of dry film or m
2
/L of the original
liquid coating.
METHOD 14.7, CR ON BLACK AND WHITE GLASS
PANELS AT A GIVEN SR OR DRY FILM THICKNESS
This is modeled after the NYPC method described in New
York Paint Club (NYPC) Method. WFT is determined with
an interchemical gage or DFT with a micrometer. The target
film thickness is bracketed experimentally to obtain two
points on a CR versus reciprocal film thickness graph and
the CR at the target thickness determined by interpolation.
The experimental CR values are corrected for W = 0.80
before plotting the graph.
French Standards Association (AFNOR)
NF-T30-075, SR AT A CR (CR) OF 0.98
Paint films are cast on clear polyester at several thicknesses
and CR values are determined after drying by measuring
reflectance over a black-and-white substrate. Dry films just
below and above 0.98 in CR are measured by weight or
micrometer to obtain experimental SRs in m
2
/kg or m
2
/L
and results interpolated to obtain the SR at exactly CR =
0.98. The introductory text points out that this method
measures true HP in preference to ISO methods that simply
compare CR values at 20 m
2
/L. It also refers to the experi-
mental film thickness not being limited to 50 m as in ISO
methods. No provision is made in this method to correct for
deviations of the white substrate from W = 0.80.
NF-T30-076, SR AT COMPLETE VISUAL HIDING
This is referred to as a simplified method. Several films
are cast on polyester to obtain one that shows full hiding
when placed over a black-and-white background. The DFT
is measured by difference with a micrometer and the HP
calculated in m
2
/L. Potential users should consider whether
this method, though simple in concept, might be exces-
sively burdensome in execution.
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590 PAINT AND COATING TESTING MANUAL 15TH EDITION
German Standards Institute (DIN)
DIN 53162, HP OF AIR DRYING NONCHROMATIC
PAINTS
This is a K-M method that is essentially the same as ISO
6504-1, but includes auxiliary test procedures for mea-
suring paint density and nonvolatile content. The Mitton
nomograph and table Mitton Graph and Table [27] are
employed.
DIN 53164, RELATIVE SCATTERING POWER OF
WHITE (TiO
2
) PIGMENTS
This method measures the K-M scattering coefficient S of
a TiO
2
pigment and reports its value as a percentage of the
scattering coefficient of a reference pigment measured in
the same way. The determination of S is based on the solu-
tion of Eq 44: P = f(R
0
, R
x
) using the Mitton monograph.
The method calls for the test pigment to be dispersed in an
alkyd or a plasticized polyvinyl chloride vehicle. R
is mea-
sured from a thick, full hiding film of the dispersion and R
0
from a nonopaque film applied on a black plastic substrate.
The SR H
x
of the pigment is determined in a unique way, by
igniting a known area of film on plastic and weighing the
residue. This method is basically the same as DIN 53162
and other K-M methods (General K-M HP Method), with
the difference that only relative values are reported. There
is no attempt to report actual scattering coefficients or to
calculate HP in physical units, although this could easily be
done on the basis of the accumulated data.
References
[1] Gardner, H. A., and Sward, G. G., Physical and Chemical
Examination of Paints, Varnishes, Lacquers and Colors, 9th
ed., May 1939, p. 10.
[2] Simpson, L. A., Measuring Opacity, Part I, Paint, Pigments
and Coatings J., Vol. 179, February 1989.
[3] Mitton, P. B., Vejnoska, L. W., and Frederick, M., HP
of White Pigments: Theory and MeasurementI, Official
Digest, Federation of Paint and Varnish Production Clubs, Vol.
33, 1961.
[4] Mitton, P. B., Paint Testing Manual, ASTM STP 500, Chap. 1.3:
HP, Physical and Chemical Examination of Paints, Varnishes,
Lacquers and Colors, 13th ed., ASTM International, West
Conshohocken, PA, 1972.
[5] Gardner, H. A., Sward, G. G., and Levy, S. A., HP and Tinting
Strength of Pigments and Paints, Scientific Section Circular,
National Paint, Varnish, and Lacquer Association, No. 362,
1930.
[6] Kraemer, E. O., and Schupp, O. E., Determination of HP of
White Paints, unpublished paper presented at the Washington,
DC meeting of the American Chemical Society, March 1933.
[7] Pfund, A. H., HP of White Pigments and Paints, J. Franklin
Inst., Vol. 188, 1919, p. 675.
[8] Pfund, A. H., HP Measurements in Theory and Application,
Proceedings, Vol. 30, Part II, ASTM International, West Con-
shohocken, PA, 1930, p. 878.
[9] Sward, G. G., and Levy, S. A., An Instrument for HP Determi-
nations, Scientific Section Circular, National Paint, Varnish,
and Lacquer Association, No. 433, 1933.
[10] Brodgen, D., The Precision of the Pfund Black and White
Cryptometer, Official Digest, Federation of Paint and Varnish
Production Clubs, Vol. 33, 1961, p. 1297.
[11] Saxena, K. G., and Chowdhry, K. K., Determination of Opac-
ity of Wet Films of Ready-Mixed Paints and Enamels, Paint-
india, Vol. 12, No. 1, 1962, p. 103.
[12] Hallet, R. L., An Instrument for Measuring the HP of Paints,
Proceedings, Vol. 20, Part II, ASTM International, West Con-
shohocken, PA, 1920, p. 426.
[13] Pfund, A. H., HP Measurements in Theory and Practice,
Proceedings, Vol. 30, Part II, ASTM International, West Consho-
hocken, PA, 1930, p. 882. Pfund, A. H., The Photoelectric Cryp-
tometer, Proceedings, Vol. 31, Part II, ASTM International, West
Conshohocken, PA, 1931, p. 876.
[14] Hanstock, R. F., The Opacity of Paints, J. Oil Colour Chem-
ists Assoc., Vol. 20, 1937, p. 5.
[15] Sawyer, R. H., HP and Opacity, Symposium on Color, ASTM STP
50, ASTM International, West Conshohocken, PA, 1941, p. 22.
[16] Switzer, M. H., Critical Analysis of the Fell HP Relationship,
Am. Paint J., Vol. 40, No. 13, 1955, p. 72.
[17] Mitton, P. B., A Mathematical Analysis of the Precision in
Determining HP, Am. Paint J., Vol. 30, 1958, p. 156.
[18] Van Eyken, W. W., and Anderson, F. T., Jr., An Improved
Method of HP Determination, Am. Paint J., Vol. 43, No. 31,
1959, p. 78.
[19] Tough, D., The Use of CR in the Measurement of HP, J. Oil
Colour Chemists Assoc., Vol. 39, 1956, p. 169.
[20] Gall, L., On the HP of Colored Pigments in Paints and Print-
ing Inks, Farbe and Lack, Vol. 72, 1966, p. 1073.
[21] Mitton, P. B., Measuring HP of Baked Coatings on Metal,
Met. Finish., Vol. 72(G), 1974, p. 44.
[22] Kubelka, P., and Munk, F., Ein Beitrage zur Optik der Farben-
striche, Z. Tech. Phys. (Leipzig), Vol. 12, 1931, p. 593.
[23] Steele, F. A., The Optical Characteristics of Paper, Pap. Trade
J., Vol. 100, No. 12, 1935, p. 37.
[24] Judd, D. B., Harrison, W. N., Hickson, E. F., Eickhoff, A. J.,
Shaw, M. B., and Paffenbarger, G. C., Optical Specification
of Light-Scattering Materials, Journal of Research, National
Bureau of Standards, Vol. 19, p. 287.
[25] Kubelka, P., New Contributions to the Optics of Intensely
Light-Scattering MaterialsPart, J. Opt. Soci. Am., Vol. 38,
1948, p. 448.
[26] Switzer, M. H., Equation for Calculating HP Index and SR
of Paints, ASTM Bulletin, No. 181, ASTM International, West
Conshohocken, PA, 1952, p. 75.
[27] Mitton, P. B., Easy, Quantitative HP Measurements, J. Paint
Technol., Vol. 42, 1970, p. 159.
[28] Mitton, P. B., to Weaver, J. C., personal communication,
1977.
[29] Mitton, P. B., Madi, A. J., and Rode, J. W., Development of a
Test Method for HP, J. Paint Technol., Vol. 39, 1967, p. 536.
[30] Hallett, R. L., HP and Tinting Strength of White Pigments,
Proceedings, Vol. 30, Part II, ASTM International, West Con-
shohocken, PA, 1930, p. 895. HP of Pigments, Proceedings,
Vol. 26, Part II, ASTM International, West Conshohocken, PA,
1926, p. 538.
[31] Titanium Pigment Company, The Handbook, 1956.
[32] Mitton, P. B., and Jacobsen, E. E., Reflectometry Method
for Measuring Tinting Strength of White Pigments, Official
Digest, Federation of Paint and Varnish Production Clubs, Vol.
34, 1962, p. 704.
[33] Simpson, L. A., Measuring Opacity, Part II, Paint, Pigment
Coatings J., Vol. 179, March 1984.
[34] Balfour, J. G., and Hird, M. S., J. Oil Color Chemists Assoc.,
Vol. 58, 1975, p. 331.
[35] Simpson, L. A., Measuring Opacity, Part III, Paint, Pigment
and Coatings Journal, Vol. 179, April 1989.
[36] Stieg, F. B., A New Look at the HP of Titanium Pigments,
Official Digest, Federation of Paint and Varnish Production
Clubs, Vol. 29, 1957, p. 439.
[37] Stieg, F. B., The Effect of Extenders on the HP of Titanium
Pigments, Official Digest, Federation of Paint and Varnish
Production Clubs, Vol. 31, 1959, p. 52.
[38] Stieg, F. B., and Ensminger, R. I., The Production and Control
of High Dry Hiding, Official Digest, Federation of Paint and
Varnish Production Clubs, Vol. 33, 1961, p. 792.
[39] Stieg, F. B., The ABCs of White HP, J. Coat. Technol., Vol.
49, 1977.
[40] Fasano, D. M., Hook, J. W., Hill, W. H., and Equi, R. S., For-
mulating High PVC Paints with Opaque Polymer Additives,
Resin Review, Vol. 372, 1987.
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591
PREFACE
IN PREPARATION OF THIS CHAPTER, THE CON-
tentsof the Fourteenth Edition of this manual were drawn
upon. The author acknowledges the author of the chapter
in the Fourteenth Edition, Julio I. Aviles. The current edi-
tion will review and update the topics as addressed by the
previous author, introduce new technology, and include
up-to-date references.
INTRODUCTION
Color is a common but complex subject that can be
described by perspective and in mathematical terms. As
early as 1666, when he was 23, Isaac Newton developed
his famous and useful Newton color circle that provided
an understanding about additive color mixing and comple-
mentary colors. His experiments with prisms demonstrated
that ordinary sunlight is made up of all wavelengths in the
visible spectrum and thus all colors. Thomas Young,
2
an
English physicist, in the early 1800s suggested that color
perception is three-fold in nature, and he speculated that
there were three kinds of nerve fibers or receptors in the
eyes retinasomething that was experimentally proven in
1959. These eye receptors are for long, middle, and short
wavelengths that correspond to the primary colors of red,
green, and blue (the RGB primaries) that had been useful
in matching many visual colors by additive mixing. Later
Hermann von Helmholtz put the qualitative analysis on a
quantitative basis wherein three parameters are used to
describe a color sensationthe well-known tristimulus
values.
While James Maxwell was examining usage of the
three primary colors in the 1860s, he found that no additive
combination would cover the entire range of hues perceiv-
able to the eye. It was found that the set of primary colors
was not unique and that more widely wavelength-separated
spectral primaries would produce a more complete range
of perceived hues. In addition, with some subtractive
combinations, the entire range of perceived colors could
be included. Maxwell also demonstrated that the hue and
saturation or chromaticity of a colored surface is in effect
insensitive to brightness. His studies are considered the
basis of modern colorimetry.
In the 1920s and early 1930s, experimental efforts by
W. David Wright and John Guild pointed out that all colors
within a particular range could be matched with the addi-
tive RGB primaries but not all spectral colors could be
matched. The lack of matching was particularly true in the
green portion of the range. However, if an amount of red
wavelength light were added to the color being matched,
all colors were possible. These quantitative studies were
expressed in the modern terms of tristimulus values for the
RGB primaries, but negative values had to be imposed for
the red values so that all colors could be matched.
In 1931 the International Commission on Illuminations
(CIE)
3
defined a color system in which all tristimulus values
were positive and all visible colors could be represented
by two color coordinates, x and y, that specify the color
point on a chromaticity diagram. The third or Y parameter
used in the CIE system for defining colors is a luminance
parameter. This CIE system has some difficulties associated
with it, and a new system was introduced in 1976. While
the 1976 CIE standard removes the difficulties, it has not
gained acceptance, and currently the 1931 CIE standard is
the basis for almost all quantitative color measurements.
Basic tristimulus color measurement is usually car-
ried out with either a colorimeter or a spectrophotometer.
Tristimulus colorimeters are a combination of an illumina-
tion source, an array of filters, and a photoelectric output
instrument. Measurements are comparative with the device
standardized by using ceramic or glass standards that have
colors similar to those of the materials to be measured. If
precise measurements are needed, spectrophotometers that
measure reflectance at each wavelength are used to deter-
mine the tristimulus values.
This brief passage into the history of color merely
scratches the surface of color technology. Color and its
management in paint and coatings are important from
both an aesthetic and a practical or economic standpoint.
It plays a role in our everyday lives and it affects our emo-
tions and moods as we react to the colors around us. From
an economic standpoint, it was well pointed out by Rich
[1], who stated, Getting the customers color right the first
time, whether it involves paint, coatings, or ink, is often the
first and most crucial test of quality.
The tinting strength of pigments is often used as a
guide for estimating relative hiding power of a pigment
or paint to completely obliterate the background to which
it has been applied. It may seem as if one is stating the
46
Mass Color and Tinting Strength of Pigments
Joseph V. Koleske
1
1
1513 Brentwood Road, Charleston, WV 25314.
2
Young is also the investigator who devised the concept of a modulus of elasticity that is known in mechanical properties as Youngs
modulus.
3
The abbreviation CIE is taken from the French title for the commission, Commission Internationale de lEclairage. The address for the
commission, which is an independent organization that was conceived in 1913, is International Commission on Illuminations, CIE Central
Bureau, Kegelgasse 27, A-1030 Wien, Austria.
MNL17-EB/Jan. 2012
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592 PAINT AND COATING TESTING MANUAL 15TH EDITION
obvious, but when light falls on a painted substrate, some
of the light is reflected from the surface and the remain-
der enters the paint or coating film. The light that enters
the film either emerges from the various faces, including
the top face, or is absorbed. If all or most of the light is
absorbed, the film appears dark in color or black, the
coating effectively hides the substrate, and the pigment
involved is said to have good tinting strength. The fac-
tors that have an effect on tinting strength and mass color
include pigment refractive index, particle size, concentra-
tion, degree of dispersion, and inherent light-absorbing
characteristics. Applied coating thickness also has an effect
on this characteristic. It has been suggested to the author
that most industrial colorists consider tinting strength as
a quality control measurement comparing a batch to a
standard of the identical materials. The ASTM definitions
of tinting strength are given in a following section dealing
with definitions.
For both mass color and tinting strength, it is the final
appearance or reflectivity (R
, of an
opaque coating, and it depends on the pigment concentra-
tion, degree of dispersion, coating thickness, and the light
absorption, K, and scattering, S, of pigments and binders.
Mass color is applicable to both chromatic and achromatic
pigments.
Tinting strength is a measure of the effectiveness with
which a unit quantity of a colorant alters the color of a
material. For scattering and absorbing colorants, both scat-
tering and absorption tinting strength must be specified
[7]. ASTM D16 [6] defines tinting strength as the power
of coloring a standard paint or pigment. ASTM E284
defines tinting strength as a measure of the effectiveness
with which unit quantity of a colorant alters the color of a
material.
Other definitions that are of interest include the fol-
lowing [7]. The listing is by no means complete and it is
given to help guide a reader/user to the terms used in the
technology. In certain cases, designation symbols are listed
to again provide guidance.
Absorption is the transformation of radiant energy to
a different form of energy by interaction with matter.
Absorption tinting strength is the relative change in
the absorption properties of a standard white material
when a specified amount of an absorbing colorant,
black or chromatic, is added to it.
Achromatic (1) for primary color sources, the computed
chromaticity of the equal-energy spectrum; (2) for sur-
face colors, the color of a whitish light, serving as the
illuminant, to which adaptation has taken place in the
visual system of the observer; (3) the perception of hav-
ing no hue, that is, as white, gray, or black.
Brightness (1) is an aspect of visual perception whereby
an area appears to emit more or less light or (2) bright-
ness of an object is the combination of lightness and
saturation. Different definitions of brightness are used
in the textile industry, the paper industry, and by dyers.
Chroma is an attribute of color used to indicate the
degree of departure of the color from a neutral color of
the same lightness. Munsell chroma is an attribute of
color used in the Munsell color-order system to indicate
the degree of departure of a color from a gray to the
same Munsell value, in steps that are visually approxi-
mately equal in magnitude.
Chromatic describes the perception of something hav-
ing a hue; not white, gray, or black.
Chromaticity Diagram is a plane diagram in which
points specified by chromaticity coordinates represent
the chromaticities of lights (color stimuli).
CIE is an abbreviation for the French title of the Inter-
national Commission on Illumination, Commissione
Internationale de lEclairage.
CIE 1931 standard colorimetric system is a system
for determining the tristimulus values of any spectral
power distribution using the set of reference color
stimuli X, Y, Z and the three CIE color-matching func-
tions x(), y(), and z() adopted by the CIE in 1931.
Colour Index International is a listing of colors by
name and number by the Society of Dyers and Colour-
ists and American Association of Textile Chemists and
Colorists [8].
Hue is the attribute of color perception by means of
which a color is judged to be red, orange, yellow, green,
blue, purple, or intermediate between adjacent pairs of
these, considered in a closed ring (red and purple being
an adjacent pair). Neutral colors are judged to have
no hue. Munsell hue is an attribute of color used in
the Munsell color-order system to indicate the hue of a
specimen viewed in daylight.
Lightness is (1) the attribute of color perception by
which a non-self-luminous body is judged to reflect
more or less light; (2) the attribute by which a per-
ceived color is judged to be equivalent to one of a series
of grays ranging from black to white.
Luminance is the luminous flux in a beam, emanat-
ing from a surface, or falling on a surface, in a given
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CHAPTER 46 MASS COLOR AND TINTING STRENGTH OF PIGMENTS 593
direction, per unit of projected area of the surface as
viewed from that direction, per unit solid angle.
Munsell Color System was developed just before the
end of the nineteenth century by A. Munsell, an Ameri-
can artist. The system is depicted as a globe with a
band of colors running equatorially and an axis of gray
values wherein white is the North Pole and black is the
South Pole. At each gray value, there is a change in
color that gradually ranges from full saturation to neu-
tral gray, and in this manner a myriad of colors could
be described by their hue, chroma, and value.
Saturation is the attribute of a visual sensation that
permits a judgment to be made of the proportion of
pure chromatic color in the total sensation.
Scattering is the process by which light or other elec-
tromagnetic radiant flux passing through matter is
redirected over a range of angles.
Scattering tinting strength is the relative change in
the scattering properties of a standard black material
(with no scattering colorant present) when a specified
amount of a white or chromatic scattering colorant is
added to it.
Shade is (1) a color produced by a dye or pigment mix-
ture including black dye or pigment; (2) an expression
of color difference from a reference dyeing such that
another dye must be added to produce a match; and (3)
a color slightly different from a reference color. Shade
is related to tint.
Tint is a color produced by the mixture of white pig-
ment or paint with a chromatic pigment or paint.
When used as a verb, tint means to adjust the color
of a test specimen to be a closer color match to the
standard. Also see Shade above.
Tristimulus values are the amount of three specified
stimuli required to match a color. In the CIE system,
these three stimuli are assigned the symbols X, Y, and Z.
TINTING STRENGTH
As mentioned above, tinting strength is a measure of the
effectiveness with which a unit quantity of a colorant
changes the color of a material. One may think of it as a pig-
ments coloring power. For colorants that both absorb and
scatter light, scattering and absorption tinting strengths
must be specified. Scattering tinting strength is the relative
change in scattering properties of a standard black material
that has no scattering colorant present when a specified
amount of white or chromatic scattering colorant is added
to it. Absorption tinting strength is the relative change in
absorption properties of a standard white material when a
specified amount of an absorbing colorant, black or chro-
matic, is added to it.
Since pigment concentration is important to coating
strength and cost, tinting strength is an important economic
factor when selecting one paint over another. There is no
particular value of tinting strength that can be stated as
desirable unless an end use is stated. In certain cases, a high
value is desirable and in other cases a low value is required
to achieve a desired color/strength effect. Pigments each
have a different ability to vary the color of a mixture. When
economy is a factor in paint formulation, stronger tinting
strength is desirable. Some colors, such as phthalocyanine
blue, are very strong in their tinting strength whereas other
colorants can be relatively weak. Tinting strength increases
as pigment particle size decreases with synthetic organic
pigments generally having greater tinting strength than
mineral pigments.
In a general sense, tinting strength is determined by
dilution of a test paint and a reference paint with a standard
mixing white paint in the case of chromatic paints or a
standard tinting color in the case of white paints. These
diluted pastes are then drawn down on a suitable substrate,
and then either instrumentally measuring tristimulus val-
ues or visually comparing the specimens. As would be
expected, the visual comparison technique has lower preci-
sion than the instrumental method. Details for preparation
of standard white paints are described [9] or a commercial
titanium dioxide-white artists paint may be used as the
standard. It should be understood that the mixing white
paint must be made with the same vehicle chemical type
acrylic, alkyd, or oilas the paint to be tested.
When color tints are considered, differences in gloss
and haze can be mistaken for a lighter tint or lower tinting
strength than really exists. In grays, these factors may be
interpreted as higher white pigment strength than exists.
Instruments cannot compensate for specular gloss or haze
differences between a sample and a standard, and this can
result in erroneous tint strengths. It is possible to equalize
gloss differences between specimens by top coating them
with a clear coating. Evaluation through the clear coating
reveals the true tinting strength differences between sample
and standard.
Tinting strength results can also be affected if the light-
ness, chroma, and saturation of the sample differ signifi-
cantly from those of the standard, since the measurements
involve matching two color variableseither lightness and
chroma or lightness and saturationby adjusting only the
amount of pigment used [10,11].
Chromatic Paints
ASTM D4838 [12] is a method used for determining the
absorption tinting strength of a chromatic test paint rela-
tive to that of a standard or reference paint of the same
chemical type. The procedures in this method are based
on dilution of paints with a standard mixing white paint
followed by instrumental measurement and calculation.
Provision is made for correcting the results for small
differences in hue or chroma (or both) between the test
and reference chromatic paints. The method is meant for
comparison of paints that contain the same chemical type
vehicle (acrylic, alkyd, or oil) and single-pigment colorants
of the same Colour Index name and number. It is unneces-
sary to have information about the amounts of pigments or
other components in the paint.
The color-measuring instrument can be either a
spectrophotometer that provides 1931 CIE tristimulus
values, X, Y, and Z for CIE standard illuminant C or a
tristimulus colorimeter providing either such tristimulus
values or colorimeter readings R, G, and B. Other test
methods or practices useful in following the results of
this test method can be found in the literature [1315].
ASTM E1347 [16] deals with a test method for the use
of a tristimulus colorimeter to evaluate specimens and
provide color coordinate and color difference values. The
device is also known as a tristimulus filter colorimeter or
a color-difference meter.
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594 PAINT AND COATING TESTING MANUAL 15TH EDITION
ASTM D387 is used to compare the color and strength
of a pigment that is being tested with a reference standard
of the same type and grade [17]. The method specifically
points out that it does not apply to white pigments. The pig-
ments are dispersed in a suitable vehicle with a mechanical
muller. Opaque drawdowns are made on white paper charts
that have a black band and a surface that is impervious to
paint liquids. These drawdowns are compared either visu-
ally or instrumentally for color and strength differences.
ASTM D3022 is similar to this method, but it utilizes a min-
iature sandmill rather than a mechanical muller to disperse
the color pigment [18].
ASTM D2066 is a related test method that is applicable
to the relative tinting strength of paste-type printing ink
dispersions [19] and is similar in nature to other referenced
ASTM test methods [12, 17]. The strength may be deter-
mined by instrumental or visual observation of manually
or automated mixed tints. The methods are applicable to
paste-type printing inks, flushed pigments, and other pig-
ment dispersions that are essentially nonvolatile under
ordinary room conditions and for which there is a wet ref-
erence standard of the same pigmentation and consistency.
If the proper choice of tinting base is used, the methods are
applicable to dispersions of any color, including black and
white.
White Paints
ASTM D2745 is a standard method for determination of
the relative tinting strength of white pigments by reflec-
tance measurements made on black tints [20]. It is only
applicable for comparing the test pigment with a reference
standard of the same type and grade. The method is carried
out by dispersing the pigment in an agreed-on, solvent-free
vehicle and then letting it down with additional vehicle
that has been tinted with a lampblack that has been pre-
dispersed in a vehicle similar in nature to the test vehicle.
Refined or low-bodied linseed oil should not be used with
this procedure. Both dispersion and let-down are done with
an automatic, mechanical muller. Tristimulus values are
determined with a colorimeter.
ASTM D332 is a test method for determination of the
relative tinting strength of white pigments by visual assess-
ment of blue tints [21]. It is only applicable for comparing
a test pigment with a reference standard of the same type
and grade. The test is conducted by dispersing specified
amounts of a white pigment and a blue tinting pigment
that conforms to specifications [22] in a refined linseed oil
with an acid number of about 4 using a glass, hand muller,
or an automatic muller. The pastes are drawn down on a
specified panel and visually evaluated for tinting strength.
A numerical rating of tinting strength is obtained by prepar-
ing dispersions with the standard white pigment and more
or less of the tinting pigment. These are compared until the
lightness of the test paste is matched. The weight of the tint-
ing pigment is used to calculate the relative tinting strength.
PIGMENT DISPERSION
Tinting strength and mass color require that pigments be
well dispersed in the binder to achieve maximum tinting
strength. Ideally, it would be desirable to break down pig-
ment agglomerates into the smallest possible individual par-
ticles, i.e., to an ultimate dispersion state. The smaller the
particle size the greater the surface area of a given weight
or mass of pigment. This then results in more intense color
production in the same volume of liquid. However, an ulti-
mate dispersion state is impractical and effectively impos-
sible to achieve. Therefore, pigments under investigation
for these properties must be processed in the same manner
and receive the same level of mechanical work. Mechani-
cal mullers, which are instruments that have two circular,
usually ground-glass grinding surfaces that contain the pig-
ment and vehicle, are used to disperse the two components.
A variety of these devices are commercially available. Devel-
opment of tinting strength is dependent on the force applied
to the glass plates, the number of revolutions used, and the
mass of pigment and vehicle used. If muller conditions,
pigment, and vehicle have not been agreed on by purchaser
and seller, the mandatory dispersing conditions given in the
Annex of ASTM 387 should be used to attain a consistent
level of tinting strength [17]. These conditions include:
Determination of the appropriate ratio of color pig-
ment to dispersing vehicle for the standard and test
pigments.
Determination of appropriate masses of pigment and
vehicle to use.
Preparation of a standard tint by application of 100 lbf
(N) to the muller plates, introducing the appropriate
mass of pigment/vehicle, and mulling the paste for 100
revolutions in two stages of 50 revolutions each. This is
then repeated on three more specimens of the standard
mixture except the mulling is carried out for 200, 300,
and 400 revolutions in stages of 50 revolutions.
Each of the four specimens is compared one to the
other for tinting strength and the minimum number of
revolutions needed to develop maximum or full tinting
strength is ascertained.
The parameters and dispersing conditions used for
three pigments that were investigated in an interlaboratory
test to determine the precision of this standard method are
given in Table 1.
TABLE 1Interlaboratory pigment dispersing parameters and specific conditions obtained
formaximum tinting strength [17]
Parameter
Pigment Type
Yellow Iron Oxide BON Red Phthalocyanine Green
Force applied, Ibf (N) 100 (440) 100 (440) 100 (440)
Total No. revolutions 100 (2 50) 200 (4 50) 400 (8 50)
Mass of color pigment, g 1.0 0.6 0.75
Mass of dispersing vehicle, g 1.7 1.4 1.8
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CHAPTER 46 MASS COLOR AND TINTING STRENGTH OF PIGMENTS 595
PIGMENT DISPERSION TECHNIQUES
It should be kept in mind that the techniques described in
this chapter pertain to preparing specimens for determina-
tion of tinting strength and mass color, and they are not
meant for pigment dispersion in general. The general topic
of pigment dispersion is discussed elsewhere in this manual
as well as in a variety of references [2331]. There is a vast
amount of literature that deals with the surface treatment
of organic pigments to improve ease of dispersibility, and
interested readers are encouraged to seek such informa-
tion in the classic work of Hayes [32], the above listed
references, and others [3335]. Detail regarding the surface
treatment of inorganic pigments is also in the literature
[3638].
Spatula and Hand Mullers
Grinding pigment/vehicle combinations can be carried out
with a spatula or a hand muller
4
by rubbing or mulling the
materials over a 3 12 in. (8 30 cm) strip area on a glass
plate. The rubbing is done by pushing the muller up one
side and pulling it down the other side of the strip area so
that all color particles receive the same amount of rubbing.
One rub is one up and down course on the strip area. Early
studies by Ayers [39] indicated that the muller gave more
reliable results than a spatula and that the rubbing surface
may vary a great deal without affecting the results. Stutzs
[40] results during investigation of the tinting strength
of white pigments also found a muller was superior to a
spatula. It was also found that a weighted or un-weighted
muller could be used without affecting the results.
Automatic Mullers
Automatic
5
or mechanical mullers have two circular glass
grinding surfaces that contain the pigment/vehicle mix-
ture. The grinding surfaces are usually constructed of
ground glass with one surface stationary and weighted to
exert a pressure of 100 psi (440 N) and the other surface
rotary with rotation effected with a motor. Because rota-
tion is about the diskcenters, paste located at the center
can receive less mulling than paste located near the edges.
To compensate for this effect, it has been found helpful to
spread the paste in a ring approximately halfway between
the edge and the center. The revolutions per mulling cycle
can be adjusted in increments of 1 to 999. Mechanical
muller advantages include very good development of tint-
ing strength, the possibility to rapidly mull small quantities
of materials, and efficient processing of a large number of
samples. The specific way to operate a mechanical muller
when determining tinting strength or mass color can be
found in the annex to Ref. [17].
LABORATORY MINIATURE MEDIA MILLS
Commercial horizontal or vertical laboratory media mills
that can process up to one quart of millbase are available.
In a general sense, media can be nonferrous or ferrous as,
for example, flint pebbles, sand, ceramic alumina, porce-
lain, stainless steel, high carbon steel spheres, etc. but for
test grinds, specified media must be used. For small grinds,
a media mill can be simulated with a laboratory dispenser
equipped with a fiber or Telfon 1 5/8 in. disk, a 200 mL
tall-form beaker, and media. Equal volumes of millbase to
media are used. Grinds may be 60.0 g for carbon black and
some organic pigments to 160.0 g for inorganic pigments.
The millbase must be carefully prepared to eliminate gross
and oversized agglomerates. Peripheral impeller speed
should be 2000 feet (610 m) per minute, and the mixture
should be ground for a set time or to a set dispersion level
such as a Hegman value of 7.0+. Advantages of media mills
include development of the highest tinting strength and
mass color, simulation of actual factory grinding condi-
tions, and low cost.
LABORATORY ROLLER MILL
Small, three-roller mills have been found useful for grind-
ing small, laboratory-size batches of paint. Rolls of such
mills are about 4 in. (10.16 cm) in diameter and 8 in.
(20.82 cm) in length. Batches as small as 5 g have been
prepared in such mills.
PALL GLASS MILL
Small quantities of metal-free pigment paste can be pre-
pared with the Pall Glass Mill [41]. The mill is a heavy
ground-glass stopper in a heavy glass joint. The mixed,
un-ground materials (18 g) are placed in the joint and the
stopper/plunger is inserted. The stopper is rotated with a
small motor at about 150 rpm. In this mill grinding pres-
sure ranges from 20 to 30 psi. The Pall Glass Mill is said
to be an improvement over hand mulling because it saves
time and because it results in greater development of tint-
ing strength.
PIGMENT CONCENTRATION
Paste viscosity has an effect on grinding efficiency, and it
is a property that determines the level of tinting strength
and mass color that is developed. Ayers [39] investigated
iron oxides, and his results indicated that color developed
faster as paste viscosity increased. A low-viscosity paste
had a reflectance of 26 % at a wavelength of 700 nm,
whereas a high-viscosity paste was darker and redder with
a reflectance of 23 %. It should be pointed out that there
is a point above which viscosity has no effect on grinding
efficiency.
MIXING TIME OF LIQUID COLORS
An important property of oil or universal liquid colorants
is the ease with which they can be incorporated into
white paints. A method for testing the speed of incorpo-
ration of such colorants has been described by Paul and
Diehlman [42]. Their method involves use of a mechani-
cal rotating bottle that contains a white paint, the liquid
colorant, and a grinding media. When the test was first
developed, No. 11 lead shot was used as the media; how-
ever, today glass beads, zirconia grinding media, and
steel shot are among the media used to avoid lead con-
tamination of the paint.
The test is conducted by charging the bottle with 550 g
of grinding media, 2 mL of the liquid colorant, and 75 mL
of white paint. The bottle is then closed with a cork that
is concave on the inner end to match the glass end of the
bottle and placed in the holder of the rotating device. The
4
Hand mullers are implements made of a hard substance such as
glass, stone, or similar material and used as a pestle to grind pig-
ment/vehicle (i.e., paint) combinations. These are seldom, if at all,
used today.
5
Automatic in this area of technology means motor driven.
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596 PAINT AND COATING TESTING MANUAL 15TH EDITION
bottle is then tilted and rotated slightly by hand to wet the
container walls.
This is followed by mechanical rotation of the bottle
until the paint is homogeneous in that no streaking of the
color is seen. The time in seconds for mixing is determined
and recorded.
OTHER RELATED TEST PROCEDURES
While the various test procedures cited above each contain
reference to a number of ASTM documents, it is worthwhile
to list some of these. Table 2 is a partial listing of such
potentially useful documents.
References
[1] Rich, D. C., Artificial Intelligence in Todays Colorant-Man-
agement Systems, Paint & Coating Industry, Vol. XIV, No. 9,
Sept. 1998, p. 48.
[2] Mitton, P. B., Chapter 1.4 Mass Color and Tinting Strength,
in Paint Testing Manual, Thirteenth Edition, G. G. Sward, Ed.,
ASTM International, West Conshohocken, PA, 1972.
[3] Aviles, J. I., Chapter 43, Mass Color and Tinting Strength, in
Paint and Coating Testing Manual, Fourteenth Edition, J. V.
Koleske, Ed., ASTM International, West Conshohocken, PA, 1995.
[4] Vlz, H. G., Industrial Color Testing, 2nd Ed., Wiley-VCH Ver-
lag GmbH & Co. KgaAm, Weinheim, Germany, 2002.
[5] Color Handbook, SpecialChems Coating & Inks For-
mulation Bulletin, Issue No. 106, August 2, 2007; www.
specialchem4coatings.com/tc/color/.
[6] ASTM D16-11, Standard Terminology for Paint, Relat-
ed Coatings, Materials, and Applications, Annual Book
of ASTM Standards, Vol. 06.01, ASTM International, West
Conshohocken, PA.
[7] ASTM E284-09A, Standard Terminology of Appearance,
Annual Book of ASTM Standards, Vol. 06.01, ASTM Interna-
tional, West Conshohocken, PA.
[8] Colour Index International, Fourth Edition Online in two
parts, http://www.colour-index.org/newusr1.asp, 2002.
[9] ASTM D4303-10, Standard Test Methods for Lightfastness
of Colorants Used in Artists Materials, Annual Book of
ASTM Standards, Vol. 06.02, ASTM International, West Con-
shohocken, PA.
[10] Zeller, R. C., The Meaning of Tint Strength, Color Res. Appl.,
Vol. 3, 1978, p. 34.
[11] Vernardakis, G., American Ink Maker, Vol. 62, No. 2, 1984, p. 24.
[12] ASTM D4838-88(2010), Standard Test Method for Determin-
ing the Relative Tinting Strength of Chromatic Paints, Annual
Book of ASTM Standards, Vol. 06.02, ASTM International,
West Conshohocken, PA.
[13] ASTM E308-08, Practice for Computing the Colors of Objects
by Using the CIE System, Annual Book of ASTM Standards,
Vol. 06.01, ASTM International, West Conshohocken, PA.
[14] ASTM D1640-03(2009), Test Methods for Drying, Curing, or
Film Formation of Organic Coatings at Room Temperature,
Annual Book of ASTM Standards, Vol. 06.01, ASTM Interna-
tional, West Conshohocken, PA.
[15] ASTM E1164-09a, Standard Practice for Obtaining Spec-
trometric Data for Object-Color Evaluation, Annual Book
of ASTM Standards, Vol. 06.01, ASTM International, West
Conshohocken, PA.
[16] ASTM E1347-06, Standard Test Method for Color and Color-
Difference Measurement by Tristimulus Colorimetry, Annual
Book of ASTM Standards, Vol. 06.01, ASTM International,
West Conshohocken, PA.
[17] ASTM D387-00(2008), Standard Test Method for Color and
Strength of Chromatic Pigments with a Mechanical Muller,
Annual Book of ASTM Standards, Vol. 06.01, ASTM Interna-
tional, West Conshohocken, PA.
[18] ASTM D3022-84(2005), Test Method for Color and Strength
of Color Pigments by Use of a Miniature Sandmill, Annual
Book of ASTM Standards, Vol. 06.01, ASTM International,
West Conshohocken, PA.
[19] ASTM D2066-07, Standard Test Methods for Relative Tinting
Strength of Paste-Type Printing Ink Dispersions, Annual Book
of ASTM Standards, Vol. 06.02, ASTM International, West
Conshohocken, PA.
[20] ASTM D2745-00(2008), Standard Test Method for Relative
Tinting Strength of White Pigments by Reflectance Measure-
ments, Annual Book of ASTM Standards, Vol. 06.01, ASTM
International, West Conshohocken, PA.
[21] ASTM D332-87(2008), Standard Test Method for Relative
Tinting Strength of White Pigments by Visual Observation,
Annual Book of ASTM Standards, Vol. 06.01, ASTM Interna-
tional, West Conshohocken, PA.
[22] ASTM D262-81(1999), Specification for Ultramarine Blue
Pigment, Annual Book of ASTM Standards, ASTM Interna-
tional, West Conshohocken, PA. (This ASTM specification is
included for historical purposesit was withdrawn in Decem-
ber 2005 because the specifications for this pigment are no
longer in the United States).
[23] Pal, R., Rheology of Particulate Dispersions and Compos-
ites, CRC Press, Taylor & Francis Group, New York, 2006,
p.440.
[24] Wissling, P., Metallic Effect Pigments: Basics and Applications,
William Andrew Publishing, New York, 2006, p. 300.
TABLE 2Related ASTM Documents
ASTM Designation Title
D282 Methods of Test for Mass Color
and Tinting Strength of Pigments
(withdrawn
a
)
D2244 Practice for Calculation of Color
Tolerances and Color Differences from
Instrumentally
Measured Color Coordinates
D3265 Standard Test Method for Carbon
Black-Tint Strength
D5326 Standard Test Method for Color
Development in Tinted Latex Paints
D6531 Standard Test Method for Relative
Tinting Strength of Aqueous Ink
Systems by Instrumental Measurement
E179 Guide for Selection of Geometric
Conditions for Measurement of
Reflection and Transmission Properties
of Materials
E284 Terminology of Appearance
E805 Standard Practice for Identification
of Instrumental Methods of Color or
Color-Difference Measurement of
Materials
E1164 Practice for Obtaining Spectrometric
Data for Object Color Evaluation
E1345 Practice for Reducing the Effect of
Variability of Color Measurement by
Use of Multiple Measurements
E1347 Standard Test Method for Color and
Color Difference Measurement by
Tristimulus Colorimetry
a
This particular method was withdrawn in 1929 and has not been
replaced. It will not be found in ASTMs listing of standards. It is
included for historical purposes.
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CHAPTER 46 MASS COLOR AND TINTING STRENGTH OF PIGMENTS 597
[25] Kunjappu, J. T., Essays in Ink Chemistry (For Paints and Coatings
Too), Nova Science Publishers, Inc., New York, 2001, p. 136.
[26] Lewis, P. A., Pigment Handbook, Properties and Economics,
2nd ed., John Wiley & Sons, Inc., New York, 1988, p. 976.
[27] Varley, D. M., and Bower, H. H., Journal of the Oil and Colour
Chemists Association, Vol. 62, 1979, p. 401.
[28] Patton, T. C., Paint Flow and Pigment Dispersion, 2nd ed.,
Wiley-Interscience, New York, 1979.
[29] Carr, W., Journal of the Oil and Colour Chemists Association,
Vol. 61, 1978, p. 397.
[30] Hafner, O., Journal of the Oil and Colour Chemists Association,
Vol. 57, 1974, p. 268.
[31] Parfitt, G. D., Dispersion of Powders in Liquids, 2nd ed., Wiley-
Interscience, New York, 1973.
[32] Hays, B. G., American Ink Maker, Vol. 62, No. 6, 1984, p. 28.
[33] Hampton, J. S., and MacMillan, J. F., American Ink Maker,
Vol.63, No. 1, 1985, p 16.
[34] Topham, A., Prog. Org. Coat., Vol. 5, 1977, p. 237.
[35] Merkle, K., and Schafer, H., Pigment Handbook, Vol. III, T. C.
Patton, Ed., Wiley-Interscience, New York, 1973, pp. 157167.
[36] Linden, H., Rutzen, H., and Wegemund, B., United States Pat-
ent 4, 167,421 (1979).
[37] Hauxwell, F., Stansfield, J. F., and Topham, A., U. S. Patent
4,042,413 (1977).
[38] Franklin, M. J. B., Goldbrough, K., Parfitt, G. D., and Peacock,
J., J. Paint Technol., Vol. 42, 1970, p. 740.
[39] Ayers, J. W., A Discussion of the Accuracy and Utility of Methods
of Test for Mass Tone and Tinting Strength, Proceedings, ASTM
International, West Conshohocken, PA, Vol. 34, Part II, 1934,
p. 497.
[40] Stutz, G. F. A., Tinting Strength of White Pigments, Proceed-
ings, ASTM International, West Conshohocken, PA, Vol. 34,
Part II, 1934, p. 521.
[41] Pall, D. B., A New All-Glass Mill, Ind. Eng. Chem. Anal. Ed.,
Vol. 14, 1942, p. 346.
[42] Paul, M. R., and Diehlman, G., Method and Apparatus for
Determining the Interval Required to Disperse Oil Colors
Throughout a Paint Medium, Proceedings, ASTM Interna-
tional, West Conshohocken, PA, Vol. 34, Part II, 1934, p. 490.
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Part 11: Physical and Mechanical Properties
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601
PREFACE
IN PREPARATION OF THIS CHAPTER, THE CONTENTS
of the fourteenth edition were drawn upon. The current
edition will review and update the topics as previously
addressed, introduce new technology that has been devel-
oped, and include additional references.
INTRODUCTION
Organic coatings are applied to a variety of substrate mate-
rials (woods, metals, plastics, ceramics) for decorative,
protective, and functional applications. In each case, it is
imperative that the coating adheres well to the substrate.
Accordingly, adhesion assessments should be an integral
part of the coating development. This may seem a straight-
forward task, but coating adhesion is, in fact, extremely
complex and often poorly understood. The growing use of
plastics to replace metals and other traditional materials
renders the issue even more complex [1,2].
The objectives of this chapter are to briefly review
salient concepts of the adhesion process and to discuss cur-
rently accepted standard test methods.
FUNDAMENTAL CONCEPTS
While the very definition of adhesion is of some contro-
versy [1], adhesion may be loosely defined as the attraction
between dissimilar bodies for one another. ASTM D907 on
Terminology of Adhesives defines adhesion as the state in
which two surfaces are held together by interfacial forces
which may consist of valence forces or interlocking action
or both. In discussing adhesion assessment, one may con-
sider the issue from two different aspects: basic adhesion
and practical adhesion. Basic adhesion signifies the sum-
mation of all interfacial, intermolecular forces, whereas
practical adhesion is used to represent the forces or work
required to disrupt the adhering system [3]. The next sec-
tion will be devoted to theories and concepts of basic adhe-
sion and will out of necessity be brief. The perspective will
be from that of a polymeric coating on a plastic substrate
[2]. Metal and metal oxide substrates will be discussed
where appropriate. The reader is referred to Refs. [47] for
a more thorough discussion.
BASIC ADHESION
Work of Adhesion
Bonding between polymeric coatings and substrates may
be viewed as the union of two contiguous polymer phases,
one a solid and the other a liquid that solidifies to form a
thin film. The reversible separation of the two phases may
be expressed by the work of adhesion
W Y Y Y
a
= +
1 2 12
(1)
where W
a
is the work of adhesion, and Y
1
and Y
2
are the
surface tensions of the two phases. The maximum force
per unit area,
2
, to effect this process is the ideal adhesive
strength [8]
2 12
0
16 9 3 =[ / ( ) ]( / ) W Z
a
(2)
where Z
0
is the equilibrium separation between the two
phases, usually about 5 . The average value W
a
for poly-
mers is typically 50 ergs/cm
2
, yielding a theoretical value
for
2
of 15 000 psi (103 mPa). For practical purposes this
value is never attained, primarily due to the fact that per-
fect inter-molecular contact is most unlikely. In fact, this
is at least an order of magnitude higher than the practical
adhesive strength usually observed. This deviation from
ideality has led to the promulgation of several theories of
adhesion, none of which are universally recognized [9].
This is not unexpected, since most theories deal exclusively
with the mechanisms of bond formation and disregard the
fact that bond strength is ultimately a function of both the
degree of bond formation, the nature of the bond (chemical
and physical), and the rheological properties of the bond-
ing phases. The strength of an adhesive bond is, in fact, a
function of all of these factors. Summary paragraphs about
basic theories of adhesion follow below.
Fracture Theory
The area of interfacial bonding between coating and sub-
strate will, in most instances, contain voids or defects. The
result is deviation between the ideal adhesive strength and
the practical limit.
Good [10] and Williams [11] have applied the theory
of cohesive fracture to coating fracture. The concept that
fracture propagates from the weakest point, a defect, is fun-
damental to fracture mechanics. The strength of a bond, in
terms of the energy required to induce fracture, is described
as a function of the defect size and the energy dissipated by
irreversible processes (plastic deformation, light emission,
and electric discharge). The general equation given is
f k EF d = ( / )
1/2
(3)
47
Adhesion
Gordon L. Nelson
1
1
Dean, College of Science, Florida Institute of Technology, 150 West University Blvd., Melbourne, FL 32901-6975.
MNL17-EB/Jan. 2012
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602 PAINT AND COATING TESTING MANUAL 15TH EDITION
where f is the fracture stress, k = (4/)
1/2
, E the elastic modu-
lus of the material, d the defect length, and F the fracture
energy or total work per unit area of fracture surface, which
is dissipated. Accordingly, the fracture energy
f W W
a i
= +
(4)
where W
a
is the work of adhesion and W
i
is the total work
for the irreversible processes. For all practical purposes W
i
is much greater than W
a
therefore [12,13]
f W
i
=
(5)
Weak Boundary Layer Theory
Proposed by several workers [1416], the weak boundary
layer theory maintains that true interfacial fracture does
not occur, and that fracture usually occurs cohesively in
a weak boundary layer, which may be near the interface
between coating and substrate. Experimental evidence has
perhaps disproved the first point [10], that true interfacial
failure can occur, but it has been shown that the second is
valid in some instances [17,18].
Of practical importance to WBL investigations is the
locus of fracture, which can occur in one or more of the
zones in Fig. 1. For a strong bond, the boundary layer (lay-
ers) must be rheologically sound and chemically durable.
The zone of failure may, of course, be studied by scanning
electron microscopy (SEM), transmission electron micros-
copy, and Fourier transform-infrared [19]. In fact, thin lay-
ers of coating have been noted where interfacial failure was
only thought to occur on visual examination.
Wetting-Contact Theory
The wetting-contact theory states that van der Waals attrac-
tive forces alone provide sufficient coating/substrate bond
strength given perfect molecular contact, and that the
extent of contact and resulting bond strength are functions
of wetting energetics [2028]. No one denies the importance
of wetting in adhesion, i.e., the lower the contact angles, the
more the interfacial area of contact, which generally yields
improved adhesion (Fig. 2).
However, thermodynamic wetting is a necessary but
not sufficient condition for the establishment of coating
film adhesion. Wetting is a kinetic phenomenon as well.
Furthermore, this model does not consider the effects of
weak boundary layers or the effects of defects or fracture
mechanics. What is the effect of surface contamination on
the contact angle?
For guidance on the measurement of contact angle,
see ASTM D7334 (WK11928) Standard Practice for Surface
Wettability of Coatings, Substrates and Pigments by Advanc-
ing Contact Angle Management.
Diffusion Theory
Voyutskii and others [2933] have proposed that coating
adhesion between high polymers arises from interdiffu-
sion. This has been validated somewhat by the observation
that adhesive strength is a function of polymer molecular
weight, structure, and contact time.
Key to this theory is the concept that no clear-cut
inter-facial boundary exists, but rather that an interphase
exists which consists of polymer chain segments from both
contiguous phases. The theory has been criticized for giv-
ing insufficient weight to the contribution of van der Waals
attractive forces. Nevertheless, for the case of solvent-borne
organic coatings applied to plastic substrates, this phenom-
enon is intuitively appealing.
Interdiffusion of coating and substrate polymer molecu-
lar segments is a function of polymer-polymer compatibility.
An interphase forms as a result of the blending of the two
phases. Although polymer pairs are generally incompatible,
Helfand and others [3438] have utilized statistical ther-
modynamics to predict that interdiffusion also occurs as a
result of the tendency for free energy at the interface to mini-
mize. A useful equation that describes interfacial thickness
as a function of the FloryHuggins interaction parameter as
derived from Hansen solubility parameters is [36,38]
a m
i
= 2( x)
1/2
/
(6)
where a
i
is the interfacial thickness expressed as the cross-
sectional area of a lattice cell, m is a lattice constant directly
proportional to nearest-neighbor contacts, and x is the Flory
Huggins interaction parameter. By this equation, interfacial
thickness increases by interdiffusion as the solubility param-
eter difference between the two phases decreases. Although
experimental verification is scarce, adhesive strength has
been shown to decrease with increasing disparity in the
solubility parameters of the two phases [39].
It is important to note that diffusion should occur in
the latter stage of bond formation, the first stage being wet-
ting to establish contact. Additional support for the theory
comes from the observation that adhesive strength between
certain high polymers increases with time [30]. This theory,
however, cannot be applicable to systems involving one or
more hard solids (metals, glass, or metal oxides).
Fig. 1Weak boundary layer theory. Possible zones of failure
(after Good [19]). Fig. 2Contact angle.
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CHAPTER 47 ADHESION 603
Chemical Adhesion
The bond strength of covalent bonds is 1 to 2 orders of mag-
nitude greater than van der Waals attractive forces. There
have been numerous applications where interfacial chemi-
cal bonds have been employed to promote adhesion. Dra-
matic increases in bond strength have been reported [40].
Coupling agents such as chrome complexes [41],
silanes [42], and titanates [43] have been used effectively,
Organic functionalities, including isoeyanates, carboxyls,
amides, amines, hydroxyls, and epoxides [43,44], have been
reacted interfacially to enhance adhesion.
Adhesive strength has been shown to increase with
functional group concentration as expressed by
f kC
n
=
(7)
where f is the adhesive strength, C the functional group con-
centration, and k and n are positive constants [45]. There,
however, appears to be an upper limit for functional group
concentration above which adhesion may tend to decrease
[46,47].
Mechanical Adhesion
In mechanical adhesion substrate roughness is thought
to provide a mechanical locking of the coating to the sub-
strate. However, if there is not intimate contact between
the coating and the substrate, then increased rough-
ness should lead to a decrease in adhesion by producing
uncoated voids. In the practical application of electroless
metals on polymer substrates, etchants are used that cre-
ate deep channels, increasing adhesion. Other examples
are anchor coats for polytetra fluoroethylene, adhesion to
porous anodic films on aluminum, and hot melt polyolefin
coatings on metals. Mechanical adhesion is also important
for porous substrates such as wood, cloth, and paper. Since
good adhesion can be obtained on smooth surfaces such
as glass, questions can be raised about the general valid-
ity of the mechanical adhesion mechanism. It should also
be noted that mechanical abrasive treatment of a solid
surface may also yield macroradicals and active secondary
chemical products, which if they do not come into contact
with atmospheric oxygen, may interact with components
of the coating. This has been shown for certain adhesives.
Active radicals or functionality would yield adhesion, bet-
ter described as mechanico-chemical adhesion than just
mechanical [7,48,49].
Electrostatic Adhesion
In the theory of electrostatic adhesion, when two dissimilar
materials are brought into contact, a charge transfer takes
place, which results in the formation of an electrical double
layer, much like a capacitor. Work would then be required
to separate the two charged layers. This is thought to be
particularly applicable to metal-polymer bonds. Indeed,
ionizing discharge has been shown to affect a copper to
acrylic bond but not copper on salt (NaCl) or glass. This
theory would not be applicable to two nonpolymer systems
[49,50].
Acid-Base Adhesion
In the acid-base adhesion theory, it is said that the strength
of the adhesive bonds is increased significantly by acid base
interactions between coating and substrate. Appropriate
modification of surface acidity or basicity of the substrate
should increase adhesion. Modification of surface acidity
or basicity of inorganic solids can increase mechanical
properties (modulus, extension to break, and toughness) of
coatings on these substrates. It has also been claimed that
the reverse is true, however [51,52].
Combination of Phenomena
The preceding theories interpret adhesion in terms of single
phenomena, each of which undoubtedly plays some role
in interfacial bonding between coating and substrate. One
should be cautioned, however, against exclusive use of a
single theory to explain the adhesion of a given system. A
more logical approach has been proposed by Allen [53].
= + + + a b c
A B C
(8)
which suggests that a combination of phenomena is more
realistic, that is, that basic adhesion is the summation of all
interatomic or intermolecular interactions at the interface.
One would think that systematic studies could be made to
assess the contribution of a given variable to the adhesion
process, with the others being held constant. This would
reveal useful information as to factors critical to coating
adhesion for a particular system. Unfortunately, being able
to accomplish that task is questionable given that adhesion
assessment not only involves factors of basic adhesion but
variation in application of the applied external stress (ten-
sile, shear, or peel) and many other factors.
It can be concluded that adhesion is an interfacial
phenomenon in which both physical and chemical forces
operate when surfaces develop to form an interface. Adhe-
sive strength is a measure of the degree to which the two
surfaces are attracted. This is a function of wettability, rela-
tive surface energetics of both phases, and of the kinetics of
wetting. For integrity of a bond at the interface between a
coating and a substrate, one needs to consider the follow-
ing factors:
1. Thermodynamics and kinetics of the formation of the
bond.
2. The forces acting near the interface in both the coating
and the substrate.
3. The cohesive forces within the coating layer.
4. Internal stresses in the coating layer.
5. The behavior of the coating layer under stress.
To understand basic adhesion one must understand
the surface chemistry, surface physics, surface architecture,
coating polymer chemistry and physics, polymer rheology,
coating internal stresses, fracture mechanics, and effects of
changes in the environment. In fact, it has been noted that
spontaneous loss of adhesion can occur due solely to inter-
nal strain of the coating [5456].
Effects of Substrates
ADDITIONAL CHEMISTRY
The adhesion of organic coatings to metals is at a high level
of development in the practical sense. The contribution of
surface energy, chemical functionality, surface irregulari-
ties, and contaminants (oxides, adsorbed water, etc.) have
been identified.
On the other hand, coating adhesion to plastic sub-
strates has presented additional complexities. Polymer
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604 PAINT AND COATING TESTING MANUAL 15TH EDITION
surfaces are often more difficult to wet and bond because
of low surface energy, incompatibility, chemical inertness,
or the presence of contaminants (oils, lubricants, plasticiz-
ers, etc.), and weak boundary layers. Surface modification
techniques have been developed to enhance adhesion. In
the absence of surface preparation, coating adhesion is
felt to be a function primarily of van der Waals and/or
polar-dipolar attractive forces, mechanical adhesion (from
surface irregularities), and interdiffusion. This latter contri-
bution to adhesion has been studied using SEM. In Fig. 3 is
presented a scanning electron micrograph of a thermoplas-
tic acrylic coating applied to modified polyphenylene oxide
(a blend of PPO and polystyrene), an important engineer-
ing thermoplastic. The first coating contains 60 % of the
recommended amount of solvent. The interface formed is
sharp and well-defined. In this instance, adhesion appears
to be due largely to mechanical and attractive forces. Fig.4
shows the same substrate and coating, which in this case
contains 100 % of the recommended amount of solvent.
The sharp interface seen in Fig. 3 is no longer present, an
intermediate zone or interphase having formed in its place.
Diffuse interface formation of this magnitude is undoubt-
edly unique to coatings applied to plastics. Bond strength
will be a function of formulation, solvent content, and dry-
ing time [2].
Organic coatings are complex formulations, thus, the
polymer chemistry at the developing coating substrate
interface will clearly be impacted by the solid surface,
whether plastic, metal, or inorganic, that is, the polymer
interface may be somewhat different than the bulk coating
(i.e., a boundary layer). Fully developed coatings may also
be porous or permeable, thus aging and weathering may
impact adhesion, as water, oxygen, and other agents pen-
etrate to the polymer coating solid interface [7,57]. Indeed,
some coatings that have acceptable adhesion while dry may
fail badly when tested under high humidity or after immer-
sion in water for several hours.
It has been shown for polyolefin-metal adhesion that
oxidation of the polymer attached to the surface occurs
through action of oxygen absorbed by the metal and the
polymer. The appearance of oxygen-containing groups in
the otherwise inert polymer should promote an increase in
the extent of interaction with the metal. Adhesion in this
case would also be increased by oxygen donor fillers [7,57].
All metals (except gold) are known to exist with an
oxide film on their surfaces. The volume of oxide formed
may be smaller than the metal reacted, and consequently
the oxide film is porous and nonprotective (alkali and alka-
line earth metals) or the volume may be larger and there-
fore protective (transition metals and aluminum). However,
in the latter case, migration of metal cations from the
surface leaves vacancies, which aggregate to form cavities.
Treatment of a metal before coating to produce a preferred
or controlled bonding surface is therefore common [7,57].
From the above discussion, it is clear that chemical inter-
action between coating and solid can occur even when not
recognized or anticipated.
Finally, a change in substrate may impact adhesion.
Weathering failures such as blistering and scab corrosion
are often regarded as adhesion failures by coatings devel-
opment chemists. Delamination of coatings in the absence
of substrate corrosion can also be produced by weathering.
A common problem involves the interfacial chalking of an
epoxy primer and a topcoat that has a high UV light trans-
mission. In the presence of UV light, moisture, and oxygen,
the epoxy primer is degraded at the interface between the
primer and topcoat, leading to delamination of the topcoat
from the primer.
Delamination of clear or semitransparent exterior
wood coatings can also occur by UV, water, and oxygen
attacking the wood substrate. Delamination of the intact
coating results when the wood substrate coating interface
is destroyed. The solution to this problem is to add organic
and inorganic UV absorbers to the coating to protect the
wood substrate from degradation.
PRACTICAL ADHESION
Given the complexities of the adhesion process, can adhe-
sion be measured? As Mittal [3] has pointed out, the answer
is both yes and no. It is reasonable to state that at the
present time no test exists that can precisely assess the
actual physical strength of an adhesive bond. But it can also
be said that it is possible to obtain an indication of relative
adhesion performance.
Practical adhesion test methods are generally of two
types: implied and direct. Implied type tests include inden-
tation or scribe techniques, rub testing, and wear testing.
Criticism of these tests arises when they are used to quan-
tify the strength of adhesive bonding. But this, in fact, is not
their purpose. An implied test should be used to assess coat-
ing performance under actual service conditions. Direct
measurements, on the other hand, are intended expressly
Fig. 3SEM of sharp interface.
Fig. 4SEM of diffuse interface.
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CHAPTER 47 ADHESION 605
to measure adhesion. Peel, lap-shear, and direct tensile are
common examples. Meaningful tests of this type are highly
sought after, primarily because the results are expressed by
a single discrete quantity, the force required to fracture the
coating/substrate bond under prescribed conditions [2].
Test Methods
In practice, a battery of tests is used to evaluate adhesion by
inducing bond rupture by different modes. Criteria deemed
essential for a test to warrant large-scale acceptance are:
use of a straightforward and unambiguous procedure,
relevance to its intended application, reproducibility, and
quantifiability, including a meaningful rating scale for
assessing performance. Test methods used for coatings on
metals are peel adhesion or tape testing, Gardner impact
flexibility testing, and adhesive joint testing including shear
(lap joint) and direct tensile (butt joint) testing. These
tests do not, in fact, strictly meet the criteria listed, but an
appealing aspect of the above tests is that in most cases the
equipment/instrumentation is readily available or can be
obtained at reasonable cost [2].
A wide diversity of test methods has been developed
over the years. In this chapter only selected test methods
developed through the consensus process will be discussed
in detail. The reader should recognize, however, that
numerous test methods have been developed that measure
aspects of adhesion [7,5861] and that there generally is
difficulty in relating these to basic adhesion phenomena
(Fig. 4).
The Tape Test
By far the most used test to access coating adhesion is
the peel test. In use since the 1930s, in its simplest version,
a piece of adhesive tape is pressed against the paint film.
The test consists of observing whether the film is peeled off
when the tape is removed. The method can be refined to
measure the force required for film removal. In other tests,
crosses or a cross-hatched pattern are cut into the coat-
ing, a tape applied and removed, and the coating removal
assessed against an established rating scale. The current
widely used version was first published in 1974 as ASTM
D3359, Standard Test Methods for Measuring Adhesion by
Tape Test. Two test methods are covered. This is one of the
top-selling ASTM test methods, regardless of field.
These test methods cover procedures for assessing the
adhesion of coating films to metallic substrates only, by
applying and removing pressure-sensitive tape over cuts
made in the film. Method A is primarily intended for use at
job sites, while Method B is more suitable for use in the lab-
oratory. The cross-hatch test, Method B, is not considered
suitable for films thicker than 5 mils (125 m). Both test
methods are used to establish whether or not the adhesion
of a coating to a substrate is at a generally adequate level.
They do not distinguish between higher levels of adhesion
for which more sophisticated methods of measurement are
required. In multicoat systems, adhesion failure may occur
between coats so that the adhesion of the coating system to
the substrate is not determined. In Test Method A an X-cut
1.5 in. (3.8 cm) long is made in the film (to the substrate)
with a sharp cutting device. A 1-in. (2.5-cm)-wide pressure
sensitive tape is applied over the cut and firmly adhered
with a pencil eraser and then removed, and adhesion is
assessed qualitatively on a 0 to 5 scale.
In Test Method B, a lattice pattern with either 6 or 11
cuts in each direction is made in the film (to the substrate),
pressure-sensitive tape is applied over the lattice and then
removed, and adhesion is evaluated by comparison with
descriptions and illustrations.
For Test Method A, the following rating scale is used:
5A = No peeling or removal.
4A = Trace peeling or removal along incisions.
3A = Jagged removal along incisions up to
1/16in. (1.6 mm) on either side.
2A = Jagged removal along most of incisions up
to 1/8 in. (3.2 mm) on either side.
1A = Removal from most of the area of the X
under the tape.
0A = Removal beyond the area of the X.
For Test Method B, 3/4 in. (1.9 cm) cross-cuts are made.
For coatings having a dry film thickness up to and
including 2.0 mils (50 m), 11 cuts are spaced 1 mm apart.
For coatings having a dry film thickness between 2 mils
(50 m) and 5 mils (125 m), 6 cuts are spaced 2 mm apart.
For films thicker than 5 mils (125 m), Method A is
used instead of Method B.
For Test Method B, adhesion is rated according to the
following scale (as illustrated in Fig. 5):
5B = The edges of the cuts are completely
smooth; none of the squares of the lattice
is detached.
4B = Small flakes of the coating are detached at
intersections; less than 5% of the area is
affected.
3B = Small flakes of the coating are detached
along edges and at intersections of cuts.
The area affected is 5 to 15 % of the
lattice.
2B = The coating has flaked along the edges and
on parts of the squares. The area affected
is 15 to 35 % of the lattice.
1B = The coating has flaked along the edges of
cuts in large ribbons, and whole squares
have detached. The area affected is 35 to
65 % of the lattice.
0B = Flaking and detachment worse than Grade
1.
Repeatability within one rating unit is generally
observed for coatings on metals for both methods, with
reproducibility of 1 to 2 units. The method is widely used
and is viewed as simple as well as low in cost.
Peel Adhesion Testing on Plastic Substrates
ASTM D3359 has drawn fire when used for substrates
other than metal, such as plastics. The central issues are
that the test may lack reproducibility and does not relate
to its intended application. Poor reproducibility is a direct
result of several factors intrinsic to the materials employed
and the procedure itself. More importantly, in this instance
the test is being applied beyond its intended scope. ASTM
D3359 was designed for relatively ductile coatings applied
to metal substrates, not for coatings (often brittle) applied
to soft plastic parts [1].
Nevertheless, the tape test enjoys widespread popu-
larity. The tape test is economical to perform, lends
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606 PAINT AND COATING TESTING MANUAL 15TH EDITION
itself to job site application, and most importantly, after
decades of use, people feel comfortable with it [42].
Unfortunately, the often unique functional requirements
of coatings on plastic substrates dictate that the tape test
as written may not be a satisfactory measure of practical
adhesion performance.
When a flexible adhesive tape is applied to a rigid
coated substrate surface and then removed, the removal
process has been described in terms of the peel phenom-
enon, as illustrated in Fig. 6.
Peeling begins at the toothed leading edge (at the
right) and proceeds along the coating-adhesive interface. It
is reasonable to assume that any coating removal is due to
a tensile force generated along this interface, which would
be a function of the rheological properties of the backing
and adhesive layer materials and the strength of the bond
between the adhesive layer and the coating surface. Note,
however, that in actuality this force is distributed over a
discreet distance (0 to A in Fig. 6), which relates directly to
Fig. 5Classification of adhesion test results. From ASTM D3359.
Fig. 6Peel profile [62].
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CHAPTER 47 ADHESION 607
the properties described [63], not concentrated at a point
(0 in Fig. 6) as in the theoretical case, though tensile force
is greatest at the origin for both. It is worthwhile to note
the significant compressive force which arises from the
response of the tape-backing material to being stretched,
which precedes the tensile force. Both tensile and compres-
sive forces are involved in tape testing.
Close scrutiny of the tape test with respect to the nature
of the tape employed and certain aspects of the procedure
itself reveal several factors, each or any combination of
which can dramatically affect the results of the test as dis-
cussed below.
The Tape Controversy
Beginning in 1991, given the withdrawal of the originally
specified tape, 3M-710, ASTM D3359 no longer specified
a specific tape. Differences in tapes can lead to different
results for reasons noted above since small changes in back-
ing stiffness and adhesive rheology cause large changes in
the tension area. It is also important to note that tapes, like
most products, are manufactured to meet minimum stan-
dards. A given lot may surpass these criteria and be suitable
for general market distribution, but a source of serious
and unexpected error for tape testing [63]. There was, in
fact, a commercially available tape test kit that included a
tape with adhesion variations of up to 50 % claimed by the
manufacturer [64]. And, of course, tapes age on storage.
Bond strengths change over time.
While there are tapes available that would appear
to deliver consistent performance, a given tape does not
adhere equally well to all coatings. For example, the peel
removal force of the tape previously recommended by
ASTM (3M-710) was examined with seven coatings. It was
found that while peel was indeed consistent for a given
coating, it varied by 25 % between the highest and low-
est ratings among coatings. This observation could be the
result of several factors, notably coating composition and
topology, but the bottom line is that no single tape is likely
to be suitable for testing all coatings. It is also useful to note
the tape test does not give an absolute value for the force
required for bond rupture, but serves only as an indicator
that some minimum value for bond strength was met or
exceeded [1,2].
Procedural Problems
The tape test is operator intensive. By design it was made
as simple as possible to perform and requires a minimum
of specialized equipment and materials that must meet cer-
tain specifications. Therefore, the burden of accuracy and
reproducibility relies largely upon the skill of the operator
and his/her ability to perform the test in a consistent man-
ner. Key steps that directly reflect the importance of opera-
tor skill include the angle and rate of tape removal and the
visual assessment of the tested sample. It is not unexpected
that different operators might obtain different results [1,2].
PEEL ANGLE AND RATE
The standard requires that the free end of the tape be
removed rapidly at as close to a 180 angle as possible. But
if peel angle and rate vary, the force required to remove the
tape can change dramatically. Nearly linear increases were
observed in peel force approaching 100 % as peel angle was
changed from 135 to 180, and similar large differences
can be expected in peel force as peel rate varies. These
effects are related in that they both reflect certain rheo-
logical properties of the backing and adhesive, which are
molecular in origin, but the most useful conclusion is that
these phenomena can make large contributions and must
be minimized to assure reproducibility [65].
VISUAL ASSESSMENT
The final step in the test is visual assessment of coating
removed from the specimen, and this can be subjective in
nature. This assessment can vary among individuals evalu-
ating the same specimen [65].
Performance in the tape test is based on the amount
of coating removed compared to a relative scale. But it was
found that the exposure of substrate can be due to factors
other than coating adhesion, arising from the requirement
that the coating be cut (hence the synonym cross-hatch
adhesion test). Justification for the cutting step is reason-
able; cutting provides a free edge from which peeling can
begin without having to overcome the cohesive strength of
the coating layer. This might be suitable for coatings applied
to metal substrates, but for coatings applied to plastics, the
cutting process can lead to false indications of poor adhe-
sion. This is due to the unique interfacial zone mentioned
earlier. For coatings on soft plastics, how deep should this
cut penetrate? Is it possible to cut only to the interface?
If microscopic examination of panels is included, in
several instances it is clearly evident that coating removal
results from substrate failure at or below the interface, not
from adhesive failure between coating and substrate. At the
same time, it is also observed that cohesive failure within
the coating layer is a frequent occurrence. The latter obser-
vation is significant in that the tape test assessment criteria
make no provision for it [1,2].
Mechanized Tape Test
A mechanized tape test was published by ASTM Committee
B 8 in 2000. The scope of ASTM B905, Test Methods for
Assessing the Adhesion of Metallic and Inorganic Coatings
by the Mechanized Tape Test, includes the assessment of
adhesion of metallic and inorganic coatings and other thin
films to metallic and nonmetallic substrates. A pressure-
sensitive tape is applied to the coated surface and then a
mechanized device is utilized to remove the tape at a regu-
lated, uniform rate and constant angle while the removal
force is simultaneously recorded (Fig. 7). Four methods are
described: A1 and A2, which do not involve cuts made to the
coating (for use on parts), and B1 and B2, which use a cross-
hatch pattern of six lines (plus six at 90) for laboratory
use. Methods 1 and 2 refer to peel angles of 90 and 180,
respectively. Methods B1 and B2 are not recommended for
polymeric substrates. For Method A coating detachment
(failure) or no coating detachment (pass) are reported ver-
sus the maximum registered peel force. For Methods B a
classification similar to ASTM D3359 is reported versus the
maximum registered peel force. The spacing of cuts, how-
ever, is 4 mm versus 1 or 2 mm in D3359. In B 905 a 90
peel angle is preferred due to the stress strain behavior of
the tape, versus the 180 peel angle of D3359.
An interlaboratory study during the development of the
test method revealed that the maximum peel force of the
tape depends significantly on the type of coating, the type
of tape, the peel rate, and the peel angle. The pressure used
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608 PAINT AND COATING TESTING MANUAL 15TH EDITION
for adhering the tape (a roller is used) was not significant.
Results for the four test methods should not be compared.
While the methods provide a regulated uniform peel rate
and constant angle of test, and most importantly provide
a way of measuring peel force, the other underlying issues
in tape testing are not overcome. If two different coatings
have different peel forces despite a single tape, peel rate,
and angle of peel, then the adhesion rating/results are still
not directly comparable.
Other Peel Tests
The corresponding test in the International Standards
Organization to ASTM D3359 is ISO 2409. The cross-
hatch test is used in ISO 2409 up to a coating thickness
of 10 mils (250 m). A single crosscut test is used above
10 mils, versus 5 mils (125 m) for D3359. A 1-mm cross-
hatch spacing is used for a coating thickness up to 60 m
for hard substrates, a 2-mm spacing for soft substrates, a
2-mm spacing for coatings 61120 m, and a 3-mm spacing
above 120m. In ISO 2409 six cuts for the 90 cross-hatch
are made in each direction. In D3359 a 1-mm spacing is
used for coatings up to a thickness of 50 m (11 cuts in
each direction) and a 2-mm spacing for coatings 50125 m
(6cuts), with the single crosscut test applied at higher coat-
ing thickness. In ISO 2409 the tape is removed at an angle
of 120 (angle away from operator) versus 180 in D3359.
The classification scheme is 0 to 5 with 0 meaning no coat-
ing detachment in ISO 2409. This is the opposite in D3359,
with ratings 5B to 0B, with 0B signifying greater than 65%
coating removal. Thus ISO 2409 and ASTM 3359, while
both being tape peel tests, differ in many significant ways,
not the least of which being that the classification schemes
signify opposite results.
Numerous tape peel tests exist in the industry. Exam-
ples include the General Motors Engineering Standard
GM 9071P-Tape Adhesion Test for Paint Finishes, which is
similar to ASTM D3359, and Boeing Specification Support
Standard (BSS) 7225, which provides more varied cross-
hatch patterns than D3359 and provides specific proce-
dures for tape testing after wet immersion.
Direct Tensile Testing
A long-used approach to coating adhesion testing is the
direct tensile test, perhaps conceptually the simplest of
all methods for measuring adhesion. A dolly or stud is
bonded to the coating film. The normally applied force
that is required to remove the film is measured. If failure
occurs at the substrate-film interface, this force is taken
to be the force of adhesion. An obvious limitation is, of
course, the strength of the adhesive bond of the stud to
the cured coating. Such methods have been available since
the 1930s. Many of these test methods have unfortunately
suffered from their own lack of reproducibility. This is not
unexpected since the forces involved are not quite as simple
as appearance would have it [5,66].
It is essential that the force is applied strictly in
the direction normal to the sample and that no bending
moment is active across the test area. Deviations from sym-
metry in the test arrangement, poor alignment, deviations
from homogeneity and of thickness of the adhesive (coat-
ing), and random variations in the strength of the bond
between film and substrate affect test results [5,66].
The stress at locations where the adhesive film is thin-
ner will be higher than the average stress and will be trans-
mitted to the film under test. Another factor may be peeling
during the test, which is not easily identified or analyzed.
The adhesive used to bond a stud to the coating has
the potential to influence the coating film properties by
penetration through the film into microcracks and possibly
into the substrate [66]. Test adhesive flexibility may also
be an issue, as well as the flexibility of the substrate, if the
sample is unrestrained.
There exists now within ASTM both laboratory and field
versions of direct tension tests for coatings. Test Method
for Measuring Adhesion of Organic Coatings to Plastic
Substrates by Direct Tensile Testing. ASTM D5179, while
limited to organic coatings on plastics, uses a restrained
sample and commonly available tensile test apparatus. The
second, Method for Pull-Off Strength of Coatings Using
Portable Adhesion-Testers, ASTM D4541, defines a class
of portable pull-off adhesion testers for field evaluation of
coating adhesion. ASTM D5179 is the successor to numer-
ous attempts to develop a reproducible coating tension test
and was approved in 1991. It will be discussed first.
ASTM D5179
This test covers the laboratory determination of adhesion
of organic coatings to plastic substrates by mounting and
removing an aluminum stud from the surface of a coating
and measuring the force required to break the coating/sub-
strate bond with a tensile tester. The test method provides an
inexpensive test assembly, which can be used with most ten-
sile test machines. The method is used to compare the pull-
off strength (commonly referred to as adhesion) of coatings
to various plastic substrates, thus allowing for a quantitative
comparison of various coating/substrate combinations.
A carefully prepared 2-cm diameter aluminum stud
is bonded directly to a coated, cured panel using a cyano-
acrylate adhesive. The adhesive is allowed to cure for 2 h
at room temperature. Adhesive buildup is removed from
around the stud. The specimen is then subjected to test on a
tensile tester equipped with an upper coupling adapter and
a restraining device (Fig. 8) to provide for sample alignment
and minimal substrate flexing. The sample bearing the stud
is installed in the restraining device, with only the stud pro-
truding. The tensile machine crosshead is lowered so the
upper coupling adaptor can be attached to the specimen.
Fig. 7Mechanized tape tester.
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CHAPTER 47 ADHESION 609
When testing thin substrates, a piece of plastic is
placed in the restraining device behind the specimen to
insure a rigid assembly. The tension test is conducted, and
pull strength recorded. Each specimen is rated according to
type of coating failure, as follows:
A = Adhesive failure of the coating from the
substrate.
C = Cohesive failure in the coating.
AC = Combination of adhesive failure at the coat-
ing/substrate interface and cohesive failure
in the coating.
S = Adhesive failure at the stud.
CS = Combination of adhesive failure at the stud
and cohesive failure in the coating.
For multilayer coatings, failure between the layers is
noted and labeled as CM. Five specimens of each coated
substrate are tested one day and five on a second day. If
one specimen differs significantly from the other four
tested at the same time, fails because of an uneven (non-
planar) stud, or for another reason performs unlike the
other four, a replacement specimen is tested. The stud and
specimen are carefully examined. The adhesive should
have been applied uniformly to the entire stud surface.
Coating should have pulled off uniformly over the entire
stud surface either with adhesive failure from the sub-
strate (A) or cohesive failure in the coating (C). If failure
is less than 90 % A or C (or CM), if the adhesive has failed
at the stud, a retest, exercising particular care in the speci-
men and stud preparation is performed. Pull strength for
the ten runs on each coating substrate combination are
averaged and reported.
The precision and bias are primarily dependent upon
the accuracy of the force measurements, the alignment of
the device, and the care exercised in stud and specimen
preparation, and in the care in testing. A ten-laboratory
round robin on ten samples gave an average standard
deviation of 29 % for reproducibility and 22 % for repeat-
ability. A range of pull strengths of 2 orders of magnitude
has been observed (Table 1) for diverse coating-plastic
combinations.
ASTM D4541
This test method defines a class of portable adhesion tes-
ters for measuring the pull-off strength of coatings. The
method covers a procedure and apparatus for evaluating
pull-off strength by determining either the greatest per-
pendicular force (in tension) that a surface area can bear
before a plug of material is detached or whether the sur-
face remains intact at a prescribed force (pass/fail). Failure
will occur along the weakest plane within the system com-
prised of the test fixture, adhesive, coating system, and
substrate and will be exposed by the fracture surface. The
method maximizes tensile stress as compared to the shear
stress applied by other methods such as scratch or knife
adhesion, and results are not comparable. It is recognized
that the pull-off strength reflects both material and instru-
mental parameters and therefore provides a relative, not
absolute, measure of adhesion. The pull adhesion testers
defined are portable and capable of applying a concentric
load and counter load to a single surface so that coatings
in the field can be tested even though only one side is
accessible. Measurements are limited by the strength of
adhesion bonds between the loading fixture and the speci-
men surface or the cohesive strength of the substrate. The
pull-off test is performed by securing a loading fixture
(dolly or stud) normal (perpendicular) to the surface of
the coating with an adhesive. After the adhesive is cured,
the testing apparatus is attached to the loading fixture
and aligned to apply tension normal to the test surface.
The force applied to the loading fixture is then gradually
increased (in less than 100 s) and monitored until either
Fig. 8Direct tensile restraining device. From ASTM D5179.
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610 PAINT AND COATING TESTING MANUAL 15TH EDITION
a plug of coating material is detached or a specified value
is reached. The nature of the failure is assessed as to the
percent of adhesive or cohesive failure, and the actual
interfaces and layers involved are identified. The pull-off
strength is computed based on the maximum indicated
load, the instrument calibration data, and the original sur-
face area stressed (Fig. 9).
This method is general and is applicable to any por-
table apparatus meeting the standards basic requirements
for determining the pull-off strength of coatings. Five appa-
ratuses are commonly recognized to meet the requirements
of the standard.
It is known that the rigidity of the substrate affects
pull-off strength results and is not a controllable test vari-
able in field measurements as defined by this standard.
For example, steel substrates of less than 1/8 in. (3.2 mm)
thickness show reduced pull-off strength results compared
to 1/4-in. (6.4-mm) thick panels.
Errors in measurement in this test result from align-
ment of the apparatus that is not normal to the surface,
poor definition of the area stressed due to improper
application of the adhesive, poorly defined glue lines and
boundaries, holidays in the adhesive caused by voids or
inclusions, improperly prepared surfaces, and sliding or
twisting of the fixture during the initial adhesive cure. Also,
scratched or scored samples may contain stress concentra-
tions leading to premature fractures. Interlaboratory data
have been obtained for four commercial test apparatus and
are presented in Table 2.
ISO 4624
Similar pull-off test methodology has been approved
through the International Standards Organization, and
the parameters involved have been carefully studied. ISO
4624, Pull-off Test for Adhesion, was approved in 1978.
ISO 4624 specifies two different tests assemblies (A and B
of Fig. 10).
Test Assembly A (Sandwich Method) consists of a
substrate painted on one or both sides, with test cylinders
(studs) with a specified diameter bonded coaxially to the
coated test surface and on the reverse. Test Assembly B
consists of a rigid substrate coated on one side, with one
test cylinder (stud) applied to that side only. While the lat-
ter is the more practical, Test Assembly A on stress analysis
shows a smoother stress distribution than B. Test Assembly
B shows strong stress peaks at the coating layer periphery.
The result is that Test Assembly B shows 20 to 60 % lower
breaking strength results than the sandwich method for
several organic coatings on metal [67].
TABLE 1Representative pull strength for
organic coatings on plastics
Sample
No. Coating Substrate
Failure
Mode
Pounds
Per Square
Inch
a
1 Lacquer Polyester/
Polycarbonate
C 58
2 Lacquer Polycarbonate A 36
3 Lacquer ABC C 82
4 Lacquer Polycarbonate A 37
5 Lacquer ABS A 93
6 Lacquer PVC AC 103
7 Enamel Polycarbonate A 308
8 Urethane ABC A 639
9 Urethane ABS A 476
10 Urethane Metal S 666
11 Enamel Metal 75% A 342
12 Lacquer PPO/Nylon C 226
13 Enamel PPO/Nylon C 226
14 Enamel PPO/Nylon A 242
a
To convert to metric, multiply by 6.89 kPa.
NOTE: ABC = acrylonitule-butadiene-styrene, PVC = polyvinyl chloride,
PPO = polyphenylent ether.
TABLE 2ASTM D 4541 interlaboratory data (psi)
a
Instrument Loading Fixture
Diameter Paint Sample
Patti
13 mm
Elcometer
20 mm
Hate 19 mm
(mean of 3 results)
Dyna
50 mm
A 1160 586 1185 201
B 1099 624 1157 185
C 1333 827 1245 190
D 1678 888 1686 297
a
To convert to metric, multiply by 6.89 kPa.
Fig. 9Portable adhesion tester. From ASTM D4541.
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CHAPTER 47 ADHESION 611
For Test Assembly B, breaking strength values have
been shown to be a function of the diameter of test cylin-
ders (studs) as well as their geometry. On the range of 10
to 28 mm diameters, a factor of 2 in breaking strength was
seen with a peak at about 14-mm diameter. It was observed
that tensile forces only affected the central part of the test
area. Even test cylinders of the same diameter, but differ-
ent shapes, gave different results, up to 45 % lower. It has
been noted that while uniform tensile stress can only be
approached, the length of the test cylinder (stud) should
be no less than half its diameter. When this is done, similar
results are achieved regardless of cylinder diameter [67].
Perhaps it is only a coincidence, but it is interesting to
note in Table 2 for apparatus meeting ASTM D4541 that the
loading fixture diameter and geometry differ significantly and
at least partially account for the greater than factor of 4 varia-
tion in test results, with the apparatus having a 50-mm load-
ing fixture diameter showing the lowest numerical results.
Substrate thickness (flexibility) has a significant effect
upon results. In a study of steel panels in the range of 2 to
30 mm thick, breaking strength increased to a thickness of
15 mm using Test Assembly B. A comparison of results with
the sandwich method for substrates above 15-mm thickness,
however, still showed breaking strength values about one
third higher for Test Assembly A. These observations can be
explained in terms of differences in stress distribution. Thin-
ner substrates show increased stress intensity at the periph-
ery, which is distinguishable up to 15-mm thickness [67].
ISO 4624 specifies that tensile stress shall not be
increased at a rate greater than 1 MPa/s, so that failure
occurs within 90 s of initial stress application. An investiga-
tion of the rate of tensile stress increase in the range 0.15 to
1.2 MPa/s yielded indistinguishable results [67].
Sample parameters are important. Coating thick-
ness (and adhesive thickness) is a key factor. The
energy stored in a 5-mil (125m) coating, by virtue of
its internal strain, increases as the coating thickness
increases and at a particular thickness can be sufficient
to overcome the work of adhesion at the interface (spon-
taneous peeling). The variation is largest at thicknesses
below 125 m (5 mils), which of course is the area of
most practical application. It was also observed that at
the lowest coating thickness for the coatings studied,
cohesive failure occurred in the uppermost parts of
the coating, leaving a very thin film of coating on the
test cylinder (stud). With thicker coatings, the fracture
propagated deeper into the coating. Through study of
the locus of failure, one can also study the effects of
environmental conditions (aging, solvents, moisture)
and of coating resin cure [67].
More recent studies have also looked at instrument
and sample parameters. Rocke et al. studied the influ-
ence of measured pull-off strength by stud area, adhe-
sive thickness, the thickness of the substrate, as well as
coating composition [68]. A comprehensive Norwegian
study involved some 1400 pull tests using three different
instruments on a three-coat paint system and on thermal
arc-sprayed ALMg5 on blast-cleaned steel, with the blast-
cleaned steel also assessed as a standard. The parameters
investigated included the effect of panel thickness on pull
strength (5, 8, and 12 mm), the effect of cure time of the
paint system on pull-off strength (8, 15, 28, 37, and 76
days after application of the top coat), the effect of four
different brands of cyanoacrylate adhesive on pull-off
strength, the effect of different temperatures on adhesive
cure or pull-off on pull-off strength (8.5C, 23C, and
70C), the effect of stud diameter on pull-off strength,
and the effect of cutting around the edge of the stud on
pull-off strength. The data reported were the averages of
10 to 30 runs [69].
Adhesion on blast-cleaned steel using an epoxy adhe-
sive showed a 2458 % increase in mean pull-off strength
in going from 5 to 12 mm thick panels. The increase in
pull-off strength for the three-coat paint system increased
3034 % from 8- to 76-day coating cure time. Four cyano-
acrylate adhesives were cured for 1, 2, 5 at 23C or 8.5C
at 50 % relative humidity on bare blast-cleaned steel. At
23C (1h) pull-off strength ranged from 25.6 to 35.4 MPa,
while at 5 h pull-off strength ranged from 29.1 to 38.2 MPa.
Corresponding data at 8.5C were 21.5 to 27.0 and 22.2
to 30.6, respectively. Testing of arc spray coated samples
at different temperatures showed an increase in pull-off
strength for one of two cyanoacrylate adhesives and not
the other and also a difference in locus of failure was also
noted. Some effect of stud size was seen, with higher mean
pull-off strength for studs at 1.57 cm
2
versus 3.14 cm
2
. Cut-
ting around the stud showed a slight lowering of pull-off
strength (under 10 %). A number of experimental factors
affect test results. A 5-mm rigid steel panel is not infinitely
thick. Cured coatings may still be undergoing changes over
long time periods. Such changes can effect adhesion. Tem-
peratures of cure coatings and adhesives may affect pull-off
strength [69].
Clearly, stress distribution changes, as altered by test
apparatus and sample parameters, can alter results dra-
matically. Pull-off strength (breaking strength) is therefore
a relative number. Comparisons must be made carefully in
concert with an examination of the locus of failure. Practi-
cally speaking, while absolute values are only approached,
relative values and studies of the locus of failure are suf-
ficient for most purposes.
Scrape Adhesion Testing
Used to a lesser extent than the preceding methods is ASTM
D2197, Test Methods for Adhesion of Organic Coatings by
Scrape Adhesion.
This test method covers the determination of the adhe-
sion of organic coatings such as paint, varnish, and lacquer
when applied to smooth, flat (planar) panel surfaces. The
materials under test are applied at uniform thickness to
planar panels, usually sheet metal of uniform surface
texture. After drying, the adhesion is determined by push-
ing the panels beneath a rounded stylus or loop loaded in
Fig. 10ISO 4624 test assemblies.
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612 PAINT AND COATING TESTING MANUAL 15TH EDITION
increasing amounts until the coating is removed from the
substrate surface.
The method is most useful in providing relative ratings
for a series of coated panels exhibiting significant differ-
ences in adhesion. The balanced-beam, scrape-adhesion
tester (Fig. 11) consists of a balanced beam to which is
secured a platform for supporting weights and a rod at an
angle of 45 that holds the scraping loop. The rod is set so
that the scraping loop contacts test surfaces directly below
the weights. The loop is a 1/16-in. (1.6-mm)-diameter rod
bent into a U shape with an outside radius of 0.1280.002
in. (3.250.05 mm) hardened to Rockwell HRC 56 to 58 and
chromium plated and polished.
At least 1/2 in. (1.3 cm) at the end of a test panel is
un-coated. The surface of the substrate must be hard
enough so that it is undamaged by the scraping loop. The
test procedure is as follows. A test panel on the sliding
platform is placed so that it may be moved away from
the operator and the uncoated portion is toward the main
beam support. Weights are placed on the weight support
using an initial amount estimated to be appropriate for the
particular coating. The beam is lowered until the loop rests
on the uncoated portion of the specimen and the full load
is applied; then the sliding platform is slowly pushed away
from the operator 1 to 2 s/in. for a distance of at least 3 in.
(76 mm). If the coating is removed, the testing is continued
using successively smaller loads (0.5-kg increments) until
the coating is not removed. If the coating is not removed
by the initial scrape, the testing is continued, using suc-
cessively larger loads (0.5-kg increments) until the coating
is removed or until the maximum load of 10 kg has been
applied. A new area of the test surface is used each time a
scrape is made. When the critical load has been approxi-
mately located, the test is repeated five times at each of the
three loadings: above, below, and at the load determined in
the first trial.
For each applied load, the number of times the coat-
ing was removed or adhered is tabulated. The load where
the scrape results change from mainly adhering to mainly
removed, ignoring the first 1/2 in. (13 mm) of the scratch
if the coating was removed, is the adhesion failure end
point.
Perhaps the most practical approach to paint adhe-
sion is assessment by the use of a paint knife. A test method
that provides guidance for such evaluations is ASTM
D6677, Test Method for Evaluating Adhesion by Knife.
TORQUE TESTS
While the scope of ASTM D3359 provides for the testing
of coatings on metal substrates only, it and other tests
discussed previously have been used to assess the adhe-
sion of coatings on wood. Little data have, however, been
published with wood as the substrate. Several papers
using a torque technique have been published [7073].
While such methods have not been standardized, it was
felt that they might be of interest to readers. In this shear
technique, studs are glued on the painted samples using
a solvent-free, dual-component epoxy glue. After the glue
has dried, a slot is drilled in the paint film around the
studs until the wood surface is reached. The studs are
removed using a recording torque wrench. The failure
load is noted and the locus of failure determined. The
shear stress (adhesion value) is calculated using the
equation T = (167I)/(d3) where I is the measured torque
(Nm), and d is the diameter of the stud (in this case, 12.5
mm). A minimum of six replicates is used for the calcu-
lation of the mean adhesion value. Adhesion values are
given in MNm
2
. Painted samples have been tested dry
and after water immersion [74,75].
UNIFORM DOUBLE-CANTILEVER BEAM TESTS
While not standardized, workers have found success with a
uniform double-cantilever beam technique for the testing of
the adhesion of coatings on wood [74,75].
Other ASTM Standards
Other ASTM standards that pertain to aspects of adhesion
measurements of films and coatings include the following:
ASTM B533 Standard Test Method for Peel
Strength of Metal Electroplated
Plastics.
ASTM B571 Standard Practice for Qualitative
Adhesion Testing of Metallic
Coatings. (This method includes
bend, burnishing, chisel-knife, draw,
file, grind-saw, heat-quench impact,
peel, push, and scribe-grind tests.)
ASTM C633 Standard Test Method for Adhesion
or Cohesion Strength of Thermal
Spray Coatings.
ASTM D3730 Guide for Testing High-Performance
Interior Architectural Wall Coatings.
(This guide includes a pull-strength
test for adhesion assessment.)
ASTM D4145 Standard Test Method for Coating
Flexibility of Prepainted Sheet. (This
method includes a tape pull-off test.)
ASTM D4146 Standard Test Method for
Formability of Zinc-Rich Primer/
Chromate Complex Coatings on
Steel. (This method is a tape test
after dome-shaped deformation.)
ASTM D7234 Standard Test Method for Pull-Off
Adhesion Strength of Coatings on
Concrete Using Portable Pull-Off
Adhesion Testers.
Fig. 11Balanced-beam scrape adhesion tester.
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CHAPTER 47 ADHESION 613
ASTM D7334 Standard Practice for Surface
Wettability of Coatings, Substrates
and Pigments by Advancing Contact
Angle Measurement.
ASTM F692 Standard Test Method for Measuring
Adhesion Strength of Solderable
Films to Substrates.
ASTM F1044 Standard Test Method for Shear
Testing of Calcium Phosphate
Coatings and Metallic Coatings.
ASTM F1147 Standard Test Method for Tension
Testing of Calcium Phosphate and
Metal Coatings.
ASTM F1842 Standard Test Method for
Determining Ink or Coating Adhesion
on Plastic Substrates for Membrane
Switch Applications. (This test is
based upon D3359.)
Additional tests exist for electrodeposits, and bending,
burnishing, and wrapping tests for coatings on wire. Tests
for adhesives have also been applied to coatings as well. Use
of reverse impact tests, lap and butt joint tests, and tensile
shear tests have been reported [1].
CONCLUSIONS
Basic adhesion is the summation of multiple phenomena.
Ideal adhesion is probably neither obtainable nor mea-
surable experimentally. Practical techniques do, however,
allow sufficient assessment of relative adhesion for most
purposes, if used with care and knowledge. Workers need
to understand both basic adhesion concepts and the factors
affecting practical adhesion for systems of their interest if
they are to make improvements in real world products.
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and Practice, Maclaren and Sons, London, 1969, p. 152.
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614 PAINT AND COATING TESTING MANUAL 15TH EDITION
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[52] Massingill, J. L., J. Coat. Technol., Vol. 63, No. 797, 1991, pp.
4754.
[53] Allen, K. W., in Aspects of Adhesion, Vol. 5, D. J. Alner, Ed.,
University of London Press, 1969, p. 11.
[54] Paul, S., J. Coat. Technol., Vol. 54, No. 692, 1982, pp.5965.
[55] Croll, S. G., Adhesion and Internal Strain in Polymeric Coat-
ings, in Adhesion Aspects of Coatings, K. L. Mittal, Ed., Ple-
num Press, New York, 1983, pp. 107129.
[56] Sato, K., Prog. Org. Coat., Vol. 8, 1980, pp. 143160.
[57] Lewis, A. F., and Forrestal, L. J., Adhesion of Coatings, in
Treatise on Coatings, Vol. 2, Part I, R. R. Myers and J. S. Long,
Eds., Marcel Dekker, New York, 1969, pp. 5798.
[58] Gardner, H. A., and Sward, G. G., Chap. 7, Paint Testing
Manual, 12th ed., Gardner Laboratory, Bethesda, MD, 1962,
pp. 159170.
[59] Corcoron, E. M., Adhesion, Chap. 5.3 in Paint Testing Manual,
ASTM STP 500, 13th ed., G. G. Sward, Ed., ASTM Interna-
tional, West Conshohocken, PA, 1972, pp. 314332.
[60] Mittal, K. L., J. Adhes. Sci. Technol., Vol. 1, No. 3, 1987,
pp.247259, bibliography.
[61] Stoffer, J. O., and Gadodia, S. K., American Paint and Coatings
Journal, Vol. 70, No. 50, 1991, pp. 3640, and Vol. 70, No. 51,
1991, pp. 3651.
[62] Wu, S., Polymer Interface and Adhesion, Marcel Dekker, Inc.,
New York, 1982, p. 531.
[63] Marion, E. Wolters, 3M memorandum, 1984.
[64] Product Bulletin, 3M.
[65] Proceedings, Symposium on Adhesion Aspects of Polymeric
Coatings, K. L. Mittal, Ed., The Electrochemical Society, 1981,
pp. 569582.
[66] Jacobsson, R. J., Thin Solid Films, Vol. 34, 1976, pp.191199.
[67] Stichfeld, J., Pull-Off Test, An Internationally Standard-
ized Method for Adhesion TestingAssessment of Rel-
evance of Test Results, in Adhesion Aspects of Polymeric
Coatings, K. L. Mittal, Ed., Plenum Press, New York, 1983,
pp.543567.
[68] Rocke, P., Dole, M., and Bouzziri, J., J. Adhes. Sci. Technol.,
Vol. 8, 1994, p. 587.
[69] Scheie, J., and Nilsen, R., Do the Adhesion Instruments Mea-
sure Accurately? What effect does the type of adhesive curing
of the paint, etc., have on the pull strength?, Report 18601,
National Institute of Technology, Norway, 1996.
[70] Holloway, M. W., and Walker, P. A., Mater. Struct., Vol. 47,
1964, pp. 812823.
[71] Ahola, P., Materials and Structures, Vol. 28, 1995, pp.350356.
[72] Ahola, P., J. Oil Colour Chem. Assoc., Vol. 74, 1991, pp. 173
176.
[73] Bardage, S. L., and Bjurman, J., J. Coat. Technol., Vol. 70, No.
878, March 1998, pp. 3947.
[74] Knaebe, M. T., and Williams, R. S., J. Test. Eval., 21(4), 1993,
pp. 272275.
[75] Knaebe, M. T., Williams, R. S., and Spence, J. W., J. Coat.
Technol., Vol. 68, No. 856, May 1996, pp. 2730.
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615
PREFACE
IN PREPARATION OF THIS CHAPTER, THE CONTENTS
of the fourteenth edition were drawn upon. The author
acknowledges the authors of the fourteenth edition. The
current edition will review and update the topics as
addressed by the previous authors, introduce new tech-
nology that has been developed, and include up-to-date
references.
The problem of resistance to abrasion exists all around
us: on floors, walls, furniture, automobiles, farm imple-
ments, construction equipment, military gear, appliances,
shoe soles, and so on. Because resistance to abrasion is a
basic factor in the durability of a coating, its measurement
is of practical importance to both producer and consumer.
Abrasion is caused by mechanical actions such as rub-
bing, scraping, or erosion from wind and water. It can take
two general forms: marring or wearing.
DEFINITIONS
Mar abrasion consists of permanent deformations that
have not ruptured the surface of a coating. The resistance
of a coating to marring is its ability to withstand scuffing
actions that tend to disfigure or change the appearance
of its surface. Some examples of potential causes of mar-
ring of organic coatings are (a) sliding an object across the
surface of furniture; (b) rubbing of a belt buckle, button,
zipper, or rough fabric on an automobile finish; (c) sliding
a toy across a wall or a refrigerator door, etc.
Wear abrasion is caused by mechanical action that
removes material from the surface of a coating. In many
cases, the removal is gradual or progressive due to repeti-
tive mechanical action.
RELATIONSHIP TO OTHER PHYSICAL PROPERTIES
Abrasion resistance is not a unique or isolated property of a
material but is rather related to other physical characteris-
tics such as hardness, cohesive and tensile strength, elastic-
ity, and toughness. Also, from the standpoint of retaining its
protective or decorative function, the thickness of a coating
can be an important factor.
Hardness, Elasticity, and Tensile Strength
Abrasion resistance is related to hardness, yet the relation-
ship is not simple. A first thought might be that the harder
a coating, the better would be the abrasion resistance;
however, this is not always true. Steel is much harder than
rubber, for example, but steel tires on an automobile,
in addition to not giving a smooth ride, would not last
long on concrete roads in comparison to the service life
of a good rubber tire. The ability of a material, such as a
rubber tire, to undergo elastic deformation and recover or
to ride with the blow is associated with good abrasion
resistance.
The energy transferred to an elastic material by an
impacting object is largely returned to the object, though
redirected, instead of being expended in the destruction
(separation and removal of material) of the impacted sur-
face. From a fundamental viewpoint, this is a consequence
of the smaller deceleration and hence smaller force gener-
ated, since force is equal to the product of mass and accel-
eration, when the impact is with a material that will deform
or give with the impacting object. If the deformation
caused by the object is not elastic, the material will yield
and flow, causing damage. Therefore, soft materials with a
low tensile strength are not abrasion resistant.
The fact that elastic materials are often abrasion resis-
tant does not mean that hard materials are not abrasion
resistant. Theoretically, however, if one is given two materi-
als of equal tensile strength, the material of lower modulus
should have the best abrasion resistance. The deceptive fac-
tor here is that a hard material usually has a much higher
tensile strength than a soft material. Thus, when a rubber
is compared with steel, materials with orders of magnitude
difference in tensile strength are being considered. The fact
that rubber is abrasion resistant emphasizes that the value
of a low modulus of elasticity and adequate tensile strength
are factors that play a role in obtaining good abrasion
resistance.
In theory, a very hard material that has a hardness and
cohesive strength adequate to completely resist any impact
force it might encounter would not be dependent on rub-
berlike elasticity to reduce or dissipate impact stresses. It
would be more abrasion resistant than the best elastic but
weaker material [1].
CORRELATION WITH END-USE PERFORMANCE
From the discussion above, it is apparent that the measure-
ment of abrasion resistance involves measuring a com-
plex combination of interrelated properties among which
there is no direct relationship. The task of devising a test
methodology that will correlate with end-use performance
is, therefore, complex and difficult but not impossible to
48
Abrasion Resistance
*
Daniel K. Slawson
1
*
This chapter is an abridged and modifed version of the chapter with the same title, written by Mark P. Morse, found in the previous edi-
tion of this manual.
1
Taber Industries, 455 Bryant St., North Tonawanda, NY 14120
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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616 PAINT AND COATING TESTING MANUAL 15TH EDITION
develop. If the test method subjects the material under test
to a composite of destructive forces similar to those met in
service, then the test method will correlateor predictthe
service performance of the material in at least a qualitative
or relative ranking respect.
When accelerated tests are being considered, even
tests that rank materials in the same sequence as actual
service tests, a quantitative correspondence with actual
service is seldom expected or obtained. Actual end-use
tests, while the most reliable in providing an indication of
a materials probable long-term durability, suffer from the
difficulties of ensuring equivalent usage and measurement,
especially when the comparison of different materials is
attempted. Because of such difficulties and because service
tests are usually very time consuming, a wide variety of
test machines have been developed to provide an accel-
erated indication of the abrasion resistance of coatings
and related materials such as laminate flooring, plastics,
linoleum, and wall coverings. In a comprehensive review
article by Harper [2], there is a list of no less than 49 dif-
ferent abrasion-causing machines. An investigation by the
International Study Committee for Wear Tests of Flooring
Performance [3], in which seven commercial, organic floor-
ing materials were systematically tested on 21 abrasion
machines of 17 different types, indicated that very few of
these machines were capable of providing a reliable com-
parison of the abrasion resistance of widely different mate-
rials that could be correlated with end-use performance. In
addition, the different machines did not correlate very well
with each other.
On the basis of a round robin conducted in 1956 by
ASTM with six different clear floor coatings evaluated by
six different abrasion test methods [4], only two of the
methods were found to correlate with actual end-use per-
formance and to have the reproducibility necessary for
acceptance as ASTM standards. These were ASTM Test
Method for Abrasion Resistance of Organic Coatings by
Falling Abrasive (ASTM D968) and ASTM Test Method
for Abrasion Resistance of Organic Coatings by Air Blast
Abrasive (ASTM D658, withdrawn in 1996). The jet abrader
(ASTM D658, withdrawn in 1996) offers greater speed and
precision of measurement [1]. More recent comparative
testing (see Comparison of Wear Abrasion Testers) indi-
cates ASTM D658 is superior to ASTM D968 and that ASTM
Test Method for Abrasion Resistance of Organic Coatings
by the Taber
) abrasion
wheels containing a wide range of silicon carbide and
aluminum oxide grains. The scrub abrasion testers use
black nylon or black hog bristle brushes, sponges, abrasive
paper, and stainless steel/nylon balls. The Linear Abraser
uses abrasive plugs (Wearasers
Abraser
(This instrument is available from Taber Industries, 455
Bryant Street, North Tonawanda, New York 14120. www.
taber-industries.com) This apparatus, Fig. 5, is widely used
for evaluating the wear abrasion resistance of organic coat-
ings. A procedure for its use is given in ASTM Test Method
for Abrasion Resistance of Organic Coatings by the Taber
Abraser (ASTM D4060), in ISO/DIN Methods 3494 and
4584. ASTM D4060 utilizes a specimen in the form of a
4-in. (10.2-cm)-diameter disk or a 4-in. (10.2-cm)-square
mounted on a turntable that is rotated at a fixed speed
under a weighted abrading wheel. A wide variety of resin
and vitrified abrasion wheels containing a wide range of
aluminium oxide and silicon carbide grits create different
types of abrasion. An important feature of the Abraser is the
wheels traverse a complete circle on the specimen surface.
This reveals abrasion resistance at all angles relative to the
grain of the specimen. A vacuum pickup is used to remove
Fig. 3Interior of a gravelometer (courtesy of the Q-Panel
Company).
Fig. 4Schiefer abrasion testing machine (courtesy of Frazier
Precision Instrument Company).
Fig. 5Taber Abraser (courtesy of Taber Industries).
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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CHAPTER 48 ABRASION RESISTANCE 619
any loose particles generated during actual tests. Wear
abrasion resistance is expressed in terms of (a) Wear Index,
which is the weight loss per specified number of revolutions
(usually 1000) under a specified load (500 or 1000 g), and/
or (b) wear cycles per mil, which is the number of cycles
required to wear through a 1-mil thickness of coating and
is reported as the number of revolutions per mil.
ASTM D6037 Standard Test Methods for Dry Abrasion
Mar Resistance of High Gloss Coatings, utilizes two test
methods to assess mar resistance by measuring the gloss
of abraded and unabraded areas. Mar resistance is directly
related to the coatings ability to retain gloss in abraded
areas. Test Method A uses a device that contains an abra-
sive wheel (Taber Calibrase
, CS-10F
Wheels resurfaced on a ST-11 Refacing Stone to create the
wear. The abrasive damage is visually judged and numeri-
cally quantified by the difference in haze percentage in
accordance with Test Method D1003 between abraded and
unabraded specimen.
Taber
Linear Abraser
The Taber
). This
instrument is designed to test virtually any size or shape
specimen in a wet or dry environment. This instrument can
also be modified to evaluate scratch resistance and color
transfer. A precision bearing on the spline shaft creates
a free-floating head. As the arm strokes, the abradant
follows the contour of the specimen, curved or flat. The
user can customize the abradant, stroke length, speed, and
weight load. A procedure for its use is given in ASTM Test
Method D6279 Test Method for Rub Abrasion Mar Resis-
tance of High Gloss Coatings.
Taber
Linear Abraser, with a scouring pad to simulate the wear
bakeware and cookware receive in extensive home use as
it is cleaned.
Taber
Reciprocating Abraser
The Reciprocating Abraser, shown in Fig. 10, referenced in
ISO 1518 Paints and VarnishesScratch Test, is used for
evaluating resistance to abrasion, scratch, and mar on most
flat or slightly contoured objects. A sliding specimen plat-
form moves in a horizontal, reciprocating motion under a
stationary tool, generating a linear wear, scratch/mar path.
RCA Abrasion Wear Tester
(This device, is available from Norman Tool and Stamp-
ing Co., 15415 Old State Rd., Evansville, IN 47711. www.
normantool.com). It is being used for evaluating the abra-
sion resistance of appliance finishes and of coatings on
television set controls. The machine abrades a 2 in. by
2 in. (5.1 cm by 5.1 cm) coated panel surface by passing
computer or polyester tape over the surface. A fresh tape
surface is presented for each cycle of abrasion. Weights
ranging from 55 to 275 g are applied to the tape depending
on the nature of the coating under test. Abrasion resistance
is reported either as the number of cycles required to pro-
duce the onset of visible scuffing or as the number of cycles
required to wear through to the substrate.
Oscillating Sand Tester
This testing device, seen in Fig. 11, is used to determine the
resistance of transparent plastics and transparent coatings
utilized in windows or viewing ports to surface abrasion.
The test specimen is mounted in a tray (so that it forms part
of the bottom of the tray) and covered with abrasive media
to a depth of 12.7 mm. The tray reciprocates in a linear
motion at a speed of 300 strokes per minute over a distance
of 100 mm. A typical test utilizes a specimen that is 100 nm
by 100 mm and is tested for 600 strokes. The results of the
test consist of measuring and recording the change in haze
Fig. 8Taber Linear Abraser (courtesy of Taber Industries).
Fig. 9Taber Large Linear Abraser (courtesy of Taber
Industries).
Fig. 10Taber Reciprocating Abraser (courtesy of Taber
Industries).
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CHAPTER 48 ABRASION RESISTANCE 621
and light transmission of the test specimen. This tester is
referenced in ASTM F735, Standard Test Method for Abra-
sion Resistance of Transparent Plastics and Coatings Using
the Oscillating Sand Method.
COMPARISON OF ABRASION TESTERS
ASTM Subcommittee D-01.23 conducted a round robin
to determine the comparative precision, sensitivity, and
correlation of four wear abrasion testing procedures. The
procedures were (a) air blast silicon carbide (ASTM D658
discontinued in 1996), (b) falling sand (ASTM D968),
(c) falling silicon carbide (ASTM D968), and (d) Taber
Abraser (ASTM D4060). The wear abrasion resistance of
four coatings with significantly different apparent resis-
tances to abrasion were tested with each device. The results
obtained from these tests are recorded in ASTM Report RR
D01-1037, which is available at ASTM Headquarters.
From the results, it was concluded that the air blast
silicon carbide test and the cycles per mil Taber Abraser
test had better sensitivity in differentiating coating abra-
sion resistances than the other test procedures. The falling
sand test, air blast silicon carbide test, and Taber Abraser
cycles per mil test ranked the coatings in the same order
as the expected performance. The falling silicon carbide
test reversed the ranking of two of the coatings. The preci-
sion exhibited by the four test procedures are as given in
Table 1.
TESTS FOR MAR ABRASION RESISTANCE
Balanced Beam Tester
A useful test for determination of mar resistance involves
the use of a balanced beam scrape tester, seen in Fig. 12.
ASTM D5178 was developed to determine the mar resis-
tance on smooth, flat surfaces. Results are expressed in
terms of force-to-mar films of organic coatings such as
paint, varnish, and lacquer when applied to smooth, flat
planar panel surfaces. This test is carried out by placing
a coated test panel on a movable platform and a weight
on the beam. The stylus is lowered gently onto the coated
surface and then the platform is pushed against the sty-
lus at a rate of 1/4 in. (6 mm) per second for a distance
of at least 3 in. (75 mm). At the end of each stroke, the
stylus is raised off the coated panel and the panel is
moved slightly to the side to provide a new test surface.
The coating is examined for marring. If none is visu-
ally observed in the initial scrape, successively greater
weights are added to the beam until marring is appar-
ent. If marring is produced in the initial scrape, testing
is continued using successively lighter weights until
the coating is not marred. The weight required to just
produce visible marring is taken as the mar resistance
value. Details about the balanced beam tester and its
operation can also be found in ASTM D2197, Test Meth-
ods for Adhesion of Organic Coatings by Scrape Adhe-
sion, ASTM D2248, Practice for Detergent Resistance of
Organic Finishes.
Taber
Shear/Scratch Tester
The Taber Shear/Scratch Tester, seen in Fig. 13, is used
to evaluate the scratch and mar resistance of organic
coatings, slate, high pressure decorative laminates, and
polymeric substrates. A specimen rotates at 0.5 or 5 rpm
and the scratching/marring occurs as the specimen comes
in contact with either the diamond or carbide tools. An
adjustable load is applied to the scratch tool. Mar resistance
is reported as the amount of weight required to just pro-
duce a barely visible scuffing or loss of gloss. This instru-
ment is referenced in ASTM C217, Weather Resistance of
Slate, EN 438-2 Decorative High Pressure Laminates
Resistance to Scratching, ISO 4586-2 High Pressure Deco-
rative LaminatesResistance to Scratching.
Fig. 11Taber Oscillating Sand Tester (courtesy of Taber
Industries).
TABLE 1Comparison of abrasion resistance
test method precision
Coefficients of Variation
Within
Laboratory
Between
Laboratories
Taber Abraser (ASTM D4060) 4 % 16 %
Air Blast Silicon Carbide (ASTM D658) 7 % 10 %
Falling Sand (ASTM D968) 9 % 35 %
Falling Silicon Carbide (ASTM D968) 11 % 45 %
Fig. 12Balanced Beam Tester (courtesy of Byk-Gardner).
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622 PAINT AND COATING TESTING MANUAL 15TH EDITION
Multi-Finger Scratch Tester (5-Finger Scratch
Tester)
This testing device, made popular by the automotive
industry, can be used for determining the scratch and mar
resistance of molded-in-color automotive plastics by use of
a linearly oriented, multi-fingered scratching device. Opera-
tion involves 1 or 7 mm, individually loaded, hemispherical
tips scratching the surface at a constant speed of 100 mm
per second. This testing device is seen in Fig. 14.
Coin Mar Test
This test consists of dragging the edge of a coin across
the surface of a coated panel and visually determining the
degree of marring produced. The procedure can be used
as a pass/fail test or for comparing the mar resistance of
coatings on a relative basis. Results will vary from labora-
tory to laboratory due to the particular coin used and the
pressure used for contact.
Fingernail Test
In this test, the back of a fingernail is dragged across the
surface of a coating and the degree of marring is visually
observed. The procedure can be used as a pass/fail test or
for comparing the mar resistance of coatings on a relative
basis.
Paperclip Mar Test
This procedure is used to determine the ability of a surface
to resist scuffing or marring. Scuffing is defined as perma-
nent damage to the coating. An example of scuffing would
be a break in the top-coat with visible flakes of coating
caused by scraping by the paperclip. A paperclip remains
in contact with the test specimen as the specimen is moved
in four directions that are parallel to each of the edges of
the specimen. The appearance is evaluated for evidence of
scuffing or marring.
Nanoscratching
ASTM D7187 Standard Test Method for Measuring Mechan-
ical Aspects of Scratch/Mar Behavior of Paint Coatings by
Nanoscratching, covers the nanoscratch method for deter-
mining the resistance of paint coatings on smooth flat sur-
faces to scratch/mar. The loss of appearance is mainly due
to surface damages created. This method uses a two step
process to quantitatively and objectively measure scratch/
mar behavior. Step one is to find the relationship between
damage shape and size. Step two is to relate damage shape
and size to visual loss of luster.
RAIN OR WATER EROSION
Rain erosion resistance of aircraft coatings has been stud-
ied in two types of testing machines [11]whirling arm and
jet. In the whirling arm tester, specimens having an airfoil
contour are fastened to the leading edges of the two arms
of a propeller-like blade that is rotated at angular velocities
equivalent to flying speeds of up to 700 mph. Simultane-
ously drops of water fall on the whirling arms. Both the
simulated air speed and the quantity of rainfall can be
varied and closely controlled. In the jet-type tester, a high-
pressure jet of water impinges on the specimen. A rotating
slotted disk in the path of the water jet breaks the stream of
water into individual drops to simulate rainfall.
In both of the above methods, having the water in the
form of individual drops is a basic principle of the test. This
is because the erosion that occurs on the leading edges of
the airfoils on high-speed aircraft flying through rain is
often the result of cavitation produced by the high-energy
impacts of a multitude of individual droplets. At very high
velocities, the water droplets, in effect, behave as tiny solid
projectiles.
MISCELLANEOUS METHODS
PEI Abrasion Tester
Designed and developed by the Porcelain Enamel Institute
to measure the abrasion resistance of porcelain enamels,
this tester has also proven to be useful in determining the
wet abrasion resistance of organic coatings. It is specified
to be used in ASTM C448, Test Methods for Abrasion Resis-
tance of Porcelain Enamels. The tester, which is pictured
in Fig. 15, has a gyrating table with positions for nine
specimens. Abrasive-retaining rings and lids are clamped
over the specimen to form individual test chambers. Each
chamber is charged with glass or stainless steel spheres,
and a slurry of abrasive particles is added through a
Fig. 13Taber Shear/Scratch Tester (courtesy of Taber
Industries).
Fig. 14Taber Multi-Finger Scratch Tester (courtesy of Taber
Industries).
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CHAPTER 48 ABRASION RESISTANCE 623
filling aperture located in the lid. The table gyrates at 300
cycles per minute to cause abrasion of the specimens. The
amount of abrasion is evaluated by measuring the loss of
gloss or loss of weight in the specimens after a specified
time period [12].
Sand on Wheel Tester
This test instrument is used for determining the resistance
of metallic materials to abrasion by means of the dry sand/
rubber wheel apparatus. The test specimen is pressed
against a rotating rubber-rimmed wheel [13]. The test speci-
men is exposed to three-body scratch abrasion as abrasive
grit is introduced between the specimen and rubber-rimmed
wheel under a specified load. The intent of this method is
to produce data that will reproducibly rank materials in
their resistance to abrasion under specified conditions. Test
results are reported as volume loss in cubic millimeters for
the particular test procedure specified. Materials of higher
abrasion resistance will have a lower volume loss. ASTM
G65 Standard Test Method for Measuring Abrasion Using
the Dry Sand/Rubber Wheel Apparatus.
END POINT MEASUREMENT
Any abrasion test is useless unless an accurate and repeat-
able endpoint can be reached. Without a precise end, the
abrasion test results can be meaningless. The most com-
mon methods for determining endpoint are as follows;
weight loss of the specimen after the abrasion test, visual
loss by inspecting the specimen either with the naked eye
or digitally. Those less common methods include gloss loss,
haze loss, and change in coating thickness.
Calibration
An important aspect of todays quality systems is the trace-
ability of testing instruments. Verification that the instru-
ments, abradants, and scratch tools are within specification
is the core to ensuring repeatable and reproducible test
results. Precision testing instruments should be calibrated
regularly to ensure accurate results.
References
[1] Roberts, A. G., Chap. 5.2, Abrasion Resistance, Paint Test-
ing Manual, ASTM STP 500, ASTM International, West Con-
shohocken, PA, 1972.
[2] Harper, F. C., The Abrasion Resistance of Flooring Materi-
als: A Review of Methods of Testing, Wear, Vol. 4, 1961, pp.
461478.
[3] International Study Committee for Wear Tests of Flooring
Performance, Performance of Abrasion Machines for Floor-
ing Materials, Wear, Vol. 4, 1961, pp. 479494.
[4] Interim Report, Abrasion Resistance of Floor Coatings,
Group 20 Subcommittee IX on Varnish, ASTM Committee
D-1, 1956.
[5] Hipkins, C. C., and Phair, R. J., The Falling Sand Abrasion
Tester, ASTM Bull. No. 143, ASTM International, West Con-
shohocken, PA, December 1946, pp. 1822.
[6] Schiefer, H. F., J. Res. Natl. Bur. Stand., Vol. 39, RR 1807,
1949, p. 1.
[7] Schiefer, H. F., Crean, L. E., and Krasny, F. F., Improved
Single-Unit Schiefer Abrasion Testing Machine, J. Res. Natl.
Bur. Stand., Vol. 42, RR 1988, 1949, pp. 481497.
[8] Schiefer, H. F., and Werntz, C. W., Text. Res. J., Vol. 22, 1952,
pp. 112.
[9] ASTM D4158, 2008, Test Method for Abrasion Resistance of
Textile Fabrics (Uniform Abrasion), Annual Book of ASTM
Standards, Vol. 07.01, ASTM International, West Conshohock-
en, PA.
[10] Hill, H. E., and Nick, D. P., Study of the Reliability of Taber
Abrasion Results, J. Paint Technol., Vol. 38, No. 494, 1966,
pp. 123130.
[11] Grace, J. K., and Frey, G. C., Laboratory Testing of the Rain-
Erosion Resistance of Aircraft Finishes, ASTM Bull. No. 168,
ASTM International, West Conshohocken, PA, September
1950, pp. 5661.
[12] Outbridge, R., Proceedings of Rubber Technology Conference,
4th, London, 1962, Preprint No. 21.
[13] Marks, M. E., and Conrad, P., Resistance of Plastics to Abra-
sive Particles, Mod. Plast., Vol. 23, 1946, pp. 165168.
Fig. 15PEI abrasion tester. (courtesy of National Bureau of
Standards).
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624
49
DYNAMIC MECHANICAL AND TENSILE PROPERTIES
are determined in all branches of materials science. There
is a large body of published structure/property information
that can be integrated with coatings research and develop-
ment. By using structure/property information, coatings
chemists can design and optimize chemical structures of
the binder components of coatings. Purposeful and enlight-
ened formulation with well-designed components makes it
possible to obtain desirable coatings performance in many
cases.
Determination of dynamic mechanical and tensile
properties requires the use of free films. This requirement
is a serious limitation because many, if not most, of the per-
formance properties of coatings are influenced by coating-
substrate interactions. Therefore, tests of coatings intact
on their end-use substrates must be thoughtfully coupled
with free film determinations. The practical utility of basic
methods described in this section is greatly enhanced when
results are interpreted in relation to results of adhesion,
abrasion, hardness, flexibility, toughness, and internal
stress tests as described elsewhere in the manual.
Dynamic mechanical analysis (DMA) and stress-strain
analysis (SSA) of tensile properties are complementary
methods in several ways. DMA involves very small strains,
whereas SSA involves the maximum strain that the sample
can withstand. Since the small strains used in DMA usu-
ally do not exceed the tensile strength or yield strength
of the sample, the method is nondestructive. This feature
facilitates property determination over a wide temperature
range on a single sample, that is, DMA is often used as a
temperature-scanning method. In contrast, SSA data are
usually obtained at a single temperature, preferably on an
instrument located in a controlled temperature and humid-
ity room. Since the sample is broken in each test, it is very
arduous to carry out SSA over a wide temperature range,
and SSA is not amenable to temperature scanning.
DEFINITIONS
Tensile Versus Shear Tests
Two types of deformation of a block-shaped sample are
depicted in Fig. 1. These deformations are used frequently
in property determinations because they can be carried out
reproducibly and treated by simple mathematics. In a ten-
sion test (Fig. 1 (A)), the sample is pulled apart with straight
line application of force, called uniaxial extension. In a
shear test (Fig. 1 (B)), one face of the cube is held stationary
and the sample is pushed sideways by application of force
at the opposite face. Note that different symbols ( epsilon
or ) are used for strain in these two tests. A single symbol
is used for stress ( sigma), but subscripts indicate the type
of test. In Fig. 1, F is force and A, B, and C are initial sample
dimensions. The product A B is the initial cross-sectional
area.
It is evident in Fig. 1 that strain is defined quite dif-
ferently in tension and shear tests. In a tension test, strain
is the fractional increase in sample length. In a shear test,
strain is the distance moved by the movable face divided
by sample thickness, i.e., the distance between the station-
ary and movable faces. In both tests, stress is force divided
by cross-sectional area, and modulus is stress divided by
strain. Since strain is unitless, stress and modulus have the
same units (force/area). It is evident in Fig. 1 (A) that cross-
sectional area will decrease as C increases. If the initial
cross-sectional area is used to calculate
t
, the resulting
E is called engineering modulus. If the change in cross-
sectional area is incorporated in the calculation, the result-
ing E is called true modulus.
The relationship between tensile modulus and shear
modulus is
E = + 2 1 ( ) G
(1)
where is Poissons ratio [1,2]. For materials that do not
undergo change in volume with strain, = 0.5, and Eq (1)
becomes E = 3G. Experimentally, is very close to 0.5 for
rubbery materials and slightly less than 0.5 for many ther-
moplastic polymers [1,2].
Definitions of Dynamic Properties
In dynamic testing, an oscillating strain is applied, and
the resulting oscillating stress is measured, or conversely
an oscillating stress is applied, and the resulting oscil-
lating strain is measured. Definitions and mathematical
treatments do not depend on which of these modes of
operation is used. Definitions and symbols used here cor-
respond to ASTM Standard D4092, Terminology Relating
to Dynamic Mechanical Measurements in Plastics. Rela-
tionships between strain, stress, and time are sketched in
Fig. 2 for tensile DMA with application of strain and mea-
surement of stress. The maximum applied strain is
0
. The
maximum resulting stress is
t,0
. Oscillation is depicted as a
sine wave, but whether or not the driver of the instrument
in use actually delivers a sine wave oscillation may depend
on the particular instrument. The sample is held under suf-
ficient tension so that it remains taut (not slack) even when
the oscillating strain is at a minimum.
Dynamic Mechanical and Tensile Properties
Loren W. Hill
1
1
9 Bellows Rd, Wilbraham, MA 01095.
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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CHAPTER 49 DYNAMIC MECHANICAL AND TENSILE PROPERTIES 625
The sine waves for strain and stress have the same
frequency, but for viscoelastic samples the waves are out of
phase by an amount, , called the phase lag. Theoretically
and experimentally, is zero for an ideal (Hookean) elas-
tic solid. If an ideal (Newtonian) liquid could be tested in
this way, would be 90. For viscoelastic materials, lies
between 0 and 90, and the value of is a rather direct indi-
cation of viscoelastic character [14].
Definitions of dynamic properties depend on the con-
cept of resolving the stress wave of Fig. 2 into two waves,
one that is in phase with strain and one that is 90 out of
phase with strain. The in-phase resolved plot represents
elastic response, and the 90 out-of-phase resolved plot
represents viscous response. In terms of modulus, the sepa-
rated responses result in the following definitions
Tensile Storage Modulus = = E
t
,
cos
0
0
(2)
Tensile Loss Modulus = = E
t
,
sin
0
0
(3)
Loss Tangent tan =
E
E
(4)
Fig. 1Deformations of test samples: A. tensile, B. shear. The two types of deformation have different definitions and different
symbols for strain, stress, and modulus.
Fig. 2Applied oscillating strain () and resulting oscillating
stress (
t
) in a dynamic mechanical analysis experiment with
tensile deformation. The phase lag () and maximum values of
strain (
0
) and stress (
t,0
) are indicated.
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626 PAINT AND COATING TESTING MANUAL 15TH EDITION
The term storage is associated with the elastic part of
the response E because mechanical energy input to elas-
tic materials is stored in the sense of being completely
recoverable. The term loss is associated with the viscous
part of the response E because mechanical energy input
to ideal liquids is totally lost through viscous heating. The
ratio E/E is viscous response expressed relative to elastic
response. This ratio reduces to sin /cos , which is tan .
Thus, the name loss tangent is appropriate.
A check of limiting values of is consistent with assign-
ment of elastic and viscous responses in Eqs (2) and (3).
When = 0, cos = 1.0 and sin = 0. By Eq (3), E is zero
and all of the response is elastic, i.e., E from Eq (2). When
= 90, cos =0 and sin = 1.0. Now E is zero by Eq (2)
and all of the response is viscous, i.e., E from Eq (3).
DMA relationships in Eqs (2) and (3) relate directly
to characterization of samples that are solid or semi-solid.
Other objectives of DMA include following viscosity and elas-
ticity changes as the cure of thermoset coatings takes place
and determining the melt-flow properties of powder coatings
before the onset of cross-linking. When viscous response is
the main interest, DMA is often carried out in shear.
The treatment for shear DMA is identical, but with
selection of appropriate shear symbols from Fig. 1, the
definitions are:
Shear Storage Modulus
cos
= G
s
,0
0
(5)
Shear Loss Modulus = = G
s
,
sin
0
0
(6)
Loss Tangent tan = =
G
G
(7)
Once the experimenters have values of
s,0
,
0
, and in
hand, it is their choice whether to express results in terms
of modulus values, Eqs (5) and (6), or in terms of dynamic
viscosity. For dynamic viscosity, the frequency of oscilla-
tion, in radians per second, is required, but this frequency
is usually known. The frequency is required because viscos-
ity is (shear stress)/(rate of shear strain). In a dynamic shear
test, rate of shear strain is the product . Definitions of
dynamic viscosity are:
Dynamic Loss Viscosity = = =
G
s,
sin
0
0
(8)
Dynamic Storage Viscosity = = =
G
s,
cos
0
0
(9)
Loss Tangent = =
tan
(10)
In the Newtonian liquid limit ( = 90), is zero by Eq
(9), and all of the response is viscous, from Eq (8). Fur-
thermore in this limit, G is zero by either Eq (9) or Eq (5),
and the viscous response could alternatively be expressed
in terms of G from Eq (6). Thus, in dynamic shear tests,
modulus and viscosity determinations are one and the same
experiment. Usually experimenters will choose Eqs (5) and
(6) when the sample has a lot of elastic character and only
a little viscous character, whereas the logical choice for
mainly viscous materials having only a little elastic charac-
ter will be Eqs (8) and (9). In principle, it would be valid to
express tensile DMA results in terms of dynamic viscosities
as well. This is not done very often, probably because vis-
cosity is strongly associated with shearing experiments, not
with tensile experiments. The close association of viscosity
with shear is the basis for omitting the word shear at the
left in Eqs (8) and (9).
The relationships between modulus values defined in
Fig. 1 and the dynamic modulus values are [14]:
E E E
2 2 2
= + (11)
G G G
2 2 2
= +
(12)
Use of complex numbers and quantities such as i = 1
has been avoided here. If readers would like definitions of
such quantities as the complex tensile storage modulus,
E
*
, they should consult Refs. [14]. Complex notation may be
convenient for mathematical derivations, but complex mod-
ulus values, with their imaginary parts, add little or nothing
to the interpretation of structure/property relationships.
Definitions of Tensile Properties
The term tensile properties logically refers to all proper-
ties that can be determined in tests that involve tensile
deformation as depicted in Fig. 1 (A). Common tests that
involve tensile deformation include stress-strain tests,
creep tests, and stress relaxation tests. Stress-strain tests
are used much more frequently than the others. Therefore,
the terms tensile properties and stress-strain properties
are often used interchangeably. Creep and stress-relaxation
tests are sometimes referred to as transient tests because
responses, either elongation or stress, change with time and
are determined as a function of time [5].
Terminology, definitions, and symbols for stress-strain
tests have been taken from earlier editions of the Paint Test-
ing Manual. Additional terminology was taken from ASTM
standards for various polymeric materials:
D2370 Test Method for Tensile Properties of Organic
Coatings
D638 Test Method for Tensile Properties of Plastics
D882 Test Method for Tensile Properties of Thin
Plastic Sheeting
D412 Test Methods for Vulcanized Rubber and
Thermoplastic Rubbers and Thermoplastic
ElastomersTension
D883 Terminology Relating to Plastics
In a stress-strain test, the sample is elongated at
constant rate. The force, also called load, required to
maintain constant rate of elongation is determined. Force
is converted to tensile stress (
t
) by division by the initial
cross-sectional area (A B in Fig. 1 (A)). Results are pre-
sented as a plot of stress (
t
) on the vertical axis versus
strain (either or 100 = % elongation) on the horizontal
axis. A hypothetical example is shown in Fig. 3 [5,6]. The
tensile modulus (E) is the slope of the initial, linear por-
tion of the plot (see Fig. 3). If the initial part of the plot is
not linear, several calculations for estimating E have been
suggested in ASTM D638. Use of the slope for E amplifies
the simple definition of tensile modulus given in Fig. 1 (A).
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CHAPTER 49 DYNAMIC MECHANICAL AND TENSILE PROPERTIES 627
Other terms used for tensile modulus include elastic mod-
ulus, Youngs modulus, and stiffness.
The first point on the plot of Fig. 3 where the slope is
zero is called the yield point. Strain at the yield point is
called elongation at yield (
Y
). Stress at the yield point is
called yield strength (
Y
). Elongation is continued until
the sample breaks. Strain at the break point is called elon-
gation at break (
B
). Stress at the break point is called
tensile strength (
B
) as shown in Fig. 3. However, in some
cases (not shown) the stress is higher at the yield point
than it is at the break point. In such cases, ASTM standards
specify that the tensile strength be indicated as the higher
value of stress and be designated as tensile strength at
yield. Practice is not uniform with regard to this latter
tensile strength terminology.
Results of transient tests have not frequently been pub-
lished for coatings. Such tests clarify viscoelastic character
quite directly. Possibly unexpected field failures of coatings
could be avoided in some cases if more attention were given
to viscoelasticity. Only the most simple form of retardation
and relaxation concepts are treated here.
In a tensile creep experiment, the sample is subjected
to constant stress,
t
, and elongation is determined as a
function of time, (t). Analysis of dependence of elongation
on time yields retardation time, . The simplest mechani-
cal model that permits definition of is the Maxwell model
as shown in Fig. 4. This model consists of a series connec-
tion of an ideal Hookean spring of modulus, E, and a dash-
pot that contains an ideal Newtonian liquid of viscosity, .
As indicated in Fig. 4, is the viscosity of the liquid in the
dashpot divided by the modulus of the spring. has units
of time. Results of the creep experiment for the Maxwell
model can be expressed as
( ) ( )
( )
t t = + 0
0
(13)
When stress is first applied, the spring extends instanta-
neously by an amount (0). Then retarded further elonga-
tion takes place due to flow in the dashpot. It is evident in
Eq (13) that the retarded elongation is linear with time. The
value of can be obtained from the product (reciprocal of
the slope) (intercept) [4,5].
In a tensile stress relaxation experiment, the sample is
elongated instantaneously by an amount , and thereafter
is held constant. Stress is determined as function of time,
(t). Analysis of the dependence of stress on time yields
relaxation time, . For the Maxwell model, values are the
same whether from creep or relaxation. For real materials,
experimentation is required to determine whether or not
retardation and relaxation values are equal. Results of the
stress relaxation experiment for the Maxwell model can be
expressed as
( ) ( )
/
t e
t
= 0
(14)
When the instantaneous elongation is applied, the time
zero response is entirely in the spring. Then the dashpot
extends with time relieving stress on the spring. It is evident
from Eq (14) that the value of can be obtained as the time
at which stress has been reduced to 1/e (0.368) of its initial
value. Alternatively, one can obtain the value of from the
negative of the reciprocal of the slope of a plot of ln (t)
versus t [4,5].
To represent mechanical response of viscoelastic poly-
meric materials, it is usually necessary to use more elabo-
rate mechanical models and to replace a single value of by
a spectrum of relaxation times [1,2].
PREPARATION OF FREE FILM SAMPLES
Methods for preparation and cure of adherent films are
described elsewhere in the manual and in ASTM Standard
Practice for Producing Films of Uniform Thickness of
Paint, Varnish, and Related Products on Test Panels (D823).
Since dynamic mechanical and tensile property determina-
tions require free films, ASTM Practice for Preparation of
Free Films of Organic Coatings (D4708), is also very useful.
Details concerning thickness measurements, which are
required for calculation of cross-sectional area, are given in
ASTM Test Method for Measurement of Dry-Film Thickness
of Organic Coatings Using Micrometers (D1005).
The most widely used method for free film preparation
involves application on release substrates, i.e., low surface
energy substrates. Four release substrates are described
in ASTM D4708. Low surface energy results in poor adhe-
sion so that the coating can be stripped from the release
substrate after it is cured. Surface tension differences
between the coating and release substrate must be care-
fully balanced. If the surface tension of the liquid coating
is higher than the critical surface tension of the release
substrate, the coating will crawl inward from the edges to
Fig. 4A mechanical model consisting of a spring and a
dashpot permits definition of relaxation time and retardation
time.
Fig. 3A hypothetical stress-strain curve for a ductile film.
Tensile properties are defined: tensile modulus (E), elongation
at yield (
Y
), elongation at break (
B
), yield stress (
Y
), and
tensile strength (
B
).
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628 PAINT AND COATING TESTING MANUAL 15TH EDITION
give nonuniform thickness. In extreme cases of crawling,
the coating will break up into unconnected puddles. There
are many types of release paper and many surface treating
agents to convert glass or metal panels into low-energy
surfaces. It is worthwhile to try several release surfaces to
find the balance that will avoid crawling but will still per-
mit separation. Tendency to crawl can be reduced by use
of high-viscosity formulations. Viscosities for draw-down
application (see ASTM D823) can be quite high compared
to those required for spray application.
Thickness is an important consideration in preparation
of samples for dynamic mechanical and tensile property
tests. Usually tests are more reproducible if samples are
thicker than normal coatings thicknesses. However, film
formation seldom occurs in exactly the same way for thick
films as for thin ones. Several reasons for dependence of
cured film properties on thickness have been discussed [5].
In our laboratory, films of 1 mil (25 m) and up have been
analyzed routinely. It has not been possible to analyze or
even handle very thin free films such as beverage can coat-
ings, which are approximately 3 to 5 m thick.
Coatings and thin plastic film samples are usually pre-
pared as rectangular strips, whereas thicker materials are
prepared as dogbone-shaped samples. The narrowing in the
middle of the dogbone tends to control where failure occurs
in tension tests, but for thin samples this narrowing causes
the cross-sectional area to be too small for many load mea-
suring cells. The dogbone shape also provides more area for
clamping, which facilitates the balance between slip-free
clamping and avoidance of rupture at the clamp.
There is extensive literature on the notch sensitivity of
polymeric materials in stress-strain tests [7]. The challenge
in preparation of high Tg coating samples is to avoid unde-
sired notches, nicks, or cracks along the edges. Small edge
cracks, which are very difficult to detect even with magnifi-
cation, can cause premature failure in tension tests. Usually
samples are die cut, and the sharpness and condition of
cutting edges of the die affect uniformity of sample edges.
DMA
Instruments and Methods Used for DMA
Many DMA practices used for plastics have been applied to
coatings as well. The broadest standard practice is:
ASTM D4065 Standard Practice for Plastics
Dynamic Mechanical Properties: Determination and
Report Procedures
Thirteen procedures for applying oscillating strain are
diagrammed in D4065, and equations are given for calculat-
ing dynamic properties for each.
Other methods are specific to the type of oscillating
deformation used:
Test Method for Plastics: DMA
D5023 FlexureThree Point Bending
D5024 Compression
D5026 Tension (most common for coatings)
D5279 Torsion (sometimes called shear)
D5418 FlexureDual Cantilever Beam
One of the reasons for rapidly expanding use of DMA
for coatings and other research is a rather long history of
improvements in the quality of automation and computer-
control of instruments. DMA instrumentation was under-
going rapid change and development in 1995 when the
last edition of this manual was published. Eighteen DMA
instruments were tabulated for coatings used prior to
1995. A great deal of consolidation has occurred in terms
of instruments offered and instrument companies active in
DMA. Table 1 lists the instruments used in eleven papers
published from 2002 to 2006. A common feature of all
these instruments is oscillatory deformation, an example
of which is shown in Fig. 2. Variable features include:
the type of deformation (tensile, shear, etc. ), free versus
forced oscillation, frequency scan versus temperature scan
versus either, sensitivity for thin film analysis, capability
of traversing the entire range of property behavior (glassy
to transition to rubbery) during a single temperature scan,
breadth and rate of temperature scan, breadth and rate of
frequency scan or range and number of frequency settings,
versatility of sample holding devices, ruggedness versus
flimsiness, amount of attention required once a run has
been started, accuracy and versatility of the associated
software for control during the run and data treatment and
plotting after the run. In several cases, newer models permit
determination of properties at several frequencies during a
single temperature scan.
The procedure for carrying out a DMA run on an auto-
mated instrument is rather simple, with details depending
on the particular instrument. Usually the associated soft-
ware includes a run program that prompts the operator
to input sample data (e.g., thickness) and settings for the
run such as initial and final temperatures, frequency of
oscillation, heating rate, etc. After the input steps, there is
usually a cooling period. The instrument takes over when
the preset initial temperature is reached. Thereafter noth-
ing is required of the operator until the run is finished.
Usually initial and final temperatures are selected to span
the glassy region, transition region, and rubbery plateau
region. For direct tensile DMA, the run program usually
contains a tensioning sub-routine, which provides constant
static tension sufficient to avoid slack in the sample in
the glassy region and then decreasing static tension as the
sample softens in the transition region. Modification of the
tensioning sub-routine is often necessary. If tension is too
high, films break in the glassy region or are pulled apart in
the transition region. If tension is too low, slack results or
the oscillatory stress falls below measurable values. Skilled
operators soon develop several modified run programs
with different tensioning parameters that are suitable for
samples of various properties and dimensions. Calibration
of DMA instruments is described in E2254 Storage Modu-
lus Calibration of DMA.
TABLE 1DMA instruments Cited, 20022006
Company
Model
Number
Number of
Citations References
Rheometrics Scientific DMTA3 Four [2931,51]
Perkin Elmer DMTA7 Three [35,54,55]
TA Instruments 2980 Two [32,56]
Polymer Laboratories PL &
(England)
Two [48,57]
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CHAPTER 49 DYNAMIC MECHANICAL AND TENSILE PROPERTIES 629
Various support materials, such as glass braids and
metal springs or shims, are used when the sample is a
viscous liquid and the objective is to follow cure as the
coating formulation is converted to a solid. Use of supports
makes it difficult to obtain absolute values of E, but rela-
tive values are often sufficient for component optimization.
The position of peaks in E or tan plots are usually not
shifted when a support is used. When coating samples do
not contain solvents, e.g., powder coatings and 100 % active
coatings, parallel plate, and cone and plate geometries can
be used.
In some cases, DMA is treated as an adjunct to thermo-
mechanical analysis (TMA). The TMA probe is driven
up and down in an oscillatory manner as temperature is
scanned. General indications of liquid-like character during
transitions can be obtained, but quantitative DMA data are
not often obtainable in this manner.
Interpretation of DMA Plots
DMA plots are shown in Fig. 5 for a clear film prepared
from an acrylic polyol (ACR) and an etherified melamine
formaldehyde (MF) cross-linker. Plots are labeled accord-
ing to Eqs (2)(4). The storage modulus level at the left
is typical of amorphous, unpigmented films in the glassy
state. The 25C data are of interest for comparison with
modulus values obtained from the slope of stress-strain
plots because SSA is usually carried out at 25C. The value
of E (25) from the computer printout corresponding to
Fig. 5 is 1.38 10
10
dynes/cm
2
. The same value expressed
in other units is 1.38 10
9
Pa or 2.00 10
5
psi (1 pascal =
1 newton/m
2
= 10 dynes/cm
2
= 1.45 10
4
pounds-force per
square inch). The recommended SI unit is Pa. The value of
E (25) is 6.86 10
8
dynes/cm
2
. Inserting E and E (25)
values into Eq (11) and solving for tensile modulus, E, we
obtain E = 1.382 10
10
. In this case E = E (25) to a very
close approximation, and the contribution of E (25) to E is
negligible. Hard, tough coatings often have tensile modulus
values from SSA ranging from 1 10
10
to 3 10
10
dynes/cm
2
[5,7,8], in agreement with the DMA value. For a quantita-
tive comparison of E from SSA and E from DMA via Eq
(11), the strain rate from SSA would have to be matched
with the oscillating frequency from DMA.
The viscous response is not always negligible relative to
elastic response, of course. The E contribution is highest
at the temperature of the maximum in tan , 79C in Fig.5.
Note that E (79) is 1.04 10
9
dynes/cm
2
, and E (79) is
5.15 10
8
dynes/cm
2
. From Eq (11), E = 1.16 10
9
dynes/
cm
2
, and E > E (79) for this case. If we actually carried
out SSA at 79 and a strain rate corresponding to 11 Hz, we
would expect to find E = 1.16 10
9
dynes/cm
2
. During the
elongation in SSA, it would not be evident that a significant
fraction of the resistance was viscous in nature. However,
after the sample broke or was released from the grips,
retraction would be delayed (not instantaneous) and part
of the deformation would be permanent.
The middle portion of the plots in Fig. 5 represents the
transition region where E drops sharply and both E and
tan go through a maximum. In coatings papers the glass
transition temperature is usually taken as the temperature
of the maximum in the tan plot, and the symbol used for
this temperature is T
g
. This definition will be used in this
chapter. Different assignments and symbols of various tran-
sition temperatures are described in ASTM E1640 Standard
Test Method for Assignment of the Glass Transition Tem-
perature by Dynamic Mechanical Analysis:
Peak temperature of the loss modulus plot = T
1
(55C in Fig. 5)
Peak temperature of the tan plot = T
t
(79C in Fig. 5)
Intercept of two E tangents= T
g
(52C in Fig. 5)
The two tangents in the last assignment are drawn
(1) along the glassy portion and (2) through the inflection
point in the transition region. The lower transition values
Fig. 5DMA plots for a clearcoat prepared from an ACR and an etherified MF resin, ACR/MF 70/30. The film was cured before
DMA for 30 min at 120C with 0.5 % para-toluenesulfonic acid. DMA was carried out at 11 Hz. See Table 2 for dynamic properties.
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630 PAINT AND COATING TESTING MANUAL 15TH EDITION
agree more closely with that obtained from differential
scanning calorimetry, but the highest value can be obtained
with better reproducibility because the tan peak is promi-
nent. Coatings often have several binder components, and
many coatings are cross-linked. These structural features
broaden the glass transition and favor use of the peak in
tan for assigning T
g
. Regardless of the data point selected
to represent T
g
, it is important to remember that T
g
depends
on rate of testing for viscoelastic materials.
The effects of changing rate of testing, i.e., frequency in
DMA, are shown in Table 2. The 11 Hz data of Table 2 cor-
respond to the run depicted in Fig. 5. A ten-fold increase in
frequency results in a 7 to 9 increase in T
g
with a slightly
stronger dependence on frequency at the higher frequen-
cies. Hartmann [9] noted that a 7C T
g
change per decade
change in frequency is used as a rule-of-thumb. Results of
Table 2 are consistent with this generalization. The height
of the tan peak is nearly independent of frequency, but
the width increases with increasing frequency. Very similar
dependence of height and width on frequency was observed
for lightly cross-linked epoxy films [9]. Values of E (min)
increase slightly with increasing frequency (Table 2). The
structural implications of E (min) will be discussed in the
next sub-section.
Height and width of tan peaks reflect structural
homogeneity and cross-link density. Homogeneous,
uncross-linked, noncrystalline polymeric materials of nar-
row molecular weight distribution usually have tan (max)
values greater than one and sometimes greater than two.
Such tan peaks are very narrow. A broader molecular
weight distribution results in a wider peak and a lower
value of tan (max). Introduction of cross-links invariably
reduces tan (max) and usually increases peak width. For
homogeneous cross-linked samples, peak width reflects the
broadness of the distribution of lengths of chains between
junction points in the network [2,3]. For sound and vibra-
tion damping, materials with both high and wide tan
peaks would be desirable, but height and width cannot be
adjusted independently [9]. High peaks tend to be narrow,
and wide peaks tend to be low. These observations have
resulted in speculation concerning a general comparabil-
ity of peak areas of the glass transition. Eventually theo-
retical treatment of peak areas may prove to be useful for
structure/property correlations.
Samples that undergo partial phase separation during
molecular weight buildup and cross-linking often have very
broad transitions [4,9,10]. Manson and Sperling [10] have
described the use of interpenetrating polymer networks to
limit and control the extent of phase separation. When T
g
values of the separate domains are close to one another, a
general broadening is observed. When T
g
values of the sepa-
rate domains are considerably different, tan plot shapes
provide considerable structural information. Observation
of two narrow peaks with low tan values between them
indicates distinct phase separation with little mixing at
domain boundaries. Observation to two broad and indis-
tinct peaks with high tan values between them indicates
diffuse domains with extended regions of varying composi-
tion at the boundaries [4,10]. Diffuse domains have also
been created in multiblock uncross-linked polymers, and
block design has resulted in controlled broadening of tan
peaks [11].
The relationships between transition width and coating
end-use performance have been presented for radiation-
cured coatings [12], polyol/melamine thermoset coatings
[13,14], gel coats [14], and can coatings [14]. Although the
glass transition is emphasized in this section, many poly-
mers are known to have multiple transitions. Low-temper-
ature transitions are observed in DMA as tan or E peaks
that are quite small compared to the glass transition peaks.
As discussed in the section entitled Relationship to Other
Mechanical Properties, good impact resistance is often
attributed to transitions that produce low-temperature loss
peaks.
Interpretation of tan peak broadening in terms of
structural nonuniformity requires considerable restraint
because in some cases broadening is caused by physical or
chemical changes that take place during the temperature
scan. In some cases, DMA has its own uncertainty principle;
the structural features that are under study are changing
during the determination. Physical changes include loss of
plasticizer or absorbed water and morphological changes
such as partial crystallization. Chemical changes include
additional cross-linking of thermoset coating during the
scan and oxidative or thermal degradation. In general, if
the temperature of processing the samples is well above the
temperature of the tan peak under analysis, there is much
less chance that properties are changing during the scan.
Determination of Cross-Link Density
For unpigmented, cross-linked coating films, the level of
storage modulus, E, in the rubbery plateau region above T
g
is an indication of cross-link density. A wide range of varia-
tion has been observed from approximately 4 10
7
dynes/
cm
2
for lightly cross-linked films to approximately 2 10
9
dynes/cm
2
for every highly cross-linked films. Increases
in E values in the rubbery plateau have been attributed
to increase in cross-link density for many types of stud-
ies: increasing cure temperature and cure time [13,1618],
increasing radiation dose in electron beam curing [15],
TABLE 2Dynamic properties of acrylic/MF clearcoat
Frequency, Hz T
g
, C Tan , max PW,
a
,C E (min), dynes/cm
2
Temperature of E
(min),C
3.5 76 0.49 45 3.3 10
8
108
11.0 79 0.49 50 3.6 10
8
112
35.0 83 0.52 55 4.2 10
8
116
110.0 88 0.52 59 4.7 10
8
121
a
PW is the peak width at half height.
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CHAPTER 49 DYNAMIC MECHANICAL AND TENSILE PROPERTIES 631
increasing the stoichiometric balance in epoxy films [2,19]
and in polyol/melamine films [13,17,18], increasing the
functionality of the cross-linker in radiation cure films [20]
and in powder coating [21,22], and increasing the molecu-
lar weight of the main film former in acrylic clearcoats [23].
Quantitative aspects of the relationship between E in
the rubbery plateau and cross-link density have been clari-
fied [18]. Cross-link density is defined as
v
e
= moles of elastically effective network chhains
per cubic centimeter of film
(15)
Cross-link density can be calculated using Eq (16)
v
G
RT
E
RT
e
= =
3
(16)
where the storage modulus values, G or E, are obtained
in the rubber plateau, T is temperature in degrees K cor-
responding to the storage modulus value, and R is the gas
constant (8.314 10
7
dynes/degrees K mole in the cgs
unit system). Inserting the 3.5 Hz data from Table 2 (E =
3.3 10
8
dynes/cm
2
and T = 108C = 381K) into Eq (16)
gies v
e
= 3.47 10
3
moles/cm
3
. Since Eq (16) has no cor-
rection for frequency dependence of E, a more accurate
value would be obtained if frequency were reduced until
E no longer depended on frequency. Extrapolation to zero
frequency was used in cross-link density calculations for
powder coatings [21]. For a polyurethane film of low T
g
but relatively high cross-link density, E plots were identi-
cal in the rubbery plateau at 11 and 110 Hz [18]; thus, no
frequency extrapolation was necessary for the is case.
Equation (16) has been called the ideal network law
with an analogy implied to the ideal gas law [18]. In an
ideal network, all chains are elastically effective. Conver-
sion in the network forming reaction is complete, and there
are no small loops or dangling ends. For ideal networks
formed by functional group reactions of terminally func-
tional (telechelic) starting material, the value of v
e
can be
calculated directly from Eq (15). The calculation requires
only a balanced chemical equation and an experimental
determination of cured film density. For example, consider
a tetrafunctional coreactant B
4
(M
n
= 3000) cured by a
trifunctional cross-linker A
3
(M
n
= 300) 4A
3
+ 3B
4
Ideal
Network (density = 1.10 g/cm
3
).
The mass of the network formed by this reactions is
10,200 g (3 3000 + 4 300), and the volume is 10,2001/.10
= 9273 cm
3
. This volume of cured film contains 24 mol of
chain ends (4 3 + 3 4) coming into junction points in
the network. By definition, a chain has two ends; therefore,
there are 12 mol of elastically effective chains in 9273 cm
3
of ideal network film. From Eq (15), v
e
= 12/9273 = 1.29
10
3
mol/cm
3
.
Equation (17), attributed to Scanlon [18,24], formal-
izes this type of calculation
v C C C fC
e f
f
= + + =
3
2
4
2
5
2
1
2
3 4 5
3
+
(17)
where C
f
is the concentration of f functional reactant
expressed in unusual units, i.e., moles of reactant per cubic
centimeter of final film. Difunctional reactants contribute
to volume but do not increase the number of moles of
chains. Therefore, there is no C
2
term in Eq (17).
Ideal network calculations have been carried out for
several types of coating such as polyester polyol/melamine
films [17], epoxy/diamine films [19], and powder coating
films [21,22]. The v
e
values calculated from reactant struc-
tures agree remarkably well with experimental v
e
values
from Eq (16).
Although v
e
is useful for network characterization,
most coating chemists can more easily visualize a network
based on the value of M
c
M
c
= weight of sample in grams that contains
one mole of elastically effective chains
(18)
If chain lengths in the network vary, one can place a bar
over M
c
and refer to this quantity as number average
molecular weight of effective network chains. Based on
Eqs (15) and (18), the relationship between v
c
and M
c
is
M
v
c
e
=
(19)
where is film density in g/cm
3
. For the 4A
3
+ 3B
4
example,
M
c
=1.10/1.29 10
3
= 853 g/mol. For the film of Table 2,
the experimental density is 1.12 g/cm
3
, and M
c
is 1.12/3.47
10
3
= 323 g/mol. Or course, a high value of M
c
corresponds
to a loose network and a low value to a tight network.
Equation (16) can be considered empirical or the
result of kinetic theory of rubber elasticity [20,2428]. The
theory was developed for networks that have very long
chains between junction points. For long chains, confor-
mations can be treated by statistical-mechanics concepts.
The chains in networks of greatest interest for coatings
are much too short for such treatments. For long chains
between junction points, results of the theory are of ten
expressed as [20]
v v v
G
gRT
e c p
= + =
(20)
where v
e
is sum of a chemical contribution, is v
p
. The physi-
cal contribution is attributed to chain entanglements [28]
or physical constraints [2527]. The factor, g, is related to
junction point displacement under stress and is reported
to depend on functionality [20,25]. If the reader chooses
to use rubber elasticity theory, Eq (16) is obtained from Eq
(20) with g = 1.0, G = G, and v
p
= 0 (relative to v
c
). It has
been shown that Eq (16) can be derived rather directly for
networks made up of short chains such that chain entangle-
ments are minimal [18].
For many years DMA has been used to determine the
extent of cure of thermoset coatings. Cross-link density (Eq
(16)) and glass transition temperature (from the maximum
in the plot of tan versus temperature) are used as mea-
sures of extent of cure. Recent examples include:
Acrylates cross-linked by hydroxyl alkyl amides [29] (2006)
Catiionic UV curable coatings [30] (2004)
UV cured acrylate/hyperbranched polyester coatings [31]
(2003)
Urethane/acrylic hybrid coatings [32] (2005)
Alternative UV cure methods for automotive clearcoats [33]
(2004)
High performance all-acrylic coatings [34] (2003)
Pigmented or nanoparticle-reinforced coatings, of
course, do not have a direct relationship between E (min)
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632 PAINT AND COATING TESTING MANUAL 15TH EDITION
and cross-link density. Finely divided particles, as well as
cross-links, cause an increase in E (min). Rodriguez et al.
[35] have reported on the effects of varying Pigment Volume
Concentration (PVC) on dynamic mechanical properties of
epoxy coatings. Soucek and Ni [36] have reported the effect
on dynamic properties of varying the content of oligosilox-
ane ceramer in a polyurethane coating for aircraft.
RELATIONSHIP TO OTHER MECHANICAL
PROPERTIES
Knowledge of dynamic properties is useful for optimiz-
ing the chemical structure of coating components. When
the binder is a copolymer, monomer ratios can be altered
to control thermosets, increasing the functionality of the
cross-linker is expected to cause an increase in cross-link
density. DMA is a very direct method for determining
whether purposeful structural changes have actually had
the desired effects.
In addition to general structure/property use of DMA,
progress is being made in establishing relationships
between dynamic properties and the results of paint test
methods for hardness, flexibility, impact resistance, and
solvent resistance. DMA has some inherent limitations in
the establishment of these property/property relationships.
The oscillatory deformation, e.g.,
0
in Fig. 2, is very small.
If the paint performance property depends critically on
large deformations, a property/property correlation should
not be expected. Results of paint performance tests usually
depend to some extent on interactions between coating and
substrate. When dependence on coating-substrate interac-
tions is dominant, a free film method such as DMA should
not be expected to correlate with results of paint tests.
DMA has helped elucidate the causes of reversals in
rank orders of hardness among films when different tests
are used [5,37]. As described elsewhere in the manual,
hardness is determined by penetration, pendulum, and
scratch test methods. The most important property for
influencing hardness is T
g
. However, even for a series of
films that have the same T
g
, considerable differences are
sometimes observed in hardness test results. We have
observed that penetration hardness depends more directly
on the E (25) value than on T
g
. Films of the same T
g
can have
quite different values of E (25). Pendulum hardness
depends more directly on E values than on E values.
This result is expected because damping of the swings of
a pendulum depends on conversion of mechanical energy
into heat through viscous effects in the coating. As noted
earlier, E is a measure of viscous response. Films that have
nearly the same E (25) values and the same penetration
hardness can have quite different E (25) values and quite
different values of pendulum hardness. The back and forth
rolling motion of a Sward Rocker is also damped by viscous
effects, and therefore depends strongly on E values. In this
case, there is also a contribution from sliding friction. Usu-
ally pendulum hardness is determined at a single tempera-
ture, but Sato [37] describes studies of damping time as a
function of temperature. Plots of the reciprocal of damping
time versus temperature have exactly the same shape as
the tan plot for the same films. Both glassy and rubbery
materials have low tan values as shown in Fig. 5. If a pen-
dulum hardness test is carried out at room temperature on
a material that is in its rubbery region at room temperature,
a careless interpretation of results is likely to conclude that
rubber is very hard. This example illustrates that DMA can
be used to understand the results of paint tests more fully.
Among the many scratch tests that have been devised,
the most widely used is pencil hardness. Although pencil
hardness results are quite reproducible when carried out
by one skilled in the art, these results sometimes do not
correlate with either penetration or pendulum hardness
results. Furthermore, there is no known dynamic property
that correlates well with pencil hardness. The plowing
action in pencil hardness failures involve large localized
deformations. A relation to stress-strain analysis, which
also involves large deformation, is more likely.
Flexibility of coatings is often measured by mandrel
bend tests and falling weight impact test (see a previous
chapter in this book). In thermoplastic polymer studies,
good flexibility and impact resistance are often associated
with low temperature peaks in E and tan plots [38].
Rubber-toughened epoxy coatings clearly show the low
temperature peak attributable to the rubber phase [39].
Polyester/melamine films have much better mandrel bend
performance than do acrylic/melamine films of similar T
g
and cross-link density. DMA scans beginning at 100C
show a weak tan peak at 70C for the PE/MF films, but
no such peak is observed for the ACR/MF films [18]. In
some cases [12,13], extreme broadening of the peak in the
E plot has been associated with improvements in flexibility
of coatings.
Pigments often increase the toughness of coatings
without broadening the transition or introducing low-
temperature loss peaks [15]. The main effect of increasing
pigment volume content (PVC = 0 to 55 %) on DMA plots
is to increase E values moderately in the glassy region
and strongly in the rubbery plateau [15]. Values of T
g
often
increase by about 5 to 10C at PVC = 0.4 relative to the cor-
responding clear coatings [15].
Solvent resistance as measured in methyl ethyl ketone
(MEK) double rub tests is related to E values in the
rubbery plateau, i.e., to cross-link density [5,13]. MEK
resistance also depends on the solubility parameter of the
coating. Although the double rub test is widely used to
determine the degree of cure of thermoset coatings, the
only ASTM method adopted relates to zinc-rich primers
(D4752). Relationships between the number of double rubs
and E(min) values are quite reproducible within a coating
type but not from type to type. For example, with acrylic
clearcoats, 200 double rubs are obtained when E(min) =
2 10
8
dynes/cm
2
[13]. Films of this type having 50 to 100
double rubs typically have E (min) values in the range of
5 10
7
to 1 10
8
dynes/cm
2
. In contrast, polyester polyol
powder coatings, cured with several types of cross-linkers,
yielded 200+ double rubs despite having E (min) values
as low as 5 10
7
dynes/cm
2
[22]. The lack of generality in
the relationship of MEK resistance to E (min) for various
coatings types is believed to result in part from differences
in solvent-polymer interactions. There may also be a weak
dependence of MEK resistance on T
g
as well as a strong
dependence on E (min).
DETERMINATION OF TENSILE PROPERTIES
Description of SSA
Instrumentation for SSA is described in detail in the ASTM
test methods listed in the section of this chapter entitled
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CHAPTER 49 DYNAMIC MECHANICAL AND TENSILE PROPERTIES 633
Definitions of Tensile Properties. In most cases, spe-
cific instruments are not identified, apparently to avoid
commercial implications, but it is generally known than
Instron
UVR-
6110, Union Carbide) and a propylene oxide triol (MW =
702) are shown in Fig. 7 [43]. The corresponding tensile
properties are given in Table 3. Films from Compositions
1 through 4 all give brittle failure (compare Fig. 6(A))
and only moderate changes in tensile properties (Table 3)
despite a large change in composition. At Composition 5
(70/30 epoxy:polyol, see Table 3) a yield point is first noted,
and thereafter very large property changes occur despite
relatively small changes in composition. Compositions in
the 4 to 6 range (see Table 3) are reported to give excellent
post formability, as required for coatings on beverage can
ends, while maintaining adequate hardness and solvent
resistance [4244].
Relationship to Other Mechanical Properties
SSA is used in a general way to assess suitability of a
binder for various coating end uses. Most coating chemists
associate modulus with coating hardness and percentage
elongation at break with coating flexibility. Quantitative
correlations of these properties are not published very
often, however. The lack of published correlations may
result from the fact, noted above, that paint tests of adher-
ent coatings depend on coating-substrate interactions,
whereas SSA is carried out on free films. ASTM Test
Method for Elongation of Attached Organic Coatings with
Conical Mandrel Apparatus (D522) describes how to calcu-
late percent elongation from the crack length in a conical
mandrel bend test. Comparison of elongation of adherent
coatings by the conical mandrel method and elongation of
the same coating as a free film from SSA would certainly
be of interest, but such comparisons were not found in the
literature.
Fig. 7Stress-strain curves for UV-cured cycloaliphatic epoxide
films flexibilized with oligomeric propylene oxide triol. Strain
rate is 40 % per minute. See Table 3 for tensile properties.
TABLE 3Tensile properties (strain rate, 40 %/min) of UV-cured cycloaliphatic epoxide films
flexibilized with oligomeric propylene oxide triol
Film Number
a
Composition
b
Tensile Modulus,
c
psi Tensile Strength, psi Elongation, % Epoxide, wt % Triol, wt %
1 90.0 10.0 3.88 10
5
9.5 10
3
6.6
2 85.0 15.0 3.72 10
5
8.9 10
3
6.6
3 80.0 20.0 3.33 10
5
8.4 10
3
7.4
4 75.0 25.0 2.95 10
5
7.0 10
3
8.1
5 70.0 30.0 2.05 10
5
4.3 10
3
16.2
6 66.7 33.3 1.48 10
5
3.7 10
3
24.3
7 63.4 36.6 0.70 10
5
2.5 10
3
54.0
8 60.0 40.0 0.26 10
5
2.0 10
3
88.4
a
Keyed to the plots in Fig. 7.
b
Weight % of polymeric binder. (Films also contain 2.9 wt % photoinitiator and 0.5 wt % flow agent.)
c
1% secant modulus. (The modulus range expressed in pascals is 2.68 10
9
, No. 1, to 1.79 10
8
, No. 8.)
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CHAPTER 49 DYNAMIC MECHANICAL AND TENSILE PROPERTIES 635
The logic of associating yield behavior in SSA with post
formability of coil coated metal was noted in 1977 [45].In
1987, Koleske [43,44] confirmed that compositions that
exhibited a yield point performed well in the demanding
post-forming operations carried out on beverage can ends.
Evans and Fogel [46] provided convincing evidence that
gloss retention during abrasion of floor coatings is related
to the area under stress-strain curves. This area, divided by
sample volume, is called work-to-break or toughness as
noted previously. The authors provide a clear example of
the need to match strain rates when attempting to correlate
SSA results with paint test results.
The field of Fracture Mechanics was well established
for analysis of cracking of plastics by the 1980s, but coat-
ings publications using Fracture Mechanics concepts began
in the 1990s. In 1992 Gregorovich and McGonigal [47]
reported that the essential work to break, obtained from
SSA plots with notched samples, correlated with resistance
to car wash marring of automotive topcoats. In 2005, Sadati
et al. [48] analyzed scratch resistance of clear coats based
on fracture energy. In 1998 Nichols et al. [49] analyzed
the fracture energy of automotive clearcoats using Frac-
ture Mechanics, and in 2002 Nichols [50] used Fracture
Mechanics concepts for anticipating paint cracking during
weathering. In 2006 Skaja et al. [51] combined DMA and
SSA data in analysis of mechanical property changes dur-
ing accelerated weathering of polyester-urethane coatings.
In 2001 Soucek et al. [52] analyzed fracture toughness of
inorganic-organic hybrids, and in 2002 Soucek and Ni [36]
used SSA and Fracture Mechanics to determine mechanical
properties of nanostructured polyurethane ceramer coat-
ings for aircraft.
Failure of attempts to correlate pencil hardness with
penetration hardness, e.g., Tukon Hardness, probably result
because the former has a strong requirement for toughness,
whereas the latter is more dependent on the modulus value
at room temperature.
DMA is much more generally applicable to determina-
tion of cross-link density (see the chapter subsection enti-
tled Determination of Cross-Link Density) than is SSA. If
the Tg of a coating binder is well below the temperature at
which SSA is carried out, then the modulus from the initial
slope of the stress-strain curve is a rubbery plateau modu-
lus and Eq (16) is valid at least in principle. In practice,
curvature in stress-strain curves and permanent deforma-
tion usually result in inappropriate modulus values. An
innovative approach to avoiding the permanent deforma-
tion problem consists of reversing the extension mode of
SSA so that a retraction plot is also obtained. Hergenrother
[53] has applied this tensile retraction method for determi-
nation of cross-link density of elastomeric polyurethanes.
CONCLUSIONS
A wide range of automated and computer-controlled instru-
ments is available for determination of dynamic mechanical
and tensile properties. Careful review of variable features is
necessary to insure suitability for property determinations
on coating samples of normal thickness. Determination
of basic physical properties makes it possible to integrate
structure/property knowledge from many polymer fields
with coatings research and development. Free film coating
data are much more useful when thoughtfully interpreted
in relation to results from tests carried out with films intact
on their end-use substrates. This review includes many
examples that illustrate the benefits of combining DMA or
SSA data with results from well controlled and documented
tests as provided by the ASTM. The goal of much of the dis-
cussion provided here is better understanding of hardness,
flexibility, post-formability, solvent resistance, and abrasion
resistance.
DMA and SSA are often complementary because
strains imposed on test samples are very different. SSA
provides information on yield behavior and failure at high
strains. DMA provides low strain properties and reveals the
viscoelastic nature of coatings very directly and quantita-
tively.
For unpigmented thermoset coatings, values of storage
modulus, E, in the rubbery plateau can be used to calculate
cross-link density. Determination of cross-link density usu-
ally makes it possible to confirm or deny that purposeful
reformulation or changes in resin structure have had the
desired effects.
References
[1] Aklonis, J. J., and MacKnight, W. J., Introduction to Polymer
Viscoelasticity, 2nd ed., Chap. 2, Wiley Interscience, New York,
1983.
[2] Nielsen, L. E., Mechanical Properties of Polymers and Compos-
ites, Vol. I, Marcel Dekker, New York, 1974.
[3] Murayama, T., Dynamic Mechanical Analysis of Polymeric
Material, Elsevier, New York, 1978.
[4] Sperling, L. H., in Sound and Vibration Damping in Polymers,
R. D. Corsaro, and L. H. Sperling, Eds., Chap. 1, ACS Sym-
posium Series 424, American Chemical Society, Washington,
DC, 1990.
[5] Hill, L. W., Mechanical Properties of Coatings, D. Brezinski,
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[6] Schurr, G. G., Tensile Strength and Elongation, Paint Testing
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[7] Takano, M., and Nielsen, L. E., The Notch Sensitivity of Poly-
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ings Science and Technology, Film Formation, Components
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Properties, and Performance, Vol. 2, 1994.
[9] Hartman, B., Sound and Vibration Damping in Polymers, R. D.
Corsaro and L. H. Sperling, Eds., Chap. 2, ACS Symposium
Series 424, American Chemical Society, Washington, DC,
1990.
[10] Manson, J. A., and Sperling, L. H., Polymer Blends and Com-
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[11] Cooper, S. L., and Estes, G. M., Multiphase Polymers, ACS
Advances in Chemistry Series 176, American Chemical Soci-
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[12] Roller, M. B., The Glass Transition: Whats the Point?, J.
Coat. Technol., Vol. 54, No. 691, 1982, p. 33.
[13] Hill, L. W., and Kozlowski, K., The Relationship Between
Dynamic Mechanical Measurements and Coatings Proper-
ties, Advances in Organic Coatings Science and Technology,
Vol. 10, Proceedings of the Twelfth International Conference
in Organic Coatings Science and Technology, A. V. Patsis, Ed.,
Technomic, Inc., Lancaster, PA, 1986, p. 31.
[14] Provder, T., Holsworth, R. M., and Grentzer, T. H., Dynamic
Mechanical Analyzer for Thermal Mechanical Characteriza-
tion of Organic Coatings, in Polymer Characterization, C.D.
Craver, Ed., Chap. 4, ACS Advances in Chemistry Series 203,
American Chemical Society, Washington, DC, 1983.
[15] Zosel, A., Mechanical Behavior of Coating Films, Prog. Org.
Coat., Vol. 8, 1980, p. 47.
[16] Skrovanek, D. J., The Assessment of Cure by Dynamic Ther-
mal Analysis, Prog. Org. Coat., Vol. 18, 1990, p. 89.
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636 PAINT AND COATING TESTING MANUAL 15TH EDITION
[17] Hill, L. W., and Kozlowski, K., Crosslink Density of High
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[45] Hill, L. W., Stress Analysis: A Tool for Understanding Coating
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637
PREFACE
IN PREPARATION OF THIS CHAPTER, THE CON-
tents of the fourteenth edition were extensively drawn
upon. The authors acknowledge the author of the four-
teenth edition, Mark P. Morse. The current edition will
review and update the topics as addressed by the previous
author, introduce new technology that has been devel-
oped, and include up-to-date references. This chapter is
an abridged and modified version of the chapter entitled
Flexibility, written by Garmond G. Schurr, found in ear-
lier editions of this manual.
DEFINITIONS
For a coating to meet its service requirements it must
exhibit appropriate properties of flexibility and toughness
to withstand cracking when it is subjected to stresses pro-
duced by shrinking or swelling, forming, mechanical abuse,
and weathering. Flexibility is the ability of a material to be
bent or flexed without cracking or undergoing other failure.
Toughness is the strength and resilience of a material; it is
the materials ability to withstand great strain imposed in
a short time period, such as an impact, without tearing,
breaking, or rupture.
INTERPRETATION
The flexibility of a coating applied to a substrate depends
not only on its ability to expand by pressure from within
the film, distensibility, but also on the coating thickness
and on the adhesion between coating and substrate. Good
adhesion tends to give better apparent flexibility than does
poor adhesion. The toughness of a coating is dependent
on its hardness, stiffness, resiliency, distensibility, and the
existence of an energy dissipation mechanism that operates
at temperatures far below room temperature and is discern-
able by dynamic mechanical measurements made over a
broad temperature or frequency range.
Generally, the bend and impact tests used to evaluate
flexibility and toughness are much more severe than actual
service conditions. This is because the tests are usually
performed on relatively fresh, un-aged coating films. Since
coating films tend to lose flexibility during use due to the
loss through volatilization of free plasticizing components
and chemical changes such as degradation, cross-linking,
and the like, these severe tests that exceed normal opera-
tional expectations are useful in predicting long-term ser-
viceability [1].
BASIC PROPERTIES AFFECTING COATING
PERFORMANCE
Both flexibility and toughness depend on very basic proper-
ties: the viscoelastic behavior of the coating and its physical
transitions and relaxations. The following is a discussion
of these properties taken from a paper by Skrovanek and
Schoff [2].
Coatings, as the polymers from which they are pre-
pared, are viscoelastic in nature, that is, they behave both as
viscous liquids and as elastic solids. The coatings have elas-
tic recovery and yet will flow with time when placed under
a stress. In general, viscoelastic behavior and mechanical
properties are markedly affected when a coating enters the
glass transition, softening point, or other relaxation. To be
certain that the properties of a coating will fulfill the needs
of its intended use, the viscoelastic behavior of the coating
should be measured, controlled, and designed to meet the
particular end use.
The softening point of a coating can be used as an
index of flexibility. The softening point is between the
temperature where the coating changes from being hard
and glassy and the temperature where it is leathery or rub-
bery. For example, if a coating has a softening temperature
region near the temperature of the forming operation, the
coating is less susceptible to failure by cracking or a similar
mechanism than if the softening region is above the form-
ing temperature. Measurement of energy storage (related
to elasticity) and energy loss (related to viscous losses) as
a function of temperature is a means of predicting impact
resistance.
Impact resistance of a paint film can be considered
as energy dissipation by vibration or rotation of various
molecular segments so that at no time will sufficient energy
be focused to cause fracture. Since the impact tests per-
formed on paint films often produce deformations beyond
the elastic limit of the films, flow within the films must take
place or fracture will occur [3].
To obtain good impact resistance, the paint film must
consist of a polymer that has a sufficiently high molecular
weight to have strong intermolecular entanglement (and
therefore, high tensile strength), but sufficiently low viscos-
ity (by choice of proper molecular constituents and limiting
molecular weight) that flow and accompanying energy dis-
sipation will take place.
Polymer viscosity increases as molecular weight
increases so that polymers with very high molecular
weights will have greater flexibility than those polymers
50
Flexibility and Toughness
John Fletcher
1
and Joseph Walker
2
1
Technical Support Manager Elcometer Instruments Ltd.UK
2
VP Sales & Marketing Elcometer Inc, Rochester Hills, Michigan
MNL17-EB/Jan. 2012
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638 PAINT AND COATING TESTING MANUAL 15TH EDITION
with intermediate or low molecular weights. At the same
time, molecular weights below the critical molecular weight
for entanglement lead to very low tensile strengths and the
mechanical behavior observed is brittleness. It has been
found that modulus is the dominant factor in the relation-
ship between the tensile properties of a coating and its
impact resistance [4].
In addition to dynamic mechanical behavior, the relax-
ation behavior as measured by dissipation or damping of
coatings has been determined by application of dynamic
electrical tests [5]. In a dielectric relaxation test, a periodic
electrical potential is applied to the sample coating situated
between a pair of electrodes. The dielectric constant and
dissipation factor are measured as a function of frequency
and temperature.
TECHNIQUES FOR MEASURING BASIC
VISCOELASTIC PROPERTIES
Thermal Mechanical Analyzer (TMA)
This instrument employs transducers to sense the position
of a vertical rod that rests on the surface of a coating sam-
ple. The instrument is usually equipped with a furnace and
program planner so that heating, cooling, and isothermal
temperature operations can be employed.
With its use, softening points and glass transitions can
be determined from plots of coating indentation as a func-
tion of temperature. Also, changes in stresses within a coat-
ing at a constant temperature (creep) can be determined
from plots of indentation versus time [2].
Dynamic Mechanical Thermal Analyzer (DMTA)
This instrument produces vibrations in a coating film over
a wide frequency range and/or temperature range. It can
scan a wide range of sample temperatures at different rates.
The resulting deformations from the sinusoidal applied
stresses are analyzed to compute values related to energy
storage and energy loss [2].
Tensile Testing
Tensile testing of organic films can measure tensile strength,
modulus and elongation of the coating materials. The area
under the stress-strain curve can be used as a measure of
the toughness of the coating.
EXTERNAL FACTORS AFFECTING FLEXIBILITY
AND TOUGHNESS
Flexibility and toughness are not constant characteristics
of a specific coating. A number of external factors affect
these properties.
Humidity
Water is a good plasticizer for almost all paint films in
that it preserves the flexibility and adhesive power of the
film. A change in relative humidity of as little as 2 % can
be detected in flexibility measurements. Some paint films,
such as those based on latexes, imbibe moisture very rap-
idly, whereas others reach equilibrium with the atmosphere
very slowly. It is imperative that tests for flexibility and
toughness are conducted in an atmosphere of controlled
relative humidity and that the specimens are conditioned
in that atmosphere for a day or more before the tests are
performed. Generally, flexibility and toughness tests are
carried out at a relative humidity of 50 5 %. The 10 %
tolerance is needed because of the difficulty in more accu-
rately controlling relative humidity in most laboratories. If
the environment cannot be controlled at this recommended
level, then the relative humidity should be measured and
reported along with the mechanical properties.
Temperature
The flexibility and toughness of coatings are dependent on
temperature. This is particularly true of thermoplastic coat-
ings, but it also is a factor for thermoset coatings. These
coatings have a definite second order transition tempera-
ture known as the glass transition temperature, T
g
. Coatings
at a temperature below T
g
are hard and brittle with poor
flexibility and impact resistance unless there is an auxil-
iary loss mechanism below T
g
or below the temperature at
which the coating is used, as exists in polycarbonates that
have a high T
g
of about 160C (at 1 Hz) and yet have excel-
lent impact resistance because of a relaxation that occurs
at about 90C (at 1 Hz). If coatings do not have this type
loss mechanism, at temperatures just above T
g
they are flex-
ible, and at temperatures substantially above T
g
they tend
to develop viscous rather than elastic properties. There is
a tendency for all thermoplastic coatings to have identical
flexibility properties if these properties are measured at the
same temperature relative to T
g
, for example, at 10C above
T
g
[1,6].
Flexibility and toughness measurements are usually
made at a temperature of 25 1C after the coatings are
conditioned at that temperature. However, there are many
instances when test are performed at lower temperatures as
might be encountered in cold climates.
Strain Rate
Strain rate is the rate at which a coating specimen is elon-
gated and is usually expressed in percent per minute, in./
in./ min or cm/cm/min. This is the rate of extension relative
to specimen size. That is, if a specimen 10 cm long is elon-
gated at a rate of 1 cm/min, it is the same as a specimen
1 cm long being elongated at a rate of 0.1 cm/min (1 mm/
min). In both cases, the strain rate is 10 % per min.
Strain rate has a great influence on the flexibility and
toughness of a coating. In general, the effect of increasing
the strain rate is similar to decreasing the coating tempera-
ture, that is, as the strain rate is increased, flexibility and
toughness decrease.
There can be critical strain rates where flexibility has
sharp changes, which are very similar to the effects pro-
duced at the glass transition temperature [7]. This means
that the strain rate used in a test must be closely controlled.
In some tests, such as a bend test, this is difficult to do. This
also means that tests performed at a low strain rate (cup-
ping test) are likely to produce different flexibility ratings
than those produced by a high strain rate (conical mandrel
test) [1,7].
It should also be noted that the temperature and
humidity of the test are significant in the results that are
obtained and should be noted as part of the test result.
FLEXIBILITY AND TOUGHNESS MEASUREMENTS
Mandrel Bend Tests
Both conical and cylindrical mandrels are used for evalu-
ating the flexibility of coatings. Even though it is difficult
to control the strain rate in these manually operated tests,
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CHAPTER 50 FLEXIBILITY AND TOUGHNESS 639
they can provide very useful flexibility ratings and are often
used to evaluate coatings applied to metal test panels.
Conical Mandrel Tests
A conical mandrel test consists of manually bending a
coated metal panel over a cone. As described in ASTM D522,
Standard Test Methods for Mandrel Bend Test of Attached
Organic Coatings, Test Method A, a conical mandrel tester
consists of a metal cone, a rotating panel bending arm, and
panel clamps. These items are all mounted on a metal base
as illustrated in Fig. 1. The cone is smooth steel 8 in. (203
mm) in length with a diameter of
1
/8-in (3.2 mm) at one end
and a diameter of 1.5 in. (38 mm) at the other end.
When a coating is applied on a
1
/32-in (0.8 mm)-
thickcold-rolled steel panel, as specified in ASTM D522, a
bend over the mandrel produces an elongation of 3 % at
the large end of the cone and of 30 % at the small end of
the cone. The coated panel is bent 135 around the cone in
approximately 1 s to obtain a crack resistance rating under
simulated abuse conditions. In some instances, longer bend
times have been found to be useful. For example, if the
percent elongation of the coating at the point of cracking is
to be determined, the method specifies a bend time of 15 s.
ASTM D6905, Standard Test Method for Impact Flexibility
of Organic Coatings, describes a procedure for determining
the ability of a coating and its substrate to resist shattering,
cracking, or chipping when the film and the substrate are
distended beyond their original form by impact. This test
method references D522 but states that D6905 is perhaps a
better way to apply the test using a rapid application of the
force. Since the impact is almost instantaneous the prob-
lems associated with time variables in the mandrel tests are
eliminated.
Since variations in temperature and humidity can
affect mandrel bend tests, it is imperative that the coated
panels be conditioned at a standard temperature and
relative humidity before performing the test, which is con-
ducted under the same conditions.
Film thickness will also influence the results of the test
and therefore the thickness of the film should be reported
along with the temperature and humidity conditions.
The crack resistance value of a coating is obtained by
measuring the distance from the furthest end of the crack
to the small end of the mandrel. This distance is converted
to cone diameter by means of a plot given in ASTM D522.
The mandrel diameter at which cracking occurs is taken as
the crack resistance value.
If the elongation of the coating at the onset of cracking is
to be reported, a bend time of 15 s is used and the diameter
at which the onset of cracking occurred is converted to per-
cent elongation from a plot given in ASTM D522 Test Meth-
ods for Mandrel Bend Test of Attached Organic Coatings.
Cylindrical Mandrel Bend Tests
When executing cylindrical mandrel flexibility tests, a
coated panel is bent manually over one or more cylindrical
rods or surfaces of different diameters. ASTM D522 Method
B states that the testing device should include mandrels
with 1-in. (25 mm),
3
/4-in. (19 mm),
1
/2 -in. (12.7 mm),
3
/8 -in.
(9.5 mm),
1
/4-in. (6.4 mm), and
1
/8-in (3.2 mm) diameters.
Examples of cylindrical mandrel testers are given in Figs
2 and 3.
The panel should be bent over a mandrel with the
uncoated side of the panel in contact with the mandrel
surface. The panel should be bent approximately 180
around the mandrel at a uniform velocity in a time of 1
s. If cracking has not occurred, the procedure is repeated
using successively smaller and smaller diameter mandrels
until cracking is apparent. The cracking-resistance value of
a coated panel is the minimum diameter at which cracking
does not appear.
Fig. 1A conical mandrel bend tester (Reprinted by
permission of Elcometer Inc.).
Fig. 2A cylindrical mandrel bend tester (Reprinted by
permission of Elcometer Inc.).
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640 PAINT AND COATING TESTING MANUAL 15TH EDITION
This testing procedure can be applied as a pass/fail
test by determining whether cracking is produced by bend-
ing over a specified mandrel diameter.
A table for converting mandrel diameter to percent
elongation is given in ASTM D522. Schuh and Theuerer [8]
derived the relationship between the diameter of a mandrel
and the elongation of a coating to be as follows:
Persent Elongation = 100(t/(2r + r)) (1)
where t is the thickness of the coated panel and r is the
radius of the mandrel.
Observed elongations are greater than values calcu-
lated from the above expression and vary with different
types of metal substrates.
Crack resistance of a coating is dependent on its thick-
ness. That is, the thicker the film, the lower the crack resis-
tance. Values of crack resistance obtained by the mandrel
bend tests should be corrected for film thickness when
comparisons are made between different coatings. ASTM
D522 contains corrections to be added to elongation values
obtained with coatings having a thickness greater than
1mil (0.03 mm) when applied to 1/8-in (0.8-mm)-thick steel
panels.
Conical mandrel bend test procedures, similar to those
given in ASTM D522, are found in ISO 6860 and BS 3900
E11. Cylindrical mandrel bend test procedures, similar to
those given in ASTM D522, are found in ISO 1519, DIN 35
152, and BS 3900 E1.
T-Bend Tests
T-bend tests are a means of evaluating the flexibility of
coated strip metal that is to be formed during a fabrica-
tion process (Fig. 4). Multiple 180 bends of the coated
metal are made, and the amount of cracking produced at
each bend is visually determined. Ratings are classified
as 0T, 1T, 2T, 3T, and so on. The 0T (pronounced zero T)
bend consists of making a 180 bend with the paint on the
outside of the bend and pressing the bend flat so there is
no space between the metal surfaces. This operation is
repeated successively to produce a 1T (pronounced one T),
2T, 3T, etc. bends. These successive bends result in two,
three, etc. thickness of the metal around the first bend.
It should be apparent that the greater the number of thick-
nesses around which the coated metal is bent, the less
severe the test.
Test results are reported as passing the smallest T-bend
on which cracks are observed. In some cases, cracking must
be detected by removal of the coating using a pressure-
sensitive tape placed on the bend edges and observing
the degree of removed coating particles. ASTM D4145,
Test Method for Coating Flexibility of Prepainted Sheet,
describes this test procedure.
A triangular-shaped specimen has been found to be
convenient for making T-bend tests as this shape leaves a
portion of each bend exposed for later examination and for
permanent record.
Alternatively the T-bend test described in D4145 can
be carried out using a die around which the deformation is
Fig. 4T-Bend test bending the coated sheet on itself (ASTM
D4145: Standard Test Method for Coating Flexibility of
Prepainted Sheet).
Fig. 3Simple cylindrical mandrels test apparatus. (Reprinted
by permission of Elcometer Inc.)
Fig. 5T-Bend test using a die around which the specimen
is bent (ASTM D4145: Standard Test Method for Coating
Flexibility of Prepainted Sheet).
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CHAPTER 50 FLEXIBILITY AND TOUGHNESS 641
made (Fig. 5). Progressively larger dies are used to progress
the test to the point where no damage to the coating results
from the bending.
Cupping Tests
A test using a relatively slow rate of forming can be con-
ducted with a Cupping Tester (Fig. 6) that pushes a punch
into the unpainted side of a coated panel until the increas-
ing deformation produces cracks in the coating. Test pro-
cedures are given in ISO TC 35, BS 3900 E4, NFT 30019,
SIS 18 41 77, DIN 50 101, and DIN 50 102. Cupping testers
can be used to simulate different forming operations. The
motorized Cupping Tester uses a spherical punch and a
range of cupping speeds can be achieved. The maximum
cupping depth is approximately 18 mm (0.7 in.). The
cupping action is stopped when cracking in the coating
is detected visually. The depth of cupping at that point is
indicated on a dial gage and is considered to be the flex-
ibility rating. The cupping tester can be equipped with a
magnifier, a stereomicroscope, or a web-cam for observing
the onset of cracking.
Forming Tests
In many industrial operations, metal is coated flat and then
formed into various shapes by drawing the coated metal.
This can be simulated directly or by elongating a coated
metal sheet. Any tension-testing instrument capable of rap-
idly elongating a metal strip can be used for determining
the ability of a coating to be drawn (drawability). A coated
metal strip is elongated at a high rate of strain until crack-
ing occurs. The elongation can be measured with an exten-
siometer [1]. Drawability would be reported as the percent
elongation obtained just before cracking is observed. Since
elongation is rate dependent, the rate of elongation used in
the test should be reported.
ASTM D4146 Test Method for Formability of Zinc-
Rich Primer/Chromate Complex Coatings on Steel pro-
vides a procedure for determining the formability of
coated strip metal. An outline of a testing machine that
can produce a sufficiently high pressure for pressing a
1 5/8-in (41-mm)-diameter indenter ball into the coated
metal is provided. The rate of forming can be adjusted
over a range of 0.2 to 1.0 in./min (4.8 to 25 mm/min). A
dial gage monitors the movement of the indenting ball.
Adhesive tape is applied over the dome formed in the
metal, and the tape is rapidly removed. The amount of
coating removed is given a rating by comparing it with a
set of photographic standards.
Impact Resistance Tests
The most commonly used impact testers drop a weight
onto an indenter resting on the surface of a coated panel
that is resting on a platform (Fig. 7). A die in an opening
in the platform allows the panel to be pushed down by
the indenter to form a dimple in the panel. The weight is
dropped through a guiding tube whose height is marked in
increments.
There are a number of possible combinations of
weights, indenter sizes, die sizes, and weight heights that
can be used in performing impact tests. The tests can be
performed by impacting either the coating directly (coating
facing upward) or indirectly (coating facing downward).
Cracking observed on or around the impact-produced
dimple is considered failure, and the force to produce the
cracking is given in inch-pounds (kilograms-meters), that
is, weight times height. The test can be performed either to
determine the inch-pounds required to produce cracking or
to determine whether a coating passes or fails at a specified
inch-pound value. ASTM D2794, Standard Test Method
for Resistance of Organic Coatings to the Effects of Rapid
Deformation (Impact), describes such a test procedure and
offers three procedures for determining the degree of crack-
ing produced in an impact deformation: (a) visual inspec-
tion with a magnifier, (b) visual inspection after application
of an acidified copper sulfate solution, and (c) use of a
pin-hole detector.
The General Electric Impact Flexibility Tool is used
for simultaneously making several indentations of different
sizes. From these indentations, conclusions can be made
regarding crack resistance and the amount of draw that a
coating applied to sheet metal can tolerate. This tester con-
sists of a steel cylinder that has knobs (segments of spheres)
of different radii machined on each end. The cylinder is
dropped onto a coated panel that is supported coating side
down by a rubber pad. The height of drop is adjusted so
that the boundary of the cylinder is just discernible. This
procedure assures that each knob is used to its limit. Eight
knobs cover a range of 0.5 to 60 % elongation. See Federal
Test Method Standard 141C, Method 6226.
ASTM G14, Standard Test Method for Impact Resis-
tance of Pipeline Coatings (Falling Weight Test), describes
a test procedure for determining the impact resistance of
pipe coatings. A fixed weight of 3.0 lb (1.36 kg) and having a
5/8-in. nose diameter is dropped through a guide tube onto
a coated pipe specimen. The height of the weight is adjusted
until the minimum height at which cracking appears is
attained. A wet-sponge pinhole detector is used to deter-
mine the presence of cracks in the coating on the impacted
pipe. An equation is given for calculating the impact resis-
tance from the weight and its height of drop required to just
produce cracking.
Fig. 6Motorized Cupping Tester fitted with a web-cam to
record the onset of cracking in the coating. (Reprinted by
permission of Elcometer Inc.)
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642 PAINT AND COATING TESTING MANUAL 15TH EDITION
A different type of impact tester was developed and
is being used at the Bell Laboratories of AT&T. A coated
panel is subjected to repeat glancing blows by a case-
hardened steel ball at the end of a short arm that is pivoted
to another arm connected to a rotating shaft. During the
test, the coated panel is mounted on a platform that moves
so that successive blows do not strike the same spot. The
energy level of the blows may be held constant, as in a
pass/fail test, or it can be adjusted by changing the speed
of the rotating shaft to determine the onset of cracking. If
the hammer energy level required to destroy the coating
is desired, a transparent, calibrated scale of shaft speed in
revolutions is superimposed over the impact pattern. This
tester is not commercially available.
There are a number of other impact testers that have
been developed over the years and used to some extent.
These include the Parlin-duPont Tester, Camp Impact Test,
Hart Impact Tester, Ball Punch, General Electric Ball Drop,
and Navy Falling Ball test. None of these testers are com-
mercially available now.
The ISO 6272 standard, Rapid-deformation (impact
resistance) tests is made up of two parts, part 1, Falling-
weight test, large-area indenter and part 2 Falling-weight
test, small-area indenter. Part 1 uses a 1 kg weight with the
20 mm diameter spherical indenter attached, whereas part
2 is based on ASTM D2794-93 (2010) and uses either a 12.7
mm or 15.9 mm indenter.
Testing of Free Films
ASTM D2370, the Standard Test Method for Tensile Prop-
erties of Organic Coatings, covers the elongation, tensile
strength and stiffness (modulus of elasticity) of organic
coatings when tested as free films. The method for prepar-
ing the uniform free films of organic coatings is given in
ASTM D4708, Standard Practice for Preparation of Uni-
form Free Films of Organic Coatings using substrates that
can be peeled from the cured film. Procedures are given for
preparing free films on three alternative substrates. These
substrates are treated FEP (fluorinated ethylene-propylene)
sheet, silicone coated paper, and halo-silane coated glass
plates. (Note: The dental foil that used to be included as
one of the substrate has been removed from this practice
because it contains mercury and is therefore hazardous.)
Cold Crack Resistance Tests
Tests in which coatings on substrates are cycled through
elevated temperature, low temperature, and room tempera-
ture environments are called cold crack tests. They have
been used in the coatings industry for many years as an
indication of the ability of a coating to resist cracking in
service and therefore are considered to be tests of coating
flexibility.
ASTM D1211 Standard Test Method for Temperature-
Change Resistance of Clear Nitrocellulose Lacquer Films
Applied to Wood is an example of such a cold crack test,
however this Standard Test Method was withdrawn without
a replacement in 2006. It described a procedure for testing
lacquer coatings applied on wood. The testing cycles consist
of 1 h at 120F (49C), 1 h at 5F (21C), and h at room
temperature. The results were reported as the number of
cycles required to produce visible cracking in the coating.
Fig. 7Falling weight impact tester. (Reprinted by permission
of Elcometer Inc.)
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CHAPTER 50 FLEXIBILITY AND TOUGHNESS 643
Automotive coatings are subjected to cold crack cycle
tests. A typical test for exterior coatings on metal panels
consists of (1) equilibration at room temperature, (2)expo-
sure in a humidity cabinet at 100F (38C) and 100 %
relative humidity for 20 h, and (3) exposure in a freezer at
22F (30C) for 4 h. After removal from the freezer, the
coated panels are allowed to stand at room temperature for
2 h. Then the coatings are visually rated for cracking. In
some cases, an exposure of 2 h in an oven at 150F (65C)
is introduced into the above cycle conditions.
A rapid cold crack test that has been developed is based
on the use of cooled air entering a transparent, insulated
box. Cold air that has been cooled at a rapid controlled rate
is introduced into the box, and the coatings are observed
for cracking. The coatings are then rated by determining
the temperature decrease from room temperature that is
required to produce visual cracks in the coatings [4].
Effects of Aging and Weathering
The ultimate measure of satisfactory flexibility and tough-
ness of a coating applied to a substrate is performance
under service conditions. Most flexibility and toughness
tests are performed on relatively fresh-coated panels, that
is, tests are usually performed after the panels have been
conditioned in a specified atmosphere for a specified
period between 24 h and 7 days. The results obtained are
applicable to service conditions if these are concerned with
post forming or service indoors without a degrading atmo-
sphere, since most coatings do not change appreciably in
their physical service properties under such conditions.
However, if the service conditions include exposure to
weathering, this factor can cause appreciable changes to
occur in the coatings properties.
The effects of moisture, temperature changes, and
exposure to sunlight (ultraviolet wave lengths) encountered
in outdoor exposure generally reduce the flexibility and
toughness of organic coatings. Therefore, it often is desir-
able to conduct tests for flexibility and toughness after peri-
ods of weathering to determine how a coating will perform
under actual weather conditions [1].
References
[1] Schurr, G. G., Flexibility, Paint Testing Manual, ASTM STP
500, 13th ed., H. A. Gardner and G. G. Sward, Eds., ASTM
International, West Conshohocken, PA, 1972, pp. 333337.
[2] Skrovanek, D. J., and Schoff, C. K., Mechanical Analysis of
Organic Coatings, Prog. Org. Coat., Vol. 16, 1988, pp. 135163.
[3] Moore, R. J., Molecular Basis for Impact Resistance of Epoxy
Paint Films, J. Paint Technol., Vol. 43, No. 554, March 1971,
pp. 3946.
[4] Morse, M. P., Physical Properties of Paint Films Relating to
Service, presented at Gordon Research Conferences, Organic
Coatings Section, 1519 Aug. 1955.
[5] Varadarajan, K., Review of Dielectric and Dynamic Mechani-
cal Relaxation Techniques for the Characterization of Organic
Coatings, J. Coat. Technol., Vol. 55, No. 704, September 1983,
pp. 95104.
[6] Tordella, J. P., Mechanical Properties of Amorphous Poly-
mers, Official Digest, Vol. 37, 1965, p. 349.
[7] Supnik, R. H., Rate Sensitivity: Its Measurement and Signifi-
cance, Mater. Res. Stand., Vol. 2, 1962, p. 498.
[8] Schuh, A. E., and Theuerer, H. C., Measurement of Distensi-
bility of Organic Finishes, Ind. Eng. Chem., Vol. 9, 1937, p. 9.
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644
INTRODUCTION
A PROBLEM OFTEN OBSERVED WITH PAINT FILMS
is the development of domed blisters. Usually these bub-
bles in the paint film are the result of osmotic activity.
Understanding the osmotic process will be very helpful
in the investigation of the cause(s) or driving force with
this mode of paint failure. Osmotic blisters may develop
between the primer paint and base substrate, between coats
of applied paints, or within the matrix of a single layer of
the composite (single or multi-coat) paint film. Although in
most cases the blisters are easily seen, it is possible to expe-
rience osmotic activity under paint films when a domed
blister is not elevated enough to be visible. When this
occurs on a steel substrate, typically, corrosion will develop
under the film. The osmotic process may be represented by
the following graphic. It is most important to appreciate
that potential solvent molecules will migrate through the
paint film one molecule at a time. One will remember that
a collection of single, individual molecules is defined as a
gas. For this reason, osmosis follows, and is controlled by,
the general gas laws.
A common definition of osmotic activity in paint
films describes the migration of solvent molecules through
the film and dissolving one or more solutes forming the
blister fluid solution. This process then continues in an
effort to dilute the blister fluid solution to the point that it
has the same concentration (actually, same vapor pressure)
as the outer contact solvent liquid. It is this differential in
vapor pressures that drive the osmotic activity.
Osmosis involves a semi-permeable membrane (as
with a paint film), a solvent, and one or more solutes. To
understand the potential interventions and investigation of
the driving forces, knowledge of the basics of osmosis are
extremely useful. Within this chapter we will review the
chemistry and physics controlling the osmotic phenomena
and present the analytical techniques that will allow one
to determine the source, or driving force, of the osmotic
activity. After determining the driving force one then has
the ability to modify the paint formulation, application
procedures, surface preparation, or service restrictions if
any of these are shown to be the cause (source). If a coat-
ing failure has occurred one may determine where the
liabilities lie as well as the extent of remediation that will be
required to allow a true long-term fix of the problem. Prob-
lems associated with faulty application such as improper
surface preparation are frequently claimed as the culprit.
But, the inclusion of a water soluble thinner or chemical
reaction under, or within, the coating matrix that produce
water soluble materials are possible. Examples of some
of these will be discussed later. Other potential sources of
osmotic problems include deficiencies in the paint specifi-
cation and unanticipated service conditions. Paint formula-
tions that include pigments, resins, or additives that are
soluble, or convert to a form that is soluble in service, can
cause osmotic problems. On rare occasions manufacturing
anomalies may lead to osmotic activity.
The investigation of osmotic activity in paint films
should involve the systematic collection of samples from the
site along with attentive observation of the blister location,
size, and shape. If within a tank, note if blister predomi-
nance is in the liquid or vapor phase of the tank (or at the
vapor/liquid interface). Are there temperature differentials
that would cause condensation? Data relating to cargo
history may be needed in tank lining failures to recognize
and explain unusual solutes found in the blister fluid and/
or coating dome analysis. The collected samples should
include blister fluid withdrawn from blisters, recovered
paint chip film blister domes, paint film samples collected
away from blistered areas, and, for internal tank lining fail-
ures within non-aqueous tank lining failures, a sample of
the material within the tank leading to the osmotic problem.
Sometimes, solutes found in the blister fluid are the
result of chemical reaction products. These reaction prod-
ucts may be generated in the blister fluid over time or gen-
erated within the coating matrix itself producing a solute
in situ. Examples of these include the highly alkaline fluid
on an underground pipeline or ships ballast tank caused by
the reduction of oxygen in systems under cathodic protec-
tion (CP). This high pH fluid may hydrolyze bound chlo-
rine from an epoxy resin or bromide from the blue-green
pigment in the fusion bonded epoxy (FBE). Tank linings
exposed to chlorinated solvents will experience generation
of hydrochloric acid (HCl) from hydrolysis of the mate-
rial within the coating film. Hydrolysis of acetate solvents
51
Understanding Osmotic Activity in Paint
Films and Determining Cause by Systematic
Analysis of Blister Fluids and Blistered
Coatings
George Mills
1
1
George Mills and Associates International, Inc., Foley, AL 36535
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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CHAPTER 51 UNDERSTANDING OSMOTIC ACTIVITY IN PAINT FILMS 645
generates acetic acid. When blister fluids are low pH, often
there will be an iron corrosion product as a solute as well.
These will be discussed later (Fig. 1).
Chemical analysis of the blister fluid along with ther-
mal out-gassing of the blister dome film, usually, will define
the cause of the osmotic activity. When strange or unex-
pected solutes are seen, the investigator may be required to
review some of the chemical reactions that could produce
these solutes in the blister fluid. While the solvent is often
water, tank linings and internal pipe coatings in non-aque-
ous service may experience osmotic activity wherein the
solvent of the osmotic blister is the product of the contact
service media. The solutes may be occluded previous cargo
materials or lower molecular weight polymer fractions
generated by the cargo material. These will be discussed in
detail later.
Most domed paint blisters will be present with the
liquid that caused the blister, although some blister domes
may be found after the liquid has escaped from the coating.
The disruption in the paint film often leads to severe corro-
sion of the substrate as seen in Fig. 2 within a ballast tank
of a large ocean going tanker.
As discussed previously the cause (driving force) of
osmotic blister formation may originate as a result of
numerous sources. While the applicator often is accused
of improper surface preparation, the service conditions
encountered and the paints formulation may be respon-
sible. The real driving force, and hopefully a correction in
the future, may be determined by systematically analyzing
the blister fluids and understanding some of the complex
chemistry that may be operative.
The physical development of osmotic blisters in a paint
film requires that a solvent be available having marginal
transmission within the paint film. This solvent will dissolve
one or more solutes under the film at the substrate, between
applied coats, or within the matrix of a single layer of the
paint film. Usually the source of the solvent is not a mys-
tery. Typically, it is water from condensation or immersion
when water contact is possible. For tanks in non-aqueous
service, the linings may experience osmotic blister forma-
tion wherein the materials in the tank constitute the solvent.
For these situations, the contact solvent will be known or
discovered upon chemical analysis. The identification of
the solutes, and the source of these solutes, may present
the investigator with a challenge. While in some cases, salts
over-coated during application have been cited as the driving
force, the real picture, usually is considerably more compli-
cated. The solutes may involve the generation of ions, with
time, under the film. A good example is the osmotic blisters
often discovered in the lining of potable water tanks at the
one year guarantee inspection after use of hypochlorite
as the purification agent. Through multiple chemical steps,
hydrochloric acid is generated at the steel interface leading
to iron chloride salts under the blisters. Fig. 3 depicts the
blisters formed in such a way within the potable water tank
onboard a very large passenger cruise ship.
The blister fluid may have become strongly acid or
strongly alkaline by generating an acid or alkali under the
film after gas phase transmission of the acid or alkaline pre-
cursors. Acids and alkalis are both strong ionic solutes and
may drive osmotic blister enlargement once initiated. Water
soluble solvents included in the paint formulation by the
manufacturer, or added at application, are another source
of solutes in which there is no additional ionic activity.
Fig. 1Osmotic blisters can form at various interfaces. This
includes under the initial primer coat at the substrate or
between intermediate coats. Individual molecules of the
solvent migrate through the polymer forming the paint
film. Some of these molecules of solvent coalesces to a liquid
forming the blister and disolves one or more solutes. The
difference in vapor pressures between the fluid in the blister
and the migrating solvent controls the direction of solvent
flow. (Graphics done by George Mills, Jr.; Building Design
Solutions, LLC.)
Fig. 2Osmotic blisters in the ballast tank of a large marine
tanker. Note that many blisters have broken open and
corrosion of the substrate is substantial. Some of these may
be driven by cathodic protection anodes installed in the tanks
that are operative only when the tank is with ballast water.
Fig. 3Osmotic blisters in a potable water tank within a large
cruise ship. Notice rust staining coming from broken blisters.
Often these initiate from water soluble solvents formulated
into the epoxy or added during application. Analysis of the
blister fluid will indicate the source of the osmotic blister
formation.
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646 PAINT AND COATING TESTING MANUAL 15TH EDITION
OSMOSIS IN PAINT FILMS
When a practitioner is asked to define an Osmotic paint
failure, the typical response is the passage of water
through a semi-permeable membrane to dissolve salts
under the paint thereby forming blisters under the film.
While this might describe a portion of such failures, the
picture is much broader than this description might imply.
The term semi-permeable is in common usage although,
often, there is little, or no, thought as to the considerable
significance of the numerical value of the semi- in this
common definition. This is true as it relates to the material
acting as the solvent as well as the materials acting as the
solutes driving the osmotic activity. It is important to appre-
ciate that this variability in migration rate/ability through
the paint film applies to both the solvent and (the often
neglected) solute(s), when these solutes are water-soluble
solvents included in the paint formulation, added during
application, or generated in service.
In this chapter on methods of determining the source
of osmotic activity in paint films, the terms blister fluid
and blister solution represent the mixture of the solvent
and one or more solutes found in the blister. By convention,
the material present in this solution in the largest amount is
considered to be the solvent. Generally speaking, the value
of the vapor pressure of the solvent in the blister fluid solu-
tion as compared to the vapor pressure of the solvent out-
side the blistered film dictates the direction of the solvent
flow. One must remember that a solvents vapor pressure
will always be depressed when the solvent has any solutes
added. In the production of pickles, the cucumber is soaked
in a strong salt brine solution wherein the water of the
brine has a lower vapor pressure than the water inside the
cucumber. In this case, the water flows out of the cucumber
causing it to shrivel to a much smaller size.
Within the blister fluid, all of the dissolved materials
are considered as the solutes and will act to depress the sol-
vents vapor pressure. Many only think of salts, over-coated
at the time of application or included in the formulation,
as potential solutes and water from either surface conden-
sation or immersion service as the solvent. While water
soluble salts are a common and strong osmotic driving
force, water soluble solvents, such as oxygenated alcohols,
have been shown to present a serious osmotic driving force.
Oxygenated alcohols are alcohols (already containing at
least one oxygen atom) that contain additional oxygen in
the form of ethers or ketones. These materials are excellent
solvents for the epoxy coatings as they cure and may be
employed in the paint formulation, but they are typically
not very volatile and remain within the coating matrix for
long periods of time. Their added oxygen in the molecule as
ether linkages (COC) usually render them water soluble.
Their water solubility also aides in displacing moisture
at the interface during application over damp surfaces.
Unfortunately, since most are totally water soluble, they
can become the osmotic driving force when liquid water
condenses on, or comes into contact with the coating, espe-
cially when insufficient time is available to allow escape
during the drying stage [1].
Water soluble reaction products such as acetic acid
remaining after hydrolysis of acetate solvents or microbial
digestion of sugars have also been seen as solutes. Acid
solutes usually cause additional corrosion of steel sub-
strates under coatings with the initially formed iron salts
becoming solutes in the osmotic process. The ferrous (Fe
+2
)
corrosion product soon converts to an insoluble ferric (Fe
+3
)
corrosion product after reaction with oxygen in the air.
If the adhesion is good and the blister dome breaks from
internal pressure, osmosis cannot continue at that blister
location since osmosis requires movement of one molecule
at a time.
There are a number of factors that dictate the degree
and speed of damage to a coating system that is experienc-
ing osmotic activity. This communication is intended to
present some important aspects useful in understanding
the process of osmosis, its damaging effects upon paint
films, and a methodology that has proven useful in the
systematic elucidation of the source of the osmotic driv-
ing force. Osmotic activity in paint films is a very common
failure mode. This chapter is intended to assist the coatings
formulator, the application contractor, the failure analysis
practitioner, and the end user in understanding the opera-
tive driving forces and demonstrate methodology useful in
determining the source of the osmotic activity after coating
failure.
Osmotic activity in paint films will be addressed in
the following steps: (1) discuss the chemistry/energetics
of the osmotic process and other chemical processes that
may accompany and exacerbate this coating failure mode;
(2) discuss some of those factors causing, or accelerating,
osmotic activity in paint films; (3) discuss a proven method-
ology employed in the systematic chemical analysis of the
osmotic blister fluids to identify the source of the activity
and the significance of the analytical data as it relates to
potential problems with the paint formulation, the specific
application, and/or the service leading to the paint failure;
and (4) present some case history examples to demonstrate
the data developed in identifying the source of the osmotic
activity.
Water is the most common solvent encountered in
paint film osmotic activity. For this reason, water systems,
primarily, will be discussed in this communication. It is
important to appreciate that other solvent/solute systems
may be encountered and are just as damaging. A common
example exists with marine epoxy tank linings containing
benzyl alcohol or nonyl-phenols and cargo materials hav-
ing marginal transmission coefficients such as the fuel
additive methyl-t-butyl ether (MTBE) and some lower
molecular weight alcohols sequenced with the presence
of water.
THE CHEMISTRY OF THE OSMOTIC PROCESS
In simpler terms, osmosis is the natural process of indi-
vidual solvent molecules migrating through the film, con-
densing, and dissolving some solute to form a solution. For
osmosis to be possible, molecules of solvent MUST travel
through the paint film ONE MOLECULE AT A TIME. By
definition, this makes the process a Gas Phase Transition
since a gas is a collection of individual molecules. For
this reason osmotic activity follows the general gas laws of
chemistry.
It is more understandable to say that the vapor pressure
of the pure solvent (outside the coating film) is greater than
the vapor pressure of the diluted solvent in the blister fluid
solution. This difference in vapor pressure thereby forces
the solvent towards the osmotic solution. This is due to the
depression in vapor pressure of the blister fluid caused by
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CHAPTER 51 UNDERSTANDING OSMOTIC ACTIVITY IN PAINT FILMS 647
the solutes present as opposed to the pure solvent. Just as
dissolved solutes will depress the freezing point, or elevate
the boiling point of a solvent (by depressing its vapor pres-
sure), the energy required to perform the chemical work,
or, simply, the osmotic driving force, has its origins in the
similar basic laws of chemistry [2].
This then leads one to the more common definition
of osmotic activity. The solvent molecules migrate through
the film and dissolve into the blister fluid solution in an
effort to dilute that solution to the point that it is the same
concentration (same vapor pressure) as the outer contact
liquid. More precisely, the process continues until the vapor
pressure of the blister fluid solution equals the partial vapor
pressure of the solvent outside the blister. (The physical
chemistry purist will speak of equating the chemical poten-
tial of the two.)
Because osmotic activity is a colligative property
of the solution, the driving force is based on the number
of individual species dissolved in the solution rather than
the individual solutes molecular weight, size, or chemical
structure. In general, this means that the effect of one mole
(90 g) of 2-butoxy ethanol/liter has the same damaging
effect as a half mole (about 29 g) of sodium chloride/liter
since the sodium and the chloride ions are each separated
in the osmotic solution and the total sum of the number of
individual species dissolved (ions) are equal to the number
of the 2-butoxy ethanol molecules in solution.
Individual movement of molecules of the solvent
through the paint film is an important concept to appreci-
ate. By definition, this is a gas phase transition since a gas,
also, exists as individual molecules. For osmotic blisters to
form in the first place there must be sufficiently compro-
mised adhesion for a condensed (liquid) phase to exist, even
if over an extremely minuscule area. Once a liquid solution
is present, at an interface (base substrate, inter-coat inter-
face, particle inclusion, etc.), the volume and, usually, the
pressure of the condensing fluid will continue to increase
until two conditions exist collectively.
In osmotic activity, the first condition is that the con-
centration of the solute within the blister fluid decreases
as the volume of pure solvent passing through the film
increases. When this concentration of driving solute in the
blister fluid equals that in the external contact fluid, the
process will stop. More precisely stated, the osmotic driving
force diminishes as the partial pressure (chemical poten-
tial) of the solution in the blister and the partial pressure of
the liquid outside the film approach the same value.
The second condition occurs when the actual pressure
that is gradually created in the osmotic blister reaches
the value that will force the pure solvent (or solutes) back
through the film. This is the process of reverse osmosis
used to purify water in certain desalination systems.
When the adhesion of the paint film is good and the
film cannot be peeled easily from the substrate by the inter-
nal osmotic pressure generated, the pressure may become
sufficient to rupture the blister. When this occurs, if the
crack remains open and liquid solvent can pass, osmotic
activity is no longer possible. This is because liquid phase
movements (as opposed to gas phase) are now operative
since there is no semi-permeable membrane. Osmosis
requires that individual molecules (i.e., separated from
each other) move through the semi-permeable membrane
(paint film) thus acting as a vapor phase transmission.
FACTORS CAUSING VARIATION IN OSMOTIC
ACTIVITY IN PAINT FILMS
While most osmotic activity in paint films is clearly visible,
osmotic activity can, and does, occur without the appear-
ance of visible domed blisters. The development of osmotic
blisters at the coating/substrate interface, whether visible or
not, depends on a large number of factors. A few of these
include: (1) the value of the paints adhesion force at that
location; (2) the degree of the depression of the glass tran-
sition temperature, T
g
, and/or plasticity of the paint film
caused by the water (or other solvent) and any migrating
solutes; (3) the concentration, and location, of available
solutes; (4) the transmission coefficients of the solvent, and
solutes, within the paint film at that location and under the
local ambient cure conditions.
For coatings like epoxies, the actual variation in trans-
mission rates are possible within a single formulation and
depend on numerous application variables. Solvent and
molecular solute transmission coefficients within a paint
film will depend on variations in the degree of mixing prior
to application, closeness to true mixed chemical stoichiom-
etry of the base and converter resins, temperature of the
substrate (and, therefore, the reacting paint mixture) dur-
ing curing, ultimate cross-link density of the formulation,
amount of carbon dioxide (CO
2
) stripped from the air by the
amino functional converter during mixing and application,
and a myriad of other variables.
Although rare, osmotic activity can occur within the
matrix of the paint film as opposed to an interface. When
this happens, bubbles of liquid will form within the coating
matrix, usually from condensation of water (or the solvent)
on the surface of some occluded particle. This requires the
osmotic pressure to develop to a value greater than the ten-
sile strength of the paint matrix at the location of the formed
bubble. Osmotic activity in this form is typically present as
very small bubbles within the paint film. The bubbles are
not spherical in nature, and they are best viewed under a
microscope. It is important to emphasize that osmotically
driven bubbles have nothing to do with any air or gas bub-
bles or voids that may have been trapped during application
and are present in the applied film [3]. Osmotically gener-
ated voids or bubbles within the coating matrix will show,
microscopically, a fractured edge as opposed to a smooth
surface for air trapped bubbles. The size of the bubbles
formed from osmotic activity that occur within the coating
matrix depends largely on the tensile strength of the coating
matrix at the inclusion and the distribution of water soluble
inclusions, either salts, pigments, or converter fractions.
Water soluble low molecular weight amine converters have
been seen in blister fluid when application occurred at cold
temperatures. Typically, these are usually at an interface as
opposed to within the film matrix and occur as a result of
reaction of the alkaline amine functional cross-linker and
the acid gas carbon dioxide.
From the above discussion, it is evident that for
osmotic activity to occur at an interface where adequate
solute is available, the value (strength) of adhesion is the
major factor that will dictate the size of the blisters formed.
When blisters form, areas having very good adhesion will
yield small blisters. Areas having compromised or lower
values of adhesion will yield larger blisters. Very large blis-
ters (16 in. diameter and greater) have been observed when
CP produced alkali salts in situ under FBE pipe coatings.
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648 PAINT AND COATING TESTING MANUAL 15TH EDITION
These coatings were applied over salt contaminated
areas of a pipe and developed within a few years time. This
very common example typically is the result of applied
cathodic protection and the production of hydroxide ion
(salts) from reduction of oxygen gas passing through the
coating and dissolving into the blister fluid. See Fig. 4.
All amorphous (i.e., non-crystalline) organic coatings
and plastics will allow small molecules to migrate within, or
diffuse through, the plastic matrix. This is the same mecha-
nism that allows a freshly applied coating, after gelling,
to lose most of its included solvents as it cures and dries.
The rate, or speed, of passage of these individual molecules
through a coating film is called its transmission coefficient
for that material and depends on numerous factors. These
include the solute size and molecular weight. Ficks Law
dictates that the diffusion rate through a polymer matrix is
inversely proportional to the square root of the molecular
weight of the migrating molecule. Diffusion rate is also
impacted by the cross-link density of the film. The trans-
mission coefficient of migrating molecules is often related
to the glass transition temperature, T
g
. Migration rates are
also impacted by the chemical and structural nature of the
matrix as well as the migrating species polarity, polarizabil-
ity, and chemical stability. This migration within a coating
matrix is normal and to be expected, although sometimes
it is undesirable. When sufficient volumes are lost after
reaching the gelled state in its curing process, cracking of
the coating from shrinkage stress development may occur.
No coating stresses can develop from volume loss before
the gel point is reached since liquid mechanics are opera-
tive within the freshly applied paint. The inclusion of these
migrating species within a coating matrix causes a decrease
in the cured films glass transition temperature, T
g
. This
dynamic, constant movement within the coating film is the
same as experienced with migrating plasticizers, chemically
blocked cross-link accelerators/enhancers, molecular cata-
lysts, as well as binder extenders such as benzyl alcohol,
nonyl-phenols, etc.
The past experience of the author has shown that the
water-soluble solutes causing osmotic blisters can come
from a number of sources. Some typical sources include
the following:
1. Water-soluble solvents purposefully formulated into
the paint by the manufacturer. The most common are
oxygenated alcohols such as 1-methoxy-2-propanol
and 2-butoxy ethanol. Some are listed in the products
material safety data sheets (MSDS) while some paint
manufacturers are reluctant to identify their presence.
2. Water-soluble solvents added at application (thinners).
While the paint or the manufacturers recommended
thinners may not contain the oxygenated alcohols, the
manufacturers recommended wash thinners may con-
tain these solvents. These have been detected in applied
paint films in past blister fluid analyses, apparently
from inadvertent inclusion by the applicator when the
wash thinner was used to thin the paint at application.
3. Salts remaining on the substrate at the time of applica-
tion. All water-soluble salts, whether sodium chloride,
sodium/potassium/lithium hydroxide, or whatever the
ionizable water-soluble salts may be, these can become
solutes in the osmotic blister fluid. Most water based
zinc silicate formulations use a binder that originates
as a water glass. This is a silicate dissolved by alkali
hydroxide. Shop primers often are not formulated above
the critical pigment volume concentration (CPVC) and
allow the hydroxide salts to become trapped within the
matrix of the shop-primer coating. These are slowly
released when used in immersion or damp, water-con-
densing service. Usually, efforts are made to water rinse
any soluble salts from the primers prior to over-coating
but with systems formulated below the CPVC, this
cannot be done effectively. Even with systems formu-
lated above the CPVC, extended curing times are always
required to minimize the availability of the soluble
alkali hydroxides. Rinsing should continue until the
dampened surface has a pH equal to the rinse water. The
lack of porosity makes this task difficult (or impossible).
In these cases, the blister fluid will be of a high pH, high
conductivity, and the ion analysis will indicate the pres-
ence of the alkali metal (Na, K, or Li) from the water
based zinc silicate primer. Ethyl silicate based zinc
primers are not as prone to the blistering in this way,
although the mineral acids used to stabilize the silicate
binder in the storage container may present a problem
if not rinsed away prior to over-coating and immersion.
4. Hydroxide salts generated in the blister fluid. The con-
tinuous generation of hydroxide ion in blister fluid will
occur when two conditions are met: (a) a liquid water
filled area exists at the steel or zinc primer interface
irrespective of how small (as opposed to intercoat
delaminated areas) allowing oxygen to migrate in; (b) a
cathodic potential exists of sufficient voltage to reduce
any oxygen that migrates into the blister fluid. The
oxygen is converted to hydroxide as it migrates into
the blister fluid.
2H
2
O + O
2
4OH
This represents the in situ production of a salt that will
drive osmotic blister activity. The blister fluid will pres-
ent with high conductivity and a high pH but may also
contain dissolved organic and inorganic moieties from
the paint. Benzyl alcohol is more soluble in alkaline
blister fluid than in neutral pH water and has been seen
in high pH blister fluid.
5. Hydrolysis of formulated, or cargo absorbed, materials
such as ester solvents or chlorinated solvents. Esters
are the reaction product of an acid and an alcohol.
Fig. 4Blisters as large as 20 in. have been seen on cathodically
protected pipelines. The fluid from the blister on the FBE
coated pipe above was highly alkaline from the reduced
oxygen production of hydroxide.
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CHAPTER 51 UNDERSTANDING OSMOTIC ACTIVITY IN PAINT FILMS 649
Hence, butyl acetate is the reaction product of butanol
and acetic acid. When this has been a cargo in a lined
tank, after washing with water we have seen hydrolysis
within the coating matrix. The butyl alcohol and acetic
acid are regenerated by soponification reaction with a
water molecule. Acetic acid that migrates to the steel
interface may produce a corrosion product with iron
that is itself somewhat soluble and becomes one of the
osmotic driving solutes. Chlorinated solvents hydrolyze
to HCl. The rate of hydrolysis is a function of the specie
undergoing hydrolysis and the alkaline strength of the
nucleophilic centers (nucleophilicity) within the coat-
ing matrix that catalyze the hydrolysis. The blister fluid
will be of a low pH (less than 7 depending on acid con-
tent). Fermentation of sugars, as in molasses cargoes
aboard ships, also produces acetic acid. Acetic acid will
migrate through the coating and initiate corrosion at
the steel interface. Analyses of the solid iron corrosion
product recovered from under ruptured blisters will
give a strong indication of acetic acid when utilizing
the pyrolysis function of the gas chromatograph mass
spectrometer (GC/MS) if this has occurred.
6. Production of sulfuric acid (H
2
SO
4
) within the slime
layer of an internal lined sewer pipe caused by the bio-
oxidation of hydrogen sulfide (H
2
S). This leads to low
pH blister fluids, and often perforation of the pipe.
7. Low molecular weight amine functional curatives
that have been blocked from the epoxy reaction by
carbon dioxide (CO
2
) or other blocking agents. For
CO
2
blocked converters, this is typically the result of
cold temperature application wherein the epoxy-amine
reaction slows or stops and the acid gas CO
2
-amine
reaction continues reasonably fast. During mixing of
the amino side of the epoxy coating or the A + B
mix, if a vortex is drawn on the mixing paint and air
is mixed into the paint, most of the CO
2
in the air will
be stripped and the resulting blocked curative will not
be available for reaction with the epoxy. This is one of
the sources of variability in the ultimate T
g
of the cured
coating. Inclusion of ketones in the amino side of an
epoxy curatives is another potential source of failures.
This happens when the amino functionality is blocked
by the formation of ketimines in the can during stor-
age. In this case, the length of time since curative
manufacturer and the past thermal history will influ-
ence the amount of ketimine that has developed in the
can. Ketimines require moisture from the atmosphere
to cure and are the curatives used in moisture cured
epoxy systems.
The data developed by the blister fluid analysis, on
occasion, will indicate additional tests useful in confirming
the source of the water soluble solutes found. This is true
when their presence cannot be explained by the MSDS of
one of the paint products involved. The MSDS for the coat-
ing material does not always include non-hazardous water-
soluble solvents. Evidence developed from work by this
laboratory on ship-bottom paints has shown that solvents
from any coat of applied paint will migrate throughout all
prior applied old layers allowing blisters to form at the steel
interface. This was demonstrated after the fresh application
of a topcoat containing an oxygenated alcohol was applied
to a ships hull over three layers of five year old, pre-existing
paint that never blistered. The analysis of the blister fluid
collected from below the original paint system indicated
the water-soluble alcohol that was present in the new paint
application. On occasion, chemical reactions in or about
the osmotic blister area will be producing the solutes. For
this reason, to establish liability, the investigator must be
prepared to accept the data from the blister fluid analysis
and seek the true chemical pathways to these solutes, even
if he must revisit his chemistry textbooks.
THE SYSTEMATIC CHEMICAL ANALYSIS OF
OSMOTIC BLISTER FLUIDS AND BLISTERED
COATINGS
A systematic analysis of the fluids removed from osmotic
blisters will provide the answers as to what drives the
osmotic activity and therefore assist in establishing liability.
In addition, the analysis often will indicate ancillary chem-
istries occurring within the blister fluid itself and/or within
the coating matrix forming the blister dome. The following
analytical methodologies have been found to provide suf-
ficient data to identify the material(s) initiating the activity
and any additional driving forces that might be developed
after blister formation.
The collection of blister fluids is best done using a
hypodermic syringe after first producing a small hole
through which the needle may be placed as seen in Fig. 5.
Usually, the coatings are too hard and brittle to force the
needle through the coating film itself. For this reason, to
minimize the chance of destroying, bending, or plugging
the needle, drilling or puncturing with a sharp nail at the
edge of the blister may be best. The solution should be col-
lected and stored in glass vials since many of the solvents
will migrate through plastic containers if the chemical
analysis is not done timely.
Ideally, many answers are provided by using a GC/MS
having the ability, first, to out-gas and identify the lower
molecular weight volatiles followed by a separate, second,
analysis of the fragments after pyrolysis at elevated tem-
perature of the residues. The pyrolysis, then, is done with-
out opening the thermal extraction (TE)/pyrolysis (Pyro)
oven. This is useful in solving some of the mysteries when
the solutes are organic in nature. Higher molecular weight
water soluble materials may be identified that are not seen
on direct injection. When this type of equipment is not
available, gas chromatograph/mass spectrometers utilizing
Fig. 5Blister fluid is being removed under water using a
small hypodermic syringe. This is in the coating within a large
concrete pool at a state aquarium. Note sharp wood chisel
used to first produce a very small hole in the coating at the
edge of the blister.
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650 PAINT AND COATING TESTING MANUAL 15TH EDITION
direct injection of the blister fluid is an alternative that will
provide good definitive data for some of the cases, but the
solvent portion is always much greater than the molecular
solutes. The ionic solutes will not volatilize and cannot be
seen by the GC. These are identified by ion chromatogra-
phy or by scanning electron microscope (SEM) with energy
dispersive x-ray (EDX) after drying the blister fluid residues
(Fig. 6).
Knowing potential sources of osmotic activity allows
narrowing the search. The sequence of procedures followed
in the blister fluid analysis yielding the most data will
include the following steps.
1. GC/MS analysis by low temperature TE/desorption
(water soluble solvents).
2. GC/MS analysis by pyrolysis analysis of non-volatiles
remaining after TE (higher molecular weight, water
soluble reaction products); Done without opening TE/
Pyro oven.
3. Determination of electrical conductivity and pH
4. Ion chromatography to identify the specific ions other
than OH
and H
+
ions seen in the pH determination.
When not available, SEM/EDX analysis of the dried
blister fluid residue will reveal the inorganics present.
While the mass spec detector suffers in its being more
difficult to perform finite concentration determinations,
its ability to provide the identity of unknown water soluble
organic solutes from their specific mass fragment finger-
print is excellent. Although it may be useful in some cases,
the absolute concentration of the specific solutes in the
blister fluid is not required to determine the source of the
osmotic activity.
After analysis of the blister fluid, additional analyses of
related coating materials will allow determining the source
of the water soluble solvents. These analytical techniques
include thermal extraction and pyrolysis analysis of the
coating materials forming the dome of the blister, as well
as coating material in the near vicinity of the blister. Test-
ing wet, un-applied, un-mixed coating materials from the
can will pinpoint specific problems if these are from the
paint formulation. If a water soluble solvent is found to be
the osmotic driving force, the comparison of the analyses
of the applied coating and the unapplied coating material
will indicate whether this bad solvent was added during
application or was included by the manufacturer in the
paint formulation. Occasionally a review of the MSDS for
the coating product will indicate the water-soluble solvent,
though from experience we have seen that the paint manu-
facturer often does not identify these solvents (Fig. 7).
GC/MS Analysis by Low Temperature Thermal
Extraction/Desorption (TE/GC/MS)
Often, the amount of available blister solution is small.
Because of the large amount of data provided by the GC/
MS thermal desorption and pyrolysis techniques, these
analyses should be performed first if only one drop of blis-
ter fluid solution is available. When salts are the primary
osmotic driving force, usually there will be ample blister
fluid sample available (Fig. 8).
The ideal GC/MS analytical instrument used for the
thermal extraction and pyrolysis analysis is a combination
of four instruments linked together. It has been described in
detail previously [4,5]. Briefly, it is a late-model GC with a
mass spectrometer used as the detector. Integrally attached
to the GC inlet is a heated transfer line of deactivated fused
silica maintained at about 325C (620F) connecting the
computer controlled TE/ Pyro oven. The very small TE/
Pyro oven has a stream of Helium sweeping any volatilized
materials into the cryogenic trap in the GC. The separation
Fig. 6The ideal analytical instrument configuration for
identifying the source of osmotic activity in paint films is a
gas chromatograph having a mass spectrometer as a detector,
a thermal out-gassing/pyrolysis attachment, and a liquid
nitrogen trapping section at the head of the GC column. To
the right is the pyrolysis and thermal out-gassing attachment.
The liquid nitrogen cryogenic focusing on capillary column
is within the GC oven as seen in Fig. 6. The components of
the analytical system are as follows: 1. Gas chromatograph;
2.Mass spectrometer; 3. Pyrolysis-outgassing controller for
solid samples; 4. Liquid nitrogen cryogenic controller; 5.
Heated crossover line from pyrolysis oven to cryogenic trap in
the GC oven; 6. Liquid nitrogen supply line from outside LN2
storage.
Fig. 7Oven of gas chromatograph housing quartz capillary
column (30 m) and quartz cryogenic focusing chamber. The
components are: 1. 30 m capillary column passing through
liquid nitrogen (LN2) cryogenic trap; 2. LN2 inlet and outlet fed
by thermostat control of LN2 valve; 3. Quartz LN2 cryogenic
chamber with electrical resistance heater to flush trapped
components onto the column at the start of the GC analysis.
Capillary column passes through the LN2 cooled cryogenic
trap. An alternative home-made cryogenic trap is a simple
styrofoam cup containing liquid nitrogen. This is placed in the
GC oven allowing a short section of the capillary column to be
manually submerged during sample out-gassing. The LN2 is
removed at the start of the GC analysis.
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CHAPTER 51 UNDERSTANDING OSMOTIC ACTIVITY IN PAINT FILMS 651
column used is a 30 m DB-5 capillary column. About 4 in.
of the front end of the column passes through a quartz
chamber plumbed to receive liquid nitrogen. This chamber
also contains a wire resistance heater capable of heating
the frozen column to 275C (527F) very quickly. A separate
computer controller is programmed to maintain 125C
(193F), initially to cryogenically trap the volatilized com-
ponents or thermally degraded fragments from the heated
polymer. The thermal desorption/pyrolysis oven operates
for about 6.5 min, going from ambient to 125C (257F) for
TE or ambient to 500C (932F) for pyrolysis. This drives
off any materials volatile at these conditions. The cryo-
genic trap maintains its cold 125C (193F) temperature
for 10min. At the end of the 10 min. collection period, the
controller shuts off the LN2, the resistance heater quickly
takes the cryogenically cooled trapped section of the column
to 275C (527F), the GC is automatically switched on, and
the mass spectrometer starts to collect data. An alternative
cryogenic trap that works very well is a simple styrofoam cup
placed in the GC containing liquid nitrogen. A loop of the
GC column is then submerged under the LN2. To start the
analysis the cup of LN2 is removed and the GC started after
the out-gassing/ pyrolysis. This provides 190C (310F)
cryogenic trapping. At this temperature, all products of inter-
est will be stopped, including carbon dioxide and acetone.
Frequently, solutes identified by the low temperature
TE analysis include the oxygenated alcohols (2-butoxy etha-
nol, 1-methoxy-2-propanol, etc.), the butanols, benzyl alco-
hol, the xylenes, ketones, acids (both organic and mineral),
and any solutes volatilized at the 125C (257F) TE condi-
tion. If the blister is being driven by hydroxyl ion being
leached from the substrate (as with some water based zinc
silicates) or generated from CP impressed currents, the pH
will be high. For high pH blister fluids, the solubility of any
benzyl alcohol binder extender and other alcohols become
much greater. These may then be seen. Typically, their con-
centrations will not be sufficiently great to continue the
development of the blisters in neutral (water) blister fluid.
Tank linings used in organic solvent service can generate
blisters from the alcohol extenders depending on the coat-
ing and service (Fig. 9).
GC/MS High Temperature Pyrolysis
(PYRO/GC/MS)
To identify the higher molecular weight solutes, without
opening the TE/Pyro oven system after the TE run, the TE/
Pyro oven controller is set for the pyrolysis programmed
conditions. The cryogenic trap is brought back down to
125C (193F) or the cup of LN2 is re-inserted. When the
cryogenic section of the separation column reaches the low
trapping temperature, the pyrolysis oven containing the
dried blister fluid sample is heated to 500C (932F). Any
organic materials that were dissolved in the blister fluid
but did not volatilize during the warming thermal extrac-
tion procedure are now subjected to the potential thermal
degradation temperature of 500C (932F). Any heavy
organic solutes will degrade to volatile components. The
identification of these components allows one to visualize
their precursors.
Determination of Electrical Conductivity
and pH
If there is sufficient blister fluid, one drop is used to deter-
mine the electrical conductivity and pH. When the conduc-
tivity is high, there is ionic activity. If the pH is alkaline, the
ionic source could be from applied CP, or a source of stray
current potential sufficient to reduce molecular oxygen to
the hydroxide. The coating may have been applied over a
water based zinc shop primer wherein all of the sodium or
potassium hydroxide could not be rinsed away. There is a
very low probability that some of the amine curative may
have been solubilized.
If the conductivity is high and the pH is neutral, as may
be the case between coating layers, the salts may be organic
acid or carbonated amine curatives. An exception is in
areas where wind blown salts are available, as on offshore
facilities and in marine applications.
If the conductivity is high and the pH is low, there is
some source of acid causing the pH depression. Unlike
the clean, non-corroded metal seen under high pH blister
Fig. 8A conductivity meter requiring only one drop of blister
fluid is used to determine electrical conductivity. Conductivity
of the blister fluid solution is a measure of the total number
of ions or salts present. Specific identification of the ions is
provided by SEM/EDX or ion chromatography. (Photo provided
by HORIBA Instruments, Inc., www.horiba.com)
Fig. 9A pH indicating a paper strip is used to determine
the pH of the blister solution. The fluid from the conductivity
meter is adequate for this determination. If there is minimal
blister fluid available, a very small spot from the hypodermic
syringe will suffice.
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652 PAINT AND COATING TESTING MANUAL 15TH EDITION
fluids, typically, the low pH fluids cause the steel to cor-
rode. The source of acid must be determined from past
history or pyrolysis of the iron corrosion product. For
cargo tank linings, this is a common problem and may
be deduced from cargo histories that are available. Acetic
acid is especially problematic. Cargoes of molasses and
natural sugar products often contain acetic acid that is
the result of bio-degradation. The transmission coeffi-
cients for acetic acid through most tank linings are such
that it often becomes the primary solute in the osmotic
activity. After desolution of iron, additional soluble
iron (II) complexes add to the solute mix dissolved in
the blister fluid. As oxygen transports across the paint
film to the blister fluid, the soluble iron (II) complex is
converted to iron (III) and precipitates out of solution.
Analysis of the rusty iron scrapings from under the blis-
ter area by pyrolysis GC/MS will often reveal which acid
has been operative, even if it is hydrochloric acid. Hydro-
chloric acid results from the hydrolysis of chlorinated
solvents. There are many different chlorinated organic
solvents stored in coated tanks as well as transported in
coated marine tankers. All will hydrolyze to some degree
to produce the HCl. The most problematic chlorinated
solvent seen by this laboratory is the cargo material allyl
chloride, CH
2
CH
2
CH
2
Cl. This material absorbs into the
tank lining and within hours after water washing, liber-
ates HCl.
Hydrogen sulfide, H
2
S, may be generated within sewer
systems that are not properly treated to control the con-
dition. Since this is an anaerobic action (occurs in the
absence of oxygen), to stop this H
2
S formation, sewer
operators will sometimes attempt to maintain a sufficient
amount of dissolved oxygen (DO) in the effluent to disallow
attack of the sulfates. Another practice is the addition of
nitrates into the effluent, since the bacteria prefer nitrates
to sulfates as their hydrogen acceptor in the energetics of
their life cycle. If the sewer system has not been properly
controlled for the production of hydrogen sulfide, sulfuric
acid will be produced from any H
2
S after reaching aerobic
conditions. This occurs readily in the crown of partially
filled pipes where air is available above the wastewater. The
resulting corrosion is called Crown Corrosion for this
reason [6]. This can destroy both steel and concrete pipe
systems after loss of coating by osmotic blister formation.
Ion Chromatography
The use of ion chromatography usually will identify the
specific ions causing the high conductivity in blister fluids.
Past experience of this laboratory has shown that the pres-
ence of hydroxyl ions from a CP induced high pH blister
fluid often will cause an increase in additional ionic species
in the blister fluid. Under blue or green coatings, bromine
may be hydrolyzed from the phthalo blues and greens pig-
ments. Chlorides may be hydrolyzed from epoxy resins in
high pH blister fluids. For this reason, the presence of the
chloride or bromide ion in the blister fluid is NOT, con-
clusively, indicative of salts over-coated during application
although these may have contributed to the diminished
adhesion exacerbating the osmotic activity. Sulfates will
be seen in oxidation of the H
2
S in sewer pipes. Sea water
evaporation and blown sea salts will contain chlorides,
bicarbonates or carbonates (depending on pH), sulfates,
and all other ions typically seen in seawater.
CASE HISTORIES OF OSMOTIC ACTIVITY
PAINT FAILURES
Case Number 1: A series of barges employed in fresh water
river trade developed blisters after being in service a num-
ber of months. The time to discovery was about a year. The
paint system included the use of a water based potassium
silicate zinc shop primer applied to the steel plate upon
arrival at the fabrication facility. After application of the
shop primer, the steel was fabricated into barges within
about a month. After fabrication of the barge, and just a few
days before launch, the finished barge was high-pressure
fresh water rinsed, allowed to dry, and over-coated with an
epoxy coating. Blisters were discovered during dry-docking
about a year later. There were no cathodic protection
anodes used. The declaration was made that there had been
no cathodic protection potentials applied to the vessel dur-
ing its moorings. Grounding a vessel to the CP system of a
dock is a practice that often occurs with vessels that trade
in flammable cargo. These barges traded in dry cargo.
Fluid was collected from a number of the blisters on
the bottom of a barge. The blister fluid was clear, the pH
of the fluid was about 13, the conductivity was measured
at 19 200 S (microsemins). Chemical analyses of the fluid
by GC/MS TE followed by PYRO indicated that a small
amount of organic solubles was present in the fluid. These
were all alcohols that had migrated from the epoxy paint
topcoat. There were no heavier molecular weight materials
seen during the pyrolysis analysis.
The analyses indicated that the water based zinc silicate
still contained sufficient water-soluble potassium hydroxide
to become the solute in the osmotic blisters. It is extremely
difficult to extract all alkali from these types of silicate films
in one short rinsing. Additionally, the curing of the silicate
film may require months to fully bind the potassium and
allow loss of the excess alkali to become minimally soluble-
salt free. (It cannot become salt-free.) The driving force
to produce blisters is just as strong for the salt potassium
hydroxide as it is for the salt sodium chloride. One would
never consider over-coating high concentrations of sodium
chloride salt. Because zinc metal is amphoteric (i.e., can
be dissolved by either acid or base) the tetrahydroxy zinc
(II) ion is just another solute driving the osmotic activity.
The organic solutes seen in the GC/MS analysis are, in part,
because of their increased solubility as the pH of the blister
fluid increases. The butanol and benzyl alcohol have lim-
ited solubility in neutral water. The 1-methoxy-2-propanol
is 100 % water-soluble and can be a problem in certain
scenarios. This water soluble solvent is sensitive to length
of drying time and ventilation. The transmission coefficient
for this oxygenated alcohol is greater than the 2-butoxy
ethanol and often will not be sufficient to generate vis-
ible osmotic blisters. The exception is in well cross-linked
epoxy systems where its mobility is more restricted. This
is an example of the importance of the numerical values
of the semi in the semi-permeable membrane part of
a typical definition of osmosis. In this case, although the
concentrations were relatively small for all alcohols, the
1-methoxy-2-propanol exacerbated the blister formation
and the hydroxide ion provided the driving force for the
continued osmotic activity (see Fig. 10 and Fig. 11).
Case Number 2: Blisters developed within the coating
system of a large floating offshore drilling platform. The
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CHAPTER 51 UNDERSTANDING OSMOTIC ACTIVITY IN PAINT FILMS 653
Fig. 10GC/MS response from the thermal extraction of blister fluid collected from the bottom of a barge. Alcohols that normally
are not appreciably soluble in water are more soluble in alkaline blister fluid. The scan is magnified to reveal the small amounts
of organic solutes.
Fig. 11Fragment pattern collected by the mass spectrometer at 13.677 min. The computer matched this pattern to 1-Methoxy-2-
Propanol, a water soluble epoxy thinner. This oxygenated alcohol can cause osmotic blisters when condensed water is possible.
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654 PAINT AND COATING TESTING MANUAL 15TH EDITION
paint system was similar to Case Number 1 with the excep-
tion that the zinc silicate was applied as a holding primer
after construction. It was a solvent based, ethyl silicate zinc
coating. The two-coat epoxy topcoat was applied during
colder months in Europe. Severe blistering occurred after
flooding the tanks for testing. The drilling platform was
delivered to the US for completion and an investigation of
the cause of the osmotic activity was done [7].
Blister fluids were collected from two types of blis-
ters based on their development location. Type one were
blisters that originated at the metal interface and were
under the full thickness of epoxy paint. Type two blisters
were between the layers of the epoxy coating. Both blister
fluids were clear as they were removed using hypodermic
syringes. These fluids were analyzed separately. The blister
fluid removed from the metal interface had a relatively high
pH of greater than 12. The pH of the fluid extracted from
blisters between layers of epoxy was neutral, pH of 7.
The GC/MS chemical analysis of the two blister fluids
was very similar even though there was a large difference
in their pH. There was a very large peak of 2-butoxy etha-
nol in each. It was very evident that the driving force for
the blister formation was the oxygenated alcohol, 2-butoxy
ethanol. A review of the MSDS for the reported coating
material did not indicate the presence of this alcohol in the
coating formulation. For this reason, it was first suspected
that the applicator might have used this water-soluble
solvent during application. This was shown to not be the
case when retained samples of the actual coating materi-
als used became available for GC/MS analysis. These were
tested and found to contain the 2-butoxy ethanol as part
of the paint formulation. The coating manufacturer was
able to determine that there was a difference in the solvent
system of the European produced material as opposed to
that manufactured in the US. The high pH of the blister
fluid removed from contact with the metal substrate was
the result of sacrificial anodes installed during the con-
struction of the platform. Oxygen that migrates into the
blister fluid at the metal interface experienced sufficient
electrical potential to cause the oxygen to be converted to
hydroxide ion producing the high pH. For blisters formed
between paint layers, there could be no electrical potential
felt between layers, although there was compromised adhe-
sion that allowed the delamination between coats of epoxy
at the blister site [8].
References
[1] Storfer, S. J., and Yuhas, S. A., Mechanism of Blister Forma-
tion in Organic Coatings; Effect of Coating Solvents, Material
Performance, July 1989, pp. 3541.
[2] The Energetics Driving Osmotic Activity: Physical Chemistry,
3rd Ed., Alberty/Daniels, pp. 170172.
[3] Mills, G. D., Sources of Bubbles, Foam, and Voids in Coat-
ings, Materials Performance, March 2000, National Associa-
tion of Corrosion Engineers, Houston, TX.
[4] Mills, G. D., Sansum, A., and Cox, G., Instruments modernes
danalyse: Possibilites et limites, European Coatings Journal,
p.960, Hanover, Germany, December, 1994.
[5] Mills, G. D., Tool of the TradeAnalyzing Paints and Raw
Materials with a Specially Configured Hyphenated Gas Chro-
matograph/Mass Spectrometer, Modern Paint & Coatings,
pp.2429, December, 1999.
[6] Design Manual: Odor and Corrosion Control in Sanitary
Sewerage Systems and Treatment Plants; EPA/625/1-85/018.
October 1985.
[7] Mills, G. D., Using a Specially Configured Composite Instru-
ment Gas Chromatograph/Mass Spectrometer (GC/MS) for
the Analysis of Paints and Raw Material, Proceedings of the
77th Annual Meeting Technical Program, FSCT, Dallas, Oct.
1999, p. 214.
[8] Mills, G. D., and Eliasson, J., Factors Influencing Early Crack
Development in Marine Cargo and Ballast Tank Coatings,
SSPC/PACE 2005, Tampa, Florida, Feb. 1, 2006.
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655
PREFACE
THIS CHAPTER REVIEWS AND UPDATES THE TOPICS
addressed by the previous authors, including up-to-date ref-
erences and expanded to include stress in multi-layer systems
and stress in physical aging.
Interest in the stress phenomena in organic coatings
is relatively new. The importance of understanding and
measuring this stress became evident as facts accumu-
lated about its role in coating degradation [110]. This is
also supported by the fact that many coatings used today
(e.g., thermosets) are more susceptible to developing
high stresses than traditional ones (e.g., alkyd paints).
It is now quite clear that stress can affect coating adhe-
sion and/or cohesion and provoke delamination and/or
cracking.
Since the development of stress is involved in practi-
cally all stages of coating life (film formation, exposure to
various climatic conditions), its measurement is essential
for a better understanding of coating behavior.
In addition, the measurement of stress can be used to
evaluate other important characteristics of a coating, such
as the glass transition temperature (T
g
) and the critical pig-
ment volume concentration (CPVC).
ORIGINS OF STRESS IN ORGANIC COATINGS
Stresses originate in organic coatings as a result of their
adhesion to the substrate. Good adhesion is, on the one
hand, indispensable for adequate substrate protection,
but on the other hand prevents the normal movement of a
coating.
The three main causes which provoke stress in an
organic coating are [11]:
1. Film formation.
2. Variation in temperature.
3. Variation in relative humidity (RH).
The stresses induced by film formation, variation in
temperature, and variation in RH are known, respectively,
as internal, thermal, and hygroscopic. The latter two
stresses are also referred to as hygrothermal (S
HT
)
It is important to realize that, due to the coating adhe-
sion to its substrate, stress exerts its action mainly in a
plane parallel to the substrate [6,12,13]. Therefore, one can
write
S
E
v
=
1
(1)
where
S = stress,
E = elastic modulus,
= strain,
v = Poissons ratio.
This relationship represents the stress equation for an
uni-axial deformation adapted for a bi-axial deformation
by dividing it with 1 v. It is therefore considered that the
coating can contract or expand only through its thickness.
In practice this might not always be so, i.e., in addition to
tangential stresses, the coating can also be subjected to
normal stresses.
Stresses are especially damaging at edges [14] where
they cannot cancel each other or in the middle of the plate
if defects or heterogeneities are present.
Film Formation
During film formation and regardless of the mechanism
involved (evaporation of solvent, coalescence, chemical
reaction, or their combination), in almost all cases the
coating tends to contract. If this contraction is prevented
by coating adhesion to its substrate and/or the mobility of
macromolecular segments is hindered, a tensile stress will
develop in the coating.
In the literature certain confusion reigns about the
denomination of the stress arising during film formation.
For example, for solvent-based coatings an author may use
these terms: cure stresses, solvent removal stresses, residual
stresses, shrinkage stresses, internal stresses. For simplifi-
cation, I suggest referring to the stress arising during film
formation as internal stress (S
F
).
If a liquid paint is applied on a substrate [8] and the
development of stress is measured as a function of time, a
number of stages can be observed (Fig. 1).
In Stage 0, the coating is still liquid and is mobile
enough to permit volume contraction, and consequently no
stress develops.
In Stage 1, the film starts to form, the volume contrac-
tion is restricted, and stress develops.
In Stage 2, a number of processes can occur. Depend-
ing on the coating composition, the evolution of stress can
include various combinations of increasing, decreasing,
and stationary stress levels. If no damage occurs to the
film (cracks, microfissures, loss of adhesion), a decrease in
stress results from relaxation processes which occur from
the moment the stress develops but only become evident at
this stage. It also follows that the measured stress values are
a result of two opposite processes, one tending to develop
stresses in the coating (in this case due to the volume
shrinkage) and the other tending to decrease them (due to
stress relaxation).
52
Stress Phenomena in Organic Coatings
Dan Y. Perera
1
1
Scientific Adviser, Coatings Research Institute (CoRI), B-1342 Limelette, Belgium.
MNL17-EB/Jan. 2012
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656 PAINT AND COATING TESTING MANUAL 15TH EDITION
Examples of stress development as a function of time
for latex coatings [15] above and below the CPVC are
shown in Fig. 2.
It is important to add that stress starts to develop in a
coating when its T
g
is at least equal to the experimental tem-
perature [6]. For solvent-based coatings (Fig. 3), this is also
confirmed by the fact that stress appears when Phase 2 of
the evaporation kinetics (the diffusion process) starts [16].
At this point in the evaporation, referred to as solidification,
the solvent volume fractions are equal to the solvent con-
centration necessary to bring the T
g
of the coating to a tem-
perature equal or higher than the experimental one [6,17].
The stresses arising in the different stages of the film
formation of the polymer lattices are also discussed in
Ref. [18]. The paper provides evidences of lateral dilatation
stress occurring during the initial stage that is attributed to
the capillary pressure.
If Eq (1) is extended to accommodate the specific effect
of internal strain,
F
[6], then
F s t
s s
V V
V
V
V
=
3 3
(2)
where
V
s
= volume of coating at solidification, and
V
t
= volume of coating at time t after solidification.
One can write [19] that
S
E
v V
dV
F
V
V
s t
S
=
1
1
3
(3)
Despite the limitations of Eq (2), which assumes that
the strain is isotropic and linear, Eqs (2) and (3) enable one
not only to better understand the factors affecting the S
F
but eventually to calculate it approximately.
Variation of Temperature
When coated substrates are exposed to variations in tem-
perature, dimensional changes are induced. If the thermal
expansion coefficients of the coating
F
T
( )
and the sub-
strates
S
T
( )
are different, which is usually the case, a ther-
mal stress (S
T
) will develop in the coating [2,7,11,20,21].
Since the thermal strain,
T
is given by
T
F
T
S
T
T
( )
(4)
the combination of Eqs (1) and (4) gives
S
E
v
dT
T
F
T
S
T
T
T
=
( )
1
2
1
(5)
Determination of T
g
A schematic description of the stress dependence on tem-
perature [19] is represented in Fig. 4.
Such dependence indicates the possibility of determin-
ing the T
g
of a coating from the stress measurement. This
is due to the fact that E,
F
T
, and v (see Eqs (1) and (5)) also
show a profound change at T
g
.
Below temperature a the coating is in the glassy region,
and above temperature b the coating is in the rubbery region.
The linear dependence of S on temperature in the glassy
region greatly facilitates the measurement of T
g
. This
linearity is due to the fact that in this region E,
F
T
, and v are
practically independent of temperature.
Fig. 2Schematic description of stress (S) dependence on time
for latex coatings: (a) and (b) PVC < CPVC; (c) and (d) PVC >
CPVC; (e) PVC < CPVC in the presence of a poor coalescent;
(f) PVC > CPVC in the presence of a poor coalescent.
Fig. 3Schematic representation of the dependence of V
S
/V
F
and stress (S) on time, V
S
= volume of solvent present in the
film; V
F
= volume of the dry film.
Fig. 1Schematic description of stress (S) dependence on time.
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CHAPTER 52 STRESS PHENOMENA IN ORGANIC COATINGS 657
Three examples of the stress dependence on tempera-
ture and T
g
determination by thermal stress measurements
[19] are shown in Fig. 5.
When the stress magnitude in the rubbery region is
small (e.g., elastomers, coatings with a low degree of cross-
linking), the T
g
can be determined with fair accuracy just by
carrying out a few measurements in the glassy region and
then extrapolating the straight line to S
T
= 0.
For coatings subjected to a significant stress in the
rubbery region (e.g., highly cross-linked thermosets), the
measurement of stress in this region might provide a way
to approximately determine the cross-link density, v
e
[22].
Since in accordance with the molecular theory of rub-
ber elasticity in its simplified form [23,24]
E v RT
r e r
= 3
(6)
and
S E
r r r
= 2
(7)
giving
v
E
RT
S
RT
e
r
r
r
r r
= =
3 6
(8)
where R, S
r
, E
r
, and T
r
are, respectively, the gas constant,
the stress, the elastic modulus, and the temperature at the
beginning of the rubbery region. If S
r
is measured and
r
is
known or determined from separate measurements (e.g., by
thermomechanical analysis), v
e
can be calculated.
Others have used the evaluation of T
g
by stress mea-
surements to investigate the effect of a pretreatment on
certain pigments [25], the state of cure of baking enamels
[22], and the modification of epoxy coatings [20,26].
Variation of Relative Humidity
Dimensional changes induced by absorption and desorp-
tion of water as a result of variation in RH is another cause
of stress development in a coating [11,27,28]. As in the
case of temperature, if a mismatch between the expansion
coefficients of the coating and the substrate exists, a hygro-
scopic stress (S
H
) will arise in the coating.
Since the hygroscopic strain
H
is given by
H
F
H
S
H
H
( )
(9)
one can write that
S
E
v
dRH
H
F
H
S
H
RH
RH
=
( )
1
1
2
(10)
where
F
H
and
S
H
are, respectively, the hygroscopic expan-
sion coefficients of the coating and the substrate.
Some examples of the S
H
dependence on RH are given
in Fig. 6.
INTERDEPENDENCE OF STRESSES
While in previous sections the various stresses (S
F
, S
T
, S
H
)
were discussed separately, in practice they can act together
in such a way that the total stress (S
tot
) is small or, as in
many cases, very important [11]
S S S S
F T H
tot
= (11)
Fig. 4Schematic representation of dependence of S, E, , and
v on temperature (T).
Fig. 5Stress (S, MPa) dependence on temperature (T, C) for three coatings at RH 0 % [an epoxy (1), a polyurethane (2), and
an epoxy/melamine system (3)].
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658 PAINT AND COATING TESTING MANUAL 15TH EDITION
The positive and negative signs are arbitrarily chosen.
The positive sign denotes a coating tendency to contract
(tensile stress) and the negative sign a coating tendency to
expand (compressive stress). S
F
is practically always positive.
Equation (11) indicates the existence of two climatic
conditions which might provoke a high stress in a coating:
1. Low temperatures and RHs induce high tensile stresses
(e.g., a dry, cold winter).
2. High temperatures and RHs induce high compressive
stresses (e.g., a humid, warm summer).
According to Eq (11) and depending on the type of
coating and the way it was cured, a number of situations
can arise. For example, for a thermosetting coating cured
at a high temperature (i.e., at T > T
g
, RH = 0 %) and then
exposed to different RHs, since S
F
0 (except for highly
cross-linked coatings), the S
tot
is given by
S S S
T H
tot
(12)
In Fig. 6, for one coating, the stress is positive regard-
less of RH, meaning that S
T
is always higher than S
H
; but
cases where negative stress values are obtained are not rare.
It could be demonstrated [11] that the same coating
conditioned in an identical environment but with different
previous histories can develop different values of stress.
Thus, a coating cured under isothermal and constant RH
conditions (e.g., 21C and 50 %) will develop a total stress
given by
S S S
F H
tot
(13)
Now, if the coated substrate is first heated at T > T
g
for
sufficient time to enable a maximum stress relaxation and
then brought back to the initial conditions (i.e., 21C and
50 % RH)
S S S
T H
tot
=
(14)
The results obtained [11] show that in certain cases
(e.g., for an epoxy coating), the S
tot
can be very different
[S
tot
(Eq (13)) = 5 MPa; S
tot
(Eq (14)) = 0.4 MPa].
Interesting cases are those where the T
g
of a coating is
close to or below the experimental temperature once they
are immersed in water or exposed to a high RH [29]. Under
such conditions S
F
or S
T
can relax and therefore S S
H
tot
.
Such a situation is illustrated schematically in Fig. 7
and for a particular epoxy coating in Fig. 8.
Once a coated substrate is immersed in water one can
observe first the development of a hygroscopic compressive
stress followed by its decrease. The time necessary to reach
zero stress is mainly dependent on the type of coating. The
withdrawal of the coated substrate from water provokes
first the development of a relatively high tensile hygro-
scopic stress followed by its decrease. The decrease in stress
(Curves 2 and 4 in Fig. 7) is due to relaxation processes
facilitated by the low T
g
of the coating. The much higher
stress values attained after the immediate withdrawal of the
Fig. 7Schematic description of the stress (S) dependence on
time at two experimental conditions (water and 50 % RH).
X = the initial stress.
Fig. 8Epoxy coating. Stress (S) dependence on time (t) at two
experimental conditions (water and 50 % RH).
Fig. 6Stress (S, MPa) dependence on relative humidity
(RH, %) for a polyester powder coating (1); an epoxy (2); a
polyurethane (3); and a latex coating (4).
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CHAPTER 52 STRESS PHENOMENA IN ORGANIC COATINGS 659
coated substrate from water (Curve 3 in Fig. 7), in compari-
son with the initial stress (S S S
F H
tot
or S S S
T H
tot
) are
due to the high hygroscopic tensile stress S S
H
tot
( )
.
The above findings are important not only for under-
standing the mechanism of the stress development in
organic coatings but also for practical reasons such as
choosing the experimental conditions of natural or accel-
erated weathering tests, i.e., the magnitude of stress
developed in a coating might depend as much on natu-
ral climatic conditions as on the type and order of cycle
selected in the laboratory.
STRESS MEASUREMENT
Equations (1), (3), (5), and (10) show that, if one knows
the values of E, , and v of a coating, then in principle the
various stresses can be calculated. However, except for
relatively simple cases, this is difficult because the above
coating characteristics can be time, temperature, and rela-
tive humidity dependent.
Therefore, efforts were made to directly determine the
stress arising in a coating. Among the methods one can find
in the literature are: optical [3033], strain gages [20,34,35],
brittle lacquer materials [36], x-ray diffraction [37], and
cantilever (beam) [2,4,8,11,27,3845].
The cantilever (beam) method appears to be the most
widely used and is suitable for determining the stress in an
organic coating. This method makes use of the fact that for
a coating under stress, applied on a substrate, the coated
substrate will deflect in the direction which relieves the
stress. Since the deflection can be measured and the elastic
properties of the substrate are known from separate deter-
minations, the stress can be calculated.
Two variations of the cantilever (beam) method are
described in the literature: a one-sided coated substrate
either (1) fixed vertically at one end [4,8,27,38] (Fig. 9) or (2)
freely supported on two knife edges [2,11,43,45] (Fig. 10).
The stress analysis of (1) is more complicated and
shows that to eliminate the effect of clamping on the coated
substrate deflection, its measurement should be made at
a distance higher than 80 mm from the clamping point
[8]. Variation (2) is much simpler to analyze and can be
designed to eliminate the effect of weight loss on the coated
substrate deflection by choosing the right distance between
the two knife edges [45].
Each variation has its advantages, but if correctly used
they should give identical results. For example (1) is more
suited to evaluate stress in water [29] and (2) to determine
the effect of temperature [2,11].
Among the techniques used to measure the deflection
of coated substrates, one can mention: capacitive trans-
ducers [44,45], laser [46], traveling microscope [4,8,27],
automatic micrometer [11]. A variety of flexible substrates
can be used, such as cold laminated steel, stainless steel,
aluminum, copper, and silicon wafers.
A commercial apparatus, the CoRI Stressmeter (Fig. 11),
is based on variation (2) and the mathematical analysis
described in Ref. [45]. This apparatus is almost completely
automatic and enables one to measure the stress from
about 5 to 110C under a variety of RHs. This instrument
requires the use of substrates that are electrically conduc-
tive, e.g., cold laminated steel, stainless steel, aluminum,
and copper.
In certain cases, such as for investigating the stress
arising in ultraviolet cured coatings, the stress measure-
ment might necessitate an elaborate set-up. In this case
the set-up might include, among others, a UV lamp, a
controlled flow gas and temperature device, an application
chamber and a video camera monitoring the deflection of
the coated substrate [47].
Mono-Layer Systems
A number of mathematical equations are proposed in the
literature to calculate the stress in a mono-layer system
[41,42], but in the authors opinion those proposed by
Corcoran [41] are the closest to the real situation (e.g., con-
siders the fact that stress develops in two directions)
S
dE t
l c t c v
dE t c
l v
S
S S
=
+
+
+
3
2 2
3 1 1 ( )( )
( )
( )
(15)
S
d E t
l c t c v
d E t c
l v
S
S S
=
+
+
+
4
3 1
4
1
3
2 2
( )( )
( )
( )
(16)
Fig. 9Schematic description of the vertically fixed at one end
cantilever (beam) method.
Fig. 10Schematic description of the freely supported beam
method.
Fig. 11CoRI Stressmeter apparatus (Courtesy of Elcometer,
Lige, Belgium).
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660 PAINT AND COATING TESTING MANUAL 15TH EDITION
where
d = deflection of the substrate (Fig. 9),
d = deflection in the middle of the substrate
(Fig. 10),
E
s
= elastic modulus of the substrate,
E = elastic modulus of the coating,
v
s
= Poissons ratio of the substrate,
t = thickness of the substrate,
c = thickness of the coating,
l(Eq 15) = length of the coated substrate between the
point at which it is clamped and the point
at which the deflection is measured (Fig.9),
and
l(Eq 16) = distance between the two knife edges
(Fig. 10).
Equations (15) and (16) assume, among other things,
good adhesion between the coating and the substrate, iso-
tropic elastic properties of the coating and the substrate,
the elastic limit of the substrate is not exceeded, and the
stress is constant throughout the coating thickness. If the
last condition is not fulfilled it means that the coating
is heterogeneous through the film thickness. Therefore,
the measurement of stress as a function of film thickness
might enable one to determine, depending of the film
composition, the distribution of the solvent, cross-link
density, pigmentation, etc., through the film thickness
[8,15,16,68,76(a),76(b),77,7981].
The second term in Eqs (15) and (16), which contains a
number of coating properties difficult to determine, can be
neglected if E
S
E and t c.
Since the substrate is flexible and deflects during a
stress measurement, in principle, part of the stress relaxes.
This relaxation is however negligible with respect to the
stresses arising in the coating. An approximate calculation,
by considering even a high elastic modulus ( ) E 2 MPa and
strain ( )
6 10
6
values, induces a negligible stress relax-
ation (0.01 MPa ) with respect to stresses usually arising
in the coating.
Most commonly, stainless steel or cold laminated steel
[4,8,11,27,44,45] shims are used. Other substrates such as
aluminum and copper can also be used.
The elastic modulus, E
s
, of each shim can be deter-
mined prior to use with the CoRI Stressmeter by applying
Eq (17)
E
Pl
d t b
S
=
3
3
4
(17)
where
P = weight placed in the middle of the substrate,
b = width of the substrate, and
d, l, t = as in Eq (16).
It is important to add that, although it is not difficult
to make the measurements, nevertheless great care is nec-
essary. One should always use the correct substrate thick-
ness, adequately condition it, and precisely calibrate the
apparatus.
Multi-Layer Systems
In many cases multi-layer systems are applied on sub-
strates to protect them against a variety of aggressive
factors. Since the mechanical characteristics of each layer
are usually different, one can expect that the stresses aris-
ing in each layer be also different. Furthermore, a mono-
layer system might become a multi-layer one if part of it
acquires mechanical characteristics different from that of
the bulk. This is typical of coatings subjected to chemi-
cal changes when submitted to natural or accelerated
weathering.
To the authors knowledge, all the relationships for
calculating the stress in multi-layer systems found in the
literature [4852] necessitate the determination of elastic
properties of each layer, coating characteristics not always
easily measurable.
To enable the determination of stress in each layer of
multi-layer systems mathematical equations that do not
necessitate the knowledge the elastic characteristics of each
layer were derived [53]:
S
E t
l c t c c v
d d
S
S
2
3
2
2 1 2
2 1
4
3 2 1
=
+ +
( )
( )
( )
(18)
S
E t
l c t c c v
d d
S
S
3
3
2
3 1 2
3 2
4
3 2 2 1
=
+ +
( )
( )
( )
(19)
where
c
1
, c
2
, c
3
= thickness of individual layers,
d
1
, d
2
, d
3
= deflection of the coated substrates
(d in Fig. 10) with one, two, and
three layers,
S
2
(Eq (18)) and
S
3
(Eq (19)) = stress in a top coat of two- and
three-layer systems, respectively.
For a three-layer coating system whose composition is
unaffected by multiple applications and curing, the deter-
mination of stress in each layer is as follows:
application of the first layer and its curing,
measurement of the deflection d
1
and of the thick-
ness c
1
,
calculation of stress S
1
from Eq (16),
application of the second layer and its curing,
measurement of the deflection d
2
and of the thick-
ness c
2
,
calculation of stress S
2
from Eq (18),
application of the third layer and its curing,
measurement of the deflection d
3
and of the thick-
ness c
3
,
calculation of the stress S
3
from Eq (19).
Procedures for coatings affected by successive applica-
tions and curing are described in Ref. [53].
Two examples by applying Eqs (18) and (19) are pre-
sented in Figs. 12 and 13, respectively. Fig. 12 shows that for
a three-layer system the highest thermal stresses are arising
in the primer. Fig. 13 illustrates the case when a single layer
system of 77 m becomes a multi-layer one, due to its expo-
sure in an accelerated weathering device. After seven days of
weathering the thermal and hygroscopic stresses arising in
the first 27 m are much higher than in the bulk.
STRESS AND PHYSICAL AGING
We are associating the stress development with physical
aging because both phenomena are mainly occurring in the
glassy region, and they are therefore unseparated.
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CHAPTER 52 STRESS PHENOMENA IN ORGANIC COATINGS 661
Physical aging is a general term that includes relax-
ation processes of a material in the glassy state, caused
by its non-equilibrium state [54]. This process is easily
explained by considering the dependence of volume (V),
enthalpy (H), and entropy (S) on temperature (T) above
and below T
g
(Fig. 14) [5458]. During cooling at T > T
g
,
due to the great mobility of polymer chain segments, V, H,
and S can follow the decrease in temperature. Below T
g
the
mobility of polymer chain segments is reduced, and V, H,
and S cannot follow any more the decrease in temperature,
meaning that the material departs from its equilibrium
state. The values of these thermodynamic quantities being
higher than in equilibrium state they will continuously
decrease until the equilibrium state is reached. The closer
the aging temperature to T
g
the higher the aging rate and
the smaller the change in property. Since the studies made
by Struik [54], this relaxation toward equilibrium is known
as physical aging.
In contrast with chemical aging that induces irrevers-
ible changes, physical aging is a reversible process. It can
be eliminated by heating the samples to T > T
g
for sufficient
time. More than 800 studies have been dedicated to various
aspects of physical aging. While certain phenomenologi-
cal models (e.g., KohlrauschWilliamsWatts) describe
Fig. 12Stress (S) dependence on temperature (T) for a three
layer acrylic/melamine system. S
1
, S
2
and S
3
indicate the stresses
arising in the primer, middle, and top layers, respectively [53].
(With kind permission of Springer Science + Business Media.)
Fig. 13Stress (S) dependence on temperature (T) (left) and on relative humidity (RH) (right) for an acrylic/melamine system after
an exposure of 7 days in a Q-Lab Corporation (QUV) device.
Fig. 14Schematic description of the dependence of volume
(V), enthalpy (H), and entropy (S) on temperature. T
a
= physi-
cally aging temperature.
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662 PAINT AND COATING TESTING MANUAL 15TH EDITION
well its kinetics, this process is not very well understood
on a molecular scale. Nevertheless, it is associated with
increased molecular packing and densification, processes
that can greatly affect important coating properties like
mechanical, thermal, and electric. Concerning mechanical
properties, which directly affect coating integrity, densifica-
tion causes the coating to become harder and more fragile.
To describe the interdependence between stress and
physical aging the thermal stress will be considered. This
interdependence was discussed in detail in Refs. [59,60]
and is schematically described in Fig. 15. Curves A and
B are typical of physically non-aged and physically aged
coatings obtained during their heating. The U-shape curve
is mainly due to the increase of E with physical aging which
in turn induces higher compressive thermal stresses (see Eq
(5)). The right side of the trough represents the decrease of
this stress with temperature due to the stress relaxation in
the rubbery region.
Studies made with thermoplastic (e.g., latex paints)
and thermosetting (e.g., waterborne, powder coatings)
systems show that the coating composition (type of binder,
presence of coalescents, degree of film cross-link density,
presence of pigments) affects the physical aging process
[61,62]. Physical aging also influences the coating durabil-
ity by increasing the stress magnitude and by decreasing
the stress relaxation rate. There are indications that physi-
cal aging affects the late stages of coalescent process.
EFFECT OF COATING COMPONENTS
Since E, , and v (Eqs (1), (3), (5), and (10)) are known to be
affected by the coating components, one should expect the
same to hold for stress development. This section will briefly
review the influence of pigmentation, solvents, and binder.
Pigmentation
It has been shown that pigmentation, both the pigment
volume concentration (PVC) and the type of filler (i.e., pig-
ments and extenders), affects the development of internal
stress [7,43,6368]. To illustrate this, examples are pre-
sented in Figs. 1621.
Figs. 16 and 17 show, respectively, the stress depen-
dence on time for a thermoplastic binder in solution and a
latex, filled with a titanium dioxide (TiO
2
). Some PVCs are
above the CPVC, and some are below the CPVC.
The different stages occurring during the film forma-
tion, discussed previously, can be recognized. In Stage 1
stress increases relatively rapidly. For latex coatings, this
stage corresponds to the transition phase of the evaporation
kinetics when the greatest part of the coalescence occurs.
Fig. 15Schematic description of the stress (S) dependence
on temperature (T), for physically unaged (A) and aged (B)
organic coatings. Segments 1 and 3 represent the glassy and
the rubbery regions, respectively. Segment 2 represents the
glass transition region [59].
Fig. 16Stress (S, MPa) as a function of time [hour (h) and day (d)] for a polyisobutyl methacrylate filled with TiO
2
. The numbers
in the figure indicate the different PVCs (%) investigated. CPVC = 51 %.
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CHAPTER 52 STRESS PHENOMENA IN ORGANIC COATINGS 663
In Stage 2 (which corresponds to Phase 2 of evaporation
kinetics), depending on the PVC and the type of filler, the
stress can decrease or first decrease and then increase. For
PVC < CPVC, this decrease is mostly due to the relaxation
process, but for PVC > CPVC is mostly due to relief pro-
cesses such as filler/binder dislocations and/or formation
of microfissures.
DETERMINATION OF THE CPVC
The plot of the maximum internal stress (Sm) as a function
of PVC enables one to determine the CPVC of a coating.
Some examples are presented in Figs. 18 and 19.
These figures, as well as other results presented in
Refs. [66,67], clearly indicate that Sm is a function of
PVC. Sm increases with PVC up to a certain PVC and
then decreases. This PVC corresponds to the CPVC,
indicating the possibility of accurately determining
this characteristic [69,70] from stress measurements,
and agrees well with the CPVCs calculated or deter-
mined by other methods (density, various mechanical
properties).
The dependence of Sm on PVC can be understood if
one considers Eq (1) and the way E, , and v are affected
by the PVC.
Fig. 17Stress (S, MPa) as a function of time for a latex (vinyl acetate/vinyl versatate copolymer filled with TiO
2
):45 % (); 50 % ();
55 % (X); 60 % (). CPVC = 52 %.
Fig. 18Maximum internal stress (Sm) as a function of PVC
(%) for a solvent-based thermoplastic binder filled with a
TiO
2
(X),a red iron oxide (), a yellow iron oxide (), and a
talc ().
Fig. 19Sm as a function of PVC (%) for a styrene acrylic
copolymer filled with a TiO
2
(), a calcium carbonate (X),
and talc ().
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664 PAINT AND COATING TESTING MANUAL 15TH EDITION
For PVC < CPVC, E increases with increasing PVC
because the E of an inorganic filler is in general higher
than that of an organic binder [71]. For PVC > CPVC, E
decreases as a result of the increasing film discontinuity
[23,72]. Since in general and v are decreased (or are little
affected) by the PVC, it follows that the increase of Sm with
PVC is mainly due to the effect of PVC on E.
Figs. 18 and 19 also show that the magnitude of Sm
is dependent on the type of filler. There are fillers which
induce a higher stress (e.g., TiO
2
, red iron oxide) than others
(e.g., CaCO
3
, talc). This is due to the filler/binder interaction
(reinforcing effect), which is determined by the nature and,
in particular, by the surface area and the acid/base charac-
ter of the binder [73].
Examples of Sm = f(PVC) for coatings containing a
mixture of fillers are presented in Figs. 20 and 21.
An examination of the results obtained with binary and
ternary filler coating systems indicates that the stress Sm
t
can be calculated approximately by means of an additive
rule
Sm n Sm n Sm n Sm n Sm
t i x x
x
x i
+ + +
=
=
1 1 2 2
1
(20)
where
n
1
, n
2
, n
i
= volume fraction of different fillers
present in the mixtures, and
Sm
1
, Sm
2
, Sm
I
= maximum stress of different single
filler systems at a given A below or
equal to 1 (A = reduced PVC, PVC/
CPVC).
For organic coatings cured at high temperatures, such
as baking paints, the CPVC can be determined by measuring
the stress as a function of temperature of paints formulated
at different PVCs. The representation of stress arising at a
temperature (in the glassy or rubbery regions) as a function
of PVC enables one to determine the CPVC (Fig. 22). As in
the case of coatings formed at room temperature, the CPVC
corresponds to the PVC that develops the highest stress.
In the literature one can also find simplified methods
to determine the CPVC of latex coatings based on the same
principle. They simply compare the force [74] or the deflec-
tion induced by the internal stress for flexible plastic sub-
strates [75](Fig. 23) coated with paints of different PVCs.
These methods can be useful, but one has to be aware
that they are valid only if both the thickness of the various
paints and the time necessary to reach the maximum stress
are the same.
Solvents
The presence of solvents in a coating can affect the mag-
nitude and especially the rate of development of internal
stress. This is illustrated in Fig. 24.
For thermoplastic binders in solution, the slower the
evaporation of a solvent from a coating, the slower is the
development of internal stress. The converse also is true.
One should note that the coating cast from fast-evaporating
solvents (Curve 1, Fig. 24) produces slightly higher stress
values than those cast from more slowly evaporating ones
(Curves 3 and 4, Fig. 24).
The results obtained were explained by using Eq (1),
the principle of plasticizing effectiveness of solvents and the
stress relaxation favored by the presence in the coating of
the slower evaporating solvent [16].
For coatings containing a mixture of solvents (Fig. 25),
both the development rate and the stress magnitude are
mainly determined by the presence in the film of the less
volatile solvent(s).
The situation may be different if the film forma-
tion is a result of solvent evaporation and cross-linking
Fig. 20Sm (MPa) as a function of PVC (%) for a thermoplas-
tic binder in solution containing a yellow iron oxide (), a
talc (), and their mixture (n = 0.5) (
); n = pigment volume
fraction.
Fig. 21Sm (MPa) as a function of PVC (%) for a latex binder
containing a TiO
2
(
adh
= the interfacial work of adhesion, a consequence of
a variety of chemical and/ or physical interactions
between the coating and the substrate. It
represents the actual physical strength of adhesive
bonds, and is known in the literature also as the
adhesion or basic and fundamental adhesion;
Fig. 24Stress (S) as a function of time in a thermoplastic
varnish cast from methyl ethyl ketone and ethyl acetate (1);
toluene (2); xylene (3), methyl isobutyl ketone and isobutyl
acetate (4), at 52 % RH and 21C.
Fig. 25Stress (S, MPa) as a function of time (day) for a
thermoplastic varnish cast from toluene (X); isobutyl acetate
(), and their mixtures [1/1 (W/W) (
).
Fig. 26Stress (S, MPa) as a function of time (h, hour; d, day)
for a styrene acrylic latex paint containing different amounts
of Texanol 5 % (X);10 % ();15 % (+); percent of Texanol
calculated by weight of binder solids.
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CHAPTER 52 STRESS PHENOMENA IN ORGANIC COATINGS 667
W
P
= work (energy) expanded in plastic deformation and
viscous dissipation occurring during the adhesion
measurement. Depending on the viscoelastic
character of the coating this work might be
important;
cU
cE
v
r
2
1
(22)
where U
r
, c, and are the recoverable strain energy, the film
thickness, and the strain.
To accommodate the effect of stress [19,28,93], Eqs (1)
and (22) are combined to give:
= cS
(23)
and the combination of Eqs (21) and (23) leads to
W W cS
T adh P
+
(24)
Equation (24) shows, among others that: (1) that in
most cases the measured adhesion (W
T
) is not identical with
inter-facial work of adhesion (
adh
) one normally expects to
measure, and (2) when the product c S overcomes
adh
the coating will spontaneously detach from the substrate;
thus, if a high stress arises in a coating, in order to prevent
its detachment, it should be applied in a thinner layer.
Fig. 28Stress (S) as a function of temperature (T, C) for a
primer/clearcoat system after different periods of weathering
(4 h UV-B at 60C and 4 h condensation at 50C) [100].
Fig. 29Stress (S, MPa) as a function of RH (%) for a primer/
clearcoat system after different periods of weathering (4h
UV-B at 60C and 4 h condensation at 50C) [100].
Fig. 30Stress (S) as a function of time of weathering (t
QUV
, hour)
for a primer/clearcoat system at two climatic conditions [100].
Fig. 31Stress (S) as a function of temperature (T) at 5 % (left)
and of RH at 21C (right) for a polyester/melamine system after
different periods of weathering (d, day) (4 h UV-B at 60C and
4 h condensation at 50C) [100].
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668 PAINT AND COATING TESTING MANUAL 15TH EDITION
Because it is energy that expresses the effect of e, ten-
sile or compressive strains are identical in their effect [87].
Since stress develops in most organic coatings, the
product c S should also be considered in adhesion tests
performed in laboratories. This fact is taken into consider-
ation in mathematical equations (25) and (26) for pull off
and peeling at 90, respectively [87].
( )
2
1 2
K
c
cS
/
(25)
F
b
cS
(26)
where
= stress applied to pull the coating from the substrate,
K = bulk modulus of the coating,
= interfacial work of adhesion,
F = force applied to peel the coating, and
b = width of the coating.
Equation (27)(for pull-off measurements of coatings
having v = 0.4) is interesting because it takes into consider-
ation the work expanded in plastic deformation (W
P
) [94].
= +
( )
c
E
S
4 286
2 572
2 2
.
.
(27)
In addition, the study demonstrates the difference between
adhesion and adherence [94] and the wrong interpretation
of data that might result if only one of them is considered.
Equations (22)(24) also indicate the possibility of
determining the adhesion of a coating (i.e., factor ) with-
out applying any external force. This is due to the fact that
at a particular film thickness a spontaneous detachment
should occur [87]. Unfortunately, this method can only be
used for badly adherent coatings. For all other coatings,
extremely high film thicknesses, difficult to apply and cure,
would be necessary. When necessary, the product c S can
also be increased by submitting the coated substrate to high
stresses, e.g., thermal stresses.
If the adhesion forces exceed the cohesive strength of
a coating the stresses arising in the coating can provoke
cracking, Assuring rather than loss of the coating from the
substrate. Such damage can occur at low stress values due
to stress concentration in the film, a consequence of the
presence of heterogeneity in the coating (e.g., bad pigment/
binder dispersion, presence of impurities, air voids, and
variation in film thickness). The verification of this prin-
ciple can be realized very approximately by determining the
stress and the ultimate properties of a coating. Since most
organic coatings are viscoelastic, it is essential that these
properties be evaluated under the conditions (strain rate,
temperature, RH) corresponding to the stress development
in the coating. A more quantitative approach of the failure
mechanism in organic coatings, but also more difficult to
Fig. 32Stress (S) as a function of temperature (T, C) at
5 % (left) and of RH at 21C (right) for an acrylic latex paint
containing coalescing agents after different periods of
weathering (d, day) (4 h UV-B at 60C and 4 h condensation
at 50C).
Fig. 33Stress (S) as a function of temperature (T, C) at 5 %
for a polyester/TGIC powder coating after different periods of
weathering (d, day) (4 h UV-B at 60C and 4 h condensation
at 50C).
Fig. 34Stress (S, MPa) as a function of RH at 21C for a
polyester/TGIC powder coating after different after different
periods of weathering (d, day) (4 h UV-B at 60C and 4 h
condensation at 50C).
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CHAPTER 52 STRESS PHENOMENA IN ORGANIC COATINGS 669
realize, mainly due to relatively low thickness of the films,
is the application of fracture mechanics principles [95].
According to certain publications these difficulties are par-
tially solved both theoretically [96,97] and experimentally
[98,99].
It is important to add that fatigue processes (e.g., due
to variation of temperature and RH) are factors decreas-
ing the overall stress at which the coatings are damaged
(delaminates and/or cracks).
DURABILITY AND STRESS DEVELOPMENT
Weathering
In most cases when organic coatings are exposed to weath-
ering (accelerated or natural), they undergo chemical and
physical modifications which are expressed in the change
of T
g
, E, , v, and cross-link density. Under such circum-
stances and according to Eqs (1), (3), (5), and (10), one can
also expect to see changes in stress development.
A more detailed discussion of the role played by stress
in the coating deterioration is given in Refs. [9,100]. It is
shown that depending on the type of coating the weathering
can affect the stress development in different ways.
In one case weathering provokes: (1) a shift of the curves
S = f(T) to higher temperatures indicating an increase of T
g
,
which in turn induced higher thermal stresses (Fig. 28),
and (2) an increase of the slope of the curves S = f(RH) due
to an increase of the coating sensitivity to moisture, which
induced higher hygroscopic stresses (Fig. 29).
The representation of the stress as a function of time of
weathering for two experimental conditions similar to those
present in the accelerating apparatus (Fig. 30) indicates
that every time the experimental conditions changed (every
4 h) the coating was exposed to an increasing hygrothermal
stress (tensile thermal stresses under dry conditions and
compressive hygroscopic stresses under wet conditions).
Another case often met in practice is represented in
Fig. 31. In this case weathering induced a relatively small
increase of T
g
and a significant upward shift of the curves
S = f(T) to higher stress values. This upward shift is a
consequence of oxidative cross-link reactions the coating
undergoes, a fact confirmed by infra red spectra measure-
ments and the stress increase in the rubbery region (Eq
(8)). The S = f(RH) curves are similar to the case described
above, showing an increase of coating hydrophylicity with
weathering.
Fig. 32 is often observed with (acrylic) latex paints
containing coalescent solvents. The shift of the curve S =
f(T) to higher temperatures, observed during the first days
of weathering, is mainly due to loss of coalescent solvents
present in the coating. The stress dependence on RH of
the unweathered coating is negligible. This is due to its
T
g
(about 21C at 0 % RH), close to the experimental tem-
perature (21 1.5C), a fact that enables a fast relaxation
of hygroscopic stresses induced by variation of RH. With
coalescing solvents departing from the coating, T
g
increases
(to about 31C at 0 % RH) and the hygroscopic stresses
become measurable.
For organic coatings possessing a good durability it is
expected that S = f(T) and S = f(RH) to be little, or not at
all affected by weathering. This is illustrated in Figs. 33 and
34. Contrary to other coatings, for this one (a polyester/
triglycidyl isocyanurate (TGIC) powder coating), the depen-
dencies S= f(T) and S = f(RH) are not changing or changing
very little with weathering. These results are in agreement
with the behavior of the coatings mentioned above under
tropical conditions. While the acrylic/polyurethane and the
polyester/melamine coatings are cracking after a few years,
for the same period, the powder coating is still undamaged.
The processes thought to lead to fissuring of the
clearcoat are described in Fig. 35. Briefly, the chemical
degradations induced by UV, water, and oxygen, which
decrease the coating cohesion, combined with the fatigue
process at steadily increasing hygrothermal stress levels are
the causes of the coating degradation.
Hygroscopic Stress and Corrosion
Due to the heterogeneous nature of most of organic coat-
ings, which possess regions of different hydrophilicity [101],
hygroscopic stresses are arising in a coating exposed to a
high RH or immersed in water [102]. They participate in
formation and/or enlargement of pathways through which
water and electrolyte can reach the metallic substrate and
thus provoke corrosion. This affirmation is based on the
observation that the coatings developing low hygroscopic
(compressive) stresses or able to relax them fast, protect
well the substrate against corrosion. Among the coatings
investigated in one study (Fig. 36), the powder coating and
Plexigum developed the lowest hygroscopic compressive
stresses and protected well the substrate against the aggres-
sive action of 0.5M NaCl electrolyte. The polyurethane,
Fig. 35Schematic representation of processes causing crack formation in a coating.
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670 PAINT AND COATING TESTING MANUAL 15TH EDITION
a system which developed high hygroscopic compressive
stresses but which relaxed relatively fast, provided only an
average protection.
References
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nomena in Radiation Curable Systems, Proceedings, Radtech,
Edinburgh, Scotland, Great Britain, 1991.
[11] Perera, D. Y., and Van den Eynde, D., Moisture and Tem-
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[12] Crackin, F. L., and Bersch, C. F., Creep Behavior of Transpar-
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Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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673
PREFACE
In preparation of this chapter, the contents of Chapter 50
Slip Resistance in the fourteenth edition were drawn upon.
The author acknowledges the author of the chapter in the
fourteenth edition, Paul R. Guvin, Jr. The current edition
will review and update the topics as addressed by the previ-
ous author, introduce new technology, and include up-to-
date references.
INTRODUCTION
FRICTION IS AN INTERESTING PROPERTY THAT IS
often taken for granted. For example, it would not be possi-
ble to walk if there were no friction between shoe soles and
the ground or other surfaces. There is also an awareness
that friction varies with the nature of the shoe bottoms
rubber, plastic, leather, etc.and of the surfaceground,
concrete, painted concrete, ice, wood floor, polished floor,
steel, etc. Automobiles would not move if it were not for
the friction between tires and road surface, would not slow
down if it were not for the friction between brake discs or
drums, and would not stop if it were not for the friction
between tires and road surface. Without friction, dishes
would not stay on a table and the slightest jostling would
cause items to slide. Many other examples could be given
of friction and slip.
At times, conditions of high friction are desirable and
other times low friction is needed. If a heavy object is to be
slid, low friction is useful. Skiers want low friction between
their skis and snow or ice and use waxes as a lubrication
to decrease friction. In the cases of polished, wet, or icy
surfaces, frictional forces are quite small and automobiles,
people, and animals have a tendency to slip. In the case of
dry concrete, neat or painted, or wood, the frictional forces
are quite high and the surface is stable and with it less
chance for slipping. It should be kept in mind that there is a
need for material combinations that result in high friction,
as in a painted or otherwise coated walkway area where a
person walking or running on the surface does not want
to slip and fall, and in low friction, as when an object is to
move smoothly and evenly by another object of similar or
different composition, as when sheets of paper move by one
another in a copy machine. Friction can be increased by use
of additives such as sand on an icy surface and decreased
by the use of lubricants such as oil, water, graphite, and
the like.
Slip is a word that has many meanings [13], but it
is obvious that slip occurs when friction is low. In certain
areas of the coating industry, slip is considered to be the
ability of an object to move in a relatively free or unencum-
bered but controlled manner as when one sheet of coated
or uncoated metal passes over another in a coating-line
feeding operation, when such sheets move along a con-
veyor system in coating, printing, fabrication, or packaging
operations, and the like. The material or coated material
must have proper slip or lubricity to allow passage
through various sections of the coating fabrication or
packaging section of the line. Slip is also important in fab-
ricating operations wherein the coated object is in contact
with a tooling system as in fabrication of bottle caps, in
bending or forming operations, and so on. In various tex-
tile lines, proper slip is need for threads to flow smoothly
and uniformly through fabrication systems and not cause
thread or yarn breaks and defective final products or lost
production.
CONCEPTS OF FRICTION
In a technical sense, friction is the force between contacting
objects that resists the relative motion of the objects. Start-
ing or static friction is the frictional force between station-
ary objects, and dynamic, kinetic, or sliding friction is the
frictional force between objects that are sliding with respect
to one another. Consider a block resting on a solid surface
as in Fig. 1. The upward force, F
U
, of the solid surface,
counterbalances the weight or mass of the block, F
N
, and
the block is at rest. F
N
is usually referred to as the perpen-
dicular or normal force. If a force, F
A
, is applied to the block
and parallel to the solid surface, the force of friction, F
F
,
resists it. If F
A
is slowly increased, at some point the block
will begin to move and slide along the solid surface without
further increase in F
A
and actually with a small decrease in
it [4,5]. Thus, the force required to move an object from rest
is greater than the force required to continue the movement
at constant velocity. At this point,
F
A
= F
F
(1)
By sliding blocks of the same material with equally smooth
surfaces but different sizes (i.e., different contact areas)
across the same surface, it has been found that the ratio
of the frictional force to the mass of the block or F
N
is
constant. The proportionality factor between the frictional
resistance force and the normal force is known as the coef-
ficient of friction, , with a distinction made between the
coefficient of static friction,
S
, and coefficient of kinetic
friction,
K
, as indicated in the following relationships:
F
F
=
S
F
N
stationary (2)
F
F
=
k
F
N
sliding (3)
53
Friction and Slip Resistance
Joseph V. Koleske
1
1
1513 Brentwood Road, Charleston, WV 25314-2307.
MNL17-EB/Jan. 2012
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674 PAINT AND COATING TESTING MANUAL 15TH EDITION
This points out that it should be stated whether a measured
or cited coefficient of friction is for the static or the kinetic
condition, however, quite often this is not done in the litera-
ture as will be illustrated below.
The friction force is often discussed in terms of an
object sliding down a solid inclined surface as indicated in
Fig. 2. When the angle of incline, , is 0, the situation is
that of Fig. 1, which becomes Fig. 2 as the angle of incline
is increased from zero to some finite value less than 90.
As the angle of the incline increases, the force compo-
nent tending to move the object down the incline, F
A
, also
increases. At some point, the slightest increase in the angle
will sufficiently increase the force component parallel to
the plane of the incline, F
A
, to a value such that F
F
is over-
come and, if unrestrained, the object begins to move down
the incline at constant speed. Thus, the object does not slide
until the force parallel to the incline, F
A
, reaches a certain
value that is equal to the frictional force, F
F
. The mass of
the object represented by vector F
M
can be resolved into
vectors F
A
and F
N
parallel and normal to the plane of the
incline, respectively. At the described condition of sliding at
constant speed, F
A
= F
F
. Since F
F
=
K
F
N
, substitution leads
to F
A
=
K
F
N
or
K
= F
A
/F
N
(4)
From the vector diagram in Fig. 2, it is apparent that
F
A
/F
N
= tan =
K
(5)
and
= arc tan
K
(6)
Thus, if
K
is known, the angle of incline, at which a block
placed on the incline will slide regardless of the weight or
mass of the block, can be determined. Note that the coef-
ficient of friction can take on values from zero to extremely
high values, but usually it has a value of between zero and
one unless special conditions are involved as, for example,
in the case of gage blocks, which are ultrasmooth, and in
contacting spectroscopically pure metals such as copper
that were outgassed in a vacuum prior to admitting other
gases such as nitrogen, oxygen, or hydrogen.
In physics, the study of friction is called tribology. In
a physics sense, friction is the resisting force that takes
place when two surfaces contact and rub against each
other. When investigating the causes of friction, it should
be accepted that the surface of materials is microscopi-
cally irregular and is not flat on an atomic scale. Although
surfaces may appear to be smooth, on a microscopic scale
they are covered with asperities and are jagged and rough.
The uneven or rough surfaces of the touching objects are
thought to be one of the main causes of friction. As the
surfaces move or tend to move, the rough surfaces interlock
and offer resistance to being moved over one another until
a certain value of applied force is reached.
From this model of rough surfaces interlocking, friction
would be expected to decrease as the surfaces are smooth-
ened. This is the actual state of affairsup to a point. If
the surfaces are made increasingly smoother, at some point
friction will increase.
2
This phenomenon, which is another
of the main causes of friction, is thought to be due to the
bonding or interaction between surface atoms and these
bonds must be broken before friction is overcome and slid-
ing can take place. Such bonding will only take place where
the surface atoms can come sufficiently close so as to be
within each others force fields. Thus with usual surfaces,
it is only asperities on one surface that make contact with
asperities on the other surface that can bond and interact
through van der Waals or other chemical forces with adhe-
sion bonds. The entire normal force is carried on the tips
of the asperities and the true or actual area of contact is
much less than the apparent or measured area. Local stress
on the contacting asperities may result in a flattening of
the asperities and produce an area of minute but intimate
contact. With metals, the deformation may be within the
elastic limit, but with plastics the viscoelastic deformation
may be permanent or a hysteresis effect may be involved. As
the surfaces are made increasingly smoother, at some point
the overall contact area between them increases and as a
result, bonding and resultant friction forces will increase.
To move a surface over another surface, the adhesive bonds
at the interface must be broken in a shear plane near the
surface of one of the materials.
The shear fracture at the minute interaction areas or
area of true contact between the dry contacting surfaces
is a part of the mechanism of dry friction theory. If it is
assumed that the interaction areas are more or less ran-
domly distributed over the apparent contact area, the fric-
tion force can be expressed as
Fig. 1A solid block resting on a solid surface with an upward
force, F
U
, and a normal or downward force, F
N
, acting on it. A
force, F
A
, acting parallel to the solid surface is applied to the
block and a friction force, F
F
, opposes the force F
A
.
Fig. 2A solid block resting on an incline. As the angle
increases, the force, F
A
, increases until the friction force, F
F
, is
overcome and the block will begin to slide.
2
Gage blocks are probably the best example of smooth surfaces
that have high friction. These devices are used to provide linear
dimensions to within given and very small tolerancesreference
blocks that can have a high tolerance of 0.000 002 in. or 0.000 05
mm are built up to make the desired linear dimension. To develop a
particular length, the appropriate blocks are slid together and held
together by forces akin to the forces between molecules or atoms.
Assembled blocks cannot be left together for long periods of time
or they will become permanently joined through the forces. See
www.claymore.engineer.gvsu.edu or www.ptb.de/en/org/5/54/543/
parendm_e.htm as well as other sites for detailed information.
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CHAPTER 53 FRICTION AND SLIP RESISTANCE 675
F
F
=
G
A (7)
where A is the actual area of contact and
G
is the aver-
age shear strength of the interaction areas. Since it is the
interaction areas that actually carry the normal force, F
N
,
between the surfaces, the following relationship also exists.
F
N
=
m
A (8)
where
m
is defined as the flow pressure or shear stress of
the softer material in the vicinity of local areas of actual
contact. If the last two equations are combined, the coef-
ficient of friction is obtained as
= F
F
/F
N
=
G
/
m
(9)
and the coefficient is independent of the contact area.
Friction coefficients involving true area of contact have
also been expressed in accord with the following relation-
ships [6]. For metals, the deformation of asperities to form
the true area of contact is approximately proportional to
the normal force, F
N
. In the case of polymeric materials,
rubbers undergo an essentially elastic deformation and the
area of contact increases with (F
N
)
2/3
indicating that the
coefficient of friction decreases with increasing F
N
. When
polymers that deform in a viscoelastic manner, the friction
force follows a relationship that has the form
F
F
= k(F
N
)
X
(10)
with k a constant. Since F
F
= /F
N
, the coefficient of friction
may be expressed as
= k(F
N
)
X1
(11)
with 2/3 < X < 1. In the case of polytetrafluoroethylene,
ithas been found that X has a value of 0.85 for over ten
orders of magnitude change in F
N
.
In a general sense, both mechanisms, the interlocking
and the bonding mechanisms, play a major role in causing
friction. Other mechanisms that may be involved in fric-
tion forces include, a gouging effect in which asperities
on a hard material may gouge a grove in a softer material
as moving objects drag and grind against each other; a
roughness effect wherein the asperities interlock and there
is a need to lift some asperities over other asperities; elec-
trostatic effects in which work must be done to separate
charged regions on the sliding surfacesan effect that may
be seen with electric insulators; and hysteresis effects in
elastic and plastic deformations at the touching points or
near them that take place with not all of the deformation
work recoverable. Heat generation and dissipation account
for the non-recoverable work.
Values for the coefficient of friction for plastics will
depend on test conditions such as humidity, material
degree of cure, moisture content, and temperature. For
example, the coefficient of friction for nylon will vary from
0.91 to 1.19 when the moisture content is varied from 0.2
to 10 % [7]. Table 1 has coefficients of static friction,
S
for
various synthetic and natural polymers when in contact
with the same polymer and with steel. In general,
S
is
greater for these polymers when sliding on the same poly-
mer than when sliding on steel. The values are abstracted
from a handbook [8] that contains many more values of
the coefficients of friction including the static coefficients
for a variety of polymers when in contact with wet and dry
snow at 0C as given in Table 2. In general, the coefficients
are lower on dry snow indicating that it should be easier to
move an object on dry snow than on wet snow. As the tem-
perature of dry snow decreases from 0C to 32C, Table
2,
S
increases with the effect dependent on the nature of
the polymer. A range of values for the coefficient of sliding
friction for a number of polymers sliding on a variety of
unnamed substrates is given in Table 3.
Examination of the data in Tables 13 indicates that
polytetrafluoroethylene has a very low coefficient of fric-
tion, and it is widely used to make slippery or low friction
surfaces. But, the polymer can quite easily erode and wear
when used in systems that have repetitious operation. The
wear factor can be improved without compromising its fric-
tional properties when it is filled with certain hard particu-
late solids. However, hard fillers can have a deleterious effect
on an opposing surface. It has been found the improved
wear while maintaining low friction or a high degree of slip-
periness can be obtained without affecting the opposing sur-
face if the polymer is irradiated with an electron beam [9].
Table 4 has values of the coefficients of kinetic fric-
tion for Nylon 6-6 in two states of smoothness (molded or
machined surface) sliding against the same surface, against
the opposite surface, or against mild steel as well as mild
steel sliding against itself or the two nylon surfaces. The
data indicate the machined nylon surface,
K
= 0.46, is
smoother than the molded nylon surface,
K
= 0.63. It also
appears that friction is less when the smoother machined
nylon surface is moving on the rougher molded nylon sur-
face than vice versa. There is very little, if any, difference in
friction when either nylon surface is moving on mild steel,
K
= 0.31 and 0.33, or when a mild steel surface in mov-
ing on either nylon surface,
K
= 0.41. The strong effect of
TABLE 1Coefficient of Static Friction,
S
,
for various synthetic and natural polymers
on self and on steel [8]
Materials in Contact Condition
S
Poly(methyl methacrylate) on
poly(methyl methacrylate)
Clean 0.8
Poly(methyl methacrylate) on steel Clean 0.40.5
Polystyrene on polystyrene Clean 0.5
Polystyrene on steel Clean 0.30.35
Polyethylene on polyethylene Clean 0.2
Polyethylene on steel Clean 0.2
Polytetrafluoroethylene on
polytetrafluoroethylene
Clean 0.04
Polytetrafluoroethylene on steel Clean 0.04
Nylon on nylon
a
Clean 0.150.25
Silk on silk Clean
b
0.20.3
Cotton thread on cotton thread Clean
b
0.3
a
Type nylon not specified.
b
Commercially clean.
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676 PAINT AND COATING TESTING MANUAL 15TH EDITION
lubricants, which will be discussed later in this chapter, is
apparent from certain data in Table 4.
Shearing processes as described above depend on the
viscoelastic nature of polymers and therefore are a function
of strain rate (sliding speed) and temperature. It has been
demonstrated that the coefficient of friction for crystal-
line polymers such as polyethylene, polypropylene, and
Nylon 6-6 depends markedly on sliding speed and passes
through a maximum [6,11]. Amorphous polymers such as
poly(methyl methacrylate) and polystyrene only show mod-
erate increases in
K
and only a slight maximum as strain
rate increases. As the temperature is increased, the depen-
dency of friction coefficient curves is shifted to the right or
to higher sliding speeds. Grosch [12] found similar effects
for
K
when a variety of rubbers (natural, butyl, styrene-
butadiene, and acrylonitrile-butadiene elastomers) sliding
on glass was examined as a function of sliding speed over
a broad range of temperatures. The viscoelastic nature of
friction is further demonstrated by subjecting the
K
, slid-
ing speed, temperature data to the WilliamsLandelFerry
reduced variables analysis [13]. The shift factor, log a
T
, fits a
continuous master curve when reduced to a reference tem-
perature. Others [1416] have obtained similar results that
demonstrate the frictional characteristics of elastomeric
materials behave in a viscoelastic manner.
Polymers are used in many facets of the electronics
industry, and frictional characteristics can play an impor-
tant role in their usage. Coefficients of friction for some
polymers used in this industry and for two lubricants used
are given in Table 5 [17]. Friction can cause tribolelectric
charging of polymers by contact and rubbing. Since poly-
mers have high resistivity, electrostatic charge can accu-
TABLE 2Coefficient of static friction,
S
, for natural polymers
under various conditions and for synthetic polymers at certain
temperatures on wet and dry snow [8].
Material Condition Temperature, C
S
Leather on Metal
a
... 0.6
Leather on Greasy metal
a
... 0.2
Leather on Wet metal
a
... 0.4
Leather on Wood ... 0.30.4
Nylon
b
on Wet snow 0 0.4
Nylon
b
on Dry snow 0 0.3
Nylon
b
on Dry snow 10 0.3
Paraffin wax on Wet snow 0 0.06
Paraffin wax on Dry snow 0 0.06
Paraffin wax on Dry snow 10 0.35
Paraffin wax on Dry snow 32 0.4
Polyethylene terephthalate on Wet snow 0 0.5
Polyethylene terephthalate on Dry snow 0 0.35
Polyethylene terephthalate on Dry snow 10 0.38
Poly(methyl methacrylate) on Wet snow 0 0.5
Poly(methyl methacrylate) on Dry snow 0 0.3
Poly(methyl methacrylate) on Dry snow 10 0.34
Poly(methyl methacrylate) on Dry snow 32 0.4
Polytetrafluoroethylene on Wet snow 0 0.05
Polytetrafluoroethylene on Dry snow 0 0.02
Polytetrafluoroethylene on Dry snow 10 0.08
Polytetrafluoroethylene on Dry snow 32 0.1
Ski lacquer on Wet snow 0 0.2
Ski lacquer on Dry snow 0 0.1
Ski lacquer on Dry snow 10 0.4
Ski lacquer on Dry snow 32 0.4
a
Commercially clean, unspecified metal.
b
Type nylon not specified.
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CHAPTER 53 FRICTION AND SLIP RESISTANCE 677
mulate in large amounts and represent serious, hazardous
consequences. For example, discharge between dissimilar
pairs can cause a spark and a resultant fire or destruction
of electronic equipment. A tribolelectric series for a number
of widely used polymers is given in Table 6 [6]. Antistatic
additives can decrease resistivity, and leakage currents can
be used to dissipate an accumulation of electrostatic charge
from friction.
ASTM DEFINITIONS/TERMINOLOGY
Table 7 contains a number of specific definitions or termi-
nology that can be found in the ASTM publications indi-
cated in the table. Although the definitions may differ in
the exact wording, they are in basic agreement with each
other and with the information given above. Terminology
related to that in Table 7 may be found in ASTM D1436
Test Method for Application of Emulsion Floor Polishes to
Substrates for Testing Purposes in ASTM D2825 Terminol-
ogy Relating to Polishes and Related Materials, as well as in
ASTM and other standards.
ASTM G115-10 Standard Guide for Measuring and
Reporting Friction Coefficients contains schematic dia-
grams for more than 20 device/test configurations for fric-
tion testing, the applicable materials for the particular test,
and the measured parameters for the standards listed in
Table 8. It is a useful guide for those involved in a friction
and its measurement. Two other definitions included in this
standard are:
triboelementone of two or more solid bodies that
comprise a sliding, rolling, or abrasive contact, or
a body subjected to impingement or cavitation.
Each triboelement contains one or more tribosur-
faces; and
tribosystemany system that contains one or more
triboelements, including all mechanical, chemical,
and environmental factors relevant to tribological
behavior.
SLIPPERINESS
In a general sense, slipperiness can be defined as the ten-
dency of something to suddenly or involuntarily slide. In
many cases, an organic polymer surface such as a coating
is involved when slipperiness in considered. In terms of the
flooring market area, for which the above definition was
written, the flooring surface could be an alkyd or polyure-
thane enamel on a porch or deck, a vinyl- or polyurethane-
coated gymnasium floor, a waxed vinyl composition floor,
an epoxy-coated concrete floor, structural steel and coated
structural steel, and so on. Slipperiness can be considered
as involving of two factorsskid resistance and slip resis-
tance. Skid may be defined as an act of sliding without rota-
TABLE 4Coefficients of kinetic friction,
K
, for Nylon 6-6 with various degrees of surface
smoothness in contact with same material or steel with and without lubricants [10].
Moving Surface Stationary Surface Lubricant
K
Nylonmolded surface Nylonmolded surface None 0.63
Nylonmolded surface Nylonmachined surface None 0.52
Nylonmolded surface Mild steel None 0.31
Nylonmachined surface Nylonmolded surface None 0.45
Nylonmachined surface Nylonmachined surface None 0.46
Nylonmachined surface Mild steel None 0.33
Mild steel Nylonmolded surface None 0.41
Mild steel Nylonmachined surface None 0.41
Mild steel Mild steel None 0.61.0
Nylonmachined surface Nylonmachined surface Graphite 0.28
Nylonmachined surface Nylonmachined surface Liquid paraffin 0.13
Nylonmachined surface Nylonmachined surface Water 0.24
TABLE 3Ranges of coefficients of sliding
friction,
K,
for various materials sliding on
various unnamed surfaces [6].
Material
K
Natural rubber 0.53.0
Nylon 6-6 0.150.40
Poly(ethylene terephthalate) 0.200.30
Poly(methyl methacrylate) 0.250.50
Poly(vinyl chloride) 0.200.90
Poly(vinyl fluoride) 0.100.30
Poly(vinylidine chloride) 0.681.80
Polybutadiene 0.41.5
PolyethyleneHigh Density 0.080.20
PolyethyleneLow Density 0.300.80
Polypropylene 0.67
Polystyrene 0.330.5
Polytetrafluoroethylene 0.040.15
Styrene-butadiene copolymer 0.53.0
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678 PAINT AND COATING TESTING MANUAL 15TH EDITION
tion, and slip can be defined as a slide that occurs suddenly
or involuntarily. The coefficient of friction is a measure of
slip with a high coefficient of friction denoting poor slip
and a low coefficient of friction denoting good slip [5]. Slip
resistance is something that is not really measurable in
common terms and is often defined by different people in
different ways but everyone realizes that it does exist and
the importance of testing for it remains regardless of the
difficulty in defining the term [18].
The importance of slip and slipperiness is evidenced
by a recent scientific symposium that was entitled The
Measurement of Slipperinessan International Scientific
Symposium [19]. The seven papers in this symposium
dealt with concepts and definitions [20], occupational
slip injuries [21], biomechanics [22], human-centered
approaches to slipperiness measurement [23], the role of
surface roughness [24], and the role of friction in slipperi-
ness [25,26]. For example, Chang and coworkers [26] stud-
ied friction mechanisms at the shoe-floor interface under a
variety of conditions that included dry surfaces, liquid- and
solid-contaminated surfaces, and icy surfaces. They con-
cluded that static friction measurements determined by
the traditional use of a drag-type device are only suitable
for dry, clean surfaces. Dynamic and stick-slip measure-
ments are needed to properly evaluate contaminated and
icy surfaces and to estimate potential risk on such surfaces.
Miller [27,28] has presented interesting discussions related
to the measurement of slip resistance and to slip resistance
standards. These discussions are readily available on the
Internet. Di Pilla [29] has also discussed the measurement
of slip resistance and the state of the technology, as it
existed in late 2001.
DETERMINATION OF THE COEFFICIENT
OF FRICTION (COF)
Three types of instruments are used to measure the COF,
and these are illustrated in Fig. 3 [30]. These devices are
drag-type meters that are based on = F
F
/F
N
, pendulum-
type meters that measure the energy loss of the pendulum as
an indirect indication of dynamic friction, and articulated-
strut devices that are based on the direct and fundamental
principle of the resolution of forces that take place when as
object slides down an incline as described above wherein
K
= tan .
3
Other instruments include torque (ASTM E510 and
G99), ball-rolling (ASTM G123), roller (ASTM D3412 and
G143), and other devices (see Table 8 for Standard titles).
Short descriptions of various devices for studying friction
and related properties that are available nationally and
internationally can be found on the Internet [18].
Recently [31], sliding experiments were performed on
amorphous polystyrene of various molecular weights using
an atomic force microscope equipped with a nanotip probe.
Friction coefficients were found to range between 0.2 and
0.45 and were similar to those found with other devices.
Velocity effects on the dynamic coefficients were slight to
nil, but there were marked effects involving the force at
which the tip is unstuck as a function of polystyrene molec-
ular weight. As molecular weight decreases, the applied
force to overcome friction increases. Overall the results
suggest that untangling of polymer molecules plays a role
in describing breakage of the contact between interacting
TABLE 5Coefficients of friction for various
coatings used in the electronics industry and
elsewhere [17].
Coating Material Coefficient of Sliding Friction
a
Epoxy coating with Teflon
fiber
0.15
Nylon 0.3
Polyethylene 0.60.8
Polyimide 0.17
Poly(methyl methacrylate) 0.40.5
Polystyrene 0.40.5
Polytetrafluoroethylene
(Teflon
TFE)
b
0.050.1; 0.04; 0.016
Poly(vinyl chloride) 0.40.5
Polyxylylene
Parylene N 0.25
Parylene C 0.29
Parylene D 0.310.33
Lubricants for comparison
Graphite 0.18
Molybdenum disulfide 0.12
a
Not designated as static or kinetic coefficients.
b
Values from different sources.
TABLE 6Tribolelectric series for a number
of widely used polymers [6].
Most Negative End of Series Polytetrafluoroethylene
Polyethylene
Poly(vinylidine chloride)
Poly(vinyl chloride)
Polyacrylonitrile
Poly(ethylene terephthalate)
Poly(vinyl alcohol)
Poly(methyl methacrylate)
Cellulose acetate
Silk
Cotton
Cellulose
Polyamide (nylons)
Most Positive End of Series Wool
Decreasing
Negativity
3
Although the COF from inclined plane testing is often referred
to as a dynamic COF,
K
, Section 10.1 of ASTM G115, Standard
Guide for Measuring and Reporting Friction Coeffcients, indicates
that such testing only yields the static coeffcient of friction. The
standard recommends that the term static friction coeffcient,
S
,
be used to describe a coeffcient calculated using a breakaway force
in a friction test rig that moves a specimen with a mechanism other
than gravity.
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CHAPTER 53 FRICTION AND SLIP RESISTANCE 679
bodies. Scratch testing with a spherical indenter has been
used to measure the friction coefficient of polydimethylsi-
loxane on stainless steel [15]. These results indicated that
the dynamic friction coefficient decreased with increasing
normal load suggesting that the viscoelastic character of
the coating influenced its frictional behavior.
Another technique involving scanning-probe micros-
copy and known as friction-force microscopy measures
the lateral force on a sliding probe caused by sliding fric-
tion [32]. The technique allows frictional processes to be
examined on a nanometer scale. It has been found that
the velocity dependence of friction has a maximum in the
friction-velocity interaction and this is related to the glass
transition temperature, T
g
. Hammerschmidt and cowork-
ers [33] have summarized some of these studies when
they used temperature-controlled friction-force micros-
copy to investigate viscoelastic relaxations of polystyrene,
poly(methyl methacrylate), and poly(ethylene terephthal-
ate) and their effect on friction. They concluded that for
polymer films the main contribution to friction was visco-
elastic mechanical loss.
SLIP RESISTANCE
One may think of slip as the antithesis of friction. While
both high and low friction are important, in the sense of
walkways, working surfaces, sidewalks, swimming pool,
bathing, and other tiled areas, and similar surfaces, there
must be sufficient friction to ensure that slipping and/or
tripping with subsequent falling and potential injury will
not occur. There are many different slip resistance testing
specifications and standards. OSHA (Occupational Safety
and Health Administration) has a standard [34] that deals
with the slip resistance of skeletal structural steel. A subpart
of this standard, Standard Number 1926.754(c)(3), indi-
cates that after July 18, 2006, workers will not be permitted
to walk on the top surface of structural steel that has been
coated with paint or similar material unless documentation
or certification indicates that the coating has achieved a
minimum average slip resistance of 0.5. This value must be
achieved when measured with an English XL tribometer
[35] or equivalent tester on a wetted surface at a testing
laboratory. The certification or documentation is to be
based on the appropriate ASTM standard test method in a
laboratory that is capable of performing the test. The cited
ASTM test methods [36] are:
ASTM F1677-96 Standard Test Method for using a Por-
table Inclinable Articulated Strut Slip Tester (PIAST).
This method is approved for dry and wet testing. The
method, which simultaneously applied the horizontal
and vertical forces, can be used on nearly all surfaces.
The device used with this method is the Brungraber
Mark II.
ASTM F1679-00 Standard Test Method for using a
Variable Incidence Tribometer (VIT). The literature
suggests that this is an excellent testing method that
is approved for both dry and wet testing on essentially
all surfaces. As in the previous method, the horizontal
and vertical forces are applied in a simultaneous man-
ner. The device used with this method is the English XL
tribometer [35], and operators using this equipment
should be certified for such use.
With the above said, it must be pointed out that ASTM
has found that these methods lack a precision and bias
statement and have a reference to proprietary apparatus
TABLE 7Definitions/Terminology for friction and slip properties taken from two ASTM
publications.
ASTM G115-10 Standard Guide for Measuring and Reporting
Friction Coefficients
ASTM D2047 Test Method for Static Coefficient of Friction of
Polish-Coated Floor Surfaces as Measured by the James Machine
Coefficient of frictionThe dimensionless ratio of the friction
force between two bodies to the normal force pressing these
bodies together.
Coefficient of frictionThe ratio of the horizontal (shear)
component of force required to overcome friction, to the vertical
(normal) component of the force applied.
Kinetic coefficient of frictionThe coefficient of friction under
conditions of macroscopic relative motion between two bodies.
Dynamic coefficient of frictionThe ratio of the horizontal
component of force required to cause a body to continue to slide
at a constant velocity, to the vertical component of the force
applied.
Friction forceThe resisting force tangential to the interface
between two bodies when, under the action of external force,
one body moves or tends to move relative to the other.
FrictionThe resistance to relative motion developed between two
solid contacting bodies at, and parallel to, the sliding plane.
Static coefficient of frictionThe coefficient of friction
corresponding to the maximum friction force that must be
overcome to initiate macroscopic motion between two bodies.
Static coefficient of frictionThe ratio of the horizontal
component of force required to a body that just overcomes the
friction or resistance to sliding, to the vertical component of the
force applied.
... Slip resistanceThe frictional force opposing movement of an
object across its surface, usually with reference to the sole or heel
of a shoe on a floor. A surface having a static coefficient of friction
of 0.5 or greater as measured by this test method is considered to
have adequate slip resistance. That is, it will provide the required
traction for preventing or markedly reducing the probability of
slipping while walking.
Stick-slipA relaxation oscillation usually associated with
decrease in coefficient of friction as the relative velocity increases
...
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680 PAINT AND COATING TESTING MANUAL 15TH EDITION
that violates certain ASTM requirements [37]. A deadline
of September 30, 2006 had been set for correcting the
deficiencies, but it was felt that this deadline would not be
met. As a result, a decision was made to withdraw ASTM
F1677 and ASTM F1679 as well as two related test meth-
ods.
4
At the same time the above was taking place, OSHA
[38] reopened and sought comments and information
regarding its Standard Number 1926.754(c)(3) and atten-
dant Appendix B [34,36]. OSHAs purpose of reopening this
matter was to consider whether to retain, amend or revoke
the provision regarding test methods for slip resistance on
skeletal structural steel and whether slip-resistant coatings
meeting the requirements could be available by July 18,
2006. Since OSHA ascertained that no progress would be
made toward meeting these goals
5
by the to-be-effective
date, the group decided in early 2006 to revoke a provi-
sion within the Steel Erection Standard that addresses slip
resistance of skeletal structural steel [39]. Readers inter-
ested in this matter would do well to follow proceedings
that probably will be found in the Federal Register and/or
ASTM literature.
English [40] has a listing of slip resistance standards
that are in wide use. Included in the compilation are the
above test methods as well as other standards from ASTM,
American National Standards Institute (ANSI), National
Fire Protection Association (NFPA), and Underwriters
Laboratories. The standards are separated by their suit-
ability for wet or dry testing. English also has a description
of other tribometers based on pendulum and drag-sled
principles.
SENSOR MATERIALS
Materials that may be used as sensors or test pads include
a broad range of known items [41]. Of course, sensors are
used in context with the tests being conducted. For friction
testing, two surfaces are required for any measurement
one is the surface of the specified material to be tested and
the other is a sensor material or the surface against which
the specified material is to be tested. The specified material
and sensor material may be the same or different, but both
must be defined and specified.
To obtain meaningful and reproducible results, it is
essential that the sensor material be selected to represent
use conditions and be well defined. Properties such as uni-
formity (surface character including flatness, roughness,
chemical composition, resilience, and shear modulus),
permanence in that chemical and physical characteristics
do not change with time, and availability in a usable form
that does not require excessive preparation should be con-
sidered when selecting a sensor. Many feel that a major
concern in sensor selection is choosing a material that will
not change as a function of time. Both sensor material and
TABLE 8ASTM Standards for measuring
friction coefficients and related technology
(other standards exist).
ASTM Title
C808-
75(2010e)
Guideline for Reporting Friction and Wear
Test Results of Manufactured Carbon and
Graphite Bearing and Seal Materials
C1028-07e1
a
Test Method for Determining the Static
Coefficient of Friction of Ceramic Tile and
Other Like Surfaces by the Horizontal
Dynamometer Pull-Meter Method
D1894-08 Test Method for Static and Kinetic Coefficients
of Friction of Plastic Film and Sheeting
D2047-99 Test Method for Static Coefficient of Friction
of Polish-Coated Flooring Surfaces as
Measured by the James Machine
D2394-83 Methods for Simulated Service Testing of
Wood and Wood-Base Finish Flooring
D271494 Test Method for Calibration and Operation
of the Falex Block-on-Ring Friction and Wear
Testing Machine
D3108-07 Test Method for Coefficient of Friction, Yarn
to Solid Material
D3412-07 Test Method for Coefficient of Friction, Yarn-
to-Yarn
D4103-
90(2009)
Practice for Preparation of Substrate Surfaces
for Coefficient of Friction Testing
E303-93(2008) Test Method for Measuring Surface Frictional
Properties Using the British Pendulum Tester
E670-09 Test Method for Side Force Friction on Paved
Surfaces Using the Mu-Meter
E707-90(1996) Test Method for Skid Resistance
Measurements Using the North Carolina State
University Variable-Speed Friction Tester
F609-05 Test Method for Using a Horizontal Pull
Slipmeter (HPS)
F695-01(2009) Practice for Ranking of Test Data Obtained for
Measurement of Slip Resistance of Footwear,
Sole, Heel, or Related Materials
F732-00(2006) Test Method for Wear Testing of Polymeric
Materials Used in Total Joint Prosthesis
G40-99 Terminology Relating to Wear and Erosion
G65-04(2010) Test Method for Measuring Abrasion Using
the Dry Sand/Rubber Wheel Apparatus
G77-98 Standard Test Method for Ranking Resistance
of Materials to Sliding Wear Using Block-on-
Ring Test
G99-05(2010) Test Method for Wear Testing with a Pin-on-
Disk Apparatus
G115-10 Standard Guide for Measuring and Reporting
Friction Coefficients
G133-
05(2010)
Test Method for Linearly Reciprocating Ball-
on-Flat Sliding Wear
G143-
03(2009)
Test Method for Measurement of Web/Roller
Friction Characteristics
a
Withdrawn, but these standards are referenced and therefore included
in above listing.
4
The other two test methods are ASTM F1678-96 Test Method
for Using a Portable Articulated Strut Slip Tester and ASTM D5859
Test Method for Determining the Traction of Footwear on Painted
Surfaces Using the Variable Incidence Tester.
5
Comments received by OSHA prior to the deadline suggested that
no signifcant progress had been made regarding the suitability of
the test methods referenced in the provision for testing slip resis-
tance or the availability of coatings that would need the slip resis-
tance requirements of the provision [39]. The fnal revocation rule
was effective January 18, 2006.
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CHAPTER 53 FRICTION AND SLIP RESISTANCE 681
test material may be the same or different and both should
be reported when the coefficient of friction is stated.
Sensors might be exemplified by leather that is used
as a primary source material when friction of flooring is
studied. For interlaboratory and specification testing, shoe
materials such as leather conforming to Federal Specifica-
tion KK-L-165C
6
[42] are used. When leather is used as
a sensor or as a test material, it should be kept in mind
that leather soaks up water and becomes somewhat sticky
which will result in high coefficients of friction being mea-
sured. Also, leather is not homogeneous in character and
can vary from piece to piece. It is important that the appro-
priate materials are used when specific testing is done. In
the case of rubber, it is recommended that a rubber con-
forming to Section 7.1 of ASTM D1630-06 Test Method for
Rubber PropertyAbrasion Resistance (Footwear Abrader)
be used. Neoprene, nitrile, and styrene-butadiene rubbers
have been used in many investigations. In another study
[43], three leathers with three levels of oil content, two
Kraton
where M
is a metal, M
+
is the metal in ionic form, and e is the number
of electrons liberated by the metal going into ionic solution.
For example, the ionic reaction for steel is Fe Fe
+2
+ 2e
and that for aluminum is Al Al
+3
+ 3e
.
The cathodic reaction, however, consists essentially of
the neutralization of the electrons that are created as the
metal goes into ionic solution. These electrons can be neu-
tralized through one of three reactions, depending upon the
cathodic environment:
Alkaline, neutral, and near-neutral chemical environ-
ments: 2H
2
O + O
2
+ 4e
4OH
H, then 2H +
1
2
O
2
H
2
O
Highly acidic: 2H
+
+ 2e
H
2
The electron movement in a corrosion cell (the chemi-
cal concept) is defined as moving from the anode through
the metallic pathway to the cathode. At the cathode, elec-
trons are neutralized by chemicals in the electrolyte. Con-
versely, current flow, used in the electrical industry and for
cathodic protection (the electrical concept) is opposite, and
by definition, electrons comprising the electric current flow
from the anode through the electrolyte to the cathode.
Fig. 4 Chemical Concept of Electron Flow and Fig.5
Electrical Concept of Current Flow [8] illustrate the
differences between the electron and current flow in the
chemical and electrical concepts.
While the illustrations of the dry cell battery (electrical
concept) and corrosion cell (chemical concept), as shown
above, depict the anode and cathode as separate entities,
in practice, anodes and cathodes are not isolated entities.
For example, all metals consist of crystals, or grains that
precipitate when molten metal is cooled from a hot melt.
Grain boundaries form between grains, and are anodic
Fig. 2Dry cell battery. (Courtesy of KTA-Tator, Inc.)
Fig. 3Corrosion cell. (Courtesy of KTA-Tator, Inc.)
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700 PAINT AND COATING TESTING MANUAL 15TH EDITION
relative to the cathodic grain. Areas of stress concentra-
tion, in a formed metal, are anodic to unstressed areas.
Where temperature differentials exist, hot areas are anodic
relative to cool areas. A scratch, nick, or abraded area on
a metal, or mechanically worked area is anodic to adjacent
unscratched or unworked areas. Oxygen concentration
differences can also result in the formation of anodes
and cathodes (the lesser oxygen concentration generally
becomes anodic, relative to an adjacent area of greater oxy-
gen concentration). An example of this is corrosion at the
waterline of a steel piling or on the wall of a dam gate. Cor-
rosion within a crevice occurs as an anode develops within
the sheltered area within the crevice relative to the more
exposed areas, which become cathodic.
Accordingly, to a greater or lesser extent, all metals
will develop anodic and cathodic areas, and will have a
comparative potential to corrode. Moreover, as corrosion
proceeds and pits and crevices develop in a metal substrate,
the anodic and cathodic areas may switch, and the anodes
will become cathodes, and vice versa.
A metal in contact with another metal may also
become an anode with the other metal becoming the
cathode. The tendency of a metal to become an anode
or cathode in combination with other metals in a given
immersion environment is its corrosion potential. The
comparative corrosion potential of a series of metals can
be tabulated as the electromotive force (EMF) series.
EMF corrosion potentials will vary from environment
to environment, and the standard EMF series is that for
sea water. Hydrogen is used as an arbitrary reference ele-
ment, with elements above hydrogen more reactive, while
those listed below hydrogen are increasing, inert with a
lesser tendency to ionize or go into ionic solution. The
EMF series for metals and solutions of their own salts
is presented in Table 2 [9], while the EMF series in sea
water is shown in Table 3 [10]. If two metals in the gal-
vanic series are coupled, the greater the potential differ-
ence between the two metals, the greater the driving force
for the more negative metal (anode) to corrode. Note
the similarities between the EMF and galvanic series
tables with that of the order of metals in order of energy
required for conversion from their ores (see Table 1).
Thus, all metals, when wetted, either by immersion,
precipitation, condensation, or even high relative humid-
ity (generally 50 % RH or more) have an inherent ability
to corrode, as the anode, cathode, metallic pathway, and
electrolyte are all present.
Although, not a prerequisite for the initiation and early
commencement of corrosion, oxygen is critical, as without
it, the corrosion reaction will slow or stop. Oxygen is a
depolarizer in that it removes hydrogen from the cathode
and allows additional electrons to be neutralized, enabling
the process to proceed. If oxygen is not present, the hydro-
gen accumulation at the cathode may result in a hydrogen
surface film, essentially isolating the electrons migrating to
the cathode from the electrolyte and slowing or stopping
their electron neutralization process.
FORMS OF CORROSION
The appearance or a manifestation of corrosion has been
categorized in various schemes by a number of authors.
Categorization by environmental condition (immersion,
atmospheric, hot, wet, dry, etc.) is one means of grouping
corrosion. Covino and Cramer [11] sub-categorize forms
of corrosion into six subsections. Four of those forms,
uniform corrosion, localized corrosion, metallurgically
influenced corrosion, and microbiologically influenced
corrosion fit under the classification of corrosion that is
not influenced by any outside process. The remaining two,
mechanically assisted degradation and environmentally
induced cracking address corrosion as influenced by
another process (Table 4).
Fontana [12] describes eight forms of corrosion that
can be identified by visual observation, in most cases with
Fig. 4Chemical concept of electron flow. (Courtesy of NACE
International.)
Fig. 5Chemical concept of electron flow. (Courtesy of NACE
International.)
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CHAPTER 55 TYPES OF METAL CORROSION 701
the naked eye, but sometimes magnification is necessary.
The listing is arbitrary, and the eight forms are more or less
interrelated, but they cover practically all corrosion failures
and problems. The eight forms of corrosion are described
in summary below, with some modifications by the writers.
The eight forms are:
1. Uniform corrosion;
2. Galvanic corrosion;
3. Crevice corrosion;
4. Pitting;
5. Intergranular corrosion;
6. Selective leaching;
7. Erosion corrosion;
8. Stress corrosion.
Hydrogen damageFontana discusses this last form
but does not consider it a corrosion phenomena.
Fig. 6 depicts each of the corrosion forms itemized
above.
UNIFORM CORROSION
Uniform corrosion is the most common form of corrosion
and it is characterized by a chemical or electrochemical
reaction that proceeds relatively uniformly over a large
area. The metal is relatively uniformly attacked, and the
rateofdeterioration of relatively uniform over all areas
where corrosion occurs.
TABLE 2Electromotive force series
Electrode Reaction
Standard Electrode
Potential E (Vs), 25C
K = K
+
+ e
2.922
Ca = Ca
++
+ 2e
-
2.87
Na = Na
+
+ e
2.712
Mg = Mg
++
+ 2e
2.34
Be = Be
++
+ 2e
1.70
AI = AI
+++
+ 3e
1.67
Mn = Mn
++
+2e
1.05
Zn = Zn
++
+ 2e
0.762
Cr = Cr
+++
+ 3e
0.71
Ga = Ga
+++
+ 3e
0.52
Fe = Fe
++
+ 2e
0.440
Cd = Cd
++
+ 2e
0.402
In = ln
+++
+ 3e
0.340
TI = TI
+
+ e
0.336
Co = Co
++
+2e
0.277
Ni = Ni
++
+2e
0.250
Sn = Sn
++
+2e
0.136
Pb = Pb
++
+2e
0.126
H = 2H
+
+2e
0.000
Cu = Cu
++
+2e
0.345
Cu = Cu
+
+ e 0.522
2Hg = Hg2
+
+2e
0.799
Ag = Ag
+
+ e
0.800
Pd = Pd
++
+2e
0.83
Hg = Hg
++
+2e
0.854
Pt = Pt
++
+2e ca1.2
Au = Au
+++
+ 3e
1.42
Au = Au
+
+ e
1.68
[SOURCE: Encyclopedia of Chemistry, Clark and Hawley, Electrochemistry,
Reinhold Publishing Co., p. 338, 1957.]
TABLE 3Galvanic series in seawater flowing
at 13 FTPS (temperature, approx. 25C)
Material
Steady-StateElectrode
Potential, V
(Saturated Calomel Half-Cell)
Zinc 1.03
Aluminum 3003-(H) 0.79
Aluminum 6061-(T) 0.76
Cast Iron 0.61
Carbon Steel 0.61
Stainless Steel, Type 430, active 0.57
Stainless Steel, Type 304, active 0.53
Stainless Steel, Type 410, active 0.52
Naval Rolled Brass 0.40
Red Brass 0.33
Bronze, Composition G 0.31
Admiralty Brass 0.29
90Cu 10Ni, 0.82Fe 0.28
70Cu30Ni, 0.47Fe 0.25
Stainless Steel, Type 430, passive 0.22
Bronze, Composition M 0.23
Nickel 0.20
Stainless Steel, Type 410, passive 0.15
Titanium
a
0.15
Silver 0.13
Titanium
b
0.10
Hastelloy C 0.08
Monel-400 0.08
Stainless Steel, Type 304, passive 0.08
Stainless Steel, Type 316, passive 0.05
Zirconium
c
0.04
Platinum
c
+0.15
a
Prepared by power-metallurgy techniques, i.e., sheath compacted
powder, hot rolled, sheath removed, cold rolled in air.
b
Prepared by iodide process.
c
From other sources.
[SOURCE: Fink, F. W., et al., the Corrosion of Metals in Marine
Environment, Battelle Memorial Institute, DMIC Report 254, Distributed
by N.T.I.S. AD-712 585-S, pp. 7, 13 (1970), with permission from NACE.]
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702 PAINT AND COATING TESTING MANUAL 15TH EDITION
GALVANIC CORROSION
This type of corrosion occurs when two metals are in con-
tact, and there is a potential difference between the metals
when they are immersed or in a wet environment. The less
resistant metal becomes anodic and the more resistant
metal becomes cathodic (see Table 3). The anodic metal
goes into ionic solution as previously described.
In a service environment where two metals are in con-
tact in a corrosive environment, galvanic corrosion can be
readily detected, as one of the metals (the anode) will be
aggressively attacked, with the most extensive deteriora-
tion closest to the other metal (the cathode). If possible,
it is best to avoid dissimilar metal contact in immersion
or wet environments unless the consequences of galvanic
corrosion are known and anticipated. However, there are
many instances of inadvertent contact between dissimilar
metals in tanks, pipelines, heat exchangers, and other fab-
ricated items. To prevent unwanted corrosion, sometimes
the dissimilar metals are both painted in an attempt to stop
galvanic attack. However, this usually makes the situation
even worse, because if any defect develops in the coating,
the galvanic attack will be concentrated at the small defect
in the coating on the anodic metal. This may lead to rapid
pitting and perforation. Painting, however, may work if
only the cathode, or more resistant metal, is painted. This
reduces the cathodic area and with a small defect in the
coating on the cathode the corrosion current will be distrib-
uted over the much larger unpainted anode. Accordingly,
pitting does not occur due to the small cathode/large anode
relationship.
Cathodic protection is the beneficial use of galvanic cor-
rosion. There are two types of cathodic protection: (1) use of
the sacrificial anode and (2) use of impressed current.
Both types of cathodic protection utilize an anode that
is designed to deteriorate and protect the cathode, which is,
by design, the metal that is to be protected.
Cathodic Protection by Sacrificial Anode
Zinc, in the form of a zinc-rich coating, or as a galvanize
layer on steel, corrodes preferentially as the anode, and pro-
tects the steel, which becomes the cathode in the galvanic
couple. The steel is usually a pipeline, tank, ship hull, or
another steel item in immersion or in the soil. For pipelines,
tank interiors, and ship hull exteriors, zinc, magnesium, or
aluminum alloy anodes in the form of blocks or ribbons of
metal, are attached or connected to the steel to be protected.
Irrespective of whether the anode is a piece of metal
or a coating, when it becomes exhausted due to sacrificial
galvanic protection, it is replaced by either a new metal
anode or a new sacrificial coating system. The costs of
replacement of the sacrificial anode are designed to be
substantially less than the cost of replacement of the struc-
ture being protected. Fig. 7 [13] illustrates a pipeline being
protected by a sacrificial anode system.
Impressed Current Cathodic Protection
In this means of corrosion protection, the normal corrosion
current is reversed beneficially to make the structure being
protected the cathode and the anode an inert material.
TABLE 4Forms of corrosionadapted from
Covino and Cramer
1. Uniform Corrosion
a. Aqueous corrosion
b. Atmospheric corrosion
c. Galvanic corrosion
2. Localized Corrosion
a. Pitting corrosion
b. Crevice corrosion
c. Filiform corrosion
3. Metallurgically Influenced Corrosion
a. Stainless steels
i. Austenitic
ii. Ferritic
iii. Duplex
iv. High Performance
b. Nickel Alloys
c. Aluminum (1xxx through 7xxx series alloys)
d. Weldment Corrosion
i. Steel
ii. Stainless steel
iii. Non-ferrous alloys
4. Mechanically Assisted Degradation
a. Erosion
b. Fretting corrosion
c. Fretting fatigue
d. Cavitation erosion
e. Corrosion fatigue
5. Environmentally Induced Cracking
a. Stress corrosion cracking
b. Hydrogen damage
c. Liquid metal embrittlement
d. Solid metal embrittlement
6. Microbiologically Influenced Corrosion
Fig. 6Depiction of forms of corrosion.
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CHAPTER 55 TYPES OF METAL CORROSION 703
Usually, an ordinary AC current is rectified to direct current
(DC) with the negative terminal of the DC supply connected
to the structure being protected, and positive terminal to
the inert anode. The choice of the inert anode depends
upon the service environment and the associated current
demand for protection. Commonly used inert anodes con-
sist of high silicon cast iron, graphite, conductive polymers,
lead alloys, precious metals (platinized titanium or tanta-
lum), and mixed metal oxides, or ceramic oxides. Fig. 8 [14]
depicts a pipeline being protected by an impressed current
cathodic protection system.
Cathodic protection, using either a sacrificial anode or
impressed current, is almost always done in conjunction
with coating the object being protected. If the object being
protected is uncoated, the current demand required to
protect the entire surface would be quite high, and accord-
ingly, the rate of consumption of the sacrificial anode, or
the power demand for the impressed current protection
system, would be quite high also. However, if the structure
being protected is coated with an appropriate coating sys-
tem, cathodic protection would be needed only at defects
in the coating system, such as pinholes, scratches, impact,
and other mechanical damage, and, as such defects usu-
ally make up only a very small percentage (generally much
less than 1 %) of a coated structures surface, the current
demand and the anode consumption is proportionally
reduced.
CREVICE CORROSION
Intensive, localized pitting can occur within crevices or
other areas shielded by corrosion products, dirt, or other
materials that enable the creation of a stagnant condition
beneath the shield. This often occurs between metals and
nonmetallic surfaces in contact. As with most forms of
corrosion, the environment must be wet or highly humid,
resulting in wetness. In general, the tighter the crevice, the
more severe the crevice attack. Crevice attack exists prin-
cipally on passive metals (stainless steel, nickel, titanium,
and aluminum-based alloys). This is because there is a
need for a large cathode (the passive surface of the metal)
to support the high rate of anodic pitting activity within the
shielded area.
Initially, crevice corrosion initiates as general corrosion
over all surfaces of the metal. The corrosion reaction con-
sists of oxidative dissolution of the metal, and reduction of
oxygen to hydroxide ions as shown below:
Oxidation: M M
+
+ e
Reduction: O
2
+ 2H
2
O + 4e
4OH
tape
adhesion or copper sulfate solution exposure for evalua-
tion. This type of examination is usually dependent on a
customers stated requirements.
A second 180 bend around the bend already made
represents a lesser level of flexure requirement. A coating
that satisfactorily passes examination on this surface, and
that already failed the 0-T test, will be considered a 1-T flex-
ibility coating. A third bend represents 2-T, etc.
Another method of evaluating the flexibility of the coat-
ing involves the use of an impact testing device as described
in ASTM 2794, Standard Test Method for Resistance of
Organic Coatings to the Effects of Rapid Deformation
(Impact). In this test, flexibility is evaluated by dropping a
large, bullet-shaped weight from a measured height down
through a cylindrical guide tube onto the uncoated surface
of a test sheet placed on a die that has a depression analo-
gous to the shaped weight. The test is termed a reverse
impact test. Microscopic examination of the impacted area
is employed for evidence of cracking in the coating. The
coating can be tested to the point of metal failure, a factor
that depends on the thickness and strength of the substrate
used. The test can also be carried out with the coated sur-
face of the test sheet placed on the die. In this case the test
is called a forward impact test.
A test that is more specific to the can industry is the
Erichsen Lacquer Testing Instrument. This device is a cup-
ping and deep-drawing cup test machine that is used for
testing coated ferrous and non-ferrous metals. In use, a cup
is actually formed from a section of coated metal and the
corners of the formed cup are examined for signs of inad-
equate flexibility.
Extraction TestingCoating components capable of
being extracted by the container contents must be below
defined concentration limits. The Food and Drug Admin-
istration has established a series of limits and has defined
certain liquids to be used for testing based on the planned
contents of the container. These can be found in Code of
Federal Regulations (CFR) 21, Section 175.300, Resinous
and Polymeric Coatings. An extraction technique is also
described in detail in this U.S.A. government publication.
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CHAPTER 62 CAN COATINGS 777
Gloss MeasurementThe specular gloss of a coated
sample is measured using a 60 gloss meter as described in
ASTM D523, Standard Test Method for Specular Gloss. The
gloss meter should be equilibrated and calibrated against
standard panels. The meter is placed over the panel to be
tested, several readings are taken at different places on the
panel, and an average of these readings is recorded. Care
must be taken to control film thickness on test panels,
since deviation in gloss level will be observed at varying
thicknesses.
Color MeasurementCustomers will assign an accept-
able level of deviation of the final color or colors of the
can-stock sheets or the cans based on a defined standard.
Spectrophotometric analysis using appropriate ranges is
reported. ASTM D2244, Standard Practice for Calculation
of Color Tolerances and Color Differences from Instrumen-
tally Measured Color Coordinates, describes techniques
used for the analysis.
Blocking ResistanceSheets of coated product are fre-
quently stacked and stored before being transported to the
next processing station. Such storage can often occur after
an oven operation, which means that the sheets are stacked
at an elevated temperature. As sheets are fed to the pile,
the pressure imposed on the lower members of the stack
can become considerable, and the sheets must resist adher-
ing to each other. Efficient and rapid movement of these
sheets individually for subsequent processing is essential to
achieve an economical container-production rate. Simple
tests are commonly developed between customer and sup-
plier to evaluate the ability of coatings to resist this sticking
phenomenon.
In one such test, a series of coated sheets or panels are
stacked face to back. Pressure, usually imposed by means
of a properly placed block of metal, is imposed on the top
sheet or panel of the stack. The stack, which can be stored
at controlled temperatures for defined periods of time, is
examined after cooling for ease of separation. The weighted
block of metal is usually of such physical dimension that
the resistance to sticking can be determined and reported
in appropriate pressure units.
Although there are a number of ASTM tests for block-
ing resistance, none are specifically designed for the
can coating area. However, readers may be interested in
reviewing ASTM D3003, Standard Test Method for Pressure
Mottling and Blocking Resistance of Organic Coatings on
Metal Substrates, which deals with the sticking of coatings
applied to coil-coated substrates prior to fabrication.
GENERAL REFERENCE
Guide to Tinplate, Publication of the International Tin
Research Institute, Unit 3, Curo Park, Frogmore, St.
Albans, Hertfordshire AL2 2DD, United Kingdom.
References
[1] European Aluminum Association, Aluminum Cans Pass for
the First Time the 50 % Recycling Rate, Press Release, Brus-
sels, Belgium, June 26, 2006.
[2] Can Manufacturers Institute, Washington, DC, www.cancentral
.com.
[3] The Aluminum Can Group, Australia, www.aluminiumcans
.com.
[4] Koleske, Joseph V., Radiation Curing of Coatings, ASTM Inter-
national, West Conshohocken, PA, 2002, pp. 1244.
[5] Crabtree, T. A., UV Curing of Two-Piece Cans: An Update,
Proceedings of RadTech 88North America, New Orleans, LA,
April 2428, 1988, p. 231.
[6] Iimure, T., UV-Cured White Base Coat for Three-Piece Bever-
age Cans, Proceedings of RadTech88North America, New
Orleans, LA, April 2428, 1988,p. 240.
[7] Matyska, K. J., UV Curing Matures at U. S. Can, RADTECH
Report, Vol. 11, No. 6, November/December 1997, pp. 2022.
[8] Thompson, R. J., Advances in UV Curing of Two-Piece Cans,
Technical Paper FC 86856, RadCure 86, Baltimore, MD, Sep-
tember 811, 1986.
[9] Huemmer, T. F., and Phooy, R. J., The OBrien Corp., Radia-
tion Curable Can Coating Composition, U.S. Patent 3,912,670,
1975.
[10] Page, A, Radiation Curing for Packaging, RadTech Report,
Vol. 20, March-April 2006, pp. 3942.
[11] StrandGauge, www.esitelecom.net.
[12] WACO Enamel Rate II, www.waco-lab-supply.com.
[13] ASTM D522, Standard Test Methods for Mandrel Bend Test of
Attached Organic Coatings.
[14] ASTM D4060, Standard Test Method for Abrasion Resistance
of Organic Coatings by the Taber Abraser.
[15] ASTM D5181, Standard Test Method for Abrasion Resistance
of Printed Matter by the GA-CAT Comprehensive Abrasion
Tester.
[16] ASTM D4145, Standard Test Method for Coating Flexibility of
Prepainted Sheet.
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778
INDUSTRIAL MAINTENANCE COATINGS COVER A
diverse range of coatings for use in a wide variety of indus-
tries. For example, coatings such as alkyds, acrylics, vinyls,
epoxies, urethanes, polyureas, silicones, and silicates can be
used to coat structures of such variety as bridges, railroad
cars, chemical process vessels, elevated water tanks, and
concrete floors. Therefore, it is obvious that because of the
many different coating chemistries and the vast range of
environments to which they might be exposed, the testing
of industrial maintenance coatings can be a broad topic.
Furthermore, a particular physical property which may be
important in one application, such as temperature resis-
tance for a stack coating, may be of little importance for
a different coating in a different environment. Therefore,
it is important to know not only what type of tests can be
run, but to appreciate the relative importance of various
tests, realizing that their ranking may change from project
to project.
In broad terms, the testing of coatings falls into one
of two categories: determining the properties of the liquid
paint, and determining the properties of the dried film.
The testing of liquid paint can involve not only determin-
ing compositional related parameters such as density or
solids content, but also application related parameters such
as dry time and sag resistance. Although dried films can
certainly be subjected to a barrage of analytical techniques
to investigate chemical composition, this would generally
be considered a separate topic, and in the context of this
chapter most of the testing on dried films is done to deter-
mine performance or physical properties, such as abrasion
resistance or adhesion.
In the past, much emphasis, not only in testing but in
specification writing, was placed on the chemical composi-
tion of the coating. In the last decade or so, the emphasis
has shifted more toward performance based requirements.
Although the performance of the coating on the substrate
is certainly of more fundamental importance than which
ingredients are in the can, the latter should not be ignored.
Indeed, it is fairly common when screening coatings for a
Qualified Products List (QPL) to base acceptance on their
performance characteristics, but also to do some basic
compositional testing of the specific batch which was sub-
mitted. The results of these compositional tests are then
used to define the characteristics of any future batches
which may be provided for specific jobs, to help insure that
production batches have similar composition (and there-
fore hopefully similar performance characteristics) to the
batch which passed the QPL testing.
TESTING OF LIQUID COATINGS
Density
The density, or weight/gallon, of a liquid coating is a rapid,
inexpensive test which, when combined with a few other
simple tests, provides a measurement indicative of the types
and relative amounts of ingredients making up the coating.
Indeed, a significant variation in density is a sign that a
production error has probably occurred.
The density of a material is generally performed with
a pycnometer, which is simply a device which has a spe-
cific, known volume at a certain temperature. In the paint
industry, the pycnometer is known as a weight-gallon cup,
and the test is performed in accordance with ASTM D1475
(Standard Test Method for Density of Liquid Coatings, Inks,
and Related Products). Briefly, a slight excess of material
is placed in the cup, such that when the lid is attached the
excess is forced out through a small hole in the center of
the lid. This assures that the cup is completely filled. The
cup and lid are weighed before and after, and the grams of
liquid paint can then be used to determine the density of
the paint, in lbs/ gal. Often, the density of the paint in lbs/
gal is simply the weight of the paint contained in the cup,
in grams, divided by 10.
Solids by Weight
The percent solids by weight of a coating, often referred to
as its percent nonvolatile by weight, is usually determined
in accordance with ASTM D2369 (Standard Test Method
for Volatile Content of Coatings). Basically, a liquid coating
consists of four types of ingredients: resins or polymers,
pigment, additives, and solvents. By determining the solids
by weight, one is determining the combined amount of the
first three ingredients. Since these are the ingredients left
behind in the dried film, it is important that a particular
production batch have the correct solids content.
Basically, the test method involves weighing a certain
amount of liquid coating into a previously weighed thin, dis-
posable aluminum dish, baking this in an oven for 1 hour at
105 to 115C, and dividing the weight of solid material left
behind by the initial weight of liquid material used.
The procedure is simple and straightforward, although
the precision and accuracy for thick, high solids multi-
component coatings is not quite as good as for simple low
solids coatings such as alkyds. In some such cases, these
coatings contain curing agents which are volatile at the
temperature of the test, meaning that they can evaporate in
the oven before they get a chance to cross-link and become
nonvolatile. This possibility is recognized by ASTM, and
63
Testing of Industrial Maintenance Coatings
Dwight G. Weldon
1
1
Weldon Laboratories, Inc., 1188 Route 30, P.O. Box 40, Imperial, PA 15126.
MNL17-EB/Jan. 2012
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CHAPTER 63 TESTING OF INDUSTRIAL MAINTENANCE COATINGS 779
for such coatings it is recommended that they be allowed
to air dry for one hour after mixing and prior to placing
them in the oven. Single component reactive coatings, such
as moisture cured urethanes, are not specifically addressed
by ASTM. However, it would seem logical to treat them in
a similar fashion to the reactive two component coatings.
Volume Solids
The percent solids by volume of a coating, often referred
to as its volume solids, is determined in accordance with
ASTM D2697 (Standard Test Method for Volume Non-
volatile Matter in Clear or Pigmented Coatings). This is a
somewhat more complicated test than either the density
or weight solids tests described above, and indeed requires
that these two tests be done in order to perform the neces-
sary calculations. Essentially, the liquid coating is applied
to small metal disks and allowed to dry. The disks are then
weighed in air, and again while suspended in water, and the
appropriate calculations are done to determine the percent,
by volume, of the nonvolatile material in the coating.
Not only is volume solids an important property relat-
ing to the composition of the coating, but it has important
practical significance. If the coating is supposed to be 70 %
solids by volume and is to be applied at 10 mils wet, it will
dry to a thickness of 7 mils. If a batch were low in solids,
say 50 % versus 70 %, and if the applicator still applied it at
the recommended 10 mils wet, he would only get a dry film
thickness of 5 mils, rather than the expected 7 mils.
Viscosity
There are many ways to measure the viscosity of a coating.
These include determining the time it takes for a coating
to drain from a cup of known volume through an orifice of
known size (ASTM methods D4212Standard Test Method
for Viscosity by Dip-Type Viscosity Cups, and D1200Stan-
dard Test Method for Viscosity by Ford Viscosity Cup), the
use of rotational viscometers using spindles, such as Brook-
field viscometers (ASTM D2196Standard Test Methods
for Rheological Properties of Non-Newtonian Materials by
Rotational (Brookfield type) Viscometer), and rotational
viscometers using paddles, such as the Stormer viscometer
(ASTM D562Standard Test Method for Consistency of
Paints Measuring Krebs (KU) Viscosity Using the Stormer-
Type Viscometer). Brookfield viscometers can produce a
much more accurate viscosity profile than a Stormer vis-
cometer, because they allow one to obtain viscosity data
over a wide range of shear rates. In contrast, a Stormer
viscometer (Fig. 1) provides only a single data point, with
the viscosity (expressed as Krebs Units, or KU) being deter-
mined under a single, low shear condition. Nevertheless,
partly because of its simplicity, the standard quality control
test for viscosity is done with the Stormer type viscometer.
When performing viscosity testing, it is important that
the temperature requirements be observed, as this can sig-
nificantly affect the results. It is also important to realize
that the viscosity of a multi-component coating can change
over time, and that viscosity should be determined as soon
after mixing as possible.
Pigment Content
The weight solids test described above provides a measure
of the total amount, by weight, of solid material in the
liquid coating. It says nothing, however, about the ratio
of pigment to vehicle, which can have a significant influ-
ence on the performance of the coating. The common
procedures for determining percent pigment are ASTM
D2371 (Standard Test Method for Pigment Content of
Solvent-Reducible Paints) for solvent borne coatings, and
ASTM D3723 (Standard Test Method for Pigment Content
of Water-Emulsion Paints by Low-Temperature Ashing) for
water-borne coatings. The first procedure involves using a
centrifuge to separate the pigment from the vehicle and sol-
vents, while the latter involves ashing a dried film of coating
after first determining its weight solids. Once a sample has
been analyzed for percent pigment and weight solids, the
percent vehicle can be calculated simply by taking the dif-
ference between the two. The only error in this procedure,
which is usually quite minor, is the inclusion of any addi-
tives as vehicle.
Sag Resistance
Sag resistance provides a measure of how thick a coating
can be applied to a vertical surface before it begins to sag.
This is important, because if the coating is intended to be
applied at 10 wet mils but sags at 5, it will have to applied
in two coats rather than one.
Sag resistance is commonly tested in accordance with
ASTM D4400 (Standard Test Method for Sag Resistance
of Paints Using a Multinotch Applicator). This involves
preparing a drawdown using a notched applicator (Fig. 2)
which applies the coating in a pattern of stripes covering a
range of thicknesses. The drawdown is then immediately
hung vertically, with the thinnest stripe at the top and
the thickest at the bottom, and subsequently evaluated to
determine the heaviest thickness which does not sag into
the stripe below it.
Fig. 1Stormer viscometer used to obtain viscosity of coatings.
(Photograph courtesy of Weldon Laboratories.)
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780 PAINT AND COATING TESTING MANUAL 15TH EDITION
Drying Time
How long it takes a coating to dry to touch, or dry hard,
can be an important practical consideration. Furthermore,
if the drying time of a particular batch is very much lon-
ger than expected, it could be an indication of a compo-
sitional problem. Drying time is commonly measured in
accordance with ASTM D1640 (Standard Test Methods for
Drying, Curing, or Film Formation of Organic Coatings at
Room Temperature). The tests are simple but subjective,
and involve such techniques as touching with ones finger
to determine set to touch times, or using a twisting motion
with ones thumb to determine dry to handle times.
Infrared Spectroscopy
Most of the above tests are rapid, require relatively inex-
pensive equipment, and provide a quick screening method
to determine if a particular batch of coating falls within
specification requirements. However, they essentially mea-
sure some type of bulk property which, although dependent
to some extent on the specific ingredients of the coating,
does not in any way actually identify these ingredients. A
powerful tool for providing compositional information on
paints and coatings, whether in the solid or liquid state, is
infrared spectroscopy.
Infrared spectroscopy is described in great detail else-
where in this volume. Simply put, it allows a material to
be identified by measuring the amount of infrared light
absorbed (or transmitted) at various frequencies. Indeed,
a spectrum is simply a graph showing the amount of
absorbed (or transmitted) infrared light as a function of fre-
quency. Two examples of infrared spectra are shown in Fig.
3. Even without understanding the underlying theory of the
process, it is obvious that the spectrum of the vinyl latex
is much different in appearance than the spectrum of the
Fig. 2A multinotch applicator used to evaluate sag resis-
tance. (Photograph courtesy of Weldon Laboratories.)
Fig. 3Infrared spectra of an epoxy (top) and a vinyl latex (bottom). (Photograph courtesy of Weldon Laboratories.)
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CHAPTER 63 TESTING OF INDUSTRIAL MAINTENANCE COATINGS 781
epoxy. The fact that different materials each have their own
unique infrared spectrum has led to them being referred to
as fingerprints.
In recent years there has been a trend in product test-
ing to obtain an infrared spectrum of the batch of coating
submitted for testing. If the batch passes all the testing
requirements and is approved, the spectrum is kept on file
in the event that a problem occurs with a later, production
batch of coating. If the spectrum shows a marked devia-
tion in composition from the originally approved batch,
it is likely that the problem is a coating one. On the other
hand, if the various bulk properties are consistent, and the
spectrum is a good match to the spectrum of the approved
batch, it is likely (but not certain) that the problem lies
elsewhere.
Although an extremely useful technique, infrared spec-
troscopy is not without its limitations. First of all, there is
more than one way to actually obtain a spectrum of a sam-
ple, and the analyst must be consistent in his methodology
in order to obtain reproducible spectra. Secondly, infrared
spectroscopy generally cannot detect ingredients which are
present at less than 4 % or 5 % unless they are somehow
separated or at least partially isolated from the mixture.
Therefore, a minor additive which might have a crucial bear-
ing on the performance of a coating, such as an ultraviolet
light absorber, would not even be detected by this technique.
TESTING OF APPLIED COATINGS
Because of the diversity of coating types, structures, and
environments encountered in the industrial maintenance
field, there are numerous tests which could be appropriate
for a given situation. Because of this, the first question to
ask when putting together a testing program, or evaluat-
ing the manufacturers published literature, is what is
this coating going to be used for?. This simple question
will help greatly in deciding which tests are appropriate,
and how much emphasis to place on each test. The follow-
ing is a list of many of the common tests which could be
appropriate for evaluating the performance of an industrial
maintenance coating. ASTM D6577 (Standard Guide for
Testing Industrial Protective Coatings) provides a good list
of the many tests available.
Adhesion
Of all the physical and chemical properties of a coating, this
one is arguably the most important. The best coating will
offer little protection if it does not stick to the substrate.
There are several methods to measure adhesion, including
such subjective, unofficial techniques as prying with a
hammer and chisel to rubbing with the edge of a coin. The
three more widely used standardized ASTM techniques,
however, include D3359, D4541, and D6677.
ASTM D3359 (Standard Test Methods for Measur-
ing Adhesion by Tape Test) is often referred to as tape
adhesion. There are two methods to choose from, A and
B, depending on the thickness of the coating. Method A
is recommended for films greater than 5 mils thick, and
involves using a cutting tool to scribe an X cut into the
specimen, followed by the application of a special pressure
sensitive adhesive tape. The tape is then rapidly removed,
and the adhesion is assessed in accordance with the
methods descriptive rating system. The ratings range from
a 5 for no peeling or removal, to a 0 for removal beyond
the area of the X. Method B, for thinner films, involves
scribing a cross-hatch pattern into the specimen, again fol-
lowed by the application and removal of tape. The ratings,
which also range from 5 to 0, are assessed in accordance
with pictorial representations of the percentage of coating
removal.
The technique has the advantage of being quick,
simple, and inexpensive, and can even be done on curved
surfaces. However, occasionally problems can be encoun-
tered with the tape not adhering well to the paint, resulting
in artificially good results. A more common problem, how-
ever, especially with thick, tough coatings, is not being able
to scribe completely through to the substrate.
ASTM D4541 (Standard Test Method for Pull-Off
Strength of Coatings Using Portable Adhesion Testers) is
often referred to as tensile adhesion. It involves using an
adhesive to attach aluminum or steel dollies or stubs to
the coating, and then using some sort of portable adhesion
tester (Fig. 4) to measure the force required to pull the stub
from the surface, hopefully taking the coating along with it.
The result is reported in psi. A variation of this test is cur-
rently being evaluated for use on coated concrete.
The advantages of this method compared to D3359
include less subjectivity and less operator error associ-
ated with not cutting completely through the coating. It
has several potential drawbacks, however, not the least of
which is the fact that the various instruments on the mar-
ket can produce widely varying results. Thus, it is critical,
when performing the test, to report which instrument was
used, and results between one coating and another should
only be compared if they were tested using the same type
of instrument. It is also not uncommon for the precision
to be relatively poor, at least for certain types of instru-
ments, so it is advisable to perform testing in duplicate or
triplicate.
The method can usually not be used on curved sur-
faces, as this changes the degree of contact and hence the
surface area tested, and, once the stubs are applied, it can
take from a few hours to overnight before the adhesive has
cured enough to test. Furthermore, some adhesives do not
bond well to the surfaces of some coatings, resulting in glue
failures rather than coating delamination. It should also be
pointed out that it is not unusual for tensile adhesion and
tape adhesion results to appear to be inconsistent. This is
Fig. 4A type of commonly used portable adhesion tester.
(Photograph courtesy of Weldon Laboratories.)
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782 PAINT AND COATING TESTING MANUAL 15TH EDITION
likely because tape adhesion applies a significant degree of
shear stress to the coating, which is absent in the tensile
testing. Thus, the coating adhesion, when assessed by tape
adhesion, can sometimes appear to be worse than the ten-
sile adhesion values would indicate.
A third, relatively new ASTM method for assessing
adhesion, is D6677 (Standard Test Method for Evaluating
Adhesion by Knife). This method involves using a knife to
cut an X into the sample, and then uses the tip of the knife
to pick or probe at the intersection of the cuts. There is a
rating system based on the ease with which the coating can
be removed. Investigators and inspectors have used similar
methods for years in subjectively determining coating adhe-
sion, and one of the main reasons for establishing D6677
was to try to standardize, at least to some extent, the vari-
ous subjective methods in use.
Corrosion Resistance
When the structure being painted is made of steel, assess-
ing the corrosion resistance of the coating is very impor-
tant. By far the most commonly used procedure is the salt
spray test, ASTM B117 (Standard Practice for Operating
Salt Spray (Fog) Apparatus). The test involves placing the
painted panels in a salt spray cabinet (Fig. 5), which essen-
tially produces a fog of warm (95F) saltwater (5 % sodium
chloride). After an agreed upon period of time, such as
1000h, the panels are evaluated for such things as blister-
ing (ASTM D714Standard Test Method for Evaluating
Degree of Blistering of Paints), rusting (ASTM D610Stan-
dard Practice for Evaluating Degree of Rusting on Painted
Steel Surfaces), and undercutting at the scribe (ASTM
D1654Standard Test Method for Evaluation of Painted or
Coated Specimens Subjected to Corrosive Environments),
if the panels were scribed (an option) before placing them
on test.
The procedure has been used for decades, and is firmly
entrenched in many specifications. Over the last ten years
or so, however, it has become somewhat controversial, and
there is a body of evidence that salt spray results do not cor-
relate very well with real world performance.
A second commonly used test procedure which has
increased substantially in popularity over the last several
years is what is known as Prohesion testing, which is
described in ASTM D5894 (Standard Practice for Cyclic
Salt Fog/UV Exposure of Painted Metal). The terminology,
however, is somewhat confusing, as Prohesion testing refers
to a procedure involving a cyclic salt fog test, which is only
one component of D5894 (the other component being accel-
erated weathering).
In D5894, the test panels (either scribed or unscribed)
are placed in a cyclic salt fog cabinet (sometimes referred to
as a Prohesion cabinet), which introduces a fog of dilute salt
water (0.05 % sodium chloride/0.35 % ammonium sulfate)
at room temperature for one h. After one h, the cabinet is
purged with warm, dry air for one hour, and the cycle is
repeated. The panels remain in the cyclic salt fog cabinet
(also described in ASTM G85, Standard Practice for Modified
Salt Spray (Fog) Testing) for a specified period of time (typi-
cally one week), after which time they are manually trans-
ported to an ASTM G154 accelerated weathering cabinet,
which uses ultraviolet light, heat, and moisture to weather
the panels, again typically for one week. The panels alter-
nate between the two cabinets, typically for a total duration
of 1000 h, and are then evaluated in the manner described
above for salt fog testing.
It is generally felt that D5894 gives better correlation
to the real world performance of coatings than does B117.
However, in both cases, and indeed with all accelerated
laboratory test methods, it is extremely difficult to use
the tests to actually predict the service life of a coating
system. The tests are primarily used to compare one coat-
ing with another, allowing them to be ranked as to which
can be expected to perform the best. There is also concern
that D5894 gives artificially poor results for zinc-rich
primers.
Accelerated Weathering
A commonly asked question of a coating is how durable
is it, or how well does it weather. The best, but also the
slowest way, to answer this question is to expose painted
panels outdoors in an environment similar to what might
actually be expected. As this can take years, there have been
various accelerated laboratory test methods developed. All
of these methods employ a combination of heat, ultravio-
let light, and moisture to weather or degrade the coating.
Broadly speaking, they fall into two categories, depending
on the source of ultraviolet light: arc devices, and fluores-
cent tube devices.
Arc devices produce ultraviolet light by passing an
electrical current through an electrode. Devices include
enclosed and open-flame carbon arcs described by ASTM
G153 (Standard Practice for Operating Enclosed Carbon
Arc Light Apparatus for Exposure of Nonmetallic Materi-
als) and D822 (Standard Practice for Filtered Open-Flame
Carbon-Arc Exposures of Paint and Related Coatings), and
Fig. 5An ASTM B117 salt fog cabinet. (Photograph courtesy
of Weldon Laboratories.)
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CHAPTER 63 TESTING OF INDUSTRIAL MAINTENANCE COATINGS 783
xenon arc machines described by ASTM G155 (Standard
Practice for Operating Xenon Arc Light Apparatus for
Exposure of Non-Metallic Materials). In all cases, water is
sprayed intermittently onto the specimens as a fine mist,
and exposure to light and darkness is alternated. A com-
monly used cycle is 102 min of light at 145F and 18 min
of light and water spray at 60F. The xenon arc devices
have become much more common than the carbon-arc
devises.
Fluorescent UV bulb devices are described in ASTM
G154 (Standard Practice for Operating Fluorescent Light-
Apparatus (for UV) Exposure of Nonmetallic Materials),
formerly known as ASTM G53. Briefly, they use fluorescent
tubes to provide the ultraviolet light, and moisture in the
form of condensation is produced by heating a trough of
water located in the bottom of the instrument. Many differ-
ent types of bulbs are available which have different spec-
tral characteristics, although most fall into what is known
as either the UV-A or UV-B region of the electromagnetic
spectrum. The UV-B region is more aggressive and can pro-
duce results in less time, but the UV-A region is generally
felt to be a more realistic test.
Regardless of which type of test is selected it must be
kept in mind that it is very difficult, if not impossible, to
predict an actual lifetime for a coating based upon accel-
erated weathering data. Weather varies dramatically from
geographic region to geographic region, and even from year
to year in the same region. Therefore, the primary use of
accelerated weathering is to compare or rank one coating
versus another.
Chemical Resistance
When one considers all the industrial environments that
painted structures can be exposed to, as well as the fact
that coatings are used to protect such things as waste
water treatment plants, off shore oil platforms, secondary
containments, and even the interiors of railroad tank cars
and chemical process vessels, it is apparent that chemical
resistance is an extremely important property. The two rel-
evant test methods for determining chemical resistance are
ASTM D1308 (Standard Test Method for Effect of House-
hold Chemicals on Clear and Pigmented Organic Finishes),
and ASTM C868 (Standard Test Method for Chemical Resis-
tance of Protective Linings).
The title of D1308 is somewhat misleading, as the
methodology can be applied to harsh industrial chemicals
as well as mild household ones. The method is broadly
written, and covers such possibilities as simple room tem-
perature spot testing, where a small amount of chemical is
applied to a test panel and covered with a watch glass for
an hour or so, to high temperature immersion testing. The
method does not go into much detail as to apparatus, time,
or temperature, and basically leaves these decisions up to
the investigator. Obviously, chemicals should be chosen
which could reasonably come into contact with the coating,
and realistic, although perhaps slightly elevated, tempera-
tures should be chosen. Although in service the coating may
be expected to perform for several years, laboratory testing
is usually carried out for no more than a few months, with
the panels being evaluated for such things as rusting, blis-
tering, cracking, softening, or delamination. If the coating
goes for a few months with little or no sign of deterioration,
it is generally assumed to be acceptable for that chemical,
even though it is not possible to predict the actual service
life in years.
While D1308 involves immersion testing, C868 is often
referred to as one-sided immersion testing, or sometimes
Atlas Cell testing, even though there may be a number of
companies which manufacture the equipment. A virtually
identical test is described in NACE TM-01-74 (Laboratory
Methods for the Evaluation of Protective Coatings and Lin-
ing Materials in Immersion Service). The apparatus used
in C868 (Fig. 6) consists of a glass cylinder, typically 5 to 7
in. in diameter, fitted with ground glass take offs for such
things as condensers, thermometers, or immersion heaters
(one variety jackets the outside of the cell with a flexible
heating element). The gasketed test panels actually form the
two ends of the cell. The cell is then filled halfway to two
thirds full with the chemical of interest, and the heating ele-
ment set to maintain the desired test temperature. The test
duration is typically from 3 to 6 months.
One of the main advantages to C868 testing is that,
since the test panels are not immersed, there are no edge
effects to worry about. Sometimes it is difficult to seal
sharp edges, and failures can occur near edges which are
more application related than coating related.
Another advantage to C868 testing, which depending
on circumstances may be more perceived than real, is the
belief that it mimics the cold wall effect. The cold wall
effect has been observed numerous times, and occurs when
the outside, non-immersed surface of the steel is colder
than the inner surface which is exposed to the contents of the
vessel. This is a more aggressive condition than if the inner
and outer temperatures are the same, and can more readily
cause blistering of the interior coatings.
Fig. 6An ASTM C868 chemical resistance cell. (Photograph
courtesy of Weldon Laboratories.)
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784 PAINT AND COATING TESTING MANUAL 15TH EDITION
At first glance, this condition would appear to be
simulated in Atlas Cell testing. However, unless the steel
test panels are rather thick, there is actually very little dif-
ference in temperature between the inner and outer walls.
A temperature gradient can be imposed by jacketing the
outer surface with a cell containing circulating water, but
in practice this is rarely done.
When doing chemical resistance testing, it is tempt-
ing to choose a temperature much higher than the actual,
expected temperature, in order to accelerate the test. Care
must be taken, however, not to choose too high of a tem-
perature. If the coating is below its glass transition temper-
ature when in actual service, but has been artificially raised
above its glass transition temperature during laboratory
testing, the possibility exists that it will have been made
more permeable as a result. Thus, it could fail in the labora-
tory, yet in actual service it could perform very well.
Abrasion Resistance
Coatings used to protect handrails or used in areas sub-
jected to heavy foot traffic need to be resistant to abrasion.
By far the two most popular methods to evaluate abrasion
resistance include Taber abrasion and falling sand.
Taber abrasion testing is described by ASTM D4060
(Standard Test Method for Abrasion Resistance of Organic
Coatings by the Taber Abraser). The test panels, which are
4 4 in.
2
with a hole in the middle, are mounted on a device
called a Taber abrader. This is essentially a turntable with a
pair of weighted abrading wheels which rest on the panel.
As the panel rotates, the abrasive wheels turn along with
it, resulting in removal of some or all of the coating. The
panels are weighed before and after testing, and the result
is usually reported as a weight loss per so many cycles
(usually 1000 cycles). Coatings with better abrasion resis-
tance lose a smaller amount of weight. When evaluating
Taber abrasion results, it is important to know the number
of cycles, the load on the wheels, and the type of wheels.
CS-17 wheels are the most common, but wheels of lesser
and greater abrasiveness can be used.
The falling sand test is described by ASTM D968 (Stan-
dard Test Methods for Abrasion Resistance of Organic
Coatings by Falling Abrasive). Essentially, the test panel is
mounted at a 45 angle beneath a tube which is attached
to a hopper. A known quantity of sand is dumped into the
hopper and impinges upon the test panel. The amount of
sand required to wear through the coating is reported. On
relatively thin, ordinary coatings such as an acrylic latex or
an alkyd, the test is relatively simple to do. On a thick, high
performance coating such as an epoxy or an elastomeric
urethane the test can be extraordinarily time consuming,
and requires large quantities of sand (an individual quan-
tity of sand is to be discarded after a certain number of
uses).
Impact Resistance
Examples of coatings which would require good impact
resistance would include coatings for overseas shipping
containers, and coatings for use on locks and dams. Most-
impact resistance tests involve dropping a weight onto a
coated panel and looking for cracking or disbonding. The
most common procedure is ASTM D2794 (Standard Test
Method for Resistance of Organic Coatings to the Effects
of Rapid Deformation (Impact), where a hemispherical
tup is rested on the panel, and a falling weight, housed in
a guide tube, is dropped from varying heights to determine
the greatest force, expressed in in-lbs, which will not crack
or disbond the coating (Fig. 7). The procedure calls for
the use of a thin gage steel panel which will deform under
the conditions of the test, although many users prefer to
use thicker steel representative of the actual article to be
coated. If the weight is dropped on the coated face, the
result is referred to as direct impact. If it is dropped on
the back of the panel, it is referred to as indirect or reverse
impact. Coatings nearly always have lower reverse impact
than they do direct impact resistance.
Flexibility
A certain amount of flexing or movement is common with
many structures. Electrical transmission towers flex and
move in the wind, thin galvanized decking can flex when
walked upon, and metal can change dimensions slightly
upon freezing and thawing. Furthermore, instantaneous
flexing can occur when a surface is subjected to a sharp
impact. Indeed, it is difficult to imagine a case where flex-
ibility would not be a desirable property of a coating. The
fact that not all coatings are flexible is because to impart
flexibility to a coating, one must often sacrifice other
properties, such as chemical resistance or resistance to
permeation.
Coatings are commonly tested for flexibility by bend-
ing a coated, thin gauge steel or aluminum panel over a
mandrel and examining the coating for cracking, in accor-
dance with ASTM D522 (Standard Test Methods for Man-
drel Bend Test of Attached Organic Coatings). The method
Fig. 7A variable impact tester used to measure the impact
resistance of coatings. (Photograph courtesy of Weldon
Laboratories.)
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CHAPTER 63 TESTING OF INDUSTRIAL MAINTENANCE COATINGS 785
describes two procedures, one using a conical mandrel, and
one using cylindrical mandrels.
The conical mandrel consists of a metal cone, 8 in. in
length, with a diameter of 1/8 ft at the narrow end to 1 1/2
in. at the wide end (Fig. 8). There are clamps for mounting
the panel, and a rotating arm which is used to bend the
panel around the mandrel. If the coating is being evaluated
for percent elongation, it is bent slowly (over a period of
15 s). If it is being evaluated for crack resistance it is bent
quickly (approximately 1 s). If cracking occurs, the distance
which the cracking extends from the small diameter end
towards the large diameter end is measured and used to
determine the coatings percent elongation. If no cracking
occurs, the percent elongation is greater than approxi-
mately 32 percent. When using cylindrical mandrels, one
usually simply reports the smallest diameter mandrel over
which the panel can be bent without cracking, although %
elongation can also be estimated.
The mandrel testing described in D522 is usually
sufficient for testing most industrial maintenance coat-
ings. However, for very flexible elastomeric coatings it is
of little use, since these coatings will have elongations of
100 % or more, far above the maximum 32 % which can
be determined by D522. In such cases, it may be desirable
to test such coatings using the so-called universal test-
ing machines, which essentially use clamps to hold free,
unsupported films of coatings between the jaws of the
machine. The sample is then stretched apart at a known
rate and a stress-strain curve obtained. Such properties as
percent elongation, tensile strength, and modulus (essen-
tially the stiffness of the sample) can be determined.
Applicable test procedures include D2370 (Standard Test
Method for Tensile Properties of Organic Coatings) and
D638 (Standard Test Method for Tensile Properties of Plas-
tics). It is often difficult, however, to test very thin free film
coatings by these methods, although coatings thicker than
about 5 mils can usually be tested.
Moisture Resistance
A coating intended to line the interior of a potable water
tank obviously requires good moisture resistance. While
salt spray and accelerated weathering tests have a moisture
component to them, they introduce other elements which
the potable water lining would not be exposed to. Since
water could certainly be considered a chemical, some type
of water immersion test could certainly be carried out in
accordance with the general chemical resistance testing
previously described by ASTM D1308. However, water or
moisture resistance is more commonly done in accordance
with either ASTM D4585, D2247, or D1735.
ASTM D4585 (Standard Practice for Testing Water Resis-
tance of Coatings Using Controlled Condensation) involves
generating water vapor by heating a pan of water located in
the bottom of the chamber. The test panels form the roof or
walls of the chamber, and since their back side is exposed to
the cooler air of the laboratory, condensation forms on the
coated front surfaces. Although this sounds like a relatively
gentle test, it is actually quite aggressive since the condens-
ing water is relatively pure and it is conducted at a slightly
elevated temperature. Coatings typically fail by blistering.
ASTM D2247 (Standard Practice for Testing Water Resis-
tance of Coatings in 100 % Relative Humidity), is somewhat
similar, except that the cabinet is designed differently and
the specimens are completely suspended inside the chamber.
Considerably different than the above methods is
ASTM D1735 (Standard Practice for Testing Water Resis-
tance of Coatings Using Water Fog Apparatus). This method
uses a chamber similar to an ASTM B117 salt fog cabinet to
expose the panels to an actual mist of water.
Hardness
Industrial maintenance coatings are commonly rated for
hardness using the pencil hardness method described in
ASTM D3363(Standard Test Method for Film Hardness by
Pencil Test). In this method, a series of pencils is used to
determine the hardest pencil lead which will not scratch or
gouge the coating. The pencil ratings, from softest to hard-
est, are as follows:
6B-5B-4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H
The test is somewhat subjective, not only because of
operator variability, but also because of possible variations
among different sets of pencils. ASTM lists a reproducibility
of plus or minus one pencil.
For thick coatings, hardness is sometimes determined
using some type of indentation tester. The two most
commonly used are the Barcol (D2583) and Durom-
eter (D2240Standard Test Method for Rubber Property-
Durometer Hardness) types. In both cases, hand pressure
is used to drive a spring loaded indenter into the coating,
and the ease of penetration is reflected on the scale (higher
numbers indicate harder coatings).
Water Vapor Permeability
It is not surprising that a coatings resistance to the perme-
ation of water vapor can have a significant bearing on its
ability to protect the substrate. In many cases, this is tested
in a very practical way by subjecting painted test panels to
wet or humid environments, such as the salt spray, accel-
erated weathering, and humidity tests described above.
A more direct way to actually measure the rate of water
vapor permeation, however, is described in ASTM D1653
(Standard Test Methods for Water Vapor Transmission of
Organic Coating Films). In this test method, free films of
coating (or films attached to a thin, porous paper substrate)
are sealed to the open mouth of a cup or dish, and essen-
tially form the lid of the cup (Fig. 9). In Method A the cup
Fig. 8A conical mandrel tester used to determine per cent
elongation. (Photograph courtesy of Weldon Laboratories.)
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786 PAINT AND COATING TESTING MANUAL 15TH EDITION
contains a desiccant, and the assembly is placed in a humid
environment. The cup is weighed periodically to measure
the amount of moisture which has passed through the
coating and into the desiccant. In Method B, which is the
more common procedure, the cup contains water, and is
placed in a dry environment. It is then weighed periodically
to determine the amount of moisture which has passed
through the coating and out of the cup.
Theoretically the procedure sounds very simple and
straightforward. In practice, however, it is not quite so
simple. It can sometimes be extremely difficult to obtain,
as the method calls for, smooth and completely continu-
ous films of uniform thickness throughout the test area.
Furthermore, if the coatings are very thin, or very brittle, it
can be a frustrating task to remove them from the release
paper or even mount them on the cups without tearing or
fracturing them.
Fig. 9A permeability cup used to determine water vapor
transmission. (Photograph courtesy of Weldon Laboratories.)
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787
IN PREPARATION OF THIS CHAPTER, THE CONTENTS
of the fourteenth edition were drawn upon. The author
acknowledges the authors of the fourteenth edition. The cur-
rent edition will review and update the topics as addressed
by the previous authors, introduce new technology that has
been developed, and include up-to-date references.
INTRODUCTION
Energy and its availability continue to drive the industri-
alization of nations. America uses a very large volume of
energy based on fossil fuels. Many times, the usage point
is a great distance from the source. Carbon-steel pipelines
continue to be the most economical means of transporting
fuel from the source to the consumption point. Many thou-
sands of miles of pipelines crisscross the landscape. As with
all carbon-steel pipe, corrosion is a major concern. Pipeline
failures [1] always make big headlines, cost large amounts
of capital to repair, and frequently disrupt needed service.
Building a major pipeline is a costly, time-consuming
project. First, an abundant source of fossil or other fuel
must be located and combined with a provider who will ser-
vice an end user. Federal, state, and local permits must be
obtained, rights-of-way purchased, and financing obtained.
From start to finish, this can be a multi-year project. To
protect the investment and to provide for safe operation,
every possible means of protection must be considered
over the life of the pipeline. The most economical means of
protection continues to be a combination of cathodic pro-
tection and protective coatings. This chapter focuses on the
role of coatings and their design, selection, and use.
MARKET
The United States Department of Commerce estimates that
loss of steel due to corrosion costs in the billions of dollars
each year in the United States alone. The market for pipe-
line coating products varies each year and depends on the
number of permits issued. At about the turn of the twenty-
first century, this market was estimated to exceed $350 bil-
lion per yearan amount that grows each year. The market
is divided between repair and rehabilitation products and
new construction products. There are five basic product
groups available for such uses.
Asphalt enamels and asphalt mastics ... 7 %
Coal tar and coal tar modified products ... 14 %
Fusion Bonded Epoxy (FBE) powder coatings ... 32 %
Polyolefins, including both bonded and extruded prod-
ucts ... 17 %
Tape products ... 30 %
The distribution of product use size will vary from
year-to-year depending on the active projects in particular
areas as well as developments and improvements within the
product areas. Table 1 contains a listing of some consider-
ations that are pertinent for such coatings.
WHY USE COATINGS?
Control of steel pipeline corrosion is a complicated process
that involves several different techniques. Internal corro-
sion protection may be accomplished with organic coatings
and/or inhibitor coatings. External corrosion protection is
almost always a combination of cathodic protection and
organic coatings. Careful selection of the coating material
in combination with proper application can result in many
years of trouble-free service. In certain regions where per-
mafrost is encountered, special considerations regarding
the environment need to be made [2].
Coatings are required to provide a wide range of
protective properties that vary from excellent mechanical
characteristics to elevated temperature resistance. On a
per-square-foot basis, coatings have proven to be the most
economical corrosion control system for steel pipelines.
The United States Department of Transportation (DOT)
recognizes the protection provided by coatings. It is a DOT
requirement that a bonded coating protect all new steel
pipelines involved in intrastate commerce.
PRODUCT DEVELOPMENT, COMPARATIVE
TESTING, AND QUALITY CONTROL
Product testing utilizing procedures or methods pub-
lished by ASTM, NACE, SSPC, and others takes place in
three distinct time frames. Several pipeline specifications,
methods, and practices are given in Table 2. The technolo-
gist will use a broad spectrum of tests to learn everything
possible about the product. The goal is to determine the
strong points of the product and possibly to correct any
product deficiencies. The basic properties of an external
coating are resistance to cathodic disbondment, adhesion,
impact resistance, flexibility, and resistance to moisture
penetration. Such failure modes have been described in
the literature [3]. Defining these properties will provide the
technologist with information used to decide whether or
not a potentially useful product is being considered. Many
other properties must be defined to generate a product
specification list.
The pipeline engineer will use a series of tests to
choose between comparable products and will use some
of these tests to establish an in-process quality program.
64
Pipeline Coatings
Alfred Siegmund
1
1
Director of Technical Services, ICO Inc., 9400 Bamboo Rd., Houston, TX 77041.
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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788 PAINT AND COATING TESTING MANUAL 15TH EDITION
The application, along with an outside quality team, will
use a limited number of in-process tests to assure product
quality.
INTERNAL PIPE COATINGS
Most of the information in this chapter refers to external
pipeline coatings. Internal pipe coatings are used, but their
use is far more complicated than the external coatings [4].
Internal coatings not only provide corrosion protection,
they can impart minimized erosion, fouling, friction, and
wearall of which are dependent on what is flowing in the
pipe. Thus, internal coatings can provide improved flow
rates (~ 5 15 %) and greater productivity, factors that will
result in decreased maintenance costs. The internal coat-
ing will be in contact with liquid or gaseous substances
such as crude and refined oil, water, air, food products,
oxygen, nitrogen, natural gas and so on. Three common
systems used are two-component epoxy polyamide/amine
combinations that cure under ambient conditions, fusion
bonded materials that are thermally cured, and air-dried,
field applied coatings based on either epoxides or urethane
chemistry.
With this strong dependence on what is being carried
in the pipeline, only this brief mention will be made of the
coating technology for internal coatings. In a general sense,
the topic is too complex for this particular chapter.
EXTERNAL COATINGS FOR REPAIR
AND REHABILITATION
The existing pipeline infrastructure is aging. Many lines
have 20, 30, or 40 years of service and are in need of repair
and maintenance, which poses a unique set of problems
[58]. First is that the pipeline will remain in service
during the work effort. This can cause problems with
temperaturehotter close to compressor stations and vari-
able in other locations. Access to buried pipe is limited due
to the confines of the associated ditch. This limits surface
cleaning and can markedly affect the choice of coating and
the long-term performance of the selected product.
Application techniques are limited to spray equip-
ment that is tractor mounted and travels along the pipeline
or traveling equipment that actually rides on the pipe.
Weather conditions are a significant consideration in the
selection and performance of the coating. Cold damp sur-
faces are not uncommon as well as hot days during summer
and in desert areas. Cure time, or time to bury, becomes an
important factor as maintaining an open ditch during cer-
tain weather condition can pose serious difficulties.
The previously mentioned concerns limit the coating
that can be effectively utilized. Waxes, oils, and greases
are still utilized as protection for elbows, valves, and other
short runs. They are generally protected by a layer of Kraft
paper or felt to allow them to be quickly buried.
Coal tar and coal tar modified products are well suited
for rehabilitation and over-the-ditch applications. There is
a wide choice of products that include but are not limited
to modified epoxides, urethanes, and associated mastics
and enamels [9]. The moisture resistance of these coatings
along with their relative ease of application makes them
a good choice for this service. Tests used for coal tar and
related products are listed in Table 3.
TABLE 2Pipeline coating specifications,
practices, and standard methods
Test
Designation Title
API RP 5L2 Recommended Practice for Internal Coating of
Line Pipe for Non-Corrosive Gas Transmission
Service
API RP 5L7 Recommended Practice for Unprimed Internal
Fusion Bonded Epoxy Coatings of Line Pipe
NACE RP
T-10D
Recommended Application, Performance
and Quality Control of Plant Applied Fusion
Bonded Epoxy External Pipe Coatings
AWWA C203 Coal Tar Protective Coatings and Lining for
Steel Water PipelinesEnamel and Tape Hot
Applied
AWWA C210 Liquid Epoxy Systems for the Interior and
Exterior of Steel Water Pipelines
AWWA C214 Tape Coating Systems for the Exterior of Steel
Water Pipelines
AWWA C215 Extruded Polyolefin Coatings for the Exterior
of Steel Water Pipelines
AWWA C217 Cold-Applied Petrolatum Tape and Petroleum
Wax Tape Coatings for the Exterior of Steel
Water Pipelines
TABLE 3ASTM test methods for analyzing
coal tar and related products (a partial
listing)
Designation Standard Test Method for
ASTM D4 Bitumen Content
ASTM D5 Penetration of Bituminous Materials
ASTM D36 Softening Point of Bitumen (Ring-and-
Ball Apparatus)
ASTM D71 Relative Density of Solid Pitch and
Asphalt (Displacement Method)
ASTM D2415 Ash in Coal Tar and Pitch
ASTM D3143 Flash Point of Cutback Asphalt with
Tag Open-Cup Apparatus
ASTM G17 Penetration Resistance of Pipeline
Coatings (Blunt Rod)
TABLE 1Considerations for repair
and rehabilitation coatings
Adhesion and
compatibility
Time to pipe burial
Coating cure time Two-component, cold-damp surfaces
Inspection Transition to existing coatings
Materials and
workmanship
Weather for over-the-ditch repair
Surface preparation Weather, temperature, rock shields
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CHAPTER 64 PIPELINE COATINGS 789
Cold-applied tapes that are applied by equipment that
rides the pipe are popular. Machines have been utilized that
clean and coat the pipe in a short time span allowing for
quick return of the pipeline to service.
Table 4 contains a listing of typical tests used to deter-
mine the acceptability of external pipeline coatings.
FACTORY OR PLANT APPLIED PRODUCTS
The majority of new pipeline construction projects use
plant-applied coatings. This allows for thorough evaluation
of the coatings before they are put in service. This involves
a coordinated effort between the coating supplier, applica-
tor, and end user. A comprehensive quality control plan can
be implemented along with in-process quality checks. All
of this leads to a project with a longer life before repairs
are needed. A variety of coatings will meet such an effort to
develop factory-applied products.
Extruded polyolefins
FBE powder coatings
Multi-layer products
Tape and wrap products
Table 5 is a listing of in-process tests that might be used
to determine coating quality. It should be pointed out that
some of the products can be field applied as indicated.
Tape and Wrap Products
These coatings mainly consist of polyolefins applied in
tape form. They are comprised of an adhesive layer and
an outer protective layer. In some instances, the two layers
are co-extruded and applied as a single tape. Most tape and
wrap products are cold applied, but there are some that
are heat fused to bond the layers together. These coat-
ings provide added moisture protection and resistance to
handling damage.
Extruded Polyolefins
The next step in process improvement was to use a ther-
mally extruded polyolefin as the outer layer of polyolefin
and thus provide for a continuous protective outer film.
This added even more moisture protection and handling
damage control. As in the tape and wrap system, an adhe-
sive prime coat comprised of a mastic, two-part epoxy,
fusion bonded epoxy, or rubber-based material is employed
[1012].
Coal Tar Enamels
Coal tar enamels are particularly suitable for coating steel
pipe. They are generally hot applied either in the yard or
in the field. In use, they are virtually unaffected by long
periods of water immersion, soil stress, punctures, or
bacteria, and they provide a relatively high electrical resis-
tance. These coatings work best in the temperature range
of 1.1 to 82C (30 to 180F). The enamels are degraded by
ultraviolet radiation and therefore should be wrapped with
Kraft paper when exposed to sunlight. Coal tar enamels
TABLE 4Typical starting point tests used to
evaluate acceptability of external coatings
Test Type Designation or Method
Abrasion ASTM D4060, Standard Test Method for
Abrasion Resistance of Organic Coatings
by Taber Abraser
ASTM G6, Standard Test Method for
Abrasion Resistance of Pipeline Coatings
Bend ASTM G10, Standard Test Method for
Specific Bendability of Pipeline Coatings
NACE RP0394, Standard Recommended
PracticeApplication, Performance, and
Quality Control of Plant-Applied, Fusion-
Bonded Epoxy External Pipe Coating
Cathodic
Disbonding
ASTM G8, Standard Test Methods for
Cathodic Disbonding of Pipeline Coatings
ASTM G42, Standard Test Method for
Cathodic Disbonding of Pipeline Coatings
Subjected to Elevated Temperatures
ASTM G95, Standard Test Method for
Cathodic Disbondment Test Of Pipeline
Coatings (Attached Cell Method)
Hot Water Soak ASTM D870, Standard Practice for Testing
Water Resistance of Coatings Using Water
Immersion
ASTM G9, Standard Test Method for
Water Penetration into Pipeline Coatings
Impact ASTM G14, Standard Test Method for
Impact Resistance of Pipeline Coatings
(Falling Weight Test)
TABLE 5Coating quality tests and related
methods
Test Type Designation or Method
Abrasion ASTM D4060, Standard Test Method for
Abrasion Resistance of Organic Coatings
by Taber Abraser
ASTM G6, Standard Test Method for
Abrasion Resistance of Pipeline Coatings
Cathodic
Disbonding
ASTM D6676, Standard Test Method for
Cathodic Disbonding of Exterior Pipeline
Coatings at Elevated Temperatures
Using Interior Heating
ASTM G8, Standard Test Methods
for Cathodic Disbonding of Pipeline
Coatings (short time test)
ASTM G80, Standard Test Method for
Specific Cathodic Disbonding of Pipeline
Coatings
Defect ASTM G62, Test Method for Holiday
Determination Detection in Pipeline Coatings
Film Thickness, Total ASTM G12, Standard Test Method for
Nondestructive Measurement Of Film
Thickness of Pipeline Coatings on Steel
Impact ASTM G14, Standard Test Method for
Impact Resistance of Pipeline Coatings
(Falling Weight Test)
Preheat Temp. Standard Temperature Measuring
Devices
Surface Prep. NACE and SSPC Specifications
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790 PAINT AND COATING TESTING MANUAL 15TH EDITION
frequently are reinforced with a fiberglass mat or embed-
ded with a felt mat as a means of protection. The products
do provide for many years of service and were the first com-
monly used external protective coatings.
Coal Tar Mastic
Coal tar mastic is heavily filled with clays, silica, fiberglass,
or similar materials. The resultant material is a highly vis-
cous mass that is cold applied to a thickness of 1.27 to 1.6
cm (1/2 to 5/8 in.). Coal tar mastic can be applied as a hot
extrusion, seamless coating. The material can be applied to
a wide range of pipe diameters for buried pipeline service.
Coal Tar Epoxides
Coal tar epoxides are two-component materials that require
mixing just prior to application. Coal tar plays two impor-
tant roles in this type of coating: (1) cost reduction and
(2) improved water resistance. The two components are
designed to air cure and provide a harder film than neat
coal tar products. Excellent adhesion is provided by the
epoxy component if optimum cure is achieved.
Coal Tar Urethanes
As with coal tar epoxides, coal tar is used primarily as a cost
reducing material. With the coal tar urethanes, the base com-
ponents are polyols and multifunctional isocyanates. The
systems can be spray applied to yield very rapid cure speeds.
This feature reduces out-of-service time for the pipeline.
These coatings have the advantages of lower cost,
excellent water resistance, a wide range of application
techniques, and long proven service lives. They can be plant
applied or over-the-ditch applied. They comprise one of the
largest group of coatings used for repair and maintenance
of existing pipelines.
In general, coal tar products have limitations in protec-
tion when combined with cathodic protection. Temperature
service is limited to 66C (150F).
Fusion Bonded Epoxy Powder Coatings (FBE)
This relatively new technology now is dominant in the
United States new pipe-construction protective-coating
market. Refinements in this technology have taken place
over the past 35 years as it grew in popularity. Drawbacks
to this coating technology are moisture absorption by the
basic epoxy powder and transportation damage due to the
film thickness specifications for this product line [1317].
Specialty products have been formulated within this
coating type. Abrasion resistant products exist for pulling
pipe under roads and rivers. Surface texture products with
improved adhesion of heavy weight cement coatings are
available [18]. In many instances, a combination of two
coats of the powder coating applied dry-on-dry are used
to gain the desired combination of end-use characteristics.
There are three levels of temperature performance prod-
ucts within the FBE product type. The standard FBE is rated
for 66C (150F). A second generation of the coating provides
for resistance to 82C (180F) is available, and a third genera-
tion that is rated for 93C (200F) has been qualified.
Multi-layer Products
The multi-layer or three-coat systems currently dominate
the external pipeline coating market outside the United
States [1921]. The system was designed to take the best
properties of each system and combine them into one prod-
uct. The product normally consists of an epoxy primer fol-
lowed by an adhesive tie-coat and then a polyolefin topcoat.
The epoxy primer provides for excellent adhesion to
the metal surface and gives excellent cathodic disbanding
resistance. The epoxides coating can be either in the form
of a liquid or an FBE powder, but the trend is toward a
powder application and thermal curing. The adhesive tie-
coat is designed to adhere to both the epoxy primer and
the polyolefin topcoat and thus provide the tie between the
coatings. The outer polyolefin topcoat gives excellent resis-
tance to water penetration and mechanical damage during
transportation and installation. Application of the outer
layer is by extruder, which will effectively increases the cost
of the overall system.
Specialty Coatings
By definition, specialty coatings are those that have
been developed and successfully applied to meet specific
needs. They have not generated sufficient business/use to
determine their survival rate or their place in the market.
There are three specialty products with sufficient merit to
mention.
The first of these coatings is a three-layer system based
entirely on powder coating products. The outer layer is
a polyethylene powder that depends on residual heat to
thermally fuse and flow the powder into a continuous film.
This limits the total film thickness that can be applied,
but it meets all of the other characteristics of a multi-layer
product.
The second product uses thermal sprayed aluminum
with a seal coat as the applied product. This system has
been applied to several offshore pipelines. The product has
an estimated life of more than 35 years. This is a totally
different coating system that utilizes sacrificial metals for
protection as opposed to the normal practice of using a
barrier product.
The third specialty system is designed for hot product
lines that operate between 93C (200F) and 149C (300F).
The desire is to provide protection on hot product lines in
areas close to compressor station where elevated surface
temperatures are encountered. The system is based on an
epoxides base coating with a composite inter membrane
and is applied as a multi-layer wrap.
Girth-Weld Products
All pipelines have connections at the welds and at other
components that cannot receive coatings at the plant [8].
They must be protected after the pipe is welded together to
form a pipeline. These are the weakest links in the system.
The coating that is on the body of the pipe may not be the
best choice for field application to the weld areas.
The most popular girth-weld products are based on
two-component epoxy products or heat-shrink sleeves. All
of the products have a corresponding girth-weld material.
Logistics, weather, and cost may prevent them from being
the product of choice for the girth-welds.
References
[1] Veazey, M. V., NTSB Determines Likely Cause of Pipeline Fail-
ure, Materials Performance, Vol. 40, No. 9, 2001, pp. 1821.
[2] Ni, L., and Cheng, Y. F., Development of Innovative Coating
Technology for Pipeline Operation Crossing the Permafrost
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
Downloaded/printed by
Universidad Nacional de Colombia pursuant to License Agreement. No further reproductions authorized.
CHAPTER 64 PIPELINE COATINGS 791
Terrain, Construction and Building Materials, Vol. 22, No. 4,
2008, pp. 417422.
[3] Papavinasam, S., Attard, M., and Winston, R. R., External
Polymeric Pipeline Coating Failure Modes, Materials Perfor-
mance, Vol. 45, No. 10, 2008, pp. 2830.
[4] Yang, X.-H., Zhu, W.-L., Lin, Z., and Huo, J.-J., Aero-
dynamic Evaluation of an Internal Epoxy Coating in a
Natural Gas Pipeline, Prog. Org. Coat., Vol. 54, No. 1, 2005,
pp.7377.
[5] Klechka, E. W., Selecting Liquid Coatings for Pipeline Repair
and Rehabilitation, Materials Performance, Vol. 39, No. 8,
2000, pp. 4657.
[6] Chang, B. T. A., and Mitschke, H. R., Selection of Field
Applied Liquid Rehabilitation Pipeline Coatings, NACE 2000,
Houston, TX, 2000.
[7] Munger, C. G., and Vincent, L. D., Corrosion Protection by
Protective Coatings, NACE 1999, Houston, TX, 1999.
[8] Moosavi, A. N., Advances in Field Joint Coatings for Under-
ground Pipelines, Materials Performance, Vol. 39, No. 8, 2000,
pp. 4045.
[9] Akbarinezhad, E., Neshati, J., and Rezael, F., Investigation
on Organic Pipeline Coating Effectiveness via Electrochemi-
cal Impedance Spectroscopy, Surf. Eng., Vol. 23, No. 5, 2007,
pp. 380384.
[10] Boyd, B. J., and Siegmund, A., Plastic Coated Tubular Goods:
Proper Selection, The Key to Success, NACE International
Corrosion 89, Houston TX, 1989.
[11] Dempster, W. A., III, The Reliability and Economics of Poly-
ethylene Coatings, The Pipeline Reliability Conference, Hous-
ton, TX, Nov. 1996.
[12] Guidetti, G. P., Rigosi, G. L., and Marzola, R., The Use of
Polypropylene in Pipeline Coatings, Prog. Org. Coat., Vol. 27,
No. 1, 1996, pp. 7985.
[13] Kehr, J. A., and Enos, D. G., A Foundation for Pipeline Coat-
ings, NACE Corrosion/00, Houston TX, 2000.
[14] Banach, J., FBE: An End-Users Perspective, NACE TechEdge
ProgramUsing Fusion Bonded Powder Coating in the Pipeline
Industry, Houston, TX, June 1997.
[15] ISO 21809-2:2007, External Coatings for Buried or Sub-
merged Pipelines Used in Pipeline Transportation Systems
Part 2: Fusion Bonded Epoxy Coatings, 2007.
[16] Miller, B., New Predictability of FBE Pipeline Coatings, Pipe-
line Gas J., Vol. 229, No. 2, 2001, pp. 58.
[17] Fore, T., and Varughese, K., First Generation of Fusion
Bonded Pipe Coating Performance After 30 Years of Service
A Case Study, NACE Corrosion 2006, Houston, TX, 2006.
[18] Townend, C. J., Worthington, R. D., and Munro, M., A Com-
parative Review of Some Modern Pipeline Coatings and Expe-
rience Gained Applying a Polyurethane-Tar Coating, Anti
Corros. Methods Mater., Vol. 27, No. 9, 1980, pp. 511.
[19] Nozahic, D., Leiden, L., and Bresser, R., Latest Developments in
Three-Component Polyethylene Coating Systems for Gas Trans-
mission Pipelines, NACE Corrosion /00, Houston, TX, 2000.
[20] Norsworthy, R., Fail Safe Tape System Used in Conjunction
with Cathodic Protection, Materials Performance, Vol. 43, No.
6, 2004, pp. 3441; Norsworthy, R., Is Your Pipeline Coating
Fail Safe?, Pipeline Gas J., Vol. 233, No. 10, 2006, pp. 6264.
[21] Howell, G. R., and Chang, Y. F., Characterization of High
Performance Composite Coating for Northern Pipeline Appli-
cation, Prog. Org. Coat., Vol. 69, No. 2, 2007, pp. 148152.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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792
SEALANTS ARE PRODUCTS INSTALLED INTO AN
opening to prevent the intrusion of air, water, dust, heat,
cold, and other materials such as gases, e.g., radon. The
liquid-applied sealant is installed into the opening by gun
or knife. It is then expected to function even though the
space (joint) it occupies is stressed because of movement of
the joint to which the sealant is applied due to expansion
and/or contraction due to temperature changes, thereby
placing significant strain upon the adhesive forces that
bond the sealant to the substrate to which it is attached.
The sealant is also expected to function regardless of
whether it is applied to a horizontal opening or a vertical
one or whether it is applied to a building facade subject
to rapid expansion and contraction or to a plaza or deck
where it is subject to puncture by spiked heels.
The opening, or gap, into which a liquid-applied seal-
ant is installed is usually called a joint. The sides of the joint
(substrates) may be made of similar or dissimilar materi-
als, generally varying in width from 0.250 to 2.00 in. (0.64
to 5.08 cm) with the depth of the installed sealant usually
about one half the width. When required, sealant backing
(preformed joint fillers) made of materials such as open
or closed cell rubber or polyurethane foam are installed
to control the joint depth. Primers are sometimes used to
improve adhesion of the sealant to the substrate.
Typical building materials that sealants are used with
are glass, steel, concrete, mortar, granite, marble, alumi-
num, various painted or coated surfaces, or wood. When
the sealant is installed into the joint, the surfaces the seal-
ant contacts must be clean, dry, sound, and free of contami-
nants or loose particles to provide an opportunity for the
sealant to perform as intended [1].
Caulks or sealants are fomulated based on oils, latex
polymers, butyl, acrylic and blocked styrene solvent-release
polymers, and polysulfide, polyurethane, and silicone elas-
tomers. The oil-based products exhibit relatively little
movement capability, generally 5 % or less, and thus they
are traditionally installed in relatively static joints. Acrylic
latex polymers can be formulated to possess significant
movement, as much as 25 %, whereas the solvent-release
butyl, acrylic, and blocked styrene sealants can move
about 10 %. The elastomerics exhibit significant move-
ment capability, with silicones moving as much as +100 %,
50%. (+100 % refers to 100 % expansion whereas 50 %
refers to 50 % compression based upon the original dimen-
sions of the installed sealant).
Though this chapter provides an overview and general
description of sealants, test methods, and specifications, it
does not address the suitability of the test methods or speci-
fications discussed nor does it differentiate between cured
short-term performance and actual long-term performance
and effectiveness of sealant products on buildings and/or
other structures [2].
POLYMERS USED IN SEALANTS
Oil-Based Caulks
Oil-based caulks are generally composed of drying oils,
mineral fillers, thixotropes, and driers. The oil oxidizes
and thereby dries slowly, though the caulk usually sets
up to become paintable within a 24 to 48 h period. Oil-
based caulking compounds are easy to apply, easy to
tool, and are available in a range of qualities. Generally,
oil-based caulks exhibit movement of about 5 %. Oil-
based caulking compounds are used primarily by do-it-
yourselfers [3].
Butyl Sealants
Butyl sealants are based on polyisobutylene or polybutene,
fillers such as talc and/or calcium carbonate and additives
such as adhesion promoters, antioxidants, and thixotropes.
Butyl sealants dry by solvent release.
Butyl sealants can be formulated to move at about 7
1
2
to 12
1
2
%. They are widely used in mobile home applica-
tions. In addition, another class of butyl sealants that are
prepared without volatile solvents are extensively used as
the primary seal in dual-sealed insulated glass because of
their very low moisture vapor permeation properties [4].
Acrylic Solvent Release Sealants
These sealants are similar to butyl sealants; however,
they are based on polymethylacrylate polymers (or poly-
ethylacrylate or polybutylacrylate polymers), resulting in
medium-high molecular weight products that, when formu-
lated with colorants, thixotropes, and additives, are used as
sealants [5].
Acrylic solvent-release sealants exhibit movement simi-
lar to butyl sealants, namely up to 12
1
2
%. Acrylic solvent-
release sealants are versatile in that they adhere to a wide
variety of surfaces and, in addition, exhibit excellent
resistance to sunlight. Two prime disadvantages of acrylic
solvent-release sealants are: (1) they often require heating
in the cartridge when applied at lower than room tempera-
tures because their viscosity may become too thick to allow
them to be easily applied and (2) they may emit acrylic
monomer, which is somewhat odiferous and may be toxic
in enclosed areas [6].
65
Sealants
Saul Spindel
1
1
Retired, 64-33 215 Street, Bayside, NY 11364.
MNL17-EB/Jan. 2012
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CHAPTER 65 SEALANTS 793
Block Copolymer Sealant
Elastomeric block copolymer sealants, usually based on
either styrene, styrene-butadiene, or isoprene, are another
class of solvent-release sealants. These polymers exhibit
excellent resistance to ultraviolet light, are effective as clear
sealants, generally adhere to a wide variety of substrates,
and are readily paintable. The sealants can be formulated
to move about 12
1
2
%.
Polyurethane Sealants
Polyurethane sealants are available as either single or
multi-component products. The one-component sealant is
derived from an in situ reaction of an isocyanate with a
hydroxyl component. These components cure by the reac-
tion of the isocyanate (NCO) with atmospheric moisture,
forming a polyurea. The sealants contain fillers, thixo-
tropes, additives, and adhesion promoters.
Two-component polyurethane sealants are usually
based on an isocyanate-terminated polyether reacted with
a hydroxyl-terminated polymer. As with other sealants, two-
component polyurethane sealants are combined with fillers,
adhesion promoters, and other additives and stabilizers.
Polyurethane sealants exhibit good movement capa-
bilities, easily exhibiting 25 % movement. They generally
adhere well to a variety of surfaces and are widely used in
commercial applications, especially where abrasion resis-
tance, i.e., traffic applications, is a prerequisite [7].
Polysulfide Sealants
Polysulfide sealants are sold as both one-component and
two-component materials. Two-component sealants are
formulated with polysulfide polymers, hiding and color
pigments, clays, and mineral thixotropes. The second, or
reactive component, consists of a curing agent (e.g., lead
peroxide), adhesion promoters, fillers, and stabilizers. Both
components are mixed just prior to use [8].
The one-component polysulfide sealants are for-
mulated with ingredients similar to the two-component
material except that the cure chemistry is different. One-
component polysulfides cure by reaction with atmospheric
oxygen and moisture and are generally relatively slow to
attain full cure.
Polysulfide sealants can be formulated to move at
25% and are used on a wide variety of surfaces. Polysul-
fides are used widely in insulated glass applications [9].
Silicone Sealants
Silicone sealants are primarily used as one-component
products usually referred to as RTV (room temperature
vulcanizing) materials. They are polysiloxane prepolymers
that react with atmospheric moisture and ultimately cure to
form an elastomer. Silicone sealants are cured generally by
one of three mechanisms, namely:
1. Acetoxy cureA reaction between methyltriacetoxy
silane with polydimethylsiloxane to form an acetoxy-
terminated polymer intermediate. This material is
then reacted with atmospheric moisture in order to
cure. Acetic acid is liberated during cure, and its odor
can readily be noted.
2. Neutral cureThese sealants are the result of
a reaction between polydimethyl siloxane with
methyltrimethoxysilane to form the intermediate.
This intermediate then reacts with atmospheric
moisture in order to cure. Alcohol is generally liber-
ated during the cure process.
3. Oxime cureIn this cure mechanism, methyl tri-
ethylmethyl ketoxime silane is reacted with ethyl
methyl ketoxime to form an intermediate that cures
when reacted with atmospheric moisture. Cyclohex-
ylamine, a heavy musty-odor material, is released
during cure.
Silicone sealants can be formulated to have a move-
ment capability of as much as 100 % and are used in
many applications, especially where long-term durability is
required. Silicone sealants are the primary sealants used in
structural glazing [10].
Acrylic Latex Sealants
Acrylic latex sealants are essentially formulated from rela-
tively high molecular weight acrylic polymers prepared by
emulsion polymerization in an aqueous media and include
fillers, surfactants, additives, and thixotropes. Acrylic latex
sealants dry by evaporation to form easily applied, highly
weatherable products that exhibit good adhesion.
These acrylic sealants can be formulated to move as
much as 25 %; however, they should not be applied at low
temperatures and are not recommended for use in continu-
ous damp or wet environments [11].
TEST PROCEDURES
The following is a brief summary of the test methods and
procedures used to evaluate sealants. Where appropriate,
reference is made to specific specifications and/or proce-
dures where these tests are covered.
Extrusion Rate
This test is performed to measure the discharge rate of
single and multi-component sealants (ASTM C603). Single-
component sealants are extruded through a cartridge of
known volume and predetermined orifice at 50 psi air pres-
sure. The time to empty the cartridge is recorded. Multi-
component systems are mixed and allowed to stand for 3h
before being extruded in order to develop information on
their application properties after mixing.
Rheological Properties (Flow and Sag)
This test is employed to determine the horizontal or vertical
flow properties of the sealant under conditions of extreme
variations in temperature (ASTM C661). Stainless steel
channels, open ended for testing vertical (non sag) sealants
and close ended for testing horizontal (self leveling or pour-
able) sealants, are filled with the sealant and exposed at an
elevated temperature (122F, 50C), and at a low tempera-
ture (40F, 4.4C). Sag (vertical displacement) is measured,
and horizontal deformation is noted.
Hardness
This test is used to measure the indentation hardness of a
cured sealant using a Shore A Durometer (ASTM C661). If a
sealant is too hard, it may be indicative of future problems
that can result in a loss of resiliency, thereby resulting in
either cohesive breaks or adhesive loss.
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794 PAINT AND COATING TESTING MANUAL 15TH EDITION
Effects of Heat Aging After Cure
Exposure to the atmosphere may cause loss of volatile
components after cure, resulting in shrinkage, hardening,
or cracking, which may affect the durability of the sealant.
This test can be used to predict premature failure (ASTM
C792). Sealant specimens are cured for 7 days at standard
conditions, then heat aged for 21 days at 158F (70C) and
evaluated for volatility (weight loss), cracking, and hard-
ness [12].
Tack-Free Time
This is the time required for the surface of a sealant to
attain a tack-free state (ASTM C679). This time may be
indicative of the time interval required for the sealant to
resist damage from light surface contact, job-site or air-
borne dirt pickup, or impinging rainfall.
Staining of Porous Substrates
This test method is useful to determine possible staining by
the sealant on porous substrates (ASTM C1248). The sealant
is applied to standard-size joint specimens made of porous
materials such as white marble or granite. The specimens
are compressed and clamped and then stored for 28 days
at various conditions including room temperature, elevated
temperature, and ultraviolet-fluorescent weathering. Upon
completion of the exposures, the specimens are evaluated
for changes in surface appearance and depth of any stain.
Adhesion and Cohesion Under Cyclic Movement
(Durability)
The primary intent of an elastomeric sealant is to fill joints
in buildings and other structures and thereby render them
impervious to the elements. These joints are considered
active, meaning that they will expand and contract with
temperature change and building movement.
This test method is designed to evaluate the ability of
the sealant to withstand expansion and contraction with
temperature change and not develop any loss of adhesion
to the substrate or any cohesive cracks (ASTM C719). When
adhesion loss to the substrate or cohesive cracks within the
sealant develop, water can penetrate, thereby resulting in
damage to the structure.
Joints are prepared using two similar substrates. The
sealant is extruded between the joints (substrates), cured,
and then immersed in water for seven days. The specimens
are then hand flexed and evaluated for adhesion loss. If no
adhesion loss is noted, the specimens are compressed and
subjected to elevated temperature (158F, 70C) for 7 days
to determine whether any heat set or deformation occurs.
These test joints are then subjected to 10 cycles of exten-
sion at room temperature and examined for loss of adhe-
sion or cohesive breaks in the extended state. If there is no
loss of adhesion or cohesive break, the test joints are then
cycled for 10 cycles of compression at elevated temperature
(158F, 70C) and expansion at low temperature (15F,
26C) to simulate joint movement during extreme tem-
perature changes. (Buildings contract when cold, thereby
opening up or expanding the joints. On the other hand,
buildings expand when hot, thereby closing or compressing
the joints.) Upon completion of this cycling, the specimens
are examined for the presence of any adhesive bond loss or
cohesive breaks.
Adhesion-in-Peel
This test is used to evaluate the adhesive characteristics of
a sealant and its ability to maintain a bond to a substrate
(ASTM C794). The sealant is applied to the substrate, cured,
and immersed in water for 7 days. After the immersion
period, the 180 peel strength of the sealant is measured
and the amount of adhesive loss to the substrate is deter-
mined. An additional set of specimens is prepared on a
glass substrate, exposed to UV radiation to simulate sun-
light, and then evaluated for the effect of the actinic radia-
tion on the interface of the sealant-to-glass bond by once
again measuring peel strength and adhesion properties of
the sealant.
Effects of Accelerated Weathering
This procedure is used to evaluate the effects of exposure to
ultraviolet radiation and water spray to simulate weather-
ing on the sealant (ASTM C793). After exposure, the sealant
is evaluated for surface cracking. After 24 h cold exposure
specimens are then bent over a 0.5 in. (1.27 cm) diameter
rod under cold (15F, 26C) temperature to evaluate low-
temperature flexibility and brittleness.
The following section lists specifications and standards
for sealants, as well as their sources.
SEALANT SPECIFICATIONS
Federal Specifications
TT-S-00227E Sealing Compound Elastomeric Type, Multi-
component (For Caulking, Sealing, and
Glazing Building and Other Structures)
TT-S-00230C Sealing Compound Elastomeric Type, Single
Component (For Caulking, Sealing and
Glazing Building and Other Structures)
TT-S-01543A Sealing Compound, Silicone Rubber Base
(For Caulking, Sealing, and Glazing in
Buildings and Other Structures)
TT-C-598B Caulking Compound, Oil, and Resin Base
Type (For Masonry and Other Structures)
TT-S-001657 Sealing Compound, Single Component-
Butyl Rubber Based, Solvent Release
Type (For Buildings and Other Types of
Construction)
OTHER SEALANT STANDARDS
Insulating Glass
ASTM E774 Standard Specification for the Classification of
the Durability Sealed Insulating Glass Units.
Highway/Bridges
SS-S-200E Sealing Compounds, Two Component,
Elastomeric, Polymer Type, Jet Fuel
Resistant, Cold Applied.
(American Association of State Highway and Transporta-
tion Officials [AASHTO]).
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CHAPTER 65 SEALANTS 795
LIST OF ASTM STANDARDS
C509 Standard Specification for Elastomeric Cellular
Preformed Gasket and Sealing Material
C510 Standard Test Method for Staining and Color Change
of Single- or Multi-Component Joint Sealants
C542 Standard Specification for Lock-Strip Gaskets
C603 Standard Test Method for Extrusion Rate and
Application Life of Elastomeric Sealants
C639 Standard Test Method for Rheological (Flow)
Properties of Elastomeric Sealants
C661 Standard Test Method for Indentation Hardness of
Elastomeric-Type Sealants by Means of a Durometer
C679 Standard Test Method for Tack-Free Time of
Elastomeric Sealants
C681 Standard Test Method for Volatility of Oil- and Resin-
Based, Knife-Grade, Channel Glazing Compounds
C711 Standard Test Method for Low-Temperature Flexibility
and Tenacity of One-Part, Elastomeric, Solvent-
Release Type Sealants
C712 Standard Test Method for Bubbling of One-Part,
Elastomeric Solvent-Release Type Sealants
C716 Standard Specification for Installing Lock Strip
Gaskets and Infill Glazing Materials
C717 Standard Terminology of Building Seals and Sealants
C719 Standard Test Method for Adhesion and Cohesion of
Elastomeric Joint Sealants Under Cyclic Movement
(Hockman Cycle)
C731 Standard Test Method for Extrudability, After Package
Aging, of Latex Sealants
C732 Standard Test Method for Aging Effects of Artificial
Weathering on Latex Sealants
C734 Standard Test Method for Low-Temperature Flexibility
of Latex Sealants After Artificial Weathering
C736 Standard Test Method for Extension-Recovery and
Adhesion of Latex Sealants
C765 Standard Test Method for Low-Temperature Flexibility
of Preformed Tape Sealants
C771 Standard Test Method for Weight Loss After Heat
Aging of Preformed Sealing Tapes
C772 Standard Test Method for Oil Migration or Plasticizer
Bleed-Out of Preformed Tape Sealants
C782 Standard Test Method for Softness of Preformed Tape
Sealants
C792 Standard Test Method for Effects of Heat Aging of
Weight Loss, Cracking, and Chalking of Elastomeric
Sealants
C793 Standard Test Method for Effects of Laboratory
Accelerated Weathering on Elastomeric Joint Sealants
C794 Standard Test Method for Adhesion-in-Peel of
Elastomeric Joint Sealants
C834 Standard Specification for Latex Sealants
C864 Standard Specification for Dense Elastomeric
Compression Seal Gaskets, Setting Blocks and Spacers
C879 Standard Test Methods for Release Papers Used with
Preformed Tape Sealants
C907 Standard Test Method for Tensile Adhesive Strength
of Preformed Tape Sealants by Disk Method
C908 Standard Test Method for Yield Strength of
Performed Tape Sealants
C910 Standard Test Method for Bond and Cohesion of
One-Part Elastomeric Solvent Release-Type Sealants
C919 Standard Practice for Use of Sealants in Acoustical
Applications
C920 Standard Specification for Elastomeric Joint Sealants
C961 Standard Test Method for Lap Shear Strength of
Sealants
C963 Standard Specifications for Packing, Identification,
Shipment and Storage of Lock-Strip Gaskets
C964 Standard Guide for Lock-Strip Gasket Glazing
C972 Standard Test Method for Compression-Recovery of
Tape Sealant
C1016 Standard Test Method for Determination of Water
Absorption by Sealant Backing (Joint Filler) Material
C1021 Standard Practice for Laboratories Engaged in Testing
of Building Sealants
C1083 Standard Test Method for Water Absorption of
Cellular Elastomeric Gaskets and Sealing Materials
C1087 Standard Test Method for Determining Compatibility
of Liquid-Applied Sealants with Accessories Used in
Structural Glazing Systems
C1115 Standard Specification for Dense Elastomeric Silicone
Rubber Gaskets and Accessories
C1135 Standard Test Method for Determining Tensile
Adhesion Properties of Structural Sealants
C1166 Standard Test Method for Flame Propogation
of Dense and Cellular Elastomeric Gaskets and
Accessories
C1183 Standard Test Method for Extrusion Rate of
Elastomeric Sealants
C1184 Standard Specification for Structural Silicone Sealants
C1193 Standard Guide for Use of Joint Sealants
C1216 Standard Test Method for Adhesion and Cohesion of
One-Part Elastomeric Solvent Release Sealants
C1241 Standard Test Method for Volume Shrinkage of Latex
Sealants During Cure
C1246 Standard Test Method for Effects of Heat Aging on
Weight Loss, Cracking, and Chalking of Elastomeric
Sealants after Cure
C1247 Standard Test Method for Durability of Sealants
Exposed to Continuous Immersion in Liquids
C1248 Standard Test Method for Staining of Porous
Substrates by Joint Sealants
C1249 Standard Guide for Secondary Seal for Sealed Insulating
Glass Units for Structural Sealant Glazing Applications
C1253 Standard Test Method for Determining the
Outgassing Potential of Sealant Backing
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796 PAINT AND COATING TESTING MANUAL 15TH EDITION
C1257 Standard Test Method for Accelerated Weathering of
Solvent-Release Type Sealants
C1265 Standard Test Method for Determining Tensile
Properties of an Insulating Glass Edge Seal for
Structural Glazing Applications
C1266 Standard Test Method for Flow Characteristics of
Preformed Tape Sealants
C1281 Standard Test Method for Preformed Tape Sealants
for Glazing Applications
C1294 Standard Specification for Compatibility of Insulating
Glass Edge Sealants with Liquid-Applied Glazing
Materials
C1299 Standard Guide for Use in Selection of Liquid-Applied
Sealants
C1311 Standard Specification for Solvent Release Sealants
C1330 Standard Specification for Cylindrical Sealant Backing
for Use with Cold Liquid Applied Sealants
C1367 Standard Test Method for Dead Load Resistance of a
Sealant in Elevated Temperatures
C1369 Standard Specification for Secondary Edge Sealants
for Structurally Glazed Insulating Glass Units
C1375 Standard Guide for Substrates Used in Testing
Building Seals and Sealants
C1382 Standard Test Method for Determining Tensile
Adhesion Properties of Sealants When Used in
Exterior Insulation and Finish Systems (EIFS) Joints
C1392 Standard Guide for Evaluation Failure of Structural
Sealant Glazing
C1394 Standard Guide for In-Situ Structural Silicone Glazing
Evaluation
C1401 Standard Guide for Structural Sealant Glazing
C1442 Standard Practice for Conducting Tests on Sealants
Using Artificial Weathering Apparatus
C1472 Standard Guide for Calculating Movement and Other
Effects When Establishing Sealant Joint Width
C1481 Standard Guide for Use of Joint Sealants with Exterior
Insulation and Finish Systems (EIFS)
C1487 Standard Guide for Remedying Structural Silicone
Glazing
C1501 Standard Test Method for Color Stability of Building
Construction Sealants as Determined by Laboratory
Accelerated Weathering Procedures
C1518 Standard Specification for Precured Elastomeric
Silicone Joint Sealants
C1519 Standard Test Method for Evaluating Durability
of Building Construction Sealants by Laboratory
Accelerated Weathering Procedures
C1520 Standard Guide for Paintability of Latex Sealants
C1521 Standard Practice for Evaluating Adhesion of Installed
Weatherproofing Sealant Joints
C1523 Standard Test Method for Determining Modulus,
Tear and Adhesion Properties of Precured Elastomeric
Joint Sealants
C1536 Standard Test Method for Measuring the Yield for
Aerosol Foam Sealants
C1564 Standard Guide for Use of Silicone Sealants for
Protective Glazing Systems
C1589 Standard Practice for Outdoor Weathering of
Construction Seals and Sealants
C1620 Standard Specification for Aerosol Polyurethane and
Aerosol Latex Foam Sealants
C1635 Standard Test Method to Evaluate Adhesion/Cohesion
Properties of a Sealant at Fixed Extension
C1642 Standard Practice for Determining Air Leakage Rates
of Aerosol Foam Sealants and Other Construction
Joint Fill and Insulation Materials
C1643 Standard Test Method for Measuring the Post
Dispensing Volumetric Expansion of Aerosol Foam
Sealants
C1681 Standard Test Method for Evaluating the
TearResistance of a Sealant Under Constant Strain
C1737 Standard Guide for Evaluating Temperature Effects
to Aerosol Foam Sealants During and After
Dispensing
D2202 Standard Test Method for Slump of Sealants
D2203 Standard Test Method for Staining from Sealants
D2377 Standard Test Method for Tack-Free Time of Caulking
Compounds and Sealants
D2452 Standard Test Method for Extrudability of Oil- and
Resin-Base Caulking Compounds
D2453 Standard Test Method for Shrinkage and Tenacity of
Oil- and Resin-Base Caulking Compounds
E2203 Standard Specification for Dense Thermoplastic
Elastomers Used for Compression Seals, Gaskets,
Setting Blocks, Spacers and Accessories
CANADIAN STANDARDS
19-GP 5M Sealing Compound, One Component, Acrylic
Base, Solvent Curing
CAN/GSB-19.13-M87 Sealing Compound, One-Component,
Elastomeric, Chemical Curing
19-GP-14M Sealing Compound, One Component, Butyl-
Polyisobutylene Polymer Base, Solvent Curing
CAN/CGSB-19.17-M90 One-Component Acrylic Emulsion
Base Sealing Compound
CAN/CGSB-19.24-M90 Multicomponent Chemical-Curing
Sealing Compound
AAMA STANDARDS
800-05
Voluntary Specifications and Test Methods for
Sealants
Back Bedding Compounds
Back Bedding Mastic Tapes
Glazing Tapes
Narrow Joint Seam Sealers
Exterior Perimeter Sealing Compounds
Non-Drying Sealants
Expanded Cellular Glazing
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CHAPTER 65 SEALANTS 797
INTERNATIONAL STANDARDS ORGANIZATION
(ISO) STANDARDS
The following standards are under the jurisdiction of Sub-
committee 8 on Jointing Products, Technical Committee
59-Building Construction:
ISO 6927 Building, ConstructionJointing Products
SealantsVocabulary
ISO 7389 Building ConstructionJointing Products
Determination of Elastic Recovery
ISO 7390 Building ConstructionJointing Products
Determination of Resistance to Flow
ISO 8339 Building Construction-Jointing Products
Sealants Determination of Tensile Properties
ISO 8340 Building Construction-Jointing Products
Sealants Determination of Tensile Properties at
Maintained Extension
ISO 8394 Building ConstructionJointing Products
Determination of Extrudability of One-
Component Sealants
ISO 9046 Building ConstructionSealants Determination
of Adhesion/Cohesion Properties at Constant
Temperatures
ISO 9047 Building ConstructionJointing Products
Sealants Determination of Adhesion/Cohesion
Properties at Variable Temperatures
ISO 9048 Building ConstructionJointing Products
Sealants Determination of Extrudability
ofSealants Using Standardized Apparatus
ISO 10563 Building ConstructionSealants
Determination of Change in Mass and
Volume
ISO 10590 Building ConstructionSealants
Determination of Adhesion/Cohesion Properties
at Maintained Extension After Immersion in
Water
ISO 10591 Building ConstructionSealants Determination
of Adhesion/Cohesion Properties After
Immersion in Water
ISO 11431 Building ConstructionSealants
Determination of Adhesion/Cohesion
Properties After Exposure To Artificial Light
Thru Glass
ISO 11432 Building ConstructionSealants
Determination of Resistance to Compression
ISO 11600 Building ConstructionSealantsClassification
and Requirements
ISO 11368 Building ConstructionSealants
Determination of Resistance to Prolonged
Exposure to Water
ISO 13640 Building ConstructionJointing Products
Specifications For Test Substrates
ISO 16938-1 Building ConstructionJointing Products
SealantsDetermination of Staining of
Porous SubstratesPart 1: Test With
Compression
ISO 16938-2 Building ConstructionJointing Products
Sealants Determination of Staining of
PorousSubstratesPart 2: Test Without
Compression
SOURCES OF SPECIFICATIONS
ASTM Standards
ASTM International
100 Barr-Harbor Drive
PO Box C700
West Conshokocken, PA 19428-2959
(610) 832-9500
AASHTO Specifications
The American Association of State Highway
And Transportation Officials
444 North Capitol Street, NW, Suite 225
Washington, DC 20001
(202) 624-5800
Federal Specifications
Business Service Center
General Services Administration
7th and D Streets, SW
Washington, DC 20407
Contact regional offices
Military Specifications
Commanding Officer
U.S. Naval Supply Depot
5801 Tabor Avenue
Philadelphia, PA 19120
(215) 697-2000
ANSI Specifications
(Also International Standards Documents)
American National Standards Institute, Inc.
1430 Broadway
New York, NY 10018
(212) 354-3300
US Army Corps of Engineers
Chief Specification Section
Box 60
Vicksburg, MS 39180
(601) 633-2531
Canadian Standards
CGSB
Canadian General Standards Board
Gatineau
Canada K1A1G6
(819) 956-0425
American Architectural Manufacturers
Association (AAMA)
1827 Walden Office Square, Ste 550
Chaumberg, IL 60173
(847) 303-5859
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798 PAINT AND COATING TESTING MANUAL 15TH EDITION
References
[1] Klosowski, J. S., Sealants in Construction, Marcel Dekker Inc.,
NY, 1989.
[2] Panek, J., and Cook, J., Construction Sealants and Adhesives,
John Wiley & Sons, NY, 1991.
[3] Chu, S. G., Sealants Based on Block Copolymers, Adhesives
and Sealants Short Course, Hercules, Inc., 1989.
[4] Lomax, J. R. and Haas Co., Acrylic Polymer Caulks and Seal-
ants, Adhesives and Sealants Short Course, 1989.
[5] Klosowski, J. S., Sealant Materials, Engineered Materials
Handbook, 1990.
[6] Sealants: The Professional Guide, Sealant, Waterproofing
and and Restoration Institute, 1990.
[7] Sherwin, M., High Performance Acrylic Latex Sealants,
Union Carbide Chemicals and Plastics Company, Adhesives
and Sealants Short Course, 1989.
[8] Shah, A., Selecting Appropriate Caulks and Sealants, Ameri-
can Painting Contractor, Vol. 68, No. 8, 1991, pp. 2234.
[9] Shah, A., Choosing a Construction Sealant, Adhesives Age,
Vol. 33, No. 5, 1990, pp. 1416.
[10] Newton, M. V., Halbe, S. D., and Krysiak, G. D., Butyl Seal-
antsFormulating, Developing, Processing, Protective Treat-
ments, Inc., Adhesives and Sealants Short Course, 1989.
[11] Prane, J. W., Sealants and Caulks, Federation monograph,
Federation of Societies for Coatings Technology, 1989.
[12] Elias, M., Redman, R., and Prane, J. W., Sealants and
Caulks, Chap. 37 of Handbook of Adhesives, 3rd ed., I. Skeist,
Ed., Van Nostrand Reinhold, New York, 1989.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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799
66
PAVEMENT MARKINGS GO RELATIVELY UNNOTICED
by most people but affect almost everyone every day. They
are used not only on city streets, highways, and interstates
but also at airports, parking lots, and many commercial
and industrial sites. A variety of materials are used for these
applications. Some have specific uses, but all must adhere
to the surface on which they are applied, show resistance
to abrasion and weathering, and perform adequately over
their expected life-times [1].
The following discussion will focus on the different
types of marking materials being used and the testing of
these materials for acceptability.
TYPES OF PAVEMENT MARKING MATERIALS
There are three general materials used for pavement mark-
ings. These include liquid coatings, thermoplastics, and
tapes. All pavement markings fall into one of these general
categories and cover a range of thickness from 8150 mils.
Glass beads or other reflective materials are used with each
of these pavement marking materials to provide for night
visibility.
Liquid Coatings
SOLVENT-BORNE MARKING
This was the standard material in use for traffic marking
for decades. These one-component materials are usually
alkyds or chlorinated rubbers that dry by the evaporation
of their solvents, followed by oxidation of their binders.
They are usually applied hot and under pressure with con-
ventional spray equipment to achieve fast-drying markings.
The advantages of using solvent-borne coatings are the vast
body of knowledge and experience with these materials
they can be applied over a wide range of environmental
conditions and have a low cost. The major disadvantages
are the need for frequent applications, especially in high-
traffic areas, the release of large quantities of solvent to the
atmosphere during drying, and the need for solvent to clean
equipment. These solvents contribute to air pollution and
become hazardous waste when used to clean equipment.
WATER-BORNE MARKING
Water-borne markings are composed of high molecular
weight acrylics and styrene-acrylic latex binders that allow
them to be successfully applied on concrete and asphalt
surfaces and over several other older markings [2]. Water-
borne materials are also one component and must be
applied under more stringent environmental conditions
than solvent-borne materials. For example, low air and
surface temperatures and high relative humidity, lengthen
the film formation and dry time of the coating. In addi-
tion, due to their corrosive nature, water-borne materials
should be handled in stainless steel equipment. However,
even with these application requirements, the reduction
in solvent emission and associated hazardous waste has
enabled these materials to be the choice of many pavement
marking entities.
These materials are used in a variety of wet thicknesses
from 15 mils for standard lines to 30 mils for High Build
lines depending on their chemical compositions.
EPOXY
This is a two-component, very durable, high-quality pave-
ment marking material. The two components (pigmented
resin and hardener) are stored separately and mixed at the
time of application. A variety of cure times can be achieved
through formulation adjustments. Close attention must be
paid to the mix ratio of the components to obtain optimum
performance and durability. Due to their durability, epoxies
are used in higher traffic areas where repeated application
of coatings would be disruptive to traffic. One disadvantage
of epoxies is the loss of color retention due to degradation
from ultraviolet (UV) sunlight exposure.
POLYESTER
Polyester is a two-component system used mainly on Port-
land cement concrete surfaces since proper adhesion is
a concern on asphalt concrete surfaces. This coating is a
durable, high-quality material that has a useful life of three
years or more. Polyester is also very durable and is useful in
high traffic areas. Adjusting mix ratios of resin and catalyst
gives appropriate cure times. Some disadvantages include
monomer emission, hazardous waste generated from sol-
vents used in equipment clean up.
POLYUREA, URETHANES, METHYL METHACRYLATE
These two-component materials are composed of pig-
mented resins and a hardener. While similar to epoxies,
these products are more durable and may contain color
or UV stabilizers. These products are relatively new to the
pavement marking industry and show good potential.
Thermoplastic
Thermoplastic (also known as hot melt) pavement mark-
ings are another durable, high-quality, single-component
marking material. They are composed of a mixture of either
maleic-modified glycerol resin esters or hydrocarbon resins
with plasticizers, pigments, and glass beads. The material is
normally melted between 400425F and is either sprayed
Pavement Marking Materials
James R. Swisher
1
1
VDOT Materials Division, 1401 E. Broad St., Richmond, VA 23219.
MNL17-EB/Jan. 2012
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800 PAINT AND COATING TESTING MANUAL 15TH EDITION
or extruded on the road to form a durable material of
thickness from 90125 mils [3]. During the melting process
constant stirring of the thermoplastic is very important for
the following reasons:
1. To prevent localized burning.
2. To prevent potential color changes in the pigments.
3. To keep the intermixed glass beads suspended.
Thermoplastic may be applied to hydraulic concrete
cement or asphalt concrete cement. Thermoplastic per-
forms best when applied on asphalt concrete cement due
to thermal bonding. If thermoplastic is being applied to
hydraulic concrete cement a primer/sealer is normally
required for proper adhesion and durability. Application
thicknesses for new stripes are usually 90125 mils, while
re-stripe thicknesses are 3060 mils.
Traditional yellow, lead chromate pigments are being
replaced with organic yellow pigments that require care-
ful formulation to ensure color continuity in both day and
night-time environments.
Thermoplastic is also used as a preformed (pre-shaped)
material for arrows, stop bars, pavement signs and text
markings. The preformed markings are melted to the road
surface using heating torches.
Pavement Marking Tapes
Pavement marking tapes can be used as a durable, long-life
marking material or as a removable or temporary mark-
ing in construction areas. All tapes are composed of three
layers: an adhesive layer, a backing material usually made
of plastic or aluminum foil, and a pigment and glass bead
layer. Application of these tapes will vary between manu-
facturers with primers being used for some tapes. While
most tapes are installed with a weighted roller, some tapes
are pressed (inlaid) into the hot asphalt. This inlay method
produces a recessed tape that is less susceptible to abrasion
from traffic and snowplow blades.
PERMANENT TAPES
These tapes can be divided into plastic-backed and foil-
backed tapes. Plastic-backed tapes are 6090 mils thick and
are used as stop bars, crosswalks, arrows, long lines, and
skip lines. These tapes may be flat or profiled. Foil-backed
tapes are greater than 20 mils in thickness and are used in
areas that are free of curves, turns, or stops.
TEMPORARY/REMOVABLE TAPE
This tape is used on construction sites or projects that
require the tape to be removed or paved over. To facilitate
removal, a plastic mesh or similar material may be added
between the adhesive layer and the backing material of the
tape. Film thicknesses are from 2530 mils.
Glass Beads (Retroreflective Optics)
Glass beads are used with pavement markings to increase
night visibility. Without the beads, most markings would
be invisible at night. Fig. 1 gives an excellent explanation
of how glass beads improve visibility. Glass beads must be
round to work. Irregular or broken beads will not retrore-
flect light efficiently back to the driver. Beads vary in refrac-
tive index (RI) from 1.50 to 1.90. The 1.50 RI beads are
most commonly used for highways, while the 1.90 RI beads
are more efficient in light return and found on airport run-
ways or in markings that are visible when wet.
Glass beads also come in a variety of sizes with a spe-
cific size distribution usually being specified. Glass beads
are applied to the binder material at the time of application
to the road surface. This is usually done by a pressurized
spray nozzle so that many of the beads (about 70 %) are ini-
tially buried in the marking material. The quantity of beads
added to a line will vary with the marking material from
6-25 lb./gal. Some marking materials like thermoplastics
have intermixed glass beads in addition to surface-applied
beads. Other productspavement marking tapeshave the
glass beads pre-applied at the time of fabrication. Some
pavement markings require the application of two separate
bead sizes with two separate bead guns. This double-drop
system is known to improve the visibility of the pavement
marking. Other retroreflective optics such as ceramics and
bead clusters are also being used to enhance night-time vis-
ibility in both dry and wet (rain) environments.
MATERIAL TESTING
Pavement marking materials are tested for conformance to
specification in the laboratory and for performance in field
evaluations.
Laboratory Testing
LIQUID TRAFFIC MARKINGS
Many of the tests performed on liquid marking materials
are standard coating tests and are referenced where appli-
cable.
Liquid Properties
1. SkinningPaints that contain binders that dry by
oxidation can form skins in a partially filled container.
Fig. 1How do glass spheres work? (from Potters Safety
Marking Spheres, Potters Industries Inc.)
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CHAPTER 66 PAVEMENT MARKING MATERIALS 801
These must be removed before use. This test can be
performed in accordance with ASTM D154, Guide for
Testing Varnishes and ASTM D2805, Standard Test
Method for Hiding Power of Paints by Reflectometry,
for Water-Bornes.
2. Fineness of DispersionCommonly called fineness
of grind, this test is not generally specified for traffic
marking except in the case of some application equip-
ment [4]. The test is performed in accordance with
ASTM D1210, Test Method for Fineness of Dispersion
of Pigment-Vehicle Systems by Hegman-Type Gage.
3. Density or Weight/GallonThe density is determined
for unbeaded paint by using ASTM D1475, Test Method
for Density of Liquid Coatings, Inks, and Related
Products.
4. ConsistencyDetermine the consistency using a pad-
dle type viscometer in accordance with ASTM D562,
Test Method for Consistency of Paints Measuring Kreb
Unit Viscosity Using a Stormer-Type Viscometer.
5. StabilityTraffic paints should remain stable in the
container for at least six months. Heat-age stability
and freeze-thaw stability are often required and can be
checked by heating and cooling a specimen through
several cycles. Use ASTM D1849, Test Method for
Package Stability of Paint, for heat-age stability and
ASTM D2243, Test Method for Freeze-Thaw Resistance
of Water-Borne Coatings, for freeze thaw stability of
water-borne paints. Use ASTM D1309, Test Method for
Setting Properties of Traffic Paints During Storage, for
the accelerated test and ASTM D869, Test Method for
Evaluating Degree of Setting of Paint, for aged paints.
6. Chemical AnalysisIdentification and quantification
of traffic paint components can be made by several
means. Infrared spectroscopy can be used for resin
identification. Use ASTM D2621, Test Method for
Infrared Identification of Vehicle Solids from Solvent-
Reducible Paints, to aid identification of solvent reduc-
ible resins. Oils and oil acids can be identified by gas
chromatography. ASTM D2245, Test Method for Iden-
tification of Oils and Oil Acids in Solvent-Reducible
Paints. White titanium pigment concentration can be
determined using either the Jones Reduction method
or the Aluminum Reduction method found in ASTM
D1394, Test Methods for Chemical Analysis of White
Titanium Pigments. Chrome yellow may be quanti-
fied using atomic absorption spectroscopy or by wet
chemical methods using ASTM D126, Test Methods for
Analysis of Yellow, Orange, and Green Pigments Con-
taining Lead Chromate and Chromium Oxide Green.
X-ray fluorescence (XRF) can be readily used to quan-
tify lead chromate and titanium dioxide content. While
expensive initially, XRF is generally much quicker than
wet methods. Many epoxy traffic markings specify an
epoxy content. Use ASTM D1652, Test Methods for
Epoxy Content of Epoxy Resins, for this determina-
tion. The amine value is also specified on many epoxy
traffic markings. Use ASTM D2074, Test Methods for
Total, Primary, Secondary, and Tertiary Amine Values
of Fatty Amines by Alternative Indicator Method for
this determination.
7. Pigment ContentASTM D2371, Test Method for
Pigment Content of Solvent-Reducible Paints, is used
for solvent reducible coatings and ASTM D3723, Test
Method for Pigment Content of Water Emulsion Paints
by Low-Temperature Ashing is used for water emulsion
paints. ASTM D4451, Test Method for Pigment Content
of Paint by Low Temperature Ashing (450C), is a low-
temperature ashing method useful for all coatings that
do not contain organic pigments.
8. Non-Volatile ContentSometimes referred to as
total solids, use ASTM D2369, Test Methods for Vola-
tile Content of Coatings to determine the non-volatile
content of the paint.
9. Volatile Organic Contentcan be determined using
ASTM D2369, Test Method for Volatile Content of
Coatings
10. Total Volume Solidscan be determined using ASTM
D2697, Test Method for Volume Nonvolatile Matter in
Clear or Pigmented Coatings.
11. Lead Contentcan be determined using ASTM
D3335, Test Method for Low Concentrations of Lead,
Cadmium, and Cobalt in Paint by Atomic Absorption
Spectroscopy.
Appearance and Physical Properties
1. No-Pick-Up TimeA quality control test that is useful
in the laboratory uses a steel cylinder fitted with two
replaceable O-rings that is rolled down a ramp over a
test stripe as shown in Fig. 2. This is a control test and
shows little correlation with field applications. The
no-pick-up time can be determined using ASTM D711,
Test Method for No-Pick-Up Time of Traffic Paint.
2. Dry-Through Dry TimeThis test is conducted at
50% and 90 % relative humidity.
3. Scrub ResistanceThis is a wet abrasion test often
specified using ASTM D2486, Standard Test Methods
for Scrub Resistance of Wall Paints.
4. FlexibilityThis test evaluates the sample after being
bent 180 over a 1/2 in. mandrel per ASTM D522, Stan-
dard Test Methods for Mandrel Bend Test of Attached
Organic Coatings.
5. Water Wash-OffThis is a new test issued in 2008
as ASTM D7377, Standard Practice for Evaluating the
Water Wash-Off Resistance of Traffic Paints Using a
Water Faucet.
6. BleedingThis test measures the amount of material
that passes from an asphalt pavement through the traf-
fic marking material. An arbitrary scale of photograph-
ic standards are used, where 10 shows no bleeding and
Fig. 2ASTM D711 equipment.
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802 PAINT AND COATING TESTING MANUAL 15TH EDITION
2 shows considerable bleeding. Use ASTM D868, Test
Method for Determination of Degree of Bleeding of
Traffic Paint, contains the photographic standards.
7. Hiding PowerHiding power (or dry opacity) is
the measure of the ability of the coating to hide the
substrate. Use ASTM D2805, Test Method for Hiding
Power of Paints by Reflectometry.
8. ColorThe color of traffic markings are usually com-
pared to a specified standard. Color differences can be
determined visually between the product and a stan-
dard. This comparison is fast and acceptable although
numerical values are not obtained. The advantage of
using color difference instruments are that they pro-
vide numerical values that can be compared to future
measurements. Visual color comparison can be made
in accordance with ASTM D1729, Practice for Visual
Appraisal of Colors and Color Differences of Diffusely-
Illuminated Opaque Materials.
To determine the color in terms of tristimulus
values or chromaticity coordinates, use ASTM E308,
Practice for Computing the Colors of Objects by Using
the CIE Systems. Color difference measurements are
instrumentally obtained by following ASTM D2244,
Practice for Calculation of Color Tolerances and
Color Differences from Instrumentally Measured
Color Coordinates. To determine the day and night-
time colors of pavement markings use ASTM D6628,
Standard Specification for Color of Pavement Mark-
ing Materials.
9. Reflectance and RetroreflectanceReflectance is
the measure of light reflected from the surface of a
material. Many pavement markings are visible during
daytime illumination due to their reflectance of light
or Luminous Reflectance Factor (Y). This reflectance
of light makes the pavement marking material appear
lighter than the pavement. To measure the Luminous
Reflectance Factor (Y), the beadless sample is gener-
ally illuminated at a 45 angle and measured at a 0
angle using the standard CIE illuminant D65. Deter-
mine the Luminance Reflectance Factor in accordance
with ASTM E1347, Standard Test Method for Color
and Color-Difference Measurement by Tristimulus
Colorimetry.
Retroreflectance is a measure of light reflected
back close to the light source. In practice, it simu-
lates the car headlights reflecting off of the pavement
marking back to the driver. In the laboratory, retro-
reflectance can be measured on a beaded sample in
accordance with ASTM D4061, Test Method for Ret-
roreflectance of Horizontal Coatings. Portable retro-
reflectometers are used to test pavement markings in
field evaluations in accordance with ASTM E1710, Test
Method for Measurement of Retroreflective Pavement
Marking Materials with CEN-Prescribed Geometry
Using a Portable Retroreflectometer. The Delta LTL-
2000 portable retroreflectometer (used by several state
Departments of Transportation) is shown in Fig.3. It is
designed to simulate the driver geometry and the visual
distance of 30 meters. After the instrument is zeroed
and calibrated, it is placed over the test line and the
reading is obtained. Retroreflectivity can also be mea-
sured on the road with a mobile vehicle equipped with
measurement instrumentation. Testing has indicated
there is similarity between readings obtained with
portable retroreflectometers and those obtained in the
laboratory using ASTM Test Method D4061.
10. Resistance to WearThis is a measure of a pave-
ment markings ability to withstand wear from traffic
[5]. The test procedure involves dropping an abrasive
sand on a dry test specimen until the material is worn
away. The test is usually performed on an unbeaded
material that is the appropriate thickness. A variation
of the test is to drop a specific volume of sand on the
specimen and calculate the amount of material lost by
weight. The abrasion resistance can be determined by
using ASTM D968, Test Method for Abrasion Resis-
tance of Organic Coatings by Falling Abrasive.
THERMOPLASTIC
Thermoplastic material (including hot melt) is supplied in a
powdered form or in block form. The material is prepared
for testing by melting a sample at its application tem-
perature under constant agitation. A guideline for testing
thermoplastics can be found in the American Association
of State Highway and Transportation Officials (AASHTO)
Standard Test Method T-250. Two methods should be fol-
lowed when sampling and preparing the thermoplastic:
ASTM D7307, Standard Practice for Sampling of Ther-
moplastic Traffic Marking Materials and ASTM D7308,
Standard Practice for Sample Preparation of Thermoplastic
Traffic Marking Materials.
Gravimetric and Chemical AnalysisThe amount
of binder, glass beads, titanium dioxide, or lead chromate
or other pigments can be determined in accordance with
ASTM D4797, Test Methods for Chemical and Gravimetric
Analysis of White and Yellow Thermoplastic Traffic Mark-
ing Containing Lead Chromate and Titanium Dioxide.
Appearance and Physical Characteristics
1. ReflectanceMeasuring reflectance on thermoplastic
is the same as for liquid coatings except a patty is used
instead of a drawdown coating [6]. Use ASTM D4960,
Test Method for Evaluation of Color for Thermoplastic
Traffic Marking Materials, to determine reflectance.
2. Softening PointThermoplastic marking material
does not have a distinct melting point but will become
gradually softer as the temperature rises. The soften-
ing point is useful in predicting the tendency of the
Fig. 3Delta, LTL-2000 portable retroreflectometer.
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CHAPTER 66 PAVEMENT MARKING MATERIALS 803
material to flow at elevated temperature. To measure
the softening point, melted thermoplastic is cast into
brass rings and allowed to cool. The ring of thermo-
plastic, which is supporting a steel ball, is placed in a
liquid bath and heated at a controlled rate. The soften-
ing point is reported as the temperature at which the
steel ball falls a distance of 1 in. The softening point
can be determined in accordance with ASTM D36, Test
Method for Softening Point of Bitumen (Ring-and-Ball
Apparatus).
3. Specific GravityThe specific gravity of the thermo-
plastic is determined on the premelted sample. The
material is ground so it will pass through a No. 30
sieve. The thermoplastic is tested in accordance with
ASTM D153, Test Methods for Specific Gravity of Pig-
ments, Method A.
4. Bond StrengthThe bond strength of thermoplastic
marking material is determined instrumentally using
concrete bricks and steel blocks. A melted specimen
is applied to a concrete brick with a drawdown blade.
Two steel cubes are placed in the hot thermoplastic,
and the excess thermoplastic is scraped away from
the cubes. After trimming, the steel cubes are removed
and the material is allowed to cool. A heated steel
cube is bonded to the thermoplastic square with an
epoxide adhesive and allowed to cure before the bond
strength can be determined on a dynamometer. The
bond strength is determined in accordance with ASTM
D4796, Test Method for Bond Strength of Thermoplas-
tic Traffic Marking Materials.
5. Impact ResistanceImpact resistance is determined
on blocks of thermoplastic using an Izod-type impact
apparatus. The procedure given in ASTM D256, Test
Methods for Determining the IZOD Pendulum Impact
Resistance of Plastics, is used except the specimen is
not notched.
6. FlowabilityThis test is a measure of the thermo-
plastic marking materials ability to flow. It is closely
related to the viscosity of the material. The test involves
melting a weighed sample in a pint can for 4 h with
constant agitation. The can is suspended at a 45
angle, allowing material to flow over the edge until the
flow ceases. The residue is weighed and the flowabil-
ity is calculated. Test the material in accordance with
AASHTO Test Method T-250.
PAVEMENT MARKING TAPE
1. Film ThicknessThe adhesive layer is removed from
the tape with a suitable solvent, and the thickness
is measured with a micrometer. The glass beads are
included in this measurement, which is in contrast to
films from liquid coatings where the glass beads are
not included.
2. Reflectance and RetroreflectanceReflectance and
retroreflectance are measured in the same manner
as liquid coatings. For information, see No. 9 under
Appearance and Physical Properties, of Section B,
Material Testing.
3. Glass Bead AdhesionA qualitative test to check
glass bead adhesion is to firmly scratch the surface of
the tape with a thumbnail. Acceptable adhesion for this
test is noted when beads are not easily removed from
the surface.
4. Tensile StrengthA 1 -in.-wide strip of tape is tested
in accordance with ASTM D638, Test Method for Ten-
sile Properties of Plastics, at a test rate of 0.25 in. /min.
5. Adhesive Shear StrengthThe adhesive shear
strength is a measure of the adhesive strength between
the tape and the pavement. A 1 3 in. piece of car-
borundum extra coarse emery cloth is applied to the
adhesive face of a 1 6 in. strip of tape with a 1 in.
overlap. A pressure of 50 psi is applied to this over-
lapped area. The specimen is then tested in accordance
with ASTM D638, at a speed of 0.50 in./min.
6. Skid ResistanceThe skid resistance of tapes are
measured on a British Pendulum Tester. This pendu-
lum impact tester measures energy loss as a rubber
slider travels over the specimen. The test can be used
in the laboratory or in the field. The values are mea-
sured in British Pendulum Numbers. The test should
be made in accordance with ASTM E303, Test Method
for Measuring Surface Frictional Properties Using the
British Pendulum Tester.
GLASS BEADS (RETROREFLECTIVE OPTICS)
1. GradationGradation of glass beads is a measure
of the sphere diameter. AASHTO specification M-247
gives three gradations of glass beads. Type 1, Type 2,
and Type IM. Additional types (III, IV, and V) will be
added as larger size glass bead sizes are specified. To
perform the test, the beads are hand sieved through
standard sieves starting with the largest opening and
progressing through to the smallest opening sieve. The
glass beads are removed from each sieve, weighed and
the percent passing each sieve is calculated. The test
is performed in accordance with ASTM D1214, Test
Method for Sieve Analysis of Glass Spheres.
2. RoundnessThe roundness of glass beads is another
measurable indication of how well a pavement mark-
ing will perform as a retroreflective media. As men-
tioned earlier, only round spheres can reflect light back
toward the light source. To test for roundness, the glass
beads are mechanically separated by controlled vibra-
tion of a glass plate held at a fixed slope as shown in
Fig. 4. The glass spheres that are round will roll down
the slope while irregular-shaped particles will roll to
the side or vibrate to the top. After testing the com-
plete sample, the percent rounds can be calculated by
weighing the amount of spheres that have rolled down
Fig. 4Glass bead roundness apparatus.
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804 PAINT AND COATING TESTING MANUAL 15TH EDITION
the slope. The test is performed in accordance with
ASTM D1155, Test Method for Roundness of Glass
Spheres.
3. Refractive IndexTo determine the refractive index
of glass beads, the beads are treated as a pigment and
are tested in that manner. Most pigments are tested
using the liquid immersion method (Becke Line meth-
od or equivalent) at a temperature of 25C.
Optical Particle Analyzers are now being used to
determine bead size and gradation. While expensive, the
optical particle analyzer allows for much quicker testing
and a higher degree of precision and quantification of bead
samples. ASTM is currently investigating the use of optical
particle analyzers.
Note on other retroreflective optics testing: Specific
test methods to characterize ceramic materials and bead
clusters have not been promulgated (Fig. 5)
FIELD EVALUATION OF MARKING MATERIALS
Field evaluation of traffic marking materials is useful in
determining the relative service life of these materials
under actual road conditions using transverse lines (Fig. 6).
Two evaluation methods are described below:
ASTM D713, Standard Practice for Conducting
Road Service Tests on Fluid Traffic Marking
Materials
This ASTM method is excellent for performing field evalu-
ations. It is broken up into two partsApplication Process
and Performance Criteria.
APPLICATION PROCESS
Location for TestsPavements should be selected where
traffic is free flowing without grades, curves, intersections,
or other phenomena that would cause excessive braking or
turning. The area should have uniform wear, full exposure
to sunlight throughout the day, and have good drainage.
Interstate highways are usually excellent choices for testing.
Wet Film Thickness MeasurementWet film thick-
ness is measured with a wet film thickness gage consisting
of a piece of metal with calibrated notches cut at various
mil thicknesses as shown in Fig. 7. The gage is placed in
a freshly applied line on a test plate and withdrawn. The
notch with the highest reading that has paint on it is the
wet film thickness. The wet film thickness is measured and
adjusted before the test line is applied to the pavement.
Film thickness for thermoplastic is usually measured
with calipers on a cooled test panel.
Glass Bead MeasurementThere are two methods that
can be used to quantify the weight of glass beads applied. The
first involves weighing a freshly applied stripe without beads
on a test panel and a test stripe with beads. The difference in
weight is used to calculate the quantity of glass beads. This
procedure is described in ASTM Method D713.
The second procedure involves collecting the beads
from the bead gun during a preset time period. The weight
of beads collected is determined and used to calculate the
application rate for the beads.
Glass bead distribution is checked on a beaded test
panel or the road surface. The beads should be evenly
distributed across the width of the stripe, approximately
70% of the beads should be buried in the material, and the
remaining beads should be 50 % embedded in the material.
Application ProceduresBefore applying any test
lines, wet film thickness, line width, glass bead application
rate, and glass bead distribution should meet the specifica-
tion. Several test lines are usually applied. One line is for
the Auto-No-Track Time determination (see next section),
while the others are for additional evaluations.
PERFORMANCE CRITERIA
Field No-Track TimeThe field no-track time is deter-
mined by driving a standard passenger car over a freshly
applied line. This is usually done at 2535 mph at the speci-
fied no-track time. Any deposit of paint on the roadway or
exposure of the pavement under the test line is considered
as not meeting the no-track requirement. No track times
Fig. 7Wet film thickness gages.
Fig. 6Applied test stripes.
Fig. 5Paint truck.
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CHAPTER 66 PAVEMENT MARKING MATERIALS 805
range from 90 s to 2 min and are dependent upon air and
road temperature, wind speed, sunlight, and humidity. The
general correlation between the laboratory no-track time
described in ASTM D711 and the field results is that a
7min dry time by D711 will indicate a 90 second dry time
in the field.
AppearanceThis is the general condition of the test
lines when viewed from a distance of 10 ft. It takes into
consideration color, bleeding, darkening, fading, dirt col-
lection, etc. This is done for each wheel track. A numerical
value is usually assigned from 0 to 10 with 10 being the
highest quality.
DurabilityThe durability of the material in each
wheel track is rated from 1 to 10 (10 indicating no mate-
rial has worn away). ASTM D913, Practice for Evaluating
Degree of Traffic Paint Line Wear, can be used as a guideline.
RetroreflectivityRetroreflectivity measurements are
made in each wheel path using a portable retroreflectom-
eter as previously described. Two ASTM methods should be
followed:
ASTM E1710, Test Method for Measurement of Retrore-
flective Pavement Marking Materials with CEN- Prescribed
Geometry Using a Portable Retroreflectometer.
Periodic Field Evaluation
Periodic inspections of the test stripes are made, usually
monthly. At each inspection, daytime appearance, durabil-
ity, color, and retroreflectance values are recorded.
Special Considerations for Pavement
MarkingTapes
Application of pavement marking tapes will vary with the
type of tape and manufacturer. Many tapes require primers
or adhesives to be applied to the pavement before applying
the tape. Most are rolled with a weighted roller after appli-
cation to assure good contact between the adhesive and the
pavement. The manufacturers instructions for application
should be followed closely.
In addition to the previously discussed evaluation crite-
ria, removable tapes are also evaluated for their ability to be
easily removed. About 90 days after application, a test line
is removed by lifting a corner with a putty knife and pulling
up the line. An acceptable tape should be removed in large
sheets and not small pieces.
AASHTOS NATIONAL TRANSPORTATION
PRODUCT EVALUATION PROGRAM (NTPEP)
In an attempt to improve traffic marking materials through-
out the country, the Federal Highway Administration
(FHWA) sponsored a research project to evaluate the feasi-
bility of Regional Test Centers for the testing of pavement
marking materials in the lab as well as in the field. This
study paved the way for the current pavement marking
evaluation program, NTPEP. While this program is admin-
istered by the NTPEP coordinator, all lab and field testing is
conducted by participating State DOTs and other research
facilities.
The intent of the program is to provide testing results so
users can make the determination of acceptance. Manufac-
turers submit pavement marking materials to the program
for laboratory testing and 2 year field (actual road) testing.
The field testing procedures are based on ASTM D713, Stan-
dard Practice for Conducting Road Service Tests on Fluid
Traffic Marking Materials. As described previously, portable
reflectometers are used in lieu of the night-time visibility
evaluation. Field testing sites are chosen based upon their
environmental conditions. The manufacturers submit their
materials for laboratory testing and then apply their materi-
als to concrete and asphalt cement road test sites. Labora-
tory tests of the materials are conducted in a designated
DOT or contracted facility. Field tests of the applied materi-
als are conducted initially and every 30 days thereafter for
the first year and every 4 months for the second year. Labo-
ratory and field test results are published periodically in the
web-based AASHTO, NTPEP, Data Mine Program.
Laboratory Testing Includes the Following:
Solvent-Borne Paint
Viscosity
No Track Dry Time
Total Solids
Pigment Content
Opacity
Settling Properties
IR Scan on Vehicle
Density
X-ray Diffraction
Water-Borne Paint
Viscosity
No Track Dry Time
Total Solids
Pigment Content
Heat Stability
Freeze-Thaw Stability
Water Resistance
Dry Opacity
Density
Degree of Settling
X-ray Diffraction
Thermoplastic
Specific Gravity
Bond Strength
Flowability
Softening Point
Low Temperature Stress Resistance
Bead Content and Grading
Impact Resistance
Daylight Reflectance
Yellowness Index
Preformed Thermoplastic
Softening Point
Low Temperature Stress Resistance
Bead Content and Grading
Impact Resistance
Daylight Reflectance
Yellowness Index
Color
Whiteness Index
Epoxy
Drying Time
Epoxide Number
Adhesion to Concrete
Hardness
Abrasion Resistance
Color
Yellowness Index
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806 PAINT AND COATING TESTING MANUAL 15TH EDITION
Preformed Tapes
Tensile Strength
Ultimate Elongation
Retroreflectivity
Whiteness Index
Adhesion
Skid Resistance
Wear Index
Field TestingInformation and Tests:
Site Location, ADT, Weather Conditions
Pavement Marking Material Description
Application Information
Retroreflectivity
Durability
Appearance/Color
Snow Plow Damage
Removability
More detailed information can be obtained through the
AASHTO/NTPEP website at www.aashto.org [7].
References
[1] Lundkvist, S.-O., and Isacsson, U., Prediction of Road Mark-
ing Performance, J. Transp. Eng., Vol. 133, No. 6, 2007, pp.
341346.
[2] Smith, D. J., and Xinge, Y., Waterborne Traffic Paint and
Bead Combination, 4th Generation, Final Report OR 06- 011,
Organization Results Research Report PD01.021, Missouri
Dept. of Transportation, October 2005, pp. 152.
[3] Lu, J. J., and Barter, T., Evaluation of Traffic Markings in
Cold Regions, J. Transp. Eng., Vol. 124, No. 1,1998, pp. 4251.
[4] Shah, V. V., and Warnke, D. A., Acetylenic-based Grind Aids
in Waterborne Traffic Paints, Mod. Paint Coat., Vol. 88, No. 3,
March 1998, pp. 3033.
[5] Tolliver, H. R., Patel, S. K., Kusilek, T. V, and Koneripalli, N.,
Wear-resistant Transporation Surface Marking Method and
Materials, U. S. Patent 6,217,252, April 17,2001.
[6] Aznar, A. C, Caprari, J. J., Meda, J. F., and Slutzky, O., Study
of Formulation Variables of Thermoplastic Reflecting Materi-
als for Traffic Marking, J. Coat. Technol., Vol. 69, No. 868,
1997, pp. 3338.
[7] AASHTO/NTPEP website, http://www.ntpep.org/Pages/ default.
aspx.
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807
INTRODUCTION
WATER REPELLENTS ARE TRANSPARENT COATINGS
formulated for the purpose of protecting porous substrates
by preventing the penetration of liquid water. Unlike water-
proofing materials and sealers, water repellents allow the
passage of water vapor and generally are not designed to pre-
vent the intrusion of liquid water under hydrostatic pressure.
Water is known to penetrate porous materials and
contribute to their deterioration [13]. Examples include
warping and swelling of wood as well as cracking and spall-
ing of concrete and masonry caused by freeze/thaw cycles
and dissolved salts. Further, chloride ions in de-icing salts
can accelerate the corrosion of reinforcing steel in concrete.
Water repellents are used to provide protection against
such damage.
Water repellents provide protection by depositing
hydrophobic compounds on the substrate, thus modifying
the surface tension of the treated area. With some treat-
ments, water may bead on the treated surface.
Compositions
Most water repellents are composed of 1 to 65 % mono-
meric or polymeric hydrophobic compounds suspended
or dissolved in a carrier solvent. The type of compounds
used to deliver the water repellency, e.g., acrylic, silconate,
silane, siloxane, metallic stearate, etc., generally classifies
the products that produce the repellency.
The carrier solvent is selected based on its compatibil-
ity with the hydrophobic compounds. Organic solvent car-
riers can be aliphatic, aromatic, or chlorinated compounds
that can be derived from petroleum distillation. These
carriers are considered volatile organic compounds (VOC)
and, in recent years, have been subject to restricted use by
state and federal air emission control regulatory agencies.
In reality, solvent borne water repellents are restricted in
many parts of the United States. Reformulation efforts have
resulted in water borne repellents that are offered by most,
if not all, manufacturers.
Classification
Water repellents also are classified as either film formers or
penetrants. As film formers, the substrate pores are filled
and there is a continuous film on the surface. Examples
of film formers include acrylic polymers or silicone elas-
tomers. In most cases, the film-forming portion of the
water-repellent is a blend of several different hydrophobic
compounds.
Water repellents that are penetrants line the pores of
the substrate and generally do not visibly alter the sur-
face of the substrate. Examples of such materials include
solutions of metallic stearates or paraffinic waxes. Pen-
etrants also include reactive chemicals such as silanes
and siloxanes that covalently bond to the silicate miner-
als in cementitious substrates. Moisture and/or alkaline
material present within the substrate may catalyze this
reaction.
SCHEDULE OF TESTING
Most of the laboratory tests used for the evaluation of water
repellents are outline in the following sections, Tests on
Physical Properties, Tests for Water Repellency of Treated
Wood, and Tests for Application on Treated Masonry. All
of the listed tests described may not be required for each
water repellent examined, and the selection of tests to be
conducted may be guided by the type and recommended
use of the treatment or as agreed on by buyer and seller.
Other tests, as agreed on, may be added.
Tests on Physical Properties
Typical physical properties tested on a liquid water repel-
lent prior to application include weight per gallon, viscosity,
drying time, color, flash point, pH, storage stability, total
solids, percent nonvolatile content, and VOC content. Many
of these tests are outlined in Section 8 of this manual on
Physical Characteristics of Liquid Paints and Coatings
and are summarized in Table 1.
Tests for Water Repellency of Treated Wood
Dimensional Stability
The relative ability of water repellents to retard dimen-
sional changes in wood submerged in water is measured
using the wood swellometer test and is detailed in Federal
Specification TT-W-572, Paragraph 3.7, Water Repellency
[4]. This test compares the swelling of untreated control
specimens with the swelling of treated specimens after
each has been submerged in water for 30 min. Similar
procedures are described in the National Woodwork Manu-
facturers Association Test Method NWMA-M-2-81 [5]; in
ASTM D4446, Standard Test Method for Determining the
Anti-Swelling Effectiveness of Water-Repellent Formula-
tions and Differential Swelling of Untreated Wood When
Exposed to Liquid Water Environments; in American
Wood Preservers Association Standard M-18, Standard
Method of Testing Water Repellency of Pressure-Treated
67
Water-Repellent Coatings
Victoria Scarborough
1
, and Thomas J. Sliva
2
1
Director of Research and Development, Sherwin-Williams Wood Care Division, 10136 Magnolia Dr., Olive Branch, MS 38654.
2
Deceased, Vice President & Technical Director, D/L Laboratories, 116 East 16th St., New York, NY 10003.
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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808 PAINT AND COATING TESTING MANUAL 15TH EDITION
Wood; [6] and in ISO/DIN 4496, Wood Test Method Deter-
mination of the Radial and Tangential Shrinkage [7].
In Federal Specification TT-W-572b, water repellent
effectiveness is measured on treated Ponderosa pine sap-
wood that is cut into 6 by 38 by 254 mm (0.25 by 1.5 by
10 in.) wafers. The wafers are cut from two adjacent speci-
mens from each of five different boards. Specimen pairs of
ten wafers are required to make a set for testing, one for
the treated wafers and one for the untreated controls. Five
wafers (one from each board) are immersed in the test water
repellent for 30 s. The wafers are cured under standard con-
ditions for four days or until constant weight is attained.
The wafers are inserted into a holding device fitted
with a micrometer at one end that is known as a swellom-
eter gage. One end of the wafer touches the base of the
gauge and the other end just touches the plunger dial of
the micrometer. The wafer apparatus is immersed in water
for 30 min, and a dial reading is made before and after
immersion.
The difference between the dial reading of the treated
and the untreated control wafers is divided by the dial
reading of the untreated control wafers and multiplied by
100. The average of these five readings represents the water-
repellent effectiveness in percent of the product. Federal
Specification TT-W-572b requires that a water repellent
exhibit a minimum of 60 % water-repellent effectiveness.
ASTM D4446 differs from the federal specification in that it
requires a 3 min dipping time for water-based water repel-
lents, and it specifies that all control untreated specimens
must swell a minimum of 0.8 cm (0.32 in.).
Water Absorption
Water-repellent effectiveness can also be measured gravi-
metrically using ASTM D5401, Standard Test Method
for Evaluating Clear Water Repellent Coatings on Wood.
Water absorption is tested by cutting matched 50 by 100 by
305 mm (2 by 4 by 12 in.) Ponderosa pine sapwood boards.
Five boards are treated with the test water repellent by
immersing for 30 s. Five boards serve as untreated controls.
After curing, the boards to constant weight under stan-
dard conditions, they are weighed, immersed in water for
30 min, removed, and reweighed. The difference between
the absorption of the treated and the untreated boards
is divided by the absorption of the untreated boards and
multiplied by 100. The average of the five treated boards
represents the water repellent effectiveness in percent of
the product.
Unlike with Federal Specification TT-W-572b, the
boards used in this test can be exposed to exterior weath-
ering cycles, returned to the conditioning room to attain
constant weight, and water repellent efficiency can be
determined over periodic exterior exposure intervals to
determine long-term effectiveness.
Beading
Water repellents for application on wood substrates can be
evaluated for their ability to form and hold a water bead
[8]. A suitable test is described in ASTM D2921, Standard
Test Method for Qualitative Tests for the Presence of Water
Repellents and Preservatives in Wood Products. After the
wood has been treated and allowed to cure, several water
droplets are placed on the wood with an eyedropper or
other device. The time required for the droplets to lose
their spherical shape and flatten out is recorded. The test
can be used to compare water-beading ability before and
after either artificial or natural weathering. The ability to
bead water does not prevent water absorption as described
in ASTM D5401 nor does it necessarily correlate with the
ability to retard dimensional changes in wood as described
in Federal Specification TT-W-572b.
Paintability
If wood is to be painted and a water repellent is used as an
undercoat, it may be necessary to evaluate the effects of the
TABLE 1Physical property tests involved in water-repellency testing
Property ASTM TitleStandard Test Method(s) for
Weight per gallon D1475 Density of Liquid Coatings, Inks, and Related Products
Viscosity D1200 Viscosity by Ford Viscosity Cup
Viscosity D2196 Rheological Properties of Non-Newtonian Materials by Rotational (Brookfield Type) Viscometer
Drying Time D1640 Drying, Curing, or Film Formation of Organic Coatings at Room Temperature
Color D1544 Color of Transparent Liquids (Gardner Color Scale)
Flash Point D56 Flash Point by Tag Closed Cup Tester
Storage Stability D2243 Freeze-Thaw Resistance of Water-Borne Coatings
Storage Stability D1849 Package Stability of Paint (Heat Aging)
% Nonvolatiles D2369 Volatile Content of Coatings
% Nonvolatiles D5095 Determination of the Nonvolatile Content in Silanes, Siloxanes, and Silane-Siloxane Blends Used
in Masonry Water Repellent Treatments
VOC Content D3960 Determining Volatile Organic Compound (VOC) Content of Paints and Related Coatings
Total Solids D2834 Nonvolatile Matter (Total Solids) in Water-Emulsion Floor Polishes, Solvent-Based Floor Polishes,
and Polymer- Emulsion Floor Polishes
pH E70 pH of Aqueous Solutions with the Glass Electrode
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CHAPTER 67 WATER-REPELLENT COATINGS 809
water repellent on the primer or topcoat. Evaluations can
include checking the adhesion of the topcoat to the sub-
strate, observing any changes in color to the topcoat, and
measuring the drying characteristics of the topcoat. These
evaluations may also be made after a periodic weathering
of the water repellent-treated surface before the topcoat is
applied.
Weathering
Substrates treated with water repellents can be subjected
to artificial or outdoor weathering, e.g., using ASTM G151,
Practice for Exposing Nonmetallic in Accelerated Test
Devices That Use Laboratory Light Sources; ASTM G154,
Practice for Operating Fluorescent Light Apparatus for UV
Exposure of Nonmetallic Materials; ASTM G90, Practice
for Performing Accelerated Outdoor Weathering of Nonme-
tallic Materials Using Concentrated Natural Sunlight; and
ASTM D4141, Standard Practice for Conducting Acceler-
ated Outdoor Exposure Tests of Coatings. The substrate
is evaluated for appearance properties such as cracking (as
shown in the pictorial standards of ASTM D661, Standard
Test Method for Evaluating Degree of Cracking of Exterior
Paints), discoloration, mold, and mildew as well as dirt
pickup. The substrate may also be evaluated for beading
ability or water-repellent effectiveness.
Tests for Application on Treated Masonry
Water Repellency
Water repellency on masonry is determined following
procedures described in Federal Specification SS-W-110c,
Paragraph 4.3.2 [9], ASTM D6489, Standard Test Method
for Determining the Water Absorption of Hardened Con-
crete Treated with a Water Repellent Coating, and ASTM
D6532, Standard Test Method for Evaluation of the Effect
of Clear Water Repellent Treatments on Water Absorp-
tion of Hydraulic Cement Mortar Specimens. Generally,
cement or mortar specimens are prepared as described in
the method. These are weighed, immersed in water, and
the amount of weight gain recorded. The same specimens
are dried to constant weight and then immersed in the test
water repellent. Three specimens are tested for each of the
water repellent under evaluation.
After the water repellent has cured, the specimens are
immersed in water for 72 h. The percent water absorbed by
the treated specimens is calculated based on the weight of
the dry treated specimens.
Other test methods related to the examination of water
repellency include ASTM C67, Standard Test Methods
for Sampling and Testing Brick and Structural Clay Tile;
ASTM C97, Standard Test Methods for Absorption and
Bulk Specific Gravity of Dimension Stone; and ASTM
C140, Standard Test Methods for Sampling and Testing
Concrete Masonry Units and Related Units.
Chemical Resistance
The resistance of a water repellent to the intrusion of vari-
ous chemicals is determined following methods modified
from procedures described in ASTM C267, Standard Test
Method for Chemical Resistance of Mortars, Grouts, and
Monolithic Surfacings and Polymer Concretes; ASTM
C67, Standard Methods for Sampling and Testing Brick
and Structural Clay Tile; Report 244 of the National Coop-
erative Highway Research Program, Concrete Sealers for
Protection of Bridge Structures [10]; and ASTM C672,
Standard Test Method for Scaling Resistance of Concrete
Surfaces Exposed to Deicing Chemicals. Cubes of mortar
are prepared and then treated, cured, and immersed in a
specified chemical solution. Uncoated control cubes are
included in the immersion. Typical chemicals used in this
test include fuels and oils, various salt solutions, and acid
and alkaline solutions.
Differences in weight gain or loss as a function of time
are measured and plotted as compared to the untreated
control. The rate of weight gain or loss over time during
immersion may be more significant than the actual differ-
ence. By charting the weight gain or loss over time, the rate
of deterioration may be determined.
Chloride ion penetration resistance is of particular
interest in testing for the resistance of water repellent-
treated masonry, since reinforcing steel in concrete will cor-
rode and deteriorate after prolonged exposure to salt and/
or salt solutions. A method for determining the resistance
of concrete to chloride ion penetration is described in AAS-
HTO Method T259 [11].
Freeze/Thaw Resistance
Freeze/thaw resistance is determined by means of ASTM
D5860, Standard Test Method for Evaluation of the Effect
of Water Repellent Treatments on FreezeThaw Resistance
of Hydraulic Cement Mortar Specimens. Treated speci-
mens are subjected to cycles of freezing and thawing and
then evaluated for weight loss and physical deterioration
such as cracking and spalling after each series of cycling.
Moisture Vapor Transmission
Because the passage of moisture vapor through masonry
may affect the long-term performance of a structure, water
repellents applied to masonry structures may be required to
demonstrate their ability to allow the passage of moisture
vapor. Several methods are available to measure moisture
vapor transmission of the applied film. These methods
include ASTM D1653, Standard Test Methods for Water
Vapor Transmission of Organic Coating Films; ASTM
D6490, Standard Test Method for Water Vapor Transmis-
sion of Non-Film Forming Treatments Used on Cementi-
tious Panels; and ASTM E96, Standard Test Methods for
Water Vapor Transmission of Materials. In a general sense,
these methods measure the rate at which water vapor passes
through a coating film. The specimen is sealed to the open
mount of a cup or dish that contains desiccant. This assem-
bly is then placed in a test chamber with a controlled atmo-
sphere. The cup or dish is exposed to a specified relative
humidity and periodic weightings are made to determine
the rate of water vapor transmission through the film. With
penetrants, the treatment is applied to a masonry substrate
and testing is conducted on treated and untreated test speci-
mens. The percent retention of water vapor transmission is
reported. Another method is described in NBS Technical
Note 883, Paragraph 2.2.2, Moisture Vapor Transmission
on Brick [12], a method that measures the moisture vapor
transmission of the treated brick rather than the film.
Efflorescence
Efflorescence is a usually white, undesirable, powdery
deposit that appears on the surface of masonry and con-
crete products [13]. It is formed by salts dissolved in water
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810 PAINT AND COATING TESTING MANUAL 15TH EDITION
that is passing through the concrete and masonry products
by capillary action. When the solution reaches a surface,
the water evaporates and leaves the salt on the surface
as efflorescence. Although usually white in appearance, it
may have other colors that depend on the nature of the
salt involved. Although harmless in itself, the deposit often
detracts from the appearance of the substrate.
There are two types of efflorescencethe powdery type
mentioned above that is easy to remove and a crystalline
form that comes about when the deposits are repeatedly
dissolved and dried out a number of times. In this cyclic
process, the crystalline form of efflorescence is formed, and
it is tightly adhered to the surface. It is more difficult to
remove than the powdery deposit and removal may require
special cleaners or acids. Factors such as low temperatures,
ground water, humidity, rain, and other water sources such
as sprinklers facilitate efflorescence formation.
Water repellents may be used to prevent the formation
of efflorescence. The efficiency at preventing efflorescence
can be measured using the method described in NBS Tech-
nical Note 883, Paragraph 2.2.2 [12]. ASTM C1400-1, Stan-
dard Guide for Reduction of Efflorescence Potential in New
Masonry Walls, ASTM D7072-04, Standard Practice for
Evaluating Accelerated Efflorescence of Latex Coatings,
and ASTM C67, Standard Test Methods for Sampling and
Testing Brick and Structural Clay Tile are useful when
investigating this phenomenon.
References
[1] Feist, W. C., and Hon, D. N-S., Chemistry of Weathering
and Protection, Chemistry of Solid Wood, R. M. Rowell, Ed.,
American Chemical Society, Washington, DC, 1983, p. 401.
[2] Clear Water Repellent Handbook, Sealant, Waterproofing, and
Restoration Institute, Kansas City, MO, 2007.
[3] Water Repellency and Dimensional Stability of Wood, Gen-
eral Technical Report FPL-50, R. M. Rowell and W. B. Banks,
Eds., United States Department of Agriculture Forest Prod-
ucts Laboratory, Washington, DC, 1985.
[4] Water Repellent for Use on Wood, Federal; Specification TT-
W-572b, General Services Administration, Washington, DC,
1969.
[5] Standard Method for Determining the Water-Repellent Effec-
tiveness of Treating Formulations, NWMA-M-281, National
Woodwork Manufacturers Association, NWMA Swellometer
Test.
[6] AWPA Book of Standards, American Wood Preservers Associa-
tion, Stevensville, MD.
[7] ISO Test Methods can be obtained in the United States from
ANSI, 11 W. 42nd Street, New York, NY, 10036 or from various
supplier on the Internet.
[8] Kalnins, M. A., and Katzenberger, C., Wettability and Water
Repellency of Wood: A Faster More Convenient Method of
Measurement, Second Cellucon Conference, Wrexham, Wales,
UK, July, 1418, 1986.
[9] Water Repellent, Odorless, Silicone Base, Federal Specifica-
tion SS-W-110c, General Services Administration, Washing-
ton, DC, June 1972.
[10] Concrete Sealers for Protection of Bridge Structure, Report
244, National Cooperative Highway Research Program, D. W.
Pfeifer and M. J. Scali, Eds., Transportation Research Board,
National Research Council, Washington, DC, 1981.
[11] Standard Specifications for Transportation Materials and Meth-
ods of Sampling and Testing, Part 2, Method T-259-78, Ameri-
can Association of State Highway and Transportation Offi-
cials, Washington, DC.
[12] Clark, E. J., Waterproofing Materials for Masonry, Technical
Note 883, United States Department of Commerce, National
Bureau of Standards, Washington, DC, 1975, p. 78.
[13] Merrigan, M., Efflorescence: Cause and Control, Masonry
Soc. J., 1986.
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Part 14: Analysis of Paint and Paint Defects
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813
68
SAMPLING
THE IMPORTANCE OF APPROPRIATE SAMPLING
FOR analytical work cannot be overemphasized. Unfortu-
nately, this topic is often not given sufficient thought, and
there is often not enough training on the subject. A clear
understanding of the nature of the problem or the reason
analysis is needed must be established prior to obtaining
a sample. It is extremely important to know the composi-
tional makeup of the bulk material from which the sample
is being taken. Without this knowledge, improper sampling
can very easily occur. The homogeneity or heterogeneity
of the sample along with its stability is very important to
consider. The composition of a sample may change once
it is removed from its natural matrix or environment due
to interactions with a container, ultraviolet light, or air,
for example. One should also know in advance what level
of precision is required of the analysis and what composi-
tional information is required.
Development of a sampling plan is one of the most
important steps in providing reliable samples and conse-
quently accurate and reliable data. The types of samples
usually encountered are as follows:
Representative Sample: A sample considered to be
typical of the bulk material and whose composition can be
used to characterize the bulk with respect to the parameter
measured.
Systematic Sample: A sample taken according to a sys-
tematic plan with the objective of investigating systematic
variability of the bulk. Systematic effects due to time or
temperature are typical matters of concern.
Random Sample: A sample selected by a random pro-
cess to eliminate questions of bias in selection and/or to
provide a basis for statistical interpretation of measure-
ment data.
Composite Sample: A sample composed of two or
more increments that are combined to reduce the number
of individual samples needed to average compositional
variability [1].
There are basically three kinds of sampling plans that
can be used in a measurement process. Intuitive sampling
plans may be defined as those based on the judgment of
the sampler. General knowledge of similar materials, past
experience, and present information about the bulk mate-
rial, ranging from knowledge to guesses, are used in devis-
ing such sampling plans. Because the samples are based on
judgment, only judgmental conclusions can be drawn when
considering the data. In the case of controversy, decisions
on acceptance of conflicting conclusions may be based on
the perceived relative expertise of those responsible for
sampling [1].
Statistical sampling plans are those based on statistical
sampling of the bulk materials and ordinarily can provide
the basis for probable conclusions. Hypothesis testing can
be involved, predictions can be made, and inferences can
be drawn. Ordinarily, a relatively large number of samples
will need to be measured if the significance of small appar-
ent differences is of concern. The conclusions drawn from
such samples would appear to be noncontroversial, but the
validity of the statistical model used could be a matter of
controversy [1].
Protocol sampling plans may be defined as those speci-
fied for decision purposes in a given situation. Regulations
often specify the type, size, frequency, sampling period, and
even location and time of sampling related to regulatory
decisions. Not specifically following any part of the proto-
col could be reason for discrediting a sample. The protocol
may be based on statistical or intuitive considerations but
is indisputable once established [1].
When decisions are based on identifying relatively
large differences, intuitive samples may be fully adequate.
When relatively small differences are involved and the sta-
tistical significance is an issue, statistical sampling will be
required [1].
General Sampling Techniques
It is obvious that the sample submitted for analysis must
accurately reflect the bulk material from which the sample
was taken. Personnel taking samples should be trained in
proper protocol for obtaining samples from bulk material.
Equally as important as training is the use of proper con-
tainers necessary for storing samples. Many types of con-
tainers can alter the integrity of the sample. A paint sample
submitted in the original container is not necessarily a rep-
resentative sample as frequently volatile components may
have already been lost or the contents may have been adul-
terated. Assumptions regarding the integrity of the sample
are extremely difficult to make, and good analysts need to
constantly bear in mind the history of the sample itself.
Detailed procedures regarding sampling of all sorts
of coatings would be impossible to write; however, ASTM
Practice for Sampling Liquid Paints and Related Pigmented
Coatings (D3925) and ASTM Practice for Sampling Indus-
trial Chemicals (E300) should be examined for detailed
recommendations.
All the precision in weighing, measuring, calculating,
and so forth has absolutely no meaning if the sample is not
Analysis of Paint
Darlene Brezinski
1
1
Consolidated Research, Inc., P.O. Box 2190, Kingsford, MI 49802.
MNL17-EB/Jan. 2012
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814 PAINT AND COATING TESTING MANUAL 15TH EDITION
a valid and representative sample. The sample taken for
analysis must totally and accurately reflect the composition
of the bulk material from which it was taken. If there is any
doubt about the integrity of the sample as a representative
sample, the analysis should not be conducted as the data
has no meaning. This becomes extremely important when
dealing with samples where the bulk is large and perhaps
not always completely homogenous [1]. In the real world
of sampling, it is often very difficult to even know if the
sample was obtained properly and if it is representative.
The analyst usually has no control over the sampling step
itself. In these cases, it becomes important for the analyst
to stress that the data are only representative of the sample
that has been analyzed and not necessarily representative
of the bulk. Rather serious management decisions can be
falsely made if the decision is based on data that is not
representative data.
Care should be taken to assure that all containers, agi-
tators, and sampling apparatus are clean and that they can
in no way contribute to contaminating the sample. Reus-
able syringes in particular can pose problems, particularly
in trace analysis, if they are not cleaned extremely well.
Contaminant materials will lead to erroneous test results
as the contaminate will be assumed part of the sample.
For pigmented coatings that are dispersions, finely divided
pigment particles may settle upon standing. Consequently,
very thorough agitation is necessary at every stage of the
sampling and analysis procedure.
Airtight storage containers are necessary to prevent
evaporation of sample material. Volatile solvents may also
diffuse through the walls of plastic containers. The loss
of volatiles subsequently introduces significant error in
such tests as viscosity, weight per gallon, and nonvolatile
content. If cap liners are used for samples, they must be
made of a nonreactive material. It is also very important in
all stages of sampling/analysis that the samples be kept at
fairly constant and consistent temperatures. Extremes of
temperatures may change the properties of some coatings.
Proper labeling of the sample cannot be stressed enough.
Labeling should be done in accordance with prior estab-
lished standard operating procedures (SOPs) for the labora-
tory. The more information available on the label, the less
likely error will be introduced either in the handling of the
sample or in the analysis. Formula composition, if known,
can be an asset to the analyst in choosing the best analytical
methods and save valuable and costly analytical time.
Laboratory Protocol
The analytical laboratory today must have SOPs. This is
standard, acceptable practice today, and laboratories that
have not implemented these procedures will find it more
difficult to maintain credibility of the data with their cli-
ents. SOPs define clearly how each step of the laboratory
operates. Clear SOPs are necessary for training, logging
samples, calibration, quality assurance, receipt of samples,
chain-of-custody, report formats, analytical methods, han-
dling of hazardous materials, etc.
Whatever kind of sampling plan is developed, it should
be written as a protocol containing procedures (SOPs) that
must be followed. It should address the following:
when, where, and how to collect samples
sampling equipment, including its maintenance and
calibration
sample containers, including cleaning, addition of sta-
bilizers, and storage
criteria for acceptance and/or rejection of samples
criteria for exclusion of foreign objects
sample treatment procedures such as drying, mixing,
and handling prior to measurements
sub-sampling procedures
sample record keeping such as labeling, recording, and
auxiliary information
chain of custody requirements [1]
Appropriate laboratory protocol has established SOPs
in place for every facet of the operation. Sample control has
to include not only the receipt and handling of the sample
but the handling and storage of the data.
Implementation of a chain-of-custody plan for each
sample is most critical to good operating practices in the
analytical lab today. It provides traceability for the sample
upon receipt and distribution of the sample for analysis.
The purpose of chain-of-custody is to ensure control of
the sample and corresponding data and that the data are
verifiable. The flow of samples for analysis and the associ-
ated paperwork must be clear to everyone involved in the
laboratory.
Analytical Quality Assurance
The validity of analytical data must be clearly established
through the documentation of quality assurance practices.
This is particularly important because often analytical
determinations and the subsequent data may be used as
evidence in a court of law. Standard operating procedures
should be established and encompass the following: record
keeping, sample homogeneity, calibrations, reference stan-
dards, calculations, laboratory housekeeping, the statistics
of inter-laboratory studies, and practical quality control.
Laboratory accreditation is becoming increasingly
important in todays environment to provide a level of
confidence in the laboratories capabilities, personnel,
testing procedures, and equipment. It establishes integrity
and reliability in the testing and the data. As regulatory
requirements become more demanding, the nature of
the analytical methodology has been changing to more
sophisticated analyses and, along with these changes, there
has been an increased emphasis on quality assurance and
quality control. Successful laboratories have made major
commitments to quality products and quality data. There-
fore, the process of verification of laboratory procedures
is becoming more important for providing precise and
accurate data.
GENERAL TESTING
Before any tests are run on the coating and prior to
separation, testing to establish some basic parameters or
conformance properties should be run. Among these are
flash point, density, water content, nonvolatile content by
weight and/or volume, and pigment or ash content. Refer-
ence should be made to elsewhere in this manual for more
information regarding determination of density, specific
gravity, and so forth.
Flash Point
The flash point of a material is defined as the lowest tem-
perature, corrected to a pressure of 760 mm Hg (101.3kPa,
1013 mbar) at which application of an ignition source
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CHAPTER 68 ANALYSIS OF PAINT 815
causes the vapor of the specimen to ignite under speci-
fied conditions of test. Flash point is one of the properties
used to classify liquids according to their flammability by
governmental regulatory agencies. Several different flash
point methods are available. The analyst must determine
which one of these methods is appropriate for the sample
to be analyzed and then follow the recommended ASTM
procedures. Both Tag open cup and closed cup methods,
Pensky-Martens closed cup, and Setaflash tester methods
are commonly used in the coatings industry. [ASTM Test
Method for Flash Point and Fire Points of Liquids by Tag
Open-Cup Apparatus (D1310); ASTM Test Method for
Flash Point by Tag Closed Tester (D56); ASTM Test Meth-
ods for Flash Point by Pensky-Martens Closed Cup Tester
(D93); ASTM Test Methods for Flash Point of Liquids by
Small Scale Closed-Cup Apparatus (D3278).] Open cup
flash points are only required in the rare customer speci-
fication. Department of Transportation regulations specify
closed-cup. Laboratories need to be certain of the shipping
requirements and the appropriate methods prior to analysis
of the sample.
Density
Density is weight per unit volume. It is a key property in
the identification, characterization, and quality control of
a wide range of paint materials. The density of water at
various temperatures is used to calibrate the volume of the
container. The weight of the paint liquid contents of the
same container at the standard temperature is then deter-
mined and density of the contents calculated in terms of
grams per milliliter, or pounds per gallon, at the specified
temperature.
Density measurements in terms of weight per gallon
are commonly used to check paint quality. If the density is
not within specification, there is a good chance that there
was a mischarge or other serious problem. This could indi-
cate further chemical analysis is required to determine the
nature of the problem. ASTM Test Method for Density of
Liquid Coatings, Inks and Related Products (D1475) is suit-
able for the determination of density of paint and related
products and components when in liquid form.
ASTM D1475 provides for the maximum accuracy
required for hiding power determinations. Automatic
equipment for measuring density is available from several
manufacturers [see ASTM Test Method for Density, Relative
Density and API Gravity of Liquids by Digital Density Meter
(D4052)]. For higher precision if working with nonpig-
mented materials, ASTM Test Method for Specific Gravity
of Drying Oils, Varnishes, Resins and Related Materials at
25/25C (D1963) can be used to determine specific gravity
and the corresponding density.
Water (Content) Determination
Control of water content is often important in controlling
the performance of paint and paint ingredients and is cer-
tainly critical in determining and controlling the volatile
organic compound (VOC) content. ASTM Test Method
for Water in Paints and Paint Materials by Karl Fischer
Method (D4017) is applicable to all paints and paint mate-
rials, including resins, monomers, and solvents, with the
exception of aldehydes and certain active metals, metal
oxides, and metal hydroxides. The Karl Fischer Method
has been evaluated for pigmented products containing
water in the 30 %70 % range; however, it is believed that
the method is also applicable for higher and lower concen-
trations. The method consists of dissolving the sample in
pyridine, or other appropriate solvent, and titrating directly
with standardized Karl Fischer reagent to an electrometric
end point.
ASTM Test Method for Water Content of Coatings by
Direct Injection into a Gas Chromatograph (D3792) is also
used for determining water in many latex systems. That
method has not been evaluated for other water reducible
paints, but is believed to be applicable. The established
working range of the method is from 40 % to 55 % water,
but there is no reason to believe that it will not work outside
of this range. In this method, a suitable aliquot of whole
paint is internally standardized, diluted, and injected into
a gas chromatograph. By choosing the correct column and
conditions, water can be separated from the other volatile
components.
Water content in pigments may be determined in
accordance with ASTM Test Methods for Common Proper-
ties of Certain Pigments (D1208).
SEPARATION OF SOLIDS AND VOLATILE
CONTENT
Separation of solids is routinely performed for determin-
ing the percent composition of the coating, i.e., % NVMs
(nonvolatile materials), % pigment, and % solvent. In many
cases, however, separation of these materials is also neces-
sary for further identification purposes, to check formula-
tion related problems, and for general problem solving.
Nonvolatile Content by Weight
Nonvolatile measurement is one of the most widely used
tests for coatings characterization. It determines the quan-
tity of coating remaining after all solvents or water and
other volatiles have been removed. When used in conjunc-
tion with volume nonvolatile content, the area covered by a
gallon of paint or coating can be determined.
It has become customary to determine the amount of
NVM, or solids, in a coating and that information is useful
to producers, users, and to environmental and health and
safety interests in comparing the coverage of competing
products and in estimating the volatile organic content.
Standard practice has been to accurately weigh by differ-
ence from a syringe a small sample of paint into a tared
aluminum foil, flat-bottomed dish. The dish is heated for a
specified temperature and time (usually to constant weight
at 105C), cooled in a desiccator, and weighed. From this
weight and the original weight of the empty dish the weight
of NVM may be calculated. The procedure is not as simple
as it first appears, and different types of coatings require
different methods. ASTM Guide for Determining Volatile
and Nonvolatile Content of Paint and Related Coatings
(D2832) is intended to aid in the selection of the proper
standard for determining the volatile and nonvolatile con-
tent of coatings. This guide should be examined carefully
and followed prior to determining nonvolatile content.
Perhaps the most commonly used method is ASTM
Test Methods for Volatile Content of Coatings (D2369).
This method is the procedure of choice for determining the
volatiles in coatings for the purpose of calculating the vola-
tile organic content (VOC) in coatings. Correspondingly,
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816 PAINT AND COATING TESTING MANUAL 15TH EDITION
the nonvolatile (NVM, or solids) is used to determine the
weight percent solids content.
Another commonly used procedure is ASTM Test
Method for Nonvolatile Content of Latexes (D4758). This
method should not be used for determining VOC of formu-
lated coatings; however, it is appropriate for obtaining the
weight percent of a commercial latex product that, when
incorporated into a coating product, constitutes the binder
content of the coating.
The nonvolatile content of resin solutions is useful to
coatings producers and users for the determination of the
total solids available for film formation and for the estima-
tion of VOC. ASTM Test Methods for Nonvolatile Content of
Resin Solutions (D1259) provides the detailed procedures.
Nonvolatile Content by Volume
A measure of the volume of dry coating obtainable from a
given volume of liquid coating is considered by some to be a
better measure of value than percentage of nonvolatile mat-
ter by weight. ASTM Test Method for Volume Nonvolatile
Matter in Clear or Pigmented Coatings (D2697) is appli-
cable to the determination of the volume of nonvolatile
matter (volume solids) of a variety of coatings. This method
is intended to provide a measure of the volume of dry coat-
ing obtainable from a given volume of liquid coating. This
value is useful for comparing the coverage (square feet of
surface covered at a specified dry film thickness per unit
volume) obtainable with different coating products.
The value obtained may not be equal to that predicted
from simple additivity of the weights and volumes of the raw
materials in a formulation. One reason is that the volume
occupied by a solution of resin in solvent may be the same,
greater, or less than the total volume of the separate ingre-
dients: such contraction or expansion in resin solutions is
governed by a number of factors, one of which is the extent
and direction of spread between solubility parameters of
the resin and solvent. The spatial configuration of the pig-
ment particles and the degree to which the spaces between
the pigment particles are filled with the binder also affect
the volume of a dry coating formulation. Above the critical
pigment volume concentration, the apparent volume of the
dry film is significantly greater than theoretical due to the
increase in unfilled voids between pigment particles. The
use of volume nonvolatile matter values in such instances
should be carefully considered as the increased volume is
largely due to air trapped in these voids.
In methods, the weight and volume of a stainless steel
disk are determined. After the disk is coated with the mate-
rial being tested, the weight and volume of the disk plus
dried coating is determined by weighing in air and then by
weighing in a liquid of known density, the volume being
equal to the quotient of the weight loss of the coated disk
(due to the Archimedes buoyancy effect) divided by the
density of the liquid displaced. The liquid may be water
or an organic liquid, such as low solvency mineral spirits,
depending on the nature of the coating being tested. From
the measured weights and volumes of the disk before and
after coating, the weight and volume of the dried coat-
ing film are calculated. Based on the density of the liquid
coating and the weight percent nonvolatile matter, the
volume of the liquid coating deposited on the coated disk
is calculated. The volume of the dried coating divided by
the volume of liquid coating, multiplied by 100, provides
the volume percent nonvolatile matter in the total liquid
coating.
Pigment Content
For most water emulsion paint systems, the pigment con-
tent (often called ash) is most often determined following
the determination of the weight percent nonvolatiles. ASTM
Test Method for Pigment Content of Water-Emulsion Paints
by Low Temperature Ashing (D3723) covers a procedure
for the pigment content determination. After weighing the
dishes for NVM, the dishes are transferred to a muffle fur-
nace and heated at a low ashing temperature of about 450C
for 1 h. Of course the analyst must keep in mind that the
method is only applicable to pigments that do not decom-
pose or lose weight at temperatures below 500C. This
would include most metal oxides, silicates, and a majority
of anhydrous inorganic salts.
A note of caution is advised, as this may be too low an
ashing temperature for some paints. Each system is differ-
ent, and one cannot assume that this temperature will be
sufficient.
To separate pigment from solvent-based paints, ASTM
Test Method for Determination of the Pigment Content
of Solvent-Reducible Paints by High-Speed Centrifuging
(D2698) should be followed. Also ASTM Test Method for
Pigment Content of Solvent-Reducible Paints (D2371) pro-
vides a centrifugation method for separation of pigment
from the vehicle.
Vehicle Separation
Separation of the vehicle from the pigment in solvent-
reducible paints is desirable and often required in order
to further characterize paint vehicles by chemical or
instrumental methods of analysis. ASTM Standard Practice
for Separation of Vehicle from Solvent-Reducible Paints
(D2372) covers the procedure for separating the vehicle
from the pigment by centrifugation.
Solvent Separation
If it is desirable to separate the solvents from the vehi-
cle, ASTM Standard Practice for Vacuum Distillation
of Solvents From Solvent-Reducible Paints for Analysis
(D3272) details a vacuum distillation procedure. For analy-
sis purposes, however, most people prefer direct injection
of paint sample into the gas chromatograph for solvent
identification.
Sample Preparation
For many types of analysis, the previously discussed sepa-
ration techniques are sufficient. Many chemical analyses
require further sample treatment in the form of either
extractions or digestions. The standard analytical tech-
niques are always applicable in these cases. Extractions are
often more attractive techniques for separating inorganic
species than precipitation methods, which are more time
consuming. Of course the extent to which inorganic and
organic species distribute themselves between two immis-
cible solvents differs greatly depending on the species and
the extraction solvents.
Decomposition of the organic material for further
analysis requires rather drastic sample treatment and
typically involves oxidation techniques. Wet ashing makes
use of liquid oxidizing agents such as sulfuric, nitric, and
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CHAPTER 68 ANALYSIS OF PAINT 817
perchloric acids. Dry ashing usually implies ignition of the
organic compound in air or in a stream of oxygen.
Sample dissolution is one of the most common opera-
tions in analytical chemistry. Because most quantitative
techniques require that samples be introduced in liquid
form, thousands of sample dissolutions are performed
every working day in analytical laboratories. Despite
the importance and widespread applicability of sample
dissolution, most conventional digestion procedures are
tediously labor-intensive, and a number of them, such as
perchloric acid digestion, are potentially hazardous to
laboratory personnel [2].
New microwave dissolution techniques make it pos-
sible to speed the preparation of solid samples by combin-
ing the rapid heating ability of microwave energy with the
advantages inherent in the use of sealed digestion vessels.
Researchers have found microwave dissolution to be faster,
more controlled, more elegant, and more amenable to
automation than conventional open-beaker or closed-vessel
techniques [2].
The advantages of microwave dissolution include faster
reaction rates that result from the high temperatures and
pressures attained inside the sealed containers. These con-
tainers are made of polymers that will not contaminate or
adsorb the sample and do not absorb microwave energy.
The caps are designed to safely vent container gas in case
of excess internal pressure buildup [2].
The use of closed vessels also makes it possible to elimi-
nate uncontrolled trace element losses of volatile molecular
species that are present in a sample or that are formed in
the course of dissolution. Such losses can easily destroy the
integrity of a measurement. In the field of elemental analy-
sis, significant percentages of elements such as arsenic,
boron, chromium, mercury, antimony, selenium, and tin
are lost at relatively mild temperatures with some open-
vessel acid dissolution procedures. Several of these ele-
ments have already been shown to be retained when closed
vessels are used [2].
Another advantage of closed vessels is a decrease in
blank values as compared to open-beaker work because
contamination from the laboratory environment is lower
and smaller quantities of reagents are used. The blank value
incurred in sample preparation is an important parameter
because it frequently determines the limit of detection [2].
Many laboratories, however, have abandoned closed-
vessel microwave digestions because of vessel ruptures.
Thus safety concerns must be of primary importance and
analysts should consult closed vessel suppliers.
CHARACTERIZATION AND CHEMICAL ANALYSIS
Analytical instrumentation has advanced significantly in
recent years primarily due to advancements in the field
of nanotechnology. Analysts constantly need to be aware
of current literature for the most appropriate method of
analysis. It is strongly recommended that particular top-
ics be searched on the Internet for relevant literature and
state-of-the-art analytical techniques, methodology, and
instrumentation.
Analytical Data
The reporting of analytical data is exceedingly important,
and every effort must be taken to ensure that the data
are sound, defensible, and meaningful. Most basic texts
on analytical chemistry discuss the appropriate statistical
methods used in dealing with data, standard deviation etc.,
as well as significant figures. An excellent text by Taylor
[1] deals with all aspects of chemical measurements and
should be examined thoroughly by all analysts. Also avail-
able is ASTM Procedure for Intralaboratory Quality Control
Procedures and a Discussion on Reporting Low-level Data
(D4210).
In the analytical laboratory, a method of measurement
(procedure) is usually followed that specifies the equip-
ment, reagents, sample handling, etc., and the instructions
to be followed. The analyst who carries out the method is
following what is called a measurement process. The most
important attribute of a measurement process is whether
it can be made to run in a state of statistical control.
Although repetition of measurement is subject to variabil-
ity, the achievement of statistical control implies that the
statistical properties of this variability are uniform over
time, so that it becomes meaningful to use measurements
over a limited time span to predict limits of variation for
both those and future measurements and to assign the level
of confidence to be associated with the limits. To achieve
statistical control, all assignable causes of significant varia-
tion are removed from the process [3].
Given the existence of statistical control, the two most
important other attributes of the process are generally
the precision and the accuracy of the results. Precision
is universally considered to be the mutual agreement of
individual measurements about some mean value (not
necessarily the true value), while accuracy refers to the
degree of agreement of individual measurements with
some true or accepted reference value of the property being
measured. When the mean value is not identical with the
reference value, the systematic difference is called the bias.
We should avoid using the terms accuracy and bias inter-
changeably; accuracy has to do with the difference between
individual measurements and some reference value, while
bias represents the systematic difference between the pro-
cess mean and the reference value [3].
Structural Analysis
All aspects of coatings manufacture, from the screening
of raw materials to finished product quality assurance,
depend on analysis data. The ultimate goal of analyses is
to identify the chemical species contained in a sample and
then determine the amount of each species. As such, both
qualitative (what) and quantitative (how much) analyses
must be performed. It is extremely important to try and
obtain all the background information regarding the sam-
ple to be analyzed as this information can often save time
and expensive analysis costs.
Organic Structural Analysis
A. Instrumental Methods
Spectroscopy is the study of the interaction of electro-
magnetic radiation with matter, that is, the interaction
of wave lengths of visible light, infrared light, ultraviolet
light, X-rays, and radio waves and their effect on chemical
substances. Spectroscopy allows the study of these effects
with instruments that give an enormous amount of infor-
mation in a short period of time with less stringent sample
requirements than is needed with classical chemical tech-
niques. All of the wavelengths in the ultraviolet, visible, and
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818 PAINT AND COATING TESTING MANUAL 15TH EDITION
infrared regions provide valuable information about the
structural makeup of molecules.
Infrared Spectroscopy (IR) provides a unique finger-
print useful in the identification of a wide variety of chemi-
cal species [4]. Certain infrared wavelengths are absorbed
in the sample by the bonds between the atoms, and the
absorbance is measured and plotted as a function of wave-
length. Since each chemical material has its own particular
and unique arrangement of atoms and bonds, its absorben-
cies are slightly different from those of all other chemicals.
Normally specific functional groups will give charac-
teristic absorbencies, and these groups can be recognized.
Thus, there are very specific absorbencies for groups such
as carbonyls, amines, alcohols, nitro groups, and isocya-
nates. Although it may not always be obvious from a spec-
trum which chemical is being examined, the analyst will
recognize these functional groups and know something
about the chemical structure.
In addition, IR can be a very valuable tool for reac-
tion kinetic studies, hydrogen bonding, dipolar attractions
and solute-solvent interaction studies, examination of the
nature of hydration and the nature of inorganic lattices
at various temperatures, and for studying the surface of a
material by attenuated total reflection (ATR) and variation
of composition with depth by variable angle ATR. These are
but a few of the numerous applications of IR in the coatings
field [4].
If more detailed information is desired and if the
sample has some degree of solubility, then nuclear magnetic
resonance (NMR) analysis can be extremely valuable. NMR
spectrometry not only provides information regarding the
functional groups that are present but it also provides
information about the location of those functional groups
relative to each other. In other words, the placement of the
functional groups in the molecule can be discerned from
NMR data [5].
If the compound is volatile and has some degree of
thermal stability, gas chromatography (GC) can be very use-
ful for identification purposes as well as for determining
purity/ impurities of materials. If a material is identified
qualitatively by GC, then that material can be further ana-
lyzed quantitatively. If the compound is not very volatile or
is unstable under GC conditions it may be possible to ana-
lyze it by high performance liquid chromatography (HPLC).
Here, as in GC, both qualitative and quantitative determina-
tions can be made [5].
For both GC and HPLC, if the peak of interest cannot
be readily identified, it can be trapped and further analyzed
by either IR or NMR techniques. Current instrumenta-
tion allows the analysis of materials like this quite readily
by offering instrument capabilities such as the following:
HPLC-MS (mass spectrometry), GC-IR, and GC-MS. These
instruments allow accurate separation of components fol-
lowed by subsequent identification.
MS can be applied to the quantitative analysis of
organic, organometallic, inorganic and ionic compounds
and materials including metals, and alloys. It is used both
to confirm the presence of known compounds and to iden-
tify compounds of unknown structure. Volatile or gaseous
samples, usually organic compounds, can be examined
using electron impact (EI) or chemical ionization (CI) to
give positive or negative ion mass spectra. Nonvolatile
samples can be examined by fast atom bombardment (FAB)
or thermospray ionization for inorganic and organic salts,
while plasma discharge ionization is used for metals and
refractory materials.
The value of MS, of course, is absolute identification of
either known or unknown compounds, particularly when
combined with information from other spectroscopic tech-
niques. Pyrolysis can also be carried out prior to ionization
inside the spectrometer and thus used for characterizing
both linear and cross-linked polymers.
Raman spectroscopy [5] is used to determine molecu-
lar structures and compositions of organic and inorganic
materials. Raman, like infrared, provides characteristic
frequencies of various functional groups. However, since
the selection rules governing the allowable transitions are
different, some frequencies may be observed in the Raman
spectrum that do not appear in the infrared and vice versa.
Some applications include:
Examination of aqueous solutions of inorganic com-
pounds. While water gives rise to intense absorptions
in the infrared, making unavailable major regions of
the spectrum for identification purposes, it is a poor
Raman scatterer, thereby allowing the observation of
vibrational transitions in the regions obscured in the
infrared.
Structural identifications of water-soluble organic
compounds such as amino acids.
Detection of weak infrared frequencies, such as
the stretching vibrations of the following groups:
C=C, C=C, SS, C S, N=N, and
OO.
Determination of configurational isomers in both the
solid and liquid state [4].
B. Chemical Methods
The techniques used in chemical analysis are of two general
types: gravimetric and titrimetric. In a titrimetric analysis,
the volume of known solution required to completely react
with a functional group is measured. This volume is then
related to the concentration of reacting species in the sam-
ple. The primary criteria for titrimetric analyses are that
the sample is soluble in a suitable solvent and a reagent is
found which fully reacts with the species of interest. Deter-
minations of acid, hydroxyl, and oxirane functional groups,
as well as elemental analysis for nitrogen content, utilize
titrimetric techniques. Titrimetric analyses are quite sensi-
tive, and measurements of concentration at the 0.1 % level
are routine. During gravimetric measurement, the weight
of material formed during analysis is used to determine the
composition of the original sample.
Classical chemical analyses can be further divided into
two categories depending upon the type of information
desired: functional group determination and the measure-
ment of elemental composition.
The presence of functional groups in polymers and
coatings can normally be determined using a combination
of chemical and instrumental measurements. Building
upon qualitative functional group information obtained
from spectroscopic techniques, quantitative analysis can
begin. In some cases specific chemical tests are also
required to confirm the presence of species indicated by
other techniques. The quantitative measurement of the
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CHAPTER 68 ANALYSIS OF PAINT 819
following chemical species is routinely performed in the
laboratory:
Acid (mg KOH/g sample) COOH + KOH COO
K
+
Amine (meq/g sample) NH
2
+ HCl NH
3
+ Cl
O stretching
v ibration will occur between roughly 1650 to 1750 cm
1
and the carbon-hydrogen stretching vibrations will always
occur between approximately 29502850 cm
1
, regardless
of the structure of the rest of the molecule. Because of
this, and after a great deal of research, tables known as
correlation charts have been developed which show where
the various functional groups absorb infrared light. These
tables are indispensable in the interpretation of infrared
spectra, and can be found in many texts on infrared spec-
troscopy [1,2].
Not only do correlation charts tabulate where certain
vibrations occur, they often provide information about
Fig. 1Electromagnetic wave. Courtesy of Spectroscopy
Atlas.
Fig. 2Electromagnetic spectrum. Courtesy of Spectroscopy Atlas.
Fig. 3Bending and stretching vibrations of a CH2 group.
Courtesy of Spectroscopy Atlas.
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CHAPTER 73 INFRARED SPECTROSCOPY 897
the strength of the absorption band. Indeed, not every
vibration in a molecule is infrared active, and there are
various rules, called selection rules, which can predict
whether or not a particular vibration will actually absorb
infrared radiation. While the selection rules are beyond the
scope of this chapter, a simplification of them is that, for
a particular vibration to absorb infrared light, and hence
result in a band in the infrared spectrum, the vibration
must produce a change in the molecules dipole moment. A
dipole moment arises from a partial separation of electric
charge, and is related to the difference in electronegativity
(the tendency of an atom to hold on to an electron) between
the vibrating atoms. The dipole moment will not change
during a symmetrical vibration of a symmetrical molecule,
and no infrared band will result. If the change in dipole
moment is small, the corresponding band will be weak. If it
is large, the corresponding band will be strong. Many times,
the intensity of a particular band is nearly as important
as its frequency in assigning it to the correct structure or
functional group.
Fig. 4Infrared spectra of methyl ethyl ketone (top) and toluene (bottom). Courtesy of Weldon Laboratories.
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898 PAINT AND COATING TESTING MANUAL 15TH EDITION
INSTRUMENTATION
There are two basic types of infrared spectrometers, dis-
persive and fourier transform. Dispersive instruments are
seldom used anymore, but may still be available in some
laboratories.
Dispersive Spectrometers
The development of dispersive spectrometers in the 1940s
brought infrared spectroscopy into everyday use in the
analytical laboratory. A simplified version of such an instru-
ment is shown in Fig. 5. This design directs an infrared
beam through the sample, and compares its intensity to
that of a reference beam which bypasses the sample. The
source of infrared light is an electrically heated wire or
ceramic rod, which produces a continuum of infrared light
spanning a wide range of frequencies. The two spherical
mirrors, M
1
and M
2
, direct this radiation along two paths,
one of which goes through the sample (the sample beam),
and one which bypasses the sample (the reference beam).
The beams are chopped so that the detector alternately
views one beam and then the other, such that the intensity
of radiation in the sample beam, at any frequency, can be
ratioed to that of the reference beam. The means of select-
ing a certain frequency of infrared light to examine is the
monochromator, which consists of narrow slits (S
1
and S
2
)
and some type of dispersive element (either a prism or a
diffraction grating).
For decades, dispersive instruments were employed for
infrared spectroscopy. However, they tended to be slow (the
author can well remember waiting 20 min for a spectrum
to be completed), and detection limits were somewhat poor.
Because of the loss of energy in the monochromator, cer-
tain accessories were often difficult to use, limiting the type
of samples which could be run. Fourier transform units
addressed these problems.
Fourier Transform Spectrometers
Nondispersive, or Fourier transform spectrometers, started
becoming popular in the 1970s, and are by far the most
common type in current use. Although they still require
a source of infrared radiation and a detector, they do not
disperse the radiation into individual frequencies, and
hence do not require a monochromator. Instead, all of the
infrared radiation is simultaneously passed through the
sample, after having passed through an interferometer, as
shown in Fig. 6.
As shown in Fig. 6, mirror M
1
collimates the energy
from the IR source onto a beamsplitter, where the energy
is divided between a stationary mirror M
2
and a moving
mirror, M
3
. The location of the moving mirror is tracked
by a small helium neon laser, such that the difference in
path length between the two beams is accurately known.
The two beams are then recombined, and subsequently
focused through the sample compartment and then on to
the detector.
The output of the detector is not an infrared spectrum
as we know it, but rather what is known as an interfero-
gram (Fig. 7), which is basically a plot of detector response
versus mirror travel, and contains all the information about
constructive and destructive interference as a function
of path length difference. It also contains all the spectral
information concerning the sample, since the different
frequencies of light will have been attenuated to one degree
or another by the sample. In order to convert the abstract
interferogram into the more commonly recognized infra-
red spectrum, a mathematical procedure known as the
Fourier transform is employed by the instruments com-
puter. It took the advent of small, fast computers to bring
the advantages of Fourier transform spectroscopy into the
commercial laboratory.
Fourier transform infrared (FTIR) has some impor-
tant advantages compared to dispersive IR, not the least
of which is speed. Rather than taking several minutes
to acquire a spectrum with a dispersive instrument, an
FTIR can obtain a reasonably good spectrum in a few
seconds.
Perhaps an even more important advantage of FTIR is
sensitivity. Because there is no monochromator, all of the
infrared radiation is passed through the sample at once,
as opposed to a small amount at a time with a dispersive
instrument. As a result, detection limits are roughly 10
to 100 times better with FTIR. As a consequence of this,
certain types of samples can be run with FTIR which
could not be run on a dispersive instrument. Furthermore,
there are certain accessories which waste considerable
amounts of energy, and were therefore difficult to use with
dispersive instruments. These accessories, such as attenu-
ated total reflectance attachments, are easily used with
FTIR equipment, and greatly enhance the versatility of the
technique.
Fig. 5Simplified double beam dispersive spectrometer.
Fig. 6Simplified fourier transform interferometer.
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CHAPTER 73 INFRARED SPECTROSCOPY 899
SAMPLE HANDLING
In the coatings industry, samples will usually be run in
the form of a solid, although liquid samples will occasion-
ally be encountered. There are several ways of obtaining
spectra of both solids and liquids, and the choice will
often depend on the type of question being asked of the
analyst.
A common way of obtaining an infrared spectrum of a
solid sample is by the use of the pressed pellet technique.
Shavings or scrapings of the sample, such as a dried paint
chip, are ground in a mortar and pestle, or by the use of a
small mechanical grinding mill, along with a carrier which
is essentially transparent to infrared radiation in the region
desired. Two very common carriers are potassium bromide
and sodium chloride powder. A ratio of roughly 1 mg of
sample to 100 mg of potassium bromide is common. The
ground sample is then placed in a special die and subjected
to perhaps 10 000 lbs of pressure in a laboratory hydraulic
press (inexpensive hand presses can also be used for the
occasional sample). This fuses the sample into a relatively
transparent pellet, which is then placed in the optical path
of the spectrometer for analysis.
The pellet technique is extremely useful and can be
used for a variety of samples. It works best for samples
which are relatively hard and brittle, since they are easiest
to grind. However, even relatively flexible samples can be
run by this method, with enough patience. Sometimes the
use of a few drops of a fast evaporating solvent, such as
methylene chloride, during the grinding operation can help
to break apart stubborn samples.
Often, especially in a laboratory dealing with fail-
ure analysis, or even for routine identification of paint
samples from a jobsite, the samples will consist of
more than one coat of paint. Care must be taken in the
analysis of such samples. Usually, if the chips are thick
enough, or if the various coats are of different colors,
scrapings of the individual coats can be obtained with
the use of a low power stereo microscope. However, if
the samples are very small and/or brittle, this may not
be possible.
Potassium bromide pellets can result in good qual-
ity spectra, require little sample, and can often be made
in a few minutes. Since the sample as a whole is being
analyzed, the spectrum will be representative of all of the
ingredients in the sample, such as resins, cross-linkers,
additives, and pigments. However, it must be kept in
mind that potassium bromide and sodium chloride are
hygroscopic. Even if stored in a desicator (a highly recom-
mended practice), a small amount of moisture is almost
inevitable. This will result in a band near 3300 cm
1
, and a
much weaker one near 1620 cm
1
. Bands due to water are
usually only a minor problem so long as one is cognizant
of them.
A more intractable problem with pellet spectra is light
scattering due to small, opaque particles dispersed in the
pellet as a result of certain types of pigmentation in the
coating. Some of the most difficult samples to analyze
include zinc-rich primers and coatings pigmented with
aluminum flake or carbon black. These particles act like
minute mirrors, resulting in light scattering and severely
sloping baselines.
Another way to obtain a transmission spectrum of a
solid is by the mull technique. In this technique, a small
amount of sample is dispersed by grinding it in a high
purity mineral oil, such as Nujol. The paste is then spread
across a salt plate, or sandwiched between two plates, and
a transmission spectrum is obtained. Mulls do not suffer
from the disadvantage of trace water, but the oils used
will have bands of their own which will show up in the
spectrum. Often, two different types of dispersing media
are required to obtain spectra over the entire region of
interest.
Fig. 7Typical interferogram.
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900 PAINT AND COATING TESTING MANUAL 15TH EDITION
The pellet and mull techniques discussed above result
in a spectrum of the bulk sample, since the infrared
radiation is passing through the sample (a transmission
spectrum). In many cases this is exactly what is needed to
characterize the coating or solve the particular problem.
However, sometimes it is desirable to obtain a spectrum
of a surface, rather than of the bulk sample. This might
be the case if one is concerned about the possibility of
oil on the back of a delaminated coating, or of a surfac-
tant exudate on the surface. The technique of choice for
investigating these types of problems is attenuated total
reflectance (ATR).
In ATR, the sample is pressed firmly against the
face of a special crystal having a high index of refrac-
tion. The infrared radiation is focused into this crystal at
such an angle that total internal reflection takes place at
the sample/crystal interface, resulting in what is called
a standing wave. This standing wave penetrates and
interacts with only the first few microns of the sample
surface, resulting in a reflectance spectrum (as opposed
to a transmission spectrum) which is very sensitive to
the surface composition of the sample. The technique
works best with soft, flexible samples which can be easily
pressed against the face of the crystal, and can be dif-
ficult to do with hard, brittle samples, especially if they
have uneven surfaces. The technique is described in more
detail by Mirabella [3].
ATR is one of those energy guzzling techniques which
has greatly benefited by the use of modern Fourier trans-
form spectrometers. While ATR spectra have been collected
for decades using traditional dispersive spectrometers, the
sample size had to be relatively large, and the process was
rather lengthy. With FTIR instruments, samples as small as
1mm
2
can be rapidly analyzed.
One of the most obvious advantages to the ATR
technique is not having to grind the sample. Therefore,
inconsistent particle size and light scattering effects are
eliminated, as are bands due to moisture in the grinding
medium. Soft, flexible samples, which would be difficult
to grind, are usually routine for ATR. Furthermore, some-
times valuable information can be obtained from a surface
spectrum which can not be obtained from a transmission
spectrum.
There are, however, several disadvantages to ATR. For
one thing, most collections of reference spectra are in trans-
mission, not reflectance. While similar, there can also be
substantial differences between the two types of spectra.
Furthermore, ATR spectra can be influenced by such
things as the angle of the incident beam of infrared radia-
tion, and the degree of contact between the sample and
the crystal. The angle of incidence will affect the depth
of penetration of the standing wave into the sample, and
hence the appearance of the spectrum. The degree of con-
tact between the sample and the crystal will also affect not
only the depth of penetration, but also the strength of the
signal. And, as mentioned above, brittle, wavy samples can
be difficult to analyze. An additional complication is the
possibility of a layering, or stratification, of the various
ingredients in the coating. Although this does not happen
often, it is possible that the ATR spectrum of the front of
a sample will look different than the spectrum obtained
from the back of the sample due to this stratification
effect.
Although the above techniques are the most common
ones for obtaining spectra of solid samples, they are cer-
tainly not the only ones. Diamond anvil cells can be used
to produce very thin films of small samples for transmis-
sion spectroscopy, extremely thin films on very reflec-
tive surfaces can be investigated by specular reflectance
techniques, and spectra can also be obtained of samples
based on the acoustic vibrations they emit from the heating
effects of the infrared beam (photoacoustic spectroscopy).
FTIR microscopes even allow spectra to be obtained from
samples as small as a few microns. Again, Mirabellas text
[3] is recommended for additional information on these
techniques.
While paint chips are a common staple of the mod-
ern analytical coatings laboratory, liquid samples are also
routinely encountered. By far the simplest technique for
obtaining a spectrum of a liquid sample, provided it does
not contain water, is to spread a small amount on a salt
plate (such as a potassium bromide crystal), allow the
solvent to evaporate, place the crystal in the optical path of
the instrument, and obtain a transmittance spectrum. This
is generally referred to as a cast film spectrum. A similar
technique is described in ASTM Standard Test Method for
Infrared Identification of Vehicle Solids From Solvent-
Reducible Paints (D2621).
If one wishes to obtain a spectrum which is represen-
tative of the sample as a whole, including solvent, a drop
of sample may be sandwiched between two crystals and a
so-called neat spectrum easily obtained. A neat spectrum
is a very simple, rapid tool for quality control, allowing a
spectral library to be easily made of all batches of a particu-
lar coating. If the sample contains fast evaporating solvents,
the procedure should be accomplished as quickly as pos-
sible. Both fixed and variable path length cells can also be
used to obtain spectra of liquid samples, but they are more
difficult to clean.
Obtaining spectra of water based samples in the above
fashions can be difficult, as water dissolves most of the
common crystal materials, as well as contributing bands
to the spectrum. Silver chloride discs, which are insoluble,
can be used, but it is often difficult to acquire high quality
spectra with them. Some of the suppliers of infrared equip-
ment produce what are essentially thin plastic disposable
cards to which liquid samples, both solvent based and
water based, can be applied. One should, of course deter-
mine which bands the cards themselves contribute to the
spectrum.
Sometimes it may be desirable to obtain an infrared
spectrum of a liquid sample after first removing the pig-
ment. Certain inorganic pigments have very strong, broad
bands which can obscure much useful information from
the resin components of the coating. The pigment can usu-
ally be removed by centrifugation, which is often made
easier by diluting the sample with a volatile solvent such
as acetone or methyl ethyl ketone. The clear supernatant
contains the resin and solvent. A small drop of this is spread
across a salt plate, the solvent removed, and a transmission
spectrum obtained of the cast film.
The above technique does not work so well with latex
samples, even if they are thinned with water. It may be pos-
sible to first break the emulsion by sonication, or to obtain
a good separation using a very high-speed centrifuge. How-
ever, a technique which works well for many types of latex
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CHAPTER 73 INFRARED SPECTROSCOPY 901
samples is to first apply them to a glass slide and allow a
brief time (perhaps 1560 min) for the bulk of the water
to evaporate. Usually, scrapings of the dried coating can
be easily re-dissolved in a suitable organic solvent, which
is then centrifuged as described above. The technique
described by ASTM Standard Practice for Qualitative Iden-
tification of Polymers in Emulsion Paints (D3168) may also
be useful in certain situations.
While the ATR technique previously described is usu-
ally associated with solid samples, liquid samples, espe-
cially if they are viscous, can often be applied directly to the
ATR crystal. There are also other ATR accessories available
from various vendors which allow liquid samples to be con-
veniently analyzed.
INTERPRETATION OF INFRARED SPECTRA
By far the most important component in the interpretation
of infrared spectra is the experience of the spectroscopist.
However, whether experienced or a novice, correlation
tables are indispensable in the process of spectral inter-
pretation. These tables list the locations of infrared bands
due to the various functional groups, and often provide
information into the relative intensities of the various
bands. There are many texts which contain such tables
[1,2], and the operational software which is supplied
with many spectrometers contains digital versions. One
simple but important rule is that, while the presence of
an expected peak may indicate the presence of a certain
functional group, the absence of an expected peak almost
certainly indicates the absence of the functional group. It
should also be kept in mind that a coating is not a pure
compound, but can be a complicated mixture of several
ingredients, each of which is contributing its own unique
spectrum to the overall spectrum of the coating. Thus,
although the Spectroscopy Atlas [1] is an indispensable
reference collection, it is not a collection of spectra of
paints and coatings, but rather of the raw materials which
go into making them. ASTM D2621 also contains many
useful reference spectra of alkyds, but again these spectra
are of unpigmented resins.
In addition to digital correlation tables, there are also
software packages which allow the spectrum of an unknown
to be searched against a digital database. These databases
provide a quick way to eliminate the majority of possibili-
ties, and can often rapidly point the investigator in the right
direction. Although there are various algorithms employed,
the goal is to generate the best matches to the spectrum of
the unknown. While sometimes very helpful, one should
never blindly accept the result of such a computer search,
since even matches with a high score of similarity can be
wrong. One reason for an erroneous match is that most of
the digital libraries only contain spectra of pure compounds
or raw materials, whereas the actual coating sample may
contain several such ingredients.
Fig. 8Infrared spectra of epoxy (top) and a vinyl latex (bottom). Photograph courtesy of Weldon Laboratories.
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902 PAINT AND COATING TESTING MANUAL 15TH EDITION
Many instrument software packages contain some
form of spectral subtraction, or difference spectroscopy
capability. The developers of this software like to point out
its ability to remove or subtract the spectral features of
known or unwanted components, such that small amounts
of hidden or masked materials can be identified. The pro-
cedures are usually interactive in nature, ideally allowing
bands from known constituents to be eliminated to reveal
the spectral features of a contaminant or other minor ingre-
dient otherwise obscured.
While spectral subtraction may be very useful in cer-
tain circumstances, when applied to most coating problems
the results should be viewed with a great deal of caution,
especially when attempting to detect compounds at low
concentrations. One of the major fallacies underlying the
technique is the unspoken assumption that the spectral
features of all of the ingredients in a complex, concentrated
mixture are purely additive in nature, and that the presence
of one compound does not interact with another and there-
fore affect the shape or locations of bands. Sometimes this
is true and sometimes it is not.
APPLICATIONS OF INFRARED SPECTROSCOPY
There are many uses of infrared spectroscopy in the coat-
ings laboratory, ranging from routine quality control proce-
dures to sophisticated problem solving investigations.
Quality Control Applications
It is not unusual for a paint manufacturer to run some
simple quality control checks on their incoming raw
materials, such as the viscosity of a resin solution or the
refractive index of a solvent. Some manufacturers extend
this QC monitoring to include infrared spectra of certain
raw materials, particularly resins. As discussed in the
section on sample handling, it is a very easy matter to
obtain a spectrum of a resin or resin solution, especially
if it is unpigmented. Establishing acceptance or rejection
criteria is another matter, however, and unless there is
a substantial difference in appearance of the spectra, it
would probably take some time until the manufacturer
has acquired enough data to begin to establish these cri-
teria for a particular product. Nevertheless, the analytical
procedure is very simple and rapid, and if problems did
crop up later with a certain product, one would then be
able to examine the spectrum of the resin which went
into that particular batch and compare it for deviations
against other such resins which resulted in successful
batches.
In addition to obtaining spectra of raw materials,
some manufacturers also obtain spectra of the finished
product. While an infrared spectrum of a finished paint
sample will not be able to provide information about very
slight differences in formulation, such as the type or level
of an additive, it will certainly reveal any major errors very
quickly. While not foolproof, it certainly provides another
level of quality control over the more traditional approach
of simply obtaining the samples viscosity and weight per
gallon. Indeed, a system for testing incoming raw materi-
als, manufactured intermediates, and finished products has
been developed [4].
Problem Solving Applications
The technical service department of any paint company is
routinely faced with such problems as what are these gel
particles in the paint?, why does this batch take so long
to cure?, why did this furniture lacquer crack?, or why
did this epoxy delaminate?. Infrared spectroscopy is an
excellent tool in helping to solve these types of problems,
and many more.
One of the simplest, most direct uses of infrared spec-
troscopy is in the generic identification of a coating. Many
Fig. 9Infrared spectrum of the layer found floating on top of paint.
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CHAPTER 73 INFRARED SPECTROSCOPY 903
times a coating does not perform as expected because the
wrong paint was used, or perhaps because the correct
paint was unknowingly applied to an existing coat of paint
with which it is not compatible. Fig. 8 shows the spectra
of an epoxy and a vinyl latex. It is obvious that the spectra
are quite different. Therefore, if an epoxy was to have been
used but an alkyd was applied instead, or if an epoxy was
applied over an acrylic latex with which it is not compat-
ible, such problems can be easily and rapidly detected by
infrared spectroscopy.
Another common problem results when a component
separates while standing in the shipping container. Fig. 9
shows the spectrum of such a float found on the surface
of a paint can. Using a micropipette, the material was
Fig. 10Spectra of a polyamide epoxy at the proper mix ratio (top) and with an excess of Part B polyamide component (bottom).
Note the difference in relative intensity of the 1640 and 1610 cm-1 bands. Courtesy of Weldon Laboratories.
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904 PAINT AND COATING TESTING MANUAL 15TH EDITION
removed and spread onto a potassium bromide plate. Even
though there was only a small amount of material, the spec-
trum was good enough to identify the layer as a mineral oil.
This clue led to the discovery that a shipment of cans had
not been adequately degreased prior to use [5].
A common failure mode involving two component
coatings, such as a polyamide cured epoxy, is failure of
Fig. 11Spectra of nitrocellulose lacquers with correct amount of plasticizer (top) and with inadequate plasticizer (bottom). Note
the difference in relative intensity of the 1730 and 1650 cm-1 bands. Courtesy of Weldon Laboratories.
Fig. 12Structure of ethyl silicate pre-polymer.
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CHAPTER 73 INFRARED SPECTROSCOPY 905
the applicator to mix the Part A and Part B components
in their proper ratio prior to applying the coating. One of
these components will contain the epoxy resin, while the
other will contain the polyamide curing agent. Failure to
mix the components in their proper ratio, often 1:1 by
volume, can result in coatings which do not cure properly
and which have inferior physical and chemical properties.
Infrared spectroscopy can often determine the approximate
mix ratio of such a coating. The procedure involves prepar-
ing drawdowns in the laboratory of the coating at different
mix ratios, and examining the spectra to see if there are
any pairs of bands which change in relative intensity in
a consistent fashion with changes in mix ratio. As Fig. 10
shows, as the mix ratio of this particular epoxy changes,
Fig. 13Spectrum of an ethyl silicate inorganic zinc-rich primer. Courtesy of Weldon Laboratories.
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906 PAINT AND COATING TESTING MANUAL 15TH EDITION
the relative intensities of several bands change, including
those near 1640 and 1610 cm
1
. The 1640 band is due to the
carbonyl vibration from the polyamide curing agent, while
the 1610 band relates to the epoxy resin. It is not surpris-
ing that the ratio of these two bands changes as a function
of mix ratio. The spectrum of the jobsite sample is then
compared to the spectra of the standards to determine its
approximate mix ratio.
It should be pointed out that, based on the authors
experience, the above technique for obtaining mix ratios of
two component coatings is only approximate, being good
to only two significant figures. Not only is there an error
associated with precisely mixing various volumesor even
weightsof viscous coatings to prepare the standards, and
errors associated with reproducibly grinding the various
samples for preparing potassium bromide pellets, but
Beers law, which relates the intensity of a band to the con-
centration of the species responsible for it, is only strictly
valid for analytes in dilute solutions. This is certainly not
the case in failure analysis, where the samples are at high
concentrations in a solid matrix.
Another problem where infrared spectroscopy proved
useful was that of a nitrocellulose furniture lacquer which
developed long, hairline cracks. Nitrocellulose is an excel-
lent resin for lacquers, as it dries quickly and produces a
hard finish with good gloss and clarity. Unfortunately, it
is also brittle, and usable coatings are only made by the
addition of a plasticizer. Although there are many types of
plasticizers available, one of the most common for nitrocel-
lulose lacquers is a non-drying alkyd such as a coconut oil
alkyd.
Fig. 11 shows the spectrum of a satisfactory lacquer
which did not develop cracks, and the spectrum of the
brittle, complaint batch. Nitrocellulose has a very strong,
characteristic band in the infrared near 1650 cm
1
, while
the band near 1730 cm
1
is due to the coconut oil plasticizer.
In comparing the relative intensity of these two bands, it
is apparent that the good lacquer contains a much greater
ratio of plasticizer to nitrocellulose than does the brittle
sample.
In certain cases, infrared spectroscopy can be a
very effective tool in problems involving the lack of
cure of a coating. Urethane coatings are very amenable
to cure studies by infrared spectroscopy [6] since the
isocyanate structure has a very distinctive band near
2300cm
1
which disappears upon curing as the isocya-
nate reacts with the polyol component, or with atmo-
spheric moisture.
Inorganic zinc-rich primers are another coating type
whose cure can be monitored by infrared spectroscopy.
Such primers consist of roughly 80 %90 % zinc dust pig-
ment dispersed in a binder which is usually based on a low
molecular weight ethyl silicate (actually an ethoxy silicate),
as shown in Fig. 12.
Because of their very high loading of zinc dust pig-
ment, which is actually above the coatings critical pigment
volume concentration (CPVC), the primers provide out-
standing corrosion protection due to their galvanic effect
(the zinc pigment will oxidize to protect the underlying
steel, in much the same fashion as galvanizing). However,
failures in the form of delamination or splitting of such
primers have occurred when topcoated with such coatings
as epoxies, often due to inadequate curing of the zinc-rich
primers prior to topcoating [7].
Fig. 13 shows the infrared spectrum of a typical inor-
ganic zinc-rich primer. It is dominated by a strong, broad
band near 1000 cm
1
due to the stretching vibrations
of the silicon-oxygen bonds in the inorganic polymer.
There are also much weaker bands near 2900 cm
1
due to
the carbon-hydrogen stretching vibrations of the ethoxy
groups on the low molecular weight prepolymers. When
these coatings cure they do so by reaction with atmo-
spheric moisture, which cleaves the oxygen-silicon bond
holding the ethoxy groups to the silicate backbone, result-
ing in the formation of silanol groups which subsequently
condense with one another to form the high molecular
weight, cured inorganic polymer. The bottom line is that
as the coating cures the ethoxy groups are cleaved and
evaporate in the form of ethyl alcohol. Since these groups
are the only source of carbon-hydrogen functionality, as
the coating cures the intensity of the carbon-hydrogen
bands will decrease relative to the intensity of the silicon-
oxygen band. This fact can be used to follow the degree of
cure of such coatings [8], including the analysis of failed
jobsite samples.
The above are just a few examples of the power of
infrared spectroscopy as a problem solving tool in the coat-
ings industry. Even if the technique does not unequivocally
solve the particular problem at hand, it can often eliminate
certain possibilities and point the investigator in the right
direction.
SUMMARY
Infrared spectroscopy has been a powerful technique for
organic and analytical chemists for over 50 years. Modern
computer controlled fourier transform instruments and
associated sampling accessories have made the technique
increasingly rapid and sensitive, and have extended its
capability to samples which would have been difficult if not
virtually impossible to analyze many years ago. Although
the technique has applications in quality control, its real
utility is as a problem solving tool. Depending on the expe-
rience and ingenuity of the analyst, IR spectroscopy can
provide solutions to a wide variety of problems concerning
the composition of materials and systems in the coatings
industry.
References
[1] An Infrared Spectroscopy Atlas for the Coatings Industry, Vols.
1& 2, D. R. Brezinski, Ed., Federation of Societies for Coat-
ings Technology, Blue Bell, PA, 1991.
[2] Socrates, G., Infrared Characteristic Group Frequencies, John
Wiley & Sons, New York, 1980.
[3] Mirabella, F. M., Modern Techniques in Applied Molecular
Spectroscopy, John Wiley & Sons, New York, 1998.
[4] Hartshorn, J. H., Compositional Assurance TestingA Sys-
tems Approach to Chemical Quality, SPIE1145, Proceedings,
7th International Conference on Fourier Transform Spectrosco-
py, D. G. Cameron, Ed., The International Society for Optical
Engineering, Bellingham, WA, 1989, p. 126.
[5] Hartshorn, J. H., Infrared Spectroscopy, Paint and Coating
Testing Manual, 14th Edition of the Gardner-Sward Handbook,
J. V. Koleske, Ed., ASTM International, West Conshohocken,
PA, 1995, pp. 829830.
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CHAPTER 73 INFRARED SPECTROSCOPY 907
[6] Weldon, D. G., Failure Analysis of Paints and Coatings, John
Wiley & Sons, Chichester, 2001, p. 175.
[7] Hare, C. H., Adhesive and Cohesive Failure in Applied
Coating Systems, J. Protective Coatings Linings, 1986, pp.
3848.
[8] Weldon, D. G., Bochan, A. J., Corbett, W. D., and Lackey,
R. O., The Cure and Topcoating of Inorganic Zinc-Rich
Primers, J. Protective Coatings Linings, 1989, pp. 2123,
169185.
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908
THE BINDERS USED IN COMMERCIAL COATINGS
are organic polymers, the molecular weights of which
greatly influence the properties of the final coating [1]. As a
necessary result of the manufacturing processes, synthetic
polymers are mixtures of compounds of similar molecu-
lar structure but varying molecular weight. For an exact
understanding of the system, one must know the molecular
weight and weight (or mole) fraction of each species, in
other words, the molecular weight distribution. For many
practical purposes, an average value of molecular weight
suffices. The final cured paint film is a cross-linked system
resembling a single massive molecule, where the concept
of molecular weight has little meaning. Molecular weight
determination is thus applied only to coating formulation
ingredients.
Many procedures have been used to determine molecu-
lar weight. We limit our discussion to the most practical
methods, for which commercial instrumentation is available
at reasonable price. Archaic methods and research methods
are omitted, as are those techniques which are suitable for
determination only of low molecular weight compounds.
MOLECULAR WEIGHT DEFINITIONS
While the molecular weight of a single molecule is a simple
concept, there are several ways to calculate the molecular
weight of a mixture. The most useful values are number
average molecular weight, M
n
and weight average molecu-
lar weight, M
w
M
n M
n
M
wM
w
n
i i
i
i
i
w
i i
i
i
i
= =
,
where M
i
denotes the molecular weight of component i,
n
i
is the number of moles of component, i and w
i
symbol-
izes the total weight of component i and is thus equal to
n
i
M
i
. Weight average molecular weight is necessarily equal
to or higher than number average molecular weight. A
mixture of equal numbers of two molecules, one weighing
100 and the other weighing 1000, has a M
n
of 550 and a
M
w
of 918. The polydispersity of this mixture, M M
w n
/ , is
1.7. This indicates that most of the mass of the example
mixture consists of higher molecular weight material, but
that comparatively small molecules are also present. The
higher the value of M M
w n
/ , the broader is the distribution
of weights of molecules in the sample. Two other measures
of molecular weight have found acceptance because they
can be directly measured by certain techniques: z-average
molecular weight, M
z
, and viscosity average molecular
weight, M
v
M
wM
wM
M
wM
wM
z
i i
i
i i
i
v
i i
a
i
i i
i
= =
2
,
11/ a
For the above-mentioned mixture of molecules of
weight 100 and 1000, the z-average molecular weight is
991. Clearly, if the actual distribution of M
n
, M
w
, or M
z
is
known, the distributions and average values of the other
two parameters may be calculated. The exponent a is
obtained from the MarkHouwink equation and is specific
to polymer type and branching as well as the temperature
and solvent of the measurement system [2].
Which molecular weight value is of greatest signifi-
cance, number average, weight average, z-average, or vis-
cosity average, depends upon the particular application of
the polymer mixture. Knowledge of M
n
and M
w
is sufficient
for most purposes. M
n
is often critical to stoichiometry of
curing reactions and controls some properties. For coat-
ings, many of the properties of the final product are con-
trolled by M
w
, with M
w
/M
n
also playing an important part.
METHODS FOR DETERMINATION OF NUMBER
AVERAGE MOLECULAR WEIGHT
End Group Analysis
Some polymers used in coatings have reactive end groups
which participate in the curing reactions. Assuming that
the degree of branching is known and that the end of each
polymer chain has such a group, methods for routine qual-
ity control may be based on determination of end groups.
Since each molecule has the same number of end groups,
the result is a number-average molecular weight. Polyure-
thane raw materials fit this description, and wet chemi-
cal methods are well-established for rapid and accurate
analysis of these compounds. Hydroxy-terminated com-
pounds are analyzed by determination of hydroxyl number
[ASTM Method for Testing Polyurethane Raw Materials:
Determination of Hydroxyl Numbers of Polyols (D4274)].
Isocyanate-terminated prepolymers are analyzed by ASTM
74
Methods for Polymer Molecular Weight
Measurement
Thomas M. Schmitt
1
1
Manager, Analytical Chemistry & Chemical Engineering, BASF Corp., 1609 Biddle Ave., Wyandotte, MI 48192.
MNL17-EB/Jan. 2012
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CHAPTER 74 METHODS FOR POLYMER MOLECULAR WEIGHT MEASUREMENT 909
Test Methods for Polyurethane Raw Materials: Determi-
nation of Isocyanate Content of Aromatic Isocyanates
(D5155). End group analysis is not limited to polyurethane
raw materials. Amine or carboxylic acid functional groups
may be determined by acidbase titration, often in non-
aqueous solvents, but the parameters of solvent, titrant,
and apparent pH at the end point must be worked out for
each compound.
End groups may also be determined by spectroscopic
methods, usually infrared, near infrared, and nuclear mag-
netic resonance spectrometry. For example, see ASTM Test
Methods for Polyurethane Raw Materials: Determination of
Primary Hydroxyl Contents of Polyether Polyols (D4273),
and ASTM Standard Practice for Polyurethane Raw Mate-
rials: Determining Hydroxyl Number of Polyols by Near
Infrared Spectroscopy (D6342).
Even polymers which are not usually thought of as
possessing functional end groups may be analyzed. This
is because molecules are often terminated by fragments
of the catalyst which initiated the reaction. An example is
polyacrylonitrile, which may be terminated by a sulfate or
sulfonate group. The analyst familiar with the mechanism
of polymerization can sometimes devise a way to measure
molecular weight based on determination of these residues.
Accurate measurement of M
n
, by end group analysis
is limited to polymers of molecular weight less than about
20 000, since the end group concentration is too low for
precise measurement above this range.
Colligative Properties Analyses
M
n
may be determined based on colligative properties, i.e.,
based on measuring changes in solvent properties which
are due to the number of molecules dissolved. These prop-
erties include vapor pressure, freezing point, boiling point,
and osmotic pressure. By derivation from fundamental
equations [25], it can be shown that, at low concentration,
the relationship between a colligative property and molecu-
lar weight reduces to
M
KC
X
n
=
rel
t t = /
0
where t and t
0
are the efflux times for polymer solution and
pure solvent, respectively. Reduced viscosity takes concen-
tration into account:
red
t t
t C
=
0
0
where C represents the polymer concentration, usually in
grams per 100 mL. Intrinsic viscosity is determined by plot-
ting against concentration several values of reduced viscosity,
extrapolating to obtain the intercept at zero concentration:
[ ] lim =
C
red
0
where [] represents intrinsic viscosity.
Some workers determine Mark-Houwink constants with
unfractionated polymers of measured M
w
, thus relating vis-
cosity to M
w
rather than M
v
. This nonrigorous approach is
viable because M
v
is usually rather close to M
w
.
Solution viscosity is an excellent method for routine
QC of relatively uniform polymers. A single analysis at
a fixed concentration and temperature will indicate that
the product falls into the stated molecular weight range.
For example, ASTM Test Method for Determining Inher-
ent Viscosity of Poly(Ethylene Terephthalate) (PET) by
Glass Capillary Viscometer (D4603), describes a method
for determining inherent viscosity (natural log of relative
viscosity, divided by concentration). ASTM Test Method
for Intrinsic Viscosity of Cellulose (D1795) describes a
one-point procedure for estimating intrinsic viscosity. The
results of such measurements can be related to molecular
weight and are useful for predicting properties of different
batches of well-understood commercial resins. Many poly-
mer chemists routinely make one-point viscosity measure-
ments to monitor synthesis experiments, reserving more
sophisticated molecular weight measurements for products
chosen for commercialization.
Melt viscosity, the viscosity of the pure polymer, is
correlated with M
w
. Equations developed to relate degree
of polymerization with melt viscosity use a temperature-
dependent function which differs for each polymer system.
As a practical matter, polymer melts are nonideal fluids,
and their true viscosity can rarely be measured with simple
equipment. Thus, melt viscosity is usually determined
because of its relation to polymer processability, rather
than as an estimate of M
w
. Melt viscosity is a useful tool for
rapid comparison of suspect resin batches to controls, espe-
cially with resins which are suspected of changing during
storage or when there are difficulties in analyzing by SEC.
Pour point, the temperature at which the polymer begins to
flow, is similarly related to molecular weight, and may be
used to estimate it.
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CHAPTER 74 METHODS FOR POLYMER MOLECULAR WEIGHT MEASUREMENT 913
REFERENCES
[1] Wicks, Z. W. Jr., Organic Coatings: Science and Technology. Vol-
ume I: Film Formation, Components, and Appearance, Wiley,
Inc., New York, 1992.
[2] Carraher, C. E., Jr., Ed., Seymour/Carrahers Polymer Chemis-
try, 5th ed., Marcel Dekker, New York, 2000.
[3] Barth, H. G., and Mays, J. W., Eds., Modern Methods of Poly-
mer Characterization, Wiley, New York, 1991.
[4] Campbell, D., and White, J. R., Polymer Characterization.
Physical Techniques, Chapman and Hall, New York, 1989.
[5] Schroeder, E., Mueller, G., and Arndt, K., Polymer Character-
ization, Hanser, New York, 1988.
[6] Wu, C., Handbook of Size Exclusion Chromatography, Marcel
Dekker, New York, 1995.
[7] Mori, S., and Barth, H. G., Size Exclusion Liquid Chromatog-
raphy, Springer, New York, 1999.
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914
INTRODUCTION
MOLECULAR STRUCTURE AND FUNCTIONAL GROUP
presence in organic paint and coating materials, typically,
are determined using infrared spectroscopy. Evaluating the
electronic structure of the binders such as the degree of
conjugated double or triple bonds and degree of aromatic-
ity may be evaluated using the more energetic ultraviolet
(UV)/visible (VIS) spectroscopy. Dyes, some colorants,
and aromatic solvents may be evaluated as well. UV/VIS
radiation energizes the electrons within the molecule while
infrared radiation causes physical movement of portions of
the molecular structure.
The use of electromagnetic radiation (EMR) for the
analysis of paints and coatings is best addressed by look-
ing at the way this energy source is absorbed by the system
under investigation. Most EMR analytical techniques,
and the instruments used to affect the measurement, will
place the sample of known thickness in the beam of the
light. The objective in this case is to determine the differ-
ence in the strength of the light beam before it enters the
sample and the strength after emerging from the sample.
This energy difference at a particular wavelength (energy)
provides information about the absorbing species concen-
tration and/or chemical makeup.
With some recent technology, the emerging beam may
be reflected from a surface. There are many sophisticated
instruments that use EMR, and they operate from the
lowest energy bands in microwaves to the highest energy
-rays. The region of the spectrum most commonly used in
the paint laboratory lies within the infrared and UV bands.
The instrumentation operative in this region can be rela-
tively low cost, and the information that can be obtained
about concentration and molecular structure, often, is very
useful.
Absorption of energy in the infrared region of the spec-
trum is different from that of UV/VIS spectrum. Infrared
absorption occurs because the atoms within a molecule or
ion can react to these specific energies by increasing the
amplitude of some vibrational mode. This mode of energy
absorption occurs because of the ability of connected atoms
to stretch, bend, or move about relative to one another. In
this case, the energy that can be absorbed in a particular
situation is dependent on such factors as strength of the
bond, mass of the atoms, interaction of adjacent species
such as the remainder of the molecule or solvents, as well
as other factors. The energy of EMR in the UV/VIS regions
of the spectrum is somewhat higher. Because this higher
energy is absorbed by the electrons within the molecular,
and sometimes, atomic orbitals, the mass of the atoms
do not play a direct role. There is a slight impact due to
atomic size in that the bonding electrons are further from
the nucleus and less energy, typically, is required to get
them motivated. This mode of energy absorption reveals
information about the bonding within the molecule or is
specific to a given species. This allows both qualitative and
quantitative determinations of species that have the ability
to absorb at these specific energy levels.
It is this electronic activation within some portions of
binder molecules that lead to UV degradation. The chalking
of epoxies is very well known. Molecular destruction occurs
when the UV energy is sufficient to form free radicals
within a molecule. The degree of degradation that follows
is related to the stability of these free radicals after forma-
tion. The stability of a free radical is a function of the ability
of the loose electron remaining after bond cleavage to be
able to roam about the molecule. Aromatic rings and con-
jugated double bonds provide this means. A free radical
occurs when the two electrons forming the bond between
atoms in the molecule split and one electron goes to each of
the atoms formerly forming the chemical bond. Any atom
attached to the phenolic oxygen on the benzene ring is very
susceptible to cleavage by UV absorption because of the sta-
bilization offered by the benzenoid ring. This is the source
of the UV degradation in bis-A epoxies.
An important quality of paints and coatings is their
visual appearance. Although the visual region of the spec-
trum is rather small, it is very important when analyzing
coating systems. Color and color stability is a very impor-
tant aspect of paints. UV/VIS spectroscopy can also provide
information on concentration of active species, wavelengths
of highest absorption, filtering efficiency of UV protection
additives and their optimal concentration, as well as other
needs. Transmission spectroscopy is useful in performing
analysis on solutions containing binders, stabilizing addi-
tives, and coloring agents such as dyes. UV/VIS reflectance
and fluorescence spectroscopy provides information about
color and general appearance.
Binders, additives, and pigments that absorb at fre-
quencies in the UV and VIS region may suffer degradation
from these energetic absorptions. While the techniques
used for UV/VIS spectroscopy may be helpful in deter-
mining the frequencies at maximum degradation and
may assist in engineering the optimum stability package
for the coating system [1], degradation testing per se is
addressed elsewhere. UV exposure testing and weathering
analysis employ test procedures such as ASTM Practice
75
Ultraviolet/Visible Spectroscopy
George D. Mills
1
1
President, George Mills & Associates International, Inc. 322 Manchester La., Foley, AL 36535, www.GeorgeMills.com.
MNL17-EB/Jan. 2012
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CHAPTER 75 ULTRAVIOLET/VISIBLE SPECTROSCOPY 915
for Conducting Tests on Paint and Related Coatings and
Materials Using Filtered Open-Flame Carbon-Arc Light
and Water Exposure Apparatus (D822), ASTM Practice for
Testing Paints, Varnishes, Lacquers, and Related Products
Using Enclosed Carbon-Arc Light and Water Exposure
Apparatus (D5031), ASTM Practice for Conducting Tests on
Paint and Related Coatings and Materials Using a Fluores-
cent UV-Condensation Light and Water-Exposure Appara-
tus (D4587), and other standards currently under revision.
The objective of this chapter is to discuss the use of
UV/ VIS spectroscopy in the analysis of coating systems
and components. It is important to be mindful of the actual
mechanism of energy absorption. This is closely tied to
molecular structure and will allow a better understanding
of the total task of engineering the coating formulation with
maximum life expectancy for the end use environment as
well as allowing the design of quality control techniques
useful at the manufacturing level. At the values of energy
levels represented by the frequencies of UV radiation, cer-
tain chemical bond energies can be surpassed. Knowledge
of the mechanism of UV absorption can be helpful in allow-
ing better choices for binders that may be susceptible to
degradation, development of UV-initiated polymerization
catalysts [2], as well as allowing judicial choices of UV sta-
bilizers for those coating systems.
It is important that the paint analyst be aware of the
principles of operation of the instrumentation used to
probe paint systems and components. This will allow for a
clear understanding of what the information received really
means. It is also very important for the analyst to know the
limitations of his instrumentation. Action taken on poor
data can be far worse than taking no action at all!
ELECTROMAGNETIC RADIATION
EMR is a form of energy that possesses both wave-like
characteristics and particle-like characteristics. The wave-
like nature allows the radiation to travel at extremely fast
velocities and to be refracted when passing between bar-
rier restraints. These restraints may be thinly opened slits
or closely spaced atoms in a crystal. Unlike sound, this
energy form may be transmitted through the vacuum of
space without a supporting medium. As a particle, when
radiation interacts with matter, it is absorbed in discrete
packets of energy called photons. The radiation is com-
posed of an electrical force field of oscillating field strength
superimposed on an oscillating magnetic force field at right
angles to one another.
If the vectorial values for the electrical and magnetic
field strength are plotted as a function of distance from
the moving point charge that is generating the EMR, the
graphical presentation in Fig. 1 is obtained. In this plot, the
magnetic field strength is represented as a vector in the xz
plane, and the overlapping plot of the electric field strength
is presented as a vector in the xy plane. The direction of
propagation is down the x-axis. This represents the plot of
a plane-polarized wave of EMR. If all waves coming from
a collection of similar radiators are in the same spacial
orientation, we call the radiation plane polarized light. In
nature, radiation coming from a collection of point sources
will usually be randomly oriented and therefore will not be
polarized. It is useful to note that when a beam of polar-
ized light passes through a collection of absorbing species
that has at least one area of asymmetry, polarized light will
be rotated to some degree. This principle is used to obtain
information about the shapes of particular molecules and
quickly gather information on their concentration.
The wavelength, is usually expressed in units of cen-
timeters, microns, millimicrons, nanometers, or angstroms.
The frequency of the oscillations, v, is the number of cycles
that occur in one second and is therefore equal to the speed
of the radiation divided by the wavelength
v = c/ (1)
the reciprocal of the wavelength is called the wave number,
and is frequently used in spectroscopy. Its units are in recip-
rocal centimeters. The wave number of the radiation, like
its frequency, is proportional to the energy of the radiation,
i.e., the higher the wave number the higher the energy of
the radiation
v = /c (2)
Fig. 2 presents the EMR spectrum and the common name
usually used for that portion of the spectrum.
It is interesting and useful to understand how this
form of energy interacts with the components of coatings.
Note that the value of the energy in the UV/VIS band of the
spectrum is relatively high and is the source of coating deg-
radation. UV radiation from the sun has wavelengths from
about 10 to 400 nm. This equates to an energy level of 3 to
124 eV [3]. This value of destructive energy is sufficiently
to cause electron excitation in atoms and molecules. When
the energy is great enough to cause the homiletic split of
Fig. 1Plot of the magnetic and electric field strength as a
function of distance of propagation away from the generating
point charge.
Fig. 2The complete electromagnetic spectrum.
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916 PAINT AND COATING TESTING MANUAL 15TH EDITION
the two electrons that form a chemical bond in a molecule,
two free radicals are formed. This is quite probable when
one (or both) fragments have some degree of stability in
the degraded condition. This is the reason for the chalking
so common in epoxies. Some crystals are susceptible to
degradation as well. See Ref. [3] for a good review of the
mechanism. The anatase form of titanium dioxide is a good
example of UV degradation of crystalline pigments. This
form of white pigment is often formulated into top coats of
paint to produce a self cleaning surface that chalks and is
rinsed away in rain.
Should the system be prone to damage from UV radia-
tion, it is certain that the system will absorb in this region.
The testing of coatings for degradation caused by these
wavelengths is treated elsewhere, but UV/VIS analysis may
assist in determining failure mechanisms, optimum UV
screening agent concentrations, measurement of residual
stabilizers after testing, and others. Current technology
provides UV/VIS instrumentation for use in various modes,
similar to that used in the infrared region. This includes
transmission mode, fluorescence mode, and specular and
diffuse reflectance modes.
BASIC INSTRUMENTATION
The basic optical path or layout of modern scanning instru-
ments has not changed appreciably over the past years with
the exception of better diode arrays. The optical diagram of a
modern instrument is presented in Fig. 3. Low-cost comput-
ers for doing sophisticated calculations, diode array detec-
tors and better diffraction gratings have allowed important
enhancements. Increased electronic noise suppression has
allowed lower cost-to-benefit ratios in the newer instru-
ments. Software now provides full instrument control,
enhanced data analysis including rapid graphics, and con-
siderable options in report generation. Three-dimensional
plotting enables easy representation of reaction mixtures,
allowing kinetics studies of active systems. While following
the curing kinetics, it is possible to see the influences of
catalysis as a function of temperature and other variables.
Principle of Operation
Basically, the classical instrument will have a source of
radiation, a method for isolating a very small band of that
radiation that is passed through the sample (the mono-
chromator section), a sample holder arranged in such a
manner as to allow passage of radiation having a low band
width, a detector to monitor the quantity of radiation pass-
ing through the sample, and a read-out or data collection
system. This is represented schematically in Fig. 4. With the
advent of the diode array detector, multi-frequencies may
now be detected at one time. The schematic for this type of
instrument is presented in Fig. 5. Here the sample is irradi-
ated with a broad band of radiation. The light that emerges
is then sent to a monochromatic device that spreads the
radiation out across an array of CCD detectors banked
in such a way as to see all of the emerging broadband
radiation. The separation of the signal occurs because each
area on the detector is read independently and the posi-
tion where the radiation falls on the detector is a function
of its wavelength (energy) for that region of the spectrum.
Those parameters that are most important for UV/VIS/
near-infrared (NIR) spectroscopy include reproducibility,
sensitivity, and wavelength range. This UV/VIS arrangement
is also used as a detector for other instruments, for example,
performing separation of UV/VIS active paint polymers and
additives as in high-performance liquid chromatography [4].
Calibration of Instruments
The calibration of instruments having absorption in the UV/
VIS/NIR wavelengths may follow ASTM E275-08 Standard
Fig. 3The optical path of a modern UV/VIS spectrophotometer (Model 920, GBC Scientific Equipment, Arlington
Heights, IL 60004).
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CHAPTER 75 ULTRAVIOLET/VISIBLE SPECTROSCOPY 917
Practice for Describing and Measuring Performance of
Ultraviolet, Visible, and Near-Infrared Spectrophotometers
[5]. Here, a mercury arc provides twelve very unique peaks
having extremely precise wavelengths for comparison with
the values reported by the instrument. Fig. 6 presents the
mercury arc emission spectrum in the UV/VIS region show-
ing the reference wavelengths. Another useful standard that
provides established specific reference peaks is holmium
glass (Corning No. 3130). This standard has the advantage
over the mercury arc in that it may be conveniently placed
within the instrument with minimum problems. That spec-
trum is presented as Fig. 7.
SPECTRAL INTERPRETATION: QUALITATIVE AND
QUANTITATIVE INTERPRETATION OF SPECTRA
The output of the UV/VIS spectroscopy instrument will
usually be a plot of absorbance versus wavelength and is
called the absorption spectrum. Absorption of the UV/VIS
radiation usually occurs when an electron within the active
portion of the sample absorbs the energy of a photon. The
molecular consequence of the energy absorption process is
for an electron to jump to a higher energy level. This loss of
energy in the incident beam is taken as the absorption and
the plot records these losses as a function of wavelength.
In most instances, the energetic electron will return to its
former stable state by liberating heat. In some instances,
the very energetic electron may step down by way of other
orbitals. The energy released may then be in the form of
radiation, but at a different wavelength. This is the basis of
fluorescence spectroscopy and adds another dimension to
analysis of some coating components.
The use of UV/VIS spectroscopy techniques to identify
an unknown is possible because the intensity of the absorp-
tion at a given frequency is characteristic of the species.
By comparing the wavelength at maximum absorption, the
intensity tables will provide probable candidates. One such
set of tables, about 80 pages, is given in Ref. [6].
The derivation of the quantitative relationship using
absorption of radiation requires consideration of the term
radiant power. Radiant power, P, is the amount of radiant
energy striking a unit area per unit time. If we use a con-
stant cell length, two factors affect the amount of power
observed at each successive location along the path of a
monochromatic incident beam as it passes through the
solution. One is the amount of power, P, at the start of each
successive arbitrary step along the way, and the other is
the number of absorbing species in the path of the radia-
tion. This can be stated as proportionality. The incremental
change in power, P, is proportional to the power of the
radiation and the number of absorbing species, N. This
may be expressed mathematically as the proportionality
P PN (3)
This yields the equality when multiplied by k, the propor-
tionality constant
P = PN (4)
The negative in the equation is the result of powers being
lost as it passes through the solution. Theoretically, by mak-
ing the intervals between measurements infinitely small,
the mathematics reduces to the differential equation
dP/P = dN (5)
If we integrate between the limits of P
0
when N = 0 and P
at some value of N and solve the differential equation, we
then have
ln(P/P
0
) = N (6)
To convert the actual number of absorbing species to a
more convenient term of concentration, c, we consider the
volume where contained and Avogadros number. Thus
N = (6.023 10
23
cbs/1000) (7)
where c is concentration in moles per liter, b is the path
length in centimeters, and s is the cross-sectional area in
square centimeters. When the constants are combined, this
yields
Fig. 4Component arrangement of the classical UV/VIS instrument.
Fig. 5Component arrangement of the modern UV/VIS instrument using a diode array detector.
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918 PAINT AND COATING TESTING MANUAL 15TH EDITION
log(P/P
0
) = bc = A (the absorbance) (8)
which is Beers law.
Beers law is the basis of all quantitative spectral mea-
surements. This law, often referred to as the Bourger-Beer
or Lambert-Beer absorption law, may be stated exponen-
tially, with intensity of the radiation rather than power, as
I= I
0
e
abc
. The logarithmic form is used more often
A = log
10
(I
0
/I) = log
10
(I/T) = abc = bc (9)
where
A = absorbance (often referred to as optical density),
a, = molar absorptivity or absorbency,
b = cell path length, cm,
c = concentration, moles/liter,
I
0
= intensity of incident radiation of the sample,
I = intensity of radiation transmitted by the sample,
and
T = (I/I
0
) = fraction of radiation transmitted by the
sample or transmittance.
The reliability and sensitivity of the quantitative method
will depend on the choice of a suitable band and suitable
solvent. The strongest band free of interference from other
sample components is usually chosen, but modern com-
puter treatment of data will frequently allow deconvolution
Fig. 6The mercury arc emission spectrum in the UV/VIS region with the corresponding reference wavelengths (from ASTM E275).
Fig. 7Spectrum of holmium glass (Corning No. 3130) showing reference wavelengths (from ASTM E275).
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CHAPTER 75 ULTRAVIOLET/VISIBLE SPECTROSCOPY 919
of overlapping spectra. Thomas and Ando have published
an interesting, low level introduction to the practical and
fundamental aspects of this technology [7]. Interested
readers might also search the Internet under the heading
Literature Ultraviolet-Visible Spectrometry or a similar
one to find several descriptions of this technology. Many of
the descriptions are free.
Other related ASTM Standards include: ASTM
E131-05, Standard Terminology Relating to Molecular
Spectroscopy; ASTM E275-08, Standard Practice for
Describing and Measuring Performance of Ultraviolet,
Visible, and Near-Infrared Spectrophotometers; and
ASTM E958-93(2005) Standard Practice for Measuring
Practical Spectral Bandwidth of Ultraviolet-Visible Spec-
trophotometer.
In general, UV quantitative measurements require
calibration in the solvent chosen for the method. A simple
calibration curve of concentration versus absorbance can
be prepared from the standards. However, it is advisable
to study all known components to determine potential
interferences.
POTENTIAL PROBLEMS
When the spectroscopist is performing quantitative deter-
minations that require a linear calibration curve, Beers law
must be applicable over the concentrations under investiga-
tion. This is not true in all instances. When deviations exist
in Beers law at the concentrations under investigation,
extrapolation from one concentration may not be truly
representative of the system concentration. Concentration
of some active species such as the high nucleophilic amino
functional aromatics used as epoxy cold- temperature
catalysts may react with the surface of metal pigments,
effectively removing them from the solution and yielding
low results.
Another potential problem occurs because Beers law
is based on monochromatic, or single wavelength, light.
While lasers can produce single wavelength radiation, they
cannot produce the variable wavelengths over the required
bandwidth. The typical band pass of analytical instruments
will depend on the technique being used to produce the
monochromatic light. The use of prisms and slits can
lead to an appreciably high band pass on the order of 10
to 20nm. Instruments with holographic gratings and auto-
matic peaking can be as low as 2 nm.
REFERENCES
[1] Bower, D. R., Chemical Criteria for Durable Automotive
Topcoats,J. Coat. Technol., Vol. 66, No. 835, 1994, pp. 565.
[2] Cazaux, F., Coqueret, X., Lignot, B., Loucheux, C, Rousseau, P.,
Flat, J. J., Leroux, S., and Verge, C, Epoxidized Polybutadiene:
A Novel Prepolymer for Cationically UV-Curable Coatings,J.
Coat. Technol., Vol. 66, No. 838, 1994, pp. 234.
[3] Mahmud, G. A., Thesis: Increasing the Coating Resistance
Against UV Degradation and Corrosion Using Nanocomposite
Coating, Wichita State University, December 2009; http://
soar.wichita.edu/dspace/bitstream/handle/10057/2523/ THE-
SES2009_35.pdf?sequence = 1.
[4] See http://hplc.chem.shu.edu/NEW/HPLC_Book/Detectors/
det_uvda.html.
[5] Annual Book of Standards Vol. 03.06; http://www.astm.org/
Standards/E275.htm.
[6] Robinson, J. W., Ed., Practical Handbook of Spectroscopy, CRC
Press, Boca Raton, FL, 1991.
[7] Thomas, M. J. K., and Ando, David J., Ultraviolet and Visable
Spectrosposcopy: Analytical Chemistry by Open Learning, 2nd
ed., John Wiley & Sons, Nov. 1996, p. 250.
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920
76
X-Ray Analysis
A. Monroe Snider, Jr.,
1
X-RAY DIFFRACTION (XRD) AND X-RAY FLUORES-
cence spectrometry (XRFS) are powerful, well-established
tools used by analytical chemists in many areas of technol-
ogy. They have great utility in the coatings industry. In areas
where they are applicable, they are frequently the quickest
and easiest techniques available. XRD is convenient for the
identification of diverse crystalline solids encountered in
paint research laboratories and production plants. It is par-
ticularly well suited for use in the identification and quanti-
tative analysis of crystalline pigments and extenders, either
when they are alone or present in paste or paint. XRFS is
useful as a stand-alone technique for elemental analysis
and as a complementary tool for use with other analytical
techniques. X-ray spectrometers typically can analyze all
elements with an atomic number of about 11 (sodium) and
higher, but some units can reach as low as atomic number
5 (boron). XRFS can span the concentration range from
parts per million to high percentages for most elements in
liquid or solid samples. Dedicated XRFS units, much lower
in cost than scanning spectrometers, can be set up to detect
and quantify one or a few specific elements. Portable XRFS
units are available for field investigations. The present sec-
tion summarizes the principles and methodology of XRD
and XRFS.
RADIATION SAFETY
Although operation of modern X-ray instruments involves
little risk to the operator when proper safety practice is fol-
lowed, it is imperative that the operator knows and follows
proper practice. Exposure to excessive quantities of X-ray
radiation is injurious to health. Therefore, users should
avoid exposing any part of their bodies, not only to the
direct beam, but also to secondary or scattered radiation
that occurs when an X-ray beam strikes or passes through
any matter. It is strongly recommended that users check the
degree of exposure by film badge or dosimeter carried on
them. X-ray instruments should not be operated with safety
interlocks, shielding, or other protective devices removed or
deactivated. Before using the equipment, all persons des-
ignated or authorized to operate X-ray instrumentation or
supervise its operation should have a full understanding of
its nature and should also become familiar with established
safe exposure factors by careful study of the American
National Standards Institute Standard N43.2-2001, Radia-
tion Safety for X-ray Diffraction and Fluorescence Analysis
Equipment [1]. Inquiries should be made of state agencies
about existing requirements.
X-RAY DIFFRACTION
Application
TYPES OF SAMPLES
XRD is widely used for the analysis of analytes that are
crystalline or polycrystalline solids, i.e., solids comprised
of atoms or ions arranged in a three-dimensional lattice
pattern [2]. The sample may be totally crystalline or may
contain one or more crystalline components interspersed
with noncrystalline material. Common types of materials
analyzed include pigments and extenders (alone, in grind
pastes, in liquid and powder paints, or in dried paint chips),
miscellaneous crystalline solids, and pretreatment on metal.
XRD also has important uses in the study of amorphous
materials such as polymers and inorganic glasses [2]. In the
case of scanning X-ray diffractometers, a flat surface of the
specimen must be presented to the X-ray beam.
Types of Information Provided
X-ray diffraction analysis permits qualitative and quantita-
tive analysis of crystalline components. It can indicate the
degree of crystallinity, crystallite orientation, and long-
range order in polymers. Long-range order in liquids has
also been studied [2].
Range of Concentrations
As a rule, crystalline components can be analyzed by
routine methods at concentrations ranging from 100 %
down to approximately 1 % or 2 %. However, the limit of
detection varies widely with the identity of the analyte of
interest, the number and identity of other components, the
quality of the instrumentation used for analysis, and the
instrument operating conditions. Analysis of components
at concentrations as low as 0.01 % has been reported [3].
Physical Principles
XRD experiments are performed by irradiating a speci-
men of crystalline or polycrystalline material with a beam
of X-rays of known wavelength and determining the angle
2 between the incident beam and each diffracted beam of
X-rays and measuring the intensity of each diffracted beam.
Diffraction occurs only at discrete angles defined by the
Bragg equation [2,4,5]
n d = 2 sin
where
n = a positive integer (usually one),
= the wavelength of the X-rays used,
1
President, Snider Scientific Consulting Group, LLC, 602 Orchard Hill Dr., Pittsburgh, PA 152382518.
MNL17-EB/Jan. 2012
Copyright 2012 by ASTM International www.astm.org
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CHAPTER 76 X-RAY ANALYSIS 921
d = the distance between layers of atoms of a set of lat-
tice planes, and
= the angle between the incident X-ray beam and the
lattice plane [5].
The wavelength of the X-rays is determined by the choice
of the x-ray tube target material, usually copper, and is thus
known. The wavelength of copper K
peak of silicon on extruded aluminum from which poorly adhering paint has been peeled: (a) peeled only; (b)
peeled and washed with hexane.
Fig. 15Plot of weight of chromate conversion coating on
aluminum sheet as a function of fluorescent signal intensity.
Each point is an average of three 10-s measurements.
TABLE 3Concentration of silicone,
determined by XRFS, in batches of resin
used in batches of paint of known extent
ofcratering
Extent of Cratering Concentration of Silicone, ppm
None 3
None 4
None 7
Bad 13
Bad 13
Worst 40
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938 PAINT AND COATING TESTING MANUAL 15TH EDITION
Dedicated x-ray analyzers have also been used to moni-
tor the amount of rutile in batches of paint in production
plants [48]. Caution: A different calibration plot must be
established for each paint formulation to be monitored,
unless the compositions of the dried paints films are essen-
tially identical in all respects other than rutile content.
Guidance on the use of X-ray analyzers to determine the
coating thickness is given in ASTM Standard Test Methods
A754/A754M, Coating Weight (Mass) of Metallic Coatings
on Steel by X-Ray Fluorescence [49], and B568, Measure-
ment of Coating Thickness by X-Ray Spectrometry [50].
ANALYSIS IN THE FIELD
Concern over the potential adverse health effects of lead
in paint in residential buildings has prompted an interest
in convenient, nondestructive methods of testing for lead.
Fully portable X-ray analyzers that can detect lead in paint
on walls and other surfaces are commercially available.
The analyzers can detect lead-containing paint beneath lay-
ers of lead-free paint, and some can provide direct readout
of the amount of lead per unit area of paint surface [51].
The accuracy and precision are not well documented. The
Department of Housing and Urban Development estab-
lished a limit of 1.0 mg of lead per cm
2
of painted surface,
a level detectable by portable analyzers [52]. Caution: In
accordance with the constraints of all X-ray fluorescence
spectrometers, matrix differences between test samples
being analyzed and reference samples used to establish
instrument calibration curves may compromise the accu-
racy of the apparent lead concentrations reported by por-
table units.
Other uses of portable analyzers include determination
of the weight of pretreatment on metal, the thickness of
paint, and the concentration of key elements in samples at
environmental cleanup sites.
SUMMARY
XRD and XRFS, used alone or in combination, can provide
valuable information about coatings, coating ingredients,
impurities, and substrates. Sample preparation effort is
minimal for both techniques. XRD offers easy qualitative
and quantitative analysis of crystalline materials in gen-
eral and pigments in particular. XRFS is widely useful for
qualitative analysis and, when suitable standards are used,
for quantitative analysis. Attractive features of XRFS for
quantitative analysis include its suitability for all elements
except a few with lowest atomic number, applicability
over a broad concentration range, tolerance of chemically
reactive specimens, and applicability to samples of diverse
physical states. Both XRD and x-ray spectrometry are suit-
able for applications including basic research, product
and process development, quality control, and practical
problem solving. The area of greatest potential growth
is the use of dedicated x-ray fluorescence spectrometers
in production plants for quality control, particularly for
on-line monitoring.
REFERENCES
[1] ANSI N43.2-2001, Radiation Safety for X-ray Diffraction,
Fluorescence Analysis Equipment, American National Stan-
dards Institute, New York, 2001.
[2] Klug, H. P., and Alexander, L. E., X-ray Diffraction Procedures,
John Wiley & Sons, New York, 1974.
[3] Schreiner, W. N., Applications Note, IC Laboratories, Amawalk,
NY, 1989, p. 1.
[4] Bragg, W. L., The Diffraction of Short Electromagnetic Waves
by a Crystal, Proc. Cambridge Philos. Soc., Vol. 17, 1912, pp.
4357.
[5] Bragg, W. H., and Bragg, W. L., The Reflection of X-rays by
Crystals, Proc. Phys. Soc., London, Sect. A, Vol. A88, 1913,
pp. 428438.
[6] Foster, B. A., and Wolfel, E. R., Adv. X-Ray Anal., Vol. 31, 1988,
pp. 325330.
[7] Tissot, R. G., and Eatough, M. O., Practical and Unusual
Applications in X-ray Diffraction Using Position Sensitive
Detectors, Adv. X-Ray Anal., Vol. 34, 1991, pp. 349355.
[8] Goehner, R. P., and Eatough, M. O., A Study of Grazing Inci-
dence Configurations and Their Effect on X-ray Diffraction
Data, Powder Diffr., Vol. 7, No. 1, 1992, pp. 25.
[9] Huang, T. C., Surface and Ultra-Thin Film Characterization
by Grazing-Incidence Asymmetric Bragg Diffraction, Adv.
X-ray Anal., Vol. 33, 1990, pp. 9199.
[10] ASTM D4451, Standard Test Method for Pigment Content of
Paints by Low-Temperature Ashing, Annual Book of ASTM
Standards, Vol. 06.01, 2008.
[11] ASTM D3723-05e1, Standard Test Method for Pigment Con-
tent of Water-Emulsion Paints by Low-Temperature Ashing,
Annual Book of ASTM Standards, Vol. 06.01, 2005.
[12] ASTM D2371, Standard Test Method for Pigment Content of
Solvent-Reducible Paints, Annual Book of ASTM Standards,
Vol. 06.01, 2001.
[13] ASTM D2698, Standard Test Method for Determination of
the Pigment Content of Solvent-Reducible Paints by High-
Speed Centrifuging, Annual Book of ASTM Standards, Vol.
06.01, 2010.
[14] Scott, R. W., Applications of X-ray Diffraction in the Paint
Industry, J. Paint Technol., Vol. 41, No. 534, 1969, pp.
422430.
[15] Scott, R. W., Treatise on Coatings, Vol. 2, Part II, Marcel
Dekker, New York, 1976, pp. 591624.
[16] ICDD Powder Diffraction File, International Centre for Dif-
fraction Data, Newton Square, PA, 2010.
[17] Jenkins, R., and Holomany, M., PC-PDF: A Search/Display
System Utilizing the CD-ROM and the Complete Powder
Diffraction File, Powder Diffr., Vol. 2, No. 4, 1987, pp.
215219.
[18] ASTM D934, Standard Practices for Identification of
Crystalline Compounds in Water-Formed Deposits by X-ray
Diffraction, Annual Book of ASTM Standards, Vol. 11.02,
2008.
Fig. 16Plot of the amount of cobalt in a drier solution as
measured by a benchtop XRFS unit versus the accepted
amount.
Copyright by ASTM Int'l (all rights reserved); Mon Aug 20 14:54:36 EDT 2012
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CHAPTER 76 X-RAY ANALYSIS 939
[19] Chung, F. H., Quantitative Interpretation of X-ray Diffraction
Patterns of Mixtures. I. Matrix-Flushing Method of Quantita-
tive Multicomponent Analysis, J. Appl. Crystallogr., Vol. 7, No.
6, 1974, pp. 519525.
[20] Chung, F. H., Quantitative Interpretation of X-ray Diffraction
Patterns of Mixtures. II. Adiabatic Principle of X-ray Diffrac-
tion Analysis of Mixtures, J. Appl. Crystallogr., Vol. 7, No. 6,
1974, pp. 526531.
[21] Hubbard, C. R., and Snyder, R. L., RIR Measurement and
Use in Quantitative XRD, Powder Diffr., Vol. 3, No. 2, 1988,
pp. 7477.
[22] Davis, B. L., Kath, R., and Spilde, M., The Reference Intensity
Ratio: Its Measurement and Significance, Powder Diffr., Vol.
5, No. 2, 1990, pp. 7678.
[23] Snyder, R. L., The Use of Reference Intensity Ratios in X-ray
Quantitative Analysis, Powder Diffr., Vol. 7, No. 4, 1992, pp.
186193.
[24] Smith, D. K., Johnson, Jr., G. G., Scheible, A., Wims, A. M.,
Johnson, J. L., and Ullmann, G., Quantitative X-ray Powder
Diffraction Method Using Full Diffraction Pattern, Powder
Diffr., Vol. 2, No.2, 1987,pp. 7377.
[25] Davis, B. L., and Smith, D. K., Tables of Experimental Refer-
ence Intensity Ratios, Powder Diffr., Vol. 3, No. 4, 1988, pp.
205208.
[26] Davis, L. D., Smith, D. K., and Holomany, M. A., Tables of
Experimental Reference Intensity Ratios, Table 2, Powder
Diffr., Vol. 4, No. 4, 1989, pp. 201205.
[27] Goehner, R. P., Advances in X-ray Analysis, Vol. 25, Plenum
Press, New York, 1981, pp. 309313.
[28] Karlak, R. F., and Burnett, D. S., Quantitative Phase Analysis
by X-ray Diffraction, Anal. Chem., Vol. 38, No. 12, 1966, pp.
17411745.
[29] Dyakonov, J., Mischenko, K., Hering, A., Unger, G., Korecky,
J., Melka, K., Zoubkova, J., Raynov, N., Thekhlanova, N.,
Rischak, G., Sidorenko, and Volkov, M., Interlaboratory Tests
of X-ray Quantitative Phase Analysis, Powder Diffr, Vol. 7, No.
3, 1992, pp. 137141.
[30] Kamarchik, P., and Ratliff, J., Quantitative Analysis of Plate-
like Pigments by X-ray Diffraction, Adv. X-Ray Anal., Vol. 26,
1983, pp. 129135.
[31] ASTM D3720, Standard Test Method for Ratio of Anatase to
Rutile in Titanium Dioxide Pigments by X-Ray Diffraction,
Annual Book of ASTM Standards, Vol. 06.03, 2011.
[32] Bertin, E. P., Principles and Practices of X-ray Spectrometric
Analysis, Plenum Press, New York, 1970.
[33] Bertin, E. P., Introduction to X-ray Spectrophotometric Analy-
sis, Plenum Press, New York, 1978.
[34] Campbell, W. C., Energy-Dispersive X-ray Emission Analysis,
Analyst (Cambridge, U.K.), Vol. 104, No. 1236, 1979, pp. 177195.
[35] Kunz, F. W., Energy-Dispersive X-ray Fluorescence Analysis of
Research Materials, Spectroscopy, Vol. 3, No. 8, 1988, pp. 1623.
[36] Valkovic, V., Markowicz, A., and Haselberger, N., X-ray Spec-
trometry, X-Ray Spectrom., Vol. 22, No. 4, 1993, pp. 199207.
[37] Kalnicky, D. J., and Ramanujam, R. S., Analytical Division,
Vol. 25 (Edmonton Spring Symposium, 1991, Part 2), 1991,
pp. 262274.
[38] Piorek, S., and Rhodes, J. R., Adv. Instrum. Control, Vol. 41,
No. 3, 1986, pp. 13551368.
[39] Driscoll, J. N., Laliberte, R., and Wood, C., Field Detection
of Lead in Paint and Soil by High Resolution XRF, American
Laboratory, Compare Networks, Inc., South San Francisco,
CA, 1995, pp. 34H34M.
[40] Leyden, D. E., Fundamentals of X-ray Spectrometry as Applied
to Energy Dispersive Techniques, Tracor X-ray, Inc., Mountain
View, CA, 1984, pp. 3945.
[41] Spec Handbook of Sample Preparation and Handling, 2007,
Spex Industries, Inc., Edison, NJ.
[42] ASTM D2622, Standard Test Method for Sulfur in Petroleum
Products by Wavelength Dispersive X-ray Fluorescence Spec-
trometry, Annual Book of ASTM Standards, Vol. 05.01, 2010,
ASTM International, West Conshohocken, PA.
[43] ASTM D6247, Standard Test Method for Determination of
Elemental Content in Polyolefins by Wavelength Dispersive
X-Ray Fluorescence Spectrometry, Annual Book of ASTM
Standards, Vol. 08.03, 2010, ASTM International, West Con-
shohocken, PA.
[44] Cianflone, R. A., Internal Report on the Determination by XRFS
of the Weight of Chromate Conversion Coating on Aluminum,
Cianflone Scientific Instruments Corporation, Pittsburgh, PA,
2001.
[45] ASTM D5723, 2010, Standard Practice for Determination of
Chromium Treatment Weight on Metal Substrates by X-ray
Fluorescence, Annual Book of ASTM Standards,Vol. 06.02,
ASTM International, West Conshohocken, PA.
[46] SPECTRO Analytical Instruments, Inc. (formerly ASOMA),
Ca, Zn, and Zr Paint Additives, X-ray Fluorescence Applica-
tion Report Number 822, Marble Falls, TX, 1995.
[47] SPECTRO Analytical Instruments, Inc. (formerly ASOMA),
Ca, Zn, and Zr Paint Additives, X-ray Fluorescence Applica-
tion Report Number 863, Marble Falls, TX, 1995.
[48] Kamarchik, P. and Cunningham, G. P., Applications of X-Ray
Techniques to Coatings Analysis, Prog. Org. Coat., Vol. 8,
1980, pp. 81107.
[49] ASTM A574/A754M, Standard Test Method for Coating
Weight (Mass) of Metallic Coatings on Steel by X-Ray Fluo-
rescence, Annual Book of ASTM Standards,Vol. 01.06, 2008,
ASTM International, West Conshohocken, PA.
[50] ASTM B568, Standard Test Method for Measurement of
Coating Thickness by X-ray Spectrometry, Annual Book of
ASTM Standards,Vol. 02.05, 2009, ASTM International, West
Conshohocken, PA.
[51] Rasberry, S. D., Investigation of Portable X-ray Fluorescence
Analyzers for Determining Lead on Painted Surfaces, Appl.
Spect.,Vol.27, No.2, 1973, pp. 102108.
[52] McKnight, M. E., Boyde, W E., and Roberts, W. E., Methods
for Measuring Lead Concentration in Paint Films, NISTIR
89-4209, U.S. Department of Commerce, 1989.
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Part 16: Specifications
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943
INTRODUCTION
COATING AND PAINT SPECIFICATIONS ARE A COM-
monality established between a customer and a supplier.
They define what a customer can expect from a supplier
and what the supplier is required to do to meet the cus-
tomers expectations. Often such agreements are between
organizations that purchase the products in large volume
for construction and maintenance projects, for resale to
distributors, or to end-use consumers. Details of how to
carry out the testing required to meet such specifications is
left to the devices or procedures (often termed standards or
test methods) of a third, uninterested party such as ASTM
International or similar groups that are listed elsewhere
in this chapter. Purchasing organizations may be federal,
state, and local governmental agencies and departments,
large industries as for example the automotive, petro-
leum, and pipe industries, public utilities, railroads, retail
companies such as Sears and Wal-Mart, universities and
other educational institutions, as well as others. However,
in certain instances, the standards used to meet the specifi-
cations can carry down to the final consumer as sometimes
evidenced on certain products, for example the listing of
volatile organic compounds on a can of paint.
Simplistically, a specification is a precise, though
detailed, statement of requirements that must be satisfied
by a material, product, system, or service that indicates the
proceduresstandards or test methodsto be followed
when determining whether each of the requirements is
satisfied [1]. Paints and coatings used in industrial new
construction may be specified in construction documents,
while such materials used in maintenance finishes or sold
through retail outlets may be described in the particular
specifications of the purchasing organization. Engineering
departments often specify finishes applied by large manu-
facturing industries, as, for example, the automotive indus-
try, the appliance industry, and the packaging industry.
Those who develop the specifications for large quantities of
original equipment, maintenance or other finishes, such as
public utilities, transportation organizations, and govern-
ment agencies, purchase on a specification basis and most
often by competitive bidding.
Coating specifications set by, for example, the United
States Navy and other government agencies will sometimes
specify that a coating or paint be manufactured according
to a specific formula or recipe that passes the require-
ments stated in particular, delineated test methods (www.
nstcenter.com). If one goes to the Technical Resources tab
at this site and clicks on Standards and Specs, items that
are used to specify many products can be found.
Federal Test Method Standard 141D, Paint, Varnish,
Lacquer, and Related Materials: Methods of Inspection,
Sampling and Testing is a document
2
that describes a
number of coating test methods used by various Federal
agencies in their specifications for a number of products.
The test methods include coating material characterization
tests, volume solids, nonvolatile content, density/weight
per gallon, drying time, spectroscopic analyses, chemical
resistance, corrosion resistance, as well as other coating
performance characteristics such as adhesion, abrasion
resistance, accelerated weathering, hardness, impact resis-
tance, and the like.
An example of a detailed specification used by the
United States Navy that specifies a paint formula is MIL-
DTL-15090D, November 6, 1996, Enamel, Equipment, Light
Gray (Navy Formula 111). To illustrate the complexity of
the requirements, within this specification, two particular
Federal and two particular Department of Defense specifi-
cations as well as two Federal Standards are included along
with two Environmental Protection Agency documents
and a reference to the Federal Register. The requirements
do not stop with these inclusions. Also included in the
specification are 28 ASTM standard test methods and stan-
dard practices and one Steel Structures Painting Council
specification. The actual formula for this paint specifies 16
specific ingredients by weight and weight percentage and
a variety of quantitative requirements for the liquid paint
and the final paint film. Military specifications such as this
one may be altered and may be superseded, as was the case
with the above-cited MIL-DTL, which superseded MIL-E-
15090C, March 30, 1982. Those interested in supplying or
bidding on contracts for the various products should main-
tain an awareness of such changes.
77
Paint and Coating Specifications
and Standards
Joseph V. Koleske
1
1
1513 Brentwood Rd, Charleston, WV 25314-2307
2
Federal specifcations and standards discussed in this chapter refer to documents of the United States of America government and are
available through the U. S. General Services Administration, Federal Supply Service, FSS Product Acquisition Center, Supply Standards
Division, Arlington, VA 22202. Downloadable versions of the documents are available on the Internet. When international or specifc country
documents are discussed, they will be noted by country designation (see Table 1 for some examples).
MNL17-EB/Jan. 2012
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944 PAINT AND COATING TESTING MANUAL 15TH EDITION
The United States General Services Administration
has a Numeric List of Federal Standards available on the
Internet (www.fss.gsa.gov/pub/fedspecs/). This site has both
numeric and alphabetical listings of Federal Standards,
Federal Qualified Products, and other publications. Also
included are ways to download the publications, costs,
addresses, and other useful information.
SPECIFICATION CONSIDERATIONS
The Construction Specifications Institute (CSI) [2] indi-
cates that the following items should be considered in a
project construction specification: scope, related sections,
referenced documents, definitions, performance require-
ments or properties, submittals, quality assurance, delivery-
storage-handling project considerations, and sequence
scheduling. Submittals also cover paint and coating prod-
uct data as well as color samples.
Material specifications in the ASTM format [3] usually
include terminology, ordering information, chemical com-
position, physical and mechanical properties, performance
requirements, sampling, physical and analytical test meth-
ods, inspection, packaging and marking, and, if needed,
quality assurance.
Donlin [4] has an excellent description of the complex
military standards system. His study summarizes informa-
tion from government manuals, standards, specifications
as well as other documents. It represents an effective way
to become familiar with the governments documentation
system that was in place when the study was developed and
make its complexity easier to understand. It is pointed out
that the federal documents were developed with govern-
ment funds, and, if unclassified, are readily available for
public use. The article also contains listing of many mil-
specs as they are often termed.
Some paint and coating specifications (for example,
those for military use) require prequalification of the
products described. Such a requirement exists when the
time to conduct tests will exceed 30 days, when quality
conformance inspection would require special equipment
not commonly available, or when the specification deals
with life survival or emergency life-saving equipment. The
specifications for such products include the requirements
for qualification, the qualification tests, and the name of
the activity responsible for qualification. Products that are
so qualified are listed on Qualified Products Lists.
SOURCES OF SPECIFICATIONS AND STANDARDS
International Sources
International specifications and standards for paints and
coatings are of interest in these days of international or
global commerce. For example, Canadian standard 1-GP-
71, Methods of Testing Paints and Pigments, is available
from the Canadian General Standards Board (CGSB). This
particular standard contains about 80 methods of analysis
in the category termed Paints and Related Products. In
Germany, the German Institute of Standardization (DIN)
develops standards. The International Organization for
Standardization
3
(ISO) is a nongovernmental network of
the national standards institutes of 146 countries who
contribute to the development, manufacturing, and supply
of products and services in an efficient, clean, safe man-
ner. ISO standards may be obtained from the American
National Standards Institute (ANSI). Table 1 is a listing of
the address and other pertinent information about these
organizations and about several other organizations that
deal in specifications and standards.
The Asian Forum for the Standardization of Informa-
tion Technology (AFSIT) is an organization that has 16
Asian country members. It deals in the promotion of the
active information exchange of technology and its stan-
dardization. It can be accessed on the Internet at www.cicc.
or.jp/ where one can find routes to the standards depart-
ment of their member countries, such as India, Republic of
Korea, Sri Lanka, Vietnam, and several others.
In the summer of 2004, ASTM International (www.
astm.org) announced that they had signed a Memorandum
of Understanding (MOU) with the national standards body
of China, the Standardization Administration of the Peo-
ples Republic of China (SAC). This is expected to accelerate
development of product and testing standards in China,
encourage greater access to ASTM standards in China,
and give a greater voice to Chinese experts in the content
of ASTM standards. This interaction furthers a history of
ASTM involvement with Asian standards organizations
such as the Chinese National Institute of Standardization
(CNIS) and the Shanghai Institute of Standardization (SIS).
A similar MOU was completed in June 2001 between ASTM
Committee D01 on Paints and Related Coatings, Materials,
and Applications and ISO TC 35 on Paints and Varnishes
[5]. The purpose was to reduce the duplication of standards
activities.
Automobile manufacturers have developed their own
standards, which may incorporate many standards and
methods of organizations such as ASTM International.
Such private industry standards can and often do differ
from one manufacturer to another and are known by their
own in-house designations. Usually these standards are
available to the public or to vendors so they can develop
products that meet the requirements of the industry. Other,
usually large scale, manufacturers also have their own
standards.
Although the list given in Table 1 is not complete, it
should provide guidance to interested parties. Wide vari-
eties of standards can be obtained (purchased) from SAI
Global (www.sai-global.com), Beuth Verlag (www.beuth.
de), British Standards (www.StandardsUK.com), and many
others at international and national sites.
Non-Government Sources
TECHNICAL SOCIETIES
Committee D-1 on Paint and Related Coatings, Materials,
and Application of ASTM (See Table 1) has developed an
extensive number, more than 670 standards, test methods,
practices, and procedures that are concerned with paints
and coatings. These standards are published as Vols. 6.01 to
6.04 of the Annual Book of ASTM Standards. They are also
available as separate standards. Standards that relate to the
ASTM test methods, procedures, and guides related to the
radiation curing of coatings have been published and are
3
ISO is a nongovernmental organization. This is a network of the
national standards of 157 countries with one member per country.
The organization is coordinated by a Central Secretariat in Geneva,
Switzerland, and it acts as a bridging network that can obtain con-
sensus on solutions that meet both the requirements of business
and needs of society.
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CHAPTER 77 PAINT AND COATING SPECIFICATIONS AND STANDARDS 945
TABLE 1Selected organizations/sources that are concerned with specifications and standards
Organization Abbreviation Mailing Address Telephone FAX E-mail Address
Web Address,
http://www.
ASTM
International
ASTM 100 Barr Harbor
Drive West
Conshohocken,
PA 19428-2959
610-832-9500 610-832-9555 service@local.astm.org astm.org
American
Architectural
Manufacturers
Association
AAMA 1827 Walden
Office Square,
Suite 550
Schaumburg,
IL60173
847-303-5664 847-303-5774 See Website for
Various
aamanet.org
American
Association of
State Highway &
Transportation
Officials
AASHTO 444 No. Capitol
St. NW Suite 249
Washington, DC
20001
202-624-5800 202-624-5806 info@aashto.org transportation.
org
American
Institute of
Architects
AIA 1735 New
York Ave., NW
Washington, DC
20006
800-AIA-3837
202-626-7300
202-626-7547 infocentral@aia.org aia.org
American
National
Standards
Institute
ANSI 25 West 43rd
Street 4th Floor
New York, NY
10036
212-642-4900 info@ansi.org ansi.org
British Standards
Institution
BSI Good Relations
Holborn Gate 26
Southampton
Bldgs. London
WC2A 1PQ UK
+44 (0) 20
7861 3188
+44 (0) 20
7861 3131
cservices@bsiglobal.
com
bsi-global.com or
StandardsUK.com
Canadian General
Standards Board
CGSB Place du Portage
11/6B1 11 Laurier
Street Gatineau,
Quebec
819-956-0425
800-665-2472
819-956-5644 See Website for
Various
Ncr.cgsb-ongc@
pwgsc.gc.ca
China
Association for
Standardization
CAS ... 010-68033227/
68048948
... cas@china-cas.com china-cas.com
Construction
Specifications
Institute
CSI 99 Canal Center
Plaza, Suite 300
Alexandria, VA
22314
800-689-2900 703-684-8436 csi@csinet.org csinet.org
French Standards
Organization
AFNOR 11, Avenue
Francis de
Pressens 93571
Saint-Denis La
Plaine CEDEX
(France)
+33 01 41 62
80 00
+33 01 49 17
90 00
webmaster@email.
afnor.fr
afnor.org
German
Institute for
Standardization
DIN DIN Deutsches
Institut fr
Normung e.V.
Burggrafenstrasse
6 19787 Berlin,
Germany
+49 30 2601-0 +49 30
26011231
See Website for
Various
din.de
Global
Engineering
Documents
GED 14 Inverness Way
East Englewood,
CO 80112
303-397-7956
800-854-7179
303-397-2740 global@iha.com global.ihs.com
(Continued)
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946 PAINT AND COATING TESTING MANUAL 15TH EDITION
TABLE 1Selected organizations/sources that are concerned with specifications and
standards (Continued)
Organization Abbreviation Mailing Address Telephone FAX E-mail Address
Web Address,
http://www.
IHS Group IHS 15 Inverness Way
East Englewood,
CO 80112
800-716-3447
+ 1-303-397-
2896
800-716-6447
+ 1-303-
3972410
info@his.com ihs.com
International
Organization for
Standardization
ISO 1 Rue de Varemb
Case Postale 56
CH-1211 Geneva
20 Switzerland
+41 22 749
0111
+41 22 733
3430
See Website for
Various
iso.org
Japanese
Industrial
Standards
JIS 1-3-1
Kasumigaseki
Chiyoda-ku Tokyo
100-8901 Japan
... ... jisc@meti.go.jp jisc.go.jp/eng
Maple Flooring
Manufacturers
Association
MFMA 60 Revere
Drive, Suite 500
Northbrook, IL
60062
847-480-9138 847-480-9282 mma@maplefloororg maplefloor.org
National
Association
of Corrosion
Engineers
NACE 1440 South Creek
Drive Houston, TX
77218
713-492-0535 ... msd@mail.nace.org nace.org
National
Association of
Pipe Coating
Applicators
NAPCA AmSouth Bank
Building 333
Texas St., Suite
717 Shreveport,
LA 71101
318-227-2769 318-222-0482 ... napca.com
National Institute
of Building
Sciences
NIBS 1090 Vermoint
Avenue, NW,
Suite 700
Washington, DC
20005
202-289-7800 202-289-1092 nibs@nibs.org nibs.org
Society of
Automotive
Engineers
SAE SAE World
Hqtrs. 400
Commonwealth
Dr Warrendale,
PA 15096
877-606-7323
724-776-4970
724-776-0790 customerservice@sae.
org
sae.org
Standardization
Admin.of the
Peoples Republic
of China
SAC Zhichun Road,
No. 4 Haidian
District Beijing,
China 100088
+86-10-
62000675
+86-10
-62033737
webmaster@sac.gov.cn sac.gov.cn
Standards
Australia
SA 286 Sussex Street
Sydney, NSW,
2000 Australia
+61 2 8206
6000
... mail@standards.org.au standards.org.au
Steel Structures
Painting Council
SSPC 40 24th Street, 6th
Floor Pittsburgh,
PA 15222
412-281-2331
877-281-7772
412-281-9992 See Website for
Various
sspc.org
Swedish
Standards
Institute
SIS SE 118 80
Stockholm,
Sweden
+46 8 555 520
00
+46 8 555
520 01
info@sis.se sis.se
Underwriters
Laboratories, Inc.
UL 333 Pfingsten
Road Northbrook,
IL 60062
847-272-8800 847-272-8129 See Website for
Various
ul.com
United States
General Services
Administration
GSA Federal Supply
Service, Supply
Stds. Division
Arlington, VA
22202
703-605-2567 703-605-9856
or -9855 or
-9852
See Website for
Various
fss.gsa.gov/pub/
fedspecs/
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CHAPTER 77 PAINT AND COATING SPECIFICATIONS AND STANDARDS 947
available in soft-cover book or CD-ROM format [6]. Other
ASTM committees have developed a myriad of tests, some
of which are related to or have an impact on the paint and
coatings industry and are available in other volumes of the
Annual Book of ASTM Standards. Many specifications and
standards of other national and international organizations
list ASTM documents as the necessary requirement for
approval.
The American Architectural Manufacturers Asso-
ciation (AAMA) publishes standards for architectural
products including organic coatings for aluminum. The
American Association of State Highway and Transporta-
tion Officials (AASHTO) has developed standards that deal
with highway-marking materials, highway materials of
construction, bridge construction and maintenance, and
other related products. The Maple Furniture Manufac-
turers Association (MFMA) publishes specifications and
standards for wood flooring and a list of conforming floor-
finish products.
The National Association of Corrosion Engineers
(NACE) has developed standards that deal with corrosion
testing, selection of corrosion-resistant materials, and
the use of coatings to reduce corrosion. Their documents
include standards for surface preparation, corrosion con-
trol, coating materials, and selection, application, and
testing of coatings and paints. They also develop standards
in cooperation with the Steel Structures Painting Council
(SSPC). This latter group deals in the same type tests as
NACE and includes quality control and contractor qualifi-
cation standards and specifications.
The Construction Specifications Institute (CSI) has
developed several SpecGuides that are used as part of
construction documentation that deals with the prepara-
tion of technical specials for paints, coatings, and applica-
tion [2]. The National Institute of Building Sciences (NIBS)
has developed a powerful electronic database termed the
Construction Criteria Base that includes the complete con-
struction guide specification of most federal government
departments and agencies as well as those of many non-
government organizations. Model building codes are also
accessible in this database, which is available in CD-ROM
format from NIBS (Table 1). This consolidated system
includes full copies of supporting documentation and the
software needed to develop contract specifications for proj-
ects including:
Applicable codes and regulations.
Construction guide specifications of major military
departments and civil agencies.
Design and estimating guidance documents.
Materials, testing, and processing documents.
Product data, available in full-color graphics.
Built-in software for search and processing functions.
Military and federal specifications and standards, com-
mercial item descriptions, and referenced nongovernment
specifications and standards are accessible in the Construc-
tion Criteria Base.
AUTOMOTIVE INDUSTRY
The automotive specifications and testing area is complex,
and numerous standards have been either adopted from
standards developed by private, technical, or governmental
organizations or developed within their own companies.
Snowwhite [7] has given an overview of the performance
requirements for automotive coatings and presents a gen-
eral specification for interior and exterior automotive coat-
ings in North America. The general requirements include
physical properties, general film and coatings properties,
durability, and chemical resistance and these are specified
by 60 tests or test methods to meet these requirements.
The listing is of documents by ASTM International, Soci-
ety of Automotive Engineers, Chrysler, Ford, and General
Motors.
TESTING LABORATORIES
Although it is left to individuals to decide on which labora-
tory to use and what standards to measure them by, one
method is to determine if a given laboratory has a quality
assurance program and the management to meet interna-
tional standards is to ascertain their accreditation. There
are two accrediting agencies for testing laboratories, and
these are:
NVLAP, National Voluntary Laboratory Accreditation
Program, that is carried out under the auspices of the
United States Department of Commerce
A2LA, American Association of Laboratory Accreditation
It is beyond the scope of this chapter to describe the
many testing laboratories that exist nationally and inter-
nationally. Readers can find many such organizations by
sourcing the Internet or the open literature.
REFERENCES
[1] ASTM D123-07, Standard Terminology Relating to Textiles,
Annual Book of ASTM Standards, Vol. 07.01, ASTM Interna-
tional, West Conshohocken, PA, 2007, pp. 171.
[2] Construction Specifications Institute (CSI), Paintings, Spec-
Guide 09900, Alexandria, VA, 1988.
[3] Form and Style for ASTM Standards, ASTM International, West
Conshohocken, PA, 2006.
[4] Donlin, N. E., Military Standards, Electronic Materials Hand-
book, Vol. 1, C. A. Dostal, Ed., ASM International, Materials
Park, OH, 1989, pp. 906916.
[5] Brooke, T., New Global Standards Strategy, ASTM Interna-
tional Standardization News, December 2001.
[6] ASTM Standards Related to Testing of Radiation-Cured Coat-
ings, ASTM International, West Conshohocken, PA, 2002,
p.582.
[7] Snowwhite, P., Performance Requirements Overview for Auto-
motive Coatings, RadTech Report, November/December 2001,
pp. 4345.
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Part 17: New Coating Technology
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951
INTRODUCTION
RADIATION CHEMISTRY AND ITS RELATIONSHIP
TO the coating and paint technology industry involves the
application of a low viscosity mixture principally com-
prised of reactive monomers and oligomers but contain-
ing, as well, conventional coating additives such as fillers,
colorants in the form of dyes or pigments, surfactants,
and so on to a substrate and exposing them to a radiation
sourceparticularly ultraviolet (UV) or electron beam (EB)
radiationfor very short periods of time. When required, as
in UV radiation curing, a small amount of photoinitiator is
included in the formulation. When exposed to the radiation
source, the mixture of materials is almost instantaneously
converted into an effectively cross-linked, high quality coat-
ing or other product [1].
Radiation technology, as applied to coatings, had its
infancy in the late 1960s and early 1970s when governmen-
tal regulation began requiring that solvent emissions from
paint and coatings be decreased and regulated. At that time,
most coatings were formulated with high molecular weight
polymers and large amounts (often 80 % or more) of inex-
pensive solvents and cosolvents that for the most part were
emitted to the atmosphere. Regulation increasingly forced
companies to decrease these emitted solvents, and it was in
this environment that new technologies such as high solids,
powder, and radiation-cured coatings were born. Changes
were slow to come into being in the stodgy (at that time)
paint and coatings business, but today each of these meth-
ods of formulation and curing has become an important
part of the coating and paint business.
RADTECH International
2
is an association for ultravio-
let and electron beam technology as related to radiation-
cured products for the adhesive, coating, ink, paint, and
related industries. This group publishes a report (RadTech
Report) five times a year, conducts UV/EB technology
expositions and conferences and publishes the conference
proceedings, has various publication and information avail-
able, and maintains a link between the various facets of the
UV/EB industry (see www.radtech.org).
CURING EQUIPMENT
Electron Beam Systems
An electron beam is a stream of electrons that is emitted
from an electron beam gun and in which the electrons
are moving at essentially the same speed and in the same
direction. Almost all substances absorb electrons, which
are small atomic sized, high energy, negatively charged
particles. Such radiation is known as ionizing radiation.
The electrons are capable of penetrating into and through
a substrate and/or a coating to reach, for example, an adhe-
sive, a pigmented paint, or other opaque liquid and thus
effect polymerization and cure of the appropriate chemical
formulation [2,3].
Basically, the sequence of events in the cure process is
as follows. While the stream of electrons is passing through
the material to be cured, individual electrons are able to
collide with an electron that is in a molecule of the uncured
compounds. This collision can result in removal of an elec-
tron from the molecule and thereby generate a free radical.
Such free radicals are able to react with ethylenic unsatu-
ration in the formulation, as is found in acrylates, and
initiate the sequence of polymerization, propagation, and
termination with the result a cured, cross-linked material.
A photoinitiator, which is required in ultraviolet radiation
polymerization systems, is not required to initiate polymer-
ization when electron beam technology is used.
In a general sense, there are two types of electron
beam processors used in curing systems [4]. The swept
or scanned beam type processors involve generation of a
relatively narrow beam of electrons that are accelerated in
a vacuum that is maintained in the high voltage section of
the device. The beam of electrons is then moved, swept or
scanned, across a metal foil window by means of an electric
or magnetic field. From the window, the beam is sent to
the process area where it contacts the reactive, liquid coat-
ing and polymerization is induced. The curtain or filament
beam processors are single or multiple linear filament emit-
ters with the filament(s) located parallel to the direction of
to-be cured product movement. A broadband or curtain
of electrons is sent to the process area where polymeriza-
tion is initiated and polymerization, as well as termination,
takes place. Since oxygen can inhibit polymerization of free
radical systems, it is important to inert the process area
with a compound such as nitrogen to obtain good surface
and through cure [5].
Ultraviolet Radiation Systems
One of the distinctions between electron beam curing
and ultraviolet radiation curing is the requirement for a
photoinitiator to be used in the later curing method. Pho-
toinitiators are compounds that are stable until exposed
to ultraviolet radiation of one or more wavelengths. When
78
Radiation Curing of Coatings
Joseph V. Koleske
1
1
1513 Brentwood Road, Charleston, WV 25314-2307
2
RadTech International NA, 7920 Wisconsin Ave., Suite 208, Bethesda, MD 20814; www.radtech.org; e-mailuveb@radtech.org
MNL17-EB/Jan. 2012
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952 PAINT AND COATING TESTING MANUAL 15TH EDITION
exposed the compounds absorb the radiation and degrade to
form a species that is capable of initiating polymerization
usually free radicals or cations, the type depending on the
nature of the system employed. Recently, Lapin [6] devel-
oped a comparison of UV and EB for printing and packag-
ing applications and described in detail the fundamental
differences in the two technologies.
If coatings are to be cured on flat stock, the curing
equipment is relatively simple in nature. An ultraviolet radi-
ation source and a means of cooling the lamp or lamps that
serve as the source. The system is comprised of a power
supply, radiation source, reflectors, and a conveyor [7].
The power supply is the control device within the system
and either stepped or variable ballast systems are used for
energy and intensity comparisons [8]. If three-dimensional
objects are to be coated, special configurations of the radia-
tion source and reflectors and/or a means of rotating the
object when in contact with the radiation are used [9].
There are two general types of ultraviolet radiation
sources [10], namely mercury vapor lamps and xenon
lamps. Mercury and mercury-doped vapor lamps are widely
used because when mercury is vaporized and ionized, it is
one of the richest sources of ultraviolet radiation. Doping
the mercury alters the transmission spectrum produced by
the lamp or bulb, and it is used to efficiently interact with
particular photoinitiators. Compounds such as the halides
of antimony, cobalt, iron, silver, and others are used alone
or in combination as the materials for doping mercury.
The lamps are sealed, transparent quartz bulbs that are of
three general typeslow pressure, medium pressure, and
high pressure. Medium pressure electrode and electrodeless
lamps are the most widely used industrial ultraviolet radia-
tion sources in the paint and coating industry.
The reflectors [11] have a variety of geometries such
as elliptical, diverging, converging, parabolic, and others.
The reflectors may be interfocused wherein the radiation is
spread over a relatively large area or they may be focused
wherein the radiation is concentrated into areas of high
intensity. The large area systems are often used when three-
dimensional objects are cured.
CHEMISTRY
Photoinitiators
Compounds that absorb ultraviolet radiation and are raised
to an excited level from which they photolyze or degrade
directly or indirectly into free radicals or cations are termed
photoinitiators. The free radicals or cations become the
polymerization initiating species and cause very rapid
polymerization of photocurable formulations based on a
variety of chemistries such as acrylates and methacrylates,
polyenes/thiols, and styrene/unsaturated polyesters, all of
which are cured by a free radical mechanism and cyclo-
aliphatic epoxide/polyol and vinyl ether systems which are
cured by a cationic mechanism. Vinyl ethers can be poly-
merized with either free radicals or cations and thus are
ingredients that can be used in combination-cure systems.
Free Radical Photoinitiators
The two main types of photoinitiators that form a spe-
cies capable of initiating polymerization of ethylenically
unsaturated compounds are the homolytic fragmentation
process type (Norrish Type I) and the hydrogen abstraction
process type (Norrish Type II). The homolytic fragmenta-
tion or -cleavage compounds directly form free radicals
capable of initiating polymerization [12]. The absorbed
radiation causes bond breakage to take place between a
carbon atom and an adjacent carbonyl group and a free
radical is formed. Hydrogen abstraction type compounds
function through a bimolecular reaction process [13].
They are activated with radiation and form free radicals by
electron extraction or hydrogen abstraction from a second
compound that is termed a synergist. After this process, the
second compound becomes the actual initiating species.
Examples of the homolytic fragmentation type compounds
are given in Table 1 and of the hydrogen abstraction type
are given in Table 2.
Synergists are compounds that have a carbon atom
with at least one hydrogen atom in the alpha position to a
nitrogen atom. For example, dimethylethanolamine has an
alpha carbon atom in the methylene group next to the nitro-
gen group. Triethylamine has three alpha carbon atoms
located on the three methylene groups next to the nitrogen
group. Synergists are usually tertiary amines, but ureas and
amides have been used as well as particular alcohols and
TABLE 1Examples of homolytic
fragmentation type photoinitiators
Compound Appearance Absorption, (nm)
2,2-Diethoxyacetophenone White solid 242325
1,Hydroxycyclohexylphenyl
ketone
White solid 208, 245
n-Butylbenzoin ethers
(mixture)
Light yellow
liquid
246325
2,2-Dimethyl-2-
hydroxyacetophenone
Clear liquid 265280,
320335
Benzil dimethyl ketal White solid 220, 254335
TABLE 2Examples of hydrogen abstraction
type photoinitiators
Compound Appearance Absorption, (nm)
Benzophenone White solid 250350
Isopropylthioxanthone Pale cream solid ~320340
2-Chlorothioxanthone Pale yellow solid 360
4-Methylbenzophenone White solid
Thioxanthone Solid
TABLE 3Some common low molecular
weight synergists
Specific Compounds
2-Ethylhexyl-p-dimethylaminobenzoate
Dimethylethanolamine
N,N-Dimethyl-p-toluidine
Triethanolamine
Triethylamine
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CHAPTER 78 RADIATION CURING OF COATINGS 953
ethers. As mentioned earlier, after the bimolecular reaction,
the synergist becomes the initiating species. Examples of
synergists are given in Table 3.
Oxygen Inhibition
Radiation excited or activated molecules are quenched and
markedly decreased in activity or made inactive by oxygen
which, of course, is present in all air environments [14].
Such quenching results in inhibition of polymerization
in formulations that involve fragmentation-type photoini-
tiators. Free radicals will react with propagating molecules
and termination with accompanying low molecular weight
and poor properties result. Oxygen inhibition can be cir-
cumvented by curing in an inert atmosphere, addition of
oxygen scavengers or waxes, use of shielding films, dye
sensitizers, surface active initiators, or high photoini-
tiator concentrations, and increasing ultraviolet radiation
intensity [1].
Cationic Photoinitiators
Cationic photoinitiators are onium compounds that are
excited by ultraviolet radiation and then photolyze to
form Lewis or Bronsted acids that will rapidly polymerize
cycloaliphatic epoxides. In the photolysis process of these
compounds, free radicals are also formed and therefore,
both epoxides and ethylenically unsaturated compounds
can be polymerized in a dual-cure process. Watt [15] has
published a detailed study of the cationic curing of epox-
ides, particularly cycloaliphatic epoxides, over the period
of 1965 to 1981.
Diazonium SaltsLewis Acids
Although presently cationic photoinitiators are used to
generate Bronsted or protonic acids from sulfonium or
iodonium salts, cationic curing of coatings began with
the use of diazonium-type photoinitiators that generated
Lewis acids. A variety of anions were used including PF
6
,
SbCl
6
, SbF
6
, BF
4
, and AsF
6
. The
commercial onium salts are known as aryl sulfonium and
aryl iodonium salts and have the counter ion MF
6
, where
M is antimony or phosphorous [17,18]. Usually, the sulfo-
nium salts were known as triarylsulfonium salts which was
a misnomer, since these compounds are complex mixtures
of sulfonium salts with the prominent species and have the
following generalized structures:
Ar S (Ar
3
)S
+
(MF
6
)
and (MF
6
)
S
+
(Ar
3
) S
(Ar
3
)S
+
(MF
6
)
and I
+
(MF
6
)
or (SbF
6
)
Abraser, 618619
Taber
data, 444
Falling sand abraser, 617
Falling-needle viscometer, 444
Fastness, 232
Fastness tests, 232
Federal Environmental Laws Administered by U.S.
Environmental Protection Agency, 4
Federal Specifcation: TT-P-320D Pigment, Aluminum
Powder and Paste for Pain, 253
Federal test method for dry opacity, 576
Federal Test Method Standard 141C, Method 4061.2:
Drying Time, 529
Federal Test Method Standard (FTMS) 141 method
3022.1, 741
Federal Test Method Std. 141, 589
Feeder driers, 39
Feldspar and nepheline syenite, 245
coatings performance, 245
properties, 245
Feldspars, 245, 246
Fell Equation, use of, 576
Felvation, 411
Ferets diameter, 408
Fermentation biopolymer polysaccharide, 355
Filiform corrosion, 283
Film casting, drawdown bars for, 508
Film casting techniques
dry coatings on substrates, 507508
free flms, 505507
wet flms for testing, 508
Film formation, 333
minimum flm forming temperature apparatus, 334
rheology and, 434
Film formers, modifers, or additives, cellulose
esters as, 29
Film porosity index, calculation of, 305306
Film preparation for coating tests, 505
equipment for flm preparation
dip coating, 512
drawdown bars, 508510
spin coating, 512
spray outs, 511512
Wire-Wound Rods, 510511
flm casting techniques
dry coatings on substrates, 507508
free flms, 505507
wet flms for testing, 508
test requirements of flms, 505
tips on practice of art, 512
Film thickness
aerospace and aircraft coatings, 742
hiding power, 570
of material to be tested, recommended, 529
Film thickness, measurement of, 514
data management, 525526
dry flm thickness (destructive methods), 517
gardner carboloy drill thickness gage, 518
gardner gage stand, 518
gardner micro-depth gage, 518519
gardner needle thickness gage, 518
micrometers and dial gages, 517518
microscope for flm thickness, 519520
dry flm thickness (nondestructive methods), 520
electronic coating thickness gages, 521523
permanent magnet thickness gages, 520521
effects of surface fnish, curvature, and substrate
composition, 523
curvature, 524525
substrate composition, 525
substrate thickness, 525
surface fnish, 523524
statistics in flm thickness measurement, 525
uncured powder coating thickness to predict fnal flm
thickness, 526
using ultrasonics, 526
wet flm thickness, 514
inmont wet flm gage (wet flm wheel), 514
needle micrometer, 517
notch gage (wet flm comb), 515517
Pfund wet flm gage, 514515
X-ray fuorescence (XRF), 526527
principle of XRF measurement, 527
Finding regulatory information
EPA sources, 1415
Fineness of grind and coarse particles
aerospace and aircraft coatings, 740
Fineness -of-dispersion gages, 410411
Fingernail Test, 622
Fish oil, 35
Flake guide, 277278
Flake-containing paint flm, 273
Flame spray coatings, 85, 86
Flash point, 141, 166, 741
PenskyMartens, 741
pot life, 741742
setafash, 741
tag, 741
Flatting agents and bodying, metallic soaps as, 38
Flevation, 410
Flexibility, 744745
Flexibility and toughness
basic properties affecting coating performance,
637638
interpretation, 637
measurements
cold crack resistance tests, 642643
conical Mandrel tests, 639
cupping tests, 640
cylindrical Mandrel bend tests, 639640
effects of aging and weathering, 642643
forming tests, 641
impact resistance tests, 641642
Mandrel Bend Tests, 638639
T-bend tests, 640
testing of free flms, 642
techniques for measuring basic viscoelastic properties
Dynamic Mechanical Thermal Analyzer (DMTA),
638
humidity, 638
strain rate, 638
temperature, 638
Tensile Testing, 638
Thermal Mechanical Analyzer (TMA), 638
Flexible packaging, 125
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INDEX 985
Fllm casting knifeMicrometers adjust blade clearance,
509
Flocculative mechanisms, thickening mechanisms,
345346
depletion focculation, 346
Fluid density, 445
Fluid resistance, aerospace and aircraft coatings,
747748
Fluorescence, 538539
Fluorescent illuminants, 541
Fluorescent Indicator Adsorption (FIA), 177
Fluorescent sources, 535536
Fluorocarbon surfactants, 322
Foam killers, 329
Foams, 328
Ford bath immersion test, 732
Ford cup viscosity data, 441
Formal HP methods, 587590
Formaldehyde, 72, 75, 79
Forming tests, 641
Fracture theory, 601602
Free binder, calculation of, 307
Free flm samples, preparation of, 627628
Free flms, 505507
Free formaldehyde, 7576
French Standards Association (AFNOR), 589590
Friction and slip resistance, 673
concepts of friction, 673677
determination of the coeffcient of friction (COF),
678679
friction for various coatings, coeffcients of, 678
kinetic friction, coeffcients of, 677
lubricants, 681682
sensor materials, 680681
sliding friction, ranges of coeffcient, 677
slipperiness, 677678
static friction, coeffcient of, 675, 676
tribolelectric series for number of widely used
polymers, 678
Friction force, 679
Fumed silica (pyrogenic silica), 363
Furnace process blacks, 206
Fusion process, metallic soaps, 38
G
G85, 298
G90, 298
G113, 298
Galvanic corrosion, 702
cathodic protection by sacrifcial anode, 702
galvanic series in seawater fowing at 13 FTPS, 701
galvanized steel cross-section, photomicrograph of,
708
impressed current cathodic protection, 702703
Gardner carboloy drill thickness gage, 518
Gardner contrast HP board, 573
Gardner gage stand, 518
Gardner micro-depth gage, 518519
Gardner needle thickness gage, 518
GardnerColeman method, 302
Gardner-Coleman test, 302
Gardner-Holdt bubble tubes, 442
Gas chromatographic (GC) techniques, 140
Gas evolution test for metallic coatings, 254
Gas state
particles of matter in solid state, 379
Gas-liquid chromatography (GLC), 175
Gassing test, metallic pigments, 254
Gellan gum, 355
German Standards Institute (DIN), 590
Glass and porcelain enamels, 708
Glass enamels, 84
test methods for, 85
testing of, 85
Glass panels, 578
Glaze 2 is sanitary-ware glaze, 81
Glazes, 81
applications for glazes, 81
lead-containing glazes, 82
leadless glazes, 8182
satin and matte glazes, 82
testing of glazes, 82
Gloss, 336, 558
appearance changes with structure size, 561
aspects of gloss and their defnition, 558
directionality, 559
distinctness-of-image, 558559
haze, 558
sheen, 558
specular gloss, 558
waviness, 559
block diagram depicting relationships of various
appearance characteristics, 559
carbon blacks (class 1), 209210
coalescing aids, 337
coatings, performance dimensions, 199200
contrast sensitivity of our eyes is highest, 562
DOI measurement, instrument for, 565
dullness measurement, instrument for, 565
instrumental measurement techniques
changes in structure spectrum compared to
changes in color measurement, 566567
goniophotometry, 561
measurement of distinctness-of-image, 563
measurement of refection haze, 561
measurement of waviness (orange peel),
563566
specular gloss measurement, 560561
Landolt Rings, 561
modern miniature glossmeter, 563
observer focuses on image of refected object, 559
observer focuses on the illuminated surface of object,
559
original surface with high amount of long-, shortand
microstructures, 565
positions of source and receptor for three geometries,
563
refected light fux distribution from semigloss surface,
560
schematic diagram of gloss meter, 562
specular gloss is dependent on refractive index, 560
structure spectrum helps to understand appearance of
surface fnishes, 565
structure spectrum with reduced short waves, 566
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986 INDEX
structure spectrums of original surface and frst
improvement step, 566
surface appearance is dominated by short waves after
longer waves were reduced, 566
very brilliant surface with a low amount of short
waves makes long waves very apparent, 567
visual gloss evaluation, 559560
development of documentary standard, 560
use of landolt rings to visually analyze distinctness
of image, 560
visual evaluation of orange peel, 560
Glycol ethers, 153
properties of, 154
Glycol ethers., 336
Glycoluril resins, 78
GM 9504P, 729
Gold bronze
properties, 251
Gold bronze pigments, 251
Gold bronze pigments
grade classifcation, 252
Gonioapparent colors, 273274
chroma shifts observed in strong interference
colors, 277
color angle, 277
color difference for specimens containing interference
pigments with refective inner layer, 279
summary of ANOVA results, 278
color difference measurement for quality control of
colors containing interference fake, 278279
color metrics, 279280
conventions for designating measurement geometry, 274
diagram of aspecular angles, 274
far-aspecular angle, 275
measurement of, 272
measurement of colors containing interference fakes,
276278
measurement of metallic color and color difference,
274276
mid-aspecular angle, 275
near-aspecular angle, 275
side-tone scattering of light, 275
standardization of, 280
Gonioappearance, 272, 537
Goniochromatism, 274
Goniophotometer, 564
Goniophotometry, 561
Goniospectrophotometer, 272, 276, 549
Gooden-Smith apparatus for surface area, 401
Gooden-Smith method, 401
GOST5494: Aluminum Pigments, 253
Granular pigments and their relation to surface
properties, 392
Graphite, 288
inorganic anti-corrosion pigments, 288
Gravel projecting machine, 618
Gravimetric adsorption apparatus, 400
Gravimetric method, 400
Gravity sedimentation, 396397
hydrometer method, 396
radioactivity method, 397
Green pigments
chrome green, 237238
chromium oxide green, 238
hydrated chromium oxide green, 238
properties of miscellaneous commercial, 232
Ground coat enamels, 82
Guar gum (GG), 354
Gum turpentine/gum spirits, 152
H
Hagen-Poiseuille equation, 444
Hall effect probes, 522
Hallet Hidimeter, 575
Hallet hidimeter, 575
Hand sieving, 394
Handbook on PVC Formulating, 141
Hand-held magnetic pull-off gages, 521
Hansa Yellow G, Pigment Yellow 1, C. I. Number 11680,
224
Hansa Yellow 10G, Pigment Yellow 3, C. I. Number
11710, 224
Hansen solubility parameters, 471472
correlate both solubility and solubility plus
environmental stress cracking, 492
and environmental stress cracking (ESC), 491493
Hansen solubility parameters for selected liquids,
481485
Hanstock method, 576
Hard-drying time apparatus, 530
Hardness
hardness test comparisons, 502
impact resistance, 502
Knoop and Pfund hardness, 501
and mar resistance, aerospace and aircraft coatings,
745746
pencil hardness, 501
Sward hardness, 501
thermal analysis, 502
Hazard Communication Standard (HCS), 3
Hazardous Air Pollutants (HAP), EPAs Clean Air Act list
of, 10
Haze, gloss, 558
Haze-and-gloss-measuring instrument, photograph of,
564
Hazen Color, 174
Heat resistance, aerospace and aircraft coatings, 748
Heat-reactive/resole resins, 93
Hectorite clay, 362
Hegman Gage, 411
Heidolph RE AX 2, 507
Helicone liquid crystal production process, 267
Heptane miscibility test, 180
Herschel-Bulkley equation, 420
Heterocyclic yellows, 226
properties, 229
structures, 228
Heteropolymer acron, half moon, 63
Heteropolymer core shell, 63
Heteropolymer internal domains, 63
Heteropolymer surface domains, 63
Hexa(methoxymethyl)melamine, 75
Hiding power, 569
bending of a light ray by refraction, 571
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INDEX 987
CR, 569570
early photometric HP methods, 575
federal test method for dry opacity, 576
Fell Equation, use of, 576
Hanstock method, 576
New York Paint Club (NYPC) method, 576
Pfund precision cryptometer, 575576
Van EykenAnderson method, 576
early visual HP methods
brushouts, 573
contrast design and visual sensitivity, 573
hallet hidimeter, 575
Pfund cryptometers, 574575
relative dry HPKrebs Method, 574
factors affecting white HP, 586
crystal and particle size, 586
flm porosity, 587
pigment concentration, 586587
pigment dispersion, 586
flm thickness, 570
formal HP methods, 587590
HP methodology
flm application, 576577
photometric measurements, 577
SR (or flm thickness) determination, 577
incomplete hiding, 569
K-M two-constant theory, 578579
calculation of HP from tinting data, 584585
determination of relative HP of untinted white
paints from tinting data, 585
Judd Graph (information included for historical
purposes), 580581
K-M HP method, 579580
K-M HP results, 583584
Mitton graph and table, 581583
scattering coeffcient and scattering power, 579
theoretical problems and practical considerations,
584
light absorption, 569
light scattering, 569
light-scattering behavior of pigmented flm, 572
microvoids for white HP, 587
opacity, 569
photometric HP end-point, 571
refractive index and relative HP
of some extender pigments, 572
of some white hiding pigments, 572
role of pigments in HP
binders and pigments, 571
colored pigments, 572573
extender pigments, 572
refractive index, 571572
white hiding pigments, 572
white pigments, 571
of some colored pigments measured with Pfund
cryptometer, 574
SR, 570
test substrates, 569
test substrates, currently used, 577
clear plastic flm, 577
glass panels, 578
painted metal panels, 578
paperboard charts, 577
visual HP end-point, 571
visual observations of contrast, 570
High solids, solvent borne coatings, 90
High solids alkyd, 41
Higher solids alkyd resins, 6869
types and end uses, 70
High-shear capillary rheometry, 445
High-solids coating resins, 72
Hildebrand parameters, 471
HLB ranges and surfactant applications, 324
Homolytic fragmentation type photoinitiators, examples,
952
Homopolymer, 63
Homopolymerization of phenolic resole resins, 96
Hot dip galvanizing, 132
Hot-dip galvanizing, 708
HP methodology
flm application, 576577
photometric measurements, 577
SR (or flm thickness) determination, 577
Hues, 592
Humidity, 638
Humidity cabinet, 733
Humidity exposure, 729
Hutto-Davis method, 401
Hydrated chromium oxide green, 238
Hydrocarbon solvents, 149152
Hydrocarbons, processes that produce, 34
Hydrogen abstraction type photoinitiators, examples,
952
Hydrogen bonding solubility parameter, calculation of,
480
Hydrogen damage, 706
Hydrometer and meniscus detail, 172
Hydrometer methods, 172
Hydrometers, 382
HydrometerSugar with Brix scale and enclosed ther-
mometer, 382
Hydrophobe modifed ASEs (HASE), 358359
HEEASE (subclass of HASE), 358
HEURASE (subclass of HASE), 359
Hydrophobe modifed cellulosics (HMC), 359360
Hydrophobe modifed nonionic synthetics (HMNS),
356358
HEAT (subclass of HMNS), 358
HEET (subclass of HMNS), 358
HEUR (subclass of HMNS), 356357
HEUUR (subclass of HMNS), 358
Hydrophobic silica, 364
Hydrophobic silicas, 362
Hydroxyethyl cellulose (HEC), 351, 353
Hydroxyl functionality, 55
Hydroxyl-functional acrylics, 55, 56
Hydroxypropyl guar (HPG), 354
Hysteresis, 446
Hysteresis effects, 457
I
ICI cone and plate viscometer, 444
ICI cone/plate high shear viscometer for determination
of HSV, 350
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988 INDEX
ICI rotothinner, 441
Illuminant metamerism, 540
Illuminating and sensing geometry, example of, 274
Illuminator, 548
Imidazoline structure, 100
Immersion testing, 732
Impact resistance tests, 641642
In-can preservation, 313314
microbicides used for, 316
Incandescent sources, 535
Incomplete hiding, 569
Indanthrone blue, 224
Individual particle sensing by light blocking and
electrical resistance, 401403
Industrial color measurement
commercial instruments, 550551
instruments using eye as detector, 547548
selection and calibration of instruments, 550
spectrocolorimeters, 549
spectrophotometers, 548549
spectroradiometers, 549
tristimulus (flter) colorimeters, 549550
Industrial maintenance coatings, testing of, 778
infrared spectra of an epoxy (top) and vinyl latex, 780
multinotch applicator used to evaluate sag resistance,
780
portable adhesion tester, 781
stormer viscometer used to obtain viscosity of
coatings, 779
testing of applied coatings, 781786
testing of liquid coatings, 778
Infnite-shear viscosity, 419
Infrared spectroscopy (FTIR), 142
Ink, pigments for, 200
Inks and overprint coatings, 125
Inmont gage (Interchemical) wet flm, 515
Inmont wet flm gage (wet flm wheel), 514
Inorganic anti-corrosion pigments, 284
ceramic pigments, 294
chromate-based compounds, 284285
graphite, 288
inorganic oxoanionic inhibitors, 289
ion-exchange pigments, 289290
iron oxides, 287288
magnesium-rich primer, 287
metal fake pigments, 293294
needle-shaped anti-corrosion pigments, 292
pigments for smart anti-corrosion coatings, 291292
protective coatings and, 282283
silicate-based pigments with non-isometric particles,
288
spinel-type pigments, 293
super primers, 290291
titanates, 288289
titanium dioxide (TiO
2
), 288
zinc ferrites, 287
zinc oxide-containing systems, 285286
zinc phosphate, 286287
zinc-rich paints, 285
Inorganic based thickeners and rheology modifers for
WB and SB coatings, 364
Inorganic colored pigments
blues, 236
browns, 238
classifcation of pigments by color, 234
greens, 237238
oranges, 237
reds, 234235
violets, 235236
yellows, 236237
Inorganic for waterborne and solventborne coating, 362
Inorganic oxoanionic inhibitors, 289
inorganic anti-corrosion pigments, 289
Inorganic thickeners for aqueous and solvent-borne
coatings, 360
clay thickners, 360363
synthetic silicas, 363364
thicker blends, 365
Instrument for refection haze measurement, 564
Instrumental and computer-aided color matching, 555
Instruments using eye as detector, 547548
Intergranular corrosion, 704
Interim Guidance on Control of Volatile Organic
Compounds in Ozone State Implementation Plans, 6
Interior of gravelometer, 618
International Commission on Illumination (Commission
Internationale de lclairage, CIE), 279, 541, 592
Intrinsic viscosity, 432
Ion-exchange pigments
inorganic anti-corrosion pigments, 289290
Ion-exchange pigments (IEPs), 289290
Iron blue, 236
Iron oxide blacks (class 3), 204
Iron oxide reds, 234
Iron oxide yellows, 237
Iron oxides, 287288
inorganic anti-corrosion pigments, 287288
ISCC-NBS System, 545
ISO 1247: Aluminum Pigments, 253
ISO 2814, 589
ISO 4624, 610
ISO 6504-1, 589
ISO 6504-3, 589
ISO 1522 Paints and VarnishesPendulum Damping
Test, 44
ISO 4624 test assemblies, 611
ISO Standard 9117, Paints and Varnishes, 529
Isobutylene, 51
Isocyanate-reactive acrylics, 5556
Isocyanates, 108109
blocked, 109
Isocyanurate or isocyanate trimer, urethane chemistry,
105
J
JASO M610, 729
K
Kaolin, 243, 246
coatings performance, 243
physical properties, 243
Karl Fischer reagent method, 180
Kauri-butanol value, 157
Kelvin-Voigt creep experiment, 429
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INDEX 989
Kelvin-Voigt model, 429
Ketimine, 90
Ketones, 89, 153
properties of, 153
purity of, 177
Kinetic coeffcient of friction, 679
K-M two-constant theory, 578579
calculation of HP from tinting data, 584585
determination of relative HP of untinted white paints
from tinting data, 585
Judd Graph (information included for historical pur-
poses), 580581
K-M HP method, 579580
K-M HP results, 583584
Mitton graph and table, 581583
scattering coeffcient and scattering power, 579
theoretical problems and practical considerations,
584
Knoop and Pfund hardness, 501
Krafft Temperature, 326
Krebs diamond-stripe HP chart, 573
Krebs type viscometer, digital, 348
Krebs units (KU), 441
KriegerDougherty model, 433
L
Lab roller mill, 506
Lab spin coating device, 512
Laboratory miniature media mills, 595
Laboratory roller mill, 595
Lacquers, 498
Lake, 215
Lake Michigan Air Directors Consortium (LADCO), 12
Lampblack process, 205
Landolt Rings, 561
Large body center, vast distance to, 378
Large-particle system, layout for, 406
Latent solvents, 157
Latex binding power index, calculation of, 306307
Latex paints, 332
Lead chromates pigments, 235
Lead-containing glazes, 82
Leadless glazes, 8182
Leafng grades aluminum pigments, 251
Leveling, 437
Licanic, 34
Light, color and, 535
color difference evaluation for color control, 551
color tolerance, 553
color-difference calculations, 551553
color matching, 555
instrumental and computer-aided color matching,
555
visual color matching, 555
color mixing
additive mixing of lights, 553
pigment mixing, 554
subtractive mixing in transparent flms, 553
color order systems, 544
color collections, 546
DIN system, 545546
Munsell system, 544545
NCS, 546
OSA-UCS system, 546
single-number color scales, 546
whiteness and tint indices, 546
yellow indices, 546
colorimetry and CIE system, 541
CIE standard observers, 541544
CIE standard sources and illuminants, 541542
uniform color spaces, 544
eye
color constancy and metamerism, 540541
perception, 539
variables of perceived color, 539540
the visual system, 539
industrial color measurement
commercial instruments, 550551
instruments using eye as detector, 547548
selection and calibration of instruments, 550
spectrocolorimeters, 549
spectrophotometers, 548549
spectroradiometers, 549
tristimulus (flter) colorimeters, 549550
light sources, 535536
color-matching booths, 536
fuorescent sources, 535536
incandescent sources, 535
natural and artifcial daylight, 535
other sources, 536
refection and transmission
fuorescence, 538539
gonioappearance, 537
opaque, transparent, and translucent flms, 536
phosphorescence, 539
retrorefection, 536
Light absorption, 207, 569
Light attenuation and scattering techniques, 404408
Light fastness, 217
Light scattering, 186, 207, 569
Light sources, 535536
color-matching booths, 536
fuorescent sources, 535536
incandescent sources, 535
natural and artifcial daylight, 535
other sources, 536
Lightness, 592
d-Limonene, 152
Linear motion, tests based on, 619
oscillating sand tester, 620621
RCA abrasion wear tester, 620
Taber
, 265
Pall glass mill, 595
Paper, pigments for, 200
Paperboard charts, 577
Paperclip Mar Test, 622
Para reds, 218
structure of, 218
Partial solubility parameters
group contributions to, 475
methods and problems in determination of,
472474
Particle
defnitions, 191
term casual contact in, 190
system measuring both large and small, 407
Particle characterization methodologies, 390, 393
adsorption of gases, 400
chromatography: Angstrom particle sizing, 403404
defnitions of particle size and shape, 408409
direct microscopic measurement using visual light
microscopes and electron microscopes, 403
drawdown techniques for texture and oversize,
409411
individual particle sensing by light blocking and
electrical resistance, 401403
light attenuation and scattering techniques,
404408
particle size by sedimentation, 3953989
particle size by sieving, 393395
particle size from surface area employing both gasses
and liquids, 398400
permeation through packed powders, 401
separation and collection: particle size by Elutriation,
411412
Particle size
analysis, 191
control, 191
defnitions of, 408
determination of sugar-sand mixture as function of
sampling techniques, 393
distributions
of commercial TiO
2
pigments, 191
of pigment grades, 190
instrument for determining particle size in real time,
399
scattering of radiation in near infrared region of
spectrum, 405
Particle-size analysis
history of, 390
importance of, 390391
metallic pigments, 253
Particle-size reference test material, role of, 412
Particle-sizing methods, comparison of, 409
Parylene, 134
Parylene coatings, 134
Pavement marking materials, 799
feld evaluation of marking materials, 804805
material testing, 800804
types of pavement marking materials, 799800
Paving sealers, 25
Payne permeability cup, 732
Pearlescent, 273
Peel adhesion testing on plastic substrates, 605606
Peeling, 285
PEI Abrasion Tester, 622623
Pencil hardness, 501
Penetration into powder, rate of, 463
Pensky-Martens fash point test cup and cover
assembly, 170
Pensky-MartensASTM D93, 168
Perceived color, variables of, 539540
Perfect white, 543
Permanent magnet thickness gages, 520521
Permeability cups, 732, 786
Permeation, 381
Permeation through packed powders, 401
Perovskite structure, 288
Perovskite structure ABO
3
, 289
Peroxide-cured silicones, 114
Pertinent ASTM test standards, 249
Perylene reds, 220221
structure of, 221
Pfund black-and-white cryptometer, 575
Pfund cryptometers, 574575
diagram of early model of, 573
Pfund crytometer, 510
Pfund flm gage, 516
Pfund Hardness Number (PFN), 501
Pfund precision cryptometer, 575576
Pfund wet flm gage, 514515
Pfund gage schematic, 515
PH measurement, metallic pigments, 254
Phase shift, 427
Phenolic novolak structure, 95
Phenolic resin
and epoxy resin, reaction, 95
products, testing of, 96
Phenolic resole resins
homopolymerization of, 96
Phenolic resole structure, 96
Phenolic starting materials, 95
Phenolics, 93, 500
frst phenolic resin based coatings, 93
phenolic resin chemistry, 9495
acid catalysis, 95
base catalysis, 9596
raw materials, 95
phenolic resins as photo-imagable coating, 94
phenolic resins in coatings
coatings based on phenolic resins, 93
coatings based on polymer alloys with phenolic
resins, 9394
testing of phenolic resin products, 96
Phenoxy, 133134, 134
Phosphate conversion coatings, 706707
Phospho-molybdate pigments, 289
Phosphorescence, 539
Photochemical smog, 34
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INDEX 995
Photochemical weathering, 729
cyclic testing, 729730
Photo-imagable coating, phenolic resins as, 94
Photoinitiator, 951
Photometric HP end-point, 571
Photometric HP methods, 575
Phthalocyanine greens, proposed structures for, 232
Pierce-Holsworth method
for CPVC, 308
pigment volume concentration calculated by, 308
Pierce-Holsworth method for CPVC, 308309
Pigment Blue 27, 235
Pigment Blue 27, C. I. Number 77510, 236
Pigment Blue 28, 235
Pigment Blue 29, 235
Pigment Blue 29, C. I. Number 77007, 236
Pigment Brown 6, 235
Pigment Brown 6, C. I. Number 77491, 77492, 77499, 238
Pigment Brown 7, 235
Pigment Brown 11, 238
Pigment concentration, 595
Pigment dispersing parameters and specifc conditions
obtained for maximum tinting strength, 594
Pigment dispersion, 594
Pigment dispersion process, 328
Pigment dispersion techniques, 595
automatic mullers, 595
spatula and hand mullers, 595
Pigment Green 15, C. I. Number 77520, 77601, 77603, 237
Pigment Green 17, 235
Pigment Green 17, C. I. Number 77288, 238
Pigment Green 18, 235
Pigment Green 18, C. I. Number 77289, 238
Pigment mixing, 554
Pigment Orange 20, 235
Pigment Orange 20, C. I. Number 77202, 237
Pigment Orange 21, 235
Pigment Orange 21, C. I. Number 77601, 237
Pigment Orange 23, C. I. Number 77201, 237
Pigment Orange 46, C. I. Number 15602, 227
Pigment Orange 60 , C. I. Number 11782, 229
Pigment Orange 62 , C. I. Number 11775, 229
Pigment packing factors, 307
comparision, 308
and oil absorption test, 308
Pigment Red 101, 235
Pigment Red 101, C. I. Number 77491, 234
Pigment Red 102, 235
Pigment Red 104, 235
Pigment Red 104, C. I. Number 77605, 234
Pigment Red 108, 235
Pigment Red 108, C. I. Number 77202 and 77196, 235
Pigment Red 113, C. I. Number 77201, 235
Pigment red 214, structure of, 222
Pigment red 224, structure of, 221
Pigment red 242, structure of, 222
Pigment red 257, structure of, 223
Pigment Violet 15, C. I. Number 77007, 235
Pigment Violet 16, 235
Pigment volume concentration (PVC), 303
Pigment volume relationships, 368
Pigment Yellow 32, C. I. Number 77839, 236
Pigment Yellow 34, 235
Pigment Yellow 34, C. I. Number 77600 and 77603, 236
Pigment Yellow 35, 235
Pigment Yellow 35, C. I. Number 77205, 236237
Pigment Yellow 36, C. I. Number 77955, 236
Pigment Yellow 37, 235
Pigment Yellow 37, C. I. Number 77199, 237
Pigment Yellow 42, 235
Pigment Yellow 42, C. I. Number 77492, 237
Pigment Yellow 43, 235
Pigment Yellow 65, C. I. Number 11740, 225
Pigment Yellow 73, 225
Pigment Yellow 73, C. I. Number 11738, 225
Pigment Yellow 74, C. I. Number 11741, 225
Pigment Yellow 75, C. I. Number 11770, 225
Pigment Yellow 97, C. I. Number 11767, 225
Pigment Yellow 98, C. I. Number 11727, 225
Pigment Yellow 116, C. I. Number 11790, 225
Pigment Yellow 184, 235
Pigment Yellow 184, C. I. Number 771740, 237
Pigmentation, Vinyl copolymer coatings, 123
Pigments, 187, 215
black (see Black pigments)
ceramic (see Ceramic pigments)
characteristics, 189
commodity composition, 191193
elemental analysis, 193
packing measures, 194
and performance, 188189
phase analysis, 190
pigment packing, 193194
pigment particle size, 190191
pigment surface, 193
surface analyses, 193
classifcation complications, requirements, 200
color measurement, 194195
colored (see Colored pigments)
colored inorganic, 235
compatibility, 199
contaminants, 194
cost of hiding, 187
dispersing, 196197
durability control, 197
durability testing, 198
effect (see Effect pigments)
effects on gloss, 198199
gloss measurement, 199
effects on paint flm durability, 197
extender (see Extender pigments)
hazards, 195
hiding power of paint flms, 196
high density as disadvantage, 187
high refractive index, 187
inorganic anti-corrosion (see Inorganic anti-corrosion
pigments)
inorganic colored (see Inorganic colored pigments)
metal fake, 293294
metallic (see Metallic pigments)
needle-shaped anti-corrosion (see Needle-shaped
anti-corrosion pigments)
oil absorption of, 300
performance, 195
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996 INDEX
dispersibility, 196197
hiding and opacity, 195
measurement of dispersibility, 197
measurements of light scattering, 195196
products for industries other than coatings, 200
protective coatings and inorganic anti-corrosion,
282283
refectance of white, gray, and black paints, 195
scattering by spheres of rutile in polymer, 187
silica shells from encapsulated, 198
for smart anti-corrosion coatings, 291292
spinel-type, 293
trace analyses, 194
white (see White pigments)
Pigments in HP, role of
binders and pigments, 571
colored pigments, 572573
extender pigments, 572
refractive index, 571572
white hiding pigments, 572
white pigments, 571
Pigments-inhibitors, environmentally friendly paints
and, 295296
Pine oil, 152
Ping-pong balls coated with solid and metallic color
paints, 273
Pipeline coatings, 787
external coatings for repair and rehabilitation,
788789
factory or plant applied products, 789791
internal pipe coatings, 788
market, 787
product development, comparative testing, and quality
control, 787
Pitting corrosion, 703704
microbiologically infuenced corrosion, 704
Plastic (yield) behavior, 424
Plasticizer absorption by pigments, 303
Plasticizer absorption for some typical pigments, 304
Plasticizers, 122123, 139
compatible with solution vinyl chloridebased
copolymers, 123
extenders, 139
family/performance grid, 140
methods of identifcation, 142
chlorine, 143
gas chromatography, 143
infrared spectrophotometry, 142
instrumental methods, 142
isolation of plasticizers, 142
liquid chromatography, 143
nitrogen, 143
phosphorous, 143
phthalates, 143145
qualitative methods, 143
sulfur, 143
performance properties
compatibility, 145
low-temperature properties, 145
permanence, 145
physical and chemical properties
acidity, 139
color, 139140
copper corrosion, 140
density and specifc gravity, 142
distillation range, 140141
ester value, 141
fash point, 141
pour point, 141
refractive index, 141
residual odor, 141
sampling, 141
typical properties, 142
viscosity, 142
water, 142
prepared with and 2-ethylhexyl (2-EH)/i-nonyl (iso-N)
alcohols, physical properties of, 143
and their compatibility with coating resins, 144
Plastics, pigments for, 200
Plastisol, 124
primers, 124
Platinum-cobalt color, 174
versus Saybolt color, 174
Polar solubility parameter, calculation of, 479480
Polyamide resins, 97, 98
in coatings, reaction of, 100
reaction with epoxy resin, 100
Polyamide structure, 100
Polyamides, 89, 97, 365
acids, 97
amines, 97
chemical properties, 9899
early history, 97
environmental/toxicity considerations, 101
physical properties, 99100
reaction of polyamide resins in coatings, 100101
synthesis of polyamides, 98
Polyaniline (PANI) layer, 288, 292
Poly(1,4-butanediol adipate) polyester polyol, 128
Polycarbodiimide, urethane chemistry, 105
Polycyclic dimer acid, 99
Poly--caprolactone polyols (PCP), 128
Polyfunctional amines, 109
Poly(glycol adipates)(PEA), 128
Polyhydric alcohols used in alkyd manufacture, 67
Polyhydroxyethers, 133134
Polymer melt and solution rheology, 432
Polymer morphologies, cross sectional representations
of, 63
Polymerization, 118119
Polymermelts, viscosity of, 432
Poly-(n-alkyl methacrylates), specifc volume-
temperature relations for, 51
Polyols, 128130
Poly-(propylene oxide) polyols (PPO), 128
Polysulfde coatings, 133
Polysulfdes, 133
Poly(tetramethylene oxide) polyols, 129
Polyurethane coatings, 102104
ASTM classifcation
type I, one-package prereacted, 102
type I polyurethanes, 105
type II, one-package moisture cured, 102103
type II polyurethanes, 105
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INDEX 997
type III, one-package heat cured, 103
type III polyurethanes, 106
type IV, two-package catalyst, 103
type IV polyurethanes, 106
type V, two-package polyol, 103
type V polyurethanes, 106
type VI, one-package, nonreactive lacquer, 103
type VI polyurethanes, 106
waterborne polyurethane coatings, 103
chemistry and reactions
basic urethane chemistry, 104105
powder coatings, 108
radiation-curable coatings, 108
waterborne polyurethane coatings, 106107
interpenetrating polymer network (IPN) coatings,
104
markets, 110
polyurethane powder coatings, 104
raw materials
additives, 109110
catalysts, 109
isocyanates, 108109
six ASTM conventional type, 105106
six ASTM conventional type polyurethane coatings,
105106
two-package polyurea and poly ( urethane-urea )
coatings, 103
Polyurethane end uses, examples of, 109
Polyurethane powder coatings, 104
Polyurethanes, 102
Poly(vinyl chloride) latex, 126
Porcelain enamels, 82
cover coat enamels, 84
ground coat enamels, 82
test methods for, 84
testing of porcelain enamels, 84
in weight percent, 83
Portable adhesion tester, 610
Portable adhesion tester, 781
Post-polymerization process, vinyl polymers for coatings, 119
Powder coating, 464465, 957
Powder coatings, 108, 126
HP and scattering coeffcient values, 583
Power law fuid, gravity drainage of, 436
Practical adhesion, 604605
direct tensile testing, 608611
mechanized tape test, 607608
peel adhesion testing on plastic substrates,
605606
procedural problems, 607
scrape adhesion testing, 611612
tape controversy, 607
tape test, 605
test methods, 605
Practical aspects of yield behavior, 426
Precipitated coatings, 296
Precipitated silica, 363
Prevention of metal corrosion with protective
overlayers,687
atmospheric corrosion of metals, 689690
coatings and overlayers for corrosion control, 692694
corrosion in aqueous solutions, 687689
corrosion of thin metal flms and microstructures,
690692
multilayer sandwich arrays, 692
simulations of galvanic interactions in multilayer
arrays, 692
thin flm materials for magnetic, optical, metal
conductor lines and microelectronic contacts, 691
Print-Free-Time, 41
Procedural problems, 607
Programmable lab spray applicator, 511
Propylene glycol monophenyl ether, 336
Protective coatings and inorganic anti-corrosion pig-
ments, 282283
certain defects and coating application, 283
coating characterization methods, 283284
concept of paint monitoring, 294295
environmentally friendly paints and pigments-
inhibitors, 295296
inorganic anti-corrosion pigments, 284
ceramic pigments, 294
chromate-based compounds, 284285
graphite, 288
inorganic oxoanionic inhibitors, 289
ion-exchange pigments, 289290
iron oxides, 287288
magnesium-rich primer, 287
metal fake pigments, 293294
needle-shaped anti-corrosion pigments, 292
pigments for smart anti-corrosion coatings,
291292
silicate-based pigments with non-isometric
particles, 288
spinel-type pigments, 293
super primers, 290291
titanates, 288289
titanium dioxide (TiO
2
), 288
zinc ferrites, 287
zinc oxide-containing systems, 285286
zinc phosphate, 286287
zinc-rich paints, 285
mechanisms for anti-corrosion protection of metal,
294
smart coatings, 295
surface preparation, 283
Protective overlays to prevent corrosion, use of
corrosion prevention with protective overlayers,
706
Pseudoplastic, 421
Pseudoplastic behavior, 418
PVD generated fakes aluminum pigments, 251
Pycnometer, 172
Pycnometer methods, 172173
Pyrazolone orange, 227
Pyrazoloquinazolone, generic structure of, 223
Pyrrolo-pyrrole, generic structure of, 223
Q
Q/C instruments, 440
effux devices (orifce fow), 440
obstructed-fow devices, 442
rising-bubble viscometers, 442
rotational devices, 441
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998 INDEX
Quinacridone reds, 219220
classifcations of, 220
translinear quinacridone showing proposed hydrogen
bonding mechanism, 219
R
Radiation curing of coatings, 951
Radiation-curable coatings, 108
Radiation-cured polyurethanes, 108
Radiation-cured powder coatings, 960
Rain or water erosion, 622
Raleigh scattering effect, 263
Ransburg megohms, 175
Rayleigh theory of light, 263
RCA abrasion wear tester, 620
Reactive crosslinking, 498500
Reactive plasticizers, 145
Reactivity concept, 13
Reactivity policy, shaping future, 14
Reasonably Available Control Technology (RACT), 7
Recovery process, 267
Reds, pigments
cadmium red, 235
iron oxide reds, 234
mercury cadmium red, 235
molybdate orange, 234
Reducible hypervalent transition metals, 296
Refectance and transmittance measurements, ASTM
standards on, 537
Refection and transmission
fuorescence, 538539
gonioappearance, 537
opaque, transparent, and translucent flms, 536
phosphorescence, 539
retrorefection, 536
Refection haze, measurement of, 561
Refractive index, 175
pigments in HP, role of, 571572
Refractive index for materials used in effect materials,
258
Refractory coatings, 85
testing of, 85
Relationship to other physical properties, 615
Relative density, 376
Relative dry HPKrebs Method, 574
Relative viscosity, 432
Relaxation time and retardation time, 627
Research rheometers /viscometers, 442
brookfeld viscometers, 443444
rotational instruments, 442443
Residual odor, 175
Resin based coatings
frst phenolic, 93
Resin modifed bituminous coatings, 25
Resins, advantages and limitations of principal coating,
710712
Resoles, 9596
with allyl chloride, modifcation of, 94
Resorcinol diglycidyl ether, 89
Retrorefection, 536
Rhamsan gum, 355
Rheology, 416
and flm formation, 434435
instrumentation, 440
Rheology and viscometry, 415416
capillary viscometers, 444445
deformation (strain), 416
dispersion rheology, 432434
extensional rheology, 431
extensional viscosity in coatings processes, 431
extensional viscosity measurement, 431
falling-needle viscometer, 444
general classifcation of fuid behavior
Newtonian fuids, 418
non-Newtonian fuids, 418
high -shear capillary rheometry, 445
ICI cone and plate viscometer, 444
leveling, 437439
measures of, 439440
polymer melt and solution rheology, 432
Q/C instruments, 440
effux devices (orifce fow), 440
obstructed-fow devices, 442
rising-bubble viscometers, 442
rotational devices, 441
research rheometers /viscometers, 442
brookfeld viscometers, 443444
rotational instruments, 442443
rheology, 416
rheology and flm formation, 434435
rheology instrumentation, 440
rheometry, 445446
nonequilibrium fow curve, 446447
oscillatory shear, 447448
rotational rheometry, 446
steady simple shear (equilibrium fow), 446
sagging, 435436
measures of, 436437
shear-thickening fuids, 422
elastic liquids (viscoelasticity), 426
mechanism of thixotropy, 423424
plastic (yield) behavior, 424
practical aspects of yield behavior, 426
static versus dynamic yield, 425
thixotropic index test, 423
thixotropy test methods, 424
time-dependent fuids, 422423
viscoelastic models, 428430
viscoelastic parameters and their measurement,
426428
viscoelasticity and industrial processes, 430431
yield stress test methods, 425426
strain rate, 416
modulus, 417418
stress, 416417
units, 418
viscosity, 417
types of non-newtonian behavior, 418
shear-dependent viscosity, 418421
shear-thinning fuids, 421
Rheology and viscosity, 343
elongational fow, 343344
shear fow, 343
Rheology modifer, 342
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INDEX 999
defned, 343
different coating rheology in architectural paints, 347
highshear viscosity (HSV