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FRP TECHNOLOGY

Fibre Reinforced Resin Systems

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FRP TECHNOLOGY
Fibre Reinforced Resin Systems

R. G. WEATHERHEAD, B. Sc.
Consultant and Resin Specialist, Epsom, Surrey, UK
(Formerly Senior Scientist with Shell Research Ltd,
Egham Research Laboratories, Surrey, UK)

APPLIED SCIENCE PUBLISHERS LTD


LONDON

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APPLIED SCIENCE PUBLISHERS LTD
RIPPLE ROAD, BARKING, ESSEX, ENGLAND

British Library Calaloguing in Publicalion Dala

Weatherhead , R, G .
FRP techno logy.
I . Fiber reinforced plastics
I. Title
668.4'94 TPll77

ISBN-13: 978-94-009-8723-4 e-ISBN-13: 978-94-009-872 1-0


DOl: 10.1007/978-94-009-8721 -0
WITH 61 TA BLES AN D 99 ILLUSTR ATIONS

© APPLI ED SCIENCE PUBLISHERS LTD 1980


Sof'tcover reprint of the hardcover I st edition 1980

All rights reserved. No part of thi s puhlication may be reprod uced, stored in
a retrieval system, o r transmitted in any form or by any mea ns, electronic,
mechanical, photocopying, recording. or otherwise. without the prior
written permission of the publisher.;, Applied Sciena: Publishers Ltd.
Ripple Road, Barking. Essex, England

Ph<><oKuinK by TI>omson Pre» Undiaj lid., New Delhi and


Galiiard IPrinle .. ) Lid .• G«a' Vormo.nh

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PREFACE

Synthetic resins have become increasingly important over the years, finding
wide application in a variety of fields. Not least have been the tremendous
strides made in the use of fibre reinforced resin systems. Although by far the
bulk of all fibre reinforced products are made from unsaturated polyester
r~sins reinforced with glass fibres, other resins and other fibres are playing
an increasingly important role. It is with this in mind that the present book
has been written. An attempt has been made to combine within one book
information on the various resin systems and reinforcing fibres in use
today, together with some properties and processing details.
Since most of the resins available are formulated products rather than
pure chemical compounds, some information has been included on
commercially available materials. For convenience, where commercial
data have been included, these have been located at the end of the
appropriate chapter or, where only limited data are presented, at the end of
the appropriate section. Such data have been included for the benefit of
designers and fabricators, to indicate the wide choice of materials available
and to enable them to select materials without having to approach a vast
number of suppliers and then to sift through an even greater number of
data sheets. It is not claimed that these lists are complete, nor that these are
the only suppliers of such materials, nor that the products mentioned are in
any way superior to any which may have been omitted, although every
attempt has been made to make the lists as comprehensive as possible. Also
included is a list of some of the test methods likely to be encountered in the
use and evaluation of fibre reinforced resin systems.
Thus this book is intended to serve not only as a text book but also as a
reference book for all those interested in commercial materials, trade
names, etc., used in the reinforced plastics industry.
As with all commercial materials, product specifications may be changed

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vi PREFACE

from time to time and whilst the data included can be used as a guide to
material selection, up-to-date information should always be sought from
the appropriate supplier.
Where trade names are mentioned, it should be borne in mind that these
are the property of various companies and before use, enquiries should be
made of those companies. Likewise, some of the processes mentioned are
covered by patents and licencing agreements and should not be used
without prior consultation with the appropriate company.
I should like to thank all those suppliers who have provided technical
data on their products for inclusion in this book and who are mentioned in
the text. In particular I should like to thank the following companies for
providing photographs and figures or for assisting in obtaining such
illustrations: Binks-Bullows Ltd; British Industrial Plastics Ltd;
Fibreglass Ltd; Hoechst AG; Huls (UK) Ltd; Johnston Pipes Ltd; A/S
Jotungruppen; K & C Mouldings (England) Ltd; Scott Bader Co. Ltd;
Shell Chemicals UK Ltd; Symes International BV; and Vetrotcx (UK)
Ltd.
I should also like to thank my brother-in-law C. A. White for reading
through the draft and offering valuable suggestions as to where improve-
ments would be beneficial.

R. G. WEATHERHEAD

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CONTENTS

Preface v

Chapter I
GENERAL INTRODUCTION 1
1.1 Introduction . 1
1.2 Why Use FRP? 2
1.3 Which Resin? 3
1.4 Reinforcements 4
1.5 Process Development 5
References 6

Chapter 2
DESIGNING IN FRP 7
2.1 Introduction . 7
2.2 Design 7
2.2.1 Material selection 9
2.2.2 Process selection . 10
2.2.3 Section thickness. II
2.2.4 Flanges and corners 12
2.2.5 Inserts. 12
2.3 Flat Sheets 12
2.4 Building and Cladding Panels 13
2.5 Hollow Structures . 13
References 14

Chapter 3
MOULDS 15
3.1 Introduction 15

VII

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VllI CONTENTS

3.2 Plaster Moulds 16


3.3 Wooden Moulds 18
3.4 GRP Moulds. 18
3.4.1 Single one-part moulds 19
3.4.2 Split moulds 20
3.4.3 Matching moulds 21
3.5 Epoxide Resin Moulds . 23
3.5.1 Single-stage casting 24
3.5.2 Two-stage casting 26
3.6 Steel Moulds. 28
3.6.1 Hot press moulding 29
3.6.2 Centrifugal moulding . 30
3.6.3 Transfer and injection moulding. 30
3.6.4 Pultrusion 31
3.7 Aluminium Alloy Moulds 31
3.8 Nickel Shell Moulds 32
3.9 Other Moulds 32
References 32
Suppliers 32

Chapter 4
MOULDING PROCESSES 33
4.1 Introduction . 33
4.2 Contact Moulding-Wet Lay-up 38
4.2.1 Hand lay-up 41
4.2.2 Spray lay-up 45
4.3 Vacuum Bag Moulding. 49
4.3.1 Wet lay-up. 49
4.3.2 Prepreg systems . 50
4.4 Pressure Bag Moulding . 51
4.5 Resin Injection or Resin Transfer Moulding. 52
4.6 Pressure Injection . 55
4.7 Vacuum Impregnation and Injection 55
4.7.1 Vacuum impregnation. 56
4.7.2 Vacuum injection moulding-Hoechst process 56
4.7.3 Vacuum injection-British Rail process 58
4.7.4 Monoforming 59
4.7.5 CSI process-Crystic Systems Ltd 59
4.8 Foam Reservoir Moulding 59
4.9 Cold Press Moulding 61

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CONTENTS IX

4.10 Hot Press/Matched Metal Moulding 62


4.10.1 Liquid resin/chopped strand mat. 63
4.10.2 Liquid resin/preform . 64
4.10.3 Sheet moulding compounds (SMC) and prepregs 65
4.10.4 Dough or bulk moulding compounds (DMC or BMC) 66
4.11 Transfer Moulding. 67
4.12 Injection Moulding 68
4.13 Filament Winding . 69
4.13.1 Wet lay-up. 70
4.13.2 Prepregs 73
4.13.3 Other applications 73
4.14 Centrifugal Moulding 73
4.15 Continuous Sheet Manufacture 76
4.16 Pultrusion 78
4.17 Sandwich Construction . 80
4.18 Moulding with Preformed Materials 81
4.18.1 C-Flex planking system 82
4.18.2 'Duradense' building system 82
4.19 Trimming and Finishing 83
References 84

Chapter 5
COMMON FAULTS FOUND IN GRP MOULDINGS 86
5.1 Introduction. 86
5.2 General Faults with Polyester Mouldings 86
5.3 Spray Moulding Faults. 98
5.4 Faults with Translucent Sheeting 99
5.5 Press Moulding Faults . 101
5.6 Resin Injection Faults . 102
5.7 Vacuum Moulding Faults 103
5.8 Filament Winding Faults 104
5.9 Centrifugal Casting Faults 105
5.10 Faults with Epoxide Resin Systems 105
Reference 108

Chapter 6
BONDING AND JOINTING REINFORCED PLASTICS 109
6.1 Introduction. 109
6.2 Adhesive Bonded Joints. 109
6.2.1 Surface preparation 111

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x CONTENTS

6.3 Mechanical Joints. 113


References 114

Chapter 7
MAINTENANCE AND REPAIR OF FRP STRUCTURES. 115
7.1 Introduction. liS
7.2 Maintenance. 115
7.3 Repairs to GRP Structures 116
7.3.1 Surface damage . 116
7.3.2 Small impact fractures 116
7.3.3 Holes. 118
7.3.4 Repair of holes where internal access is impossible 119
7.3.5 Repairs to pipes. 120
Reference 121

Chapter 8
SITE APPLICATION OF LAMINATES 122
8.1 Introduction. 122
8.2 Steel Structures 124
8.2.1 Initial preparation 125
8.2.2 Laminate application 126
8.2.3 Alternative laminating procedure 128
8.2.4 Alternative resin systems 129
8.3 Concrete Structures 129
8.3.1 Crack treatment. 130
8.3.2 Preparation of concrete substrate 131
8.3.3 Application of the laminate. 134
8.4 Wooden Structures 135
8.5 Repairs to Pipelines-Concrete, Steel or Thermoplastic. 136
8.6 On-site Tank Production 137
References 138

Chapter 9
POLYESTER RESINS . 139
9.1 Introduction. 139
9.2 Polyester Resins 140
9.2.1 Glycols 141
9.2.2 Unsaturated acids 142
9.2.3 Saturated acids . 143

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CONTENTS xi

9.2.4, Monomers . 144


9.2.5 Inhibitors . 147
9.3 Commercial Resins 148
9.3.1 Gelcoat/topcoat resins. 150
9.3.2 General purpose resins 151
9.3.3 Chemical resistant resins 152
9.3.4 Reduced flammability resins 157
9.3.5 Low styrene emission resins 159
9.3.6 Low shrink/low profile polyester resins 160
9.3.7 Special purpose resins. 162
9.3.8 Casting resins 164
9.3.9 Foamed polyester resins 167
9.3.10 Commercially available polyester resins 202
References 203

Chapter 10
CATALYSTS, ACCELERATORS AND INHIBITORS
FOR UNSATURATED POLYESTER RESINS 204
10.1 Introduction . 204
10.2 The Curing Reaction 206
10.3 Catalysts or Initiators 209
10.3.1 Diacyl peroxides. 210
10.3.2 Ketone peroxides 212
10.3.3 Hydroperoxides . 215
10.3.4 Dialkyl and diaralkyl peroxides 216
10.3.5 Peroxyesters 217
10.3.6 Perketals (peroxyketals) 220
10.4 Accelerators or Promoters 221
10.4.1 Metal compounds 221
10.4.2 Tertiary amine accelerators. 223
10.4.3 Mixed metal salt/t-amine accelerators. 224
10.5 Inhibitors 224
10.6 Commercially Available Materials. 239
References 239

Chapter 11
EPOXIDE RESINS 240
11.1 Introduction 240
11.2 The Resins 242

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XII CONTENTS

11.2.1 Bisphenol A based resins 242


11.2.2 Glycidyl ester resins 245
11.2.3 Glycidyl amine resins 246
11.2.4 Glycidyl ethers of novolac resins. 246
11.2.5 Brominated resins 247
11.2.6 Other resins 247
11.3 Diluents. 248
11.3.1 Reactive diluents. 248
11.3.2 Non-reactive diluents 252
11.4 How to Choose an Epoxide Resin. 254
11.5 Commercially Available Resins 262
References 262
Chapter 12
CURING AGENTS FOR EPOXIDE RESINS 263
12.1 Introduction . 263
12.2 Selection of Curing Agent 264
12.3 Amine Curing Agents 266
12.4 Anhydride Curing Agents 274
12.4.1 Accelerators for anhydride cured systems 282
12.5 Polyamide Curing Agents 282
12.6 Other Curing Agents 283
12.7 Some Typical Laminating Systems. 287
12.7.1 Site applications. 287
12:7.2 Alternative to polyester resin 289
12.7.3 Electrical laminates 290
12.7.4 Carbon fibre composites 292
References 293
Curing Agent Suppliers. 293
Some Suppliers of Formulated Curing Agents 294
Chapter 13
OTHER RESIN SYSTEMS 295
13.1 Introduction . 295
13.2 Furane Resins 295
13.3 Vinyl Ester Resins. 299
13.4 Friedel-Crafts Resins 301
13.5 Silicone Resins 304
13.6 Polyimide Resins 305
13.7 Phenolic Resins 306
13.8 Melamine and Urea - Formaldehyde Resins 306
References 307

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CONTENTS XIll

Chapter 14
REINFORCEMENTS .308
14.1 Introduction . 308
14.2 Surfacing Tissue 310
14.3 Glass Fibre Reinforcements 312
14.3.1 Continuous filament rovings 313
14.3.2 Chopped strands. 315
14.3.3 Chopped strand mat 317
14.3.4 Continuous strand mat 319
14.3.5 Woven glass fabrics 319
14.4 Carbon Fibre. 323
14.5 Aromatic Polyamide (Aramid) Fibres 327
14.6 Other Reinforcing Fibres 329
14.6.1 Polyester fibres 329
14.6.2 Polyacrylonitrile fibres 330
14.6.3 Nylon. 330
14.6.4 PVC and PVDC . 330
14.6.5 Cotton 330
14.6.6 Sisal 330
14.6.7 Asbestos 330
14.6.8 Paper. 331
14.6.9 Jute 331
14.6.10 Boron fibres 331
14.7 Commercially Available Reinforcements 348
References 348

Chapter 15
DOUGH AND SHEET MOULDING COMPOUNDS
AND PREP REGS . 349
15.1 Introduction . 349
15.2 Dough and Bulk Moulding Compounds (DMC, BMC). 350
15.3 Sheet Moulding Compounds (SMC) 352
15.3.1 Manufacture of SMC . 352
15.4 Prepregs. 355
15.4.1 Manufacture of prepregs 356
15.5 Commercial Products 358
References 371

Chapter 16
FILLERS AND PIGMENTS. . 372
16.1 Introduction . 372

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XIV CONTENTS

16.2 Mineral Fillers 376


16.2.1 Carbonates. 376
16.2.2 Silica and silicates 378
16.2.3 Aluminium silicates and clays 379
16.3 Glass Fillers . 380
16.4 Metal Oxide Fillers 381
16.5 Metallic Powder Fillers . 383
16.6 Other Fillers . 384
16.7 Thixotropic Additives 386
16.8 Flame Retardant Fillers. 386
16.9 Pigments and Dyes 387
References 388

Chapter 17
MISCELLANEOUS MATERIALS 389
17.1 Internal Lubricants 389
17.2 Skin Formers. 389
17.3 Light Stabilisers 390
17.4 Release Agents and Sealing Compounds 390
17.4.1 Wax release agents 390
17.4.2 Polyvinyl alcohol (PV A) 391
17.4.3 Spray release agents 391
17.4.4 Silicone release agents. 391
17.4.5 Sheet release agents 392
17.4.6 Cellulose acetate. 392
17.4.7 Nitrocellulose 392
17.4.8 Shellac 392
17.5 Core Materials 393
17.5. I Balsa wood. 393
17.5.2 Firet Coremat 394
17.5.3 Intercel 395
17.5.4 Honeycombs 396
17.6 Coupling Agents 396
References 398
Some Suppliers 398

Chapter 18
LAMINATING EQUIPMENT 399
18.1 Introduction . 399
18.2 General Equipment 399

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CONTENTS XV

18.2.1 Rollers 399


18.2.2 Brushes 402
18.2.3 Catalyst dispensers 402
18.2.4 Mixing and metering equipment. 402
18.2.5 Casting equipment 403
18.2.6 Mixers 403
18.2.7 Light sources for curing polyester resins 403
18.3 Spray Equipment for Polyester Resin Systems 403
18.3.1 Catalyst injection 404
18.3.2 Catalyst spray 405
18.3.3 Twin pot system . 406
18.3.4 Filler spray equipment 406
18.3.5 Flock gun 407
18.3.6 Roving cutters 407
18.4 Equipment for Saturating Glass Mat 407
18.5 Gelcoat Application Equipment 408
18.6 Resin Injection Equipment 409
18.7 Epoxide Resin Spray Equipment 409
18.8 Epoxide Resin Metering Equipment 409
18.9 Furane Spray Equipment 410
Suppliers 410

Chapter 19
HANDLING AND SAFETY PRECAUTIONS 411
19.1 Introduction . 411
19.2 General Precautions 411
19.2.1 Remedial measures 412
19.3 Epoxide Resins 414
19.4 Curing Agents 415
19.4.1 Aliphatic amines .' 415
19.4.2 Aromatic amines. 415
19.4.3 Cycloaliphatic amines . 415
19.4.4 Polyamide curing agents 415
19.4.5 Anhydride curing agents 416
19.4.6 Other curing agents 416
19.5 Furane Resins 416
19.6 Polyester Resins 416
19.7 Peroxide Catalysts. 417
19.8 Fillers and Pigments 419
19.9 Barrier and Cleansing Creams 420

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XVI CONTENTS

Chapter 20
TEST SPECIFICATIONS 421
20.1 Introduction . 421
20.2 Chemical Properties 421
20.2.1 Acid value of unsaturated polyester resins 421
20.2.2 Chemical resistance 422
20.2.3 Acetone extractables 422
20.2.4 Chlorine content. 422
20.2.5 Epoxide content . 422
20.2.6 Hydroxyl content of unsaturated polyester resins 423
20.2.7 Organic peroxides 423
20.2.8 Water resistance. 423
20.3 Fire and Smoke Tests 424
20.3.1 Flammability tests 424
20.3.2 Smoke evolution tests. 425
20.4 Mechanical Properties 425
20.4.1 Compressive strength and modulus 425
20.4.2 Flexural strength and modulus 425
20.4.3 Tensile strength and modulus 426
20.4.4 Interlaminar shear strength (lLSS) 426
20.4.5 Impact strength 426
20.5 Physical Properties. 427
20.5.1 Density and specific gravity. 427
20.5.2 Gel time 427
20.5.3 Hardness-indentation 427
20.5.4 Shrinkage 428
20.5.5 Viscosity 428
20.6 Thermal Properties 428
20.6.1 Heat deflection temperature 428
20.6.2 Martens heat deflection temperature 429
20.6.3 Coefficient of expansion 429
20.6.4 Flash point. 429
20.7 Electrical Properties 430
20.7.1 Arc resistance 430
20.7.2 Dielectric constant (permittivity) and power factor 430
20.7.3 Dielectric breakdown voltage and dielectric strength 430
20.7.4 Dust fog tracking and erosion 431
20.7.5 Volume and surface resistivity 431
20.8 Miscellaneous Test Specifications 431
20.8.1 Colour 431

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CONTENTS XVlI

20.8.2 Loss on ignition for GRP . 431


20.8.3 Visual defects in mouldings. 431
20.8.4 Reinforcements . 431
20.8.5 General specifications. 432
References 433

Appendices
1 Trade Names 434
2 General Material Suppliers 439
3 Company Names and Addresses 440
4 Units, Prefixes and Conversion Factors 448

Index 451

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Chapter 1

GENERAL INTRODUCTION

1.1 INTRODUCTION

During the past thirty years and more, vast strides have been made in the
use of fibre reinforced thermosetting resins until today their use is
commonplace.
Only a few years ago one would hear that such-and-such an object was
made from 'Fibreglass'. Today, whilst this term is still used, a much more
common term is GRP and one frequently hears of someone who owns a
GRP boat. GRP mostly stands for Glass Reinforced Polyester, although it
is also used to describe other glass reinforced plastics. With the increasing
use of fibres other than glass as reinforcing materials, a new term has been
coined and that is FRP. This stands for Fibre Reinforced Plastics and can
cover both thermoplastics and thermosets. In the context of this book,
FRP has been used to cover just the thermosetting resins reinforced with
fibrous materials, and then not every material, as will become apparent on
reading through the book.
A fibre reinforced resin system is a composite material consisting of a net-
work of reinforcing fibres embedded in a matrix of thermosetting resin. Other
materials such as fillers and pigments may also be present, although they
are not an essential part of the composite. In general, the resin used consists
of a syrupy liquid which, when combined with a suitable catalyst or
hardener, can be cross-linked into a hard infusible solid. By impregnating
the fibrous material, frequently in the form of a cloth or mat, with the
catalysed resin and allowing the resin to cure, the composite material or
laminate is formed. This process is carried out in a mould which may be
open or closed. The resultant product is a fully cured moulding which is an
exact replica in reverse of the original mould surface.
In general, where glass is used as the reinforcing fibre the product is

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2 FRP TECHNOLOGY

referred to as a laminate, whereas if carbon fibre is used as reinforcement


the product is referred to as a carbon fibre composite.
The aim of this book is to try to compare and contrast the different resins
available for contact moulding but which may also be used for press and
other moulding processes.

1.2 WHY USE FRP?

The answers to this question are many and varied and may be simple or
complex. Indeed, with the family of materials which can be classified as
FRP, one should not expect a simple answer.
If we consider firstly glass reinforced polyester resins, then it is possible
to summarise the advantages as follows:
1. Thermoset.
2. Advantageous strength/weight ratio and rigidity.
3. Moulding size virtually unlimited.
4. Ease of fabrication.
5. Wide range of manufacturing techniques.
6. Low capital outlay-for hand lay-up.
7. One-off or few-off mouldings are possible at reasonable cost.
8. Considerable design versatility.
9. Can be combined with other materials, e.g. foams for buoyancy.
10. Excellent water resistance.
11. Resistant to a wide range of chemicals.
12. Resistant to weathering and UV exposure.
13. Can be coloured to give a maintenance-free finish.
14. Fire retardant-if required.
15. Transparent/translucent-if required.
16. Good electrical and thermal properties.
Similar comments apply to glass reinforced epoxide resin systems
although cure and handling characteristics and cured properties are a little
different.
With carbon fibre reinforced resin systems the composites are, of
necessity, black and so some of the above advantages do not apply.
However, in this case specific strength and modulus are sufficiently greater
than those of most other materials, including metals, that such composites
are highly attractive to designers for applications where weight is of prime
concern.

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GENERAL INTRODUCTION 3

Another factor which is relevant to any material selection process is cost.


In the case of FRP, since the major resins-polyester and epoxide-are
derived from oil, cost is related to crude oil price. In view of the world
shortage of crude oil and the continual price increases being applied, FRP
costs will continue to rise. What long term effect this will have on FRP
consumption will depend on a variety of other economic factors. Certainly
in some areas one can foresee FRP being priced out of the market. However,
in general the prospect for the future is unlikely to be as bleak as some
would have us believe.

1.3 WHICH RESIN?


Here only a brief description of the resins used will be given since they are
dealt with in more detail later in the book.l.2.3
By far the most widely used of all laminating resins are the unsaturated
polyester resins. These comprise an unsaturated polymeric material
prepared from a dihydric or polyhydric alcohol reacted with a dibasic or
polybasic acid, dissolved in a liquid monomer such as styrene. A whole
family of resins can be prepared in this way to meet a wide range of
fabrication and end use requirements. The essential part of these resins is
that they are unsaturated and can be cross-linked or cured through the
unsaturated links to give hard, infusible, insoluble, thermoset solids. This is
accomplished with the aid of an organic peroxide catalyst either at room
temperature or by the application of heat. This reaction is described as free
radical polymerisation. By using an unsaturated monomer such as styrene,
which also cross-links into the system, there are no solvents or other
volatile materials to be eliminated during cure.
The next most important class of resins used are the epoxide resins. These
differ both in chemical structure and method of polymerisation from the
unsaturated polyester resins. The resin itself may be a low molecular weight
liquid or a low melting solid. This is reacted with a curing agent or hardener
to form a cross-linked structure. The resin and curing agent react together
by a conventional chemical reaction and so the curing agent has to be
present in sufficient quantity to link each of the epoxide resin molecules
together. Typical curing agents used are polyamines and organic anhyd-
rides. Cure can be brought about at ambient and elevated temperatures
with no evolution of volatile matter during cure. One advantage that
epoxide resins have over polyester resins is reduced shrinkage (1-2%)
during cure. Polyester resins generally shrink 5-8% on cure due to the
different type of curing reaction which takes place.

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4 FRP TECHNOLOGY

The third class of resins encountered are the vinyl ester resins. These
combine part of the chemical backbone of an epoxide resin with the curing
mechanism of a polyester resin. Essentially an epoxide resin is converted to
a polyester resin by reaction with a suitable unsaturated organic acid. The
resultant polymer is then dissolved in styrene and used in a similar manner
to a polyester resin. The advantages gained are the ease of processing of a
polyester resin coupled with improved chemical resistance due to the
reduced number of ester linkages present in the molecule.
Fourthly we have the furane resins. These were first used in the
preparation of acid resisting cements but, with the development of
improved catalyst systems, can now be used for laminating. Furane resins
comprise a furfuryl alcohol polymer blended with furfural as reactive
diluent. Cross-linking is by means of an acid catalyst. The resultant
polymer is black. The main advantage that a cured furane resin offers over
other laminating systems is exceptional chemical resistance, even to such
materials as perchlorethylene and glacial acetic acid. Cured furane resins
also exhibit very low smoke emission under fire conditions.
Finally, as far as this book is concerned, come the Friedel-Crafts
polymers--typified by the 'Xylok't resins. These are condensation products
of aralkyl ethers and phenols and are similar in structure to phenolic
novolac resins. They require heat cure with a controlled post cure, using a
curing agent such as hexamine. When fully cured they give composites with
good thermal stability and excellent electrical properties.
Other resins such as phenolics, silicones, polyimides and melamine- or
urea-formaldehyde resins are also used with reinforcements and, while
some of these are mentioned briefly, few details have been included in this
book. These resins are all processed by hot press moulding techniques. A
typical example of a melamine-formaldehyde faced phenolic laminate
would be one of the many decorative laminates used on kitchen furniture,
etc.

1.4 REINFORCEMENTS

Reinforcements comprise fibrous materials used to strengthen cured resin


systems. Virtually any fibrous material may be used, although in practice
the list is quite small. Fibre length may vary from about 3 mm, as used in
dough moulding compounds, up to several hundreds of metres for filament
winding applications.
t'Xylok' is an Albright & Wilson trade name.

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GENERAL INTRODUCTION 5

One type of fibre predominates and that is glass fibre. The bulk of all
glass fibres used for laminating are made from E-glass or electrical grade
glass. This is a high strength, low alkali content glass and is discussed in
more detail in Chapter 14.
Another fibre which is becoming increasingly important, particularly
where high strength or rigidity is required, is carbon fibre. The availability
of continuous strand carbon fibre filament has extended the areas in which
reinforced resin systems can be used and, although the price is much higher
than that of glass fibre, the considerably superior specific strength and
modulus of carbon fibre composites make them extremely attractive for
many applications. One important area is in the manufacture of high speed
reciprocating parts, where any weight reduction without loss of strength or
rigidity, enables a machine to be operated either faster or more efficiently at
the same speed.
Whilst various synthetic polymer fibres based on acrylics and polyesters
find application as surfacing tissues, the recently developed aramid fibres
are finding increasing application in the preparation of high strength/high
modulus composites, the aramid fibre acting as the sole reinforcing fibre.
Other fibres which find some application as reinforcing materials include
asbestos, cotton, sisal, rayon and wool.

1.5 PROCESS DEVELOPMENT

When polyester resins were first used for the manufacture of glass reinforced
composites, the hand lay-up or bucket and brush technique was all that was
available. Gradually this situation has changed until today very many
different fabrication processes are in use. These various processes were
developed to improve laminate consistency, reduce labour content, reduce
mixing errors, increase production rate and for various other reasons. Each
of these processes has an important part to play in the further development
of the industry.
In recent years the trend has been away from the labour intensive hand
lay-up technique towards more automated techniques. This situation is
likely to continue in the future, particularly towards closed mould
processes, to combat the likelihood of increasingly stringent legislation
being introduced to control styrene levels in workshop atmospheres and
general contact with resin systems.
Whilst some may see this as the start of the decline of the FRP industry,
others will see it as just another development problem. Whichever way

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6 FRP TECHNOLOGY

future developments go, hand/spray lay-up techniques will undoubtedly


continue to play an important though lesser role, since there will still be
occasions where hand/spray lay-up provides the only practical way of
fabricating many types of moulding.

REFERENCES

1. Judd, N. C. W. and Wright, W. W. (1978) Reinforced Plastics, February, 39.


2. Clarke, G. M. and Norwood, L. (1978) Reinforced Plastics, November, 370;
(1979) Plastics & Rubber; Materials & Applications, 4 (2), May, 87.
3. Weatherhead, R. G. (1979) Reinforced Plastics, May, 148.

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Chapter 2

DESIGNING IN FRP

2.1 INTRODUCTION

Fibre reinforced plastics offer almost unlimited possibilities for shape, size
and colour and can be produced with a variety of surface finishes.
Sandwich construction can be used to produce rigid lightweight mouldings,
whilst if unidirectional carbon fibre is used as reinforcement, exceptional
strength to weight ratios can be achieved. However, before any object can
be made it has to be designed. With FRP, whilst considerable scope exists
for designers and architects, due consideration must be given to the
processing and cured properties of the material to be used. In this chapter
an attempt will be made to indicate some of the criteria which need to be
considered during the design of an FRP object. It will be assumed that
other materials such as wood, metal or concrete have been ruled out.

2.2 DESIGN

In the first instance the customer or designer will produce a rough sketch of
an idea for a component. This sketch will then slowly be developed into the
final design, with material parameters and design tolerances specified.
Factors which influence design are resin selection, reinforcement selec-
tion and moulding process. The choice of moulding process will be affected
by the number of mOUldings to be produced, production rate, moulding
complexity and size of moulding. Another factor which may need to be
considered is the means by which the finished moulding will be transported
to its final destination. In the case of very large objects this may mean that
several moulded parts have to be produced for assembly on site.
In many cases the final design will be a compromise between the

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Table 2.1 Typical properties of various fibre reinforced composites 00

Glass Tensile Flexural Flexural


content Specific strength strength modulus ILSS
Material (% wt.) gravity (MPa) (MPa) (GPa) (MPa)

Polyester DMC 10 1·89 21 83 7


15 1·85 27 96 9
30 1·85 41 124 10
Epoxy DMC 30 1·75 100 180 16
65 1·78 140 300 25
Polyester SMC 25 1·85 68 190 10
Hot press moulding/chopped strand mat 40 1·5 124 240 11 ;il
Hand lay-up/chopped strand mat 30 1·49 103 194 8 '"C:I
Spray lay-up 28 1-49 103 194 8 ;j
Cold press moulding/continuous g
filament mat 20 1.44 90 172 7
Unidirectional E-glass/epoxy 65 2·0 1000 1400 40 80 ~t"'
Woven roving/chopped strand mat, 8><
600:450 g/m 2 43 1·5 190 390 11

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Carbon
content
Fibre type (% vol.)
Unidirectional carbon Type HTM-S or 1 60 1-6 930 1200 180 70
fibre/epoxy Type HTS-S or 2 60 1·5 1620 1720 131 100
Type A-S or 3 60 1·5 1440 1520 115 110
Hyfil T 130 60 1·5 1300 1600 132 80
Satin weave carbon
fibre/epoxy Toray T 300 65 530 940 63 62
DESIGNING IN FRP 9

requirements of the designer and the moulder. In this respect there should
be considerable liaison between designer and moulder to ensure that the
final moulding meets as many of the original design requirements as is
possible, taking into account production rate and moulding cost. Often all
requirements may be met with no difficulty. Typical composite properties
are shown in Table 2.1.
A useful booklet which describes moulding with GRP from planning
through to production has been produced by Bayer. 1 Useful data may also
be found in literature produced by other polyester resin suppliers and
conference reports. 2 Also, recently published, is an interesting article
describing the design and manufacture of the British Rail high speed train
cab. 3

2.2.1 Material selection


Let us now consider material selection. This includes resin and reinforce-
ment selection. Some of the factors which need to be considered are listed
below. Not all of these will be relevant in each case and other factors may
have to be added to the list (see also references 1-3 and Chapter O.
1. Mechanical/physical properties:
Strength/weight ratio.
Specific gravity.
Is strength, stiffness or impact resistance of prime importance?
Is fatigue life important?
Is the component structural or non-structural?
2. Thermal properties/fire resistance:
Heat deflection temperature.
Operating temperature.
Coefficient of expansion.
Humidity conditions.
Fire resistance.
3. Chemical resistance:
Will contact be with liquids or gases, aqueous or solvent solutions?
Is it a mixture or single component?
Is contact continuous or intermittent?
Will the composition change from one period to the next?
What are the operating temperatures and temperature fluctuations?
Is the material acidic, alkaline, oxidising or reducing?
4. Biological:
Is food contact involved?
Are bacteria, microbes or termites likely to cause a problem?

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10 FRP TECHNOLOGY

5. Electrical properties:
Breakdown voltage, tracking resistance.
Surface and volume resistivity.
Dielectric constant, dissipation factor (tan 15).
6. Outdoor weathering:
UV exposure.
Will the moulding be subjected to tropical, marine, European or
arctic climate and for how long?
7. Clarity and colour:
Transparent, translucent or opaque.
Colour.
Surface finish.
Resistance to yellowing.
8. Which performance specifications have to be met:
Food contact-F.D.A. approval.
Marine-Lloyd's Register of Shipping.
-Det Norske Veritas.
Other approvals.
9. Performance testing and guarantees:
Who carries out testing and to which specifications and under which
conditions if a choice exists?

2.2.2 Process selection


Once the above factors have been considered, process selection can begin.
Here other factors have to be considered, some of which may well be
influenced by material choice and operating temperature. Some of these
points are listed below.
Moulding size-is the moulding small, medium or large?
Unit cost-this includes material and production costs.
Is a gelcoat required?-not possible with SMCjDMC.
Number of mOUldings and production rate. Is it a one-off moulding or
are 10 000 mouldings required? This affects not only choice of
moulding process but also the type of mould to be used.
Is one smooth surface acceptable?-if so, an open mould process can be
used, or must both surfaces be smooth? - in which case a closed mould
process is necessary.
How does section thickness vary?
What is the overall shape?
Can the moulding be produced by filament winding, pultrusion,
continuous sheet production or some other automated process?

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DESIGNING IN FRP 11

Are there any undercuts? If there are, then a split mould will be needed.
Are the major surfaces flat, of single curvature or double curvature?
With large flat surfaces, must these be free from shrink marks? If so, then
a hot cured low profile resin system will be needed.
Are there any sharp edges or small radii to be accommodated? If so, then
a press moulding process may be needed.
Is sandwich construction required?
Are ribs or buoyancy panels to be included in the moulding?
Is precise fibre alignment required to obtain design strength in any
particular direction?
Is heat cure required to achieve maximum chemical or thermal
resistance? If the moulding is large, is there a suitable press or post
curing oven available or must a heated mould be used?
Once these questions and perhaps others have been answered it is
probable that the choice of manufacturing process will have been narrowed
down to just one or two processes, in which case design can then proceed.
Alternatively the production process may have been selected at an early
stage and design and material selection geared to this.
Whichever process and materials are selected for a particular moulding,
consideration must be given during mould design to demoulding and lay-
up. For ease of demoulding, components should be designed with an
adequate taper and without undercuts, unless a split mould is used. Mould
preparation, lay-up and demoulding is more complicated if a split mould is
used.
A summary of the various moulding processes available can be found in
Table 4.1.

2.2.3 Section thickness


Section thickness can affect a number of factors, including mechanical
strength, material costs, production costs, cycle times and peak curing
temperature.
By increasing the reinforcement to resin ratio, mechanical strength can
be increased for any given laminate thickness. This can also be affected by
the type of reinforcement used. Typical reinforcements which may be used,
listed in order of increasing strength, include chopped strands, woven
rovings and unidirectional rovings.
Care must be taken during the production ofthick sections to ensure that
there is not excessive heat build-up from exothermic heat of reaction. This
can result in discoloration of the moulding and can also produce distortion
and shrinkage marks. Thick sections may have to be built up in stages,

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12 FRP TECHNOLOGY

allowing the exothermic heat to dissipate at each stage. Since FRP


laminates are generally poor thermal conductors, this may be a relatively
slow process and will clearly slow down production rate. Care must also be
taken to ensure that no delamination occurs when the final moulding is put
into service.

2.2.4 Flanges and comers


Flanges can provide adequate stiffening on small mouldings without the
need to incorporate ribs. Their design will depend to some extent on the
moulding process, particularly with regard to the radius of the corner.
Some typical recommended minimum radii are given below.
Hand/spray lay-up 6mm
Pressure/vacuum bag 12mm
Preform/matched die moulding 3mm
SMCjDMC O·5mm

2.2.5 Inserts
Inserts for the subsequent assembly of panels can be incorporated with
little difficulty, particularly with hand or spray lay-up techniques.
Generally the laminate will be increased in thickness around the insert to
hold it in place and to provide adequate stress distribution. Many different
threaded inserts are available with large perforated heads to ensure
adequate bonding and to prevent them from being pulled out during use
(see Fig. 6.2).

2.3 FLAT SHEETS

These can be produced by continuous laminating by machine in a similar


manner to corrugated sheets. Other methods used include hot press
moulding with sheet moulding compounds and hand/spray lay-up. With
hand/spray lay-up a slow curing resin system will generally give a better
distortion-free laminate than a fast curing system.
I t is only since the introduction of low profile sheet moulding compounds
that it has been possible to produce large flat mOUldings, free from shrink
marks, by hot press moulding techniques. Hot press moulding offers
considerable production advantages for such items as vehicle bodies where
high production rates are necessary.
Where ribs have to be added to flat sheets for stiffening, these should be
applied after the laminate has cured, otherwise shrinkage will occur

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DESIGNING IN FRP 13

~~~~~~-:::: Lam; na te

Fig. 2.1 Laminate lay-up over preformed rib.


resulting in sink marks appearing on the opposite side of the laminate.
Ribs are frequently made from preformed profiles applied to the
laminate and then over laminated, each successive layer of mat placed over
the rib being slightly larger than the preceding one to ensure adequate load
distribution. These profiles, which may be hollow or solid, may consist of
rigid foam, paper rope, cardboard, preformed laminates or a variety of
other materials. A typical lay-up is shown in Fig. 2.1.

2.4 BUILDING AND CLADDING PANELS

These can be produced in a variety of ways, as flat or contoured sheets, or


by sandwich construction. Great care should be taken in the design ofjoints
to withstand thermal movements and in the case of cladding panels, to
resist weathering and rain penetration. Further information on design and
specification of G RP cladding can be found in a conference report on this
topic. 4

2.5 HOLLOW STRUCTURES

These may consist of structures open on one side only, such as tanks,
troughs and boats, all of which can be produced by conventional
techniques. Alternatively they may consist of structures open on two sides,
such as pipes. Here, filament winding or centrifugal casting can be used for
production. With filament winding, pipes of up to about 400 mm diameter
can be made on a solid mandrel; above this size a split or collapsible
mandrel should be used. The mandrel predetermines the inside diameter of

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14 FRP TECHNOLOGY

the pipe. With centrifugal casting the mould determines the external
diameter.
With filament winding, where greater chemical resistance is required
than can be obtained with the resin system alone, a liner may be applied to
the mandrel surface before winding commences. This liner may be a
thermoplastic such as PVC or a synthetic rubber, depending on end use.
Closed hollow structures can be made by filament winding on a water
soluble or low melting wax or alloy mandrel. In this case the mandrel can
only be used once and is removed after winding and cure is completed. Such
structures find application as pressure vessels for storage and particularly
as pressure vessels for rockets and other space activities. Such vessels are
frequently made with epoxide resin systems.

REFERENCES

1. Designing with Glass Reinforced Leguval. A Moulding from Planning through to


Production. Bayer, W. Germany.
2. Designing with Fibre Reinforced Materials. Conference Report, 27~28
September 1977. I.Mech. E., London.
3. Gotch, T. M. (1979) Plastics & Rubber International, 4, May/June, 119.
4. Hollaway, L. (Ed.) Design & Specification of GRP Cladding. Conference.
19 October 1978. Manning Rapley Publishing Ltd, Croydon, Surrey.

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Chapter 3

MOULDS

3.1 INTRODUCTION

Before any moulding process can be undertaken a suitable mould must be


made. This is one of the most important steps since it affects the quality of
the moulding and ease of production. A poor quality mould can result in
many scrap mOUldings.
With the wide range of possible moulding processes available, many
different types of mould are required. These can be made from a similarly
wide variety of materials including wood, plaster, concrete, epoxide and
polyester resins, non-ferrous metals, steel or a combination of these.
However, the most commonly used material is glass fibre reinforced
polyester (GRP).
Factors which affect choice of mould material include the number and
size of the mOUldings to be produced, the type and finish required and the
moulding process. For long runs, matched metal moulds are invariably
Table 3.1 Moold life of different mould materials

Process suitability

Press moulding
Number of Hand/spray
Mould material releases lay-up cold hot

Plaster 1-5 feasible


Wood 1-100 feasible
GRP-stitfened 100-2000 common
GRP-filled with
concrete 100-3000 common
Steel up to 1 million common

15

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16 FRP TECHNOLOGY

used but, where only a few mouldings are to be produced, wooden or


plaster moulds will often suffice. Intermediate quantities of mouldings,
ranging from a few hundreds to a thousand or so, are generally produced
using GRP moulds, with epoxy moulds becoming more common as the
number of mouldings increases above this. Typical mould life for a number
of different mould materials is shown in Table 3.1.
Whichever mould material is chosen, the finished moulding will
reproduce an exact replica of the mould surface in reverse, and moulding
accuracy and tolerance will be governed by the accuracy and rigidity with
which the mould is made.

3.2 PLASTER MOULDS

These can be divided into two broad categories: those made as master
patterns for GRP mould production or those used directly for moulding.
An example of the latter type can be found in the filament winding of
cylinders and spheres where the mould is used once and then has to be
broken up to extract it from the moulding.
In general, it is unlikely that a solid block of plaster will be used as a
pattern; more probably a wooden frame will be prepared which will then be
covered with plaster. A typical plaster pattern is shown in Fig. 3.1. This
consists of a wooden frame suitably prepared with braces and stringers to
keep it rigid. It must be solid enough to support the weight of plaster to be
used and must not distort during preparation of the GRP mould. Wire
netting is fixed to the frame to act as support for the plaster. Next several
layers of plaster reinforced with hessian are applied, followed by a layer of
plaster roughly shaped to the final pattern. The pattern is finished with a
thin layer of plaster carefully applied to bring it to the correct dimensions
for the mould. This final layer must be accurately finished and well polished
to ensure a smooth surface. It is preferable to use a low expansion type of
plaster for this application. Once the pattern has been completed it should
be allowed to dry for at least 24 h before hardening at between 60 and 80°C
for an hour or two. After the plaster pattern has been hardened its
dimensions should be checked to ensure that no changes have taken place.
Any oversize areas can be very lightly rubbed down.
Since plaster moulds are porous the surface must be sealed with a
solution of shellac, cellulose acetate, nitrocellulose or polyvinyl alcohol
before waxing and polishing. More than one coat of sealer may be

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MOULDS 17

main longitudinal mlmbrr


longitudinal slringlrs

hessian

Iransnrsc ribs
Fig. 3.1. Construction of a plaster pattern. (Courtesy of Scott Bader Co. Ltd.)

necessary depending on the porosity of the surface. It is this surface which


will be reproduced on the GRP mould and hence on the final mouldings
and so extreme care at this stage will be well rewarded.
Whilst a pattern of this type is generally used to prepare a G RP mould it
can also be used to make a prototype moulding. Clearly, if this is the case, it
will have to be made in the shape of the mould rather than as a prototype of
the finished moulding.
With the filament winding of spheres and cylinders some form of
disposable mandrel has to be used, since these are continuous structures
with only a small hole at either end. One procedure is to use a plaster or clay
mandrel which is strong enough to withstand the winding process but
which can be washed out with water after use. Such mandrels can be hollow
cast in two sections and then assembled and coated with a further layer of
plaster to give a smooth continuous finish
Once such a mandrel has been prepared, it must be dried and sealed with
a water soluble sealer such as polyvinyl alcohol. Filament winding can then
be carried out directly or the mandrel can be coated or wrapped with a
synthetic rubber or other type of liner.

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18 FRP TECHNOLOGY

3.3 WOODEN MOULDS

These may be carved from solid blocks of wood or constructed from several
pieces stuck together. Plywood or block board can be used for flat surfaces.
Whichever procedure is adopted the quality of the mould affects the quality
of the moulding. The skills required for mould making are those needed in
coach building or cabinet making.
By the use of split moulds, undercuts and return angles can be
incorporated in mouldings. However, where split moulds or ones with
movable parts are to be used great care must be taken in their construction
and in the fixing of locating pins. By careful design, moulds can be
constructed in such a way that minor modifications can enable a series of
mouldings of different length to be produced, as might be required for G RP
cladding units.
After completion the mould surface must be rubbed down until it is
completely smooth and then sealed with an appropriate sealing compound
such as shellac, cellulose acetate, polyester or epoxide resin. This sealer
must be allowed to dry thoroughly before polishing with a silicone-free wax
polish. Several applications of wax are better than trying to apply one thick
coating. The final coat of wax must be polished to a high gloss finish.
In addition to acting as moulds for short production runs, wooden
moulds are also frequently used as patterns for the production of GRP
moulds.

3.4 GRP MOULDS

These are made from glass reinforced polyester resin systems by hand or
spray lay-up techniques, on patterns which may be made from wood,
plaster or any other suitable material. One of the main reasons for the
prevalence of such moulds is that moulders have all the necessary materials
readily to hand.
In preparing a pattern for a GRP mould, due account should be taken of
the shrinkage of the resin system during cure. Once the pattern has been
completed, it must be sealed to make it non-porous and then polished to a
high gloss finish using a silicone-free wax polish. This should be applied in
several layers polishing each as it is applied. As many as six coats of polish
may be necessary. Next the pattern should be coated with a release film of
polyvinyl alcohol by cloth, sponge or spray, making sure that this film is
completely uniform with no imperfections and no dust, hairs or other

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MOULDS 19

foreign particles present. This film must be allowed to dry thoroughly


before any resin is applied to it, otherwise the laminate may stick to the
pattern and cause irreparable damage.
During the design of a mould, consideration should be given as to how
the edge of the mould will be finished. In many cases, if suitably reinforced,
the edge can act as a guide for trimming 'green' mouldings.

3.4.1 Single one-part moulds


The gelcoat should be applied to the suitably released pattern by brush,
roller or spray, to a thickness of about 0·6 mm. This is roughly double the
thickness recommended for mouldings, to allow for rubbing down during
the life of the mould. To assist in this rubbing down process, the gelcoat can
be applied in three layers of alternate colours, for example, black, green,
black. In this way rubbing down can be controlled with no fear of going
down to the glass reinforcement. The colours should preferably contrast
with that to be used for the final moulding. If mOUldings are to be produced
which do not require a high gloss finish, a self-releasing gelcoat can be used
for the mould surface.
When the gelcoat has cured sufficiently to give a tacky surface, a coat of
laminating resin system is applied, into which is placed a layer of surfacing
tissue followed by a layer of 300 g/m 2 chopped strand mat. This should be
thoroughly consolidated with a laminating roller to eliminate all voids.
Further resin and reinforcement are applied by either hand or spray lay-
up techniques, allowing the resin to gel between the application of each two
layers of reinforcement. This is to prevent any exotherm from occurring
and to prevent any stresses from being built into the laminate which may
distort the mould during use. The total laminate thickness should be about
double that of the mouldings to be produced from the mould. (Full details
of hand and spray lay-up procedures can be found under Contact
Moulding in Chapter 4.)
To prolong the life of a mould a heat resistant resin system may be used.
Once the final coat of resin system has been applied, the mould should be
allowed to cure for at least two weeks at room temperature. In addition a
post cure of several hours at 65-70°C can be given to prevent distortion
during use.
Large moulds should be stiffened with ribs on the reverse side. These can
be constructed from plastic or metal tubing, foamed plastic or paper rope.
Wooden ribs may also be used but these may cause distortion ofthe mould
after prolonged use. The formers should be shaped to the contours of the
mould and covered with two or three layers of resin impregnated glass

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20 FRP TECHNOLOGY

reinforcement. It is essential that the main laminate is cured and is of


adequate thickness before application of the ribs, to prevent contraction of
the resin around the ribs causing sink marks in the laminate surface.
The mould should not be removed from the pattern until it is fully cured.
Any modifications or fixings which need to be applied to the mould are best
carried out whilst the mould is still on the pattern, providing this does not
impede removal from the pattern.
Most moulds will require mounting on a frame so that they stand flat on
the floor or can be rotated or tilted. Such frames may be of wooden or
tubular metal construction and should be sufficiently rigid to prevent
distortion of the mould during use. They can also be used to support the
mould during post cure.
Where greater rigidity of the mould is needed, the back can be filled with
a rigid polyurethane foam composition, foamed in place.

3.4.2 Split moulds


Where deep draw mOUldings or ones with undercuts are to be produced

Temporary
barrier 1'ilIt-- Laminate 1.It!I-- Laminate
with flange
support 1.~~~I4-1~-- Conti nuous
rovings
Gel coat
;,:.;.;.~_Pattern

Stage 1 Stage 2

Metal plate

Continuous
rovings Laminate
Gelcoat

Pattern

Stage 3
Fig. 3.2. Method of constructing a split mould. (Courtesy of Scott Bader Co. Ltd.)

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MOULDS 21

which would be difficult or impossible to remove from a one-piece mould,


split moulds can be used. Here a temporary barrier should be fitted to the
pattern so that the first half of the mould can be made with a flange (see
Fig. 3.2). The flange area should be about 50% thicker than the mould shell
to ensure adequate life. The first half of the mould is left in place, the
temporary barrier removed and the second half of the mould manufactured
using the suitably released flange as former. A metal plate can then be
laminated onto either side of the flange to assist in supporting the bolts used
to clamp the flange halves together. Once the resin has cured, holes can be
drilled to take fixing bolts. These should be spaced at about 150 mm
intervals.
The mould should not be removed from the pattern until all necessary
work has been carried out. Mould release can be assisted by using
compressed air carefully applied between the mould and the pattern.
Release can also be assisted by filling the gap between the mould and the
pattern with water to soften and dissolve the polyvinyl alcohol release
agent. If the mould has to be struck in any way, extreme care should be
taken to ensure that this does not result in star patterns forming in the
gelcoat.
Any imperfections in the mould surface can be removed by rubbing with
fine abrasive such as grade 600 wet emery paper followed by a fine cutting
paste or by using a metal polish. Before use, the mould surface must be
thoroughly polished to a high gloss finish using a silicone-free wax polish
applied in several thin coats.

3.4.3 Matching moulds


Where matching moulds are required for processes such as resin injection,
foam reservoir moulding or cold press moulding, a full size pattern of the
final moulding is generally required. If this is available the two halves of the
mould can be made in a similar way to making a split mould but
incorporating appropriate injection and vent tubes along the join between
the two halves. The dictates of the process will govern which attachments
are necessary. Locating dowels must also be accurately positioned.
With thin mOUldings an alternative procedure is to make a pattern of the
outside of the moulding and then make the negative mould. This negative
mOUld, after full cure, is then used as a base on which to construct a model
of the moulding using sheets of pattern maker's wax. When the required
thickness of wax has been applied the positive mould is constructed on top.
During construction of the wax pattern due consideration must be given to
the provision of drainage channels and vent/injection points. The positive

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22 FRP TECHNOLOGY

mould must be accurately made, allowing for resin shrinkage, so that the
mould cavity is of the correct size. An oversize mould will only waste
expensive materials each time a moulding is made.
For cold press moulding the back of the mould should be filled with a
material capable of withstanding continuous loading in a press. One such
material is concrete, although a filled resin system may also be used. Here,
after the final layer of glass reinforcement has been applied to the mould, a
further layer of resin is applied at a rate of about 400 g/m 2 , into which is
sprinkled a layer of broken stone chips. After the resin has been fully cured
the back of the mould is filled with the concrete or resin mix which bonds
around these stone chips. Both halves of the mould should be similarly
treated.
Where GRP moulds are used for cold press moulding the moulding
cannot be trimmed as part of the moulding cycle. To maintain pressure on
the resin and prevent it from being squeezed out leaving air bubbles in the
moulding, the mould should be constructed with a pinching area. During

Laminate
~_..,.-=---"I- Mould cavity
~\7-I=n=-~ Laminate
Stone chips

Concrete or
Resin

Lower press plate


Fig. 3.3. Pinch area for cold press moulding. (Courtesy of Synres
International BV.)

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MOULDS 23

final closure of the mould this allows air to escape but retains the resin. For
mouldings up to about 5 mm in thickness, the pinching area should be
sufficient to compress two layers of glass mat in a gap of 0·4-0·5 mrn. For
thicker mouldings the pinching area should accommodate three or four
mat thicknesses. In addition, it is useful to incorporate a drainage channel
into which surplus resin can drain. An example of such a design is shown in
Fig. 3.3.
When not in use, moulds should be stored flat to prevent distortion and
protected from dust and moisture. In use, continuous scrutiny is necessary
so that any imperfections which occur can be immediately rectified.
Sharp instruments must always be kept away from mould surfaces.
Properly treated, GRP moulds can give excellent service.

3.5 EPOXIDE RESIN MOULDS

Epoxide resin moulds can in some ways be considered as intermediate


between GRP and steel moulds. They have long service lives with many
thousands of mOUldings being produced from one mould. Since epoxy
moulds generally have a specific gravity of around 1,8, there is a
considerable weight saving over steel moulds. Also, unlike steel, epoxy
moulds will not corrode and therefore do not require protecting with grease
during storage. If damaged, they can frequently be repaired with no long
term detrimental effect. Steel moulds on the other hand are in most cases
impossible to repair if damaged.
Epoxide resins also offer several advantages over polyester resins for
mould making. They exhibit negligible shrinkage during cure, remain
dimensionally stable once cured and can be cast in thick cross-sections with
low exotherm, providing that the correct system has been selected. In the
main, the properties of epoxide resin systems are governed by the choice of
curing agent or hardener rather than the resin, although the final cured
properties depend on both the resin and curing agent used.
Two basic methods are used for making epoxy moulds, namely
laminating and casting. The laminating procedure is virtually identical to
that used with polyester resin systems and so will not be described here. The
mixing ratio of resin to hardener recommended by the supplier should be
used at all times. Whilst generally there is a tolerance of ± 10% on hardener
proportion, outside this limit problems may well arise. The proportion of
hardener must never be changed (unless recommended by the supplier) in
the hope that this will increase or decrease gel time. Whilst such changes in

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24 FRP TECHNOLOGY

gel time will occur, their effect will be completely negated by the
considerably inferior properties of the 'cured' system which, if usable, will
have a much shorter service life. For example, halving or doubling the
proportion of curing agent will generally result in the formation of a
solvent soluble adduct rather than a fully cross-linked resin system. The
main group of curing agents which tolerate a reasonable variation in
proportion are the polyamides and then only certain ones. However, even
here variation causes marked differences in cured properties. In general,
cure time can be shortened by increasing cure temperature; the alternative
is to use a different hardener. In all cases the resin supplier's recom-
mendations should be followed at all times.
The casting technique can be divided into two categories, single-stage
casting and two-stage casting. These will be described separately although
many features are the same for both. In both cases a master pattern will be
required together with a box to surround it to act as a mould for the casting.
This mould box should allow sufficient space around the pattern to prevent
damage to the sides of the mould during use. Too large a box will only
waste resin.
The pattern can consist of a wooden, plaster, metal, plastic or epoxy
former made to the shape of the final production moulding. If a porous
pattern is used this must be sealed with an appropriate sealer, such as a
nitrocellulose lacquer or polyvinyl alcohol. As with other moulding
processes the use of a release agent is essential. The pattern and mould box
should be polished to a high gloss with a wax polish and then coated with a
film of polyvinyl alcohol. Alternatively a silicone grease or spray applied
silicone release agent can be used. However, if any modification to the
epoxy mould is at all likely, a non-silicone release agent is preferred, since
then no contamination of the epoxy surface will occur to prevent adhesion
of any further resin.

3.5.1 Single-stage casting


Once the pattern has been coated with release agent it should be heated to
about 50°C for a short time to warm the surface. It should then be placed in
the mould box, also coated with release agent, in readiness for casting
(Fig. 3.4). The epoxide resin system should be carefully mixed to ensure
that there are no air bubbles present and then carefully poured in a steady
stream into one corner of the box, taking care to avoid trapping any air.
The purpose of warming the pattern is to lower the viscosity of the resin mix
as it comes into contact with the pattern and hence get thorough wetting of
the surface with no trapped air bubbles. Bolts and other fixing devices can

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MOULDS 25

Mould box
Cast resin
Release agent
Pattern

Fig. 3.4. Single-stage casting.

be embedded in the resin before gelation. They will of course need


supporting in position until the resin has gelled.
Epoxide resin systems in general show negligible post gelation shrinkage
but there can be shrinkage up to this point. To overcome this, a feeding
head similar to that used in the casting of metals can be utilised, providing
that the bulk of material in the head is considerably smaller than that of the
casting, otherwise the resin in the head may gel before that in the casting.
The cast resin should be allowed to cure overnight and then given a
gentle post cure in an oven. The resin supplier's recommendations should
be heeded on this point. Once the casting has cooled to room temperature it
can be removed from the box and pattern. Mounting and any other
modifications can be carried out at this time.
For large castings the resin system used should have a long gel time and
hence low exotherm. This prevents stresses from being built in during cure.
To reduce cost and improve wear resistance, fillers are usually added to the
casting resin system. These include slate powder, silica flour or sand,
marble flour, calcium carbonate and aluminium powder. Slate powder and
silica flour give hard wearing compositions which are difficult to machine,
whilst the other fillers give compositions with lower wear resistance but
easier machinability. Aluminium powder also increases the thermal
conductivity of the system. All fillers must be dry before adding to the resin
system.
Typical filler loadings used with a low viscosity casting resin system are
given in Table 3.2. These proportions may vary somewhat from one resin
system to another, and will be affected by the particle size distribution of
the filler. Proportions are given as parts weight of filler per 100 parts weight
of epoxide resin/hardener mix.
For the most satisfactory castings the filler should be stirred into the
resin system under vacuum to eliminate all entrained air. If vacuum

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26 FRP TECHNOLOOY

Table 3.2 Filler loadings to give a pouring mix

Filler For pouring mix

Marble flour (dolomitic) 100-200


Calcium carbonate 100-200
Silica flour 80-150
Sand 200- 300
Slate powder 70-130
Aluminium powder 100-150
Glass fibres (5-6 mm) 10

equipment is not available then the mix should be stirred slowly, with the
blade of the mixer well below the surface. Any entrained air may then be at
least partially removed by low to medium frequency vibration or by
pouring the mix through a fine mesh sieve. Just standing the mix is rarely
effective. An alternative procedure is to heat the epoxide resin and filler to
between 50 and 80°C before mixing. Once this blend has cooled to about
30°C the hardener can be added. Some stirring whilst the blend cools may
be necessary to prevent the filler from settling out into a solid mass.

3.5.2 Two-stage casting


This procedure is used for thick castings, the object being to produce a
mould with a normal surface finish but a cheaper core. Two procedures can
be adopted.
In the first procedure the pattern and mould box are prepared as for
single-stage casting and coated with release agent. A thixotropic epoxide
resin gelcoat is then applied to a thickness of 2- 3 mm and allowed to gel.
This layer may be reinforced with surfacing tissue and chopped strand mat
if desired. Once the resin system has gelled a sand filled epoxy mix is
carefully tamped in. Fixing bolts can be inserted before the resin cures. The
whole system should then be allowed to cure at least overnight before
giving it a gentle post cure. The casting can be removed from the mould
once it has cooled.
In the second procedure the pattern is firmly located in the mould box
and covered with a layer of modelling clay or plasticine about 3 mm thick.
This is covered with a layer of cellophane or polyethylene film. To aid
removal of air during the final stage of casting, 10 mm diameter tubes
should be placed vertically on top of the release film. These should be of
sufficient height to protrude from the filled mix. The sand filled epoxy mix is

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MOULDS 27

then poured in and tamped smooth. Fixing bolts should be positioned


before the resin gels and at the same time provision made for relocating the
casting in exactly the same position in the mould box. The core should be
allowed to cure at least overnight before removal (see Fig. 3.5).
Once the core has been removed from the pattern and box and all
surfaces have been thoroughly cleaned and coated with release agent, the
pattern and mould box can be re-assembled. Care must be taken to ensure
that the pattern is in exactly the same position as before.
The core surface must also be cleaned, preferably by lightly sand or grit

~~---------Vent tubes

/i-,~q-- fi 11 ed res in core

~I~H+---Plasticine

---tW~-- Pattern
.~~~~~~~~~~

Mould box
Stage 1

_ - - - Vent tube

/-:~*---Fi11ed resin core

..L...J1"Ii'~--facing resin being


poured in
Pattern

Stage 2
Fig. 3.5. Two-stage casting.

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28 FRP TECHNOLOGY

blasting. Any mix which has penetrated the air release tubes must be
removed. A coat of the facing resin mix is then painted onto the surface of
the core before it is relocated in the box over the pattern. Unless the core is
relocated in exactly the correct position there will be insufficient gap
between the core and the pattern to accommodate the facing resin.
The facing resin mix is prepared and poured carefully into the gap
between the mould box and the core down one of the tubes, ensuring that
all air is displaced and the gap between the core and the pattern is
completely filled with resin mix. The resin system should be allowed to cure
at least overnight before giving a gentle post cure. Once the casting has
cooled to ambient temperature it can be demoulded and mounted ready for
use.
An alternative procedure which may be used is to pour the facing resin
system into the mould box and then carefully lower the core into position,
ensuring that it is accurately located over the pattern.
Lightweight fillers such as vermiculite or phenolic micro-balloons can
be used as alternatives to sand for large castings where mould weight may
give rise to handling problems. These will, however, result in a decrease in
the compressive strength of the system, which may be unimportant.
Where matching moulds are required, the first half maybe constructed as
described above and used as the pattern for constructing the second half. In
this case either a pattern of the object to be moulded must be placed over
the first half or sheet wax must be used to construct a pattern on top of the
first half. The second mould can then be made in the same way as the first
half.

3.6 STEEL MOULDS

These are required for hot press, centrifugal, transfer and injection
moulding and pultrusion. They may also be used with other moulding
processes. The fabrication of steel moulds is a highly skilled operation best
left to experienced tool makers and so will only be considered briefly here.
Tool steel and Meehanite, flame hardened and hard chrome plated are
undoubtedly the best materials, although other metals such as zinc and
aluminium may also be used. In designing the mould, an adequate taper
must be incorporated to permit easy removal of the moulding.
The use of mould release agents is essential with all metal moulds,
silicones being the most popular. Either spray or bake-on types may be
used" and several mouldings may be obtained from one application.

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MOULDS 29

However, if the moulding is to be painted then silicones should be avoided.


The type and amount of release agent to use will be found by experience.
With new moulds there is often a 'wearing-in' period where the moulding is
difficult to remove; however, once several mouldings have been made and
the release agent has been thoroughly worked into the mould surface, these
problems usually disappear. With dough moulding compounds, release
agents are frequently included in the compound so that once the mould has
been run-in no further application of release agent is necessary. In this way
automatic operation can be achieved.

3.6.1 Hot press moulding


With hot press moulding, matched metal moulds are used in a wide variety
of shapes and sizes, the only limiting factor being the capacity of the press.
Where glass mat or preforms are used, provided sufficient pressure is
available (usually about I MPa) the mould should be designed to cut otT the
protruding fibres just prior to full closure (Fig. 3.6). In this way air will
escape during the first part of the closing cycle, with the resin retained as the
mould finally closes. Full closure of the mould is regulated by stops which
also control moulding thickness. With this type of mould design minimal
trimming of the moulding is needed .
An alternative design, suitable for use where insufficient moulding
pressure is available, is shown in Fig. 3.7. Here the mould compresses the

Fig. 3.6. Mould with cutting edge. Fig. 3.7. Mould with pinching edge.
(Courtesy of Synres International BV.)

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30 FRP TECHNOLOGY

protruding glass fibres to achieve a similar effect to that obtained above.


Air passes easily out through the fibres but resin is retained. Mouldings
produced in this way require trimming, which increases production costs.
This design of mould may also be made from an epoxide resin system.
Whilst moulds used for pressing powders can sometimes be used to press
sheet and dough moulding compounds, they are unsuitable for use with
mat or preforms.
Since matched metal moulds are used between the heated platens of a
hydraulic press, consideration should be given to temperature gradient
across the mould. To avoid distortion of the moulding the temperature
difference over the whole mould surface, both top and bottom, should not
exceed 2·5°C.
If mouldings with undercuts are to be fabricated, split moulds are
necessary. With deep draw mouldings effective tapers are necessary to
facilitate demoulding. Such a taper should not be less than 1°.

3.6.2 Centrifugal moulding


Most moulds used for centrifugal moulding are cylindrical and made from
tool steel with a hard chrome finish. Tapered moulds may be used for rods
and tubes according to one patented process. 1 Whichever mould design is
used, the mould must be evenly balanced about its central axis to prevent
any asymmetrical thrust on the bearings during rotation.

3.6.3. Transfer and injection moulding


Moulds used for transfer and injection moulding can be of single- or multi-
cavity design and are broadly similar to those used for the injection
moulding of thermoplastic materials. However, thermosets are generally
harder, more rigid and less easily deformed than thermoplastics and so
moulds must be designed for the particular material to be processed. They
are usually made from hardened tool steel and chrome plated to about
0·07 mm thickness. An experienced mould maker familiar with thermosets
should be consulted with regard to component and mould design and
mould manufacture. However, some of the factors which should be
considered are given below.
With injection moulding, the mould design should include provision for
efficient ejection. This is frequently more difficult than with thermoplastics.
The design should permit easy removal of flash, with bolt holes, dowel pins
and slides kept away from the mould cavity, unless an escape groove
separates them.

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MOULDS 31

Since thermosets are relatively high in viscosity compared with thermo-


plastics, gates and runners should be designed without rapid changes of
direction or other obstructions which will impede flow. Streamlining the
feed can be far more beneficial than increasing feed cross-section. Similarly,
an increase in gate size may be far more preferable than increasing the size
of the feed system. Cavity location should be considered and arranged, as
far as possible, so that the distance from the sprue to the cavity is the same
for all cavities. The sprue should be marginally larger than the orifice size of
the barrel nozzle and should have about a 2° taper. It should be
remembered when selecting the moulding process that all the material in
the sprue and runners will be scrap and should preferably constitute a small
proportion of the total material used. Scrap material cannot be reground
and reused without having a detrimental effect on mouldings.
Provision should always be made for adequate venting of the cavities to
prevent entrapped air from causing porous mouldings. If venting is not
possible, for example in blind recesses, then the application of vacuum to
the cavity just prior to injection should be used. Only a relatively low
vacuum is necessary to be completely effective. This will permit faster
injection speeds to be used, with a notable improvement in moulding
quality.

3.6.4 Pultrusion
With pultrusion, heated dies rather than moulds are used. These should be
made from hard chrome plated, hardened tool steel for preference. Two
types of die are used, those through which fibres impregnated with resin
from a resin bath are drawn and those which incorporate injection nozzles
to impregnate the fibres within the die. These need to be designed to suit the
particular equipment being used. As with matched metal moulds an
experienced die maker should be employed.

3.7 ALUMINIUM ALLOY MOULDS

These are light in weight with high rigidity and provide a good quality
finish. They are not as hard wearing as steel moulds and can therefore be
more easily damaged. They are, however, easier to machine.
One example of a large aluminium alloy mould was that used for the
manufacture of HMS Brecon, a 60 m long mine sweeper.

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32 FRP TECHNOLOGY

3.8 NICKEL SHELL MOULDS

A nickel shell backed by a resin core can give a life similar to that achieved
with steel but at reduced mould cost. Such moulds can be used for the resin
injection moulding process. 2

3.9 OTHER MOULDS

Examples of these include wax, water soluble hot-melt thermoplastics and


inflatable balloons used for the manufacture of cylinders and spheres by
filament winding. The reason for using these materials is ease of removal
once the winding has been completed and the resin cured. Hollow plaster
and wax mandrels can be used. These are made in two halves which are then
joined together to form the finished mandrel.

REFERENCES

1. British Patent 1 358 360, Usui Research Laboratory, Japan.


2. Anon. (1976) 'Nickel shell moulds', Reinforced Plastics, May, 126.

SUPPLIERS

General material suppliers are listed in Appendix 2.


Suppliers of epoxy tooling compounds:
Borden (UK) Ltd
Ciba-Geigy Plastics & Additives Company
Devcon Ltd.

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Chapter 4

MOULDING PROCESSES

4.1 INTRODUCTION

The wide range of thermosetting resins and reinforcements available and


their ability to be used under a variety of processing conditions, has
resulted in the development of an extensive range of processing techniques.
The purpose of this chapter is to detail these techniques as far as possible.
Since polyester resins are the most widely used resins and glass fibre the
most widely used reinforcement, moulding processes have been described
with these materials in mind. Where a process is also suitable for use with
other resins, albeit perhaps with slight modifications, this has been
indicated.
Polyester resins can be readily processed without pressure, using cheap
moulds, to produce a wide variety of finished products. Due to this ability,
an extensive market developed for glass reinforced polyester products
fabricated by the wet lay-up or contact moulding process. Initially,
manufacture was by hand lay-up using chopped strand mat or woven glass
rovings as reinforcement. However, with the development of suitable spray
equipment, spray lay-up has achieved great importance. Here, the
catalysedJesin and chopped rovings are simultaneously sprayed onto the
mould surface until the desired laminate thickness has been built up. Today
contact moulding accounts for the major part of all GRP mouldings
produced. One of the reasons for this is the extreme adaptability of the
process. Metal inserts can be built into the mouldings and additional
reinforcement can be applied to areas of high stress. In addition,
strengthening ribs can be laminated onto the moulding as desired.
Whilst polyester resins will gel fairly rapidly, demoulding cannot
generally take place until at least several hours after application ofthe resin
system and mostly not sooner than 24 h. Thus rapid mould turn around

33

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w
~
Table 4.1 Summary of moulding processes

Contael moulding
------
Process Hand lay-up Spray lay-up Vacuum bag/pressure bag

Resin system Liquid-polyester, Liquid - polyester, Liquid - polyester, epoxy


epoxy, furane epoxy Prepreg -epoxy
SMC-polyester
Reinforcements Glass, carbon. other Glass Glass. carbon. other
Fibre content. glass (% by wt) 25-35 25-35 25-60
Normal laminate thick-
ness (mm) 2- 25, generally 2- 10 2-25, generally 2-10 2-6
Typical cure tempera- "1
ture ('C) Ambient to about 40 Ambient to about 40 Ambient to 50 for liquid resins, ::e
"0
80-160 for SMC and prepreg -l
Type of mould needed Single-GRP. wood. Single-GRP, wood. Single-GRP, epoxy or metal tTl
t'l
etc. etc. ::c
Moulding size limitation [n principle-none [n principle-none Capacity of vacuum equipment or Z
compressor, capacity of autoclave 0
t'"
Moulded in-ribs Yes Yes Yes
- inserts for fixing Yes Yes Generally no 8-<
- foam panels Yes Yes Generally no

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Equipment needed Rollers and brushes Spray and chopper gun. Hand/spray lay-up, automatic tape
rollers laying machine, autoclave/vacuum
pump/compressor
Number of mouldings
to justify mould cost From one upwards From one upwards From one upwards
Production rate Low Low Low
Labour content High High High
Quality of moulding Dependent on opera- More dependent on Two smooth surfaces
tor, one smooth operator, one smooth
surface surface
Typical products Boats, building Boats, building Aircraft sections, various panels, general
panels, general panels, general
Resin injection/ Compression moulding
Foam reservoir resin transfer Vacuum
Process moulding moulding impregnation Cold press Hot press

Resin system Liquid-epoxy, Liquid-polyester, Liquid-epoxy, Liquid - polyester, Liquid, prepreg,


polyester epoxy polyester epoxy SMCjDMC-
polyester
Reinforcements Glass mat/open Continuous strand Glass, carbon, Glass, carbon, other
cell foam mat other
Fibre content, glass
(% by wt) Variable 25-30 25- 50 25-50 25-70
Normal laminate
thickness (mm) 2 upwards 2-6 2-10 1-10 1-10
3::
Typical cure tempe- 0
rature ("C) Ambient to about Ambient to about Ambient to about C
150 40-50 100-170 r
50 50
Type of mould
needed Double GRP or Double GRP or Matched metal, Double GRP, Matched metal "Z
C'l
light metal light metal GRP metal
Moulding size limita-
tion Mould dimensions Mould dimensions Mould dimensions Press size Press size
'"'0"
I"J
t'!'I
Moulded in (/J
(/J
-ribs Yes Yes Yes Yes Yes

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t'!'I
(/J
-inserts for fixing Generally no Generally no Generally no Yes Yes
-foam panels Yes Yes Yes Generally no No
Equipment needed Hand equipment Resin injection Vacuum pump Hydraulic press Hea ted press
pump
Number of mouldings
to justify mould From one upwards Generally 100- Generally 100 100-1000 1000 upwards
cost 1000
Production rate Moderate Moderate Low High High
Labour content Moderate to high Moderate Moderate Low Low
Quality of moulding Good, two smooth Good, two smooth Good, two smooth Good Excellent
surfaces surfaces surfaces A II surfaces smooth
Typical products Automotive, fur- Boats, various Radomes, aircraft Automotive, industrial,
niture, various nose cones, electrical
various VJ
'-"
V.J
0\

Table 4.1 (Continued)

Process Transfer moulding Injection moulding Filament winding Centrifugal moulding

Resin system DMC -polyester, DMC -polyester, Liquid - polyester, Liquid-polyester,


epoxy, other resins epoxy, other resins epoxy epoxy
Prepreg-epoxy
Reinforcements Glass, carbon, others Glass, carbon, others Glass, carbon, other Glass
continuous fibres
Fibre content, glass (%by wt) 10-65 10-65 60-80 25-40
Normal laminate thickness
(mm) 1-6 1-6 2-25 2-25 "rj
Typical cure temperature (0C) 155-170 Polyester 135-185, Ambient to 170 Ambient to 50 ::c
"0
epoxy 160-220 ...,
Type of mould needed Metal Metal Steel, plaster, etc. Steel m
Machine capacity Machine capacity Machine size, gene- Machine size, gene- ('J
Moulding size limitation
rally 6 m diameter, rally 6 m diameter ::c
Z
6 m long 0
t"'
Moulded in-ribs Yes Yes Externally, yes No
- inserts for fixing Yes Yes No No 8-<
-foam panels No No Yes No

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Equipment needed Transfer moulding Injection moulding Filament winding Centrifugal moulding
press machine machine machine
Number of mouldings to
justify mould cost Over 1000 Over 1000 From one upwards 100 upwards
Production rate High Very high Moderate Moderate
Labour content Low Low Medium Low
Quality of moulding Good, all smooth Good, all smooth Good, inside smooth Good, both surfaces
faces faces smooth
Typical products Small-to-medium Small-to-medium Tanks, pipes and Pipes and tubes
sized components sized components tubes
Continuous sheet
Process moulding Pultrusion

Resin system Liquid - polyester, Liquid - polyester,


epoxy epoxy
Prepreg -epoxy
Reinforcements Glass Glass, carbon, aramid
Fibre content, glas~ (% by wt) 25-35 60-75
Normal laminate thickness :.::
(mm) 2-6 600 x 250 0
TypiCal cure temperature (0C) 50-120 100-160 c::t""
Type of mould needed Metal rollers or sheet Hardened steel die 0
Moulding size limitation Width of machine 600 x 250 mm, die Z
dimensions Cl
Moulded in-ribs No Variety of cross- '"d
sections ~C"J
-inserts for fixing No No
tTl
[J>
-foam panels No No [J>
Equipment needed Sheet moulding machine Pultrusion machine

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f}1
Number of mouldings to
justify mould cost Continuous output Continuous output
Production rate Up to 12 mlmin Up to I mlmin
Labour content Low Low
Quality of moulding Good Good
Typical products Roofing lights, etc. Variety of cross-sec-
tions, rods, tubes,
etc.

\J.l
-...J
38 FRP TECHNOLOGY

cannot be achieved by contact moulding. Process developments have


therefore centred around ways of shortening moulding time to achieve a
more rapid tum around. In addition, some of the processes developed have
resulted in mouldings with two smooth surfaces instead of the one
produced by contact moulding.
These processes include the following; vacuum/pressure bag
moulding-where the laminate is prepared by conventional wet lay-up
techniques and vacuum or pressure and heat are applied to the moulding to
speed up cure; hot or cold press moulding utilising matched metal or G RP
moulds; resin injection or resin transfer moulding; filament winding;
pultrusion; continuous sheet manufacture; transfer and injection mould-
ing using dough moulding compounds. These processes and some charac-
teristics of them are summarised in Table 4.1.
Since mouldings produced by many of the processes described have to be
trimmed afterwards, a section on trimming and finishing has been included
at the end of this chapter.

4.2. CONTACT MOULDING-WET LAY-UP

Contact moulding is the most commonly used method for the manufacture
of both small and large reinforced polyester products such as boat hulls,
vehicle bodies, GRP building panels and cladding, ducts and tanks and
many other mouldings where small production runs are required. A single
mould is used, with the laminate applied to the suitably released mould
surface. The result is a moulding with only one smooth surface, that in
contact with the mould. Moulding thickness is generally in the range
2-10 mm although there is no basic upper limit; indeed for large boat hulls

3~~~~~~~~~~~~~----Topcoat
--Chopped strand mat
_____ CSM or woven ravings

illllllllllll.~ Chopped strand


Surfacing
____ Ge 1coa t
tissuemat

--;:0;;;;:;:;;;;;;;;;;;;:;:;:;:::;;;;;:;;;;::;;:;::;;;;:::::::: R1 f· 1
§4~~~?~~lttl""~~J\*~f4 e ease 1 m
~~~~~ ~~l
Fig. 4.1. Typical laminate construction.

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MOULDING PROCESSES 39

much thicker sections are necessary. Mouldings should not, however, be


less than 2 mm in thickness. A typical laminate lay-up is shown in Fig. 4.1.
Since the resins most widely used with this process are the polyester
resins, moulding procedure has been described with these in mind.
Comments relating to epoxide and other resin systems are given at the end
of this section.
The mould is frequently made from GRP using one of the specially
developed tooling grade polyester resins. Such moulds generally have a life
of between 500 and 1000 releases. Other mould materials used include
tooling grade epoxide resin systems, wood, plaster of paris and metal
supported on a suitable framework. A metal mould will give the greatest
number of releases and provide the longest working life but will be the most
expensive to produce.
Two fabrication techniques are used:
(a) hand lay-up;
(b) spray lay-up.
Mould preparation and gelcoat application is the same for both
techniques.
Before use, the mould surface must be coated with a good quality
silicone-free wax and thoroughly polished to give a smooth glossy finish.
For a new mould several applications of wax may be necessary to build up
sufficient thickness. A mould release agent such as polyvinyl alcohol is then
generally applied using spray or sponge rather than brush, since brushing
can result in a streaky finish. For the best results two coats should be
applied, allowing the first to dry before application of the second coat. It is
essential that the mould is completely covered, leaving no bare patches,
since the gelcoat will reproduce any defects in this release film. Care at this
stage is well rewarded by the quality of the moulding produced. The
advantage of using polyvinyl alcohol as the release film is that the moulding
will separate readily from the mould and the release film can then be
washed off both the mould and moulding with water.
When the release agent is completely dry, the gelcoat is applied by brush
or spray. With brush application a wide brush with long soft hairs is
preferred and two coats are generally necessary to prevent brush marks
from showing, the second coat being applied once the first has sufficiently
cured (2-4 h). With spray application, the full thickness can be applied in
one coat (Fig. 4.2). Gelcoats are supplied specifically for either brush or
spray application and usually differ in their degree of thixotropy. Final
gelcoat thickness should be between 0·3 and 0·6 mm (400-500 g/m2) and

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40 FRP TECHNOLOGY

Fig. 4.2. Spray application of a polyester gelcoat. (Courtesy of Binks-Bullows


Ltd.) (Photograph: Rackhams of Lichjield)

uniform over the whole mould surface. Gel time of the gelcoat in bulk
should preferably be about 15 min. Styrene fumes should be extracted from
the mould using a suitable extraction system to ensure even gelation of the
gelcoat.
The condition of the gelcoat can be determined by touching it. If it feels
tacky but is not easily removed by the finger, then it is ready for application
of the next coat of resin system.
In some cases a surfacing tissue may be used to reinforce the gelcoat. This
is applied immediately after the gelcoat while the resin is still wet and lightly
rolled to displace all air bubbles outwards. This procedure does, however,
result in a lower quality surface finish. Also, since the durability of the
moulding depends on the quality of the exposed surface, this procedure is
not recommended where the moulding is to be subjected to wet or chemical
environments. A surface tissue may, however, be applied with the first coat
of laminating resin where it is beneficial in protecting the reinforcement,
particularly when the moulding is used in wet or chemical environments. In
this way the resin-rich surface provided by the gelcoat is preserved.
Most moulding faults can be traced back to insufficient care during
application of the gelcoat. Insufficient film thickness can result in excessive
evaporation of styrene monomer from the gelcoat so that it dries instead of
cures. Too rapid an application of the second layer of gelcoat or the
laminating resin, before the first layer has cured, can result in a wrinkled

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MOULDING PROCESSES 41

finish. Too thick a gelcoat can, even several months after demoulding,
crack and craze and is also more sensitive to impact on the reverse side of
the moulding, when cracks and other damage may occur.

4.2.1 Hand lay-up


Once the gelcoat has sufficiently cured, a coat of laminating resin system is
applied by brush, paint roller or spray followed by the first layer of chopped
strand mat (preferably 300 g/m 2 or less) or if desired a surface tissue. Since
surface tissues are relatively expensive they are generally only used where a
very high quality finish is needed or where the mOUldings are to be subjected
to chemical environments and therefore good durability is essential.
Sufficient resin should be applied to wet out completely this first layer of
reinforcement so that all trapped air can be forced out by rolling with a split
washer or similar type oflaminating roller. At the corners of the mould the
glass mat should be cut and butted together to ensure that bridging does
not occur. Rolling here may be best accomplished by the use of a single
washer roller or a stippling brush. The resin to glass ratio at this stage
should be about 2: 1. Once all the air has been displaced and the mat
thoroughly impregnated with resin it can be advantageous to allow this
layer to gel before laminating is continued (Fig. 4.3).
With large moulds, where more than one sheet of chopped strand mat
has to be applied to cover the surface, these sheets may either be butted
together and the joint compacted using a stippling brush with a rotating
motion to spread the strands across the joint or applied with about 30 mm
overlap. It is essential that joints in different layers are staggered to prevent
either excessive laminate thickness or laminate weakness at the join.
At one time it was common to pigment the laminating resin to the same
colour as the gelcoat; however, this can prevent trapped air bubbles from
being seen and in particular can mask any bridging over sharp corners.
Frequently now a clear laminating resin is used.
For convenience of working it is general to cut all required layers of
reinforcement to the correct size, using an accurate template, before
laminating is commenced.
Further layers of resin and chopped strand mat are then applied using
the same technique as with the first layer, thoroughly consolidating each
layer before application of the next. Several different weights of chopped
strand mat are available as well as a variety of glass cloths and woven
rovings. Where woven rovings are used these should be alternated with
layers of chopped strand mat. Several suppliers offer combined woven
rovings and chopped strand mat to reduce labour costs and to prevent the

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42 FRP TECHNOLOGY

(a) Consolidating the edge of a laminate with a split washer roller.

(b) Resin application with a lambswool roller.


Fig. 4.3. Hand lay-up laminating using chopped strand mat. (Courtesy of AjS
Jotungruppen, Norway.)

chopped strand mat from being omitted by mistake. Although woven


rovings give increased strength and stiffness to the moulding they are more
difficult to wet out with resin and do not conform readily to mould shape.
Layers of reinforcement are built up wet on wet until the desired thickness
of laminate has been achieved. However, with thick mouldings it is
necessary to proceed in stages, allowing the resin to cure after each stage.
This is to prevent the laminate from becoming unmanageable and moving
on the mould surface. Also, unless care is taken in choice of catalyst system,

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MOULDING PROCESSES 43

excessive exotherm may occur causing warping and discolouration of the


moulding.
To obtain a homogeneous laminate free from air bubbles, sufficient resin
system should always be placed in the mould to completely wet out the glass
mat prior to placing the mat in the mould. Rolling will then displace the air
outwards. If, on the other hand, resin is applied to non-impregnated glass
mat there is every probability that air bubbles will be trapped in the
laminate. These trapped air bubbles will then almost certainly result in the
failure of the moulding in service, particularly if the moulding comes into
contact with liquids.
Where a reinforcing core material is to be used, this should be laid into
wet resin and over laminated with glass and resin to form an integral part of
the laminate. Similarly, where GRP ribs are to be incorporated these
should be preformed and laid into wet resin and overlaminated before the
final laminate thickness has been achieved. Preformed GRP ribs should
preferably be at the 'green' stage so that they form an integral part of the
cured structure. The bulk of the laminate should have partially cured
before ribs are inserted if sink marks are to be avoided in the gelcoat
through shrinkage of the resin around the ribs.
Metal fastenings may be built in during the laminating stage for the later
attachment of the cured moulding to appropriate frameworks. These
should be of the 'Bighead' type with perforated flange heads. The laminate
should be tapered away from these fixings to spread the applied load during
service.
Where the moulding is required to have a reasonably smooth finish a
surfacing tissue may be applied at the same time as the last layer of chopped
strand mat. With simple mouldings with flat areas or those with surfaces
curved in only one direction, a relatively flat glossy surface can be obtained
by covering the wet laminate with a layer of Cellophane or Melinex
sheeting and rolling to ensure that all air bubbles are displaced towards the
edge of the mOUlding.
A topcoat of pigmented resin is often applied to the partially cured
laminate to serve as additional protection to the glass mat, provide a
decorative finish, balance up the gelcoat and, to some extent, give a
smoother finish. The quality of the finish will depend on the degree of
smoothness of the final layer of reinforcement. This side will always show
the structure of the final layer of reinforcement, which cannot be
adequately masked with a topcoat.
When the laminate has partially cured, that is at the 'green' stage, the
edges can be trimmed with a sharp knife. If, however, trimming is left until

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44 FRP TECHNOLOOY

the laminate has been demoulded, carborundum or diamond tipped


trimming tools will almost certainly be required and trimming is much
more difficult at this stage.
The moulding should be allowed to mature for several hours or even
overnight before removal from the mould and certainly until any exotherm
has dissipated. To speed up demoulding the laminate may be heated to
about 60 0 e for 1 h in the mould, allowed to cool and then demoulding
commenced. Demoulding by hand can be facilitated by the use of
compressed air and the careful use of wedges. Demoulding can also be
assisted by filling the gap between the moulding and the mould with water
to dissolve the PVA release agent. The inside of the laminate should not be
struck in any way since this can result in damage to the gelcoat. After
demoulding, the polyvinyl alcohol release agent can be washed off with
water.
Post cure is usually carried out after demoulding and generally not
before the moulding has been cured for either at least 24 h at room
temperature or 1 h at 60°C. Where post curing is to be carried out, the
moulding should be adequately supported to prevent distortion. A typical
post cure would be 3 h at 80 a e for a general purpose resin system. If,
however, the resin manufacturer recommends an alternative post cure
schedule, this should be followed.
During the post curing stage any air bubbles trapped in the moulding are
likely to show up as blisters under the laminate. If these occur under the
gelcoat there is little chance of effecting an adequate repair. Elsewhere it
may be possible to repair them.
The finished moulding will usually contain between 30 and 35% by
weight of glass reinforcement, although this may vary with type of
reinforcement used.
To ensure that uniform mOUldings are consistently produced, a working
temperature of I8-20 o e should be maintained in the workshop, with
humidity kept below 70% R.H.

Epoxide resins
With epoxide resin systems similar laminating procedures are used.
However, since volatile monomers are absent, cure of gelcoats in very thin
films will still take place, but relatively slowly. This does not mean that very
thin gelcoats are recommended. Whilst some gelcoats are available
commercially, these mostly have to be formulated by the moulder. Most of
the other comments given under polyester resins are equally applicable to
epoxide resin systems. However, gel times are generally longer and post

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MOULDING PROCESSES 45

cure schedules somewhat different. Post cure schedules recommended by


the resin suppliers should be followed.
Ciba-Geigy have recently introduced a resin system, Araldite XD 927
with gelcoat XD 928, which is claimed to offer the advantages of an
epoxide resin system in cured properties with the processing ease of a
polyester system (see Chapter 12, Section 12.7.2 for further details).

Furane resins
Furane resins can be processed in a similar way to polyester resins.
Generally those reinforcements recommended for use with epoxide resins
are also suitable for use with furane resins.

Advantages and disadvantages of hand lay-up


Advantages Disadvantages
1. Simple technique. 1. High labour content.
2. Low capital costs-cheap 2. Low production speed.
moulds. 3. Moulding quality is dependent
3. Large complex shapes can be on operator skill.
produced. 4. Mouldings have only one
4. No process limitation on smooth glossy surface.
moulding size.

4.2.2 Spray lay-up


Once the gelcoat has sufficiently cured the laminate can be applied. If a
surface tissue is to be used a layer of laminating resin is applied to the
gelcoat either by brush, roller or spray and the surface tissue, previously cut
to shape, laid in the wet resin and rolled carefully to displace all trapped air
outwards. The laminate is then built up from chopped fibre rovings and
polyester resin sprayed simultaneously onto the mould. Continuous
rovings are fed to an air driven chopper unit attached to the spray gun,
where they are cut into suitable lengths 02-62 mm) and conveyed to the
mould surface by the stream of polyester resin from the spray gun. Three
types of spray equipment are available:
(i) The catalyst injection system where pre-accelerated polyester resin
is fed to the spray gun and mixed with a pre-determined proportion
of peroxide catalyst in the gun head.
(ii) The catalyst spray system where pre-accelerated polyester resin and
peroxide catalyst are both fed to the spray gun and sprayed
separately so that the two streams of material mix outside the gun
but before reaching the mould surface.

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46 FRP TECHNOLOGY

(iii) The twin pot system where pre-accelerated and pre-catalysed


polyester resin are fed separately to the spray gun and sprayed so
that the two streams of material mix outside the gun head but before
reaching the mould surface.

All spray guns and ancillary equipment contaminated with catalysed


resin must be thoroughly cleaned immediately after use to prevent clogging
from gelled resin particles and to prevent such particles from contaminat-
ing the laminate.
Before spray lay-up is commenced the gel time of the resin system should
be checked by spraying a small quantity of resin system without glass, into
a can. Also, the resin/glass ratio should be checked to ensure that the spray
gun and chopper unit are functioning correctly. Generally the resin to glass
ratio will be between 2· 5: I and 3· 5: l.
The first layer of polyester resin and glass fibre should be thinly applied
(approx. 1 mm) and rolled carefully, first with a short-nap mohair roller
and then with a metal laminating roller to ensure that the catalysed and

Fig. 4.4. A typical spray gun and chopper unit in use. (Courtesy ofK & C Mouldings
(England) Ltd.)

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MOULDING PROCESSES 47

accelerated resins are thoroughly mixed and the glass completely wetted out.
Care should be taken to ensure that no air bubbles are trapped in this layer
and that the resin/glass mixture completely wets the gelcoat with no
bridging in the corners. This layer oflaminate should preferably be allowed
to gel before further application of resin or glass. Figure 4.4 shows a typical
spray gun, fitted with a chopper unit, in use.
Subsequent layers of resin/glass can be built up at about 2 mm per time,
rolling thoroughly as before between each application to disperse all air
inclusions. If thicker layers are applied between rolling, difficulty will be
experienced in removing all trapped air and an inferior laminate will result.
This procedure is continued until the required laminate thickness has been
achieved. A stronger laminate can be produced if alternate layers are
sprayed at 90° to each other.
As with hand lay-up, woven rovings can be incorporated into the
laminate to increase stiffness and to strengthen it. If these are to be used
sufficient resin system must be sprayed into the mould prior to applying the
woven rovings so that on rolling the resin system displaces the air outwards
as the resin is forced through the reinforcement. Resin sprayed on top of
poorly wetted rovings will result in air entrapment. The woven rovings
should be cut to size prior to laminating and should always be alternated
with sprayed laminate to give a strong composite structure. Without this
layer of sprayed laminate in between each layer of woven rovings, there is a
risk that the laminate will fail in shear when flexed in service.
The largest area practicable should be sprayed at anyone time prior to
rolling, to minimise overspray. Care should be taken to ensure that each
sprayed layer is thoroughly consolidated before the resin begins to gel.
Where very thick laminates are to be made, it may be desirable to build
the laminate up in several stages, allowing the resin to gel after each stage.
In this way excessive exotherm can be prevented and the laminate remains
controllable during application.
Reinforcing core materials, pre-formed ribs and 'Bighead' fasteners may
be built into the laminate during its construction. These are placed in wet
resin once most of the laminate thickness has been built up and further resin
and glass sprayed over to complete the moulding.
Spray rates can generally be varied between 2 and 10 kg oflaminate per
minute with most spray equipment.
With deep moulds styrene fumes should be removed from the mould
using an appropriate extraction system to ensure uniform cure of the
laminate.
As with hand lay-up, a surfacing tissue may be applied to the final layer

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48 FRP TECHNOLOGY

of sprayed laminate to give a relatively smooth resin-rich finish. This can


then be coated with a topcoat to balance up the laminate and seal all the
glass reinforcement in.
Cure, trimming, post cure and demoulding are the same as for hand
lay-up.

Epoxide resins
A similar spray technique can be employed with epoxide resins.
However, due to the different mixing ratios of resin to curing agent,
polyester spray equipment is generally unsuitable. The resin and curing
agent can either be pre-mixed and sprayed through a single-component
spray gun or used separately with a two-component gun fitted with
appropriate metering pumps to ensure that the correct resin/curing agent
ratio is maintained. This will generally vary from 4: 1 up to 5: 3. With some
resin systems heated two-component spray equipment may have to be
used. All other laminating procedures are the same as for polyester resins.

Furane resins
Equipment has recently become available for spray lay-up with furane
resin systems. Procedures are similar to those used with polyester resin
systems.

Advantages and disadvantages of spray lay-up


Advantages Disadvantages
1. Spray equipment is portable. 1. Mouldings have only one
2. Capital outlay is small smooth surface.
compared with other 2. Uniformity of lay-up depends
mechanised techniques. even more than with hand lay-
3. Rovings are used, the least up on the skill of the operator.
expensive form of 3. Spray lay-up is uneconomical
reinforcement. for small volume production.
4. Production rates can be higher 4. An even spray pattern is
than with hand lay-up since difficult to achieve on small
shorter gel times can be moulds.
tolerated.
5. Reduced labour costs are
obtained with high volume
production.

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MOULDING PROCESSES 49

4.3 VACUUM BAG MOULDING

Vacuum bag moulding can be used both with wet lay-up systems and
prepregs. It is suitable for limited production runs and for the manufacture
of complex components which cannot be made practically by compression
moulding. Both large and small components can be made and it is
frequently used for the production of aircraft parts. One advantage that
prepreg systems have over wet lay-up is that unidirectional prepregs can be
used and accurate fibre alignment achieved. This can be essential for
aerospace applications where strength to weight ratio is of prime impor-
tance.
Epoxide and polyester resin systems are equally suitable for processing
by vacuum bag moulding as are glass, carbon and synthetic fibre
reinforcements.

4.3.1 Wet lay-up


A single mould is used-either male or female-to which the laminate is
applied by either hand or spray lay-up (for details see Section 4.2). Before
gelation of the resin, pressure is exerted on the moulding by means of a
flexible bag, frequently made from neoprene. This is brought about by
sucking air out of the bag with a vacuum pump. It is generally necessary to
tailor the bag to the shape of the mould to prevent wrinkles from forming in
it and the laminate (see Fig. 4.5). Heat is frequently applied to speed up
cure.
The mould is coated with release agent and the wet lay-up applied by
either hand or spray techniques and consolidated. A porous release cloth or
film is then placed directly onto the wet resin to permit easy separation from
the rest of the bagging material. This release material may consist of a light
glass cloth fabric (70 gjm 2 ) coated with PTFE or a Cellophane or
Clamp
... .... - + To vacuum pump

GRP lay-up

'il lil l i-jj;::::;;::IW!;) Mould

Fig. 4.5. Vacuum bag moulding.

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50 FRP TECHNOLOGY

Vacuum bag Pressure p]a te


~~~~~~~~~~~~~~NO:n-porous reI ease film

,. .....~__, ~~9~~
~
· ~"'-~··lil. I~.'I~"'I.:~·~·~<~·II~I·~~~~~B~I:ee~der
Clamp
cloth

~ Vacuum Ii ne

Fig. 4.6. Flat sheet vacuum bag moulding.

halocarbon film with holes I mm diameter punched 20 mm apart. Layers


of bleeder cloth are next placed over the release material. The number of
layers will depend on the component thickness and amount of resin to be
absorbed. These layers ensure efficient removal of air and surplus resin
from inside the bag. Glass mat, jute or paper cloths may be used as bleeder
cloths. These should extend some 100-200 mm on either side of the
component. With flat mouldings a pressure plate may be placed over the
laminate to give a smooth top surface and to equalise the pressure. If this is
done, a further layer of bleeder cloth is generally placed over the pressure
plate to ensure that all air pockets are eliminated. Edge dams of
compressible material may be placed around the edge of the lay-up to
prevent excessive sideways movement and tapering of the moulding
(Fig. 4.6).
Once all the various layers are in position the vacuum bag is placed over
the whole assembly and sealed around the edges. Vacuum is then slowly
applied. As air is withdrawn from the bag, air pockets and wrinkles can be
smoothed out using a roller. Where heat cure is to be used the whole
assembly is transferred to an oven or autoclave. The cure cycle will depend
on the resin system being used. Vacuum should only be released after the
moulding has cooled to room temperature. After cure the moulding is
removed from the vacuum bag, the bleeder cloth and release film stripped
off and the edges trimmed. Post cure can then be given if necessary.
A variation of this technique, using matched G RP or aluminium powder
filled epoxide resin moulds, has been developed by British Rail. 1 This
process is essentially the same as the standard technique except that
matched moulds are used.

4.3.2 Prepreg systems


Prepreg systems used with vacuum bag moulding include polyester sheet

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MOULDING PROCESSES 51

moulding compounds, epoxide resin impregnated cloths, unidirectional


glass and carbon fibre systems.
The prepreg is cut to shape and placed in the mould by hand, taking care
to ensure that all trimmings are excluded from the mould. Where
unidirectional prepregs are used these are generally cross-plied at some pre-
determined angle to provide maximum strength, perhaps in one direction,
in the cured moulding.
Automated tape laying machines have been developed for accurately
placing glass or carbon fibre prepreg tapes onto flat or contoured moulds.
These build up individual layers of prepreg to any desired fibre orientation.
These machines can eliminate time consuming and expensive hand lay-up
techniques and provide a fast, accurate, reproducible method for laying-up
prepreg ready for moulding.
Once the prepreg has been placed in the mould it is covered with an
appropriate layer of perforated release film or fabric and bleeder cloth. The
procedure thereafter is identical to that used for processing wet lay-up
systems, except that with prepreg, heat cure is essential. The application of
heat causes the resin to melt and flow together to give a uniform composite.
The vacuum bag technique can be combined with the pressure bag
technique, whereby pressure is applied to the outside of the bag once the
bag has been evacuated. This has the advantage that a higher pressure can
be applied to the laminate than can be achieved by vacuum alone. In
practice this is generally accomplished by using an autoclave. The bag is
first evacuated then pressure is applied and finally the vacuum lines are
vented to the atmosphere. Where pressure is applied by means of an
autoclave, normal strength moulds can be used since the pressure is applied
to all sides of the mould. If, however, pressure is applied to one side of the
mould only, then a stronger mould may be necessary.
Since thin sections are often moulded by the vacuum bag technique,
great care needs to be taken in the removal of the laminate from the mould
and in stripping off the release film, since damage to the laminate can easily
occur.

4.4 PRESSURE BAG MOULDING

This is similar to vacuum bag mOUlding. Both prepreg and wet lay-up
systems can be used, with pressure applied to the outside of an inflatable
bag placed over the laminate. The advantage of this technique over vacuum
bag moulding is that a higher pressure can be applied to the laminate.

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52 FRP TECHNOLOGY

Air pressure 1; ne

1 Pressure plate
1 Clamp
... To resin trap

r-....r-t- - Pressure bag

- GRP lay-up

Mould

Fig. 4.7. Pressure bag moulding.

However, where pressure is applied to one side of the mould only, then a
very strong mould must be used. The alternative is to use an autoclave,
whereby heat and pressure can be applied simultaneously and to all sides of
the mould. Higher pressures can be achieved using an autoclave than are
possible with a pressure bag alone.
Lay-up is more or less identical to that used for vacuum bag moulding
except that the perforated release sheet is replaced by a solid release film
and bleeder fabric is unnecessary since excess resin is squeezed to the edge
of the mould (Fig. 4.7).

4.5 RESIN INJECTION OR RESIN TRANSFER MOULDING

Resin injection or resin transfer moulding (RTM)2.3.4 is an intermediate


process between contact moulding and cold press moulding, suitable for
use with polyester and epoxide resin systems. Although this process has
been known for some time, it is only recently that several moulders in the
UK, Italy and Japan have adopted it for boat building. The process is
generally suitable for runs of between 100 and 1000 mouldings.
Mouldings produced by resin injection have two smooth moulded
surfaces and can be made in matched GRP or lightweight metal moulds
(see also pressure injection, Section 4.6). Although moulds have to be
stiffened to withstand injection pressure they do not have to be as heavy as
for cold press moulding. Both mould halves are designed to fit tightly
together with a rubber gasket seal and are usually fitted with quick release

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MOULDING PROCESSES 53

clamps. Injection points, usually more than one, are situated at the lowest
part of the mould and vent points at the highest part to allow air to escape.
An overspill area is built into the mould to ensure that after trimming, a
good quality moulded edge is left. This is shown schematically in Fig. 4.8.
Accurate mould design is essential to ensure that mouldings of the
correct weight and dimensions are produced. Any excess moulding
thickness will only waste expensive materials. Since injection pressures of
up to 2 MPa are used the mould must be designed accordingly.
As with other moulding processes both mould halves are cleaned,
polished and coated with release agent. A gelcoat is then applied to both
halves and allowed to cure. Reinforcement, cut to shape, is placed in one
half of the mould and the mould closed. The reinforcement most often used
is continuous filament mat although chopped strand mat and woven
rovings, with a layer of continuous filament mat or chopped strand mat in
contact with the mould surface, may also be used. If chopped strand mat is
used it must have a styrene insoluble binder to prevent the fibres from being
washed away as the resin is injected. If desired, a surfacing tissue can be
used between the gelcoat and the reinforcement. The total weight of
reinforcement used is generally of the order of 30% by weight of the finished
mOUlding.
If ribs, stringers, frames or foam buoyancy panels are to be included in
the moulding these are placed in appropriate positions within the mould
before closure. They are usually wrapped with glass mat prior to insertion.
Resin is injected under pressure, starting with the lowest injection point,
making sure first that all vents are open. Injection pressure can be up to
2 MPa, with volume ranging from o· 5 to 10 kg/min, depending on mould

_____ Air release valves ______

Mould

. """o---Continuous filament
mat

+ Injection point
Fig. 4.8. Resin injection.

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54 FRP TECHNOLOGY

size and equipment available. Either twin pot or catalyst injection systems
are available, both offering different advantages for different types of
operation.
Vent holes are closed once the resin starts to exude from them. Similarly
injection points are sealed once they are finished with, the final one being
sealed when the mould has been completely filled. The injection nozzle can
then be removed and the equipment used on another mould, thus making
full use of it.
The moulding is generally allowed to cure at room temperature,
although it may be transferred to an oven if required. Minimal trimming is
necessary after cure. Demoulding is the same as for contact moulding,
except that both halves of the mould have to be removed.
Resin systems should be designed for injection and should have low
viscosities to ensure adequate penetration through the reinforcement. A
high reactivity low exotherm system is preferred, with a pot-life long
enough to permit the mould to be completely filled before gelation of the
resin and preferably before any noticeable viscosity increase occurs. The
system used should also have low shrinkage on cure to prevent shrinkage
marks from marring the surface of the moulding. Care must be taken in
selecting the catalyst/accelerator system, taking into account moulding
thickness, to ensure that excessive exotherm does not occur. If this
happens, distortion of the moulding may occur and certainly mould life will
be shortened. Acetylacetone peroxide is often used as catalyst with a cobalt
octoate accelerator. Reactivity can be boosted by using dimethylaniline as
additional accelerator.
The advantages of the resin injection process over contact moulding are
summarised below.

Advantages
1. Two smooth moulded surfaces.
2. Constant shape and weight mOUldings.
3. Higher moulding quality than can be achieved with a one-part mould.
4. Ribs and other parts can be moulded in one operation.
5. Styrene emission is reduced since it is a closed mould process.
6. Cure is less susceptible to draughts and changes in workshop
temperature.
7. Lay-up is cleaner and less wasteful.
8. Labour costs are reduced.
9. Rapid mould tum-around can be obtained. Cycle times of 1· 5 h have
been claimed for small mouldings.

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MOULDING PROCESSES 55

Disadvantages
1. Accurately made matched moulds are needed and several may be
required to keep the injection equipment fully utilised.
2. Capital costs of equipment and moulds are higher.

4.6 PRESSURE INJECTION

Pressure injection is virtually the same as resin injection. However, mOUlds


are generally heavier and of more solid construction. Chrome plated
matched metal moulds, generally with provision for heating, are used,
mostly with epoxide resin systems.
One area where pressure injection is of prime importance is in the
manufacture of radomes for aircraft. All civil aircraft and most military
aircraft are fitted with nose radomes. These house radar transmitting and
receiving equipment and are radar transparent. They are classified as Class
1 structural parts whose failure during flight, take-off or landing could
jeopardise the safety of the aircraft.
Rigid matched metal moulds are used since radomes have to be
constructed to very high tolerances. Radomes are usually of sandwich
construction, with an inner and outer skin 1 mm thick and a non-metallic
honeycomb or foam core about 9 mm thick. One exception to this is the
nose cone of Concorde. 5 • 6 This is solid, 9 mm thick, constructed from E-
glass reinforced epoxy with approximately 45% glass content. This radome
is some 3·2 m long and is elliptical in shape, with a major axis of 3· 2 m and a
minor axis of 1 m.
Reinforcements are usually of the woven or knitted type, tailored to
shape. Reinforcement and core material is placed in the suitably released
mould, the mould closed and resin injected under pressure. Heat cure is
accomplished by fitting heating coils to both the outside and inside of the
mould. Great care is needed to ensure that bubble-free mouldings are
produced.

4.7 VACUUM IMPREGNATION AND INJECTION

Vacuum impregnation is an alternative process to resin injection. In some


ways it is more suited to epoxide resin systems which contain no volatile
monomers, than to polyester systems which contain volatile styrene;
however, both resin systems may be used. Vacuum impregnation is used for

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56 FRP TECHNOLOGY

the manufacture of nose cones, radomes and circuit breaker tubes from
heat cured epoxide resin systems.
An alternative process, used with polyester resins, is vacuum injection.
The only real difference is the way in which the resin is drawn into the
mould. Various processes are in use and are described below. These
processes can be used for the manufacture of a wide range of products,
including boats and train cabs.

4.7.1 Vacuum impregnation


Heated matched metal moulds are used, with a highly polished or chrome
finish. The mould surface is treated with an appropriate release agent such
as a silicone. Reinforcement is then placed in position and the top half of
the mould lowered over the bottom half. The reinforcements used may
consist of woven or knitted glass cloth tailored to size. Quick release clamps
are used to hold the two halves of the mould together.
Once the mould has been assembled it is either lowered into a resin bath
or fitted in such a way that resin can be fed to the bottom of the mould.
Vacuum is applied to the top of the mould to suck the resin system up
through the reinforcement until it completely fills the mould. Care must be
taken to ensure that there is an adequate supply ofresin at the bottom of the
mould to prevent any air from being drawn in. It is also important to ensure
that the resin system has been degassed under vacuum prior to use,
otherwise degassing will take place in the mould, resulting in void
formation in the laminate. External or internal heating may be applied to
the mould to effect gelation and cure of the resin system. Once cure has been
completed, demoulding and trimming can take place.
Mouldings can be made to very high tolerances by this technique.
Advantages
1. Two smooth surfaces on the moulding.
2. Constant shape and weight mouldings to very high tolerances.
3. Closed mould process-no fume emission.
Disadvantages
1. If used with heated matched moulds these are expensive.

4.7.2 Vacuum injection moulding - Hoechst process


The Hoechst vacuum injection process 7 • 8 is a combination of vacuum bag
moulding and resin injection. It was developed by Hoechst to overcome the
disadvantages of the other two processes. To take full advantage of the
process, special moulds and resins are necessary. The process can be used

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MOULDING PROCESSES 57

for the production of boat hulls as well as many other types of moulding.
Moulds are made from GRP, the lower half being of rigid construction
6-8 mm thick, whilst the upper half is more flexible and only 3-6 mm
thick. It is this flexible half which is the essence of the process. A vacuum
channel is built into the mould around the periphery for mould closure
(Fig. 4.9).
A resin with a viscosity of about 200 mPa s at 20 e is needed for this
0

process.
As with other moulding processes the mould surfaces are waxed,
polished and coated with PVA release agent. If a ge1coat is to be used, this is
applied to the mould surface and allowed to cure prior to filling the lower

Vacuum

1 Pressure of 0 66- 0 .80 kp/cm 2 (660-800 mbar) below atmospheric


2 Trap for excess resin
3 Lower mould po<1ion
4 UlJper mould partlon
5 Vacuum lead to reSIn suchon channel
6 Cut·olt valve
7 ResIn supply reservOir
8 Injection connector
9 Peripheral resIn suction channel
10 Peripheral sponge rubber gasket
11 Peripheral sponge rubber gasket
12 Pressure of ca. 013 kp/cm2: (130 mbar) below atmospheric
13 GRP moulding
14 Vacuum clOSIng channel

Fig. 4.9. Construction a/two-part vacuum injection mould/or the Hoechst process.
(Courtesy 0/ Hoechst AG.)

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58 FRP TECHNOLOGY

half of the mould with reinforcement. The use of a gelcoat does, however,
increase production time.
The reinforcement is cut to shape and fitted into the lower half of the
mould. Gasket material is placed around the edge of the mould to form a
channel and the top half of the mould lowered into position. The
reinforcements used may be chopped strand mat with a styrene insoluble
binder, continuous strand mat or a combination of chopped strand mat
and woven rovings. Glass content of the finished moulding can range from
25 to 50% depending on the type of reinforcement used. Surface tissue may
be included if desired. As with other moulding processes, foam panels,
balsa wood and ribs can be moulded in.
Once the upper half of the mould is in position, vacuum is applied to the
gasket channel to close the mould and render it airtight. Catalysed resin is
next injected, either under pressure (0·05-0·2 MPa) or by gravity feed (1 m
head), until the calculated amount has been added. The resin feed is then
shut off. More than one injection point may be used on large moulds.
Finally the air remaining in the mould is sucked out, when the flexible top
half forces resin to flow through the reinforcement until the mat is
thoroughly impregnated and compacted. Vacuum is maintained until the
resin has cured. Demoulding and trimming is carried out in the normal
way.

Advantages
1. Relatively low capital cost (similar to resin injection).
2. Fast mould turn-round.
3. Low labour costs.
4. Two smooth moulded surfaces.
5. Suitable for large mouldings.
6. Undercuts are possible.
7. Reduced styrene emission through the use of a closed mould process.

4.7.3 Vacuum injection-British Rail process


British Rail have developed a vacuum injection technique to meet their
specific requirements. 1 Matched moulds are used, made from either a
polyester tooling system or from an aluminium filled epoxy system. Mould
closure is by means of vacuum applied to an outer channel. The mould is
then evacuated and resin poured in, in a similar manner to that used in the
Hoechst process. Gelcoats are used and inserts, such as plywood cores, may
be included. By careful mould design, with loose mould pieces, undercuts
may be moulded in.

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MOULDING PROCESSES 59

4.7.4 Monoforming 9 • 10
This system is offered by J. Coudenhove GmbH, for use with polyester
resin systems. Lightweight matched moulds are used with positive pressure
resin injection and vacuum to hold the mould halves together and aid in
consolidation of the laminate. The lower half of the mould is of rigid
construction, supported on a suitable framework. The upper half is
generally a sandwich of glass reinforced epoxy with a balsa wood core.
Mould costs are claimed to be about three times those of a mould used for
hand lay-up, but only one-fifth to one-half of the cost of moulds needed for
resin injection. Resin viscosity for use with the process should be of the
order of 200-400 mPa s.

4.7.5 CSI process-Crystic Systems Ltd l l


This process uses lightweight matching moulds with combined pressure
and vacuum for injection of the resin. The process is offered under licence
by Crystic Systems Ltd from whom full details may be obtained. It is due to
this licensing arrangement that few details are available.

4.8 FOAM RESERVOIR MOULDINGt

Foam reservoir moulding (FRM) is a low pressure technique for the


production of lightweight rigid composite structures with two smooth
surfaces. Mouldings produced by this process have high strength to
stiffness ratios. The process was initially developed for use with epoxide
resin systems by Shell Research Ltd but can also be used with polyester
resin systems. To date most applications and developments have been with
epoxide resin systems.
Male and female moulds are required which, due to the low moulding
pressure needed (0·1 MPa), can be manufactured from GRP for moderate
temperature cure or lightweight metal for higher temperature cure. As with
other moulding processes, care must be taken in preparing the mould
surface and the application of release agent. Due to the nature of the
process, moulding is always to stops.
The composite system used for this process consists of an open-celled
flexible foam impregnated with resin system, sandwiched between two
layers of glass reinforcement. The glass can be in the form of either chopped
strand mat or woven fabric, depending on the shape and performance

t A patented process.

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60 FRP TECHNOLOGY

requirements of the moulding. Surfacing tissue may be included on either


side if required. The foam used comprises two sheets of small open-celled
flexible urethane foam with a density in the region of 12-15 g/litre. One
side of each sheet of foam is coated with the resin system, which may
contain pigments and fillers, and the two layers sandwiched together, resin
side inwards. This gives a resin foam sandwich which is dry to handle.
Shelf-life depends on the resin system used and storage temperature.
To produce a moulding, glass or other reinforcement is placed in the
mould followed by the resin foam sandwich. Further glass reinforcement is
then placed over the foam and the mould closed slowly to stops. As the
mould is closed resin is forced through the foam into the reinforcement,
displacing the air. Generally a compression ratio of 10: 1 is used. By careful
selection offoam thickness and amount of reinforcement and resin system,
a fully impregnated composite results. Heat is applied to cure the resin
system. Pressure is maintained throughout the cure cycle. Once the resin
system has cured the mould is cooled and demoulding can take place.
Complex mould shapes can be readily produced since the foam takes up
the mould shape and presses the reinforcement against the mould surface.
Thus ribs can be moulded into one side of the laminate without having to
add additional foam or reinforcement, making lay-up more simple. In this
way optimum use can be made of the reinforcement (Fig. 4.10).
Clearly, by varying the foam thickness and amount of glass reinforce-
ment used, a wide range of composites with differing properties can be

Mould
Fig. 4.10. A typical FRM composite.

Table 4.2 Typical properties of FRM composites

Specific gravity 0·6-1·4


Flexural strength 60-625 MPa
Flexural modulus 0·8-35 GPa
Impact strength 2·5-12·75 J

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MOULDING PROCESSES 61

produced. Typical ranges for some properties are shown in Table 4.2. Full
details can be obtained from Shell Chemicals UK Ltd who license the
process.

4.9 COLD PRESS MOULDING

This is an intermediate process between contact moulding and hot press


moulding. Inexpensive GRP tools are used and only a lightweight
hydraulic press is necessary to produce mouldings with two smooth
surfaces. Moulding pressure is not usually greater than O· 5 MPa.
Although called cold press moulding, mould temperatures are usually
between 40 and 50°C. This is brought about by the heat of reaction of the
resin system during gelation and cure. However, to ensure that consistent
mOUldings are produced, the mould is often heated at the start of a
production run. By utilising the exothermic heat produced during cure to
heat the mould, the moulding cycle is reduced, mould life extended and
reject rate reduced.
Moulds are frequently made from GRP, although light metal alloy
moulds may also be employed. Average mould life for GRP moulds is 1000
releases, although 2000 releases have been known. To ensure that the
moulds do not distort during use they are generally mounted on a steel
frame and back filled with a pressure resistant material such as concrete, or
a filled resin composition. The mould tools consist of accurately made
matching male and female moulds, designed to pinch the reinforcement at
the edge of the moulding, to allow air to escape but retain the resin.
Without this pinching area there is a risk of air entrapment and resin loss
leading to a higher percentage of rejects. For most mouldings this pinching
area should allow for two mat thicknesses to be compressed (see Fig. 3.3).
Unlike hot press moulding, the surplus reinforcement cannot be trimmed off
in the mould. Mould surfaces are best coated with a release agent which
permits many releases without recoating so that acceptable production
cycles can be achieved.
Moulding thickness is usually within the range 2-5 mm and is uniform
throughout the whole mOUlding. Above 8 mm thickness, problems can
arise through either excessive exotherm, resulting in a scorched or distorted
moulding, or an excessively long cure cycle to prevent this. Undercuts are
not practical since split moulds are prone to troubles.
The reinforcing material-which may be glass mat or woven fabric-is
cut to shape and placed in the mould. With deep draw mouldings a preform

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62 FRP TECHNOLOGY

is more suitable (for details of preparation see Section 4.10.2). A surfacing


tissue may be used on one or both sides of the moulding to achieve a resin-
rich surface free from fibre pattern. Whilst gelcoats may also be used, their
use results in a much longer and generally unacceptable production cycle.
Once the correct amount of reinforcement has been placed in the mould,
the cold curing resin system is poured in and the press closed with a strong
deceleration towards the end of the stroke. The resin displaces the air and
impregnates the reinforcement. Since the resin system used should have a
short gel time and a short cure time, it can only be mixed immediately prior
to use. The exothermic heat generated during gelation accelerates the cure
of the resin system and permits a relatively short moulding cycle to be used.
This may be between 6 and 30 min depending on moulding size and
thickness. Once the moulding has been released from the mould it can be
trimmed. The glass content of the finished moulding can be up to 50% by
weight. This is roughly twice that which can be achieved with contact
moulding.
One way of obtaining a very short gel time with ease of mixing and very
low material wastage is to use a two-component mix. One component is
prepared with a cobalt accelerator and benzoyl peroxide catalyst, the other
with dimethylaniline accelerator and cyclohexanone peroxide catalyst.
These two components are then mixed immediately prior to use to give a gel
time of 3-4 min and a moulding cycle time of about 10 min. Both
components are stable for at least one working day.

4.10 HOT PRESS/MATCHED METAL MOULDING

This process is one of the most economical for the high volume production
of small-to-medium sized components from either polyester or epoxide
resin systems. Mouldings have two smooth surfaces and can be made to
relatively high tolerances. Due to high tooling costs, this process cannot
generally be justified for short runs.
Heated matched metal moulds are used, mounted in a hydraulic press
fitted with automatic opening and closing and accurate speed control.
Moulds are generally fabricated from tooling steel with flame hardened
edges to trim the moulding during the press cycle (see Fig. 3.6). Moulds
used with sheet moulding compounds often have ejectors fitted but these
are rare on moulds used with liquid resin systems. The mould surface
should be highly polished and may be chrome plated to ease removal of the
moulding. Such moulds generally have a life of about 100 000 releases. To

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MOULDING PROCESSES 63

prevent warping of the moulding the temperature difference over the whole
mould surface should not exceed 2· 5°C.
Mould design is of great importance for efficient production cycles and
must take into account the material to be used. Also an adequate taper
must be built into the mould to permit easy ejection of mouldings. This is
described in more detail in Chapter 3.
A high production rate can be achieved with cycle times ranging from 1
to 8 min. This is governed by moulding temperature and pressure, type of
resin/catalyst system used and moulding wall thickness. As a general guide
a press time of 2 min is used for a wall thickness of 2 mm or less, above this
it is general to allow 1 min per millimetre of wall thickness. Press
temperatures are usually in the range lOO-170°C, with temperatures of
I OO-130°C being more common with polyester resins. Pressures used vary
between O' 5 and 15 MPa depending on mould dimensions and the material
being processed.
Silicone release agents may be used to facilitate demoulding, although
generally, once a mould has been 'run-in', particularly with moulding
compounds where metallic soaps are used as internal release agents, further
application becomes unnecessary. If a moulding is to be subsequently
painted, great care must be taken in choosing a release agent that will not
interfere with adhesion of the paint. This is also true if adhesives are to be
used on the moulding.
Several methods exist for producing mouldings by the hot press
technique; these are: liquid resin/chopped strand mat; liquid resin/
preform; sheet moulding compounds or prepregs; dough moulding
compounds. Each of these will now be described in turn.

4.10.1 Liquid resin/chopped strand mat


This procedure is only suitable for simple relatively flat shapes. The
chopped strand mat reinforcement is cut to shape and the required amount
placed in the mould A mat bound with a styrene insoluble binder is
preferred since this prevents the fibres from being displaced during the
press cycle. If desired a surfacing tissue may be placed on either side of the
mat to give a resin-rich finish and to mask the fibre pattern. With flat
mouldings, woven cloths may be used, but these can distort if used with
contoured mouldings.
The pre-mixed resin system is poured over the reinforcement and the
mould closed. Mould closure is carried out rapidly at first but more slowly
as final closure approaches, to allow air to escape and full impregnation of
the mat to take place. By cutting the mat slightly larger than the moulding

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64 FRP TECHNOLOGY

dimensions, the excess glass acts as a filter to allow air to escape whilst
retaining the resin. With correct mould design this excess is cut off during
the final closure of the mould. Mould closure is usually regulated by stops
to predetermine the moulding thickness and prevent too much resin from
being squeezed out. Since a liquid resin system is used, a relatively low
moulding pressure is all that is necessary (0·5-2·5 MPa).
To reduce moulding costs, increase the rigidity of the moulding and
reduce shrinkage and hence improve surface finish, fillers such as calcium
carbonate, china clay or talc may be added to the resin system.
For preference the resin system should be of high reactivity and medium-
to-high viscosity at 25°C, to prevent it from running through the
reinforcement and polymerising at the mould surface before the mould has
been closed. With polyester resin systems, benzoyl peroxide is frequently
used as catalyst without an accelerator. With this catalyst a large batch of
resin can be prepared at anyone time, since shelf-life at room temperature
is of the order of one week. Fibre content of the finished moulding is usually
within the range 25- 50%.

4.10.2 Liquid resin/preform


With complicated shapes, to ensure a uniform distribution of glass, it is
preferable to use a preformed glass mat rather than chopped strand mat. In
this way even glass distribution is assured.
The equipment required for preforming consists of a chopper gun and a
preform screen of the same shape and size as the mould, mounted on a
turntable and connected to an exhaust fan. The preform screen is made
from perforated steel sheet or wire mesh.
Continuous glass rovings are fed to the chopped unit and cut into lengths
of between 5 and 50 mm. These fibres are blown by fan onto the preform
screen whilst it is rotated and are held in place by a slight vacuum from an
exhaust fan. Once the preform screen has been evenly covered to the
required thickness, a small quantity of an aqueous emulsion binder is
sprayed over the fibres to bond them together. This is to give the preform
sufficient strength to be removed from the screen and handled. Emulsion
binders may be made from polyester resin, urea-formaldehyde resin,
polyvinyl acetate and acrylic resins. A styrene insoluble binder is often used
to prevent displacement of the fibres during the pressing operation. Wire
reinforcement may be incorporated into the preform to strengthen the edge
of the moulding.
Once the binder has been applied, the preform and screen are placed in a
forced draught oven for 2-3 min at 125-140°C to dry. When cold the

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MOULDING PROCESSES 65

preform is removed from the screen and is ready for use. To aid production
a large batch of preforms may be prepared first and stored ready for use.
An alternative method of making a preform is to prepare a slurry of
chopped fibres and emulsion binder and draw the screen through this until
the required thickness of fibres has been deposited. The screen is then
removed from the slurry, drained and the preform dried as before.
To prepare a moulding, the preform is placed in the suitably released
mould and the correct amount of catalysed resin poured over it. The mould
is then closed and excess resin squeezed out. The procedure used is then the
same as that for liquid resin/chopped strand mat moulding. Cure
temperature and cure time depend on moulding size and resin formulation.
With deep mouldings it is preferable to invert the mould to prevent the
fibres from being squeezed into the bottom of the mould as closure takes
place (Fig. 4.11). With correct mould design, trimming takes place in the
mould.

4.10.3 Sheet moulding compounds (SMC) and prepregs


These consist of reinforcement which has been pre-impregnated with resin
in sheet form. They may be dry and rigid or soft and tacky; made from
chopped strands, woven fabrics or unidirectional filaments.
Sheet moulding compounds usually consist of a filled polyester resin
system reinforced with chopped glass fibres, whilst prepregs consist of
woven fabrics or unidirectional fibres impregnated with epoxide or other
resin systems. Preparation details are given in Chapter 15.
I

Fig. 4.11. An inverted mould for hot press moulding. (Courtesy of Synres
International BV.)

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66 FRP TECHNOLOGY

SMC or prepreg is cut to shape and the required number of layers


sandwiched together, placed in the mould and pressed. Where necessary
the mould should be treated with a mould release agent first. Pressure,
temperature and cure time depend on the particular resin formulation used
and component thickness. Cure time for a typical polyester sheet moulding
compound is around 1 min per millimetre of wall thickness.
Moulding is usually to stops, to prevent excessive exudation of resin
when pressure is applied. In certain cases contact pressure may be applied
for a predetermined time to heat the prepreg and partially advance cure so
that when full pressure is applied only limited resin flow occurs. This is
more usual with epoxide resin systems than with polyester resins.
Mouldings produced from SMC are smooth on all surfaces and show
almost no glass structure. Glass content is usually within the range
20- 35%. Moulding thicknesses within the range 1· 5-6 mm are common,
while above 10 mm thickness delamination may occur. For thick sections,
dough or bulk moulding compounds are preferred.
With correctly designed moulds, trimming takes place within the mould,
thus limiting finishing just to the removal of flash. Since SMC must deform
to fill the mould cavity, pressures substantially higher than those used with
liquid resin systems are necessary-typically 3-7 MPa. Ejectors and split
moulds, to accommodate undercuts, are common practice, which with the
high viscosity resin systems used for SMC rarely cause sticking problems.
Release agents are unnecessary once the mould has been 'run-in' since
internal release agents are incorporated in the formulation.
Low profile SMC can be used to improve surface finish where large flat
areas are to be moulded, by eliminating sink marks.
Epoxide resin based prepregs are used for the preparation of printed
circuit board laminates for electrical applications. Here a sheet of copper
foil, coated with a suitable oxide film to assist adhesion to the resin system,
is placed on one or both sides of the layers of prepreg before placing the
whole sandwich in the press. Melinex or Cellophane film may be used as
release agent to prevent damage to the copper film and contamination with
release agent. Pressing is invariably to stops between two parallel heated
platens. Cure time depends on the system used but is generally longer than
with polyester systems. Cure temperature may also be higher. Glass
contents of up to about 70% by weight are usual.

4.10.4 Dough or bulk moulding compounds (DMC or BMC)


Dough moulding compounds (DMC) or Premix are dough-like materials
consisting of a mixture of glass or sisal fibres, polyester or epoxide resin

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MOULDING PROCESSES 67

plus catalyst and a filler such as calcium carbonate. Similar types of


phenolic resin based moulding compounds are also available. Fibre length
is normally in the region of 3-12 mm with about 15-20"/0 addition by
weight. This material is referred to as Bulk Moulding Compound (BMC) in
the USA. However, in Europe, bulk moulding compound is often used to
refer to a better quality formulation, designed to give mouldings with
improved performance and finish. Both types of compound can be
prepared in rope or billet form to suit moulding requirements.
The correct weight of compound is placed in the suitably released mould
and the mould closed to stops. Pressures used range from about 4 to 7 MPa.
With polyester DMC or BMC, moulding temperature is usually within the
range 120-150°C and cure time about 2 min, although this may vary from
about 45 s up to about 8 min. With epoxide resin DMC, the cure
temperature range is higher at ISO-170°C, with cure time between 10 and
20 s per millimetre of wall thickness.
With correctly designed moulds trimming takes place in the mould,
leaving only flash to be removed after demoulding. Split moulds, fitted with
ejectors, may be used and are similar to those required for processing SMC.

4.11 TRANSFER MOULDING

Transfer moulding is used for the manufacture of small components and is


particularly useful with multi-cavity tools and where small inserts are to be
moulded in. Materials used are polyester and epoxide dough moulding
compounds, although a new liquid resin injection technique is reported. 12
Heated steel moulds, preferably hard chrome plated, are used, which
may be of multi-cavity design. Tooling costs are higher than for compres-
sion moulding since appropriate gates and runners must be included in the
mould.
A pre-weighed quantity of DMC is placed in a heated transfer pot by
hand. A punch or ram compresses the ma terial and causes it to flow into the
heated tool cavity where it cures. The tool is mounted between the platens
of a press.
Factors to be considered with transfer moulding are transfer and tool
clamping pressures and transfer time. To reduce transfer time and increase
overall efficiency the moulding compound may be pre-heated in an oven or
high frequency pre-heater such as a micro-wave oven.
Mould temperatures range from 155 to l70°C both for polyester and
epoxide resin compounds, with moulding pressures ranging from 5 to

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68 FRP TECHNOLOGY

100 MPa depending on the type of compound to be processed, mould


design and temperature. Cure time in the mould (excluding pre-heat time)
is usually of the order of 10- 30 s per millimetre of wall thickness for both
types of compound.

4.12 INJECTION MOULDING

Injection moulding, a technique used extensively for the processing of


thermoplastic materials, has also been developed to process thermosetting
resin systems. 12. 13 Due to high mould costs it is generally only suitable for
the large scale production of small-to-medium sized components.
Materials processed in this way are polyester and epoxy DMC and also
phenolics, ureas, melamines and diallyl phthalate moulding compounds.
These latter materials are generally more difficult to process than either
polyester or epoxy DMC.
Thermoset mouldings produced by injection moulding are used widely in
the electrical and automotive fields, thus large production runs are
common.
Injection moulding has advantages over both compression and transfer
moulding in that the process is more automated and far higher production
rates can be achieved. Although mould costs are higher than for
compression moulding, overall finished component costs are generally
lower. With small weight components, scrap from runners can be high
compared with compression moulding but for large mouldings this
becomes relatively insignificant. Injection moulding is also better for thick
parts since, with the pre-heating of the DMC before injection into the
mould, shorter moulding cycles are possible.
Whilst injection moulding machines designed specifically for processing
thermoset materials are available, a number of manufacturers offer
replacement screw and barrel assemblies and stuffer hoppers to convert
conventional thermoplastic injection moulding machines to process
thermosets.
Moulding compound is transferred in the cold state by pressure from the
material hopper into the main injection chamber. Here it can be pre-
heated before injection into the heated mould tool. Injection, through a
special nozzle, can be either by ram or screw pressure. If screw feed is used,
the screw must be of the type designed to process thermosets as opposed to
thermoplastics.
Early machines were designed with vertical clamping pressure on the

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MOULDING PROCESSES 69

mould but today horizontal machines are mostly used. Since thermosetting
materials are liquid until gelation occurs, clamping pressure has to be
maintained on the mould until the resin has cured. Unless this is done,
excessive flash will form. Heated matched metal moulds are used, which
may be of multi-cavity design. These moulds must be designed for use with
thermosetting resins, taking into account the fact that thermoset mould-
ings are harder, more rigid and less easily deformed than thermoplastics.
A typical temperature sequence for injection moulding DMC would be:
feed hopper and feed zone-ambient temperature; metering section
50~60°C; nozzle 80~90°C; mould temperature 135~ 185°C for polyester
DMC or 160~220°C for epoxy DMC; injection pressure 80~160 MPa.
Cure time is generally of the order of I o~ 20 s per millimetre of wall
thickness. Very little finishing of mOUldings is necessary.
Where fully automatic moulding machines are used, hydraulic ejection
with perhaps a 'joggle' facility is necessary, since thermosets have a
tendency to stick in the mould.
A survey of injection moulding equipment for use both with thermo-
plastics and thermosets has been compiled recently.14

4.13 FILAMENT WINDING

Filament winding is a technique used for the manufacture of pipes, tubes,


cylinders and spheres and is frequently used for the construction of large
tanks and pipework for the chemical industry. By suitable design, filament
wound structures can be fabricated to withstand very high pressures in
service. In general, products fabricated by filament winding have the
highest strength to weight ratios and can have glass contents of up to 80%
by weight. A typical example of a filament wound polyester pipe is shown in
Fig. 4.12.
The process is suitable for use both with polyester 15 and epoxide resin
systems and a variety of fibres including glass, carbon, aramid and metals,
providing that these materials are available in continuous filament lengths.
Glass fibre is by far the most common reinforcement used and will be used
as the example in the description of the process.
Filament winding is basically a simple process, although numerous
modifications have been developed to improve product quality. Mouldings
can be produced by either a wet lay-up process or from prepreg.
In recent years filament winding has been extended to the continuous
production of pipe using a continuous steel band mandrel. In this way

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70 FRP TECHNOLOGY

Fig. 4.12. Large diameter 'Fibajio 'filament wound GRP pipes moulded by Red/and
Pipes Ltd using Crystic polyester resin/rom Scott Bader. (Courtesy 0/ Scott Bader
Co. Ltd.)

continuous lengths of pipe can be produced, with diameters ranging from


about O· 3 to 3· 5 m.

4.13.1 Wet lay-up


With the wet lay-up process glass rovings are drawn through a resin bath to
impregnate them with resin. The impregnated rovings are then wound
under tension round a rotating mandrel (Fig. 4.13). Generally the feed
head supplying the rovings to the mandrel traverses backwards and
forwards along the mandrel.
The mandrel, which may be segmented for large diameter pipes, is
generally wrapped with a release film, such as Cellophane, prior to
wrapping with glass and resin. The mandrel may incorporate some means
of heating the resin system, such as embedded electric heaters, or provision
for steam heating. Alternatively, the fully wrapped mandrel and laminate
may be transferred to a curing oven to effect cure.
In order to provide a resin-rich, corrosion resistant inner lining to the
pipe, the mandrel may be wrapped with a surfacing tissue followed by one
or two layers of chopped strand mat or woven tape prior to filament
winding. This first layer is usually allowed to cure partially before winding
commences to prevent the resin from being squeezed out into the main
laminate.

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MOULDING PROCESSES 71

Fig. 4.13. An epoxy pipe being filament wound.

The winding angle used during construction of pipes or tanks depends on


the strength/performance requirements and may vary from longitudinal
through helical to circumferential, as shown in Fig. 4.14. Often a com-
bination of different winding patterns is used to give optimum perfor-
mance. Accurate fibre alignment is possible.
For pipe construction, steel mandrels are generally used. However,
where cylinders or spheres are to be made, an alternative material has to be
used so that it can be removed once the resin system has cured. In these
cases the mandrel can be made from wax, a low melting metal alloy, or an
inert plaster held together with a water soluble binder. Clearly, in these
cases the mandrel can only be used once. Material choice for the mandrel
will depend on the cure cycle needed for the resin system.
In addition to winding with continuous filament rovings, machines have
been developed which permit winding with tapes or slit-width chopped
strand mat and woven rovings. These reinforcements may be used alone or
combined with continuous filament rovings. Thus considerable design
flexibility exists for the production of large simple shapes.
Improved chemical resistance can be achieved by the use of a thermo-
plastic or synthetic rubber liner. If the liner is sufficiently rigid it can be
supported on a light frame and used as the mandrel, if not then it can be
wrapped round the mandrel first. A grade of polypropylene is available

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72 FRP TECHNOLOGY

~III IIIIIII II ~ Hoop

Hoop + Hel ical

Hel i cal

Longitudinal

Fig. 4.14. Filament winding patterns.

which has a woven glass cloth partially rolled into one side to improve
adhesion of the resin system (Celmar).
Dunlop has recently developed a new process for pipe production to
produce pipes in the range 200-2000 mm diameter. 16 Essentially the
process is similar to conventional filament winding. A mandrel, suitably
coated with release agent, is wrapped with an epoxide resin impregnated
glass tape. Over this is wound a 150 mm high-strength steel strip angled to
give 50% overlap. Epoxide resin system is applied to the steel strip to ensure
that each layer is fully encapsulated. From three to 13 layers of steel may be
applied to satisfy different pressure ratings. The pipe is finished by
wrapping with further resin impregnated glass tape and the resin system
cured. Pipe produced in this way has excellent corrosion resistance coupled
with a high strength/weight ratio. It is said to provide up to 50% weight
saving over conventional steel pipe.
Various processes are available for the 'on-site' construction of large
filament wound storage tanks. By manufacturing these on site, transport

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MOULDING PROCESSES 73

problems are overcome and integral structures can be produced. With the
various processes either horizontal or vertical mandrels are first con-
structed from preformed GRP sheets. These are then wrapped with resin
impregnated glass rovings. Further details of these processes can be found
in Chapter 8.

4.13.2 Prepregs
Filament wound vessels can be produced from prepreg tapes and rovings.
This technique is often used with carbon fibre to reduce fibre damage
during the winding operation and to permit the use of resin systems which
cannot be handled by wet lay-up techniques. Here, it is essential to use a
heated mandrel to melt the resin and hence displace air and consolidate and
cure the laminate. Resin content of the laminate can be controlled more
accurately with prepreg since the prepreg can be made with exactly the right
resin content. The use of prepregs also makes for cleaner operation.

4.13.3 Other applications


Filament winding has been used to provide a protective laminate on the
outside of steel pressure pipes where external corrosion can take place. An
example of this use is in the protection of the splash zone of steel riser pipes
used on sea based oil and gas production platforms. Here, care has to be
taken in the design of such a composite structure since the coefficient of
expansion of the filament wound glass wrap can be lower than that of the
steel core. If such a composite structure is produced using a heat cured resin
system (say 120°C cure) and then subjected to subzero temperatures in use,
the steel pipe can shrink away from the laminate and permit entry of water
by capillary action. Thus the object of wrapping the pipe to prevent
corrosion can be defeated, since corrosion can then still take place under
the laminate. Once the bond has broken it can never be remade.

4.14 CENTRIFUGAL MOULDING

Centrifugal moulding or casting is a method used for making cylindrical


objects with uniform wall thickness. It is mainly used for the production of
large diameter pipes, up to 5 m in diameter, from either polyester or vinyl
ester resin systems, although epoxide resin systems may also be used. Pipes
produced in this way are void-free and smooth on both the inner and outer
surfaces. Threaded sections can be moulded into the external wall if

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74 FRP TECHNOLOGY

required. More recently, a system has been developed for producing


tapered and curved poles by centrifugal casting. 1 7
Moulds need to be bored and polished to a mirror finish and of sufficient
strength to withstand, without distortion, the high G-force exerted during
spinning. A steam jacket or other means of heating may be built into the
mould to cure the resin system, or alternatively hot air may be blown
through the mould.
Release agents used include silicones, bake-on PTFE types or PVA,
although silicones are generally preferred. If the exterior of the finished
pipe is to be painted then a silicone release agent should not be used.
Choice of resin system must depend on application and a heat cured resin
may be used, particularly where chemical resistance is required. In
addition, the process lends itself to the use of several different resin systems
incorporated in the one pipe, such as an abrasion resistant outer skin, a
general purpose centre and a chemically resistant inner skin. The resin
system used should have some degree of flexibility to give good impact
resistance to the pipe, coupled with good chemical resistance. To achieve
both of these requirements in the one resin system may require a
compromise in properties.
Various methods of fabrication can be used. With large diameter
moulds, glass and resin can be applied by the hand lay-up technique using a
slow gel resin system so that the whole mould can be coated and the mould
spun before gelation of the resin takes place. Here, it is necessary to tailor
the reinforcement to shape to avoid overlaps.
Alternatively, the reinforcement may be wrapped round a mandrel,
inserted into the mould and then unwound onto the mould surface. The
mandrel is removed before resin is injected into the mould. With this
technique a faster gelling resin system may be used. Woven fabrics and
chopped strand mat are suitable reinforcements.
A third method, capable of being fully automated, is generally preferred.
Here, resin and glass are applied to the mould surface utilising a travelling
feeder arm fitted with a chopper and spray gun, which passes slowly
backwards and forwards through the mould whilst the mould is rotated.
The laminate can be built up in layers ofO' 5-1 mm thickness per pass. Once
the reinforcement and resin system have been placed in the mould it is
rotated at up to 2500 revolutions per minute (rpm) depending on mould
diameter, the larger the mould diameter the slower the speed. For example,
with a 2 m diameter mould a rotation speed of about 180 rpm is used. At
this speed the mould surface is rotating at about 68 kmjh (42'4 mph).
After the main resin system has gelled, a chemically resistant topcoat

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MOULDING PROCESSES 75

may be applied while the mould is still rotating. Mould rotation is


continued until all the resin has cured.
In all of the above techniques, a relatively flexible glass reinforced resin
pipe is produced, with properties similar to some of those made by filament
winding. To produce stiffer pipes a modification to the spray technique has
been developed and is in use commercially.1s Stiffer pipes, particularly in
the larger diameter range, offer considerable advantages in handling and
installation and maintain their shape during installation.
With this modified process, which is fully automatic, the mould is coated
with release agent and rotated at a suitable speed. The feeder arm is
designed in such a way that it can deliver programmed amounts of resin,
chopped glass and a filler such as sand, to the mould surface as it moves in
and out of the mould. In this way a layer of abrasion resistant sand filled
resin system can be applied to the mould surface. Over this is applied a layer
of glass reinforced resin. By suitable design of the chopper unit, fibre
orientation can be controlled. Next a layer of sand filled resin is applied
followed by a further layer of glass reinforced resin. Depending on the type
and size of pipe to be produced, several more layers ofGRP alternated with
filled resin may be added. Finally the inner surface is coated with a suitable
chemically resistant layer of resin, which may be lightly filled or reinforced,
to give a smooth corrosion resistant lining.
The equipment used can be programmed to feed materials to the mould
to build up the pipe wall thickness at a rate of between O· 5 and 1 mm per
pass and to compact the materials by centrifugal force throughout the
whole production cycle. Once the final layer of resin has been applied, hot
air is passed through the mould to assist curing of the resin system. The
mould is cooled to ambient temperature to assist removal of the finished
pipe, which is pushed out using a hydraulically operated ram. Using this
technique, rigid hard wearing pipes can be produced, tailored to meet end
user requirements. A typical pipe construction is shown in Fig. 4.15. This is
a simplified version of the pipes produced commercially, to illustrate pipe
construction. In practice several more layers of glass and sand filled system
may be incorporated in the pipe wall. A range of bends and joints is also
available to meet most needs.
In the Usui process I?, 19 for producing tapered pipes, the glass fibre
reinforcement is wound round a tapered mandrel to make a preform. This
is inserted into the mould in the centrifugal machine and the mandrel
removed. Resin is poured in and the mould tilted to a pre-determined angle
and then rotated until the resin has cured.
To produce a curved tapered pipe, a flexible mould is used. This is bent to

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76 FRP TECHNOLOGY

Prot.ective coat (resin end sand)


~~----GRP

-'~r---- Resin and sand

Mr-~n---GRP

Wearing coat (resin)

Section through pipe wall

Fig. 4.15. Construction of a typical rigid centrifugally cast pipe. (Courtesy of


Johnston Pipes Ltd.)

the required shape once the preform has been placed in position. It is also
claimed that base plates can be simultaneously moulded on by this method.
These base plates are first preformed and then inserted into the mould
where they become firmly bonded into the pole. Typical applications
include poles for street lighting, flag poles and aerials.

4.15 CONTINUOUS SHEET MANUFACTURE

Continuous machine processing is used for the production of most


corrugated roof sheeting and also for flat clear, translucent and decorative
sheeting. For the purposes of this book, only those processes for which
polyester resins and, to a limited extent, epoxide resins are used will be
described. It should be noted, however, that the decorative laminates used
in building and transport applications are in the main manufa~tured from
melamine faced phenolic resin/paper laminates.
Several patented processes exist for continuous sheet production, all of
which are similar in broad principle.
Resin and glass reinforcement are sandwiched between two sheets of
release film, such as Melinex, Mylar or Cellophane and passed through

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MOULDING PROCESSES 77

~Reinforcement

Cell ulose film


I
Nip rollers

I
Resin Cutter

o
, 0 / \

o 00 Curing oven

----Cellulose film
000 I
'---------'
o
Fig. 4.16. Continuous sheet manufacture.

rollers to consolidate the laminate before curing in an oven (Fig. 4.16).


Resin is applied to the release film either by spray or trickle process, care
being taken to ensure that application is uniform. Glass reinforcement is
laid in the resin and a second layer of release film applied. This sandwich is
passed through a series of rollers to expel all air bubbles and consolidate the
laminate to the correct thickness. During the next stage the laminate
sandwich is either passed directly through an oven to produce flat sheet or
through rollers or dies and then an oven to produce corrugated sheet. Once
cured the sheet is trimmed to the required width and cut into suitable
lengths. Depending on the process, corrugations may run longitudinally or
transversely. Production speeds of up to 12 m/min are possible.
To produce clear sheeting the refractive index of the resin system must
match that of the glass reinforcement. For this reason special resins have
been developed which match the refractive index of E-glass. For trans-
lucent sheeting A-glass may be used but, due to its low refractive index, it is
unsuitable for use in transparent sheeting. In any case today A-glass is
rarely found.
Generally the glass reinforcement used consists of chopped strand mat
with a soluble polyester powder binder or chopped rovings deposited
directly into the resin film. However, for certain applications woven fabrics
may be used. With the latter and to a much lesser extent with chopped
strand mat, the glass cloth may be drawn through a resin bath and excess
resin removed between doctor blades or rollers, before placing between two
layers of release film and processing as before.
With high quality sheeting a surfacing tissue may be used to ensure a
resin-rich finish. Such sheeting must be installed with the resin-rich surface
exposed to the weather.
Resin systems are generally specifically formulated for each machine,

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78 FRP TECHNOLOGY

since gel time and viscosity must suit the particular operating conditions of
the machine. Resin systems used include those suitable for producing clear
fire retardant sheeting.
By the correct choice of resin system, sheeting can be manufactured
which will not yellow to any extent after exposure to tropical weather
conditions for several years. However, to ensure that this is the case the
resin system must be chosen with care and must be fully cured. Also the
release film must be removed before installation and the laminate should
contain not less than 75% by weight of resin. In other cases the resin content
of the laminate may fall between 65 and 75% by weight.
Decorative sheeting can be produced with an attractive printed pat-
terned surface by incorporating a suitably patterned surfacing sheet. This
surfacing sheet can consist of a glass surfacing tissue onto which the pattern
has been specially printed or alternatively a dress fabric may be used. In
both cases the colours used in the printing process must be compatible with
the resin and must not run. Many dress materials are suitable but, since
they often do not wet out as thoroughly as glass fibre, the material should
be ironed fiat first.

4.16 PULTRUSION

Pultrusion is a technique used for producing continuous fibre reinforced


sections in which the orientation of the fibres is kept constant during cure.
The process is suitable for use with both polyester and epoxide resin
systems, reinforced with glass, carbon or synthetic fibres. An infinite
number of profiles can be produced using appropriate dies and includes
rods, tubes and fiat and angled sections. All profiles have high strength and
stiffness in the lengthwise direction, with fibre content generally around
60-65% by volume.
The reinforcements used consist of continuous fibres such as glass
rovings or continuous carbon fibre tows, woven rovings or chopped strand
mat or a combination of the two, depending on the strength and rigidity
required in the moulded profile.
Two processes are available which use liquid resin systems. In the first the
reinforcement is drawn through an impregnating bath containing catalysed
resin (Fig 4.17a). For this process, a resin system with a long pot-life at
room temperature is necessary. The reinforcement is then drawn through a
heated die which removes excess resin, determines the cross-sectional shape
and cures the resin system.

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MOULDING PROCFSSFS 79

Rei nforcement

n injection

Rei nforcement

Fig. 4.17. Pultrusion (aJ using a resin bath; (bJ by resin injection.

In the second process the reinforcement, accurately positioned 20 and


under tension, is drawn through a heated metal die where impregnation of
the fibres and cure of the resin system takes place (Fig. 4.17b). Here, by the
use of appropriate resin injection equipment, a short pot-life system can be
used. Typical resin injection pressures are between 0·1 and 0·5 MPa. To
speed up cure, the reinforcement may be pre-heated to about 100°C before
passing through the die. Production rates of 1 mjmin can be achieved. By
careful design of the pulling mechanism, consistent profiles can be
produced with no bending or twisting ofthe fibres. With some resin systems
a tunnel oven may be required after the die to give a suitable post cure.
Apart from the wet processes it is also possible to make pultruded
sections from prepregs. The forming procedure is the same as that used
with wet resin systems. The prepreg is drawn through a heated die which
melts the resin, compresses the prepreg into the required shape and cures
the resin. This is a somewhat cleaner process than that using a resin bath.
It is reported 21 that sandwich panels are being produced in the USA by
pultrusion. In this process a plywood core is completely encased in a 3 mm
thick glass polyester skin, resin penetrating the plywood during production
to give increased bond strength and moisture resistance.
Also from the USA is a report 21 of a pultrusion process for the
manufacture of copper clad printed circuit boards (US Patent 4 012 267).
This uses a liquid resin process and eliminates the need to make an
intermediate prepreg.

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80 FRP TECHNOLOOY

More recently 22 Pultrex have pultruded an 8 mm diameter rod with a


1 mm thick carbon fibre skin, using a polyester resin as the matrix.

4.17 SANDWICH CONSTRUCTION

With sandwich construction, a core of some material is coated on both


sides with a laminate (Fig. 4.18). The effect of this is to produce a composite
material with increased stiffness, increased thermal insulation and in many
cases increased buoyancy. These factors must of course depend on the type
and thickness of the core material used. Many articles are made by
sandwich construction techniques utilising both polyester and epoxide
resin systems. Some examples are aircraft floor panels, building panels,
boats and surf boards.
Core materials used include balsa wood, 23 plastic foam and honeycombs
of paper, glass fibre or metal (see also Chapter 17). Since several different
types of plastic foam are available, some comments on these may be useful.

Expanded PVC
This is available in several different grades, both plasticised and
unplasticised. If the foam has a surface skin this should be roughened to
improve adhesion. Apart from this,qnplasticised PVC foam requires no
special treatment. With plasticised PVC foam, prolonged contact with
polyester resin may cause attack and so the foam may require sealing first.

Expanded polystyrene
This is severely attacked by the styrene present in polyester resins and
must be sealed before use. This can be done with a solvent-free epoxide
resin system, preferably reinforced with one layer of woven glass cloth. For
maximum bonding of a polyester to an epoxide resin system, the polyester

Laminate
11I1I1I1I1I1I1I1i1l1l1l1t~Topcoat
;~~;:;;:~g~;;;;;;.~;;;;;;;;.;::::=:
;
Core ma teri a1
Laminate
Surf acin9 tis sue
Gelcoat
Re 1ease film
Typical sandwich construction.

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MOULDING PROCESSES 81

should be applied soon after the epoxy has gelled. If this cannot be done
then the epoxy surface should be abraded before application of the
polyester resin. Most solvent-free epoxide resin systems cause little or no
attack on polystyrene foam, but it is always advisable to check the system
out on a small piece of foam first.

Phenolic foam
This is usually of open cell construction and hence will absorb a low
viscosity resin system into its pores. It is not attacked by either polyester or
epoxide resins but should be sealed with a thixotropic resin system before
use.

Polyurethane foam
This is available both as rigid and flexible foam. Generally the rigid foam
is used as core material, since the purpose of the core is to increase rigidity.
Pre-moulded slabs and blocks can be used, the only pre-treatment
necessary being the removal of dust from the surface, providing that a
closed cell foam is used. If an open cell foam is used this must be sealed with
a thixotropic resin system first. If the foam has a skin on the surface this
should be abraded before use.
Where blocks or slabs of foam are to be bonded to a pre-moulded
laminate, an epoxide resin adhesive should be used, preferably abrading the
laminate before application of the adhesive.
Urethane foams can also be foamed in situ, in which case no special
surface treatment of the laminate is necessary except to ensure that it is
clean, dry and grease-free.

Fabrication techniques
These include contact moulding, resin injection and compression
mOUlding. Depending on the process and the type of core material used
either liquid resin systems or prepregs may be used. Reinforcements used
include glass, carbon and aramid fibres and may be in the form of chopped
strands, woven fabrics or unidirectional fibres, depending on strength and
rigidity requirements.

4.18 MOULDING WITH PREFORMED MATERIALS

Two processes have been developed to speed boat building without the
need for expensive moulds and patterns. Both processes use lightweight
wooden frames on which to construct the boat hull.

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82 FRP TECHNOLOGY

4.18.1 C-Flex planking system


F.G. Industries market C-Flex planking. This is designed to eliminate
expensive mould and pattern making in boat construction. C-Flex
planking consists of parallel rods of glass fibre reinforced polyester
alternating with bundles of continuous glass fibre rovings, all held together
by two layers of lightweight open weave cloth. It conforms to curves
without having to be deformed.
In use the C-Flex planking is fixed to wooden frames spaced 450 mm
apart. These frames form the shape of the hull or deck and may be of a
temporary or permanent nature. Over this is applied one layer of chopped
strand mat (225 or 300 g/m2) impregnated with polyester resin. This is
followed by, for example, two layers of Linrovmat (600: 150) applied with
the unidirectional reinforcement at right angles to the C-Flex planking.
Next one layer of Fabmat (300: 150) is applied. The surface is then coated
with a filled finishing compound, rubbed down and finished with a
polyurethane paint.
Full process details and materials can be obtained from F.G. Industries
(UK) Ltd.
C-Flex planking is available as CF 21 (2·1 kg/m2) and CF 13
(1·3 kg/m2).
Width 30'5 cm
Lengths 30 and 75 m
Tensile strength 466 MPa
Tensile modulus 21'7 GPa
Compressive strength 321 MPa
Glass content 42-43% wt

4.18.2 'Duradense' building systemt


Tyler Mouldings have developed the 'Durandense' system of boat
construction to eliminate the cost of producing a pattern and mould for
one-off designs. In this process, pultruded G RP battens are fixed to wooden
frames spaced about 450 mm apart. The outer surface is then laminated by
hand lay-up using say three layers of 300 g/m 2 chopped strand mat and
finished with a gelcoat. Once the resin has cured, the frames are removed
from inside (except every fifth frame to retain shape) and the inside is
laminated in the same way as the outer skin. Bulkheads can be in-
corporated as required.

t A patented process.

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MOULDING PROCESSES 83

Properties of 'Duradense' battens


Pultruded G RP
Glass content 65% wt
Widths 25 and 50 mm
Thickness 3·85 mm
Lengths up to 12m
Longitudinal tensile strength 414 MPa
Longitudinal tensile modulus 22 GPa
Longitudinal flexural strength 515 MPa
Longitudinal compressive strength 193 MPa
Impact strength 128 J/25·4 mm notch
Specific gravity 1·8
Water absorption 0·5%
Barcol hardness 45-60
Full details of the process and materials can be obtained from Tyler
Mouldings Ltd.

4.19 TRIMMING AND FINISHING

Mouldings produced by many of the processes described earlier in this


chapter need to be trimmed after moulding. Wherever possible this should
be carried out while the resin is still in the 'green' stage and the moulding
still in the mould. By suitable design and construction of the mould edge,
this can be used as a trimming guide. Trimming can be carried out with a
sharp knife held at right angles to the laminate, cutting towards the mould
rather than away from it. Alternatively shears or scissors may be used. Care
must be taken not to distort the moulding at this stage.
Once fully cured, FRP products are difficult to trim and special cutting
tools may be required. A range of carborundum and diamond tipped
cutting tools is available from several different suppliers. Such cutters
should be fitted with an efficient dust extraction system to prevent
operators from breathing the dust generated during cutting. A disk type
cutter is often preferred to a saw type cutter.
To prevent delamination during trimming or drilling operations, the
moulding should be supported and clamped as close to the cutting line as
possible. Holes up to about 5 mm diameter may be drilled with con-
ventional high speed drills but above this diameter and up to about 10 mm
diameter, carbide tipped drills are preferable. Over 10 mm diameter,

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84 FRP TECHNOLOGY

cutters should be used. Drilling should be started from the gelcoat side,
with a block of wood or similar material firmly clamped to the back of the
moulding.
For tapping and threading, high-speed nitrided and chrome plated taps
are suitable. Holes and blanks can be punched in a similar manner to that
used with sheet metal.
All surfaces exposed by machining or drilling should be sealed with a
suitable lacquer to prevent ingress of water or chemicals.
Most FRP products will be self-coloured and will not therefore require
painting. However, occasions may arise when this is necessary, for example
to repair scratches or other blemishes, or to add a pattern or lettering, or
with boats, to apply an anti-fouling paint. In all of these cases the moulding
must be thoroughly cleaned to remove all traces of release agent or polish.
PVA release agent can be washed off with warm water. Normal wax
release agents and polishes require washing off with white spirit or a similar
proprietary cleaner. If a silicone containing release agent has been used
then an abrasive cleaner will be required. Similarly, if the moulding has
been contaminated with oils or greases, then an abrasive cleaner may be
required. In each case the final rinse should be with clean, fresh water.
A good check for the presence of a release agent is to apply clean, fresh
water to the surface of the mOUlding. If the water breaks into small
globules, there is a release agent present. If the water remains in a fairly
uniform sheet, the surface will take a fresh coat of paint. In all cases
cleaning must be continued until the water no longer breaks into small
globules.
Once the surface is thoroughly dry it can be painted. The first coat should
be a suitably formulated primer. This may be epoxy or polyurethane based
and will be in either case a two-pack system. After this the undercoat and
topcoat can be applied, allowing the correct cure time between coats.
Various suppliers offer paints designed for use on FRP mOUldings. In all
cases the paint manufacturer's recommendations should be followed
completely to obtain a satisfactory finish.

REFERENCES

1. Gotch, T. M. (1979) Reinforced Plastics, April, 117.


2. Penn, L. (1977) Reinforced Plastics, July, 201; August, 243; September, 279.
3. Coudenhove, J. (1979) Reinforced Plastics, May, 158.
4. Anon. (1978) Modern Plastics International, August, 10.
5. Anon. (1978) Shell Polymers, 2 (2), 36.

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MOULDING PROCESSES 85

6. Meades, G. F. (1978) Reinforced Plastics, March, 78.


7. British Patent 1 008 136, Hoechst AG, UK.
8. Anon. (1977) Reinforced Plastics, October, 321.
9. Coudenhove, J. (1979) Reinforced Plastics, January, 12.
10. Anon. (1979) Modern Plastics International, June, 12.
11. Anon. (1979) Reinforced Plastics, July, 219.
12. Anon. (1978) Modern Plastics International, April, 12.
13. Anon. (1979) Modern Plastics International, June, 36.
14. Anon. (1979) Plastics & Rubber Weekly, Part I-16th March, 17; Part 2-
23rd March, 13.
15. Anon. (1979) Reinforced Plastics, March, 78.
16. Anon. (1978) Reinforced Plastics, May, 142.
17. British Patent 1358360, Usui Research Laboratory, Japan.
18. British Patents 1 167 137, 1 205 787,1 224506,1 328 116, Basler Stuckfarberei
AG, Switzerland; and 1 122 415, Aktiebolaget Hoganasmetoder, Sweden.
19. Anon. (1977) Reinforced Plastics, June, 168.
20. Anon. (1979) Vetrotex Fibreworld, No.7, 3.
21. Anon. (1978) Modern Plastics International, May, 58.
22. Anon. (1979) Reinforced Plastics, January, 7.
23. Anon. (1976) Reinforced Plastics, July, 192.

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Chapter 5

COMMON FAULTS FOUND IN GRP


MOULDINGS

5.1 INTRODUCTION

In this chapter, many of the faults found in GRP mouldings are described,
together with an indication of their possible causes and remedies. General
faults are described first, followed by those faults associated with specific
processes. Although the faults described in Section 5.2 are those found
with polyester resin based laminates, similar faults may occur with epoxide
resin based laminates, which are also covered in Section 5.10.

5.2 GENERAL FAULTS WITH POLYESTER MOULDINGS

In this section, those faults applicable to both hand and spray applied
laminates are covered. Other faults associated specifically with spray
application are dealt with in Section 5.3.

Wrinkle finish (elephant skin) (Figs. 5.1 and 5.2)


This is one of the most common faults with gelcoats. The cause is
insufficient cure of the gelcoat before the laminating resin is applied. The
monomer (styrene) in the laminating resin partially dissolves the gelcoat
and causes swelling and then wrinkling.
1. Check gelcoat thickness (0·3-0·5 mm; 400-500 g/m2) and increase if
necessary.
2. Check that the resin formulation is correct.
3. Check catalyst addition and mixing efficiency.
4. Check the effect of the colour paste addition on cure.
5. Increase workshop temperature to IS-20°C.

86

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COMMON FAULTS FOUND IN GRP MOULDINGS 87

Fig. 5.1 Wrinkle finish on a GRP moulding. (Courtesy of Scott Bader Co. Ltd.)

Fig. 5.2. Close-up of wrinkle finish. (Courtesy of A/S Jotungruppen, Norway.)

6. Delay application of the laminating resin system until the gelcoat has
cured sufficiently.

Pinholing (Fig. 5.3)


Surface pinholing occurs where small air bubbles are trapped in the

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Fig. 5.3. Pinholing (photomicrograph) . (Courtesy of Scott Bader Co. Ltd.)

ge1coat before gelation. Pinholes can also be caused by dust particles


settling on the mould surface.
1. Ensure that the mould surface is dust-free.
2. Check resin viscosity-thin with styrene if necessary.
-reduce amount of thixotropic agent.
3. Wrong choice of release agent can lead to poor wetting by the ge1coat
and hence result in pinholing-check release agent. This should not
occur with PVA as release agent.
4. A void mixing air into the resin when adding catalyst or colour paste.
5. Check spray gun capacity-if too high this can result in pinholing.
6. Check atomising pressure-this may be too high.
7. Check formulation-excess catalyst can cause air bubbles to be
trapped due to premature gelation.
8. If methyl ethyl ketone (MEK) peroxide is used, check that the correct
grade is used. Some grades can cause bubbling.

Variations in gloss
This can show up as either patches of matt finish or an overall matt finish.
Causes are either premature removal of the laminate from the mould or
poor application of the wax release agent.

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COMMON FAULTS FOUND IN GRP MOULDINGS 89

Fig. 5.4. Flaking gelcoat. (Courtesy of British Industrial Plastics Ltd.)


1. Ensure that excessive wax is not applied and that the mould is
adequately polished before applying the gelcoat.
2. Check that the laminate is adequately cured before removal from the
mould.

Flaking gelcoat (Fig. 5.4)


This is due to faulty adhesion between the gelcoat and the laminate. It
can occur when the laminate is demoulded, particularly if struck during the
demoulding process. There are several possible reasons.
1. Insufficient polishing of the mould surface, so that the gelcoat sticks
to the mould.
2. Use of a soft mould wax which penetrates the gelcoat-change the
wax polish.
3. Contamination of the gelcoat surface before application of the
laminate and hence no adhesion between the laminating resin and the
gelcoat.
4. The gelcoat has been cured for too long before application of the
laminate.
5. Poor laminate consolidation.

Internal dry patch (Fig. 5.5)


This occurs when the glass mat is insufficiently wetted by the resin
system. Several causes are possible.
1. Insufficient consolidation of the laminate during application.

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Fig. 5.5. An internal dry patch. (Courtesy of Scott Bader Co. Ltd.)

2. Resin applied to dry mat rather than the mat being correctly laid into
wet resin.
3. More than one layer of mat applied before consolidation. Only one
layer should be applied at a time.
4. Resin system has too high a viscosity to adequately wet out the
mat-reduce the viscosity of the resin system by adding a small
amount of styrene.
5. Gel time is too short to permit adequate consolidation before
gelation. Reduce accelerator level, change catalyst, or add an
inhibitor to extend gel time.

Delamination
This can occur between two layers of reinforcement, particularly if two
layers of woven rovings are used without chopped strand mat between
them.
1. Insufficient resin system applied to the laminate-ensure even and
adequate resin application.
2. Poor wetting of the glass mat-use a lower viscosity resin system.
3. Contamination at the interface. This may occur where the first layer

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COMMON FAULTS FOUND IN GRP MOULDINGS 91

of laminate has been allowed to cure prior to application of the next


layer.
4. Over cure of the first layer of laminate prior to application of the
second layer. Reduce intercoat time or roughen the first layer prior to
application of further resin system.
5. Always ensure that one layer of chopped strand mat is placed on
either side of each layer of woven rovings so that no two layers of
woven rovings touch.

Spotting
Small spots appear all over the gelcoat surface. This can be due to poor
dispersion of pigments, fillers or thixotropic additive, or dust on the mould
surface.
1. Ensure that the mould surface is clean and well polished before
application of the gelcoat.
2. Check mixing efficiency.
3. Use a triple roll mill, high speed shear stirrer or equivalent method to
disperse pigments.

Colour variations
Colour variations can become apparent as bands or streaks of colour or
changes in colour intensity. There are several possible causes.
1. Pigment flotation due to poor pigment dispersion, or the use of a
mixture of pigments. Mix more thoroughly or change pigment paste
(see also spotting, above).
2. The use of excessive atomising pressure.
3. Spray gun too close to the mould surface.
4. Gelcoat applied too thickly on vertical surfaces, resulting in runs and
sags and hence uneven thickness. Increase the amount of thixotropic
additive used.
5. Uneven gelcoat thickness-apply more evenly.

Fibre pattern (Fig. 5.6)


The pattern of the glass mat shows through the gelcoat after demoulding.
1. Gelcoat has been applied too thinly-increase thickness or use a
surfacing tissue between the gelcoat and the laminate.
2. Laminate was applied before the gelcoat had sufficiently cured.
3. Laminate was demoulded too quickly.

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Fig. 5.6. Fibre pattern. (Courtesy of Scott Bader Co. Ltd.)

4. Exothermic temperature rise in the laminate was too high


-reduce catalyst/accelerator level.
-change catalyst system.
-apply thinner sections at a time.

Fish eyes or craters (Fig. 5.7)


These appear as patches of pale colour and craters in the gelcoat and can
be caused by inadequate wetting of the mould surface by the gelcoat. This
rarely occurs if polyvinyl alcohol is used as release agent. It can, however,
result from the use of silicone modified wax release agents.
1. Check release agent-use a non-silicone containing one or preferably
PYA.

Blisters and bubbles (Fig. 5.8)


Blisters and bubbles may be found in patches, or all over the surface.
They may appear shortly after demoulding, during post cure (if carried out
after demoulding), or not for several months. They can be caused by air or
solvent trapped between the gelcoat and the laminate, or the wrong choice
of resin system or reinforcement for the particular service conditions. 1

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COMMON FAULTS FOUND IN°GRP MOULDINGS 93

Fig. 5.7. Fish eyes and craters. (Courtesy of British Industrial Plastics Ltd.)

Fig.5.B. Blisters and bubbles. (Courtesy of A/S Jotungruppen, Norway.)

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Fig. 5.9. Crazing or cracking. (Courtesy of AIS Jotungruppen, Norway.)

1. Insufficient impregnation of the glass mat during applica-


tion~compact more thoroughly.
2. Contamination of materials, particularly the gelcoat, with water or
cleaning solvent~ensure that brushes and rollers are dry before use.
3. High temperature cure with the wrong catalyst~change catalyst.
4. High service temperature, moisture or chemical attack-use a
different resin system.

Crazing or cracking (Fig. 5.9)


This may occur immediately or some months after cure. Fine cracks
appear in the surface of the resin and may be first noticeable as loss of gloss.
There are many possible causes.
1. Gelcoat too thick~keep within 0'3-0,5 mm.
2. Unsuitable choice of resin system.
3. Faulty dosage of catalyst.
4. Excessive styrene added to the gelcoat.
5. Resin system under cured.
6. Excess filler added to the resin system.
7. Poorly designed moulding resulting in abnormal strains during
use~redesign mOUlding.
8. Laminate has been subjected to impact (see also 'Star cracking').

Star cracking (Fig. 5.10)


This shows up as a star-like pattern of cracks in the gelcoat and is caused
by impact on the reverse side of the laminate.

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COMMON FAULTS FOUND IN GRP MOULDINGS 95

Fig. 5.10. Star cracking. (Courtesy of Scott Bader Co. Ltd.)

I. Use a more resilient gelcoat.


2. Reduce the thickness of the gelcoat (0'5 mm maximum).

Sink marks
Sink marks can occur over ribs or inserts due to shrinkage of the resin
system during cure. They can be overcome by allowing the laminate to
partially cure before moulding in the ribs or inserts.

Chalking
Excessive chalking of the surface can occur during service life due to
several causes.
1. Insufficient cure of the gelcoat-check thickness and accelerator and
catalyst levels.
2. Use of an unsuitable filler or pigment.
3. Use of excessive filler or pigment.
4. Wrong choice of resin formulation for the service conditions
involved.

Pull-away (Fig. 5.11)


The gelcoat releases from the mould before the laminate is applied,

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Fig. 5.11. Pull-away of gelcoat. (Courtesy of A(S Jotungruppen. Norway .)


especially in corners or angles. This is frequently due to styrene vapour
settling in the bottom of the mould.
1. Position the mould so that styrene vapour can flow out, or use a
suitable extractor system, or both.
2. Avoid excessive gelcoat thickness in critical areas.
3. Reduce catalyst level.

Yellowing
Yellowing of the gelcoat may occur on exposure to light. This can be
caused by any of the following:
1. The presence of moisture during laminating-ensure that all ma-
terials used are dry. Keep the working area dry.
2. Wrong choice of resin-use a UV stabilised resin.
3. Use of benzoyl peroxide/amine accelerator system-change to a
different catalyst system, i.e. one less prone to yellowing.
4. Insufficient cure of the laminate.

Tackiness
The surface of the laminate exposed to the air remains tacky due to
undercure of the exposed surface.

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COMMON FAULTS FOUND IN GRP MOULDINGS 97

1. Avoid laying-up under cold, damp conditions.


2. Use an air-drying resin for the final coat.
3. Check and possibly increase the catalyst or accelerator levels.
4. Increase the cure temperature.
5. Add paraffin or wax to the topcoat.

Discoloured and distorted areas


Discoloured and distorted areas are usually caused by exceSSIve
exotherm during cure.
l. Adjust accelerator/catalyst levels or change to a different system.
2. Reduce the thickness of the laminate applied at anyone time, to
prevent excessive exotherm.

Distortion of the laminate


The laminate distorts after removal from the mould.
1. The laminate was insufficiently cured when demoulded.
2. Insufficient strengthening ribs were moulded in.
3. Balance the gelcoat by applying a resin-rich layer or topcoat to the
reverse side of the laminate before demoulding.
4. Modify the moulding design to compensate for bowing.

Poor hardness and low rigidity


This can result from undercure of the laminate.
l. Check accelerator/catalyst levels.
2. Avoid laying-up under cold damp conditions.
3. Ensure that the glass mat is stored under dry conditions.
4. Check thai there is sufficient reinforcement present.
5. Post cure the mOUlding.

Resin leaching (Fig. 5.12)


The resin is leached out of the laminate during service, either by
weathering or when the laminate is immersed in a liquid. There are several
possible causes.
1. The resin system was undercured-ensure full cure and post cure the
moulding before putting it into service.
2. The wrong resin system was used for the particular application - use a
more weather or chemical resistant resin system.
3. The service temperature was too high for the particular resin-change
to a more heat resistant system.

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Fig. 5.12. Severe leaching. (Courtesy o/Scott Bader Co. Ltd.)

5.3 SPRAY MOULDING FAULTS

Apart from those faults already described in Section 5.2, the following may
occur with spray lay-up.

Undercure
This can be caused by variable output from the spray gun due to
malfunctioning of the equipment, blocked or dirty hoses and blocked or
dirty nozzles.
I. Service the equipment regularly.
2. Check the hoses.
3. Check and clean the nozzles.
4. Check that correct levels of accelerator and catalyst have been used.
5. Check that the correct output is being delivered to the spray head.

Varying glass content


Varying glass content in the cured laminate may be due to uneven
application. A high cross-wind may deposit the glass in a different position
from the resin system.

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COMMON FAULTS FOUND IN GRP MOULDINGS 99

1. Check that the chopper unit is running smoothly and supplying a


uniform quantity of chopped glass fibres.
2. Ensure that the resin and glass are evenly applied-increase in-
spection.
3. A void displacement of the glass fibres when consolidating with a
roller.

Reduction in mechanical strength


The mechanical strength of the laminate can be reduced if the glass
strands are cut too short, the laminate is poorly compacted or insufficient
glass is present.
1. Compact the laminate more thoroughly.
2. Check that the average fibre length is between 50 and 60 mm.
3. Check that the correct resin to glass ratio is used.

5.4 FAULTS WITH TRANSLUCENT SHEETING

These show up as fibre pattern, speckling and flecking (Figs. 5.13- 5.15).
They may have several different causes.
1. Poor consolidation of the laminate (Fig. 5.16) through insufficient
rolling.

Fig. 5.13. Fibre pattern. (Courtesy of Scott Bader Co. Ltd.)

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100 FRP TECHNOLOGY

Fig. 5.14. Speckling due to undissolved binder. (Courtesy of Scott Bader Co. Ltd.)

Fig. 5.15. Flecking. (Courtesy of Scott Bader Co. Ltd.)

2. A resin system with too short a gel time was used-decrease the
accelerator level, change the catalyst or add an inhibitor to the system
to lengthen gel time.
3. The wrong type of chopped strand mat was used so that the binder
dissolved too slowly in the resin system.
4. The wrong resin system was selected. Choose a resin system with a
cured refractive index similar to that of E-glass.

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COMMON FAULTS FOUND IN GRP MOULDINGS 101

Fig. 5.16. A poorly consolidated laminate (left) compared with a correctly prepared
laminate (right) .

5.5 PRESS MOULDING FAULTS


Porous surface
This may be due to several different causes.
1. Too little moulding compound was placed in the mould
- increase the amount used per moulding.
2. The moulding compound flows too easily
-use a stiffer compound.
-delay application of pressure.
-reduce pressure.
-modify mould design.
3. The moulding compound is too stiff
-adjust consistency.
-apply pressure sooner.
-increase moulding pressure.
-modify mould design.
4. Mould temperature too high, resulting in premature cure
-reduce mould temperature.
-apply pressure sooner.
-increase pressure.
5. Trapped air
-ensure that the mould is correctly vented.

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Surface blisters
1. The mould is locally too cool-ensure uniform heating.
2. Trapped air-ensure that the mould is correctly vented.
3. Damp moulding compound-store in a dry place.

Spotty surface
1. The mould is too hot-reduce mould temperature.
2. Pigment decomposition due to overheating-reduce cure tempera-
ture.
3. Contamination of the moulding compound.

Matt surface
1. The mould surface is insufficiently polished.
2. Excess release agent has been applied-mop up surplus.
3. The moulding compound was damp-store in a dry place or pre-heat.
4. The mould surface was too cold-increase temperature.
5. Moulding under cured-increase moulding time or cure temperature.

Mouldings stick to or jam in mould


1. Moulding compound too soft or too damp-dry and pre-heat.
2. Low shrinkage-modify mould design to increase taper.
3. Too few ejectors-increase number of ejectors.
4. Undercuts-modify mould design and use a correctly designed split
mould.

Moulding distorts
1. Mould temperature uneven-ensure uniform temperature over the
whole mould surface, with not more than 2·5°Cdifference on any part
of the mould.
2. Excessive exotherm-reduce cure temperature.
-change moulding compound.
-reduce moulding thickness.

5.6 RESIN INJECTION FAULTS

Glass mat displaced


This can occur during resin injection if the binder used on the glass mat

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COMMON FAULTS FOUND IN GRP MOULDINGS 103

dissolves too readily in the resin system. Two alternatives exist, either to use
a mat with a less soluble binder or to use continuous filament mat.

Trapped air
1. Injection pressure too high-reduce pressure.
2. Too little resin injected-increase resin quantity.
3. Feed pipe is in the wrong position-place feed pipe at lowest point in
the mould.
4. Vent pipes in the wrong position-place vent pipes at the highest
point in the mould.
5. Resin leakage through poor seal-ensure that the mould seal is tight.

Insufficient impregnation
1. Resin viscosity is too high-use a lower viscosity resin system.
-increase resin temperature.
2. Flow path is too long or too narrow
-modify mould.
-modify equipment feed pipe.
-increase the number of feed points.

Variation in wall thickness


The moulding wall thickness varies due to deformation of the mould
during resin injection.
1. Increase the mould wall thickness.
2. Apply strengthening ribs to the mould.
3. Decrease injection pressure.

5.7 VACUUM MOULDING FAULTS

Insufficient impregnation
1. Mould not sealed properly-check mould seals.
2. Resin viscosity too high-use a lower viscosity resin system.

Trapped air
1. Insufficient evacuation-increase evacuating time.
-modify mould design to eliminate blind
holes.

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Bubble formation
1. Vacuum too high causing styrene to boil-reduce vacuum.

5.8 FILAMENT WINDING FAULTS

These comments apply equally well to polyester and epoxide resin systems
used for filament winding.

Insufficient impregnation
1. Resin viscosity too high-reduce viscosity or change system.
2. Unsuitable roving-change to a more suitable roving.
3. Impregnation time too short-reduce winding speed or enlarge resin
bath.

Trapped air
1. Poor impregnation-enlarge resin bath or reduce winding speed.
2. Resin system cures too fast-reduce accelerator level.
-use an alternative system.

White or un impregna ted fibres in laminate


1. Roving tension too high so that resin is squeezed out-reduce roving
tension.
2. Resin viscosity too low-add thixotropic additive.
3. Squeeze or doctor rollers too tight-loosen rollers.

Fuzz formation
1. Roving tension is too high-reduce tension.
2. Poor guiding of fibres-use a guide ring or comb.

Glass fibres break


Glass fibres break during the winding process.
1. Excessively high tension-reduce tension.
2. Poor guide-correct.
3. Unsuitable roving-change to a more suitable roving.

Low glass content


1. Increase roving tension.
2. Increase doctor or squeeze roller tension.

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COMMON FAULTS FOUND IN GRP MOULDINGS 105

5.9 CENTRIFUGAL CASTING FAULTS

Wrinkling
1. Poor insertion of reinforcement-take more care in positioning mats
and cloths.

Dry spots
1. Too little resin-check resin/glass ratio.
2. Too Iowa rotation speed-increase.

Cracks on the inside of the pipe


1. Too much resin-reduce resin content.
2. Too rapid a cure-reduce accelerator level or cure temperature.
3. Resin system too brittle-use a more flexible resin system.

Tacky surface
1. Air inhibition-finish with a correctly formulated topcoat.
-add paraffin or wax to the topcoat.
- increase cure temperature.

Pipe warps
1. Non-symmetric glass distribution-improve lay-up.

Pipe sags
1. Pipe withdrawn from the mould before the resin was fully cured.
2. Resin system too flexible-reduce the level of flexibiliser.

5.10 FAULTS WITH EPOXIDE RESIN SYSTEMS

Streaking and colour variation


Streaking and colour variations can occur in pigmented systems due to
poor pigment dispersion or wrong choice of pigment. Some of the possible
causes and solutions are listed below.
1. Pigment flotation due to poor dispersion or the use of a mixture of
pigments-ensure that the pigment is thoroughly ground into the
resin or change to a different pigment.
2. The use of excessive atomising pressure with spray application.
3. The spray gun was too close to the mould surface.

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4. The resin system has run after application-increase thixotropy of


the system.
5. Uneven thickness-apply more uniformly.
6. If an aromatic amine curing agent such as diaminodiphenylmethane
(DDM) has been used, the laminate may vary in colour from wine
red, through brown to green. This is due to the curing agent. The only
solution is to change to a cycloaliphatic amine, aliphatic amine or
anhydride curing agent.

Pinho ling
Pinho ling occurs when small air bubbles are trapped in the ge1coat before
gelation, or if the mould surface is coated with dust.
1. Ensure that the mould surface is dust free.
2. Use heated two-component spray equipment or heat the mould
surface prior to application of the ge1coat.
3. Wrong choice of release agent can lead to poor wetting by the ge1coat.
This should not happen if PVA is used as release agent.
4. A void mixing air into the resin system when stirring in the curing
agent.

Flaking
Poor mould release due to adhesion of the resin to the mould.
1. Ensure that the mould surface is thoroughly coated with release
agent.
2. Use a suitable release agent-PYA or silicone.
3. Poor consolidation of the laminate so that air bubbles are trapped
between the laminate and the ge1coat.
4. Contamination of the ge1coat before application of the laminate.

Internal dry patch


This has the same causes as given in Section 5.2 under 'Internal dry
patch'. If the resin viscosity is too high it can be reduced by heating both the
resin system and the mould.

Tacky surface
With polyamide, aliphatic amine and some alicyclic amine curing agents,
used under cold or high humidity conditions, amine bloom may occur on
the surface. This is caused by reaction between the amine and carbon
dioxide and moisture in the air. Several possible solutions exist.

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COMMON FAULTS FOUND IN GRP MOULDINGS 107

1. Wait at least half an hour after mixing the resin system before using it,
to allow some pre-reaction to take place in the mixing pot. This can
only be done with long gel time systems.
2. Partially adduct the amine with either an epoxide resin or a reactive
diluent before use. This will give a curing agent with a different mixing
ratio and possibly different cured properties.
3. Change to a different resin/curing agent system.
4. If the laminate is tacky in patches, this is probably due to poor
mixing~ensure that the resin and curing agent are thoroughly mixed
before use. This may be more difficult than with a polyester resin
system, due to the higher viscosity of the epoxide resin system.

Poor laminate hardness


This may be due to under cure or the use of the wrong mixing ratio.
1. Check cure temperature and time. Post cure if necessary.
2. Check resin/curing agent mixing ratio.
3. Check for solvent contamination.

Blistering or bubbling
This is shown in Fig. 5.17. There are several possible causes.

Fig. 5.17. Blistering of a site applied laminate.

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1. Poor pigment dispersion or the wrong choice of pigment.


2. Solvent entrapment, if a solvent based gelcoat has been used.
3. Wrong resin system for the service conditions.
4. Poor adhesion of the gelcoat or topcoat to the laminate.

REFERENCE

1. Anon. (1979) Reinforced Plastics, March, 72.

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Chapter 6

BONDING AND JOINTING REINFORCED


PLASTICS

6.1 INTRODUCTION

As applications for fibre reinforced plastics increase, so does the need for
reliable methods of joining them to each other and to other materials. Since
FRP composites are often markedly anisotropic, simple bonding tech-
niques are often inadequate.
With FRP composites, many of the elements which go to make up a
structure, such as beams and plates, can be moulded into one item, thus
reducing the number of joints needed. However, these sections may have to
be joined together in such a way that any applied load is safely transmitted
through the joint. Examples of such joints are to be found in pipelines and
chimney stacks, cladding panels for buildings and marine structures.
In general terms two broad methods of jointing FRP composites are
used. These are by means of an adhesive bond or by mechanical means
using bolts or screws. Load transfer is best achieved through adhesion
rather than through mechanical interlocking, thus often both methods will
be used on a single joint. These methods are discussed briefly in the
following sections. Further information may be found in conference
reports 1 , 2 and other publications. 3 • 4

6.2 ADHESIVE BONDED JOINTS

With bonded joints some form of adhesive is used to bond two or more
items together. These items may be of similar FRP construction or may be
FRP bonded to some other material such as metal, wood or concrete.
In all cases consideration must be given to the design of the joint, with
special care being taken to ensure efficient load transfer through the joint.

109

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110 FRP TECHNOLOGY

Bonded joints are most efficient when subjected to shear loads and least
efficient when subjected to peel loads, thus joints should be designed so tha t
they are only subjected to shear loads wherever possible. In practice pure
shear loads can rarely be achieved and peel forces have to be allowed for.
With peel forces, the highest stress loading is found at the edge of the joint
and is affected by the design of the joint, the relative rigidity of the
adherends and the properties of the adhesive.
Work has been carried out on the efficiency of various joints used in G RP
boat hulls by Smith and Pattison. 2 They have shown that with a simple lap
joint, efficiency is only 30% but this can be increased to 60% with a butt
strap joint, 70% with a scarf joint and 90% with a stepped joint. Thus,
wherever possible, a scarf or stepped joint should be used rather than a
simple lap joint. The efficiency of double-lapped composite joints in
bending has also been investigated. 5 Configurations of various joints are
illustrated in Fig. 6.1.

Simple lap (30%)

Double lap

Tapered lap
~~------------~

II Butt strap (60%)

Scarf joint (70%)

Stepped joint (90%)

Stepped multiple lap

Fig. 6.1. Configurations of adhesive bonded joints.

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BONDING AND JOINTING REINFORCED PLASTICS III

Further information on the design of joints for marine applications can


be found in publications issued by Lloyds Register of Shipping3 and Det
Norske Veritas. 4
With any bonded joint, in addition to design considerations, several
other factors need to be considered. These are the selection of an adhesive
compatible with the materials to be joined and which will have adequate
service life, and the surface preparation of the adherends to be joined. This
latter step may include the use of a special primer. Other factors relating
specifically to the adhesive may also have to be considered such as viscosity,
wet out of the adherend, method of application, bond line or adhesive
thickness, whether or not a filler or reinforcement has to be added to the
adhesive to obtain adequate bond strength, and cure schedule.
Most of the adhesives used for bonding FRP composites are of the
thermosetting type. A number of companies offer a wide range of these
based on epoxy, polyester, urethane and other resin systems. Technical and
performance data are usually available on request. The advice of these
specialist companies in the selection of an adhesive for a particular
application can be invaluable. A full list of adhesive and material suppliers
may be found in Adhesives Directory.6
A recent development in the adhesives field has been the introduction of
toughened adhesives which exhibit high peel strengths. One such adhesive,
F 241 from Permabond Adhesives Ltd, is based on acrylic and epoxide
resins. This is a two-part adhesive in which one part is applied to one
adherend and the other part to the other adherend. The two adherends are
then sandwiched together with light clamping pressure. Cure may take
from 2 to 20 min to reach adequate handling strength, depending on
temperature and substrate. Full cure takes 24 h.

6.2.1 Surface preparation


With all adhesive bonding applications surface preparation of the ad-
herends is of vital importance. Here brief details of methods of preparation
generally recommended for a number of materials likely to be bonded to
FRP composites will be given.

GRP
Wherever possible bonding to GRP should be carried out while the
laminating resin is still in the 'green' stage. At this time the surface may just
require wiping with an acetone soaked rag, although some abrasion of the
surface may be desirable. Once the laminate is fully cured the following
procedure should be adopted.

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112 FRP TECHNOLOGY

1. Remove all traces of release agent by washing with water or white


spirit/MEK or a proprietary cleaner.
2. Abrade-preferably down to the glass reinforcement.
Where it is known that a GRP laminate is to be bonded in a particular
area then a strip of woven glass cloth may be applied to the laminate during
lay-up and peeled off while the resin is still at the 'green' stage. This will
leave the underlying reinforcement partially exposed and provide an
excellent surface for bonding.

Aluminium and aluminium alloys


1. Degrease.
2. Abrade or etch with sulphuric acid plus chromic acid.

Ferrous alloys (excluding stainless steel)


1. Degrease.
2. Abrade-preferably by sand/grit/shot blasting to a white metal
finish or etch with dilute phosphoric acid.

Stainless steel
1. Degrease.
2. Abrade-by sand/grit/shot blasting or etch with an oxalic acid/
sulphuric acid mixture.

Copper and brass


1. Degrease.
2. Abrade or etch with acidic ferric chloride solution.

Thermoplastics
1. Degrease.
2. Most thermoplastics only require abrading followed by a wipe with
methanol or acetone.
Polyolefines require oxidising by flame or chromic acid.
Polyester films (polyethylene terephthalate) require etching with hot
concentrated caustic soda.
Fluorocarbon polymers require etching with a solution of sodium in
liquid ammonia or sodium in naphtha.

Wood
1. Abrade.
2. Dry the surface.

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BONDING AND JOINTING REINFORCED PLASTICS 113

CFRP
1. Degrease.
2. Abrade.
Note In all cases, dust and other contaminants must be removed from the
surface prior to application of the adhesive. A solvent wipe can be
beneficial in removing dust.
Degreasing may be carried out with proprietary degreasing solvents
or by detergent wash.
All substrates should be thoroughly rinsed with distilled water and
dried after etching unless otherwise specified.

6.3 MECHANICAL JOINTS

Mechanical joints find application where bonding is impractical, un-


economic or where parts may have to be removed and replaced at some
time. Such joints can be made using conventional bolts, screws or rivets or,
preferably, the wide range of purpose designed fasteners. These latter
consist of bolts and sockets made with large perforated washer heads so
that they can be permanently laminated into the moulding. 7 The large
perforated heads ensure adequate stress distribution and prevent the
fasteners from being pulled out during use. Typical examples of some
'Bighead' fasteners are shown in Fig. 6.2.
For low load connections, holes can be drilled and tapped in FRP
composites and threaded bolts inserted. Alternatively, self-tapping inserts

Fig. 6.2. Some examples of 'Bighead' fasteners supplied by Bighead Bonding


Fasteners Ltd. One fastener on the right is shown embedded in a laminate.

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114 FRP TECHNOLOGY

can be used. 8 • 9 Such connections are unsuitable where high loads are likely
to be exerted around the bolts. In these situations the large washer headed
fixings are invaluable.
Where rivets are used, these may have to have a washer placed between
the rivet head and the laminate to reduce local damage caused by digging-in
of the head.
Care needs to be taken in the design of bolted joints to ensure adequate
stress distribution around the bolt heads. Some work has been carried out
on this subject with particular emphasis in recent years on the bolting and
riveting of carbon fibre composites for aircraft structures. 1 Further work is
necessary, particularly to correlate data in such a way that they are of use to
designers.
With pipe joints, some success has been met by using well tried concrete
and steel pipe jointing techniques. These may be of the butt/strap type,
socket and spigot type with sealing rings, or flange type. Which type of joint
will best serve a particular application must depend on installation and
operational factors. Design guidelines on jointing are given in BS 4994 but
since this was compiled (1973) various improvements in joint design have
been made. Further improvements are likely to come as pipe manufac-
turers and end users gain more experience in the handling and installation
of FRP pipes.

REFERENCES

1. Jointingin Fibre Reinforced Plastics. Symposium, 4-5 September 1978, Imperial


College. IPC Science and Technology Press, London.
2. Smith, C. S. & Pattison, D. Designing with Fibre Reinforced Materials.
Conference, 27-28 September 1977, Paper C230j77. I.Mech.E., London.
3. (a) Code of Practice for the Construction of Reinforced Plastic Yachts;
(b) Rules for the Application of GRP to Fishing Craft. Lloyds Register of
Shipping, London.
4. Rules for the Certification of Boats. Det Norske Veritas, Oslo.
5. Allred, R. E. and Guess, T. R. (1978) Composites, 9, April, 112.
6. Adhesives Directory. Published yearly by A. S. O'Connor & Co. Ltd, Richmond,
Surrey.
7. Stanley, K. E. (1978) Reinforced Plastics, September, 290.
8. Anon. (1977) Reinforced Plastics, October, 311.
9. Anon. (1978) Reinforced Plastics, October, 321.

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Chapter 7

MAINTENANCE AND REPAIR OF FRP


STRUCTURES

7.1 INTRODUCTION
Fibre reinforced thermosets, although strong and hard wearing, can
become damaged during use. This is particularly true of GRP boats. In
many cases such damage can be adequately repaired, providing that the
correct procedures are followed. However, regular maintenance of GRP
structures can prevent some of this damage from occurring. A useful
booklet on maintenance and repair has been published by International
Paint, Yacht Division. 1

7.2 MAINTENANCE
In the main, regular maintenance of FRP structures is unnecessary; indeed
it is for this reason that FRP composites find such wide application as
building panels, for marine applications and in chemical plant. However,
with GRP boats, regular maintenance can preserve the gelcoat and prolong
the life of the boat. Similar comments apply to GRP vehicle bodies and
other components likely to be subjected to continuous wear and tear.
Generally all that is required is to wash the boat once a year with warm
water containing a mild detergent. Oil stains and old polish can be removed
with proprietary cleaners formulated for such applications. Paint strippers
should never be used since these will damage the gelcoat. When the surface
is clean and dry, the application of a suitable wax polish will ensure that the
high gloss finish of the gelcoat is maintained. With vehicles these
procedures may have to be adopted at more frequent intervals.
Whilst maintenance is being carried out the surface should be thoroughly
inspected for scratches, abrasions and any other damage. Such damage can
usually be repaired.

115

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116 FRP TECHNOLOGY

7.3 REPAIRS TO GRP STRUCTURES


When a GRP structure has been damaged, before a repair can be carried
out certain factors need to be considered. These are the degree of damage
and the construction of the structure-whether or not a repair will render
the structure suitable for the use for which it was originally intended.
Assuming that the damage can be repaired and the structure rendered
usable once more, the following repair techniques may be applied. These
techniques are mostly only suitable for repairing mouldings produced by
contact moulding or related closed mould techniques. They are rarely
suitable for the repair of mouldings made by hot press, transfer or injection
moulding techniques.
A typical moulding in need of repair from time to time is a G RP boa t and
this example will be used to describe repair techniques. Similar repair
techniques are used both with polyester and epoxide resin laminates.
Whilst polyester resins may be used to repair polyester mouldings, epoxide
resin systems may be used to repair either type. With care and some
patience, repairs can frequently be made which are virtually invisible from
one side.

7.3.1 Surface damage


This is damage to the gelcoat or first layer of reinforcement only. First
remove all loose and protruding material and ensure that the damaged area
is clean, dry and grease-free. Next, grind and abrade the damaged area and
the surface for a short distance around to ensure good adhesion of the
repair resin. A thixotropic resin system should be used and this should be
applied carefully over the whole of the damaged area and surrounding
abraded area. This should be thicker than necessary just to fill the damaged
area to allow for shrinkage, grinding and polishing. A film of Cellophane
can be used to give a smooth finish and hold the resin in place. This will also
prevent ajr inhibition where a polyester resin is used.
Once the repair resin has cured it can be smoothed down with, for
example, waterproof emery paper, starting with No. 400 and finishing with
No. 600. Care should be taken not to damage the existing gelcoat. The
repaired area should then be further smoothed with a fine rubbing
compound or metal polish and finally given a good polish with a high
quality wax polish.

7.3.2 Small impact fractures


These are small areas of damage such as cracks, rather than holes which are
dealt with in Section 7.3.3. Such cracks may extend right through the

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MAINTENANCE AND REPAIR OF FRP STRUCTURES 117

laminate. It is assumed that access can be obtained to both sides of the


laminate; if not, then the procedure described in Section 7.3.4 should be
followed.
The crack should be enlarged from the impact side into a V -shaped
groove, making sure that all damaged laminate is removed down to the
bottom of the crack. This groove may have to be extended right through the
laminate.
Abrade the back of the laminate to at least 75 mm on all sides of the
groove and remove all dust. Cut four pieces of chopped strand mat
(450 g/m 2 ), the first being 25 mm larger all round than the groove, the
others each being cut progressively larger by about 12 mm all round. The
amount of resin system needed for the repair should be between 2i and 3
times the weight of chopped strand mat used.
A coat of resin system should be applied to the back of the laminate to
cover the whole of the abraded area. Into this should be placed either the
smallest or the largest piece of mat, taking care to ensure that it is
symmetrically located around the groove. Resin should be worked through
the mat until it is evenly distributed and all entrained air removed. The
process should be repeated until all four layers of mat have been applied.
Entrained air can be removed by rolling the laminate with a suitable size of
laminating roller or by using a brush with a stippling action. The laminate
should then be allowed to cure at least overnight before proceeding further
with the repair (Fig. 7.1, stage 1). Cure time will depend on ambient
temperature and if this is low then a longer cure time may be necessary. It is
generally recommended that polyester resins are not used at temperatures
below 15°C.
Strips of mat should be cut to the dimensions of the groove. The groove
should then be coated with a layer of laminating resin and the first strip of
mat inserted. Resin should be worked through the mat until it is fully
impregnated and free from trapped air as previously. Further strips of mat
should then be applied until all but about 2 mm of the groove has been
filled. The laminate should be left to gel (Fig. 7.1, stage 2).
Next the surface should be filled with a pigmented, thixotropic, filled
resin system until the resin protrudes slightly above the level of the
surrounding gelcoat. Once this layer has cured it can be rubbed down until
it is level with the surrounding gelcoat. A coat of pigmented topcoat can
then be applied over the whole abraded area. This should be covered with a
sheet of Cellophane and smoothed flat with a squeegee (Fig. 7.1, stage 3).
When the resin has cured, the Cellophane can be removed and the topcoat
rubbed down and polished to a high gloss finish.

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118 FRP TECHNOLOGY

Stage 1

of CSM

Stage 2
lr-------- Chopped strand mat

Stage 3

~~liliil~O=II~i=:
.; New ge 1coat
Ce 11 ophane

Fig. 7.1. Repair of small impact fracture.

7.3.3 Holes
This repair technique can be used where the laminate has been severely
damaged and access can be obtained to both sides. If not, then the
procedure described in Section 7.3.4 should be used.
A hole should be cut around the damaged area making sure that all
damaged laminate is removed. The edges of the hole should be filed down
to a wedge shape, preferably working from both sides, to give the shape
shown in Fig. 7.2. The back of the laminate should be sanded down at least
75 mm all round the hole and all dust and loose particles removed.
For large holes a temporary mould should be built around the hole on
the gelcoat side, contoured to the shape of the original moulding. For small
holes a sheet of metal or hardboard will suffice. This temporary mould may
be fixed to the laminate with bolts, using large washers where contact with
the laminate occurs. The bolts should be close to, but clear of, the repair
area. Before fixing in position, the temporary mould should be polished to a
high gloss finish with several coats of silicone-free wax polish and finally
coated with PVA release agent.
A layer of suitably pigmented gelcoat should be brush applied to the
temporary mould surface from the back of the laminate, taking care to

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MAINTENANCE AND REPAIR OF FRP STRUCTURES 119

Temporary mould New

Laminate repai r
Fig. 7.2. Hole repair where access can be obtained to both sides of the damaged
laminate.

work it well into the cut edges of the laminate at the mould surface. Once
this has cured a second layer of gelcoat should be similarly applied and
allowed to cure.
Meanwhile, pieces of chopped strand mat should be tailored to fit the
hole, preferably using the same weight as in the original laminate, if known.
When the gelcoat is touch dry, a coat of laminating resin system should be
applied, into which is placed the first layer of mat. Resin should be worked
through the mat using a brush with a stippling action to ensure that all air
bubbles are worked out, particularly at the cut edges of the old laminate.
This procedure should be repeated until the hole has been filled flush with
the existing surface. The resin system should then be allowed to cure before
proceeding further.
Once the resin has cured the temporary mould can be removed and the
bolt holes plugged with a filled resin system. Now the back of the laminate
should be covered with four to six layers of chopped strand mat in exactly
the same way as for small impact fractures. This laminate should preferably
just cover the previously filled bolt holes as well.
Any low spots or blemishes on the gelcoat side can be filled with
pigmented gelcoat and finally sanded smooth and polished. The final finish
is unlikely to be as good as the original moulded finish and the repaired area
will most likely always be just visible.

7.3.4 Repair of holes where internal access is impossible


Occasions may arise where a structure needs repair but access can only be
gained to the outer surface. Here a slightly different repair procedure has to
be adopted.
The damaged laminate must be cut out as for other types of repair and

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120 FRP TECHNOLOGY

the edge filed to a wedge shape. For preference the hole should not be
circular. The back of the laminate around the edge of the hole must then be
abraded with coarse sandpaper and all loose dust particles removed. Next a
piece of strong cardboard or thin plywood should be cut somewhat larger
than the hole but of such a size that it can be manoeuvred through the hole;
hence the reason for not cutting a circular hole. Two pieces of wire are
pushed through the board or wood, positioned so that it can be pulled
firmly against the back of the laminate.
Two pieces of chopped strand mat, fully impregnated with resin system
and cut to about the same size as the wood or cardboard plug are placed on
the plug and the whole assembly tightened against the back of the laminate
by twisting the protruding wires around a rod on the front of the laminate
(Fig. 7.3, stage 1). The resin system is then allowed to cure overnight.
The next morning the wires are cut off as close to the new laminate as
possible. The repair is then completed as for small impact fractures; see
Section 7.3.2.

7.3.5 Repairs to pipes


In some instances damaged pipes may be able to be repaired by similar
techniques to those already described. However, in this case it is the
internal surface which must be smooth. In addition, in order to restore at
least some of the hoop stress to the pipe, the repair should be wrapped with

Stage 1
Temporary support

Stage 3 Cellophane
i~~~i~llieliiiirRepair gelcoat
Fig. 7.3. Repair to hole where access to back of laminate is impossible.

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MAINTENANCE AND REPAIR OF FRP STRUCTURES 121

woven glass tape or continuous rovings or a combination of the two, taking


the wrapping many times around the pipe until sufficient thickness of wrap
has been built up.
Any such repair should be tapered at the edges to prevent any sudden
change in the rigidity of the pipe. Clearly, doubling the thickness of a pipe
in a small area will increase the rigidity and decrease the flexibility of the
pipe in that area. This effect should be considered when making a repair.
With any pipe repair, care should be taken to select a resin system with a
similar or better chemical resistance than that used for the original pipe,
otherwise failure may occur at the repair. Also care should be taken to
ensure that no glass fibres protrude through the resin system and thus come
into contact with the contents of the pipe. If this does happen any liquids
present are likely to wick up the fibres and result in more widespread
damage.

REFERENCE

I. The Manual of Glass Fibre Maintenance. International Paint Ltd, Yacht


Division, Southampton. Also Beetle Polyester Resins, British Industrial Plastics
Ltd, Warley.

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Chapter 8

SITE APPLICATION OF LAMINATES

8.1 INTRODUCTION

Apart from the wide and varied use of fibre reinforced resin systems under
factory conditions, where the working environment can be controlled,
these materials are also used under site conditions. Here, frequently the
resin systems have to be applied under prevailing conditions, which may
range from hot dry deserts through to freezing northern latitudes.
Clearly, with such a range of working conditions great care has to be
exercised in choosing the resin system to be used. Under many circum-
stances epoxide resin systems come to the fore in spite of their generally
higher cost. For example, where ambient temperatures reach 40-50°C
under desert conditions the lack of volatile constituents, such as styrene, in
epoxy systems means that they can be handled without undue risk to
operators and without any fear of under cure through styrene loss. In
addition, the shelf-life of epoxide resins and curing agents is not shortened
by storage under such conditions. Indeed it is known that one such system
was stored for three years in an open compound in the Sahara Desert
before use. When examined and used after that time the system showed no
detrimental effect. This does not mean, however, that resin suppliers either
recommend or condone such action.
At the other extreme, where temperatures approach O°C and where
substrates are damp, epoxy systems, if correctly chosen, frequently offer
better adhesion than polyester systems, whilst if a polyester system is used
it will almost certainly be with an amine accelerator and benzoyl peroxide
as catalyst. In general, resin systems are not recommended for use below
DoC unless some form of heat cure can be provided and unless the substrate
is completely free from ice.

122

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SITE APPLICATION OF LAMINATES 123

Between these climatic extremes both epoxy and polyester systems find
wide application.
One area where epoxide resin systems are frequently used is in the lining
and repair of steel storage tanks, in particular those used for the storage of
crude or refined oil products. The application techniques used can equally
well be applied to a variety of other steel structures and are described
below. In certain areas of the world, notably the United States of America,
polyester resins and latterly vinyl ester resins have been used successfully
for oil tank repairs instead of epoxide resin systems. The basic application
principles are the same and will not be described separately.
Another major area where laminate linings and repairs are used is on
concrete structures. Concrete frequently develops shrinkage cracks and
through settlement of structures major cracks can develop. These permit
either entry or loss of liquids including water and effluent. In addition,
concrete is liable to chemical attack, particularly under acid conditions.
Laminates are frequently used to overcome such problems. The choice of
resin system must depend on circumstances such as application conditions,
temperature~ both applicational and operational ~and chemical environ-
ment. Polyester, vinyl ester and epoxide resin systems are all used for such
applications. A typical example of a concrete structure frequently in need
of repair is a swimming pool. Here a laminate, when properly applied, is
eminently successful.
A third area where site applied laminates are used is in the jointing
and repair of pipelines. These may be GRP, steel or concrete. The general
procedure is to plug the leak and bandage the pipe with a resin impregnated
woven tape. This can serve as a permanent joint or a temporary or
permanent repair.
Apart from lining and repair applications, several companies have
developed processes for the construction of GRP tanks on site. These are
mostly constructed from preformed sections assembled on site and then
wrapped with resin impregnated continuous glass rovings. By this means
very large tanks can be assembled without the problems of transporting
them to site after factory construction.
There are no doubt many other applications where laminates have been
successfully used. Two which come to mind are the DJ.Y. car and boat
repairs. Here kits are available, complete with full instructions on how to
carry out the repair. In all cases a successful repair depends on adequate
surface preparation, correct choice of material for the repair and com-
petent application.

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124 FRP TECHNOLOGY

8.2 STEEL STRUCTURES

In the main, resin glass laminates are used either to completely line steel
tanks to provide corrosion protection or to provide a leak tight repair to
corroded tanks. In the first case the laminate will cover the walls and floor,
in the second it may only be required over the floor and about O· 5 m up the
walls. With old riveted tanks the problem is frequently leakage through
rivets which have worked loose over the years. Here a seam repair may be
quite adequate.
To illustrate the procedures necessary to carry out a tank repair let us
consider a large crude oil storage tank of approximately 100 m diameter,
with a floor area of 7854 m 2 (84 540 ftl), located in a desert in the Middle
East, which is leaking through corrosion around some of the seams and
overall pitting of the floor. A typical tank is shown in Fig. 8.1.
Such a tank will be offully welded construction with overlap welds and a
floating roof, supported on numerous legs when the tank is empty. Access
will typically be through two manholes and a sludge port, although it may
be possible to cut a large hole through the side of the tank if this is strictly
necessary. Headroom around the sides of the tank is likely to be about 2 m
reducing to about 1·5 m towards the centre of the tank. Numerous
projections will be found protruding from the roof on the underside,
particularly around the side of the tank. During the summer months the
working temperature inside the tank will reach 40- 50°C or higher,
dropping at night below dew point so that condensation occurs on all

Fig. 8.1. A typical large capacity floating roof crude oil storage tank.

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SITE APPLICATION OF LAMINATES 125

surfaces. This condensation may run down the sides of the tank and carry a
thin film of oil onto the working surface. Due to the prevailing temperature
conditions an epoxide resin system will almost certainly be selected for the
repair.
The following is a typical repair procedure but does not comprise a
working specification.

8.2.1 Initial preparation


The tank should be gas-free, grease-free and lead-free when handed over to
the contractor. All valves and pipes should be blanked off to prevent grit
from getting into them or oil from seeping out. Suitable power supplies,
ventilation and lighting facilities should then be installed.
The floor of the tank and approximately I m up the shell plates should be
grit-blasted to a dull grey metal finish; Swedish Standards Association SIS
05 59 00 grade SA 24 or Steel Structures Paint Council, USA Standard
SP6-63 is suitable. Since used grit and dust will cover the freshly blasted
surface, blasting can generally continue for 6- 8 h without noticeable
deterioration of the clean steel surface, even under high humidity
conditions. All grit and dust should then be removed, finishing with a
vacuum cleaner to remove the final layer of dust. The exposed steel surface
must then be immediately primed with a properly formulated two-pack
epoxide resin primer (either amine adduct or polyamide cured). Zinc-rich
primers are not recommended since they have too Iowa cohesive strength
for adequate bonding of the laminate. This procedure is repeated daily until
the grit-blasting has been completed. The tank should then be thoroughly
cleaned, including the underside of the roof, to remove all grit and dust.

f
Holes greater than 1 cm in diameter should be covered with a grit-blasted
and primed steel plate, which may be stuck in position with the laminating
. Resi" "hesive Steel plate

I Re""-;tY~~I..",,,~~ l I l
Fig. 8.2. Holes in tank floor filled with resin putty or covered with new steel plate.

f ~eSin putty

I
Fig. 8.3. Overlap weld.

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126 FRP TECHNOLOGY

t
I
6 - 10 em
filled resin fillet
I
.j.

: '
:..G - 10 em .. :
I '

Fig. 8.4. Curb angle fillet.

resin system (Fig. 8.2). Smaller holes and pitted areas should be filled with a
resin based putty to give a smooth surface on which to apply the laminate
(Fig. 8.2). Likewise overlap welds (Fig. 8.3) and the curb angle between
floor and shell plates (Fig. 8.4) should be filled, the latter using a sand filled
resin mix. Badly pitted or corroded areas should then be covered with a
laminate so that they receive a double thickness laminate by the time the
tank has been completed.

8.2.2 Laminate application


A typical laminate consists of two la yers of chopped strand rna t (300 g/m 2)
or two layers (450 g/m2), plus a surfacing tissue, impregnated with an
epoxide resin system. The resin system generally used consists of a fairly
low viscosity resin O· 5- 2·1 Pa s) such as Epikote 816t, together with a two-
part curing agent such as Curing Agents DX ISO and DX 15It or
Ancamine TL and TLS:::' These are formulated aromatic amine based
curing agents specifically developed for tank laminating applications. One
of the components is fast reacting, the other slow reacting, so that they can
be blended together in any ratio to accommodate a wide variety of
application temperatures within the range 5°C to about 50°C, providing
that the blend is always used in the correct proportion. Full details of the
use of these systems can be found in the manufacturer's data sheets.
For ease of application a 50% overlap of chopped strand mat is usual
(Fig. 8.5), with the laminate built up wet on wet. A flood coat of resin
system is applied by brush or roller and the first layer of mat placed on top.
tShell Chemicals U.K. Ltd.
!Anchor Chemical Co. Ltd.

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SITE APPLICATION OF LAMINATES 127

Surfacing tissue

~ Chopped strand mat with 50% overlap


Fig. 8.5. Laminate with 50";;' mat overlap.

The mat is then rolled with a laminating roller to ensure thorough wetting of
the glass. Further resin is applied followed by the second layer of mat. Next
the surfacing tissue is applied and the whole laminate rolled to ensure
thorough wetting of the reinforcement and to displace all air bubbles. The
procedures used are similar to those used for hand lay-up contact
moulding. The finished laminate should contain between 70 and 75% by
weight resin, 25~ 30% glass.
Although a surfacing tissue is not essential it does help to ensure that
there are no pinholes in the laminate, particularly since most binders used
on chopped strand mats are insoluble in epoxide resin systems and so the
mat retains its original structure in the laminate. It also covers all the fibres
in the mat and prevents them from sticking up and gives a resin-rich
chemically resistant finish which is easy to clean.
Where roof leg supports are encountered the usual procedure is to jack
them up, apply the laminate to the tank floor and then while the resin
system is still wet, a 12 mm thick, 450 mm square steel plate is placed on top
of the laminate under the leg. The leg is then lowered and the resin system
allowed to cure. The weight of the leg forces the plate into the laminate and
this helps to bond it in position. The purpose of the steel plate is to prevent
the leg from cutting through the laminate each time the tank is emptied
(Fig. 8.6).
Once the laminate has cured it should be checked for pinholes using a
high voltage holiday detector (set at 1O~ 12 kV). Any pinholes found can be
covered with another layer of laminate. Before this is applied the cured
laminate should be sanded down and coated with resin. A layer of chopped
strand mat and surfacing tissue can then be applied in the normal way.
If required, the whole laminate can be coated with a topcoat once all
defects have been rectified. This may consist of a further coat of the
laminating resin system or alternatively a coat of a fully pigmented epoxide
resin based paint. Where the tank is to be used for storage of refined
petroleum products, this topcoat must pass the normal requirements for
gum leaching, etc.

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128 FRP TECHNOLOGY

Roof support leg

r-i'-----....,L- Stee 1 p1ate

Steel tank floor

Fig. 8.6. Roof leg support plate.

One point worth noting is that since operators have to walk across the
cured primer and laminate at various stages during the operation, con-
tamination of the surface by oily residues can occur. These residues can be
removed by wiping the surface to be overcoated, with clean rags soaked in a
suitable degreasing solvent, e.g. xylene.
With riveted tanks, in addition to the above procedures, it is necessary to
fill around the rivet heads to ensure a smooth surface is available for
laminating (Fig. 8.7).

8.2.3 Alternative laminating procedure


Although hand lay-up with chopped strand mat is probably the most

putty

Fig. 8.7. Filled resin system applied to riveted seams.

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SITE APPLICATION OF LAMINATES 129

widely encountered procedure for tank repairs, spray lay-up is also used.
Here, a resin spray gun fitted with a chopper attachment is used, the
procedure adopted being very similar to that used for factory operations.
The resin and glass are sprayed onto the steel substrate and thoroughly
rolled to ensure complete wetting of the glass and to dispel all trapped air
bubbles. A minimum of two passes with the spray gun is necessary to give
adequate pinhole-free coverage. The resin system may be different from
that used for hand lay-up but choice will still be governed by application
conditions.
With spray application, the quality and particularly the thickness of the
finished laminate is very much more dependent on operator skill than
where chopped strand mat is used. With a final laminate thickness of
between 2 and 3 mm, it is clear that only 1 mm under or over thickness on
an area of 7854 m 2 can result in a very substantial difference in material
consumption. In addition, very careful selection of spray equipment is
necessary to ensure that any cross-winds blowing through the tank do not
deposit the glass in a different position from the resin. This has been known
to occur, resulting in a poor quality, variable thickness laminate. With
modern equipment this should not be a problem.
A further modification is the incorporation of glass flakes into the resin
system. This is claimed to increase the chemical resistance of the resin by
providing a glass-rich surface.

8.2.4 Alternative resin systems


Where climatic conditions permit, polyester and vinyl ester resin systems
can be used. Application procedures are similar to those used with epoxide
resin systems. Although a polyester primer is often used, properly
formulated epoxide resin primers can be equally effective.

8.3 CONCRETE STRUCTURES

Polyester and epoxide resin systems are equally effective for the lining and
repair of concrete structures. The main criteria for deciding which to use
are: service conditions; application temperature; environmental con-
ditions; and material cost (only applicable if either material is suitable).
Concrete, unlike steel, is prone to cracking. These cracks may be small
surface cracks, static settlement cracks or moving cracks, i.e. ones which
open and close as the load on the structure fluctuates or ones which
open and close with temperature changes. There are also invariably

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130 FRP TECHNOLOGY

Fig. 8.8. Laminate failure at junction between steel and concrete.

expansion joints built into the structure. Surface cracks and static cracks
can invariably be filled and a laminate applied over them. Moving cracks
and expansion joints, however, present a much more difficult proposition
and the use of a rigid laminate may be impractical. Since the sealing of such
cracks can vary widely from one location to the next, the advice of an
experienced contractor should be sought-indeed the solution may lie
elsewhere than with a laminate. Figure 8.8 shows the effect of bridging a
joint between a concrete bottom in a steel tank and the steel manhole.
Temperature fluctuations and movement of the tank wall on filling and
emptying the tank resulted in a split in the laminate. This allowed fuel to
seep into the concrete and subsequently leak from the tank.

8.3.1 Crack treatment


With purely surface cracks it is probable that the normal preparation
techniques described in Section 8.3.2 will suffice, no special treatment being
required.
With deeper or wider cracks and ones which allow fluids either into or
out of the structure, it is normal to pressure grout these with either an
epoxide resin or polyester resin grout. The normal procedure is to chase out
the crack, inset pressure injection non-return valves or just plastic tubes at
about 15 cm intervals and then cement these in place with a fast setting
resin putty, making sure that this also seals the intervening length of crack

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SITE APPLICATION OF LAMINATES 131

Fig. 8.9. Plastic grouting tubes in position in a crack.

(Fig. 8.9). The resin grout is then pumped in under pressure, taking care
that the pressure used is not high enough to cause further damage to the
structure. Once the grout has cured the protruding injection tubes can be
broken off and the whole area made good with a resin putty.
The alternative to grouting is just to chase out the cracks and fill with a
resin putty (Fig. 8.10). This, however, will leave the crack open to the
environment on one side and may give rise to problems at a later date.

8.3.2 Preparation of concrete substrate


The concrete must be mechanically sound, clean, dry, free from oil, grease
and animal fats, paint and any other contaminants. It should also be at
least 28 days old. If oil and grease are present these are best removed by
scrubbing with a detergent solution. Paint can be removed by one of the
mechanical preparation techniques given below. If acid etching is to be

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132 FRP TECHNOLOGY

resin

Concrete

Fig. 8.10. Crack in concrete chased out and filled with a resin based putty.

used for surface preparation then the paint must be removed first. In this
case the paint can probably be removed with a wax-free paint stripper.
Concrete less than 28 days old will not have developed 'full' strength,
thus preparation of the surface by any means is likely to cause considerable
damage. Additionally, the curing reaction of the concrete will still be taking
place and since this involves water, application of a laminate will either seal
in the excess water present or deprive the concrete of water if forced drying
techniques have been used. The surface may also be highly alkaline, which
may inhibit cure of the resin system at the interface between the resin and
the concrete. The end result may well be an inferior laminate with poor
adhesion to the concrete. Whilst these remarks are generally true, there
may be circumstances where the concrete can be treated after a shorter cure
period. Here, the advice of an experienced resin contractor is essential.
Where it is known that a laminate is to be applied to a concrete surface at
the design stage, a wood float finish should be specified. This will give a
fairly smooth surface without too deep a layer oflaitance. It should also be
impressed on the contractor that the same care should be taken in finishing
the concrete as would be the case if no laminate was to be applied. Blow
holes and poor compaction of the concrete, particularly on vertical
surfaces, can result in an expensive filling operation before a laminate can
be applied.
Laitance is the fine layer of cement which comes to the surface when
concrete is placed. It has poor cohesive strength and is very weakly bonded
to the body of the concrete.
The concrete surface should be grit-blasted to remove alliaitance and
other loose material, preferably until the aggregate has been exposed. A

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SITE APPLICATION OF LAMINATES 133

light flash blast is rarely sufficient and the degree of blasting may well be
equivalent to that needed for a steel substrate. Alternative techniques,
generally only applicable to horizontal surfaces, include scabbling, scarify-
ing or grinding with a mechanical grinder. Once the surface has been
adequately prepared, all loose material should be removed and the surface
finally cleaned with a vacuum cleaner. If wet scabbling or grinding has been
carried out the surface may be covered with hard packed dust. This must be
removed before any resin is applied.
If the prepared concrete surface is badly pitted it may be necessary to
apply a filled resin system to give a smooth surface on which to apply the
laminate. Where a graded sand filler is available a filler to binder ratio of up
to about 10: 1 may be used, although a finer filler may sometimes be
preferable.
Grit-blasting or other mechanical means of surface preparation ge-
nerates a large volume of grit and dust, which if carried out in a factory,
may result in damage to equipment, particularly if it settles on moving
parts. An alternative procedure is to use acid etching. Here a 10-15%
solution of hydrochloric acid is applied to the concrete at a rate of about O· 5
litre/m 2 using a stiff brush to work the acid into the surface. (Commercial
muriatic acid~concentrated hydrochloric acid~is a 30% solution.) This
should cause bubbling of the surface. If this does not occur then it is
probable that the concrete has been hardened with a silicate treatment or
modified in some other way, in which case mechanical surface preparation
will have to be used. The normal safety precautions applicable to the
handling of acids must be observed while acid etching is carried out. Also
all metal machine parts should be carefully covered with a layer of grease or
strippable coating to protect them from the possible corrosive effects of
hydrochloric acid fumes.
Once bubbling has ceased the surface should be washed thoroughly with
water. If any acid remains this can be neutralised with a dilute solution of
ammonia, followed by washing with water. The concrete must then be
allowed to dry to ensure adequate adhesion of the resin system.
If cracked reinforced concrete is to be etched, it is preferable to flush the
surface with water first to fill the cracks with water to minimise penetration
of the acid. In this case neutralising with dilute ammonia solution after
etching is desirable.
Once the concrete surface has been adequately prepared and is dry, it
should be coated with a primer by brush, roller or spray. This should seal
the surface in readiness for application of the laminate.
With a polyester primer the addition of up to 25% by weight of styrene is

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134 FRP TECHNOLOGY

desirable to assist penetration of the concrete. With an epoxide resin primer


this should be unpigmented and preferably solvent based, although a low
viscosity solvent-free system may be acceptable.

8.3.3 Application of the laminate


The laminate can be applied by hand or spray lay-up techniques using
either a polyester or epoxide resin system.
With hand lay-up a typical laminate would consist of two or more layers
of chopped strand mat (either 300 gjm 2 or 450 gjm 2 ) plus a surfacing
tissue. Alternatively two or more layers of plain weave cloth (300 gjm 2 )
plus a surfacing tissue may be used. These should be applied with either a
5-8 cm overlap or a 50% overlap (Fig. 8.5). Final laminate thickness
should be not less than about 2· 5 mm.
The resin system should be applied to the substrate by brush or roller and
the glass mat placed in the resin. The resin should then be worked through
the mat using a laminating roller, until the mat has been completely wetted
out, with no resin-starved areas and no visible air bubbles. This procedure
should be repeated with each layer of mat until the desired laminate
thickness has been achieved, when the surfacing tissue should be applied.
With thick laminates it may be necessary to allow the system to gel after
several layers of mat have been applied to prevent the laminate from
becoming unmanageable and to prevent excessive exotherm build-up.
Whichever system is adopted the surfacing tissue should be applied before
the resin system in the last layer of mat has gelled. On vertical surfaces it
may be necessary to add a thixotroping agent to the resin to prevent run-
off.
With spray lay-up, resin and chopped glass fibres are deposited onto the
substrate and rolled thoroughly to ensure complete wetting out of the fibres
and displacement of all trapped air bubbles. A minimum of two passes
should be used, aiming for a minimum laminate thickness of about 2· 5 mm.
If a thick laminate is to be applied by spray lay-up it may be necessary to
build up the required thickness in stages, allowing the resin system to get
between each stage.
Once the laminate has been completed it should be thoroughly inspected
for any obvious pinholes, poorly wetted glass, resin-rare areas, entrapped
air bubbles or exposed glass fibres. Defects can be repaired by sanding
down the area concerned plus at least 10 cm all round and then applying a
further layer of mat well impregnated with the resin system. Defects can be
seen fairly readily if an unpigmented laminating resin system has been used
but can be masked by a pigmented system.

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SITE APPLICATION OF LAMINATES 135

For maximum chemical resistance a topcoat of resin should be applied.


This may differ from the laminating resin system and will have been
selected to give maximum chemical resistance. It may also be pigmented or
filled to give a decorative or abrasion resistant finish.
With polyester systems either a commercial topcoat should be used or
paraffin wax (0·6%) added to the resin to ensure that air inhibition does not
occur. The system should be formulated to have a gel time of not more than
15 min.
Full cure of the topcoat will generally take about I week at normal
ambient temperature after which time it should be rubbed with an acetone-
soaked rag to check for cure. If it is softened or dissolved then it is under
cured. To rectify this may mean sanding down to the laminate and re-
application of the topcoat.

8.4 WOODEN STRUCTURES

Laminates may be successfully applied to wooden structures to render


them impermeable. Two examples are the coating of wooden boat hulls and
the lining of wooden tanks or troughs. These operations may be carried out
both on site and under factory conditions.
Firstly, the wood surface must be thoroughly cleaned and old paint, etc.,
removed. Grease and dirt may be removed with a degreasing solvent. The
surface should then be rubbed down with a coarse sandpaper to give a
rough finish to improve adhesion of the resin system. This is particularly
important with hardwood surfaces. All sharp edges should be rounded off.
Before any resin is applied the wood surface must be thoroughly dry. A
prime coat of resin should be applied and allowed to soak into the surface.
In the case of a polyester, this would consist of the resin plus catalyst and
accelerator, diluted with styrene (2 parts resin to I part styrene). With an
epoxide resin system a two-pack unpigmented solvent based system,
diluted with thinners, would be used.
Once the primer has cured, all holes and cracks can be sealed with a resin
based putty. The surface is then ready to receive the laminate. This may be
applied by hand lay-up, using chopped strand mat (I layer, 450 g/m 2, or 2
layers, 300 g/m2), or by spray lay-up. To produce a relatively smooth finish
a surfacing tissue should be applied while the laminating system is still wet.
When the resin has cured any protruding glass fibres should be smoothed
off with fine sandpaper. The surface should then be sealed with one coat of

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136 FRP TECHNOLOGY

gelcoat plus one coat of topcoat, in the case of a polyester laminate, or two
coats of an epoxy paint, in the case of an epoxy laminate.
Care should be taken in finishing off the laminate at the edges. These
should preferably be butted up to a strip of wood or trimmed and feathered
down before applying the topcoats. The resin system should be allowed to
fully cure before being put into service.

8.5 REPAIRS TO PIPELINES-CONCRETE,


STEEL OR THERMOPLASTIC

Where pipeline repairs are contemplated the factors which need to be taken
into account include the following: accessibility; pipeline operating
temperature and pressure; application conditions; pipeline contents. There
may also be local factors which have a bearing on the choice of material for
the repair.
Whichever type of pipeline is to be repaired, whether it is steel, concrete,
GRP or thermoplastic, the first thing to consider is the choice of resin
system to be used. In principle, epoxide, polyester and vinyl ester resin
systems can all be used. In practice choice will depend on circumstances.
Repairs to G RP pipes are also discussed in Chapter 7.
The second factor to be considered is surface preparation. The best
preparation technique for steel or concrete is grit blasting. However, this is
frequently impractical and so alternatives have to be used. In all cases rust,
paint, tape wrapping, oil, grease and other contaminants must be removed.
The substrate should then be roughened by hand wire brushing, mechani-
cal sanding or hand sanding with an abrasive paper or cloth. Mechanical
wire brushing usually causes polishing rather than roughening and is
therefore usually unsuitable.
If the hole or crack is of a reasonably large size it should be plugged by
some appropriate means. This may be by filling with a fast setting resin
putty, by hammering in lead strips or covering with a sheet of steel or some
other material. Next a coat of resin system is applied by brush or roller and
a woven tape wrapped around the pipe. Resin system and tape are then
applied alternately until sufficient laminate thickness has been built up. By
using fast setting resin systems and applying heater bands around the pipe
rapid cure can be achieved, with the pipe being returned to service shortly
after the repair has been completed.
Modifications which have been used include wrapping the laminate with
aluminium or steel sheet held in place with steel bands and also clamping on

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SITE APPLICATION OF LAMINATES 137

preformed metal collars. In these ways quite adequate temporary and


sometimes permanent repairs can be made with a considerable saving in
cost and time compared with replacing a section of pipe.

8.6 ON-SITE TANK PRODUCTION

To avoid the problems of transporting large factory-made tanks to site and


to shorten erection time, several firms have developed techniques for the
fabrication of large tanks on site. Construction time is generally con-
siderably less than that required for the erection of similar size steel or
concrete tanks.
Fontana Products Ltd, Australia, manufacture lightweight large ca-
pacity storage tanks in kit form. 1 These are known as 'ribbed' tanks and
have capacities of up to 90 m 3 . Recently this range has been extended to
include tanks with capacities of up to 880 m 3 . Whilst with this latter range
diameter is kept constant at 12· 5 m, height is increased from 1·83 m for a
220 m 3 tank up to 7·32 m for a 880 m 3 tank. Wall thickness varies from 9 to
22mm.
The bottom and sides of the tank are made from preformed GRP sheets
with a resin-rich gelcoat, assembled together using a polyester putty. All
joints are covered on the inside of the tank with glass mat laminate followed
by a topcoat. The external shell is reinforced with alternate layers of
pultruded GRP rods and spray lay-up. Finally a topcoat of resin is applied.
The tank top is made from 21 factory moulded segments assembled
round a central dome.
Other companies make large tanks on site by filament winding. Selip
SpA, ltaly,2 use preformed GRP sheets to construct a horizontal mandrel
up to 6 m diameter by 20 m long. This is then rotated and wrapped with
resin impregnated rovings by normal filament winding techniques. These
tanks find use as storage tanks and silos. Vetroresina SpA, Italy, also
construct large tanks on site in a similar way. 3 They transport all necessary
filament winding equipment and preformed panels to site and wind in situ.
They have constructed tanks up to 8· 5 m diameter by 10 m high in this way.
Two other companies have developed techniques for filament winding
on site onto vertical mandrels. In both cases a vertical mandrel is
constructed from GRP sheets. This is then wrapped using a filament
winding machine mounted on a track which runs around the tank. In the
process developed by Sovap SA, France, 2 winding commences at the top
and moves downwards. Maximum diameter is 10 m. In the process

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138 FRP TECHNOLOGY

developed by Holson SpA, Italy,2 winding is carried out from bottom to


top. Maximum diameter is 25 m.

REFERENCES

1. Anon. (1978) Reinforced Plastics, May, 144.


2. Anon. (1979) Modern Plastics International, August, 14.
3. Anon. (1976) Vetrotex Fibreworld, No.2, 15.

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Chapter 9

POLVESTER RESINS

9.1 INTRODUCTION

Polyester resins can be divided into two classes, (i) the so-called saturated
polyester resins such as polyethylene terephthalate or 'Terylene', a
thermoplastic material used for injection moulding and fibre production
and (ii) the unsaturated polyester resins which can be cross-linked, by the
addition of a suitable catalyst, into thermoset polymers. It is only these
latter materials which will be considered here.
Unsaturated polyester resins are variously referred to as UP resins,
polyester resins or just simply polyesters.

Fig. 9.1. Post Office Building, London. Clad with white GRP panels moulded by
Anmac Ltd, with Crystic resin from Scott Bader. (Courtesy of Scott Bader Co. Ltd.)

139

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140 FRP TECHNOLOGY

Fig. 9.2. Terminal 2 passenger walkway, Heathrow Airport, London. Moulded in


GRP by Anmac Ltd, with Crystic resin from Scott Bader. (Courtesy of Scott Bader
Co. Ltd.)

Unsaturated polyester resins form the bulk of all resins used for
laminating applications and are without doubt the best known for
laminating. They are also used for button manufacture and to a lesser
extent for the manufacture of synthetic marble and as encapsulating resins.
Many different types of resin are now available from a large number of
suppliers. Many of these resins have been developed for specific end use
applications or for use with specific processes such as continuous sheet
production or resin injection.
Some typical applications of polyester resins in buildings are shown in
Figs. 9.1 and 9.2.

9.2 POLYESTER RESINS

The basic materials used to make a polyester resin are a dibasic organic acid
or anhydride and a dihydric alcohol (glycol). To obtain a polymer chain
which can be cross-linked into a thermosetting resin, a proportion of the
dibasic acid must contain an unsaturated group or double bond. This

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POLYESTER RESINS 141

unsaturation must be non-aromatic otherwise cross-linking will not take


place. For example, styrene (vinylbenzene) will react through the pendant
vinyl group in the presence of a peroxide catalyst, whilst the benzene
nucleus does not react.

Styrene

A simple polyester resin might be prepared from propylene glycol,


maleic anhydride (unsaturated) and orthophthalic anhydride (saturated
-in this context). By varying the ratio of the two anhydrides, the
cross-linking reactivity of the polyester can be varied from high to low. A
high reactivity polyester resin contains a high proportion of unsaturation.
The polymer formed in this way is a solid or semi-solid thermoplastic
material which could be converted into a thermoset by the addition of a
suitable catalyst; it would, however, be far too brittle for commercial use.
By varying the glycol and dibasic acids used, a whole family of polyester
resins can be made.
In order to convert this thermoplastic material into a usable resin for
laminating, a further component is necessary. This is a low viscosity,
unsaturated monomer such as styrene. This monomer acts as a solvent for
the polymer chain, viscosity reducer and cross-linking agent. During cure
the monomer links the polymer chains together through the unsaturated
reactive groups, to give a usable product.
Thus it can be seen that there are four components needed to produce a
usable resin, namely: (i) a glycol, (ii) an unsaturated dibasic acid, (iii) a
saturated dibasic acid and (iv) a reactive monomer. One further component
is needed to obtain a liquid polyester resin with an acceptable storage life
and that is an inhibitor. This is added after the polyester resin has been
manufactured, to prevent premature gelation during storage.
Each of these components will now be discussed briefly in turn.

9.2.1 Glycols
Many different glycols are commercially available, over a wide price range.
Clearly, from a commercial point of view, the cheapest glycol, providing
that it gives a satisfactory resin, will be chosen.
The simplest glycol is ethylene glycol. This can be used but gives
polyester resins with a marked tendency to crystallise and which have
limited compatibility with styrene. For this reason it is generally used in

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142 FRP TECHNOLOGY

conjunction with other glycols or, if used alone, the resin is acetylated or
propionylated.
The next glycol in the series is propylene glycol (propane-l ,2-diol). This
gives non-crystallising po)yester resins completely compatible with styrene
and is also relatively cheap. Thus it is used in the bulk of all polyester resins
produced today.
Other glycols in use include the following:
Diethylene glycol - This gives resins with improved flexibility.
Dipropylene glycol - This gives some improvement in flexibility
coupled with better chemical resistance.
Neopentyl glycol - This gives resins with improved chemical
resistance, particularly to alkalis, and im-
proved hydrolytic stability. It may need
blending with other glycols to improve the
styrene compatibility of the resin.
Polyester resins with high chemical resistance are frequently made from
bisphenol A [2,2-bis(4-hydroxyphenyl)propane] or its hydrogenated ho-
mologue [2,2-bis(4-hydroxycyclohexyl)propane]. These resins exhibit im-
proved alkali resistance in addition to generally high chemical resistance.
Such resins are usually heat cured to obtain maximum chemical resistance.
In order to produce a glycol suitable for reacting with organic acids, the
bisphenol A may be pre-reacted with ethylene oxide or propylene oxide.
Flame retardancy can be introduced into the molecule by using
chlorinated or brominated diols. One such product is Diol III from U gine
Kuhlmann. This is N N' -bis (ethan-2-0 1) diamino-octachlorodiphenyl.
Resins prepared from this diol not only exhibit flame retardancy but also
high chemical resistance. An example of a brominated diol is dibromo-
neopentyl glycol. This again gives some fire retardancy coupled with
improved chemical resistance.
By incorporating a small proportion of a polyhydric alcohol, say 5%, a
hard heat resistant resin can be produced. Examples of polyhydric alcohols
in use include glycerol, pep.taerythritol and mannitol.

9.2.2 Unsaturated acids


The unsaturated acid present in the polymer chain enables it to be cross-
linked. The higher the proportion present, the higher the degree of cross-
linking, the higher the heat distortion temperature of the cured resin, but
the lower the elongation at break and tensile strength. This component also

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POLYESTER RESINS 143

affects the reactivity ofthe resin. The higher the degree of un saturation, the
higher the reactivity of the resin.
Reactivity and cured properties can be modified by blending a saturated
dibasic acid with the unsaturated dibasic acid. This procedure is adopted
with most commercially available resins.
The most commonly used unsaturated acid is maleic acid
(m.p. 132-140°C), generally used as the anhydride (m.p. 60°C) due to its
lower melting point. An alternative acid is fumaric acid, the trans isomer of
maleic acid. Although maleic acid isomerises to give fumaric polyester
resins, those prepared from fumaric acid generally have higher softening
points and a greater tendency to crystallise.
Other unsaturated acids, such as chloromaleic acid, itaconic acid and
citraconic acid may be used but are more expensive and therefore polyester
resins based on these acids are uncommon. Problems with stability of such
resins may also arise, particularly with those based on itaconic acid.
Although chloromaleic acid contains 26% chlorine, this is insufficient to
make it an attractive candidate for flame retardant polyester resins, unless
supplemented by other chlorine containing components.

9.2.3 Saturated acids


The term saturated is used to describe those dibasic acids or anhydrides
which do not contain pendant double bonds which react in the presence of
a peroxide catalyst. They may, however, contain an aromatic nucleus.
The use of orthophthalic anhydride in unsaturated polyester resins was
first suggested to reduce or avoid problems with crystallisation. Resins
prepared with orthophthalic anhydride (often just called phthalic anhyd-
ride since it is the only isomer capable of forming an anhydride) are clear
and have good compatibility with styrene. Since it is a relatively cheap
anhydride and is readily available, and since polyester resins prepared from
it have good all-round properties, it has remained one of the most widely
used anhydrides.
The next most commonly encountered saturated acid is isophthalic
acid. This gives tougher cured resins with improved long term water
resistance and lower volatile loss on heating than resins prepared from
orthophthalic anhydride. Isophthalic polyesters are also used where some
improvement in chemical resistance is required.
The other isomeric form, terephthalic acid, is also used to make polyester
resins. These exhibit properties similar to the ones produced from the other
two isomers.

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144 FRP TECHNOLOGY

(]Cco" (]CCOOH COOH COOH

I
0-.
CO
/0 0-.'
COOH & 0-. COOH ¢ COOH
Phthalic anhydride Ortho- Iso- Tere-
phthalic acids

Flame retardant or reduced flammability resins can be produced from


chlorinated or brominated acids. Two commonly used are tetrachloroph-
thalic anhydride and HET anhydride (hexachloro-endo-methylene-
tetrahydrophthalic anhydride-also known as chlorendic anhydride).
HET anhydride is the more effective due to its higher chlorine content of
55% against 49· 5%. It gives clear flame retardant polyester resins with
improved chemical resistance. Laminates prepared from such resins are
initially colourless but may darken with time even when formulated with
UV absorbers.
Cl
Cl Cl CO

/""
Cl*CO
/"', "'0
0-. /
o
Cl CO CI CO
CI
CI
Tetrachlorophthalic anhydride HET anhydride

Flexibility can be built into the resin by replacing part or all of the
saturated acid by an aliphatic dibasic acid such as adipic acid or sebacic
acid. Resins made from these acids are generally added to conventional
resins to improve flexibility and impact resistance; such resins are rarely
used alone.
By carefully blending two or more dibasic acids together, resins with a
wide range of intermediate properties can be obtained. Thus resins can be
tailored to suit a wide variety of end uses.

9.2.4 Mooomers
The monomer serves two purposes: (i) to act as solvent for the polyester
resin to produce a liquid with a suitable handling viscosity and (ii) to cross-

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POLVESTER RESINS 145

link the polyester chain to give a fully cross-linked thermoset structure.


Styrene is the most frequently used monomer due to its low viscosity, low
cost and ready availability. Another monomer, methyl methacrylate, or
alternatively n-butyl methacrylate, may be used where cured resins with
excellent clarity and UV stability are required. Such resins are used for the
manufacture of transparent roof lights and corrugated sheeting, where
their low refractive index, similar to that of E-glass, renders the glass
virtually invisible (see Table 9.0.

Table 9.1 Refractive indices of resins and glass

Refractive
Material index, n~

Orthophthalic polyester/styrene }·569


Orthophthalic polyester/styrene/light
stabilised }·560
Orthophthalic polyester/methyl methacrylate 1·552
HET acid polyester 1·550
E-glass 1·548
C-glass 1·520

When legislation was introduced to limit the level of styrene fumes in


workshop atmospheres to 100 ppm, other monomers were considered as
alternatives to styrene.! - 3 These alternatives were generally found to be
either too expensive or offered no improvement over styrene in Threshold
Limit Value (TLV). Some of these alternatives are listed in Table 9.2.
A number of devices are available for the detection and monitoring of
styrene fumes.! These may be used for the continuous monitoring of
workshop atmospheres or be used for monitoring the atmosphere breathed
by individual operators. This latter type is worn by the operator.
Diallyl phthalate is used as monomer in prepreg systems and some
moulding compounds because of its lower volatility than styrene. It is,
however, difficult to cure at room temperature and so is restricted to heat
cured systems. Cured systems are tougher than those containing styrene.
Resins containing a-methylstyrene are more flexible than those contain-
ing styrene and show lower shrinkage on cure. Thus a-methylstyrene is
sometimes used in the formulation of potting and encapsulating com-
pounds.
Halogenated monomers which have been considered for improving the
flame retardant properties of polyester resins include dichlorostyrene and

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~
-
Table 9.2 Properties of some monomers

Explosive
Vapour Refrac- Volume limits
Specific Boiling Flash pressure tive Viscosity shrinkage (% v/v in air)
gravity point point at 25°C index at 25°C TLV on cure
Monomer at 20°C (0C) (OC) (mm Hg) n 25 (mPa s) (ppm) (%) Lower Upper ;il
D "C

Styrene 0·902 145 31 6 1·5439 0·75 100 17 1·1 6·1


til
(')
a-Methylstyrene 0·906 165 58 1·5359 0·94 100 =:
Chlorostyrene 1·094 187 80 I 1·5611 0·7 50 12 ~
Vinyltoluene 0·896 167 60 2 1·5393 0·77 100 12·6 0·8 11·0 §
Divinylbenzene 0·908 195 24 1·5748 0·98 1·1 6·2 ><

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Methyl acrylate 0·952 80 10 1-4020 0·50 10
Methyl meth-
acrylate 0·943 100 10 38 1·4118 0·84 100 21 2·1 12·5
n-Butyl acrylate 0·89 145 48 10 0·9 10
Diallyl phthalate 1·13 290 166 1 1·519 9·0 11·8
Triallyl cyanurate 150 1·5069
POL¥ESTER RESINS 147

dibromostyrene. Whilst these reduce flammability to a limited extent, their


use has been restricted due to high price.
One of the best monomers found to impart self-extinguishing properties
to polyester resins is diallylbenzene phosphonate. This gives excellent self-
extinguishing properties with almost no effect on other properties. High
cost has, however, limited its use.
Triallyl cyanurate can be used as monomer to produce heat resistant
polyester resins.

9.2.5 Inhibitors
Once the polyester polymer has been dissolved in a monomer, the system
may gel at room temperature in the absence of a catalyst-indeed styrene is
well known for its ability to polymerise on its own in the absence of an
inhibitor. To prevent this from occurring and to obtain an acceptable
storage life for the resin, an inhibitor is added. This is normally added after
the polycondensation reaction has been completed and before the resin is
dissolved in the monomer.
Inhibitors are generally reducing agents which absorb free radicals by

200

2
160
u
0

cv
. 3
So.
......,
~
120

s..
cv
0-
S 80
cv
I-

40

20

0 10 20 30 40 50 6U

Time, minutes
Fig. 9.3. Effect of inhibitor on gel time and cure rate. Formulations: 1, resin
(Vestopa1150) 100, MEK peroxide 2, cobalt accelerator (1% Co) 0·3; 2, resin
(Vestopal 150) 100, M EK peroxide 2, cobalt accelerator O· 3, inhibitor ( 1% solution)
1 ;3, resin (VestopaI150) 100, MEKperoxide 1, cobalt accelerator (1% cobalt) 0·14.
(Courtesy of Hills (UK) Ltd.)

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148 FRP TECHNOLOGY

donating hydrogen atoms and hence prevent those free radicals from
polymerising the resin. Clearly, once an inhibitor has been exhausted, any
further generation of free radicals will cause gelation of the resin.
When a peroxide catalyst is added to a pre-accelerated resin the first
reaction is to neutralise the inhibitor and it is this reaction which accounts
for the initial period of apparent inactivity of the system. Where a longer gel
time is required with no reduction in rate of cure, then additional inhibitor
can be added to the system. This is preferable to reducing the catalyst or
accelerator proportion, since then a slower rate of cure results (Fig. 9.3).
Typical of the inhibitors used commercially are hydroquinone, t-
butylcatechol and substituted benzoquinones. These are used in amounts
ranging from 100 to 300 ppm. The actual amount of inhibitor needed to
stabilise a resin will vary from one resin to another and whether or not the
resin is for tropical use. In practice a mixture of inhibitors may be used to
achieve optimum stabilisation whilst maintaining optimum reactivity.
Where an inhibitor is used to increase gel time, the amount added will be
of the order of 1% of a 1% inhibitor solution. This is equivalent to 100 ppm
of pure inhibitor. The effect of such an addition is to increase gel time from,
say, 18 min up to about 50 min without altering reactivity. This is
illustrated in Fig. 9.3.

9.3 COMMERCIAL RESINS

Let us now consider the various types of commercially available un-


saturated polyester resins. These can be divided into eight different classes
or groups as follows:
1. Gelcoat/topcoat resins.
2. General purpose resins.
3. Chemical resistant resins.
4. Reduced flammability resins.
5. Low styrene emission resins.
6. Low profile/low shrink resins.
7. Special purpose resins.
8. Casting resins.
Many of these resins are available in reactivities ranging from high
through medium to low. They may also be available non-accelerated or
pre-accelerated-generally with a cobalt accelerator, and with or without a
thixotroping additive. Other variations include low, medium or high

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Table 9.3 Typical properties of cured polyester resins

Cast resin properties Laminate properties

Flexural Tensile Tensile Percen- Per- Flexural Tensile Tensile


strength strength modulus tage elon- HDT centage strength strength modulus
Polyester resin type (MPa) (MPa) (GPa) gation (DC)" glass (MPa) (MPa) (GPa)
"t1
2·0-4·0 55-110 30 150 90 7 0
Orthophthalic 100 65-75 3-2
Isophthalic 140 70-85 3-5 3-5 75-130 30 230 120 8
Neo-pentyl glycol 130 70 H 2-4 110 30 170 90 7
~
Isophthalic/neo- ~
pentyl glycol 130 60 H 2·5 90-115 30 160 90 7
HET acid 80 40-50 3·2 1·3-4·0 55-80 30 150 85 7 ~....
Isophthalic/HET
zV>

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acid 85 55 3·2 2·9 70 30 150 90 7
Bisphenol A 130 60-75 3·2 2·5-4·0 120-136 30 170 90 7
Chlorinated paraffin 110 50-60 H 1·2-4·8 55-80 30 140 90 7
Isophthalic/chlori-
nated paraffin 90 60 2·0 4·8 50 30 140 100 7

aHDT = heat deflection temperature.

......
.j:>..
\(;)
150 FRP TECHNOLOGY

viscosity and additional stabiliser for tropical use. A comparison of typical


properties of a number of different types of resin is given in Table 9.3.
Selection of a resin for a particular application depends on a number of
factors and is dealt with in Chapter 2.
Several manufacturers add colour indicators to their resins to indicate
degree of cure. These indicators change colour once the catalyst has been
added and continue to change as cure progresses. Some examples of such
indicators are phenothiazine and N-substituted p-phenylenediamines. In
order to obtain colour sensitivity these need to be added in high
concentrations. Commercially the preferred colour change is from blue to a
pale muddy colour.
Three examples of such indicators and their colour changes are given
below.
Phenothiazine brown -4 green
NN -diphenyl-p-phenylenediamine red brown ~ yellow orange
NN -bis(1-ethyl-3-methylpentyl)- blue~red
p-phenylenediamine
A list of most of the commercially available unsaturated polyester resins
marketed in the UK is given in Table 9.6 at the end of this chapter.

9.3.1 Gelcoat/topcoat resins


The gelcoat is the first layer of resin applied to the released mould surface
and forms the wearing surface of the finished moulding. It serves to protect
the laminate against weather, moisture and chemicals and gives a
decorative pigmented finish. In order to protect the laminate from damage
during service the gelcoat must be resilient when cured so that it can
withstand knocks and abrasions. Resilience is necessary since at most the
gelcoat will only be reinforced with a surfacing tissue. Thickness is
generally of the order of 0·4 mm, equivalent to 450 g/m 2 of resin.
Gelcoats may be clear or pigmented depending on application. Where
high performance or high chemical resistance is required they are
invariably reinforced with a surfacing tissue of either C-glass or synthetic
fibre to provid~ additional protection to the underlying laminate and to
mask the fibre pattern. In practice, the gelcoat may be applied in the normal
way and backed up with a surfacing tissue so that a resin-rich surface is
obtained and the laminate protected by both the resin-rich layer and the
surfacing tissue.
Most gelcoat resins contain a thixotropic additive to prevent runs and
sags from forming during application and cure. Generally they are

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POLYESTER RESINS 151

available in two types, (i) for brush application and (ii) for spray
application. These usually only differ in viscosity and thixotropy.
General purpose gelcoat resins are based on orthophthalic or isophthalic
resins, the latter type offering improved water, chemical and impact
resistance. Where superior weathering resistance is required, the gelcoat
will invariably be of the isophthalic type and may contain a blend of methyl
methacrylate and styrene as monomers.
Some manufacturers offer fire retardant gelcoats based on HET acid or
HET acid/isophthalic blends, while others recommend their normal
isophthalic resins. Care has to be taken in selecting a fire retardant gelcoat
for outdoor applications since many of these exhibit inferior weathering
resistance.
Where chemical resistance is required, gelcoats are available based on
isophthalic, isophthalic/HET acid, isophthalic/NPG and bisphenol A
resins. Choice depends on the precise chemical environment and service
temperature.
In addition to gelcoat resins, there is also a range of topcoat resins
available. These are similar to gelcoat resins with one important difference
and that is they do not suffer from air inhibition during cure. This is
generally achieved by adding a wax to the resin which migrates to the
surface during the initial stage of cure.
Topcoat resins serve to protect the underlying laminate, give a tack-free
decorative finish and balance up the laminate by giving a resin-rich surface.
The finish obtained is never of the same quality as the gelcoat finish since it
is not a moulded surface.
Where repairs or ribs, etc., have to be bonded to topcoats, thorough
cleaning of the surface with an abrasive cleaner and roughening must be
carried out prior to application of the new resin, otherwise complete release
of the new resin will inevitably occur.
As an alternative to using a polyester resin as gelcoat, Rohm & Haas
have developed an acrylic moulding powder which can be extruded in sheet
form, thermoformed and used in place of a conventional gelcoat. 2 The
effect is not only to produce a decorative finish on the moulding but also to
rigidise it. The acrylic 'gelcoat' can be used in most processes where a
conventional gelcoat is at present employed.

9.3.2 General purpose resins


These are mostly orthophthalic resins with good all-round properties. They
have for many years been used for boat building, but are slowly being
replaced by isophthalic polyester resins due to the reduced water absorp-

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152 FRP TECHNOLOGY

Fig. 9.4. The first all-G RP offshore lifeboat moulded by Halmatic Ltd,from Crystic
resin supplied by Scott Bader, for the Royal National Lifeboat Institution. Length
16·5 m. (Courtesy of Scott Bader Co. Ltd.)

tion of the latter. Lloyd's Register of Shipping have stated that it is their
intention to phase out orthophthalic polyester resins from their list of
approved resins in due course. A typical GRP boat is shown in Fig. 9.4.
Many different orthophthalic polyester resins are available, designed for
a variety of application and processing techniques. They cover a wide range
of viscosities, reactivities and gel times and can vary from relatively soft to
hard rigid cured resins.
Other resins which fall into the general purpose class are the terephthalic
acid and some isophthalic acid based polyesters, although this latter group
also come under the heading of chemical resistant resins.

9.3.3 Chemical resistant resins


For maximum chemical resistance any resin system used in a chemical
environment must be fully cured, preferably at a temperature 10-20°C
above that to which it will be subjected in service.
Clearly before any resin system can be selected, the service conditions,
environment and temperature must be specified. Only then can a particular
type of resin be chosen. With mild chemical environments several different
types of resin may be available, but for severe conditions choice may be
restricted to only one resin.

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POLYESTER RESINS 153

Table 9.4 Some chemical resistance data for polyester and vinyl ester resins

Resin code Resin type Supplier

Crystic 474/198 Orthophthalic Scott Bader Co. Ltd


Crystic 491/272 Isophthalic Scott Bader Co. Ltd
Crystic 392 Isophthalic/ Scott Bader Co. Ltd
NPG
Crystic 600 Bisphenol Scott Bader Co. Ltd
Atlac 382 Bisphenol Honeywill-Atlas Ltd
Atlac 580 Vinyl ester Honeywill-Atlas Ltd
Beetle 844 Bisphenol British Industrial Plas-
tics Ltd
Cellobond A261j
1973 HET acid BP Chemicals Ltd
Hetron 197 HET acid Ashland Chemicals.
UK Agent-Garrick
Chemical & Equipment
Co. Ltd
Hetron 901 Vinyl ester Ashland Chemicals

Maximum working temperature (OC)

"
~ "1"
t-
N 0
0 ~ t2 b;
~ "1"
0"\
"1"
0"\
r<) \.Q
N
00
0
00 ~
00
:: 0"\ .....
0
0"\
'-
.::l .::l r<) on ..c:, ___
(;)..... ::
(;) ::
:: .~ .~
" ~"
';;; ~ \0 ...... ....
(;)

" '"
::
';;;
'" t- ~
~

0 \...)t- ut- \...)t- ~'"


-N
\...) ~ ~ ~ <t: ~ ~
Acetic acid, aq. 70 NR 25 55 65 71 71 70 30 70
98 NR NR NR NR 35
Acetone 10 25 NR NR 25 82 82 NR
100 NR NR NR NR NR NR 25" NR NR NR
Acrylic acid 100 NR 35 25 25 NR
Aluminium sulphate Sat. 55 50 75 95 104 93 100 70 120 90
Ammonia, aq. 5 NR 25 35 60 45 70
28 NR NR 25 35 25 50
Amyl acetate 100 NR NR NR 25 25 NR 25" 30 25
Antimony trichloride,
aq. Sat. NR NR 25 30 25 25
Aviation fuel-Avtag 100 30 25 25 25 25 25 30 40
-Avtur 100 45 30 30 35 25 25 30 40
-Avgas 100 30 NR NR 25 25 25 30 40
Barium hydroxide, aq. 10 NR NR 25 30 66 66 70 NR
Benzyl alcohol 100 30 25 NR 25 25 25 25 38
Brine 55 50 75 95 104 93 100 80 100 90
Butyl alcohol 100 35 30 30 30 25 25 35 35 NR
Calcium hypochlorite 17 NR NR 45 50 25 50
10 80 40

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154 FRP TECHNOLOGY

Table 9.4 (Continued)

Maximum working temperature (OC)


...
----
~
---C
'<t"
r-
'<t"
.::l
-
0-
'<t"
.::l
N
0-
('f'l

.::l
0
0
\0
-1:.,
N
00
('f'l
0
00
\f")
~
00
~~
;:0-
<::>-
r-
0-
;:
-
0
0-
;:
-;;; -;;; -;;;
..C)~
<::>
t- ~"
~ ....
" <::>- ~

a
;: ~
~
~\O
t- t- t-
\,,) \,,) \,,) \,,) ~ ~ ~ \,,)< ~
~N
~
Chloroacetic acid 25 30 40 60 70 104 93 30
50 NR 25 40 60 60 60 30 30 60
Chlorine water Sat. NR 25 50 55 25 25 90 70
Chromic acid, aq. 10 45 45 60 55 25 25 30 60
30 NR NR 30 30 NR NR 25
Diallyl phthalate 100 50 50 50 70 82 82 100 60
Diesel fuel 100 40 35 30 40 50
Dimethyl phthalate 100 50 50 50 70 66 66 60
Ethylene glycol 100 70 55 75 95 104 93 100 100 120
Ferric chloride, aq. Sat. 50 45 70 90 104 93 100 80 90
Formic acid, aq. 20 30 35 60 70 30 30 25 45
50 NR 25 50 55 25 25 25
75 NR NR 35 40 NR
Furfural 15 NR NR 35 25 25 NR
Heavy aromatic
naphtha 100 40 NR NR 25 25 25 30
Heavy plate
solution 65 50 75 80
Hydrochloric acid 20 45 35 60 70 104 93 80 60 110
35 35 25 35 30 25 25 65 30 30 75
Hydrogen peroxide
20 vol. NR NR 65
65 30 30
100 vol. NR NR 25
25 NR
Industrial meths. 100 25 2525 25 25 25 30 40
Kerosene (domestic) 100 50 3530 30 66 66 100 80 60
Lactic acid, aq. 44 55 9550 75 104 93 100 80 90 90
Lubricating oil 100 95 9050 45 104 93 110
Methyl alcohol 100 35 3025 30 25 25 30 50 30
Nitric acid 10 45 6025 60 66 66 60 90 70
40 NR NR NR
25 25 25 25
Perchloric acid, aq. 10 NR 5025 55 30 30
25 NR NR 35
30 30 NR
25 35
Petrol, 98 octane 100 30 2525 NR 25 25 30 40
Phenol I 25 25 25 80 80
Sat. NR NR NR NR NR NR NR NR
Phosphoric acid 85 55 50 75 95 104 93 80 60 120 25
Plating solutions
Cadmium cyanide NR NR 80 104 93 NR

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POLYESTER RESINS 155

Table 9.4 (Continued)

Maximum working temperature (OC)


...--.,
~
'-
..,.r--
..,. ..,......
0\
N
0\
r<'\
8
\(;) N
00
r<'\
0
.,...
00
;00 ~~
S::0\
0-
r--
0\

--- ° E
s::
s::
-
0
0\

~
s::
..,
.~ .~
.., .~
t;
.~
t; '-' '-' ~ ~
~~ ~
t> t> t> t> ~ ~ ~
1;N
d ~ ~ ~ ~ ~ ~ ~ ~< ~ ~
Chrome NR NR 30 25 NR NR 90
Gold 50 45 70 90 104 93 90
Lead 50 45 70 90 104 93 90
Nickel 50 45 70 90 104 93 80
Platinum 80 82 82
Silver 40 30 50 90 104 93
Potassium
carbonate, aq. 10 NR NR 30 80 66 66 30 40
40 NR NR NR 30 25 25 30 40 45
Potassium
ferricyanide Sat. 55 50 75 95 104 93 80 90 80
Potassium
hydroxide, aq. 30 NR NR 40 50 25 25 25 NR
Potassium
permanganate Sat. NR NR 30 35 104 93 60 65 70
Sea water 55 50 75 95 104 93 100 80 80 80
Sodium carbonate, aq. 10 NR 25 35 80 82 82 30 50 50
25 NR NR 30 75 71 71
Sodium hydroxide 10 NR NR 50 60 66 25 30 NR 80
Sat. NR NR NR 80 104 25 NR
Sodium hypochlorite 14 NR NR 60 55 75 NR
Sulphuric acid 50 80 60 80 100 104 93 100 70 65 85
75 NR NR 25 40 25 25 30 60 65 65
Tartaric acid, aq. Sat. 55 50 75 95 104 93 100 80 120 80
Toluene 100 25 NR NR NR NR NR 30 30 25
Trichloroacetic
acid 25 NR 30 50 60 90 25
50 NR NR 30 50 104 93 30 40 90 25
Turpentine 100 30 25 25 30 40
White spirit 100 35 25 25 30 50
Xylene 100 40 NR NR 25 25 25 30 50 38 NR

a Intermittent contact.
b Concentration by weight in water where less than 100%.
aq. = aqueous; NR = not recommended; Sat. = saturated.
All laminates were made with a resin-rich finish in contact with the reagent.

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156 FRP TECHNOLOGY

The weak link in the polyester molecule is the ester group and it is this
that needs protecting from chemical attack. This can be accomplished by
increasing the degree of cross-linking of the resin and by hindering attack
by placing bulky groups around the ester links.
Intermediate levels of chemical resistance can be obtained with isoph-
thalic polyester resins. These will vary somewhat in performance depend-
ing on their precise formulation.
A higher level of chemical resistance can be obtained by replacing the
propylene glycol with neopentyl glycol to give an isophthalicjNPG resin.
Chemical resistance can be further increased by using bisphenol A
derivatives or by using HET acid to make the resin.
Most suppliers have built up considerable data over the years on the
resistance of their resins to particular environments 3 and are in the best
position to advise on specific requirements. Some selected data are given in
Table 9.4 to serve as an indication of the types of chemicals which can be
resisted by fully cured polyester resins. Typical examples of the use of
chemically resistant polyester resins in chemical plant are shown in
Figs. 9.5 and 9.6.

Fig. 9.5. A scrubber unit moulded in GRP using Crystic 600 polyester resin-a
chemical resistant grade. (Courtesy of Scott Bader Co. Ltd.)

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POLYESTER RESINS 157

Fig. 9.6. GRP gas main for sulphuric acid plant. Moulded by Viking Industrial
Plastics Ply, Australia, with Crystic polyester resin. (Courtesy of Scott
Bader Co. Ltd.)

9.3.4 Reduced flammability resins


Resins with reduced flammability are required for many applications where
fire risks exist, such as in building and transport applications. A typical
example of the use of a fire retardant resin for the construction of building
panels is shown in Fig. 9.7. Today, resins are available which have been
designed to meet many of the different regulations and specifications. Some
of the specifications likely to be encountered are listed in Chapter 20.
Earlier in this chapter, various ways of producing self-extinguishing
resins were discussed. These can be summarised as follows:

(a) By using a chlorinated or brominated monomer.


(b) By using a chlorinated or brorninated glycol.
(c) By using a chlorinated or brominated acid, either saturated,
unsaturated or both.
(d) By using other types of fire retardant monomers.

Other materials such as chlorinated hydrocarbons, trichloroethyl phos-

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158 FRP TECHNOLOGY

Fig. 9.7. GRP panels for car park moulded with Crystic 345 fire retardant resin by
Durapipe and Lambert Sales Ltd. Internal surfaces coated with Crystic Fireguard
resin. (Courtesy of Scott Bader Co. Ltd.)

phate or bromine containing compounds may also be incorporated into


the resin to give some degree of flame retardancy. Not all of these methods
are equally effective as will be seen by the different classifications given to
the different commercial resins. There are also commercial reasons why all
resins do not meet the most stringent fire requirements.
Flame retardancy can be enhanced by adding antimony trioxide to
halogen containing resins. This does, however, render them opaque. Other
fillers, such as aluminium hydroxide 4 and zinc borate, may also be used (see
also Chapter 16 on fillers).
With all laminates resin/glass ratio and component design can affect
flammability. In particular, the higher the glass content of a laminate the
lower the flammability with any particular resin system.
A further way of aiding fire retardancy is to coat the laminate with an
intumescent coating. This expands on contact with a fire and protects the
laminate from flames for some considerable time, depending on the
intensity of the fire. Direct flame contact converts the coating to a
carbonaceous foam filled with an inert gas and in so doing reduces spread
of flame. It may also be used on materials other than GRP for the same
purpose. One example of such a coating is Crystic Fireguard from Scott
Bader.

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POLYESTER RESINS 159

9.3.5 Low styrene emission resins


With the continued emphasis on improving working conditions, resin
suppliers have been ,seeking ways of reducing styrene emission from
unsaturated polyester resins during the pre-gelation stage. 5 • 6 The aim has
been to help users maintain workshop levels of styrene below the Threshold
Limit Value (TLV), without the use of excessive ventilation-which can
lead to other problems. Various approaches have been made to the
measurement of styrene concentrations in air.! This can be done using
permanently installed monitors or by equipping operators with portable
measuring devices.
The Threshold Limit Value for styrene was set by the American
Conference of Governmental Industrial Hygienists (ACGIH) in 1976 at
100 ppm (420 mgJm 3)7 and this value was adopted by the UK Health &
Safety Executive. The TL V for styrene in Sweden was set at 50 ppm, half
the UK level.
The TLV is expressed as the time weighted average concentration for an
8 h working day and a 40 h working week. The maximum allowable
concentration is 150 ppm, but if this occurs then it must be compensated for
by an equivalent period at a lower level to keep the average below 100
ppm.
Various approaches to the problem have been considered, such as (i) the
use of alternative less volatile monomers, (ii) reduction of the styrene
content of the polyester resin and (iii) the use of film forming or other
incompatible additives.

The use of alternative monomers


At present the use of alternative monomers does not offer a realistic
solution since all are either more expensive than styrene or offer no
improvement in TLV over styrene (see Table 9.2).

Reduction in styrene content in the resin


Experiments have shown that reducing the styrene content of a resin
from 42 to 35% does result in a reduction in the atmospheric styrene level.
However, the effect of such a reduction is to increase the viscosity of the
polyester resin. To compensate for this a lower molecular weight base
polyester has to be used, with the result that some reduction in cured
properties also occurs. In practice a compromise has to be reached.

Film forming or other additives


The most common and most effective approach to the reduction of

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160 FRP TECHNOLOGY

styrene emission from a laminate has been the addition of film forming
materials, essentially incompatible with the resin. Such resins are fre-
quently referred to as 'Environmental Resins'.
Wax additives have been used for many years to prevent air inhibition of
exposed surfaces. Such additives also reduce styrene emission. However,
where wax containing polyester resins are used with multi-stage laminating
processes there is a risk of subsequent delamination, particularly under
impact conditions.
Other additives S (undisclosed) have been developed which do not suffer
this disadvantage. These have proved to be more effective than paraffin wax
but only with thixotropic resins. If the thixotroping agent is removed,
styrene emission remains at the unmodified level. The effectiveness of such
additives is illustrated in Table 9.5.
With all environmental resins, styrene emission remains at the same level
as with normal resins while the laminate is being worked since the resin
surface is continually being changed. It is only once the laminate has been
put on one side that the film forming additive can exert its effect. As with all
hand or spray lay-up processes adequate ventilation must be provided.
9.3.6 Low shrink/low profile polyester resins
Some 12 years or so ago the first low shrink/low profile unsaturated
polyester resins became commercially available. Since that time, whilst
some major advances have been made, their acceptance has been notice-
ably slower than at first expected.
With normal unsaturated polyester resins containing about 35% of
styrene, shrinkage of about 8% usually occurs during cure. With large flat
mouldings this high shrinkage results in sink marks and a generally poor
quality finish, unacceptable for many applications.
Table 9.5 Effect of environmental additive on styrene emission

Beetle polyester resin


840 840E a

Gel time at 2SOC. 1· 5% Catalyst SD2 (min) 30 30

Styrene level in ppmb after 15 min 67 30


30 min 68 51
45 min 60 43

aE refers to the environmental grade of resin containing the additive.


bTaken 7·5 cm above the centre of a 75 cm x 75 em laminate. Styrene absorbed
in alcohol and the level measured by UV spectroscopy.

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POLVESTER RFSINS 161

Whilst some reduction in shrinkage can be achieved by the use of


alternative monomers, such as vinyltoluene and t-butylstyrene, higher
viscosities and incompatibility can result.
Developments for low and zero shrink unsaturated polyester resins have
centred around the use of thermoplastic additions. Since the first claim,
made in a French patent in 1957, that thermoplastics soluble in or swollen
by styrene could be used to reduce shrinkage, numerous patents have
appeared, covering the use of practically all types of thermoplastic
materials. Some 39 companies had been granted some 116 patents up to the
end of 1977. 8
Examples of some of the thermoplastics presently being used are
polyvinyl acetate homo polymers and copolymers, polycaprolactones from
Union Carbide, cellulose acetate butyrate from Eastman Kodak and
acrylic polymers from Rohm & Haas.
One theory for the low shrinkage, subscribed to by Peltzer et al.,9 is that
the low shrinkage of the cured polyester resin is due to void formation
during cure, through monomeric styrene diffusing out of the thermoplastic
leaving behind hollow microspheres. They consider this to be the
mechanism in the case of polystyrene and polyethylene additions.
However, Atkins et al. 10 consider that the voids are formed in the cured
resin due to thermal expansion of the thermoplastic during cure of the
unsaturated polyester resin. Subsequent cooling results in voids around the
thermoplastic inclusions.
Whichever mechanism is correct, void formation seems to be either a
necessary part, or a by-product, of that mechanism. It also seems that there
must be some incompatibility between the polyester and the thermoplastic
to produce low or zero shrinkage.
In general, the recommended level of thermoplastic additive lies
between 10 and 20% of the weight of unsaturated polyester resin, the exact
amount depending on the particular additive used and its effect on process
variables such as viscosity. The major use of such resins has been in
formulating sheet and dough moulding compounds where shrinkage
marks present a major problem.
Whilst many zero shrink compositions have been formulated, few of
these have overcome all the problems of moulding the low profile parts
required by the automotive industry. Some additives result in surfaces with
poor paint adhesion, whilst others give systems which are unsuitable for
pigmentation. Also, difficulties can be encountered in achieving con-
sistently high quality mouldings free from micro-porosities. Where ribs and
bosses are moulded in, there is still a tendency for sink marks to appear on

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162 FRP TECHNOLOGY

the moulded surfaces. This is probably caused by the significantly higher


exotherm developed during cure in these thicker sections.
Other factors which affect shrinkage are type and quality of filler,
reinforcement, catalyst and thickening agent; moulding temperature and
pressure; part shape and thickness. These must all be taken into account in
addition to the selection of the low profile additive to be used.
As far as is known at present, none of these low profile systems is suitable
for room temperature cure; all require heat cure for the effect of the
additive to be seen.
Various resins and additives are available commercially, as are low
profile and zero shrink sheet and dough moulding compounds.

9.3.7 Special purpose resins


This classification is used to describe those resins which do not con-
veniently fit into the previous categories or which have been designed for
use with particular processes.

Flexible resins
Flexible resins are those which in the cured state are soft and rubbery.
They are prepared by replacing part or all of the saturated acid with a
dibasic aliphatic acid such as adipic or sebacic acid. In so doing, the
chemical resistance of the cured resin is generally reduced and water
absorption increased.
Their main applications are in increasing the flexibility and impact
resistance of the more rigid laminating systems and in casting and
encapsulating systems.

Resins for sheet moulding compounds


Various types of resin can be used for SMC production. All must be of
consistent quality, with carefully controlled water content. Low viscosity
resins are used which can be chemically thickened by the addition of
calcium oxide or magnesium oxide. This pre-thickening characteristic must
be consistent from batch to batch, with rapid thickening and stable final
viscosity. The resin used must also be stable for several months in the
presence of a catalyst, yet cure fast at elevated temperature to ensure a short
moulding cycle.
Many sheet moulding compounds contain low profile additives to ensure
that high quality mOUldings can be produced free from .sink marks.
A typical use of a sheet moulding compound is the construction of a road
tanker cab as shown in Fig. 9.8.

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POLYESTER RESINS 163

Fig. 9.8. Road tanker cab mouldedfrom Crystic SMC by Bifort Engineering Ltd.
Tools by J. J. Harvey Ltd. (Courtesy of Scott Bader Co. Ltd.)

Resins for dough moulding compounds


Various types of resin can be used for DMC and BMC although in the
UK and Europe, BMC resins are generally of higher quality than those
used for DMC.
Whichever resin is used it should be capable of taking a high filler loading
and remain sufficiently viscous to carry glass fibres and filler to all parts of
the mould during the moulding cycle. The resin also needs to be stable for
several months in the presence of a catalyst, yet cure rapidly at processing
temperature to provide a short moulding cycle for high production rates.
As with resins used for SMC, the resin must have consistent properties,
both in the liquid and cured state, and consistent reactivity.
Many commercially available dough moulding compounds contain low
profile additives to ensure that consistent high quality mouldings are
produced, free from sink marks.

Resins for prepregs


Resins used for prepregs are generally of the heat resistant type, with a
high viscosity brought about by the addition of up to 5% of a polyhydric
alcohol during manufacture. Since prepregs are expected to have a shelf-life
of several months at room temperature, a low volatility monomer is
needed, thus diallyl phthalate is used in place of styrene as monomer.
Prepregs may be prepared by impregnating the reinforcement with an

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164 FRP TECHNOLOGY

acetone solution of the catalysed resin. During manufacture the acetone


evaporates to leave a slightly tacky prepreg.

Light cured resins


Unsaturated polyester resins are available which can be cured by
exposure to visible light at the blue end of the spectrum, centred on a
wavelength of 420 nm. These consist of conventional polyester resins
incorporating a special catalyst system.
They are only suitable for use in open moulding processes and mostly for
transparent laminates where light can penetrate the laminate. Small
pigment loadings (0· 5%) and some filler loadings can be tolerated, but light
transmission decreases as filler loading increases. Thus cure time increases
with filler loading. Aluminium hydroxide (alumina trihydrate) and
Ballotini glass spheres are the most satisfactory fillers for use with these
resins.
The advantages claimed for these resins are:
(i) No catalyst addition necessary by the user, therefore no mixing
errors are likely to occur.
(ii) Resin does not gel on brushes and rollers and so cleaning is easier.
(iii) Surplus resin can be used again since it will not cure until exposed to
an appropriate light source.

Other speciality resins


Other speciality resins are available with good adhesion to acrylic
sheeting for bath manufacture, or good adhesion to rigid PVC for the
manufacture of chemical plant and pipes.
Where process requirements dictate, special reactivity or viscosity resins
can generally be obtained from most suppliers. These may be of the
standard type or chemical or fire retardant resins.
Further modifications, where resins are intended for the manufacture of
roof domes and sheeting, are the incorporation of UV stabilisers and
optical brighteners.

9.3.8 Casting resins


Polyester resins are widely used for button manufacture. Here the resin
needs to be either colourless or very light coloured and colour stable after
cure. When cured the resin should exhibit good hot water resistance,
hardness and impact resistance. Also, the resin must exhibit good punching
properties immediately after gelation and good machineability after cure.

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POLYES1ER RESINS 165

For fast production rates, a high reactivity, low viscosity resin, with fast
air release is needed. Various resins are available which meet all of these
requirements.
Several production techniques may be used depending on the type and
number of buttons required.
Fancy buttons, in single or double relief, may be cast in a mould with a
small opening to permit introduction of the resin system. Moulds can be
made from silicone rubber, flexible PVC or polyethylene.
Where buttons are to be machined to produce the relief pattern, sheets of
resin are made by centrifugal casting and the blanks punched out while the
resin is still flexible, before full cure, generally between 30 min and 2 h after
casting. Various different buttons are shown in Fig. 9.9.
Clear colourless resins are also used for encapsulation. Here, the resin
must exhibit rapid air release for bubble-free castings. Low viscosity resins
are used, preferably with some degree of flexibility to withstand impact.
The resin should also be resilient, crack resistant and have moderate to low
shrinkage during cure, with low exotherm. Where filled systems are used,
the colour of the resin is unimportant and brown or straw coloured resins
may be used. For some applications good electrical properties are also
required.
Where decorative castings are to be produced, such as paper weights, the

Fig. 9.9. Various polyester resin buttons.

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166 FRP TECHNOLOGY

objects to be encapsulated must be free from moisture, otherwise this will


cause cloudiness in the cured resin system. The objects to be encapsulated
should be dipped in acetone for 5-10 min before encapsulation, followed
by immersion in a mixture of equal parts of uncatalysed polyester resin and
acetone, then in pure uncatalysed polyester resin and finally in the catalysed
resin. A low catalyst level should be used to give a long gel time and hence
negligible exotherm, to prevent damage to the specimen. A cure time of up
to several weeks may be necessary to achieve full cure. Where plants or
animals are encapsulated, these may change colour or the colours may fade
completely within a short period of time. An example of an orchid bloom
encapsulated in a block of polyester resin is shown in Fig. 9.10. In this case
the flower was bright orange in colour and has shown no sign of fading after
two years' encapsulation.

Fig. 9.10. An orchid bloom encapsulated in a clear polyester resin.

With the encapsulation of electrical components, either clear or filled


resin systems may be used. Here, the colour of the resin system is generally
unimportant and straw coloured or pale brown resins may be used. Fillers
such as alumina, silica flour and calcium carbonate are often added to the

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POLYFSTER RFSINS 167

resin system to disperse exothermic heat and reduce shrinkage during cure.
Electrical components may be embedded using metal or plastic moulds,
or potted using metal or plastic containers which remain part of the finished
component. In this latter case, thin walled metal or polystyrene containers
may be used. With polystyrene, excellent adhesion to the polyester resin is
obtained and if a thin-walled container is used it follows the shrinkage of
the resin on curing. Vacuum encapSUlation is often used to ensure complete
penetration of the resin into the component and bubble-free castings.
Casting resins are also used for making synthetic marble. Here, chunks
of marble are encapsulated in polyester resin. When cured the blocks are
sawn and polished and used in a similar way to whole marble slabs. By so
doing, marble waste can be fully utilised. Resins used for this application
must have good adhesion to marble, good impact resistance, good elasticity
to permit sawing, minimum shrinkage and good polishability. They must
also be heat resistant and resistant to most foodstuffs, since slabs cut from
blocks are frequently used as table tops. Low exotherm systems must be
used to prevent shrinkage stresses from occurring, since a typical block
would be 3·05 m long by 1·25 m wide and 0·83 m deep. Marble flour and
pigment paste may be added to the resin system prior to casting. The cast
blocks are usually stored for at least 1 week after cure before being sawn
into slabs and polished.

9.3.9 Foamed polyester resins


Whilst foamed polyester resins offer some of the advantages of other
foamed plastic materials, they cannot be produced simply by adding a low
boiling solvent, as is the case with polyurethanes.
One company, Cellmico Ltd, has developed the 'Mitex' system of
producing foamed polyester resins, based on Leguval polyester resins from
Bayer. In this process, foaming is brought about by the liberation of carbon
dioxide within the resin system, by the addition of an organic carbonic acid
derivative and activator. Benzoyl peroxide is used as catalyst, without an
accelerator, to cure the polyester resin. Since the foaming takes place
separately from the curing reaction, foam height can be controlled up to
3 m before gelation of the resin. Cream time-the time to the start of
foaming -can be controlled to between 30 s and 15 min, to give considerable
freedom of processing. The foam produced is largely open celled, with a
coarser pore structure and greater cell wall thickness than many other
foams. Due to this open cell structure, Mitex foam blocks can 'breathe' and
thus permit water vapour transmission.

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168 FRP TECHNOLOGY

Mitex foam can be filled with lightweight fillers and glass reinforcements
such as chopped strand mat and continuous filament mat. It can be used to
produce lightweight sandwich panels and to provide thermal and sound
insulation. The cured foam has a low coefficient of expansion, good
weathering resistance and is self-extinguishing. Mechanical properties
depend on density and filler and reinforcement levels.

9.3.10 Commercially available polyester resins


A fairly comprehensive list of resins commercially available in the UK
is given in Table 9.6 (pp. 170-203). This embraces many resins
manufactured elsewhere in Europe and imported into the UK, as well as
one range imported from the USA. Some of the data are mean values based
on information given in the appropriate data sheets. Test methods used in
obtaining these data are indicated in code form, where known, with a
breakdown of the code at the end of the table. Each of the suppliers
mentioned may also offer other grades, designed for specific processes and
experimental grades. They may also change resin specifications from time
to time and thus render some of the data out of date. Current specifications
can always be obtained from the appropriate supplier, as can a more
detailed list of applications for each resin, since only limited information
has been included about each resin.
Resins supplied by the following companies are listed:
Supplier Agent for Trade name
Arcode Ltd Chimimportexport, Nestrapol
Romania
Astor Chemical Ltd Polastor
Bayer UK Ltd Leguval
BP Chemicals Ltd Cello bond
British Industrial Plastics Ltd Beetle
Cargill Blagden Ltd
Cray Valley Products Ltd Synolac
Freeman Chemicals Ltd Stypol
Garrick Chemical & Equipment Ashland Chemicals Hetron
Co. Ltd
Hoechst AG, Resinous Chemicals
Division of Berger Chemicals Alpolit
Honeywill-Atlas Ltd Atlac
Hiils (UK) Ltd Vest opal

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POLYESTER RESINS 169

International Paint Ltd,


Industrial Division
KWR Chemicals Ltd CdF Chimie Norsadyne
Pechiney U gine Kuhlmann Ltd Ukapon,
Ukadiol
Rohm & Haas (UK) Ltd Paraplex
Scott Bader Co. Ltd Crystic
Synres (UK) Ltd Synolite
Synthetic Resins Ltd Uragel,
Uralam
Vetrotex (UK) Ltd A/S Jotungruppen Norpol
Freeman Chemicals
Ltd
International Paint
Ltd
Pechiney U gine
Kuhlmann Ltd
Warwick Chemical Ltd Polymaster

REFERENCES

I. Verlaan, F. (1977) Reinforced Plastics, September, 271.


2. Truelove, J. W. (1977) Reinforced Plastics, June, 174.
3. Burbridge, J. F. (1977) Reinforced Plastics, December, 387.
4. Banin, D. (1977) Reinforced Plastics, May, 142.
5. Whitfield, L. (1978) Reinforced Plastics, January, 13.
6. Clarke, G. M. and Millman, A. F. (1978) Composites, 9 (4), 237.
7. Anon. (1979) Reinforced Plastics, February, 39.
8. Chandler, R. H. (1978) TTIS Publication No.7, R. H. Chandler Ltd,
Braintree, Essex.
9. Peltzer, B., Kampf, G. and Schulz-Walz, H. J. (1976) AVK 13th International
Conference on Reinforced Plastics, Freudenstadt, October 1976, Paper No. 38.
10. Atkins, K. E. et aI., (1976) 31st Annual Technical Conference. Reinforced
Plastics/Composites Division of Society of Plastics Industry, Section 2-E.

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Table 9.6 Commercial polyester resins

Resin properties Cured properties


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'"
0 -s
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II<:I'""
Supplier -~v ">::: '- '"",'"" ~
~ " '" 0 '" .., r...~
Trade name 8N h ~~ >::: '" '--
" Q c
'~~ "'-5.."
Product code Type
"'" ..s::
~ ::~ V3~ CI:l ::t:: ~~ ~ ~~ Remarks

Arcode Ltd- Agent for Chimimportexport, Romania


Nestrapol 120 flexible 0-8-0-9 30 8 60 (0-6) Plasticising resin
140 flexible 0-45-0-55 30 6 65 (1-0) Encapsulating, putties
140B flexible 0-45-0-55 30 5 65 (1-0) Adhesives, putties
...,0
- 220 1-0-1-3 34 50 5 (Q.3) Encapsulating, casting
220B 1-0-1-3 34 50 5 (0-3) Cold press moulding
220S 1-0-1-3 34 50 5 (0-3) Light stabilised, sheeting
431 1-0-1-2 33 Button grade
432 )-0-)-2 33 Button grade, more

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flexible than 431
450 )-0-1-3 34 55 2 (0-3) Chemical resistant

Astor Chemical Ltd


Polastor PA02A 0000 isophthalic 1-10 0- I -0-2 90 38 )5 Semi-rigid, water resistant
PA02C 0000 isophthalic 1-10 0-3-0-4 90 38 15 Semi-rigid, water resistant
PA02Eoooo isophthalic 1-10 0-5-0-6 90 38 15 Semi-rigid, water resistant
PA02G 0000 isophthalic 1-10 0-7-0-8 90 38 15 Semi-rigid, water resistant
PA04D 0000 isophthalic, 1-10 0-35 30 30 Plasticising grade
flexible
PA23COOOO isophthalic 1-10 0-3-0-4 125 25 )5 Rigid, chemical resistant
PA37J 1010 fire retardant 0-9-)-0 90 Impregnation
120 Potting
PA37J 7007 fire retardan t 0·6-0·7
28 30 Bonding paste, light
PA04T 7193 isophthalic, 2·2
green
flexible Bonding paste, dark green
1·2 28 35
PA04Z 7892 isophthalic,
flexible
102G 30lH 30lH 502G
Test methods BS 2782

Bayer UK Ltd 2 20 General purpose, thick


1·11 1·3a 34 7 50 60
Leguval N 22 laminates
1·15 1·9- 32 7 70 85 4 18 Hot press moulding
N30 2 General purpose
1·13 0·65 a 35 70 60
N50 2 General purpose, roof
1·13 0·65a 35 7 70 60 15
N50S light stabilised
lights
1·13 0·6P 37 70 60 2 Thixotro pic version
;:: N50T ofN 50
1·13 1-4a 35 8 105 50 2 21 General purpose
W 16
1·11 1·5a 35 8 120 35 I· 5 29 Good heat resistance
W20
1·14 1·la 40 115 85 3·5 24 High strength
W25 isophthaiic

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1·07 1·6a 41 7 110 70 2-4 Chemical resistant
W35 neopentyl glycol
1·06 1·4a 43 115 60 2·5 Chemical resistant
W37 isophtha lic/NPG
1·09 3·5 a 38 7 115 75 4·0 15 Chemical resistant
W41 bisphenol A
1·03 0·6a 50 7 120 60 2·5 IS Chemical resistant
W45 bisphenol A
1·17 1·1" 30 8 55 60 4·8 24 Flame retardan t
F24 chloroparaffin/
isophthalic
1·35 2·8 a 25 5 80 40 I· 3 12 Self-extinguishing,
F 30 HET acid
clear
1·30 0·7a 29 6 55 40 1·7 18 Self-extinguishing,
F 30 S HET acid
light stabilised
1·18 2·5a 29 7 80 60 1·8 14 Flame retardan t
F 35 chloroparaffin
1·12 1·la 34 6 RT 8 80 Putties, mortars
E 70 flexible
1·13 ).0- 26 6 RT 10 30 88 Flexibiliser
E 81 flexible
Table 9.6 (Continued)

Resin properties Cured properties

~
., ~
::::
0: """"' "S -~
~~
~
.2,. '- ~
~
'-
~
::: <:) s:
'" u
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~ '"
-~ -<:>
-~u " '~" '-
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Supplier ., D -\(
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$" f... ~~
-;; ~
t...~
<.J
'"'"
Trade name 8~ ...'" ~ -5'- ~ "''-
Q
Product code Type '" ~~
(1),- (I) Remarks
~ ~~ "'" ::t: ~~ ~ ~~
Leguval (contd)
E 90 flexible 1-09 1-2" 30 6-7 RT 10 50 Improved water resis-
tance over E 81
E 91 flexible 1-09 0-25" 33 6 RT 100 50 Sealing compounds
K 14 1-10 I-I" 35 100 Putties
-.J K27 1-13 3-0- 30 8 75 50 2-0 16 Putties
tv
K41 bisphenol A 1-09 3-5" 38 7 115 75 4-0 15 Chemical resistant
K65 tetrahydro- 1-12 0·85" 33 7 RT 8 65 37 Putties, sealing
phthalic compounds
K 70 flexible 1·12 I-I" 34 6 RT 8 80 85 Putties, floors

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LP 15 low profile 1-05 2-3" 50 110 Hot press moulding

Test methods DIN 4 6 7 7 9

BP Chemicals Ltd
Cello bond
A253/67 orthophthalic 1-07 0-19 45 92 Methyl methacrylate,
light stable
A259/204 orthophthalic 1-07 0-28 41 Vacuum impregnation
of castings
A259/214 flexible 1·13 0-82 24 Stoppers
A2593 flexible 1-13 0-16 36 Flexibiliser
1·26 T 38 72 BS 476 pt 7 class I,
A261/65 fire retardan t,
opaque
orthopht halic BS 476 pt 7 class I,
fire retardan t 1-60 0·9 22 80
A261/383 opaque
T 46 120 Fire retardan t, chem-
A261/1973 RET acid 1·12
ical resistant
= Retron 1973
0·33 41 73 General purpose
A262/249 orthophthalic 1·11
38 100 Filament winding,
A262/288 orthophthalic 1·11 0·39
hot press moulding
0·35 40 78 General purpose
A262/400B orthopht halic 1·10
0·36 36·5 63 General purpose, low
A262/420BLE orthophthalic 1·12
styrene emission
0·66 38 Stoppers
A262/424 orthophthalic 1·10
0·58 38 72 General purpose
A2622 orthophthalic I·ll
T 42 78 General purpose
A265/500B orthophthalic 1·09
0·9 41 100 White pigmented,
...,..... A265/51 IB/NI56 orthophthalic 1·12
acrylic baths
T 39·5 64 Low styrene emission,
A265/520BLE orthophthalic 1·10
general purpose
T 40 75 General purpose
orthophthalic 1·12

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A2656 130 Good chemical and
A266 I special 1·\2 0·53 37
heat resistance
T 39 65 BS 476 pt 7 class 2,
A271/77B orthophthalic 1·14
clear
T 28 94 BS 476 pt 7 class 2,
A271/84B fire retardan t 1·37
translucent
45 72 Methyl methacrylate,
A2712 orthophthalic 1·12 0·18
light stabilised
20 Gelcoat, BS 476 pt 7
A272/1 special, fire 1·54 T
class I
retardan t Gelcoat, BS 476 pt 7
orthophthalic 1-47 T 20 56
A272/3A class 2, opaque
Table 9.6 (Continued)

Resin properties Cured properties

0
.,
---- ;: ";5 .~
';:: ~ ---- i>IJ ----
~ '"
~ ~ 0: '- ~
0:
I: '- <:l 0: El
i>IJ <..J G !::
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., .~ .::l
0
<..J <:1-----
.2\..l '"i>IJ<:I '-
Supplier ., 0 ..:.: .... ~
:s.
<..J
'0:" .5 f... ~~
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Trade name 8~ "
'~:6 ~<:l
"''-
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Product code Type ~ ~B ~~ ~ ::r:: ~~ 1<5 ~ ~ Remarks

Cellobond (contd.)
A273j302A isophthalic 1·12 T 39 105 Weather, water
resistant
A273j380A isophthalic '·06 T 50 80 Flexible spray geicoat
A273j381A isophthalic I· I3 T 32 80 Flexible brushing
~ geicoat
A273j281AjN129 orthophthalic 1·32 T 32 68 Spray gelcoat, con-
tainers
A273j365AjN180 orthophthalic '·32 T 30 42 Roller geicoat, con-

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tainers
A2784 isophthalic 1·09 0·99 42 118 Marine, etc.
A2785CV isophthalic 1·09 T 43 118 Thixotropic version
of A2784
A283j270 isophthalic 1·11 0·56 36 80 Chemical resistant,
hot press moulding
A284j34 special 1·13 0·7 37 134 Non-shrink DMC
A360j82A orthophthalic 1·10 T 42 76 General purpose
A360j151 orthophthalic 1·15 T 32 Amine accelerated
for stoppers
A360j212B orthophthalic 1·09 T 45 64 Spray lay-up
A360j212C orthophthalic 1·09 T 45 64 Long gel time version
of A360j212B
A360j215C orthophthalic 1·10 0·36 40 74 Long pot-life resin
A370/111B orthophthalic 1·06 T 45 58 Fast cure, general
purpose
A3700A orthophthalic 1·11 T 40 58 Containers
A7ll/24 isophthalic 1·18 0·6 44 130 Low shrink for DMC
A7ll/26 isophthalic 1·\0 1·8 34 97 High reactivity
for SMC
A7ll/31 special 1·09 1·79 43 80 High reactivity for
SMCjDMC
A711/34 isophthalic 1·09 0·55 41 125 Non-shrink for DMC

Test methods BS 3532 and BS 2782 5 6

British Industrial Plastics Ltd


Beetle 8181 isophthalic 1·14 2·4T 31 6 59 69 23 Resilient gelcoat
8182 isophthalic 1·22 2·2T 29 6 58 69 24 White version of 8181
...,v. 8185 fire retardant 1·23 2·3 T 35 11 98 31 18 BS 476 pt 7 class I
or 2
8187 isophthalic 1·13 T 38 7 68 67 22 Spray version of 8181
8188 isophthalic 1·21 T 35 7 67 67 23 Spray version of 8182
828T 1·12 T 34 8 94 56 22 Thixotropic paste
823 E wax modified 1·11 T 39 8 62 46 14 Air cure

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836 E 1·10 0·4T 42 9 59 48 10 Low reactivity,
general purpose
837 E 1·11 0·4T 42 9 59 48 10 High reactivity,
general purpose
840 E 1·11 0·4T 42 9 59 48 10 Medium reactivity,
general purpose
844 bisphenol AI 1·04 0·75T 48 9 125 56 24 Chemical resistant
hydrog.
bisphenol A
849 reduced flam- 1·17 0·33 T 39 11 72 36 15 BS 476 pt 7 class 2
mability
Table 9.6 (Continued)

Resin properties Cured properties

~
~
.:
-<: S
t>
.;;: '" 0;,
<l ~ ~ 1::: ~ ~
... C 1::: C
be v :::" .S ..t:)
''"""
.2v " '"~ '- '" '"
<::s~
Supplier 'S, 1::: ..\( 10..~
,,~
" ~~ f..., ~~
",Cl.,
Trade name ~
"... ~
""< " ... Q
"'" ..:::
Product code Type ~ s=~ ~~ V)
" :t: ~~ ~ ~ ~ Remarks

Beetle (contd.)
854 reduced 1·17 0·33 T 39 11 72 36 15 BS 476 pt 7 class 2
flammability
855 reduced 1·54 0·55 T 23 4 60 10 12 BS 476 pt 7 class 1
flammability
-..J 856 reduced 1·15 0·33 T 39 10 81 38 19 Clear, UV stabilised
0-
flammability
8564 reduced 1·16 T 36 II 70 37 21 BS 476 pt 7 class 2,
flammability translucent
859 orthophthalic 1·11 0·31 42 10 112 48 18 Resin injection

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862 isophthalic 1·09 0-43 40 8 73 76 23 Stoppers, etc.
864 E 1·11 0·4 T 42 9 59 48 10 Fast cure, general
purpose
865 E 1·09 0·2T 47 9 60 45 9 Medium-fast cure,
general purpose
867 E 1·12 0-4 T 42 9 59 48 15 White pigmented,
similar to 840 E
868 methyl meth- 1·10 0·25 44 7 85 45 21 Light stabilised
acrylate
870 HET acid 1·13 0·35 T 44 7 115 44 16 Reduced flammabi-
lity = Hetron 1973
872 1·11 0·2 T 44 9 92 50 19 Acrylic baths
873 isophthalic 1·07 T 49 7 95 62 18 High quality resin
874 I·ll T 38 9 102 54 20 Chemical resistant,
mould making
876 E 1·12 T 40 9 82 48 15 Marine and tropical
use
878 E 1·12 T 40 9 82 48 15 Pre-accelerated
version of 876 E
8797 1·15 2·5 <0·5 Pigment dispersing
resin
8110 wax modified 1·11 0·54 39 8 62 46 14 Contains paraffin
wax
8116 1·11 0·54 39 8 62 46 14 Casting resin
8123 1·15 3-3 28 8 65 61 16 Hot press moulding
8128 1·12 0'88 35 8 95 56 22 Moulding compounds
8134 flexible 1·12 0·35 33 Flexibiliser,
castings

Test methods BS 2782 6 8 9 E = environmental grade


-..I
-..I
Cargill Blagden Ltd
400 1·14 0·5 T 84 69 3 (0'24) High impact
strength, moulds
513 1·09 0·3 T 62 1·7 (0,2) Fast cure, marine,

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etc.
804 1·12 0·6-0·7 Low exotherm,
marble casting
8211 1-08 0·38 T 65 1·8 (0,2) High production rate
8213 1·09 0·4-0·5 T 62 1·7 (0'2) Rapid cure, hand/spray
8214 1·09 0·4-0·5 T 62 1·7 (0,2) Rapid cure, hand/spray
8215 1·08 0'07-0·1 62 1·8 (0'2) High production,
high filler
8216 1·08 0·2-0·25 Filled mouldings
8217 1·08 0·06-0·1 Filled mouldings
8218 1·08 0·15-0·22 Filled mouldings
8219 1·08 0·1-0·15 Filled mouldings
Table 9.6 (Continued)

Resin properties Cured properties

.:
---.., t; -S .S:
.2 ~ --- ~---
. ~ ~ ~ '-- ~
~ '-
..:
c.... . ..:
I>C U '"
::; .S: ]
'" 0
.... ·£u '- <::---
Supplier .., 0 ..: ....~
<:>...,
'" ~~
.:; 1:1.,
... ~
Trade name
$....
5 h
""", " Q
~ "''-
'~~ .. <:>
Product code Type '" v;~ t:;j I>C Remarks
~ ~~ ~ ::t: ~~ ~ E
8220 1· \0 OA-0·5 T 65 1·8 (0·2) Low exotherm, large
mouldings
8221 1·\0 0·4-0·5 T 65 1-8 (0,2) Low exotherm, long
trim time
8224 1·08 0·43 T 65 1·8 (0,2) Winter use, fast cure
....,
00 8243 J.08 0·43 T 65 1·8 (0,2) Low exotherm, short
trim time
8245 1·08 0043 T 65 1·8 (0,2) Low exotherm, small
mouldings

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8249 J.08 0·39 T 65 1·8 (0,2) Low exotherm, large
mouldings
8255 J.09 OA-0-5 T 62 1·7 (0,2) Fast cure, short
trim time
8256 J.09 0·4-0·5 T 62 1·7 (0,2) Fast cure, short
trim time
8263 1.09 0-4-0·5 T 62 1·7 (0,2) Fast cure, hand/spray
8285 I·!O 0-4-0-5 T 65 1.8 (0'2) Low exotherm, long 'green' time
8286 1· \0 OA-0·5 T 65 1·8 (0,2) Low exotherm, long 'green' time
8314 flexible 1,140-35-0·4 6·9 80 (0,7) Encapsulation, stoppers
8318 flexible 1·14 004-0045 Encapsulation, stoppers
8336 flexible 1·15 o· 35-0'45 6·9 80 (0'7) Adhesives
8400 1·14 0·5 T 84 69 3·0 (0,24) Slow gel, fast cure, moulds
8411 1·08 0·4-0·5 T 65 1·8 (0,2) Fast demould
8446 1·03 0·4-0·5 Good chemical resistance
8450 isophthalic 1·09 0-4-0'5 T 115 69 2·0 Chemical resistant
8490 isophthalic 1·11 0·9 115 69 2·0 Corrosion resistant, pultrusion
8525 fire retardant 1-3 0·6-0·7 T 100 38 (0,18) General purpose
8530 1-08 0-4-0·5 T 65 1·8 (0'2) Low exotherm, hand/spray
8540 1·08 0·4-0·5 T 65 1·8 (0'2) Low exotherm, large mouldings
8575 fire retardant 1·3 0·6-0·7 T 100 38 (0,18) Medium gel and cure
8593 isophthalic 1·17 2·8 83 75 4·0 (0,24) Craze and impact resistant
8704 0·1-0·16 Transformers
8725 1·05 0·05-0·1 Water emulsions
8801 1·14 1·1 Marble casting
8804 1·12 Marble casting
8808 1·14 Marble casting
.... 8809 l·ll Casting, fast demould
'" 88ll 1·12 0·08 Casting, fast demould
8831 1·13 1·4 Casting, fast demould
8881 1·14 1·2 Low exotherm, casting
8882 1·14 1·2 Low exotherm, marble casting

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8884 1·12 0·6-0·7 Low exotherm, marble casting
8885 1·12 0·6-0·7 Low exotherm, marble casting
8911 1·14 2·8 71 68 1·8 (0'2) Matched metal moulding
8942 1·14 2·2 90 67 1·8 (0,22) Matched metal moulding
8953 1·17 2'6-3·0 83 75 4·0 (0,24) Hot press moulding
8960 flexible 1·05 0·8-1·1 9-4 65 (0-4) Flexibilising resin
8974 1·17 2'6-3'0 90 82 2·9 (0,24) Matched metal moulding, BMC

Cray Valley Products Ltd


Synolac 6311 flexible 0'8-1'1 28 Flexi biliser
6314 6'5-8·0 For pigment dispersions
6320 isophthalic 40-55 40 Gelcoat, brush application
Table 9.6 (Continued)

Resin properties Cured properties

~
~
.:
:; ~ ·9
.~ '" -::
. ~ ~ ~ ~
~ :::: ~
c ~ ::::
~ '-> G ·9 ]
0 <::s~
'->
Supplier
---.~u '~" '"
:s, '" 0
::::
'" -'< --- ~~ ... ~
Trade name c.., .5 h ",1:1., "'---
"'" '"
~~ ... c:::
~c
Product code Type ~ "'"
~~ V3~ ~ ::t:: ~~ iii ~r Remarks

Synolac (contd.)
6321 isophthalic GeIcoat, spray version of 6320
6322 35-55 37 White, light stabilised geIcoat
6323 12-25 44 Spray version of 6322
6325 NPG 40-55 33 GeIcoat, brush application
co 6327 35-55 GeIcoat, tooling grade
0
- 6329 T 58 Flexible topcoat
6340 silica filled 0'6-0·8 31 Contact moulding
6344 0'6-0·8 32 74 Contact moulding

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6344-002 0·23-0·28 40 74 General purpose, fast cure
6344-060 T Paste for stoppers
6344-211 0-45 35 74 Pre-accelerated version of 6344
6344-302 0·25 40 74 Injection moulding
6345 0·5-0·9 33 77 Contact moulding,
sheet grade
6345-211 0·45 36 77 Pre-accelerated 6345
6345-213 0·2 45 77 Low exotherm, long
gel time
6345-214 0·28 39 77 White pigmented 6345
6345-217 0·45 34 77 Low exotherm, long
gel time
0·23-0·2 8 37 74 Injection moulding
6354-00 2 fire retardan t
0·3-0,35 32 72 BS 476 pt 7 class 2,
6356 fire retardan t
filled
0'6-0·7 35 97 High HDT
6370 orthopht halic
J.3-1·7 31 100 Chemical resistant
6375 White, acrylic baths
6382 orthopht halic 0-45 37 97
0·45 40 97 Improved version of
6383
6382
0·45 40 97 Unpigme nted 6383
6384
0·7-1·0 40 85 Chemical resistant,
6390 pipes, etc.
1·0-1·2 29 120 Chemical resistant
6392 fire retardan t
0·75 40 100 Semi-rigid, pipes,
6393 isophthalic
tanks
0·6-0·9 40 95 Tanks, containers
6394 isophthalic
0·7-0·9 40 100 Chemical resistant
00 6395 isophthalic
1-4-1,9 48 Zero shrink, hot press
6401 low profile
moulding
1'0-1'5 49 Hot press moulding
6403 low profile
1·1-1·8 35 Hot press moulding
6404

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0·5-0·6 34 BS 476 pt 7 class 2,
6410 fire retardan t
unfilled
0·35-0-45 20 72 Filled, fire retardan t
6416 fire retardan t
0·45 25 72 Filled, BS 476 pt 7
6417 fire retardan t class 1
10-20 34 Ge1coat
6420 fire retardan t
0·7 57 Spray gelcoat for
6421 acrylic sheet
40 47 Brush version of 6421
6422 For use in low profile
Synocryl 4008 powder
systems
Table 9.6 (Continued)

Resin properties Cured properties


;: ";'5 ·9
~ --- ~
---
~ '- ~
.s. ~---'" ~
'-
>: c
c .... >:
~ '""'
G
0
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.~ 0 ~~ .... ~
$'""' '>:" .....5~ !-. .;;; Q.;,
Trade name ~ ~'-
'""' "N "
'~~ .... ..Sl
Product code Type ~ ~~ C;S~ c55 § ~~ r..) ~eo Remarks

Freeman Chemicals Ltd


Stypol 40-1050 flexible 1·01 0·04 34 5 177 Potting
40-1051 fire retardant 1·1-1-4 29 Crack resistant cast-
ing resin
40-1054 flexible 0·04 40 Chokes and trans-
OC>
N formers
40-1070 isophthalic 1·14 2·5-3·1 32 75 80 3·3 23 Hot press moulding
40-1080 thermoplastic 3-8-4·5 40 Low profile additive
solution

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40-1096 isophthalic 1·10 0·18-0·25 40 90 65 2-4 19 Pipes and tanks
40-1097 special 0·96 0·9-1-1 37 Contains diallyl
phthalate
40-2012 orthophthalic 1·14 0·75-0·85 32 8 35 Flexibilising resin
40-2417 orthophthalic 1·2 204-2·9 29 75 56 1·3 30 Hot press moulding
40-2756 orthophthalic 1·18 T 33 60 45 1·8 35 Fire retardant, BS 476
pt 7 class 2
40-2769 fire retardant 1·55 T 27 75 12 18 Filled, BS 476 pt 7
class 1
40-2989 isophthalic 1·08 T 48 110 65 204 20 Resilient, corrosion resistant
40-3250 orthophthalic 1·11 0·13-0·16 33 80 Flexible jointing resin
40-3252 orthophthalic I· I2 0·12-0-15 34 80 Flexible jointing resin
40-6003 orthophthalic H5 1-4-1'6 30 72 85 5·5 22 SMC,DMC
40-6006 isophthalic 1·09 0·95-1·05 42 110 45 2·5 30 High reactivity, SMC, DMC
40-6020 orthophthalic 1·11 0·92-1·07 33 115 40 1·1 25 High reactivity, SMC, DMC
40-6021 orthophthalic 1·11 0·92-1·07 33 115 40 1·1 25 Rigid, high reactivity, DMC
40-6207 orthophthalic 1·52 4·8-7·7 14 6 Filled, resilient cast-
ing resin
40-6502 orthophthalic 1·46 1·5-2·1 21 10 80 Flexible, filled cast-
ing resin
40-6749 Ge1coat
40-6754 orthophthalic 1·53 T 25 45 49 H 32 Fire retardant gelcoat
40-6764 isophthalic 1·15 T 35 53 63 4·5 20 Resilient, brush gelcoat
40-6878 orthophthalic 1·2 0'17-0·26 40 65 65 1-8 18 Hand lay-up, containers
40-6879 orthophthalic 1·14 T 38 70 65 1·8 20 Hand/spray lay-up,
containers
40-6990 orthophthalic, 1·10 T 40 100 30 1· 3 25 High reactivity, sanitary
00 clear ware
w
- 40-6993 orthophthalic, 1·10 T 40 100 30 I· 3 25 High reactivity, sanitary
white ware
40-7488 1·12 0'92-1'07 34 150 27 0·9 40 Use with low profile
additive for SMC, DMC

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40-8200 bisphenol 1·04 2·6 7·5 130 43 SMC, DMC, matched metal
moulding

Test methods BS 2782 and BS 3532 4 5 6 8 8 9

Garrick Chemical & Equipment Co. Ltd-Agent for Ashland Chemicals


Hetron 72 1·22 2·2 33 Chemical resistant, press
moulding
72L 1·20 0·65 39 Chemical resistant,
winding
72S fire retardant 1·20 0·65 39 Press moulding, SMC, DMC
Table 9.6 (Continued)

Resin properties Cured properties

.:
-S ·S
~
.S,. ---"" --- ---
~ .::: ~ '- ~
t:
~ '- C
" t:
. <> ... G r ·s
Supplier <> .21..1
..., 0
~ ~ ""
..!(
...t: ~
$ c.,.., ... ~~
f.... ~ '-
.S 'r;;
i...... -"
Trade name ...<> <>", ... Q
~
Product code Type ~~ ~~
"J,,- ~ ::::; ..s
t.:i Remarks
~ ~~ ~r
Hetron (contd.)
92 fire retardant 1·33 2·2 29 Press moulding, pultrusion
92AT fire retardant 1·29 0·5 36 Chemical resistant
92FR fire retardant 1·29 0·5 33 Chemical resistant
00 92FS fire retardant I· 3 0·11 38 Chemical resistant
"" 197 fire retardant 1·2 2·0 31·5 Chemical resistant,
press moulding
197-3 fire retardant 1·14 0·5T 42 Chemical resistant, fila-
ment winding

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197P fire retardant 1·14 0'5T 42 Chemical resistant, fila-
ment winding
197L fire retardant 1·17 0·55 38 Chemical resistant, fila-
ment winding
197AT fire retardant 1·25 0·5 37·5 Chemical resistant, fila-
ment winding
197A fire retardant 1·15 0·5 T 45 High impact, chemical
resistant
197-8515 1·15 0·28 40 High impact, filament
winding
700 bisphenol AI 1·03 0·5 50 Chemical resistant
fumarate
700C bisphenol AI 1·03 0·5 50 Chemical resistant
fumarate
28091 brominated 1·5 0·7 28·5 Fire retardant,
(37% Br) SMC,DMC

Hoechst AG, Resinous Chemicals


Alpolit UP 092 1·10 0·7 37 90 28 2·0 17 General purpose
VUP 37/1 1·14 1·0 33 72 4·5 Casting resin for buttons
VUP 79 1'!3 T 32 7 66 4·5 Thixotropic button resin
UP 130 flexible 1·12 0,7-0,9" 35 8 24 70 FiexibiJising resin
UP 201 1·12 1,2-1,5" 33 7 74 59 1·6 Amine accelerated,
stoppers
UP 220 1·11 0·23 42 68 30 1·1 16 General purpose
UP 223 light stabilised 1·12 0·6 35 51 54 Encapsulating, clear
UP 231 flexible 1·10 0,3-0·5 34 8 3 75 Amine accelerated, stoppers
UP 270 1·12 0·5 38 71 33 1·7 12 General purpose
0;; UP 363 1·10 0·35 37 108 28 1·1 38 Hot water tanks
"" UP 375 isophthalic 1·15 25 T 35 68 44 1·8 10 Gelcoat, marine
UP 376 1·30 25 T 32 63 44 1·6 15 White gelcoat
UP 404 self-extinguishing 1·2 0·19 33 7 74 39 2·2 Clear, BS 476 pt 7
class 2

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UP 462 chlorinated 1·24 0·35 35 86 11·6 0·3 13 Fire retardant, chemical
resistant
UP 468 fire retardant 1·45 0·54 28 58 20 1·0 7 BS 476 pt 7 class 2,
filled
UP 745 terephthalicl \·06 0·8" 44 7 145 50 2·3 Chemical resistant
NPG
UP 746 isophthalicl 1·06 1·6 " 45 8 60 2·5 Chemical resistant
NPG

Test methods DIN 2 4 II 12 6 7 7 9

Honeywill-Atlas Ltd
Atlac 382 E propoxylated
bisphenol 1·16 solid 0 Chemical resistant,
solid resin
Table 9.6 (Continued)

Resin properties Cured properties

.:
"' ,0 ·9
.~
,. '" .,
~
"' -S
"<
"'
.'-
~ ::: '- ~
ci' -! ::: c
c !: :::
~ "~ G
0
" ·9 '"
Supplier .Sv '- '" ~"'
"::: -"t
$'" ~ 0 " ~~ ,~
Trade name ·5 h ~Q.; ~ " '-
'"" "'~ "~:6 .. ~ -9
Product code Type ~ ~~ C;S~ ~ ::r: ~~ [.:,l ~ ~ Remarks

Atlac (contd.)
382-05A bisphenol 1·03 0·4-0·55 50 140 70 2·5 Solution of 382
A/fumarate in styrene
00 387 flexible 1·03 32-45 0 For blending with 382
0-
480 terephthalic Chemical resistant, general
purpose resin
490-05 terephthalic 1·10 0·6 40 125 49 1·8 30 Chemical resistant, general
purpose resin

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711-05A fire retardant 1·23 0-45-0'6 120 Chemical resistant
4010 flexible blend 1·02 0·24-0'34 50 96 68 4·0 Blend of 382/387-40/10

Hills (UK) Ltd


Vestopal 11 0 1·!7 1·0 30 7-8 70 90 4·0 Gelcoat, hand lay-up
120L light stabilised 1·13 0·8 33 7·3 70 55 1·5 Continuous processing
120T 1·11 0·5 38 7·5 75 40 1·5 Marine, pipes, etc.
121L light stabilised 1·11 0·4 36·5 8·0 70 65 1·5 Continuous sheet processing
123L light stabilised 1·10 0·15 43 8·0 75 60 1·5 Continuous sheet processing
140L light stabilised 1·11 0·6 30 7·8 70 70 lO Continuous sheet processing
141L light stabilised 1·10 0-4 33 7·8 70 65 2·5 Continuous sheet processing
145 1·12 1·1 30 7·1 75 80 3·0 Hand lay-up, gel-
coats, etc.
145T 1·10 0·3 T 39 7·5 85 70 2·0 Hand/spray lay-up,
gelcoats
150 1·13 1·0 34 8 110 85 3·5 Cold press moulding,
gelcoats
151 1·13 1·0 34 8 110 85 3·5 SMCjDMC
150T 1·12 0·5 T 42 7·5 115 70 2·0 Hand/spray lay-up,
gelcoats
150B 1·13 1·0 34 8 110 85 3·5 Cold press moulding,
hand/spray
152 1·10 0·25 41 8 90 55 2·0 Press moulding, gel-
coats, etc.
160 1·10 0·8 33 7·5 100 75 2·2 Various, gelcoats
160T 1·09 0·5 T 37 7·5 100 70 2·0 Hand/spray lay-up,
.- gelcoats
00 221L flame retardant 1·31 0·55 30 6·5 95 40 1·5 Light stabilised, sheets
.....
250 flame retardant 1·22 1-4 28 8 80 85 2·5 Various, gelcoats
251 flame retardant 1·17 1-4 30 7-8 90 90 3,0 SMCjDMC
252 flame retardant 1·17 1-4 30 7-8 90 90 3·0 Hand lay-up, press
moulding

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310 flexible 1·17 1·0 27 7·1 50 25 20 Flexibilising resin
320 flexible 1·13 0·95 25 7·3 12 25 Flexibilising resin
330 flexible 1·13 0·25 30 6·5 4 80 Flexibilising resin
400 special 1·11 4·5 35 5·1 105 80 2·5 Hand lay-up, gelcoats
X2814 experimental 1·08 1·0 40 7·3 145 50 1·5 Hand Jay-up, gelcoats,
chemical resistant
510 1·07 J·O 38 8 115 80 2·5 Hand Jay-up, press
moulding
511 J.07 1·0 38 8 115 80 2·5 SMC, DMC
530 1·10 1·0 40 7·6 130 65 2·2 Hand Jay-up, press
moulding
710 1·13 0·4 33 6·6 10 45 Amine accelerated,
putties
Table 9.6 (Continued)

Resin properties Cured properties

""""' ;:; "S ·9


.,.;:, "" """"' """"'
~
~ ~ ~ '-
~ ::: '- e.'"
c
l: '- :::
:3 "-
'"
"< G
0 ';; ·9 1S<::1--'"
<.J .S\.) '~" '- ",""""'
Supplier :s, -'C ~ .... ~
"" 0 '"
E
Trade name <.J 8'" ·s"- f.... 1;~ ~ ,'!l'-
'" "' ..... ~~ Cl .:=
Product code Type ~ ~~ V)L C;S :t; ~~ t..j ~ r Remarks

Vestopal (contd.)
730 1·13 1·0 34 8 105 85 3·5 Amine accelerated, putties
810 1·13 0·4 33 6·6 10 45 Non-accelerated, putties
8Il 1·12 0·4 35 6·7 10 45 N on-accelerated, putties, etc.
00 830 1·13 1·0 34 8 105 85 3·5 Non-accelerated, putties, etc.
00
- Test methods DIN 2 4 11 6 7 7

International Paint Ltd, Industrial Division Pigmented resins also available

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5560 C 8007 orthophthalic 1·10 0·22 T 45 76 43-4 2·5 14 General purpose
5560 C 8008 orthophthalic 1·12 0·5 T 40 70 54·5 2·8 15 General purpose
5560 C 8009 orthophthalic 1·10 0·22 T 45 76 43-4 2·5 14 General purpose
5560C 8016 orthophthalic 1·12 0'5 T 40 70 54·5 2-8 15 General purpose
5561 C 8813 fire retardant 1·18 0·3 T 39 70 34·6 12 BS 476 pt 7 class 2,
clear
5561 X 0009 fire retardant J.32 0·3 T 32 74 37·3 12 BS 476 pt 7 class 2,
opaque
5566C 8003 isophthalic 1·10 0·26 44 III 23 Hand/spray lay-up,
injection
5566 C 8095 flexible, iso- 1·10 0·32 45 83 78·8 4·0 23 Hand/spray lay-up,
phthalic injection
5567 C 8000 orthophthalic 1·10 0·26 T 45 74 42·7 2·5 14 Hand/spray lay-up
5567 X 0004 orthophthalic 1·12 0·30 42 91 22 White, bath manufacture
5567 C 8026 orthophthalic 1·10 0·27 40 72 51·7 2·0 16 Resin injection
5567 C 8060 orthophthalic 1·10 0·27 T 43 70 48·0 18 Hand/spray lay-up,
fast cure
5567 C 8106 isophthalic Clear, resin injection
5568 Z 0001 fire retardant l-41 0-45 30 69 21·5 9·5 Filled, BS 476
pt 7 class I
5618 C 8005 isophthalic Brush gelcoat, clear
5618XOOO5 isophthalic Brush gelcoat, white
5618 X 0007 isophthalic Brush gelcoat, white,
fire retardant
5619 C 8005 isophthalic Spray gelcoat, clear
5619 X 0005 isophthalic Spray ge1coat, white
oc
'-&)
- Test methods 4 5 6 7 9

KWR Chemicals Ltd- Agent for CdF Chimie


Norsadyne 70 1·10 0·35 42 9 108 44 3·2 20 Chemical resistant grade

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71 1·09 0·65 40 9 101 56 3·3 16 Chemical resistant grade
83 flexible 1·14 0·35 28 8 37 14 27 51 Flexible resin
213 FM low shrinkage 1·07 0·4 3 98 23 1·7 47 Low shrink, encapsulation
249 1·10 0·35 37 8·5 99 70 3·0 20 Fuel tank grade
292 orthophtha1ic 1·10 0·35 37 9 89 60 2·0 18 General purpose
294 T 1·10 0·35 37 8·5 98 69 3-0 21 Food industry grade
297 1·18 5·0 20 7 50 63 4·9 25 Hot press moulding
453 self-extin- 1·25 0-4 30 8 94 67 3-8 22 Fire retardant
guishing
502 1·11 0·25 38 9 60 34 H 16 High clarity for
roofing sheets
533 1·10 0·2 38 8·5 69 62 3·0 18 Casting resin
574 orthophthalic 1·11 0·25 38 8 68 56 2·0 13 General purpose
Table 9.6 (Continued)

Resin properties Cured properties

.:
;: ~ .s=
.S ---'" -:: ~
---
;. ~ '-
~ s::: ~ ~ ~
~ '- c .... s::: c
be G ;:;" .s=
"~ 0 i~
Supplier .2\") ""s::: '-
... ~
$" '" 0 ~~
Trade name c'" ""'.s...." f.... ",Q., ~ ~'-
Type
" "'" "~~ § ~
Product code ~ ~';j ci;~ ~ ~~ ~ ~ ~ Remarks

Norsadyne (contd.)
601 1·10 0·14 38 8·5 80 64 4-4 23 Translucent, building grade
904 1·11 0·35 38 For SMC
~
- Test methods 6

Pechiney Ugine Kuhlmann Ltd


UkaponD 09 1·15 4·8-5·2 27 6·6 75 62 3·0 Hot press moulding

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D09BS 1·12 0·85-0·95 35 8·0 80 44 1·5 Casting, encapsulation
D 13 T orthophthalic 1·15 T 28 55 2·4 Ge1coat
DIS 1·14 2·0-2·2 30 7·5 77 55 2-4 Hot press moulding
D18RC 1·12 0·85-0·95 33 8·2 80 52 2·2 Coatings
D 20 1·12 0·6-0·65 36 8·2 84 52 2·2 Cold press moulding
D 26 1·10 0·22-0·25 42 8·2 90 50 1·9 Hand/spray lay-up, injection
D 35 R 1·07 0·06-0·08 50 10 95 58 2·1 Polyester concrete
D 320R 1·12 0·67-0·75 36 7·3 69 59 2·7 Continuous sheet pro-
cessing
D 325 1·11 0-4-0-45 38 7-3 70 50 1·8 Vacuum casting
D 328 SN 1·10 0·2-0·25 43 7·6 70 50 1·8 Sandwich panels
D 416 R2 1·13 1·2-1·3 34 8·0 72 45 1·3 Buttons
D 420 R 1·12 0·6-0·65 36 8·2 84 57 2-4 Contact moulding
D 426 1·10 0·22-0·25 44 8·4 86 58 2·3 Hand/spray, injection
D 426T 1·10 0·65-0· 75 40 8A 86 58 2·3 Hand/spray lay-up
D 428 T 1·09 0·3-0·38 42 8·4 86 58 2·3 For tropical use
D 430 TN 1·100·37-0·43T42 8·4 90 56 2·2 Long pot-life, general
purpose
D 1524 N 1·12 0,3-0·35 39 8·5 62 60 2·8 Good impact strength
D 1207 MRL methyl meth- 1·12 0·27-0·29 40 9·4 66 65 3·2 Continuous sheet
acrylate production
D 2522 RU 1·10 0·65-0·7 36 8·4 73 63 3·8 Continuous sheet
production
D 2530 TS 1·08 0·4-0·5 T 45 8-5 78 69 3·8 Fast production rate
D 2730 VU 1·09 0·14-0·17 45 9-2 74 57 2-2 Continuous sheet
production
D 2807 F 1·17 4-8-5'2 24 5-4 47 45 3·0 Hot press moulding
D 3232 isophthalic 1·07 OA-0'45 46 8·4 96 75 3·3 Corrosion resis-
::0 tant, SMC
- D 3319 1·14 2·0-2·2 34 8-0 60 79 4·8 SMC
D 3325 S 1·!2 O· 55-0·65 40 8·2 70 60 3·0 Containers
D 3422 VU H2 0-65-0-7 39 8- I 54 54 2-2 Continuous sheet
production

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C 60-150 0 Pigment dispersing resin
C5 1·19 <30 0 Pigment dispersing resin
C 113 TIL isophthalic I- 14 5·0-6·0 T 28 8·3 60 45 9·1 Clear gelcoat
C 1I5 T isophthalic 1-14 17·5-22 T 34 8·3 60 45 9·1 Gelcoat and addition
to other resins
C ll8 isophthalic 1-14 0'6-0,65 34 8·3 60 45 9-1 Ge1coat, cold press
moulding
C 215 T3 orthophthalic 1-15 4-0-5-0 T 30 5- I 60 49 H Clear gelcoat
C 420 1-13 1-2-1'3 35 57 68 4-5 Buttons, coatings
CIF 5100 self-extin- 1·66 1·4-1·6 26 Cold press moulding,
guishing etc.
Table 9.6 (Continued)

Resin properties Cured properties

~
.:
;;: ~ .:=:
~ "" -S
';: ~ ~ ~
---~ ~
~ I:: C
'-- c\..l I::
~ b/) G ~ .:=: oC)
""<:1---
I.> .2u '<:I" ~
Supplier .., 0 I::
'" """'~ Io...~
$ f...
Trade name I.> 8~ "'.5..." ~~ "''--
'" "
'~~ ~c
Product code Type ~ :::~ ~~ t5 § ~~ 1:<l ~ E" Remarks

Ukapon (contd.)
CIF 75185 self-extin- 1·49 0·9 -1·0 24 91 Filled, contains no
guishing chlorine
::0
N
CIF 76176 self-extin- I· 38 0·32-0·37 36 60 Filled, contains no
guishing chlorine
F210 flexible 1·18 104-1·6 25 6·7 IS 30 Flexi bilising resin
F 335 flexible 1·02 0·6-0·65 50 9·5 4·7 140 Flexibilising, casting
F 418 J flexible 1·12 0·6-0·65 34 8·8 18·5 18 Putties

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F 531 S flexible 1·16 0·2-0·25 36 6·3 10 90 Pipe jointing
IF 220 R chlorinated diol 1·20 0·4-0·45 36 8-4 101 51 3·2 Self-extinguishing
IF 520 chlorinated diol 1·24 0,6-0·65 34 7·) 75 55 3·0 Self-extinguishing
IF 1126 self-extin- 1·14 0'11-0·13 50 8·8 52 48 4·8 Contains no chlorine
guishing
IF 1217 S 1·27 0·25-0·3 50 7-3 42 5·4 U sed in CIF 5100
IF 1325 fire resistant 1·22 1,2-104 40 8·1 130 65 2·9 SMC
T 120 SI 1·10 1·05-1·15 40 8·5 125 41 1·5 Heat resistant, SMC
T 215 MRL methyl meth- 1·16 0·22-0·25 41 7·5 85 56 2·3 Transparent sheets, etc.
acrylate
T 215 MARL methyl meth- 1·10 0·14-0·17 43 7·5 87 55 2·2 Transparent roof lights
acrylate
T 216 1·13 1·2-1·3 32 7·6 106 50 1·9 Cold press moulding
T 260WDC 1·08 0·11-0·15 39t t Without styrene
for SMC
T 723 J 1·09 0·6-0·65 38 9·5 81 45 1·4 Putties
T 620 1·12 1·4-1'6 32 7·3 79 64 3·5 Cold press moulding,
winding
T 623 1·10 0·6-0·65 35 8·1 86 70 3-8 Transparent, injec-
tion moulding
T 624 PS J.09 0·27-0·32 40 8·2 90 70 3-8 Centrifugal moulding
T 928 1·\0 0·85-1·0 42 8·6 140 25 1·0 Low shrink with
75131 and 75132,
low profile with 76118
Ukadiol 220 S chlorinated diol 1·22 0·6-0·65 40 6·8 100 55 2-4 Self-extinguishing
~
t.H Test methods ISO 6 8 8

Rohm & Haas (UK) Ltd


Paraplex P-340 1·12 0·97 30 Used with low profile
additives to give low/

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zero shrink SMC/DMC
P-543 low profile 0·98 1·2 67 Acrylic polymer/
additive styrene syrup
P-681 low profile 0·98 1·32 70 Acrylic polymer/
additive styrene syrup
P-701 low profile Acrylic polymer/
additive styrene syrup
P-713 low profile 0·98 I· 5 70 Thermoplastic polymer/
additive styrene syrup
Table 9.6 (Continued)

Resin properties Cured properties

~
---- ;;; -S .9
.~ '" ~ ---- ~
----
~ ~ ~ "-- ~
I::
"-- <::> I::
'"::!
b< ~o, .9 ]
.~\.,) '~" o:s----
Supplier o, 0
"I::
'" ~ "'----
:s-" <::>.,., ""~
Trade name ·5
t.... ~~ ~ "'''--
"
'" '-'"" "
'""----
c.~
...
..0: ~
Product code Type ~ ~~ CIl~ CIl ~ ~~ t<l ~ ~ Remarks

Scott Bader Co. Ltd


Crystic
::0 Gelcoat IPA orthophthalic 1·12 T 72 65 2·0 17 Resilient gelcoat,
"" moulds
Gelcoat 33PA isophthalic 1·15 T 33 52 60 4·0 20 Resilient, moulds,
vehicles
Gelcoat 39PA isophthalicj 1·24 T 28 60 60 H 21 Resilient, light

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HET acid stabilised
Gelcoat 46PA isophthalic 1·40 T 65 35 1·1 17 Light stabilised, low
fire hazard
Gelcoat 47PA HET acid 1·48 T 65 35 1·0 18 Light stabilised, low
fire hazard
GeJcoat 65PA isophthalic 1·11 T 36 75 70 2·5 17 Resilient, marine
applications
GeJcoat 68PA isophthalic 1·10 T 65 65 3·0 17 Spray application
GeJcoat 69PA isophthalicj
NPG 1·10 T 90 65 2·5 15 Chemical and water
resistant
Fireguard 75PA HET acid 1·35 T 53 Intumescent coating
II3PA orthophthalic 1·10 T 62 65 2·0 16 Low styrene emission,
general purpose
189LV orthophthalic 1·15 0·36 38 60 70 4·0 13 Tough, long 'green' stage
189MV orthophthalic 1·l7 0·9 33 56 70 4·0 13 Tough, long 'green' stage
191LV orthophthalic 1·11 0·35 36 66 60 2·0 19 Clear, light stabilised
193HR orthophthalic 1·11 0·18 40 64 65 2·3 22 Methyl methacrylate,
light stabilised
196 orthophthalic 1·12 0·9 33 72 69 2·3 16 Resilient, general purpose
198 orthophthalic 1·11 0·65 36 110 60 2·1 25 Chemical resistant
199 isophthalic 1·10 0·6 38 130 62 2·5 25 Good temperature and
chemical resistance
272 isophthalic 1·10 0·35 41 75 75 3·5 16 High performance,
winding, etc.
302 HET acid 1·33 1·05 27 60 55 1·9 12 BS 476 pt 7 class 2
306 HET acid 1·18 0·35 31 52 48 4·0 30 Light stabilised, fire
retardant
323PA orthophthalic 1·20 0·8 33 70 43 1·4 13 BS 476 pt 7 class 2,
:c
v. opaque
328PA orthophthalic 1-39 T 60 35 I· 3 26 Opaque, low fire
hazard, class 2
345PA orthophthalic/ 1-45 T 72 30 0·6 12 BS 476 pt 7 class 1,
HET acid opaque

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346PA HET acid 1-48 T 64 35 0·5 12 BS 476 pt 7 class 1,
opaque
385PA isophthalic/ 1·15 T 70 55 2·9 30 BS 476 pt 7 class 2,
HET acid clear
386 HET acid 1·33 0·2 50 46 1·5 12 BS 476 pt 7 class 1,
light stable
389PA orthophthalic 1·l7 T 60 50 2·0 20 BS 476 pt 7 class 2,
clear
390 isophthalic 1·14 0·95 52 68 6·0 20 Tough, flexible, gelcoats
392 isophthalic/ 1·07 0·8 90 70 3·0 14 Laminates on uPVC
NPG
Table 9.6 (Continued)

Resin properties Cured properties

s::'
.::. 0: "S ;;-.: ·9
.;:
--'"
~ ~ --
~ be ----
'-- ~
~ '--
s:: <::>
<::> s::
be <J G
.....s:: .Q
'"
<J
, ~ ·9
Supplier .~<;,.)
., 0
~ '--
:s <::>",
"'< .. -- ~~
<J .5 ~ 'E;~ ~'--
...s::
Trade name .. l:!'" ""---- ... ~
~
<::>
Product code Type ~ s:~ ~~ ~ ::t:: ~~ t<i ~ ~ Remarks

Crystic (con/d.)
405PA orthophthalic 1·12 T 69 65 2·0 18 Marine use
406PA orthophthalic \·10 T 62 65 2·0 16 Low exotherm, fast
mould release
~
- 471PA orthophthalic 1·1\ T 72 69 2·0 17 Spray, short mould
release
474PA orthophthalic 1·10 T 110 60 2·1 25 Thixotropic version
of 198
491PA isophthalic 1·1\ T 40 75 75 2-9 19 High performance, chem-

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ical resistant
504 orthophthalic 1·1\ 0·35 67 65 1·8 18 Cold press moulding
505 orthophthalic 1·19 0·52 62 60 1·4 12 Low fire hazard,
cold press
506 orthophthalic 1·1\ 0·35 75 69 2·0 17 Resin injection, cold
press, clear
586 fatty acids 1·14 0·31 45 Flexibilising, putties
600PA bisphenol 1-04 0·75 47 120 70 4·0 17 Chemical resistant
625MV isophthalic 1·13 0·8 94 65 2·2 18 High performance
17449 DCPD modified 1·10 0·38 115 60 2·0 27 Heat resistant

Test methods BS 2782 and BS 3532 4 5 6 8 8 9


Synres (UK) Ltd
Synolite 235 orthophthalic T 6·5 58 Topcoat
302 HET acid 1·18 1·7-2·2 32 6 120 35 1·2 Chemical resistant,
= Hetron 197
336 orthophthalic 1·13 0,6-0·8 32 6·5 74 74 2·5 Buttons
339 1·12 0·55-0·75 32 6·7 74 68 5·0 Buttons
364 Low exotherm, low shrink,
resin injection
367LS 1·100·12-0·14 39 6·8 68 52 2·5 Corrugated sheets
373 bisphenol A 1·03 0·5-0·7 41 5·9 136 43 1·5 Chemical resistant
375 orthophthalic 1·14 1·3-1·7 31 6·5 94 49 1· 3 General purpose
377 1·07 0·7-1·0 40 6·9 91 68 3·0 Good adhesion to PVC
400 1·14 1·3-1·8 31 6·5 99 44 2·5 SMC, DMC
544 orthophthalic 1·13 0-6-0·8 32 6·5 74 74 2·5 General purpose, food
contact
545 1·12 0·5-0·7 33 6·8 77 49 1·2 General purpose
573 orthophthalic 1·13 0·7-0'9 33 5·4 76 38 1·9 Low reactivity, low
::0
..... shrink
574 orthophthalic 1·13 0·7 ~0·9 33 5-4 76 38 1·9 High reactivity
version of 544
594 isophthalic 1·12 0·6 -0·9 41 7·0 95 78 5·0 Resilient, general
purpose

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595 isophthalic 1·12 0·7-0·9 40 H 95 64 1· 3 Rigid, chemical resis-
tant
711 flexible 1·05 0·8-1·1 28 5·1 9-4 65 Mortars, etc.
822 HET acid 1·28 1·8-2·2 25 7·0 82 98 2·8 Self-extinguishing,
hot press
823LS HET acid 1·27 0·6 26 5·8 46 24 10 Light stabilised,
sheets
892 HET acid 1·34 1·6-2·2 29 6·1 90 34 1-4 Fire retardant, chem-
ical resistant
922 T 6·0 Thixotropic paste,
8% Aerosil
940 isophthalic T 7·0 95 Ge1coat based on
594LS
Table 9.6 (Continued)

Resin properties Cured properties

i
o,
""" ~ .S::
C- ~ ~ """
.;: ~ ~
~ I:: ~ ~ e.
C
'-- c .. I:: o,
G ~
.:::'o," .S
0
t .S\.) '-- <::I"'
Supplier ., 0
$" c.,.,
.."I:: t-. "'--- t...~
~'--
.. .....5""<::I
Trade name ... ~~ ~c
.." ~~ ~
Product code Type ~ "'"
~~ VJt... ~ ::t; ~~ ~ ~ E' Remarks

Synolite (contd.)
943 orthophthalic 1-14 T 6·5 94 49 1-3 High reactivity
version of 375
945 orthophthalic T 6-3 45 Gelcoat based on
~ 544LS/711
00

Synthetic Resins Ltd


Dragel 34-01A fire retardant 2-3" 65 45 3-0 (0-18) Clear gelcoat
34-02A isophthalic 2-5-3-5 79 69 H (0-28) Clear gelcoat

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34-308A isophthalic 2-2-3-2 115 66 2-2 (0-09) Gelcoat, tooling,
marine, etc_
54-01A isophthalic 2-5-3-5 79 69 3·4 (0-28) White version of
34-02A
259A flexible 2-0-3-0 53 38 3-5 (0-17) Gelcoat
633A fire retardant 1-5-2-5 50 38 3-0 (0-06) White gelcoat
644A 1-5-2-5 67 49 2-0 (0-06) Gelcoat also as low
viscosity grade
DralamLSE 25-01A 0-3-0-4" 70 45 2-0 (0-13) Low styrene emission,
GP resin
LSE 27-0IA 0-3-0-5 140 59 2-5 (0-06) Low styrene emission,
chemical resistant
LSE 28-02A fire retardant 0-35-0-45" 58 29 I-I (0,17) BS 476 pt 7 class 2, clear
33-01A T Thixotropic paste,
adhesives
33-072A 0·15-0·25 70 38 1-4 (0·13) Hand/spray lay-up
33-402NA 0·5-0·6 106 42 3·2 (0·09) Filament winding
80-1403 orthophthalic 2·0-2-6 106 29 2·0 (0·13) Hot press moulding
80-1405 isophthalic 2·2-3·0 82 73 3·0 (0·13) Hot press moulding
83-1571 low profile 1·5-2·0 Low shrink, SMC
90-1001 0·6-0·9 Pigment grinding resin
228A 0·15-0·3 70 59 1·5 (0·1) General purpose
466/6A Thixotropic bonding paste
500A 0·2-0·4 130 35 2·0 (0·07) Chemical resistant
BH 703F 0·6-0·8 94 (0·1) Low colour casting resin
1346 0·1-0·14 78 50 1·1 (0·08) Translucent sheets
1347 fire retardant 0·1-0·14 50 37 1·2 (0·23) Translucent sheets
1355A fire retardant 0·35-0·45 82 29 1·1 (0·13) White, BS 476 pt 7
class 2
~
- 1368A 0·3-0·5 140 60 2·5 (0·06) Chemical resistant
1385 fire retardant 0·25-0·35 78 50 1·7 (0·1) Resin injection
2073A 0·3-0·5" 90 Acrylic bath reinforce-
ment
4620 0-4-0·6" 115 56 2·0 (0·16) Chemical resistant

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5320 bisphenol 0·3-0·6 115 60 3·0 (0·1) High chemical resistance
8005 0·2-0·3 92 52 1·5 (0·08) Resin injection
8048S 0·2-0·35 70 59 1·5 (0·1) Spray lay-up, fast cure
8151 flexible 0·35-0-45 (0·55) Flexibilising resin
8227A 0·4-0·5 73 48 1·7 (0·11) Surface coating resin
8726AHT 0·15-0·3 70 59 1·5 (0·1) Hand/spray lay-up
8748A 0·3-0·5 70 59 1·5 (0·1) Hand/spray lay-up
8800A 0·5-0·8 92 31 0·9 (0·07) Cold press moulding

Test methods 6 8 8 9

Vetrotex (UK) Ltd-Agent/or A/S Jotungruppen


NorpoI40-00 1·13 1·2-1·7" 30 7 127 High reactivity, tooling
40-20 1·10 1·0-1·2 T" 43 6 125 High reactivity, chem-
ical resistant
Table 9.6 (Continued)

Resin properties Cured properties

~
~ --"" ~ -;:: ,0
.;; ~ ~-- ~
'Sl"
~ '-- ~ ~
'-- ~ S;
~ "" ~ v ';; "Sl ~~
.2v " <::
Supplier ., 0 ~ ~
:s." ~~ 10..~
Trade name .5 f.... .,Q" ~ ,,'--
"" ~~ """~~ ... Q
Product code Type ~ ~~ V3~ C'l
"" ::t:: ~~ "
~ ~ ~ Remarks

Norpol (contd.)
42-00 orthophthalic 1·12 1·2-1·7a 34 6 80 64 1·5 General purpose
42-04 1·12 1·2-1·7a 34 6 80 64 1·5 Tropical grade
N
8 43-01 orthophthalic 1·11 0·6-0·7a 35 5 65 54 1·6 Light stabilised,
sheets
44-20 1·10 0·9-1·1 Ta 43 6 68 1·4 Fast cure, spray
44-30 1·10 0·9-1·1 T" 43 6 68 ~ 104 Slow cure, spray
44-70 orthophthalic 0·9-1·1 Ta 43 6 54 104 Fast cure, hand/spray

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1·10 68
44M-75 1·10 0·85-1·1 T" 42 6 65 50 1·6 Low styrene emission
44-80 orthophthalic 1·10 0·9-1·2 Ta 42 6 65 50 J.6 Low exotherm
44M-85 )·)0 0·8-),) Ta 42 6 65 50 ),6 Low styrene emission
45-50 orthophthalic 1·10 0·5-0·6" 34 3 Light stabilised, clear,
casting
48-00 1·13 )·2-],7" 34 7 84 68 H Chemical resistant
68-00 isophthalic 1·10 0·8-]·D" 37 ]30 50 I· 5 SMC,DMC
72-00 isophthalic 1·13 1·2-1'7" 34 7 83 70 3·0 Oil tanks, pipes, etc.
72-70 isophthalic 1·11 1·0-1·3 T" 7 88 69 2·8 Oil tanks, pipes, etc.
73-00 flexible, isophthalic 1·13 1·2-1·7" 34 7 52 66 6·0 FlexibiIiser, high impact resistance
80-20 chlorinated paraffin 1·21 0·7-0·9 T" 37 6 72 59 1·6 Opaque, self-extinguishing
90-00 bisphenol Chemical resistant
GA acrylic/ 1·2 13-16 T" 35 6 83 54 2·2 Gelcoat, hand
isophthalic application
GA acrylic/ 1·2 9-12 T" 40 6 83 54 2·2
- Gelcoat, spray
isophthalic application
GI isophthalic 1·2 13-16 Ta 35 6 74 49 2·6 Gelcoat, hand
application
GI isophthalic 1·2 9-12 Ta 40 6 74 49 2·6 Gelcoat, spray
application
GM 925 1·2 11-13T" 35 6 102 40 1·6 Gelcoat, hand, tooling
GM 925 1·2 9-12 T" 40 6 102 40 1·6 Gelcoat, spray, tooling
GM 930 1·2 11-13Ta 35 6 76 60 3·3 Flexible gelcoat, hand,
tooling
GM 930 1·2 9-12 T" 40 6 76 60 3·3 Flexible gelcoat,
spray, tooling
N
:= Test methods ISO 6 8 8

Warwick Chemical Ltd


Polymaster
9 TAC LSE orthophthalic 1·\2 0-4-0·5 T 37 70 General purpose

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9 TSE AC LSE self-extin- 1·31 0-4-0·5 T 32 65 BS 476 pt 7 class 2
guishing
B9TA bisphenol 1·05 0·4-0·5 T 50 135 Manufactured from
Atlac 382
19 T LSE isophthalic 1·10 0·4-0·5 T 45 110 Chemical resistant
15 T 1·12 1·2-l-6T 31 65 Thixotropic, general
purpose
129 T GAC isophthalic 1·14 2·0-2·5 T 34 65 Resilient gelcoat
I 29 T GAC white isophthalic 1·14 2·0-2·5 T 34 65 Resilient gelcoat
230 AC 1·13 0,45-0,55 35 72 Pre-accelerated
version of 312/35
312/35 LSE 1·12 0·5-0·6 35 72 General purpose
1188 1·13 0·3-0·35 37 125 High HDT
Table 9.6 (Continued)

Resin properties Cured properties

~ ,,'
~
~ ,0 9
'" ~ "Sb()
.;:
=- ~
~ ~ ~
c
1:'b() "c b() V
"..
;;;'" ~
."---"
" '"<:! 0 9 '"
<:!~
Supplier .2v "'~ ... ~
:$
" '" f.., ~
Trade name ~ .5 ~~ "'---
~~ Q
"'.'"" ..
"""...,
Product code Type
"'" "'~ "c Remarks
~ ~~ ~ :t:: ~~ i'il ~~
::::"
Polymaster (contd.)
1209 AC 1-12 0-2-0-25 35 50 Colourless casting
resin
1592 flexible 1-17 0-6-0-8 28 Amine accelerated
N 1704
0 1-24 T 32 Amine accelerated
N
bonding paste
1775 AC 1-22 T 32 Resilient bonding paste
1959 1-!7 0-1-0-14 0 For colour pastes
2003 fire retardant 1·28 0-35-0-38 29 65 BS 476 pt 7 class I,

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clear
2110 1·12 0-1-0-15 40 90 Resin injection
2123 self-extin- 1-16 0-1-0-15 30 75 BS 476 pt 7 class 2,
guishing resin injection
2136 light stabilised 1-13 0-17-0-18 33 65 Translucent sheet
2197 TAC LSE self-extin- 1-48 0-5-0-6 T 31 70 Opaque, BS 476 pt 7
guishing class I
2345 AC methyl I-ll 0,14-0-16 40 50 Translucent sheet
methacrylate
2580 1-16 1-0-1-2 28 Amine accelerated for
site use
2685 TAC LSE self-extin- 1·200·25-0·3T 33 55 Clear, BS 476
guishing pt 7 class 2
I 2722 TAC LSE isophthalic 1·16 0-4-0·5 T 42 115 General purpose
2774 self-extin- 1·18 0·24-0·28 30 Clear, BS 476
guishing pt 7 class 2
2774 AC self-extin- 1·20 0·14-0·16 40 53 Clear, BS 476.
guishing pt 7 class 2
12798 T/GAC isophthalic 1·14 1-0-1·2 T 40 65 Gelcoat
2946 TAC LSE isophthalic 1·11 0·3 T 37 70 Laminating resin
2946 TAC LSE isophthalic 1·11 0·3 T 37 70 White laminating resin
white

Test methods ASTM 6 LSE = low styrene


emission

~ ·Viscosity measured at 20°C.


!jJ
Notes. Styrene content: this is more correctly volatile content, since some resins may contain methyl methacrylate in this figure, or perhaps
other monomers as well.
Test methods: Specific gravity 1= BS 3532; 2 = DIN 51757; 3 = NFT 51063(a).
Viscosity 4=DIN 53015=BS 188 = ASTM D 445-74.

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Styrene content 5 = BS 2782 Method 107B; II = DIN 16945.
Shrinkage 12 = DIN 16946.
HDT 6 = ASTM D 648-72 = ISO/R 75 = BS 2782 Method 121 A & B = DIN 53461.
Tensile strength 7 = ASTM D 638-77a = DIN 53455;
and elongation 8 = BS 2782 Method 320 A-F (301 A, 302 D) = ISO/R 527.
Water absorption 9 = BS 2782 Method 502 G = ISO/R 62 = DIN 53475.
10 = ASTM D 570-77.
Chapter 10

CATALYSTS, ACCELERATORS AND


INHIBITORS FOR UNSATURATED
POLYESTER RESINS

10.1 INTRODUCTION

Most unsaturated polyester resins consist of a solution of a polyester in


styrene monomer. The styrene serves two purposes: firstly it acts as a
solvent for the resin and secondly it enables the resin to be cured from a
liquid to a solid by cross-linking with the polyester chain, without the
evolution of any by-products. This curing or cross-linking is achieved at
room temperature by adding a catalyst (or initiator) plus an accelerator (or
promoter) and at elevated temperatures just by adding a catalyst and
heating.
The catalysts used are invariably organic peroxides. Since these are
chemically unstable as a class of compounds, of which some can
decompose explosively in the pure form, they are mostly supplied as
solutions, dispersions or pastes in a plasticiser or as a powder mixed with an
inert filler to stabilise them. Often diluted peroxides are described as
'phlegmatised' with a plasticiser such as dimethyl phthalate. This indicates
that they have been made safer to handle or stabilised with a plasticiser.
Since organic peroxides are hazardous materials to handle, due note should
be taken of the safety recommendations issued by the various manufac-
turers (see Chapter 19). Most organic peroxides are used at between 1 and
4% based on the resin weight.
The most commonly used accelerators are either those based on a cobalt
soap or those based on a tertiary amine. Other types of accelerators may be
used for specific applications and include quaternary ammonium com-
pounds, vanadium, tin and zirconium salts. Cure can also be accelerated by
exposure to UV light. For certain applications mixed cobalt/tertiary amine
accelerators are used to give very short gel times. Accelerators are usually
used at between o· 5 and 4% based on the resin weight.

204

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UNSA TURA TED POLYESTER RESINS 205

Catalysts and accelerators should never be mixed together since this will
result in violent decomposition of the peroxide with the risk of fire and
explosion.
Although the wide range of catalysts available gives considerable scope
in selecting a system with the desired pot-life, occasions can arise when it is
desired to lengthen the pot-life without altering gel and cure times so that
demoulding is not affected. This can be accomplished by adding an
inhibitor to the system. This is in addition to the inhibitor already present in
the resin. Some inhibitors increase pot-life, gel time and cure time whilst
others just extend gel time-such an effect is shown in Fig. 10.1.
In order to achieve the optimum cured properties from the resin system,
the catalyst and accelerator must be chosen with care and the correct
amount used. Suppliers generally recommend particular catalyst!
accelerator combinations for use with each of their resins, together with rec-
ommended proportions. These systems have been arrived at by experimen-
tation and when used as recommended will give cured resins with optimum
properties-mechanical, chemical, etc. Often more than one catalyst/accel-

200

2
160
u
0

3
~

III
L. 120
.....It!
::I

L.
III
0-
S 80
III
I-

40

20

0 10 20 30 40 50 60

Time, minutes
Fig. 10.1. Effect of inhibitor on gel time and cure rate. Formulations: 1, resin
(Vestopal150) 100, MEK peroxide 2, cobalt accelerator (1% Co) 0·3; 2, resin
(Vestopal150) 100, MEKperoxide 2, cobalt accelerator (1% Co) 0·3, inhibitor (1%
solution) 1; 3, resin (Vestopal150) 100, MEKperoxide 1, cobalt accelerator (1%
Co) 0·14. (Courtesy of Huls (UK) Ltd.)

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206 FRP TECHNOLOGY

erator system is recommended to take account of the variety of processes


which might be used in production.
Also available are pre-accelerated resins. Here all that the fabricator has
to do to get the resin to gel and cure is to add the correct amount of catalyst.

10.2 THE CURING REACTION

Cure of unsaturated polyester resins takes place by free radical polymeri-


sation through the unsaturated groups (double bonds) both in the polyester
chain and the styrene or other monomer. This is shown schematically
below. The free radicals are provided by the peroxide as it decomposes and
it is the rate at which these free radicals are produced which governs the gel
and cure time of the resin.
I I
-C=C-R-----C=C-R- -C--C-R~-C-R-
+
I I
Q-c=C o-C=C ~ 0-"
- I
0-"C--C
- I
C-C
+
-C=C--R--C=C-R- -C--C-R~-C-R-
I I
A polyester resin will begin to cure as soon as the catalyst has been
added. However, with heat cured systems and, in particular, sheet and
dough moulding compounds, to all intents and purposes cure does not
progress until a certain minimum temperature has been reached. This is the
activation or critical temperature of the organic peroxide. This temperature
is lowered in the presence of an accelerator.
Once sufficient free radicals have been formed the resin starts to cross-
link. This reaction is exothermic and the heat evolved can raise the mix
temperature to above 150°C very quickly. As the temperature increases so
does the rate of production of free radicals. Under the worst circumstances
this produces a run-away exotherm with an exponential temperature rise. If
this happens while the catalysed resin is in bulk in the mixing pot, the
exotherm can be violent enough to decompose the resin. The result is
copious black smoke and possible ignition of the resin. In a laminate, the
temperature rise may well be lower due to the smaller bulk of resin involved
and the greater surface area available to conduct heat away. However, if an
uncontrolled exotherm does occur this will result in a scrap moulding and

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UNSATURA TED POLYESTER RESINS 207

Peak exotherm
150

o
u 100
~

~
:::l
+->
E 50
QJ Gel time
0-
S
~ 25

10 20 30 40 50 60
Time, minutes
Fig. 10.2. A typical exotherm curve.

possible damage to the mould. A typical exotherm is shown in Fig. 10.2.


Here it can be seen that there is only a gradual rise in temperature until gel-
ation takes place (about 10°C rise starting at room temperature). After
this the temperature rises very rapidly. Once the peak exotherm has passed,
the mix cools slowly to room temperature as the reaction slows down and
heat is conducted away. When this stage has been reached the bulk of the
peroxide catalyst has been used up.
The consequences of excessive exotherm during the moulding process
can be discolouration and stress cracking-neither of which is acceptable in
the finished moulding. It is for these reasons that care must be taken in the
selection and use of catalyst/accelerator systems.
Of importance in determining which organic peroxide to use with which
process are: decomposition rate, half-life, critical temperature and active
oxygen content of the peroxide. All but active oxygen content are
interlinked.

Active oxygen content. This is the percentage of active oxygen


( - 0 - 0 -) in the peroxide assuming it is 100% pure. It gives an
indication of the number of free radicals available assuming normal
decomposition. However, since double cleavage may also occur it can only
be used as a guide. As an example, pure benzoyl peroxide has an active
oxygen content of 6'60% but is more frequently supplied as a 50% paste with

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208 FRP TECHNOLOGY

an active oxygen content of 3·2%. Various methods are used for determin-
ing active oxygen content. 1

Critical temperature. This is the mlmmum temperature at which a


peroxide starts to rapidly form free radicals. This may also be referred to as
the 'kick-oir temperature. Generally only those peroxides with critical
temperatures within the range 60-130°C are used for cross-linking
polyester resins.

Half-life. This is a convenient way to express rate of decomposition of an


organic peroxide at a specified temperature and is taken as the time for half
of the peroxide originally present to decompose. This is generally
determined on a 5 mol% solution in benzene. A dimethyl phthalate
solution may also be used but this gives a different result. Other molar
concentration solutions may also be used.

The curing of a polyester resin can be considered to take place in three


stages.
1. Gelation-where the resin changes from a free-flowing liquid to a soft
gel.
2. Hardening-where the resin cures from a soft gel to a hard material
capable of being removed from the mould.
3. Final cure or maturing-where the resin achieves its full mechanical
and chemical properties. This can take from several hours at elevated
temperatures to several weeks at room temperature. This may also be
referred to as post cure. For room temperature cured systems,
maturing or post curing may be carried out at elevated temperature.
Such post curing should always be carried out immediately following
the hardening stage while there is still sufficient residual peroxide
available to complete the cure. If this is delayed for several days
permanent undercure may result due to exhausted catalyst. Clearly
different systems will require different post curing conditions.
Several parameters can be changed to modify the curing process. These
can be summarised as follows:
A reduction in catalyst content will increase gel time.
A reduction in accelerator content will increase gel time.
The converse of these is also true.
Increasing the cure temperature reduces gel time.
Increasing film or laminate thickness reduces gel time.
The addition of fillers tends to increase gel time.

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UNSA TURA TED POLYESTER RESINS 209

10.3 CATALYSTS OR INITIATORS


Catalysts or initiators for unsaturated polyester resin systems consist of
organic peroxides. These may be supplied as powders, pastes or liquids, all
of which must be thoroughly dispersed in the resin to ensure uniform cure.
Organic peroxides can be divided into two broad classes-the true
peroxides such as benzoyl peroxide and the hydroperoxides such as cumene
hydroperoxide. Some, such as MEK peroxide, are considered to be mixed
peroxides. The peroxides are usually subdivided into various chemical
types as will be seen later in the chapter. All are, however, generally just
referred to as peroxide catalysts.
The most commonly encountered peroxide catalysts for room tempera-
ture cure are MEK peroxide, cyclohexanone peroxide and acetylacetone
peroxide-each of which is used with a cobalt accelerator. In addition,
benzoyl peroxide accelerated with a tertiary amine is sometimes used.
F or elevated temperature cure benzoyl peroxide is most frequently used.
There are, however, numerous other peroxides available for specific
applications and specific temperature ranges. For example, where a non-
yellowing system is needed, a catalyst other than benzoyl peroxide is
preferred. Here, t-butyl peroctoate may be used. Where a very high degree of
cure is required to avoid tainting of food stored in contact with a moulding,
a mixed catalyst system may be needed.
Since pigments often contain traces of metals which can act as
accelerators for peroxide catalysts, care has to be taken in selecting not only
the pigment but also the catalyst used. Di-t-butyl peroxide and the
perketals are generally unaffected by trace metals in pigments. Perketals
can only be used for elevated temperature cure since no accelerator is
known to promote room temperature cure.
When selecting any catalyst, 2 consideration must be given to cure
temperature and gel time with the particular resin to be used. The choice is
further affected by moulding process and whether or not a short, medium
or long curing cycle is required. With moulding compounds such as SMC
and DMC, shelf-life of the catalysed system is also of importance. This can
sometimes be adequately prolonged by adding additional inhibitor to the
system (see Section 10.5).
Three broad processing temperature groups exist:
Room temperature cure (20- 50°C)-contact moulding, cold press
moulding, resin injection.
Intermediate temperature cure (50-100°C)-continuous laminating
filament winding.
High temperature cure (l00-160°C)-hot press moulding, SMC, DMC.

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210 FRP TECHNOLOGY

Peroxide catalysts can be conveniently divided into six different chemical


types. These are described below together with a list of commercially
available materials (Table 10.5 at the end of this chapter).
Manufacturers generally classify their organic peroxide products ac-
cording to a hazard rating. Details of two such ratings will be found at the
end of this chapter. So far only two organic peroxides have quoted TLVs:
these are benzoyl peroxide and MEK peroxide.

10.3.1 Diacyl peroxides


General formula: 0 0
II II
R-C-O-O-C-R'
The most commonly encountered diacyl peroxide is benzoyl peroxide, or
more correctly dibenzoyl peroxide. Others found in use include 2,4-
dichlorobenzoyl peroxide, diacetyl peroxide and dicaprylyl peroxide. They
may be used both in room temperature and elevated temperature cured
systems, although an amine accelerator is needed to promote cure at room
temperature.
Benzoyl peroxide
Molecular weight 242·2
Active oxygen content 6'6%
TLV 5 mg/m 3
Melting point 103-5°e
Critical temperature 70°C
Maximum storage temperature 2ye
Half-life: Temperature eC) 72 88 92 102 136
Time (h) 10 2 1 0·5 0·017
The pure material is a white granular solid, soluble in a variety of organic
solvents but insoluble in water. It is normally stored damped with water or
as a paste in phthalate plasticiser. It is also available as a paste in tricresyl
phosphate where fire retardant properties are required. Care should be
taken to ensure thorough dispersion of the paste in the polyester resin to
obtain uniform cure.
Benzoyl peroxide is used without an accelerator for heat cured systems
and finds application in SMC, DMC, filament winding, compression
moulding and for the manufacture of continuous sheeting. For room
temperature cure a tertiary amine accelerator is necessary. Cobalt accele-
rators are ineffective. The amine accelerated system can be used for hand
and spray lay-up, body stoppers and putties, and site applications.

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UNSA TURA TED POLYESTER RESINS 211

Amine accelerated systems have a tendency to yellow and craze on


ageing, probably due to the lower degree of cure obtained with these
systems than with cobaltjhydroperoxide systems. In spite of this, the
system has important uses in the temperature range 1O-25°C. Normal
usage is 2% by weight of a 50% paste.

2.4-Dichlorobenzoyl peroxide
Molecular weight 380
Active oxygen content 4·28%
Critical temperature 60°C
Maximum storage temperature 25°C
Half-life: Temperature COc) 50 60 70 80
Time (h) 17·8 8·2 1·4 0·5
2,4-Dichlorobenzoyl peroxide is used with an amine accelerator either
alone or in combination with benzoyl peroxide to obtain gelation of
polyester resins down to O°C, providing that a post cure above 15°C is given
to ensure full cure. It has a low peak exotherm when used below 70°C and
can be used to produce fairly large crack-free castings. It finds use in
contact moulding, hot press moulding and low temperature curing systems.

Dilauroyl peroxide
Molecular weight 404
Active oxygen content 4·0%
Critical temperature 65°C
Maximum storage temperature 25°C
Half-life: Temperature COc) 50 62 70 80 100
Time (h) 60 10 3 I 0·1
Dilauroyl peroxide is used in heat cured systeIlls over the temperature
range 60-80°C. It is effective some 10-15°C below the temperature needed
to obtain full cure with benzoyl peroxide. It does not affect the yellowing of
polyester resins. It is a powder which is directly soluble in the resin.

Diacetyl peroxide
Molecular weight 118
Active oxygen content 13·6%
Critical temperature 75°C
Maximum storage temperature 25°C
Half-life: Temperature COc) 50 70 100
Time (h) 190 7·3 0·2

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212 FRP TECHNOLOGY

Diacetyl peroxide is only suitable for use in heat cured systems and finds
application in SMC and DMC. No yellowing of cured systems is observed
on ageing.

Di-n-octanoyl peroxide (caprylyl peroxide)


Molecular weight 286
Active oxygen content S·6%
Critical temperature 60°C
Maximum storage temperature 1O°C-refrigerated
Half-life: Temperature (0C) SO 70 100
Time (h) 63 3·S 0·1
This peroxide finds use in hot press moulding and continuous laminating
systems.

10.3.2 Ketone peroxides


General formula:

R'-<::>-R' H~O H-~+H 0'

This is perhaps the most common class of peroxides used with polyester
resins. Two commonly encountered ketone peroxides are methyl ethyl
ketone (MEK) peroxide and cyclohexanone peroxide. These are used for
cold curing polyester resins in the presence of a cobalt accelerator. Whilst
they are described as peroxides they are in fact mixed peroxides containing
a number of different products. Cyclohcxanone peroxide is also used at
lS0°C to prevent staining of metal moulds.
Other peroxides included in this class are acetylacetone peroxide, methyl
isobutyl ketone peroxide and various ketone peroxide mixtures. The
typical chemical structure for the pure ketone peroxide is shown on the left
above whilst the hydroperoxide structure is shown on the right.

Methyl ethyl ketone peroxide


Molecular weight 176
Active oxygen content 18·2%
TLV 0·2 ppm (1·S mg/m 3 )
Critical temperature 80°C
Flash point 6S-104°C

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UNSA TURA TED POLYESTER RESINS 213

Maximum storage temperature


Half-life: Temperature caC) 120 ISO
Time (h) 6·0 0·2
MEK peroxide is very explosive in its pure form and is therefore always
supplied diluted with a plasticiser such as dibutyl phthalate. It is used
for the room temperature cure of polyester resins in conjunction with a
cobalt accelerator, over the temperature range lS-2S°C. It slowly
decomposes at room temperature with the evolution of gas and should be
stored in vented containers. Many different grades are available with
different reactivities. Dyed solutions are also available to assist in mixing.
Often a blue dye is used which disappears during cure. Normal usage is
1-2% for laminates and 2-4% for gelcoats.

Cyclohexanone peroxide
Molecular weight 228
Active oxygen content 13-1%
Critical temperature 88°C
Melting point 7SoC
Maximum storage temperature 2SoC
Half-life: Temperature eC) 70 80 90 100 120
Time (h) 140 34 9 7·7 0·9
Cyclohexanone peroxide is available as a pure powder, a SO% paste in a
phthalate plasticiser and in solvent solution. Like MEK peroxide it is a
mixture of different compounds. I t is used with a cobalt accelerator over the
temperature range 0- 2SoC but, if used below ISoC, a post cure above this
temperature is necessary to achieve full cure. Tertiary amine accelerators
can also be used but polyesters cured in this way have a tendency to yellow
with age. It is often used in body stoppers with a mixed tertiary
amine/cobalt accelerator. It can also be used without an accelerator to cure
polyester resins at temperatures above 160°C.
Very long pot-life systems can be obtained by using a manganese
accelerator. Another accelerator sometimes used is vanadium octoate.
Cyclohexanone peroxide offers several advantages over MEK peroxide.
It generally gives a lower peak exotherm, is less sensitive to cure
temperature and has a lower tendency to yellow in transparent sheeting. It
is also preferred when a low stress cure is desired.

Acetylacetone peroxide (3 ,5-dimethyl-3 ,5-dihydroxy-l ,2-dioxolane)


Molecular weight 134

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214 FRP TECHNOLOGY

Active oxygen content 11·9%


Critical temperature 95°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 142 170 233
Time (h) 10 1 0·017
Acetylacetone peroxide is used with a cobalt accelerator to give very fast
cure even with levels of 0·5% peroxide. When used at the same level as
MEK peroxide a slightly shorter gel time is obtained, with demou1ding
possible less than 1 h after gelation. In this respect it behaves somewhat like
a benzoyl peroxide/tertiary amine system but without the yellowing effect.
Due to its heat of reaction it is not recommended for laminates thicker than
3-4 mm. Since cure progresses rapidly through the soft to hard stage,
trimming with a knife is virtually impossible.
Acetylacetone peroxide catalysed resin without an accelerator present
has a far longer pot-life than the equivalent MEK peroxide system and has
been described as having an outstanding pot-life.
Acetylacetone peroxide should never be diluted with acetone since the
hydrogen peroxide present will react with acetone to form crystalline
acetone peroxide which is extremely shock sensitive.
It finds application as a catalyst in general room temperature cured
systems and in particular in resin injection systems.

Methyl isobutyl ketone (MIBK) peroxide


Molecular weight 232
Active oxygen content 13-8%
Critical temperature 50°C
Flash point (as supplied) 74°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 100
Time (h) 19·6
Polyester resins catalysed with MIBK peroxide have very long gel times
at room temperature with rapid cure above 60°C, so this catalyst is
generally used in the temperature range 60-120°C. It is often combined
with benzoyl peroxide, t-butyl peroctoate or 1,1-bis(t-butylperoxy)-3,3,5-
trimethylcyclohexane. It is particularly useful in the manufacture of
corrugated sheeting and for filament winding due to its low critical
temperature and relatively low exotherm. It can be used at room
temperature with a cobalt accelerator. The effect of various catalyst blends
on cure time at 80°C is shown in Table 10.1.

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UNSA TURA TED POLYFSTER RFSINS 215

Table 10.1 Effect of different catalyst blends on cure time at sooC


(Compiled from Luperox GmbH data sheets)

Accele-
rator Kick-off Cure Peak Pot-
1% Co temp. time exotherm life
Catalyst (% wt) (0C) (min) (0C) (min)

1·5% MIBKP 60 6·0 196 8


1·5% MIBKP 0·5 55 4·7 179 1
1·0% MIBKP + O· 5% t-butyl
peroctoate 60 6·0 182 10
1·0% MIBKP + 0·5% t-butyl
peroctoate 0·5 55 4·8 184
1·0% MIBKP+0·5% benzoyl
peroxide 60 6·0 182 10
1·0% MIBKP + 0·5% benzoyl
peroxide 0·5 55 4·8 180

MIBKP - Luperox MIK.

Ketone mixtures
Various mixed ketone peroxides are available based on unspecified
ketones. These have generally been formulated for specific applications.
10.3.3 Hydroperoxides
General formula: R3 - C - 0 - 0 - H
Only two hydroperoxides are found in common use, namely, t-butyl
hydroperoxide and cumene hydroperoxide. Both can be used with cobalt
or vanadium accelerators.
t-Butyl hydroperoxide
Molecular weight 90
Active oxygen content 17·7%
Critical temperature 88°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 100 120 130 150
Time (h) 170 12 3·2 0·4
This was one of the earliest hydroperoxides in use but is not so widely
used today due to its lower stability compared with MEK peroxide or
cyclohexanone peroxide. It can be used with a vanadium accelerator for
surface coating and dip coating applications. It has an inhibiting effect on
MEK peroxide/cobalt systems and lowers peak exotherm. It can be used
alone for elevated temperature cure.

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216 FRP TECHNOLOGY

Cumene hydroperoxide
Molecular weight 152
Active oxygen content 10·5%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature caC) 115 130 150
Time (h) 472 113 10
Cumene hydroperoxide can be used in high temperature cured dip
moulding compounds or combined with benzoyl peroxide for intermediate
cure temperatures. For example, with a blend of these two peroxides used
to cure a polyester resin at 70°C, the benzoyl peroxide starts to cure the
resin and when the temperature reaches 100°C the cumene hydroperoxide
takes over.
Cobalt and vanadium accelerators can be used with cumene hydro-
peroxide to give systems with long working times and good final cure.
Such systems find application with air drying topcoat resins.

10.3.4 Dialkyl and diaralkyl peroxides


General formula: R3 -C-O-O--C- R3
Several examples of this group of peroxides are in use to cure polyester
resins, mostly with heat cured sheet and dough moulding compounds.

Dicumyl peroxide
Molecular weight 270
Active oxygen content 5·9%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature (0C) 100 120 135 150
Time (h) 100 6·8 1·0 0·2
Dicumyl peroxide is generally used in potting compounds and sheet and
dough moulding compounds. It has an exceptionally long pot-life coupled
with good elevated temperature cure. It cannot be accelerated.

Di-t-butyl peroxide
Molecular weight 146
Active oxygen content 10·9%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature caC) 100 120 150
Time (h) 210 20 0·8

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UNSATURATED POLYESTER RESINS 217

Di-t-butyl peroxide is used for hot cured systems where a long catalysed
pot-life is needed. Pot-life is not influenced by pigments. As supplied, di-t-
butyl peroxide is a highly volatile liquid; this limits its storage life and
hence its use.

t-Butyl cumyl peroxide


Molecular weight 208
Active oxygen content 7·7%
Critical temperature 110°C
Maximum storage temperature 25°C
Half-life: Temperature Cc) 110 130 150
Time (h) 35 3·6 0·42
t-Butyl cumyl peroxide gives systems with a long pot-life coupled with
good elevated temperature cure. It finds use in SMC, DMC and hot press
moulding systems.

2,5-Dimethyl-2,5-bis( t-butylperoxy ) hexane


Molecular weight 290
Active oxygen content 11·0%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 119 138 175
Time (h) 10 1·0 0·017
Whilst this peroxide gives systems with a very long pot-life and good
mechanical strength of moulded parts, it requires a high moulding
temperature. It finds use in SMC, DMC and hot press moulding
compounds.

10.3.5 Peroxyesters
General formula: R3-C-O-O-C-R
II
o
Several different types ofperoxyesters are found in use, mostly for hot press
moulding and sheet and dough moulding compounds. They can be used
over a wide range of processing temperatures from about 70°C to above
IS0°C.

t-Butyl peroxybenzoate
Molecular weight 194
Active oxygen content 8·2%

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218 FRP TECHNOLOGY

Critical temperature 90°C


Maximum storage temperature 25°C
Half-life: Temperature eC) 90 100 120 150
Time (h) 70 17 1·6 0·05
t-Butyl peroxybenzoate can be used alone as a catalyst for hot press
moulding in the temperature range 130-150°C or accelerated with cobalt
or vanadium salts at somewhat lower temperatures. It gives systems with a
longer shelf-life than those containing benzoyl peroxide. It is also used to
cure diallyl phthalate resins.

t-Butyl peroxydiethylacetate
Molecular weight 188
Active oxygen content 8·5%
Critical temperature 65°C
Maximum storage temperature 10°C-refrigerated
Half-life: Temperature eC) 50 70 90 100
Time (h) 330 19 1·7 0-46
This peroxide catalyst finds use in SMC, DMC and hot press moulding
compounds.

t-Butyl peroxyester
This peroxide catalyst is used for filament winding, hot press moulding
and continuous sheet manufacture over the temperature range 60-1 00°c.

t-Butyl peroxyisononanoate (t-butyl peroxy-3 ,5,5-trimethylhexanoate)


Molecular weight 230
Active oxygen content 6·9%
Critical temperature 80°C
Maximum storage temperature 20°C
Half-life: Temperature eC) 70 100 120 130
Time (h) 700 14·7 1·5 0·3
This peroxide catalyst can be used as an alternative to t-butyl per-
oxybenzoate for filament winding and hot press moulding.

t-Butyl peroctoate (t-butyl peroxy-2-ethylhexanoate)


Molecular weight 216
Active oxygen content 1.4%
Critical temperature 70°C

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UNSATURATED POLYESTER RFSINS 219

Maximum storage temperature 20°C


Half-life: Temperature eC) SO 70 90 100
Time (h) 330 16 1-4 O·S
t-Butyl peroctoate is used for hot curing above 60°C. It finds application
in filament winding, continuous sheet manufacture, hot press moulding
and SMC and DMC. It gives less yellowing than benzoyl peroxide. It can be
used with cobalt and vanadium accelerators.

Di-t-butyl diperoxyphthalate
Molecular weight 310
Active oxygen content 10·3%
Critical temperature 9SoC
Maximum storage temperature 2SoC
Half-life: Temperature (0C) 100 120 ISO
Time (h) 21 1·2 0·01
This peroxide catalyst gives systems with a long pot-life. It is used for hot
press moulding at temperatures above IS0°C.

t-Butyl peroxypivalate
Molecular weight 174
Active oxygen content 9·2%
Critical temperature SO°C
Maximum storage temperature O°C-refrigerated
Half-life: Temperature (0C) SO 70 90
Time (h) 23 1·9 0·16
t-Butyl peroxypivalate is used for hot press moulding in the temperature
range 90-110°C where it gives a short cure cycle. It can also be used for
continuous sheet production. If accelerated with a cobalt or vanadium
accelerator it can be used in the temperature range SO-70°C. It gives less
yellowing than benzoyl peroxide. The major disadvantage is that it requires
refrigerated storage.

2,5-Dimethylhexane-2,5-diperoxybenzoate
Molecular weight 386
Active oxygen content 8·3%
Critical temperature
Maximum storage temperature 2SoC
Half-life: Temperature caC) 100 118 ISS
Time (h) 10 1 0·017

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220 FRP TECHNOLOGY

This catalyst finds application in hot press moulding compounds with a


short cure cycle.

4,4-Di-t-butyl peroxy-n-butyl valerate


Molecular weight 302
Active oxygen content 10·6%
Critical temperature 80°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 70 90 100 120
Time (h) 630 l35 l3 1· 5
This catalyst finds application in hot press moulding compounds, SMC
and DMC.

10.3.6 Perketals (peroxyketals)


R'
I
General formula: R 3 -C-O-O-C-O-O-C-
I
R3
R'
Perketals are used as catalysts in hot cure moulding compounds. They are
less sensitive to metal compounds, pigments, etc., than t-butyl perbenzoate
and are therefore very suited to use in pigmented moulding compounds,
SMC and DMC. They can be used at elevated temperatures with a
vanadium accelerator but no accelerators are known to promote cure at
room temperature.

2,2-Bis( t-butylperoxy )butane


Molecular weight 234
Active oxygen content 13-6%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 110 115 l30
Time (h) 10 2 0·3
This catalyst finds application in hot press moulding, SMC and DMC.

1,1-Bis ( t-butylperoxy ) cyclohexane


Molecular weight 260
Active oxygen content 12·3%
Critical temperature 85°C
Maximum storage temperature 25°C

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UNSATURATED POLYESTER RESINS 221

Half-life: Temperature Cc) 95 113 130


Time (h) 10 1 0·13
This catalyst finds application in hot press moulding, SMC and DMC.

1,l-Bis( t-butylperoxy ) -3,3 ,5-trimethylcyclohexane


Molecular weight 302
Active oxygen content 10·6%
Critical temperature 86°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 85 100 115 130
Time (h) 27 3·8 0·71 0·17
This catalyst finds application in hot press moulding, SMC and DMC.

10.4 ACCELERATORS OR PROMOTERS

These are materials which when used in conjunction with an organic


peroxide catalyst increase the rate at which that peroxide breaks down into
free radicals. Thus they accelerate the cure of the polyester resin in a
controlled manner. They are mainly used to enable otherwise unsuitable
peroxides to be used to cure polyester resins at ambient temperature,
although they may also be used to reduce the cure temperature of heat
cured systems. They can be divided into two classes of materials-metal
compounds and tertiary amines.
Metal compounds such as cobalt naphthenate are excellent accelerators
for hydroperoxides and mixed peroxides but have little or no effect on true
peroxides. Tertiary amines, on the other hand, work well with peroxides
and are often used in conjunction with cobalt naphthenate as co-
accelerators for mixed peroxides such as MEK peroxide.
Generally the pre-accelerated resins available commercially contain a
cobalt salt as accelerator.
Accelerators must at all times be kept well away from organic peroxides
and never mixed with them since violent decomposition of the peroxide will
result.
Some of the commercially available accelerators are listed in Table 10.6
at the end of this chapter.

10.4.1 Metal compounds


These are usually metal salts or soaps supplied in solutions of various

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concentrations in plasticisers, solvents or styrene. Cobalt salts are the most


common ones used although vanadium salts may also be encountered.
Other metal soaps such as manganese and copper may sometimes also be
used. These, however, tend to give gel times of several hours at room
temperature and are best used with heat cured systems where a short gel
time can be obtained, coupled with a long pot-life (Table 10.2). With all
metal salts, solutions in phthalate plasticisers generally have better storage
lives than those in styrene.

Cobalt accelerators
These are based on such materials as cobalt siccatolate, naphthenate or
octoate. Solutions are available with cobalt concentrations ranging from
O' 5 to 10%. The more concentrated solutions are either diluted before use or
added directly to large batches of resin to reduce the amount of diluent or
plasticiser added. The typical level of cobalt used with a normal polyester
resin is between O' 5 and 2% of a solution containing I % of cobalt. Cobalt
accelerated resins tend to be pale pink in colour.

Manganese accelerators
Manganese salts are occasionally used as accelerators for polyester resin
systems. They give long gel times at ambient temperature when used to
accelerate ketone peroxides (Table 10.2).

Vanadium accelerators
Vanadium accelerators are used to accelerate ketone peroxide catalysed
polyester resins for low temperature cure or peroxyester and perketal
catalysed systems at elevated temperatures. They give faster hardening
Table 10.2 The effect of cobalt and manganese accelerators on gel time of a general
purpose polyester resin

Gel time (min)

5(/'/0 Cyclohexanone
peroxide paste, 50% MEK peroxide,
2"/0 addition 2"/0 addition

Temperature eC) 20 40 50 20 40 50

Accelerator
Cobalt salt (l % Co) 22 13 9 18 13 8
Manganese salt (l % Mn) 316 55 25 495 88 41

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UNSA TURA TED POLYESTER RESINS 223

with ketone peroxides than can be achieved with cobalt accelerators.


Normal dosage is between 0·2 and 4% of a 0·5% solution, based on the
resin.

10.4.2 Tertiary amine accelerators


Generally only three tertiary amines are used as accelerators, the most
common being dimethylaniline. They are used to accelerate peroxide
catalysts such as benzoyl peroxide to give ambient temperature cure.
Dimethylaniline is also used as a co-accelerator in cobalt accelerated
systems with ketone peroxide catalysts. Tertiary amines are generally used
at between 1 and 4% of a 10% solution. One disadvantage of amine
accelerated systems is their tendency to yellow with age.
An indication of the difference in accelerating effect shown by the three
commonly used tertiary amines can be seen in Table 10.3.

NN-Dimethylaniline
This is normally referred to as dimethylaniline. It gives normal gel times
and quick cure when used to accelerate diacyl peroxide catalysed systems.
It can also be used as a co-accelerator with cobalt accelerated ketone
peroxide catalysed systems to reduce gel times. In this respect it is of
particular use in cold press moulding and resin injection systems.

N N- Diethylaniline
This is normally referred to as diethylaniline. It gives long gel times
coupled with fast cure at room temperature when used as an accelerator in
benzoyl peroxide catalysed resin systems.

Table 10.3 Effect of different tertiary amines on gel time of a general purpose
polyester resin

Material Proportions (parts by weight)

General purpose polyester resin 100 100 100


Benzoyl peroxide, 50% paste 2 2 2
Diethylaniline 1·5
Dimethylaniline 1·5
Dimethyl-p-to1uidine 1·5

Approx. gel time at 20°C (min) 100 20 5

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224 FRP TECHNOLOGY

Table 10.4 Effect of mixed accelerator on gel time of a general purpose polyester
resin system

Material Proportions (parts by weight)

General purpose polyester resin 100 100 100 100 100 100
Cyclohexanone peroxide (50%) 2 2 2 2
MEK peroxide (50%) 1 1
Cobalt naphthenate (1 % Co) 1 1·5 1· 5
Dimethylaniline (10%) 0·1 0·75
Dimethyl-p-toluidine
---- .-~~-----~-.

Gel time at 20°C 36 23 16 18


at 25°C 8 2
----------

NN-Dimethyl-p-toluidine
Dimethyl-p-toluidine gives short gel and cure times in conjunction with
benzoyl peroxide catalysed resin systems. It is used where short moulding
cycles are needed with ambient temperature cure.

10.4.3 Mixed metal salt/t-amine accelerators


These provide extremely short gel and cure times when used to accelerate
ketone peroxide catalysed systems. They are particularly suitable for use in
cold press moulding and resin injection systems where fast mould turn
round is required. They generally consist of a plasticiser solution contain-
ing 2% cobalt and 10% dimethylaniline. Their effect on gel time is shown in
Table 10.4.

10.5 INHIBITORS

When polyester resins are manufactured, inhibitors are added to ensure


adequate shelf-life of the resin. However, occasions may arise where the
pot-life of a system needs to be prolonged. This can be achieved by adding a
further small quantity of inhibitor to the system. Some inhibitors increase
gel time and cure time as well as pot-life, whilst others just increase pot-life
without influencing gel and cure times, so that demoulding can still take
place soon after gelation. If pot-life is lengthened by decreasing accelerator
proportion rather than by using an inhibitor, then gel and demoulding
times are both prolonged (see Fig. 10.1).

giridharvzm1@gmail.com
UNSA TURA TED POLYESTER RESINS 225

Two inhibitors which are used to prolong pot-life are t-butyl catechol
and di-t-butyl-p-cresol. Some of the commercially available inhibitors are
listed in Table 10.7.

10.6 COMMERCIALLY A V AILABLE MATERIALS

Tables 10.5-10. 7list some of the commercially available organic peroxide


catalysts, accelerators and inhibitors, respectively. Hazard classifications
for the various organic peroxides listed are given at the end of Table 10.5.

REFERENCES

1. Chalkley, N. J. and Whalley, C. (1978) Proc. Anal. Div. Chern. Soc., 15,
December, 327.
2. Simmonds, 1. (1974) Reinforced Plastics, February, 41.

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Table 10.5 Commercial peroxide catalysts tv
tv
0'1
Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code

Benzoyl peroxide
Akzo Chemie UK Ltd
Lucidol Soft powder + 25% water 75 4·9 A
Lucidol B-50 Paste in phthalate plasticiser 50 J3 D 1, 2, 4, 6, 7, 8, 10
Lucidol B-25 Paste in phthalate plasticiser 25 1·7 D 1, 2, 4, 5, 6, 7, 8, 9, 10
Lucidol M-60 Paste in phthalate plasticiser 60 3·9 D 1,2,4,6, 7, 8, 10 >rj
~
Lucidol C-50 Paste in phosphate plasticiser 50 J3 D 1,2 '"C
Lucidol S-50 Paste in silicone fluid 50 3·3 D ..,
ttl
("')
Lucidol G-20 White powder in calcium sulphate 20 1·3 C 10, 12 :I:
Lucidol 50 PO White powder 50 3·3 C 5 Z
0
Lucidol40 Pourable emulsion 40 2·65 D 1, 2, 5, 6, 7, 8, 9 t"'
Lucipal E White powder BP/amine complex 16 1·1 C 10,11 8-<

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Interox Chemicals Ltd
Interox BP 70P Paste 70 4·6 3
Interox BP 60P Phthalate paste 60 3·9 4 1,2,6
Interox BP 50P Phthalate paste 50 3·3 4 1,2,6
Interox BP 50 FT Soluble powder 50 J3 4 1, 2, 4, 5, 6, 11
Interox BP 60 P CL Paste in Cerechlor 60 3·9 4 4,5,6, 11
Luperox GmbH
Luperco ANS-50 Phthalate paste 50 3·3 1,2, 3, 6, 8, 12
Luperco BP Phthalate paste 55 3-6 1,4,6, 10
Luperco ANS-50-AT Phthalate paste 50 3·3 10
Luperox FL Plasticiser suspension 36 2-4 2,3,6
Luperco ANS-60 Phthalate paste 60 4·2 3, 6, 7, 12
Scott Bader Co. Ltd
Catalyst powder B Paste 50 3·3 6

2,4-Dichlorobenzoyl peroxide
Akzo Chemie UK Ltd
Peradox SD White powder + 50% water 50 2·0 A
lnterox Chemicals Ltd
Interox DCLBP 50PSi Paste in silicone oil 50 2·1 4
c::
Dilauroyl peroxide Z
U'.>
Akzo Chemie UK Ltd ..,>
Laurydol Granular 98 3-94 B 12 c::
Laurydol B-40 Phthalate paste 40 1·6 D 4, 12 ~
@
lnterox Chemicals Ltd 0
Interox LP Powder 95 4·0 4
0-=
t""
Diacetyl peroxide -<
Akzo Chemie UK Ltd
rn
@
Trigonox RM-25 Solution in dimethyl phthalate 25 H E 7 ~

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Di-n-octanoyl peroxide (caprylyl peroxide) ~Z
Akzo Chemie UK Ltd U'.>

Perkadox SE-8 Solid 98 5·5 6

MEK peroxide
Akzo Chemie UK Ltd
Butanox LPT Solution in phthalate plasticiser 8·4 G 3,9, L
Butanox M-50 Solution in phthalate plasticiser 9·0 G 1,2,4, 8, 11, 12, 13, H
Butanox AM-50 Solution in phthalate plasticiser 10·75 G 1,2,4, 13, VH
Butanox B-50 Solution in phthalate plasticiser 9·0 13,H N
G N
I, 2, 4, 8, 11, 12, 13, VH -..J
Butanox PC Solution in phthalate plasticiser 7·9 G
Table 10.5 (Continued)
IV
IV
00
Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code

MEK peroxide (contd.)


Butanox M-30 Solution in phthalate plasticiser 5·5 G 1,2,4, 8, 11, 12, 13, H
Butanox HA Solution in phthalate plasticiser 9·0 G I, 2, 4, 8, 9, 11, 12, 13
Butanox FRJHA Solution in low flam. plasticiser 9·5 GJLH I, 2, 4, 12, VH
Butanox LA Solution in phthalate plasticiser 9·4 G 3, 6, 8, 9, 11, 12, L
Butanox M-ll0 Solution in phthalate plasticiser 11·0 G I, 2, 4, 8, 11, 12, 13, VH
"1j
Butanox LA20EA Solution in phthalate plasticiser 1·9 H 10 :>cI
"C
Interox Chemicals Ltd ...j
t!l
Interox MEKP NA2 Phthalate solution 50 10·0 4 1,2, H ("l

1,2, 11, H :I:


Interox MEKP NA3 Reduced hazard 50 10·0 5 Z
Interox MEKP SA2 Phthalate solution 50 ll'O 3 1,2,3,4, 5, VH 0
t"'
Interox MEKP LA2 Phthalate solution 50 9-4 3 1,2, 11, L
Interox MEKP NA5 Phthalate solution 30 9·0 4 1,2,4, M
8-<

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Luperox GmbH
Luperox DDM-S Phthalate solution 50 8·4 1,2, 3, 8, 9, 11, L
Luperox GZ-N Phthalate solution 50 9·0 1,2,3,4, H
Luperox S-55 Phthalate solution 50 9·3 1,2,4, VH
Luperox Delta-K Phthalate solution 50 11·0 4, VH
Luperox GH Plasticiser solution 50 10·4 I, 2, 3, 4, 11, H
Luperox DNF 10·6 I, 2, 8,9, H
British Industrial Plastics Ltd
Catalyst 347 Medium reactivity
Freeman Chemicals Ltd
Stypol Catalyst 24 High reactivity
Scott Bader Co. Ltd
Catalyst L High reactivity
Catalyst M Medium reactivity
Catalyst 0 Low reactivity
Synthetic Resins Ltd
Catalyst Quickset Extra Solution 50

Cyclohexanone peroxide
Akzo Chemie UK Ltd e
Cyclonox White powder 95 12·3 B 13 z
rJ>
Cyclonox E White powder 95 6·9 B 13 >
..,
Cyclonox M -60 Phthalate paste 60 7·8 D 1,2,4, 10, II, 12, 13 e
Cyclonox B-50 Phthalate paste available 50 6·5 D 1, 2, 4, 10, II, 12, 13 ~
pigmented til
0
Cyclonox C-50 Phosphate paste 50 6·5 D I, 2 '1:1
Cyclonox B-25 Phthalate paste 25 3·2 D 10 0
t"'
Cyclonox LE-50 Liquid 50 5·3 G 11,13 -<ttl
Cyclonox LTM-50 Liquid 6·3 G I, 2, 4, 11, 13 rJ>
50
Cyclonox LTM til~

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20EA Liquid 20 2·5 H 10
Interox Chemicals Ltd
~
52rJ>
Interox CHP 50PFO Phosphate paste 50 6·5 4 I, 2
Interox CHP NAI Phosphate solution 50 6·0 4 1, 2
Interox CHP 50PT Thixotropic paste 50 4 10
Interox CHP 50PT Black thixotropic paste 50 4 10
Interox CHP 37PT Grey thixotropic paste 37 4 10
Luperox GmbH
Luperco CH90 Powder + 10% water 90 11·7 13
Luperco JDB-50-T Paste in dibutyl phthalate 50 6·5 1, 10 N
N
Luperco CH-S Plasticiser solution 50 5·4 1,2,3,4,6,10,13 \0
N
Table 10.5 (Continued) w
0

Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code

Cyc1ohexanone peroxide (contd.)


Scott Bader Co. Ltd
Catalyst paste H Paste
Catalyst liquid H Solution
'"!l
Acetylacetone peroxide :=
'1:1
Interox Chemicals Ltd -l
tTl
Interox AAP SA3 Solution 35 4·0 5 1, 2, 3, 4, 5, 14 (")
::t:
Luperox GmbH Z
0
1,2, 3,4, 5, 14 t"'
Luperox 224 Plasticiser solution 35 4·0
8><:

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Methyl isobutyl ketone peroxide
Akzo Chemie UK Ltd
Trigonox HM Liquid 10·1 G 3,4,9, 12
Interox Chemicals Ltd
Interox MIBK Solution 60 10·0 3 3,9

Ketone mixtures
Akzo Chemie UK Ltd
Trigonox 40 Liquid 4·0 G 1,2, 5, 11, 12
Trigonox 48 Liquid 9·5 G water filled polyesters
Trigonox XOM-2 Phthalate solution G 4
Luperox GmbH
Luperox Delta-M Plasticiser solution 45 7-4 1,2,3,4
Luperox 43-M Liquid 8·7 3,4

t-Butyl hydroperoxide
Akzo Chemie UK Ltd
Trigonox A-75 Solution in di-t-butyl peroxide 75 13-2 F 13
Interox Chemicals Ltd c:
Interox TBHP 70 Aqueous solution 70 12-4 3 ztil
...,;I>
Luperox GmbH c:)1;1
Luperox H 70 X Aqueous solution 70 12·4 13 ;I>
;;l
Cumene hydroperoxide 0
'tI
Akzo Chemie UK Ltd 0
t"'
Trigonox K -80 Mixed solvent solution 80 7·9 F 5, 14, 15 ><:
!}l
Luperox GmbH ;;l
Luperox CU80 Solution in cumene 80 8·4 15 )1;1

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Dicumyl peroxide ~
Akzo Chemie UK Ltd Z
til
Peradox SB Crystalline solid 95 5·6 B 6,7
Peradox BC-40 Powder + calcium carbonate 40 2·4 B
Luperox GmbH
Luperco 500-R Crystalline solid 99 5·9 6,7
Luperco 540 Powder + silicate 40 2·4 6,7
Luperco 540G Powder + silicate + calcium 40 2·4
carbonate N
w
Table 10.5 (Continued)
N
t;J
Active N

Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code

Oi-t-butyl peroxide
Akzo Chemie UK Ltd
Trigonox B Liquid 95 10·6 F 7
Interox Chemicals Ltd
Interox OTBP Liquid 95 10·6 4
'f1
Luperox GmBH :xl
"C
Luperox Oi Liquid 97 10·6 6,7
;j
("')
t-Butyl cumyl peroxide :t
Akzo Chemie UK Ltd z
0
Trigonox T Liquid 95 7·3 E 6,7 t'"
8><:

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2,5-Dimethyl-2,5-bis(t-butylperoxy)hexane
Luperox GmbH
Luperox 101 Liquid 90 9·9 6,7

Mixed peroxides
Akzo Chemie UK Ltd
Trigonox KSK Liquid 5·7 G 6, 7
Trigonox KSM Liquid 6·2 G 6,7

t-Butyl peroxybenzoate
Akzo Chemie UK Ltd
Trigonox C Liquid 97 7·9 F
Trigonox CM-50 Solution in dimethyl phthalate 50 4·1 E 6, 7, 13
Interox Chemicals Ltd
Interox TBPB Liquid 95 7·8 3
Interox TBPB 50Ff Phthalate solution 50 4·1 3
Luperox GmbH
Luperox P Liquid 98 8·1 6,7

t-Butyl peroxydiethylacetate
Akzo Chemie UK Ltd
Trigonox 27 Liquid 95 8·1 E 3,6,7
e
Z
CIl
t-Butyl peroxyester
Luperox GmbH ...,>
Luperox DPIO Liquid in plasticiser 80 6·6 3,4,6 e
:=
>
...,
tTl
t-Butyl peroxyisononanoate
Akzo Chemie UK Ltd '"0
"
0
Trigonox 42 Liquid 94 6·5 F 3,6 r
><:
Trigonox 42PR Liquid 94 5·9 F 3,6 tTl
CIl

Interox Chemicals Ltd @


:=

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Interox TPBIN Liquid 95 6·6 4 3,6 :=
Luperox GmbH
rn
Luperox 270 Liquid 98 6·8 6,7
Z
CIl

t-Butyl peroctoate
Akzo Chemie UK Ltd
Trigonox 21 Liquid 95 7·0 F 4,13
Interox Chemicals Ltd
Interox TBPEH Liquid 95 7·0 3
N
Luperox GmbH w
w
Luperox 26-R Liquid 98 7·25 6,7
N
......
Table 10.5 (Continued) .j::..
--~

Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code

Di-t-butyl diperoxyphthalate
Akzo Chemie UK Ltd
Trigonox EM-50 Phthalate solution 50 5·2 E 6
'rj
t-Butyl peroxypivalate :=
Akzo Chemie UK Ltd ."
o-!
Trigonox 25/75 Liquid 75 6·9 F 6 ttl
n
Interox Chemicals Ltd ::t::
Z
Interox TBPPI 75 AL Hydrocarbon solution 75 6·9 3 0
t"'

2,5-Dimethylhexane-2,5-diperoxybenzoate
8><:

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Interox Chemicals Ltd
Interox DHPB Powder 95 7·5 3 6

4,4-Di-t-butyl peroxy-n-butyl valerate


Akzo Chemie UK Ltd
Trigonox 17/40 White powder + calcium carbonate 40 4·0 C 6,7

Mixed peroxyesters
Akzo Chemie UK Ltd
Trigonox 33 Liquid G 6,7
Trigonox 37 Liquid G 6,7
2,2-Bis (t-butylperoxy) butane
Interox Chemicals Ltd
Interox BU 50 WO Phthalate solution 50 6·8 4 6,7
Luperox GmbH
Luperox 220 Solution in dibutyl phthalate 50 6·8 6,7

1,1-Bis(t-butylperoxy)cydohexane
Interox Chemicals Ltd
Interox CH 50 Phthalate solution 50 6·2 4 6,7 e
Z
Luperox GmbH V>
:>
Luperox 331-50 Solution in dibutyl phthalate 50 6·1 6,7 >-l
e~
:>
1,I-Bis(t-butylperoxy)-3,3,5-trimethylcydohexane >-l
ttl
Akzo Chemie UK Ltd 0
Trigonox 29/40 Solid + calcium carbonate 40 4·2 C '"d
0
Trigonox 29B-50 Liquid 50 5·3 E 6,7, 13 t""'
-<
ttl
Interox Chemicals Ltd V>
>-l
Interox TMCH 50FT Phthalate solution 50 5·2 4 6,7 ttl
~

giridharvzm1@gmail.com
~
Luperox GmbH ttl
V>
Luperox 231-50 Solution in dibutyl phthalate 50 5·28 6,7 Z
Luperco 231 XL/G Powder 40 4·23 V>

Luperco 231 XLP Paste 40 4·23

Ketal peroxides
Luperox GmbH
Luperox 43-M Plasticiser solution 50 8·6 3,4
Luperox 233-50 Solution in dibutyl phthalate 50 5·47 7
Luperco 233 XL/G Powder 40 4·37 7
N
Luperco 233 XLP Paste 25 2·74 7 w
Vl
tv
.....
0\

Table 10.5 (Continued)


APPLICATION CODES
1 = Hand lay-up 6= Hot press moulding 11 = Encapsulation
2 = Spray lay-up 7= SMC, DMC, BMC 12 = Low temperature cure
3 = Filament winding 8= Bisphenol resins 13 = Coatings
4 = Corrugated sheets 9= Vinyl ester resins 14 = Resin injection
5 = Cold press moulding 10 = Repair putties 15 = Topcoats
~
;;j
VH = very high reactivity (gel time 5-10 min.)
H = high reactivity (gel time around 10 min.)
M = medium reactivity (gel time around 20 min.)
L = low reactivity (gel time around 35 min.)
><:
!

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HAZARD CLASSIFICATIONS
Akzo Chemie UK Ltd
A Powders, when in a dry state are explosive on ignition, friction or percussion, but are normally stored and transported
in a damped-with-water condition to keep them relatively safe.
B Powders, transported and used in the dry state, flammable - will burn furiously on ignition-but not explosive.
C Powders, diluted with inert extenders, are relatively safe.
D Pastes, with plasticisers, very flammable.
E Liquids, in plasticiser solution, flammable-flash point over 43°e.
F Liquids, flammable-flash point over 100e. c
G Liquids, in plasticiser solution, flammable-flash point over 80°e.
z
~
G/LH Low hazard ketone peroxides.
H Liquids, flammable-flash point below 100e. ~
~
Interox Chemicals Ltd ~
I The material is sensitive to friction or mechanical shock. (3
2 The material can be detonated by an explosive priming charge or it decomposes with explosive violence when heated t""
unconfined, as when involved in a fierce external fire. -<
tTl
en
3 Though not detonatable nor explosive when heated unconfined, the material may decompose violently. The rate and ;:;l
magnitude of the heat released may be sufficient to propagate decomposition through the mass. Included in Hazard ::c

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Rating 3 are also materials which have a relatively short half-life at normal air temperature and therefore require
refrigerated storage. ~
4 The material is thermally stable and does not support propagating decomposition, but it is readily flammable and burns
Z
en
fiercely when ignited.
5 The material is flammable only with difficulty and/or burns only slowly when ignited.
6 The material is non-flammable.

tv
w
-..l
238 FRP TECHNOLOGY

Table 10.6 Some commercial accelerators

Accelerator
Supplier
Product code Description

Cobalt accelerators
Akzo Chemie UK Ltd
NL 48 S O· 5% Cobalt solution in styrene,
flash point 31°C
NL49 S 1·0% Cobalt solution in styrene,
flash point 31 DC
NL 51 S 6'0% Cobalt solution in styrene,
flash point 31 cC
NL51P 6·0% Cobalt solution in dioctyl phthalate,
flash point 150°C
NL 53 A \0% Cobalt solution in white spirit,
flash point 43°C
All as cobalt siccatol
Luperox GmbH
Accelerator CS I % Cobalt solution in styrene, as octoate
Accelerator CW 1% Cobalt solution in dioctyl phthalate, as
octoate
Accelerator C6 6% Cobalt solution in xylene, as octoate
Accelerator CIO 10% Cobalt solution in xylene, as octoate
Freeman Chemicals Ltd
Stypol accelerator 16 6% Cobalt as naphthenate
Scott Bader Co. Ltd
Accelerator E 0·4% Cobalt solution in styrene, as octoate
Accelerator G 1·0% Cobalt solution in styrene, as octoate
Accelerator R 6·0% Cobalt solution in styrene, as octoate
Synthetic Resins Ltd
Accelerator SC 0'6% Cobalt solution, as naphthenate
Accelerator C 6·0% Cobalt solution, as naphthenate

Manganese accelerators
Akzo Chemie UK Ltd
Manganese siccatol 10% Solution

Vanadium accelerators
Luperox GmbH
Accelerator VX 0·5% Vanadium solution

Dimethylaniline
Akzo Chemie UK Ltd
NL 63/100 100% NN-Dimethylaniline

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UNSATURATED POLYESTER RESINS 239

Table 10.6 (Continued)

Accelerator
Supplier
Product code Description

Dimethylaniline (contd.)
Luperox GmbH
Accelerator AS 10% Amine solution in styrene
Accelerator A W 10% Amine solution in dioctyl phthalate

Diethylaniline
Akzo Chemie UK Ltd
NL 64/100 100% NN-Diethylaniline
Luperox GmbH
Accelerator AE 10% Solution in styrene

Dimethyl-p-toluidine
Akzo Chemie UK Ltd
NL 65/100 100% NN-Dimethyl-p-toluidine
Luperox GmbH
Accelerator DW 10% Amine solution in dioctyl phthalate.

Mixed cobalt/amine accelerators


Luperox GmbH
Accelerator DAC-I02 A plasticiser solution containing 2%
cobalt and 10% dimethylaniline

Table 10.7 Some commercially available inhibitors

Supplier
Product code Description

Akzo Chemie UK Ltd


Inhibitor NLC 10
Luperox GmbH
Inhibitor TC 10% solution of t-butyl catechol in styrene. Use
0·01-0·2%with a ketone peroxide catalysed
system.
Inhibitor TEK 10"/0 solution of di-t-butyl-p-cresol in styrene.
Use 0·05-0·6% with a ketone peroxide
catalysed system.
Inhibitor DDS-3 Solution in xylene. Use with ketone peroxide
catalysed system. Increases pot-life without
altering gel or cure time.

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Chapter 11

EPOXIDE RESINS

11.1 INTRODUCTION

Epoxide or epoxy resins are materials which contain two or more

epoxide groups -!!.-'c- or more generally glycidyl groups


~/O\
-O-CH 2 -CH-CH z per molecule. The same terms are, however, also
used to describe the cured materials. The uncured resins range from free
flowing liquids to high melting solids, which can be cured or cross-linked
into hard infusible materials by reaction with an appropriate curing agent.
The curing reaction is brought about by the addition of a suitable di- or
poly-functional curing agent to the resin. Typical curing agents include
primary and secondary amines, polyamides and organic anhydrides. These
are generally used in roughly stoichiometric proportions with the resin and
may require heat to effect cure. Other curing agents used are the catalytic
curing agents, such as the boron trifluoride complexes. These are used in
catalytic amounts and may require either ambient temperature or heat
cure. No by-products are evolved during cure. The resultant cured resins
are generally hard thermoset materials with excellent mechanical, chemical
and electrical properties.
Epoxide resins are widely used in coating, adhesive, flooring, laminating
and casting applications. Hardly any industry today does not use an
epoxide resin composition of some sort; indeed they are even found in
many homes in the form of a two-pack adhesive-perhaps the best known
being the 'Araldite' adhesives from Ciba-Geigy Plastics & Additives
Company.
For many applications the straightforward reaction of a resin with a
curing agent gives a product suitable for immediate use. For other

240

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EPOXIDE RESINS 241

applications the basic formulation may need to be modified to improve


handling and curing characteristics, mechanical or other properties. Such
modifications can be brought about by the addition of di1uents, flexibi-
lisers, fillers and pigments, reinforcements, fire retardants and accelerators.
The effect of some of these on resin properties will be dealt with later in this
chapter and also in the following chapter on curing agents.
One of the main advantages which epoxide resins have over polyester
resins is their low shrinkage during cure. This is generally between 1 and 2%
but can be reduced to virtually zero by the addition of fillers.
Epoxide resins are usually classified according to their epoxide equiva-
lent weight or Epoxy Molar Mass (EMM). This is the equivalent weight in
grams of resin containing one epoxide group. Alternatively this may be
expressed as epoxide content, which is the number of equivalents per
kilogram of resin. Thus an epoxide equivalent or EMM of 500 is the same
as an epoxide content of 2·0. Epoxide equivalent is determined by direct
titration of a solution of resin in an appropriate solvent with hydrobromic
acidt or perchloric acid using crystal violet as indicator.
Resins used for laminating applications fall into two broad classes:
(a) the liquid resins-used mostly for wet lay-up and site applications,
although some are used for prepregs, and (b) the low molecular weight solid
resins-used in solution for making prepregs.
The unmodified bisphenol A resins (diglycidyl ether of bisphenol
A-DGEBA) are generally used for heat cured wet lay-up systems. These,
when cured with an amine such as diaminodiphenylmethane (DDM), have
excellent mechanical and electrical properties, with a heat deflection
temperature above 150°C. They also have excellent chemical resistance.
With site applications, the viscosity of the basic resin is generally too high
for convenient use and so a diluent is added to lower the viscosity. This can
also serve to improve ambient temperature cure by increasing the mobility
of the system. Most ambient temperature cured epoxide resin systems have
a heat deflection temperature of about 50°C. This can, in some cases, be
raised by giving the system an elevated temperature post cure. This is often
accomplished when the laminate is put into service.
Resins used for electrical laminates may be liquid or solid depending on
whether a wet lay-up or prepreg technique is used. For prepreg manufac-
ture either a liquid resin, EMM 190-250, or a fairly low molecular weight
solid resin, EMM 450-900, is used. These can both give rigid tack-free
prepregs. Where tacky prepregs are required liquid resins are always used.

tBS 2782 Method 407A; ASTM D-1652.

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242 FRP TECHNOLOGY

Flame retardant laminates are generally prepared from brominated resins.


For convenience, resins and diluents are discussed in this chapter and
curing agents and accelerators in the next.

11.2 THE RESINS


These can be conveniently divided into six classes of resins: bisphenol A
based; glycidyl esters; glycidyl amines; novolacs; brominated resins;
cycloaliphatic and other resins.

11.2.1 Bispbenol A based resins


These were the first resins to be produced commercially and form some 95%
of all epoxide resins available today. They range from medium viscosity
liquids through to high melting solids and are all prepared by the reaction
between epichlorohydrin and bisphenol A. The different resins are formed
by varying the proportions of the two reactants. With some ten times excess
epichlorohydrin the product is virtually pure monomer, i.e. two molecules
of epichlorohydrin plus one molecule of bisphenol A. As the proportion of
epichlorohydrin is reduced, so the molecular weight of the resin is
increased. All the resins produced in this way consist of mixtures of
different molecular weight species and it is this molecular weight distri-
bution which governs the viscosity/melting point of the resin.

/'"
° ~I~
CH 3
2 CH2---CH~H2CI + HO~T~'-'H
CH 3
Epichlorohydrin Bisphenol A

~
/0", r ?H /0", l
CH2---CH~H2+R~H2~H~H2±R-CH2~H---CH2
Diglycidyl ether of bisphenol A
n = 0, 1, 2, 3, etc.
n = 0 represents the pure diglycidyl ether of bisphenol A.

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EPOXIDE RESINS 243

1 2 3 4 5 6

Fig. 11.1. A typical thin layer chromatogram showing epoxide resins of different
molecular weights. 1, Epikote828, EMM 182-194; 2, Epikote834, EMM 225-280;
3, Epikote 1001,EMM 450-500;4, Epikote 1004, EMM 850-900; 5, Araldite 7065,
EMM 455-500; 6, Araldite XD761, EMM 2500-4000. Chromatogram developed
twice in chloroform, silica gel G plate, visualised with chromic acid spray and
heated to 100°C.

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244 FRP TECHNOLOGY

The different molecular weight species present in an epoxide resin can be


separated by thin layer chromatography.! A typical chromatogram
showing the molecular weight distribition of several different resins is
shown in Fig. 11.1. Using thin layer chromatography it has been found
possible to examine the purity of various resins and to account for some of
the differences found between substantially identical resins.
The commercially available liquid resins (EMM range 180-196) have a
tendency to crystallise during storage. This is due to their relatively high
purity. Most contain in excess of 90% of the pure diglycidyl ether of
bisphenol A, which is a colourless crystalline material with a melting point
of 44· 5-46°C and an EMM of 170 (molecular weight 340). These resins can
therefore be considered to be supercooled liquids. In order to prevent
crystallisation during storage, manufacturers sometimes add a small
proportion of higher molecular weight resin. Unfortunately this causes an
increase in viscosity. One alternative procedure which has been adopted
recently is to make a bisphenol F resin and blend this with the bisphenol A
resin in the ratio of about 70/30 A/F. The resultant blend has a lower
viscosity and negligible tendency to crystallise, while cured properties

1000
800
600
400 "\.\.
\r\.
1\",
200

100
80
60
40 "-
\. '""'\

'" "
20

10
8

:II 4
6
, '-.:
'R
> ""-. '-

"
'~ 2
A/F "-
:> 1 ~
o 10 20 30 40 50 60 70 80 90 100
Temperature ·C

Fig. 11.2. Viscosity/temperature characteristics of bisphenol A and A/F based


epoxide resins. A resin = Epikote 828; A/ F resin = Epikote DX 235. (Courtesy of
Shell Chemicals UK Ltd.)

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EPOXIDE RESINS 245

remain virtually the same. One disadvantage, however, is the higher cost of
making a bisphenol F resin due to the lower conversion efficiency of the
process.

HO-o-CH2-o-0H

Bisphenol F

A typical viscosity/temperature curve for a bisphenol A resin is shown in


Fig. 11.2 alongside that for a typical A/F blended resin.
Typical uses of the unmodified liquid DGEBA resins in laminating
applications are: filament winding, pultrusion, vacuum impregnating,
contact moulding and, to a limited extent, site application. They are also
used for the manufacture of tacky prepregs from glass and carbon fibres.
They can be cured with a wide range of curing agents both at ambient and
elevated temperatures.
A more detailed description of these resins and their curing agents can be
found in the Handbook of Epoxy Resins. 2 Although this book is now some
13 years old most of the contents are still applicable today.

11.2.2 Glycidyl ester resins


The structure of a typical glycidyl ester resin is as follows:
o 0
II /'"
0 : C - -O--{:H,---t:H---CH,

C-O--{:H 2 --{:H--CH 2

oII "0' /
Whilst numerous resins of this type can be made from all types of di-
acids, few are in commercial production. A resin such as the one shown
above offers considerable advantages over the bisphenol A based resins in
terms of viscosity, outdoor weathering and tracking resistance. Such resins
are used for high voltage electrical insulators and heat cured laminates. In
general, resins of this type are used with anhydride curing agents, to give
systems with viscosities and reactivities ideally suited to vacuum impreg-
nation, laminating and casting applications. These resins cannot generally
be used with normal ambient temperature curing agents due to lack of
adequate cure.

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246 FRP TECHNOLOGY

11.2.3 Glycidyl amine resins


The general structure of a tetra-functional glycidyl amine resin is as
follows:

/""
o o
CH 2--CH-CH 2 CH 2
/""
-CH----CH 2
~ /
N-R-N
/ 2
CH 2--CH-CH "" CH2-CH----CH2
~/
o ""/
0
Such resins can be made from most diamines and may be liquids or
solids. One such resin is the tetraglycidyl amine of 4,4' -diamino-
diphenylmethane. Other resins may be based on secondary amines such as
hydantoin, where a diglycidyl amine resin results.
Few resins of this type are commercially available. Those which are
available are mostly cured with anhydrides to give products with good high
temperature strength retention and good resistance to nuclear radiation.
These systems are used for wet lay-up laminating and filament winding.

11.2.4 Glycidyl ethers of novolac resins


Novolac resins are produced when phenol and formaldehyde react together
in acid solution. The simplest novolac is bisphenol F. Most, however, have
higher molecular weights, thus:

J: r J: 1
Gt-rH,UtcH,-6
OH

where n can be anywhere from 0 to about 10.


These resins are then reacted with epichlorohydrin to form glycidyl ether
novolacs. The bisphenol F resin is a liquid while the higher molecular
weight resins are solids.
Such resins, when cured, offer high temperature stability and good
chemical resistance but have the disadvantage, with certain curing agents,
of having a low strain at break (1-1'5%). Thus they can fail by interlaminar
shear if used in 90° cross-plied carbon fibre composites, due to the strain
induced by the negative coefficient of thermal expansion of the fibre along
its length.

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EPOXIDE RESINS 247

Normally the curing agents used with epoxy novolac resins for prepregs
are aromatic diamines and boron trifluoride complexes. Anhydrides are
used for wet lay-up (heat cured) and filament winding processes.

11.2.5 Brominated resins


Various commercial brominated resins are available with different bromine
contents. They may consist of resins prepared from tetrabromobisphenol A
alone or blends with normal bisphenol A resins. The structure of the
diglycidyl ether of tetrabromobisphenol A is:

/~o
CHz---CH--CHz-O -p-I:Q-
Br

'I '\
-
CH

C
I
'I '\
-
Br

/~
0

O-CHz-CR--CH z

Br CH 3 Br

These resins are used to confer flame retardancy to composites. They are
mostly used in the manufacture offire retardant printed circuit boards, for
example to NEMA Grade FR4 specification, 3 where cure is effected with
dicyandiamide.

11.2.6 Other resins


Various other resins are available which do not readily fall into the previous
categories. These include such resins as the cycloaliphatic resins where one
of the epoxide groups is on a cycloaliphatic ring:

o
/~
~R-0-CH2-CH--CHz

0'0
or the tetraglycidyl ether of tetraphenylene ethane.
Some of these other resins have been developed under various govern-
ment and military contracts specifically to provide high performance
composites for aerospace applications. One resin which proved to be of
considerable interest for use in carbon fibre composites was
bis(epoxycyclopentyl) ether. Unfortunately, due to production difficulties,
this resin is no longer available. Other resins are, however, now available
which fulfil a similar role.

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248 FRP TECHNOLOGY

11.3 DILUENTS

Diluents are added to epoxide resins primarily to lower viscosity and thus
improve handling characteristics. They also modify the cured properties of
the resin. In general terms, the higher the proportion of diluent added to the
resin the lower the viscosity and the lower the mechanical properties and
chemical resistance of the cured system. The level at which properties start
to drop dramatically varies from one diluent to another. Most cause little
concern up to between 10 and 15% addition.
Diluents can be divided into two classes: (a) the reactive diluents such as
the monoglycidyl ethers and (b) the non-reactive diluents. The reactive
diluents are the most widely used, since they form an integral part of the
cured structure and cannot be leached out.
Most resin manufacturers supply a range of diluted resins designed to
meet specific end-user needs. These cover a wide range of viscosities, with
diluent concentrations generally within the range 0- 20%. Many of these
resins have been specifically formulated for end uses other than laminating.

11.3.1 Reactive dilueots


These are in the main monoglycidyl ethers although some diglycidyl ethers
such as butane-I,4-diol diglycidyl ether are used. Only the monoglycidyl
ethers will be discussed here. Those in common use are listed in Table 11.1.
Since these compounds contain only one epoxide group per molecule,
they can be considered as chain stoppers in that they reduce the
functionality of the system and therefore reduce cross-link density. They
also alter the epoxide equivalent weight of the blend. This may need to be
taken into account when calculating the correct proportion of curing agent
to use. In practice, with most reactive diluents, the difference is small and
can be ignored-see Table ILL
When used to dilute DGEBA resins prone to crystallisation, some
diluents increase this tendency, while others have little or no effect. The
increased tendency of the resin to crystallise is due to the lower viscosity of
the blend and the solubility of the higher molecular weight components in
the diluent. To overcome this tendency in commercial resins, manufac-
turers often either use a less pure, higher molecular weight starting resin or
blend two resins of different molecular weights together. Thus there are
several 'non-crystallising' diluted grades of resin commercially available.
Crystallisation usually occurs when resins are stored under fluctuating low
temperature conditions around O-lOoC and can be enhanced by the
presence of fillers. With higher temperature storage the problem does not

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EPOXIDE RESINS 249

Table 11.1 Reactive diluents

EMMo!
Molecular resin +
weight 15%
Diluent ( EMM) diluent" Comments

Butane-l,4-diol diglycidyl ether 10 1b 168


n-Butyl glycidyl ether (nBGE) 130 178 High odour
Glycidyl methacrylate 142 181 High odour
Phenyl glycidyl ether (PGE) 150 183
2-Ethylhexyl glycidyl ether
(2EHGE) 156 184 High odour
lso-octyl glycidyl ether (lOGE) 156 184 High odour
Diethylene glycol monobutyl
glycidyl ether 162 185
Cresyl glycidyl ether (CGE) 165 186 Low odour
p-t-Butylphenyl glycidyl ether 206 192
Epoxide 7 (Cg-C 10 glycidyl
ether)' 229 195 High odour
Epoxide 8 (C 12 -C 14 glycidyl
etherY 286 200 Low odour
Dibromocresyl glycidyl
ether (BROq 360 204 Fire retardant
Dibromophenyl glycidyl
ether (D.E.R. 599) 308 201 Fire retardant

a Standard DGEBA liquid resin of EMM 190-resin/diluent ratio 85/15.


EMM calculated on a reciprocal basis, thus:
85 15 100
-----+-----
resin EMM diluent blend
EMM EMM
b Since this is a diglycidyl ether the equivalent weight has been quoted.
C From Procter & Gamble Ltd.

usually occur. Once a resin has crystallised it can be returned to the liquid
state by warming to above 50°C, followed by thorough stirring to ensure
uniform diluent distribution.
Each of the different diluents behaves quite differently in its viscosity
reducing effect and also in its effect on mechanical properties. Fig. 11.3
shows the effect of some of the common diluents on the viscosity of a typical
liquid DGEBA resin. Clearly, the actual viscosity resulting from the
addition of a particular level of diluent to a resin must depend on the
viscosity of the base resin before dilution.

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250 FRP TECHNOLOGY

10
9
8
7
6
5

1
0·9
0-8
01
~
0·6
0
"- 0·5
>= 0·4
..
..
0
v
0·3
>

0-2

5 10 15 20
Diluent, %
Fig. 11.3. The effect of various reactive diluents on the viscosity of a standard
DGEBA resin.

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EPOXIDE RESINS 251

The effect of addition of 15% and 20% diluent to a standard DGEBA


resin cured with triethylenetetramine (TETA) is shown in Table 11.2. The
differences in tensile strength become less as the diluent concentration is
decreased. Most diluents cause a slight increase in gel time compared with
the undiluted resin.
The levels of diluents used in commercial resins are usually a compro-
mise between viscosity reduction and loss of mechanical properties, since
frequently the demand is for the lowest viscosity resin coupled with the
highest level of mechanical properties from the cured system.

Table 11.2 Effect of diluent on gel time and tensile strength of DGEBA resin cured
with TETA

Gel time at 20°C


on 100 g mix (min) Tensile
strength
Diluent (%) Isothermal Adiabatic (MPa)

None (DGEBA resin EMM 190) 0 45 31 77

n-Butyl glycidyl ether 15 59 36 85


20 70 76

Phenyl glycidyl ether 15 45 94


20 46 74

2-Ethylhexyl glycidyl ether 15 50 40 70


20 55 63

Iso-octyl glycidyl ether 15 50 40 70


20 56 63

Diethylene glycol mono butyl 15 60 72


glycidyl ether 20 65 68

Cresyl glycidyl ether 15 46 34 87


20 48 87

p-t-Butylphenyl glycidyl 15 50 91
ether 20 53 94

Epoxide 7 15 86 38 66

Epoxide 8 15 86 38 63

All systems cured with TETA (13 phr) for 1- 5 days at 20°C + 2 h at 120°C.

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252 FRP TECHNOLOGY

10
~,
~
9
8 ~
~
"'" I'...
" '"
7 .~.

", ~
~

,
5
4
~
3
~
""" ~
2
~ ~
DBP

1
~""
" ,,"'-....
~
0·9
0 0'8
0-
0'7
>.. 0·6 "'-'"~ Benzvl alcoh 01
0'5
~

0
:;( Furfuryl ale ohol
> 0·4
0·3

(}2

5 10 15 20
Diluent, %
Fig. 11.4. The effect of non-reactive diluents on the viscosity of a standard DGEBA
resin.

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EPOXIDE RESINS 253

In addition to those diluents mentioned above is dibromocresyl glycidyl


ether (BROC). This is a fairly low viscosity monoglycidyl ether with a
bromine content of 48-50%, which is used as a fire retardant additive
rather than a diluent. It finds application in electrical laminating systems,
for example in the production of fire retardant printed circuit boards.

11.3.2 Non-reactive diluents


A wide variety of non-reactive diluents or extenders can be added to
epoxide resin compositions either to reduce viscosity or to reduce cost or
both. These include such materials as liquid coal tars, pine oil, cumarone
indene resins, phthalate plasticisers, benzyl alcohol and furfuryl alcohol.
Most of these materials are used in what can be described as civil
engineering applications, that is flooring, coating, repair mortars and
adhesive applications. Three, however, may be used in laminating appli-
cations. These are dibutyl phthalate (DBP), and benzyl and furfuryl
alcohols. They are generally only used in room temperature cured systems.
Benzyl alcohol is also used as a diluent in curing agent formulations. The
effect of these three diluents on the viscosity of a typical DGEBA resin is
shown in Fig. 11.4.
Where non-reactive diluents are used, due allowance must be made when
calculating the proportion of curing agent to use with the resin blend. In the
equation given under Table 11.1 the term for the diluent is zero and so the
epoxide equivalent weight of the blend is given by:
100 x EMM of resin
EMM of blend = ~------
percentage resin
Table 11.3 Effect of non-reactive diluents on properties of
DGEBA resin

Tensile
strength Elongation
Diluent (%) (MPa) (%)
None 0 77 6·8
Benzyl alcohol 20 46 3·5
Furfuryl alcohol 20 35 5·4
Dibutyl phthalate 20 54 5·5

Resin system: Epikote 828/Epikure T (100/20) or


Epikote 828/Epikure T/diluent
(80/16/20).
Cure schedule: 1 week at 20°C + 2 h at 60°C.

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254 FRP TECHNOLOGY

It has been found in practice that of the various phthalate plasticisers


available, dibutyl phthalate is the most satisfactory one for use with
epoxide resins. It is usually used in proportions of up to 20% and does not
show any tendency to migrate to the surface of the cured resin on ageing.
Benzyl and furfuryl alcohol are good viscosity reducers for liquid
epoxide resins and both act to some extent as accelerators. Furfuryl
alcohol, however, has a tendency to change colour with age and can result
in slightly brown coloured laminates.
In some formulations these two diluents can be interchanged, although
at the 20% level there is a difference in cured properties-see Table 11.3.

11.4 HOW TO CHOOSE AN EPOXIDE RESIN

For most wet lay-up heat cured systems the resin chosen will be the
standard liquid DGEBA resin EMM 183-195. For prepreg preparation
either the same liquid resin or a solid resin with an EMM 400- 500 will be
used.
For special applications, such as where a fire retardant system is
required, then a brominated resin or brominated diluent will be used.
Where high temperature performance is needed, either a polyfunctional
resin or an epoxy novolac used with an appropriate curing agent will give
better performance than the standard resin. For outdoor weathering or
improved tracking resistance the glycidyl ester resins offer superior
performance.
When it comes to site applied laminates, resin viscosity is important and
it is here that the diluted resins are used. Various blends of resin and diluent
are available commercially, covering a fairly broad viscosity range. As
a general rule, the lower the viscosity, the higher the diluent level and the
lower the cured properties. Thus, wherever possible, a low level of diluent
is preferable. Choice is generally restricted to viscosity/handling characteri-
stics-some diluents being less pleasant to handle than others.
Many of the grades of diluted resins available have been developed for
applications other than laminating, often for their ability to take high filler
loadings. In these cases, the filler often compensates for a reduction in
mechanical properties of the cured system.
With all resins, cured properties are very dependant on the curing agent
used, particularly as far as chemical resistance is concerned, but also with
respect to other properties. ,Thus for any particular application, system
properties must be considered, rather than just resin properties alone.

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EPOXlDE RESINS 255

11.5 COMMERCIALLY AVAILABLE RESINS

A fairly comprehensive list of epoxide resins commercially available in the


UK is given in Table 11.4. Only limited information about each resin
has been given; further data may be obtained from the resin suppliers.
Some resins, such as those only used for coating and other non-laminating
applications, have been omitted. Other resins, of an experimental nature,
may also be available but are not included in Table 11.4. Since manufac-
turers change resin specifications and product ranges from time to time, the
data given should only be used as a guide and current information obtained
from the appropriate supplier.
Resins supplied by the following companies have been included:
Supplier Trade name
Berger Chemicals (Reichhold Albert Chemie AG) Beckopox
Borden (UK) Ltd Epophen
Boston Chemical Co. Ltd
CdF Chimie. UK Agent-KWR Chemicals Ltd Lopox
Ciba-Geigy Plastics & Additives Company Araldite
Croda Resins Ltd Plastokyd
Dow Chemical Co. Ltd. UK Agents- D.E.R., D.E.N.
K & K Greeff Chemical Group Ltd
Thomas Swan & Co. Ltd
Grilon (UK) Ltd Grilonit
Schering Chemicals Ltd Eurepox
Shell Chemicals UK Ltd Epikote
Synres (UK) Ltd Eporex
Synthetic Resins Ltd Uranox

REFERENCES

l. Weatherhead, R. G. (1966) Analyst, 91, 445.


2. Lee, H. and Neville, K. (1967) Handbook of Epoxy Resins, McGraw-Hill Book
Company, New York.
3. NEMA Publication No. Ll.I-197l. National Electrical Manufacturers
Association, Washington, DC, USA.

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N
VI
0-.
Table 11.4 Commercial epoxide resins

Supplier Epoxy Viscosity


Trade name molar at 25°C Specific
Product code mass (Pa s) gravity Comments

Berger (Reichhold Albert Chemie A G) Other high molecular weight resins also available
Beckopox EP 128 190-210 0·5-1·0 1·12 100% reactive modified resin for laminating and casting
EP 130 185-200 0·5-0·9 1·13 100% reactive modified resin for laminating and casting
EP 133 230-250 1·2-1·6 1·14 Plasticised resin for casting, cable jointing, etc.
EP 134 230-250 2·1-3·1 1·14 Plasticised resin for coatings and flooring 'tj
EP 135 185-200 5·0-8·5 1·15 100% reactive resin for laminating and casting ~
'Ii
EP 139 180-190 6·0-10·0 1·16 Unmodified general purpose resin
EP 140 185-195 1·16 Unmodified resin for tooling and laminating ;l
10-15 (")
EP 144 230-280 0·5-1·0" 1·17 Unmodified resin for coatings and adhesives :I:
Z
EP 151 400-500 25-35 1·08 Internally plasticised resin, 100% reactive 0
t"'
EP 200 245-265 75 1-40 100% reactive self extinguishing resin for laminating
EP 300 370-440 Solid 1·18 Solid resin for casting and laminating 8-<

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Borden (UK) Ltd Other products also available
Epophen EL-5 185-200 10-16 1·16 Medium-high viscosity DGEBA resin for laminating, etc.
EL-1O 200-220 220-40 1·2 Unmodified DGEBA resin
EL-17 185-200 10-16 1·2 Medium viscosity DGEBA resin
EL-18 190-205 2.0-2.5 1·15 DGEBA resin containing reactive diluent
EL-23 190-205 1.0-1.3 1.2 DGEBA resin containing reactive diluent
EL-24 190-205 0.6-0.9 1·2 DGEBA resin containing reactive diluent
EL-25 185-200 6-9 1·2 Unmodified DGEBA resin
EL-26 190-205 0.7-1.l 1·14 DGEBA resin containing reactive diluent
Boston Chemical Co. Ltd
ER 1 185-200 11-15 1·16 Unmodified DGEBA resin
ER2 195-207 1·2-1·8 1·14 DGEBA resin containing reactive diluent
ER 3 212-232 3·3-5·0 1·16 Flexible resin

CdF Chimie Other high molecular weight resins also available


Lopox L 199 180-195 6-10 1·14 Liquid DGEBA resin, unmodified
200 180-195 10-14 1·16 Liquid unmodified DGEBA resin
200SC 180-195 10-14 1·16 Liquid unmodified DGEBA resin
MB 200 180-195 0'7-1'1 1·14 Low viscosity DGEBA resin containing reactive diluent
440 385-415 0·0<Jb-0·11 1-04 Solid DGEBA resin
500 470-520 O' 13b -O· 19 1-04 Solid DGEBA resin
m
~
0
Ciba-Geigy Plastics and Additives Co. Aslo available-a range of tooling resins, curing agents and ~
gelcoats 0
m
Araldite GY 250 192-196 10-15 1·18 Medium-high viscosity DGEBA resin
GY 257 172-204 0,48-0,54 1·15 Modified epoxy ~
GY 261 192-204 0·9-1·6 1·17 Low viscosity resin containing reactive diluent Z
CI>
GY 278 192-200 1,2-1,6 1·14 Low viscosity resin containing reactive diluent

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GY279 200-212 1·2-2·2 1·12 Low viscosity resin containing reactive diluent
GY 280 233-278 1·18 Semi-solid DGEBA resin
GY 292 217-238 5-10 1·16 Medium viscosity modified resin
CT 200 370-435 1·18 Solid DGEBA resin
CY 219 194-200 10-15 1·18 Medium-high viscosity DGEBA resin for laminating, etc.
LY 558 175-182 Semi-solid epoxy novolac resin
LY 560 172 1·5-3·0 1·15 Liquid DGEBA resin for laminating
LT 579 182-200 Solid polyfunctional resin for laminating
MY 720 128-137 1·19 Viscous polyfunctional epoxide resin for laminating
MY 750 188-198 10-16 1·18 Medium viscosity DGEBA resin
MY 753 227-238 1·6-2,4 1·18 Plasticised liquid DGEBA resin tv
VI
-.)
Table 11.4 (Continued) N
VI
00
Supplier Epoxy Viscosity
Trade name molar at 25°C Specific
Product code mass (Pa s) gravity Comments

Araldite (contd.)
MY 778 188-200 0'6-1'0 1·18 Liquid DGEBA resin containing reactive diluent
7065 455-500 Solid 1·19 Solid DGEBA resin for prepregs
8011 455-500 Solid Solid brominated resin, 21% Br, for laminating
8047 222-244 Semi-solid brominated resin, 18-22% Br, for laminating
LZ 1620 GB 454-500 Solid brominated resin, 80% solids in MEK, 19-23% Br
XD 927 140-150 1-0-1,5 1·17 Low viscosity laminating resin "!j
:=
o-g
XD 928 Gelcoat for XD 927
XD 955 172-185 4,5-6,5 1·17 DGEBA/F blended resin t;l
XD 761 2500-4000 1·19 Supplied as 50% solution of high molecular weight DGEBA t"l
resin for coating applications (TLC Fig. 11.1)
:=
~
t""
Crodo Resins Ltd Other types of resin also aviailable 8-<
Plastokyd SC 480 295-310 0'1-0'15< Silicone modified epoxy for laminating, etc.; 25% silicone

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Dow Chemical Co. (UK) Ltd Other resins also available
D.E.R.321 182-192 0'5-0'7 1·14 DGEBA resin containing CGE
D.E.R.324 195-213 0·5-0·7 1·10 DGEBA resin containing C 12 -C 14 glycidyl ether
D.E.R.330 182-189 7-10 1·16 Undiluted DGEBA resin
D.E.R.331 186-192 11-14 1·16 Undiluted DGEBA resin
D.E.R.332 172-176 4-6 1·16 High purity DGEBA resin
D.E.R. 334 176-186 0'5-0'7 1·13 DGEBA resin containing nBGE; withdrawn in Europe
D.E.R.337 230-250 0·4-0·8 d 1·16 High viscosity DGEBA resin
D.E.N.431 172-179 1·1-1·7' 1·21 Epoxy novo lac
D.E.N.438 176-181 20-50' 1·22 Epoxy novo lac
D.E.N.439 191-210 ]·22 Semi-solid epoxy novolac
D.E.R.511 445-520 1·40 Solid brominated resin containing 18-20% bromine
D.E.R.542 350-400 1·79 Semi-solid brominated resin containing 44-48% bromine
D.E.R.599 308 0·25 max. 1·77 Dibromophenyl glycidyl ether
D.E.R. 661 475-575 1·16 Solid DGEBA resin for prepregs
D.E.R.662 575-700 1·19 Solid DGEBA resin
D.E.R.671 475-550 1·19 Solid DGEBA resin
D.E.R. 732 305-335 0·05-0·1 1-06 Flexible polyglycol diepoxide
D.E.R.736 175-205 0·03-0·06 1·14 Flexible polyglycol diepoxide
XD 5567·01 170-183 5-7 1·19 Blended bisphenol A/F resin
XD 7475 175-187 0·8-1·0 1·19 Blended bisphenol A/F resin containing nBGE

Grilon (UK) Ltd Other resins also available


Grilonit ES 101 370-415 0·4-0·75" 1·19 Solid DGEBA resin trj
ES 102 435-476 1·1-}-6' 1·20 Solid DGEBA resin '1:)
0
ES 103 190-208 0·07-0·15" 1·22 Solid resin for laminating ~
ER 201 445-510 1·40 Solid brominated resin, 19-21% Br S
trj
ER 202 330-385 1·79 Semi-solid brominated resin, 45-49% Br
ER 203 240-260 1·40 Semi-solid brominated resin, 24-26% Br ~
CJl
EL 301 182-196 7·5-10 1·17 Medium viscosity DGEBA resin Z
CJl
EL 302 185-200 10-12'5 1·17 Medium-high viscosity DGEBA resin

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EL 303 185-200 12,5-15 1·17 Medium-high viscosity DGEBA resin
EL 304 192-206 15-25 1·17 High viscosity DGEBA resin
EL 305 182-196 9-13 1·17 Medium viscosity DGEBA resin
EL 306 175-189 6-7·8 1·19 Medium viscosity DGEBA/F blended resin
EL 307 225-280 1·18 Semi-solid DGEBA resin
EV 401 179-196 0,5-0·9 1·13 Low viscosity resin containing a reactive diluent
EV 402 182-188 0·56-0·25 1·14 Low viscosity resin containing a reactive diluent
EV 403 189-200 4·5-6·0 1·16 Medium-low viscosity resin containing a reactive diluent
EV404 189-200 3·0-4'0 1·16 Medium-low viscosity resin containing a reactive diluent
EV 405 196-204 11-13 1·16 High viscosity resin containing a reactive diluent
Medium-low viscosity resin containing a reactive diluent N
EV406 158-173 2'6-3·0 1·16 VI
Low viscosity resin containing a reactive diluent \0
EV 407 141-153 0·7-0·85 1·16
Table 11.4 (Continued) IV
0-
0
Supplier Epoxy Viscosity
Trade name molar at 25°C Specific
Product code mass (Pa s) gravity Comments

Grilonit (contd.)
EY 408 120-127 0,18-0,22 1·14 Low viscosity resin containing a reactive diluent
EY 409 175-188 1·2-1·6 1·15 Medium-low viscosity resin containing a reactive diluent
EP SOl 220-240 2·0-2'6 1·15 DGEBA resin containing a plasticiser
EP 502 227-244 1·1-1·5 1·14 DGEBA resin containing a plasticiser
EF 601 196-212 4·5-5·0 1·16 100% reactive flexibilised resin
EF602 213-232 1-3-1·6 1·15 100% reactive flexibilised resin ;il
EF603 227-250 0·4-0·5 1·14 100% reactive flexibilised resin '"Cl

EF 604 185-200 3·0-4·0 1·16 100% reactive flexibilised resin ;l


~
EF 605 185-200 0·7-1·1 1·16 100% reactive flexibilised resin =:
EF 606 185-200 0·25-0·33 1·16 100% reactive flexibilised resin Z
0
t"'
Schering Chemicals Ltd Other resins also available 8-<
Eurepox 703 227-255 0-4-0'8 1·18 High viscosity DGEBA resin

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708 185-200 12-19 1·17 Medium viscosity DGEBA resin
710 178-196 9·0-13 1·17 Medium viscosity DGEBA resin
716 182-190 7·0-10 1·16 Medium viscosity DGEBA resin
720 182-192 6,5-9,0 1·17 Medium viscosity DGEBA resin
730 182-189 7·0-10 1·16 Medium viscosity DGEBA resin
761 217-233 1·2-1·6 1·14 Low viscosity modified DGEBA resin
780 178-196 0·7-1·1 1·11 Low viscosity modified DGEBA .resin
7000 365-420 1·2 Solid DGEBA resin
7001 445-500 1·19 Solid DGEBA resin
7002 590-715 1·19 Solid DGEBA resin
7003 700-875 1·19 Solid DGEBA resin
Shell Chemicals UK Ltd Other resins also available
Epikote 191 145-165 0-32-0-4 1-22 Low viscosity diglycidyl ester resin
210 240-270 1-20 Semi-solid modified resin for prepregs
213 190-210 0-7-1-1 1-15 Low viscosity DGEBA resin containing reactive diluent
214 190-210 10-15 1-16 Medium viscosity DGEBA resin, low crystallisation grade
215 200-220 0-8-1-2 1-10 OdourJess, low viscosity DGEBA resin, low surface tension
216 190-210 5-0-6-0 1-15 Medium viscosity DGEBA resin containing reactive diluent
220-B-80 400-440 1-09 80% solution of solid DGEBA resin in MEK for prepregs
DX235 175-185 6-5-9-5 ]-17 Medium viscosity DGEBA/F blended resin
DX285-B-80 640-750 ]-5-2-5 Brominated resin, 80% solids in MEK, 40% bromine
solution
808 188-198 6-5-9-5 ]-16 Medium viscosity DGEBA resin ttl
815 180-200 0-7-1-1 1-14 Low viscosity DGEBA resin containing nBGE C3
~
816 195-215 1-5-2-1 1-l3 Low viscosity DGEBA resin containing reactive diluent ....
I:)
817 210-240 2-0-2-5 1-15 Low viscosity plasticised DGEBA resin ttl
827 180-190 8-0-10 1-16 Medium viscosity unmodified DGEBA resin
828 182-194 10-15 1-16 Medium-high viscosity unmodified DGEBA resin ~
834 225-280 0-4-0-79 1-18 High viscosity unmodified DGEBA resin Z
til

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836 290-335 1-19 Semi-solid unmodified DGEBA resin
1001 450-500 1-19 Solid unmodified DGEBA resin, also available in solution
1002 575-700 1-19 Solid DGEBA resin
1004 850-940 1-19 Solid DGEBA resin
1045-A-80 450-500 1-22 80% solution in acetone of brominated resin for prepregs

Synres (UK) Ltd Other products available


Eporex 2000 184-194 1-16 Liquid DGEBA resin for coatings
2050 190-210 Non-crystallising resin for coal tar epoxies
2200 230-270 High viscosity resin for high solids varnishes
5000 450-500 Solid resin for coating applications N
0'>
t-.J
0'1
t-.J

Table 11.4 (Continued)

Supplier Epoxy Viscosity


Trade name molar at 25°C Specific
Product code mass (Pa s) gravity Comments

Synthetic Resins Ltd Other products available


Uranox 602 178-186 0-5-0-7 1-13 Low viscosity DGEBA resin containing reactive diluent
604 186-192 10-15 1-16 Medium-high viscosity DGEBA resin ~
."
605 223-230 1-2-1-6 1-13 Low viscosity DGEBA resin containing diluent ;j
607 200-210 0-7-1-2 1-14 Low viscosity DGEBA resin containing reactive diluent g
625 230-250 1-16 Semi-solid DGEBA resin Z
631 233-240 1-4-1-8 1-13 Low viscosity, low reactivity, plasticised DGEBA resin 0
632 280-290 1-8-2-2 1-14 Low viscosity, high reactivity modified DGEBA resin §
-<

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• 70% in butyl diglycol.
b 40% solids in butyl carbitol.
c 70% in xyloljoxitol acetate_
d 70% in Dowanol DB glycol ether_
eat 52°e.
f at 120°C_
g 70% solution in butyl dioxitol.
Chapter 12

CURING AGENTS FOR EPOXIDE


RESINS

12.1 INTRODUCTION

These are known variously as curing agents, hardeners, activators or


catalysts. They are required to convert liquid and solid epoxide resins into
tough infusible thermoset polymers. Most curing agents promote this
curing reaction by opening the epoxide ring and become chemically bound
into the resin in the process. Others, the catalytic curing agents, cause self-
polymerisation of the epoxide resin through the epoxide groups. These
reactions may occur at room temperature with some curing agents or at
elevated temperatures with others.
The curing reaction is an exothermic process which, with some systems,
may cause an unacceptable rise in temperature reSUlting in charring and
possible ignition of the system, whilst in others the exotherm is in-
significant. Cure may be accomplished in as little as 30 s or take several days
or even weeks. With ambient temperature curing systems, full cured
properties are not generally reached for 1- 2 weeks.
Although the epoxide group will react with some 50 or so other chemical
groupings, for the most part, particularly in laminating and adhesive
applications, only four groupings are encountered. These can be classified
as amines (both primary and secondary), organic anhydrides, catalytic
curing agents and polyamides. This last group are used more for adhesive
and coating applications than for laminating.
Since epoxide resin systems are used for tooling or mould making and as
adhesives for bonding cured laminates together, as well as for laminating, a
wider range of curing agents will be discussed than is required solely for
laminating applications.
The reactivities of epoxide groups differ depending on their location.
They may be ring situated, internal or terminal. Terminal epoxide groups

263

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264 FRP TECHNOLOGY

Table 12.1 Examples of formulated amine curing agents

Adduct Adduct
Blend S blend SE blend TE

IPD 100 100 55


TMD 45
Benzyl alcohol 88 88 88
Salicylic acid 12 12
Benzyldimethylamine 12
Liquid epoxide resin, EMM 190 20 40

Proportion used with liquid resin, EMM 190 45 53 58

also differ in reactivity depending on whether they are glycidyl ethers,


glycidyl esters or glycidyl amines. In some cases accelerators may be
required to ensure that adequate cure occurs. Due to the complexity of the
various curing mechanisms these will not be discussed here. Details can be
found elsewhere.!
In addition to the straightforward range of chemical compounds used as
curing agents, numerous formulated products are available. These may
consist simply of blends of amines with other amines or diluents, adducts
with epoxide resins or glycidyl ether diluents, or more complicated
formulations. Many such formulations also contain an accelerator to
promote or speed-up cure at ambient temperature. These products are
frequently formulated for specific end use applications, where simple
compounds prove inadequate. The number of formulated curing agents on
the market is continually changing and so no attempt has been made to list
these products here. The reader is referred to the trade literature published
by the curing agent suppliers.
To illustrate the types of formulated products which can be made, three
examples are given in Table 12.1. These formulations have been taken from
trade literature published by Veba-Chemie AG, the supplier of the amines
concerned.

12.2 SELECTION OF CURING AGENT

In selecting a curing agent the first consideration must be given as to where


the laminate is to be made. For site applied in situ laminates, an ambient
temperature curing system will be needed. This restricts the choice, for

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CURING AGENTS FOR EPOXIDE RESINS 265

most practical purposes, to liquid amine curing agents. Here, several


formulated aromatic amine based curing agents are available which
combine low viscosity, reasonable pot-life and good handling characteris-
tics with excellent cured properties and chemical resistance.
Examples of this type of curing agent, used widely on site for laminate
repairs to oil storage tanks, etc., are Curing Agents DX 150 and DX 151
from Shell Chemicals UK and Ancamine TL and TLS from Anchor
Chemical Co. Both suppliers offer one fast and one slow reacting curing
agent, formulated so that any blend of the two may be used, provided the
total amount of curing agent added is kept constant (Table 12.15,
Section 12.7.1).
A system developed as an alternative to polyester systems for ambient
temperature moulding is XD 927 from Ciba-Geigy, with gelcoat XD 928.
This system provides excellent cured properties, coupled with good
handling characteristics in the uncured state (Tables 12.3 and 12.15).
With ambient temperature cured factory prepared laminates, various
other formulated amine curing agents are available from resin and curing
agent suppliers. Here the choice must depend on the properties required of
the finished laminate. These may be good electrical properties, good
mechanical properties, high HDT, high impact strength, light colour or
some combination of these. Details of some of these systems are given later
in this chapter.
With heat cured systems, the curing agent used is often selected on the
basis of viscosity, gel and cure time to fit a particular process. Choice must
of course take into account other properties such as electrical performance,
outdoor weathering resistance and perhaps strength retention at elevated
temperature. Some useful data are given in Tables 12.2 and 12.3 and
Tables 12.6 and 12.7 (Section 12.4). Other data may be obtained from the
various material suppliers.
In general, with the standard DGEBA resin EMM 190, heat cured amine
systems provide ex,::ellent mechanical and electrical properties coupled with
excellent chemical resistance and HDTs around l50 a C. With anhydride
curing agents, the systems used generally have low viscosities coupled with
long pot-lives. Cured properties are excellent, with better outdoor weather-
ing resistance than amine cured systems. Some anhydride cured systems
have very high HDTs and excellent strength retention at elevated
temperatures. Selection must depend on process and performance require-
ments and once these have been defined the resin/curing agent system can
be selected.

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266 FRP TECHNOLOGY

12.3 AMINE CURING AGENTS

Amine curing agents may be primary or secondary amines, aliphatic,


alicyclic or aromatic. In simple terms the reaction with an epoxide resin is
an addition reaction where the amine links directly with the epoxide group
to form a combined polymer, with hydroxyl groups formed during the
reaction. Thus the amine needs to be present in a roughly stoichiometric
proportion to ensure full cure. In practice, this proportion may need to be
modified slightly to achieve optimum cured properties.

o R
OH R
/ \ / I /
R-CH-CH + HN R-CH-CH-N
\
R " R
The primary aliphatic amines react with DGEBA resins at room
temperature to give products with excellent properties, but only react
slowly with non-glycidyl ether resins. Those amines which are com-
mercially available are generally polyamines and may contain both
primary and secondary amine groups. The ones commonly encountered
either alone, or partially adducted to improve handling characteristics,
include ethylenediamine, diethylenetriamine (DT A), triethylenetetramine
(TETA), dimethylaminopropylamine and trimethylhexamethylenedi-
amine (TMD). These may be blended with polyamides for adhesive
applications to improve flexibility.
The alicyclic amines may contain primary, secondary and tertiary amine
groups and may also require an accelerator to ensure full cure at room
temperature. Examples of these materials are N-aminoethylpiperazine
(AEP) and isophoronediamine (IPD). Salicylic acid and phenol are
frequently used as accelerators for these materials.
The aromatic amines are generally used alone for heat cured systems or
in solution, with an accelerator, for room temperature cure. They are
widely used for laminating applications and give cured products with
excellent mechanical, electrical and chemical resistance up to fairly high
temperatures. Typical examples of aromatic arnines in common use are
4,4' -diaminodiphenylmethane, m-phenylenediarnine and diarninodiphenyl-
sulphone. All three are solids and so need to be dissolved in the resin prior
to gelation.
A list of commonly used amines, together with some properties, is given
in Tables 12.2 and 12.3.
Care should be taken when handling all amine curing agents and in

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CURING AGENTS FOR EPOXIDE RESINS 267

particular the aliphatic and alicyclic amines, which can cause skin
dermatitis. All normal precautions should be taken to avoid skin contact
and inhalation of vapours.
Each of the amines will now be discussed briefly in turn.

Ethylenediamine (EDA)
EDA is a mobile, fuming liquid which is used to cure liquid DGEBA
resins at room temperature. It is unpleasant to handle and so is mostly
adducted with resin and used for coating applications, frequently in
solution.

Trimethylhexamethylenediamine (TM D)
TMD is a colourless, low viscosity, aliphatic branched chain diamine
consisting of a blend of two isomers. It can be used to cure liquid DGEBA
resins alone or more generally as an activator for IPD. TMD is often
partially adducted with resin and the viscosity of the adduct reduced with
benzyl alcohol. Salicylic acid can be used as accelerator for room
temperature cure. It is mostly used for coating and flooring applications.

Diethylenetriamine (DTA)
DT A is a mobile, almost colourless, fuming liquid used to cure liquid
DGEBA resins at room temperature. It can be used for tooling and
laminating applications and is often blended with polyamides for adhesive
applications. It is not as unpleasant to handle as EDA. Cure under high
humidity conditions causes surface bloom.
Handling can be improved by reacting DT A with ethylene oxide to give
2-hydroxyethyldiethylenetriamine.

2-Hydroxyethyldiethylenetriamine (T)
This is often referred to as Amine T. It is an almost colourless low
viscosity liquid used to cure liquid DGEBA resins at room temperature. It
is more pleasant to handle than DTA but can still give rise to bloom on
cured surfaces under high humidity conditions. It is used for casting,
adhesive and wet lay-up laminating-often with diluted resins.

Dipropylenetriamine (DPTA)
DPTA is a colourless to pale yellow mobile liquid used with liquid
DGEBA resins for coating and casting applications. If used immediately
after mixing, the surface is prone to bloom. It can be adducted with resin to
reduce this tendency.

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268 FRP TECHNOLOGY

Table 12.2 Some properties of amine curing agents

Number of
Mol. Equiv. active Calc.
Curing agent Form wt wt/NH hydrogens phr·

Ethylenediamine EDA 60 15 4 8
Trimethylhexamethylene-
diamine TMD L 158 39·6 4 20
Diethylenetriamine DTA L 103 20·6 5 II
Dipropylenetriamine DPTA L 131 26 5 14
Triethylenetetramine TETA L 146 24·3 6 13
Tetraethylenepentamine TEPA L 189 27 7 I
Dimethylaminopropylamine DMAPA L 102 51 2 7
Diethylaminopropylamine DEAPA L 130 65 2 7
2-Hydroxyethyl DTA T L 147 37 4 20
rn- Xylylenediamine rnXDA L 136 34 4 18
N-Aminoethylpiperazine AEP L 128 42·6 3 22
Isophorone diamine IPD L 170 42·6 4 22
Cyclohexylpropylenediamine CHPDA L 156 52 3 27
3,3' -Dimethyl-4,4' -diamino-
dicyclohexylmethane DMACM L 238 60 4 32
Diaminodiphenylmethane DDM S 198 49·5 4 27
rn-Phenylenediamine MPD S 108 27 4 14·5
Diaminodiphenylsulphone DDS S 256 64 4 33

·With liquid DGEBA resin EMM 190.


bThese values may vary with purity of material.

Triethylenetetramine (TETA)
TET A is a mobile pale yellow liquid used to cure liquid DGEBA resins at
room temperature. It is used for casting, tooling and wet lay-up laminating
applications, often with diluted resins. HDT of the cured system can be
increased by giving an elevated temperature post cure. Cured properties are
similar to those obtained with DT A. Cure under high humidity conditions
can result in bloom on the surface.
Tetraethylenepentamine (TEPA)
TEPA is a liquid aliphatic polyamine with reactivity and cured
properties similar to those of TET A. It is mostly used for coating
applications from solution.
Diethylaminopropylamine (DEAPA)
DEAPA is an aliphatic amine containing a tertiary amine group which
acts as a catalytic curing agent at room temperature. For this reason it is
used at only 4-8 phr rather than the level expected from calculation based
on two active hydrogens. It is often used in adhesive formulations.

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CURING AGENTS FOR EPOXIDE RESINS 269

Table 12.2 (Continued)


Vapour
Flash Viscosity pressure Pot-life" at
Specific point at 20"C at 20 CD
m.p. b.p. 20 e (min)
D
Some
gravity (ct (mPa s) (mm Hg) (DC) ("C) 50g 500g suppliers<

0·90 43 1·5 10·7 11 117 40 4,8

0·87 102 5·6 0·03 -80 232 60 14


0·95 102 30 0'03 207 25 2,4,7,8,12
0·928 125 110/10mm 30 3
0·98 143 50 0·01 277 26 2,4,7,8,12
0·998 162 <0·01 333 30 4,8
0·818 45 5-10 5 135 3h 7
0·828 63 2 1 169 3h 120 7
1·035 250 30 2,7,12
1·052 134 6·8 14 247 10
0·98 93 17 0·1 -18 222 17 5
0·92 110 18 <0·01 10 247 60 14
0·92 103 < 10 llO/lOmm 30 3,12

0·95 175 125 21O/20mm 180 3,12


1·056 89 8h 2,7,8,12
62 8h 2,4,7
175 4,7

CListed at the end of this chapter.


S = solid; L = liquid; phr = parts per hundred resin.

Dimethylaminopropylamine (DMAPA)
DMAPA is a similar curing agent to DEAPA and is used for similar
applications.
m-Xylylenediamine (mXDA)
mXDA is a colourless low viscosity liquid amine which gives excellent
cured properties with DGEBA resins after heat cure, but which requires the
addition of an accelerator and diluent to complete cure at room tempera-
ture. It is mostly adducted with a resin or glycidyl diluent to overcome
problems of amine bloom. The adducts are used for coating and wet lay-up
laminating applications and cure well at room temperature.
N-Aminoethylpiperazine (AEP)
AEP is a mobile liquid giving cured systems with excellent impact
resistance after full cure. Whilst cure will take place at room temperature, a
post cure of 2 h at 100°C is necessary to develop full properties, particularly
impact resistance. It gives a short pot-life and high exotherm with liquid
DGEBA resins. It is often used in formulated amine curing agents.

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Table 12.3 Some properties of amine cured epoxide resin systems
Cast resin properties"

Volume
Tensile Tensile Elongation Flexural Permittivity Loss resistivity
Curing strength modulus at break strength at 23°C tangent (lOglO
agent HDT(°C) (MPa) (GPa) (%) (MPa) at 1 kHz at 1 kHz ohm em) Typical cure schedule

EDA 7 days/23°C or gel/23°C + 2 hfl oooe


TMD 92 98 4·0 0·023 16 7 days/23°C + 2 h/lOOoe or
1 h/80oe + 2 h/150oe
N
...., DTA 95 70 H 5·3 4·2 0·040 7 days/23°C or gel/23°C + 2 h/lOOoe
0
TETA 96 62 3·6 2·6 4·3 0·009 16 7 days/23°C or gel/23°C + 2 h/l00oe
DEAPA 90 60 4·2 0·016 24 h/20oe + 24 h/65°e
T 95 50 3·5 6·0 110 4·0 0·025 15 7 days/20°C or gel/20°C + 2 h/ 100°C
IPD 150 82 2-8 116 3-9 0·016 16 1 h/80oe + 4 h/150oe

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eHPDA 95 65 2·7 90 4·1 0·016 16 1 h/80oe + 4 h/150oe
DMAeM 152 76 2·6 102 4·1 0·013 16 1 h/80oe + 4 h/150oe
DDM 155 80 2·8 5·2 117 4·1 0·006 15 1 h/l00°C + 4 h/150oe
MPD 155 82 II 6·5 4·2 0·018 16 1 h/lOOoe + I h/200°C
DDS 193 78 3·1 6·0 4·0 0.(J.t7 2 h/l30°C + 2 h/200°C
XD 927 55-120 90 3·1 6·0 100 16 h/25°C + 5 h/80°C

'With liquid DGEBA resin EMM 190.


CURING AGENTS FOR EPOXIDE RESINS 271

Isophorone diamine (IPD) (3-aminomethyl-3,5,5-trimethylcyclohexyl-


amine)
IPD is a colourless low viscosity liquid at room temperature. It gives
excellent cured properties with liquid DGEBA resins after heat cure, but
requires the addition of a diluent and accelerator to produce a usable
system for room temperature cure (see Table 12.1). It can be used for
casting and laminating applications.

Cyclohexylpropylenediamine
This is a colourless low viscosity cyclo-aliphatic polyamine used for
casting and laminating applications. Heat cure is required to achieve
optimum properties, although when used with an accelerator, co-curing
agent or diluent, cure will take place at room temperature. It can be used
with liquid DGEBA resins and gelled at room temperature. It is
intermediate in reactivity between the aliphatic and aromatic amines.
Typical accelerators for room temperature cure are salicylic acid, phenol
and triphenyl phosphite.

3,3' -Dimethyl-4,4' -diam inodicyclohexylme thane


This is a colourless, low viscosity, cyclo-aliphatic diamine used for
casting and laminating applications. Heat cure is necessary for optimum
cured properties but it will cure at room temperature in the presence of
accelerators, co-curing agents or diluents. Typical accelerators for room
temperature cure are salicylic acid, phenol and triphenyl phosphite. It must
be stored in closed containers to prevent reaction with carbon dioxide and
it may crystallise during storage at room temperature. It can be melted by
gently warming. It can be used as an alternative to DDM for heat cured
systems.

4,4'-Diaminodiphenylmethane (DDM)
DDM is also known as methylenedianiline (MDA), although this latter
name is mostly used in the USA. DDM is an off-white solid at room
temperature and is supplied either as a powder or flake. Normal mixing
procedure is to melt the DDM at about 100°C and add to the resin, also at
100°C. Once the resin and curing agent have been thoroughly mixed the
blend can be cooled to about 50°C to prolong pot-life. At 50°C with a liquid
DGEBA resin, pot-life is about 2 h.
DDM can be used for wet lay-up laminating, casting or prepreg
preparation. For prepreg preparation both the resin and curing agent are
dissolved in solvent-either methyl ethyl ketone or acetone.

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272 FRP TECHNOLOGY

DDM dissolved in a liquid DGEBA resin will react at room temperature,


in the absence of solvents or accelerators, to form a tack-free 'B-staged'
system. This is a system which is partially reacted but which will melt and
flow with the application of heat. It is on this basis that tack-free prepregs
can be prepared. Shelf-life of such prepregs is between 1 and 3 weeks at
room temperature but can be considerably prolonged with refrigerated
storage.
One major advantage that DDM has over many other curing agents is
the ability to cure liquid DGEBA resins down to about O°C in solution in
the presence of an accelerator such as phenol or salicylic acid. Several pre-
accelerated solutions of DDM are commercially available. These are used
for a variety of applications, including site applied laminates for repairs to
oil storage tanks. The solvents generally used are high boiling ones, such as
cresols, sulphalane, etc., which remain in the cured resin system as
plasticisers. To prevent precipitation of the DDM during storage of such
solutions, a small quantity of resin or monoglycidyl ether diluent may be
added to form a partial adduct with the DDM. Depending on the level of
accelerator used, cure can proceed slowly with low exotherm or rapidly
with a high exotherm. Cure rate can be controlled far better than with the
aliphatic amine cured systems.

m-Phenylenediamine (MPD)
MPD is a colourless crystalline solid at room temperature which rapidly
darkens on exposure to light. It can either be added as a powder to resin at
80°C and dissolved with stirring or both resin and MPD can be heated to
about 65°C and thoroughly mixed. In either case irritating fumes are given
off. Once mixed the blend should be cooled to room temperature to prolong
pot-life. Skin and clothes turn brown on contact with MPD. These stains
resemble those obtained from walnut shells and are very difficult to remove.
Although MPD can be used both for wet lay-up and prepreg manufac-
ture, it finds limited use due to its unpleasant handling characteristics.

4,4' -Diaminodiphenylsulphone (DDS)


DDS is a free flowing pinkish powder with a fairly high melting point. It
is usually used at about 10% excess of stoichiometric proportion in
unaccelerated systems. It can be accelerated with boron trifluoride
complexes, typically BF 34OO-a boron trifluoride-monoethylamine com-
plex.
The mixing procedure normally used for casting or wet lay-up laminat-

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Table 12.4 Properties of different resins cured with DDS

Laminate properties, 70"10 woven glass cloth

Flexural Permittivity at Loss tangent at


strength
Resin system Mixing ratio (MPa) Retention J kHz J MHzi J kHz J MHzi
0
Liquid DGEBA resina/DDS 100/36 570 70% at 150 e
Liquid DGEBA resin" /
DDSjBF 3 400 100/36/1 540 73% at l200e 5'0-5·4 0,006-0,01
tv Liquid DGEBA resin"/
.....
..., DDS/BF 3 400 100/20/1 490 84% at l200e 5·6 0·009
Liquid DGEBA resin" /
DDM/DDS 100/15·5/15'5 520 68% at l200e 5,0-5,4 5·3 0,004-0,007 0·016
Epoxy novolac resinb /

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DDS 100/40 550 65% at 1900e 5,1-5,3 0,009-0,011
Brominated resine /
DDS/BF 3 400 100/28/2 540 5·0-5·4 0·025-0'045

"Araldite MY 750; Epikote 828, etc.


b Araldite LY 558; Epikote 154, etc.
e Araldite 8047.
dAfter 24 h in water at 23°C.
274 FRP TECHNOLOGY

ing is to warm the resin to about 130-140°C and add the DDS slowly with
stirring until it is all dissolved (about 20 min). Pot-life at 130°C is about I h.
If an accelerator is to be used the blend should be cooled to below 100°C
before adding it.
DDS is used more as a curing agent in prepreg systems than for wet lay-
up. Here the resin and DDS are both dissolved in a ketone solvent such as
acetone or MEK. Prepreg without an accelerator would normally be dried
for about 20 min at 150°C, while if an accelerator is present, drying time
would be about 15 min at 115°C. During this drying period partial reaction
occurs between the resin and curing agent.
Laminates prepared from a liquid DGEBA resin cured with DDS show
good strength retention up to about 150°C (Table 12.4). DDS can also be
used to cure resins other than those based on bisphenol A. Some properties
of such systems are given in Table 12.4.

12.4 ANHYDRIDE CURING AGENTS

These consist of organic anhydrides and are used in roughly stoichiomet-


ric proportions with epoxide resins. The cured systems generally exhibit
better thermal stability and radiation resistance than amine cured systems,
with heat deflection temperatures as high as 305°C. In most cases an
accelerator, such as a tertiary amine, is required to promote cure since,
without it, the anhydride will not react directly with the epoxide group.
Whilst stoichiometric proportions of anhydrides can be used, in practice
it has been found that optimum cured properties are usually achieved when
a molar ratio of anhydride to epoxide resin of 0·S5 :1 is used. This is usually
increased to I: 1 when a tertiary amine accelerator is added. With many
anhydrides, due to the complexity of the resin/anhydride reaction, cured
properties are very dependent on cure schedule and final cure temperature.
The factors which govern cured properties are gel time and temperature,
post cure time and temperature, type and amount of accelerator, hydroxyl
content of the resin, proportion of anhydride used and amount of free acid
present in the anhydride.
Of the wide variety of anhydrides available only a few are in common
use and many of these are variations on a theme, e.g. the methylated and
hydrogenated derivatives of phthalic anhydride. Some of the anhydrides in
use are listed in Table 12.6 together with typical cure schedules.
Anhydride curing agents can be divided into three categories based on
handling convenience: (a) the liquids-which can be blended with liquid

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CURING AGENTS FOR EPOXIDE RESINS 275

epoxide resins just by mixing, (b) the low melting solids-such as


hexahydrophthalic anhydride-which require melting before addition to
warm resin, and (c) the high melting solids-these are generally used in
solution forprepreg preparation or in powder form in powder coating
systems.
Summarised below are some details of methods of incorporating the
various anhydrides into liquid epoxide resins. Cured properties, where
available, are listed in Table 12.7, together with suggested accelerator levels
(Table 12.6).
Since anhydrides have a tendency to pick up moisture during storage and
are thus converted into the free acids-which act as accelerators-they
should always be stored in dry sealed containers.
Various liquid eutectic blends can be prepared from some of the solid
anhydrides to make them more readily usable. This may in some cases be at
the expense of HOT. Three examples are given in Table 12.5.
Anhydrides can be used both for wet lay-up and prepregs and, in many
cases, give systems with low viscosities and long pot-lives. High tempera-
ture resistance can often be improved by using resins other than those
based on bisphenol A (Table 12.8).

Phthalic anhydride (EP A)


This was the first anhydride used to cure epoxide resins. It is a solid which
readily sublimes on heating and is difficult to incorporate in epoxide resins
for this reason. The normal procedure used is to add the solid phthalic
anhydride to resin at 120°C and stir until all the anhydride has dissolved.
Adequate ventilation must be provided to remove the subliming anhydride.
Due to this problem phthalic anhydride is only used for casting appli-
cations.

Tetrahydrophthalic anhydride (THPA)


THPA is a white powder with a melting point of 100°C and a vapour
Table 12.5 Properties of anhydride eutectic blends

Crystallisation HDT"
Anhydride blend e
temperature C) phr eC)
HHPA/NMA (60/40) -20 85 112
HET/NMA (40/60) + 15 95 112
HET/HHPA (40/60) + 10 85 128

a 1 phr accelerator with liquid DGEBA resin EMM 190.

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276 FRP TECHNOLOGY

Table 12.6 Properties of some anhydride curing agents

Mol. m.p.
Anhydride curing agent Form wI. ("C) phrc

Phthalic anhydride EPA S 148 128 45


Tetrahydrophthalic anhydride THPA S 152 100 50-70
Methy1tetrahydrophthalic
anhydride MTHPA L 166 4 85-95
Nadic anhydride NA S 164 93
Nadic methyl anhydride NMA L 178 4 80-90

Chlorendic anhydride HET S 370 239 100


Hexahydrophthalic anhydride HHPA S 154 35 80
Methylhexahydrophthalic
anhydride MHPA L 168 88
Trimellitic anhydride TMA S 192 168 33
Pyromellitic dianhydride PDMA S 218 286 28-31
Dodecenylsuccinic anhydride DDSA L 266 130

a I phr accelerator, 25 g mix.


"Without accelerator.
CWith liquid DGEBA resin EMM 190.

pressure below o· S mm Hg at temperatures up to 130°C, thus sublimation is


negligible under normal conditions. It can be incorporated into the resin by
melting at lIS-120°C and adding to resin at a similar temperature. After
mixing, the blend can be cooled to about 90°C to prolong pot-life.
Alternatively, THPA can be added to resin at about 90°C with continuous
stirring until all has dissolved. It can be used for prepreg preparation from
acetone solution (SS-60% concentration).

Methyltetrahydrophthalic anhydride (MTHPA)


MTHPA is a low viscosity liquid and can therefore be stirred into liquid
resins at room temperature. At 2SoC pot-life varies from 2'S to 7'S h
depending on accelerator level. Initial mix viscosity is of the order of
O·S-O·g Pa s.

Endomethylenetetrahydrophthalic anhydride (nadic anhydride-NA)


Nadic anhydride is a crystalline solid soluble in liquid DGEBA resins
at 100-130°C, but it precipitates out below go°e. It can be used for wet lay-
up and prepreg preparation. To achieve maximum HDT a long high
temperature post cure is necessary. Nadic anhydride is not commonly used.

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CURING AGENTS FOR EPOXIDE RESINS 277

Table 12.6 (Continued)


Accelerator Some
(phr) Pot-life" Typical cure schedule supp/iersJ

0·05-0·1 30 min/120°C 2 h/130°C + 10 h/150°C 2,4,7


0'5-2'5 11 h/90°C 2 hj80°C + I hj200°C or 4 h/150°C 2,4,7,14

0'5-2'0 3 h/60°C I h/lOO°C + 3! hjl500C 6,14


0'5-2'5 2 h/90°C I h/ 100°C + 20 hj260°C
0·5-4·0 21 h/90°C I h/ 100°C + IS h/260°C or 4,7,12
3 h/120°C + 8 hj I 80°C + 6 h/260°C
none 3! h/90°Cb I h/lOO°C + I h/200°C 4,7
0'5-2'5 2 h/90°C 2 h/80°C + I hj200°C or 4 h/150°C 2,4,7,12,14

0'5-2'5 2 h/90°C I h/lOO°C + 4 h/125°C 7,14


none 10 min/125°Cb I h/120°C + 6 h/2S0°C 1
none 6 h/90°C· 3 h/120°C + 20 h/220°C 14
1'0-2'0 > 7 days/20°C 6 h/l00°C 4,7,9

dListed at the end of this chapter.


S = solid; L = liquid; phr = parts per hundred resin

Methyl endomethylenetetrahydrophthalic anhydride or nadic methyl anhy-


dride (NMA)
NMA is a pale yellow liquid at room temperature which, in the absence
of an accelerator, will give a pot-life of several months at room temperature
with liquid DGEBA resins. Maximum HDT varies considerably with cure
schedule, as do mechanical properties. NMA can be used both for wet lay-
up and prepreg preparation. HDT up to 280°C can be achieved with some
of the high functionality resins (Table 12.8). NMA is used in electrical
laminating and filament winding applications.
Optimum HDT, flexural and tensile strengths are each achieved with a
different cure schedule as shown in Table 12.9.

Chlorendic anhydride (BET) (hexachloroendomethylenetetrahydro-


phthalic anhydride)
RET anhydride is a high melting white powder used to confer fire
retardant properties on epoxide resin systems. Such systems, however, have
limited thermal stability. It can be used with antimony trioxide to improve
fire resistance. It can be dissolved in a liquid DGEBA resin at IOO-120°C.
For prepreg preparation HET anhydride can be dissolved in an

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Table 12.7 Some properties of anhydride cured epoxide resin systems

Typical cast resin properties Laminate properties

Tensile Tensile Elongation Permitti- Loss Flexural Flexural Tensile Resin/


HDT strength modulus at break vityat tangent at strength modulus strength glass ratio
(max) (MPa) (GPa) (%) 1 kHz 1 kHz (MPa) (GPa) (MPa)
Anhydride (0C)

EPA 110 82 3·0 4·1 3·6 0·002


N
....,
00
THPA 120 81 2·7 4·5 H 0·003 690 21 25/75
MTHPA l30 88 3·2 3-5 0·006 500 40/60
NA 305 360 14 30/70
NMA 218 90 3·3 2·7 3·5 0·004 545 23 418 38/62

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HET 186 82 3·2 2·6 3-3 0·006 568 26 382 27/73
HHPA l30 85 2·7 7·0 3·2 0·009 625 26 400 40/60
TMA 189 21 2·5 0·9 4·0 0·007
PDMA 290 22 z.s 4·0 0'002 502 23 40/60
DDSA 78 50 2·4 3·5 z.s 0·006 516 25 40/60

All properties with liquid DGEBA resin EMM 190.


Table 12.8 Comparison of properties of different epoxide resins cured with anhydride curing agents

Cast resin properties Laminate properties

HDT Permittivity Loss tangent Flexural


(max) at at strength Resin/glass
Resin system Mixing ratio CC) 1 kHz 1 kHz (MPa) Retention ratio

Liquid DGEBA resina/HHPA/DY


N 063 100/80/2 125 3'2-3-5 0·005-0·01 530 58% at 110°C 40/60
-..l
10 Epoxy novolacb/HHPA/DY 063 100/90/2 160 304-3'7 0·005-0·01 470 58% at 145°C 40/60

Liquid DGEBA resina /NMA/DY 063 100/85/1 190 304-3'6 0·003-0·005 480 52% at l30°C 38/62
Epoxy novolacb/NMA/DY 063 100/85/1 250 3,7-3,9 0·003-0·005 450 65% at 190°C 40/60

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High functionality resinc/NMA 100/140 260 3,7-3·9 0·005-0'01 520 67% at 190°C 40/60

"Resin such as Araldite MY 750.


bResin such as Araldite MY 558.
cResin such as Araldite MY 720.
DY 063 is triamylammonium phenate.
2S0 FRP TECHNOLOGY

Table 12.9 Effect of cure schedule on properties of NMA cured DGEBA resin

Property Gel conditions Post cure

Optimum HOP 218°C 2·8 h/107°C 20 h/256°C


Optimum flexural strengthb 158 MPa 2·2 h/115°C 20 h/188°C
Optimum tensile strengthb 90MPa 3·0 h/90°C 20h/161°C

"2·2 phr accelerator benzyldimethylamine (BOMA)


b2·5 phr accelerator BOMA

MEK/toluene (S·S: 1) mixture. No accelerator is necessary with HET


anhydride. Whilst HET anhydride used to be used for the preparation of
fire retardant prepregs, it has been superseded by brominated resins.

Hexahydrophthalic anhydride (HHPA)


HHPA is a waxy solid melting at about 35°C. It is generally stirred into
resin at 40- 45°e when it easily dissolves to give a homogeneous low
viscosity mix (0·25-0·35 Pa s at 40°C). HHPA can be used to make
prepregs as well as for wet lay-up laminating. It is also frequently used for
casting applications.

Methylhexahydrophthalic anhydride (MHPA)


MHPA is a liquid at room temperature and can be mixed with liquid
DGEBA resins over the temperature range 20-S0°C. Pot-life at 20 e is 0

about I week. It is normally used with a tertiary amine accelerator for


casting and laminating applications.

Trimellitic anhydride (TMA)


TMA is a white crystalline powder with a melting point of 16S°C. It can
be dispersed in a liquid resin by stirring, in which case the system has a pot-
life of about 3 days at room temperature. Alternatively it can be added to
resin at 125°e when it dissolves. Pot-life at 125°e is only about 10 min. The
use of an accelerator is unnecessary due to the presence of a free carboxylic
acid group. Resins cured with TMA exhibit good elevated temperature
properties. For prepreg systems TMA can be dissolved in acetone. TMA is
often used in powder coating formulations.
Pyromellitic dianhydride (PDMA)
PDMA is a slightly off-white crystalline material with a high melting
point. It is soluble in liquid DGEBA resins at elevated temperatures but,
due to its high reactivity, the system may gel before all the anhydride has

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CURING AGENTS FOR EPOXIDE RESINS 281

Table 12.10 Properties of some PDMA/anhydride blends

DGEBA resin EMM 190 100 100 100


PDMA 31 20 20
Maleic anhydride 20
Phthalic anhydride 28

Pot-life at 90°C (min) <10 10 20


HDT eC) 290 290 207
Tensile strength (MPa) 22 26 31
Tensile modulus (GPa) 2·7 2·9 3·7

dissolved. For this reason it is often used in blends with other anhydrides
such as maleic anhydride or phthalic anhydride, the maleic
anhydride/PDMA blend showing superior heat resistance.
With mixed anhydrides the resin should be heated to about 70°C prior to
addition of the anhydride, followed by continuous stirring and warming to
120°C. Once all the anhydride has dissolved, the mix should be cooled to
90°C to prolong pot-life. Some properties of mixed anhydride systems are
given in Table 12.10.
PDMA is often used in solvent solution for making prepregs. Solubility
of PDMA in various solvents is shown in Table 12.11.

Dodecenylsuccinic anhydride (DDSA)


DDSA is a pale yellow, low viscosity liquid (0·3 Pa s) at room
temperature which can be stirred into liquid resins with little difficulty. It
provides a long pot-life system and gives a flexible cured resin with a low
HDT. It is usually blended with other anhydrides to provide flexibility
without significantly altering electrical properties. It requires an accele-
rator to effect cure.

Table 12.11 Solubility of PDMA in various solvents

Temperature PDMA (g per


Solvent eC) 100 g solvent)

Acetone 20 7
56 9
Dimethyl sulphoxide 20 20
120 95
Dimethyl formamide 20 16
140 100

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282 FRP TECHNOLOGY

Table 12.12 Effect of different accelerators on exotherm and HDT

Time to peak Peak


Proportion exotherm temp. HDT
Accelerator (phr) (min) eC) eC)
K54 or DMP-30 0·6 12 192
1·0 9 199 124
BDMA 0·6 14 176
1·0 9 198 126
1-Methylimidazole 0·6 9 249 143
1·0 7 258
-----
Resin system: Liquid DGEBA resin EMM 190/MTHPA (100/85)
Temperature: 121°C, 12·5 g sample.

12.4.1 Accelerators for anhydride cured systems


Various accelerators can be used with epoxy/anhydride systems to
promote cure. They include tertiary amines, organic ammonium salts and
imidazoles. They are generally used in the range 1-5 phr. Some examples
of accelerators in use are:
Benzyldimethylamine (BDMA)
Tris(dimethylaminomethyl)phenolt
I-Methylimidazole (DY 070 from Ciba-Geigy)
N-Butylimidazole
2-Ethyl-4-methylimidazole
Triamylammonium phenate (DY 063 from Ciba-Geigy)
The imidazoles generally give systems with higher HDTs than either
BDMA, K54 or DMP-30, as can be seen in Table 12.12.

12.5 POLYAMIDE CURING AGENTS

The polyamides used to cure epoxide resins are all reactive compounds with
free amine groups. They may be amidopolyamines, aminopolyamides or
imidazolines. They are mostly used in coating systems and to a lesser extent
in adhesive formulations. They are rarely used for laminating.
Manufacturing procedure depends on the type of polyamide to be
produced. In general they are derived from polyamines reacted with mono-
or di-basic carboxylic acids. The carboxylic acids used are mostly those
tK54 from Anchor Chemical Co. or DMP-30 from Rohm & Haas.

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CURING AGENTS FOR EPOXIDE RESINS 283

obtained from fats and oils such as soya, tall oil, castor oil, etc. A typical
dicarboxylic acid used is the dimer acid prepared from linoleic acid by a
Diels-Alder reaction. Imidazolines are prepared by the high temperature
reaction of a polyamine with a carboxylic acid to cause ring closure.
Numerous polyamide curing agents are commercially available, includ-
ing water dispersible ones, ranging from low viscosity liquids to semi-
solids. Most can be used over a wide range of mixing proportions. For
example Versamid 125-a typical aminopolyamide-can be used in
proportions from 50 to 100 phr with a liquid DGEBA resin; however,
cured properties vary considerably over this range.
Some suppliers of polyamide curing agents are listed below:

Supplier Trade name


Anchor Chemical Co. Ltd Ancamide
Ciba-Geigy Plastics & Additives Co. Araldite
Cray Valley Products Ltd Versamid, Genamid,
Synolide
Croda Resins Ltd Plastamid
Grilon (UK) Ltd Grilonit
Hoechst AG (Reichhold Albert Chemie AG) Beckopox
Schering Chemicals Ltd Euredur
Shell Chemicals UK Ltd Epikure
Thomas Swan & Co. Ltd Casamid
Synthetic Resins Ltd Uracure
Thiokol Chemicals Ltd Thiokol
Victor Wolf Ltd Wolfamid

12.6 OTHER CURING AGENTS


Several other types of curing agent are used with epoxide resins for
laminating applications or in moulding compounds. One of the frequent
requirements is for good shelf-life of one-pack systems. This is of particular
importance with prepregs and moulding compounds. To achieve this it is
often necessary to use blocked compounds, that is ones which decompose
or re-arrange on heating to produce a reactive material. Examples of these
include the boron trifluoride complexes and dicyandiamide. Other curing
agents not classified elsewhere are the substituted imidazoles. Several
examples of these curing agents are described in this section (Tables 12.13
and 12.14).

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N
00
.j::.

Table 12.13 Properties and cure schedules for various epoxide resin curing agents

Prepreg drying Shelf-life Some


Curing agent Form m.p. (0C) phr" schedule at 23°C Cure schedule suppliersD

Dicyandiamide S 207-209 4b 4-6 min/150°C Up to 6 months I h/80°C + O· 5 h/200°Cc 2,4,7 "11


S 98 3 4,7,12
::c"C
BF3400 15 min/130°C Several weeks 4 h/120°C + 4 h/175°C
2-Ethyl-4-methylimidazole L 4 4 h/60°C + 2 h/150°C t;l
(')
8 8 h/60°C
N-n- Butylimidazole L 4 6 h/60°C Z
=
0
K54 or DMP-30 L 10 I h/80°C 2,7,11,13 t""
K 61 B L 10-12 4 h/65°C or I h/lOO°C 2,7,12 §

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·With liquid DGEBA resin EMM 190.
bWith solid DGEBA resin EMM 500.
CWithout accelerator.
dListed at the end of this chapter.
S = solid; L = liquid; phr = parts per hundred resin.
Table 12.14 Properties of various cured epoxide resin systems

Cast resin properties Laminate propertieS' (j


c::
:0;1
Elongation
....
Tensile Flexural Flexural Z
HDT strength at break strength modulus 0
Curing agent phr" (0C) (MPa) (%) (MPa) (GPa) >
~
Z
o-j
Dicyandiamide 4 125< 500c 28 C V'
BF3400 3 176 58 1·8 620 21 "1
0
2-Ethyl-4-methylimidazole 4 160 40 1·8 :0;1
2·3 40 t!l
8 110 67 710 "Ii
N-n-Butylimidazole 4 132 90 7·0 ~
K54 or DMP-30 10 90 73 5·7 S

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t!l
K 61 B 12 80 76 4·7 516

·Parts per hundred with liquid DGEBA resin EMM 190.


~
Z
V'
b Approximately 70% satin weave glass cloth.

CWith solid resin EMM 500.

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00
VI
286 FRP TECHNOLOGY

Dicyandiamide (Dicy)
Dicyandiamide is a solid curing agent used with solid DGEBA resins for
the preparation of prepregs from solution. It is only sparingly soluble in
solvents and so the ones which have to be used are 2-methoxyethanol,
acetone/water (3/2) or dimethylformamide, the former being preferred.
Prepreg has a shelf-life of up to 6 months at room temperature and is
generally used for the preparation of printed circuit boards (NEMA Grade
G.IO). Although cure takes place fairly rapidly in the temperature range
150-170°C, accelerators are sometimes used to reduce cure time or cure
temperature. A typical accelerator would be BDMA used at 0·1-0·4 phr,
with a typical cure schedule of }h at 165°C.

Boron trifluoride complexes


A number of different boron trifluoride complexes are used as curing
agents for epoxide resins. The most important one for laminating
applications is the boron trifluoride monoethylamine salt. These materials
are all catalytic curing agents and are therefore used in small proportions.
They may be used as sole curing agent or as accelerators for other curing
agents. Depending on which compound is used, cure can take place at room
temperature or elevated temperature.

Boron trifluoride monoethylamine


Boron trifluoride monoethylamine, often referred to as BF3MEA or
BF 3400, is a white crystalline solid melting close to its dissociation
temperature (about 90°C). It hydrolyses and becomes inactive as a curing
agent on exposure to moisture. It can be dissolved in liquid DGEBA resins
at about 80-85°C for small batches or made into a paste with resin at 50°C
for larger batches. Alternatively it can be used in solution for prepreg
preparation. It should not be dissolved in acetone since this solvent is
invariably wet and can cause deactivation of the curing agent under some
circumstances. Methyl ethyl ketone presents no such problems.
BF 3400 is normally used at about 3 phr with a liquid DGEBA resin and
such a blend has a pot-life of about 4 months at 25°C. Castings and
laminates are usually gelled at 100-120°C followed by a high temperature
post cure (Table 12.13). It is also used to cure epoxy novolac resins and as
an accelerator for DDS cured systems.

2-Ethyl-4-methylimidazole
2-Ethyl-4-methylimidazole is a liquid which can be used either as sole
curing agent at 4-8 phr or as an accelerator for anhydride cured systems. It

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CURING AGENTS FOR EPOXIDE RESINS 287

acts as a catalytic curing agent with liquid DGEBA resins. It can be used in
casting and laminating formulations and is particularly suitable for
filament winding applications. Laminates show some 70% flexural strength
retention at 70°C after a cure of 2 h at 60°C.

N-n- Butylimidazole
This is a liquid curing agent which can be used to cure liquid DGEBA
resins. It gives long pot-life systems with relatively low temperature cure
(60°C). It is used in casting and laminating systems.

Other imidazoles
Various other substituted imidazoles and their salts are available, many
of which are used as curing agents for epoxide resins. Some of these salts
can be used in prepreg formulations since they require heat to initiate the
curing reaction, by dissociation of the salt into its component parts. They
can provide excellent cured properties with short, low temperature cure
schedules.

Tris-2,4,6-dimethylaminomethylphenol (K54 or DMP-30)


This curing agent is commonly known as K54 from Anchor Chemical
Co. or DMP-30 from Rohm & Haas. It is used both as sole curing agent
and as an accelerator for anhydride and amine/polyamide cured systems. It
finds widespread use in a variety of applications.

K61 B
This is the tris-2-ethylhexoate salt of K54 and is available from Anchor
Chemical Co. It is used for wet lay-up laminating and casting applications.
It gives a 4-6 h pot-life at 25°C with liquid DGEBA resins.

12.7 SOME TYPICAL LAMINATING SYSTEMS

12.7.1 Site applications


Whilst many different curing agent blends may be used for site applied
laminates, two systems have been specifically developed for such appli-
cations. These are curing agents DX 150andDX 151 from Shell Chemicals
and A,ncamine TL and TLS from Anchor Chemical Co. Both systems have
one fast reacting and one slow reacting curing agent, designed to be
blended in any proportion, providing that the blend is always used at the
recommended level with the resin. In this way, two curing agents can be

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Table 12.15 Properties of some epoxide resin systems used for hand lay-up laminating

Resin Epikote 816 Epikote 816 Epikote 816 Epikote 816 Epikote 816 Araldite XD 927
Curing agent DX 150 DX 151 Ancamine TLS Ancamine TLS Epikure J14 Araldite XD 927

Mixing ratio (parts by


weight) 100/50 100/50 100/60 100/60 100/40 100/36
Mix viscosity at 25°e
(Pa s) 1·2 0·8 0-4 0·8
east resin properties
eure schedule 7 days/20oe 7 days/20De 7 days/20oe 7 days/20oe 7 days/23°e 16 h/25°e
+ 5 h/80oe
Tensile strength (MPa) 59 56 56 46 46 80
Elongation at yield (%) 4·5 4·5 4·5 4·5 4·5 4·5
t-.J Flexural strength at
00
00
break (MPa) 95 90 103 68 80 95
Flexural modulus (GPa) 2-45 2·06 2·35 1·86 2·3 3·0
HDT (0C) 50 47 50 48 43 90
Laminate properties

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eure schedule 7 days/20oe 7 days/20oe 7 days/20oe 7 days/20oe 7 days/23°e 7 days/20oe
+ 1 day/50oe + 1 day/50oe + 1 day/50oe + 1 day/50oe
Tensile' strength (MPa) 96 100 98 98 80
Flexural strength at
break (MPa) 112 112 112 128 120" 415
Flexural modulus (GPa) 4·13 4·28 4·14 3-61 4·13 17
Glass content (%) 33 33 33 33 25 60

"Two layers of chopped strand mat (450 g/m 2 ) plus surface tissue.
bWoven glass cloth laminate, 12 ply.
C Increases to 170 MPa after 3 weeks cure at 23°e.
CURING AGENTS FOR EPOXIDE RESINS 289

used to provide a system with a fixed pot-life of say 2 h, over a very wide
range of ambient temperatures from about 5°C up to about 50°C. Some
properties of these systems are given in Table 12.15.
The reinforcement generally used is chopped strand mat-preferably
one recommended for use with epoxide resins. Most binders used on
chopped strand mats are insoluble in epoxide resin systems and so fibre
pattern remains the same as in the mat as supplied (Fig. 12.1).

12.7.2 Alternative to polyester resin


Ciba-Geigy have developed a system, XD 927, with gelcoat XD 928, which
is claimed to offer similar moulding characteristics to polyester resin
systems whilst retaining the excellent cured properties of an epoxide resin
system. This system gives reasonable mould turn-round coupled with
higher than normal HDT after room temperature cure.
XD 927 is a two part, solvent-free, low viscosity system (mix viscosity
about 0·8 Pa s at 25°C). The curing agent is based on an aliphatic
polyamine. Some cured properties of this system are given in Table 12.15.
The system can be used for hand lay-up, vacuum impregnation and
filament winding with glass, carbon and aramid fibres.

Fig. 12.1. A typical epoxide resin based laminate.

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290 FRP TECHNOLOGY

12.7.3 Electricallaminates
These cover a wide range of applications including printed circuit board
laminates, filament wound switch links or tie bars, stator restraining rings
and woven or knitted glass reinforced radomes. Many different systems
may be used to meet the various requirements of these different appli-
cations. Properties of some of the systems used are given in Tables 12.3 and
12.7; other systems are mentioned below.

Printed circuit board laminates


Printed circuit boards can be divided into four classes according to the
NEMA specifications. 2
G-lO General purpose laminates.
FR -4 General purpose, flame resistant laminates.
G-l1 Temperature resistant laminates.
FR-S Temperature resistant, flame resistant laminates.
These are all glass cloth based epoxide resin laminates clad on at least one
side with copper foil. In the main, prepreg systems with long shelf-lives are
used to manufacture such boards (see Fig. IS.2).
The general purpose laminates can be prepared using dicyandiamide as
curing agent. For G-IO laminates the typical resin used is a solid DGEBA
resin with an EMM of 4S0~SOO (Araldite 706S, Epikote 220-B-80 and
others). These resins have been designed to give high copper peel strengths.
Temperature performance can be improved by replacing part of the
DGEBA resin with 20% of an epoxy novolac resin.
FR-4 laminates can be prepared in a similar way using a brominated
resin in place of the standard resin. Again, temperature performance can
be improved by incorporating about 20% of an epoxy novo lac resin. This
can increase flexural strength retention at 1000e from about 20% to
over 6S%.
G-ll and FR-Slaminates can be prepared using DDS/BF 3 400 as curing
agent. Here SO% retention of flexural strength can be achieved at lS0°C.
The resin used for G-l1 laminates is either a liquid DG EBA resin, EMM
18S~ 19S, or a 1: 1 blend of solid DGEBA resin, EMM 4S0~ SOO, with an
epoxy novolac resin. For FR-S laminates a brominated resin is used either
alone or blended with an epoxy novo lac resin. Typical laminate properties
are given in Table 12.16.
At one time HET anhydride was used with DGEBA resins to achieve
FR-4 and FR-S grade laminates. However, due to the volatility ofthe HET

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Table 12.16 Typical properties of systems conforming to NEMA specifications

Flexural Water Copper peel Permittivity Loss tangent


strength absorption strength at at
NEMA Grade (MPa) (%) (kN/m) 1 MHz 1 MHz Typical resin system

G-IO 450-550 0-05-0-07 2-1-2-3 4-7-5-2 0-024-0-026 Solid DGEBA resin/Dicy


450-500 0-05-0-08 2-0-2-3 4-7-5-2 0-020-0-026 Solid DGEBA resin/epoxy
novolac/Dicy
tv
'Cl FR-4 450-500 0-05-0-07 1-9-2-1 4-7-5-2 0-021-0-023 Brominated resin/Dicy
- G-ll 450-550 0-05-0-15 1-9-2-2 5-0-5-4 0-006-0-01 Liquid DGEBA resin/
DDS/BF 3 400
450-550 0-05-0-08 1-9-2-2 5-0-5-5 0-006-0-015 Liquid DGEBA resin/epoxy

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novolac/DDS/BF 3400
FR-5 440-540 0-02-0-1 1-8-2-2 5-0-5-4 0-025-0-045 Brominated resin/
DDS/BF 3 400
450-550 0-05-0-14 1-8-2-2 5-0-5-4 0-021-0-045 Brominated resin/epoxy
novolac/DDS/BF 3400
292 FRP TECHNOLOGY

anhydride during prepreg manufacture and the short shelf-life of such


prepreg, this curing agent is rarely used today.

Filament winding and impregnating systems


Here, most of the undiluted liquid resins may be used with most
anhydride or amine curing agents. Choice depends on final cured
performance requirements and possible process restrictions. Some perfor-
mance data are given in Tables 12.3, 12.7 and 12.14. A typical filament
wound epoxy pipe is shown in Fig. 12.2.

12.7.4 Carbon fibre composites


With carbon fibre composites the requirement is for resin systems which
enable the full performance of the carbon fibres to be realised. Thus high
performance systems with good elongation at break are preferred.
For many applications carbon fibre prepregs are used. Here, for ease of
handling and to prevent damage to the fibres during handling and to ensure
accurate alignment of fibres during lay-up, flexible tacky prepregs are used.
If a rigid prepreg were to be used, then fibre damage would inevitably result
during handling. To produce tacky prepregs, liquid or semi-solid resins are
used. These may be of the conventional type, modified bisphenol A type,
glycidyl amines or epoxy novolacs.
Curing agents used for prepreg preparation must give systems with

Fig. 12.2. A typical filament wound epoxy pipe.

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CURING AGENTS FOR EPOXIDE RESINS 293

Table 12.17 Properties of some composite systems

Unidirectional
Composite propertieS' E-glass

Flexural Flexural Flexural Flexural


ILSSb strength modulus strength modulus
Resin system (MPa) (MPa) (GPa) (MPa) (GPa)

Liquid DGEBA resin/DDS 80 1600 132


Liquid DGEBA resin/DDS/
BF3400 65 1600 132
Epoxy novolac/BF 3 400 60 1500 140
Epikote 21O/BF 3 400 80 1600 130 l500 c 50c
Epikote 231/Epikure
OX 137 80 1550 140 l35()d 36 d
Epikote 210/Epikure
OX 137 80 1600 150 l40Qd 37d
Araldite MY 720/DDS 100 1700 131
Araldite MY 720/DDS/
BF 3400 80 1700 132

·Carbon fibre Type II, 60% fibre volume, properties measured at 20°C.
blnterlaminar shear strength.
c 70% glass by weight.
d65% glass by weight.

reasonable shelf-lives, even though refrigerated storage may be used.


Examples of some of the systems in use are given in Table 12.17.
These resin systems may also be used with glass and aramid fibres, both
continuous filament and woven fabric, and also to produce hybrid, mixed
fibre composites.

REFERENCES
1. Lee, H. & Neville, K. (1967) Handbook of Epoxy Resins, McGraw-Hill Book
Company, New York.
2. NEMA Publication No. LI.I-1971. National Electrical Manufacturers
Association, Washington, DC, USA.

CURING AGENT SUPPLIERS


(see Tables 12.2, 12.6 and 12.13)
Code Supplier
1 Amoco Chemicals UK Ltd

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294 FRP TECHNOLOGY

2 Anchor Chemical Co. Ltd


3 BASF United Kingdom Ltd
4 Berger Chemicals (Reichhold Albert Chemie AG).
5 Berol Kemi (UK) Ltd
6 British Chemical Products & Colours Ltd
7 Ciba-Geigy Plastics & Additives Company
8 Dow Chemical Co. Ltd. UK Agents- K & K Greeff Chemical
Group Ltd
9 K & K Greeff Chemical Group Ltd
10 Mitsubishi Gas Chemicals
11 Rohm & Haas (UK) Ltd
12 Shell Chemicals UK Ltd
13 Thomas Swan & Co. Ltd
14 Veba-Chemie AG. UK Agents-Brenntag (UK) Ltd

SOME SUPPLIERS OF FORMULATED CURING AGENTS

Anchor Chemical Co. Ltd


Berger Chemicals (Reichhold Albert Chemie AG)
Borden (UK) Ltd
Boston Chemical Co. Ltd
CdF Chimie. UK Agent-KWR Chemicals Ltd
Ciba-Geigy Plastics & Additives Company
Grilon (UK) Ltd
Schering Chemicals Ltd
Shell Chemicals UK Ltd
Thomas Swan & Co. Ltd
Synthetic Resins Ltd

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Chapter 13

OTHER RESIN SYSTEMS

13.1 INTRODUCTION

Apart from polyester and epoxide resins, several other resins are used for
laminating applications and in moulding compounds. These include vinyl
ester resins, furane resins, Friedel-Crafts polymers, polyimide resins,
silicone resins, phenolics, and melamine- and urea-formaldehyde resins.
Of these, only the furane, vinyl ester and Friedel-Crafts resins will be
discussed in detail, although some comments will be made about the other
resins.
Vinyl ester and furane resins can be considered to be complementary to
polyester and epoxide resins, since they can be processed in similar ways
and extend the range of uses to which FRP composites can be applied. The
other types of resin extend the range of press moulded composites which
can be made. Each of the other resins mentioned requires processing at
elevated temperature and under pressure.

13.2 FURANE RESINS

Furane resins consist of a furfuryl alcohol polymer blended with furfural as


reactive diluent. The polymer may be prepared by homopolymerisation of
furfuryl alcohol or copolymerisation with formaldehyde, using an acid
catalyst, the former being the more important type. When cross-linked
these polymers exhibit exceptional chemical resistance except under
oxidising conditions. Like the early Ford cars they come in any colour as
long as it's black.
Furane resins have traditionally been used as binders for chemical

295

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296 FRP TECHNOLOGY

resistant tile grouts and cements, as hard wearing coatings on mould tools
and as binders for foundry cores. With the continual demand for GRP
systems with improved chemical resistance for the manufacture of chemical
plant, they are an obvious candidate for laminating applications.
Unfortunately furane resins require acidic catalysts such as p-
toluenesulphonic acid, phosphoric acid or hydrochloric acid generators.
Such systems tend to be difficult to handle for laminating applications. One
of the problems has been to find a catalyst which will give an adequate
working pot-life, coupled with relatively slow increase in viscosity of the
catalysed resin. This is necessary to ensure adequate wetting out of the glass
reinforcement. Another problem has been brittleness of the gelcoat-which
severely limits gelcoat thickness.
These problems have been overcome by the Quaker Oats Company with
their 'Quacorr' 1001 resin and catalyst 2001. Indeed a number of very large
vessels have been successfully constructed from this resin system by the
hand lay-up technique. 1,2
Also available are two flame retardant, low smoke emission resins,
'Quacorr' 1500FR and 'Quacorr' l200FR, both used with catalyst 2001.
All of these systems can be successfully used and cured at room
temperature. The proportion of catalyst used is fairly critical and should
generally be within the range 3-4%.
Another supplier of a furane resin system for laminating applications is
Borden (UK) Ltd, who supply resin P 910 with catalyst P 911. They also
supply a furane resin for coating applications.
Whilst furane resins can be processed by normal hand lay-up and
filament winding techniques, they are somewhat different in handling
characteristics and smell from polyester resins. Contact with the skin or
clothing causes brown or black discolouration. Like polyester resins they
must be used in well ventilated areas. Threshold Limit Values for furfuryl
alcohol and furfural are compared with those for other materials in
Table 13.1.
Recently, spray equipment has been introduced by Venus Products for
th~ spray lay-up of furane resin systems and is available from CT (London)
Ltd, from whom details may be obtained.
Why use furane resins? When fully cured they provide probably the best
chemical resistance of any thermosetting resin in non-oxidising conditions.
For example, laminates immersed at room temperature for 1 year in methyl
ethyl ketone or perchlorethylene show greater than 99% flexural strength
retention, while after 6 months at 65°C in glacial acetic acid flexural
strength retention is still some 79%. Polyester and epoxide resins disinte-
grate under these conditions. Maximum continuous service temperature is

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OTHER RESIN SYSTEMS 297

Table 13.1 Threshold limit values (TLV)

Boiling point
TLV(ppm)a ("C)

Furfural- skin 5 162


Furfuryl alcohol-skin 5 170
Acetone 1000 56
2-Butanone (MEK) 200 80
Methyl methacrylate 100 100
Styrene 100 145

a Taken from the Health & Safety Executive Guidance Note EHI5j76.

about 150°C, depending on environment. For elevated temperature use


an elevated temperature post cure is recommended.
Another major advantage of furane resin laminates is very low smoke
emission under fire conditions. For example, 'Quacorr' 1500FR comes
under the following BS 476 classifications: Part 6-class 0; Part 7-
class 1; Part 8-pass. Thus furane laminates are ideal candidates for
ventilation ducting and other building components.
Some work has been carried out on the development of furane pre-
pregs. 3,4 Here it has been shown that Lewis acid complexes, such as
BF 3400 (boron trifluoride/monoethylamine complex), act as latent
catalysts whilst giving adequate cure under press conditions. Cure
temperature with this catalyst is between 120 and 140°C.
Although it is possible to make combined furane/polyester laminates,
where the furane laminate is applied to the mould first and then overlaid
with a polyester resin laminate, this is not recommended. The disadvan-
tages are firstly, the difficulty of getting adequate adhesion of the polyester
to the fully cured furane resin and secondly, the difference in flexibility
between the two systems. Both can result in delamination at the interface
during use.
Glass reinforcement used with epoxide resins is equally suitable for use
with furane resins, powder bonded mats being generally the most
satisfactory. Where woven rovings are used these should preferably have a
light open weave to ensure adequate wetting by the resin. Carbon fibre can
also be used as reinforcement. With surfacing tissues, C-glass does not wet
out very well, whilst synthetic fibre tissues tend to soak up a lot of resin,
particularly if used as the outer layer. However, both types may be used
satisfactorily provided care is taken during application.
Release films such as polyethylene terephthalate (Meline x or Mylar) and
PTFE are excellent, with polypropylene film as next best. Where waxes are

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298 FRP TECHNOLOGY

used these must be hard waxes (Carnauba wax) since soft waxes inhibit
cure. Also, waxes stick to the laminate surface and so the mould must be
rewaxed each time it is used. PVA and silicones are attacked by the resin
and Cellophane is embrittled, so none of these should be used as release
agents.
If a furane resin laminate is to be used as a lining for a steel or concrete
Table 13.2 Typical properties of forane resin laminates

Quacorr JOOI/2001 Quacorr J500FR/200J

Laminate thickness (mm) 3 6 9 3·2


Glass content (%) 25 32 34 25
Flexural strength (MPa) 125 138 150 125
Flexural modulus (GPa) 4·8 5·5 6·2 5·2
Tensile strength (MPa) 69 83 96 76

Coefficient of thermal expansion 1·16 X 10=5 in/in;oF


Heat deflection temperature greater than 230°C
Specific gravity 1·4-1·6

Table 13.3 Some commercially available furane resins


-----------------------------------~

Viscosity Gel time


Supplier at 25°C Specific at 25°C
Resin code (mPa s) gravity (min) Comments

Borden (UK) Ltd


P 910 resin 300-450 55-75 Laminating resin
P 911 catalyst Used at 3%
Cascote FL-3 4-8 0·97 Coating resin
Catalyst FX-2 <25 1·3 Used at 10 phr

Garrick Chemical & Equipment Co. Ltd- UK Agent for Ashland Chemicals
Hetron 800 250 1·2 15 Laminating resin
Catalyst 801 L Used at 4 phr
Hetron 800FR 450 1· 2 15 Fire retardant
laminating resin
Catalyst 801 L Used at 5 phr

Quaker Oats Ltd, Chemical Division


Quacorr 1001 450 1·22 21 Laminating resin
Quacorr 1200FR Fire retardant
Quacorr 1500FR Fire retardant
Catalyst 2001 1·37 Used at 3-4 phr

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OTHER RESIN SYSTEMS 299

vessel then great care has to be taken in the design of the system and
application of the resin, since the acid catalyst will attack the substrate and
cause lack of bond. To overcome this the substrate must first be thoroughly
sealed with a suitable primer, such as an amine cured epoxy resin system.
This coating must be checked to ensure that it is pinhole free and all amine
must be washed off the surface until it is neutral. The laminate can then be
applied. The difference in coefficient of expansion between the laminate
and the substrate must be considered during the design of the lining, to
prevent delamination in service.
Some typical laminate properties are given in Table 13.2 and com-
mercially available materials in Table 13.3.

13.3 VINYL ESTER RESINS

Vinyl ester resins were developed specifically for the manufacture of


reinforced plastic components for use in corrosive environments. They
have similar cured properties to those of epoxide resins, coupled with the
ease of processing of polyester resins. They contain styrene as monomer
and can be cross-linked by peroxide catalysts. The typical chemical

1=
structure is shown below.

CH 2 =CH-C-
oII c4c OH
I
H 2 -CH-CH 2 -R n
OH
I 0
II
H 2 -CH-CH 2 -O-C-CH=CH 2

0-
CH 3

R=-0-o-~
-
~.~
I~ CH 3
Although based on bisphenol A, the structure is different from that of a
conventional bisphenol polyester, which has ester groups and double
bonds in the repeat unit. Vinyl ester resins contain a reduced number of
ester links-two per molecule-and a reduced number of double
bonds-again two per molecule, situated at either end of the molecular
chain. The main backbone is the bisphenol A epoxy structure. Thus in the
cured resin there are fewer ester linkages and hence improved chemical
resistance, whilst the terminal double bonds result in a tougher, more
resilient resin structure. Styrene emission and flash point are similar to
those of polyester resins and so similar handling precautions are necessary.
Vinyl ester resins can also be made from brominated resins to give fire
retardant grades.

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300 FRP TECHNOLOGY

Vinyl ester resins can be processed in a similar way to polyester resins.


For ambient temperature cure either MEK peroxide with a cobalt
accelerator, boosted if required by the addition of dimethylaniline, or
benzoyl peroxide accelerated with dimethylaniline may be used. For
elevated temperature cure benzoyl peroxide paste or t-butyl peroxyben-
zoate may be used, with cure at 120-J65°C. Other peroxide catalysts may
also be used. Due to the low viscosity of the resins high glass contents can be
achieved in the cured laminates. Where resin drainage is a problem, fumed
silica (1-2%) may be added to provide thixotropy.
Table 13.4 Typical cured properties of vinyl ester resins

Property Cast resin Laminate

Flexural strength (MPa) 130-140 150 180


Tensile strength (MPa) 70-80 136 150
Tensile modulus (GPa) 3·3 6·7 8·5
Elongation at break (%) 5-6
Heat deflection temp (0C) 95-125
Glass content (%) 28 a

aChopped strand mat plus surface tissue.


bCSM + woven rovings.

Table 13.5 Some commercially available vinyl ester resins

Styrene Viscosity
Supplier content Specific at 25°C HDT
Product code (%) gravity (mPa s) ("C)

Dow Chemical Co. Ltd


Derakane 411-45 45 1·04 500 100
Derakane 412-45 45 1·04 500 100
Derakane 470-45 45 1-03 75 150
Derakane 510-A-40" 40 1·22 300 110

Garrick Chemical & Equipment Co. Ltd- UK Agent for Ashland Chemicals
Hetron 901 45 1·05 500

Honeywill-Atlas Ltd
Atlac 580-05 47 350-500 118

Synthetic Resins Ltd


Uralam 31-345 45 1·04 400-600 100

a Brominated novolac based resin, can be used with antimony trioxide.

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OTHER RESIN SYSTEMS 301

As with polyester resins air inhibition can occur, which can be overcome
by the addition of a small proportion of paraffin wax to the final coat of
resin. This addition will, of course, prevent or impair adhesion of any
further layers of resin without thorough surface preparation.
The main uses of vinyl ester resins are in the manufacture of chemical
plant, pipes, storage tanks, etc., where high chemical resistance is required.
Some typical properties of vinyl ester resins are shown in Table 13.4 and
some commercially available materials are given in Table 13.5.

13.4 FRIEDEL-CRAFTS RESINS

Friedel-Crafts resins are so called because of the reaction used in their


preparation. That is the introduction of alkyl or acyl groups into an
aromatic ring in the presence of certain catalysts. This reaction dates back
to 1885. They are also known as phenol-aralkyl resins commercially.
Until the late 1950s polyester, epoxide and other resin systems were
capable of meeting the demands of the aerospace industry. However, as the
demand for more heat resistant materials increased, the search went on for
resin systems capable of withstanding temperatures in excess of 200°C for
reasonably long periods. It was known that polymers containing a large
number of aromatic or heterocyclic rings were stable at high temperatures
and so ways were sought of producing usable resins of this type.
Not only was it necessary to produce the resin, but also a curing
mechanism which would enable the resin to be cross-linked without the
evolution of harmful by-products. Some of the first prepolymers formed
liberated hydrogen chloride during cure which, due to its highly corrosive
nature, was clearly unacceptable.
One line of development, followed by Albright & Wilson Ltd, was to
react aralkyl ethers with phenolic compounds to produce a prepolymer
which could be cured in several different ways. A simple example of a
pre polymer is shown at the top of p. 302.
Resins of this type are marketed by Albright & Wilson Ltd under the
'Xylok' trade mark. 4 ,5 Two curing mechanisms are used, one relying on
the reaction between the ortho and para positions of the phenolic ring with
hexamine (hexamethylenetetramine) with the liberation of ammonia
(British Patent I 150 203), the other relying on the reaction between
epoxide groups and phenolic hydroxyls (British Patent I 305551). No by-
products are eliminated during this reaction.
Xylok resins can be readily processed into laminates, tapes and moulding

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302 FRP TECHNOLOOY

OH
6 + CH,-O-CH,--Q-CH,-O-CH,
lhea!.
SoCI.

rr IHl OH
(3t-CH,-cr=H,-Q±cH,--Q-cH,-t6
compounds. With laminates the reinforcement is impregnated with the
resin and pre-cured for about 10 min at 130-165°C, followed by pressing at
165-175°C under a pressure of 3.5- 7 MPa. A post cure at between 175
and 250°C is necessary to develop full high temperature properties.

Table 13.6 Typical properties of Xylok resin based laminates

Xylok 210 Xylok 237

Specific gravity 1·77 1·80


Flexural strength at 20°C (MPa) 551
at 180°C (MPa) 448
Tensile strength at 20°C (MPa) 434 404
at 200°C (MPa) 282
at 250°C (MPa) 300
Tensile modulus at 20°C (GPa) 3·7
Interlaminar shear strengthG (MPa) 87·5
Water absorption, ASTM D-570 (%) 0·14
BS 2782 502D (mg) 5·2
Permittivity at 50 Hz 5·0
at 1 MHz 5·0
Loss tangent at 50 Hz 0·006
at 1 MHz 0·()()9
Volume resistivity (lOglO ohm cm) 13-4
Surface resistivity (IOglO ohm) 10·8
Glasscloth, Marglass 116T -finish P705 P738

·Short beam shear, 3:1 span to depth ratio.

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Table 13.7 Commercial phenol-aralkyl resins

Solids Specific Viscosity Flash


content gravity at 25°C poinF
Product code (%) Solvent at 25°C (mPa s) (OC) Comments

Xylok209 50 2-ethoxyethanol 1-06 1,5-6·0 Hexamine cured resin supplied in


Xylok 210 60 MEK 1·03 2'5-5·0 4~} three different solvents for
Xylok 211 55 IMS 1·00 1·5-6·0 13 laminating applications. Service
use up to 250 0 e
w Xylok 214 55 IMS 1·02 2·0-5'0 13 One pack, for use with phenolic
0
w resols
Xylok 225 100 0·06-0·8" Granular solid for moulding
compounds. Used with phe-
nolic resins
2,5-6,0

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Xylok 337 resin 60 MEK 1·04 Epoxy cured. Mixing ratio 1:1. For
Xylok hardener 90 MEK 1·13 1,0-3,0 laminating applications up to
2ODoe
n
"Powder density.
b Abel closed cup.

MEK = methyl ethyl ketone.


IMS = industrial methylated spirits.
304 FRP TECHNOLOGY

Reinforcements which may be used include glass, mica, glass-backed mica


tape, asbestos and carbon fibre.
Moulding compounds can be prepared by dry blending or hot-milling in
a similar way to phenolic moulding compounds. Xylok 225 may also be
blended with phenolic resins to upgrade temperature performance.
Where hexamine is used as curing agent, flexural strength retention of a
glass cloth laminate, heat aged for 1000 h at 250°C and tested at 250°C, is
greater than 80%. This decreases to around 50% after 2000 h. With epoxide
cured resins, heat aged for 1000 h at 200°C and tested at 200°C, flexural
strength retention is some 90%.
Xylok resin/glass laminates are finding application in motor windings
designed to operate continuously at 160°C; heating panels designed to
operate at up to 200 and 400°C under certain circumstances; high
performance transformers-where no deterioration has been observed
after 11 000 h operation at 200°C; compressor blades and a variety of other
applications where high temperature performance is required. Typical
cured laminate properties are shown in Table 13.6 and commercial resins in
Table 13.7. For details of moulding compounds see Chapter 15.

13.5 SILICONE RESINS


Silicone resins, 6.7 or polyorganosiloxanes, differ from all the other resins
Table 13.8 Typical properties of glass cloth laminates 7

ASTM
test Silicone
Property Units method resin

Laminating temperature °C 160-250


Laminating pressure MPa 0·2-14
Tensile strength MPa D638 70-265
Tensile modulus GPa D638 10-14
Flexural strength MPa D790 70-265
Compressive strength MPa D695 170-320
Impact strength, Izod kJjm 2 D256 25-70
Water absorption, 24 h (3 mm thick) % D570 0·07-0·65
Heat resistance, continuous °C 200-370
Dielectric strength (3 rom thick) kVjmm D 149 7-19
Dielectric constant at I MHz D 150 3·7-4·3
Dissipation factor at 1 MHz D 150 0·005-0·01
Arc resistance s D495 150-250

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OTHER RESIN SYSTEMS 305

in that they have an inorganic backbone based on silicon rather than


carbon. They may be considered as derivatives of silica (Si0 2 ) with methyl
( -CH 3 ) and phenyl ( -C6HS) groups attached to the chain. Cross-linking
is brought about by heating in the presence of a catalyst such as cobalt
naphthenate, zinc octoate, triethanolamine or morpholine.
Silicone resins are generally supplied as solutions in toluene or xylene
and are therefore used for the preparation of prepregs, with either glass or
asbestos mats as reinforcement. Prepreg preparation is similar to that used
with epoxide resin systems. Once the solvent has evaporated, layers of
prepreg can be hot pressed and cured to give composites.
Fully cured silicone/glass cloth laminates have outstanding thermal
stability, with little change in mechanical and electrical properties after
prolonged heating at temperatures of up to 250°C. They are, however,
affected by steam and are attacked by strong alkalis. Compared with other
laminates, those based on silicone resins have relatively poor mechanical
strength (Table 13.8). Due to this and their relatively high cost, silicone
resin based laminates have not found wide commercial acceptance.

13.6 POLYIMIDE RESINS


Polyimide resins are the most thermally stable of all organic resins
presently available. 7 The fully reacted resin, prepared by reacting a diamine

Table 13.8 (Continued)

Melamine-- Urea-
Polyimide Phenolic formaldehyde formaldehyde Polyester Epoxide
resin resin resin resin resin resin

200-300 135-175 135-150 135-180 20-150 20-185


0·5-5 0·1-14 7-13 14-56 0-0·8 0-13
300-450 60-350 175-500 42-91 125-455 245-595
18-30 8-17 14-17 7-10 7-20 14-25
450-600 100-560 245-595 70-126 88-630 280-735
330-480 235-520 170-590 170-310 140-410 240-550
65-80 20-95 25-80 1-2 100-185 30-130
0·2 0·12-2·7 0·2-2·5 0·4-0·8 0·15-2·5 0·04-0·3
260 120-260 150 75 95-175 105-150
12-22 12-28 8-24 12-16 10-28 16-30
4·7 3·7-6·6 6,0-9·0 6·8 3·0-4·0 4·5-5·3
0·005 0·005-0,05 0·011-0·025 0·25-0·35 0·007-0·03 0·01-0·03
50-180 tracks 175-200 80-150 80-140 15-180

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306 FRP TECHNOLOGY

with a dianhydride, is insoluble and infusible. Due to this, a two-stage


reaction is necessary, with composites fabricated from the intermediate
polyamic acid. This intermediate polymer is unstable and has to be stored
in a polar solvent under dry refrigerated conditions.
Moulding is normally carried out at about 300°C, with a post cure at up
to 400°C to obtain full thermal stability. Water is eliminated during cure
and complicates the moulding process.
Thermal stability is excellent, although water absorption is high. Typical
mechanical and electrical properties are shown in Table 13.8.

13.7 PHENOLIC RESINS

Phenolic or phenol-formaldehyde resins have been used since the early


1900s. They are prepared from phenol, or more generally cresols and
xylenols, and formaldehyde, under either acidic or alkaline conditions,
depending on the type of resin required. These are referred to as novolacs
and resols. They both require heat to effect cure and pressure to produce
laminates and mouldings.
Resols are produced by reacting phenols with excess formaldehyde
under alkaline conditions. They are spirit soluble and are used for
laminating and some moulding compositions. They can be cross-linked by
heating alone.
Novolacs are produced by reacting formaldehyde with excess phenol
under acidic conditions. Cross-linking is effected by the addition of
hexamethylenetetramine (hexamine) and the application of heat. Such
resins are used for the preparation of moulding compounds.
Phenolic resins exhibit good thermal stability, acceptable electrical
properties, excellent water and chemical resistance-except for alkalis,
which attack them. Some laminate properties are given in Table 13.8.

13.8 MELAMINE AND UREA-FORMALDEHYDE RESINS

These are prepared by reacting either melamine or urea with formaldehyde,


under acid conditions. Melamine-formaldehyde resins will cross-link
when heated alone, whilst urea-formaldehyde (U-F) resins require the
presence of an acid catalyst.
Urea-formaldehyde resins are used to produce light coloured moulding
compounds with a-cellulose as filler. This filler is essential to provide high

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OTHER RESIN SYSTEMS 307

strength and mouldability. They exhibit good electrical properties at low


frequencies and good tracking resistance, when cured. They have better arc
resistance than phenolic resins, since they do not carbonise under arc
conditions. They are less resistant to water than phenolic resins and should
not be used where prolonged contact with hot water is likely. They are not
resistant to acids or strong alkalis. Urea-formaldehyde resins find
application in lighting fittings and as light diffusers, since when filled with a-
cellulose they give a translucent milky white product. They may also be
used as the outer skin of decorative laminates (Formica type) where kraft
paper is used as the reinforcing material. The bulk of the laminate is usually
kraft paper reinforced phenolic resin.
Melamine-formaldehyde resins are colourless and can be used to
produce colourless, translucent mouldings and laminates. When filled with
a-cellulose, mouldings are harder and more heat and chemical resistant
than those produced from urea-formaldehyde resins. They also have a
considerably lower water absorption. Unlike the U - F resins, they may be
filled with asbestos, to give composites with improved heat resistance.
Melamine-formaldehyde faced laminates are harder than those based
on U - F resins and so find widespread application as table tops and other
decorative applications where a hard wearing surface is required. They
have excellent resistance to hot water and are therefore used for tableware,
for such items as cups and plates.

REFERENCES

1. Downing, P. A. (1978) The Chemical Engineer, April, 272.


2. Corrosion 77. Symposium, San Francisco, USA. Papers 158-164.
3. Oswitch, S. (1972) Reinforced Plastics, July, 194.
4. Whelan, A. and Brydson, J. A. (1975) Chapter 5 in Developments with
Thermosetting Plastics. Applied Science, London.
5. Harris, G. I., Edwards, A. G. and Coxon, F. (1976) Chimica Petrolchimica, VI,
July-August, 403.
6. Freeman, G. C. (1962) Silicones-An Introduction to their Chemistry and
Applications, Plastics Monograph No. C.16. The Plastics Institute-Ilitre Books
Ltd, London.
7. Judd, N. C. W. and Wright, W. W. (1978) Reinforced Plastics, February, 39.

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Chapter 14

REINFORCEMENTS

14.1 INTRODUCTION

Reinforcements are used with resin systems to improve the mechanical


properties of the cured resin and to provide a usable product. Industrially,
by far the most important fibre used with polyester and epoxide resin
systems is glass fibre. This can be used in a variety of forms, such as
continuous rovings, woven rovings and cloths and random chopped
strands, all meeting particular processing needs.
More recently, the development of high strength carbon fibres! has
opened up wider horizons for the use of reinforced plastics. The high
strength and rigidity of carbon fibre reinforced resin systems, coupled with
their low density, makes them ideal candidates for applications where
strength to weight ratio is of prime importance. Typical areas of use
include aerospace applications and reciprocating machine parts where the
low momentum of carbon fibre composites compared with metal parts
permits either faster machine operation or conventional operating speeds
with less wear and lighter-weight ancillary equipment.
Even more recent has been the development of high strength synthetic
aramid or aromatic polyamide fibres. 2 The use of these fibres can provide
up to 30% weight saving over glass and up to 50% over aluminium alloys.
Other synthetic organic fibres are generally only to be found as surfacing
tissues, since their strength to weight ratios in composites are generally
insufficient to make them attractive. Surfacing tissues made from polyacry-
lonitrile and polyester (polyethylene terephthalate) are readily available.
As might be expected with the introduction of expensive high perfor-
mance fibres, various ways of reducing cost whilst maintaining at least
some of the high performance properties have been sought. Glass/carbon
fibre,3,5,6 glass/aramid fibreS and carbon/aramid fibre 4 ,5,6 composites

308

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Table 14.1 Typical properties of reinforcing fibres and some materials with which they compete

Ultimate Specific
tensile Tensile tensile Specific
Specific sirength modulus strength modulus
Fibre gravity (GPa) (GPa) (GPa) (GPa)

A-glass 2·45 3·1 72 1·26 29


E-glass 2·56 3-6 76 1·40 29
R-glass 2·58 4·4 85 1·70 33
S-glass 2·49 4·5 86 1·80 34 ~
.."
Type I, carbon fibre, high modulus 1·87 2·1 330 1·12 176 0
~
Type II, carbon fibre, high tensile strength 1·76 2·6 235 l-48 133 ('"l
m
Type III, carbon fibre 1·82 2·3 200 1·26 110 s::m
Aramid fibre, Kevlar 29 l-44 2·76 58 1·92 40 Z
o-j
Aramid fibre, Kevlar 49 1·45 2·94 130 2·03 90 r.n

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Asbestos 2·5 0·7-104 135-170 0·28-0,56 54-68
Cotton 1·6 0'3-0'7 0·19-0·44
Sisal 1· 3 0·8 0·61
Aluminium (bulk) 2·8 0·5 75 0·18 27
Steel 7·8 1·0 200 0·13 26
Titanium DTD 5173 4·5 0·96 110 0·21 25
Boron 2·62 H 344 1-30 130
Beryllium (bulk) 1·82 1·03 310 0·57 170

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310 FRP TECHNOLOGY

have all been prepared and evaluated. Frequently the effect being sought is
only a slight increase in the rigidity of a glass reinforced system and this can
readily be achieved by the addition of a small proportion of carbon fibre
into the system. A variety of different hybrids can be prepared, each of
which may be of use in a particular situation. Clearly, therefore,
considerable design scope exists.
Another fibre used as a reinforcement in resin systems is asbestos. This
provides composites with greater stiffness than can be obtained with glass
reinforcements alone. Asbestos reinforced composites also have improved
water and chemical resistance. Thus a layer of asbestos reinforced resin
may be used to provide a chemically resistant liner to a GRP vessel.
Various other fibres are used in dough moulding compounds where cost
is of prime importance. These include cotton, sisal and cellulose (wood,
paper).
A comparison of the properties of some of the different fibres in use is
shown in Table 14.1.
For convenience this chapter has been divided into the following
sections:

Surfacing tissues
Glass fibre reinforcements
Carbon fibre reinforcements
Aramid fibre reinforcements
Other fibre reinforcements

A list of some of the commercially available materials is included at the


end of the chapter, whilst others are included in the appropriate sections.

14.2 SURFACING TISSUE

This is known variously as surface or surfacing tissue, mat or veil. It


consists of a thin randomly distributed fibrous mat designed to reinforce
the resin-rich surface of GRP mouldings and improve surface finish. Of
similar construction, but generally slightly thicker, is overlay mat. A typical
tissue construction is shown in Fig. 14.1.
Surfacing tissues (including overlay mats) are available in several
different thicknesses ranging from about 0·08 to O· 34 mm, with weights
ranging from about 30 to 60 g/m2. They may be manufactured from glass
or synthetic fibres such as polyacrylonitrile or polyester. Glass surfacing

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REINFORCEMENTS 311

Fig. 14.1. Surfacing tissue.

tissues are invariably made from C-glass, a chemically resistant type of


glass (see Section 14.3).
The advantages of using surfacing tissues can be summarised as follows:
I. They provide a resin-rich finish with improved chemical and weather-
ing resistance.
2. They ensure an adequate bond between the resin-rich surface layer
and the bulk laminate.
3. They help to prevent the formation of hair cracks in the gelcoat.
4. They help to mask the pattern of the underlying glass reinforcement.
5. They provide a degree of elasticity to the surface layer to improve
impact and abrasion resistance.
Where an overlay mat is used in the topcoat of a contact moulding, there
is an additional advantage in that it prevents fibres from protruding from
the resin and giving a hairy finish. This is important since protruding fibres
can be damaged and permit water or other liquids to wick up them and thus
weaken the laminate. An overlay mat also helps to balance up the laminate.
Patterns, trade names and designs can be printed onto surfacing tissues.
In this case a clear gelcoat needs to be used so that the pattern may be seen.
One company offers a printing service as well as a range of tissues.
Some of the commercially available materials are listed in Table 14.10.

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312 FRP TECHNOLOGY

14.3 GLASS FIBRE REINFORCEMENTS

Continuous filament glass fibres were introduced as a reinforcement for


plastic materials some 30 or so years ago, although they were first produced
commercially in the UK in about 1930.
Many different types of glass are available which can be converted into
usable fibres; however, for commercial reasons only a few basic com-
positions are used. At one time 'A' or Alkali glass was quite common as the
basic material for glass fibre production. Today this has been virtually
completely superseded by 'E' or Electrical grade glass. E-glass is a very low
alkali content borosilicate glass which provides good electrical and mecha-
nical properties, coupled with good chemical resistance. Compositions of
some of the glasses likely to be encountered are shown in Table 14.2.
Another glass produced in commercial quantities for fibre production is
C-glass, a special chemical resistant glass. This is used in the manufacture
of surfacing tissues to provide additional chemical resistance over E-glass.
For specific applications 'R' and'S' glasses are available as fibres. These
are high strength glasses used mostly for aerospace applications.
Two basic processes exist for producing continuous filament glass fibres:
(a) from marbles or (b) by direct melt. The latter process is today of greater
importance.
Table 14.2 Compositions and properties of various glasses

Composition (%)

A C E R S

Si0 2 72-0 64·6 52-4 60·0 64·4


A1 2 0 3 , Fe 2 0 3 1·5 4·1 14·4 25·0 25·0
CaO 10·0 13-4 17·2 9·0
MgO 2·5 3·3 4·6 6·0 10·3
Na 2 0, K 2 0 14·2 9·6 0·8 0·3
B2 0 3 4·7 10·6
BaO 0·9

Specific gravity 2·45 2·45 2·56 2·58 2·49


Refractive index 1·512 1·520 1·548 1·523
Single fibre tensile strength (GPa) 3·1 3·6 4-4 4·5
tensile modulus (GPa) 72 76 85 86
Softening point Cc) 700 690 850 990

(Courtesy of Fibreglass Ltd)

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REINFORCEMENTS 313

In the direct melt process molten E-glass is drawn through a large


number of very accurately dimensioned holes or bushings in a heated
platinum alloy crucible. A constant head of glass is maintained under
accurate temperature control so that when the fibres are wound onto a high
speed mandrel or collet (running at several thousand metres per minute) the
required diameter strands are produced to tight tolerances.
All glass fibres must be sized when produced. This size determines the
process ability of the fibres and prevents inter-fibre abrasion. It also helps
to hold the filaments together during processing into twisted yarns and
fabrics.
With fibres intended for reinforcement, the size also acts as a processing
aid during moulding. A typical size will contain four different components:
(i) a coupling agent to promote bonding of the resin matrix to the
fibre-usually an organic silicon compound or silane; (ii) a film forming
polymer to act as binder-often a polyvinyl acetate emulsion; (iii) a
lubricant-usually an acid amide; (iv) other materials such as antistatic
additives to give particular properties to the fibres.
With fibres intended for textile production the size consists of starch, oils
and lubricants. Once coated the fibres are twisted into yarns and
subsequently woven into fabrics. After weaving the size is usually burnt off
and the required finish applied. This finish will depend on end use.
In Europe fibres are classified by fibre diameter, by what is known as
'tex'. This specifies the weight of 1000 m of a strand composed of
approximately 200 filaments. For example, a strand of average filament
diameter of 10 f.1.m, which weighs 40 g per 1000 m, has a tex of 40.
The various types of glass reinforcements used with thermosetting resins
are described below. Commercial materials are either listed at the end of
each section, where the list is small, or at the end of the chapter.

14.3.1 Continuous filament rovings


Continuous filament glass rovings consist of one or more strands
(200 filaments) of fibres parallel wound, without twist, into a spool or
cheese (Fig. 14.2). The number of strands and spool size depend on end use.
For some applications split strands are used whereby a strand may be split
into two or four. In most cases fibres are coated with a polyester compatible
In SIze.
Different types of roving are produced to meet the needs of different
processes. An indication of these differences is given below, as each
particular type of process is considered.

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314 FRP TECHNOLOGY

Fig. 14.2. A typical roving cheese. (Courtesy of K & C Mouldings (England) Ltd.)

Spray lay-up
Here the roving should chop easily 7 and exhibit good fibre integrity with
excellent wet out, minimum air entrapment and low static build up. The
strands are usually medium hard with a fibre diameter of about 10 !lm.
Normally a full 40 tex strand is used. Similar rovings are used for the
preparation of preforms.

Chopped strand mat


Here the roving should chop easily and disperse uniformly during the
mat forming stage. The fibres should be capable of being firmly bound in
the mat whilst giving excellent wet out in use. A medium hard strand is used
with a fibre diameter of about 10 !lm. Either full or split strands can be
used.
F or clear sheet production, split strand rovings are preferred so that fibre
visibility is reduced. These rovings are mostly made from colourless or
'water white' glass.

Sheet moulding compounds


The strands used for SMC are medium hard to extremely hard and are
designed to chop well, give maximum resin penetration and retain strand

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REINFORCEMENTS 315

integrity for good flow characteristics during moulding. They are also
designed to give some breakage during moulding to reduce surface
waviness and to produce minimum fibre visibility in the finished moulding.
Fibre diameter varies from 10 to 14 Jlm and full strand construction is used.

Filament winding and pultrusion


These rovings are usually made from strands which vary from soft to
very soft, several strands often being combined. Care is taken to ensure that
the strands are as parallel and equal as possible. Recent developments have
resulted in rovings with equal tension in all fibres. Fibre diameter ranges
from 10 to 14 Jlm.

Weaving
Rovings intended for weaving need to be similar to those used for
filament winding, that is soft or very soft. They also need to be highly
ribbonised to prevent the strands from separating during weaving. The
resultant woven rovings must exhibit good wet out. Fibre diameter varies
from 10 to 14 Jlm.

Classification offibres
Fibres have been classified, wherever possible, according to the BSjISO
code- for example EC 10 40 2400. Here EC indicates E-glass continuous;
10 indicates the nominal filament diameter in 11m (microns); 40 indicates
the weight per 1000 m (tex); 2400 indicates the roving yield or total weight
per 1000 m.
Table 14. J 1 lists the commercially available rovings classified as far as
possible by the BSjISO code.

14.3.2 Chopped strands


Chopped strands are used in the manufacture of dough moulding
compounds and may also be used as reinforcement for thermoplastic
materials. They are usually supplied in lengths ranging from 3 to 50 mm
(see Table 14.3).
Also available are milled fibres produced by hammer milling continuous
filament fibres. Fibre lengths vary from 0·08 to 0·2 mm. These fibres are
generally used as a filler for resin systems used in casting, encapsulating and
tooling applications. They can also be used to improve the surface of a
laminate by reducing or eliminating crazing and shrinkage and can also be
used as thixotroping agents (see Table 14.4). Loadings of up to 40% weight
are possible.

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Table 14.3 CommerciaUy available chopped strands
w
Supplier 0'1
-
Product code Size BS/ISO code Fibre length (mm) Applications

c.G.T. (Glass Fibre) Ltd


Chopped strands EC 13 3,6, 12 DMC

Fibreglass Ltd
FGCS 1401 EC 13 38 3, 6, 12, 25 DMC-epoxy, polyester
FGCS 1617 EC 13 38 3, 6, 21, 25, 50 DMC, preforms

Montedison Group. UK Distributor-Plastichem Ltd


CS 308A Silane 6, 13 DMC-epoxy, polyester ;a
Owens-Corning Fiberglas (UK) Ltd
...,"C
ttl
('l
832 3, 6, 12 DMC, BMC :=
z
0
Silenka UK Ltd t"'
0
8030 EC 10 160 6, 12 Non-woven mats and felts 0
8036 Silane EC 10 80 6, 13 DMC-epoxy, polyester ><:

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Vetrotex (UK) Ltd
K35 Silane EC 10 80 6, 13, 25, 50 DMC-polyester
K52 Silane EC 10 80 3 DMC-epoxy, polyester
Silane EC 14 150 6, 13,25 DMC-epoxy, polyester
P343 Silane EC 10 160 6, 13 Epoxy, phenolics
Silane EC 14 300 6, 13 Epoxy, phenolics
PS24 Silane EC 10 160 6, 13 Plaster, paper
VB/OI Silane EC 10 40 3,6 Epoxy, phenolic, melamine
MDS Silane EC 10 40 6, 13 DMC, plaster
P3 Silane EC 10 40 3,6, 13,25, 50 DMC
P5 Silane EC 10 40 3, 13 Epoxy, phenolic
REINFORCEMENTS 317

Table 14.4 Commercially available milled fibres

Supplier
Product code Finish Length Applications

TBA Industrial Products Ltd


ECL 9 O· 19 mm Gelcoats, thixotroping agent

Vetrotex (UK) Ltd


ECI0C Chrome O·2mm Various
EC lOS Silane O·2mm Polypropylene
EC lOW Water O'2mm Thermoplastics

14.3.3 Chopped strand mat


Chopped strand mat (CSM) is one of the most widely used of all
reinforcements for GRP and, although the tendency has been towards
mechanisation and spray lay-up in recent years, the introduction of
legislation to control styrene emission has resulted in a move towards
closed mould processes where CSM can again be used.
As its name implies, chopped strand mat is composed of randomly

Fig. 14.3. Chopped strand mat.

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318 FRP TECHNOLOGY

distributed chopped rovings bonded together to form a uniform mat. The


usual fibre length is 50 mm, with mat weights ranging from 225 to
600 g/m2. A typical mat construction is shown in Fig. 14.3.
Since CSM is used in a wide variety of processes, many of which need
mats with different handling characteristics, a wide range of products is
available. Two different types of binders are generally used to hold the
fibres in position, namely liquid and powder binders. An example of the
former type is polyvinyl acetate emulsion while the latter type is often a
bisphenol polyester powder.
Mats are available with medium binder contents in the range 3-6;'"
based on a high solubility binder or with a high binder content of 13-17%
and a low solubility binder (this refers to the solubility of the binder in
styrene). CSM with high binder solubility is used where complete wet out is
required in a short time with short gel time resins. A liquid binder generally
imparts greater drape than a solid binder. High binder content CSM is used
to prevent the fibres from flowing with the resin during press moulding
processes and SMC preparation.
Fibres are normally finished with either a silane or chrome size
compatible with all polyester resins. Some mats are better than others for
use with epoxide resin systems. Binders are rarely completely soluble in
epoxide resin systems and so fibre pattern usually remains distinct in the
cured laminate.
In addition to normal chopped strand mats, several products are avail-
able which combine chopped strand mat with glass fibre tissue, woven ro-
vings or unidirectional rovings. The CSM may be bonded to the rovings
with an emulsion or powder binder or be mechanically bonded. Mechani-
cal bonding is usual with lightweight rovings or glass fibre tissue. This type
of mat is also known as needled mat since the chopped strands are needled
into the other material. Such mats exhibit good drape qualities and very
fast wet out. These products have been included here although they could
equally well have been included in the section on woven rovings.
The main reason for developing these combined mats was to reduce
handling during hand lay-up. If woven rovings are used alone there is a
tendency for delamination to occur between the various layers of rovings in
the cured laminate. To overcome this a layer of CSM is inserted between
each layer of rovings. By using the combined mat this problem can be
eliminated without increasing labour costs. Also there is no fear that the
CSM will be omitted by mistake, and only one material needs to be stocked.
Details of the various products available are given in Table 14.12. Most
of these products are available in widths of about 1 m with some available

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REINFORCEMENTS 319

in other widths as well. Full details of widths and packaging can be


obtained from the material suppliers.

14.3.4 Continuous strand mat


Continuous strand mat consists of multiple layers of continuous glass
fibres deposited randomly in a swirl-like pattern. The fibres are bonded
together with either a high or low solubility binder in a similar way to
chopped strand mat.
The uses of continuous strand mat are similar to those of chopped strand
mat. However, continuous strand mat has improved drape and handling
characteristics which make it particularly suitable for matched-die mould-
ing with deep mould cavities or complex curves. It is also finding increasing
use as a reinforcement in the resin injection process since the fibres are not
displaced by the injected resin as can occur with CSM.
Details of some of the products available are given in Table 14.5.

14.3.5 Woven glass fabrics


These can be divided into two classes, those prepared from rovings and
those from yarns. Woven roving is made from E-glass rovings by weaving
the untwisted rovings into cloth. The rovings are first treated with a special
size to assist in the weaving process. To prevent laminates failing by

Table 14.5 Continuous strand mats

Supplier Weight
Product code Binder (gjm 2 ) Applications

Owens-Corning Fiberglas (UK) Ltd


M 8603 Powder 600 Press moulding,
resin injection, etc.
M 8610 Powder 600 Press moulding,
resin injection, etc.

Vetrotex (UK) Ltd


Unifilo Sj8 Low 375 Pressure moulding at high
solubility, 450 temperature and pressure
solid 600
Unifilo Lj9 High 375 Pressure moulding at moderate
solubility, 450 temperatures and pressures
solid 600

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320 FRP TECHNOLOGY

interlaminar shear between layers of woven rovings, these are generally


interspersed with layers of chopped strand mat. Two manufacturers offer
combined products so that only one material needs to be stocked and there
is then no chance of forgetting to insert the CSM.
Yam based cloths or fabrics are woven from continuous filament glass
fibre which has been sized with a textile size and then twisted before
winding onto a bobbin. The size protects the yam during weaving and
ensures that it can be easily processed. The twist, which may be between 20
and 40 turns per metre, enables a uniform cloth to be woven. Most fabrics
are made from E-glass, although some are available woven with C-glass for
improved chemical resistance.
The size is usually burnt off or washed off after weaving with yam and
replaced with an appropriate finish compatible with the resin system to be
used. Ifheat cleaning is carried out at a relatively low temperature the size is
charred or caramelised, which leaves the cloth brown in colour. A full heat
treatment leaves the cloth colourless.
Various finishes are applied to heat cleaned fabrics to improve bonding
of the resin system to them. These include chrome, silane, vinylsilane,
epoxy silane and amino silane treatments and may have to be specified when
the cloth is ordered.
One important effect of the use of these finishes or coupling agents on
glass fibres is to reduce the tendency of water to wick up the glass fibres
when the laminate is immersed in, for example, sea water. The net result is a
smaller reduction in flexural strength with continuous immersion and thus
improved performance and longer life of the laminate.
Yams used for weaving may be single, plied, cabled or multiple wound.
Single yams, subjected to only one twisting process, are unbalanced and
tend to untwist back to the original shape. They are used for the
preparation of plied, cabled and multiple yams and as the warp strands in
weaving. (Warp strands run the length of the cloth.)
Plied yams are made by twisting two or more single yams together.
These are generally balanced and have no tendency to untwist. They are
used to make tapes, fabrics and wire wrapping materials.
Cabled yarns are made by twisting two or more plied yarns together,
giving a third twist to the yam. They are used in the manufacture of
reinforced rope and high strength cordage and as sewing yarns.
Multiple wound yarns consist of several yams wound together without
further twisting. These are used in the electrical industry for wire covering
and braiding.
Woven fabrics, whether made from yam or rovings, are available in a

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REINFORCEMENTS 321

number of different weaves, the variety being greater for yarn based fabrics.
Examples of these are given below.

Plain weave
Here each warp and weft thread passes over one thread and under the
next (Figs 14.4 and 14.5). These fabrics often have good resistance to
distortion and give reproducible laminate thicknesses. Plain weave is also
known as taffeta. Materials are available made from yarn and rovings.

Twill weave
With twill weave the number of warp ends and weft picks which pass
over each other can be varied. In a 2 x 1 twill, weft yarns pass over one and
under two warp ends, while in a 2 x 2 twill the weft yarns pass over two and
under two warp ends (Fig. 14.6). This produces a regular diagonal pattern
on the cloth. Twill weave cloth has good drapability and somewhat
improved laminate strength. It can be made either from rovings or yarns.
Twill weave is also known as serge.

Satin weave
Here the number of warp ends and weft picks which pass over each other
before interlacing is greater than with twill weave and the interlacing is
always with one crossing thread (Fig. 14.7). In consequence one side of the
fabric consists mostly of warp threads, the other weft threads. Satin weave
cloth has excellent drapability and imparts high tensile and flexural
properties to a laminate. This weave is used both with rovings and yarns.

Leno weave
In this type of weave the warp yarns are twisted between each weft yarn.
This imparts stability to very open fabrics and stops slip. This weave is only
used with yarn.

Mock leno weave


Here the warp and weft yarns are gathered into groups with gaps
between them to produce an open weave fabric (Fig. 14.8). This weave is
only produced from yarn.

Unidirectional weave
Here the warp threads are held together by fine weft threads so that the
fabric is mostly unidirectional in structure (Fig. 14.9). With this type of

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322 FRP TECHNOLOGY

i :m:m:
:!: :::: II
:!j
~:!'
:i; :!;
m
Wi: I:::
:i ::i [:,'

miHm i!: ~~:


Fig. 14.4. Plain weave roving. Type Fig. 14.5. Plain weave cloth. Type
266; weight 848 g/m2. 123X; weight 136 g/m2.

Fig. 14.6. Twill weave roving. Type Fig. 14.7. Satin weave cloth. Type 284 ;
271; weight 750 g/m2. weight 865 g/m 2.

Fig. 14.8. Mock leno weave cloth. Fig. 14.9. Unidirectional roving. Type
Type 138; weight 288 g/m2. 280; weight 610 g/m2.

(All materials illustrated are supplied by Marglass Ltd, whose codes are given.)

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REINFORCEMENTS 323

construction maximum tensile strength is obtained in the direction of the


warp threads. Cloths can be made from yarns or rovings.
Commercially most products can be obtained in a range of widths. Full
details of these and roll sizes can be obtained from the various suppliers.
Table 14.13 (pp. 343-5) lists some of the materials available.
Woven cloths find use in electrical insulation boards, printed circuit
boards, circuit breaker tubes, vehicle bodies, storage tanks, boats, moulds
and a variety of other applications. 8
Woven rovings are used for a variety of applications. They increase the
strength and rigidity of mouldings and can be very cost effective. They are
best used with large mouldings which have minimum curvature since, in
general, they do not readily deform or drape.

14.4 CARBON FIBRE

Although carbon fibres have been known for very many years,l it was not
until around 1964 that the first high strength, high modulus carbon fibres
were produced. These first fibres were produced at the Royal Aircraft
Establishment, Farnborough, the process being covered by British Patent
1 110791. Prior to this the only carbon fibres available were oflow strength
and generally unsuitable for use as reinforcing fibres.
In the 1880s Thomas Edison used carbon fibre as the filament material in
incandescent lamps. This was later to be replaced by tungsten filaments. It
was not until the late 1950s that interest in carbon fibre as a reinforcing
material arose. This was mainly due to the need for high strength, light
weight, thermally stable materials for the aerospace industry, much of
which could be met by the use of carbon fibre. Developments therefore
went ahead to try to produce continuous high strength fibres.
In the USA, developments centred around the use of cellulose fibre as a
precursor (US Patents 3 454 362 and 3 503 708) whilst in the UK
polyacrylonitrile fibre was used (British Patent 1 110791). Other pre-
cursors examined were lignin and pitch, both in Japan.
Today high strength, high modulus carbon fibres are available in large
quantities prepared both from cellulose and polyacrylonitrile precursors,
whilst somewhat lower strength fibres are available based on a special
hydrocarbon pitch. In all processes the carbon fibres are produced by
controlled oxidation and carbonisation of the precursor fibre at tempera-
tures of up to about 2600°C. This results in a high strength fibre. By
subsequently increasing the temperature to about 3000°C the high strength

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324 FRP TECHNOLOGY

Table 14.6 Carbon fibre precursors

Carbon
content Carbonisation yield
Precursor material (% wt) (% wt)
Cellulose fibre 45 10-15
Polyacrylonitrile 68 40
Lignin ~70 50
Hydrocarbon pitch 95 85-90

carbon fibre can be converted into a high modulus graphite fibre. Both
forms are commercially available today.
Considering the various processes available for manufacturing carbon
fibres, the conversion of polyacrylonitrile fibre to carbon fibre is somewhat
more efficient than that using cellulose fibre, due to the higher carbon
content of the precursor. In Table 14.6 are shown the carbon contents and
yields of the various starting materials. Properties of fibres resulting from
these various precursors are given in Table 14.7.
When considered in terms of composite properties, carbon fibre
reinforced resins offer more to the designer than any other material in
current use, in terms both of strength and rigidity. The materials which
approach closest to CFRP are boron composites, beryllium and titanium.
Composites are usually prepared by some form of pressure moulding
technique and have a typical fibre volume of about 60%, although hand lay-
up carbon fibre composites can be prepared with lower fibre contents. Test
results are mostly quoted at 60% fibre volume, if necessary after a simple
arithmetical adjustment.
Carbon fibres are generally surface treated to improve the bonding of the
resin matrix to the fibres. They are also frequently sized with a resin to aid
handling and to prevent damage during processing.
Like glass fibres, carbon fibres can be obtained in a number of different
forms, from continuous filament tows (this is equivalent to roving in glass
terms) to chopped fibre mat. Composites with the highest strength and
modulus result from the use of unidirectional reinforcement. Examples of
three types of carbon fibre reinforcements are shown in Figs. 14.10-14.12.
Carbon fibre is manufactured as continuous filament twist-free tow,
consisting of 5000, 6000, or 10 000 individual filaments, depending on
manufacturer. These tows are then used for the manufacture of other
materials. Apart from pure carbon fibre products several hybrid products
are available, consisting of alternate tows of glass and carbon fibres.

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Table 14.7 Properties of some carbon fibres

Tensile Tensile Carbon


Diameter Specific strength modulus Elongation content ~
Fibre precursor Fibre type Trade name (11m ) gravity (GPa) (GPa) (%) (% wt) Z
"!l
0
~
("l
Hydrocarbon pitch Carbon Kureha 10·5 1·6 1·03 2·5 99·5 ttl
Lignin Carbon 10-15 1·5 0·6 1·5 90 ~
Cellulose Graphite Thornel 6·6 1·67 2·0 390 0·6 99·9 Z
"'!
Polyacrylonitrile Carbon Graphil HT 8 1·76 3·2 230 '"

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Polyacrylonitrile Graphite Graphil HM 8 1·87 2·4 330

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N
Ul
326 FRP TECHNOLOGY

Fig. 14.10. Carbon fibre aligned sheet. Continuous carbon fibre warp with fine
carbon fibre weft.

Fig. 14.11. Unidirectional woven carbon fibre tape. Unidirectional carbon fibre
warp, fine glass fibre weft.

Fig. 14.12. Continuous carbon filament aligned mat.


(All products illustrated are manufactured by Hyfil Ltd.)

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REINFORCEMENTS 327

Carbon fibre, unlike any other reinforcing fibre, has a negative coefficient
of thermal expansion along the fibre axis but a positive transverse
coefficient of thermal expansion. This means that any resin system
reinforced with carbon fibres must be capable of absorbing this strain. This
is particularly true where 90° cross-plied composites are made.
One of the first resin systems reinforced with carbon fibre was an epoxy
novolac resin cured with a boron trifluoride complex. The unreinforced
cast resin has a strain of between 1 and 1· 5% at break, which is only of the
same order as the strain set up within the matrix when the composite is
cooled from processing temperature to ambient temperature. Thus some of
the early cross-plied composites made with this resin system failed almost
immediately. Today, where such a resin system is needed to give high
temperature performance, fibre orientation is restricted to a maximum
angle of 30°.
Most resin systems developed for use with carbon fibre reinforcement
have a strain at break of between 4 and 6% to accommodate adequately the
differences in coefficients of thermal expansion between resin and fibre.
Thus cross-plied composites can be made for service over the temperature
range - 40°C to above 100°C. The actual upper temperature limit depends
on the matrix used and may be as high as 200°C in certain circumstances.
Some of the commercially available materials are listed in Table 14.14
(pp. 347-8).

14.5 AROMATIC POLYAMIDE (ARAMID) FIBRES

High performance aramid fibres i ,2,9 became commercially available as


reinforcing materials for synthetic resin systems in 1972. These fibres offer
advantages in strength/weight ratio over glass fibres, combined with
excellent impact'resistance in the finished laminate.
Two types of fibre are available from Du Pont under the trade name
KEVLAR-KEVLAR 29 and KEVLAR 49. KEVLAR 29 has roughly
half the modulus and twice the elongation of KEVLAR 49 and is more
suitable for use in areas where high impact resistance is of primary
importance.
Aramid fibres are finding use in a wide variety of applications.
KEVLAR 49 composites are being used for aircraft parts, for example, as
ceiling panels and other interior parts of the Lockheed L-l 0 11 aircraft.
Such composites also offer advantages in the construction of sports goods,
ranging from canoes and kayaks to golf shafts and tennis rackets.

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328 FRP TECHNOLOGY

Another use ofKEVLAR 49 is in the manufacture of high strength ropes


and cables. These find application as mooring cables.
The main properties of KEVLAR fibres can be summarised as follows:
Excellent strength and stiffness/weight ratio.
Excellent impact resistance.
Outstanding creep rupture characteristics.
Good fatigue resistance.
Insensitive to notching.
High resistance to organic solvents, fuels and lubricants.
Good acid and alkali resistance.
Good vibration damping properties.
Superior dielectric properties to glass.
Self-extinguishing with low smoke emission.
Continuous operation possible up to about 180a C.
Typical mechanical properties of the two fibres are shown in Table 14.8.
Aramid fibres are unaffected by normal resin cure cycles up to about
180 a C but will completely oxidise at temperatures above 400°C. They are
normally used as reinforcement in epoxide resin matrices.
The machinability of KEVLAR 49 composites is somewhat different
from that of composites based on more brittle fibres, such as carbon and
glass, and requires a shearing action. Machining is more analogous to
wood finishing and so some tool redesign and change in procedure from
that used with normal composites is necessary.
Aramid fibres, which are pale yellow in colour, are available as yarns,
rovings and woven fabrics (Table 14.9).
Hybrid laminates consisting of carbon fibre/KEVLAR 49 reinforced
epoxy have been prepared and evaluated for impact resistance. 4 Results
obtained indicate that higher impact resistance can be obtained than with
either fibre alone.

Table 14.8 Typical properties of aramid fibres

Property KEVLAR KEVLAR


29 49

Specific gravity 1-44 1·45


Tensile strength (GPa) 2·76 2·94
Tensile modulus (GPa) 58 130
Elongation at break (%) 4·0 2·6
Filament diameter (pm) 12·1 11·9

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REINFORCEMENTS 329

Table 14.9 Some aramid fibre products

Supplier
Products

Du Pont De Nemours International SA


Yarns KEVLAR 29 yarns-200 400 1000 1500 15000 (denier.)
KEVLAR 49 yarns-195 380 1140 1420 (denier)
Rovings KEVLAR 49 rovings-4560 7100 (denier)

Fothergill & Harvey Ltd


Woven fabrics

Product Weight Thickness Threads/dm


code Weave (g/m2) (mm) Warp Weft
--------

KEVLAR 29 D 217 Plain 171 0·23 75 75


D 218 Plain 216 0·27 63 63
D 220 8 x 8 matt 541 0·74 157 157
D 235 Plain 279 0·38 122 122
D 236 Plain 351 0·53 llO 95
D 237 2 x 2 matt 473 0·62 138 138
D 265 Plain 61 0·11 134 134
D 271 Plain 108 0·20 244 228
KEVLAR49 D 158 8 end satin 164 0·23 189 189
DI72 Plain 60 0·11 134 134
D203 Plain 175 0·24 67 67
D 208 Plain 218 0·33 67 67
D 219 8 x 8 matt 512 0·70 157 157
D244 4 end satin 220 0·30 150 71
D267 4 end satin 175 0·24 67 67
D268 4 end satin 218 0·33 67 67
PW 153 4 x 4 matt 358 0·54 110 110

14.6 OTHER REINFORCING FIBRES

14.6.1 Polyester fibres


Polyester or polyethylene terephthalate fibre is used to make surfacing
tissues which can be used to provide improved chemical and abrasion
resistance. The surfacing tissues may be of normal random construction
(see Fig. 14.1) or lightweight woven fabrics. Polyester fabrics are rarely
used as the main reinforcement, although when they are, they give
laminates with very high impact resistance and excellent chemical and

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330 FRP TECHNOLOGY

abrasion resistance. They may be used in combination with glass


fibre reinforcements.

14.6.2 Polyacrylonitrile fibres


Polyacrylonitrile fibres are used to make surfacing tissues which can
improve the chemical resistance of laminates. Tissues may be of con-
ventional construction (Fig. 14.1) or lightweight woven fabrics.
Polyacrylonitrile fibre is rarely used as the main reinforcing fibre.

14.6.3 Nylon
Nylon fabrics may be used as reinforcements for epoxide resin systems to
give flexible laminates with high impact, abrasion and chemical resistance.
They are mostly combined with glass fibre reinforcements for specialised
applications and are rarely used alone.

14.6.4 PVC and PVDC


Polyvinyl chloride and polyvinylidene chloride fibres can be used to make
chemically resistant surfacing tissues and lightweight woven fabrics to
provide a chemical resistant finish on a moulding. Their use is not common
and they are rarely, if ever, used alone as the main reinforcement.

14.6.5 Cotton
Cotton fibres provide a cheap fibrous reinforcement for use in dough
moulding compounds-mostly phenolic resin based. They are rarely used
in polyester or epoxide resin compositions, although printed fabrics can be
used to provide a decorative finish for such applications as walling panels.
Here the printing ink must be insoluble in the resin and not discoloured by
the catalyst.

14.6.6 Sisal
Sisal is another cheap fibrous material which is used in phenolic based
dough moulding compounds but rarely with polyester or epoxide resin
systems.

14.6.7 Asbestos
Asbestos is frequently used with phenolic resins in dough moulding
compounds to provide rigid, hard wearing, temperature resistant com-
posites. Such composites are used as friction brake pads on vehicles and a
variety of different machines; they have many other applications. Asbestos

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REINFORCEMENTS 331

can also be employed with epoxide and polyester resin systems to provide
composites with increased rigidity over glass and improved water and
chemical resistance.
Asbestos is available in a number of different forms, although chrysotile
asbestos-a hydrated magnesium silicate-is the most commonly used as a
reinforcement. It is available as paper, cloth, mats and ropes, all of which
find widespread use as reinforcements in phenolic resins but far less use in
epoxide and polyester resin systems. With legislation pending on the
restriction of the use of all forms of asbestos, it is debatable how much
longer asbestos will be used as a reinforcing material, except perhaps/where
no alternative can be found.

14.6.8 Paper
A variety of printed papers, such as wall paper, may be used to provide
decorative finishes to polyester mOUldings. Where such printed papers are
used they must obviously be able to be thoroughly wetted by the resin
system, and the printed colours must not run or change in contact with the
resin or catalyst. They find uses in decorative wall panels, coffee table tops
and other similar applications. Printed papers are also used widely to
provide the decorative finish to melamine based laminates.

14.6.9 Jute
Work is being carried out in India on the use of jute fibres as a
reinforcement for polyester resins 10 since this is a cheap readily available
fibre. Jute can be used as woven cloth or in yarn form for filament winding.
A variety of objects including houses, grain silos and fishing boats have
been evaluated.

14.6.10 Boron fibres


Boron fibres are used as reinforcement in epoxide resin systems for
aerospace applications. They are expensive to produce and find far less
application than carbon fibres. Initially the only boron fibres available
consisted of boron clad tungsten fibres; however, now boron clad carbon
fibres are also available which show only about 5% reduction in strength
over boron clad tungsten fibres and are some 25% cheaper.
Values of specific tensile strength and modulus of boron fibres and
composites are similar to those obtained with carbon fibres.
Both types of fibre can be obtained from Afco Products Inc., Somerville,
Mass, USA.

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332 FRP TECHNOLOGY

14.7 COMMERCIALLY AVAILABLE REINFORCEMENTS

Tables 14.1 O-14.l4list some of the commercially available reinforcements.


Table 14.10 lists surfacing tissues; Table 14.11 glass rovings; Table 14.12
chopped strand mats; Table 14.13 woven glass cloths and woven rovings;
Table 14.14 carbon fibre products.

REFERENCES

1. Phillips, L. N. (1978) Plastics & Rubber International, 3 (6), 239.


2. Morgan, P. W. (1979) Plastics & Rubber: Materials & Applications, February, I.
3. Lovell, D. R. (1978) Reinforced Plastics, July, 217; August, 252.
4. Dorey, G., Sidey, G. R. and Hutchings, J. (1978) Composites, 9(1), 25.
5. Anon. (1978) Modern Plastics International, May, 62.
6. Anon. (1978) Modern Plastics International, January, 10.
7. Mai, M. (1977) Kunststoffe, 67, January, 2.
8. Anon. (1979) Vetrotex Fibreworld, No.7, 23.
9. Hodd, K. A. and Turley, D. C. (1978) Chemistry in Britain, 14, November, 545.
10. Winfield, A. G. (1979) Plastics & Rubber International, 4 (Jan/Feb), 23.

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Table 14.10 Surfacing tissues

Supplier Fibre type Binder Weight Thickness Applications


Product code (g/m2 ) (mm)

Bondina Industrial Ltd. UK Distributor-Newgate Simms Ltd


T. 1745 Po1yacry1onitrile Styrene insoluble 35 0·34 Filament winding, length
orientated fibres
T.1773 Po1yacrylonitrile Styrene soluble 22 0·29 Hand/spray lay-up, etc.
6020 Polyester Polyester 170 0·28 Artwork and manuscript
restoration
6050 Polyester None 30 0·08 Filament winding ~
>t1
6010 Polyester None 60 0·13 Filament winding 0
~
6750 Polyester Acrylic 60 0·13 General n
ttl
6755 Polyester Acrylic 120 1·2 Filament winding
~
Fibreglass Ltd ..,Z
I:I".l

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FPL 498 Pl5 C-glass Polystyrene 30 General, polyester, epoxy
FPL 498 P23 C-glass Polystyrene 50 General, polyester, epoxy
FPL498 C64 C-glass Polystyrene 27 0·25 General, polyester, epoxy
Overlay F 499 C-glass Polystyrene 44 General, polyester, epoxy

Montedison Group. UK Distributor-Plastichem Ltd


411 C-glass Acrylic 30 Hand lay-up, filament winding

Owens-Corning Fiberglas (UK) Ltd


M-514 C-glass Polyester silane 33 General
w
w
w
VJ
VJ
~

Table 14.10 (Continued)

Supplier Fibre type Binder Weight Thickness Applications


Product code (gjm2 ) (mm)

TBA Industrial Products Ltd


ACM I C-glass 27 0·3 General

Vetrotex (UK) Ltd


~
'1i
MS 30 Glass PYA 30
MS 40 Glass PYA 40 0·9
08} Type A for contact moulding, trl
MS 50 Glass PYA 50 1·0 Type N for compression moulding n
:=
MS 60 Glass PYA 60 1·1 Z
0
t""
VPB Industrial Fabrics 8-<
N 27 Polyester None 0·15 General, continuous filament

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N 34 Polyester None 0·23 General, continuous filament
N 44 Polyester None 0·24 0·24 Heavy duty applications,
continuous filament
N75 Polyester None 0·30 0·30 Electrical, continuous filament
Drape veil Polyester None 0·40 Hand lay-up, continuous filament
Printing service available for
printing designs on veils
REINFORCEMENTS 335

Table 14.11 Glass rovings

Product code
Supplier Type Finish BSjlSO code Applications

e.G.T. (Glass Fibre) Ltd


214 Hard Chrome (Volan) EC 1040 2400 Spray lay-up
253 Medium Silane EC 10 40 2400 Spray lay-up, CSM
hard
254 Hard Silane EC 10 40 2400 Spray lay-up, SMC
EC 15925520
284 Silane EC 10 40 2400 DMC
EC 15 180 5400
651 Soft Silane EC 13 136 1220 Winding, weaving
EC 13 136 2440
653 Medium Chrome (Volan) EC 10402400 Spray lay-up,
hard CSM, SMC

Fibreglass Ltd
Muhi:spray Chrome EC 10 40 2400 Spray lay-up
EC 10 80 2400
EC 10804800
Supn:spray Silane EC 1040 2400 Spray lay-up, SMC,
EC 10404800 sheet
Supr.<:preg Medium Silane EC 10 160 2400 SMC, DMC
hard EC 14802400
Supr~spray CC Silane EC 1040 2400 Centrifugal
casting
XRE 25 Silane 2400 Pultrusion
4800
Supr.<:wind Silane EC 13 2100 Filament winding,
EC 13 2400 pultrusion
EC 13 4700
Equ~rove Silane EC 13 600 Equitension for
EC 14 750 filament winding,
EC 17 1200 weaving
EC 21 1800
EC 17 2400
Supr~ave Silane EC 10 2400 Weaving

Montedison Group. UK Distributor-Plastichem Ltd


Vitrofil V 191 A Silane 1200} Even tension for
2400 filament winding
Vitrofil V 190 X Silane 600 Weaving
1200
2400
Vitrofil V 251 RP Silane 600 Weaving
890
1200
Vitrofil V 197 Chrome-silane 2400 Spray lay-up
Vitrofil 407 FX Silane 2400 SMC
Vitrofil 417 F 2360 SMC
Vitrofil 417 X Silane 2400 SMC

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336 FRP TECHNOLOGY

Table 14.11 (Continued)


Norsk Glassfiber A/S. UK Agent-Brandhurst Co. Ltd
R 437 Medium Silane EC II 45 2400 Spray lay-up
hard
RP 438 Silane EC 17 1200 Filament winding,
EC 17 2400 weaving, SMC
R 451 Silane EC 11 302400 SMC
R462 Medium Silane-chrome EC II 452400 Spray lay-up
hard EC 11 454700
R474 Hard Chrome EC II 452400 Spray lay-up
EC 11 454700
-~--------

Owens-Corning Fiberglas (UK) Ltd


BT 57 RX3 2480 SMC
BT 89V Chrome 2400 Spray lay-up
495 Silane 2430 SMC--pigmented
R 496 Silane 2350 Spray lay-up
816 Araton 1180 Weaving
2220
825 Chrome 2380 Spray lay-up
2410
840 Silane 2250 SMC-non-
pigmented
R 853 Silane 2350 Continuous sheet
R 859 Araton 1200 Filament winding,
2400 epoxy
R 886 Silane 2350 Spray lay-up
R 891 Araton 1200 Filament winding,
2400 continuous processing
4800
-----------------,--,,--
Scandinavian Glasfiber Ltd
RSK 62 Medium Silane-chrome EC 9 2400 Spray lay-up
hard EC 9 4700
RK 74 Hard Chrome EC 9 1200 Spray lay-up
EC 9 2400
EC 9 4700

Silenka UK Ltd
051 Silane 300 Winding, pultrusion,
600 weaving
900
1200
2400
4800
058 Silane EC 10 1200 Weaving
EC 10 2400

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REINFORCEMENTS 337

Table 14.11 (Continued)


Product code
Supplier Type Finish BS(ISO code Applications

Silenka UK Ltd (contd.)


423 Chrome EC 10 40 1200 Spray lay-up
EC 10 40 2400 (also with red
EC 10 40 3600 tracer), preform
EC 10404800
436 Silane EC 10402400 Spray lay-up, sheet
471-S Hard Silane + anti- EC 13 40 2400 SMC
static agent
871-S Hard Silane + anti- EC 13 80 2400 SMC
static agent

TBA Industrial Products Ltd


ECR 101 Chrome EC 2400 Spray lay-up,
35% glass
ECR 144 Chrome EC 2400 Spray lay-up,
35% glass
ECR 1313 Silane EC 2400 Spray lay-up,
40% glass
ECR 333 Silane EC 1200 Even tensioned for
EC 2400 filament winding
EC 4800
----~---~~-.--

Vetrotex (UK) Ltd


CIl Chrome EC 10402400 Spray lay-up
P7 Chrome~silane EC 10402400 Spray lay-up
P207 Chrome~silane EC 10402400 Spray lay-up
R82 Chrome EC 10402400 Spray lay-up
K26 Chrome EC 10802400 Spray lay-up,
preform
K931 Silane EC 10402400 Spray lay-up,
preform
EC 10 80 2400 Spray lay-up,
preform
K923 Chrome EC 10402400 Spray lay-up
P3 Silane EC 10 40 2400 CSM, preform
P23 Silane EC 10 102400 CSM
EC 10 20 2400
P223 Silane EC 10 20 2400 CSM
EC 10 40 2400
K247 Silane EC 10 10 2400 CSM
EC 10402400
K92 Silane EC 10801200 Weaving, pultrusion
EC 10 80 2400
PI2 Silane EC 1040 1200 Weaving, winding
EC 10402400
EC 14 150 1200
EC 14 1502400

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338 FRP TECHNOLOGY

Table 14.11 (Continued)


RSI Silane EC 14 150 150 Weaving, winding
EC 14 150 300
EC 14 150 600
EC 14 150 1200
EC 14 1502400
K43 Silane EC 10 160 2400 Winding, pultrusion
EC 10 160 9600
EC 14 1504800
K937 Silane EC 14 1502400 Winding, pultrusion
P145 Silane EC 14 300 2400 Winding, pultrusion
S22 Silane EC 14 300 2400 Winding, pultrusion
P231 Silane EC 1480 2400 SMC
P217 Silane EC 10 40 2400 Centrifugal
moulding

Table 14.12 Chopped strand mat reinforcements


Product Fibre
code BS/ISO length Weight
Supplier Binder Finish code (mm) (g/m2) Applications

e.G.T. (Glass Fibre) Ltd


ES 22 Emulsion Silane EC 11 24 300 Hand lay-up
450
600
ES 33 Polyester powder Silane EC 11 24 300 Hand lay-up or
450 machine
600 processing.
Transparent
laminates
ES 63 Polyester powder Silane EC 11 48 450 Hand lay-up or
600 machine
900 processing.
Transparent
laminates

F.G. Industries (UK) Ltd


This range includes CSM combined with woven and unidirectional rovings
Woven CSM
Fabmat Polyester powder CSM/woven
3OO} {150 rovings
600 300 Hand lay-up,
winding
800 450

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REINFORCEMENTS 339

Table 14.12 ( Continued)


Product Fibre
code BS/ISO length Weight
Supplier Binder Finish code (mm) (g/m2) Applications

F. G. Industries (UK) Ltd. (contd.)


{' 50 CSM/un;d;=
Linrovrnat Polyester powder 600 300 tional rovings.
450 Hand lay-up,
winding

HP Fabmat
800
{ISO CSM/crimp free
300 woven roving.
450 Hand lay-up,
press, winding,
pultrusion
Total

Fabmat M Mechanical 600 CSM/lightweight


900 woven
1200 roving. Resin
1500 injection,
pultrusion, press
moulding
MBmat Mechanical 450 CSM/cotton scrim or
600 glass fibre tissue
900 Press moulding
1200

Fibreglass Ltd
Equc:mat Liquid Silane EC 1227 38 300 Hand lay-up, fast
450 wet out
600
Supr~mat Liquid Silane EC 1227 38 225 Hand lay-up. Fast
51 300 wet out. Suitable
51 450 for epoxies
EC 1351 51 600
51 750
51 900
Supr~mat Polyester powder Silane EC 1240 51 225 Hand lay-up, SMC
PB 51 300 Translucent
mouldings
51 450 Suitable for
epoxies
51 600
Supr~mat Polyvinyl acetate Silane EC 1227 51 450 SMC
SMC

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340 FRP TECHNOLOGY

Table 14.12 (Continued)


Supremat EC 1020 51 Machine made
TS translucent sheet.
Range of weights
available
Multemat Liquid Silane EC 13 38 51 300 General purpose
51 450
51 600
NOTE Fibreglass Ltd also sell Fabmat and Linrovmat made by F.G. Industries.

Montedison Group. UK Distributor~Plastichem Ltd


631 C Powder 300 Hand lay-up
375
450
600
500 E Emulsion 300 Hand lay-up. Good
375 wet strength
450
600
CM 630C Polyester 225 Hand lay-up
300
450
600

Norsk Glassfiber A/S. UK Agent~Brandhurst Co. Ltd


M 112 Emulsion EC 11 40 300 Hand lay-up
450
600
900
M 112 HL Emulsion EC 11 40 As M 112 but high
binder content for
slow wet out
M 210 Polyester powder EC 10 30 300 Hand lay-up
450
600
M 210HL Polyester powder EC 1030 450 SMC. High binder
content
M 219 Polyester powder Araton EC 10 20 225 Gelcoat back-up.
300 Fast
450 wet out. Good
drape
M 222 Polyester powder Araton EC 10 20 450 Translucent
laminates
600 Hand lay-up, SMC
M 225 Polyester powder Araton EC 10 20 300 Translucent
laminates
450 Good wet strength
600 Domes, etc.

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REINFORCEMENTS 341

Table 14.12 (Continued)


Product Fibre
code BS/ISO length Weight
Supplier Binder Finish code (mm) (g/m2) Applications

Norsk Glassfiber A/S (contd.)


M 226 Polyester powder Araton EC 10 20 300 Winding. Good wet
450 strength

Owens-Corning Fiberglas ( UK) Ltd


M 705 Emulsion 300 Hand lay-up
375
450
600
750
900
M711 Powder 150 Hand lay-up.
Gelcoat back-up

Scandinavian Glasfiber Ltd


MK
10 AA Polyester powder Silane EC 11 25 450 Mechanical
processing
MK 12 Emulsion Silane EC 9 25 300 Hand lay-up
EC 9 50 450
600
900
1200

Silenka (UK) Ltd


CHT-mat Polyester powder Silane EC 1020 50 450 Continuous
50 600 processing,
SMC. High
translucency
H-mat Polyester powder Silane EC 1020 50 300 Hand lay-up
EC 10 40 50 450
50 600

N. V. Syncoglass S.A. UK Agents-Brandhurst Co. Ltd


Syncoglas make a wide range of mats consisting of woven, unidirectional and bi-directional
rovings backed by various weights of chopped strand mat. The range is too large to list.

TBA Industrial Products Ltd


Mat 71 225 General purpose.
300 Hand lay-up.
450 Fast wet out
600
Mat 74 225 General purpose
300 Soft, high bulk
450
600

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342 FRP TECHNOLOGY

Table 14.12 (Continued)


Mat 75 300 High integrity,
450 relatively
600 slow wet out
Mat 77 Silane 300 General purpose
450 Hand lay-up
600 Fast wet out
Mat 80 Polyester powder 300 Hand lay-up, good
450 clarity laminates
600
Mat 81 Polyester powder 225 Gelcoat back-up.
300 Fast wet out.
High clarity
Mat 90 Polyester powder Silane 450 For closed mould-
600 ing processes
Mat 91 Polyester powder Silane 450 Good dry strength
600 for winding
- ---~,-. --_.------ .. -----~~-.--------'"--.-- ,-----

Vetrotex (UK) Ltd


MI Solid. High EC 10 10 50 300 Contact moulding
solubility EC 1020 50 450 Fast wet out
EC 1040 50 600
M4 Liquid. High EC 10 40 50 300 Contact moulding,
solubility 450 good drape
600
M 113 Solid. High EC 10 10 50 225 Contact moulding,
solubility 300 fast wet out
375
400
450
600
EC 10 40 50 300
450
M 123 Solid. High EC 1040 25+50 450 Contact moulding,
solubility 600 fast wet out
UBIA 10 Solid. High EC 10 10 50 225 Translucent sheet,
solubility contact moulding
UBIA 20 Solid. High EC 1020 50 300 Transparent sheet,
solubility contact moulding
UBIA 40 Solid. High EC 1040 50 375 General purpose,
solubility 450 fast wet out
600
M 212 Solid. Low EC 10 10 50 450 Press moulding
solubility EC 10 40 50 300
450
600
M 312 Solid. Low EC 10 10 50} {300 Press moulding
solubility EC 1040 50 450
M 612 Special, medium
solubility
EC
EC
10 10
10 40
50}
50 {:gg SMC

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REINFORCEMENTS 343

Table 14.13 Woven glass cloths and rovings

CG.T. (Glass Fibre) Ltd


Woven rovings: weight (g/m2) 340, 490, 600, 800

F.G. Industries (UK) Ltd


F.G. Industries make a range of woven and unidirectional rovings bonded to
chopped strand mat. For details see under chopped strand mat (Table 14.12).

Fibreglass Ltd
Fibreglass Ltd supply Fabmat and Linrovmat made by F.G. Industries. For
details see under chopped strand mat (Table 14.12).

Fothergill & Harvey Ltd


Fothergill & Harvey manufacture a wide range of standard fabrics under the
trade name 'Tyglas'. These products are too numerous to list. Fabrics are available
in plain, satin, twill and mock leno weaves, in thicknesses ranging from 0·08 to
0·84 mm. Some of these are classified under BS 3396, others under US MIL-Spec.
MIL-C-9084. These are all woven from E-glass yarn.

Various finishes are available as follows:


Code Finish BS 3396
165 Heat cleaned Part 2 level H 1966
196 Amino silane
205 Methacrylatochromic chloride, Volan type Part 3 grade C 1970
208 Vinylsilane Part 3 grade S 1970
223 Methacrylatopropoxysilane Part 3 grade S 1970
256 Epoxysilane
These finishes are recommended with the following resin systems:
Resin Finish code
Polyester 205, 208, 223, 256
Epoxy 196, 205, 256
Melamine 196
Phenolic 196
Silicone 165
Also available are the following plain weave fabrics for electrical applications
and laminating. All are made from E-glass.
Weight Thickness Threads/dm
Code Weave (g/m2) (mm) Warp Weft
Y 487 Plain 37 0·038 205 197
Y 271 Plain 37 0·043 217 213
Y 693 Plain 51 0·051 252 181
Y 547 Plain 78 0·076 177 173
Y 336 Plain 108 0·08 236 228
Y 399 Plain 125 0·13 252 197
Tyglas woven rovings (E-glass)
Bidirectional
Y 709 Plain 200 0·23 67 63 BS 3749 RP6

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344 FRP TECHNOLOGY

Table 14.13 (Continued)

Y 700 Plain 270 0·25 47 43 BS 3749 RP8


Y 070 Plain 280 0·30 24 22
Y 706 2/1 Twill 406 0·43 39 35
Y 023 Plain 540 0·71 12 12
Y 073 Plain 550 0·53 24 22
Y 116 Plain 600 0·56 20 16 BS 3749 RP18
Y 621 Plain 675 0·69 32 24
Y 702 3/1 Twill 770 0·69 32 32 BS 3749 RT22
Y 920 Plain 815 0·84 20 16 BS 3749 RP25
Y 103 Plain 855 0·89 20 18
Unidirectional
Y 119 Plain 640 0·51 26 24
Y 996 Plain 776 0·63 32 20
A range of tapes is also available.

Tyglas staple fabrics


Y 199 2/2 braken 1675 1·78 142 53 E-glass
twill
Y 650 Plain 562 0·79 30 39 C-glass
Y 652 Plain 597 0·46 79 67 C-glass
Y 653 2/2 broken 1135 lAO 83 51 C-glass
twill
Y 654 2/2 broken 738 0·74 128 150 C-glass
twill
Y 655 2/2 twill 740 0·89 98 83 C-glass
Y 656 Plain 352 0·51 47 39 C-glass
Y677 2/2 broken 1630 1·68 142 53 C-glass
twill

Marglass Ltd
Woven ravings
269 Plain 270 0·3 47 43 Silane finish
263 Plain 339 0·33 61 55 Silane finish
280 Unidirec- 610 0·61 26 24 Silane finish
tional
271 Twill 750 0·58 32 32
316 Plain 610 0·59 16 12
364 Twill 646 0·61 31 24 Volan finish
266 Plain 848 0·69 20 16 Silane finish

Woven fabrics
7T Plain 186 0·15 142 126
IIOJ Mock lena 366 0·41 146 102
IllS 2/2 twill 329 0·28 118 118
113J Plain 176 0·18 59 67
116S 8 end satin 302 0·20 220 213

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REINFORCEMENTS 345

Table 14.13 (Continued)

116T 8 end satin 302 0·20 220 213


117S 4 shaft sa tin 441 0·38 189 118
123X Plain 136 0·13 252 157
127S Plain 186 0·15 142 126
128S Plain 241 0·23 142 102
138G Mock leno 288 0·38 106 106
155G 4 shaft satin 285 0·28 189 118
177S Plain 292 0·28 106 98
179 Plain 98 0·08 252 173
203 Plain 78 0·13 118 106
254 2/2 twill 186 0·15 147 126
274 Plain 200 0·18 165 126
277 Plain 142 0·13 135 176
284 8 shaft satin 865 0·69 165 142
344 Plain 230 0·65 173 83
378 4 shaft satin 288 0·23 189 118
383 Plain 127 0·13 220 142
397 Plain 240 0·12 87 173
----
Woven rovings and fabrics are available in the following finishes:
Code Finish BS 3396
P 701 Heat cleaned Part 2
P 702 Caramelised
P 703 Chrome Part 3 grade C
P 704 Vinylsilane Part 3 grade S
P 705 Aminosilane
P 734 Silane Part 3 grade S
P 738 Epoxysilane
These are suitable for use with resins as follows:
Resin Finish
Epoxide P 705, P 738
Polyester P 734, (P 704)
Phenolic P 705, P 734, P 738
Silicone P 701
Melamine P 705

Montedison Group. UK Distributor-Plastichem Ltd


Woven rovings, silane finish
Code Weave Weight Thickness Threads/dm
(g/m2 ) (mm) Warp Weft

0976 Plain 330 30 25


1296 Plain 400 35 23
1566 Plain 500 25 24
1864 Plain 600 25 18
2454 Plain 840 20 15

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346 FRP TECHNOLOGY

Table 14.13 (Continued)

Norsk Glassfiber. UK Agent-Brandhurst Co. Ltd


W 638 630 Woven roving,
Araton finish.
820 Good drape

N. V. Syncoglass S.A. UK Agent-Brandhurst Co. Ltd


A wide range of combined woven rovings and chopped strand mat materials are
available. Full details from UK Agents

TBA Industrial Products Ltd


Woven rovings
ECK6 Plain 200 0·20 67·0 63-0
ECK 8 Plain 280 0·30 47·3 43·3
ECK 10 Plain 360 0·35 61·0 55·2
ECK 12 Plain 400 0·45 39·4 31·5
ECK 18 Plain 600 0·55 19·7 15·8
ECK 24 Plain 830 0·85 19·7 11·8
ECK 25 Plain 830 0·85 19·7 15·8
ECK 27 Plain 920 0·90 19·7 9·8
ECK 16 Unidirec- 560 0·50 19·7 15·8 Weft/warp ratio, 5: I
tional
ECK 997 Unidirec- 510 0·52 19·7 14·8 Weft/warp ratio, 10: I
tional

Yarn based cloth


EK 121 Plain scrim 110 0·13 79 83
EK 141 Plain scrim 175 0·18 59 67
EK 161 Plain 240 0·23 142 102
EK 171 Plain scrim 200 0·21 71 71
EK 221 Twill 330 0·30 118 118
EK 241 Plain 330 0·38 63 55
EK 351 Twill 630 0·51 122 83
EK 401 Broken twill 440 0·38 189 126
EK 411 Broken twill 570 0·58 189 87
EK 451 Plain 330 0·46 81 79
Various glass yarn fibre tapes are also available.
.--~--~----

Vetrotex (UK) Ltd


Woven rovings
10 Plain 760 1·20 16 16
39 Plain 500 0·65 22 20
49 Plain 270 0·30 40 37
131 2/2 Twill 580 0·75 25 22
161 2/2 Twill 830 1·30 18 17
803 Plain 580 0·70 26·5 23
804 Plain 670 1·10 19 9
806 Plain 830 1·30 19 15·5

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REINFORCEMENTS 347

Table 14.14 Commercial carbon fibres

Courtaulds Ltd
Courtaulds 'GrafiI' carbon fibre, manufactured from polyacrylonitrile precursor,
is available in several different forms as follows:
Ultimate tensile Young's
Specific strength modulus
Fibre type gravity (GPa) (GPa)
Grafil A High strain 1·82 2·55 185-215
Grafil XA Super A, high performance 1·82 3·2 230
Grafil HT High tensile strength 1·76 3·27 220-250
Grafil HMHigh modulus 1·87 3·39 310-345
Grafil 0 Oxidised acrylic 1-35
Continuous filament tow
Generally supplied with o· 5% epoxy resin in lengths of 200- 2000 m. Each tow
contains 10000 filaments of approx. 8,um diameter.
A vailable sized with 2- 3% of either Shell Chemicals 'Epikote' 834 epoxide resin
or Scott Bader 'Crystic' 189 MV (polyester resin) or available unsized.
E = epoxy size S = surface treated
Grafil E/A-S; Grafil E/XA-S; Grafil E/HT-S; Grafil E/HM-S.
Short staple fibre
Available in all fibre types in lengths of 3 mm and 6 mm.
Unidirectional woven fabrics
Two types are available:
75/G Unidirectional Grafil continuous tow (warp) secured with a weft of 330
decitex glass or polyester yarn.
75/GE Unidirectional Grafil continuous tow alternated with 1200 tex E-glass
(warp) secured with a weft of 330 decitex glass or polyester yarn.
Grafil high modulus continuous ribbon
This consists of two, three, or five 10 000 filament tows of high modulus carbon
fibre in a knitted glass fibre tape 16 mm wide.
GrafilO
Grafil 0 is a new product recently introduced. It consists of an oxidised acrylic
fibre suitable for processing on normal textile machinery and is available as tow,
tops, yarn, woven or knitted fabrics. It can be used for making carbon/carbon
composites.

Hyfil Ltd
HYFIL-Torayca carbon fibre, manufactured from polyacrylonitrile precursor, is
available in only one fibre type.
Continuous fibre sheet
This consists of continuous collimated tows of 6000 filaments held together with
less than 0·5% of fine weft material, also carbon fibre.

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348 FRP TECHNOLOGY

Table 14.14 (Continued)

Fibre cross-section is off-round by a factor of 0·92.


Specific Tensile strength Tensile
Diameter gravity (GPa) modulus (GPa)
HYFIL-Torayca-
130 7·3 f.Lm 1·76 2·35 230
Normally supplied without surface treatment as HYFIL-Torayca-130 but also
available as: -130-S surface treated to improve fibre/resin bond
-130-C sized with 5% Epikote 828 (epoxide resin)
-130-S-C surface treated and sized
Chopped fibre
HYFIL-Torayca-130 dry carbon fibre is available in lengths of 4 mm, 6·3 mm,
12·5 mm and 25 mm.
Continuous filament aligned mat
HYFIL-Torayca-130-CFAM
This consists of two parallel plies of continuous filament HYFIL-T orayca -130
carbon fibre oriented 0°/90°, needled in the vertical direction to bond them together.
It has excellent drape and handling characteristics.
Fibre weight per unit area 275 g/m 2
Tape width 460mm
Tape length 2-50m
Uncompressed thickness 2mm
Moulded thickness (50% fibre volume) 0·31 mm
Woven tape
This is available as unidirectional carbon fibre tows with a weft of fine glass fibre:
alternate tows of carbon and E-glass with a weft of fine glass fibre and a square
weave of carbon fibre and a weft of 600 tex glass strands.
HYFIL-Torayca-130-C-Ol Unidirectional tape, carbon fibre warp, 44 tex glass
weft.
HYFIL-Torayca-Z tape-Ol Unidirectional woven tape. Warp: balanced array of
35 carbon tows, 36 E-glass tows 600 tex: weft: 44 tex
E-glass.
HYFIL-Torayca-Z tape-02 Hybrid woven tape-square weave. Warp: carbon
tows; weft: 600 tex E-glass.

Albright & Wilson Ltd.


Albright & Wilson supply Kureha carbon fibre products from Kureha Chemical
Industry Co. Ltd, Japan. These carbon fibres are made from a special hydrocarbon
pitch.

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Chapter 15

DOUGH AND SHEET MOULDING


COMPOUNDS AND PREPREGS

15.1 INTRODUCTION

With hot press moulding, injection and transfer moulding processes, the
most convenient procedure is to use a pre-formed moulding compound to
which all necessary ingredients have been added. This eliminates mixing
errors and enables faster production rates to be achieved.
Moulding compounds can be divided into three broad categories:
(i) Dough or Bulk Moulding Compounds (DMC, BMC).
These compounds consist of a resin system containing chopped
fibre reinforcement and a filler. Pigments may be added if required.
The resin system may be polyester, epoxide, phenolic,
melamine-formaldehyde, urea-formaldehyde or one of several
others.
(ii) Sheet Moulding Compounds (SMC).
These are invariably polyester resin based and consist of chopped
strand mat or chopped rovings impregnated with a filled resin
system, to which pigments and other additives have been added. As
its name implies it is supplied in sheet form.
(iii) Prepreg.
Prepreg is used to describe a reinforcement which has been
pre-impregnated with a resin system prior to use. Generally fillers are
absent from such a system. Whilst the term mostly refers to
reinforcement impregnated with an epoxide resin system, other
resin systems are encountered, such as certain types of polyester
resin and polyimide resins.
All three types of material require heat to soften and consolidate the resin
system and to effect cure. Products are available which can be processed by

349

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350 FRP TECHNOLOGY

either low or high pressure techniques. Low pressure techniques include


vacuum and pressure bag moulding and filament winding, whilst the high
pressure techniques used include hot press moulding, transfer and injection
moulding.
A word of warning has recently been issued by the British Plastics
Federation regarding the recycling of scrap thermoset-DON'T! This
could lead to product failure and prosecution under the proposed product
liability legislation. Scrap reground thermoset can only act as additional
filler, unlike scrap thermoplastic which can melt, flow and mix with new
material. Since the moulding compound has been formulated with the
optimum amount of filler, any additional filler (reground scrap) will only
produce a considerably inferior non-uniform moulding compound and
many scrap mouldings.
Broad details of the manufacture of these various materials and some of
the commercially available products are described below.

15.2 DOUGH AND BULK MOULDING COMPOUNDS


(DMC, BMC)

Dough and bulk moulding compounds were developed to enable a more


automated production process to be used for the hot press moulding of
polyester resin systems. In this way GRP components could be made to
compete with those manufactured from other materials.
Dough moulding compound consists of a dough-like mixture of resin,
fibre reinforcement and filler to which pigments and other materials may be
added. The reinforcement used may be glass, cellulose, cotton or other
fibrous material. Manufacture is usually carried out in a high shear Z-blade
mixer, after which the compound is often extruded into rope form. To
achieve a dry moulding compound a high filler loading is used.
In the UK and Europe, bulk moulding compound or BMC usually refers
to a compound based on isophthalic polyester resin, formulated to give
improved moulding quality. However, in the USA bulk and dough
moulding compounds are the same.
Polyester DMC is frequently made from conventional orthophthalic
polyester resins although other resins may be used for specific applications.
Moulding compounds are also available based on phenolic, epoxy, diallyl
phthalate and other resin systems.
Usually polyester DMC contains glass fibre strands, with fibre lengths

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DOUGH AND SHEET MOULDING COMPOUNDS AND PREPREGS 351

ranging from 3 to 12 mm and a fibre content of between 15 and 20%. These


limits are dictated by the high shear loads created during manufacture and
extrusion into usable form. A typical formulation is given below:
Parts by weight
Polyester resin 100
Benzoyl peroxide (catalyst) 1-2
Filler 200
Pigment dispersion 10-15
Glass reinforcement 45-70
Aluminium stearate (release agent) 3-4
Additional inhibitor may also be added to prolong the shelf-life of the
compound.
It is essential that all materials used are of consistent quality, particularly
the resin, so that a consistent moulding compound is produced. 1
The glass fibres are added once the other materials have been thoroughly
blended together, to reduce damage to the fibres. 2 This also makes mixing
easier.
With BMC the filler content may be reduced and a thickening agent such
as magnesium oxide added. In this way improved moulding quality and
finish can be obtained.
Low profile additives are available for polyester systems which, when
incorporated, reduce shrinkage on cure. These additives are thermoplastic
materials used at levels ranging from 5 to 20% of the resin, depending on
which additive is used (see also Section 9.3.6).
The filler is added to provide a dry compound. It also reduces cost,
shrinkage and pigment loading. The principal fillers used are calcium
carbonate (preferably surface treated), talc (magnesium silicate), dolomite
(calcium magnesium carbonate) and china clay. Particle size should be in
the region of 5 ,um for even filler distribution.
Mould release can be facilitated by the addition of an internal release
agent to the formulation. Typical materials used are metal soaps, for
example aluminium or zinc stearates.
It has been reported recently 3 that improved surface finish can be
obtained by coating the heated mould with a precatalysed polyester resin
powder prior to loading the BMC. This results in a smooth, durable finish
and eliminates post-moulding painting.
Table 15.1 (see pp. 359-63) lists some of the commercially available
dough and bulk moulding compounds.

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352 FRP TECHNOLOGY

15.3 SHEET MOULDING COMPOUNDS (SMC)

Following the introduction of dough moulding compounds it was seen that


several advantages could be gained, particularly in the manufacture of
large flat mouldings, if a compound was available in sheet form. Thus sheet
moulding compounds were developed. These invariably are based on
unsaturated polyester resin systems reinforced with chopped glass fibres,
although it is reported 4 that PPG Industries in the USA are manufacturing
SMC incorporating carbon fibres and carbon/glass fibres. Other hybrid
possibilities include carbon/aramid and glass/aramid composites.
SMC differs from DMC in that it has a higher fibre content, usually
20-35% and longer fibres, 21-55 mm. Mouldings made from SMC
therefore have somewhat higher mechanical properties.!
Low profile additives are frequently incorporated into the system to
reduce shrinkage during cure. This enables large flat mouldings free from
sink marks to be produced (see also Section 9.3.6).
Development work is reported 5 to be in hand on the use of unidirectional
carbon fibre facing plies over conventional SMC. This produces a
considerable increase in strength and rigidity of the moulding whilst
decreasing overall density. Another development, about which more will
undoubtedly be heard in the future, is thick moulding compound (TMC).6
This is similar to SMC but has a thickness of up to 2 in, with random fibre
distribution, against! in for SMC. It is claimed to yield mouldings with
more uniform properties.

15.3.1 Manufacture of SMC


A continuous polyethylene or Cellophane film is coated with a suitably
formulated polyester resin system into which is deposited a layer of either
chopped strand mat (450 g/m2) or chopped rovings. A second layer of
polyethylene film, similarly coated with resin system, is placed over the
reinforcement and the sandwich thus formed is passed through a series of
rollers to press the glass fibres into the resin and ensure thorough wetting of
the reinforcement by the resin. The sandwich is then wound into a roll and
allowed to stand while the resin thickens (Fig. 15.1).
In use the SMC is cut to the required shape and both layers of
polyethylene film are removed. The SMC can then be placed in the mould
and pressed.

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Polyethylene
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C'l
SMC wind-up

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354 FRP TECHNOLOGY

A typical formulation for a sheet moulding compound is given below:

Parts by weight
Polyester resin 100
t-Butyl peroxybenzoate (95%) 2-3
Zinc stearate (release agent) 3-4
Magnesium oxide (thickening agent) 2-3
Pigment dispersion 5-8
Filler 140-180
Thermoplastic additive 5-20
CSM or chopped rovings 50--100

Most manufacturers supply resins specially formulated for SMC


production. These resins need to be of low initial viscosity to ensure
thorough wetting of the glass reinforcement. However, once the glass has
been wetted the resin must thicken so that a relatively tack-free easy to
handle sheet of moulding material is produced. This thickening is usually
brought about by the addition of a thickening agent such as calcium oxide
or magnesium oxide to the resin. This reacts with the resin causing a large
increase in viscosity shortly after its addition. For consistent results the
water content and other properties of the polyester resin must be tightly
controlled. 7 The other ingredients used must also have consistent
properties.
The filler is added to reduce the amount of resin required per moulding
and hence to reduce cost. It also helps to reduce shrinkage of the resin
system and the amount of pigment needed. Calcium carbonate, preferably
surface treated, is frequently used as filler although talc (magnesium
silicate), dolomite (calcium magnesium carbonate) or china clay may also
be used. Filler particle size should preferably be around 5 11m to give good
distribution in the resin and prevent a filtering effect by the glass mat during
moulding.
To assist mould release, once the mould has been run-in, an internal
release agent is added to the formulation. A typical internal release agent
would be zinc stearate, added at about 3-4% based on the resin. Care is
needed in the selection of an internal release agent if the moulding is to be
painted or bonded with adhesive.
Where large flat panels are to be moulded, conventional SMC can result
in sink marks on the surface. To overcome this problem considerable
development work has been undertaken on the addition of thermoplastic
additives to the formulation (see Section 9.3.6). Today many low

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DOUGH AND SHEET MOULDING COMPOUNDS AND PREPREGS 355

profile/low shrink sheet moulding compounds are available, some of which


exhibit zero shrinkage on cure.
Table 15.2 (see pp. 364-5) lists some of the commercially available sheet
moulding compounds.

15.4 PREPREGS

Prepregs consist of woven fabric, continuous unidirectional fibre reinforce-


ment or random chopped fibre sheets impregnated with a resin system.
These differ from sheet moulding compounds in that fillers, pigments and
other additives are rarely, if ever, present. Most prep regs are based on
epoxide resin systems although polyester, polyimide and other resin based
prepregs are available. Reinforcements used include glass, carbon and
aramid fibres.
One of the major outlets for epoxide resin based woven glass cloth
prepregs is in the production of printed circuit boards for electronic
applications. Epoxide resin systems are used since, apart from good
electrical properties, they provide high mechanical strength, good dimen-

Fig. 15.2. A typical printed circuit board viewed/rom the component side.

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356 FRP TECHNOLOGY

sional stability, good adhesion to copper foil, fire retardancy (certain


grades), good colour, low moisture absorption and resistance to heat
ageing up to reasonable operating temperatures. They also have good
resistance to the etching chemicals, cleaning solvents and fluxes used to
prepare the finished boards. A typical printed circuit board viewed from the
component side but showing the copper foil pattern through the board, is
shown in Fig. 15.2.
Other outlets for prepregs include filament winding and pultrusion,
where both woven and unidirectional prepregs are used, and the manufac-
ture of aircraft components and sports goods. For many aircraft com-
ponents unidirectional prepregs are used so that, by suitable orientation of
the fibres during lay-up, composites can be produced with maximum
strengths in any particular design direction. By this means substantial
weight saving can be obtained.
Unidirectional prepregs are often made with resin systems which remain
tacky so that when each layer of prepreg has been placed in the required
position light pressure will cause it to stick to the layer underneath and
prevent disorientation as subsequent layers are added.

15.4.1 Manufacture of prepregs


Two methods of manufacture are used: (i) from resin solution and (ii) from
solvent-free resin systems.

( i) Preparation from solution


Here the fibre reinforcement (woven cloth, rovings, etc.) is drawn
through a solution of the resin system contained in a bath and then
through a doctor blade or metering roller assembly to control resin pick
up. The impregnated reinforcement then passes through a vertical
heating zone to evaporate the solvent and partially advance the cure of
the resin system. After this the prepreg is cooled and either wound into a
roll or cut into sheets. Tacky prepregs are sandwiched between two
layers of release film, such as silicone impregnated paper or polyethylene
film, prior to winding or cutting into sheets. A typical treater for
producing prepreg is shown schematically in Fig. 15.3.
Either liquid or solid resins may be used, generally dissolved in a low
boiling solvent, which also dissolves the curing agent. Two of the
solvents which are frequently used are acetone and methyl ethyl ketone
(MEK), although 2-methoxyethanol has to be used with Dicy cured
epoxide resins.

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DOUGH AND SHEET MOULDING COMPOUNDS AND PREPREGS 357

Reinforcement

Nip rollers

~~~~--ReSin bath

Fig. 15.3. A typical vertical treater for making prepregs.

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358 FRP TECHNOLOGY

(ii) Preparation from solvent-free systems


Prepregs made from solvent-free resin systems are produced in a
similar way to sheet moulding compounds in that the reinforcement is
sandwiched between two layers of resin system applied to suitable release
film. With epoxide resin systems heated rollers may be used to melt or
lower the viscosity of the resin and ensure adequate wetting of the fibres
by the resin system.

Whilst with polyester sheet moulding compounds and prepregs the


polyester resin is thickened by adding a thickening agent, such as
magnesium oxide, with epoxide resin systems this is usually accomplished
by advancing the cure of the resin system with heat until either a slightly
tacky or tack-free prepreg is obtained. Cooling the prepreg to room
temperature then virtually stops any further cure from taking place. Such
prepregs have shelf-lives of from several weeks to several months at 20 C,
G

depending on the particular curing agent used.


Although conventional polyester resins containing styrene could be used
for prepreg production, the volatility of the styrene would result in a short
storage life. Because of this most polyester prepregs contain diallyl
phthalate as monomer. Here, volatility is no longer a problem.
The advantage claimed for solvent-free impregnation is that superior
composites can be produced with consistent properties. With solvent based
prepreg systems, particularly those using carbon fibre as reinforcement,
there is always the possibility that some solvent entrapment may occur and
result in composites with inferior properties. Experience has shown that in
most cases this fear is unfounded.
Another advantage of solvent-free systems is the cost saving in not
having to use a solvent which can rarely be adequately recovered after use.
With gas fired treaters the waste solvent is burnt along with the gas to
provide heating to dry the prepreg.

15.5 COMMERCIAL PRODUCTS

Some of the commercially available products are listed in this section.


Table 15.1 lists some commercial dough and bulk moulding compounds;
Table 15.2 some sheet moulding compounds; Table 15.3 some commercial
prepregs.

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Table IS.1 Some commercial dough and bulk moulding compounds
Mould Tensile Flexural Flexural
Product Reinforce- Specific shrinkage strength strength modulus Water
code ment gravity (%) (MPa) (MPa) (GPa) absorption Comments

British Industrial Plastics Ltd (mg) All polyester resin based


Type G Glass 1·73 0·15 41 92 9·9 20 General purpose, low shrink
Type GjB Glass 1·73 0·15 41 92 9·9 20 General purpose, reduced flammability
Type E Glass 1·6 0·15 25 65 9·0 8 General purpose, low specific gravity
Type KjX Glass 1·67 0·3 45 71 7·5 30 General purpose, rope form
Type Nl Glass 1·71 None 55 105 8·9 40 Nil shrinkage
Type N7jB Glass 1·74 None 50 80 9·3 35 Nil shrinkage, reduced flammability
Type N3jX Glass 1·68 None 48 75 7·5 35 Rope form similar to Nl
Type N4jB Glass 1·80 0·05 41 90 8·5 30 Reduced flammability, similar to N3jX
Type P Glass 1·95 0·03 30 70 10·0 35 Fast cure
w
v. Type PjB Glass 1·95 0·03 30 70 10·0 35 Fast cure, reduced flammability
\0
Type G7jB Glass 1·73 0·15 40 90 9·5 20 High power, arc resistant, reduced
flammability

Test methods, BS 2782 509A 100B 301A 304E 302D 502G

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Ciba-Geigy Plastics and Additives Company (%)b
Araldite
NU 471 1·95 0·6-0,8 80 0·03 Epoxy based mineral filled, CjT
NU 475 Glass 1·8 0,6-0·8 110 0·04 Epoxy based glass fibre filled, CIT
NU 480 Glass 1·8 90 0·04 Epoxy based, I
NU 481 1·8 90 0·04 Epoxy based mineral filled, I
NU 482 Glass 1·9 80 0·03 Epoxy based, low viscosity, I
Neonite
EG 60 30% glass 1·75 0·3 100 180 16 0·07 Epoxy based, CjT
EG61 30% glass 1·75 0·3 100 180 16 0·07 Epoxy based, CjT
EG 62 65% glass 1·78 0·05 140 300 25 0·08 Epoxy based, C
DG 10 40% glass 1·82 0·05 100 200 18·5 0·07 Diallyl phthalate based, CjT
Table 15.1 (Continued)

Mou/d Tensile Flexural Flexural


Produc/ Rein[orce- Specific shrinkage strength strength modulus Water
('Ode melll gravily (%) (MPa) (MPa) (GPa) Comments
ahsorptlOn

Ciha-Geigy Plastics and Additives Company (con/d.)


Ampal (mg)'
PG 310 Glass 2·1 0'2-0'5" 55 <45 Polyester based, CITII
PG 315 Glass 2·0 0,5-0·6" 45 < 30 Polyester based, self-extinguishing, CITII
PG 350 Cellulose 1·75 0·9-1'0- 65 < 300 Polyester based, ClTII
PM 360 Glass 1·85 0·7-0·8" 65 < 100 Modified polyester based, CITII
PM 380 Glass 2·1 0,4-0,6" 65 < 140 Polyester based, CITII

Test methods, DIN 53479 "53464 53452 53452 bR 62


ISO R 527 c53472
w
0-
0 C = compression moulding; T = transfer moulding; I = injection moulding.

Freeman Chemicals Ltd (mg)


Freemix All po/yes/er resin based. All suitable for compre-

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ssion, transfer or injeclion moulding
43-2021 Glass 1·7 0·15 45 95 7 20 High strength, all colours but white
43-2026 Glass 1·8 Nil 45 100 9 25 Self-extinguishing, limited colours
43-2029 Glass 1·85 0·1 50 90 8·5 25 Fire retardant, limited colours
43-2035 Glass 1·8 0·05 50 95 8·5 20 Low shrink, all colours
43-2065 Glass 1·7 0·02 50 110 7 10 Bisphenol A, chemical resistant
43-2122 Glass 1·85 0·05 45 90 9 20 Low shrink, limited colours
43-2125 Glass 1·8 0·15 45 90 8·5 15 Electrical grade, all colours
43-2137 Glass 1·85 0·1 35 85 7 25 Fast cure, white, limited colours
43-2140 Glass 1·8 0·2 55 120 10 15 High strength, electrical, all colours

Test methods, BS 2782 509A 106A 30lA 304A 302D 502F


PermaN Gloucester Ltd (mg)
Permaglass All polyester resin based. Mechanical properties
listed are highest values quoted in data sheets
K509/442 Glass 1·71 0·15 69 110 10·7 13-18 Contains asbestos
K509/463 Glass 1·72 0·15 65 110 II 11-18 Self-extinguishing, contains asbestos
K509/602 Glass 1·73 0·2 65 124 10 \5-22 Contains asbestos
K515/1542 Glass 1·88 +0·12" 53 101 7·7 49·5
K519/479 Glass I·M!" 0·15 62 110 9·6 16-25 Self-extinguishing, contains asbestos
K525/IOO Glass 1·83 0·02 35 93 8·7 10-20 Fire retardant, stress free
33/DP/I Glass 1·7 69 138 8·2 10-90 Electrical grade
33/DPR/2 Glass 1·7 62 138 8·2 10-30 Flame retardant

Test methods, BS 2782 30lA 304A 502F

"Expansion

..., Premix Fibre-Glas Ltd (%)


'" Premi-glas All polyester based compounds
1000 BMC 15% glass 2·0 0·3 34 96 0·5 Low cost, high strength
30% glass 2·0 0·3 48 138 0·5
1100 BMC-

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LS 15% glass 1·85 0·1 27 96 0·2 Low cost, high strength
22% glass 1·85 0·1 34 110 0·2
30% glass 1·85 0·1 41 124 0·2
2000 BMC 15% glass 1·9 0·3 34 103 0·3 Arc resistant, electrical
30% glass 1·95 0·3 41 124 0·3
2100 BMC-
LS 15% glass 1·8 0·1 34 90 0·2 Arc resistant, electrical
22% glass 1·82 0·1 41 103 0·2
30% glass 1·85 0·1 48 117 0·2
Also available as CR-SX series
2003 BMC 10% glass 1·9 0·3 21 83 0·\ Appliance/business machines
15% glass 1·9 0·3 27 96 0·1
22% glass 1·92 0·3 34 110 0·2
30~{; glass 1·95 0·3 41 124 0·2
Table 15.1 (Continued)

Mould Tensile Flexural Flexural


Product Reinforce- Specific shrinkage strength strength modulus Water
code ment gravity (!:,) (MPa) (MPa) (GPa) absorption Comments

Premix Fibre-Glas Ltd (contd.)


2103 BMC- (%)
LS 15% glass 1·8 0·1 34 90 0·2 Appliance/business machines
22% glass 1·82 0·1 41 103 0·2
30% glass 1·85 0·1 48 117 0·2
3000 BMC 15% glass 1·9 0·3 34 103 0·1 Non-track, arc resistant
30% glass 1·95 0·3 41 124 0·1
3100 BMC-
LS 15% glass 1·8 0·1 27 90 0·2 Non-track, arc resistant
22% glass 1·83 0·1 34 110 0·2
30% glass 1·85 0·1 48 117 0·2
t..l
a- 4000 BMC 15% glass 1·78 0·3 27 103 0·15 Bisphenol A, corrosion resistant
N
22% glass 1·79 0·3 34 117 0·12
30% glass 1·85 0·3 41 151 0·12
4100 BMC-
LS 15% glass 1·74 0·1 27 103 0·15 Bisphenol A, corrosion resistant

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22% glass 1·77 0·1 34 117 0·15
30% glass 1·79 0·1 41 144 0·15
6000BMC 5% glass 1·95 0'2-0'4 20 55 0·1 Phenolic replacement
10% glass 1·89 0·2-0·4 27 69 0·1
15% glass 1·85 0·2-0·4 34 83 0·1
20"10 glass 1·82 0·2-0·4 41 103 0·1
6100 BMC-
LS 5% glass 1·87 0·1 20 55 0·1 Phenolic replacement
10% glass 1·80 0·1 27 69 0·1
15% glass 1·79 0·1 34 83 0·2
20% glass 1·75 0·1 41 103 0·2
7100 BMC 15% glass 1·78 0·02 27 103 Low profile, automotive
22% glass 1·80 0·02 34 117
Primi-ject
1000 series 5% glass 2·05 0-2-0'5 20 55 0·1 Phenolic replacement for existing tooling
10% glass 2·02 0'2-0'5 27 69 0·1
15% glass 1·90 0'2-0'5 34 83 0·1
20% glass 1·85 0·2-0·5 41 103 0·1
lJOO series 5% glass 2·03 0·1 20 55 0·2 Phenolic replacement for existing tooling
10% glass 2·00 0·1 27 69 0·2
15% glass 1·85 0·1 34 83 0·2
20% glass 1·80 0·1 41 103 0·2

Test methods, ASTM D-638 D-790 D-570


w
a-.
w Moulding Powders Ltd (mg)
Synmold All based on Xylok resins
SX 563 Glass 1·7 0·1-0·3 55 80 5-10 Glass filled
SX 564 1'7 0·1-0·3 50 70 5-10 Silica filled

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SX 566/9 Asbestos 1·7 0,1-0,3 50 70 5-10 Asbestos filled
SX 644 Glass 1·81 0,2-0,3 55 75 5-10 Glass/mineral filled
SX 650 Glass 1·75 0·1-0·3 55 80 5-10 Glass filled
SX 652 Glass 1·77 0·1-0·3 50 75 5-10 Glass/mineral filled

Test methods, BS 771/1959


BS 2782 502F
Table 15.2 Some conwnercially available sheet moulding compounds
Mould Tensile Flexural Flexural Water
Product Reiriforce- Specific shrinkage strength strength modulus absorption
code ment gravity (%) (MPa) (MPa) (GPa) (%) Comments

Freeman Chemicals Ltd


Flomat All polyester based compounds
506 General purpose
511 For timber facing
516 25% glass 68 193 9 Fire retardant
518 25% glass 68 172 9 Fire retardant, corrosion resistant
521 Automotive, good finish
523 20"10 glass 55 137 8 General purpose, max_ temp_ 140°C
534 22% glass 65 154 10 Low shrink, fire retardant
535 25% glass 68 193 12 Low shrink, high gloss, up to 150°C
536 35% glass 75 227 14 High impact, up to 130°C
..., 539 Low shrink, good flow
.j>. 541 Low shrink; fire retardant-Class I BS 476 pt 7
'"
Test methods, BS 2782 30lA 304A 302D

Premix Fibre-G/as Ltd All polyester based compounds

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1200 SMC- 15% glass 1-85 0-1 41 124 General purpose, low shrink
LS 22% glass 1-85 0-1 62 158
30% glass 1-85 0- I 96 200
2200SMC- 15% glass 1-75 0-1 41 110 0-3 Electrical grade, arc resistant
LS 22% glass 1-77 0-1 55 124 0-3
30% glass 1-80 0-1 69 138 0-3
2203 SMC- 15% glass 1-75 0-1 41 110 0-3 Appliance, business machine grade
LS 22% glass 1-77 0-1 55 124 0-3
30% glass 1-80 0-1 69 138 0-3
3200 SMC- 15% glass 1-75 0-1 41 lIO 0-3 Arc resistant, non-track
LS 22% glass 1-77 0-1 55 124 0-3
30% glass 1-80 0-1 69 138 0-3
4200 SMC- 15% glass 1-75 0-15 41 110 0-15 Bisphenol based, corrosion resistant
LS 22% glass 1-78 0-15 55 130 0-12
30% glass \-80 0-15 82 151 o 12
""/0 glass 1'~V V'V" O~ 1'14 V·.O
30% glass 1·85 0·02 86 172 0·25

Test methods, ASTM D·638 D·790 D·570

Scott Bader Co. Ltd All polyester based compounds


M 125 25% glass 1·75 60-80 150-170 8-10 0·2 General purpose
M 225 25% glass 1·78 60-80 150-170 9-11 0·15 Reduced fire hazard, HET acid
based, medium/low shrink
M 325 25% glass 1·80 50-70 130-150 8-10 0·16 Automotive grade
M 525 25% glass 1·78 60-80 155-175 8-10 0·19 Furniture grade
M825 25% glass 1·70 55-75 140-160 8-10 0·12 IsophthaJic based, flexible grade
M 925 25% glass 1·78 60-80 150-170 8-10 0·23 Chemical/electrical grade
NOTE: Each series of products is available with glass contents of 20%,25%, 30% and 35%, the second and third figures indicating the glass content
Various other types are available in each series as foJlows:
M 100 series M 100 General purpose
w M 100 B High impact grade
'"v. M 100 D Toughened grade
M 100 M Super white only

M 200 series M 200 Medium shrink grade BS 476 pt 7 class II


M 200 A Medium shrink grade. HET acid based, reduced fire hazard BS 476 pt 7 class I

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M 200 B Low shrink grade BS 476 pt 7 class I

M 300 series M300 Minimal shrinkage, automotive grade


M 300 B Reduced fire hazard
M 300D Alternative to M 300
M 300G Alternative to M 300 B

M 500 series M 500 Furniture grade readily pigmented


M 500 A Furniture grade, reduced fire hazard

M 800 series M 800 Flexible grade, medium shrinkage, based on isophthalic polyester

M 900 series M 900 Chemical/electrical grade. Low voltage


M 900 A Mild chemical environment grade
M 900 B Bisphenol grade for corrosion resistance
M 900 C High voltage electrical grade
Table 15.3 Some commercial prepreg systems
w
g::
Ciba-Geigy Plastics & Additives Company
Ciba-Geigy make a wide range of sheet adhesives, prepregs, honeycombs and laminates. Details of some of these products are
given below.
Fibredux long life prepregs
Unidirectional glass, carbon or aramid fibre laminating Fibredux 913-low temp. curing epoxy
prepregs Fibredux 914-high temp. operating epoxy
Woven glass fibre adhesive prepreg Fibredux 916-low temp. curing flame retardant epoxy
Fibredux 917-speciallow smoke, fire, toxicity phenolic
Fibredux 918-high temp. operating epoxy
Unidirectional carbon, glass or aramid or woven glass fibre Fibredux nO-versatile low temp. curing epoxy
adhesive prepreg ~
'"Ii
Typical cured mechanical properties of Type 2 carbon fibre/epoxy composites

Resin system Flexural strength (GPa) Flexural modulus (GPa) ILSS (MPa)

Fibredux 913 C 1·50 130 92



Fibredux 914 C 1·52 131 100 ><:

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Courtaulds Ltd
Continuous unidirectional carbon fibre prepreg tape is available based on all four grades of carbon fibre manufactured by
Courtaulds Ltd: Grafil A-S; Grafil HT-S; Grafil HM-S; Grafil XA-S.

Resin systems

Epikote 21O/BF 3 400 Epoxy for use over the temperature range - 40°C to + 150°C.
Cure: 1 h at 170°C
HC 3501 epoxy For use over the temperature range - 4WC to + 180°C.
Cure: i h/175°C
Hyfil Ltd §
Continuous unidirectional carbon fibre prepreg tape made from HYFIL-Torayca-130 carbon fibre. ~
Resin systems Dwell time Cure time Post cure ~I:)

R7B Epikote 828/DDS/BF 3 400 4j min/160°C 30 min/160°C 60 min/170°C


R12A Epikote 231/DX 137 2-4 min/120°C 60 min/120°C 60 min/120°C ~
R8A Epikote 828/DDS 45 min/150°C 60 min/170°C 120 min/180°C
+ 120 min/200°C §
R7L Blend of R 7 B & R 8 A 1-3 min/150°C 30 min/150°C 60 min/160°C b
R13B Araldite nO/DDS/BF 3 400 15-20 min/140°C 180 min/180°C
R14A Araldite LY558/BF 3 400 15 min/120°C 60 min/165°C 120 min/180°C ~
R 16A Solventless polyester 10 min/100°C 30 min/100°C 8
1. Carbon fibre prepreg This is manufactured from solventless resin systems.

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Availability: 200 m continuous tape}
~
moulds to 60% carbon fibre volume ~V>
1·2 m sheets >
Z
2. Glass fibre prepreg This is manufactured from a lightweight square weave glass cloth from solventless resin systems. I:)
Availability: 300 m rolls based on 0·025 mm or 0·04 mm thick cloth
3. Unidirectional glass prepreg This is manufactured from E-glass rovings from solventless resin systems. ~
"C
Availability: 200 m rolls }
Resin system R 7 H ~
1·2 m sheets

\.»
0\
-..J
\;J
0'1
00

Table 15.3 (Continued)


Typical cured properties of carbon fibre composites, 60% fibre volume

Resin code Prepreg shelf-life Tensile Tensile ILSS Comments


(weeks) strength modulus
(GPa) (GPa) (MPa) '!1
-20°C + 20°C ~
'C
;;l
R7B 26 8 1·2 131 65 Good all-round system (')
R8A 26 1 1·3 131 80 Good properties up to 170°C ::t:
Z
R7L 26 13 1·2 131 70 Fire retardant system 0
t""
R12A 13 1 1·2 131 70 Low temp. cure
R13B 13 1 1·3 131 80 High performance system, up to 180°C 8-<

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R14A 26 13 1·2 131 60 Epoxy novolac system, low strain. Not
recommended for crossplies greater than
± 30'
Rl6A 26 60 Polyester system
Fothergill & Harvey Ltd
Carboform preimpregnated carbon fibre is supplied in the following forms based on high modulus, high strength and
intermediate modulus fibres.
Sheet Unidirectional-standard sizes up to 1220 x 920 mm; nominal moulded ply thickness, 60% fibre volume, d
0·127mm. ~
Tape Unidirectional-rolls up to 100 m long; widths from 19 mm to 500 mm. @
Woven fabric Range available based on plain weave fabric, 5-end satin and 8-end satin fabric. >
~
Code Weave Weight Thickness Threads/dm
(g/m2 ) (mm) Warp Weft
!9
~
A 001 8-end satin 374 0·40 94 91 3:
A 002 Plain 192 0·25 47 47 ~t""
A 004 5-end satin 283 0·30 70 70 d
Z
Based on Torayca T300, 3000 filament carbon fibre yarn. o
83:
Typical mechanical properties with code 69 resin

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Code Test Flexural Flexural Tensile ILSS
strength strength (;l
direction modulus
(GPa) (GPa) (GPa) (MPa)
i
~
d
A 001 Warp 0·96 65 0·55 62 ."

Weft 0·93 62 0·52 62 ~


."
A 002 0·86 62 0·55 58
A 004 Warp 0·91 60 0·54 66 ~
(;l

Weft 0·86 57 0·50


Also available is a design, moulding and finishing service for composite materials based on carbon, glass and Kevlar prepregs \.H
0"1
and SMC and DMC. \0
W
-J
o

Table 15.3 (Continued)

Product Resin type Shelf-life Maximum Composite properties, 60% carbon fibre volume,
code ( weeks) operating Type 2 fibre, 20 c C
- ISoC + 20°C temp. ('C)
Flexural Flexural ILSS Comments
strength modulus
(GPa) (GPa) (MPa)

69 Modified epoxy 26 4 180 1·72 131 100 High temperature "rj


~
resistant system "C
o-j
87 Modified DGEBA epoxy 26 4 150 1·50 135 65 General purpose system m
("l
91 Modified DGEBA epoxy 26 1 90 1·55 130 75 Low temperature cure. :z::
1200 e z
0
92 Epoxy 26 90 1-40 124 70 Low temperature cure, t'"
1200 e 8-<
94 Epoxy 52 4 80 1-60 120 75 Low temperature cure,

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125°e, modified flow
control
95 Epoxy 52 4 80 1·70a 120' 90 a Low temperature cure,
0
120 e
Micanite & Insulators Co. Ltd
This company manufactures a range of prepregs to customer requirements.

a Type 3 fibre.
DOUGH AND SHEET MOULDING COMPOUNDS AND PREP REGS 371

REFERENCES

I. Brown, B. and Bowyer, G. (1978) Paper 15, Reinforced Plastics Congress 1978,
Brighton, UK.
2. Burns, R. and Pennington, D. (1978) Paper 16, Reinforced Plastics Congress
1978, Brighton, UK.
3. Anon. (1979) Modern Plastics International, May, 11.
4. Anon. (1978) Modern Plastics International, October, 52.
5. Anon. (1978) Modern Plastics International, May, 62.
6. Anon. (1980) Modern Plastics International, January, 28.
7. Seamark, M. J. (1978) Paper 26, Reinforced Plastics Congress 1978, Brighton.
UK.

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Chapter 16

FILLERS AND PIGMENTS

16.1 INTRODUCTION

Although fibre reinforced materials primarily comprise a resin system plus


a fibrous reinforcement, other components are frequently added to
produce decorative effects, aid handling, improve moulding characteristics
and cured properties. These materials include fillers, pigments, thixotropic
additives and fire retardant additives, all of which are dealt with in this
chapter. Other additives such as internal lubricants, light stabilisers and
core materials are dealt with in Chapter 17.
Fillers are used to modify the properties of resin systems either during
processing or in the cured state or perhaps both. Often the primary reason
for adding a filler is to reduce the cost of the system; however, invariably,
other properties are modified as well. To maximise the benefits of using a
filler, the correct type and grade needs to be chosen with care, taking into
account the moulding process and end use of the mOUlding.
Almost any powdered material may be used as a filler; indeed such
materials as crushed egg shells and ground coconut shells have been used.
The most common fillers, however, are those obtained from natural
deposits such as chalk, slate, quartz or clays. These may be wet or dry
ground to produce suitable powders, or subjected to chemical treatments to
purify them. Other fillers used include metal powders and glass spheres and
flakes. These latter fillers are invariably more expensive than the natural
mineral fillers but can offer considerable advantages in certain appli-
cations. One disadvantage that most fillers have is a tendency to trap air in
the resin system, which can result in porous mouldings. This can usually be
overcome by careful mixing.
In the main the factors which govern filler selection are cost, density,
resin absorption by the filler, filler loading and particle size distribution.
372

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FILLERS AND PIGMENTS 373

Additional factors which need to be taken into account are the effect of the
filler on the properties of the liquid and cured systems. Some of these
factors are listed below although not all are applicable to each filler.
(i) The effect of the filler on the liquid resin system.
Increases viscosity.
Increases bulk.
Produces thixotropy.
With polyester resins-accelerates or retards cure.
Reduces exotherm.
Abrasive fillers cause wear on moulds during processing.
(ii) The effect of the filler on cured resin properties
Reduces cost.
Renders opaque-most fillers.
Increases impact resistance.
Decreases flexural strength.
Increases rigidity.
Reduces shrinkage.
Reduces water absorption.
Increases abrasion resistance.
Modifies electrical and thermal properties.
Reduces flammability.
Raises heat deflection temperature.
Abrasive fillers make machining difficult.
Several hundred fillers are available commercially, many of which are of
specialised interest only. Those which find widespread use are the various
grades of calcium carbonate, quartz and silica flours, talc and various clays
such as china clay.
Most fillers have a particle size within the range 0·015).lm up to 80 ).lm.
The smaller the particle size the greater the increase in viscosity of the resin
system for any given filler loading. The smallest particle size fillers, such as
silica aerogel or fumed silica (0·015 ).lm), are used at about 5% addition to
produce thixotropy. The coarser fillers may be used at up to 600% addition.
Where fillers are used in laminating systems it is preferable that particle
size is kept below 10 ).lm so that the filler is not filtered out by the glass fibres
during processing. This is particularly true with sheet and dough moulding
compounds and liquid injection systems.
With non-laminating applications such as flooring, graded silica sand is
frequently used as filler. Here, particle size distribution may range from
about 53 ).lm up to 1-2 mm and filler to binder ratios of 7: 1 are common.

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Table 16.1 Some properties of fillers

Coefficient
Oil of thermal
Bulk absorption expansion
Specific density Hardness value ( in/in Particle
Filler gravity (g/ml) (moh) (g/IOO g) cC x 106 ) pH shape Principal uses

Aluminium hydroxide [AI (OHhl 2·4 0·4-1·3 2·5-3·5 20-40 8'5-9'5 Irregular f
Aluminium oxide (alumina) 3·7-4·0 1'3-1·6 9 10-50 7 3·6 Irregular a, d, S, i
Aluminium silicate 2·6 0·6-1·6 2-20 Platelike c, p, s
Antimony trioxide 5·3-5·9 1·3-1·6 10-15 2-3 Irregular f
Armospheres 0·6 0·4 Spherical I
Barium sulphate 4·3-4'5 2'5-4'5 5-15 4-5 Irregular p
Barium titanate 5,5-5·9 1·3-1·6 16-19 Irregular d
Bentonite 2-6-2·7 30-55 8'5-10 Platelike t
w Calcium aluminium silicate 2·65 6,0-6,5 g
~ Calcium carbonate-ground 2·7-208 0·8-0·9 3·0 5-15 0'5-0'9 9-10 Irregular g, p, s
- precipitated 2-6-2·7 0·8-0·9 3·0 15-60 0·5-0·9 9-10 Irregular g, p, s
-coated 2·6-2'8 0·8-1·0 3·0 5-15 0'5-0·9 9-10 Irregular g, p, s
Calcium magnesium carbonate

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(dolomite) 2·8-2·9 1·1-1·3 g
Calcium silicate 208-2·9 4'5-5'5 20-45 9-10 Acicular g
Calcium sulphate 2·4-2·9 0·6-1·0 2·0-3·5 5-10 3-5 Irregular g, s
China clay (kaolin) 2·5-2-6 1-2 25-45 4-8 Platelike p, t
Fillite 0,3-0,7 Spherical I
Glass-solid spheres 2·48 1·5 5·8 8·5 Spherical c, g
- hollow spheres 0·15-0'38 Spherical I
- flakes, C-glass 2-45 Platelike c
Graphite 2·2 0'6-4·0 Platelike b, e, p
Iron oxides 304-5·1 Irregular p
Kieselguhr 1·8-2·3 80-125 5'5-7
Lead oxides 8·8-9-4 Irregular p
Magnesium aluminium silicate
(Fuller's earth) 1-8-2-5 0-3-0-6 30-50 Irregular
Magnesium carbonate 1-8-2-8 0-15-0-6 3-0 70-80 10-4 Irregular f, p
Magnesium oxide 2-7-3-7 55-70 10-5 Irregular t
Mica 2-7-304 0-3-0-4 2-5-3-0 50-70 18-27 7-8 Platelike c, d, i
Phenolic microballoons 0-2-0-25 0-1-0-15 Spherical I
Pumice 2-2-2-3 8-9 I
Q-cell Spherical I
Silica 2-6-2-7 1-0-2-0 7 15-40 0-15-3 7-8 Irregular a, g, i, S
Slate 2-9 0-7-0-9 25-45 6-7 Irregular a, g
Talc (magnesium silicate) 2-4-3-0 1-0-2-0 1-2 20-45 7-9 9-10 Platelike g
Vol
...., Titanium dioxide 3-9-4-2 6-7 20-30 7-1-9-2 Platelike p
v. Vermiculite 2-2-2-6 0-1-0-2 6-5-7-5 Expanded I
Plates
Zinc oxide 5-6-6-0 10-15 Platelike p
Zirconium oxide 5-0-7-0 1-2-1-4 Irregular d

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Zirconium silicate (zircon) 4-6 1-7-1-9 3-0 Irregular a, c, d, i, S

a = abrasion resistance b = thermal conductivity c = chemical and moisture resistance


d = dielectric properties e = electrical conductivity f = flame retardancy
g = general purpose i = improves electrical and thermal
properties 1 = lightweight filler
p = pigmentation s = dimensional stability t = thixotropy
376 FRP TECHNOLOGY

Similar types of composition may be used as backing material for GRP


moulds and patterns and for filling in holes in concrete structures before
laminating.
Various properties of a filler affect mix viscosity. These include particle
size and shape, oil absorption value and filler loading. The smaller the
particle size the higher the viscosity, also the higher the oil absorption value
the higher the viscosity for any given filler loading. Certain clays are pH
sensitive and when used with amine cured epoxide resin systems may give
disproportionately high viscosities.
Some of the commercially available fillers, together with some proper-
ties, are listed in Table 16.1.

16.2 MINERAL FILLERS

Many different mineral fillers are used with thermosetting resins to modify
cured properties. These are mostly derived from naturally occurring
deposits and suitable fillers may be obtained by crushing and sieving
natural minerals or by refining and purifying.

16.2.1 Carbonates
Calcium, magnesium or mixed calcium/magnesium carbonates can be
found naturally occurring in various parts of the world. These find
widespread use as fillers both for laminating and casting applications.

Calcium carbonate
By far the most commonly used filler for polyester resin systems is
calcium carbonate. This occurs naturally as chalk, limestone and marble
and may contain traces of other minerals. High purity calcium carbonate
or whiting is prepared by precipitation from solution, particle size
depending on the method of manufacture. Ultra-fine grades, with a particle
size of 0·05 /-lm, are prepared by precipitation.
Calcium carbonate fillers, as normally obtained, have a high surface area
and hence high resin absorption. Whiting, the semi-amorphous form, has a
higher resin absorption than the crystalline calcite form. To permit higher
loadings to be used, calcium carbonate is often surface coated with
stearates or resin emulsions.
Dough and sheet moulding compounds are often filled with calcium
carbonate. Such compounds should not, however, be used where mould-

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FILLERS AND PIGMENTS 377

ings have to resist strong acids. Cured resin systems filled with calcium
carbonate can be readily machined since this filler is non-abrasive.
Crystalline forms: Calcite -rhombohedral-specific gravity
2·71
Aragonite -orthorhombic-specific gravity
2·93
(Aragonite transforms into calcite on heating)
Available fillers: Chalk or whiting -quarried, pulverised and
slurried. Varies in purity
depending on quarry.
Semi-amorphous.
Limestone -Predominantly calcite.
May be contaminated
with magnesium
carbonate, silica, clays,
iron compounds and
organic matter.
Available wet or dry
ground.
Marble - A polycrystalline calcite
formed when limestone
is subjected naturally to
heat and pressure.
Available wet or dry
ground.
Precipitated - High purity whiting. It
consists of a mixture of
calcite and aragonite.

Magnesium carbonate
This occurs naturally as magnesite (MgC0 3 ) and dolomite
(MgC0 3 .CaC0 3 ). Pure magnesium carbonate is prepared by precipitation
which, when carried out at a low temperature and from dilute solution,
produces the light carbonate. This is usually assigned the formula
MgC0 3 .Mg(OH}z.3H 20. At higher temperatures and concentrations the
heavy carbonate is formed. This is considered to have the formula
MgC0 3 ·Mg(OH)2.4H 20.
Magnesium carbonate can be used as a filler in its own right or to

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378 FRP TECHNOLOGY

supplement antimony trioxide as a fire retardant filler in laminating and


casting resin systems.

16.2.2 Silica and silicates


Silica (Si0 2 ) is the most abundant material in the earth's crust. It occurs in
crystalline form as quartz (virtually pure silica), and less pure in the form of
sand and flint.

Silica sand and flour


Washed, dried and graded silica sand is used as a filler both for polyester
and epoxide resin systems. It is used in tooling and flooring applications
and in concrete repair mortars.
Ground, purified silica or quartz flour is used where a hard abrasion
resistant filler is needed. It exhibits low thermal expansion and good
electrical insulation properties. It is used extensively as a filler for epoxide
resin systems for electrical applications.
Silica is a highly abrasive filler and can cause damage to mould surfaces
during processing. Also, silica filled parts are very difficult to machine and
require the use of tungsten carbide or diamond tipped tools.

Talc
Talc consists of hydrated magnesium silicate and is a very soft mineral
with a plate-like structure. When used as a filler in thermosetting resin
systems it improves their electrical insulation, heat and moisture resistance.
Talc filled systems exhibit good machinability. Talc may be used as a filler
for sheet and dough moulding compounds.

Calcium silicate
Calcium silicate occurs naturally as the meta silicate wollastonite. It is
available in a variety of grades from fibrous to finely divided particles and
forms a useful filler for thermosetting resin systems. It is frequently used in
paint compositions. It provides excellent electrical and thermal insulation
properties.

Kieselguhr
Kieselguhr or diatomaceous earth is a form of silica consisting of the
fossil remains of diatoms-microscopic single-celled plants with a silica cell
wall. It comprises some 70-90% hydrated silica with the rest made up of
impurities.
It is used as a filler in thermosetting resin compositions to improve heat

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FILLERS AND PIGMENTS 379

resistance and electrical properties. Due to its porous structure it gives


compounds with a lower density than those obtained using other forms of
silica. It is an abrasive filler and can cause damage to mould surfaces. Filled
systems are difficult to machine.

Zircon
Zircon or zirconium silicate is used as a filler where very high abrasion
resistance is required. Because of this, zircon filled systems are extremely
difficult to machine. Filler loadings as high as 600 phr are possible.

16.2.3 Aluminium silicates and clays


Included under this heading are china clay (kaolin), bentonite, slate, mica,
vermiculite and pumice. All can be used as fillers for thermosetting resin
systems, the finer ones offering advantages as flow control agents and
thixotropic additives. Slate is often used to provide a hard wearing finish to
GRP mould surfaces.

China clay (kaolin)


The basic composition of china clay is an aluminium silicate with traces
of other metal atoms present. Normally the china clays used as fillers for
thermosetting resin systems are fine white powders. Since they have a plate-
like structure they are useful where smooth high gloss surfaces are required.
The very fine grades also act as flow control agents and thixotropic
additives.
Where superior electrical properties are required, calcined china clays
can be used.

Bentonite
Bentonite is a montmorillonite clay containing a number of different
metal atoms. Due to its weakly bonded structure it can be easily cleaved
and has a soapy feel. It is also highly absorptive.
Bentonite is mainly used in coating applications where it serves as a
thickening agent.

Slate
Slate consists of a highly compacted sedimentary clay with definite
cleavage planes. In powder form it provides a cheap abrasion resistant grey
filler often used to produce a hard wearing finish to GRP moulds. The
machining of slate filled compositions is difficult and requires the use of
special tools.

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380 FRP TECHNOLOGY

Mica
Mica or potash mica consists of potassium/aluminium substituted
pyrophyllite (aluminium silicate). Other substituted micas are also found.
The potassium atoms form weak bridges between silica layers resulting in a
thin sheet structure with individual sheets less than 25 flm thick. These
sheets exhibit excellent dielectric strength and low thermal conductivity,
coupled with good flexibility.
Due to its excellent electrical properties, ground mica finds wide
application in the electrical industry as a filler for thermosetting resins. It
improves electrical properties, heat, crack and moisture resistance and also
exhibits good anti-settling properties in liquid resin systems. In laminates,
mica increases rigidity, imparts better dimensional stability and reduces
cost. It can be used in spray lay-up formulations as well as hand lay-up and
moulding compounds.

Calcium aluminium silicate


Calcium aluminium silicate is a hard white filler with high hardness but
less angular particles than silica. It is therefore less abrasive and can be used
as an alternative to silica flour.

Vermiculite
Vermiculite is a natural crystalline silicate material which can be split
into inelastic sheets. When heated it loses water and expands about ten
times in volume to produce a lightweight granular material. It is in this
form that it is most commonly encountered.
Vermiculite is used as a low density bulk filler for polyester and epoxide
resin systems where light weight is important, such as the backing material
for GRP moulds.

Pumice
Pumice is a very lightweight cellular volcanic silica lava ejected from
volcanoes, which floats on water. It can be used as a lightweight filler in
resin systems.

16.3 GLASS FILLERS

Glass is available in various forms as a filler for thermosetting resin


systems. In fibre form it constitutes the major reinforcing fibre for
thermosetting resin systems (see Chapter 14). Other forms used are solid or
hollow spheres, flakes and ground glass.

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FILLERS AND PIGMENTS 381

Solid glass spheres


Solid glass micro-spheres, known as Ballotini, are available in a range of
sizes from 20 11m up to 1000 pm in diameter. They are made from soda glass
(A-glass). To improve adhesion of resin systems they are available coated
with a silicone coupling agent. They can be used at fairly high loadings with-
out greatly increasing viscosity due to their low resin absorption and
spherical shape.
When used in laminating systems, Ballotini glass beads increase the glass
content of the laminate with a resultant increase in flexural strength and
modulus. Due to this higher glass content, water absorption is decreased
and chemical and abrasion resistance increased.

Hollow glass spheres


Hollow glass spheres or glass bubbles are available in a range of densities
from 0·15 to O· 38 g/cm 3 , with particle sizes between 20 and 130 pm. They
can be used as a filler in laminating systems and can be sprayed with the
resin using conventional spray equipment, providing that the loading is
below 10%. Above this level modification to the spray nozzle and other
parts may be necessary. Due to their low density, glass bubbles tend to float
on the resin surface and so continuous agitation is necessary to maintain a
homogeneous mix. Since the glass spheres are hollow, with thin walls, they
can be damaged by high mixing speeds and so high shear stirrers must be
avoided.
One advantage of using hollow spheres is a reduction in the density of the
cured system. Thus this filler can be used to produce lightweight cores in
laminates. A further advantage, mostly applicable to casting systems,
putties, etc., is ease of machining of cured parts.

Glass flakes
Glass flakes are used in gelcoat and topcoat systems to provide a glass-
rich finish by aligning parallel to the surface. In this way they improve
water and chemical resistance and provide high wear and abrasion
resistance. Typical flake thickness is 3-4pm with sizes of 0·4, 0·8 and
3·2mm.

16.4 METAL OXIDE FILLERS

Various metal oxides are used as fillers or pigments in thermosetting resin


compositions. When used as pigments they need to be thoroughly

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382 FRP TECHNOLOGY

dispersed in the resin either by the use of a triple roll mill, ball mill or high
speed disperser or by one of the other methods used in paint manufacture.
In certain cases micronised grades are available for ease of dispersion.

Alumina
Pure alumina (AI 2 0 3 ), prepared from bauxite, the principal ore, is
used as a filler to improve thermal conductivity, hardness and abrasion
resistance. It is chemically inert with a low coefficient of thermal expansion.
Calcined bauxite is used as a surface dressing on polyester and epoxide
resin floors and laminates to produce a non-skid surface.

Aluminium hydroxide
Aluminium hydroxide (Al(OHh) is employed as a flame retardant filler 1
but has to be used at high loadings to achieve this. It decomposes into
aluminium oxide (alumina) above 200°C and it is this mechanism which
gives it its fire retardant properties. The water vapour thus formed
displaces oxygen and blankets the fire. This takes place without the need for
halogenated compounds to be present. It can also be used at lower loadings
in combination with other fire retardant additives.

Antimony trioxide
Antimony trioxide is used extensively in polyester resins to reduce
flammability. It is used in conjunction with halogenated compounds
since it is the volatile antimony chloride or bromide, formed under fire
conditions, which effectively blankets the fire by displacing the oxygen
necessary to sustain burning. Since it is a white powder it also acts as a
pigment and produces opaque white systems. It may also be used in
halogen containing epoxide resin systems for the same purpose.

Iron oxides
Various oxides of iron are used as pigments and fillers for resin systems.
These vary in colour from black through brown and red to yellow,
depending on chemical composition. Similarly, specific gravity varies from
5·11 for Fe 2 0 3 to 3·4 for the naturally occurring yellow oxide.

Lead oxides
Lead oxides are generally used only as pigments in resin
systems-particularly in primers for coating applications. Both litharge
(PbO) and red lead (Pb 3 0 4 ) are used.

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FILLERS AND PIGMENTS 383

Magnesium oxide
Magnesium oxide can be used as a filler to improve heat dissipation in
cured thermosetting resin systems. It is also used as a thickening agent in
polyester sheet moulding compounds. Here it produces a large increase in
viscosity of the polyester resin shortly after its addition. This slight delay in
its thickening effect is necessary to enable the resin system to be processed
into sheet form. Once the sheet moulding compound has been prepared the
resin must thicken rapidly so that it can be cut into sheets and handled.

Titanium dioxide
Pure titanium dioxide has two crystalline forms-rutile and anatase. By
far the most important for plastics applications is the rutile form. Whilst
titanium dioxide can be used in high loadings as a filler, its principal use is
as a white pigment. It is generally regarded as the standard white pigment.
It also acts as an effective UV absorber and improves the weather
resistance of cured resin systems.

Zinc oxide
Zinc oxide is another white oxide used as a pigment in resin systems and
also to impart hardness and heat stability. It is not such a good white
pigment as titanium dioxide.

Zirconium oxide
Zirconium oxide is occasionally used as a filler in epoxide resin systems
to improve dielectric properties. It can also be used as a pigment.

16.5 METALLIC POWDER FILLERS

Powdered metal fillers can be added to resin systems to produce a purely


decorative effect or to improve some specific property such as electrical or
thermal conductivity. Several metals are available both as flakes and
powders. Since metal fillers are more expensive than many of the mineral
fillers they tend only to be used where they offer specific advantages.
Some of the commonly encountered metallic fillers are listed in
Table 16.2 together with an indication of their applications. Bulk density
depends on particle size and shape and may be very much less than true
density.
Metallic fillers have little or no effect on the rate of cure of epoxide resin
systems but can accelerate or retard the cure of polyester resins. It is

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384 FRP TECHNOLOGY

Table 16.2 Metal powder fillers

Metal Specific gravity Applications and advantages

Aluminium 2·7 Flake or powder. Decorative, improves


impact resistance, thermal and electrical
conductivity and machinability
Bronze Decorative
Copper 8·9 Decorative. Improves thermal and elec-
trical conductivity and machinability
Iron 7·8 Magnetic, improves abrasion resistance
Lead II· 3 Provides radiation protection and sound
insulation
Silver 10·5 Decorative. Improves electrical and
thermal conductivity
Stainless 7·9 Flake and powder. Decorative, improves
steel abrasion resistance
Zinc 7·1 Provides corrosion protection to iron and steel
-"'-----._-

therefore good practice to check the effect of the intended filler on cure rate
and cured properties. This should be carried out on filler of the same type
and from the same source as that to be used for production, since fillers
from different sources may well have different effects.

16.6 OTHER FILLERS

Various other fillers are used which do not fall into the other classifications.
Some of these are dealt with below.

Barium sulphate
Barium sulphate or barytes (BaS0 4 ) can be used as a general purpose
filler in thermosetting resin systems. It is also known as Blanc Fixe in the
precipitated form. This form finds application as a white pigment in coating
systems. Systems filled with barium sulphate are opaque to X-rays.

Barium titanate
Barium titanate is used as a filler in epoxide resin castings where very low
stable dielectric properties are required.

Calcium sulphate
Calcium sulphate can be used as a filler both as gypsum (CaS0 4 .2H zO)

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FILLERS AND PIGMENTS 385

and as plaster-of-Paris (CaS0 4 .iH 2 0). In the latter form it can serve to
absorb traces of water in the resin system. It can also be used to intensify
some colourants used in plastics materials.

Carbon black
Various carbon blacks are used as pigments in resin systems. They may
also be used to reduce surface and volume resistivity to prevent static build-
up. In this connection acetylene blacks prove useful with epoxide resin
systems. Care must be taken with polyester resin systems since some carbon
blacks can inhibit cure.

Graphite
Graphite is used as a black pigment and to increase electrical conductivity
of cured resin systems.

Hollow carbon microspheres


Hollow carbon micro spheres are available under the trade name
'Krecasphere' from Albright & Wilson Ltd, with a particle size distri-
bution around 200 /Lm. They can be used as a lightweight, electrically
conducting filler with excellent chemical and thermal stability. True density
is 0·4 g/cm 3 , with bulk density half this.

Phenolic micro-balloons
Phenolic micro-balloons consist of miniature hollow spheres of phenolic
resin. They provide a lightweight rigid cured structure suitable for backing
moulds or thin laminate sections.

Lightweight inorganic fillers


These can all be used to give lightweight filled systems.

Armospheres - These consist of hollow spheres of a glassy complex


inorganic silicate. They are available in particle sizes
from 20 to 200 /Lm.
Fillite - This filler consists of glass-hard inert silicate spheres
ranging in size from 5 to 300/Lm in diameter. Filler
loadings of up to 70% are possible. It can be used as filler
in sheet and dough moulding compounds. 2
Q-cell - This is a lightweight filler consisting of hollow inorganic
micro spheres of exceptional whiteness. Filler loadings
of up to 20% are possible.

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386 FRP TECHNOLOGY

16.7 THIXOTROPIC ADDITIVES


With contact moulding, either by hand or spray lay-up, one of the major
problems encountered is resin drainage from sloping or vertical surfaces.
This results in considerable variation in resin/glass ratio and can lead to
resin-rich or resin-starved laminates. Also, where such variations occur,
there can be considerable differences in mechanical properties of the
laminate.
The most effective way of overcoming this problem is to make the resin
thixotropic. By so doing the resin remains handleable and thoroughly wets
the reinforcements without draining from vertical surfaces. Thus a
homogeneous laminate can be produced.
Most polyester resin manufacturers offer a range of thixotropic resins
designed with these requirements in mind. Also available are viscous
thixotropic pastes designed for addition to other resins to provide any
desired level of thixotropy.
One of the most common thixotropic additives is silica aerogel or fumed
silica. This has a very small particle size, around 0·015 11m, and a very high
surface area. Generally only about 2% addition is needed to produce
thixotropy. It can be used equally effectively with epoxide and polyester
resins, although the addition of a small proportion of water or glycol may
be necessary to enhance its effect.
With epoxide resin systems, the addition of a small amount (0· 5%) of
triethanolamine acetate, a polyhydric alcohol or water may be used to
improve thixotropy when fumed silica is used as thixotroping agent.
Other thixotropic additives used with polyester resins include hy-
drogenated castor oil and long chain aliphatic amine modified bentonite
clays. Certain other finely divided fillers also produce a degree of
thixotropy when added to resins, but these generally need to be added in far
larger amounts than fumed silica and can, with polyester resins, con-
siderably modify reactivity. Examples of these include some china clays
and various metal oxides.

16.8 FLAME RETARDANT FILLERS


Apart from the variety of chlorinated and brominated compounds which
have been discussed in Chapters 9 and 11, various inorganic materials are
used either alone or in combination with halogenated organic compounds.
These include antimony trioxide (by far the most common), aluminium
hydroxide and various borates and phosphates.

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FILLERS AND PIGMENTS 387

With polyester resin systems most fire retardant additives are in-
corporated by the resin manufacturer to achieve a balance between fire
retardancy and cured properties. This balance of properties is frequently
only possible by the use of more than one fire retardant additive and can
only be achieved after extensive development work.
Fire retardancy can be further increased by adding inert fillers to the
system and by reducing the overall resin content of the laminate.
With polyester resin systems, chlorinated compounds are mostly used,
whilst brominated compounds tend to be favoured with epoxide resin
systems. (It is generally preferable to keep chlorinated compounds out of
systems to be used for electrical applications, hence the use of brominated
epoxide resins.)

Antimony trioxide
This is a dense white powder used in conjunction with halogenated resins
to produce fire resistance. It can only be used where opaque laminates are
acceptable. It is equally effective with polyester and epoxide resin systems.
Under fire conditions the antimony trioxide reacts with the halogen present
in the resin to form volatile antimony chloride or bromide which blankets
the fire by starving it of oxygen.

Aluminium hydroxide
This is a white powder used alone to produce fire retardancy. It works by
decomposing to alumina and water above 200°C and it is this water vapour
which blankets th( fire. It is also known as alumina trihydrate.

16.9 PIGMENTS AND DYES

Polyester and epoxide resin systems can be coloured with transparent dyes
or pigments. Where dyes are used these must be compatible with the system
and should not react with either the peroxide catalyst in the case of
polyester resins, or the amine or anhydride curing agent in the case of
epoxide resin systems.
Transparent dyes are normally dissolved in a suitable solvent, such as
styrene or dibutyl phthalate, and then added to the resin system. Levels
normally used range from about 0·01% up to 0·2%.
Pigments can be obtained commercially as powders or as dispersions in
polyester resins, epoxide resins or phthalate plasticisers. Most moulders
prefer to use pre-dispersed pigment pastes since these can be stirred into the

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388 FRP TECHNOLOGY

resin system without specialised dispersing equipment. Unless pigments are


thoroughly dispersed in the resin system-particularly in the case of
gelcoats-uneven colouring and streaks can result.
Pigment pastes are prepared by dispersing the powdered pigment in a
suitable resin or plasticiser using a triple roll mill, ball mill, high speed shear
disperser or other types of equipment used in the manufacture of paints.
These pastes are generally used at between O· 2% and 10% depending on the
particular colour pigment used and the intensity of colour required.
Certain pigments, when used in polyester systems, can have accelerating
or inhibiting effects. Thus when a new pigment is to be used, it is advisable
to check for such an effect, and adjust the accelerator level as necessary.
Pigments rarely, if ever, have an accelerating or retarding effect on the cure
of epoxide resin systems.
A very wide range of coloured pigment pastes is available to meet the
needs of most moulders. This includes pigment pastes designed to match
those on the British Standard Colour Chart. With all colour matching, the
colour of the resin to be pigmented must be taken into account, as must the
effect of cure on the colour. All colour matching must therefore be carried
out on the cured resin system and not on the liquid resin.
Not all pigment pastes are compatible with all resin systems for which
they are principally designed. Compatibility should therefore be checked
prior to large scale use.
In addition to the normal range of pigments and dyes available, it is also
possible to incorporate pearlising pigments and metal flake pigments, for
decorative effects. These are dispersed without ball milling, to preserve
their decorative effect. Pearlising pigments are widely used in polyester
button formulations.
Apart from the general suppliers listed in Appendix 2, the following
companies supply pigment pastes suitable for use both with polyester and
epoxide resin systems.
Harrison Mayer Ltd.
Llewellyn Ryland Ltd.

REFERENCES

1. Banin, D. (1977) Reinforced Plastics, May, 142.


2. Methven, J. M. (1979) Reinforced Plastics, August, 252.

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Chapter 17

MISCELLANEOUS MATERIALS

17.1 INTERNAL LUBRICANTS

Where resin systems are processed by hot press moulding, transfer or


injection moulding, and particularly where sheet and dough moulding
compounds are processed by these techniques, it is a considerable
disadvantage to have to apply release agent to the mould either between
each moulding or after several mouldings have been made. This can be
overcome completely by the use of internal release agents in the moulding
compound. Thus automatic moulding lines can be operated in a similar
way to those used for processing thermoplastic materials. With a new
mould, the application of an external release agent to the mould surface
may be necessary for the first few mouldings, until sufficient thickness of
release agent has been built up and the mould run-in. After this no further
application of release agent should be necessary.
Typical release agents used in sheet and dough moulding compounds are
metal soaps based on stearic acid. Two examples are zinc stearate and
aluminium stearate. These are generally used within the range 2-6% based
on resin content. Too high a level can present a problem if the moulding is
to be painted after moulding.

17.2 SKIN FORMERS

With polyester resin systems cured in open moulds, air inhibition of the
exposed surface can result in a tacky surface which does not fully harden.
This is caused in part by loss of monomer and partly by air inhibition of
cure. This can be overcome by adding a small amount of a suitable wax or
similar compound to the resin. As the resin cures, the wax comes out of

389

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390 FRP TECHNOLOGY

solution and forms a thin protective film on the surface. Normally between
0·01 and 0·1 %addition of paraffin wax is sufficient. Several manufacturers
offer topcoat resins, containing wax or other additives, designed to cure
fully on exposed surfaces.
One problem which can arise with the use of these materials where
bonding, coating or repairs are to be carried out is lack of adhesion of the
new material. This can be overcome providing that adequate surface
preparation is carried out first to remove all traces of wax and other
contaminants.
Air inhibition is not a problem with epoxide resin systems in general,
although amine bloom can arise with certain aliphatic amine curing agents
used under high humidity conditions. This can be overcome by either
partially adducting the amine before use or by allowing the system to stand
for a short time after mixing before it is used.

17.3 LIGHT STABILISERS

Where polyester resin mouldings or translucent sheets are to be used


externally it is important that no discolouration should occur with
prolonged exposure to sunlight. The main cause of discolouration is
exposure to UV light which causes degradation of the resin system. To
overcome this problem up to 1% of a UV light stabiliser may be added to
the resin system. The compounds used for this purpose are hydroxybenzo-
phenone derivatives such as 2-hydroxy-4-methoxybenzophenone, phenyl
salicylate and acetylsalicylic acid.
These compounds may be used in combination with triethyl phosphite
and epoxidised oils.

17.4 RELEASE AGENTS AND SEALING COMPOUNDS

Mould release agents are used to ensure complete demoulding of the


laminate from the mould. They may be of the wax type, PYA solution type
or film release agents. Where a mould surface is porous a mould sealing
compound may be applied first.

17.4.1 Wax release agents


Wax release agents are mostly used in the form of wax polishes. They are
usually made from high grade Carnuba wax and contain no silicone

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MISCELLANEOUS MATERIALS 391

additives. Various suppliers offer proprietary wax paste polishes based on


Carnuba wax. Hard, medium and soft grades are available.
Also available, for use on moulds which have been broken-in, are various
liquid mould release agents designed to clean and wax the mould surface in
one operation, thus eliminating wax build-up.
When properly applied, wax polishes can be buffed up to give a high
gloss finish. Normally the polish is applied as several thin coats, each being
polished in turn before application ofthe next. As many as six coats may be
necessary to achieve adequate thickness. No attempt should be made to
reduce the number of coats applied by increasing the thickness of each coat
since this will not produce the desired finish.

17.4.2 Polyvinyl alcohol (PVA)


PV A is used as a mould release agent over the waxed and polished mould. It
is available as a solution in water or preferably a methanol/water mixture
for faster evaporation of solvent. A coloured dye is often added to make it
more visible on the surface of the mould. One advantage that PVA has is
that it is water soluble and so can be washed off the moulding and the
mould surface just with clean water. With large mOUldings which are
difficult to demould, water can be injected between the mould and the
laminate to dissolve the PVA and thus facilitate release.
PVA is normally applied by sponge or spray since brush application can
leave brush marks in the film which are then reproduced in the gelcoat of
the moulding.

17.4.3 Spray release agents


Various spray release agents are available in aerosol cans. These differ in
their suitability as release agents for polyester or epoxide resin systems and
the types of mould surfaces on which they can be used. Those available
include silicones, PVA, waxes, PTFE and mixed release agents.
With epoxide resin systems, silicone release agents are effective but
should not be used with polyester resin systems, except for hot press
moulding, nor should they be used where a moulding is to be painted, since
they are extremely difficult to remove. They can vary in their effectiveness
as release agents and so should be checked for suitability before full scale
use.

17.4.4 Silicone release agents


Silicone release agents are suitable for use with epoxide resin systems but
can interfere with mould release of polyester resin systems and should

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392 FRP TECHNOLOGY

therefore be avoided for such use, except for hot press moulding. Neither
should they be used with polyurethane foams since they may cause
defoaming. Various silicone sprays, emulsions, solutions and greases are
available.
Two silicone release agents which are very effective with epoxide resin
systems are Releasil7 Compound-a non-melting translucent grease
having the consistency of petroleum jelly up to 250°C-and DC 20 Release
Coating-a 50% solution ofa silicone compound in a hydrocarbon solvent.
This replaces Releasil 14, a similar type of material. Both materials
are manufactured by Dow Corning Ltd, and supplied by Hopkin &
Williams.

17.4.5 Sheet release agents


Several sheet materials can be used as release agents for polyester and
epoxide resin systems. These include regenerated cellulose (CeIIophane),
ceIIulose acetate, polyethylene terephthalate (Melinex, Mylar) and po-
lyethylene. These are used in sheet moulding processes such as the
manufacture of corrugated roofing sheets and also in bag moulding
processes. Generally Cellophane or cellulose acetate are preferred for these
latter applications. Also available are embossed release films from
Embossed Film Developments Ltd.
Polyethylene film is used as a release film in the preparation of sheet
moulding compounds, whilst prepregs are frequently sandwiched between
two layers of silicone coated paper during storage.
Also available are sheet waxes. These are intended more for pattern
making than as release agents but wiII also facilitate mould release.

17.4.6 Cellulose acetate


Where porous moulds are used, such as wood or plaster, the surface
generaIIy needs to be sealed prior to application of the wax release agent.
This can be accomplished by the application of one or two coats of a
solution of cellulose acetate.

17.4.7 Nitrocellulose
Nitrocellulose solution can be used to seal the porous surface of plaster
moulds prior to application of wax polish.

17.4.8 Shellac
Shellac can be used in a similar way to nitrocellulose and cellulose acetate
solutions as a sealer for porous plaster and wooden moulds and patterns.

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17.5 CORE MATERIALS

Core materials are used to provide stiffness, thermal insulation and light
weight to composite structures. Where such materials are used in boat
construction they also serve to increase buoyancy.
A variety of materials may be used and include balsa wood, plastic foams
and honeycombs of paper, glass fibre laminate or metal. Some comments
on the different types of plastic foams available are given in Chapter 4,
Section 17.

17.5.1 Balsa wood


Balsa wood 1 is a naturally occurring lightweight wood with a specific
gravity of 0·09-0·25. Laminates can be readily built up on a balsa core to
produce a sandwich construction which exhibits a high rigidity/weight
ratio. Balsa sheets supplied for use as core materials mostly consist of end
grain blocks of balsa attached to an open weave fibreglass scrim. This
ensures that the sheets can be easily contoured to fit most mould surfaces
without laborious cutting in the workshop (Fig. 17.l). Some typical
properties of balsa wood are given in Table 17.1. Balsa wood is approved
by Lloyds Register of Shipping for marine applications.

Fig. 17.1. A typical end grain balsa wood panel showing back and front view.

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394 FRP TECHNOLOGY

Table 17.1 Properties of balsa wood

Specific gravity 0·096 0·17 0·25


Compressive strength, parallel to grain (MPa) 5·1 13-1 20·3
Compressive modulus, parallel to grain (GPa) 2·27 5·29 8·02
Compressive strength, perpendicular to grain (MPa) 0·57 1·0 1·36
Compressive modulus, perpendicular to grain (GPa) O'll 0·25 0·38
Flexural strength, parallel to grain (MPa) 5·68 1l·8 17·5

Suppliers: The Balsa Wood Company Ltd.


Solarbo Ltd.
17.5.2 YIJ'ett Coremat
Firet Corematl is a multi-dimensionally orientated non-woven fabric of
synthetic fibres (polyester) incorporating closed cell plastic spheres
(PVDC, polyvinylidene chloride). These spheres take up about 50% of the
volume of the material (see Fig. 17.2).
By using Firet Coremat as the core material in a laminate, greater
thickness and rigidity can be obtained without increasing resin con-
sumption. It can be incorporated in the same way as woven rovings or

Fig. 17.2. Firet Coremai viewed from the top and with a section through, showing
the PVDC microspheres (approx. x 25 magnification).
t Trade mark.

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MISCELLANEOUS MATERIALS 395

chopped strand mat. Coremat is approved by Lloyds Register of Shipping


for use in marine applications. Whilst it is suitable for use with all polyester
resins, amine cured epoxide resins may interact with the PVDC micro-
capsules.
Typical properties of Firet P .1414 impregnated with polyester resin are
given below:
Density (gjcm 3 ) 0·6-0·65
Compressive yield strength (MPa) 7·0
Supplier: Lantor UK Ltd.
Grades available: P .1414- styrene insoluble binder.
P.2424-styrene soluble binder.

17.5.3 Intercel t
Intercel is a polyester syntactic foam honeycomb lightly bonded to
300 gjm 2 glass fibre chopped strand mat (Fig. 17.3). It can be applied by
normal hand lay-up techniques with the cell side facing either up or down.
It can also be used as core material in spray applied laminates. As with

Fig. 17.3. Intercel core material showing back and front views.

tTrade mark.

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other core materials it gives laminates with increased rigidity without


increasing resin consumption. It is available as 600 x 900 mm sheets.
Supplier: Intercel (Esplana) Ltd.

17.5.4 Honeycombs
A variety of honeycombs can be used as core materials for sandwich
construction where low weight and high stiffness is required. Such
honeycomb cored laminates find application as flooring, decking, par-
titions and furniture, where weight saving and rigidity are of prime
importance, for example in aircraft, marine structures and vehicle and
caravan bodies.
Aluminium and phenolic resin impregnated polyamide honeycombs are
available in a range of densities either alone or with glass reinforced epoxy
or bonded aluminium facing skins. These can all be used in wet lay-up
laminating or with prepregs to produce lightweight sandwich composites.
Supplier: Bonded Structures Division of Ciba-Geigy Plastics and
Additives Company.
Product availability:
Aerowebt Type 3003 Aluminium honeycomb.
Aerowebt Type Al Phenolic impregnated polyamide
honeycomb.
Aerolamt F board Aeroweb Type 3003 faced with glass
fibre reinforced Araldite epoxy skins.
Aerolamt M board Aeroweb Type 3003 with Reduxt
bonded aluminium facing skins.
All products are available in a range of densities.

17.6 COUPLING AGENTS

Coupling agents are applied to glass reinforcements to improve the


bonding of the resin matrix to the glass. In so doing they increase the
mechanical properties of composites immersed in fluids. Without the use of
coupling agents, liquids-particularly water-wick up the glass fibres
weakening or destroying the bond between the resin matrix and the glass.
This results in reduced mechanical properties of the laminate. By the use of
an appropriate coupling agent applied to the glass, this loss in strength on
immersion can be considerably reduced.
tTrade mark.

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MISCELLANEOUS MATERIALS 397

Coupling agents have also been used with fillers. One example, as might
perhaps be expected, is the coating of glass spheres (Ballotini) with
coupling agents to improve their bonding into the resin matrix. In other
cases silane coupling agents have been added to the resin system to act on
all fillers present. This tends to be a less efficient way of using them. More
recently it has been shown that silane coupling agents can offer beneficial
results when applied to aluminium hydroxide (alumina trihydrate) used as
a flame retardant filler. 3 Here the coupling agent serves to reduce the
viscosity of the system containing surface treated alumina trihydrate and
thus permits higher loadings to be used, with a resultant improvement in
burning resistance. Silane coupling agents can also be applied to other
fillers, such as clays, to enable increased filler loadings to be used. Normal
usage in this context is o· 5-1 % silane.
The coupling agents mostly used on glass reinforcements are silanes
although a chrome based size is also used. A number of different silane
coupling agents are available commercially, some of which are listed below.
A description of the chemistry and mechanism of silane coupling agents
can be found elsewhere. 4,5
Supplier: Union Carbide Corporation, USA
Product code:
A-I51 Vinyltriethoxysilane
A-I62 Methyltriethoxysilane
A-I63 Methyltrimethoxysilane
A-In Vinyltris(2-methoxyethoxy)silane
A -17 4 y- Methacryloxypropyltrimethoxysilane
A-IIOO y-Aminopropyltriethoxysilane
Other products are also available.
Other coupling agents suitable for addition to the resin matrix to
improve bonding to fillers are the organo-titanium compounds. 6 These are
used at loadings of O· 5-1 % based on filler content and permit higher filler
loadings to be used than would otherwise be possible. They are particularly
effective with clay fillers although they give similar results with most
inorganic fillers. Some of those recommended for use in polyester and
epoxide resin systems are listed below. Various related compounds are also
recommended for use in thermoplastic materials. 6
Supplier: Kenrich Petrochemicals, Inc. USA
Product code: Compound type and use
KR-41 B Tetra-isopropyl di(dioctylphosphito)titanate. Amine cu-
red epoxy.

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398 FRP TECHNOLOGY

KR -46 Tetra-octyloxytitanium di( dilaurylphosphite). Amine cu-


red epoxy.
KR - 55 Tetra-(2,2-diallyloxymethyl-I-butene)oxytitanium di(di-
tri-decyl) phosphite. Amine/amide cured epoxy.
KR-138S Titanium di(dioctylpyrophosphate)oxyacetate. Amine
cured epoxy.
KR-9S Isopropyl tridodecylbenzenesulphonyl titanate. Polyester.

REFERENCES

1. Anon. (1976) Reinforced Plastics, July, 192.


2. Anon. (1976) Reinforced Plastics. November, 329.
3. Berger, S. E., Prokai, B., Schwarz, E. G. and Montagne, M. (1978) Paper:],
'The role of silanes in the processing and properties of reinforced plastics,'
Reinforced Plastics Congress 1978, Brighton, UK.
4. Sterman, S. and Marsden, J. G. (1968) Chapter 7 in Fundamental Ajpects of
Fibre Reinforced Plastics Composites, R. T. Schwartz and H. S. Schwartz (eds.),
Interscience, New York.
5. Plueddemann, E. P. (1974) Chapter 6 in Interfaces in Polymer Matrix
Composites, Academic Press, New York.
6. Monte, S. J. and Sugerman, G. (1978) Plastics & Rubber; Materials &
Applications, 3, August, 117.

SOME SUPPLIERS

Some suppliers of mould release agents and polishes in addition to those


listed in Appendix 2 :
Bewax Products Ltd.
Ferro (Great Britain) Ltd. (Mirrorglaze)
KWR Chemicals Ltd. (Abel waxes)
Tak Chemicals Ltd.
Treplade Ltd.

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Chapter 18

LAMINATING EQUIPMENT

18.1 INTRODUCTION

With the wide range of moulding processes available, an equally wide range
of processing equipment is necessary. In this chapter, equipment used for
hand and spray lay-up, resin injection/transfer moulding and related
processes will be described and some suppliers indicated. More specialised
equipment such as that used for hot press moulding, pultrusion, filament
winding, injection or transfer moulding and continuous laminating
processes will not be covered.
In the case of spray equipment, most has been designed for use with
polyester resin systems, since these form the bulk of all resins applied by the
spray lay-up process. However, equipment is available which has been
designed specifically for use with epoxide resin systems. Here different
metering requirements have to be met and different viscosity materials
handled. Such equipment is described separately.
Spray equipment can be used alone for the application of gelcoats and
topcoats or in combination with a chopper unit for the simultaneous
spraying of glass and catalysed resin systems. These items are discussed
separately.
A list of suppliers has been included at the end of the chapter with code
letters to indicate who supplies which type of equipment. Full details of
such equipment can be obtained from each supplier.

18.2 GENERAL EQUIPMENT

18.2.1 RoUers
Rollers form an essential part of all hand and spray lay-up laminating

399

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400 FRP TECHNOLOGY

techniques, as well as finding application with certain other processes.


They can be divided into two classes, those used for resin application and
those used for consolidation and air release. A selection of laminating
rollers is shown in Fig. 18.1.

." , •• ,,11 •• "11111."

'tn'"","""".,·'"

Fig. 18.1. A selection of laminating rollers. (Courtesy of K & C Mouldings


(England) Ltd.}

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LAMINATING EQUIPMENT 401

Resin application rollers


Rollers used for resin application are generally made from lambswool or
mohair (slightly longer pile) and are used to apply resin both to the mould
surface and to the laminate. They are made in a variety of sizes with long or
short handles to meet the needs of most moulders.

Laminating rollers
Laminating rollers are used to consolidate the laminate and to assist in
removing trapped air from it. Various different types are available to meet
all moulding requirements. These are described below.

(a) Bristle rollers. These consist of nylon bristles on a polypropylene or


wooden core. The bristles penetrate the laminate to release trapped air.

(b) Dimple rollers. These are rollers covered with a fabric having
protruding dimples in it. They are used for air release and consolidation of
the laminate.

(c) Washer rollers. These consist of alternate large and small washers
made from either metal or plastic washers. In the case of the plastic washers
the large and small washers are moulded in one piece. The shaft and handle
can generally be interchanged with those used on mohair rollers. Also
available are single, double and triple washer rollers for use in consolidat-
ing the laminate in corners or along edges.

(d) Finned rollers. Various finned rollers similar to washer rollers can be
obtained. These are made from a solid block of material and have vertical
or circumferential serrations. They are available made from Teflon (PTFE)
or polyethylene coated aluminium.

(e) Paddle rollers. These are extruded aluminium rollers with thin ribs
running along the length of the roller. They give fast wet out and good air
removal and find wide application. Two different diameters are available.

(f) Spring rollers. These comprise a steel spring mounted so that it will
flex in any direction. They are useful for consolidating laminates on curved
surfaces. Cured resin can be removed by the use of suitable solvents but
should not be burnt off since this can spoil the temper of the spring.

Most of the rollers described above are available in several different

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402 FRP TECHNOLOGY

lengths and two or more diameters. In addition many can be fitted with
extension handles. Some types are also available specifically designed for
use on the end of broom handles.
Some suppliers: F, G, J, K.
18.2.2 Brushes
Brushes can be used for the application of gelcoat resins and also for
applying resin to reinforcements, particularly in corners and along edges.
Light coloured brushes are recommended for use with light coloured
laminating systems so that any brush hairs which become dislodged are not
visible in the cured laminate.
For gelcoat application a wide brush with long soft hairs is preferable to
avoid brush marks and streaks.
Some suppliers: F, G, J, K.
18.2.3 Catalyst dispensers
With hand lay-up and other processes which require the regular metering of
catalyst by hand, the use of a catalyst dispenser can help to eliminate
mixing errors. Various different types of unit are available. One common
type is the plastic squeezy bottle. Here a tube protrudes from the top of the
bottle and is surrounded by a graduated cylinder. Catalyst is squeezed out
until the cylinder contains the required amount. The catalyst is then tipped
into the resin. Two sizes are available, graduated from 2 to 15 ml or 15 to
60ml.
Another type is the Finn & Fram catalyst meter-dispenser. This can be
adjusted to deliver the exact amount of catalyst required on pressing a
plunger. Units are available to fit standard one-gallon plastic bottles or to
fit larger containers.
Some suppliers: F, G, J, K.

18.2.4 Mixing and metering equipment


Conscious of the need to prevent mixing errors when resins are used with
conventional hand lay-up techniques, manufacturers have produced
metering and mixing equipment for dispensing catalysed resin into buckets.
Pre-accelerated resin and catalyst are pumped to the mixing head as
required and delivered into a bucket. This eliminates separate weighing and
mixing apparatus.
Where machine processes such as sheet making or filament winding are
used, equipment is available which delivers predetermined amounts of pre-
accelerated resin and catalyst to a small mixing chamber. The mixed system
then flows out of the mixing chamber into the impregnating bath.

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LAMINATING EQUIPMENT 403

Where necessary a solvent flushing system is built into the mixer.


Some suppliers: C, F.

18.2.5 Casting equipment


This is similar to the standard metering and mixing equipment, with the
added advantage that it can be used with heavily filled resin systems. It
operates on the pumped catalyst injection principle. Foot control and
automatic shot timers form part of the standard equipment.
A supplier: D.

18.2.6 Mixers
Various mixers may be required to blend catalyst, accelerator, pigments
and fillers into the resin. These may be air driven or operated by electric
motors. Air driven motors are preferred where low flash point materials,
such as polyester resins, are to be mixed, since these eliminate the possibility
of a spark from the motor igniting the material.
Mixers of many different sizes are available, fitted with a range of mixing
heads. Mixers with speeds of up to 10 000 rpm are readily obtained.
Selection depends on specific workshop requirements.
Where stopping compounds are to be mixed, a much slower turning
dough or Z-blade mixer is required. A similar mixer is also required for the
preparation of dough moulding compounds. Such mixers are available in a
variety of sizes from bench top models up to full size production units.
Some suppliers: F, G.

18.2.7 Light sources for curing polyester resins


Where polyester resins have been designed for light cure (Impolex K resins
from ICI-now available from BP Chemicals Ltd), a special light source is
required, radiating at 420 nm, the blue end of the visible spectrum.
Suitable lamps can be obtained from Thorn Lighting (400/800 W) or
Strand Glass Fibre Ltd. Higher power lamps are available through Deval
Graphic Services Ltd (800 Wand 2000 W). These lamps are all of the metal
halide type emitting visible light with a wavelength centred at 417-420 nm.

18.3 SPRAY EQUIPMENT FOR POLYESTER RESIN SYSTEMS

Spray equipment for use with polyester resin systems can be divided into
three types, catalyst injection, catalyst spray and twin pot systems.
With each of these systems the spray gun is fitted with a chopper unit

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designed to chop continuous glass rovings into suitable lengths. Fibre


length can generally be adjusted within the range 12-63 mm.
Metering equipment and resin/catalyst containers can either be trolley
mounted or wall mounted, with a boom to hold hoses and rovings. Output
will depend on the size of the unit chosen and can be geared to production
needs.
Airless spray systems are generally preferred since these do not inject
compressed air into the resin system and hence do not cause air entrapment
or overspray fog.
Broad details of equipment available are given below. Specific details
may be obtained from the various suppliers listed at the end of the chapter.

IS.3.1 Catalyst injection


With the catalyst injection system, catalyst and resin are fed to the gun
either by pump or under pressure from a pressure pot (Fig. 18.2). With the
pump system, liquid catalyst is supplied by catalyst pump to the mixing
head of the spray gun where it is mixed with pre-accelerated resin, again
pumped to the spray head. The two pumps are coupled together so that
accurate metering is obtained irrespective of resin or catalyst viscosity.
Catalyst level can generally be adjusted over the range 0·5-5%. Mixing
takes place either statically or mechanically within the spray head. Catalyst

Catalyst

Roving Solvent Resin +


Acce 1era tor
Fig. 18.2. Catalyst injection system.

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LAMINATING EQUIPMENT 405

is drawn from the container in which it is supplied, thus eliminating


contamination problems. Resin can be drawn from drums or bulk supply.
With the pressure pot system, catalyst under low pressure is delivered to
the spray head and injected into the resin, which may be delivered under
pressure or by pumped supply. Mixing takes place within the gun head.
Spray guns are available with one or two spray nozzles. One nozzle guns
are preferred for narrow intricate parts and where a low output is required.
With the one nozzle guns the chopper unit is fitted above the spray head so
that chopped fibres fall into the resin stream. With the twin nozzle guns the
chopper unit ejects chopped fibres either between the two spray heads, so
that all the fibres are saturated with resin before they reach the mould
surface, or above the resin stream, so that the fibres drop into the resin.
Both nozzles discharge the same resin mixture.
All guns are fitted with a built in solvent flushing system to clean the
mixing chamber and spray nozzles after use. Guns and chopper units are
powered by air motors.
Some suppliers: C, D, H.

18.3.2 Catalyst spray


This is similar to catalyst lDJection in that similar equipment is used
(Fig. 18.3). The difference is that, instead of mixing the resin with the
catalyst in the spray head, catalyst is either injected into the resin stream
after it leaves the gun or sprayed alongside the resin stream so that mixing

Catalyst

Roving Res;n +
Accelerator
Fig. 18.3. Catalyst spray system.

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takes place externally. This eliminates the need to flush the gun head
regularly with acetone and thus reduces fire risk.
Equipment is available operating on the twin pump or pressure pot
system.
Some suppliers: A, F, G, H.

18.3.3 Twin pot system


With the twin pot system, generally two pressure pots are used, one
containing resin plus catalyst, the other resin plus accelerator. These two
components are fed through separate hoses to the spray head. Once at the
spray head the two components can either be mixed in the head and
sprayed through a single nozzle or sprayed through two separate nozzles in
such a way that the two streams of resin mix in mid-air. The chopper unit is
placed so that chopped fibres either fall into the resin stream or, in the case
of some twin nozzle systems, chopped fibres are ejected between the two
resin streams. Metering equipment is available operating either with two
pressure pots or with two pumps using non-pressurised containers
(Fig. 18.4).
Some suppliers: Pressure pot system A, C, F.
Pumped system D.

18.3.4 Filler spray equipment


An attachment is available which can spray dry powder fillers at the same

Res;n +
Catalyst

Roving Res in +
Accelerator
Fig. 18.4. Twin pressure pot system.

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LAMINATING EQUIPMENT 407

time as resin and chopped glass. This can be particularly useful with
lightweight fillers which tend to float on the top of the resin if mixed in prior
to application. With this attachment the gun can be used to spray outer and
inner skins of normal polyester/glass composition without filler and an
inner core of polyester/lightweight filler with or without glass, to make a
sandwich construction.
A supplier: C.
Several ofthe spray guns on the market can be adapted, by changing the
nozzle, to spray filled systems. Where filled systems are to be sprayed,
wherever possible, non-abrasive fillers should be used to prevent excessive
wear on the gun and pumps.
A supplier: G.

18.3.5 Flock gun


One chopper gun on the market is designed to chop rovings into 3 mm
lengths and blow them onto the gelcoat. This provides a rough surface on
the gelcoat and ensures an excellent bond to the laminate. This procedure is
also claimed virtually to eliminate voids between the gelcoat and the
laminate. Other cutter units can be fitted to the gun to cut fibre lengths of
12, 17 and 35 mm.
A supplier: C.

18.3.6 Roving cutters


Apart from those roving cutters designed for attachment to spray guns,
larger cutters are available for independent use. These can be used in
conjunction with filament winding machines to place a layer of chopped
rovings between the continuous rovings or used in continuous sheet
manufacture or for SMC manufacture.
Some suppliers: C, G.

18.4 EQUIPMENT FOR SATURATING GLASS MAT

Where woven rovings, continuous strand mat or chopped strand mat have
to be used or where processors prefer to use hand lay-up techniques, a
system is available which combines the advantages of automated mixing
with hand lay-up processing. This equipment is suitable for use where very
large mouldings such as boat hulls or building panels are produced.
The equipment available operates on the catalyst injection principle with

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internal mixing. The catalysed mix is fed to a lambswool-type roller or to a


solvent resistant paint brush through the handle. By this means catalysed
resin can be accurately applied where it is required without the need for
bucket mixing.
The equipment contains a built in flushing system for cleaning the mixing
chamber and roller or brush. Cleaning may be by solvent alone or with an
air/solvent mixture.
Some suppliers: F, C.

18.5 GELCOAT APPLICAnON EQUIPMENT

Gelcoats can be hand applied by brush or roller or spray applied.


To assist in brush application, equipment has been produced, operating
on the catalyst injection principle, which feeds catalysed resin through a
paint brush handle to the bristles of a brush. This eliminates normal mixing
problems and enables a short gel time system to be used.
For spray application of gelcoats various spray guns are available, most
operating on the airless spray principle. These may be of the catalyst
injection type or based on the twin pot system. Mixing is carried out either
within the spray head to ensure that the mix is homogeneous or externally,
where the resin and catalyst streams are designed to mix before reaching the
mould surface. Heated equipment is available to further reduce the chance
of getting porosities in the gelcoat.
By careful design of spray head, air entrainment and styrene emission
can be kept to a minimum.
With the pressure pot system, resin and catalyst are both contained in
pressurised containers and delivered to the spray gun under pressure. The
resin is sprayed through one fluid tip whilst the catalyst is either injected
into the atomising air through a controlled venturi at the side of the head or
is expelled through a concentric orifice round the main fluid tip. In either
case the two fluids become thoroughly mixed by the atomising air stream as
it leaves the gun.
Also available are single pot gravity feed spray guns. With these the resin
must be pre-mixed and must therefore have a fairly long gel time.
Some suppliers: Twin pressure pot system A, F.
Catalyst injection A, C, D, F, H.
Catalyst spray A, E, H.
Single pot, pre-mix A, I.
Brush C.

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LAMINATING EQUIPMENT 409

18.6 RESIN INJECTION EQUIPMENT


With the advent of resin injection or resin transfer moulding, various
suppliers have produced equipment designed for this process. Such
equipment invariably operates on the catalyst injection principle with
pumped metering and internal mixing. Mixers are designed to ensure that
no air entrainment occurs during mixing so that a bubble-free mix is
delivered to the mould.
With some equipment, controls can be preset to deliver a fixed quantity
of resin.
All equipment incorporates built in solvent flushing to clean out the
mixing head and dispensing tube.
Some suppliers: A, C, D, F.

18.7 EPOXIDE RESIN SPRAY EQUIPMENT


Epoxide resin systems frequently have higher viscosities than polyester
resin systems and in order to spray them adequately the resin and curing
agent components are often preheated. Delivery of resin and curing agent
to the mixing unit is generally by pump, with recirculation of the unmixed
material to ensure that minimal temperature drop occurs. Different pump
units are available to cover the normal range of mixing ratios used with
epoxide resin systems.
Resin and curing agent may be pre-mixed on demand in a mixer fitted to
the control unit and delivered through a single hose to the spray gun.
Alternatively, both components may be delivered to the gun and mixed
internally at the gun head either statically or mechanically, depending on
material viscosity. All units are fitted with integral solvent flushing
facilities.
Where long hoses are used these may have to be heated to prevent an
unacceptable temperature drop between the resin/curing agent drums and
the spray gun.
Chopper units can be fitted to the gun in a similar way to those used with
polyester spray guns. Most spray lay-up systems are custom built.
Some suppliers: G, L, M.

18.8 EPOXIDE RESIN METERING EQUIPMENT


This is similar to equipment used with polyester resins. Metering pumps are
available to suit most mixing ratios of resin to curing agent. For high

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viscosity systems heated resin and curing agent drums are used. Mixing is
internal in a mixing head either by static or mechanical means. A solvent
flushing system is built into the mixing head.
Some suppliers: G, L, M.

18.9 FURANE SPRAY EQUIPMENT

Equipment has been developed recently for the spray lay-up offurane resin
systems. This incorporates a special corrosion resistant catalyst hose and
pump, to cope with the highly aggressive catalysts used with furane resins.
It operates on the catalyst injection - internal mixing principle, with catalyst
and resin pumps interlinked to ensure accurate catalyst/resin ratios.
Catalyst level can be adjusted over the range 1-12% with an accuracy of
± 0·1 %. Pollution is kept to a minimum by the use of a controlled spray
pattern from a low-pressure airless spray gun.
A supplier: D.

SUPPLIERS

Code Supplier
A Binks-Bullows Ltd.
B BMS Plastics Ltd.
C J. Coudenhove (UK)
D CT (London) Ltd.
E The DeVilbiss Company Ltd.
F K & C Mouldings (England) Ltd.
G Newgate Simms Ltd.
H Ransburg-Peabody Ltd.
I The Shelter Island Co. Ltd.
J Strand Glassfibre Ltd.
K Vetrotex (UK) Ltd.
L Prodef Engineers Ltd.
M Spracon Equipment Services Ltd.

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Chapter 19

HANDLING AND SAFETY


PRECAUTIONS

19.1 INTRODUCTION

Resins, catalysts, curing agents, solvents and other ancillary materials have
been used in industry for many years with complete safety. However, like
all chemical materials, they have to be handled sensibly and carefully if all
hazards are to be avoided. Material manufacturers and suppliers in-
variably give advice on handling, storage and safety precautions and this
advice should be followed.
In this chapter an attempt has been made to summarise the currently
accepted handling recommendations issued by the various material
suppliers. From time to time these recommendations may change as more
information becomes known about specific materials. Whilst the recom-
mendations given below may be taken as a general guide, specific
recommendations must be obtained from the appropriate supplier. Also
where any doubts exist or where problems arise, up to date information
should be obtained from the material supplier. Advice may also be
obtained from the Health and Safety Executive.
Disposal of most, if not all, of the resins and curing agents mentioned is
notifiable under the Control of Pollution Act 1974.

19.2 GENERAL PRECAUTIONS

With the handling of all synthetic resins, catalysts, curing agents and
solvents, mixing and application procedures should be devised which
minimise skin contact and vapour exposure.
Skin contact can be minimised by the use of protective barrier creams
and the wearing of protective gloves. Eye contact can be avoided by the

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wearing of appropriate protective goggles, face shields or glasses.


With materials which give off fumes or vapours, these should be handled
in areas provided with suitable exhaust ventilation. This should always be
arranged so that fumes are drawn away from and not towards the operator.
With certain materials, threshold limit values (TL V) for exposure to fumes
are laid down by law. Details of these materials and their TLVs can be
found in Guidance Note EH15/76, and any amendments to this, issued by
the Health and Safety Executive.
Where ovens and heated presses are used, exhaust ventilation should
always be provided to take fumes away from the work place.
Personal hygiene should always be maintained at a high level to avoid
possible skin irritation, etc. Where persons are known to have sensitive
skins or have become sensitised to a particular material, they should not be
permitted to work with materials likely to cause skin irritation without a
doctor's prior permission. Before taking a break for smoking, eating,
drinking or toilet purposes, all operators should wash their hands with an
appropriate cleansing agent or soap and water, whichever is the more
effective. Skin irritation can arise if materials on hands are transferred to
parts of the body which are not normally exposed. Also some of the
materials handled may be toxic if put into the mouth.
Open cuts, abrasions or irritated skin should never be exposed to resins,
curing agents or solvents.
Gloves should be washed free from contamination before removal so
that resins, etc., do not come into contact with the skin or get transferred to
the inside of the gloves. If this happens there is not much point in wearing
the gloves. All contaminated clothing and overalls should be thoroughly
laundered before re-use. Where splashing is at all likely to occur the use of
face masks and plastic or rubber aprons is strongly recommended.
Hazards can invariably be reduced by careful design of workshop layout
and mixing areas. This should include provision for the easy cleaning up of
accidental spillages and disposal of contaminated materials.

19.2.1 Remedial measures


Facilities should always be provided for the prompt treatment of accidental
eye or skin contamination.

Eyes
First aid in the case of accidental contamination of eyes should consist of
immediate and continued washing of the eye for at least 10-15 min with
copious amounts of clean water. If other treatment is recommended for

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HANDLING AND SAFETY PRECAUTIONS 413

contamination with specific chemicals this must be clearly indicated in the


workshop and first aid areas, with appropriate supplies of cleaning
material readily to hand. The injured person should then be referred to a
doctor if there is any suspicion of eye damage or irritation or any doubt as
to the effectiveness of the treatment. Some factories automatically require
all eye contamination to be referred to a doctor after first aid treatment.

Skin
After accidental or unavoidable skin contact all affected areas should be
cleaned with a cleansing cream followed by washing thoroughly with soap
and water. If this is ineffective, washing with fresh clean solvent such as
acetone, methyl ethyl ketone or another appropriate solvent can be carried
out. Solvents should never be used around open wounds. The use of all
such solvents on the skin should be kept to the absolute minimum and a
refatting cream applied once the contaminated area has been thoroughly
cleaned. Contaminated solvents should never be used.
Where skin irritation, burns or other damage has occurred the advice of
a doctor should be sought without delay.

Inhalation
The individual concerned should be removed to fresh air and kept at rest
until any symptoms of respiratory irritation distress have disappeared.
Artificial respiration should be given if necessary. The affected individual
should not be left alone until recovery is complete. Where materials are
handled which are known to give off harmful fumes, e.g. certain
isocyanates, then the appropriate remedial measures must be taken. This
may well include immediate referral to a doctor. In any case, if distress
symptoms do not disappear quickly, immediate medical help should be
sought.

Ingestion
If large amounts of resin are ingested, the mouth should be washed out
with water and a large quantity of water drunk. Immediate medical
attention must be sought. With ingestion of other materials the recom-
mendations given for those particular materials should be followed and
immediate medical attention obtained.

Spillages
In the case of most spillages-resins and curing agents-these should be
soaked up with sand, sawdust or other proprietary absorbent material and

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414 FRP TECHNOLOGY

then shovelled into drums for disposal. Where catalysed resin is spilt care
should be taken to ensure that when the material plus absorbent is placed in
a drum, excessive exotherm does not occur which could result in the
generation of fumes or ignition. This could then constitute a fire risk.
Where peroxide catalysts are spilt these must be absorbed with a non-
flammable material such as vermiculite. The area can then be thoroughly
flushed with clean water. Peroxide soaked absorbent must not be stored in
closed containers and should be destroyed immediately (see Section 19.7).
Protective clothing should always be worn when dealing with spillages.

19.3 EPOXIDE RESINS

In the main the handling and use of epoxide resins presents few hazards.
The unmodified liquid DGEBA resins are described as being mild-to-
moderate primary skin irritants whose irritation potential is increased by
prolonged skin contact. They are mild-to-non-sensitisers. Similarly most
liquid resins containing reactive diluents are mild-to-moderate primary
skin irritants. However, the diluents present may render these resins mild-
to-strong sensitisers. This depends on the chemical nature of the diluent
involved.
Solution grades of resins may be mild-to-moderate skin irritants due to
the effect of the solvents present, which give greater wetting and skin
contact. These solvents also remove natural fats from the skin and render it
more liable to attack.
The other types of resins encountered are similarly potential skin
irritants and possible skin sensitisers.
Many of the low viscosity reactive diluents used in epoxide resins are
more or less irritating and sensitising to the skin; thus additional care needs
to be taken when handling them.
Details of the effect of any particular resin on skin contact may be
obtained from the resin supplier.
Fully cured epoxide resins are practically non-toxic, non-irritant and
non-sensitising to the skin. One of the major uses of epoxide resin systems is
in the lining of containers and cans for food and drink storage.
Dust produced during the machining of epoxide resins and composites
could present a health hazard and so dust extraction procedures and
precautions to prevent inhalation of dust should be observed and dust
levels maintained within the TL V of 10 mg/m 3 recommended by the Health
& Safety Executive.

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HANDLING AND SAFETY PRECAUTIONS 415

19.4 CURING AGENTS

These can be divided into several different classes. In all cases protective
clothing should be worn and the materials used in well ventilated areas.
These materials have been used industrially for many years and, providing
all sensible precautions are taken, no hazards should arise. The general
precautions (Section 19.2) should be followed unless otherwise stated.
Eye contact can result in acute eye irritation and so goggles should be
worn when handling all curing agents.

19.4.1 A1ipbatic amines


These include such materials as diethylenetriamine and triethylene-
tetramine. They are low molecular weight, volatile materials which are
strong irritants and potent sensitisers. Undiluted, they are alkaline, caustic
materials which can cause burns and severe tissue damage to skin, mucous
membranes and eyes. The vapours are irritating to the eyes, face, mucous
membranes and respiratory tract.
All contact should be avoided. Accidental contact should be dealt with
immediately by flushing the affected area with copious supplies of clean
water (eyes and skin) and removal to fresh air in the case of fumes. Where
any skin damage has occurred or is suspected the advice of a doctor should
be sought immediately.

19.4.2 Aromatic amines


The solid aromatic amines such as DDM are less caustic, less irritating and
less sensitising than the aliphatic amines, even when used in solution. DDM
is a toxic chemical known to cause liver damage in human beings. It can be
absorbed through the skin and so all contact should be avoided. Normal
handling precautions should be followed.

19.4.3 Cycloalipbatic amines


These vary in their skin irritation and sensitising effect depending on type
and molecular weight. They may behave similarly to the aliphatic amines or
the aromatic amines. They are extremely irritating to the eyes. All normal
contact should be avoided. Contaminated areas should be washed down
with copious supplies of clean water.

19.4.4 Polyamide curing agents


These materials are skin irritants and therefore all normal contact should
be avoided. They vary from mild to moderate skin irritants and are

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416 FRP TECHNOLOGY

generally non-sensitising to the skin. They are extremely irritating to the


eyes. Normal precautions should be followed.

19.4.5 Anhydride curing agents


These are irritating to the skin, eyes, mucous membranes and respiratory
tract and may cause burns. Some, such as phthalic anhydride, may cause
skin sensitisation. All exposure to dust and vapour and particularly to
fumes given off during heat cure should be avoided. Normal handling and
safety precautions should be followed.

19.4.6 Other curing agents


These may vary widely in their effects. Specific data should be obtained
from the material suppliers.

19.5 FURANE RESINS

The handling of furane resins presents no exceptional hazard. Normal


handling precautions should be followed. Furane resins cause eye irritation
and prolonged skin contact may cause irritation and should be avoided.
Gloves and safety goggles should be worn when handling them.
Catalysts used with furane resins are generally strongly acidic, somewhat
corrosive to the skin and severely irritating to the eyes. All contact should
therefore be avoided. In the case of eye contact the eyes should be flushed
with water for 15 min and a doctor consulted immediately.
Furane resins and catalysts should be used in well ventilated areas.
Spillages can be dealt with by absorbing the resin with sand or other inert
absorbent.

19.6 POL YESTER RESINS

The handling of polyester resins, catalysts and accelerators presents no


exceptional hazard providing that normal handling precautions are
followed.
Polyester resins are moderate-to-severe skin irritants. There is little
evidence of skin sensitisation although allergic reaction may occur with
especially susceptible individuals. Eye contact can result in acute eye
irritation and so goggles should be worn when handling all materials.
Since most polyester resins contain flammable low flash point solvents,
such as styrene or methyl methacrylate, they come under the scope of the

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HANDLING AND SAFETY PRECAUTIONS 417

Highly Flammable Liquids & Liquefied Petroleum Gases Regulations


1972.
Threshold limit values are laid down for exposure to styrene, methyl
methacrylate and various other materials commonly encountered with
polyester resins and therefore adequate ventilation must be provided at all
times.
All machining of cured polyester resins and laminates must be carried
out in such a way that dust is removed and precautions taken to maintain
dust concentrations within the TL V of 10 mg/m 3 recommended by the
Health and Safety Executive. If dust levels exceed the TLV, approved dust
masks must be worn.
Spillages present a fire hazard as well as a health hazard and should be
dealt with promptly. Dry inert absorbent materials should be used to
absorb spilt resin and then disposed of in an approved manner. The use of
flammable absorbents constitutes a fire risk, although they may be used
provided they are promptly disposed of afterwards.

19.7 PEROXIDE CATALYSTS

Peroxide catalysts are strong oxidising agents and should always be


handled with caution. Protective gloves, overalls and goggles should
always be worn when handling them. They should always be handled in
well ventilated areas and inhalation of fumes avoided. Scrupulous cleanli-
ness must be observed at all times and contaminated containers never used.
Excess catalyst should never be returned to the original container.
No smoking should be observed in all areas where peroxides are used or
stored.
Eye contact should be avoided at all cost. If, however, in spite of all
precautions, eye contact should occur, the eye should be immediately
flushed with copious supplies of clean water and medical attention
obtained.
In the case of skin contact the skin should be immediately washed with
water and when free from peroxide a refatting cream should be applied.
If peroxide is swallowed, a large quantity of water must be drunk and
vomiting induced. Immediate medical attention must be obtained.
With spillage, an inorganic absorbent such as sand, kieselguhr, vermi-
culite, etc., should be used to mop up the peroxide. This should then be
immediately disposed of. Rags, paper towels or sawdust should not be used
since these may ignite.

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Contaminated clothing should never be left around; again, this may


ignite if there is sufficient peroxide contamination.
Organic peroxides burn very fiercely and may even explode. Small fires
may be drenched with a water spray, large fires should be left to the fire
brigade who should be called in the event of any peroxide fire and informed
of the type of fire.
Peroxides may be disposed of by mixing with an equal weight of sawdust
and burning in heaps of 1-2 kg total weight on open ground. The pile
should be ignited with a burning rag held on a 6 ft pole. This must only be
carried out under adequate supervision.
Peroxide catalysts must be stored in a cool non-combustible store with a
hard floor, well away from other materials and in the original containers.
They must not be stored in direct sunlight or near heat sources. They must
never be stored near accelerators.

ORGANIC PEROXIDE

Fig. 19.1. Hazard warning label for organic peroxide. Black printing on yellow
background.

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HANDLING AND SAFETY PRECAUTIONS 419

NEVER MIX PEROXIDE CATALYSTS WITH ACCELERATORS


-VIOLENT DECOMPOSITION MAY RESULT.
All peroxide catalysts must be appropriately labelled as such (Fig. 19.1).

19.8 FILLERS AND PIGMENTS

Fillers and pigments are particulate materials which can contribute to


general dust levels in the atmosphere. Some of these materials can give rise
to health problems when inhaled and appropriate precautions may need to
be taken with their handling and use, particularly with silica containing
materials.
Dust is also created during the machining of composite materials and
appropriate dust extractors and masks should be used during such
operations.
According to the Technical Data Note 14-Health: Dust in Industry
issued by the Department of Employment & Productivity, HM Factory
Inspectorate, dusts can be divided into four hazard groups. These are listed
below together with some of the materials contained within them. Further
data may be obtained by reference to Note 14.
Group I: Very Dangerous
Silica which has been heated
Crocidolite or blue asbestos
Group II: Dangerous
Silica, e.g. quartz, etc.
Asbestos other than crocidolite
Group III: Moderate Risk
Asbestine
Talc
Mica
Kaolin
Kieselguhr-unheated
Cotton dust
Graphite
Several others
Group IV
Alumina
Barytes

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Carborundum
Cement
Glass and glass fibre
Iron oxide
Limestone-silica free
Magnesium oxide
Silicates other than those previously mentioned
Titanium dioxide
Zinc oxide
Zirconium oxide and silicate
Several others

19.9 BARRIER AND CLEANSING CREAMS


Some suppliers of barrier and cleansing creams are listed below. These
suppliers may offer more than one product and their advice should be
sought as to the suitability of a product for a particular use.
Trade name Description Supplier
Rozalex-No.9 Barrier cream Izal Ltd, Thorncliffe,
No. 42 Hand cleaner Chapeltown, Sheffield, S30
4YP.

Kerocleanse 22 Hand cleaner Kerodex Ltd, Innoxa


Kerodex 71 Barrier cream House, 436 Essex Road,
London, N .1.
Sarosol Hand cleaner Sandeman Bros Ltd, 50
Bilsland Drive, Maryhill,
Glasgow.
Centisolve Hand cleaner Walkers (Century Oils) Ltd,
Dept of Industrial Hygiene
& Safety, Hanley, Stoke-
on-Trent.
Hand cleaners may also be obtained from the following GRP suppliers:
BMS Plastics Ltd.
K & C Mouldings (England) Ltd.
Strand Glass Fibre Ltd.
Vetrotex (UK) Ltd.

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Chapter 20

TEST SPECIFICATIONS

20.1 INTRODUCTION

Most people involved with fibre reinforced plastics encounter test specifi-
cations at some time. In this chapter, some of the more commonly
encountered specifications are listed, together with brief comments about
some of them. Six series of test specifications are mentioned, although not
necessarily comprehensively, namely: ASTM-American Society for
Testing and Materials; BS- British Standards Institution;
DIN - Deutsche Normenausschuss; ISO-International Standards
Organisation; EN-European Standard; IP - Institute of Petroleum.
Wherever possible, indications are given as to the similarity or equivalence
of the various standards mentioned.
= equivalent, although not necessarily an identically worded test
method.
1= similar but not equivalent test method.

20.2 CHEMICAL PROPERTIES

In this section are included such properties as acid value, epoxide content
and chemical resistance.

20.2.1 Acid value of unsaturated polyester resins


In general, a solution of the resin in an appropriate solvent is titrated with
an alcoholic solution of potassium hydroxide using phenolphthalein or
thymol blue as indicator. Acid value is expressed as mg KOH per g.
BS 2782 Method 432B = ISO 2114 = BS 3532 Appendix H

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=1= ASTM D 1639- 70 (reapproved 1976)


=1= DIN 53402 = DIN 53183

20.2.2 Chemical resistance


Various different test methods are in use.
Resistance to 50 chemical ASTM D 543-67 (reapproved 1978)
reagents.
Thermosetting resins used ASTM C 581-74
in GRP.
Reinforced plastic laminates for self-supporting structures for use in a
chemical environment. ASTM C 582-68 (reapproved 1974)

20.2.3 Acetone extractables


Determination of acetone soluble matter in phenolic moulding materials
after moulding. BS 2782 Method 451 B : 1978
Determination of acetone soluble matter (resin content of the material in
the unmoulded state) of phenolic moulding materials.
BS 2782 Method 451 C: 1978
= ISOjR 380
Acetone extraction of phenolic moulded or laminated products.
ASTM D 494-46 (reapproved 1972)
Acetone extraction of phenolic mouldings. DIN 53700

20.2.4 Chlorine content


Total chlorine content of epoxy resins (oxygen bomb method).
ASTM D 1847-73
Hydrolysable chlorine content of liquid epoxy resins (the sample is
retluxed with alcoholic potassium hydroxide and the amount of
potassium hydroxide consumed is determined).
ASTM D 1726- 73
Determination of easily saponifiable chlorine in epoxide resins and
related materials. BS 2782 Method 433B: 1979
= ISO 4583
Determination of inorganic chlorine in epoxide resins and glycidyl esters
(using silver nitrate). BS 2782 Method 433A: 1979
= ISO 4573

20.2.5 Epoxide content


The epoxide equivalent weight of an epoxide resin is determined by
titrating a solution of resin in glacial acetic acid or chlorobenzenej

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TEST SPECIFICATIONS 423

chloroform (l: 1) with a glacial acetic acid solution of hydrobromic


acid, using crystal violet as indicator.
Epoxide equivalent weight = epoxy molar mass (EMM) = equivalent
weight in grams of resin containing one epoxide group.
Epoxide number = number of equivalents per kilogram = epoxide con-
tent
= 1000-7- epoxide equivalent weight.
BS 2782 Method 407A
=fASTM D 1652-73
In an alternative method used by some resin producers, a solution of
resin in glacial acetic acid is titrated with perchloric acid (O·IN in glacial
acetic acid) in the presence of a stoichiometric excess of cetyltrimethyl-
ammonium bromide (Cetavlon), using crystal violet as indicator. A similar
result is obtained.

20.2.6 Hydroxyl content of unsaturated polyester resins


A sample of resin dissolved in acetic anhydride-pyridine mixture, is
warmed or refluxed, diluted with water and titrated with either alcoholic
potassium hydroxide or alcoholic sodium hydroxide, using phenol-
phthalein as indicator. Hydroxyl value is expressed as mg KOH per g. In the
BS method, ethyl acetate is used as solvent and toluene-4-sulphonic acid as
catalyst.
ASTM E 222- 73
=f DIN 53240 = DIN 53183
=f DIN 53246
=f BS 2782 Method 432C:1978
= ISO 2554

20.2.7 Organic peroxides!


ASTM E 298-68 (reapproved 1973)

20.2.8 Water resistance


This may be determined by measuring weight increase after various
immersion periods in either cold or boiling water. Figures quoted in
Table 9.6 are weight increases after immersion in water at 23°C for 24 h.

Water absorption at 23°C


BS 2782 Method 502F = ASTM D 570-77 (in parts)
=1= BS 2782 Method 502G = ISOjR 62 = DIN 53475
=1= DIN 53472

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Boiling water absorption


BS 2782 Method 503B = ASTM D 570- 77 (in parts)
=i= BS 2782 Method 503C = ISO/R 117
=i= DIN 53471

Water vapour absorption at 23°C


BS 2782 Method 504A
=i= DIN 53473

20.3 FIRE AND SMOKE TESTS

A very wide and varied series of tests is available for measuring the fire
resistance of plastic materials. 2

20.3.1 Flammability tests


BS 2782 Methods 508 A-E.
BS 476 Part 3 External fire exposure, roof test.
Part 7 Surface spread of flame tests for materials.
BS 3532 Specification for unsaturated polyester resins sys-
tems for low pressure fibre reinforced plastics.
Appendix B Method of test for flammability of cast resin.
BS 3840 Polyester dough moulding compounds.
BS 4584 Metal clad base materials for printed circuit boards.
Part 1 Methods of test. Flammability 2.3.2.
DIN 53459 Testing of plastics. Determination of the resistance
to incandescence by the Schraum and Zebrowski
method.
British Railways Specification 602
Specification covering general purpose polyester
resin for manufacture of laminates for railway use.
Appendix 1 Flammability test.
Ministry of Technology Specifications D.T.D. 5537 and D.T.D. 5549
Aircraft material specifications for unsaturated
polyester resins.
Appendix 9 Method for determining flammability.
ASTM D 635- 77 Rate of burning and/or extent and time of burning
of self-supporting plastics in horizontal position.
ASTM D 229- 77 Rigid sheet and plate materials used for electrical
insulation. Flammability and flame resistance.

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TEST SPECIFICATIONS 425

ASTM D 757- 77 Incandescence resistance of rigid plastics in a horiz-


ontal position.
ASTM D 2863- 77 Minimum oxygen concentration to support candle-
like combusion of plastics.
ASTM E 84- 77a Surface burning characteristics of building ma-
terials.
ASTM E 162-76 Surface flammability of materials using a radiant
heat energy source.
UL 94 Self-extinguishing classification for plastics.
(Underwriters Laboratories Inc., Chicago, USA)

20.3.2 Smoke evolution tests 3


Arapahoe smoke test 4 Smoke density chamber method for evaluating
the potential smoke generation of building ma-
terials. NBS Technical Note 757 (January 1973).
ASTM D 2843- 77 Density of smoke from the burning or decom-
position of plastics.
Ohio State University (OSU) testS

20.4 MECHANICAL PROPERTIES

20.4.1 Compressive strength and modulus


The compressive strength or crushing strength of a resin system may be
determined by these test methods. Sample dimensions differ for each of the
test methods.
BS 2782 Method 303A
=1= ASTM D 695- 77
=1= DIN 53454

20.4.2 Flexural strength and modulus


With these test methods the flexural strength and modulus or bending
strength of materials subjected to three-point loading may be determined.

Cast resin or laminate


BS 2782 Method 335A
= ASTM D 790- 71
= ISOjR 178
=1= DIN 53452

Laminates
BS 2782 Method 1005: 1977 = EN 63

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20.4.3 Tensile strength and modulus


Various different test methods are in use, utilising different sizes of test
specimens and different test speeds. Other test methods may be used with
laminates.
BS 2782 Methods 320 A - F
= ISO/R 527
f- ASTM D 638- 77a
f-DIN 53455
f- ASTM D 1708-66 (reapproved 1970) Micro tensile test specimens.
ASTM D 349-68 Testing laminated round rods used for electrical
(reapproved 1972) insulation.
ASTM D 348- 75 Rigid tubes used for electrical insulation.
ASTM D 651-75 Tensile strength of moulded electrical insulating
materials.
ASTM D 2290- 76 Apparent tensile strength of ring or tubular plastics
(by the split disc method- NOL ring method 6 ).
ASTM D 2585-68 Preparation and tension testing of filament wound
pressure vessels.
ASTM D 3039- 76 Tensile properties of oriented fibre composites.
BS 2782 Method Determination of tensile properties of G RP
1003: 1977 laminates.
=EN 61

20.4.4 Interiaminar shear strength (ILSS)


BS 2782 Method 341A:1977 Determination of apparent ILSS of
reinforced plastics.

20.4.5 Impact strength

Izod notched specimen


BS 2782 Method 306A
= ISO/R 180
+ASTM D 256- 73
+ DIN 53453
Charpy notched specimen
BS 2782 Method 35lA
= ISO/R 179
f- ASTM D 256- 73
+DIN 53453

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TEST SPECIFICATIONS 427

20.5 PHYSICAL PROPERTIES

20.5.1 Density and specific gravity

Density bottle or pycnometer method


BS 3532 Appendix F
ASTM D 1475-60 (reapproved 1974)
DIN 51757

Density of cured resins


DIN 53479
ISO/R 1183

20.5.2 Gel time

Tecam type mechanical gel timer


BS 3532 Appendix K
BS 2782 Method IIID

Gel time and peak exotherm


ASTM D 2471- 71

20.5.3 Hardness-indentation

Shore hardness
ASTM D 2240- 75
= DIN 53505

Barcol hardness
ASTM D 2583- 75
= BS 2782 Method 1001
=EN59

Rockwell hardness
ASTM D 785-65 (reapproved 1976)

Ball indentation hardness


DIN 53456
BS 2782 Method 365D
=ISO 2039

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428 FRP TECHNOLOGY

20.5.4 Shrinkage
ASTM D 2566-69 (reapproved Linear shrinkage of cured
1975) thermosetting resins during cure.
ASTM D 1299-55 (reapproved Shrinkage of moulded and
1971) laminated thermosetting plastics
at elevated temperature.
DIN 16946 Shrinkage of polyester resins
during cure.

20.5.5 Viscosity
Viscosity may be determined as either dynamic viscosity or kinematic
viscosity.

Dynamic viscosity, (poise), Pa s


10 poise = 1 Pa s
1 cP = 1 mPa s
ISO 2555 1974 (e) Brookfield Synchro-Iectric viscometer.
ASTM D 2393-68 Brookfield Synchro-Iectric viscometer.
(reapproved 1972)
BS 3900 part A 7 Cone and plate viscometer.
DIN 53015

Kinematic viscosity, (stokes), mm 2 j s


1 St = 100 mm 2 js
1 cSt= 1 mm 2 js
BS 188 Ubbelohde suspended level and reverse
ASTM D 445- 74 flow viscometers.
DIN 51562
BS 3900 Part A6 BS flow cups.
DIN 53211 Flow cups.
ASTM D 1200- 70
(reapproved 1976) Ford cup.

20.6 THERMAL PROPERTIES

20.6.1 Heat deflection temperature (HOT)


This is determined as the temperature at which a bar of rigid material
deflects by a specific amount when subjected to a bending stress under a

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TEST SPECIFICATIONS 429

three-point load. Two stress levels may be used: (a) 1·8 MPa (264lbfjin 2 )
and (b) 0-45 MPa (66lbfjin 2 ). Rate of heating: 2 ± 0·2°Cjmin. Sample
immersed in mineral oil or silicone oil.
BS 2782 Method 121A and B
= ASTM D 648- 72
= ISOjR 75
= DIN 53461

20.6.2 Martens heat deflection temperature


This is determined as the temperature at which a bar of rigid material
deflects by a specific amount when subjected to a bending stress under a
four-point load. Rate of heating: 50 =l= lOCjh in air. Three specimen sizes
permitted.
DIN 53458 and DIN 53462

20.6.3 Coefficient of expansion


ASTM D 696- 70 (reapproved 1978) Linear expansion.
ASTM D 864-52 (reapproved 1978) Cubical expansion.

20.6.4 Flash point


The sample under test is heated in the appropriate apparatus at a controlled
rate and a small flame is applied to the vapour at regular intervals. Flash
point is taken as the lowest temperature at which the vapour ignites.

Tag closed cup-for flash points below 93°C


ASTM D 56-70

Tag open cup


ASTM D 1310-72

Pensky-Martens closed tester-the sample is heated and stirred


ASTM D 93-73
=BS 2839
= IP 34/67
= ISO 2719

Pensky- Martens open tester


BS 4688:1971
= IP 35/63

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430 FRP TECHNOLOGY

Cleveland open cup-for flash points above 79°C


BS 4689: 1971
= ASTM D 92- 76
=IP 36/67
= ISO 2592

Abel apparatus
Statutory method-BS 3442 Part 1 1974=IP 33/59
Non-statutory method-BS 3442 Part 2 1974 = IP 170170

20.7 ELECTRICAL PROPERTIES

20.7.1 Arc resistance


ASTM D 495- 73 Arc resistance, dry, of solid electrical insulators
determined under high voltage, low current con-
ditions.

20.7.2 Dielectric constant (permittivity) and power factor


These may be measured at several different frequencies.
At 50 Hz
BS 2782 Method 205B
= ASTM D 150-74
= DIN 53483

At 10 kHz
ASTM D 150-74
= DIN 53483

At 1 MHz
BS 2782 Method 207B
~ASTM D 150-74
=j= DIN 53483

20.7.3 Dielectric breakdown voltage and dielectric strength


Dielectric breakdown voltage and dielectric strength of electrical insulating
materials at power frequencies.
BS 2782 Method 201A
=1= ASTM D 149-75
=1= DIN 53481

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TEST SPECIFICATIONS 431

20.7.4 Dust fog tracking and erosion


Dust fog tracking and erosion resistance of electrical insulating materials.
BS 5604
=IEC 587
ASTM D 2132-68 (reapproved 1973)
DIN 53480 Tracking index.

20.7.5 Volume and surface resistivity


BS 2782 Methods 202A and 203A
i= ASTM D 257-76
i= DIN 53482

20.8 MISCELLANEOUS TEST SPECIFICAnONS

20.8.1 Colour
In this context colour refers to the natural colour of resins and not to
standard paint or pigment colours. Two methods are used.
Gardener scale ASTM D 1544-68 (reapproved
1974)
Platinum~coba1t (Hazen) scale BS 3532 Appendix E
= BS 5339:1976
= ASTM D 1209~69 (reapproved
1974)

20.8.2 Loss on ignition for GRP


BS 2782 Method 1002:1977
=EN60
= ISO 1172
20.8.3 Visual defects in mouldings
ASTM D 2562- 70 (reapproved Classifying visual defects in parts
1977) moulded from reinforced thermo-
setting materials.
ASTM D 2563- 70 (reapproved Classifying visual defects in glass
1977) reinforced plastic laminate parts.

20.8.4 Reinforcements
BS 3396 Woven glass fibre fabrics for plastics reinforce-
ment.

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432 FRP TECHNOLOGY

Part 1 1966 Loom state fabrics.


Part 2 1966 Desized fabrics.
Part 3 1970 Finished fabrics for use with polyester resin
systems.
BS 3496: 1973 E-glass fibre chopped strand mat for the rein-
forcement of polyester resin systems.
BS 3691 :1969 Glass fibre rovings for the reinforcement of
polyester and epoxide resin systems.
BS 3749 Woven roving fabrics of E-glass fibre for the
reinforcement of polyester resin systems.
BS 3779:1974 Glass fibre woven tapes for electrical purposes.
ASTM D 2150-70 Woven roving glass fabric for polyester glass
(reapproved 1977) laminates.
ASTM D 2660- 70 Woven glass fabric, cleaned and after finished
(reapproved 1977) with acrylic silane type finishes for plastic la-
minates.
ASTM D 579- 78 Woven glass fabrics, woven from glass fibre
yarns.
ASTM D 578- 78 Glass fibre yarns.
ASTM D 580- 78 Woven glass tapes.
ASTM D 3098- 72 Woven glass fabric, cleaned and after finished
with epoxy-functional silane type finish for plas-
tic laminates.

20.8.5 General specifications


BS 2782: 1970 & 1975 Methods of testing plastics.
BS 3532: 1962 Unsaturated polyester resin systems for low
pressure fibre reinforced plastics.
BS 3534 Epoxide resin systems for glass fibre reinforced
plastics.
Part 1 Wet lay-up systems.
Part 2 Pre-impregnating systems.
BS 3815:1964 Epoxide resin casting systems for electrical appli-
cations.
BS 3816:1964 Cast epoxide resin insulating material for electri-
cal applications at power frequencies.
BS 3840 Polyester dough moulding compounds.
BS 4045 : 1966 Epoxide resin pre-impregnated glass fabrics.
BS 4154:1967 Corrugated plastic translucent sheets made from
thermosetting polyester resins (glass fibre rein-
forced).

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TEST SPECIFICATIONS 433

BS 4584 Metal clad base materials for printed circuit


boards.
BS 4994: 1973 Vessels and tanks in reinforced plastics.
ASTM D 2996- 71 Filament wound reinforced thermosetting resin
(reapproved 1977) pipe.
Grade 1 Epoxy.
Grade 2 Polyester.
ASTM D 2997-71 Centrifugally cast reinforced thermosetting resin
pipes.
Grade 1 Epoxy.
Grade 2 Polyester.
ASTM D 1201-62 Thermosetting polyester moulding compounds.
(reapproved 1969) General specification.
ASTM D 1763-76 Epoxy resins.
ASTM D 3013-77 Epoxy moulding compounds.

REFERENCES

1. Chalkley, N. J. and Whalley, C. (1978) Proc. Anal. Div. Chem. Soc., 15,
December, 327.
2. Flammability Test Methods for Plastics-An International List. Chemical
Industries Association (CIA), Fire Retardants Group.
3. Anon. (1978) Modern Plastics International, 8, July, 53.
4. Anon. (1977) J. Fire & Flammability, July, 300.
5. Smith, E. E. (1972) Fire Technology, 8, August, 237.
6. Barnet, F. R. (1965) Trans. J. Plastics Inst., October, 177.

giridharvzm1@gmail.com
Appendix 1

TRADE NAMES

The descriptions of products and trade names given below are derived from
technical literature received from suppliers in the UK. They may not cover
all products supplied, nor is the firm listed necessarily the owner of the
name. Overseas owners of names are given in parentheses.
AEROLAM Composite honeycomb-sandwich board-Ciba-
Geigy Plastics & Additives Company.
AEROSIL Thixotroping agent-Bush, Beach & Segner
Bayley Ltd.
AEROWEB Honeycomb cores-Ciba-Geigy Plastics &
Additives Company.
ALPOLIT Polyester resins-Hoechst AG/Resinous
Chemicals.
AMPAL Polyester moulding compounds-Ciba-Geigy
Plastics & Additives Company.
ANCAMIDE Polyamide curing agents-Anchor Chemical Co.
Ltd.
ANCAMINE Amine curing agents-Anchor Chemical Co. Ltd.
ARALDITE Epoxide resins-Ciba-Geigy Plastics & Additives
Company.
ARMAFLO Centrifugally cast pipes-Johnston Pipes Ltd.
ARMOSPHERES Hollow silicate spheres-Vetrotex (UK) L!d.
ATLAC Polyester and vinyl ester resins-Honeywill-Atlas
Ltd.
AVDELBOND Adhesives-Permabond Adhesives Ltd (formerly
A vdel Adhesives Ltd).

BALLOTINI Glass spheres-Plastichem Ltd.


BECKOPOX Epoxide resins and hardeners- Hoechst
AG/Berger Chemicals.

434

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TRADE NAMES 435

BEETLE Polyester and other resins-British Industrial


Plastics Ltd.
BELCOBALSA Balsa wood-The Balsa Wood Co. Ltd.
BIDIMAT Non-woven glass reinforcement-Brandhurst Co.
Ltd (NV Syncoglas SA).
BUTANOX MEK peroxides-Akzo Chemie UK Ltd.

CARBOFORM Carbon fibre prepregs-Fothergill & Harvey Ltd.


CASAMID Epoxy curing agents-Thomas Swan & Co. Ltd.
CASCOTE Synthetic resins-Borden (UK) Ltd.
CELLOBOND Polyester resins- BP Chemicals Ltd.
CELMAR Glass fabric backed polypropylene-British
Celanese Ltd.
C-FLEX Glass fibre/pultruded rod reinforcement F. G.
Industries (UK) Ltd.
CONTOURKORE Balsa wood-The Balsa Wood Co. Ltd.
CRYSTIC Polyester resins-Scott Bader Co. Ltd.
CYCLONOX Cyclohexanone peroxide-Akzo Chemie UK Ltd.

DELTAMAT Glass mat reinforcement-Fibreglass Ltd.


DERAKANE Vinyl ester resins-Dow Chemical Europe.
DOWNLAND Spray equipment-K & C Mouldings (England)
Ltd.
DURADENSE Pre-formed boat building pultrusions-Tyler
Mouldings Ltd.

EPIKOTE Epoxide resins-Shell Chemicals UK Ltd.


EPIKURE Epoxy curing agents-Shell Chemicals UK Ltd.
EPOPHEN Epoxide resins-Borden (UK) Ltd.
EPOREX Epoxide resins-Synres (UK) Ltd.
EPOXIDE 7 & 8 Glycidyl ethers-Proctor & Gamble Ltd.
EQUEMAT Chopped strand mat-Fibreglass Ltd.
EQUEROVE Glass rovings- Fibreglass Ltd.
EUREDUR Epoxy curing agents-Schering Chemicals Ltd.
EUREPOX Epoxide resins-Schering Chemicals Ltd.

FABMAT Combined chopped strands/woven rovings- F. G.


Industries (UK) Ltd.
FIBREDUX Prepregs-Ciba-Geigy Plastics & Additives
Company.

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436 FRP TECHNOLOGY

FILLITE Silicate spheres- Fillite (Runcorn) Ltd.


FlRET COREMAT Synthetic reinforcement-Lantor UK Ltd.
FLEXON Adhesives-Permabond Adhesives Ltd.
FLOMAT SMC-Freeman Chemicals Ltd.
FREEMIX DMC-Freeman Chemicals Ltd.

GENAMID Polyamide curing agents-Cray Valley Products


Ltd.
GRAFIL Carbon fibre-Courtaulds Ltd.
GRILONIT Epoxide resins-Grilon (UK) Ltd.

HETRON Synthetic resins-Garrick Chemical & Equipment


Co. Ltd (Ashland Chemicals).
HYDRA-CAT Epoxy spray equipment-Spracon Equipment
Services Ltd.
HYFIL Carbon fibre- Hyfil Ltd.

INTERCEL Reinforcement-Intercel (Esplana) Ltd.


INTEROX Peroxide catalysts- Interox Chemicals Ltd.

KEVLAR Aramid fibres-Du Pont de Nemours


International SA.
KRECASPHERE Hollow carbon spheres-Albright & Wilson Ltd.
KUREHA Carbon fibres-Albright & Wilson Ltd (Taiyo
Kaken Co. Ltd, Japan).

LAROMIN Amine curing agents-BASF United Kingdom


Ltd.
LAURYDOL Peroxide catalysts-Akzo Chemie UK Ltd.
LEGUVAL Polyester resins- Bayer UK Ltd.
LIND RIDE Anhydride curing agents- British Chemical
Products & Colours Ltd.
LINROVMAT Chopped strands/unidirectional rovings-F. G.
Industries (UK) Ltd.
LOPOX Epoxide resins-(CdF Chimie).
LUCIDOL Peroxide catalysts-Akzo Chemie UK Ltd.
LUCIPAL Peroxide catalysts-Akzo Chemie UK Ltd.
LUPERCO Peroxide catalysts-Akzo Chemie UK Ltd.
LUPEROX Peroxide catalysts-Akzo Chemie UK Ltd.

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TRADE NAMES 437

MELINEX Polyester film-ICI Ltd.


MIRRORGLAZE Mould polishes-Ferro (Great Britain) Ltd.
MITEX Foamed polyester resins-Cellmico Ltd.
MONOFORMING Moulding process-J. Coudenhove (UK).
MULTE.MAT Chopped strand mat-Fibreglass Ltd.
MULT~SPRAY Rovings-Fibreglass Ltd.
MYLAR Polyester film-Du Pont (UK) Ltd.

NEONITE Chopped prepregs-Ciba-Geigy Plastics &


Additives Company.
NESTRAPOL Polyester resins-Arcode Ltd (Chimimportexport,
Romania).
NORPOL Polyester resins-Vetrotex (UK) Ltd (A/S
Jotungruppen).
NORSADYNE Polyester resins-KWR Chemicals Ltd (CdF
Chimie).

OXITOL Ethers of ethylene glycol-Shell Chemicals UK


Ltd.

PARAPLEX Low shrink polyester resins-Rohm & Haas (UK)


Ltd.
PERADOX Peroxide catalysts-Akzo Chemie UK Ltd.
PERMAGLASS DMC-Permali Gloucester Ltd.
PLASTAMID Polyamide resins-Croda Resins Ltd.
PLASTOKYD Alkyd and epoxide ester resins-Croda Resins Ltd.
POLASTOR Polyester resins-Astor Chemical Ltd.
POLYMASTER Polyester resins-Warwick Chemical Ltd.
PREMI-GLAS DMC-Premix Fibre-Glas Ltd.
PREMI-JECT DMC-Premix Fibre-Glas Ltd.

Q-CELL Hollow silica spheres-Plastichem Ltd.


QUACORR Furane resins-Quaker Oats Ltd.

REDUX Adhesives-Ciba-Geigy Plastics & Additives


Company.

STYPOL Polyester resins-Freeman Chemicals Ltd.


SUPREAVE Rovings- Fibreglass Ltd.
SUPRE.MAT Chopped strand mat-Fibreglass Ltd.

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438 FRP TECHNOLOGY

SUPREPREG Rovings-Fibreglass Ltd.


SUPR~SPRAY Rovings-Fibreglass Ltd.
SUPR~WIND Rovings-Fibreglass Ltd.
SYNMOULD Moulding powders- Moulding Powders Ltd.
SYNOCRYL Acrylics and low profile additives-Cray Valley
Products Ltd.
SYNOLAC Polyester and other resins-Cray Valley Products
Ltd.
SYNOLIDE Epoxy curing agents-Cray Valley Products Ltd.
SYNOLITE Polyester resins-Synres (UK) Ltd.

TAK Release agents-Tak Chemicals Ltd.


THIOKOL Epoxy curing agents-Thiokol Chemicals Ltd.
THORNEL Carbon fibre-Union Carbide Corporation.
TORAYCA Carbon fibre-Hyfil Ltd.
TRIGONOX Peroxide catalysts-Akzo Chemie UK Ltd.
TRIHYDE Alumina trihydrate-Plastichem Ltd.
TYGLASS Glass cloths-Fothergill & Harvey Ltd.

UDIMAT Glass reinforcement-Brandhurst Co. Ltd (NV


Syncoglass SA).
UKADIOL Polyester resins-Pechiney Ugine Kuhlmann Ltd.
UKAPON Polyester resins-Pechiney Ugine Kuhlmann Ltd.
UNIFILO Continuous filament mat-Vetrotex (UK) Ltd.
URACURE Epoxy curing agents-Synthetic Resins Ltd.
URAGEL Polyester gelcoats-Synthetic Resins Ltd.
URALAM Polyester resins-Synthetic Resins Ltd.
URANOX Epoxide resins-Synthetic Resins Ltd.

VENUS Spray equipment-CT (London) Ltd.


VERSAMID Polyamide curing agents-Cray Valley Products
Ltd.
VESTOPAL Polyester resins-Hiils (UK) Ltd.
VITROFIL Glass reinforcements-Plastichem Ltd
(Montedison Group).

WOLFAMID Polyamide curing agents-Victor Wolf Ltd.

XYLOK Phenol aralkyl resins-Albright & Wilson Ltd.

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Appendix 2

GENERAL MATERIAL SUPPLIERS

The following companies supply polyester resins, catalysts and accele-


rators, reinforcements, release agents and a whole range of other sundries
used in the preparation of GRP mouldings.
BMS Plastics Ltd.
Bondaglass-Voss Ltd.
GRP Materials Supplies Ltd.
K & C Mouldings (England) Ltd.
Newgate Simms Ltd.
Strand Glass Fibre Ltd.
Trylon Ltd.
Vetrotex (UK) Ltd.

439

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Appendix 3

COMPANY NAMES AND ADDRESSES

Afco Products Inc., 44 Park Street, Somerville, Mass. 02143, USA.


Akzo Chemie UK Ltd, 12--14 St. Ann's Crescent, Wandsworth, London
SW182LS.
Albright & Wilson Ltd, PO Box 80, Old bury, Warley, West Midlands B69
4LN.
Amoco Chemicals UK Ltd, St George Chamber, The Forum, Stevenage,
Hertfordshire SG 1 lBA.
Amoco Chemicals Europe, 7 Rue Versonnex, 1207 Geneva, Switzerland.
Anchor Chemical Co. Ltd, Clayton, Manchester MIl 4SR.
Anmac Ltd, Daleside Road, Nottingham.
Arcode Ltd, Plantation House, Mincing Lane, London EC3M 3DX.
Ashland Chemical Co., Resins & Plastics Division, PO Box 2219,
Columbus, Ohio 43216, USA (UK Agent-Garrick Chemical &
Equipment Co. Ltd.)
ASTM (American Society for Testing and Materials), 1916 Race Street,
Philadelphia, Pa 19103, USA.
Astor Chemical Ltd, Tavistock Road, West Drayton, Middlesex UB7
7RA.

Badische Anilin- u. Soda-Fabrik AG, 6700 Ludwigshafen, Germany.


The Balsa Wood Co. Ltd, Green Dragon House, 64 High Street, Croydon,
Surrey CRO 9XN.
BASF United Kingdom Ltd, PO Box No.4, Earl Road, Cheadle Hulme,
Cheadle, Cheshire SK8 6QG.
Farbenfabriken Bayer AG, 509 Leverkusen-Bayerwerk, Germany.
Bayer UK Ltd, Bayer House, Richmond, Surrey TW9 lSJ.
Berger Chemicals, Resinous Chemicals Division, Wellington Mills,
Dunston, Co. Durham NEll 9HQ. (Hoechst AG.)

440

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COMPANY NAMES AND ADDRESSES 441

Berol Kemi (UK) Ltd, 55-57 Clarendon Road, Watford, Hertfordshire.


Bewax Products Ltd, Birchill Road, Kirkby Industrial Estate, Liverpool
L337TF.
Bifort Engineering Ltd, Preston New Road, Blackpool, Lancashire FY3
9TT.
Bighead Bonding Fasteners Ltd, Unit 15, Elliott Road, West Howe
Industrial Estate, Bournemouth, Dorset BHll 8LZ.
Binks-Bullows Ltd, Brownhills, Walsall, West Midlands WS8 7HW.
BMS Plastics Ltd, Higgins Lane, Burscough, Lancashire.
Bondaglass-Voss Ltd, 158 Ravenscroft Road, Beckenham, Kent.
Bondina Industrial Ltd, Greetland, Halifax, West Yorkshire HX5 8Nl.
Borden (UK) Ltd, North Baddesley, Southampton S05 9ZB.
Boston Chemical Co. Ltd, Thorp Arch Trading Estate, Wetherby, West
Yorkshire LS23 7BZ.
BP Chemicals Ltd, Wellington House, 60-68 Wimbledon Hill Road,
Wimbledon, London SW19 7PD. Head Office: Devonshire House,
Piccadilly, London WIX 6A Y.
Brandhurst Co. Ltd, PO Box 70, Wellington Road, High Wycombe,
Buckinghamshire HP 12 3PS.
Brenntag (UK) Ltd, Regal House, Twickenham, Middlesex TWI 3QY.
British Celanese Ltd, Chemical & Plastic Sales Dept, PO Box 5, Spondon,
Derby DE2 7BP.
British Chemical Products & Colours Ltd, 22 Buckingham Street, London
WC2N 6EF.
British Industrial Plastics Ltd, PO Box 6, Popes Lane, Oldbury, Warley,
West Midlands B69 4PD.
BSI Sales Department (British Standards Institution), 101 Pentonville
Road, London Nl 9ND.
BTR-Permali RP Ltd, Hydroglass Works, Bristol Road, Gloucester GLl
5TT.
Bush, Beach & Segner Bayley Ltd, 175 Tottenham Court Road, London
WIP OB1.

Cargill Blagden Ltd, Piperell Way, Haverhill, Suffolk CB9 8PH.


CdF Chimie, Department Resines et Thermodurcissables, Tour Gan,
Cedex 13, 92082 Paris-La Defense, France. (UK Agent-KWR
Chemicals Ltd.)
Cellmico Ltd, McTay House, Port Causeway, Bromborough, Merseyside.
C. G. T. (Glass Fibre) Ltd, 61A Top Moor Side, Holbeck, Leeds LSll
9LU.

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442 FRP TECHNOLOGY

CIA Publications (Chemical Industries Association), 93 Albert


Embankment, London SEl.
Ciba-Geigy Plastics & Additives Company, Duxford, Cambridge CB2
4QA.
J. Coudenhove GmbH, A-2103 Langenzersdorfnear Vienna, Probst-Peitl-
Strasse 60, Austria.
J. Coudenhove (UK), 67 High Street, Titchmarsh, Kettering,
Northamptonshire NNl4 3DF.
Courtaulds Ltd, Carbon Fibres Unit, PO Box 16, Coventry CV6 5AE.
Cray Valley Products Ltd, St Mary Cray, Orpington, Kent BR5 3PP.
Croda Resins Ltd, Crabtree Manorway, Belvedere, Kent DAl7 6BA.
Crystic Systems Ltd, Wollaston, Wellingborough, Northamptonshire
NN97QJ.
C T (London) Ltd, Walnut Tree House, Woodbridge Park, Guildford,
Surrey GUI IEL.

Degussa, Postfach 2644, D-6000 Frankfurt 1, Germany.


Det Norske Veritas, PO Box 300, Hovik, Oslo, Norway.
Deutsche Normenausschuss, Berlin 30, Germany.
Deval Graphical Services Ltd, Newhouse Laboratories, Bovingdon,
Hertfordshire HP3 OEL.
Devcon Ltd, Theale, Reading, Berkshire RG7 4AB.
The DeVilbiss Co. Ltd, 45 Holborn Viaduct, London ECIN 2PH.
Dow Chemical Co. Ltd, Heathrow House, Bath Road, Hounslow,
Middlesex TW5 9QY.
Dow Chemical Europe, Leland I, Doan-strasse 3, 8810 Horgen,
Switzerland.
Dow Corning Ltd, Reading Bridge House, Reading RG 1 8PW.
Dunlop Ltd, Head Office, Dunlop House, 25 Ryder Street, St. James's
Street, London SWl7 6PX.
Dunlop Ltd, Engineering Group, Foleshill, Coventry CV6 4AA.
Du Pont de Nemours International SA, Textile Fibres Dept., 50-52 Route
des Acacias, CH-1211, Geneva 24, Switzerland.
Du Pont (UK) Ltd, 18 Bream's Buildings, Fetter Lane, London EC4.
Durapipe & Lambert Sales Ltd, Norton Canes, Cannock, Staffordshire
WSl13NS.

Eastman Chemical International AG, PO Box 66, Kodak House, Station


Road, Hemel Hempstead, Hertfordshire HPI IHA.

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COMPANY NAMES AND ADDRESSES 443

Embossed Film Developments Ltd, Madoc Works, Welshpool, Powys


SY217BE.

Ferro (Great Britain) Ltd, Womboume, Wolverhampton WV5 SDA.


F. G. Industries (UK) Ltd, Virginia Villas, High Street, Hartley Wintney,
Hampshire RG27 SNW.
Fibreglass Ltd, Reinforcements Division, S1. Helens, Merseyside WAlO
3TR.
Fillite (Runcom) Ltd, Arkwright 12, Astmoor Industrial Estate, Runcom,
Cheshire.
Fontana Products Ltd, Brisbane, Queensland, Australia.
Fothergill & Harvey Ltd, Composites Division, Summit, Littleborough,
Lancashire.
Freeman Chemicals Ltd, PO Box S, Ellesmere Port, South Wirral L65
4AH.

Garrick Chemical & Equipment Co. Ltd, 13 Garrick Street, London


WC2E 9AR.
Grilon (UK) Ltd, Drummond Road, Astonfields Industrial Estate,
Stafford ST16 3EL.
GRP Materials Supplies Ltd, Bertie Road, Milton, Portsmouth,
Hampshire.

Halmatic Ltd, Brookside Road, Havant, Hampshire.


Harrison Mayer Ltd, Plastics Division, Meir, Stoke-on-Trent ST3 7PX.
J. J. Harvey (Manchester) Ltd, Oldham Street, Denton, Manchester M34
3SL.
Hoechst AG, Resinous Chemicals, Wellington Mills, Dunston, Gateshead
NEl19HQ.
Farbwerke Hoechst AG, Verkauf Kunstharze, Reichold-Albert Cassella,
D-6 Frankfurt (M) 61, Postfach 610132, Germany.
Honeywill-Atlas Ltd (now Atlas Chemical Industries (UK) Ltd), Cleeve
Road, Leatherhead, Surrey KT22 7SW.
Hopkin & Williams, PO Box 1, Romford, Essex RMI lHA.
Hiils (UK) Ltd, Cedars House, Famborough Common, Orpington, Kent
BR67TE.
Hyfil Ltd, Avonmouth Road, Avonmouth, Bristol BSll 9DU.

Imperial Chemical Industries Ltd, Plastics Division, PO Box 6, Bessemer


Road, Welwyn Garden City, Hertfordshire AL7 lHD.

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444 FRP TECHNOLOGY

Intercel (Esplana) Ltd, 49 Masons Hill, Bromley, Kent BR2 9HP.


International Paint Ltd, Industrial Division, 380 Richmond Road,
Kingston-on-Thames, Surrey.
International Paint Ltd, Yacht Division, 24-30 Canute Road,
Southampton S09 3AS.
Interox Chemicals Ltd, PO Box 8, Kingsway, Luton, Bedfordshire.
Izal Ltd, Thorncliffe, Chapletown, Sheffield S30 4YP.

Johnston Pipes Ltd, Doseley, Telford, Salop TF4 3BX.


AjS Jotungruppen, PO Box 305, N-3201 Sandefjord, Norway.

K & C Mouldings (England) Ltd, Spa House, Shelfanger, Diss, Norfolk


IP222DF.
Kenrich Petrochemicals, Inc., Foot of E. 22nd St., Bayonne, N.J. 07002,
USA.
Kerodex Ltd, Innoxa House, 436 Essex Road, London Nl.
K & K Greeff Chemical Group Ltd, Suffolk House, George Street,
Croydon, Surrey CR9 3QL.
Kureha Chemical Industry Co., 1-8 Nihonbashi Horidome-cho, Chuo-ku,
Tokyo, Japan.
KWR Chemicals Ltd, Caroline House, 55-57 High Holborn, London
WCIV 6EF.

Lantor UK Ltd, St. Helens Road, Bolton BL3 3PR.


Laporte Industries Ltd, PO Box 8, Kingsway, Luton, Bedfordshire LU4
8EW.
Llewellyn Ryland Ltd, Haden Street, Birmingham B12 9DB.
Lloyds Register of Shipping, 71 Fenchurch Street, London EC3M 4BS.
Luperox GmbH, PO Box 480,887 Gunzburg, Germany. (UK Agents-
Vetrotex (UK) Ltd, and Newgate Simms Ltd.)

Marglass Ltd, Sherborne, Dorset.


The Micanite & Insulators Co. Ltd, Westinghouse Road, Trafford Park,
Manchester M17 1PR.
Mitsubishi Gas Chemicals, Dusseldorf, Germany.
Montedison Group-Vitrofil, Via Andrea Appiani 12,20121 Milano, Italy.
Moulding Powders Ltd, Lamberhead Industrial Estate, Pemberton,
Wigan.
3M United Kingdom Ltd, 380-384 Harrow Road, London W9 2HU.

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COMPANY NAMES AND ADDRESSES 445

Newgate Simms Ltd, PO Box 32, Chester CH4 OEJ.


Norsk Glassfiber AjS, 4760 Birkeland, Norway. (UK Agent-Brandhurst
Co. Ltd.)

A. S. O'Connor & Co. Ltd, 26 Sheen Park, Richmond, Surrey.


Owens-Corning Fiberglas (UK) Ltd, Crossways, Silwood Road,
Sunninghill, Ascot, Berkshire, SL5 OPY.

Pechiney Ugine Kuhlmann Ltd, Chemical Division, Station House,


Harrow Road, Wembley, Middlesex HA9 6EL.
Permabond Adhesives Ltd, Woodside Road, Eastleigh, Hampshire S05
4EX.
Permali Gloucester Ltd, Bristol Road, Gloucester GL1 5SU.
Plastichem Ltd, Curtis Road, Dorking, Surrey RH4 lXA.
Premix Fibre-Glas Ltd, 28 Firth Road, Houstoun Estate, Livingston, West
lothian, Scotland.
Procter & Gamble Ltd, Industrial Chemicals Sales Division, PO Box 9,
Hayes, Middlesex UB4 OJD.
Prodef Engineers Ltd, 1163 Bristol Road South, Birmingham B31 2SL.
Pultrex Ltd, 12 Conway, Stephenson Road, Clacton-on-Sea, Essex.

Quaker Oats Ltd, Chemicals Division, Spring House, Glossop Road,


Sheffield SID 2GW.

Ransburg-Peabody ltd, Block C, Weybridge Trading Estate, Weybridge,


Surrey K TI5 2R T.
Redland Pipes Ltd, Redland House, Reigate, Surrey.
Reichhold-Albert Chemie AG-see Hoechst AG.
Resinous Chemicals, Wellington Mills, Dunston, Gateshead NEll 9HQ.
Rohm & Haas (UK) Ltd, Lennig House, 2 Mason's Avenue, Croydon,
Surrey CR9 3NB.

Sandeman Bros ltd, 50 Bilsland Drive, Maryhill, Glasgow.


Scandinavian Glasfiber AB, Box 129-130, S-311 01 Falkenberg, Sweden.
Scandinavian Glasfiber ltd, The Banking Court, High Street, Bracknell,
Berkshire RG 12 1DL.
Schering Chemicals Ltd, Industrial Chemicals Division, The Brow,
Burgess Hill, West Sussex RH15 9NE.
Scott Bader Co. Ltd, Wollaston, Wellingborough, Northamptonshire
NN97RL.

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446 FRP TECHNOLOGY

Shell Chemicals UK Ltd, Villiers House, 41-47 Strand, London WC2N


5LA.
The Shelter Island Co. Ltd, Church House, Thrumpton, Nottingham.
Silenka BV, PO Box 50, Hoogezand, Netherlands.
Silenka UK Ltd, The Parade, Frimley, Camberley, Surrey.
Solarbo Ltd, Commerce Way, Lancing, Sussex BN15 8TE.
Spracon Equipment Services Ltd, 22/25 County Road, Maidstone, Kent.
Strand Glass Fibre Ltd, Brentway Trading Estate, Brentford, Middlesex
TW88ER.
Thomas Swan & Co. Ltd. Crook hall Works, Consett, Co. Durham DH8
7ND.
N. V. Syncoglass S. A., Industriepark BI, 9140 Zele, Belgium. (UK
Agent~Brandhurst Co. Ltd.)
Synres International BV, Slachthuisweg 30, 3151XN, Hoek van Holland.
Netherlands.
Synres (UK) Ltd, Six Acre House, 17 Town Square, Sale, Cheshire M33
lXZ.
Synthetic Resins Ltd, Edwards Lane, Speke, Liverpool L24 9HR.

Taiyo Kaken Co. Ltd, 17-19 Nihinbashi Koami-cho, Chuo-Ku, Tokyo,


Japan. (UK Agent~Albright & Wilson Ltd.)
Tak Chemicals Ltd, Hayes Lane, Lye, Stourbridge, West Midlands DY9
8PJ.
TBA Industrial Products Ltd, Glass Fibre Division, PO Box 40, Rochdale,
Lancashire 0 L12 7EQ.
Thiokol Chemicals Ltd, Station Tower, Station Square, Coventry CVI
2GH.
Thorn Lighting Ltd, Thorn House, Upper St. Martin's Lane, London
WC2H9ED.
Treplade Ltd, 137 High Street, Epsom, Surrey.
Trylon Ltd, Wollaston, Wellingborough, Northamptonshire NN9 7QJ.
Tyler Mouldings Ltd, 56/58 Morley Road, Tonbridge, Kent TN9 IRP.

Ugine Kuhlmann, Division Plastiques, Tour Manhattan, Place de I 'Irish,


Cedex 21, 92087 Paris Defense 2, France.
Union Carbide Corporation, Carbon Products Division, 270 Park
Avenue, New York, NY 10017, USA.
Union Carbide UK Ltd, Chemicals Division, PO Box 2LR, 8 Grafton
Street, London WI.

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COMPANY NAMES AND ADDRESSES 447

VPB Industrial Fabrics, 26 Brown Street, Manchester M2 IDN.


Veba-Chemie AG, Department EP, 466 Gelsenkirchen-Buer, Germany.
(UK Agent-Brenntag (UK) Ltd.)
Vetrotex International, 18 Route des Acacias, PO Box 154, CH-1211,
Geneva 24, Switzerland.
Vetrotex (UK) Ltd, Unit A3, Beadle Trading Estate, Hithercroft Road,
Wallingford, Oxfordshire OXIO 9RA.
Viking Industrial Plastics Pty, Australia.

Walkers (Century Oils) Ltd, Dept ofIndustrial Hygiene & Safety, Hanley,
Stoke-on-Trent.
Warwick Chemical Ltd, 54 Willow Lane, Mitcham, Surrey CR44NA.
Victor Wolf Ltd, Victoria Works, Croft Street, Clayton, Manchester Mil
4RR.

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Appendix 4

UNITS, PREFIXES AND CONVERSION


FACTORS

SOME DERIVED UNITS BASED ON THE INTERNATIONAL


SYSTEM OF UNITS

Frequency hertz Hz
Force newton N
Stress pascal Pa (= N/m2)
Pressure bar bar (= 105 Pa)
Energy joule J
Impact strength joules per square
metre J/m 2
Power watt W
Thermal conductivity watts per metre kelvin WjmK
Thermal trans- watts per square
mittance metre kelvin Wjm 2 K
Specific heat joules per kilogramme
kelvin J/kgK
Viscosity-dynamic pascal second Pa s (= 10 poise)
-kinematic square millimetre
per second mm 2 Is (= cSt)

STANDARD PREFIXES

Prefix Symbol Factor


tera T 10 12
giga G 109
mega M 106
kilo k 103

448

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UNITS, PREFIXES AND CONVERSION FACTORS 449

deca da 101
deci d 10- 1
centi c 10- 2
milli m 10- 3
micro f.1 10- 6
nano n 10- 9
pico p 10- 12

CONVERSION FACTORS-BRITISH TO METRIC AND S.I. UNITS

Length thou x 25.4 = micrometres (f.1m)


= microns
inches x 25.4 = millimetres
Area square inches x 645.16 = square millimetres
Volume cubic inches x 16.3871 = cubic centimetres
gallons x 4.5459 = litres
Mass ounces x 28.4 =grammes
pounds x 0.454 = kilogrammes
ton x 1016 =kg
Pressure and
stress I bf/in 2 x 0.0703 = kg/cm 2
Ibf/in 2 x 0·00689 = N/mm2 = MN/m 2 = MPa
Pa=N/m 2
tonf/m 2 x 15.44 =MPa
tonf/m 2 x 154.4 = bar
Energy ft I bf x 1.356 =J
Thermal
conductivity BTU in/ft2h deg F x 0·145 =W/mK
Viscosity poise x 0.1 = Pa s (Pascal seconds)
centipoise (cP) =mPas
stoke x 100 =mm 2 /s
centistoke (cSt) =mm 2 /s

giridharvzm1@gmail.com
INDEX

Where Tables are referred to the page numbers are given in italics.

Accelerators for polyester resins Aluminium hydroxide, 158, 164,374,


amines, for, 264, 266, 267, 271, 272 382, 387, 397
anhydrides, for, 274, 277, 279, 282 Aluminium oxide, 374,382,419
cobalt, 54, 62, 205, 209, 212, 213, Aluminium silicate, 374, 379
214,215,216,219,221-4, Aluminium stearate, 351, 389
238 Amido polyamines, 282
manganese, 213, 222, 238 Amine
mixed metal/amine, 224, 239 adducts, 264, 267, 269
tertiary amine, 223-4, 238-9 bloom, 267, 268, 269
vanadium, 213, 215, 216, 219, 220, curing agents, 266-74
222,238 Amine T, 253, 267, 268,270
Acetone extractable material, 422 N-aminoethyl piperazine (AEP), 268,
Acetyl acetone peroxide, 54, 209, 269
213-4,230 Amino polyamides, 282
Acid etching of concrete, 133 Anhydride
Acids accelerators for, 274, 275, 276, 279,
saturated organic, 143 280,282
unsaturated, 142 curing agents, 274-82
Acid value of polyesters, 421 eutectic blends, 275
Acrylic sheet, 151 Antimony trioxide, 158, 374, 382, 387
Activation temperature, 206, 208 Aramid fibres, 69, 293, 308, 309,
Active oxygen content, 207 327-9
Adhesive joints, 109-11 Armospheres, 374, 385
Adhesives, 81, 111, 282 Asbestos fibre, 309, 310,330,419
Adipic acid, 144, 162
Air inhibition of polyesters, 116, 135,
151 Ballotini, 164, 381, 397
Aliphatic amines, 266-8 Balsa wood, 58, 59, 80, 393-4
Alumina, 374, 382, 419 Barium sulphate, 374, 384,419
trihydrate (AI(OHh), 158, 164,374, Barium titanate, 374, 384
382, 387, 397 Barrier creams, 420
Aluminium Bauxite, 382
bulk properties, 309 Bentonite, 374, 379
moulds, 31 Benzoyl peroxide
powder, 25, 26, 50, 384 commercial products, 226
451

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452 INDEX

Benzoyl peroxide--contd. Brushes, 402


DMC, in, 351 Building panels, 13
properties of, 210 Butane-l A-diol diglycidyl ether, 248,
uses of, 62, 64, 122, 167,209,210, 249
214, 215, 223 Buttons, polyester, 164-5
vinyl ester resins, with, 300 n-Butyl acrylate, 146
Benzyl alcohol, 252, 253, 264, 267 t-Butyl catechol, 148, 225, 239
Benzyldimethylamine, 264, 280, 282, t-Butyl cumyl peroxide, 217, 232
286 n-Butyl glycidyl ether, 249, 251
Beryllium, bulk properties, 309 t-Butyl hydroperoxide, 215, 231
BF 3 400, 284, 285, 286 N-n-butyIimidazole, 282, 284, 285,
diamino diphenyl sulphone, with, 287
272, 273, 290, 293 n-Butyl methacrylate, 145, 146
furane resins, with, 297 t-Butyl peroctoate, 209, 215, 218-19,
Binder 233
CSM, for, 318 t-Butyl peroxybenzoate, 217-8, 232,
emulsion, 64, 313, 318 300, 354
polyester powder, 77, 318 t-Butyl peroxydiethyl acetate, 218,
styrene insoluble, 63, 64 233
2,2-Bis(t-butylperoxy)butane, 220, 235 t-Butyl peroxyester, 218, 233
1,I-Bis(t-butylperoxy)cycIohexane, t-Butyl peroxy isononanoate, 218, 233
220,235 t-Butyl peroxypivalate, 219, 234
1,I-Bis(t-butylperoxy)-3,3,5- p-t-Butyl phenyl glycidyl ether, 249,
trimethylcycIohexane, 221, 250, 251
235 t-Butyl styrene, 161
2,2-Bis(4-hydroxycycIohexyl)propane,
142
2,2-Bis(4-hydroxyphenyl)propane, 142 Calcium aluminium silicate, 374, 380
Bisphenol A Calcium carbonate, 25, 26,64,351,
epoxies, 241, 242-5 354, 374, 376--7
hydrogenated, 142 Calcium magnesium carbonate, 25,
polyesters, 142, 149, 151, 156 351,354, 374, 377
chemical resistance of, 153-5 Calcium oxide, 162, 354
vinyl ester resins, 299 Calcium silicate, 374, 378
Bisphenol F resins, 244-5, 246 Calcium sulphate, 374, 384
Blisters, 92, 102, 107 Carbon black, 385
BMC, 67, 349--51,360-4 Carbon fibre, 308, 323-7
Bondeq joints, 109-11 aligned sheet, 326
Boron fibre, 309, 331 cellulose precursor, 323, 324, 325
Boron trifluoride complexes, 240, 247, commercial products, 347-8
327 composites, 2, 5, 8, 292-3
monoethylamine, 272, 273, 284, continuous filament mat, 326
285,286,290,293,297 fibre properties, 309, 325
British Rail process, 50, 58 filament winding with, 69
Brominated epoxide resins, 247, 290 polyacrylonitrile precursor, 323,
Brominated polyester resins, 142, 144, 325
157 prepregs, 73,366-70
Bronze powder, 384 puitrusion with, 78

giridharvzm1@gmail.com
INDEX 453
Carbon fibre-contd. Chopped strands, 315, 316
resin systems for, 293 Chrome plated moulds, 28, 55, 56, 62,
SMC, 352 67
Carbon microspheres, 385 Chrome size, 318, 320
Casting, 164-7 Citraconic acid, 143
equipment for, 403 Cleansing creams, 420
Cast moulds Cobalt accelerators, 222
single-stage casting, 23, 24-6 commercial products, 238
two-stage casting, 26-8 cure, effect on, 147,205
Catalyst(s) polyester resins, with, 54, 62, 205,
commercial data, 226-37 209,213,214,215,216,219,
dispensers, 402 224
peroxide, 204-21 vinyl ester resins, with, 300
Catalytic curing agents, 268, 283-7 Cold press moulding, 35, 61-2
IX-Cellulose, 306 moulds for, 21-3
Cellulose acetate, 16, 18, 392 Colour change indicators, 150
Centrifugal moulding, 36, 73-6 Composite properties, 8, 293
buttons, 164-5 Concrete repairs, 129-35
moulds for, 30 Contact moulding, 34, 38-48
C-Flex planking, 82 hand lay-up, 34, 41-5
Chalk,377 spray lay-up, 34, 45-8
Chemical resistance, 9 Continuous strand mat, 319
furane resins, of, 296 use of, 53, 58
polyester resins, of, 142, 153-5 Copper powder, 384
vinyl ester resins, of, 153-5 Core materials, 393-6
China clay, 64, 351, 354,374, 379 plywood,58
Chlorendic anhydride, 144,276,277 sandwich construction, in, 80
Chlorinated paraffin, 149 types of foam, 80-1
Chlorine content, 422 use of, 43, 47, 53, 58
Chloromaleic acid, 143 Cotton, 309, 330, 350
Chlorostyrene, 146 Coupling agents, 320, 396-8
Chopped strand mat, 317-9 organo-titanium; 397-8
binders for, 318 silane, 397
centrifugal moulding, for, 74 Crack repair, 130
commercial materials, 338-42 Crazing, 94
continuous sheet manufacture, for, Cresyl glycidyl ether, 249, 250, 251
77 Critical temperature, 206, 208
filament winding, for, 71 Crystallisation
foam reservoir moulding, for, 59 epoxide resins, of, 244, 248, 249
GRP moulds, in, 19 polyester resins, of, 141, 143
hand lay-up, for, 33,41 Crystic Systems process, 59
hot press moulding, for, 63 Cumene hydroperoxide, 209, 216, 231
puItrusion, for, 78 Cure, test for, 40, 135
repairs, for, 117, 119, 120 Curing agents for epoxide resins,
resin injection, for, 53 263-93
rovings for, 314 amine, 126,240,265-74
site use, for, 126, 134, 135, 288, 289 anhydride, 240, 274-82
SMC, for, 352 accelerators for, 282

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454 INDEX

Curing agents for epoxide resins Diethylaminopropylamine (0 EAPA),


-contd. 268,270
catalytic, 240, 283 Diethylaniline, 223, 239
polyamide, 240, 282 Diethylene glycol, 142
safety and handling, 415 Diethylene glycol mono butyl glycidyl
stoichiometry, 266, 274 ether, 249, 251
suppliers, 293-4 Diethylenetriamine (DTA), 267, 268,
Cycloaliphatic epoxide resins, 247 270
Cyclohexanone peroxide, 62, 209, Diglycidyl ether of bisphenol A, 241,
213,222,229 244
Cyclohexylpropylenediamine, 268, Dilauroyl peroxide, 211, 227
269,271 Diluents for epoxide resins, 248-54
non-reactive, 253
reactive, 248--53
Dimethylaminopropylamine, 268, 269
Delamination, 12, 90 Dimethylaniline, 54, 62, 223, 224,
Demoulding, II, 33, 44 238,300
Design, 7-14 2,5-Dimethyl-2,5-bis(t-butylperoxy)-
Diacetyl peroxide, 211, 227 hexane, 217, 232
Diallylbenzene phosphonate, 147 3,3' -Dimethyl-4,4' -diamino
Diallyl phthalate, 145, 146 dicyclohexylmethane, 268,
catalyst for, 218 270, 271
moulding compound, 68 2,5-Dimethylhexane-2,5-
prepregs, 163 diperoxybenzoate, 219, 234
Diaminodiphenylmethane (DDM), Dimethyl phthalate, 204, 208
241,246,268,270,271,273 Dimethyl-p-toluidine. 224, 239
Diaminodiphenylsulphone (DDS), Di-n-octanoyl peroxide, 212, 227
268,270,272,273,290,291, Diol III, 142
293 Dipropylene glycol, 142
Diatomaceous earth, 378 Dipropylenetriamine (DPTA), 268
Dibromocresyl glycidyl ether, 249, Divinylbenzene, 146
253 DMC, 29, 66, 67, 68, 349-51
Dibromoneopentyl glycol, 142 commercial materials, 36~
Dibromophenyl glycidyl ether, 249 properties of, 8
Dibromostyrene, 147 DMP 30, 282, 284, 285, 287
Di-t-butyl-p-cresol, 225, 239 Dodecenylsuccinic anhydride, 276,
Di-t-butyl diperoxyphthalate, 219, 234 278,281
Di-t-butyl peroxide, 209, 216, 232 Dolomite, 351, 354, 374, 377
4,4-di-t-butyl peroxy-n-butyl valerate, Duradense building system, 82
220,234 Dyes, 387
Dibutyl phthalate, 253
Dicaprylyl peroxide, 212, 227
2,4-Dichlorobenzoyl peroxide, 211, Electrical laminates, 290-2
227 Emulsion binders, 64, 318
Dichlorostyrene, 145 Encapsulation, 145, 165--7
Dicumyl peroxide, 216, 231 Environmental resins, 160
Dicyandiamide, 247, 283, 284, 285, Epichlorohydrin, 242
286,290,291 Epoxide 7, 249, 250, 251

giridharvzm1@gmail.com
INDEX 455
Epoxide 8, 249, 250, 251 Fasteners, 43, 47, 113
Epoxide(s) Faults
content, 241, 422 centrifugal casting, with, 105
equivalent weight, 241, 249, 253, epoxide resin mOUldings, with,
422 105-8
resins, 240-62 filament winding, with, 104
bisphenol A, 242-5 polyester mouldings, with, 8fr99
bisphenol F, 244, 246 press mouldings, with, 101
brominated, 242, 247, 253, 290, resin injection, with, 102
291 translucent sheets, with, 99
carbon fibre composites, for, 292, vacuum moulding, with, 103
293 Fibre
commercial, 255-62 classification, 315
curing agents for, 263-94 finishes, 320
cycloaliphatic, 247 pattern, 91, 99
diluents for, 248-54 properties, 309
DMC, 66, 67, 68, 359 Filament winding, 13, 36, 69-73
flame retardant, 242, 254, 290 epoxy pipes, 72
gelcoat, 26, 289 glass reinforcement for, 315
gener;ll, 3, 123, 126, 134 on-site, 137
glycidyl amine, 246, 292 prepregs, with, 73, 356
glycidyl ester, 245 specifications, 433
glycidyl ether, 242 spheres, 17
hand lay-up, 44 wet lay-up, 70, 292
laminate properties, 273, 278, winding angle, 72
279, 285, 288, 305 Fillers, 26, 372-87
moulding with, 55 safety and handling, 419
moulds, 23-8, 58 Fillite, 374, 385
novolac resins, 246, 273, 290, Fire retardant
291, 292, 327 epoxies, 242, 247, 253, 254
pipes, 69, 73 fillers, 386
polyester replacement, 265, 288, furanes, 296
289 polyesters, 142, 144, 157
prepregs, 51, 65, 66 tests, 424
primer, 125, 129 Firet coremat, 394
safety and handling, 414 Fish eyes, 92
specifications, 432 Flanges, 12, 20
spray lay-up, 48 Flash point,
Epoxy Molar Mass, 241, 249, 253, 422 amines, of, 269
Ethylenediamine, 266, 267, 268, 270 monomers, of, 146
Ethylene glycol, 141 tests for, 429
Ethylene oxide, 142, 267 Flexible polyester resins, 145, 162
2-Ethylhexyl glycidyl ether, 249, 251 Foam core, 53, 55, 58, 80
2-Ethyl-4-methylimidazole, 282, 284, Foamed polyester resins, 167
285,286 Foam reservoir moulding, 35, 59-61
Eutectic anhydride blends, 275 Foams
Exotherm, 12, 25, 43, 54, 61, 205, expanded polystyrene, 80
207, 263, 282 expanded PVC, 80

giridharvzm1@gmail.com
456 INDEX

Foams-contd. Half-life of peroxides, 208


phenolic, 81 Hand lay-up, 5, 19,33,34, 41-5, 126~
polyurethane, 20, 81 134, 135
open-celled, 59 Handling precautions, 411-420
Friedel-Craft polymers, 4, 301-4 Hardener proportions, 23, 266, 274,
Fumaric acid, 143 283
Furane resins, 3, 295-9 Heat deflection temperature, 428
hand lay-up, 45 cured epoxide resins, of, 270, 278,
safety and handling, 416 279,281, 282, 285, 288
spray lay-up, 48 cured polyester resins, of, 170-203
equipment for, 410 effect of accelerators on, 282
Furfural, 295, 297 Martens, 429
Furfuryl alcohol, 253, 295, 297 Heat resistant resins, 304
HET acid polyesters, 144, 149, lSI
chemical resistance of, 153-5
Gelcoat, 19,39,44, 150,289 HET anhydride, 144,275,276,277.
flaking off, 89 278,290
spotting, 91 Hexahydrophthalic anhydride,
spray application, 39, 40 HHPA, 275, 276, 278, 279,
Gel time, 46, 427 280
Glass Hexamine, 301, 304, 306
fibre, 312-23 Hoechst vacuum injection process,
binders for, 53,63,64,77,313, 56-8
318 Hollow structures, 13
A-glass, 77, 309, 312 Honeycombs, 55, 80, 396
C-glass, 312 Hot press moulding, 35, 62-7
E-glass, 77, 309, 312 moulds for, 29
R-glass, 309, 312 Hydantoin resins, 246
S-glass, 309, 312 Hydrogenated castor oil, 386
production, 312 Hydroquinone, 148
size, 3\3, 318 2-H ydroxyethyldiethylenetriamine,
tex, 313 253,267,268,270
flakes, 129, 374, 381 Hydroxyl content, test for, 423
spheres, 164,374,381,397
Glycerol, 142
Glycidyl amine resins, 246, 292 Imidazole
Glycidyl ester resins, 245 accelerators, 282
Glycidyl ether diluents, 248 curing agents, 284, 285, 286, 287
Glycidyl ether resins, 242 Imidazolines, 282
Glycidyl methacrylate, 249 Inhibitors for polyesters, 147,205,
Glycols, 141 224,239, 351
Graphite Injection moulding, 36, 68
fibres, 309, 323, 325 moulds for, 30
powder, 374, 385 Inserts, 12, 43,47, 113-4
Grit blasting, 125, 132 Intercel, 395
Grouting, 130 Intemallubricants, 63, 66, 351, 354,
GRP moulds, 18-23,38,59,61 389
advantages of, 2 Intumescent polyesters, 158

giridharvzm1@gmail.com
INDEX 457
Iron Magnesite, 377
oxides, 374, 382, 420 Magnesium aluminium silicate, 375
powder, 383 Magnesium carbonate. 375, 377
Iso-octyl glycidyl ether, 249, 251 Magnesium oxide, 162, 354.375, 383,
Isophorone diamine, IPO. 264, 268. 420
270,271 Magnesium silicate (talc). 351, 354.
Isophthalic polyesters. 144. 149, 151. 375.378
350 Maintenance of GRP. 115
chemical resistance of. 153-5 Maleic acid. 143
Itaconic acid, 143 Maleic anhydride. 141, 143.281
Mannitol, 142
Marble poWder. 26. 377
Marble. synthetic 167
Joints, 13, 109-114 Martens HOT, 429
Jute fibres, 331 Matched metal moulds. 29, 55. 62
moulding, 62-7
Mechanical joints. 113
K 54, 282, 284, 285, 287 Melamine formaldehyde resins, 305,
K6IB, 284. 285, 287 306
Kaolin (china clay), 351, 354, 374, Metering equipment, 402, 409
379,419 Methyl acrylate, 146
KEVLAR fibres, 327-9 Methylenedianiline, MOA, 271
Kieselguhr, 374, 378,419 Methyl ethyl ketone peroxide, 205,
209, 212, 222, 300
commercial products, 228
Methylhexahydrophthalic anhydride,
Laitance, 132 MHPA, 276, 280
Laminate I-Methylimidazole, 282
properties, 8, 285, 288, 293 Methyl isobutyl ketone peroxide, 214,
strength retention. 273 230
Laminating equipment, 399-410 Methyl methacrylate, 145,146, 151,
epoxide resins, with, 287-93 297
systems for site use, 287-9 IX-Methylstyrene, 145, 146
Lead Methyltetrahydrophthalic anhydride,
oxides, 374, 382 276,278
powder, 384 Mica, 375, 380, 419
Leno weave, 321 Milled fibres, 315,317
Light Mitex foamed polyesters, 167
polyesters, cured by, 164 Mixers, 402, 403
sources, 403 Mock leno weave, 321
stabilisers, 390 Monoforming, 59
Limestone, 377 Monomers, 144-7,146
Linings Moulding processes, 33-84
concrete tanks, for, 129-36 Mould(s),15-32
steel tanks, for, 124-9 aluminium, 31
Low profile/low shrink resins, 66, box, 24,26
160-2, 351, 352 chrome plated, 28, 30, 31, 55, 56,
Low styrene emission resins, 159 62,67

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458 INDEX
Mould(s)-contd. Outdoor weathering, 254
cold press moulding, 22
epoxide resin, 23-8, 39, 58
single-stage casting, 24 Paper, 331
two-stage casting, 26 Paraffin wax, 135, 301, 390
GRP, 18-23 Patterns, 16, 18, 21, 24, 26
matching, 21 Pentaerythritol, 142
one-part, 19 Peroxides
split, 20 commercial data, 225-36
hot press moulding, 29 diacyl,210
injection moulding, 30 dialkyl, 216
life, 15 diaralkyl,2l6
matched metal, 29, 55, 62 half-life, 208
nickel shell, 32 hazard classification, 236-7
pattern, 16, 24 hydroperoxides, 215
plaster, 16, 32, 39, 71 ketone, 212
release, 21, 44 organic, 209-21
split, 18, 20 perketals, 209, 220
steel, 28, 62 peroxyesters, 217
transfer moulding, 30 safety and handling, 417-19
wax, 32, 71 Phenol, 266, 271, 272
wooden, 18,39 Phenolic microballoons, 28, 375, 385
Phenolic resins, 68, 305, 306
Nadic methyl anhydride, NMA, 275, m-Phenylenediamine, MPD, 268, 270,
276, 277, 278, 279 272
optimum cured properties, 280 Phenyl glycidyl ether, 249, 250, 251
Phlegmatised peroxides, 204
Needle mat, 318
Phthalic anhydride (ortho), 141, 143,
NEMA laminates, 247, 290, 291
275, 276, 278, 281
Neo-pentyl glycol polyesters, 142,
Pigments, 387
149, 151, 156
safety and handling, 419
chemical resistance of, 153-5
Nickel shell moulds, 32 Pinch area of mould, 22, 61
Pinholes, check for, 127
Nitrocellulose, 16, 24, 392
Pinholing, 87, 106
Novolac
epoxide resins, 246, 290, 291, 292, Pipes
centrifugally cast, 73-6
293,327
epoxy, 292
phenolic resins, 306
filament wound, 69-73
Nylon fibres, 330
Dunlop process, 72
joints, 114, 136
Oil tank, repairs to, 120
repairs, 124--9 Usui process, 75
riveted tanks, 128 Plain weave cloth, 319-23
Orthophthalic acid, 144 Plaster moulds, 16, 32, 39, 71
Orthophthalic anhydride, 141, 143, patterns, 16, 18, 21, 24, 26
275, 276, 278, 281 Polyacrylonitrile fibres, 308, 310, 323,
Orthophthalic polyesters, 145, 149, 151 324, 330
chemical resistance of, 153-5 Polyamide curing agents, 282

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INDEX 459
Polyester fibres, 310, 329 Pot-life
Polyester resins. 139-203 epoxide resins, of, 269, 277, 281
acid value of, 421 polyester resins, of, 205
bisphenol, 149, 151, 152 Powder
chemical resistance of, 153-5 binder, 77, 318
casting, 164 coating, 280
chemical resistance of, 153-5 Preforms, 62, 64
test for, 422 Prepregs, 65, 255-8, 349
commercial resins, 168-203 commercial materials, 366-70
curing reaction, 206 diallyl phthalate, 145, 163
DMC, for, 163 furane, 297
fire retardant, 142, 157 hot press moulding of, 65
flexible, 144, 162 manufacture of, 356
foamed,167 pressure bag moulding of, 51
gelcoat, 150 systems for, 272, 274, 276, 283,
general purpose resins, 151 286,290,291,293
chemical resistance of, 153-5 unidirectional, 49, 51, 356
HET acid, 144, 149, 151 vacuum bag moulding of, 49, 50
chemical resistance of, 153-5 Pressure bag moulding, 34, 51
hydroxyl content of, 423 Pressure injection, 55
isophthalic, 144, 149, 151,350 Primers, 84, 125,133,135
chemical resistance of, 153-5 polyester, 133
light cured, 164 zinc rich, 125
low profile/low shrink, 160, 351, Printed circuit boards, 247, 286, 290,
352 291,355
low styrene emission, 159 Process selection, 10
methyl methacrylate containing, Propylene glycol, 141, 156
150 Propylene oxide, 142
neo-pentyl glycol based, 142, 149, PuItrusion, 37, 78-80
151, 156 moulds for, 31
chemical resistance of, 153-5 prepregs, 356
orthophthalic, 141, 143, 145, 149, reinforcements for, 315
151 sections, 83
chemical resistance of, 153-5 Pumice, 375, 380
pipes, 70, 73 PVA. See Polyvinyl alcohol
prepregs, for, 163 PVC and PVDC fibres, 330
primer, 133 Pyromellitic dianhydride, 276, 278,
properties of, 149, 170--203, 305 280
safety and handling, 416
SMC, for, 65, 162
speciality resins, 164 Q-cell, 375, 385
specifications for, 432
topcoat, 150, 389
Polyhydric alcohols, 142, 163 Radomes,55
Polyimides, 305 Refractive index
Polyvinyl alcohol, 16, 17, 18,21,24, cured resins, of, 77, 145
39,44, 57, 74, 84, 391 glass, of, 145, 312
Post cure, 19, 44 monomers, of, 146

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460 INDEX

Reinforcements, 308--48 Sheet moulding-contd.


specifications for, 431 continuous, 12, 37, 76--8
Release agents, 24, 28, 39, 390-2 Shellac, 16, 18, 392
internal, 63, 66, 351, 354, 389 Shrinkage on cure, 3, 23
polyvinyl alcohol, 16, 17, 18, 21, epoxide resins, of, 241
24,39,44,57,74,84,391 polyester resins, of, 169-203
PTFE,74 Silane coupling agents, 318, 320,
sheet, 392 396-7
silicone, 24, 28, 63, 74, 84, 391 Silica flour, 25, 26, 375, 378, 419
spray, 391 fumed, 386
wax, 39, 84, 390 sand, 25, 26, 28, 126, 378
Remedial treatment, 412--4 Silicone
eyes, 412 release agents, 24, 28, 63, 74, 84,
ingestion, 413 391
inhalation, 413 resins, 304
skin, 413 rubber moulds, 165
spillages, 413 Silver powder, 384
Repairs to GRP, 116--20 Sisal, 309, 330
Resin Site application, 122~38, 265, 287
injection, 35, 52~5 Skin formers, 389
equipment for, 409 Slate, 25, 26, 375, 379
properties, cured Smoke emission of furanes, 297
epoxide, 270, 273, 278, 279, 285, Smoke tests, 425
288 Spillages of resins, 413
Friedel-Craft polymers, 302 Split moulds, 18, 20, 30
furane, 298 Spray equipment
polyester, /49, 170-203 catalyst injection, 45, 404
Ribs, 12, 19,43,47,53,58,60 catalyst spray, 45, 405
Rollers, 399--402 epoxide resins, for, 409
Roving cutters, 407 filler spray, 406
Rovings, 45,77,78, 313-15, 335~8 flock gun, 407
furane resins, for, 296, 410
gelcoat, 408
Safety precautions, 411~20 polyester resins, for, 45, 403-7
Salicylic acid, 264, 266, 267, 271, 272 twin pot, 46, 406
Sandwich construction, 80 Spray lay-up, 19, 33, 34, 45-8, 129,
Satin weave cloth, 321 134, 135
Sealing compounds, 17, 18,390,392 rovings for, 314
Sebacic acid, 144, 162 Stainless steel powder, 384
Sheet moulding Steel moulds, 28~31, 62
compounds, 50, 65-6, 349, 353-5 Steel tank repairs, 124--9
carbon fibre, 352 Styrene, 141, 145, /46,159,204
commercial, 364-5 TLV, 145,146,159,297
low profile/low shrink, 12,66,355 Surface preparation of
manufacture, 352 aluminium, 112
properties cured, 8, 364-5 carbon fibre composites, 113
reinforcements for, 314 concrete, 131
thick, 352 copper and brass, 112

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INDEX 461
Surface preparation of-contd. Triamylammonium phenate, 279, 282
GRP, III Trichloroethyl phosphate, 157
moulds, 39 Triethanolamine acetate, 386
stainless steel, 112 Triethylenetetramine, TETA, 251,
steel, 112, 125 268,270
thermoplastics, 112 Trimellitic anhydride, 276, 278, 280
wood, 112 Trimethylhexamethylenediamine, 264,
Surfacing tissue, 19,26,40,41,43, 267, 268, 270
45,47,60, 70, 126, 134, 135 Trimming, 83-4
commercial, 333-4 'green' stage, at, 19, 43
construction of, 310 mould, in, 29, 66
Triphenyl phosphite, 271
Tris-(dimethylaminoethyl)phenol, 282,
Talc, 64, 351, 354,375,378,419 284, 285, 287
Tank Twill weave cloth, 321
on-site construction of, 137
repair, 124--9
Tertiary amines as, Undercuts, 18, 20, 30
accelerators Unidirectional weave, 321, 326
anhydrides, for, 274, 280, 282 prepregs, 65, 366-70
peroxides, for, 209, 210, 211, Urea-formaldehyde resins, 305, 306
213, 214, 223 UV stabilisers, 390
commercial, 239
Test methods, 421-33
Tetrabromobisphenol A, 247 Vacuum
Tetrachlorophthalic anhydride, 144 bag moulding, 34, 49-51
Tetraethylenepentamine, TEPA, 268 impregnation, 35, 55-9
Tetrahydrophthalic anhydride, injection, 56
THPA, 275, 276, 278 British Rail process, 58-9
Tex,313 Crystic Systems process, 59
Thermoplastic additives, 161 Hoechst process, 56-8
Thick laminates, 42, 47 Monoforming, 59
Thick moulding compound, 352 Vanadium accelerators, 213,215,216,
Thin layer chromatography, 243, 244 219, 220, 222, 238
Thixotropic additives, 379, 386 Vermiculite, 28, 375, 380
Threshold limit value, TLV, 145,146, Vinyl ester resins, 3, 73, 123, 129,
159, 296, 297 299-301
Titanium chemical resistance of, 153-5
dioxide, 375, 383, 420 Vinyl toluene, 146, 161
properties of, 309 Viscosity
Tooling, moulds, 15-32 effect of diluents on, 250, 252
Topcoat resins, 43, 48, 74, 127, 135, test methods, 428
15(}-1,389
Tracking resistance, 254, 431
Trade names, 434 Water resistance tests, 423
Transfer moulding, 36, 67 Wax
moulds for, 30 additives, 151, 160, 389
Triallyl cyuranate, 146, 147 moulds, 32, 71

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462 INDEX

Wax-contd. Woven rovings-contd.


paraffin, 389 commercial products, 343-6
pattern makers, 21, 28, 392 Wrinkle finish, 86-7
polish, 16, 18,21,24,39, 115
release agents, 39, 84, 390
Weaving, 315 Xylok resins, 301--4
Wet lay-up, 34, 38--48,49-51 m-Xylylenediamine, MXDA, 268, 269
Whiting, 377
Wollastonite, 378
Wooden Yarn, 319, 320
moulds, 18
patterns, 16, 18, 19, 24
structures, linings for, 135 Zinc borate, 158
Woven glass cloth, 41, 61, 74, 77, Zinc oxide, 375, 382, 420
134,319-23 Zinc powder, 384
commercial products, 343-6 Zinc stearate, 351, 354, 389
Woven rovings, 33,41,47,53,58, Zirconium oxide, 375, 383, 420
323 Zirconium silicate (zircon), 375, 379.
chopped strand mat, with, 318 420

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