Aci SP-153 Vol1,2 Book - 1995

--``,`,-`-`,,`,,`,`,,`---
Copyright American Concrete Institute

Provided by IHS under license with ACI
No reproduction or networking permitted without license from IHS Not for Resale
A C 1 SP-153 VOL*I 95 0662747 0520955 415 =
Fly Ash, Silica Fume, Slag, and
Natural Pozzolans in Concrete
Proceedings
Fifth International Conference
Milwaukee, Wisconsin, USA, 1995
Editor --``,`,-`-`,,`,,`,`,,`---
V.M. Malhotra
No reproduction or networking permitted without license from IHS
Volume 1
Not for Resale
SP-153
A C 1 SP-153 V O L S I 95 O662949 0520956 3 5 1
DISCUSSION of individual papers in this symposium may be submitted in

accordance with general requirements of the AC1 Publication Policy to AC1
headquarters at the address given below. Closing date for submission of
discussion is January 1, 1996. All discussion approved by the Technical
Activities Committee along with closing remarks by the authors will be
published in the May/June 1996 issue of either AC1 Structural Journal or
AC1 Materials Journal depending on the subject emphasis of the indi-vidual
paper.
The Institute is not responsible for the statements or opinions expressed in

its publications. Institute publications are not able to, nor intended to,
supplant individual training, responsibility, or judgment of the user, or the
supplier, of the information presented.
The papers in this volume have been reviewed under Institute publication
procedures by individuals expert in the subject areas of the papers.
Copyright O 1995
AMERICAN CONCRETE INSTITUTE
P.O. Box 19150, Redford Station
Detroit, Michigan 48219
--``,`,-`-`,,`,,`,`,,`---
AI1 rights reserved including rights of reproduction and use in any form or
by any means, including the making of copies by any photo process, or by any
electronic or mechanical device, printed or written or oral, or recording for
sound or visual reproduction or for use in any knowledge or retrieval system
or device, unless permission in writing is obtained from the copyright
proprietors.
Printed in the United States of America
Editorial production Victoria Lunick
Library of Congress catalog card number 95-76270

A C 1 SP-153 V O L X I 95 Ob62949 0520957 298
PREFACE
The Canadian Centre for Mineral and Energy Technology

(CANMET) of Natural Resources Canada, Ottawa, has played a significant
role in Canada for over twenty-eight years in research on fly ashes, ferrous
and nonferrous slags, and silica fumes, in order to conserve both resources
and energy. 111 July-August 1983, CANMET, in association with the Ameri-
can Concrete Institute and the U.S. Corps of Engineers, sponsored a five
--``,`,-`-`,,`,,`,`,,`---
day international conference at Montebello, Quebec, Canada, on the Use

of Fly Ash, Silica Fume, Slag and Other Mineral By-products in Concrete.
The main purpose of the conference was to bring together representatives
from industries, universities, and government agencies to present the latest
information on these materials and to explore new areas of needed re-
search. The two volume proceedings of the conference containing 62 papers
from 15 countries were published as AC1 Special Publication SP-79.
In 1986, CANMET, in association with the American Concrete Insti-
tute, the Canadian Society for Civil Engineering, and a number of organ-
izations in Spain, sponsored the Second International Conference on the
subject of Fly Ash, Silica Fume, Slag, and Natural Pozzolans in Concrete.
The conference was held April 21-25, 1986, in Madrid, Spain. The two
volume proceedings of the conference containing 72 papers from more than
20 countries were published as AC1 Special Publication SP-91.
In 1989, CANMET, in association with the American Concrete Iristi-
tute, Norwegian Institute of Technology, and several other organizations in
Canada and Norway, sponsored the Third International Conference on the
above subject. The conference was held June 18-23, 1989, in Trondheim,
Norway. The two volume proceedings of the conference containing 83
papers from more than 25 countries were published as AC1 Special Publi-
cation SP-114.
tute, Electric Power Research Institute, U.S.A., and several other or-
ganizations in Canada and Turkey, sponsored the Fourth International
Conference on the subject. The conference was held May 3-8, 1992, in
Istanbul, Turkey. More than 130 papers from 32 countries were received
and reviewed in accordance with the policies of the American Concrete
Institute; 89 papers were accepted for publication as AC1 Special Publi-
cation SP-132.
tute, Electric Power Research Institute, U.S.A., Canadian Electrical

Provided by IHS under license with ACI iii
A C 1 SP-153 V O L X I 95 m Ob62949 0520958 124 m
Association, Montreal, and several other organizations in Canada and the

United States, sponsored the Fifth International Conference on the subject.
The conference was held June 4-9,1995, in Milwaukee, U.S.A. The two vol-
ume proceedings of the conference containing 62 papers Com 23 countries
were published as AC1 Special Publication SP-153.
To all those whose submissions could not be included in the confer-
ence volumes, the Institute and the Conference Organizing Committee ex-
tend their appreciation for their interest and hard work. The accepted
papers have been published in two volumes. The first volume contains
papers dealing with fly ash and natural pozzolans, and the second volume
consists of papers dealing with silica fume, slag, and other materials. Some
papers could have been published in either volume because the material
covered more than one subject.
In addition to the papers which have been published in these vol-
umes, more than 20 other papers were presented. Most of these papers
were published as supplementary papers, and the authors have been
encouraged to publish them in technical journals of their choice.
Thanks are extended to the members of the "Paper Review Panel"
which met as Cascais, Portugal, June 5-9, 1994, to review the papers.
Without their dedicated effort it would not have been possible to publish
these volumes before the conference. The cooperation of the authors in
accepting reviewers' suggestions and revising their manuscripts accordingly
is greatly appreciated.
The help and assistance of Mr. H. S . Wilson, Consultant, Ottawa,
Gordon D. Brearly and Maria Venturino of CANMET are gratefully ac-
knowledged in the administrative work associated with the conference, and
in processing of the manuscripts both for AC1 proceedings and the supple-
mentary volume. Thanks are also extended to A. Bilodeau (Chairman) and
Messrs. B. Fournier and R. Chevrier (Members) of the Slide Review Panel
for their services to ensure that the slides meet the CANMET/ACI cri-
terion.
As an integral part of the conference, a special symposium to honor
Dr. Narayan Swamy, Prof. Dept of Civil Engineering, University of Shef-
field, U.K., was held during the conference. The papers presented at this
symposium have been published in a separate volume.
--``,`,-`-`,,`,,`,`,,`---
V. M. Malhotra, Editor
Chairman, CANMET/ACI Fifth International
Conference on Fly Ash, Silica Fume, Slag
and Natural Pozzolans in Concrete
June 1995

Provided by IHS under license with ACI iv
A C 1 SP-1-53 V O L X I 95 W Obb2949 0 5 2 0 9 5 9 Ob0 m
Organizing Committee
on
Fly Ash, Silica Fume, Slag
Milwaukee, Wisconsin
1995
V. M. Malhotra H. S. Wilson
Chairman Secretary-Treasurer
Members
T. W. Bremner
H. L. Isabelle
W. S. Langley
V. S . Ramachandran
--``,`,-`-`,,`,,`,`,,`---
Dedicated to Members of the "Paper Review Panel" who assisted in the

review of the manuscripts.

Provided by IHS under license with ACI V
A C 1 SP-153 V O L X I 95 H 0662949 0520760 882 =
CONTENTS
PREFACE ........................................... ...

111
PROPERTIES O F HIGH-VOLUME FLY ASH CONCRETE MADE

WITH HIGH-EARLY STRENGTH ASTM TYPE III CEMENT
by A. Bilodeau and V. M. Malhotra . . . . . . . . . . . . . . . . . . . . . . . . . 1
STRUCTURAL CONCRETE INCORPORATING HIGH

VOLUME O F FLY ASH
by D. Galeota, M. M. Giammatteo, and R. Marino . . . . . . . . . . . . 25
USING MEDIUM- T O HIGH-VOLUME FLY ASH BLENDED

CEMENTS T O IMPROVE T H E SULFATE RESISTANCE O F
HIGH-LIME FLY ASH CONCRETE
by J. R. Prusinski and R. L. Carrasquillo .................... 43
PROCESSED FLY ASH FOR HIGH PERFORMANCE

CONCRETE
by H. A. W. Cornelissen, R. E. Hellewaard, and J. L. J. Vissers ... 67
--``,`,-`-`,,`,,`,`,,`---
EFFECT O F FLY ASH COMPOSITION ON THERMAL

CRACKING IN CONCRETE
by M. D. A. Thomas, P. K. Mukherjee, J. A. Sato,
and M. F. Everitt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
A MODEL FOR PREDICTING T H E COMPRESSIVE

STRENGTH O F STRUCTURAL FLY ASH CONCRETE
by F. de Larrard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
LONG-TERM PERFORMANCE O F GROUT CONTAINING

FLY ASH AND BRINE
by A. A. Al-Manaseer and M. D. Haug . . . . . . . . . . . . . . . . . . . . . 109

A C 1 SP-153 V O L S I 95 O662949 0520963 719
PROPERTIES O F MORTAR MIXTURES CONTAINING

HIGH AMOUNTS O F VARIOUS SUPPLEMENTARY
CEMENTITIOUS MATERIALS
by C. Talbot, M. Pigeon, J. Marchand, and H. Hornain . . . . . . . . . 125
PRODUCTION O F SULFATE-RESISTANT CONCRETE

CONTAINING HIGH-CALCIUM FLY ASH AND SODIUM
SULFATE ADMIXTURE
by R. B. Freeman and R. L. Carrasquillo . . . . . . . . . . . . . . . . . . . . 153
INFLUENCE O F PARTICLE SIZE DISTRIBUTION ON T H E

EFFECTIVENESS O F TYPE-F FLY ASH IN SUPPRESSING
EXPANSION DUE T O ALKALI-SILICA REACTIVITY
by M. A. Bérubé, A. Carles-Gibergues, J. Duchesne,
and P. Naproux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
EXPANSIVE CEMENT PRODUCED FROM AFBC ASH BY

ALKALI SULPHATE ACTIVATION APPROACH
by W. Jiang and D. M. R o y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
ACTIVE B - q S CEMENT FROM FLY ASH AND KILN DUST

by A. Xu and S. L. Sarkar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
T H E INFLUENCE O F HIGH EARLY STRENGTH (HES)

MINERALIZED CLINKER ON THE STRENGTH
DEVELOPMENT O F BLENDED CEMENTS CONTAINING
FLY ASH, SLAG OR GROUND LIMESTONE
by S. Kelham, J. S. Damtoft, and B. L. O. Talling . . . . . . . . . . . . . . 229
MIXTURE PROPORTIONING FOR HIGHLY-FLOWABLE

CONCRETE INCORPORATING LIMESTONE POWDER
by K. Sakata, T. Ayano, and A. Ogawa . . . . . . . . . . . . . . . . . . . . . 249
PROPERTIES O F LIGHTWEIGHT AGGREGATE PRODUCED

FROM A HIGH CALCIUM FLY ASH
by G. Baykal, T. Özturan, M. Savas, and K. Z. Ramadan . . . . . . . . 269
FIVE-YEAR EXPOSURE TEST ON LONG-TERM PROPERTIES

O F CONCRETES CONTAINING FLY ASH, BLAST-FURNACE
SLAG AND SILICA FUME
by T. Sasatani, K. Torii, and M. Kawamura . . . . . . . . . . . . . . . . . . 283
MOVEMENT O F IONS THROUGH MORTAR MIXED WITH

MINERAL ADMIXTURES
by N. Otsuki, S. Nagataki, and M. Hisada . . . . . . . . . . . . . . . . . . . 297
--``,`,-`-`,,`,,`,`,,`---

Provided by IHS under license with ACI viii
A C 1 SP-153 VOLXI 75 m 0662749 0520962 6 5 5 m
PROPERTIES O F CONCRETE WITH BAGASSE ASH AS FINE

AGGREGATE
by B. K. Baguant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
MECHANICAL TREATMENT O F FLY ASHES: STRENGTH

DEVELOPMENT AND WORKABILITY O F MORTARS
CONTAINING GROUND FLY ASHES
by J. Monzó, J. Pay& E. Peris-Mora, and M. V. Borrachero . . . . . . 339
INFLUENCE O F FINENESS AND SOLUBLE SILICA CONTENT

O F FLY ASHES ON THEIR STRENGTH DEVELOPMENT
WITH RESPECT T O AGE
by R. V. Ranganath, R. C. Sharma, and S. Krishnamoorthy . . . . . . 355
IMPROVEMENT O F CHARACTERISTICS O F ROLLER

COMPACTED CONCRETE BY CLASSIFIED FLY ASH
by T. Fukute, K. Nakano, and M. Ishii . . . . . . . . . . . . . . . . . . . . . . 367
CLASS C FLY ASH AS A SHRINKAGE REDUCER FOR

CEMENT PASTE
by S. Tangtermsirikul, T. Sudsangiam, T. Deesawangnade,
and P. Nimityongskul . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
--``,`,-`-`,,`,,`,`,,`---
CONSTRUCTION EXPERIENCE WITH CLSM FLY ASH
SLURRY FOR UNDERGROUND FACILITIES
by B. W. Ramme, T. R. Naik, and H. J. Kolbeck . . . . . . . . . . . . . .403
A STRENGTH DEFINITION FOR T H E WATER-TO-CEMENT

MATERIALS RATIO
by A. Hassaballah and T. H. Wenzel . . . . . . . . . . . . . . . . . . . . . . . 417
UTILIZATION O F FLY ASH IN T H E DEVELOPMENT O F A

COST-EFFECTIVE CEMENTITIOUS PRODUCT
by S. L. Sarkar, A. Kumar, D. K. Das, and G. Banerjee . . . . . . . . . 439
MORPHOLOGY AND SELECTED PROPERTIES O F FLY ASH

by P. K. Rohatgi, P. Huang, R. Guo, B. N. Keshavaram,
a n d D . Golden . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
COMPARATIVE TESTING O F PORTLAND CEMENT, FLY

ASH, GROUND GRANULATED BLAST FURNACE SLAG
AND SILICA FUME CONCRETES FOR POTENTIAL
DURABILITY
by P. C. Taylor, P. E. Streicher, G. Goch, and L. Fliss . . . . . . . . . . 479

ix Not for Resale
A C 1 SP-I153 V O L * I 95 0662749 0520763 591 =
HEAT TREATMENT O F FINE-GRAINED CEMENTLESS

CONCRETE BASED ON HIGH-CALCIUM FLY ASH AND
SLAG FROM THERMAL POWER PLANTS
by S. I. Pavlenko . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
USE OF FLY ASH, BLAST FURNACE SLAG AND CHEMICAL

GYPSUM FOR T H E SYNTHESIS OF CALCIUM
SULFOALUMINATE-BASED CEMENTS
by G. Belz, J. Beretka, M. Marroccoli, L. Santoro, N. Sherman,
and G. L. Valenti . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
MEXICAN NATURAL POZZOLANS AND THE EVALUATION

OF T H E SPECIFICATIONS RELATED TO THEIR USE
by R. Uribe-Afif and R. E. Rodriguez-Camacho . . . . . . . . . . . . . . . 531
RUBBER ADDED FLY ASH FOR UNDERGROUND

PETROLEUM TANKS
by G. Baykal and K. Köprülü . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
EFFECTIVENESS O F FLY ASH IN REDUCING EXPANSION

O F CONCRETE MADE WITH REACTIVE AGGREGATES
FROM NEW BRUNSWICK, CANADA
by B. Fournier, W. S. Langley, and V. M. Malhotra . . . . . . . . . . . . 561
--``,`,-`-`,,`,,`,`,,`---

Provided by IHS under license with ACI X
A C 1 SP-153 V O L * I 95 IOb62949 0520964 4 2 8 I
SP 153-1
Properties of High-Volume Fly Ash

Concrete Made with High Early-
Strength ASTM Type 111 Cement
by A. Bilodeau and V. M. Molhotra
SvnoDsis: Canada Centre for Mineral and Energy Technology (CANMET)

has an ongoing project dealing with the role of supplementary cementing
materials in concrete technology. As a part of this program, a new type of
concrete known as high-volume fly ash concrete has been developed. In this
type of concrete, the water and cement (ASTM Type I) contents are kept very
low, i.e. about 115 and 155 kg/m3, respectively, and the proportion of low-
calcium fly ash in the total cementitious materials content is about 56 per cent.
This type of concrete has excellent mechanical properties and durability
characteristics.
In spite of very good properties shown by the high-volume fly ash
concrete, one concern about the use of this type of concrete is its performance
at early ages due to its low cement content and the slow reaction process of the
fly ash. This can be an obstacle for the use of this type of concrete when
compressive strengths over 10 MPa at one day are needed or when proper
curing cannot be provided for a long period of time. One way to improve the
early-age properties of this type of concrete is to use ASTM Type III portland
cement. Therefore a study was undertaken to develop engineering data base
on the high-volume fly ash concrete using ASTM Type III cement. Concrete
mixtures were made using ASTM Type III portland cement from a source in
the U.S.A., and three low-calcium fly ashes also from sources in the U.S.A.
A reference mixture (without fly ash) was also made for comparison purposes.
The use of ASTM Type III cement instead of Type I cement noticeably
improved the early-age strength properties of the high-volume fly ash concrete
incorporating the fly ashes investigated in this study, and this without having
any detrimental effect on the long-term properties of the concrete. The one-
day compressive strengths were about 5 to 8 MPa higher than those of the
high-volume fly ash concrete made with the same fly ash and Type I cement.
The use of Type III cement also shortened slightly the setting time of the high-
volume fly ash concrete. The durability characteristics and the drying
shrinkage of high-volume fly ash concrete made with ASTM Type III cement
were no different than those for the concrete made with Type I cement.
Kevwords: Chloride ions; compressive strength, drying shrinkage; flexural

strength; flv ash; freeze thaw durability; hieh earlv-strength cements;
modulus of elasticity; splitting tensile strength; superplasticizer
--``,`,-`-`,,`,,`,`,,`---

Provided by IHS under license with ACI 1
A C 1 SP-153 V O L I I 95 W Obb2949 0520965 364 w
2 Bilodeau and Malhotra
--``,`,-`-`,,`,,`,`,,`---
AC1 member Alain Bilodeau is a concrete research engineer, Advanced

Concrete Technology Program, CANMET. His current research interests are
primarily in the areas of the use of supplementary cementing materials and
durability of concrete. He has published several papers on concrete technology
and is a member of the CSA Committee on Concrete Materials and
Construction.
AC1 honorary member V. Mohan Malhotra is Program Principal, Advanced

Concrete Technology Program, CANMET. He is a former member of the
AC1 Board of Direction and has served on numerous AC1 and ASTM
committees. He is a prolific author, editor, and researcher, and has received
many awards and honors from AC1 and other institutions throughout the
world.
INTRODUCTION
In 1990, CANMET undertook a project to develop data base on high-

volume fly ash concrete incorporating selected fly ashes and cements from the
U.S.A. This investigation was performed for the Electric Power Research
Institute (EPRI), Palo Alto, California, under a subcontract with Radian
Canada Inc., Mississauga, Ontario. Eight fly ashes, covering a wide range of
chemical compositions, and two ASTM Type I portland cements from two
different sources were used in the study. Regardless of the type of fly ash and
irrespective of the brand of cement used, all air-entrained high-volume fly ash
concretes performed well as regard to workability, bleeding, setting time,
temperature rise, and mechanical properties. They also exhibited excellent
durability characteristics in freezing and thawing cycling, resistance to
chloride-ion penetration, resistance to sulphate attack, and water permeability
tests (1, 2).
In spite of the excellent properties shown by the high-volume fly ash

concrete in the above mentioned study, one concern about the use of this type
of concrete is its performance at early ages due to its low cement content and
the slow reaction process of the fly ash. This can be a disadvantage for the
use of this type of concrete when high-early strengths at one day are needed
or when proper curing cannot be provided for a long period of time. For
example, in the field, a certain level of strength at early age is needed to
remove the formwork. In the above mentioned investigation, one-day
compressive strengths ranging from 3.1 to 13.9 MPa were obtained, depending
on the cement-fly ash combination. The one-day compressive strength of 3.1
MPa could be considered unacceptable for some applications (1).

A C 1 SP-153 VOL81 95 m Ob62949 05209bb 2TO m
Milwaukee Conference 3
One way to improve the early-age strength of the concrete is to use

ASTM Type III portland cement. A previous investigation at CANMET has
shown that the use of Type III cement in high-volume fly ash concrete
increased significantly the early-age strengths (3). Therefore the above
EPRURadian study was extended to develop engineering data base on the high-
volume fly ash concrete using ASTM Type III cement. In this new phase,
concrete mixtures were made using one ASTM Type III portland cement from
a source in the U.S.A. and three of the low-calcium fly ashes used in the
previous study with Type I cement (1, 2). A reference mixture without fly ash
was also made for comparison purposes. Some mechanical properties and
durability characteristics were determined, and the results are presented in this
paper.
SCOPE
Four air-entrained concrete mixtures involving eight O. 11 m3 batches

were made. The water-to-(cement+fly ash) ratio [W/(C+FA)] was kept at
0.32 for all the high-volume fly ash concrete mixtures. The water-to-cement
ratio of the reference concrete was kept at 0.45 to obtain concrete with
strength comparable to that of the fly ash concrete at 28 days. The proportion
--``,`,-`-`,,`,,`,`,,`---
of fly ash in the concrete mixtures was 58 per cent by weight of the
cementitious materials.
The properties of the freshly mixed concrete were determined. These

included, unit weight, slump, air content, setting time, and bleeding. The
adiabatic temperature rise was monitored on 152x305-mm cylinders. A
number of specimens were cast, moist-cured, and tested for the determination
of the mechanical properties of concrete. These included compressive,
flexural, and splitting-tensile strengths at various ages, Young’s modulus of
elasticity, and drying shrinkage.
A number of specimens were also cast to determine the air-void

parameters, the resistance to freezing and thawing cycling, and the resistance
to chloride-ion penetration.
MATERIALS
ASTM Class F fly ashes from three sources in the U.S.A., and one
ASTM Type III portland cement also from the U.S.A. were used in the
concrete mixtures. The materials used in this program are described below.

A C 1 SP-I153 V O L * I 95 W O662949 0520967 137
Portland Cement
ASTM Type III portland cement was from the same source as one of
the Type I cements used in the original study (1, 2). The chemical analysis
and physical properties of the cement are given in Table 1.
Flv Ash
--``,`,-`-`,,`,,`,`,,`---
Three fly ashes from sources in the U.S.A. were used. These fly ashes
were the same as used in the original study with Type I cement (1, 2). Fly
ashes FA1 and FA2 had low C a 0 contents of 2.88 and 4.49 per cent,
respectively, whereas fly ash FA3 had a C a 0 content of 9.51 per cent'. The
chemical analysis and physical properties of the three fly ashes are also given
in Table 1.
Aggregates
The coarse aggregate was a crushed limestone (19-mm maximum size),

and the fine aggregate was a natural sand. To keep the grading uniform for
each mixture, both the fine and coarse aggregates were separated into different
size fractions that were then recombined to a specific grading. The grading
and physical properties of the aggregates are given in Tables 2 and 3.
Supemlasticizer
A commercially available sulphonated naphthalene formaldehyde

condensate superplasticizer was used. This superplasticizer is available as a
dark brown aqueous solution with 40 per cent solids.
Air-Entraining Admixture
A synthetic resin type air-entraining admixture was used in ail the

mixtures.
MIXTURE PROPORTIONS
Three high-volume fly ash concrete mixtures and one reference mixture
without fly ash were made in February and March 1993. Two 0.11 m3
'Fly ashes FAl, FA2 and FA3 correspond to the fly ashes F2, F4 and F8 in
the original investigation.

A C 1 SP-153 V O L X I 95 0662749 0520968 073
batches were made for each mixture in order to cast a sufficient number of
specimens for testing. The concrete mixtures were made in a laboratory
counter-current mixer with the fly ash added as a separate ingredient.
The proportioning of the concrete mixtures is summarized in Table 4.

For all the mixtures, the graded coarse and fine aggregates were weighed in
a room dry condition. The coarse aggregate was then immersed in water for
24 h, the excess water was decanted, and the water retained by the aggregates
was determined by the weight difference. A predetermined amount of water
was added to the fine aggregate which was then allowed to stand for 24 h.
The water-to-cementitious materials ratio, as well as the water, cement

and fly ash contents were kept constant for the three high-volume fly ash
mixtures, and these were very similar to those used in the original study with
ASTM Type I cement (1, 2 ) . The water-to-cement ratio of the reference
concrete was 0.45, which was chosen to obtain concrete with 28-day
compressive strength similar to that of the high-volume fly ash concrete. All
mixtures were air-entrained, with the target air content of 5.5 f 0.5 per cent.
The dosage of the superplasticizer was adjusted to give a slump of 150 f 25
mm.
PROPERTIES OF FRESH CONCRETE
The properties of the freshly mixed concrete, Le., temperature, slump,

unit weight and air content, are given in Table 5.
PREPARATION AND CASTING OF TEST SPECIMENS

--``,`,-`-`,,`,,`,`,,`---
Two batches were made for each mixture in order to obtain sufficient
test specimens.
Batch A
Twelve 152x305-mm cylinders and three 75x102x406-mm prisms were

cast from Batch A of each mixture. The 152x305-mm cylinders were used for
the determination of compressive strength at various ages, and the prisms were
used for determining the flexural strength at 14 days.
Batch B
Eight 152x305-mm cylinders, ten 76x102x390-mm prisms and three

102x203-mm cylinders were cast from Batch B of each mixture. The

A C 1 SP-153 VOLJI 95 W Obb2949 0520969 TOT W
152x305-mm cylinders were used for determining the compressive strength,

the Young’s modulus of elasticity, the splitting-tensile strength at 28 days, and
the autogenous temperature rise of concrete. The prisms were used for
determining the freezing and thawing resistance and the drying shrinkage of
concrete. The 102x203-mm cylinders were used for the determination of the
resistance of concrete to chloride-ion penetration. One container of
approximately 7 L capacity was filled with fresh concrete for determining the
bleeding of concrete.
Compaction and Curine, of Test Suecimens
For all batches, the cylinders and prisms were cast in two layers, with
--``,`,-`-`,,`,,`,`,,`---
each layer being compacted using an internal vibrator for the 152x305-mm
cylinders and a vibrating table for the prisms and the 102x203-mm cylinders.
After casting, all the moulded specimens were covered with plastic sheets and
water-saturated burlap, and left in the casting room for 24 h. They were then
demoulded and transferred to the moist-curing room at 100 per cent relative
humidity until required for testing. The only exception was the prisms for the
drying shrinkage tests which were stored in lime-saturated water.
TESTING OF SPECIMENS
The schedule of testing is shown in Table 6. The adiabatic temperature

rise of the concretes was measured by means of thermocouples embedded in
the centres of two 152x305-mm cylinders of fresh concrete placed in an
autogenous curing chamber. This curing chamber was somewhat similar to
that described in Procedure C of ASTM C 684: Making, Accelerated Curing
and Testing Concrete Compression Test Specimens. The temperature of the
concrete was recorded at 30-minute intervals for about 48 h.
Two cylinders from Batch A were tested at various ages up to one

year. For control purposes, two 152x305-mm cylinders from Batch B were
also tested in compression at 28 days. Two 152x305-mm cylinders from Batch
B were used for the determination of the Young’s modulus of elasticity at 28
days; also two 152x305-mm cylinders from the above batch were used for
determining the splitting-tensile strength at 28 days. Three prisms,
75x102~406mm in size, from Batch A were tested in flexure at the age of 14
days. Four 76x102x390-mm prisms, cast from batch B of all the mixtures
were used for determining the drying shrinkage of concrete; two of these
prisms were subjected to the drying shrinkage after 7 days of initial storage in
lime-saturated water whereas the two remaining prisms were kept in the lime-
saturated water for reference purposes.

A C 1 SP-153 VOL*I 95 O662949 0520970 7 2 1
Following 14 days of initial moist-curing, six prisms, 75x102~390mm

in size, from Batch B were used for determining the freezing and thawing
resistance of concrete using ASTM C 666, Procedure A, freezing and thawing
in water. Two of these prisms were broken in flexure to determine the initiai
flexural strength before freezing and thawing cycling. Sawn sections of these
prisms were used for determining the air-void parameters of the hardened
concrete. Prior to the freezing and thawing testing, the temperature of the
four remaining prisms was reduced to 4.4 1.7"C by placing them in a cold
water tank. The initial and all subsequent measurements of the freezing and
thawing specimens and the reference specimens were made at this temperature.
After the initiai measurements, two test specimens were subjected to freezing
and thawing cycling and the two companion prisms were placed in the moist-
curing room for reference purposes. After the completion of the freezing and
thawing test, the reference and the freezing and thawing prisms were tested in
flexure.
The resistance of the concretes to the chloride-ion penetration was

--``,`,-`-`,,`,,`,`,,`---
determined at the ages of 7, 28 and 91 days on disks cut from 102x203-mm

cylinders from Batch B, using the method outlined in ASTM C 1202.
TEST RESULTS
The data on the bleeding, the setting time, and the maximum
temperature rise of the concrete are given in Table 7. The autogenous
temperature rise of the concrete is illustrated in Fig. 1. Densities of the test
cylinders at one day and the compressive strength test results at different ages
are given in Table 8. The compressive strength development of the concrete
is illustrated in Fig. 2. The Young's modulus of elasticity test results
determined at 28 days are given in Table 9. The flexural strength at the ages
of 14 and 91 days, and the 28-day splitting-tensile strength are shown in Table
10. The drying shrinkage test results are summarized in Table 11 and 12, and
illustrated in Fig. 5 . The air-void parameters of the hardened concrete are
given in Table 13. A summary of the test results after 300 cycles of freezing
and thawing, including the durability factors, is given in Table 14. The
flexural strengths of the reference prisms and the test prisms after 300 cycles
of freezing and thawing are shown in Table 15. The data on the resistance of
concrete to the chloride-ion penetration are summarized in Table 16.

A C 1 SP-153 V O L X I 95 Obb2949 0520973 668
DISCUSSION OF TEST RESULTS
Dosage of the Supemlasticizer and Slump
The dosage of the superplasticizer varied noticeably depending on the

kind of fly ash used, and ranged from 3.6 to 6.8 L/m3 of concrete (Table 4).
This is somewhat higher than the dosage used in the corresponding mixtures
made with the fly ashes from the same sources and the Type I cement (i).
This is probably due to the higher fineness of the Type III cement.
Some superplasticizer was needed in the reference concrete to obtain

the target slump, and this is due to the higher fineness of the cement, and the
relatively low water content of the mixture at water-to-cement ratio of 0.45.
Air Content and Dosage of the Air-Entraining Admixture
The dosages of the air-entraining admixture (AEA) of the high-volume

fly ash concretes made with ASTM Type III cement were slightly higher than
those used in the corresponding mixtures made with the ASTM Type I cement;
and this is, once again, due to the higher fineness of the Type III cement
(Table 4) (2).
Concrete mixtures made with fly ashes FA2 and FA3 required similar
dosages of AEA; however, the dosages of AEA for the concrete mixture
incorporating fly ash FA1 was significantly higher than for FA2 and FA3 fly
ashes, and this was probably due to the higher carbon content of the FA1 fly
ash.
As expected, the dosage of the AEA for the reference concrete was
noticeably lower than those for the high-volume fly ash concrete mixtures.
Bleeding of Concrete
The total amount of the bleeding water was negligible for all the high-
volume fly ash concretes, and was very low at 0.8 x 10’ mL/cmZ for the
reference concrete (Table 7). These results were in line with those obtained
with the corresponding high-volume fly ash concrete mixtures made with the
ASTM Type I cement (I).
Settim Time of Concrete
The initial and final setting times of high-volume fly ash concretes
ranged from 6:34 to 7:33 h:min., and from 8:23 to 9:08 h:min., respectively
(Table 7). As expected, the reference concrete set much faster, with initial
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 S 0662949 0520972 5 T 4
and final setting times of 4:51 and 5:25 h:min., respectively. The slower
setting of the high-volume fly ash concrete was due to the low cement content
of this type of concrete. However, the setting times for the high-volume fly
ash concretes in this investigation probably may not cause any practical
problems in field applications.
For fly ashes FA1 and FA2, both the initial and final setting times of
the concretes made with ASTM Type III cement were of the same order or
slightly shorter than those of the corresponding concretes made using the Type
I cement; for fly ash FA3, both the initial and final setting times were
significantly shorter when Type III cement was used (i).
The potential reduction in the setting time of the high-volume fly ash
concrete made using ASTM Type III cement instead of Type I cement might
have been partly offset by the higher dosages of the superplasticizer in the
mixtures incorporating the finer Type III cement, especially for concrete made
with fly ashes FA1 and FA2.
Autogenous Temperature Rise
The data in Table 7 show that the maximum temperature rise of about
17.5"C was very similar for the three high-volume fly ash concretes
investigated. The maximum temperature rise for the reference concrete was
considerably higher at 35.9"C.
The maximum temperature rise of the fly ash concretes made with
ASTM Type III cement was higher (from 3.6 to 4.8"C) than those of the
--``,`,-`-`,,`,,`,`,,`---
corresponding concretes made with the Type I cement, and this was due to the
faster hydration of the Type III cement (i).
Figure 1 shows that all the high-volume fly ash concretes had very
similar heat evolutions. It also illustrates the much higher temperature in the
reference concrete, and that the peak temperature was attained much sooner
in the reference concrete than in the fly ash concrete.
As in previous investigations (4, 5), the above results demonstrate the

potential of high-volume fly ash concrete system for reducing the temperature
rise in large concrete members due to its low cement content and slow reaction
process of the fly ashes.

A C 1 SP-153 V O L X I 95 IObb2949 05209’73 430 W
Comuressive Strength
The data on the compressive strength of the concrete are given in Table
8 and illustrated in Fig. 2 . The one-day compressive strength of the reference
concrete (28.3 MPa) was noticeably higher than that of the high-volume fly
ash concrete which ranged from 16.5 to 17.1 MPa. Following this, the
strength development of the reference concrete was slower than that of the fly
ash concrete, especially between 7 and 91 days. The compressive strength of
the reference concrete was slightly lower at 28 days, and significantly lower
at 91 days and one year than that of the fly ash concretes.
Figures 3 and 4 illustrate the compressive strength development at early

ages, and up to one year, respectively, of high-volume fly ash concrete made
with ASTM Type I and Type III cements. The data are the average values of
the test results obtained with the same fly ashes used in this investigation, and
the previous study with Type I cement (1). The average one-day compressive
strength of the high-volume fly ash concretes made with Type III cement is
about 6.5 MPa higher than that obtained for the corresponding concretes made
--``,`,-`-`,,`,,`,`,,`---
with ASTM Type I cement (Fig. 3). The average strength development of the
concrete made with the Type III cement was slightly faster up to 28 days than
that of the concrete made with the Type I cement. The objective of increasing
significantly the early-age strength of the high-volume fly ash concrete by
using ASTM Type III cement appears to have been achieved. However, the
data illustrated are based on the averaged values, and this trend is not
representative for all the fly ashes. For example, the fly ash FA3 showed
slower strength development with the Type III cement than with Type I cement
after one day.
The compressive strength of the high-volume fly ash concretes at 28

and 91 days ranged from 45.0 to 47.5 MPa (Batch A), and from 54.8 to 59.6
MPa, respectively (Table 8). These values are noticeably higher than the
corresponding strengths of the concretes made with ASTM Type I cement, as
illustrated in Fig. 4. The 91-day compressive strength of concrete made with
Type III cement is of the same order as the one-year compressive strength of
concrete made with Type I cement. The increase in the compressive strength
between 91 days and one year was less for the concrete made with ASTM
Type III cement than for concrete made with Type I cement. However, the
former concrete produced significantly higher compressive strength at one year
than the latter.
Young’s Modulus of Elasticity
The Young’s modulus of elasticity at 28 days ranged from 35.9 to 38.0

GPa for the high-volume fly ash concrete, and was 33.1 GPa for the reference

A C 1 SP-153 V O L X I 95 I0662949 0520774 377 =
concrete (Table 9). These results are in accordance with those of the previous
investigations, and demonstrate the high values of the modulus of elasticity of
the high-volume fly ash concrete (1, 3, 5 , 6, 7, 9, 10). As mentioned in
earlier studies, this could be due to the unhydrated fly ash particles acting as
fine aggregate, and thus contributing to an increase in the restraint against
deformation.
Flexural Strength
The flexural strengths of the high-volume ñy ash concrete ranged from

5.3 to 5.6 MPa at 14 days, and from 6.2 to 6.9 MPa at 91 days (Table 10).
The flexural strength of the reference concrete was 6.2 and 5.9 MPa at 14 and
91 days, respectively.
For each fly ash, the flexural strength of the concrete made with ASTM
Type III cement was slightly higher than that of the corresponding concrete
made with Type I cement (1).
Splitting-Tensile Strength
The 28-day splitting-tensile strength of the high-volume fly ash concrete

ranged from 3 . 2 to 4.1 MPa, and was 3.6 MPa for the reference concrete
(Table 10). These values are about 7 to 9 per cent of the 28-day compressive
strength, and are comparable with other published data for conventional
portland cernent concrete of similar compressive strength (8).
The ratios of the splitting-tensile to compressive strengths of the

concrete made with ASTM Type III cement are slightly lower than those of the
concrete made with ASTM Type I cement in the previous investigation (1).
This is probably due to the higher level of the compressive strength of the
concrete made with Type III cement, because the ratio of splitting-tensile to
compressive strengths tends to decrease with an increase in the level of
compressive strength (8).
Drying Shrinkage
The drying shrinkage strains of the high-volume fly ash concrete after
448 days of drying ranged from 497 to 6 7 8 ~ 1 0(Table
.~ 11). These values are
similar to those of the corresponding concretes made with ASTM Type I
cement in the previous investigation (1).
The shrinkage of the reference concrete (688~10.~) is of the same order

as the highest shrinkage strain obtained for the high-volume fly ash concretes
--``,`,-`-`,,`,,`,`,,`---
(Fig. 5).

A C 1 SP-153 V O L X I 75 Obb2949 0520775 203
Air-Void Parameters of the Hardened Concrete
Ali the concretes exhibited good air-void parameters with spacing

factors ranging from 0.074 to O. 174 mm which are less than the recommended
value of about 0.230 mm for freezing and thawing durability (Table 13).
Resistance to Freezing and Thawing Cycling
The durability of concrete prisms to repeated cycles of freezing and

thawing was determined from weight, length, resonant frequency, and pulse
velocity measurements of test specimens before and after freezing and thawing
cycling, and by calculating the durability factors (Tables 14). At the end of
the freezing and thawing cycling, the reference and test prisms were broken
in flexure (Table 15). The test data after 300 cycles indicate that all the test
prisms performed excellently in freezing and thawing with durability factors
equal to or greater than 100.
All the high-volume fly ash concrete test prisms have shown some
weight loss due to surface scaling, (Table 14). The reference concrete did not
show any weight loss nor surface scaling. However, the weight loss of the
high-volume fly ash concrete made with the Type III cement is noticeably
lower than that of the corresponding concrete made with the Type I cement in
the previous investigation (2). This improvement is probably due to the
greater maturity of the concrete made with ASTM Type III cement at the time
of testing.
Resistance to Chloride-Ion Penetration
The data in Table 16 show that all the high-volume fly ash concretes
investigated exhibited high resistance to the chloride-ion penetration, especially
at 28 and 91 days. These results are in accordance with those of previous
investigations (2, 7, 9, 10).
The use of ASTM Type III cement instead of Type I cement did not
improve the resistance to chloride-ion penetration at 28 and 91 days of
concrete incorporating fly ashes FA2 and FA3, but slightly increased that of
the concrete made with the fly ash FA1 (2). There are no data on the
resistance to chloride-ion penetration at 7 days of concretes incorporating the
above fly ashes and Type I cement. It is possible that the effect of the Type
III cement would have been visible at that early age.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 I0662949 0520976 1 4 T I
CONCLUSIONS
The use of ASTM Type III cement instead of Type I cement improved
significantly the early-age compressive strengths of high-volume fly ash
concrete incorporating the fly ashes investigated in this study. The one-day
compressive strength ranged from 16.5 to 17.1 MPa, these values being about
5 to 8 MPa higher than those of the high-volume fly ash concrete made with
the same fly ashes but using Type I cement. The use of the Type III cement
had no detrimental effect on the long-term strength development of the high-
volume fly ash concrete; on the contrary, the concrete made with this cement
resulted in higher compressive strengths at one year than those made with
ASTM Type I cement.
The use of ASTM Type III cement shortened the setting time of the
high-volume fly ash concrete slightly, and this could be an advantage in some
applications.
The durability characteristics and the drying shrinkage of the high-

volume fly ash concrete made using ASTM Type III cement were no different
from the concrete made with Type I cement.
The use of Type III cement increased the autogenous temperature rise
of the high-volume fly ash concrete slightly as compared with that of Type I
cement; however, the rise was stili much lower than that of the reference
concrete.
In general, the properties of the high-volume fly ash concrete

investigated were as good as or better than those of the reference concrete of
equivalent 28-day compressive strength.
--``,`,-`-`,,`,,`,`,,`---
ACKNOWLEDGEMENTS
Grateful acknowledgement is made to Dean Golden, Senior Project

Manager, EPRI, Palo Alto, California, and Dr. E.E. Berry, President, Radian
Canada Inc., Mississauga, Ontario, and Dr. Min-Hong Zhang, formerly of
Radian Canada, Inc., but currently employed at CANMET, for helpful
discussions during the progress of the investigation. Thanks are extended to
R. Chevrier and K.E. Painter of CANMET for performing various aspects of
the laboratory investigation.

A C 1 SP-I153 V O L * I 95 m 0662949 0520977 08b m
REFERENCES
1. Carette, G.G., Bilodeau, A., Chevrier, R.L. and Malhotra, V.M.

"Mechanical Properties of Concrete Incorporating High Volumes of Fly
Ash from Sources in the U.S." AC1 Materials Journal, Vol. 90, No.
6, November-December 1993, pp. 535-544.
2. Bilodeau, A., Sivasundaram, V., Painter, K.E. and Malhotra, V.M.

"Durability of Concrete Incorporating High Volumes of Fly Ash from
Sources in the U.S." AC1 Materials Journal, Vol. 91, No. 1, January-
February 1994, pp. 3-12.
3. Giaccio, G.M. and Malhotra, V.M. "Concrete Incorporating High-

Volumes of ASTM Class F Fly Ash", ASTM Cement, Concrete and
Aggregates, Vol. 10, No. 12, 1988, pp. 88-95.
4. Sivasundaram, V. "Thermal Crack Control of Mass Concrete", MSL

Division Report MSL 86-93 (IR), Energy, Mines and Resources
Canada, Ottawa, Canada, 1986, 32 pp.
--``,`,-`-`,,`,,`,`,,`---
5. Langley, W.S., Carette, G.G. and Malhotra, V.M. "Structural

Concrete Incorporating High-Volumes of ASTM Class F Fly Ash",
AC1 Materials Journal, Vol. 86, No. 5, 1989, pp. 507-514.
6. Malhotra, V.M. "Superplasticized Fly Ash Concrete for Structural

Applications", AC1 Concrete International, Vol. 8, No. 12, December
1986, pp. 28-31.
7. Sivasundaram, V., Carette, G.G. and Malhotra, V.M. "Properties of

Concrete Incorporating Low Quantity of Cement and High-Volumes of
Low Calcium Fly Ash", AC1 Special Publication SP-114, Vol. 1,
1989, pp. 45-71, (Editor, V.M. Malhotra).
8. Neville, A.M. "Properties of Concrete", Third Edition, Pitman

Publishing Limited, London, 1981.
9. Sivasundaram, V., Carette, G.G. and Malhotra, V.M. "Mechanical

Properties, Creep, and Resistance to Diffusion of Chloride Ions of
Concretes Incorporating High-Volumes of ASTM Class F Fly Ashes
From Seven Different Sources", AC1 Materials Journal, Vol. 88, No.
4, 1991, pp. 407-416.

A C 1 SP-1.53 V O L * I 95 6 0662949 0520978 T L 2
10. Bilodeau, A. and Malhotra, V.M. "Concrete Incorporating High

Volumes of ASTM Class F Fly Ashes: Mechanical Properties and
Resistance to De-Icing Salts Scaling and to Chloride-Ion Penetration";
AC1 Special Publication SP-132, Vol. 1 , 1992, pp. 319-349, (Editor,
V.M. Malhotra).
TABLE 1 - PHYSICAL PROPERTIES AND CHEMICAL ANALYSIS OF

CEMENT AND FLY ASH
~~ ~ ~~
ASTMlypm ASTM Class F Fiy Ash

Cement
FA1
PhVsicai Ropertier
Fineness - passing 45 pm. % 95.6 79.5

- Blaine, mzkg 495 224
Specific Gravity 3.06 2.26 2.42 2.39
Compressive Strength of
51-mm cubes, MPa: - 3 d 35.7
-7d
-28d
39.7
45.9 A :
Chemical Analysis
Silicon dioxide (SiOJ, %

1 19.76 53.64
Aiuminum oxide (Ai,OJ, % 5.65 27.42
Ferric oxide (FqOJ. % 2.02 7.74
Calcium oxide ( G O ) ,% 63.07 2.88
Magnesium oxide (MgO), % 2.39 0.99
Sulphur trioxide (Sod, % 3.91 0.37 0.92
Sodium oxide (N&O),% 0.34 0.38 1.43 3.08
Potassium oxide (K,O),% 0.98 2.42 2.40 1.22
Loss on ignition,% 1.41 1.49 0.95 0.30
b u e Potential Compound
Comr>osition
;.ti.
c,s 54.6
C8 15.4
C3A 11.6
CAW 6.1
Strength Activitv Index
with Portland Ceinenfi
7 daYs
28 days I 83.1
90.5
* These values were obtained with an ASTM lyp I cement
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 m O b b 2 9 4 9 0520979 959 m
TABLE 2 - GRADING OF AGGREGATES
?%ate
Cumulative
Percentage Percentage
Retained Retained
19.0 mm 0.0 4.75 mrn 0.0
12.7 mm 40.0 2.36 rnm 10.0
9.5 mm 65.0 1.18 mm 32.5
4.75 mm 100.0 600 pn 57.5
300 pn 80.0
150 pn 94.0
Pa 100.0
TABLE 3 - PHYSICAL PROPERTIES OF AGGREGATES
C o m Aggregate Fine Aggregate
Specific Gravity 2.69 2.7

Absorption, 96
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 R 0662949 0520980 670 R
TABLE 4 - CONCRETE MIXTURE PROPORTIONS

W/(C+FA)* sh. %A,** SP,*"
kglm' mLh' um'
0.32 FA1 214 1192 642 640 6.8
0.32 FA1 214 1192 642 575 6.3
0.32 FA2 214 I202 647 185 4.1

0.32 FA2 213 1195 643 185 4.1
0.32 FA3 212 1189 639 185 3.6

0.32 FA3 214 1202 647 180 3.7
0.45 O 1041 694 90 2.5

0.45 O 1054 702 85 2.5
-- -- -
TABLE 5 - PROPERTIES OF FRESH CONCRETE

-
iatch cement. Fly I
. Ur Content, remp.,
kglm' jource kglm' Q OC
- -- - -
I A 155 FA1 214 5.8 21
B 155 FA1 214 6.1 21
2 A FA2 214 5.9 21

B FA2 213 2325 6.0 21
--``,`,-`-`,,`,,`,`,,`---
3 A FA3 212 2310 6.2 21

B 0.32 FA3 214 2335 5.7 21
4 A O 6.6 22
B 0.45 O 6.2 22
--

A C 1 SP-153 V O L * I 95 Ob62949 0520981 507
TABLE 6 - TESTING SCHEDULE OF CONCRETE

Batch Ten Age oftesting, days
O 1 3 7 14 28 91 365
I I I I I I I
Setting Time (ASTM C 403) FreshCnme<e
A Compression (ASTM C 39) 2 cyl. 2 cyl. 2 cyl. 2 cyl. 2 cyl. 2 cyl.
F i e m (ASTM C 78) 3 prisms
Bleeding ( A m C232) Fresh Concrete

Adiabatic Temperature Rise Fresh Concrete
compression c4sI-Mc 39) 2 cyl.
B Young's Modulusof Elasticity (ASTM C 469) 2 cyl.
SpliIting-Tensile ( A m C 496) 2 cyl.
hying Shrinkage (AsIn( C 157) Two prisms wem e@ io air drying after 7 days ofwater curing.
Two prisms w m kept in water fw refererice pupose.
Flexure íASïM C 78) 2 pisms
Freezing and Thawing After i4 dnys of moist curing, two prisms were exposed io freezing
(ASTM C 666. Rocedure A) and thawing cycling. Two prisms were k e p in the m0ist-g room
until the end of the frraing and thawing cycling.
Resistance to Chiaidclon Penetration
(ASTM C 1202) 2 disks 2disks 2disks
Air-Void Parameters ( A m C 457) 2 mples
TABLE 7 - BLEEDING, SETTING TIME, AND MAXIMUM

TEMPERATURE RISE OF CONCRETE
Mumtre W/(C+FA) Fiy Ash Total Bleeding Setting Time, h:min Maximum
No. Source Water Temperature Rise,
~ c m * x l O ' initial Finai OC
1 0.32 FA1 negligible 733 855 17.2

2 0.32 FA2 negligible 6:34 8:23 17.6
3 0.32 FA3 negilgible 7:27 9:08 17.5
4 0.45 0.8 451 526 35.9
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L X I 95 Obb2949 0520982 443
TABLE 8 - DENSITY OF CYLINDERS AND COMPRESSIVE

STRENGTH OF CONCRETE
ai.
Wm’
-
Id
-
COn
3d
- -
119 I55 FA1 214 2365 16.5 25.5 31.1 45.9
119 155 FA1 214 2365 455
0.32 118 I54 FA2 214 2380 17.1 25.2 31.0 45.0
0.32 117 154 FA2 213 2.385 47.7
0.32 FA3 212

--``,`,-`-`,,`,,`,`,,`---
117 153 2365 16.6 24.7 322 475

0.32 119 155 FA3 214 2365 48.4
O 2330 28.3 31.5 35.2 415

O 2330 41.7
--
152 x 30kmn C y l i
TABLE 9 - YOUNG’S MODULUS OF ELASTICITY OF CONCRETE
0.32
TABLE 10 - FLEXURAL AND SPLITTING-TENSILE STRENGTHS OF

CONCRETE
Mixture No. W/(C+FA) Fly Ash
Source -Tq-%-
FiexuraiStren ,MPa Spt itting-Tensile
Strength at 28 days,
MPa
1 0.32 FA1 3.2

2 0.32 FA2 4.1
3 0.32 FA3 5.6 6.7 3.5
4 0.45 6.2 5.9 3.6

TABLE 11 - DRYING SHRINKAGE OF CONCRETE PRISMS*
1 MixtUre
No.
0.32
0.32
0.45 617
* The prisms were tined for seven days in lime-saturated water before being subjected to drying
TABLE 12 - LENGTH CHANGE OF PRISMS STORED IN WATER*
Mixture W/(C+FA) Fly Ash shiinkage/ExpansionStrain.xiû4

No. source
0.32 FA1
0.32 FA2 -14
0.32 FA3
0.45
* The prisms wem continuouslystonxi in lime-saturatedwater

"+" means expansion
"-" means shrinkage
TABLE 13 - AIR-VOID PARAMETERS OF HARDENED CONCRETE

Mixhire
No. mm' /mm'
0.155
0.32 35.0 0.074
0.45 28.5 0.174
nie Canadian Standard Assonation (CSA) requirement for freezing and thawing
durability is 0.230 mm
TABLE 14 - SUMMARY OF TEST RESULTS OF CONCRETE

PRISMS AFTER 300 CYCLES OF FREEZING AND THAWING
Ry Ash Per Cent Change at ihe End oí F&ng and niawing Cycling Durability
soinrp Weight I I I
Length Pulse Velocity Resonant Frequency Facm
FA1 -0.27 0.011 1.18 0.62 101
FA2 -0.12 0.017 1.26 0.15 100
0.32 FA3 -0.25 0.036 1.14 0.01 100
4 0.45 0.19 0.012 1.28 I .87 104
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-253 V O L X I 75 m Ob62749 05209ôL1 216 m
TABLE 15 - FLEXURAL STRENGTH OF REFERENCE PRISMS AND

TEST PRISMS AFTER FREEZING AND THAWING CYCLING
Fiexunil S m g h of 76x102x390-mm Prisms, MPa
TABLE 16 - RESISTANCE OF CONCRETE TO CHLORIDE-ION

PENETRATION
0.32 FA2 2738 240

0.32 FA3 2184 668 247
4 0.45 ma 4863 2783
--``,`,-`-`,,`,,`,`,,`---
-- I l#---ba -I
Reference Concrete
I I I
I
O 5 10 15 20 25 30 35 40
Time. hours
Fig. 1-Autogenous temperature rise of concrete

A C 1 SP-153 V O L * I 95 m Obb2949 0520985 1 5 2
70
60
g 50
+Fly Ash FA1
dE *
v)
+Fly Ash FA2
tFly Ash FA3

-5 30
o
ICement: ASTM Type III1 -a- Reference
k Comte
o 20 +Q
U
O4 1 II
I
I I I
O 50 100 150 200 250 300 350 400
Age. drys
Fig. 2-Compressive strength development of high-volume fly ash

concrete and reference concrete made with ASTM Type III cement
50 T
ASTM Type m Cement
5
ON O 5 10 15 20 25 30
Age, &Ys
Fig. 3-Early-age compressive strength development of high-volume

fly ash concrete made with ASTM Type I and Type III cements based
on averaged values of test results obtained with the same three fly
ashes
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL*I 95 E 0662949 0 5 2 0 9 8 6 O99
70 - ASTM Type lïï Cement
60 a- \
m
ASTM Type I Cement
O4 I
O 50 I O0 150 200 250 300 350 400
Age. days
Fig. &Long-term compressive strength development of high-volume

--``,`,-`-`,,`,,`,`,,`---
fly ash concrete made with ASTM Type I and Type I I I cements based
on averaged values of test results obtained with the same three fly
ashes
700
600
500 +Fly Ash FA1

7
z
1
cn
400
+Fly Ash FA2
tFly Ash FA3
l!
v,
300
200
-IFReference
Concrete
O 100 200 300 400 500
Duration of Drying. days
Fig. &Drying shrinkage strain versus duration of drying of concrete

after 7 days of initial water curing

A C 1 SP-153 V O L X I 95 m Obb29Y9 0 5 2 0 9 8 7 T25 m
SP 153-2
Structura I Concrete Incorpo rating

High Volume of Fly Ash
by D. Galeota, M. M. Giammatteo, and R. Marino
Synopsis: The purpose of this study was t o examine the mechanical and durability
properties of high-volume fly ash concretes for structural applications.
Four concrete mixtures were prepared with the amount of fly ash, from Italian
source, varying from 0 t o 50 percent by weight of total cementitious materials.
A large number of concrete specimens were cast and tested in order t o determine
the compressive, flexural and splitting-tensile strength, modulus of elasticity,
fracture parameters, concrete-steel bond properties, drying shrinkage and
durability properties.
The results of this study showed that high-volume fly ash concrete has
considerable potential in a wide variety of structural applications.
Kevwords: Bonding; compressive strength; drying shrinkage; m;

flexural strength; fly ash; fracture properties; freeze thaw durability;
modulus of elasticity; splitting tensile strength; strength
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0662949 0520988 961
26 Galeota, Giammatteo, and Marino
D.Galeota is associate professor of Structural Design at the University of

L'Aquila, Italy. Dr. Galeota has published several papers dealing with new
concrete materials, prestressed concrete and construction engineering Currently,
he is a member of the AICAP Committee, Special Concretes
M M.Giammatteo is associate professor at the Structural Engineering Department

of the University of L'Aquila, Italy His research interests include new concrete
materials, nonlinear design and precast and prestressed concrete structures
behavior
R.Marino is Research and Development Manager at Calcestruzzi S.p.A.,

Ravenna, Italy Dr. Marino is the author of several technical papers dealing with
concrete technology
INTRODUCTION
In recent years research in Canada, United States and other countries has
led to a better understanding of the chemical-physical characteristics of concrete
incorporating fly ash (1, 5 , 8) In particular, extensive testing has shown that
mechanical and durability characteristics of high-volume fly ash concrete are
generally comparable and sometimes better than normal portland cement concrete
(2, 6, 7 )
Currently coal fired electric power plants in Italy produce about 750,000
tons of fly ash per year. In absence of specific national code recommendations,
approximately 92 percent of all the fly ash produced is utilized in cement,
concrete and in other minor applications In spite of the extensive use of fly ash,
until recently in Italy very few studies have been carried out on the use of fly ash
in concrete
This study focused on the ways in which high-volume of low-lime fly ash
influences the main mechanical and durability properties of concrete and the
economic benefits obtained from the reduction of the amount of cement used.
A large number of concrete specimens incorporating fly ash were cast and
tested in order to determine their behavior under compression, modulus of
elasticity, behavior in tension, fracture parameters, concrete-steel bond
characteristics, drying shrinkage, durability properties, including freezing-thawing
resistance, permeability, and sulphate and chloride resistance The test recuits
were analyzed and the influence of fly ash on the above Characteristics of concrete
was studied
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 IObb2949 0520989 8 T ô
EXPERIMENTAL PROGRAM
--``,`,-`-`,,`,,`,`,,`---
A comprehensive experimental program was designed to investigate the

mechanical properties at various ages of concretes incorporating high volumes of
low-lime fly ash. Four concrete mixtures (A, B, C, D) were prepared in order to
obtain the same workability (given slump=l8Omm) and the same
water/(cement+fly ash) ratio (Wí(C+FA)=0.42).
The dosage of the superplasticizer was adjusted by exploratory tests.

Concrete mixture A was designed in order to obtain a specific compressive
strength of about 45MPa at the age of 28 days.
Ordinary portland cement (comparable to ASTM Type III), river sand,

crushed limestone and fly ash (comparable to Class F) from Italian sources were
used. The amount of fly ash incorporated varied from O to 50 percent by weight
of total cementitious materials. Tables I, I I and III show the concrete mixture
proportions and the physical-chemical characteristics of the cement and fly ash.
From each concrete mixture (A, B, C, D) the following specimens were

cast :
a) behavior under compression (compressive tests, according to UNI 6132
Italian Standard, comparable to I S 0 4012/1, and according to UNI 9771
Italian Standard, comparable to ASTM C215, for determination of dynamic
modulus of elasticity): twentyone 150x 150x 150mm cubic specimens, twelve
l50x300mm cylindrical specimens;
b) behavior under tension (flexural and split-cylinder tests, according to UNI
6133 Italian Standard, comparable to ASTM C293 and according to UNI
6135 Italian Standard, comparable to ASTM C496): twelve 1OOx 10Ox400mm
prismatic specimens and twelve 15Ox300mm cylindrical specimens;
c) bond properties (pull-out tests, according to RILEMKEB-FIP, RC6): twelve
200x200x200mm cubic specimens; only a short length (5 times the bar
diameter db) of a db=l6mm deformed reinforcing bar (Type Feb44k,
f =435MPa) was embedded in each specimen;
d) Jacture energy (notched-beam tests, according to RILEM TC5O-FMC and
RILEM TC89-FMT): twelve 1OOx 1OOx840mm notched-beam specimens;
e) drying shrinkage (test according to UNI 6555 Italian Standard, comparable to
ASTM CI 57): twelve 1OOx 10Ox400mm prismatic specimens;
f ) freezing and thawing resistance (test according to UNI 7087 Italian Standard,
comparable to ASTM C666, procedure B): three 1 OOx 10Ox400mm prismatic
specimens;
g) autogenous temperature rise: four 150x 150x 150mm cubic specimens;
h) water permeability (test according to ISODIS 703 i ) : two 150x 150x 150mm
cubic specimens;
i) resistance to chloride-ion penetration (test according to UNI 7928 Italian
Standard): two 15Ox300mm cylindrical specimens;

A C 1 SP-153 V O L t I 95 = Ob62949 0520990 5LT
j) resistance to sulphate-ion penetration (test according to UNI 8019 Italian

Standard): two 15Ox300mm cylindrical specimens;
k) air voids parameters (test according to ASTM C457): one 15Ox300mm
cylindrical specimen.
ANALYSIS OF RESULTS
Compressive Strength
Table IV and Fig. 1 show the average (3 specimens) compressive strength

(R,) development of cubic specimens (continuously moist cured) after 1 , 3, 7, 28,
60, 90, 365 days of curing. It can be seen that all concretes containing fly ash (B,
C, D) developed adequate early age strength (at 3 days) for structural
applications. After 90 days concrete C reached the same compressive strength as
that for the reference concrete without fly ash (A). Strength gap between
concretes A, B, C and D became relatively small at one year (Fig.2) in percentage
terms with respect to concrete A. In particular concrete C showed the highest
compressive strength at one year age.
A similar trend can be seen in Table V and Fig.3 and 4, showing the
average ( 3 specimens) compressive strength (fc) and the peak strain ( E ~ )
development of cylindrical specimens after 28, 60, 90, 365 days of curing.
Typical compressive stress-strain curves (WE) for the tested cylindrical specimens
are shown in Fig.5. Fly ash substantially influenced both the ascending and the
descending branch of the stress-strain curves. The ascending branch for the
concretes B, C, D at 28 days of age were less linear compared with that of
concrete A (2), and they began to deviate from linearity at a stress (indicated in
Fig.6 as 01) about 55-60 percent of respective compressive strength (Fig.6). At
later ages substantial increase in the ratio ol/fc occurred. From 28 to 365 days
there was a significant increase in the steepness of the descending branch
--``,`,-`-`,,`,,`,`,,`---
(indicated in Fig.7 as S) of the stress-strain curves for concretes B, C, D (more

brittleness, Fig.7). Nevertheless, concrete containing fly ash showed a more
ductile failure than concrete A at 90 and 365 day ages.
Dynamic Modulus of Elasticity
The dynamic modulus of elasticity (Ed) was evaluated from cylindrical specimens
after 28, 60, 90, 365 days. Table VI and Fig.8 show that fly ash concretes
exhibited, at all ages, suitable high average values (3 specimens) of modulus of
elasticity for structural applications, even if they were slightly lower than those of
the reference concrete A. On the basis of analysis of the test results, the relation
[Eq.2.1-15] of MC90 ( 3 ) , with equation power 0.3 instead of 0.33 and
coeficient or~=2.54GPainstead of 2.1 SGPa, is more suitable for predicting the
dynamic modulus at 28 days (Fig.9):

A C 1 SP-153 VOL*I 95 0662949 0520991 Y56
where:
fcm average compressive strength [ m a ] ,
=
fcm, 10 MPa,
=
E 2.54 GPa.
C ~=
Flexural Strength
Table VI1 shows the average ( 3 specimens) flexural strength development (fct,fl)
afier 28, 60, 90, 365 days. The average values of fct,fl at different ages were
found to range from 11 to 13 percent of the corresponding compressive strength
fc for concrete A, from 11 to 19 percent for concrete B, from 12 to 14 percent for
concrete C and from 10 to 16 percent for concrete D (4). From 90 to 365 days
there was a remarkable increase (up to 70 percent) in fct,fl for concretes B, C, D.
The values of f,t,fl at 28 days can be estimated using the following approximate
relation, based on test results:
--``,`,-`-`,,`,,`,`,,`---
fct,fl = 0.72Jfcm
Splitting-Tensile Strength
The average (3 specimens) splitting-tensile strength (fct,s ) at different ages is

shown in Table VIL After 28 days of age, the ratio fct,fl/(t,sp was often higher
for concretes B, C, D than for reference concrete A, particularly at 365 days.
However fly ash did not seem to substantially influence the values of fct,sp.
Bond of Concrete to Steel
The average values ( 3 specimens) of bond stress of concrete to steel at different

slip values (0.01, 0.1, 0.3mm) and of bond strength (TI) together with peak slip
(SI) are shown in Table VIII. In most cases, bond failure occurred due to the
crushing and shearing of the concrete between the bar ribs, while steel stress was
above yielding stress (fy=435MPa). In a few cases splitting failure of concrete
specimens was dominant. From 28 to 365 days there was a remarkable increase
(up to 60 percent) in TI for concretes B, C, D (Fig. 10).
Fracture Energy
The average values ( 3 specimens) of fc, fracture energy (GF), characteristic

length (a,,), fracture toughness (KI,) and critical crack tip opening displacement
(CTOD,) are listed in Table IX. Fig.1 1 show typical load-displacement and load-
crack mouth opening displacement (CMOD) curves. It can be seen from Table IX
that GF generally increased as f, increased. The brittleness of concretes was
evaluated by the characteristic length (9):

A C 1 S P - 1 5 3 V O L X I 95 Obb2949 0520992 392 W
All tested concretes tend to be slightly less tough than normal strength concrete
(Table IX, for normal strength concrete tch=200 to 500mm). The fracture
parameters Kic, CTOD, showed a similar trend.
Drying Shrinkage
The drying shrinkage test results after 1 day of initial moist-curing are
given in Fig.12. The shrinkage strain values after 365 days (50 RH and 20fl'C)
for all concretes are comparable or lower than other published data (8) for
portland concrete of similar strength. Concrete A, B and C had similar shrinkage
values beyond 90-day age. Concrete D showed more shrinkage than concretes A,
B and C at all ages.
Freezinq and Thawinq Resistance
After 60 days of water-curing, freezing and thawing resistance of all

concretes was determined by measuring the relative dynamic modulus (durability
factor) at every 25 freezingthawing cycles (Fig. 13) up to failure.
In a single 12 hour cycle the specimens were cooled from 5"C+2"C to

-25"C*2"C in air and then warmed to 5"Ci2"C in water. Concretes A an B failed
after the first 25 cycles. Concretes C and D failed the freezing-thawing testing
after 230 cycles. These findings are in line with other published data on non-air
entrained concretes containing fly ash (8).
Autogenous Temperature Rise
All concretes containing fly ash showed a reduced rate of heat generation.
It can be seen (Fig.14) that the larger the quantity of cement replaced by fly ash,
the lower the contribution to early-age heat generation.
Water Permeability
Fig. 15 shows the average values (2 specimens) of the test results at 365
days of age obtained at water pressure varying between 100 and 7OOkPa. In order
to determine the water depth penetration the specimens were broken after the
test. Except for concrete D (50% fly ash), the other concretes A, B, C showed
low water permeability, with equivalent permeability as the no fly ash concrete
(mix A).
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0 6 6 2 9 4 9 0520993 229 m
Resistance to Chloride-Ion Penetration
In this test, one face of each test specimen at 365 days of age was exposed
to a CaC12 solution (0.27 mol/l) for 30 days. Concretes B, C, D showed excellent
resistance to chloride-ion penetration (Table X).
Resistance to Sul~hate-IonPenetration
In this test, one face of each test specimen at 365 days of age was exposed
to a Na2S04 solution (0.50 mol/l) for 30 days. Concretes B, c,
D showed no
measurable ion penetration as shown in Table X.
Air Voids Parameters of Hardened Concretes
At 365 days of age the air voids parameters for all concretes were
determined following a microscopic technique. It can be seen from Table XI that
fly ash improved the specific surface, the spacing factor and the average diameter
of the bubbles. In particular concrete c showed the most favorable parameter
with low spacing factor of 0.5 1 5mm.
ECONOMIC ANALYSIS
The constituent costs of concrete A, B, C, D (average costs in Italy) are

shown in Table XII. It can be seen that if the concrete cost per m3 is plotted
against fly ash percentage, an almost linear concrete cost reduction can be
--``,`,-`-`,,`,,`,`,,`---
observed.
CONCLUSIONS
The following conclusions can be drawn from this study:

- Ail concretes incorporating fly ash (B, C, D) showed adequate early age
compressive strength (at 3 days) for structural applications.
- Beyond 28 days of age the gap in compressive strength for fly ash concretes
became smaller compared to plain concrete, in particular after one year the
compressive strength of concrete C exceeded the compressive strength of no-
fly ash concrete A.
- Fly ash substantially influenced the shape of the compressive stress-strain
curves. From 28 to 365 days of age there was a significant increase in the
steepness of both the ascending and the descending branch of the compressive
stress-strain curves, indicating brittleness.
- The dynamic modulus of elasticity measured at 28, 60, 90, 365 days was lower
for concretes B, C, D than that for concrete A, however it was quite good for
structural applications.
- The flexural strength at 365 days was higher for fly ash concretes B, C, D.
The splitting tensile strength was similar at ail ages to that observed for no-fly
ash concrete.

A C 1 SP-153 VOL*I 95 Obb2949 0520qqLi 1 6 5
32 Galeotr, Giammatteo, and Marino
- From 28 to 365 days of age there was a high bond strength gain (up to 60
percent) between concrete and steel for concretes incorporating fly ash.
- Calculation of the fracture parameters showed that all tested concretes tended
to be slightly less tough than normal strength concrete.
- Fly ash did not cause notable change in shrinkage behavior except for concrete
D (50% fly ash).
- At 365 days of age, concretes incorporating fly ash exhibited in geGeral good
characteristics in water permeability (except 50% of fly ash mix), in resistance
to chloride-ion and sulphate-ion penetration tests.
- Freezing an thawing durability of all concretes was poor because air was not
entrained in all concretes.
REFERENCES
1. AC1 Committee 226, "Fly Ash in Concrete", Materials Journal, ACI, Vo1.84,
No.5, September-October 1987, pp.381-409.
2. Berry E.E., Hemmings R.T., Zhang M.H., and Malhotra V.M., Supplemental
Proceedings: Fourth International Conference on Fly Ash, Silica Fume, Slag,
and Natural Pozzolans in Concrete, High Volume Fly Ash Concrete Session,
Prepared by Radian Canada Inc. and CANMET, published by EPIU, Palo
Alto, CA, 1992.
3. CEB-FIP Model Code 1990, Final Draft, Bulletin d'Information N.203, July
1991.
4. Langley W.S., Carette G.G., and Malhotra V.M., "Strength Development
and Temperature Rise in Large Concrete Blocks Containing High Volumes
of Low-Calcium (ASTM Class F) Fly Ash", CANMET, Report MSL 90-24
(OP&J) Draft, Ottawa, Canada, 1990.
5. Malhotra V.M. (Editor), "Supplementary Cementing Materials for
Concrete", CANMET Publication, Ottawa, Canada, 1987.
6. Malhotra V.M., "CANMET Investigations Dealing with High-Volume Fly
Ash Concrete", CANMET - Advances in Concrete Technology, Editor:
V.M. Malhotra, Ottawa, Canada, 1992, pp.433-470.
7. Naik T.R., Singh S.S., and Hu W.Y., "High-Volume Fly Ash Concrete
Technology", Prepared by Center for By-products Utilization, The
University of Wisconsin, Milwaukee, Department of Civil Engineering &
Mechanics, published by EPRI, Palo Alto, CA, 1992.
8. RILEM, "Fly Ash in Concrete. Properties and Performance", Report of
Technical Committee 67-FAB, Use of Fly Ash in Building. Edited by K.
Wesche, 1991, E&FN SPON.
9. RILEM, Report 5 (89-FMT), "Fracture Mechanics Test Methods for
Concrete", Edited by S.P. Shah and A.Carpinteri, 1991, Chapman an Hall.
,
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L * I 75 0662949 0520995 OTL
TABLE 1 - MIXTURE PROPORTIONS AND PROPERTIES OF

FRESHLY MIXED CONCRETE
Slump (mm) I 180 I 180 I 180 1 180

Unit Weight (kg/m3) 1 2454 I 2426 I 2417 I 2408
( I ) Portland Cement ENV197-1 CEM I 42.513 (European Prestandard),

comparable to ASTM Type III
(2) Sulphonated Naphthalene Formaldehyde Condensate.
By weight of cement + fly ash.
CEMENT
Bogue
Physical Properties Chemical Analysis Potential
Compounds
- Cornnosition
.-
sio, c,s % 57.5
~
keness-passing 9pm %I 38.2 % 20.54
- B1ain e (m2/kg: 410 4 0 3 % 5.88 12.5

-
;pecific Gravity (gícm3] 3 02 Fe203 YO 2.59 9.0
Iompressive Strength Ca0 YO 62 5 5 7.0
-3 days (MPa) 30.2 McO YO 2.23

-7 days (MPa) 14.8 Na,O YO 0.34
-28 days ( m a ) 52.0 K*O % 0.40
jetting Time so3 % 2.42
-initial (min) 175 Loss on YO 2.40

Ignition
-Final (min) 235 Insoluble YO 1.50
- Residue - -
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0662949 0520996 T38

FLY ASH
Chemical Arialysi
Fineness-passing 45pm % 79 sio, YO 45.71
-Blaine (m2/kg) 450 A1203 YO 29.73
Specific Gravity (dcm3) 2.20 Fe203 YO 4.21
Ca0 YO 4.75
McO YO 1.13
Na20 % 0.31
K*O YO 1.14
Tio, YO 1.34
p205 % 0.96
--``,`,-`-`,,`,,`,`,,`---
MnO YO 0.04
Loss on Ignition % 7.0
Activity with Cement % -
89.5
TABLE 4 - COMPRESSIVE STRENGTH DEVELOPMENT OF CUBIC

SPECIMENS
Compressive Strength R,

A C 1 SP-I53 V O L X I 95 Ob62949 0520997 974
Milwaukee Conference
= 35
TABLE 5 - COMPRESSIVE STRENGTH DEVELOPMENT AND PEAK

STRAIN OF CYLINDRICAL SPECIMENS
Compressive Strength fc (MPa), Peak Strain E,, (%O)

Concrete Fly (Average Values/Std Deviations)
Ash
TABLE 6 - DEVELOPMENT OF DYNAMIC MODULUS OF ELASTICITY
09 0.9 0.6 0.7

I3 30 37.9 40.5 41.9 43.9
1.3 0.3 1.4 o.5
C 40 39 9 42 2 43.9 45.8
0.2 06 0.5 o.5
D so 39.0 40.6 40.1 43.3
0.5 0.3 1.3 o. 1
TABLE 7 - FLEXURAL AND SPLITTING-TENSILE STRENGTH
DEVELOPMENT
Fly Asli Flexural Strength fc-,fl Splitting-Teiis. Str. f,t,Cp
Concrete (%) (Av. Val./Std Dev.) (MPs) (Av. Val./Std Dev.) (h1Pa)
I I I 2 8 d I 6 0 d 9 0 d 365d 2 8 d 6 0 d 9 0 d 365d
--``,`,-`-`,,`,,`,`,,`---
A O 5.1 6.0 6.6 8.6 4.3 5.5 5.4 5.8

0.7 0.7 0.6 0.3 0.3 0.5 0.0 0.5
B 30 4.4 6.4 7.9 11.1 4.6 4.5 5.0 5.3
0.2 0.4 0.2 0.1 0.1 0.5 0.2 0.3
C 40 5.2 5.2 5.8 9.9 4.6 4.1 5.1 6.0
0.4 0.6 0.4 1.1 0.2 0.1 0.3 0.3
D 50 4.2 5.3 5.6 9.7 4.0 5.4 5.2 5.5
I I I 0.1 I 0.5 0.5 0.5 0.1 0.4 0.4 0.7

A C 1 S P - I 1 5 3 V O L 5 1 95 W 0662949 0520998 8 0 0
TABLE 8 - BOND PROPERTIES
Conc.
days) ‘5001
Bond Stresses ~ 0 . 0 1 ,~ 0 . 1 ~ ~ (MPa),
Bond Strength ri (MPa), Peak Slip SI (mm)
~
I 4verage V hies and 5 iDeviatio s)
‘50 1 ro rl
0.3
-1
SI
A O 28 8 9 ( 1 7) 20.6 (3.9) 24.9 (3.9) 27.6 (3.0) 1.02 (0.24)
60 13 3 (3 3) 22.1 (3.5) 26.2 (3.5) 27.7 (3.2) 0.98 (0.22)
90 122(45) 22.7 (2.0) 26.7 (1.8) 29.1 (0.6) 1.16 (0.38)
- 365 95(45) 20.7 (3.0) 26.2 (1.7) 28.2 (1.0) 1.14 (0.74)
B 30 28 Si(13) 15.8 (2.3) 19.4 (2.7) 21.1 (3.1) 1.01 (0.07)
60 7 5 (2 9) 18.7 (1.9) 23.2 (1.8) 25 9 (1.6) 1.32 (0.3 I )
90 142(1 6) 22.5 (1.7) 25.8 (0.9) 26.6 (0.3) 0.67 (0.07)
- 365 8 S ( 1 1 6) 21.8 (0.1) 25.8 (O. 1) 27.6 (O. I ) 0.78 (0.09)
--``,`,-`-`,,`,,`,`,,`---
C 40 28 11 2(25) 18.3 ( i .4) 20.9 (1.4) 2 1.7 (1.5) 0.74 (O. 1 I )

60 126(20) 21.7(1.6) 24.8 (1.5) 25.8 (1.1) 0.88 (0.27)
90 13 9 ( 2 7 ) 22.6 (0.6) 25.1 (0.4) 26.1 (O. i ) 0.96 (0.04)
365 10 1 ( 2 2) 24.2 (O. I ) 28.4 (0.4) 28.7 (0.3) 0.32 (0.02)
D 50 28 7 8 ( 1 2) 13.5 (2.2) 16.3 (2.8) 17.6 (2.9) 0.75 (O. 18)
60 10 1 ( I O) 18.5 (1.0) 21.6 (1.6) 22.8 (2.1) 0.86 (0.08)
90 124(20) 18.6(1.4) 21.5 (1.1) 22.3 (1.7) 0.62 (0.21)
- 365 1 6 5 ( 1 2) 23.2 (0.9) 26.2 (1.6) 28.2 (1.8) 1.10 (0.08)

A C 1 SP-153 VOL*I 95 m 0662947 0520999 7Y7 m
TABLE 9 - FRACTURE PROPERTIES
Compressive Strength fc (MPa)

Concrete Fly Age Fracture Energy GF ( N h )
Ash Characteristic Length fch(mm)
(Average Values and Std 1 eviations)
(%) :daYs) fC GF [ch
A O 28 47.9 94.0 (16.0) 205.7 (35.1)
60 52.7 101 .O (16.4) 143.9 (23.3)
90 54.6 113.6 (32.8) 174.0 (50.1)
365 67.3 112.0 (3.0) 162.6 (4.3)
B 30 28 40.1 98.0 (3.6) 175.6 (6.5)
60 47.6 101.4 (19.3) 203.1 (38.6)
90 50.6 98.7 (23.4) 165.4 (39.2)
365 58.9 94.8 (18.7) 146.4 (28.9)
C 40 28 43.7 89 6 (5 8) 1 69.0 ( 1 1 .O)
60 54.3 70.6 (7.5) 177.2 (18.7)
90 57.4 108.6 (7.9) 183.2 (13.3)
365 71.6 86.5 (7.4) 110.0 (9.3)
D 50 28 40.2 92.1 (17.0) 224.4 (41.3)
60 46.0 74.1 (16.7) 103.1 (23.2)
90 51.6 114.4 (20.4) 169.8 (30.3)
365 59.0 67.0 (18.0) 96.0 (3 1.6)
Fractnre Toiighness KI, ( M P a G )
Concrete Fly Critical Crack Tip Opening Displacement
Ash CTOD, (nini) --``,`,-`-`,,`,,`,`,,`---
(Average Values and Std Deviations)

W) Ki, CTOD,
A O 1.704 (0.554) 0.0162 (0.0028)
2.877 (2.370) 0.0165 (0.0031)
1.676 (0.681) 0.0143 (0.0032)
2.556 (1.010) 0.0200 (0.0013)
B 30 2.163 (1.206) 0.0218 (0.0053)
1.904 (0.520) 0,0171 (0.0004)
2.356 (0.056) 0.0160 (0,0008)
2.022 (0.620) 0.0142 (0.0015)
C 40 2.01 1 (0.421) 0.0183 (0.0019)
2.062 (0.318) 0.0164 (0.0008)
1.994 (0.795) 0.0156 (0.0030)
365 1.710 (0.238j 0.0151 (0,0014)
D 50 28 1.772 (0.678) 0.0187 (0.0025)
60 1.124 (0.121) 0.0140 (0.0016)
90 1.684 (0.076) 0.0184 (0.0016)
365 1.438 (0.292) 0.0129 (0.0019)

A C 1 SP-153 V O L * I 95 Obb2949 0521000 Ob7
TABLE 1O - RESISTANCE TO CHLORIDE-ION AND SULFATE-ION

PENETRATION
Concrete Fly Ash Depth of Chloride-Ion Depth of Sulphate-Ion

(%) Penetration (Av. Values) Penetration (Av. Values)
(mm) (mm)
A O 12 3.5
6 30 no penetration no penetration
C 40 no penetration no penetration
D 50 no penetration no penetration
Concrete Fly Ash Specific Air Void Spacing Average

(YO) Surface Content Factor Chord
(mm-1) ("/.I (ni ni Intercept
(mm)
A O 7.46 1.8 1 .O38 0.536
B 30 7.46 2.0 0.991 0.530
C 40 16.74 1.4 0.515 0.239
--``,`,-`-`,,`,,`,`,,`---
D 50 12.20 1.8 0.634 0.328
Concrete
Const i tlients A B C D
Cost ($/ni3) (Dosage (kg/m3))
Cement 26.5 (380) 18.5 (266) 16.0 (230) 13.2 (190)
Aggregat es 24.3 (1910) 23.9 (1880) 23.8 (1870) 23.7 (1860)
Fly Ash 0 (0) 1.0 ( i 14) 1.4 (150) 1.7 (190)
Superplasticizer 2.8 (3.8) 4.7 (6.4) 5.2 (7.2) 5.6 (7.6)
Total cost 53.6 48.1 46.4 44.2
% of Mixture A Cost 1 O0 89 86 82

A C 1 SP-I153 V O L X I 95 0662949 0 5 2 L O O L T T 3
loo 1
I 'Oo 7
60-
40 -
M-
O J , , I , , I , I
O 100 2w 3w 4M U 20 40 80
M e . days Fly Ash. percent
Fig. l-Compressive strength Fig. 2-Compressive strength versus

versus age-Cubic specimens percentage fly ash-Cubic specimens
U J I ' I '
I
' -e
-.-
-tMa A (On Fty Ash)
I
Mu B (30% Fly Ash)
MI C (4wb Fly Ash)

MnD(5XFtyAsh)
' , ' -1
40 i
0-J7---
, , 1
~
, , ,
O 1w 200 300 4w O 20 40 M1
Ag". days
Fig. 3-Compressive strength Fig. M o m p r e s s i v e strength versus
versus age-Cylindrical specimens percentage fly ash-Cylindrical
specimens
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L M I 95 M Obb2949 0523002 93T M
80
80
h
a
vi40
2
üi
20
O
--``,`,-`-`,,`,,`,`,,`---
O 2 4 6 8 10
Strain (%)
ml SU days
I
t MIXAI
o 2 4 6 8 1 0 o 2 4 6 8 10
Strain (g.) Strain (%)
Fig. -tress-strain curves (o-€)

at 28, 60, 90, and 365
days-cylindrical specimens
10
+ Mo: A (0% Fly Ash)
-e Mix E (30% Fly Ash)

MM C (4w6 Fly Ash)
*- Mir O (50% Fly Ash)
.
.- y--
-----e
Lo
I--
w , />.+
/-/a
0 5 t I I v
O loo 2w 3w 4w
100 xx) 300 4w
Age. days Age, days
Fig. -,fe ratio versus age Fig. 7-Descending branch slope

versus age for stress-strain curves

A C 1 SP-153 V O L * I 95 0bb2949 0523003 876
c
o 4 5
I' /=
421
41
i
Ed = aE10 (fcm /f cmo
I
./
d i =/ /
/
-.-
/
* ,
,
I
!1
Mn: A (0% Fly Ash)
O
+- Mix B (30% Fly Ash) MixC
i
~
Mu C (4049 Fly Ash)
35 +
O 100
I
(*-
I
200
Age, days
MU D (509a Fly Ashi
' I
m
'-1 37
1
c 40 44
i,28 MPa
I
48
Fig. &Dynamic modulus of Fig. +Dynamic modulus of elasticity

elasticity versus age versus compressive strength at
28 days
32 7
16- 7-
í~ - m - T
i ,
o 1 0 2 0 3 0 4 0 5 0
Fly Ash, percent
Fig. 1&Bond strength versus percentage fly ash

1
-1 2wo
ifmi i\
i l
i i \
\\
\
O 1 ' 1 \ ,
O00 O20 o40 O60 om 100 ow O10 OM O30 o40 o53
Load-Line Deflection. mm Crack Mouth Displacement. m
Fig. 11-Typical load-displacement and load-CMOD curves

--``,`,-`-`,,`,,`,`,,`---

42
A C 1 SP-153 VOLS1 95
Galeota, Giamrnatteo, and Marino
= 0662949 0523004 702
o
f
-----Y-
I
I+ -.-
-0-
1 -0-
Ma A (0% Fly Ash)
Ma B (30% Fly Ash)

M U C (40% Fly Ash)
M U D (5[1% Fly Ash)
~ ~-
'
1
1
I
7
O loo m 3w 40 O 100 m m
Age. days Number of cydes
Fig. 12-influence of fly ash on Fig. 13-Durability factor versus

drying shrinkage versus age number of freezing and thawing
cycles after 28 days of curing
Mtx El (30%Fly Ash)
+- Mix C (40% fly Ash)

--``,`,-`-`,,`,,`,`,,`---
Mix D (50% Fly Ash)
OJ, I 1 , I , I , ,
O 40 80 120 160 O 1 0 2 0 3 0 a ) M
Time, burs
fly Ash. percent
Fig. 14-Influence of fly ash on Fig. 15-Depth of water penetration

autogenous temperature rise versus percentage fly ash

A C 1 SP-I153 V O L X I 95 W Obb2949 0523005 649
SP 153-3
Using Medium- to High-Volume

Fly Ash Blended Cements to
improve the Sulfate Resistance
of High-Lime Fly Ash Concrete
by J. R. Prusinski and R. L. Carrasquillo
Svnousis: Concrete placed in contact with a sulfate environment can severely

degrade due to formation of expansive compounds such as ettringite. The use of
low-calcium fly ashes in concrete have been successful in mitigating these
expansions. However, some high-calcium ashes have the potential to cause
increased expansion of the concrete, leading to accelerated deterioration. This
research focuses on producing cements interground with Class C fly ash, which
can be used to produce sulfate-resistant concrete. ASTM Type I and Type II
cements were blended with a sulfate-susceptible Class C ash in amounts from 0%
to 70% fly ash. Concrete was produced using a standard Texas Highway
Department 306 kg/m3 mixture and the various interground and unblended
cements. Specimens were soaked and monitored monthly for 3 1/2 years in a
10% sodium sulfate solution to accelerate sulfate attack. Results indicate that
certain specimens made with interground cements having fly ash contents between
25% and 70%, and additional blended gypsum, achieved lower expansion than
control specimens made with Type II, Type V, or 0% CSA cements alone. This
was true for fly ash/cement blends using both Type I and Type II cements.
Compressive strengths of the fly ash blends, through 365 days, attained levels
generally comparable to or better than the controls.
Keywords: Blended cements; chemical attack; durability; expansion; fly

ash; lime flv ash; sulfate attack; sulfate resistance
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L 8 1 95 = 0662949 0523006 5 8 5 =
44 Prusinski and Carrasquillo
J. R. Prusinski manages coal ash product and market development efforts at

Houston Lighting & Power Company. An AC1 member, he belongs to several
committees including AC1 201 (Durability of Concrete) and AC1 232 (Fly Ash
and Natural Pozzolans in Concrete). He holds a B.S. in Civil Engineering from
the University of Michigan (Ann Arbor), an M.B.A. from the University of
Houston, and is a registered Professional Engineer.
R. L. Carrasquillo is professor of Civil Engineering at The University of Texas

at Austin and Associate Director of the Center for Aggregates Research. He is
an active researcher and is most recognized for his contributions in the areas of
concrete production, durability, materials and construction practice. He serves
on committees for ASTM, ASCE, TRB and ACI. He has received recognition
for his teaching, research, writing and speaking, and is an AC1 Fellow.
INTRODUCTION
Durability of concrete structures, pavements, and foundations is an issue of

paramount importance. Billions of dollars are required annually to repair the
nation’s infrastructure; engineers, constructors, owners, and the public want to
ensure that these funds produce end-products which provide long, serviceable
lives with maximum life-cycle benefits.
--``,`,-`-`,,`,,`,`,,`---
Concrete Sulfate Attack and Fly Ash Effects
Sulfate attack on concrete is the most prevalent form of chemical attack on

concrete structures. Exposure to sulfate-bearing soils and seawater are the two
principal environments where concrete can severely degrade if proper precautions
are not taken. Researchers have found that high levels of C3A in cement lead to
deleterious expansions of the sulfoaiuminates in the hydrated concrete with the
formation of ettringite (1-3).
Moderate to low C3A cements (e.g. ASTM C150 Type II, Type V, or 0% C3A
cements) are.effective in minimizing these reactions. Use of certain pozzolans
as a cement replacement, principally Class F fly ash, have also been shown to be
effective in mitigating the effects of sulfates (4). However, investigations have
indicated that certain Class C (high-lime) fly ashes can have a detrimental effect
on concrete exposed to a sulfate environment (5,6). This is illustrated by Fig. 1,
which demonstrates that over time, the sulfate expansion of concrete made with
a particular Class C fly ash combined with Type II cement is significantly higher
than the expansion resulting from concrete made with Type II cement done (7).

A C 1 SP-153 VOL*I 75 Obb2947 0521007 411
Researchers have proposed that fly ashes containing calcium aluminate-rich

glasses are more prone to sulfate attack than ashes which are rich in silica or
silica-aluminate glasses (8). Many Class C ashes contain calcium aluminate-rich
glasses undergo pozzolanic reaction with the pore fluid in concrete containing
sulfate to produce C,ASH,, (monosulfoaluminate). C,ASH,, is stable as long as
sulfates in the pore water surrounding the compounds are in low concentrations.
At higher concentrations, the monosulfoaiuminates become unstable and converts
--``,`,-`-`,,`,,`,`,,`---
to ettringite (C6AS3H,,), with a significant volumetric increase. This causes

internal strains and cracking (1-3, 9, 10).
Houston Lighting & Power Class C Fly Ash
Houston Lighting & Power company (HL&P) has generated a high quality Class
C fly ash produced from sub-bituminous Wyoming Powder River Basin coal since
1978. Since that time, HL&P, along with its ash marketer JTM Industries, Inc.
(JTM), has found uses for up to 70% of its Class C ash annually, most of it for
use in ready-mixed concrete applications (1 1). The availability of this ash in the
Houston area has allowed the Texas Department of Transportation, along with
counties, cities, and private industry to take advantage of the workability and
durability-enhancing characteristics of fly ash concrete (FAC). In addition, FAC
end-users enjoy lower ready-mixed costs, and HL&P customers benefit from
reduced fly ash disposal costs. However, tests performed at the University of
Texas at Austin discovered that FAC made with certain Class C ashes, including
HL&P’s, produced detrimental sulfate-induced expansions (12). This has
eliminated a whole region from HL&P’s Class C market area-4.e. those locations
which lie within 25 miles of the Gulf Coast. The W. A. Parish Generating
Station, where 300,000 tons of HL&P’s Class C ash is generated annually, is
located only 30 miles from this coastal zone.
This situation results in several negative effects. From an environmental

standpoint, more landfill space is needed to dispose of unused fly ash. Also,
cement requirements are greater in coastal areas or other sulfate environments.
Not only is cement two to four times the cost of fly ash, but cement production
is energy-intensiveand emits significant amounts of carbon dioxide. Financially,
coastal ready-mixed producers, HL&P customers and the utility itself would lose
the incentive of lower ready-mixed costs and decreased disposal costs.
In response to this situation, HL&P and JTM initiated a five-year effort to

determine methods of improving the sulfate resistance of Class C FAC (13). One
of the methods investigated was using cements interground and blended with
HL&P’s Class C ash. The focus of this paper will be to describe the results of
this investigation.

A C 1 SP-153 VOL*I 95 0662949 0523008 358
RESEARCH SIGNIFICANCE
More than 50 million tons of fly ash are produced each year in the United States,
but only about 25% is used (14). Some of the Class C fly ashes produced, such
as Houston Lighting & Power Company’s W. A. Parish ash, cannot be used in
sulfate environments, but are otherwise high quality ashes which can improve
both the unhardened and hardened properties of concrete. Finding methods to use
these ashes in sulfate environments will lower cost and improve concrete
properties in some areas that have not been able to take advantage of the available
Class C ashes. Additionally, electric utilities, and ultimately their customers,
would realize significant cost savings resulting from avoided disposal costs.
Patent applications have been submitted for several of the methods investigated.
OBJECTIVES
The objective of this study was to develop methods of producing sulfate-resistant

concrete using a Class C fly ash which had been found to cause undesirable
sulfate-induced expansions in concrete. Several methods were investigated to
accomplish this goal, looking both at adding fly ash as a mineral admixture (along
with chemical admixtures) and intergrinding fly ash with portland cement to
produce interground blended portland-pozzolan cements. This paper will focus
on discussing the latter method where fly ash was interground in amounts from
0% to 70% by mass of portland cement. Additional gypsum was included in some
blends to account for the chemistry of the fly ash.
--``,`,-`-`,,`,,`,`,,`---
Overview
The test program consisted of monitoring the performance of different concretes

made with W. A. Parish fly ash under severe sulfate exposure conditions.
Performance was evaluated in terms of expansion over time, mass loss over time,
and visual examination to determine the time to first cracking.
The basic (control) mixture proportions consisted of a standard 306 kg/m3 Texas
Highway Department concrete pavement mixture:
306 kg/m3 Portland Cement

929 kg/m’ Crushed Limestone
962 kg/m3 Sand
146 kg/m3 Water
Both ASTM CI50 Type I and II portland cements were investigated for use as
base cements in the portion of the investigation which focused on blended,

A C 1 SP-353 VOL*I 95 = 0662949 0523009 294
interground cements. W. A. Parish fly ash was interground with portland

cement clinker to produce ASTM C595 Type IP and IIP portland cements
(although the 40% limit on pozzolan addition was purposely exceeded in several
blends). In some blends, additional gypsum was interground to supply the fresh
concrete with a sufficient quantity of sulfate ions to stabilize the ettnngite. The
amount of additional gypsum interground was based upon the "sulfation point"
of the particular cementífly ash blend. The sulfation point is defined as the point
where a stoichiometric balance of sulfate is provided to react all the C,A and
other reactive aluminates in the fly ash completely. The three levels of gypsum
added were one, two and four times the sulfation point. A summary of the test
variables pertaining to the concrete mixtures made with the blended cements is
shown in Table 1.
A total of 16 separate cement blends were developed, with one concrete mixture
made from each blend. Control mixtures using Type I and II cement without fly
ash were also batched. At least three replicate specimens for exposure testing
were cast from each concrete mixture. In addition, twenty-one 100-mm by 200-
mm concrete compressive strength cylinders were cast from each batch and tested
--``,`,-`-`,,`,,`,`,,`---
at 3, 14, 28, 180 and 365 days.
Ma terials
The materials used in the study are found throughout central and eastern Texas.
The coarse aggregate is a Georgetown, Texas crushed limestone chosen because
it is a high quality aggregate that is not susceptible to alkali-silica reaction. In
this study, high alkalies would likely be encountered. The fine aggregate is
Colorado River sand. This sand is a sound aggregate and has a reliable field
record in concrete throughout Texas. Both of these aggregates were successfully
used in previous University of Texas studies (7, 10, 12) and are commercially
readily available.
The fly ash used in this study was produced during base load operations at
HLBrP's W. A. Parish Generating Station from a sub-bituminous Wyoming
Powder River Basin Coal. All samples used in the study were collected at one
time to provide a consistent, representative sample. The fly ash met ASTM C618
requirements, as shown in Table 2. Table 2 also reports the results of the
mineralogical X-ray diffraction analysis performed on the ash.
Cement clinker was obtained from commercial cement plants located in central
Texas. Typical physical and chemical analyses for Types I and II cement
produced from these clinkers are included in Table 3. These cements have C,A
contents of 11.1 % and 6.0%, respectively.
Natural gypsum and anhydrite were also obtained from commercial cement plants
and are used in this study.

A C 1 SP-I153 VOL*I 75 IObb27Li7 052l1010 Tob =
48 Prusincki and Carrasquillo
Mixing water used was potable tap water. No air-entraining admixture, high-
range water reducer or other chemical admixtures were added to the concrete.
Production of Intereround Blended Cements
As previously noted, fly ash can be added to concrete as a mineral admixture, or

it can be interground and blended with portland cement. Intergrinding the fly ash
with clinker and gypsum provides some advantages over addition as an admixture
(10, 15-17):
1. Agglomqated fly ash particles tend to be dispersed;

2. Partially crystalline shells, which surround glass and restrict its
ability to react, are crushed;
3. Fly ash glass is crushed, increasing reactive surface area;
4. Increased dispersion, crushing and surface area of the fly ash
particles, in conjunction with grinding of clinker and gypsum,
allows for an intimate and uniform blend of fly ash, cement and
gypsum particles which normally cannot be duplicated when fly
ash is added as an admixture at a batch plant;
5. Additional ground gypsum can be added to compensate for the C3A
and other reactive aluminates in the fly ash to optimize cement
performance.
The interground cements enumerated in Table 1 were produced in a scaled-down

version of industrial ball mills which are used in the production of portland
cement. The laboratory ball mill had a 100-1volumetric capacity, with dry batch
size of 40 kg. It discharged into a fully enclosed housing. The drum rotated at
about 40 revolutions per minute and contained approximately 500 steel balls.
--``,`,-`-`,,`,,`,`,,`---
Gypsumklinker ratios for Type I and Type II cements were determined by

producing a laboratory-ground cement with the same SO3 content as the
corresponding commercially available cement. Also, the grinding time was
adjusted to yield the same Blaine air permeability as the commercial cements.
Mixinp and Standard Concrete Tests
Concrete mixing was completed under laboratory conditions in a .O85 m3 electric

mixer according to ASTM C192. The fresh concrete of each mixture was tested
for slump according to ASTM C143. A slump of 100 to 125 mm was the
specified nominal value used in this study. Water content was adjusted slightly
for each batch to achieve this slump. The compressive strength of concrete was
determined by testing 100-mm by 200-mm cylinders according to ASTM C39.
The cylinders were used to confirm the compressive strength of the concrete
mixture at ages previously noted.

A C 1 SP-153 V O L J I 95 0662947 05210LL 9 q 2 =
Sulfate Exposure Testing
U.S. Bureau of Reclamation Method 4908 was the procedure chosen to provide
accelerated sulfate testing (18). It is used as a standard method to test concrete
rather than mortars, as in ASTM C452 or C1012. It is similar to ASTM C1012
in that it allows for the evaluation of pozzolan and slag blended cements.
In the test method, 75-mm by 150-mm concrete cylinders are continuously soaked
in a 10% sodium sulfate solution (Method B of the test procedure). The
specimens have stainless steel gage studs embedded into their ends for length
measurements. Specimens are exposed to the sulfate solution after being moist
cured for 14 days. The sulfate resistance of the concrete is determined by
monitoring expansion, weight loss and cracking at 30 day intervals. Measurement
of mass loss and time to first cracking are additional tests used to support this
study and are not part of USBR 4908.
The USBR standard has three options: Method A - continuous soaking in a 2.1 %
sodium sulfate solution; Method B - continuous soaking in a 10% solution; and
Method C - alternate soaking and drying in a 2.1 % solution. Method B has been
determined to be a true acceleration of tests in more dilute solutions, with no
observable abnormalities in the manner of sulfate attack (19). Also, this method
has been found to be approximately as harsh as the soaking/drying of Method C
(4).
RESULTS
Basis of Comparison
This paper is based on 3 1/2 years of expansion data. The principal method of
reporting results of sulfate deterioration will be expansions. These expansions are
compared to a control mixture made with Type II cement. This mixture is a
standard specified by the Texas Highway Department when concrete is placed in
sulfate environments. In addition, expansions resulting from high sulfate-resistant
Type V and 0% CSA cements are also included for comparison. These
expansions were reported in another study using identical mixtures and exposure
conditions (12). Specimen failure occurred when the cylinder broke into pieces
and could no longer be measured for expansion. Mass loss and time to first
cracking were found to be strongly correlated to expansion, and are not reported
in this paper.
Concrete strengths from 3 to 365 days are also presented to demonstrate both the
short-term and long-term strength effects of the various blends.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - I 1 5 3 V O L S I 95 E 0662949 052LOL2 889 m
50 Prucinski and Carrasquillo
TvDe II/Class C Flv Ash Intereround Blended Cements
Fig. 2 shows linear expansions for Type II cement blended with 25% fly ash and
various levels of gypsum. The two specimens with the lowest amounts of added
gypsum (II/25/0 and 11/25/1) failed prior to the end of the reporting period. The
specimens with the highest levels of gypsum (IV2512 and II/25/4) remained intact.
However, only the highest gypsum specimen, II/25/4, produced expansions lower
(by 29%) than the Type II control. Expansions of all the 25% blended cements
were significantly greater than the Type V and 0% C3A cements. Compressive
strengths, compared to unblended Type II cement concrete, were higher for ail
25% fly ash blends at all ages except for the II/25/4 blend which had 12% and
9% lower strength at 3 and 14 days than the control. However at 28 days,
--``,`,-`-`,,`,,`,`,,`---
compressive strengths of the fly ash blends increased from 1% to 13 % and at 365
days, strengths increased from 14% to 32%. Addition of fly ash gypsum at one
to two times the sulfation point tended to increase compressive strengths from 14
days and beyond, when compared with the 25% blended cement with no
additional fly ash gypsum (II/25/0). Adding four times the sulfation point of fly
ash gypsum resulted in compressive strengths lower than blend II/25/0 at all ages.
Fig. 3 shows linear expansions for Type II cement blended with 35 % fly ash and
various levels of gypsum. As with the 25% fly ash blends, gypsum addition
equal to one and two times the sulfation point (II/35/0 and 11/35/1) resulted in
specimen failure prior to the end of the reporting period. The specimens where
gypsum was added at two and four times the sulfation point (II/35/2 and II/35/4)
produced expansions which were not only 81 % to 89% less, respectively, than
the Type II control, but were also 30% and 61 % lower than concrete made with
0% C3A cement (at 1036 days). Compressive strengths, compared to unblended
Type II cement concrete, were higher for all 35% fly ash blends at all ages
except for 3 day (all blends) and 14 day (II/35/4 blend only). At 3 days, strength
reduction ranged from 3% to 20% lower compared with the Type II control.
However, the 35% blends achieved 7% to 18% higher strengths at 28 days and
25% to 38% greater strengths at 365 days. Higher levels of fly ash gypsum (2
and 4 times the sulfation point) tended to increase compressive strength at 3 days,
while reduce strengths at later ages, when compared to the 35% blend with no
additional fly ash gypsum.
Fig. 4 shows linear expansion for Type II cement blended with 50% fly ash and
gypsum at four times the sulfation point. This blend achieved a 93% reduction
in expansion compared to the Type II control, and a 68% reduction compared
with 0% C3A cement (1036 days). Compressive strength was higher than the
Type II control at all ages except 3 and 14 days. A 15% reduction was noted at
3 days, which reversed to a 5% strength gain by 28 days. At one year, the 50%
fly ash blend showed a 25% strength improvement over the control.

A C 1 SP-353 V O L X I 75 IObb2747 0523033 715
Tvpe TIClass C Flv Ash Interpround Blended Cements
Fig. 5 shows linear expansions for Type I cement blended with 25% fly ash and
two levels of gypsum: no added fly ash gypsum and gypsum added to account
for four times the sulfation point. In this case, both 25 % fly ash samples (I/25/0
and I/25/4) failed prior to the end of the reporting period. Compressive strengths
for the high-gypsum sample were greater than the Type II control @y 6% to
35%) for all ages greater than 3 days. In addition, 3 day strength was only 3%
less than the control. Compressive strengths for the sample with no additional
gypsum were not available except at 365 days.
Fig. 6 shows linear expansions for Type I cement blended with 35% fly ash and
two levels of gypsum: no added fly ash gypsum and gypsum added to account
for four times the sulfation point. Specimen 1/35/0, with no added gypsum,
failed before the end of the reporting period. The high-gypsum specimen (I/35/4)
produced expansions 85 % lower than the Type II control and 50 % lower than the
0% C3A cement. Compressive strengths for both samples, compared to
unblended Type II cement concrete, were higher for all ages, except for the 3 and
14 day strengths of the high-gypsum specimen (3% to 4% less than the control).
At 28 days, strengths were 9% to 22% higher, and at 365 days were 16% to 36%
higher. Adding a high level of gypsum tended to decrease compressive strength
when compared to the 35% no-gypsum blend.
Fig. 7 shows linear expansions for Type I cement blended with 50%, 60% and
70% fly ash, and gypsum added to account for four times the sulfation point.
Each of these samples produced expansions significantly lower (93 % to 95 % less)
than the Type II control. Also, these cement blends yielded expansions 72% to
80% lower than 0% C3A cement. Compressive strengths for the 50% and 60%
fly ash samples (I/50/4, I/60/4), compared to unblended Type II cement concrete,
were greater for all ages 28 days and above, increasing from 8% to 25%. The
70% fly ash sample produced strengths lower than the Type II control from 3 to
28 days (23% to 40% lower). 365 day strengths were 15% greater than the
control, however. Of the three high volume fly ash samples, the 60% sample
achieved the greatest compressive strength levels, and the 70% the lowest.
DISCUSSION
Effect of Gypsum Addition
One of the important variables in this investigation was to add gypsum to

compensate for the reactive alumina in the fly ash. The study found that the
beneficial effects of intergrinding alone, without additional gypsum, produced
expansions far in excess of the Type II control concrete. The addition of gypsum
to account for between one and four times the sulfation point decreased sulfate
expansions in every case. Higher levels of gypsum produced lower expansions.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*:I 95 nbb2949 0521014 6 5 1 =
In fact, comparing both the 25% and 35% fly ash additions blended with Type
II cement, increasing gypsum addition from two to four times the sulfation point
cut expansions (already significantly lower than the Type II control) almost in
half.
Increasing gypsum additions had variable effects on compressive strength.

Gypsum levels of one and two times the sulfation point tended to produce
compressive strengths comparable to the 25% and 35% fly ash/Type II cement
blends without gypsum addition. The highest level of gypsum addition, four
times the sulfation point, tended to lower concrete strength somewhat for 25 and
35% fly ash additions, blended with both Type I and II cements.
Effect of Flv Ash Addition
Intergrinding W. A. Parish fly ash into Type I and II cements, without

compensating for the reactive alumina through blending of additional gypsum,
produces concrete with unacceptable sulfate expansions. However, if gypsum is
added between two and four times the sulfation point, sulfate expansions can be
dramatically reduced below that of Type II cement alone, and in many cases
below Type V and 0% C3A cements. Fig. 8 graphically illustrates this concept
by plotting specimen expansions versus fly ash addition. The figure shows that
compared with 25% fly ash addition blended with Type II cement, adding 35%
to 50% fly ash lowers expansions to below those of high sulfate-resistant Type
--``,`,-`-`,,`,,`,`,,`---
V and 0% C3A cements. In addition, blending 35% to 70% fly ash with a non-
sulfate resistant Type I cement results in producing sulfate-resistant concrete with
expansions 50% to 80% less than 0% C,A cement.
Table 4 illustrates that compressive strengths, compared to the Type II control,

were higher for all levels of fly ash addition at 28 days and beyond, except for
the 70% fly ash addition. 28-day compressive strengths increased up to 22%
(I/35/0) and 365 day strengths increased up to 38% (II/35/2) when compared with
the control. Fly ash addition tended to decrease compressive strengths below 28
days. At 3 and 14 days, 25% and 35% fly ash additions resulted in compressive
strengths that ranged from a 7% strength increase to a 20% decrease when
compared with the control. High percentages of fly ash addition (50% to 70%)
had a more pronounced effect on 3-day strength, yielding strength decreases
ranging from 15% to 40% lower than the control. By 14 days, most fly ash
blends (except 70% fly ash) exceeded, or were within IO%, of the Type II
control compressive strength. Fig. 9 illustrates the compressive strength trends
noted above for those specimens using the highest two levels of gypsum added.

A C 1 SP-153 V O L U I 95 0662949 O521015 598
Effect of Cement Tvrie
Both Type I and II cements have been used to blend with various levels of fly ash
and gypsum. At the 25% to 35% levels of fly ash addition, Type II cement
blends appear to allow greater reductions in sulfate expansions than equivalent
Type I blends. For instance, at 25% fly ash, blending with Type II cement
(blend II/25/4) allowed the development of concrete with lower sulfate expansions
than an unblended Type II control. Using Type I cement at the 25 % fly ash level
resulted in unacceptable expansions at any of the gypsum levels attempted. At
35% fly ash, highly sulfate resistant concrete was achievable using both Type I
and II cements (both of which expand less than Type V and 0% C,A cements);
however, the Type I cement (I/35/4) resulted in 43 % higher expansions than the
Type II blend (II/35/4). At 50% fly ash addition, this tendency reversed. The
Type I blend (1/50/4) achieved 19% lower expansions than the Type II blend
(II/50/4). Again, both of these blends performed better than the moderate and
high sulfate resistant controls. At high levels of fly ash addition (60% and 70%),
only Type I cement was investigated. Expansions for these blends were the
lowest for any of the fly ash or control mixes tested.
The effects of cement type on concrete strength were somewhat variable.

Comparing Type II and I cement concretes with no fly ash (II/O/O and I/O/O)
reveals virtually identical compressive strengths at all ages. With fly ash
interground in amounts from 25% to 35%, Type I cements, with some
exceptions, tended to achieve higher compressive strengths than equivalent Type
II blends at both early and later ages. Most strengths were within +/- 10% of
each other. At the 50% fly ash level, neither Type I nor II blends appeared to
have a systematic advantage for compressive strength. At the 60% and 70%
levels of fly ash blending (Type I cement only), 3 day strengths were suppressed
to levels below the Type II control; however the only mixture not able to achieve
greater 28 day-strength than the control was the 70% blend (I/70/4).
CONCLUSIONS
The principal finding from this study is that substantial sulfate resistance can be
achieved--equal to or greater than Type II, V, or 0% C3A cements--by using Type
I and II cements blended and interground with a Class C fly ash. This is
particularly significant because the Class C fly ash used has been shown to
decrease sulfate resistance when added as a mineral admixture. Additionally,
Type I cement, with its ordinarily high C3A content, normally cannot produce
sulfate resistant concrete. Specifically:
1. Interground blended cements containing Type II cement and 25% Class C

--``,`,-`-`,,`,,`,`,,`---
fly ash can be produced having a sulfate resistance equal to or better than
that of Type II cement.

A C 1 S P - 1 5 3 V O L * I 75 m 0662’749 0 5 2 L O L b 424
54 Prusinski and Carrasquiiio
=
2. Increasing fly ash contents to levels from 35% to 50% and intergnnding
with Type II cement improves sulfate resistance to better than that of Type
V or 0% CSA cement.
3. Interground blended cements containing Type I cement and 35 % Class C

fly ash can be produced having a sulfate resistance better than that of
Type V or 0% C,A cement.
4. Increasing fly ash contents to levels from 50% to 70% and intergrinding
with Type I cement further improves sulfate resistance.
5. Intergrinding Class C fly ash with Type I or II cements without additional

gypsum to account for the reactive aluminates in the fly ash does nut
improve sulfate resistance to levels which exceed the Type II control.
6. Blending in additional gypsum at levels equal to 2 to 4 times the sulfation

point of the fly ash improves the sulfate resistance of both Type I and II
cements interground with Class C fly ash.
7. Producing interground, blended cements with Type II cement and Class

C fly ash is more effective in increasing sulfate resistance than Type I
cement, when fly ash levels are between 25% and 35%. At the 50% fly
ash level, Type I cement is more effective in improving sulfate
resistance. Type I cement blended with 50% to 70% fly ash produced the
lowest sulfate expansions in the study.
8. Fly ash contents between 25 % and 60% improved compressive strength,

compared to the Type II control, at 28 days and above. At earlier ages,
these fly ash blends produced compressive strengths equal to or slightly
less than the Type II control. Fly ash content of 70% produced
compressive strengths less than the control through 180 days.
REFERENCES
1. Lea, F.M., The Chemistrv of Cement and Concrete, Chemical Publishing

Company, Inc., New York, 1970, 727 pp.
2. Mehta, P.K., Concrete: Structure. Pro-perties and Materials, Prentice-

Hall, Inc., New Jersey, 1986, 450 pp.
3. Mindess, S. and Young, J.F., Concrete, Prentice-Hall, Inc., New Jersey,

1981, 671 pp.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L * I 95 O662949 052LOL'i 3 6 0
4. Dikeou, J.T., "Fly Ash Increases Resistance of Concrete to Sulfate

Attack," Bureau of Reclamation, Water Resources Tech. Publication,
Research Report No. 23, 1976, 16 pp.
5. Dunstan, E.R., "A Possible Method for Identifying Fly Ashes That Will
Improve the Sulfate Resistance of Concretes," Cement. Concrete. and
&recates, Vol. 2, No. 1, 1980, pp 20-30.
6. Tikalsky, P.J. and Carrasquillo, R.L., "Influence of Fly Ash on the

Sulfate Resistance of Concrete," AC1 Materials Journal, Vol. 89, No. 1,
1992, pp. 69-75.
--``,`,-`-`,,`,,`,`,,`---
7. Center for Transportation Research, Sulfate Resistance of Concrete

Containing Flv Ash, Study # 3-5/9-87-481, University of Texas at
Austin, 1988.
8. Tikalsky, P.J. and Carrasquillo, R.L., "Fly Ash Evaluation and Selection
for Use in Sulfate-Resistant Concrete," AC1 Materials Journal, Vol. 90,
NO. 6, 1993, pp. 545-551.
9. Mehta, P.K., "Effect of Fly Ash Composition on Sulfate Resistance of

Cement," Journal, American Concrete Institute, Vol. 83, No. 6, 1986,
pp. 995-1000.
10. Freeman, R.B. Optimization of the Physical and Compositional

Characteristics of Flv Ash Cement for the Production of Sulfate-Resistant
Concrete, Ph.D. dissertation, the University of Texas at Austin, 1992.
II. Prusinski, J.R., Weber, J.L., Martinez, C.G. and Nichols, M.E.,
"Houston Lighting & Power Company's Coal Combustion By-products
Utilization Program: A Decade of Success," Proceedings of the Sixteenth
Biennial Low-Rank Fuels SvmDosium, Energy and Environmental
Research Center, University of North Dakota, 1991, pp. 345-360.
12. Tikalsky, P.J., Effect of Flv Ash on the Sulfate Resistance of Concrete,
Ph.D. dissertation, the University of Texas at Austin, 1989.
13. Carrasquillo, R.L., Effects of W. A. Parish Fly Ash on the Sulfate

Resistance of Concrete. Interim Report, Carrasquillo Associates, June
1993.
14. American Coal Ash Association, 1991 Coal Combustion By-product--

Production and Consumption," 1993,
15. Bernhausen, H., "PFA in Blended Cement - Its Production and

Application," World Cement, Vol. 19, No. 6, 1988, pp. 250-255.

A C 1 SP-153 V O L X I 95 Ob62949 052101ô 2T7
56 Prucinski and Carrasquillo
16. Stoltenberg-Hansson, E., "Fly Ash Cement: Production Methods,

Materials, Properties, and Energy Savings," Fly Ash and Coal Conversion
By-Products: Characterization. Utilization. and Disposal IT, Materials
Research Society Symposia Proceedings, Vol. 65, 1986, pp. 19-26.
17. Freeman, R.B., and Carrasquillo, R.L., "Influence of the Method of Fly
Ash Incorporation on the Sulfate Resistance of Fly Ash Concrete,"
Cement & Concrete Composites, Vol. 13, 1991, pp 209-217.
18. United States Bureau of Reclamation, "Test Procedure for Length Change
of Hardened Concrete Exposed to Alkali Sulfates, " USBR 4908-86, 1986.
19. Tuthill, L.H., "Resistance of Cement to the Corrosive Action of Sodium

Sulphate Solutions," Journal, The American Concrete Institute, Vol. 33,
--``,`,-`-`,,`,,`,`,,`---
1957, pp. 83-106.

A C 1 SP-153 VOL*I 95 I0 6 6 2 9 4 9 0523039 133 I
TABLE 1 - TEST VARIABLES FOR BLENDED, INTERGROUND

CEMENTS
--``,`,-`-`,,`,,`,`,,`---
* Additional gypsum (above cement gypsum) stated as a multiple of the amount of gypsum
required to reach the fly ash sulfation point.

A C 1 SP-153 V O L r I 95 Ob62949 0521020 955
TABLE 2 - W. A. PARISH FLY ASH PHYSICAL, CHEMICAL, AND

MINERALOGICAL ANALYSIS
Chemical A ~ l v ~ k Mineralogical Analysis
Compound Percent Mineral Percent

SiO, 34.4% 4.0%
18.7% Mullite 3.1%
Spinel 1.6%
Hematite
SiO,+AI,O, +Fe,O,
Periciase 1.2%
z: 1 :)1: 1 1
1.86% Anhydrite 0.8%
"]A'"
Loss on ignition 0.32% Menvinite 2.6%
Moisture content 0.32% Sum of crystalline phases 17.1 %
Retained on 45pm sieve 14.3% Loss o n ignition 0.32%
Pozzolanic activitv I 92% I Autoclave expansion I ~~

0.01 %
Specific gravity 2.68 Water requirement 90 %
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 75 0662949 0 5 2 1 0 2 1 891
TABLE 3 - CEMENT PHYSICAL AND CHEMICAL ANALYSIS
Item
sio,
Type 1
20.3%
l I-
mposition
AlP. 5.8%
Fe203 2.5% 3.3% I 3.2% I 3.8% I

II
Loss on ignition 0.9% 0.6%
Insoluble residue 0.2 % 0.4%
Total alkalinity 0.1%

54.6%
0.6%
57%
OS%
62.2% 70.0% I
1 c*s
C J
16.9%
11.1%
19.5%
6.0%
16.2%
3.6%
3.8% I
0.0%
11.6%
Physical Analysis
-- I 362
Vicat Initiai set, min
Vicat Final set. min 258 210
I r A u t o c t a v e expansion I 0.01 x 1
3 day strength cube, MPa 26.2 25.1 _- 27.3
7 day strength cube, MPa 33.8 32.2 -- 35.0
--``,`,-`-`,,`,,`,`,,`---

TABLE 4 - COMPRESSIVE STRENGTH
Blend I Cem. I Fly I Fiy Ash I Compressive Strength (MPa)
Day Day Day Day -

h Y
IW25/0
Iüî511
Ií
II
25
25
25
O
1
23.2
22.0
36.8
37.3 ::::I I
40.7 47.8
47.8
50.8
53.6
--``,`,-`-`,,`,,`,`,,`---
IV2512 II 2 22.9 35.9 49.0 51.6
iW25/4 II 25 4 19.2 31.0 36.9 I 44.4 I 46.7
III390 II 35 O 18.6
17.3
21.0
I 1 I I
36.6
35.8
36.7
I
43.1
42.1
41.5
I
I
I
50.9
50.7
46.0
I
I
I
*
51.5
56.0
IV35/4 50.6
IU50/4 50.7
U25/0
-
51.7
U2514 21.0 36.2 54.7

-
Y3510 35 21.8 I 38.2
-
55.0
Y35/4 35 20.8 I 33.1 47.3
I/50/4 39.4 I 45.6148.9

Y6014
I
I I I
40.7 I
I
48.0 I 50.6
1
U7014 13.1 25.2 28.2 39.8 46.8
IYO/O 21.7 34.2 36.5 40.2 40.6
wo/o I O O 21.7 33.1 35.8 39.3 39.5

Cntrl
8 Data not available.

** Fly ash gypsum level indicates multiple of fly ash sulfation point.
Note: Compressive strength based on average of at least three 100-mm X 200-
mrn cylinders.

A C 1 SP-153 V O L X I 95 O662949 0523023 6 6 4
MiIwaukee Conference 61
E F F E C T O F FLY ASH CONTENT

TSDHPT Type B Fly Ash, Slump: 6-7 Inch
1O0
80
.-
r
O 0.1 PERCENT EXPANSION
o 60
8
--``,`,-`-`,,`,,`,`,,`---
i
O
vi 40
C
Q
W
x.
20
O
O 1O0 200 300 400 500
Time, Days
Fig. I-Comparison of sulfate expansions-Class C fly ash added as

mineral admixture in University of Texas study
1% c e -
,/' 1
0.8%
1 /' ,&@
I
I
~
1 1 1 1 1 1 1 1 1 1 1 1 1 l I I
28 140 252 984 478 688 700 812 S?4 1038 114û 1260
81 lse 308 420 5%? 644 756 868 s8olo9212w
Number of Days After Casting inaakM.p.cmn,
mur.
Fig. 2-Comparison of sulfate expansions-Type II cement blended

with 25 percent fly ash

A C 1 SP-153 VOL*I 95 IOb62949 0523024 5 T 0 W
0.8%
0.6%
i / Blend ly35B
-------.
Oypsun:WSulkdknR
Blendw
-
0.4% Gypsum: 4X SilltaHai Ft
...............
-
Type II caibol
TypeVcwibd
0.2%
.- .--*
096c3Acontrd
n
0% budonawmpsd
I 140 252 984 478 588 mo 812 924 1096 1148 1260 hormon.p.dmnr.
8) 1 w 308 420 s32 644 758 888 9 8 0 1 0 9 2 1 2 0 4
Number of Days After Casting
Fig. 3-Comparison of sulfate expansions-Type II cement blended

Eicpansion W)
O.á%
--``,`,-`-`,,`,,`,`,,`---
0.6%
0.4%
0.2%
28 140 252 984 476 588 7M) 812 û24 1wB 1148 1260
8) 1 9 6 3 m 4 2 0 ~ 6 4 4 7 5 6 8 6 8 9 8 0 1 0 a 2 1 2 0 4
Fig. M o m p a r i s o n of sulfate expansion-Type II cement blended


A C 1 SP-153 VOL*I 75 I0662947 0521025 437
0.8%
0.6%
0.4%
0.2%
0%
Number of ûap After Casting
Fig. 5-CompariSon of sulfate expansions-Type 1 cement blended

0.6%
0.4%
0.2%
-,'
& I
&.........................................
0%
-7, I I I I I I I I I I
æ i«) 252 w 478 mo e12 924 io38 1148 1260

84lSB3084m5326447588889801Dge12w
Fig. &-Comparison of sulfate expansions-Type I cement blended

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-<53 V O L * I 95 0662949 0521026 3 7 3 =
O.&
0.6%
0.4%
84 198 sm 420 632 644 768 868 880 1092 1201

Number of ûays Mer Casting
Fig. 7-Comparison of sulfate expansions-Type I cement blended

with 50 to 70 percent fly ash
0.1% - - ~ - -- khL.;.... --
c ---i--.-*
- -
- T . 3...........
......
-
o......................O
~
--``,`,-`-`,,`,,`,`,,`---
I l l I l

A C 1 SP-I153 V O L S I '75 m 0662749 0523027 20T
-- -----,- ...--
...........................
.. .- ..... .o-.......,,.---a-.,~.*........
~
~ ~
-....e
7 c
7
........... ....
*----
.
.
I
-
2o
10 -
tr .
&-..............
%
9.*
~~
..............
.=-. c ; . . .
-...%...................0..........
. -
.
.....-*-*
. . ~~
I l l I I I
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 E Obb2949 0523028 146
SP 153-4
Processed Fly Ash for High

Performance Concrete
by H. A. W. Cornelissen, R. E. Hellewaard,
and J. L. J. Vissers
SvnoDsis: In the present research project, fly-ash has been

mechanically processed to 1 to 5 micron particle size. Mortars and
concretes were made from these processed fly-ashes. In the paper, the
results of the micronised fly-ash are compared to the results gained
with air classified fly-ash, silica fume and blends.
It was found that using ground fly-ashes, very fluid mixtures can be
produced with excellent strength and durability properties.
Because of the growing interest for ultra-fine supplementary cementing
materials (SCM’s) for high performance concrete, attention is needed to
micronise fly-ashes in an economical way.
Kevwords: Compressive strength; flv ash; hieh Derformance concrete;

micronizing; mortars (material); particle size distribution; silica fume;
temperature; workability
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 I0662749 0521029 082
68 Cornelissen, Hellewaard, and Vissers
The authors are employed by KEMA Nederland B.V., the Netherlands;

H.A.W. Cornelissen as head of the By-products and Construction
Quality group, R.E. Hellewaard and J.L.J. Vissers as assistant and head
of the laboratory.
INTRODUCTION
In modern concrete technology, the use of high performance

concretes (high strength and high durability) is becoming more and
more common. At the same time there is a tendency towards concrete
mixes which need only minor compaction energy for optimal filling of
the formwork. These concretes have a high slump and must therefore
be very stable in order to assure homogeneity. For the proportioning of
these concrete mixtures, special additives and ultra fine SCM’s like
silica fume, are needed. However, the availability of these ultra fine
SCM’s is very limited. Because of the developments indicated, it is
expected that the need for ultra fine SCM’s will strongly increase. That
is why it was decided to process fly-ash to particles in the one micron
range. This will result in a valuable product and an important market for
fly-ash.
It is well known from the literature, that the fineness of fly- ash is
of major influence on concrete properties. In earlier research [ l ] , fly-ash
fineness was increased by air classification; others [2] realised this by
grinding to particle sizes down to between about 5 and 10 micron. The
ultra-fine range was also reached in Japan [3], by vaporization at about
2400 OC and condensation of fly-ash. The present project, investigates
whether fly-ash can be micronised economically to less than 5 p m and
to see if the performance of this product in mortar and concrete is
satisfactorily.
MATERIALS
--``,`,-`-`,,`,,`,`,,`---
The effects of the various types of SCM’s were tested in mortar

and in concrete with normal hardening Portland cement (PC-A).
A typical fly-ash (code AI) was used (57.0% SiO,, 26.4% AI,O,
4.4% Fe,O, 4.2% C and 1.8% Cao). The fine fraction (code AC) was
collected in the bag-filter of an air classifier [ l ] , whereas the ultra-fine
fraction (code AG) was obtained by grinding. The resulting particle size

A C 1 SP-353 V O L * I 95 E Ob62949 0523030 õ T 4
distributions are given in Fig. 1. An impression of the particle shapes is

shown in Fig. 2 for the air classified versus the ground fly-ashes. By
grinding the shape changes from round into angular.
Some characteristic data are given in Table 1. It can be seen that

the mean particle size being 21.6 ,um for the input fly-ash was reduced
to 9.9 ,um for the air classified fly-ash and to 1.6 ,um for the ground one.
In Table 1, the grading modulus [4] is presented. This grading modulus
(G) proved to be a valuable parameter for the description of the effect
of the fly-ash grain size distribution on mortar and concrete properties.
--``,`,-`-`,,`,,`,`,,`---
G = (6/(1/dl) - (l/d2))/ln(d2/dl)
In the formula, d l and d2 represent the diameters of the smallest

and the largest size particles of a group between two successive
sieves. Between these sieves the size distribution is assumed to vary
linearly to a log scale.
The silica fume (code SF) involved, had a SiO, content of 92%
(m/m) and a mean particle size of 0.12 pm. In the tests, a 50% to 50%
(m/m) combination of SF and AG was also applied. This SCM was
denoted as SA. In this research project the emphasis lies on plain
mortar and concrete properties. The effect of combination of SCM?son
alkalinity and protection of reinforcement is part of further research.
COMPOSITIONS AND PREPARATIONS
Mortar
The mortar compositions, according to the European standard

EN 196, contained 22% (m/m) PC-A cement, 67% sand and 11% water
(water to cement ratio 0.50). In order to reach fresh mortar spreads in
the same range for all mixtures, superplasticizer (SP) was added
(spread 175 mm plus-minus 10 mm). This spread was measured with
the Hagermann apparatus (DIN 1060, part 3). The effect of the SCM?s
was tested by additions of 5%, 10% and 15% (m/m cement) to the
reference mixture. Ground fly-ash and silica fume were handled in a
dispersion. After casting and demoulding, the
40 mm x 40 mm x 160 mm specimens were stored in water at 20 OC.
An overview of the various mixtures is given in Table 2. As expected, a
higher SCM content requires more superplasticizer. This is especially
true if the ultra-fine silica fume is involved. The angular shape of the
ground fly-ash did not result in an extra doses of superplasticizer (SP).

A C 1 SP-153 V O L * I 95 Ohb29Qq fl-521031730 m
Concrete
In the concrete compositions, 360 kg/m3 PC-A cement was

used; the maximum grain size of the river gravel was 31.5 mm.
Because a major objective was to realize high fluid mixtures, the fresh
concrete slumps were 230 plus-minus 40 mm. This resulted in a water
to cement ratio of 0.32 for the mixtures containing SCM’s and 0.35 for
the reference mixture (no SCM added). If needed, superplasticizer was
added. The amounts of SCM added were 5%, 10% and 15% (m/m
cement). Three reference mixtures were selected, having similar w/c
(CREFl), similar SP content (CREF2) and about similar workability
(CR EF3).
All cubes (150 mm) were stored in a fog room at 20 OC until time
of testing. During the first 50 hours after casting, the development of
temperature was recorded.
Details of the concrete mixtures are presented in Table 3. For

these types of mixtures, the spread (no-jolting) is recommended for the
assessment of workability. The addition of ground fly-ash (AG) and the
50-50 combination SF and AG gave excellent results as can be seen
from Fig. 3. This also means that for a given concrete spread the
amount of water can be reduced, resulting in higher strength and
durability. Because of the high specific surface, mixtures with only SF
showed lower workability. No segregation and bleeding occured with
exception of the reference mixtures and the mixtures with 5% SCM,
where just a slight tendency was observed. --``,`,-`-`,,`,,`,`,,`---
RESULTS
Mortar
The effect of addition of SCM’s was studied in mortars by

keeping all other variables as constant as possible. Only the amount of
SP was adjusted in order to obtain similar workabilities and thus similar
compaction grades. It is known that the addition of SP has a minor
influence on strength (at given w/c). The SCM materials are important
for filling the inter-particle spaces and for their pozzolan effects. This
should be expressed by the development of strength. The results are
given in Table 4. The addition of SCM improves the values of the
reference mix. As can be seen, SCM types AG, SF and SA give better
results than type AC. The effect of the amount of SCM is more
pronounced at increasing age and depends on the type of SCM as
well. Types AG, SF and SA seem more effective than type AC.

A C 1 SP-153 VOL*I 95 0662949 0521032 677
In order to determine the "binding-factor",generally called the

efficiency factor or k-factor, the relation between water to cement ratio
and compressive strength was measured for a series of reference
mixes. The k-factor was calculated according to:
in which (Wv/Cv) and (Wb/Cb) represent the water to cement ratios of

equal strength mixtures containing SCM's and with no SCM,
respectively. The SCM to cement ratio is given by (f/Cv). Because the
binder (cement) content of the reference mixes was different from the
mixtures where SCM was added (cement plus SCM), the determination
of the efficiency factor was not fully according to the standards in which
an equal binder content is prescribed. Therefore, the efficiency factors
(k-values) are given as values related to the k-value of mixture MACO5
(the absolute
k-value of this mix was 0.99). The relative 28 day k-factors were
calculated and are presented in Table 4 as well. In general, the results
indicate that higher SCM content mixtures show lower relative k-values.
Moreover, the relative k-values are higher for the ground fly-ashes (AG)
in comparison with the classified fly-ashes. Silica fume and the
combination SCM (SA) gave the best results.
The mass of the individual mixtures was calculated. For a given

type of SCM, the effect of the SCM content seemed not to be
significant. The type of SCM, however, resulted in higher mass for the
mixtures with type AC and lower mass for mixtures with types SF and
SA.
The development of the compressive strength is plotted in Fig. 4

for mixes containing 10% SCM in comparison with the reference
mixture. The results indicate that the applications of SF, ground fly-ash
(type AG) only, or in combination with silica fume (type SA) develop to
higher strengths than the reference mixture and the mix containing AC
SCM.
Concrete
Concretes were made to simulate actual conditions for the

addition of SCM's. The positive effect of the ground fly-ashes on
workability was already discussed in the preceding paragraphs. After
casting the fresh concretes, the development of temperature was
followed during the first 50 hours by means of thermocouples placed in
the centre of the cubes. The results are given in Fig. 5. It can be
observed that addition of SCM gives a quicker temperature rise
--``,`,-`-`,,`,,`,`,,`---

(development of hydration), especially if silica fume is added. The

behaviour of the three other types of SCM’s (AC, AG and SA) is about
similar. It is noted that in mass concrete structures, the maximum
temperature will be significant higher than in these 150 mm cubes (in
polyethylene moulds).
After 3, 7, 28 and 91 days curing, the compressive strength was

determined. The values are listed in Table 5, whereas the 7 days
strengths are also plotted in Fig. 6. If similar spread range is taken as
starting point, then the results should be compared to reference
concrete type CREF2. It can be seen that the addition of SCM’s results
in increasing strength for all types of SCM’s. Up to 7 days curing the
differences between types and amounts of SCM’s are marginal. The
results after 28 days curing indicate that the strength values are
significantly higher for the mixtures with higher SCM content, especially
in the case of SCM types AG, SF and SA. As Table 5 shows, however,
SCM type AC is clearly less effective than types AG, SF and SA at later
ages.
SCM’s ate also used for durable concretes. Therefore an

indication of the permeability was obtained by the standard water
penetration test (according to DIN 1048, part 5). The penetration depths
are given in Table 5. It can be seen that the permeabilities were low.
Because of the variations, no significant effects can be identified.
CONCLUSIONS
By appropriate grinding it is possible to micronise fly-ash to sizes

under 5 pm. The effect of addition of these ground fly-ashes on
properties of mortar and concrete was determined and compared to
the effects of air classified fly-ash, silica fume and combinations of these
two types of supplementary cementing materials (SCM). It was found
that in mortar with the ground fly-ashes no higher amount of
superplasticizer was needed for a given spread. In concrete, the fluidity
was positively effected by these types of SCM’s.
Ground fly-ashes also result in higher strength in comparison

--``,`,-`-`,,`,,`,`,,`---
with air classified fly-ash in concretes having similar spread. The

“binding-factor” (k-value) as tested in mortars proved to be in between
these factors of air classified fly-ashes and silica fume.
It can be concluded that ground fly-ashes are excellent SCM’s

for concretes. It is, however, a challenge to produce these SCM’s in an
economical way.

A C 1 SP-153 V O L J I 75 I0662749 0523033 503
Not for Resale
A C 1 SP-153 V O L * I 75 0662749 0523034 4 4 T
ACKNOWLEDGEMENT
This research project was financially supported by the Dutch electricity

production sector and SENTER, center for Technology, Energy and
Environment, The Hague, the Netherlands.
--``,`,-`-`,,`,,`,`,,`---
REFERENCES
Cornelissen, H.A.W., Gast, C.H. "Upgrading of fly-ash for

Utilization in Concrete";
Flv Ash. Silica Fume, Slaa - and Natural Pozzolans in Concrete.
Proc. Int. Conf. Istanbul.
AC1 SP 132, Vol. 1, 1993, pp. 457-470.
Härdtl, R. "Effectiveness of Fly Ash Processing Methods in

Improving Concrete Quality"; Waste Materials in Constructions,
ISBN 0-444-89089-0, 1991, pp. 399-406.
Matsufuji, Y. et Al. "Study on Properties of Concrete with Ultra-

fine Particles Produced from Fly Ash"; FIV Ash. Silica Fume. Slaq
and Natural Pozzolans in Concrete. Proc. Int. Conf. Istanbul. AC1
SP 132, Vol. 1, 1993, pp. 351-365.
Hughes, B.P., Al-Ani, M.N.A. "fly-ash Fineness and its Use in

Concrete"; Maaazine of Concrete Research, Vol. 41, No. 147,
June 1989, pp. 99-105.
TABLE 1 - GRAIN-SIZE DISTRIBUTION CHARACTERISTICS OF

PROCESSED FLY ASHES
----pz ~ ~
ij$l
Fly-ash D-50* D-90* Grading modulus
1
(1/mm)
525
OT)-:assified 994
ground 5390
* 50 and 90 percentile of the particle size distribution

A C 1 SP-153 V O L * I 75 m 0bb2749 0521035 38b m
TABLE 2 - MORTAR COMPOSITIONS (FOR THREE 40 x 40 x 160-

mm SPECIMENS) AND HÄGERMANN SPREAD
~~
Sample Cement fly-ash SF SP spread

code (9) (9) (9) (9) (mm)
MREF 450 O O 0.50 0 174
MAC05* 450 22.5 O 0.50 0 172

MACIO 450 45.0 O 0.50 0.5 181
MAC15 450 67.5 O 0.50 1.1 182
MAGO5 450 22.5 O 0.50 0 170

MAG10 450 45.0 O 0.50 0.5 173
MAG15 450 67.5 O 0.50 1.1 169
MSF05 450 O 22.5 0.50 1.7 173

MSFlO 450 O 45.0 0.50 3.4 173
MSF15 450 O 67.5 0.50 5.1 172
MSA05 450 11.3 11.3 0.50 0.9 177

MSAlO 450 22.5 22.5 0.50 2.0 173
MSAl5 450 33.8 33.8 0.50 3.0 172
* M = mortar, AC = classified; 05 = % SCM (m/m cement)

TABLE 3 - CONCRETE COMPOSITIONS AND WORKABILITY DATA
-
Sample Cernent fly-ash SF w/c SP Slump Spread Spread
code (kg/m3) (kg/m3) (kg/rn3) (%I** (mm) (no jolting) (joking)
- - (mm) (rnrn)
CREFI 360 O O 0.32 2.75 170 320 420
CREF2 360 O O 0.35 2.5 220 470 540
CREF3 360 O O 0.32 2.5 150 320 410
CACO5 360 18 O 0.32 2.5 190 330 420

360 36 O 0.32 2.5 230 430 520
CAC10 360 54 O 0.32 2.5 250 500 570
CAC15
360 18 O 0.32 2.5 230 420 520
CAGO5 360 36 O 0.32 2.5 240 540 600
CAG10 360 54 O 0.32 2.5 270 610 > 700
CAG15
360 O 18 0.32 2.5 220 400 500
CSFO5 360 O 36 0.32 2.5 220 350 470
CSFIO 360 O 54 0.32 2.5 190 320 440
CSFI5
360 9 9 0.32 2.5 230 490 580
CSAO5 360 18 18 0.32 2.5 260 600 > 700
CSA1O 360 27 27 0.32 2.5 270 600 > 700
CSA15
**
C - mcrete; ac = type of SCM; i i=9( m cemt 4/ m
superplasticizer as weight percentage of cement pl i 0.2 SCM
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 IObb2949 0523036 212
TABLE 4 - COMPRESSIVE STRENGTH VALUES OF MORTARS

CONTAINING INDICATED TYPES AND AMOUNTS OF SCMs
Sample SCM IS a Compressive strength (MPa) k/k(MAC05) Mass

code (kg/m3)
28 days 91 days 28 days 28 days
MREF 51.2 65.9 -- 2310
--``,`,-`-`,,`,,`,`,,`---
MACO5 54.3 70.7 I .o 2310

MACIO AC 54.4 71.1 0.5 2310
MAC15 54.2 73.3 0.3 2290
MAGO5 41.8 56.0 71.4 1.5 2290

MAG10 44.3 60.3 77.2 1.4 2280
MAG15 48.3 63.4 79.6 1.2 2280
MSFO5 31.O 40.8 59.2 70.5 2.5 2250

MSF10 31.2 42.3 61.7 75.5 1.6 2230
MSFl5 SF 32.3 46.2 68.7 80.2 1.8 2230
MSAO5 SA 30.6 41.9 59.3 70.2 2.5 2260

MSAlO 43.0 64.2 70.3 2.0 2250
MSA15 42.4 66.9 81.7 1.6 2240
* mean values of six tests
TABLE 5 - PROPERTIES OF HARDENED CONCRETE CONTAINING

INDICATED TYPES AND AMOUNTS OF SCMs
SCM I Cornpressive strength (MPa) WP
- 3 days 7 days 28 days 91 days 28 days

CREFI no O 56.0 68.7 81.8 90.6
CREF2 no O 38.8 49.8 64.2 69.3
CACO5 AC 5 56.3 68.2 83.6 92.3 3

CAC10 AC 10 52.3 64.9 81.6 93.7 O
CAC15 AC 15 49.7 62.3 79.8 92.4 3
CAGO5 AG 5 53.0 65.3 80.0 85.9 5

CAG10 AG 10 52.6 66.2 86.2 96.0 2
CAG15 AG 15 55.0 69.6 95.8 105.9 1
CSFO5 SF 5 55.1 69.4 94.0 95.3 O

CSF10 SF 10 58.3 70.6 96.6 103.9 2
CSFl5 SF 15 57.9 74.3 99.3 104.8 6
CMAO5 SA 5 53.4 66.7 86.5 92.9 3

CMA10 SA 10 56.9 71.4 93.2 99.3 4
CMAl5 SA 15 59.0 73.9 97.1 103.4 5

A C 1 SP-I153 V O L * I 95 m 0662949 0523037 359 m
undersize (%)
1 O0
50
O
o. 1 1 10 1 O0 1 O00
particle size ( p r n )
Fig. l-Particle-size distributions of classified and ground fly ashes in

comparison with input fly ash
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 E Obb29Y9 0521038 095 =
--``,`,-`-`,,`,,`,`,,`---
Fig. 2-Scanning electron micrographs showing typical classified fly

ash (upper) and ground fly ash (lower picture)

A C 1 S P - 1 5 3 V O L X I 75 I0662949 0523039 T 2 1
concrete spread (mm)

1 O00
900 -
BOO -
700 -
600 -
500 -
400
300
200
1O0
O
REF AC AG SF SA
type of SCM
Fig. &Effect of various types and amounts of SCMs

on concrete spread
f’c (7d) (N/mm2)
loo I SCM
o : 5%
b : 10%
c : 15%
-1 ! AG
Fig. 4-Compressive strength development for

mortars containing 10 percent SCM versus no SCM
--``,`,-`-`,,`,,`,`,,`---

SF SA
type of SCM

A C 1 SP-153 VOL*I 95 0662947 0523040 743
iernperoture (OC)
30
20
AC -AG ------- SF -SA -CREFZ

concrete plus
102 SCM
n I I I I I I I I I
O 10 20 30 40 50
curing in hours
Fig. +Temperature development during first 50 hr

for concretes indicated
f’rn (N/rnmZ)
70
SA
SF
60 AG
AC
50
40
30
20 mortar plus
102 SCM
10
o
o 3 7 28
oge in doy
Fig. €&Compressive strength (7 days) for concretes

containing indicated amounts and types of SCMs
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 I0662949 052L04L b ô T I
SP 153-5
Effect of Fly Ash Composition on

Thermal Cracking in Concrete
by M. D. A. Thomas, P. K. Mukherjee,
J. A. Sato, and M. F. Everitt
Synopsis: This paper reports the results fiom a laboratory investigation of the
effect of fly ash on the temperature rise and early-age tensile strain capacity of
concrete. Twelve different fly ashes, with a wide range of chemical compositions,
were used in various proportions (25%, 40% and 56%) in the study. The results
of conduction calorimeter tests show that the rate of heat development was
strongly influenced by the composition of the ash. Generally, the rate and
quantity of heat evolved increased with the calcium level of the fly ash. High-
calcium ashes (>20% Cao) did not significantly reduce the 7-day heat of
hydration when used at a replacement level of 25%. However, the heat of
hydration decreased as the level of replacement was increased for all ashes tested,
regardless of composition. Consequently, even high-calcium ashes may be
effective in reducing the temperature rise in concrete, provided they are used at a
sufficient level of replacemeiit. Flexural tests were camed out on concrete prism
at early ages and the tensile strain capacity was determined as the strain (in the
tensile fibers) at 90% of the flexural strength. Tlie flexural strength decreased
with higher levels of replacement, however. the strain capacity was similar or
slightly higher iii fly ash concretes (compared with control specimens) at 3 and 7
days. These results imply that the beneficial effect of reduced temperature rise in
fly ash concrete is not necessarily offset by a reduced capacity to resist thermal
strains.
Keywords: Calcium; cracking ffracturind; flexural strength; flv ash; heat

of hydration; temperature rise; tensile stress
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 IObb2949 0523042 516
82 Thomas et al
M.D.A. Thomas is an Assistant Professor in the Department of Civil Engineering

at the University of Toronto. He is a member of AC1 Committee 201 (Durability)
and a consulting member of AC1 Committee 350 (Environmental Structures).
P.K. Mukherjee is a Senior Engineer in the Concrete Technology Section of

Ontario Hydro Technologies, Toronto, Canada. He served as Chairman of CSA
A5 Technical Committee on Hydraulic Cement and is a member of AC1
Committee 365 on Service Life Prediction.
J.A. Sato is a Senior Engineer in the Concrete Technology Section of Ontario

Hydro Technologies, Toronto, Canada.
M.F. Everitt is a techniciadpetrographer in the Concrete Technology Section of

Ontario Hydro Technologies, Toronto, Canada.
INTRODUCTION
The use of fly ash to control temperature rise in concrete has been common
practice for many decades, especially in the construction of massive structures ( 1 -
4). Indeed, Mehta (5) claims that most gravity dams in the U.S.A., constructed
since 1960. contain between 25% to 35% fly ash. However, thermal cracking has
been reported in a number of fly ash concrete structures, including two large
dams containing between 20 to 30% fly ash (6.7). Some studies have indicated
that the benefits of reduced temperature rise may be offset by reduced tensile
strain capacity in fly ash concrete (8). This is attributed to increased stiffiiess and
reduced creep in fly ash concrete which leads to higher stresses for a given
thermal strain. Similar findings have been reported for slag concretes (9); the
reduced temperature rise due to the partial replacement of portland cement with
slag was accompanied by a proportional decrease in tensile strain capacity.
Reliable thermal-stress analysis requires an accurate prediction of the

temperature distribution with time and the mechanical properties of the concrete
(e.g. strength, elasticity, creep, tensile strain capacity) which may change rapidly
at early ages as the concrete matures. The use of fly ash (or other replacement
materials) will have a significant influence on all these parameters and
assumptions based on measured properties of Portland cement concrete are not
valid for fly ash concrete.
The effect of fly ash on the heat of hydration of cement and temperature rise
in concrete has been well-documented for field studies (l,S), and laboratory
studies using conduction calorimetry ( I O- 13), semi-adiabatic tests on insulated
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 IObb2949 0521043 4 5 2 I
concrete specimens (13-17), "true-adiabatic" tests ( 18) or large-scale concrete

specimens (19,20). However, most of this work has focused on ASTM Class F
ashes and there are comparatively few data for Class C ashes. Earlier studies by
Dunstan (2 I ) indicated that the rate of heat development generally increases with
the calcium content of the ash and ashes high in calcium may produce little or no
decrease in the heat of hydration (compared to plain portland cement) when used
at normal replacement levels. Similar results have been reported for studies on
insulated mortar specimens ( 16), where the use of high-calcium ash (> 30% Cao)
was found to retard the initial rate of heat evolution but did not reduce the
maximum temperature rise. However, Carette ( I 7) reported that there was no
consistent trend between ash composition and temperature rise for concretes
containing high levels of fly ash (56% by mass of cementitious material); calcium
levels of the ashes used in the study ranged up to 20% Cao.
This paper reports preliiniiiary results from an ongoing study at Ontario

Hydro Technologies (OHT) to evaluate the effect of fly ash on thermal cracking
in concrete. Twelve fly ash samples, representative of the wide range of Class F
and Class C ashes available throughout Canada and the U.S.A., and two different
Portland cements are included in the study. The effect of these ashes on the heat
of hydration, and early-age flexural stress and tensile strain capacity of concrete
is reported.
METHODS
--``,`,-`-`,,`,,`,`,,`---
The chemical composition of the two Portland cements (CSA Type I O) and
twelve fly ashes used in the study are given in Table 1. The ashes were collected
fiom thermal power stations across Canada and the U.S.A., and provide a wide
range of chemical compositions. All of these ashes are commercially available and
are currently used a s supplementary cementing materials in concrete.
The heat of hydration of combinations of portland cement and fly ash (25%,
40% and 56% replacement) were determined using conduction calorimetry. A
waterisolids ratio of 0.50 was used for all tests and the temperature of test was
maintained at 20°C. Future tests are planned to be carried out at a range of
temperatures from 10°C to 50°C.
Flexural tests were carried out on concrete prisms (90 x 100 x 400 mm)
under third point loading at I. 3 and 7 days. A 50 mm foil strain gauge was
mounted to the tensile fibers in the constant moment section of the prism.
Loading was applied at 0.28 MPa (outer fiber stress) per minute. Results are
presented for a series of mises, Table 2, cast with JO0 kg/m3 total cementitious
material (PC + fly ash), 0.50 water to cemetititious materials ratio and two
replacement levels (25% and 56%) of four fly ashes.

DISCUSSION OF RESULTS
Cumulative heat development curves for PC 1 blended with various fly ashes
are shown in Figures 1 to 3. The heat development of fly ash pastes was clearly
dependent on the nature of the fly ash. For blends with 25% fly ash, the 7-day
heat of hydration ranges from 276 kJ/kg (Ash B and E) to 351 kJ/kg (Ash C).
The use of 25% of Ash C (25%) made little difference to the rate of heat
development except for a slight reduction during the first two days. The shape of
the curves in Figure i suggest that the total heat output from this blend might
actually exceed that from the control mix (100% PC i). Higher proportions of ash
resulted in a decreased rate of heat evolution for all the ashes tested (Figures 2
and 3).
Figure 4 shows the 7-day heat of hydration values plotted against the sum of
the oxides (SO, + Abo, + Fe,O,) of the fly ash. ASTM classifies fly ash as Class
F or Class C if this sum is above or below 70%, respectively. It is clear froin
Figure 4 that Class F ashes are generally inore effective in reduciiig the rate of
heat development compared with Class C ashes. All the blends of 25% Class F
ash meet the CSA specification for Type 20 cement iii terms of 7-day lieat output
(< 300 kJikg).
Figure 5 shows the same data plotted against the C a 0 of the asli. Figure 6
shows similar data for blends of ash with PC2. The heat output was higher for all
the ashes when combiiied with PC2 and this was especially noticeable for the
low-calcium ashes. The rate of heat developmeiit geiierally increased as the
calcium coiiteiit of the ash iiicreased. Ashes with very high calcium levels (Ash C ,
G arid M) showed little or i10 decrease in the heat of hydration when used at the
25% replacement level. At higher levels of replaceineiit. however, Iiigli-calcium
fly ash became more effective in reduciiig the rate of heat development, eveii to
the point of lowering the 7-day heat output to below that specified for a low-heat
Portland cement (< 275 kJikg for CSA Type 40).
High-calcium ashes typically contain quantities of free lime, C,A, alkali

sulphates aiid anhydrite (CaSO,) which react hydraulically and rapidly compared
to the pozzolaiiic reaction of Class F ash. In addition, the calcium aluiniiio-
silicate glasses characteristic of Class C ash are more reactive than the less
soluble silica-rich glasses found iii Class F ashes (22,23). The hydratioii of higli-
calcium ashes may even occur at a sirnilar rate to portland cement. n i e slower
reactioii of these ashes at high replacement levels is due to the reductioii of
alkalis from the portlaiid ceineiit. The reactioii of glass pliases in both Class F aiid
C ashes is affected by the concentration of alkalis and this is demonstrated by the
increased heat of hydration observed for all ashes blended with PC2; this portland
cement has a much higher alkali content (0.94% Na,O,) compared with PCI
(0.580/, Na,O,).
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I 95 I0662949 0523045 225
The results of this study would suggest that in order to achieve equal
reductions in temperature the level of replacement should increase with the
calcium content of the ash. For example, the data in Figure 5 show that for ash
blended with PCI to quahfy as low-heat cements (< 275 kJ/kg at 7 days), the
following replacement levels would be required:
low-calcium ash (< 10% Cao) 25 - 30% ash

moderate-calcium ash ( 1O - 20% Cao) 30 - 40% ash
high-calcium ash (> 20% Cao) 40 - 50% ash.
Of course, these replacement levels are based on isothermal tests on cement

pastes for one particular portland cement. In practice, the effect of ash on the
--``,`,-`-`,,`,,`,`,,`---
temperature rise of concrete would also vary depending on the content and
composition of the portland cement, and the temperature of the fresh concrete
(18). Verbeck (24) has shown that the pozzolanic reaction follows an Arrhenius'
relationship, increases in temperature producing proportionally greater increases
in reaction rate. Thus, the contribution of the fly ash to the amount of heat
evolved may be expected to increase as the temperature of the concrete
increases; this factor is eiiminated in isothermal tests. Furthermore, various
physical (e.g. fineness) and mineralogical (e.g. glass content, nature and
distribution of crystalline phases) properties of the ash may be expected to
influence its reactivity and its effect on the rate of heat development.
Despite the limitations of the present study, the results serve to demonstrate
that the effect of fly ash on the temperature rise in concrete varies widely.
Current guidelines, such as the AC1 rule ofthumb (25), where ash is assumed to
contribute half the heat of the cement. it replaces, are clearly inadequate for
predicting the temperature rise in concrete. Isothermal calorimetry tests on PC/fly
ash blends at temperatures from 10°C to 50°C together with adiabatic tests on a
wide range of concretes are currently being camed out at Ontario Hydro
Technologies to provide further information on the interdependence of the
pozzolaiiic reaction and temperature.
The results from flexural strength tests on concrete prisms are shown in
Table 3. The early-age strength is reduced by the presence of fly ash especially at
high levels of replacement, irrespective of the composition of the ash. It should
be noted that these concretes were designed to equal cementitious content and
water to cementitious materials ratio as opposed to equal strength and
workability. These mixes form part of a much wider study using a range of
cement contents and water to cement ratios but serve to demonstrate the effects
of ash composition and ash replacement level on thermal cracking.
Thermal stresses are produced by restraint to contraction on cooling, the

amount of stress being related to the maguitude of the temperature drop, the
coefficient of thermal expansion, modulus of elasticity and stress relaxation due

to creep. It is often assumed for the purposes of design, that compressive stresses
induced during heating are relieved by creep and that tensile stresses are induced
immediately once the concrete starts to cool from its maximum temperature
(25,26). Iffiirther effects of stress relief are ignored (worst case), then the stress
induced due to cooling from the peak temperature to ambient is given by:
where: CT = thermal stress

a = coefficient of thermal expansion
T, = peak temperature
T, = ambient temperature
R = restraint factor
E = average modulus of elasticity during cooling.
if the stress exceeds the tensile strength of the concrete then cracking
occurs. Table 3 shows that for concrete of constant water to cementitious
materials ratio, the early-age flexural strength of fly ash concrete is reduced
compared to portland cement concrete. However, the modulus of elasticity is
also affected by the presence of ash and this wili affect the magnitude of stress
induced by a given temperature change. The resistance to thermal cracking can
be better evaluated by the tensile strain capacity of the concrete (26). Concrete
will crack ifthe tensile strain capacity, q,is exceeded; i.e. cracking occurs when:
The tensile strain capacity of the concretes tested in flexure is shown in

Table 3. The strain capacity reported is the strain at 90% of the failure load
rather than the strain at failure. This value was easier to measure than the failure
strain and better represents the strain at the onset of cracking. Although the strain
capacity at one day was reduced for many of the fly ash concretes compared to
the control, there is parity at 3 days and, in most cases, the strain capacity in fly
ash concrete exceeds the control at 7 days, irrespective of ash composition.
Since fly ash has no effect on the restraint factor and negligible effect on the
coefficient of thermal expansion, this being largely a fùnction of the aggregate
(27,28), the use of suitable quantities of ash may be expected to reduce the risk
of thermal cracking by controlling the magnitude of the temperature rise. These
results would suggest that the beneficial effect of reduced temperature rise in fly
ash concrete is not necessarily offset by a reduced capacity to resist thermal
strains. However, the effects of creep and stress relaxation have not been
considered here, nor have the effects of autogenous temperature rise on fly ash
reaction and the development of concrete properties. These effects are currently
under study.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 B 0662949 0523047 O T ô
CONCLUSIONS
I . Heat of hydration studies were carried out on blends of portland cement and
twelve different fly ashes. The results show that the rate of heat evolution and
the 7 day heat of hydration increases with the calcium content of the ash.
2. The heat of hydration decreased with increasing levels of fly ash replacement
(25% to 56%) for all the ashes tested. The level of ash required to produce a
given reduction in heat output increases with the calcium content of the ash.
3. The rate of heat evolution was greater for fly ashes blended with high-aikali
cement compared with low-aikali cement.
4. Flexural tests were performed on concrete specimens proportioned to equal

cementitious material and water to cementitious materials ratio. The results
show that the early-age flexural strength decreased with increasing ash
--``,`,-`-`,,`,,`,`,,`---
content.
5 . The tensile strain capacity (determined at 90% of flexural strength) was,

generally, lower in fly ash concretes at one day compared with control
specimens. However, fly ash concretes had similar or slightly higher strain
capacity compared with the control concrete at 3 and 7 days. There was no
consistent trend between strain capacity and ash composition.
ACKNOWLEDGMENT
This project was partially funded by the Canadian Electrical Association

(CEA). The views expressed are those of the authors and not necessarily those of
the CEA.
REFERENCES
Mustard, J.N. and MacInnis, C. "The Use of Fly Ash in Concrete by Ontario
Hydro." Engineering Journal, December, 1959, pp. 74-79.
Elfert, R.J. "Bureau of Reclamation Experiences with Fly Ash and other
Pozzolans in Concrete." Proceedings of the Third International Ash
Utilization Symposium, Pittsburgh, 1973, pp. 80-93.
Lamond, J.F. "Heat of Hydration of Mass Concrete when Pozzolans, Slags
and Chemical Admixtures are Used." Proceedings of a Joint ACI-RILEM
Symposium on Technology of Concrete when Pozzolans, Slags and Chemical
Admixtures are Used, Autonomous University of Nueva Leon, Monterrey,
1985, pp. 635-645.

A C 1 S P - 3 5 3 V O L + I 95 m Obb2747 O523048 T 3 4 m
88 Thomas et al
4. Lane, R.O. and Best, J.F. "Properties and Use of Fly Ash in Portland Cement
Concrete." Concrete International: Design & Construction, Vol. 4, No. 7,
1982, pp.81-92.
5. Mehta, P.K. "Pozzolanic and Cementitious By-Products h Concrete -
Another Look." Proceedings of the Third International Conference on the
Use of Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete, (Ed.
V.M. Malhotra), Vol. I , AC1 SP-I 14, American Concrete Institute, Detroit,
1989, pp. 1-43.
6. Smith, D.M. Mechanical Properties of Mass Concrete at Early Ages.
Technical Report SL-9 1- 14, U.S.A.E. Waterways Experiment Station,
Vicksburg, MS, I99 1..
7. Norman, C.D. and Anderson, F.A. "Re-analysis of Cracking in Large
Concrete Dams in the U.S. Army Corps of Engineers." Proceedings of the
--``,`,-`-`,,`,,`,`,,`---
FiReenth international Congress on Large Dams, Lausanne, Switzerland,
1985.
8. Bainforth, P.B. "In-Situ Measurement of the Effect of Partial Portland
Cement Replacement using either Fly ash or Ground Granulated Blast-
Furnace Slag on the Performance of Mass Concrete." Proc. of the Institution
of Civil Engineers, Part 2, Vol. 69, 1980, pp. 777-800.
9. Thomas, M.D.A. and Mukhejee, P.K. "An Evaluation of the Effect of Slag
on Thermal Cracking in Concrete." Proceedings of the Third Canadian
Symposium on Cement and Concrete, National Research Council, Ottawa,
1993, pp. 196-210.
10. Melaiid, I. "Influence of Condensed Silica Fume and Fly Ash on the Heat
Evolution in Cement Pastes." Proceedings of the First International
Conference on the Use of Fly Ash, Silica Fume, Slag and Other Mineral By-
Products in Concrete, (Ed. V.M. Malhotra), AC1 SP-79, Vol. 2, American
Concrete Institute, Detroit, 1983, pp. 665-676.
1 I . Tenoutasse, N. and Marion, A.M. "Characterization of Belgian Fly Ashes and
their Behaviour in Cement Paste." Proceedings of the Second International
Conference on the Use of Fly Ash, Silica Fume, Slag and Other Mineral By-
Products in Concrete, (Ed. V.M. Malhotra), AC1 SP-91, Vol. 1, American
Concrete Institute, Detroit, 1986, pp. 5 1-76.
12. Douglas, E.E.A. and Malhotra, V.M. "Characterization of Ground-
Granulated Blast-Furnace Slags and Fly Ashes and their Hydration in
Portland Cement Blends." Cement, Concrete and Aggregates, Vol. 12, No. 2,
1990, pp. 38-46.
13. Dunstan, M.R.H. Rolled Concrete for Dams - A Laboratory Study of the
Properties of High Fly Ash Content Concrete. Technical Note 105,
Construction Industry Research and Information Association, London, 1981.
14. BlundeU, R. and Brome, R.D. "Large Pours in Pressure Vessels."
International Conference on Experience in the Design, Construction and
Operation of Prestressed Concrete Pressure Vessels and Containments for
Nuclear Reactors, Institution of Mechanical Engineers, London, 1975, pp.
345-369.

A C 1 SP-353 V O L t I 95 m Obb2949 0 5 2 3 0 4 9 770 m
15. Omojola, A. The Effect of Pozzolan on the Strength and Heat of Hydration
of Concrete, Research Report 014J/74/1700, Taylor Woodrow, Southall
(U.K.), 1974.
16. Barrow, R.S., Hadchiti, K.M., Carrasquillo, P.M. and Carrasquillo, R.L.
"Temperature Rise and Durability of Concrete Containing Fly Ash."
Proceedings of the Third International Conference on the Use of Fly Ash,
Silica Fume, Slag and Natural Pozzolans in Concrete, (Ed. V.M. Malhotra),
Vol. 2 AC1 SP- 114, American Concrete Institute, Detroit, 1989, pp. 33 1-
347.
--``,`,-`-`,,`,,`,`,,`---
17. Carette, G., Bilodeau, A., Chevrier, R.L. and Malhotra, V.M. "Mechanical
Properties of Concrete Incorporating High Volumes of Fly Ash fiom Sources
in the U.S."AC1 Materials Journal, Vol. 90, No. 6, 1993, pp. 535-544.
18. Bamforth. P.B. "Heat of Hydration of PFA Concrete and its Effect on
Strength Development." Proc. ASHTECH '84: Ash Technology &
Marketing, CEGB, London. 1984.
19. Samarin, A., Mum, R.L. and Asliby, J.B. "The Use of Fly Ash in Concrete -
Australian Experience." Proceedings of the First International Conference on
the Use of Fly Ash, Silica Fume, Slag and Other Mineral By-Products in
Concrete, (Ed. V.M. Malhotra), AC1 SP-79, Vol. I , American Concrete
Institute, Detroit, 1983, pp. 143- 172.
20. Langley, W. S., Carette, G.G. and Malliotra, V.M. "Strength Development
and Temperature Rise in Large Concrete Blocks Containing High Volumes of
Low-Calcium (ASTM Class F) Fly Ash." AC1 Materials Journal, Vol. 89, No.
4, 1992, pp. 362-368.
2 I . Dunstan. E.R. Fly ash and fly ash concrete, Report No. REC-ERC-82-1. U.S.
Bureau of Reclamation, Denver, 1984.
22. Roy, D.M., Luke. K. and Diamond, S. "Characterization of Fly Ash and its
Reactions in Concrete." Proceedings MRS Symposium, Materials Research
Society, Pittsburgh, 1984.
23. Halse. Y., Pratt, P.L., Dalziel, J.A. and Gutteridge, W.A. "Development of
Microstructure and other Properties in Fly Ash-OPC Systems." Cement and
Concrete Research, Vol. 14, No. 4, 1984, pp. 491-498.
24. Verbeck. G. 1960. "Chemistry of the Hydration of Portland Cement."
Proceedings of the 4th International Symposium on the Chemistry of Cement,
Washington, D.C., pp. 453-465.
25. American Concrete Institute. Mass Concrete. AC1 207. IR-87, ACI, Detroit,
1987.
26. Harrison, T.A. Early-Age Thermal Crack Control in Concrete. CIRIA Report
9 I , Construction Industry Research and Information Association, London,
1981.
27. Brome. R.D. "Thermal Movement of Concrete.'' Concrete, Current Practice
Sheet 3PCIOóIl. November, 1972, pp. 51-52.
28. Rhodes, J.A. "Thermal Properties." Significance of Tests and Properties of
Concrete and Concrete Making Materials, ASTM STP- 169B, American
Society for Testing and Materials, Philidelphia, 1978, pp, 242-266.

A C 1 SP-153 V O L X I 95 0662947 0 5 2 3 0 5 0 692
90 Thomas et al
- ? -
G e
a -
b 12 i n N:
I
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 IOb62949 05210.51 5 2 9
d 00
d 00
m N
N N
7
vl z
v)
Z
0 O O
I- O O
U N
a
N
a I
W
U
3
+
?5 O W
9
2
W
O 2
I-
W
U
o ---
ici O
Z
8 -
0.
O
I
(u
N d
W t- vi
-1 r- r-
m
;i
19 19
vi in
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 m 0 b b 2 9 4 9 0523052 465
92 Thomas et al
v1
x
m
U
. t
v1
U
m
m
x
-
d
-
v1
x
d
r-
v1
x
m
rl
m
x
-
d
s
v
in
N
io
in
io
in
io
in
Gu mu Gu
s s s
m io
d
F
.t
4
in
3 hi
m
N
.r
N
d v V V
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 I0662949 0523053 3 T 1
t
/ i /
j Control r.
o
100
Fig. 1-Effect of fly ash on cumulative heat development
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L * I 95 H Obb2949 0 5 2 3 0 5 4 238 a
94 Thomas et al
I I
---
PCI + Fly ash B
I l
~ control
! 40%ash
--``,`,-`-`,,`,,`,`,,`---
I I l
----
Fig. 2-Cumulative heat development of cement with Fly Ash B

A C 1 SP-153
2
3
c
-
O
c
al
k
al
U
c
L
mal
400
300
200
----
7
VOL*I 9 5 I0662949 0523055 I174
PCI + Fly ash C
J
25% ash
40% ash
r
Q)
>
'P
-m3
,,I,
o
5
100
Fig. 3-Cumulative heat development of cement with Fly Ash C
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 V O L t I 95 0 6 6 2 9 4 9 0523056 000
96 Thomas et al
40
350
8
8
Class C Class F
Control PC1 (noash)
8 8
300 8
C
O
'0
* * 8
I
8
L 8
B
c
8 I I
I CSA Maximum for Type 40 - 275 KJiKg I

--``,`,-`-`,,`,,`,`,,`---
200
150
50 60 70 ao 90 1O0
Sum of oxides (% SiOZ+AI203+Fe203) of fly ash
Fig. &Effect of fly ash composition on heatof hydration

A C 1 SP-153 VOL*I 95 0662749 0523057 T 4 7 9
400
350 I
m
Conirol PC1 (no ash) 8
8 8
a- 300
C
O
FJ
z
r
*o CSA Maxir irn for Type 40 - 275 KJn@
ii
250 * -- --t
l o
2i
m
* [ 7 ~ o
O
?t
*
o U
o
1- t
200
O 8 250mflyash
* 400mflyash
o 560mflyash
150
O 10 20 30
Ca0 content of fly ash (X)
Fig. &Effect of fly ash calcium content on heat

of hydratiowPC1
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 I0 b b 2 9 4 9 0523058 983 =
98 Thomas et al
l i
I
c
c
2
O
m
250
II CSA Maximum for Type 40
-
I
i
- 275 KJIKg
II o
m
n
4
200
25%flyash
* 400mfiyash
o 560mflyash
I I
150
O 10 20 30
C a 0 content of fly ash (%)
Fig. &Effect of fly ash calcium content on heat of

hydration-PC2
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L r I 95 m 0662949 0523059 B L T
SP 153-6
A Model for Predicting the

Compressive Strength of Structural
Fly Ash Concrete
by F. de Lorrord
Synopsis: In this paper, an adaptation of a previous model (the generalized

--``,`,-`-`,,`,,`,`,,`---
Féret's law with account for the Maximum Paste Thickness) for structural fly
ash concrete is presented. A kinetics term is introduced to predict the
compressive strength development between 7 and 365 days. On a set of data
taken from the literature, the mean accuracy of the model is equal to 2.1 m a .
Moreover, formula only incorporate a limited number of parameters, that can be
easily determined from standard mortar or concrete tests. Therefore, the model
appears to be suitable for a computer-aided concrete mixture proportioning
software.
Kevwords: Comuressive strength; flv ash; high performance concrete;

mathematical models; pastes

99
A C 1 SP-153 VOL*I 95 IObb2949 0521060 5 3 1
100 de Larrard
AC1 Member François de Larrard is head of the 'Mix-Design and

Rheology Section', at Laboratoire Central des Ponts et Chaussées, Pans,
France. He has published a number of works in the field of high-
performance concrete technology.
INTRODUCTION
Fly ash from thermal power stations constitutes a valuable residue for concrete
technology [i]. Many researchers have already proposed equations for
evaluating contribution of fly ash to the compressive strength of concrete. In
most cases, these equations take into account the fly ash through an activity
coefficient defined as the ratio between the mass of the fly ash and the mass of
the cement it replaces, from the mechanical strength viewpoint [2]. However,
when the proportions of mixturees change, this coefficient is not constant.
Moreover, the models proposed generally have to do with concrete having low
mechanical properties [3].
At a time when fly ash selected by size is appearing on the market [4], including
categories which are both clearly differentiated and, hopefully, regular, it is
important to quanti@ the influence of fly ash on the mechanical properties of
concrete. An attempt is thus made in this article to construct a model consistent
with a general theory linking concrete composition and mechanical properties,
applicable to the entire range of structurai concretes, up to high-performance
concrete, and capable of being incorporated in computer assisted mixture
proportioning software [5]. The paper thus looks into how general concepts
such as maximum paste thickness [6] and contribution to the strength of a
pozzolan, demonstrated for silica fume concrete [7], could be applied to fly ash
concrete. We have confined ourselves here to a single set of experimental data,
exceptional in its richness and consistency.
MODELLING FROM DATA PROVIDED BY KIM et al. [SI
Kim et al. wished to determine the application potential of a special source of

Korean fly ash (see Tab. 1). They thus prepared 26 different concretes, with a
wide range of waterkement and fly-ashkement ratios. The concretes contained
sulphate-resistant portland cement and crushed calcareous aggregates with a
maximum size of 13 mm. For low water-binder ratios, a superplasticizer of the
naphthalene sulphonate type was used. Seven control concretes, with increasing
cement proportions, did not contain any fly ash. From each of these
--``,`,-`-`,,`,,`,`,,`---
compositions, a series of fly ash concretes was generated, substituting an

A C 1 SP-153 V O L W I 95 IObb2949 052LObL 478
increasing proportion of fly ash. The compressive strengths on 150x300 mm

cylinders after 3, 7, 28, 90, 180 and 365 days were measured, with the
specimens cured in water. Aii these results appear in Tab. 2.
- of concrete wt-
28-dav strenvth
It was recently shown [6] that allowance for two basic parameters (water +
voiddcement ratio and maximum paste thickness) made it possible to predict
fairly well the 28-day compressive strength of portland cement concretes. It
however appeared that the contribution of the second parameter was less
significant for crushed limestones than for rounded aggregate. Here, optimizing
the exponent of the maximum paste thickness in the modified Féret law actually
produces a value 0.126 lower than the 0.16 exponent found previously. The
expression:
283. MPFs'26
fc =
w +v
(1 + 3.1-)'
C
in whichfc is the compressive strength (in MPa), w is the water volume, v the
voids volume (in Um3) and c the cement mass (in kg/m3), smoothens out the
28-day results with an average error of 1.3 MPa, a value comparable to the
measurement error. The maximum paste thickness is calculated as follows [ 6 ] :
MPT = D ( c - 1) (2)
where D is the maximum s i e of aggregate, g the volume of aggregate and g*

the packing density of aggregate.
. . .
Hard-
Baron et al. [9] recently showed that after 7 days, the experimental compressive
strengths of conventional concretes (watedcement ratios near 0.5) were linearly
related with the logarithm of the time . This result is corroborated by the present
--``,`,-`-`,,`,,`,`,,`---
data. It is surprising that the slope of the line practically does not depend on the
28-day strength level (see Fig. i). Equation (i) is thus enriched with a kinetic
term with a unique coefficient:
fc = 283. MPT4s'26.
C
in which t is the time in days. The average error, as of 7 days, is 1.4 MPa here.
On the other hand, this model overestimates the 3-day strength, which is still
consistent with the observations of Baron et ai. [9].

A C 1 SP-353 V O L X I 95 0662949 0523062 304
102 de Larrard
The contribution of fly ash remains to be taken into account. For silica fumes,
we have defined an equivalent cement proportion cq [7], of the following form:
c4 = c . [ l . 4 - 0 . 4 e x p ( - ~ ~ ~ / c ) ] , (4)
expression in which csf/c designates the silica fumdcement weight ratio and kcN
a silica fume pozzolanic activity coefficient. This equation expresses the fact
that the contribution of silica fume decreases as its proportion increases. The
effect levels off when almost ail the lime released by hydration of the cement is
consumed. The coefficient kcsf can take on different values around an average
of about 11, depending on the alkali content of the silica fume [ 101.
The main phenomenon at the origin of the beneficial effect of fly ash on strength
--``,`,-`-`,,`,,`,`,,`---
being the same for silica fumes (the pozzolanic reaction), it is sound to use the
same expression, with a di€Ferent coefficient kfa
for each phase. Such a set of
coefficients was determined by optimization on the set of experimental data. As
could be expected, kf"
increases as a function of time, and is also linearly related
to the logarithm of time (see Fig. 2):
kr0 =2.67log(t/2.15).
Extrapolating this expression before 3 days, it is found that the pozzolanic

reaction begins oniy after 2.15 days, which appears to be reasonable considering
the slowness of the phenomenon.
Replacing c with ceq in the equation (4), all the results are smoothened out
(including the 3-day strengths) with an average error of 2.1 MPa (see Fig.3). If
we remove, from the 26 mixtures, the compositions F3 and E3, that are
questionable as compared to the others, the error drops to 1.7 ma. Accuracy is
thus almost as good as that obtained with pure portland cement concrete.
DETERMINATION OF PARAMETERS
FOR A GENERAL FLY ASH CONCRETE MODEL
As the concepts used in this modelling are general, the constructed model may
be considered to apply to the case of concrete made with other sets of
components. The expression would then be:
fc=K,,.S,.MPT-".
-
where

A C 1 SP-b53 V O L U I 95 E Obb2949 0523063 240
--``,`,-`-`,,`,,`,`,,`---
cw = c[l. 4 -0. 4exp(-kf, (t).fa/c)] (7)
- a would take on the values 0.16 or O. 13 dependmg on whether the aggregates

are rounded gravel or crushed aggregate;
- Ka@ parameter depending on the quality of the aggregate (essentially its bond
with the paste) would be calibrated on a 28-day control concrete test (i which
it will be the oniy unknown parameter);
- the parameter b would depend on the cement. It may be easily expressed as a
h c t i o n of the 7- and 28-day strengths of a standard ISOl mortar:
b=0.223.(1--)s,
s
l8
- for the parameter kf,(t), what is needed is a test either on concrete or on

mortar, at age f and with a mixture in which 25% of the total binder weight
would be fly ash. For a normal fly ash mortar (maximum aggregate size equal to
2 mm), the expression of the compressive strength becomes:
blog(t/ 28) +(l+ 3.1-
assuming that these mortars contain 260 l/m3 water and 3% air. For a strength
resultfc, the term Ceq is obtained and applied to the following formula:
(10)
The same procedure camed out at two ages, for example 7 and 28 days,
produces two values of kfa
If the evolution depicted in Fig. 2 is still
corroborated, it is easy to deduce a linear relationship between kfa and the
logarithm of time on these two values; it is then possible to predict the strength
at any age, up to 1 year. Beyond this period, the model may of course be
expected to overestimate the strengths, because compressive strength, unlike
the logarithm, cannot tend towards infinity. The correspondence between 28-
day activity index and the coefficient kfa is given in Fig. 4.
CONCLUSION
A wide range of fly ash concretes were made by Kim et al. with the same set of
constituents, for waterlcement ratios varying between 0.3 1 and 0.66 and Siico-
aluminous ash replacement rates between O and 20%. The 3-day and l-year
*sandlcementlwatermass proportions: 3/1/0.5.

A C 1 SP-153 V O L W I 95 m Ob62747 0521Ob4 187
104 de Larrard
compressive strengths were measured on all these concretes. The following

conclusions, formulated for these data, probably have a more general value,
which remains to be verified:
1) The compressive strength between 7 days and 1 year foilows a linear law as a
function of the logarithm of time ; for comete without fly ash, the slope of this
law is independent of the waterkement ratio.
2) The modified Féret law with allowance for the maximum paste thickness,
which we proposed in the past to predict the 28-day strength of ordinary
concrete and silica fume concrete is also applicable to fly ash concrete, with a
lower activity coefficient (here 3 instead of Il);
3 ) Combining a kinetic term and a statistical kfa vs. logtime equation with
Féret's law, an operating model was built for all the mixtures, and all ages; its
average precision on ali the data is 2.1 MPa;
4) If this type of model were valid for most of the silico-aluminous ash (ASTM
class F), their contribution to the strength of the concrete would be entirely
characterized by a coefficient for each age considered; in addition, if, as in the
presented data, this coefficient evolves lieariy as a function of the time
logarithm, the effect of the fly ash could be identified from tests on two mortar*
compositions (control mortar and mortar with 25% fly ash) at different ages (for
example, 7 and 28 days).
The model presented is thus weli-suited for integration in a computer assisted

concrete mixture proportioning software, whose operation requires parameters
of constituents identified on the basis of standard tests.
REFERENCES
[l] BERRY E.E., MALHOTRA V.M., "Fly Ash in Concrete", Supplementary

Cementing Materiais, CANMET SP 86 8-E, March, 1987.
[2] POITEVIN P., "Classification, propriétés et emploi des fines et ultra-fines",

Stage ENF'C "Ingénierie du matériau béton: formuler pour maîtriser", Paris,
Octobre, 1992.
[3] HEDEGAARD S.E., HANSEN T.C., "Modified watedcement ratio law for
compressive strength of fly ash concretes", Materials and Structures, Vol. 25,
pp. 273-283, 1992.
* or concrete.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 Obb2949 052LOb5 O13
[4] CARLES-GIBERGUES A., NAPROUX P., "Les micro-cendres et leur

emploi dans les bétons", Rencontres scientifiques de Génie Civil, Toulouse,
1994.
[SI DE LARRARD F., FAU D., "BETONMIX - Software for Computer-Aided

Mix-design of Concrete", Research Engineers (Europe) Limited, London, 1994.
[6] DE LARRARD F., TONDAT P., "Sur la contribution de la topologie du

squelette granulaire à la résistance en compression du béton", Materials and
Structures, RILEM, Vol. 26, pp. 505-516, 1993.
[7] DE LARRARD F., LE ROY R., "The Influence of Mix-Composition on the

Mechanical Properties of Silica-Fume High-Performance Concrete",
Proceedings of the 4th International CANMET-AC1 Conference on Fly Ash,
Silica Fume, Slag and Natural Pozzolans in Concrete, AC1 SP 132-52, V.M.
Malhotra, Ed., Istanbul, May, 1992.
181 KIM J.K., PARK Y.D., SUNG KY., LEE S.G., "The Production of High-
Strength Fly Ash Concrete in Korea", 4th CANhET/ACI International
Conference on Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete,
Supplementary papers, Istanbul, May, 1992.
[9] BARON J., BASCOUL A., ESCADEILLAS G., CHAUDOUARD G.,

"From clinker to concrete - an overall modelling". Materials and Structures,
RILEM, Vol. 26, pp. 319-327, 1993.
[lo] DE LARRARû F., GORSE J.F., PUCH C., "Comparative Study of

Various Silica Fumes as Additives in High-Performance Cementitious
Materials", Materials and Structures, RILEM, Vo1.25, pp.265-272, 1992.
TABLE 1 - CHARACTERISTICS OF FLY ASH USED BY KIM ET AL.'
Si02 Al203 Fe203 Ca0 MgO Na20 K20 L.0.I Spec. Blaine
(%) (Yo) (%) ("Yo) (Yo) (%) ("Yo) Grav. fineness
(cm2/g)
55.1 34.9 3.7 3.6 1.2 0.44 0.73 6.8 2.06 3318
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L 8 1 95 S Obb2949 0523066 T 5 T
106 de Larrard
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 0662949 052LOb7 9 9 b
-0
1 10 loo loo0
log t (days)
Fig. l-Strength development of concrete without

fly ash, between 7 days and 1 year. Curves are
closely related, with comparable slopes. References
deal with names of batches, as given in Table 2
'T
1 10 loo loo0
log t (days)
Fig. 2-Evolution of fly ash activity

coefficient as function of time
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 V O L * I 95 0662949 0523068 822 =
108 de Larrard
OD -
0 2 0 4 0 6 0 8 0 1 0 0
fc exp (MPa)
Fig. 3-Comparison between model

and experimental values for data
of Kim et aL8
--``,`,-`-`,,`,,`,`,,`---
7
4
G3
2
O
0.65 0.7 0.75 0.8 085 0.9 0.95 1
I28
Fig. 4-Correspondence between 28-day

activity index and pozzolan activity
coefficient. Activity index is ratio
of strength of 3:0.75:0.25:1 (sand-
cement-fly ash-water) mortar by
strength of control OPC mortar.
Activity coefficient is taken from
Eq. (7)

A C 1 SP-153 VOL*I 95 U 0662949 0523067 '769 U
SP 153-7
Long-Term Performance of Grout

Containing Fly Ash and Brine
by A. A. Al-Manaseer and M. D. Haug
SvnoD&: This paper describes the performance of a cement-based grout

recommended for possible use to control brine inflows in potash mines. The
grout consists of Type III high early strength cement, fly ash, and sodium
saturated brine. Specimens were prepared, and submerged in containers filled
with brine to cure under confining pressures of O, 3.40, 6.9 MPa (O, SOO, and
1000 psi). The isotropic confining pressures were designed to simulate
different mining environments and to accelerate penetration of brine into the
specimens so that long-term performance could be evaluated. Tests were
conducted at different ages to determine the compressive strength, splitting-
tensile strength, and static and dynamic modulus of elasticity. The performance
of grout mixtures containing brine with 0 and 40% fly ash over the three year
test program seems to be in an acceptable range. Confining pressure can
adversely affect the physical properties results of grout over time. This
investigation found that a reduction in the physical properties was occurring
after two years, especially when the grout was subjected to a confining
pressure. The grout with fly ash exhibited a more scattered data under different
confining pressures than grout with no fly ash, however it showed a better
long-term performance. Generally, fly ash grouts stored under zero confining
pressures were found to perform better than those subjected to high confining
pressures.
Kevwords: Age; durabiliiy; flv ash; grout; pressure; salt water; tesis
--``,`,-`-`,,`,,`,`,,`---

Provided by IHS under license with ACI 1o9
A C 1 SP-153 VOL*I 95 S 0662949 0521070 480 m
110 Al-Manaseer and Haug
AC1 member Akthem A. Al-Manaseer is an Associate Professor in the

Department of Civil Engineering and Construction at Bradley University,
Peoria, Illinois, U.S.A. He obtained his Ph.D. from the University of Glasgow,
Scotland, in 1983. Dr. Al-Manaseer is the chairman of AC1 Committee 209,
Creep and Shrinkage in Concrete, and a member of AC1 Committee 227,
Radioactive Waste Management. His research interests are in concrete
technology and in the numerical applications of computers to concrete
structures.
Moir D. Haug is a Professor of Civil Engineering at the University of
Saskatchewan, Saskatoon, Saskatchewan, Canada. Dr. Haug obtained his Ph.D.
from the University of California, Berkeley, in 1980, in Construcrion
Engineering and Management. He has been involved for many years in
--``,`,-`-`,,`,,`,`,,`---
research on the design of bulkheads to prevent flooding of potash mines.
INTRODUCTION
The possibility of brine inflow is a major concern in underground potash

mines. A great effort has been made in the past few years to study these inflows
and then investigate different methods of predicting, preventing, and
controlling them. Most brine inflows have occurred through fractures and
fissures in the limestone of the Dawson Bay Formation which overlays the
potash beds. Different types of grout have been used to seal these fractures and
fissures. These grouts have included chemical and cement-based grouts. In
some of these mines, pure cement mixed with brine has been successfully
injected to control brine inflow.(') The use of brine as a mixing fluid reduces
the chemical gradient between the grout and the brine-filled fractures in the
Dawson Bay's limestone. This technique may also contribute to improved long-
term performance of the grout. However, while some initial success has been
achieved in grouting fractures to halt or slow the rate of brine inflow, the long-
term performance and stability of these grouts is important to ensure safe
continued mining for the anticipated 50-100 year future life of these mines.
The liquid brine contains mainly sodium, potassium, calcium, and
magnesium at various proportions. Test results were reported by Buck et. al.@)
on grout mixtures containing brine for possible use to plug boreholes in salt
rocks. These grouts were found to have acceptable characteristics with no
detrimental effects on composition of microstructures. A sanded version of the
previous grout was also reported by Buck et al.(3)This grout was found to be
workable, had reduced permeability and bleeding, and a compressive strength
of 34.5 MPa (5000 psi). The grout was recommended for repository sealing in
a salt host rock based environment. Wakeley and Burkes(4)investigated shear
strength and ion movements across the interfacial surfaces between a grout
mixed with brine and rock salt. A chemical bonding was observed and chloride
ions were found to be higher near the interfacial surfaces. In another study by
D ~ m o n e (sodium
~) silicate sea water grouts were investigated. These grouts
have shown that they obey similar strength versus water/cement laws to

A C 1 S P - 3 5 3 V O L U I 95 Obb2949 0523073 317 I
conventional grouts. Unconfined swelling was observed that may lead to some
long-term degradation. A study by Smith and Calverd6) found that sea water
reduces the time of setting and early strength development in concrete. A
previous study conducted by Al-Manaseer et. al(7)had shown that setting time
can be delayed up to five days on concrete mixed with brine and admixtures. In
another study by Al-Manaseer et. al@)microstructral behavior of grout mixed
with brine was investigated. The study showed that the microstructue of brine
grout have a film of a gel-like substance covering the entire surface of the
hydrated products. This was identified to be mainly sodium chloride salt.
In summary, data available on the use of brine in grout mixtures is
limited. These grouts may have important applications, such as in the case of
sealing shafts and tunnels in a repository, and sealing brine flow in potash
mines. However, the long-term performance and stability of these grouts is not
fully understood. In order to address this area a research program was
conducted. This study was undertaken to determine the physical properties of
grout mixture consisting of high early strength portland cement, brine, and O or
40% fly ash. The grout was stored in brine under different confining pressures.
The mechanism by which fly ash and brine affect the compressive strength,
splitting-tensile strength, and static and dynamic modulus of elasticity over
three years, was studied.
MATERIALS
Grout included in this study consists of ASTM Type III high early
strength portland cement, Saskatchewan lignite fly ash, and brine. Tables 1 and
2 show the chemical composition and physical properties of the cement and the
fly ash. Table 3 gives the chemical composition of the brine.
Two grout mixtures were investigated. The first mixture was prepared
with ASTM Type III cement and brine. The second mixture was prepared with
60% Type III cement, 40% fly ash, and brine. No admixtures were used. Both
mixtures had a brine/(cement + fly ash) (Le., B/(C+FA)) ratio of 1.75. Since the
solid content of the brine was 28.4%,an adjusted water/(cement + fly ash) (Le.,
W/(C+FA)) ratio of 1.25 will be equivalent to the brine/(cement + fly ash) ratio
of 1.75.
TESTING EQUIPMENT
Four specially designed pressure vessels (Fig. I ) were constructed to

store grout specimens under pressures of 3.4 MPa (500 psi), and 6.9 MPa (loo0
psi). The cylindrical part of each vessel, had a total length of 1015 mm (40 in.)
and an outside diameter of 405 mm (16 in.). The vessels were manufactured
using a stainless steel (Le., Type 316L) pipe with a thickness of 20 mm (0.75
in.). In order to minimize the cost of construction and to keep the project within
the proposed budget, it was necessary to construct the heavy end plates of the
vessels using a 75 mm (3 in.) thick high-strength mild-steel. The plates were
manufactured with a double O-ring sealing system. This was important to
avoid any leakage that might occur due to the high pressure maintained inside
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 W 0662749 0 5 2 3 0 7 2 253
the vessels. All plates were torch cut prior to machining on a large lathe. In
order to prevent any corrosion that may occur due to the aggressive brine
environment, the end plates of the vessels were nickel plated. Sixteen 20 mrn
(0.75 in.) high-strength bolts were required to hold the top and the bottom
plates onto the pipe.
The completed pressure vessels were assembled and tested prior to use.
Each vessel was filled with brine and pressurized with a maximum pressure of
10.3 MPa (1500 psi). The deflection was carefully monitored through thirteen
dial gauges mounted at different locations of each tank, as shown in Fig. 2. The
maximum deflection recorded was 0.20 mm (0.008 in.) at a pressure of 8.2
MPa (1200 psi). No deflection readings were taken above that pressure.
The thin nickel plating on the end plates was found to be easily
scratched during the opening and closing of each container. This raised some
concern on the possibility that corrosion might develop during the five year
expected life of the vessels. Therefore, it was decided that another preventive
measure should be taken into consideration. The bottom inside portion of the
vessels were coated with a rubber epoxy compound, while the top inside
portion was greased with silicon.
A hydraulic oil system was initially designed and constructed to
pressurize the vessels. However, for concerns about sample contamination, it
was decided that nitrogen gas tanks should be used.
LABORATORY PROGRAM
The grout was initially mixed for five minutes, at a room temperature of
2loC (71°F), in a 125 L (33 gal) plastic container using a high speed hand held
mixer. After mixing, the viscosity of the grout was measured using a Marsh
funnel. The Marsh funnel measures the time necessary for 1 L of grout to pass
a 5 mm (0.2 in.) diameter orifice located at the bottom of a standard 30' funnel.
The Marsh funnel time reading for both grouts was approximately 45-50
--``,`,-`-`,,`,,`,`,,`---
seconds. The viscosity Marsh cone time reading for the brine was 34 seconds.
In order to investigate the homogeneity of the fresh grout, the percent final
bleed at different time was determined using a method described in ASTM C
940.
Grout was poured into 75 x 150 mm (3 x 6 in.) cardboard mold cylinders
conforming to ASTM C 470 (Fig. 3), to cure at room temperature for 48 hours.
The specimens were then demolded and stored in a brine saturated environment
under different confining pressures of O, 3.4, and 6.9 MPa (O, 500, and 1000
psi). The specimens stored under zero pressure were put in sealed plastic
containers filled with brine, while the specimens stored under confining
pressures of 3.4, and 6.9 MPa (500 and 1000 psi) were put inside the pressure
vessel containers. The samples were removed and tested at ages of 40 days, 90
days, one year, two years, and three years (Fig. 4). At each age the compressive
strength (ASTM C 39), tensile strength (ASTM C 496), static and dynamic
modulus of elasticity (ASTM C 469 and ASTM C 215) was determined. An
average obtained from testing of at least three individual cylinders was used

A C 1 SP-153 VOL*I 95 Obb2949 0521073 19T
to determine each property. The static modulus of elasticity was measured

directly while performing the compression test,while the dynamic modulus of
elasticity was calculated using the resonant frequency readings recorded from a
resonant frequency meter.
TEST RESULTS
The percent final bleed observed for grouts mixed with brine and
containing O and 40% fly ash is shown in Fig. 5. The grout containing 40% fly
ash had a bleed of 0.25%, compared to 4.25% for the grout with no fly ash. The
absence of bleed channels in the grout with 40% fly ash indicated that a more
homogenous grout can be obtained than grout with no fly ash.
The compressive strength test results versus age for grout containing 0%
and 40% fly ash, are shown in Fig. 6. It can be observed that the compressive
strength increases with age for all mixes under different confining pressures up
to two years. However, after two years, a decrease in strength was observed for
specimens stored under confining pressures of 3.4 and 6.9 MPa (500 and 1000
psi). Brine infiltration into the specimens appeared to affect the compressive
strength for grouts with and without fly ash. In general, the compressive
strength of grouts containing fly ash exhibited higher strength than those with
no fly ash.
The splitting-tensile strength test results are shown in Fig. 7. Tensile
strength was found to increase with age up to 90 days. After that age, the
results were more scattered. In general, the splitting-tensile strength was found
to be inversely related to the confining pressures. For example, specimens
subjected to a high confining pressure will had the lowest splitting-tensile
strength. For grout with fly ash, the data on the splitting-tensile strength were
more scattered than those for grout containing no fly ash.
The static modulus of elasticity of the different grouts versus age is
shown in Fig. 8. The data from this graph indicate that the static modulus of
elasticity is affected with age and confining pressure. The static modulus of
elasticity for grout with no fly ash was found to increase between 40 and 90
days, then decreases to a constant value after that age. This reduction indicates
that grouts made with no fly ash become more ductile with time. However,
these grouts were still showing an increase in their compressive strength
between one and two years (Fig. 6). The static modulus of elasticity of grout
with fly ash seems to increase in value, achieving a maximum at one year, then
showing a continuous decrease with age. Increasing the confining pressure on
grout specimens with fly ash lower the value of static modulus of elasticity.
The longitudinal resonant frequency test was used to determine the
dynamic modulus of elasticity and to evaluate the overall quality characteristics
of the grout. In most cases, the dynamic modulus of elasticity of grout with fly
ash (Fig. 9) seems to be equal or higher to that for grout with no fly ash. This
indicates that fly ash grout is denser and less permeable than grout with no fly
ash. The dynamic modulus of elasticity increases with age for specimens
subjected to zero confining pressures, however, its value generally decreases
for specimens subjected to confining pressures after one year.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL81 95 0 0662749 0521074 O26 =
SUMMARY
The long-term performance of grout observed over three years for mixes
containing brine with O and 40% fly ash appear satisfactory. Confining
pressures are found to be adversely affect the physical properties over time.
This investigation showed that a reduction in the physical properties was
occurring after two years of confinement. Reductions was more renounced
especially for grout subjected to high confining pressures. The grout with fly
ash exhibited a better long-term performance than the grout with no fly ash.
Generally, fly ash grouts stored under zero confining pressure were found to
perform better than those with no fly ash.
CONCLUSIONS
The following conclusions were made on the performance of cement-

based grouts mixed with brine and containing O or 40% fly ash.
1 . Long-term performance of grout with fly ash, measured over a period of
three years, was found to be better than that from grout with no fly ash.
--``,`,-`-`,,`,,`,`,,`---
2. Grout with fly ash showed a lower final bleed than grout with no fly ash.
This suggests that fly ash grout is more homogenous and should have fewer
bleed channels.
3. The compressive strength of grout containing fly ash exhibited higher
strength than grout with no fly ash, for all ages. Brine infiltration into the
specimens due to confining pressures, seems to adversely affect the
compressive strength for both grouts.
4. The splitting-tensile strengths, measured up to three years, show a similar
pattern to that obtained from the compressive strength data. The splitting-
tensile strengths were found to increase with age up to 90 days, then showed
a scattered pattern.
5. The static modulus of elasticity for grout with no fly ash was found to
increase up to 90 days, then decreases to a constant value after that age. For
grout with fly ash, the static modulus of elasticity seems to increases i n
value, achieving a maximum at one year, then showing a continuous
decrease with age.
6. In most cases, the dynamic modulus of elasticity of grout with fly ash was
found to be equal or higher than with no fly ash, at all ages. The dynamic
modulus of elasticity increases with age for specimens subjected to zero
confining pressures. In general, its value was found to decrease for
specimens subjected to higher confining pressures after one year.

A C 1 SP-153 V O L X I 95 I0 6 6 2 9 4 9 0523075 Tb2 =
ACKNOWLEDGMENT
The authors are grateful to the Saskatchewan Potash Producer's

Association for their assistance and financial support. The authors would like
also to acknowledge Dr. Alan Coode from Central Canada Potash and Lionel
Wong, Dan Stott and Dale Pavier from the University of Saskatchewan for
their valuable contribution to the experimental program.
REFERENCES
1. Herget, G. A., "Field test program to evaluate the use of waste salt backfill
in Saskatchewan potash mines," Final report submitted for the potash
industry in Saskatchewan, CANMET, Ottawa, 1985, 166 pp.
2. Buck, A.D., Rhoderick, J.P., Mather, K., Reinhold, R.E., Boa, J.A.,
"Modification of Bell Canyon test (BCT) 1-FF grout," US Army Corps of
Engineers, Report No. SL-83-18, 1983, 11 pp.
3. Buck, A.D., Boa, J.A., Walley, D.M., "Development of a sanded expansive
salt grout for repository sealing application," US Army Corps of Engineers,
Report No. SL-85-1I , 1985, 1 1 pp.
4. Wakeley, L.D., Burkes, J.P., "Distribution of Chloride in a salt-saturated
grout in contact with halite rock," Cement and Concrete Research, Vol. 16,
1986, pp. 267-274.
--``,`,-`-`,,`,,`,`,,`---
5. Domone, P.L., "The properties of low strength silicate/portland cement

grouts," Cement and Concrete Research, Vol. 20, 1990, pp. 25-35.
6. Smith, R.C., Calvert, D.G., "The use of sea water i n well cementing,"
Journal of Petroleum Technology, Vol. 27, 1975, pp. 498-499.
7. Al-Manaseer, A.A., Haug, M.D., Nasser, K.W., "Compressive strength of
concrete containing fly ash, brine and admixtures," AC1 Materials Journal,
Vol. 85, 1988, pp. 109-116.
8. Al-Manaseer, A.A., Haug, M.D., Wong, L.C., "Microstucture of cement-

based grouts Containing fly ash and brine," AC1 special publication SP 132,
Vol. 1, 1992, pp. 635-654 (Editor: V.M. Malhotra)

A C 1 SP-153 VOL*I 95 W 0662949 0523076 9T9
TABLE 1 - CHEMICAL COMPOSITION AND PHYSICAL PROPERTIES

OF ASTM TYPE III PORTLAND CEMENT
Chemical Composition % ASTM Type III ASTM C 150

Cement Specifications
Silicon dioxide (SiO,) 20.70
Aluminum oxide (Alzo3) 4.49
Iron oxide (Fez03) 3.13
Calcium oxide (Cao), total 61.54
Calcium oxide (Cao), free 1.70
Magnesium oxide (MgO) 3.90 6.0 max
Sulfur trioxide (SO3) 3.34 3.5 max
Loss of ignition 1.70 3.0 max

Insoluble residue 0.20 0.75 max
Alkalies (Na2 + 0.658 K20) 0.60 0.60
Physical test results
Initial setting time in minutes (vicat test) 80.0 45.0 min
Autoclave expansion, % 0.12 0.80
Compressive strength ,MPa
1 day 25.9 12.4
(3760 psi) (1 800 psi) min
3 days 31.2 24.1
(4525 psi) (3500 psi) min
7 days 47.8
(6930 psi)
Percent passing 45-pm (No. 325) sieve = 96.3

Blaine fineness = 537 m2/kg
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 m 0 6 6 2 9 4 9 0523077 ô 3 5 m

OF SASKATCHEWAN LIGNITE FLY ASH*
Chemical Composition, % Saskatchewan ASTM C618

Fly Ash Specifications
Class C
Silicon Dioxide (SiO,) 46.80

Aluminum oxide (A1,0,) 2 1.90
Iron oxide (Fe203) 3.90
Total (SO, t AI,O, t Fe,03) 72.60 50.0 min
Sulphur trioxide (SO3) 0.80 5.0 max
Calcium oxide (Cao) 12.40
Available alkalies (Na20) 3.64 1.5 max
Moisture content 0.09 3.0 max
Loss of ignition 0.61 6.0 max
Physical test results

Fineness % retained on 45-ym
(No. 325) sieve 19.8 34.0 max
Pozzolanic activity index
with portland cement, %
ratio to control at 28 days 75.0 75.0 min
with lime at 7 days, MPa 6.4 5.5 min
(925.0 psi) (800.0 psi)
Water requirement, % of control 91.0 105.0 max
Autoclave expansion, % 0.07 0.8 max
Specific gravity 2.36
*Data were provided by the Saskatchewan power corporation
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 V O L * I 75 0662747 0523078 771
TABLE 3 - CHEMICAL COMPOSITION OF BRINE WATER
Constituents mgPiter
Canons
Total hardness* 39600
Calcium Hardness* 32500
Magnesium Hardness* 7100
Sodium as Na 95600
Potassium as K 4500
Iron as Fe less than 0.05
--``,`,-`-`,,`,,`,`,,`---
Manganese as Mn less than 0.03

Anions
P. alkalinity" 0.00
Carbonate as CO, 0.00
Total Alkalinity* 18
Bicarbonate as HCO, 22
Chloride as C1 178700
Nitrate as NOJ less than 0.2
Fluoride as F 0.0
Sulfate as SO4 486
Total dissolved solids
By evaporation at 103'C 333600
By conductivity at 25'C 426160
Appearance: Clear, colorless

Odor
H2S
PH 6.3
*expressed as CaCO,

A C 1 SP-153 V O L U I 95 IObb29Y9 0523079 608
Fig. l-High-pressure grout testing equipment in operation
Fig. 2-Location of dial gage:-

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 IObb2949 0 5 2 3 0 8 0 32T
--``,`,-`-`,,`,,`,`,,`---
Fig. M e m e n t grout poured inside 75 x 100-mm (3 x 6-in.)
cardboard cylinder molds
Fig. -rout specimens taken out for testing

A C 1 SP-153 VOL*I 95 I0662949 052LOô1 266
0 % Fly Ash
tJ U/(C+FA) = 1.75
I
-
I
I
-
I
I
40% Fly Ash
I I
O
O 20 40 60 80 1O0
Time (min.)
Fig. %Final bleed versus time for grout mixed with brine
z 5
5
L
U
* 4 0.0 MPa, O%FA
.- 3.4 MPa, 0%FA
gaJ 3 6.9 MPa, O%FA
L 0.0 MPa, 40%FA
3.4 MPa, 40%FA
o2 2 6.9 MPa, 40%FA
--``,`,-`-`,,`,,`,`,,`---
O
O 1 2 3 4
Age (years)
Fig. M o m p r e s s i v e strength at different ages and pressures

A C 1 SP-153 V O L U I 95 IObb2949 0523082 I T 2 I
h t Ø
--``,`,-`-`,,`,,`,`,,`---
---o-.
0.0 MPa, O%FA
5.4MPa,O%FA
* 6.9 MPa, O%FA
---*--
0.0 MPa, 40%FA
3.4 MPa, 40%FA
+ 6.9 MPa, 40%FA
0.2 -
I I I I
0.0
O 1 2 3 4
Age (Years)
Fig. -/-Splitting tensile strength at different ages and pressures
4000
c
h
3000
h
.-u
Y
._
-
Y
l
A
m
L
2000 0.0 MPa, O%FA
O
3.4MPa,O%FA
-
lA
a
a
6.9 MPA, OZFA
0.0 MPa, 40%FA
U
E" 1000
3.4 MPa, 40%FA
6.9 MPa, 40%FA
O
O 1 2 3 4
Age (Years)
Fig. û-static modulus of elasticity at different ages and pressures

A C 1 SP-L53 VOL*I 95 U Obb2949 0523083 O39
3000 r
I
- - - O - - 0.0 MPa, O%FA

* 3.4 MPa, O%FA
6.9 MPA, O%FA
---*-- 0.0 MPa, 40%FA
3.4 MPa, 40ZFA
6.9 MPa, 40ZFA
3000
O
' 1
I
2
I I
3 4
I
Age (Years)
Fig. &Dynamic modulus of elasticity at different ages and pressures
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - I 1 5 3 VOL*I 95 IObb2949 0521084 T75
SP 153-8
Properties of Mortar Mixtures

Containing High Amounts of Various
Supplementary Cementitious Materials
by C. Talbot, M. Pigeon,
J. Marchand, and H. Hornain
ABSTRACT
As part of a series of experiments designed to develop binary and ternary

blended cements for use in structures exposed to freezing and thawing cycles in
the presence of deicer salts, thirty-nine mortar mixtures were made. Five
different portland cements (two Canadian type 10 cements, two ASTM type I
cements, and one Canadian type 30 cement), seven fly ashes (three class F fly
ash, one class CF fly ash, and three class C fly ash), and two blast furnace
slags were used as cementitious materials. The waterkementitious material ratio
of all mixtures was fixed at 0,40, and the amount of supplementary cementitious
material (as a percentage of the total mass of binder) was 0% for the five
portland cement reference mixtures, 20% for nine mixtures, and 40% for the
other twenty-five mixtures. The compressive strength of all mortars was
--``,`,-`-`,,`,,`,`,,`---
measured after 7, 28, and 90 days of curing in water. The pore size distribution
(with mercury intrusion porosimetry) and the chloride ion permeability of all
mortars were determined after 28 days of curing. This paper presents the results
of all the tests that were performed, The results of the tests carried out to analyze
the portland cements, the fly ashes, and the slags are also given in the paper. It
was found that certain mixtures containing 40% of supplementary cementitious
material had an excellent 28 day strength, a very low chloride ion permeability,
and a very small average capillary pore size.
Kevwords: Cement types; compressive strength; chloride ions; fly ash;

hydration; microstructure; mortars (material); Rermeabiliw, porosity;
slags
A C 1 SP-353 V O L X I 95 O b b 2 9 4 9 0 5 2 3 0 8 5 901
126 Talbot et al
Biographical Sketches
AC1 fellow Michel Pigeon is professor of civil engineering at Laval

University, Quebec, Canada.
Caroline Talbot is a PhD student at Laval University. She obtained her

MSc from that university in 1992.
Jacques Marchand is assistant-professor of civil engineering at Laval

University, Quebec, Canada. His research interests are in the areas of
durability of concrete, mass transport processes in cement-based materials
and performance of dry concretes.
Hugues Hornain is technical manager of the L.E.R.M. (Laboratoire

--``,`,-`-`,,`,,`,`,,`---
d’Études et de Recherches sur les Materiaux) Paris, France.

A C 1 SP-153 V O L * I 95 IObb29Llî 052LOôb 848 W
INTRODUCTION
The use of supplementary cementitious materials, such as fly ash and

slag, has often been found to significantly reduce the concrete deicer salt scaling
resistance, even in low water to cementitious material ratio mixtures [ 1-41, The
reasons for this, however, are not quite clear, particularly if one considers that
these materials have, in many cases, been found to refine the hydrated cement
paste pore structure and reduce the long-term concrete permeability [5-71.
This paper presents the results of a series of tests performed on thirty-

nine mortar mixtures made with five different cements (from two plants), seven
different f l y ashes, and two slags. These tests are part of an ongoing research
program on the use of supplementary cementitious materials in concrete, which
is aimed at the development of binary and ternary blended cements for use in
structures exposed to freezing and thawing cycles in the presence of deicer salts.
RESEARCH PROGRAM
The tests described in this paper were carried out, first to characterize the
various cementitious materials that were selected, and mainly to determine the
best combinations of cementitious materials and cements that could be used to
make concretes with an adequate salt scaling resistance. Various techniques,
such as X-ray diffraction and BET specific surface measurements, were used to
characterize the materials that were selected. Mercury intrusion porosimetry,
rapid chloride ion permeability tests, and compressive strength measurements
were used to evaluate the properties of the mortar mixtures.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 V O L X I 95 = Obb2949 052L087 784
128 Talbot et al
MATERIALS
Cement
The five different cements that were used were the following : two
Canadian type 10 cements from two different plants (IOB and IOW), two
ASTM type I cements from the same two plants (IB and IW), and one Canadian
type 30 cement from one of these two plants (30B). The chemical analysis and
the physical properties of these cements are given in Tables 1 and 2. It was
considered that the composition and fineness of these five portland cements
covered a sufficient range.
Fly ash and slag
Of the seven fly ashes that were selected, three can be classified as
ASTM Type F (Fl, F2, and F3), three as ASTM Type C (Ci, C2, and C3),
and one is referred to as CF in this text. The physical properties and the
chemical analysis of these cementitious materials are given in Tables 3 and 4.
The chemical analysis of the two slags (SL1 and SL2) can also be found in
Table 3. Considering the data in Table 3 and 4, ash F3 could be classified as a
CF ash because of its C a 0 content. It is also clear that the high Na20 content of
ash C2 could prevent its use as a class C ash.
The results of the qualitative analysis of the fly ashes using the X-ray
diffraction technique are presented in Table 5. In this Table, the amount of each
mineral in any given fly ash is indicated very approximately in the following
way : “x” for a low amount, “xx” for a moderate amount, and “xxx” for a high
amount.
Aamegate
The same granitic fine aggregate from a local source was used for all
--``,`,-`-`,,`,,`,`,,`---
mortar mixtures. Its physical properties and its grading are given in Table 6.

A C 1 SP-153 V O L X I 95 = 0662947 0 5 2 L O ô ô 610 W
MIXTURE PROPORTIONS AND

PREPARATION OF THE TEST SPECIMENS
For all mortar mixtures, the water to cementitious material ratio was
kept constant at 0.4. It was considered that such a ratio was approximately the
maximum possible value in order to fabricate concretes containing significant
amounts of supplementary cementitious materials that could be resistant to
deicer salt scaling[ 1-41. All cementitious materials were homogenized in a
closed mixer before being used. The fine aggregate was oven dried, and
absorption was taken into account to calculate the amount of water in the
mixture. The amount of aggregate was adjusted in order to obtain a mortar flow
of 100% (f15%), and the cementitious material to fine aggregate ratio thus
varied from 1: 2.3 to 1: 3.1. The mixing procedures described in the Canadian
standard (CAN3-AS-Mg) were followed. The proportions of the thirty-nine
mortar mixtures are presented in Table 7. Figure 1 shows the identification code
for these mixtures. The results in Table 7 show that, with only a few
exceptions, the value of the flow was within the selected range, i.e. 85% to
115%.
It can be seen in Table 7 that the maximum level of replacement of

cement by fly ash or slag is 40%. This value was selected considering that it
would be very difficult to develop deicer salt scaling resistant concrete mixtures
containing more than such an amount. It can also be seen that certain fly ashes
were used in only a single mixture, whereas other fly ashes were used in a
relatively large number of mixtures. This is simply due to the fact that the
number of mixtures required to test all possible combinations of materials (at
two levels of replacement, 20% and 40%) was too large.
The test specimens were prepared in two different batches : one for the
compressive strength specimens (nine 50 mm cubes per mixture), and one for
the mercury intrusion porosimetry and rapid chloride ion permeability test
specimens (one 200 x 225 x 75 mm slab per mixture). After demolding, all
specimens were cured in lime saturated water until the time of testing. The 200 x
225 x 75 mm slabs were cored to obtain the specimens required for the chloride
ion permeability tests, and to obtain the samples needed for the mercury
intrusion porosimetry tests.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1-53 VOL*I 75 W 0bb2749 0523087 5 5 7
130 Talbot et al
EXPERIMENTAL PROCEDURES AND TESTS RESULTS
Compressive strenah
The compressive strength was measured according to the procedure

described in the Canadian standard (CAN3-A5-M83). For each mixture, three
cubes were tested after 7 days of curing, three after 28 days, and three after 91
days. The test results are shown in Table 8.
The values in Table 8 show that the 91 day compressive strength of all
mixtures is relatively high, irrespective of the cementitious materials that were
used. Generally, the 9 1 day strength of the mixtures containing supplementary
cementitious materials is slightly lower than that of the reference mixtures.
Certain mixtures containing supplementary cementitious materials have a
strength approximately equal to that of the reference mixtures, and a few even
have a slightly higher one.
Since it was not possible to test all possible combinations of cement and
supplementary cementitious materials, it was not possible to carry out a valid
statistical analysis of the complete test results. Furthermore, in view of the
normal variability of this type of test results, it was considered inappropriate in
most cases to compare the results from any two specific mixtures. Nevertheless,
the results clearly indicate that the lowest 91 day strength was obtained with the
mixtures containing 40% of ash C2 (48 MPa), and 40% of F3 (5 1 MPa). The 7
day strength of these mixtures is not significantly lower than that of the other
similar mixtures, but the increase between 7 and 91 days is quite small. In
comparison, it can be noted that the strength of the mixture containing 40% of
ash F1 increased from 30 MPa at 7 days to 60 MPa at 91 days. Such an increase
is a good indication of the reactivity of this ash. The results also clearly indicate
that, in average, the type of cement had little influence, and that the use of slag
does not cause significant strength reduction at 28 days.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 O662949 0523090 2 7 9
Table 10 presents the results of the measurement of the reactivity of ashes F1,
F2, C2, and CF. These results were obtained using the Chapelle test which
measures the quantity of C a 0 fixed per unit weight of ash after a given time
period (a test which is not therefore suited for ashes that already contain free
lime such as C1 and C3). They indicate that the C2 ash has the lowest potential
of reactivity, which explains the small increase in compressive strength with
time for mixture 10BC2-40.
Ranid chloride ion permeabilitv
--``,`,-`-`,,`,,`,`,,`---
For each mortar mixture, the chloride ion permeability was determined,
after 28 days of curing, in accordance with the procedure described in the
ASTM C1202 standard. Two specimens (cores 50 mm in length and 100 mm in
diameter) were tested for each mixture as prescribed by the standard.
The ASTM C 1202 rapid chloride permeability test basically consists of

measuring the flow of electric current through a concrete specimen in contact
with a sodium chloride solution on one side and with a sodium hydroxide
solution on the other side, when subjected to a difference of potential of 60V.
Since the electrical charges are carried by the ions (mostly alkali and hydroxide
ions) in the pore solution, the current depends not only on their mobility, which
is related to the pore structure, but also to their concentration in the pore water.
The results of the rapid chloride permeability tests are also shown in
Table 8. All values are relatively high, compared to those for concretes with
similar water to cementitious material ratios, since the paste content of mortars is
always much higher than that of concretes. The chloride permeability of the
various mixtures can not, therefore, be evaluated according to the usual
classifications.
In most cases, the chloride permeability of the mixtures containing

supplementary cementitious materials is lower than that of the reference
mixtures. This may be related in part to the refined pore structure of these
mortars (see the following section), and in part to the lower C/S ratio of the
CSH in pastes containing fly ash and slag, since sodium and potassium tend to
be included in these low calcium CSH [15]. This phenomenon reduces the

A C 1 SP-353 V O L S I 95 m 0662949 0523093 105 m
132 Talbot et al
amount of alkalies in the pore water solution, and thus the electrical
conductivity. The mixtures containing ashes C1 and C3 have a high
permeability, but these two ashes have a low Si02 and high C a 0 content, and
therefore probably did not cause a significant reduction of the amount of alkalies
in the pore water solution.
Although pore solution analyses were not performed on all types of

pastes, the data presented in Table 11 tend to confirm the influence of the
concentration of sodium and potassium in the pore solution (which varies with
the characteristics of the cementitious materials) on the value of the chloride ion
permeability. This Table presents the results of the analysis of the pore water
solution performed on three samples of each of three following paste mixtures at
28 days of curing : 10B, 10CF-40, and 10BC3-40. The higher chloride ion
permeability of the mixtures containing the C3 ash (from = 8000 C to = 17000
C), as compared to that of the mixtures containing the CF ash (= loo0 C to =
--``,`,-`-`,,`,,`,`,,`---
5000 C) may be related to the higher level of alkalies contained in the pore
solution of the mixtures made with the C3 ash.
The rapid chloride permeability test is an interesting technique to obtain

information in a relatively short period of time, but theoretical considerations, as
well as the results described, clearly show that the value of the chloride
permeability that is obtained varies not only with the pore structure, but also
with the concentration of the alkalies and other chemicals in the pore water
solution. The relationship between porosity and chloride permeability exists (see
Fig. 2 ) , but the data is scattered. In this respect, it is interesting to consider the
test results for the mixture containing the C2 ash which has a low potential of
reactivity, the lowest compressive strength, a capillary pore system coarser than
that of the reference mixture, but a low chloride permeability. Since this ash also
has a low Si02 - C a 0 ratio, it could have been expected that only a small
amount of alkalies would be included in the CSH from the pozzolanic reaction,
and that the measured chloride permeability would be high. Although no results
are available concerning the analysis of the pore water solution for this mixture,
it seems clear that, for reasons that are not known, the amount of alkalies in the
pore water was low. This demonstrates the difficulty in properly interpreting the
results from the rapid chloride permeability test.

A C 1 SP-153 V O L + I 95 H 0662949 0523072 041
Mercury intrusion porosimetry
The mercury intrusion porosimetry tests were performed on specimens

cured for 28 days. In order to reduce the microstructural damage that can be due
to drying (because of the large tensile forces created by the water menisci during
drying), the specimens were immersed in isopropanol for at least 21 days after
curing. After this period of isopropanol-replacement, they were placed in the
vacuum pump for 48 hours, and then tested using an apparatus with a 207 MPa
capacity. The isopropanol-replacement technique has been found to reduce very
--``,`,-`-`,,`,,`,`,,`---
significantly the increase in the average size of the capillary pores that can be
due to drying [8-91. DAY et al. [7] have also noted that the permeability after
isopropanol replacement is much lower than that measured after simple drying.
The test results for all mortar mixtures are presented in Table 9. Each
result in this Table represents the average value for two test specimens. In order
to better visualize the differences between the various mixtures, the pore system
was separated into four basic categories : F1 (> 0.9 pm), F2 (from 0.9 pm to
0.06 pm), F3 (from 0.06 pm to 0.009 pm), and F4 (from 0.009 pm to 0.006
pm). Although it has been shown that damage to the pore structure can occur
when mercury is forced into the pores of most hydrated blended cement pastes,
such damage does not normally occur until the pressure reaches very high
values (Le. approximately 100 MPa) [8, 10-1 i]. The information in the Table
can thus be considered valid, particularly for the larger pore sizes. However,
again in view of the normal variability of the test results, it was considered
inappropriate in most cases to compare the results for any two specific mixtures.
The results in Table 9 indicate that, with the exception of ash C2 which
has a low potential of reactivity, and thus a higher total porosity, the total
porosity is almost the same for all mixtures. For the mixtures with a total
porosity lower than that of the reference mixture, it can be hypothesized that the
volume of very small pores which can not be filled with mercury at the
maximum pressure is higher.
Figure 3 shows, for the mixture made with cement 10B and ail mixtures
made with the same cement and containing 40% fly ash, the values of the ratio
of the volume of class F2 pores to the sum of the volumes of class F3 and class

A C 1 SP-153 VOL*I 95 0662947 0523093 T B B
134 Talbot et al
F4 pores. This Figure indicates that, again with the exception of ash C2 which
has a low potential of reactivity, the use of supplementary cementitious materials
generally causes a refinement of the capillary pore structure. The results in Table
9 clearly indicate that the volume of the F2 pores decreases with the use of fly
ash and slag, although the volume of the larger pores ( F l ) remains
approximately constant. These results are in contrast with those obtained by XU
[I21 (who also found that fly ash mortars continuously cured under water
generally had a finer pore structure than that of ordinary Portland cement
mortars, but only at a replacement level of 30% or less), and with those
obtained by LI and Roy [13] (who found that the use of fly ash lead to an
increase in the volume of both larger and smaller pores, as well as in the total
pore volume).
FELDMAN [14] studied thepore structure of blended cement pastes by

mercury intrusion porosimetq, methanol and helium pycnometry . His results
tend to indicate that blended cement pastes have a discontinuous pore structure
mainly composed of narrow-necked pores. At a high intruding pressure, these
"neck" points are overcome, so that the apparent intruded volume at this
pressure increases [ 10, 141. This can lead to a misinterpretation of the mercury
intrusion porosimetry tests results. Nevertheless, it is clear that, for all the
various combinations of supplementary cementitious materials and portland
cement tested, at all levels of cement replacement up to 40%, and with the
exception of ash C2 which has a very low reactivity potential, the use of
supplementary cementitious materials (and particularly slag) generally caused a
significant refinement in the pore structure. The results presented further show
that the type of cement had little influence. Although no direct relationship can
be established between pore structure characteristic and strength, the data
indicate a positive influence of pore structure refinement on strength.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 E Obb2949 0521094 914
CONCLUSION
The tests described in this paper were performed in order to select the
best combinations of cementious materials and cement. Considering the data
obtained, as well as the impossibility to perform a valid statistical analysis, these
tests simply allowed to determine the materials (ash C2 and perhaps ash F3) that
lead to a lower overall performance (in strength and pore structure refinement).
Therefore, the main conclusion from the various tests described in this paper is
that all the materials tested but ash C2 (and perhaps also ash F3) can be used to
fabricate concretes with good engineering properties, and also to attempt to
develop blended cements that can be used to fabricate concretes that will be
exposed to freezing and thawing cycles in the presence of deicer salts.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L a I 95 0662947 0523095 850
136 Talbot et al
REFERENCES
BILODEAU, A., MALHOTRA, V.M., ( 1993),Concrete incorporating high

volumes of ASTM class FJly ash: Mechanical properties and resistance to
deicing salt scaling and to chloride-ion penetration, AC1 Special
Publication SP 132, Edited by V.M. Malhotra, pp. 3 19-349.
BILODEAU,A., MALHOTRA,V.M. (1993), Deicing salt scaling resistance
--``,`,-`-`,,`,,`,`,,`---
of concrete incorporating supplementary cementing materials: Canmet

research, Proceedings of the International Workshop on the Resistance of
Concrete to Freezing in the Presence of Deicing Salts, August 30-31,
Québec City, Canada, pp. 191-228.
D. (1989), Deicer scaling resistance of lean concrete containing
WHITING,
f l y ash, AC1 Special Publication SP-114, Edited by V.M. Malhotra,
pp. 349-372.
REID,E., PIGEON,M., PLEAU,R. (1993), The frost durability of high-
strength concretes made of a Class Ffly ash, Proceedings of the Half-Day
Open Session, Network of Centers of Excellence on High Performance
Concrete, Québec City, June 10, pp. 19-36, (in French).
MANMOHAN, D., METHA,P.K. (198 I), Influence of pozzolanic, slag
and chemical admixtures on pore size distribution and permeability of
hardened cementpastes, Cement. Concrete and Aggregates, Vol. 3, No 1,
pp. 63-67.
FELDMAN, R.F., CARETTE,G.G., MALHOTRA, V.M. (1990), Studies
on mechanisms of development of physical und mechanical properties of
high-volume fly-ash cement pastes, Cement and Concrete Comuosites,
Vol. 12, pp. 245-251.
DAY,R.L., JOSHI,R.C., LANGAN,B.W., WARD,M.A., Measurement
of the permeability of concretes containing fly ash, Proceedings of the
Seventh International Ash Utilization Svmposium, Vol. 2, Orlando, USA,
pp. 811-821.
FELDMAN,R.F., BEAUDOIN, J.J. (1991), Pretreatment of hardened
hydrated cement pastes for mercury intruding measurements, Cement and
Concrete Research, Vol. 2 I , No 2-3, pp. 297-308.
MARSH,B.K., DAY,R.L., BONNER,D.G., ILLSTON,J.M. (1985), The
effect of solvent replacement upon the pore structure characterization of
Portland cement paste, Proceedings of the RILEMKNR International
Symposium on Principles and ApDlications of Pore Structural
Characterization, Milan, Italy, J.M. Haynes and edited by P. Rossi-Doria,
pp. 365-374.
FELDMAN,R.F. (1984), Pore structure damage in blended cements
caused by mercury intrusions, Journal of the American Ceramic Society,
Vol. 67, Na 1, pp. 30-33.

A C 1 SP-153 V O L M I 75 = Ob62949 052L076 7 9 7
[i 11 BEAUDOIN,J.J. (1979), Porosity measurements of some hydrated

cemetitious systems by high-pressure mercury intrusion -
Microstructural limitations, Cement and Concrete Research, Vol. 9, No 6,
pp. 77 1-781.
S.L. , Hydration and properties of f l y ash concrete ,

[ 121 XU, A., SARKAR,
Mineral Admixtures in Cement and Concrete, Progress in Cement and
Concrete - Volume 4, Edited by S.N. Gosh, ABI Books Private
Limited, New Delhi, India, pp. 175-225.
[13] Li, S., ROY, D.M. (1986), Investigation of relutions between porosity,
pore structure and CI- diffusion of f l y ash and blended cement pastes,
Cement and Concrete Research, Vol. 16, No 5, pp. 749-759.
[14] FELDMAN,R.F. (1983), Significance of porosity measurements on

hiended cement peqkmance, AC1 Svecial Publication SP-79, pp. 415-
433.
[15] DUCHESNE, J., BERUBE,M.A. (1994), Effect of supplementary

cementing materiais on the composition of cement hydration products.
Advanced Cement Based Materials. (accepted)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 D Obb2949 0523097 6 2 3
138 Talbot et al
TABLE 1 - CHEMICAL ANALYSES OF CEMENTS
20.43 21.20 20.40 2 1.O5 2 1.62

--``,`,-`-`,,`,,`,`,,`---
5.13 4.38 5.08 4.36 4.45

2.66 3.01 2.56 2.97 2.88
63.19 63.46 62.93 63.09 63.19
2.22 2.07 2.25 3.28 3.29
3.53 2.86 4.52 2.34 2.26
0.17 0.12 0.20 0.13 O. 14
0.85 0.56 0.90 0.39 0.4 1
0.22 0.20 0.2 1 0.2 1 0.22
0.09 0.05 0.09 0.04 0.04
Freelime 0.38 0.38 0.38 0.44 0.4 1

LOI 2.26 1.46 1.69 2.47 2.13
Bogue's composition
c3s 54 55 50 57 52
c2s 18 19 20 18 22
C3A 9 7 9 7 7
c4* 8 9 8 9 9

A C 1 SP-153 V O L + I 95 H Obb2949 0521098 5bT
TABLE 2 - PHYSICAL PROPERTIES OF CEMENTS
10 B IB 30 B low IW
Blaine ( m 2 k g )
specific surface 356 361 516 424 397
% passing
45 pm sieve 94 95 100 93 85
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L * I 95 0 6 6 2 9 4 9 0.521099 4Tb
140 Talbot et al
TABLE 3 - CHEMICAL ANALYSES OF FLY ASHES AND SLAGS
Si02 36.2 66.3 33.2 41.5 52.7 46.3 32.5 36.5 37.4
Ai203 19.3 18.5 19.0 22.6 23.5 20.6 19.5 10.1 10.1
Fe203 5.3 2.9 5.7 19.9 3.8 5.6 5.9 0.7 1.3
Ca0 27.1 7.3 19.6 5.9 12.5 18.1 28.2 33.6 37.1
Mgo 4.4 1.5 3.4 1.1 1.2 4.5 4.6 15.6 12.4
so3 1.5 0.2 4.0 1.4 0.3 1.8 2.9 3.8 2.0
Na20 1.4 0.4 10.0 1.4 3.6 0.5 1.9 0.5 0.2
K20 0.4 1.0 0.7 1.2 0.5 0.3 0.3 0.5 0.3
Ti@ 1.6 1.4 1.3 1.0 0.9 1.0 2.2 0.7 0.4
MnO 0.02 0.2 0.04 0.03 0.11 0.22 0.03 -
p205 1.3 - 0.6 0.3 0.1 0.3 1.0 -
Cao3 0.02 0.02 0.02 0.02 0.01 0.01 0.02 -
SrO 0.4 0.1 0.8 0.2 0.1 0.6 0.5
LOI 0.3 0.2 1.1 3.5 0.8 0.3 0.4
Fly ash classificationaccording to ASTM C 6 18-91:

(Si02+AL203+Fe203)min.% = 70 for Class F and 50 for a Class C
SOsmax.% = 5 for a Class F and a Class C
Available alkaìies,as N a 2 0 , m a . % = 1.5 for a Class F and a Class C
the available alkalies content must be taken into account for alkali-aggregate
reaction
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 VOL*I 95 111 0662949 052LIIOO T 4 8 W
TABLE 4 - PHYSICAL PROPERTIES OF FLY ASHES
CI FI C2 F2 CF F3 C3
--``,`,-`-`,,`,,`,`,,`---
Density 2.61 2.31 2.63 2.51 2.09 2.63 2.65

Specificsurface(m2/kg) 325 225 425 246 327 272 385
% retained 40 pm 13.09 19.31 12.19 14.62 16.12 15.26 9.27
Specific surface BET (&g) 0.8 0.5 0.8 1.2 1.2 0.6 1.5
Pozzolanic index (NF EN 196-1 standard)*

7d 0.86 0.71 0.75 0.75 0.76 0.8 0.94
28d 0.94 0.80 0.76 0.83 0.89 0.94 0.98
91d 1.03 0.92 0.83 0.97 1.08 0.99 1.03
~~ ~
*: ratio compressive strength of cement+ash paste and pure cement paste

A C 1 SP-153 V O L J I 95 O662949 0521101 984 = 1
I
142 Talbot et al I
TABLE 5 - MINERALOGICAL ANALYSES OF FLY ASHES (DRX)
Detectedminerais C1 F1 C2 F2 CF F3
c3
Qual-@ xx xxx x xx xx xxx xx

Merwinite X X X
Mullite. X xx X X
Magnetite X
Ca0 X X X
Mgo X X
Na2S04 X
Cas04 X X X
x: low amount
xx: moderate amount
xxx: high amount
--``,`,-`-`,,`,,`,`,,`---
TABLE 6 - FINE AGGREGATES PROPERTIES
Sieve(mm) 1 2 . 5 1 0 . 0 5 . 0 2 . 5 0 1 . 2 5 0 . 6 3 0.315 0 . 1 6
0.080
%passing 100 99.5 96.2 92.2 82.8 56.8 24.3 6.9 1.2
Density: 2.70
Absorption: 0.9 %

A C 1 SP-1.53 V O L * I 9.5 I0662949 0521102 B I O
TABLE 7 - MIXTURE PROPORTIONS (AS BATCHED)
Slag Fine
Mixture Cement Fly ash Water aggregate Binder:Fine agg Flow
Reference mixture
10B* 3036 O 1153 7589 1:2.5 93
1OB 3086 O 1234 7714 1:2.5 100
1B 3086 O 1234 77 14 1:2.5 110
30B 3086 O 1234 7714 1:2.5 73
low* 3026 O 1150 7564 1:2.5 86

low 3086 O 1234 7714 1:2.5 102
IW 3086 O 1234 7714 1:2.5 85
CI
10BC1-40 1852 1234 1234 9023 1:2.9 92
FI
10BF1-40 1852 1234 1234 9344 1:3.0 101
c 2
10BC2-40 1852 1234 1234 9644 1:3.1 97
F2
10BF2-40* 1852 1234 1173 7650 1:2.5 88
10BF2-40 I852 1234 1234 7714 1:2.5 106
10BF2-20 2469 617 1234 7714 1:2.5 98
1BF2-40 1852 1234 1234 7714 1:2.5 106
IBF2-20 2469 617 1234 1114 1:2.5 105
30BF2-40 i 852 1234 1234 7137 1:2.3 98
1OWF2-4O1 1852 1234 1173 7522 1:2.4 91
iOWF2-40 1852 1234 1234 7392 1:2.4 96
1W2-40 1852 1234 1234 7329 1:2.4 101
CF
IOBCF-40* 1852 1234 1173 8679 1:2.8 99
IOBCF-40 1852 1234 1234 7714 1:2.8 112
10BCF-20 2469 617 1234 7714 1:2.5 112
IBCF-40 1852 1234 1234 8679 1:2.8 99
IBCF-20 2469 617 1234 7714 1:2.5 112
30BCF-40 1852 1234 1234 1714 1:2.5 110
IOWCF-40* 1852 1234 1173 8583 1:2.8 94
1OWCF-40 1852 1234 1234 8583 1:2.8 103
1WCF-40 1852 1234 1234 7714 1:2.5 111
*: W/B=0.38
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 VOL*I 95 0662949 052IIL03 7 5 7
144 Talbot et ai
TABLE 7 (CONT’D.) - MIXTURE PROPORTIONS (AS BATCHED)
Slag Fine
Mixture Cement Fly ash Water aggregate Binder:Fine agg F l o w
F3
1OBF3-40 1852 1234 1234 8679 1:2.8
c 3
10BC3-40 1852 1234 1234 8679 1:2.8 112
10BC3-20 2469 617 1234 7964 1:2.6 96
1 BC3-40 1852 i 234 1234 8679 1:2.8 113
lBC3-20 2469 617 1234 7714 1:2.5 1 I5
30BC3-40 1852 1234 1234 7714 1:2.5 115
1OWC3-40 i 852 1234 1234 8679 1:2.8 101
1WCF-40 1852 1234 1234 8679 1:2.8 106
Slag1
10BSLI-40 1852 I234 1234 7834 1:2.5 102
--``,`,-`-`,,`,,`,`,,`---
10BSL1-25-CF-15 1852 463 772 1234 7714 1.2.5 100
10BSL1-25-F2-15 1852 463 772 1234 7714 1.2.5 96
Slag2
10BSL2-40 1852 1234 1234 7834 1:2.6 93
IOBSL2-25-CF-15 1852 463 772 1234 7714 1.2.5 103

A C 1 SP-153 VOL*I 95 0662949 0521104 693
TABLE 8 - COMPRESSIVE STRENGTH AND CHLORIDE ION

PERMEABILITY RESULTS
Mixture Compressive strength Chloride ion permeability (28

days)
íMW (Coulombs)**
7days 28days 9ldays
Reference mixture
IOB* 52 69 65 5100
1OB 53 63 60 6960
IB 51 69 71 7370
30B 65 13 78 7060
low* 63 77 81 7650
low 59 78 69 8260
Iw 56 72 78 9140
c1
10BC1-40 38 53 61 1 1440
F1
1OBFl-40 30 45 60 2910
c 2
10BC2-40 38 44 48 2920
F2
lOBF2-40* 36 52 61 2490
10BF2-20 44 57 72 4910
10BF2-40 33 46 57 3370
IBF2-20 39 57 12 7500
IBF2-40 30 44 60 7160
30BF2-40 37 52 62 3550
10WF2-40* 37 57 13 3620
lOWF2-40 32 51 61 5230
IWF2-40 30 47 64 7480
CF
10BCF-40* 39 60 69 1390
IOBCF-20 43 62 62 3270
IOBCF-40 33 52 59 1770
IBCF-20 42 62 71 5290
IBCF-40 31 52 71 3990
30BCF-40 39 60 69 1970
IOWCF-404 39 67 77 2350
IOWCF-40 36 59 65 3140
IWCF-40 34 51 15 4650
* : W/B ratio of 0.38

** : average of 2 specimens
--``,`,-`-`,,`,,`,`,,`---

TABLE 8 (CONT?D.)- COMPRESSIVE STRENGTH AND CHLORIDE
ION PERMEABILITY RESULTS
Mixture Compressive strength Chloride ion permeability (28

days)
(MPa) (Coulombs)**
7days 28days 9ldays
F3
1OBF3-40 36 54 51 3670
C3
10BC3-20 49 66 65 8030
10BC3-40 40 56 66 10170
IBC3-20 46 66 69 11890
IBC3-40 32 51 63 15010
30BC3-40 46 58 53 8700
1OWC3-40 37 55 63 14090
IWC3-40 33 53 59 17520
Slag 1
10BSL1-20 44 56 65 4870
IOBSL 1-40 41 65 76 3350
IOBSLI-25-CF-15 38 61 68 3010
lOBSLl-25-F2-15 38 58 64 3510
1OBSL 1-25-C3- I5 40 64 79 4640
lOBSLl-25-C3-15 38 54 58 2800
Slag 2
10BSL2-20 45 62 66 3890
IOBSL2-40 52 80 86 2940
IOBSL2-25-CF-15 44 70 70 2590

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 m 0662949 052LLOb 4bb m
TABLE 9 - MERCURY INTRUSION POROSIMETRY RESULTS**
Mixture Class F1 Class F2 Class F3 Class F4 Total porosity
% % % YO %
Reference mixture
1 OB* 1.20 4.12 6.90 0.99 13.23
1OB 1.38 2.96 7.66 0.72 12.71
E3 0.99 1.61 9.13 0.98 12.71
30B 0.85 4.72 6.12 0.72 12.42
low* 0.81 1.54 6.46 0.61 9.42

low 0.88 1.66 7.56 0.66 10.75
lw 0.75 1.41 9.87 0.66 12.70
c 1
IOBC 1-40 0.84 0.87 9.48 0.95 12.13
F1
I OBF 1-40 1.13 1.36 8.85 0.61 12.06
--``,`,-`-`,,`,,`,`,,`---
c 2
10BC2-40 1.81 4.82 7. I4 0.66 14.42
F2
10BF2-40* 1.38 1.11 6.88 0.7 I 10.02
10BF2-20 0.67 1.63 9.4 1 0.91 12.63
10BF2-40 0.78 1.23 9.56 0.93 12.50
IBF2-20 0.60 2.00 9.93 1.16 13.70
IBF2-40 0.80 0.92 10.35 0.92 12.99
30BF2-40 0.71 1.14 9.67 0.98 12.49
10WF2-40* 0.77 0.68 8.54 I .20 1 I .20

10WF2-40 0.7 1 1.69 10.29 0.98 13.67
IWF2-40 0.5 1 I .57 8.77 0.93 11.81
CF
IOBCF-40* 0.70 OS8 6.50 1.73 9.50
IOBCF-20 0.8 I I .O4 7.95 1.25 11.02
IOBCF-40 0.94 0.96 7.64 0.8 1 10.35
IBCF-20 0.80 1.20 9.19 1.49 12.76
IBCF-40 1.27 0.99 7.72 1.11 I l .O8
30BCF-40 0.68 0.93 7.40 1.15 10.14
1OWCF-40* 0.8 1 OS3 7.30 1.77 10.40

10WCF-40 0.74 0.89 7.96 1.42 11.00
IWCF-40 0.50 0.60 6.58 1.86 9.52


A C 1 SP-153 V O L X I 95 = Ob62949 052l1107 3T2
I
148 Talbot et al
TABLE 9 (CONT’D.) - MERCURY INTRUSION POROSIMETRY

RESULTS**
--``,`,-`-`,,`,,`,`,,`---
Mixture Class F1 Class F2 Class F3 Class F4 Total porosity
% % % % 70
F3
10BF3-40 1.30 1.25 9.19 1.41 13.12
c 3
10BC3-20 0.53 0.97 8.60 1.01 11.10
10BC3-40 0.50 I .o2 7.97 1.O9 10.58
IBC3-20 0.62 0.64 8.16 1.26 10.67
IBC3-40 1.21 1 .O9 8.26 1.47 12.01
30BC3-40 0.70 0.60 8.20 1.40 10.90
1OWC3-40 0.93 0.96 8.82 1.33 12.05
IWC3-40 1S O 0.84 8.50 1.57 12.45
Slag 1
IWSI-20 I .O5 2.73 7.46 0.87 12.10
IOBSL 1-40 0.87 0.95 6.19 0.9 1 8.92
10BSL1-25-CF-15 1.02 1.13 7.83 1.61 11.59
10BSL1-25-F2-15 0.64 0.92 7.23 1.14 9.92
10BSL1-25-C3-15 0.44 0.78 6.26 I .86 9.34
10BSL1-25-C3-15 0.86 1.O3 8.02 0.70 10.62
Slag 2
10BSL2-20 0.75 1.27 7.80 0.95 10.76
1OBSL2-40 0.64 0.64 5.43 I .42 8.10
10BSL2-25-CF-15 1.31 1.22 6.04 1.61 10.17
Class Fi > 0.9 pm

0.9 pm < Class F2 > 0.06 pm
0.06 pm < Class F3 > 0.009 pm
O.DO9 pm < Class F4 > 0.006 pm


A C I S P - VOLXI
~ 95 m o w w q 0 5 2 1 , m 239 m
TABLE 1O - MEASUREMENT OF REACTIVITY POTENTIAL AS GIVEN

BY CHAPELLE TEST
Fly ash F1 F2 c2 CF
TABLE 11 - CHEMICAL ANALYSES OF PORE SOLUTION*
Mixture AI- S- Na+ K+ Caz+

(ppm) (ppm) (ppm) (ppm) (pprn)
10B-1 3.9 142 83 457 27.3

10B-2 13.6 108 93 604 34.4
10B-3 4.8 77 75 459 47.9
10BCF-40-1 60 57 85 142 30.0
10BCF-40-2 63 92 121 169 94.0
IOBCF-40-3 58 42.5 80 149 45.4
1OB C3-40- 1 12.9 70 210 330 15.7
1OBC3-40-2 12.8 24.5 154 33 1 50.1
10BC3-40-3 31.4 84 177 228 155.0
* : made on 28 day hydrated cement pastes
J-T -L
1OB CF 40
Type 10 plant B Cement replacement with
supplementary material (%)
Ash or slag used
Fig. 1-Identification code
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 Obb2949 0 5 2 1 1 0 9 I175
150 Talbot et al
................................ ...........
:
--``,`,-`-`,,`,,`,`,,`---
.............. <....:......................
1000 5000 9000 13000 17000

Chloride Ion Permeability (ASTM C1202 Coulombs)
Fig. 2-Relationship between total porosity and ASTM C1202

A C 1 SP-153 V O L * I 9 5 I0662949 052LL10 9 9 7
0.7
0.6
0.5
.s
Y
?
!Ì 0.4
d
m
Y
x
L
I
0.3
0.2
o. 1
--``,`,-`-`,,`,,`,`,,`---
OE+O ~ 3
m
cl
O
m
2
Mixtures
Fig. %Refinement of porosity; Class F2/F3 + F4 ratio

A C 1 SP-153 VOL*I 95 m 0662949 0 5 2 l l l L 823 m
SP 153-9
--``,`,-`-`,,`,,`,`,,`---
Production of Sulfate-Resistant
Concrete Containing High-Calcium Fly
Ash and Sodium Sulfate Admixture
by R. B. Freeman and R. L. Carrasquillo
Svnoosis: Partial replacement of a moderately sulfate-resistant cement with a

high-calcium fly ash may result in either increased or decreased sulfate
resistance for concrete. These effects of fly ash have been related to, among
other factors, changes in the permeability of concrete and changes in the
stability of hydrated calcium aluminates in the presence of sulfate-bearing
solutions.
The objective of this study was to investigate the effects of using
anhydrous sodium sulfate as a chemical admixture in concrete made with
Class C fly ash. The sodium sulfate admixture was expected to influence the
sulfate resistance of concrete by increasing the availability of sulfate ions
during the hydration of calcium aluminates. The admixture was also expected
to increase the rate of pozzolanic reactions by increasing the. concentration of
alkali ions in solution. In addition to studying the effects of the sodium sulfate
admixture on sulfate resistance, its effects on mixing water requirements,
compressive strength, and permeability were examined.
The fly ash was introduced into the concrete by two methods: partial
replacement of portland cement with fly ash at the time of mixing concrete and
intergrinding of fly ash with portland cement clinker and gypsum, as in the
production of blended cements. A commercially-available ASTM C I50
Type II cement and five ASTM C 618 Class C fly ashes were used. The fly
ashes replaced the portland cement (or the cement clinker plus gypsum) at a
levei of 35 percent by volume. For each source of fly ash, fourteen concrete
mixtures were produced: 7 mixtures included Type II cement and fly ash with
various amounts of the sodium sulfate admixture and 7 mixtures included
blended fly ash cement with various amounts of the sodium sulfate admixture.
The use of sodium sulfate as a concrete admixture, in amounts ranging
from 2 to 5 percent by mass of cement, resulted in improved sulfate resistance
for concrete containing Class c fly ash. in many cases, suifate resistance
exceeded that of Type II cement concrete without fly ash. Additional effects of
the sodium sulfate admixture included increased compressive strengths at early
ages and lower permeabilities at early ages.
Keywords: Admixtures; Alkalies; blended cements; durability; flv ash;

mineralogical analysis; sulfate resistance

A C 1 S P - I 1 5 3 VOL*I 95 I0 6 6 2 9 4 9 052LLL2 i b T
154 Freeman and Carrasquillo
Reed B. Freeman is an assistant professor of civil engineering at Mississippi

State University. He obtained his PhD from The University of Texas at Austin
in 1992.
Ramon L. Carrasquillo is Professor of civil engineering at The University of

Texas at Austin. He is also the assistant director of The International Center
for Aggregates Research. Dr. Carrasquillo is an active member of AC1
Committees 201, Durability of Concrete; 21 1, Proportioning Concrete Mixtures;
232, Fly Ash and Natural Pozzolans in Concrete; and 363, High Strength
Concrete.
--``,`,-`-`,,`,,`,`,,`---
INTRODUCTION
The variable effects of ASTM ( I ) C 618 Class C fly ashes concerning the
sulfate resistance of concrete are well-documented, Several authors (2, 3, 4, 5)
have made advances toward understanding the aspects of fly ash chemistry and
mineralogy which determine whether a fly ash improves or decreases the
sulfate resistance of concrete.
With an interest in increasing the use of fly ash derived from coals in the
western states, some researchers have directed their energies toward improving
the sulfate resistance of concrete containing non-sulfate-resistant Class C fly
ash. These efforts for producing sulfate-resisting fly ash concrete have
typically involved changing the proportions of concrete ingredients. For
example, studies have examined the possibility of compensating for chemical
durability problems with decreased concrete permeability by decreasing mixing
water contents (5) or by increasing total cement plus fly ash contents (6).
These methods have typically resulted in delayed deterioration at best.
Some researchers (7, 8) have also examined the possibility of increasing

the percent replacement of cement by Class C fly ash. With replacements as
high a 50 percent by mass, these mixtures have in general been non-sulfate-
resistant. More specifically, increasing fly ash contents from 35 percent to 50
percent for both Type I cement and Type V cement concrete worsened their
resistance to sulfate attack (7).
In the present study, improvement is attempted by chemical means. The

authors believe that increasing the sulfate and alkali contents in certain Class C
fly ash/Type II cement concrete mixtures may improve their sulfate resistance.
The sulfate and alkali contents of these fly ashkement mixtures were increased
by dissolving anhydrous sodium sulfate in the concrete mixing water.

A C 1 SP-153 VOL*I 95 IObb2949 0521113 bTb M
This research was conducted to develop a method for improving the

sulfate resistance of concrete containing high-calcium fly ash. The results
demonstrate some benefits of using a relatively inexpensive chemical
admixture: anhydrous sodium sulfate. Since the admixture may be dissolved
in a portion of the mixing water, it may be easily applied to concrete
containing either interground fly ash cement or fly ash added as a mineral
admixture. This research offers a small contribution toward increased potential
use of high-calcium fly ash in concrete.
BACKGROUND
In the mid-I 970's, Dunstan ( 2 ) began an investigation to evaluate the

performance of concrete containing fly ash from power plants in the western
United States. These relatively new power plants were burning lignitic and
subbituminous coals and, therefore, were producing fly ash of a different
composition than the traditional Class F fly ash from bituminous coal.
Relative to the Class F fly ashes, these new fly ashes generally showed
less SiO,, AI,O,, and Fe,O, on chemical analysis. The new fly ashes generally
contained more Cao, SO,, and Na,O equivalent. In 1977, ASTM C 618 was
revised to cover these new fly ashes as Class C.
One of the more disturbing conclusions from this study was that when
Class C fly ashes were used in concrete, they had variable effects on the sulfate
resistance of Type II-cement concrete. Dunstan developed a Resistance Factor
(R-Factor) to quantify the potentially harmful behavior of the fly ashes:
R=(C-5)/F, where C and F are the bulk chemical C a 0 and Fe,O, values of fly
ash, respectively.
As is evident from the R-Factor equation, Dunstan's fly ashes were more
apt to decrease sulfate resistance as their C a 0 value increased. He attributed
this behavior to the tendency for the high-calcium fly ashes to contain
crystalline compounds of calcium and relatively large proportions of calcium
aluminosilicate glass. Both of these constituents had a tendency to contribute
to the formation of sulfate-susceptible hydration products. Dunstan also found
that fly ashes were less apt to be harmful to sulfate resistance as their Fe,O,
values increased. The iron was believed to promote the formation of iron-rich
ettringite, which has been shown to cause minimal expansions ( I O).
In the early 198O's, P.K. Mehta (4) considered both the chemistry and
mineralogy of fly ash in his explanation of the variable effects of fly ash on the
sulfate resistance of hardened cement paste. He correlated fly ash composition
with both the mineralogy of fly ashkement hydration products and the
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOL*I 95 m Ob62949 052LLL4 532 M
performance of hardened paste in a sulfate environment. Mehta replaced a

Type I cement with fly ash at levels of 25 percent and 40 percent by mass.
Testing consisted of immersing hardened cement paste cubes (12.7 mm) in
4 percent sodium sulfate solution and monitoring their compressive strengths.
The 11 Class C fly ashes included in Mehta's study had variable effects on
the sulfate resistance of Type I cement paste. Of interest to the present study
were three Class C fly ashes derived from lignitic coals which had either
"satisfactory" or "excellent" effects on sulfate resistance. Even though the bulk
chemical C a 0 values of these fly ashes ranged from 19.2 to 25.0 percent, they
improved the sulfate resistance of Type I cement paste cubes. Mehta attributed
the sulfate resistance of the Class C fly ashkement mixtures to their tendency
to form ettringite prior to sulfate exposure. Ettringite remains stable in the
presence of additional sulfate ions. Each of the three Class C fly ashes which
performed well contained greater amounts of SO, and Na,O equivalent than is
permitted by ASTM C 618 mandatory and optional chemical requirements,
respectively. Their unique compositions may have contributed to their
beneficial effects on sulfate resistance.
EXPERIMENTATION
Materials
The commercially available ASTM C IS0 Type II cement and both the
clinker and gypsum used for its production were obtained from a plant in
Texas. An abbreviated physical and compositional analysis is shown in
Table I . Its tricalcium aluminate content of 6.00 percent is typical for
commercially available ASTM Type II cements. The cement producer also
provided compositional data for the cement clinker, including 0.8 percent SO,
and 0.7 percent Na,O equivalent.
All five fly ashes were derived from Wyoming subbituminous coals and
were obtained from power plants in Texas. Each fly ash conformed to the
requirements for ASTM C 618 Class C, as shown by their physical and
compositional data in Tables 2 and 3.
The fly ashes have been arbitrarily labeled CI through CS. Fly ash C4
contained the lowest amount of calcium oxide at 23.1 percent, as shown in
Table 3. Fly ash CS contained the highest amount of calcium oxide at
33.9 percent. Fly ash C2 contained the lowest amount of crystalline material at
--``,`,-`-`,,`,,`,`,,`---
14.4 percent, as shown in Table 4, while fly ash CS contained the highest
amount of crystalline material at 38.5 percent. The average composition of
amorphous phases within fly ashes CI through C3 was similar, as shown in
Table S. Relative to fly ashes CI through C3, fly ash C4 contained a low

A C 1 SP-153 V O L W I 95 IObb2949 0521115 479 I
amount of calcium in its glassy phases and fly ash C5 contained a low amount
of silica in its glassy phases.
The concrete sand was a natural river sand with a fineness modulus of
approximately 3.0. The sand met ASTM ( I ) C 33 grading requirements and is
known not to be reactive with alkalies. The coarse aggregate was a crushed
limestone used commercially in ready-mix concrete. It had a 19.0-mm nominal
maximum size and met the grading requirements for ASTM C 33 No. 6
aggregate.
Procedures
For each fly ash source, two types of concrete mixtures were produced:
one in which fly ash was added as a mineral admixture at the time of batching
concrete and one in which the fly ash was interground in producing blended fly
ash cement. For both methods of including fly ash, fly ash replaced 35 percent
of the cement by volume.
Prior to producing blended fly ash cements, the Type II cement was
reproduced in the laboratory by grinding cement clinker and gypsum in a steel
ball grinding mili. A grinding time of 135 minutes in the laboratory ball mill
was determined as that which produced a cement of similar fineness as the
plant-produced cement, as shown in Table 6. A clinker/gypsum mass ratio of
20 in the laboratory yielded a sulfur trioxide content similar to the plant-
produced cement. Knowing the sulfur trioxide contents of both the clinker and
the cement, the gypsum was determined to be approximately 96 percent pure.
As a final check of the similarity between the laboratory-produced cement

and the plant-produced cement, compressive strengths of 76 by 152-mm
(3 by 6-in) cylinders were compared after 28 days of moist curing, as shown in
Table 6. During subsequent fly ash cement blending operations, the grinding
time and the clinker/gypsum ratio for the Type II cement portion of the blends
remained constant. As the ball mill was charged, 35 percent of the volume of
cement clinker and gypsum was replaced by fly ash.
Concrete mixtures had a cement factor of 307 kg/m3 and a slump of 150
to 180 mm. The amount of mixing water required to achieve the desired
slump was monitored and reported as a water to (cement + pozzolan) ratio.
Laboratory mixing of concrete was performed according to ASTM (1) Standard
C 192. When sodium sulfate was required as an admixture, the anhydrous
chemical was dissolved in the mixing water.
All concrete specimens were demolded within 24 to 36 hours after casting

and were immediately placed in a 23 OC, 100 percent relative humidity
moisture cabinet. All compressive strength testing was performed with two
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0bb2949 0523336 305
replicates of 76 by 152-mm specimens. All tests were performed at loading

rates of 0.14 to 0.34 MPa per second, in accordance with ASTM ( I ) C 39.
The permeabilities of hardened concrete mixtures were evaluated by their

resistance to the flow of chloride ions in saturated pores, following procedures
of AASHTO T277 (1 1). Each concrete mixture was tested after 13 days and
90 days of moist curing. The results of each test are reported as the average
permeability of three replicate specimens from 102 by 204-mm cylinders.
Sulfate exposure testing generally followed the procedures outlined by The

United States Bureau of Reclamation Standard 4908 (12). Sulfate exposure
specimens consisted of concrete cylinders of dimensions 76 by 152 mm, with
about one-third of a 19 mm long stainless steel gage stud protruding from each
end. The gage studs allowed for monitoring the lengths of specimens. As a
modification to USBR procedures, sulfate exposure specimens remained in the
moisture cabinet until companion cylinders reached strengths of 24 MPa, at
which time exposure was initiated.
Sulfate exposure for all mixtures involved continuous soaking of four

concrete cylinders in a ten percent sodium sulfate solution. Changes in the
sulfate concentration of the exposure solution were monitored indirectly
through pH measurements. The solution was replaced whenever its pH
exceeded 10.0. Minimum and maximum time spans between solution
replacement, independent of pH, were set at two weeks and six months,
respectively.
Sulfate attack on concrete may manifest itself either as rapid expansion or

as mass loss with delayed expansion, depending on the chemistry of
cementitious materials, permeability of concrete, and sulfate exposure
conditions. These two manifestations of deterioration are demonstrated by the
two Class C fly ash concrete mixtures in Fig. 1. The mixture that contained
35% Class C fly ash exhibited rapid expansion, while the mixture that
contained 25% Class C fly ash exhibited mass loss with delayed expansion.
After two years of exposure, the 25 percent Class C fly ash mixture had only
expanded an amount similar to the Type II cement mixture. However, its mass
loss at two years was an indicator of reduced long-term sulfate resistance. A
mixture that contained 35% Class F fly ash is also included in Fig. 1 to show
adequate resistance to sulfate attack.
As part of a larger study, approximately 60 concrete mixtures were used to

determine exposure test duration and procedure requirements. These mixtures,
which included both ordinary cements and fly ash cements, were exposed to
the ten percent sodium sulfate solution for four years. A test duration of two
years was judged to be adequate to provide accurate comparisons between the
long-term sulfate resistance of blended fly ash cement concrete and Type II
cement concrete, as long as both linear expansion and mass loss were
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 75 IObb2747 052LLL7 2 Y 1 I
considered. Mass loss could be ignored only if the test duration was at least
three years. With interest of keeping test durations as short as possible, the
two-year option was chosen.
A parameter termed Sulfate Susceptibility Rating (SSR) was developed to

serve as a tool for quantifying the sulfate resistance of concrete, as measured
by the two-year exposure test. The SSR accounts for deterioration in the forms
of both expansion and mass loss. It also provides for direct comparisons of
sulfate susceptibility with Type II-cement concrete.
The SSR for any fly ash concrete which did not fracture or lose mass
within the two-year exposure period was calculated as a ratio of linear
expansions:
linear expansion (%) of mixture i
SSRI =
linear expansion (%) of control Type II cement concrete
The maximum SSR attainable by expansion was defined as 2.0. The SSR for
any fly ash cement concrete that either lost mass or fractured within the two-
year test duration was also defined as 2.0. This value was chosen simply to
identify the mixtures as being much more susceptible to sulfate attack than
Type II cement concrete, that had an SSR equal to 1.0.
Eauivalent Tricalcium Aluminate Contents
The objectives of this study included examining the relative proportions of

calcium aluminates, sulfates, and alkalies in blended fly ash cements and
examining the effects of these constituents on sulfate resistance. Therefore, a
method for quantifying each of these constituents in fly ashkement blends was
required. Sulfates in both cement and fly ash were quantified as sulfur
trioxide, as determined by chemical analyses. Alkalies in the form of sodium
and potassium oxides, present in both cement and fly ash, were quantified as
molar mass equivalent Na,O: %Na,O + 0.658 x %K,O. Calcium aluminates
in cement were quantified as tricalcium aluminate (C,A) since C,A in cement
is largely responsible for its susceptibility to sulfate attack. Quantifying
calcium aluminates in fly ash was more difficult due to the complex nature of
the fly ash crystalline and glassy phases.
Based on a review of available mineralogical data for high-calcium fly

ash, approximately one-third of the bulk chemical alumina was estimated to be
present as part of reactive calcium aluminate phases (6). These phases include
calcium-modified aluminosilicate glass, crystalline tricalcium aluminate, and
sodalite structures. One-third of the bulk chemical alumina contents were then
converted to "equivalent tricalcium aluminate contents" with the molar mass
ratio of C,A/Al,O, (= 2.65), as shown in Table 7.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 V O L * I 95 = 0662949 052111B
Since estimates of Na20 equivalent, SO,, and C,A (or C,A equivalent) for
the Type II cement and each of the fly ashes were available, these same
compositional characteristics could be calculated for the fly ash cements, as
shown in Table 8. These compositional characteristics apply to both
interground fly ash cements and "fly ash cements" that involved adding fly ash
as a minerai admixture at the time of batching concrete. For each fly ash
cement, the approximate ratio of SO, to equivalent C,A was 0.3.
The mass percentages of Na,O equivalent, SO,, and C,A equivalent were
also calculated for various levels of sodium sulfate admixture, as shown in
Table 9. In addition to mixing each fly ash concrete without the chemical
admixture, each was remixed with six levels of the sodium sulfate in order to
produce total SO, to equivalent C,A ratios of approximately 0.4, 0.5, 0.6, 0.7,
0.9, and i . i .
RESULTS
A complete summary of results is available in Table 10, however the

following discussion presents a portion of results. When similar trends were
observed for several fly ash concrete mixtures, the results for one or two
mixtures were selected and displayed as support for the discussion.
Mixing water requirements were compared on the basis of the water to

(cement + pozzolan) ratio needed to attain the desired slump of 150 to
180 mm. Relative to Type II-cement concrete, concrete containing fly ash
cements required approximately the same amount of mixing water, as seen in
Fig. 2 and 3. There was not a substantial difference between the mixing water
requirements of concrete containing blended fly ash cement and concrete
including fly ash as an admixture. Sodium sulfate admixture generally
decreased mixing water requirements, although these effects were small and
unpredictable.
The trends observed relative to the compressive strength of concrete were

similar for each of the five fly ashes included in this study, so the results for
fly ash C4 are presented as typical. Relative to Type II-cement concrete,
mixtures containing fly ash C4 as an admixture and no sodium sulfate
admixture exhibited lower 3-day and lower 28-day compressive strengths, as
shown in Fig. 4(a). Adding sodium sulfate to these concrete mixtures
increased the strength gained in the first three days of moist curing, but did not
significantly affect the strength gained between 3 days and 28 days. In terms
of both 3-day strengths and 28-day strengths, the optimum SO, to C,A
equivalent ratio was in the range of 0.6 to 0.9.
Relative to adding fly ash C4 as an admixture, intergrinding the fly ash

with cement clinker and gypsum significantly increased both the 3-day and the
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 = 0662749 052LLL9 014
28-day compressive strengths, as shown i n Fig. 4. Adding sodium sulfate to

these blended cement concrete mixtures was generally not beneficial for
strength. A slight increase in early-age strength gain was typically
--``,`,-`-`,,`,,`,`,,`---
accompanied by a slight decrease in strength gain between 3 days and 28 days.
Fly ashes C4 and C5 were used to examine both the effects of fly ash and
sodium sulfate admixture on the permeability of hardened concrete. After two
weeks of moist curing, the permeability of concrete containing interground fly
ash cement without sodium sulfate admixture was equal to or greater than the
permeability of Type II cement concrete, as shown in Fig. 5. After 3 months
of moist curing, the permeability of concrete containing interground fly ash
cement without sodium sulfate admixture was significantly less than the
permeability of Type 11 cement concrete. The addition of approximately 4 to
5 percent sodium sulfate admixture by mass of blended fly ash cement
decreased significantly the permeability of concrete that had moist-cured for
two weeks, as shown in Fig. 5 . After 3 months of moist curing, the
permeability of these concrete mixtures were comparable with the fly ash
cemcnt mixtures without sodium sulfate admixture.
The trends i n resistance to sulfate attack were similar for concrete

containing each of the five fly ashes, so the results for fly ashes C4 and C5 are
presented as typical. Concrete containing these fly ashes without sodium
sulfatc admixture were significantly more susceptible to sulfate attack than
Type II cement concrete, as shown in Fig. 6 and 7 . The addition of 2 to
5 percent sodium sulfate admixture produced fly ash cement concrete which
was less susceptible to sulfate attack than Type II cement concrete. This was
true both for mixtures in which fly ash was added as an admixture and for
mixtures which included interground fly ash cement. l n terms of minimizing
susceptibility to sulfate attack, the optimum SO, to C,A equivalent ratio was in
the range of 0.5 to 0.6.
As the SO, to C,A equivalent ratio of the blended fly ash cements
approached unity, the susceptibility of concrete to sulfate attack became higher
than that of a similar concrete containing Type II cement without fly ash.
Under these conditions, it is likely that excessive sulfate was available
internally, after the fly ash cement concrete had hardened. Therefore, the
concrete was subjected to a form of internal sulfate attack manifested by
expansion.
Relative to mixtures in which fly ash was added as an admixture, mixtures

containing interground fly ash cements were more receptive to improved
resistance to sulfate attack. The intergrinding process may have improved the
ability of fly ash to react with sodium sulfate while the concrete was fresh.
The improved reactivity may have resulted from a change in the particle size
distribution of fly ash and/or a change in the degree of particle dispersion.

A C 1 SP-153 VOL*I 75 0662947 0521120 8 3 6
The composition of the fly ashes also seemed to affect the receptiveness of
concrete to improved resistance to sulfate attack. For example, relative to
concrete containing fly ash C5, concrete containing fly ash C4 was resistant to
sulfate deterioration under a wider range of SO, to C,A equivalent ratios.
Relative to fly ash C5, fly ash C4 contained a lower bulk calcium oxide
content and was more amorphous.
SUMMARY
The use of Class C fly ash in concrete is often limited by the susceptibility
of the hardened concrete to deterioration in sulfate environments. In this study,
the sulfate resistance of hardened concrete containing Type II cement and high-
calcium fly ash was improved by using anhydrous sodium sulfate as a chemical
admixture during mixing operations. The Type II cement was replaced by
Class C fly ash at a level of 35 percent by volume. Sodium sulfate was
incorporated into the mixture by dissolving it in the mixing water.
In order to quantify the relationship between sulfates and reactive calcium

aluminates in fly ash cement, an "equivalent tricalcium aluminate" content was
calculated for each fly ash. This calculation involved the simplifying
assumption that approximately one-third of the bulk alumina, as reported in
chemical analyses of high-calcium fly ash, exists as a component of either
crystalline or amorphous reactive calcium aluminates. Optimum resistance to
sulfate-related deterioration was achieved when the SO, to C,A equivalent ratio
of fly ash cement was in the range of 0.5 to 0.6. Relative to mixtures in
which fly ash was added as an admixture, interground fly ash cements were
particularly receptive to improvements in their resistance to sulfate attack.
Although all the fly ash cements responded to the sodium sulfate admixture,
the fly ash which seemed least receptive to improvements included relatively
high proportions of both bulk calcium oxide and crystalline material.
At optimum SO, to C,A equivalent ratios for the fly ash cements, the
corresponding alkali contents were in the range of 2 to 3 percent by mass.
These elevated alkali contents seemed to increase the reactivity of the high
calcium fly ashes, perhaps by facilitating the dissolution of their amorphous
phases. The increased reactivity of fly ash was made apparent by both
increased compressive strength of fly ash concrete at 3 days and decreased
permeability of fly ash concrete at two weeks.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 E 0662949 0 5 2 1 1 2 1 7 7 2 =
ACKNOWLEDGEMENT
The authors wish to thank the Texas Department of Transportation and the
Federal Highway Administration for the funding of the research study
presented herein.
REFERENCES
I. American Society for Testing and Materials, Annual Book of ASTM

Standards, 1991.
2. Dunstan, E.R., "A Possible Method for Identifying Fly Ashes That Will
Improve the Sulfate Resistance of Concretes," Cement. Concrete. and
Aggregates, American Society for Testing and Materials, Vol. 2, No. 1,
1980, pp. 20-30.
3. Manz, O.E., McCarthy, G.J., Dockter, B.A., Swanson, K.D., Johansen,

D.M., and Steinwand, S.J., "Sulfate Resistance of Lignite and
Subbituminous Fly Ash Concrete: Test Results and Proposal for an
Improved R-Factor," Presented at the Katharine and Bryant Mather
Symposium on Concrete Durability, AC1 SP-100, 1987, 19 pp.
4. Mehta, P.K., "Effect of Fly Ash Composition on Sulfate Resistance of

Cement," AC1 Journal, American Concrete Institute, Vol. 83, No. 6, 1986,
pp. 995- 1000.
--``,`,-`-`,,`,,`,`,,`---
5. Tikalsky, P.J. and Carrasquillo, R.L., "Influence of Fly Ash on the Sulfate
Resistance of Concrete," AC1 Materials Journal, Vol. 89, No. 1, American
Concrete Institute, 1992, pp. 69-75.
6. Freeman, R.B., "Optimization of the Physical and Compositional

Characteristics of Fly Ash Cement for the Production of Sulfate-Resistant
Concrete," Ph.D. Dissertation, The University of Texas at Austin, 1992,
498 pp.
7. Day, R.L. and Konecny, J., "Resistance of Fly Ash Mortars to Sulphate
Attack in a Controlled Environment," Flv Ash and Coal Conversion Bv-
Products: Characterization. Utilization. and Disposal VI, Materials
Research Society Symposia Proceedings, Vol. 178, Materiais Research
Society, 1990, pp. 2 i 7-233.

A C 1 SP-153 V O L * I 95 m 0662947 0521122 609 m
8. Joshi, R.C., Day, R.L., Langan, B.W., and Ward, M.A., "Engineering
Properties of Concrete Containing High Proportions of Fly Ash and Other
Mineral Admixtures," Fly Ash, Silica Fume. Slan. and Natural Pozzolans
in Concrete, Proceedings, Second International Conference, Spain,
American Concrete Institute, SP-9 i , i 986, pp. 1-23.
9. Dikeou, J.T., "Fly Ash Increases Resistance of Concrete to Sulfate Attack,"

Bureau of Reclamation, Water Resources Technical Publication, Research
Report No. 23, 1976, 16 pp.
10. Kalousek, G.L. and Benton, E.J., "Mechanism of Seawater Attack on

Cement Pastes," Proceedings, American Concrete Institute, Vol. 67, 1970,
pp. 187-191.
1 I . American Association of State Highway and Transportation Officiais,

"Rapid Determination of the Chloride permeability of Concrete", AASHTO
T277-83, Standard Suecifications for Transportation Materials and Methods
of Sampling and Testing, 14th Edition, 1986.
12. United States Bureau of Reclamation, "Length Change of Hardened

Concrete Exposed to Alkali Sulfates," USER Report No. 4908, 1986, 3 pp.
--``,`,-`-`,,`,,`,`,,`---
TABLE 1 - PHYSICAL AND COMPOSITIONAL ANALYSES RESULTS

FOR ASTM TYPE II CEMENT
Percent bv Mass I Blaine *
54.0 21.8 6.00 9.74 2.97 0.63 3350

A C 1 SP-153 V O L J I 95 IObb2949 0521123 545 I
TABLE 2 - PHYSICAL CHARACTERISTICSOF ASTM CLASS C FLY

ASHES
Retained Pozzolanic Water

Density Soundness Shrinkage
45 pm Sieve Acitivity Reqm't
(Mg/m3) @) Index (%I (%) (9%)
15.1 95.6 .O45 .o02 90.7

!:6
2.70
13.2
18.9
94.4
91.6
.O05
.O32
.O10
-.O07
89.0
89.9
I I I
22.0 102.1 -.O04 -.O06 92.4
10.4 91.5 .IO0 -.O05 88.2
--``,`,-`-`,,`,,`,`,,`---
Note: Tests were performed in accordance with ASTM (1) C 204 and C 311 procedures.
Pozzolanic Activity Index: determined with portland cement at 28 days
Soundness - autoclave expansion
Shrinkage - increase in drying shrinkage of mortar bars at 28 days
TABLE 3 - BULK CHEMICAL COMPOSITIONS OF ASTM CLASS C

FLY ASHES
1 I
Percent by Mass
Na,O Loss on
SO, A120, Fe20, Ca0
A"zh "7 equiv. ignition
Note: Tests were performed in accordance with ASTM ( I ) C 114 and C 311 procedures

A C 1 SP-353 V O L x I 95 Obb29LIq 0523324 483 W
TABLE 4 - MINERALOGICAL COMPOSITIONS OF ASTM CLASS C

FLY ASHES
Percent by Mass * I
I Ah I I I I I Mw I Qz I I I I
1.11Ash As C,A Hm Lm MI Mu So Sp 0th Total
--``,`,-`-`,,`,,`,`,,`---
qfq-+
I
C4
l
1.0
I
0.0
I
1.9
2.0 3.5
-3.3
I
3.1
I 0.6 I
I
5.1
6.1
I
1
0.6
I 0.3' "
0.5 I I
2.4 21.7 I
C5 II 2.9 I 2.6 I 2.3 1.8 I 2.5 I 3.4 2.4 I 4.5 I 7.2 I 2.7 1.3 I 4.9 II 38.5 II
* estimated by x-ray diffraction analysis: Ah=anhydrite, As=alkali sulfates,
C,A=tricalcium aluminate, Hm=hematite, Lm=lime, MI=melilite, Mu=mullite, Mw=merwinite,
Qz=quartz, So=sodalite structures, Sp=ferrite spinel, Oth=other
TABLE 5 - GLASS COMPOSITIONS OF ASTM CLASS C FLY ASHES
II II Percent bv Mass * II
Na 2O Total
FeP, Ca0 so3 equi", Other **
3.7 22.8 1.5 1.6
3.3 24.4 i .6 1.1
4.5 24.5 1.6 1.7 3.6
3.6 19.7 1.5 2.0 I .4

2.0 24.1 0.9 0.4
* estimated by subtracting the oxide compositions of crystalline phases from the bulk oxide
compositions of fly ashes
** crystalline material + amorphous material + loss on ignition = 100%

--``,`,-`-`,,`,,`,`,,`---
TABLE 6 - COMPARISON OF LABORATORY-PRODUCEDAND

PLANT-PRODUCED TYPE II CEMENTS
Blaine Air Retained

Production Density
Strength *
Plant 7.5 3.10 2.97 30.3

Laboratory 11.3 3.06 3.00 32.8
* compressive strength of two 76 by 152-mm cylinders at 28 days
TABLE 7 - EQUIVALENT TRICALCIUM ALUMINATE CONTENTS OF

HIGH-CALCIUM FLY ASHES
Total Alzo, as Equivalent

Fly Ash A1203 Reactive C-A C,A
(%) (%I * (%) **
22.9 7.63 20.2
19.9 6.63 17.6
22.2 7.40 19.6
22.4 7.47 19.8
20.2 6.73 17.8
* one-third of the total Ai,O,

** 2.65 x (Alzo, as reactive GA), where 2.65 = molar mass ratio, C,A/Al,O,

A C 1 SP-153 VOL*I 95 I0662949 0521125 318
168 Freeman and Carracquillo
TABLE 8 - COMPOSITIONS OF FLY ASH CEMENTS

--``,`,-`-`,,`,,`,`,,`---
* based on a cement replacement of 35 percent by volume

** Type II cement partially replaced by Class C fly ash
t C )A equiv. + SO + Na *O equiv. = 100%
Note: Tricalcium aluminate and sulfur trioxide contents of Type II cement were 6.0 percent
and 3.0 percent, respectively.

A C 1 SP-153 V O L X I 95 0662949 0521127 190
TABLE 9 - ALKALI, SULFATE, AND TRICALCIUM ALUMINATE

CONTENTS OF TYPE Il CEMENT CONTAINING CLASS C FLY ASH
AND SODIUM SULFATE ADMIXTURE
--``,`,-`-`,,`,,`,`,,`---
* percent by mass of cement

** Na,O equiv. + SO, + C,A equiv. = 100%

A C 1 SP-153 V O L X I 95 m Obb2949 0521128 O27 m
TABLE 10 - SUMMARY OF RESULTS

--``,`,-`-`,,`,,`,`,,`---
* fly ash replacement for Type II cement at a level of 35% by volume

** sodium sulfate admixture (percent by mass of cement)
t percent linear expansion
tt age at initiation of mass loss (days)

A C 1 SP-153 VOL*I 95 Ob62949 0 5 2 1 1 2 9 Tb3
--``,`,-`-`,,`,,`,`,,`---
TABLE 10 (CONT’D.) - SUMMARY OF RESULTS
* fly ash replacement for Type II cement at a level of 35% by volume

** sodium sulfate admixture (percent by mass of cement)
t percent linear expansion
tt age at initiation of mass loss (days)

A C 1 SP-153 VOL*I 95 = 0662949 0521130 7 8 5
172 Freeman and Carracquillo
0.4 1
n
0.3
o
*g 0.2
W
a 1 I
//
8
.s
Cement concrete
35% class F Fiy Ash

d o
I
O 200 400 600 800 loo0 1' 30
Duration of Exposure (days)
(a)
O 200 lo00
--``,`,-`-`,,`,,`,`,,`---
400 600 800 1 00

Duration of Exposure (days)
(b)
Fig. l-Representative behaviors of concrete in 1O percent

sodium sulfate solution, including: a) linear expansion;
and b) net mass change

A C 1 SP-353 V O L X I 95 = 0662949 0521331 b13
1.o
I 0 35% Class C fly ash by volume
(5 fly ashes added as admixtures)
i2 0.81
slump = I50 to 180 mm
O
N I
L
a
8 0.6-
I 8 m o
pi
c
+ 8
$ *5 0.4-
--``,`,-`-`,,`,,`,`,,`---
E
3 0.2- no sodium sulfate admixture
Type II cement concrete
0.0 0.2 0.4 0.6 0.8 1.0 1.2
s o 3
C3A equiv.
Fig. 2-Mixing water requirements for concrete in which

fly ash was added as mineral admixture
0 3.5% Class C fly ash by volume
M
8 0.8
f3N slump = 150 to 180 mm
zfz
* 0.6-
3 0.4-
E
6 0.2-
no sodium sulfate admixture
Type II cement concrete
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
s o 3
C 3 A equiv.
Fig. %Mixing water requirements for concrete containing
interground fly ash cement

A C 1 SP-153 VOL*I 95 m Obb2949 0521132 5 5 8 m
II cement concrete (3 days)
0.3 0.4 0.5 0.6 0.7 0.9 1.1

so3
C3A equiv.
--``,`,-`-`,,`,,`,`,,`---
ii cement concrete (28 days)

Type ïi cement concrete (3 days)
no sodium sulfate admixture
bD
5 50
40
0
-2 30
rn
rn
& 20
0 10
u 0
0.3 0.4 0.5 0.6 0.7 0.9 1.1
so3
C,A equiv.
(b)
Fig. 4-Compressive strengths of concrete containing
Fly Ash C4: a) added as admixture; b) interground

A C 1 SP-153 V O L U I 95 m 0662949 0521133 4 9 4 m
"
14 90
Duration of Moist Curing (days)
Fig. &Rapid chloride ion permeability of concrete
containing interground fly ash cement
4
bD
CI
.i( pe II cement concrete
Y
$Y 3
.&
z
0
w
:
v1
o 1
Y
(d
2
1
v1
o
0.3 0.4 0.5 0.6 0.7 0.9 1.1
so3
C3A equiv.
--``,`,-`-`,,`,,`,`,,`---
Fig. €&Sulfate susceptibility of concrete containing

Fly Ash C4 and various levels of sodium sulfate admixture

A C 1 SP-353 VOL+I 95 W 0662949 0523334 320
--``,`,-`-`,,`,,`,`,,`---
0.3 0.4 0.5 0.6 0.7 0.9 1.1

$03
C3A equiv.
Fig. 7-Suifate susceptibility of concrete containing Fly

Ash C5 and various levels of sodium sulfate admixture

A C 1 SP-153 VOL*I 95 E 0662949 0521135 267 E
SP 153-10
Influence of Particle Size

Distribution on the
Effectiveness of Type-F Fly Ash
in Suppressing Expansion Due
to Alkali-Silica Reactivity
by M. A. Bérubé, A. Carles-Gibergues,
J. Duchesne, and P. Naproux
SvnoDsis: The effectiveness of fly ash (FA)in suppressing concrete expansion

due to alkali-silica reactivity (ASR) is thought to be largely affected by its particle
size distribution and composition, in particular the glass and alkali contents. This
study is particularly concerned with the effect of particle size. A low-alkali type-F
fly ash was screened to obtain different size fractions (>65 pm, <22 pm, and <11
Fm). The fly ash was also ground to obtain different Blaine fineness, from 3 100
(natural fly ash) to 8800 cm2/g. The activity index of the various fly ash samples,
including the b u k fly ash, was determined on mortar samples made with 25% F A
by mass as cement replacement. The effectiveness of the same samples was
investigated through the Accelerated Mortar Bar Method ASTM C 1260 (or CSA
A23.2-25A), in the presence of a well known alkali-silica reactive aggregate from
Canada, a siliceous limestone (Spratt Quarry, Ottawa, Ontario), at a 30% cement
replacement by mass. High performance concrete was also made with the same
FA samples at a 25% cement replacement level, using a high range water-reducing
admixture (HRWRA), with an alkali-silica reactive aggregate from France
(Tournesis quarry), then stored in air at 100%relative humidity and 60°C. Such
an accelerated expansion test is currently under investigation in France to test the
potential for ASR expansion of job concrete mixtures. This study indicated that,
irrespective of the procedure used to get a finer sample (screening or grinding),
the finer the fly ash under investigation, the higher its activity index and the
greater it! effectiveness in suppressing expansion due to ASR.
Keywords: Accelerated tests; alkali aggregate reactions; concretes;

expansion; flv ash; limestone; mortars (material); particle size
distribution; tests
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L X I 95 D O b b 2 ï Y î 052LL3b L T 3
178 Berube et al
I
Dr. Marc-André Bérubé is professor in the Department of Geology and
Geological Engineering, Laval University, Sainte-Foy, Québec, Canada. A
member of the Centre de Recherche Interuniversitaire en Béton (CRIB
Sherbrooke-Laval), he is particularly involved in the field of alkali-aggregate
reactivity, dealing with aggregate characterization, reaction mechanisms,
preventive measures and repairs.
Dr. André Carles-Gibergues is professor in the Département de Génie Civil,
Institut National de Science Appliquée, Université Paul Sabbatier, Toulouse,
France. A member of the Laboratoire des Matériaux de Construction, his research
work mostly deals with performance of fly ash in concrete.
Dr. Josée Duchesne is presently a postdoctorate fellow in the Department of Earth
Sciences, University of Waterloo, Waterloo, Ontario, Canada. She is currently
studying the role of mineral admixtures in the presence of alkali-silica reactive
aggregates, particularly the reaction mechanisms involved.
Dr. Pierre Naproux is engineer at Electricité de France and he obtained recently a
Ph.D. degree in the Département de Génie Civil, Institut National de Science
--``,`,-`-`,,`,,`,`,,`---
Appliquée, Université Paul Sabbatier, Toulouse, France. He is currently studying
the effect of particle sizing and grinding on performance of fly ash in concrete.
INTRODUCTION
Fly ashes (FA) can suppress expansion due to alkali-silica reaction (ASR)
in concrete provided that they are used in sufficient amounts, Le. at least 20% to
30% by mass as cement replacement, and their alkali content is not higher than 4
to 5% Na20eq (1,2). Their effectiveness against ASR is attributed to: i), alkali
reduction and consequent pH decrease in the concrete pore solution, as a result of
formation of low CIS cement hydration products which can entrap much more
alkalies than hydrates from ordinary portland cements (3), and 21, likely also in
part to the lower permeability of FA concrete, which reduces the migration rate of
aikali ions towards the reactive aggregate particles.
The chemical composition and the pozzolanic activity of fly ash particles
depend largely on their size. For instance, a number of previous studies have
shown that: I), the alkalies are more abundant both in the coarsest and the finest
size fractions (4),and 2), the finer the particle size, the higher the pozzolanic
activity, regardless of the process used to increase the fineness (5,6).
This study was undertaken in order to establish if increasing the fineness,
for instance by grinding or selective sorting, may improve the effectiveness of
low-alkali type-F fly ash in suppressing expansion due to ASR in addition to
increasing the pozzolanic activity and the strength.

A C 1 SP-153 V O L X I 95 .
I0662949 0523337 03T .
I
MATERIALS AND METHODS

Material Preparation and Characterization
Cements -- Three cements were used in this study. Two type I Canadian
cements A and B were used in accelerated expansion tests on mortar bars, and one
French HPR cement (early high strength cement quite similar to a type III portland
cement) was used for accelerated expansion tests on high-performance concrete
prisms. Table 1 shows the characteristics of the cements, where Rcld, Rc2d,
Rc7d, and Rc28d are the characteristic strengths, in MPa, obtained after 1, 2, 7,
and 28 days, respectively, for mortar samples made with a cement : aggregate :
water ratio of 1 : 3 : 0.5, in accordance with the AFNOR NF P15-301 standard.
Preparation of Flv Ash Samples -- Ail FA samples tested in this study and
given in Table 2 were prepared from the same initial fly ash batch. The original fly
ash sample is noted BA for «bulk ash». Samples G12 and G8 were prepared by
grinding the original ash such as to get 90% of the material smaller than 12 pm
and 8 pm («d90»), respectively. The three other samples tested were obtained by
selective screening; the finest samples F22 and F11 have 90% of their particles
smaller than 12 pm and 8 pm, respectively, while the coarsest sample C65 has
90% of its particles coarser than 65 pm.
Size Distribution and Chemical Comoosition of Flv Ash Samoles -- The
size distribution obtained by laser measurement and the chemical composition of
each FA sample are shown in Fig. 1 and Table 2, respectively.
Specific Surface of Fly Ash Samoles -- The Blaine specific surface of each
FA sample is also given in Table 2. However, the flowing time was too short to
be measured in the case of C65; the corresponding value given in Table 2 was
calculated assuming particle sphericity.
--``,`,-`-`,,`,,`,`,,`---
Pozzolanic Activitv of Flv Ash Samples -- The standardized activity index

«IN» indicated in Table 2 corresponds to the ratio between the 28-day strength of
a mortar sample containing 25% FA as cement replacement by mass, and made
with a water : (cement + fly ash) ratio of 0.5 (W/C+FA), and the equivalent
strength of a control mortar without fly ash (W/C = 0.5). The modified activity
index «ILL» is determined on control and blended mortar samples containing the
HPR cement, 1.5% of a high range water-reducing admixture (HRWRA) (on a
dry basis), and with water added to obtain a constant workability of 12 seconds
using the «maniabilimeter» developed in France at the Laboratoire Centrai des
Ponts et Chaussées (LCPC). As a result, the W/C+FA varied from 0.30 to 0.35
from one sample mortar to another.
Expansion Tests on Blended Mortars and Concretes

Accelerated mortar-bar and concrete-prism expansion tests were used in
this study for determining the effectiveness of the various FA samples in
suppressing expansion due to ASR.

A C 1 SP-1-53 V O L r I 95 m 0662949 0523338 T ï b m
180 Berube et al
Accelerated Mortar-Bar Method in NaOH at 8OoC-- Since first proposed in

South Africa by Oberholster and Davies (7) for testing aggregates for alkali-silica
reactivity, the accelerated mortar-bar method, where mortar bars are immersed in a
1N NaOH solution for two weeks, has been extensively used all over the world
for determining the potential reactivity of concrete aggregates (8). A slightly
modified method has been recently included in the ASTM (C 1260) and CSA
(A23.2-25A) standards. The method was also used with success for determining
the effectiveness of pozzolans and slags in suppressing expansion due to ASR,
using a 14-day, 0.1% expansion limit criterion for the acceptance of blended
mixtures (9-12).
The aggregate used in this study is a highly alkali-silica reactive limestone
from the Spratt Quarry (Ottawa, Ontario, Canada). This aggregate contains large
amounts of reactive microcrystalline quartz. The expansion tests have been
performed with two different cements and two different alkali contents, Le. with
cement A (1.05% Na20, ) increased to 1.25% Na20eq by adding NaOH to the
mixing water (first serie$, or with cement B (0.89% Na20eq) without alkali
addition (second series). For comparison, one set of control mortar bars (without
fly ash) has been prepared and tested in both series of tests. Cement A was used
with FA samples BA and G12; cement B was used with the other FA samples.
Mortar bars were made in accordance with ASTM C 1260 or CSA A23.2-25A,
using a W/C+FA of 0.5, and with 0% (controls) or 30% as cement replacement
by mass of all above FA samples.
Accelerated Concrete-Prism Method in Air at 100% Relative Humiditv and
-- This accelerated method where concrete prisms are stored in air over water
at 60°C and =loo% relative humidity, is in the process of being adopted as a
standard in France for testing the performance of job concrete mixtures with
respect to ASR, without any modification to the concrete proportions or to the
alkali content. The test is also proposed for evaluating the performance of
particular cement-pozzolan or cement-slag combinations in the presence of alkali-
--``,`,-`-`,,`,,`,`,,`---
reactive aggregates. A 2-month, 0.02% expansion limit criterion has been

proposed for acceptance of concrete mixtures after comparison with the standard
concrete prism method AFNOR NF P18-587, where the prisms are stored in air
over water at 38°C and =loo% RH (13).
In the present study, the performance of all FA samples was evaluated in
the presence of the reactive siliceous limestone from the Toumesis quarry, which
is proposed as a reference reactive aggregate in France. Concrete prisms were
made with the Toumesis limestone coarse aggregate and a non reactive sand, the
HPR cement, 1.5% melamine-based HRWRA by mass of cementitious materials,
0% (controls) or 25% FA as cement replacement by mass, and with a fixed
cementitious content (cement + fly ash) of 475 kg/m3. The W/C+FA varied from
0.30 to 0.35 from one mixture to another in order to maintain a constant
workability. In fact, all concretes tested corresponded to high-performance
concretes that were considered for the construction of a particular bridge viaduct.
All other specifications related to the preparation of the concrete specimens,
storage conditions and measurements are described in the AFNOR NF P18-587
standard.

A C 1 SP-153 VOL*I 95 W Ob62949 0 5 2 3 3 3 9 902
RESULTS AND DISCUSSION

Chemical Comaosition of Flv Ash Samales
The chemical composition is the same for the original (BA) and the ground
--``,`,-`-`,,`,,`,`,,`---
(G12, G8) fly ash samples since the only change is physical due to grinding (see
Table 2). The only differences between these samples concern the pozzolanic
activity index IN, and are totally attributed to variations in particle size (or specific
surface). The higher the specific surface, the higher the activity index as a result
of better filling and greater surface area for exchange between the cement paste
and the FA particles. On the other hand, the samples obtained by screening have
different compositions. As previously observed (4), the finest fraction F11 ( < i l
p) and the coarsest fraction C65 (%5 p) contain slightly more alkali (Na20 )
than the bulk ash (sample BA). Fig. 2 shows the alkali percentage in the fly a%
under study as a function of particle size. Similar alkali distributions with particle
size have also been observed by Electricite de France (EDF) for a number of type-
F fly ash.
However, all FA samples tested in this study contain a low-alkali content
(1.29% to 1.47% Na20eq), and the differences from one sample to another are
relatively small such as they should not induce «per se» significant changes
regarding ASR. However, the use of cements with different alkali contents in the
accelerated mortar-bar tests, i.e. 1.25% and 0.89% Na20eq for cement A and B,
respectively, could have a greater influence on the expansion results obtained in
these tests.
Pozzolanic Activity of Flv Ash Samdes

As expected, the finer the FA sample, the higher the pozzolanic activity
indices IN and ILL (see Table 2), whichever the method used for reducing the
sample fineness (grinding or screening). The results for IN are all under unity,
which indicates that the addition of fly ash reduces the 28-day strength. However,
the mortars made with HRWRA and a low W/C+FA, and incorporating aii refined
FA samples G12, G8, F22, and F11, show a higher strength than that of the
corresponding control mortar (Le. ILL > 1).
One can also observe that the use of a low W/C+FA and HRWRA resulted
in a higher activity index (i.e. ILL > ïN) at least with the two fine FA samples
G12 and F11, with the reverse for the coarsest ones C65 and BA (Le. ILL e IN)
(see Table 2). The results for C6.5 and BA are however not surprising since both
activity indices IN and ILL do not correspond to mechanical strengths but rather
to the ratio between two strengths (blended mortar/control mortar). The control
mortar used when measuring the index ILL and made with a lower W/C+FA has a
much higher strength than the other control used for obtaining IN.
However, the comparison of the two activity indices IN and ILL obtained
for a given FA sample may indicate if this sample is more appropriate for use in
normal concrete ( i t . when IN > ILL) or in high-performance concrete (i.e. when
IN < ILL) (14). Moreover, the standard index IN is more realistic for correlation
with the results of the expansion tests on mortars, which were also made with a
W/C+FA of 0.5, while the modified index ILL will be used for comparison with

the results of the expansion tests on high-performance concretes, which were also
made with 1.5% HRWRA, 25% fly ash as cement replacement by mass, and a
low W/C+FA ranging from 0.30 to 0.35.
Results of ExFansion Tests on Mortar and Concrete Samiiles

-
Accelerated Tests on Mortar-Bars in IN NaOH at 80°C -- Despite

significantly different alkali contents in both series of tests, the expansion
obtained after 14 days were exactly the same for the two corresponding controls,
i.e. 0.325% and 0.323%, respectively. This confirms that the expansion results in
the accelerated mortar-bar method are quite insensitive to the mortar alkali content;
however, in the absence of pozzolan or slag, and provided that the alkali content
--``,`,-`-`,,`,,`,`,,`---
remains between reasonable limits (10, 12, 15). It is recommended that the alkali
content of all bars be controlled to 1.25% Na20eq of the cement mass when
testing pozzolans and slags (10, 12). The greater influence of the initial aikali
content on mortar-bar expansion, in the presence of pozzolan or slag, is explained
by the lower permeability of the blended mortar mixtures compared to control
mortars, since equilibrium between the pore solution and the 1N NaOH
immersion solution is not achieved within the testing period of 14 days (12).
The results shown in Fig. 3 indicate that 30% of each FA sample, except
for the coarsest sample C65, is effective in suppressing expansion due to ASR,
and can reduce expansion below the proposed limit of 0.1% after 14 days.
However, the expansion with C65 is just over the limit for acceptance, which is
not so bad considering that the reactive aggregate used is very reactive. Moreover,
it is clear from these results that reducing the fineness of the fly ash, by grinding
or screening, results in lower expansion and higher effectiveness against ASR
than with the bulk ash (BA).
Accelerated Tests on Concrete-Prisms in Air at 100% Relative Humidity
and 60°C -- As shown in Fig. 4, the results obtained for the high-performance
concrete specimens incorporating 25% FA as cement replacement by mass are in
line with those above for mortar samples, with the highest expansion obtained
with the coarsest ash C65, and the lowest expansion observed with the finest ash
G8. However, an important difference between the two types of expansion tests
performed in this study concerns the fact that all concretes, even the control,
satisfied the 2-month, 0.02% expansion limit criterion first proposed in France for
acceptance of concrete mixtures with regards to ASR (13), despite Lhe presence of
an aggregate that is also considered in France as very reactive.
However, these results are easy to explain considering that all concrete
specimens were made with a low-alkali cement (0.65% NasOeq) and a low-alkali
fly ash (1.29% to 1.47% Na20q), for a total alkali content of only 3.1 kg/m3
Na20q for the control, and between 3.9 and 4.1 kg/m3 Na20, for the blended
concretes. Moreover, the total effective alkali content is only 2.3 kg/m3 Na20q
for the FA concretes when ignoring the alkalies in the ash. Recent studies have
indicated that fly ashes with less than 3 to 4% Na20eq do not contribute aikali to
the concrete pore solution, and entrap a large fraction of the alkalies from the
cement (2, 3, 16). In the recent modifications to the CSA A23.1 and A23.2
standards regarding AAR and associated test methods, the Canadian Standard
Association specifies that the aikali content of fly ashes containing less than 4.5%

A C 1 SP-153 VOL+I 95 I O662949 0521141 560
Na2OWbe ignored in the calculation of the total (effective) concrete alkali content,
and the concrete mixtures be accepted for which the other constituents
(cement, ...) do not contribute more than 3.0 kg/m3 NazOeq It is interesting to
note that the control concrete tested in this study is just under the 2-month, 0.02%
expansion limit criterion proposed in France for concrete acceptance, while its
total and effective alkali content is very close to the limit of 3.0 kg/m3 Na2Oeq
proposed for concrete acceptance by CSA as well as many other agencies.
Based on the above results, the accelerated concrete prism method
performed in air at ~ 1 0 0 %relative humidity and 6OoC looks of interest in
particular because it allows evaluation of job concrete mixtures without any
modification to concrete proportions and alkali content. However, based on recent
work, it seems that the test duration will be increased to 3 months for the majority
of rock types and to 5 months for others whose the nature is not completely
defined, using the same expansion limit criterion for acceptance (0.02%).
However, using the new proposed limit of 0.02% expansion, after 3 months (90
days), the control concrete tested in this study would be just at the limit, with all
blended concretes incorporating the fly ash tested of any size being accepted (Fig.
4).
, )
Comaosition and Activity
Mortar Expansion and Flv Ash Fineness -- Fig. 5 presents the expansion
data obtained after 14 days in the accelerated mortar-bar method as a function of
the Blaine specific surface of the FA fraction used in the blends. This figure
clearly shows that the finer the FA fraction obtained by screening, including the
bulk ash which falls between C65 and F22 in size, the lower the expansion
(empty symbols). Recall that all blended mortars were made using a fixed
W/C+FA of 0.5, therefore the results do not take account for the lower
permeability that could be obtained in practice for concrete blends incorporating --``,`,-`-`,,`,,`,`,,`---
HRWRA.
The fly ash sample ground to pass a 12-pm sieve (G12) may appear less
effective than the fly ash size fraction screened to pass an 11-pm sieve (F1l),
which presents about the same specific surface. At first, this could be related to
the fact that many fly ash particles are constituted by an outside layer of
amorphous and more reactive glass covering a more crystalline and less reactive
internal core (17, 18, 19); these particles are broken during grinding (G12), while
not by screening ( F l l ) , then a greater proportion of the exposed surface area
corresponds to crytalline material. However, the mortars made with G12 and BA
are the only blended mortars that were made with cement A, which is significantly
richer in alkali (1.25% Na20e after NaOH addition) than the other cement B
(0.89% Na20eq) used for all other blends, while recent results indicated that the
initial alkali content is more critical when testing pozzolans and slags in the
accelerated mortar-bar method (10, 12). If all blends had been made with the
cement increased to 1.25% Na20e , as suggested (10, 12), the expansion
obtained with fly ash samples C65, j22, F11 and G8 would likely have been
slighly higher, however, again much lower than the O. 1% expansion limit for the
last three FA samples. The correlation then obtained would have been even better
than in Fig. 5. In other words, at equivalent alkali content, the fly ash fineness

A C 1 SP-353 V O L * I 95 Obb2949 0523342 4 T 7 9
184 Bérubé et al
seems to be the most important factor which influences the effectiveness of a

fly ash against ASR, while the procedure used to modify the fineness is
considered less critical.
The overall good correlation between fly ash fineness and expansion in the
accelerated mortar-bar method where specimens are immersed in an alkali-rich
NaOH solution, is related to the fact that coarser particles react more slowly,
therefore consume less rapidly the alkali ions that remains available for ASR for a
longer time in the pore solution.
Mortar ExDansion and Flv Ash ComDosition -- The variations in
expansion observed from one mortar blend to another cannot be explained by
variations in the alkali content (1.29% to 1.47% Na20eq) of the various FA
samples tested, nor by variations in the sulfate content (0.44% to 0.61% SOS),
which contents are both low and not very different from one sample to another. In
fact, one cannot observe any correlation between: i), expansion and alkali
content, and 2), alkali content and sulfate content. A correlation may appear
between mortar expansion and sulfate content, for the various size fractions
obtained by screening, including the bulk ash. However, this correlation is an
artefact which results from the excellent correlation between sulfate content and
fineness (see Table 2). This point is supported by the other fact that the expansion
greatly varies for the samples obtained by grinding, for which the chemical
composition is exactly the same and which only differ in fineness.
Concrete Expansion and Flv Ash Activitv Index -- Fig, 6 presents the
expansion obtained after 2 months in the accelerated concrete-prism method as a
function of the modified pozzolanic activity index ILL. Again, a good correlation
is observed between concrete expansion and pozzolanic activity. This is not
surprising considering that a more reactive fly ash, i.e. with a higher activity
index, normally produces pozzolanic hydration products in greater amounts
andlor more rapidly, therefore entraps the alkali ions in greater amounts and/or
more rapidly. However, in the present study, the main difference between the
various samples tested concerns fineness, such as an excellent correlation would
be observed on a graph showing the activity index as a function of fineness, in
accordance with the following mechanisms:
IN PRESENCE OF A FINER FLY ASH:
pozzolanic reaction products are more rapidly produced
and portJandite is more rapidly consumed;
strength increases more rapidly;
there is a hipher activitv index;
alkali ions are entrapped in pozzolanic reaction products,
then decrease more rapidly in the pore solution;
pH decreases more rapidly in the pore solution;
alkali-silica reaction is reduced;
exDansion due to ASR is reduced.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 75 I0bb2747 0 5 2 1 1 4 3 333
On a graph of activity index as a function of fineness, one would observe

that the ground sample G12 (ILL = 1.00) presents a modified activity index lower
than the screened sample F11 (ILL = 1.20), despite a similar specific surface (see
Table 2). As for mortar expansion, which was also higher for G12 than for F1 1,
this could be explained by the fact that a greater proportion of the GI 2 particles
(or of their total exposed surface) may correspond to crystalline material, which
may indicate in turn that screening gives better results than grinding, for materials
with similar specific surface.
The clear correlation observed in the present study between expansion and
fly ash fineness holds in our case because all samples presented similar alkali
contents, In fact, as recently demonstrated, the effectiveness of pozzolans and
slags, including fly ash, is mostly related to the alkali content rather than to the
activity index. Indeed, the less effective fly ash tested by Duchesne and Bérubé
(1, 2) in presence of two very reactive aggregates was the one with the highest
pozzolanic index (more portlandite consumed), but the one with the highest alkali
content. Evenmore, the higher pozzolanic activity of this particular fly ash is
mostly attributed to its higher alkali content, which results in a higher pH in pore
solution, which in turn promotes pozzolanic reaction between portlandite and
reactive fly ash particles.
CONCLUSION
The main objective of the present study was to determine if the process of
increasing the fineness of a given type-F fly ash, which contributes to increase its
pozzolanic activity, may also contribute to increase its effectiveness in
suppressing concrete expansion due to ASR. The answer is clearly positive
whatever the procedure used to obtain a finer material. In this respect, grinding
the fly ash appears a little less beneficial than screening it to obtain a size fraction
of the same specific surface. The original fly ash that was investigated in this
study is a low-sulfate and a low-alkali type-F ash. The conclusions from this
study could not hold for other fly ashes with different compositions. In particular,
a high-alkali fly ash should not be effective in suppressing expansion due to ASR,
whatever its fineness, even if its activity index should still increase when
increasing fineness.
ACKNOWLEDGEMENTS
The work reported in this paper is part of a larger research program
conducted in France on the beneficiation of fly ashes for use in concrete. This
program has been financially supported by the CEMETE, a division of Electricité
de France (EDF), through a research contract between the CIFEREE and the
Laboratoire des MatCriaux de Construction of the Institut National de Science
AppliquCc, Université Paul Sabbatier, Toulouse. The IMGM of the Ecole des
Mines of Ale& is also acknowledged for the preparation of the fly ash samples
tested in this study.
--``,`,-`-`,,`,,`,`,,`---

REFERENCES
1. Duchesne, J., and Bérubé, M.A., "Effectiveness of Supplementary
Cementing Materials in Suppressing Expansion Due to ASR: Another Look
at the Reaction Mechanisms - Part 1: Concrete Expansion and Portlandite
Depletion," Cement and Concrete Research, Vol. 24, No. 1, 1994, pp. 73-
82.
2. Duchesne, J., and Bérubé, M.A., "Effectiveness of Supplementary
Cementing Materials in Suppressing Expansion Due to ASR: Another Look
at the Reaction Mechanisms - Part 2: Effect of the Pore Solution Chemistry,"
Cement and Concrete Research, Vol. 24, No. 2, 1994, pp. 221-230.
3. Duchesne, J., and Bérubé, M.A., "Effect of Supplementary Cementing
Materials on the Composition of Cement Hydration Products," Advanced
Cement Based Materials, 1994, on press.
4. Naproux, P., "Micronisation des cendres volantes," Internal Report,
Ele6tricité de France, 1991.
5 . Carles-Gibergues, A., and Vaquier, A., "Influence du broyage sur la
rkactivité d'une cendre volante," Revue des Matériaux de Construction, No.
1, 1985.
6. Tanaka, H., Wignarajah, S., Sugimoto, K., Ukila, K. and Ishii, H.,
"Characteristics of Concrete Incorporating Sorted Fly Ash," Proc. 4th
CANMET/ACI Int. Conf. on Fly Ash, Silica Fume, Slag and Natural
Pozzolans in Concrete, Istanbul, Turkey, AC1 SP-132, 1992, pp. 971-985.
7. Oberholster, R.E., and Davies, G., "An Accelerated Method for Testing the
Potential Alkali Reactivity of Siliceous Aggregates", Cement and Concrete
Research, Vol. 16, 1986, pp. 181-189.
8. Bérubé, M.A., and Fournier, B, "Accelerated Test Methods for Alkali-
Aggregate Reactivity," Advances in Concrete Technology, V.M. Malhotra
ed., CANMET/EMR, Ottawa, Canada, 2nd ed., 1993, pp. 991-1044.
9. Davies, G., and Oberholster, R.E., "Use of the NBRI Accelerated Test to
Evaluate the Effectiveness of Minerai Admixtures in Preventing the Alkaii-
Silica Reaction," Cement and Concrete Research, Vol. 17, No. 1, 1987, pp.
97- 107.
10. Berubé, M.A., and Duchesne, J., "Evaluation of Testing Methods for
Assessing the Effectiveness of Mineral Admixtures in Suppressing
Expansion Due to Alkali-Aggregate Reaction," Roc. 4th CANMET/ACI Int.
Conf. on Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete,
Istanbul, Turkey, AC1 SP- 132, 1992, pp. 549-575.
11. Duchesne, J., and Bérubé, M.A., "An Autoclave Mortar Bar Test for
Assessing the Effectiveness of Mineral Admixtures in Suppressing
Expansion Due to AAR," Proc. 9th Int. Conf. on AAR in Concrete, The
Concrete Society, London, U.K., 1992, pp. 279-286.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0 0662949 052L145 106
--``,`,-`-`,,`,,`,`,,`---
12. Bérubé, M.A., Duchesne, J., and Chouinard, D., "Why the Accelerated
Mortar Bar Method is Reliable for Evaluating the Effectiveness of
Supplementary Cementing Materials in Suppressing Expansion Due to
Alkali-Silica Reactivity," Cement, Concrete, and Aggregate, to be published
in the issue of June 1995.
13. Bollotte, B., "Mise au point d'un essai de performance d'un béton vis-à-vis
de l'alcali-réaction," Proc. 9th Int. Conf. on AAR in Concrete, The Concrete
Society, London, U.K., 1992, pp. 110-116.
14. Naproux, P., "Les microcendres (cendres volantes traitées) et leurs emplois
dans les bétons hydrauliques," Ph.D. thesis, INSA-UPS, Toulouse, 1994,
286 pp.
15. Hooton, R.D., "Interlaboratory Study of the NBRI Rapid Test Method and
CSA Standardization Status," In: Canadian Developments in Testing
Concrete Aggregates for Alkali-Aggregate Reactivity, Ministry of
Transportation of Ontario, Downsview, Canada, Report EM-92, 1990, pp.
225-240.
16. Duchesne, J., and Bérubé, M.A., "Available Alkalies From Supplementary
Cementing Materials," AC1 Materials Journal, Vol. 91, No. 3 , 1994, pp.
289-299.
17. Carles-Gibergues, A., "Les ajouts dans les microbetons: influence sur
l'auréole de transition et sur les propriétés mécaniques," Ph.D. thesis, INSA-
UPS, Toulouse, 198 I.
18. Hulett, L.D., and Weinherger, A.J., "Some Etching Studies on the
Microstructure and Composition of Large Aluminosilicate Particles in Fly
Ash from Coal Burning Power Plants," J. American Chemical Society, Vol.
14, No. 8, 1980.
19. Hernmings, R.T., and Berry, E.E., "On the Glass Coal Ashes: Recent
Advances," Mat. Res. Soc. Symp. Proceedings, Vol. 113, 1988, pp. 3-38.

A C 1 SP-153 VOLaI 95 = 0662949 052LL46 042
188 Bérube et al
TABLE 1 - CHARACTERISTICS OF CEMENTS
OXIDE or
PHASE í%) HPR A B
20.22 20.40 20.90
4.99 5.45 4.92
2.70 2.46 2.37
64.39 63.04 63.55
1.48 2.49 2.04
1.26 2.79 2.67
0.90 1.14 0.97
0.06 0.25 0.25
NayOq 0.65 1 .o0 0.89
so1 3.30 3.02 2.9 1
Loi 2.11 0.96
Insoluble Residue 1.20
c3s 65.00 52.78 55.13
c2s 8.95 18.67 18.34
C3A 8.65 10.29 9.03
c4AF 8.21 7.47 7.21
BLAINE(cm2/g) 4800 3500
~~~
STRENGTH (MPa)]
Rcld ~26.00
Rc2d 40.60
Rc7d 54.80
Rc28d 65.00
l: Measured on morta n accordance with AFNOR 1 7 P15-301.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 0662949 0521147 T ô 9 =
TABLE 2 - PHYSICAL AND CHEMICAL CHARACTERISTICS OF FLY

ASH SAMPLES
OXIDE or ,Y ASE iAMpL

PHASE (%) C65 BA F22 G12
Si02 57.10 56.60 57.20 56.60
30.80 3 1.30 32.60 3 1.30
5.30 5.80 4.50 5.80
3.42 2.89 2.75 2.89
0.84 0.73 0.70 0.73
1.98 1.78 1.76 1.78
O. 17 O. 14 0.14 0.14
1.47 1.31 1.29 1.31
0.61 0.55 0.46 0.55
3.20 2.62 2.70 2.62
58.30
420
- 59.00
58.80
5690
3100
58.80
6800
IN (standard)
ILL (modified)
0.57
0.37
0.77
0.7 1 1.04
0.79
1.o0
0.84
1.20 I 1.22
-
loo j=xY- F22
1oo lo1 102

Particle si72 (pn)
Fig. 1-Particle-size distribution of each fly ash sample

tested (laser measurements)
--``,`,-`-`,,`,,`,`,,`---

9--4
- 1
Avera e content
--``,`,-`-`,,`,,`,`,,`---
IA
O,O I I I I I I I
-
13' I I I I I I
Fig. 2-N%0 (A) and 40 (B) contents in each

size fraction of bulk fly ash tested (Sample BA)

A C 1 SP-153 VOL*I 95 I0662949 0521149 ô51 I
Accelerated Mortar Bar Method
I
(Immersion in 1N NaOH at 80°C)
0.35 I
+control
jl
0.30 -+I-- C65
+BA
h
8 0.25 ---H-~~~
W
-+- G12
Em
.r(
0.20 +
G *a
a
x
0.15
w
0.10
0.05
0.00
O 2 4 6 8 10 12 14
Time (days)
Fig. %Expansion results in accelerated mortar-bar tests
Accelerated Concrete Prism Method

(Storage in air at 100% R.H. and 60°C)
O 30 60 90
Time (days)
--``,`,-`-`,,`,,`,`,,`---
Fig. 4-Expansion results in accelerated concrete-prism tests

A C 1 SP-153 V O L + I 95 = Ob62949 0521150 573
192 Berube et al
h 0,12
fi
4 0,lO
, .
e,
Y
0,08
id
0,06
so
v
I r
I I . I I
0 3000 6OOo 9 m
Specific surface (cm2/g)
--``,`,-`-`,,`,,`,`,,`---
Fig. &Fourteen-day expansion results in accelerated

mortar-bar tests as function of fly ash fineness
(specific surface)
0,0035
W '
0,O 0,2 0,4 0,6 0,8 1,0 1,2 1,4
Modified activity index (ILL)
Fig. 6-Two-month expansion results in accelerated

concrete prism tests as function of fly ash-
modified activity index

A C 1 SP-153 V O L U I 95 0662947 0521151 4 0 T
SP 153-11
Expansive Cement Produced from

AFBC Ash by Alkali Sulphate
Activation Approach
by W. Jiang and D. M. Roy
Svnopsis: This paper presents the results of exploratory experiments using

AFBC ash to produce a new kind expansive cement. The principles for design of
the compositions and theoretical consideration are discussed. The tests were
carried out to examine the XRD pattern and the pozzolanic activity of the the
AFBC ash used. The expansive properties of this cement and its effects on
--``,`,-`-`,,`,,`,`,,`---
porosity, pore structure, heat evolution, setting time, resistance to chemical

attack, leaching effect, and strength of hardened cement paste are analyzed in
detail. A kind of warm-pressed AFBC ash expansive cement product is also
prescnkd. The present results indicated that the sulfoaluminate of AFBC ash can
be used as an expansive component. This kind of expansive cement could be
used to chemically induce compressive stress in the mortar and thereby reduce the
size and amount of shrinkage cracks that frequently occur in portland cement
concrete during drying. The results suggest an economically and environmentally
acceptable approach.
Keywords: Alkali aggregate reactions; chemical attack; expansive

cements; fly ash; hydration; mix proportioning; porosity; pozzolanic
reactions; strength; tests

A C 1 SP-I153 V O L X I 95 I0 6 6 2 7 4 9 0521152 34b
194 Jiang and Roy
W. JIANG is a research assistant in the Materials Research Laboratory at The

Pennsylvania State University, where he is a candidate for the degree of Ph.D. in
the Materials Program under the guidance of Dr. D.M. Roy.
D.M. ROY is a professor of materials science, emerita, with the Materials
Research Laboratory and Department of Materials Science and Engineering at
Pennsylvania State University. Roy was the first to make ultrahigh-strength
cement, has done extensive research on radioactive waste confinement in cement,
is author of some 350 research publications; and is member of the National
Academy of Engineering and recipient of the American Ceramic Society's 1982
Jeppson Medal and Award and the 1987 Copeland Award.
INTRODUCTION
--``,`,-`-`,,`,,`,`,,`---
Two years ago, in Rio de Janeiro 143 nations, including the US., reached a
compromise on a treaty aimed at controlling global warming by reducing
emissions of carbon dioxide and other greenhouse gases. The accord is to be
signed at the United Nations Conference on Environment & Development
(UNCED), popularly called the Earth Summit. One of the most critical
environmental problems we are facing today is acid rain. The main cause is the
burning of fossil fuels, as the result of which sulphuric acid and carbon dioxide
are added to the atmosphere. Atmospheric fluidized-bed combustion (AFBC) is
one of but a few choices that offers a promise to use high sulfur coal, in an
environmentally acceptable manner (i). In this process, a technology which is
now approaching full-scale commercial application, finely-ground limestone and
coal are suspended, or fluidized, in the combustion chamber. Fig 1 shows a
typical AFBC coal boiler (2). The sulfur in the coal reacts with calcium oxide
from the limestone and oxygen to form calcium sulfite; the weight percent of SO3
in the ash is around 10-20 %. This technology generally produces a high volume
of dry waste by-products that differ significantly from those produced in
conventional coal combustion processes. Another major devolopment effort in
advanced pressurized fluidized bed combustion (PFBC) offers several
advantages, and this kind of combustion method make PFBC ash a more valuable
by-product than AFBC ash (3). U S . coal industry officials believe that more
electric utilities would install AF'BC to comply with the Clean Air Act
Amendments of 1990. Also coal officials are hoping a clean coal technology
proposal by the U.S. cement research and development (R & D) community can
provide a solution to the thorny issue of scrubber waste disposal. A wide range
of demonstrations of use AFBC ash is presently underway in the United States
(4,5). These applications include commercial concrete slabs, masonry units for
mine ventilation application, and road base structural layers(6). Commercial-
grade sulfuric acid also is produced in the process. In this paper, a solution that a
new expansive cement can be produced by directly using atmospheric fluidized-
bed combustion (AFBC) ash was offered. An earlier paper (7) reported a
preliminary feasibility test..

A C 1 SP-153 VOL*I 95 0 6 6 2 9 4 9 0521153 282 =
BACKGROUND
Expansive Cement
Mather (8) said: “The problem the maker and marketer of expansive cement
faces is how to convince the cement user that it is to his advantage to have a
cement that expands. The phenomena that make expansive cement expansive are
also phenomena that are well known to be destructive -- and have been so
recognized for a long time.” It has long been known that expansion associated
with ettringite formation (hydrolysis of sulfoaluminate) was responsible for both
deleterious and beneficial phenomena in portland cement concrete. In
unrestrained hardened concrete, ettringite formation can cause cracking by
development of tensile stresses which are frequently high enough to exceed the
tensile strength of concrete. On the other hand, ettringite formation under
restraint can be utilized to develop compressive stresses of either low magnitude
in shrinkage-compensating concrete, or of high magnitude in self-stressing
concrete (9). At the beginning of the 1940s, this positive effect was the basis for
the invention of expansive cement. Expansive cements are used to chemically
induce compressive stress in steel-reinforced concrete and thereby reduce the size
and amount of shrinkage cracks that frequently occur in portland cement concrete
during drying. There are three different types of sulfoaluminate expansive
cements: K, M, and S. Type K expansion is caused by the formation of ettringite
as a result of a chemical reaction of calcium sulfoaluminate, C4A$, with lime,
--``,`,-`-`,,`,,`,`,,`---
gypsum, and water. Type M is based on CA and C12A7 and Type S on C3A
reaction with lime, gypsum, and water to form thecalcium aluminate sulfate
hydrate, ettringite (10). The expansion of cement also can be produced by
hydration of periclase (MgO), the delayed expansive properties of which were
recently studied in detail ( 1 i). However the mechanism of ettringite expansion
has been a subject of controversy. The theories extended to explain the expansion
mechanism include one in which the expansion of concrete is a direct result of
crystallization pressure due to the formation and growth of ettringite crystals( 10).
The other theory proposes that the ettringite which forms as a result of a solution
process and in the presence of lime, exists in a colloidal form which imbibes
water and swells to produce expansion (12). Whether expansion is by
crystallization pressure or swelling/water imbibition, the process can be quite
damaging especially if the duration of expansion is long or the magnitude large.
Damage resulting from the formation of microcracks leads to loss of strength and
increase in permeability. In restrained hardened concrete, ettringite formation can
be utilized to develop compressive stresses and its “self-compaction” effect under
restrained conditions will reduce the porosity and the size and volume of
macropores, which is benefical to improving the physical and mechanical
properties of hardened cement paste. (So may the delayed expansive properties of
MgO be, if not excessive).
The purpose of this study was to ascertain the effect of using the
sulfoaluminate of AFBC ash as an expansive component. The original
hypothesis was that this kind of expansive cement could be used to chemically
induce compressive stress in steel-reinforced concrete and thereby reduce the size
and amount of shrinkage cracks that frequently occur in portland cement concrete
during drying. This experimental investigation intends in turn to demonstrate the
possibility of producing an expansive cement from atmospheric fluidized-bed
combustion ash, with reference to the opening of the new field of utilization of
these interesting by-products, very abundant in the United States. The
sulfoaluminate of this ash can be used as an expansive component.

196 Jiang and Roy
Alkali Sulfate Activation

This experimental investigation intends to produce an expansive cement from
atmospheric fluidized-bed combustion ash by an alkali sulfate activation
approach, which could be categorized as a kind of alkali activation. The principle
of the alkali activation of slag has been known for more than 50 years. In the past
decade worldwide, the increasing interest in this topic has expressed the effort
made by the cement R & D community to meet the challenge of the increasing use
of solid waste and increasingly stringent environmental legislation. The recent
research project in the Materials Research Laboratory shows that the alkaline
activation principle could be employed fully for many kinds of solid waste,
industrial by-products, and some natural resources in the cement and concrete
industry. The benefits of such cement appear to be outweighed by the problems
they could create. There are four main benefits: to produce various energy-
efficient clinkerless cements; to improve the performances of blended very early
high-strength cements; to create relatively greater durability and enhance the long-
term performance; and to use solid waste, industrial by-products and natural
resources to the utmost.
Since the late 1960s, the utilization of elemental sulfur in the building materials
industry has attracted the attention of investors in many countries. One reason is
that cheap sulfur became available in early 1970s following the stringent
application of the new environmental pollution law. One of the distinct
advantages of sulfur concrete is very rapid and high devclopment of strength once
the material has solidified from its molten state. The amount of strength increase
and the speed with which strength is developed, are often much higher than those
obtained in conventional portland cement concrete (14, 15, 16). In the past two
decades, sulfoaluminate cements have been developed extensively in China; now
the annual production is about a half million tons. Expansive and self-stressing
cements are the main species in this series (17). Ettringite is a main hydration
product of sulfoaluminate cement, and now ettringite-based cement has frequently
been found in the literature (18, 19). Sabatelli and Valenti investigated the
influences of alkali sulfate on properties of pozzolanic cernents(20), and Yang and
Scrivener reported the effect of sulfate addition on microstructure development
and expansion of cement paste (21). Research of Manzoori, et al. on inorganic
transformation of low-rank coals with high sodium and sulfur during AFBC is
informative (22). The warm pressed AFBC ash expansive cement products are
similar to those of Jakob and Mortel (23), who provided a German example using
the same type of ash for autoclaved aerated concrete.
MATERIALS AND EXPERIMENTS

Materials
The elemental analysis (wt % oxides) of the AFBC ash for the study is shown
in Table 1 and the chemical composition of cement and granulated blast-furnace
slag are shown in Table 2. The raw material investigated in this experiment was a
kind of AFBC ash in which the weight percent of SO3 was around 16 %. The
ground, granulated blast-furnace slag (30 %) was added as a stabilizer to take up
excess calcium sulfate slowly and bring the expansion to an end. MgO, 1.5 %,
was used as an additional expansive component. Aluminate cement, sodium
sulfate, N a ~ S 0 4and potassium aluminum sulfate, KAI(SO4)2.12H20 (alum)
served as activators. A comparison of the mixtures is given in Table 3.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L + I 95 = 0662949 052LL55 055 =
The pozzolanic activity index of AFBC ash with portland cement was
examined by the method based on ASTM C 31 1. The data compared with the
conclusions based on variation in electrical conductivity of AFBC ash in a
saturated Ca(OH)2 solution According to Luxan et al. (24), the pozzolanic activity
can be estimated using the variation in electrical conductivity. AFBC ash is an
inherently variable material. The variability is due to differences in the inorganic
components of the source coal, in the coal preparation and combustion condition
and in ash collection and handling methods. No two utilities have all of these
factors in common, each plant's AFBC ash is unique; therefore a characteristic
test is necessary.
Mixture proportioning
The composition mixture proportions of expansive cement made from
atmospheric fluidized-bed combustion ash were based on the following concepts.
It is necessary in expanding cements that the formation of calcium sulfoaluminate
should occur at a time when the hardened cement paste has developed some
strength but is still sufficiently extensible to accommodate some limited expansion
without signficant cracking. The formation of calcium sulfoaluminate requires the
presence of calcium, aluminum and sulfate ions in an alkaline environment.
Fly ash can be activated by reaction with a solution with high pH, in that the
bonds in the network structure of glassy fly ash are easily broken and hydration
of the fly ash is promoted (24). However, the alkalis generally used, such as
NaOH, Na2C03, and water glass, et al., are relatively expensive, often
hygroscopic, and potentially harmful in the handling process to the operators.
Neutral salts such as sodium sulfate and potassium aluminum sulfate (alum) are
alternatives which could be used to replace the above species with similar effects,
and are also less expensive as well as less difficult to handle (25). Nevertheless,
in this work, sodium sulfate and potassium aluminum sulfate (alum) have another
important effect that their final reaction product, ettringite, will contribute to the
expansion. Sodium sulfate and alum used in this study were analyzed reagents.
Process
(a) Hydrothermal treatment is a preconditioning step. Jones et al. (4) first
suggested using a preconditioning step (prehydration) of FBC ash in concrete,
which will control heat release and molar volume expansion. In an AFBC, the
limestone completely calcines resulting in a large amount of free lime in the ash.
In a PFBC, the higher partial pressure of CO;! inhibits calcination and this results
in less than 1% of free lime in the ash. The free lime causes cement products
made from PFBC ash to be less prone to the secondary rsactions and cracking
that have plagued AFBC cement products (26). Often dolomite, which has a high
magnesium content, is used as the sulfur sorbent. Magnesium oxide promotes
secondary reactions in cements (3). The hydration of AFBC ash results in
substantial heat generation as a result of the hydration of both C a 0 and CaS04, as
shown in the following equations:
(1) C a 0 (s) + HzO(1) = Ca(OH);!(s) AH" = -64.4 KJ/g-mole
--``,`,-`-`,,`,,`,`,,`---
(2) CaS04(s) + 2H20(1) = CaS04,2H*O(s) AH0 = -17.2 KJíg-mole
In addition, molar volume expansions of 97% and 42% (of the original solid)
occur for reactions (1) and ( 2 ) , respectively. If these reactions were permitted to
proceed uncontrolled in the concrete, severe heat incursions and expansions

A C 1 SP-153 V O L * I 95 H 0662949 0521156 T 9 1 I
198 Jiang and Roy
would occur, causing detrimental effects on the concrete. In this investigation,

AFBC ash with added lime with a waterlsolid ratio 0.5 after a hydrothermal
processing had become a cementitious material. The hydrothermal processing
took place in a vessel at less than 200 "C at saturated steam pressure. The
hydrothermai processing of AFBC ash is based on a solid-liquid or sol-gel
reaction to produce a chemically binding reaction under pressure in a sealed
vessel. So it provides the following advantages: firstly no sulfur is emitted to the
environment; secondly, its cost is relatively low because the reaction takes place at
less than 200 "C.
(b) Wurm-pressing treatment. When applying heat and pressure
simultaneously, strengths an order of magnitude higher than those of normal
cement paste have been achieved previously. Enormous increases in strength
resulted from the removal of most of the porosity and the generation of very
homogeneous, or fine microstructures. Porosities as low as about 1.7% (27)
were achieved; the microstructures were relatively featureless and dense.
Recently this technique was used in an experimental nuclear waste solidification
process. By warm-pressing, the nuclear wastes are solidified with slag and fly
ash to form samples resembling a synthetic rock, aiming at further improvement
in long-term stability and high-volume reduction of the product compared to the
conventional technologies. Advantages of the technique that may arise include the
following: relatively small amounts of water are added to the cement; a uniform
density distribution is obtained; microstructural defects are not introduced.
Experimental Procedures
The warm-pressing experimental set-up is shown in Fig. 2 . This process
skipped the preconditioning hydrothermal step, and was different from that used
before (7). First, all the starting materials were mixed, then the mixtures were
subject to the warm pressing process, at 200 "C and 30 MPa; for 1 hour. The
modified formulation of mixture 1 especially for warm pressing is shown in Fig.
3 . The setting time was measured according to ASTM C 191. The heat evolution
curves of the cements were measured with an isothermal conduction calorimeter
with 0.44 water-to-cement ratio and performed for two days. Mortars were cast
normally, and the compressive strengths of mortars were determined using 50
mm. cube specimens (ASTM C109). The cementitious material : Ottawa sand
ratio was 1: 2.75. The water-to-cement ratio was 0.44. The specimen was
removed from the mold 24 hours after starting the mixture, and immersed in
distilled water at 20 O C ; the compressive and flexural strengths of the specimens
were tested at ages of 1,3, 7, 14,28, and 90 days. Free and restrained
expansion measurements were conducted on small beams having dimension
10x10~40 mm. Expansion strains recorded are an average for 6 replicate
samples. After curing in moisture at 20 "C for 1 day, cement paste prisms for the
free expansion were demolded to measure the original length; the prisms were
then stored in water at 20 OC, up to the predetermined age to measure the length
changes and calculate the expansion percentage of the prisms. While the cubes
were two-dimensionally restrained by the molds, they were held in the mold until
the predetermined ages. Small masses of paste of approximately 2 g. each were
broken off daily from 2 replicate beams for water content and MIP (mercury
intrusion porosimetry) measurements. These samples were washed twice in
acetone to stop hydration, and placed in an oven at 105 "C for two days. Then
they were weighed to determine the evaporable water content, as compared with
the moist state. Samples for MIP were dried in an oven for 7 days before their
pore size distributions were determined.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 06627Y7 052L157 928
Other Tests
(a) DiTusion coeficient measurements. The steady state diffusion test which
was originally set by Hansson and Berke (28) was carried out on the pastes of
the mix listed in Table II; however an ionAnalyzer ORION EA 920 interfaced to a
computer was used by us. Slices of the paste, approximately 3 mm thick were
then cut from the cylindrical specimens and were glued to the neck of a plastic
bottle in the bottom of which a hole was cut. The bottle was then inverted, set on
a rack in a tank containing 1 M NaCI solution saturated with Ca(OH)2 and filled
to the level of the tank solution with a half saturated Ca(OH)2 solution. Four to
six samples of each mix were tested. The amount of chloride diffusing through
the paste slices was determined by periodically measuring the chloride content of
solution in the bottles using a chloride ion-selective electrode. Greater detail of
the test is given elsewhere (29).
(b) Leaching test. The pH of fluids of cement paste is expected to decrease
with time as water leaches out soluble ions or as a result of reaction under
exposure conditions. In each experiment an approximately 10 g sample of
hydrated cement granules was placed in an air-tight, thick-walled polyethylene
container to which a known mass of deionized water was added. Three parallel
experiments, A, B, and C, were carried out. The water was left then to
equilibrate with the solids for one day with gentle agitation on an orbital shaker.
The leachant was then decanted and the process repeated to build up the
relationship between aqueous chemistry and ratio V N o , where Mo is total mass
of anhydrous cement, and V is the total volume of water which has passed
through the cement. Since the ionic strength of the leachate falls as leaching
continues, the quantity of liquid added on each cycle was gradually increased
from SO ml to loo0 ml as the experiments progressed. The pH of each leach
batch was measured. The test is described in greater detail elsewhere (29).
(c) Resistance for chemical attack. The mortar specimens were immersed in
5% Na2S04 solution, and an acetic acid acid solution having 3.0 pH for two
months, after which the compressive strengths were measured.
--``,`,-`-`,,`,,`,`,,`---
RESULTS AND DISCUSSIONS

The Pozzolanic Activitv of AFBC Ash
According to Luxan et al. (24), pozzolanic activity begins when the electrical
conductivity exceeds 0.4 mS/cm, and this limit is reached with AFBC Ash. Fig.
4 shows the correlation between pozzolanic activity index of ASTM C 3 1 1 and
variations in conductivity, similar to Sugita et al. (30). The results of AFBC ash
used by us show the high electrical conductivity, the larger pozzolanic activity
index compared to the reference fly ashes and flue dust. Combined with the
results of ASTM C 31 1, an electrical conductivity exceeding 0.5 mS/cm was
recommended. Fig. 5 gives the XRD pattern of the raw AFBC ash. The main
phases were anhydrite, tricalcium aluminate, hematite, and lime.
Free exnansion behavior
When the expansion of AFBC ash was compared to ordinary portland
cement, it was found to be a signficant value at the 0.65 % level after 7 days. As
expected, this value of expansion will be satisfactory to make an expansive
cement (3 i). The expansion of AFBC ash was compared to ordinary portland
cement. Fig. 7 shows that hardened specimens of AFBC exhibit a 7 day

200 Jiang and Roy
expansion of 0.65 % and that the expansion changes little thereafter; portland
cement shrinks by 0.28%. Two different particle-size distributions were tested,
the finer in size displayed less expansion (Fig 6). Naturally, the hydration
reaction and the corresponding expansion of finely divided particles in the
structure occurred more rapidly while the specimen was in the mold, and
measurements after removal did not exhibit much expansion.
Porositv and Pore-size Distribution
The strength of cementitious materials is strongly dependent on both the total
porosity and the maximum pore size in the materials. Compared with the
cumulative pore volume and pore size distribution of the free expansion sample,
restrained samples show a decreased cumulative pore volume of the paste as can
be expected due to the reduced expansion. It is evident from Table 4 that the total
porosity of the unrestrained mortar of the expansive cement increases when
compared to similar data for the OPC. Meanwhile, the total porosities of the 2-
dimension-restrained cubes are less than those of the unrestrained. This implies
that the unrestrained expansion due to ettringite formation makes the hardened
cement mortars more porous, while the 2-dimension-restrained expansion makes
the mortars more compact, i.e. results in a “self-compaction” in the hcp. The
mercury pore volume vs. compressive strength under restrained condition of
mixure 1 compared to non-activated mixture 3 is given Fig. 8.
Heat Evolution and Products due to Hvdration
The heat evolution attendant to the mixing of the water with solids and the
subsequent reaction were measured and recorded. Fig. 9 shows the rate of heat
evolution at 20 “C. It exhibited an early sharp peak at 20 minutes after reaction,
while the main reaction peak occurs at about 13 hours. It is obvious that setting
happens in the acceleratory period. The rate of heat evolution for expansive
cement is very large within 10 hours at an earlier time of hydration, and then
reduces gradually. The shape of the heat evolution curve for the expansive
cement is similar to that of portland cement, but the second peak on the heat
evolution curve for the expansive cement occurs later than the OPC by 1.5 hours.
At the termination of the calorimetric experiments, microstructural development
was investigated, using scanning electron microscopy. Some properties of this
expansive cement are listed in Table 5. According to X-ray diffraction (7), the
hydration products of 90 days shows that the position of the strongest peak varies
between 0.307 and 0.301 nm, which means that Caz+ ions in C-S-H may be
replaced by Na+ or K+. This is consistent with the fact as reported by Roy (32),
that the composition of C-S-H formed in the AFBC ash expansive cement is
different from that of the ordinary portland cement, containing not only a lower
C/S ratio but also a high alkali content.
Resistance to Chemical Attack

Fig. 10 shows the change of compressive strength of mortar specimens with
AFBC compared with portland cement, obtained by immersion in acetic acid
solution. With added AFBC the compressive strength of mortar is increased in
comparison with the control mortar. This means that the addition of AFBC
makes the mortar more durable to acid attack. When specimens were immersed in
5% Na2S04 solution, for ordinary portland cement the strength decrease by IO%,
while the AFBC expansive cement increases 4.5%. Apparently, Na2S04
continues to develop strength as an alkali activator.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 D 0662749 0521159 ï T O
LeachinE of alkali-activatedcement
A graph of pH as a function of VA40 for alkali-activated cement leached in
deionized water is presented in Fig. 1 1. Also shown are curves predicted from
solution equilibrium data. Atkinsori et al. (33) proposed using pH to estimate the
distribution of hydrated phases or CdSi ratio in the C-S-H system from the
--``,`,-`-`,,`,,`,`,,`---
equilibrium data. More detail has been described in elsewhere (29).

Alkali-activation effect
The alkali-activation effect was measured by the effective diffusion
coefficient. The effective coefficient for steady state diffusion of chlorides
through these pastes was determined from Fick’s Ist. law, and the value of D
(effective diffusion coefficient) is 10-15 m k The values of D for the pastes with
granulated AFBC ash additives are dotted versus the concentration of additive in
Fig. 12 and show a clear trend of de‘creasing diffusion rate with increasing
AFBC.
Warm Dressed Droducts
Photos of the warm pressed experimental set-up and of warm pressed AFBC
expansive cement samples are shown in Fig. 13 and 14. The strength of the
samples, total pore volume and bulk density are listed in Table 6.
CONCLUSION
It is feasible to use AFBC ash in producing an expansive cement, if the value
and rate of the expansion are proper. The present results indicated that the
sulfoaluminate of AFBC ash can be used as an expansive component. This kind
of expansive cement could be used to chcmically induce compressive stress in the
mortar and thereby reduce the size and amount of shrinkage cracks that frequently
occur in portland cement concrete during drying.
The implication is that the increases of the total porosity found in the
unrestrained mortar should be carefully evaluated. Whether expansion is by
crystallization pressure or swelling/water imbibition, the increase of total porosity
can be quite damaging+specially if the duration of the expansion is long or the
magnitude large. Damage resulting from the formation of microcracks will lead to
loss of strength and increase in permeability.
The porosity of the AFBC ash-type expansive cement pastes is different from
portland cement pastes. Unrestrained expansion increases the total porosity in the
mortar. Restrained expansion can produce a “self-compaction” in the mortar,
causing the reduction of total porosity. The results suggest an economically and
environmentally acceptable approach. Exactly how the expansive mechanism
works is not entirely clear, and the stability and durability of this cement need to
be examined further.
ACKNOWLEDGEMENT
The authors acknowledge the partial financial support of NSF Grant MSS
9123239 and EPA Grant No. 819482012. AFBC ash was supplied by the Fort
Drum Cogeneration Plant from N.Y.

A C 1 S P - 1 5 3 V O L X I 95 Obb2949 052LLb0 412
202 Jiang and Roy
REFERENCES
1. Durao, D.F.G., Azevedo, J., Carvalho, M.G., Ferrao, P.,
Moreira, L. and Pereira, J. (1988). Fluidised Bed Combustion of Coals
and Different Types Wastes, in Fluidized Bed Combustor Design,
Construction and Operation, edited by Sens, P.F. and Wilkinson, J.K.
(Elsevier Applied Science Publishers Ltd., Essex, England), pp. 27-36.
2 . Keairns, D.L., Williams, G.C., Georgakis, C. Chrostowski, J.,
Newby, R. and Ulerich, N.H. (1987). Sulfur Emission Control, in
Atmospheric Fluidized-Bed Combustion: A Technical Source Book (National
--``,`,-`-`,,`,,`,`,,`---
Technical Information Service, US. Department of Commerce, Springfield,

VA), pp. 7- 1-7-86.
3. Wheeldon, J.M., Drenker, S.G., Booras, G.S., and McKinsey,
R.R. (1993). An Assessment of Pressurized Fluidized-Bed Combustion
Power Plants. In FBC and AFBC Project and Technology, edited by Boyd,
T.J. and Mahr, D. (The American Society of Mechanical Engineers, New
York), P. 5.
4. Jones, C.E., Bland, A.E., Rose, J.G. and Jarrett, M.N. (1987).
Utilization of Pulverized Fuel Ash and Fluidized Bed Combustion Ash in
AFBC concrete, in Proceeding: Eighth International Ash Utilization
Symposium, EPRI, Vol. II, 55-1-12.
5. Goodwin, R.W. (1993) Combustion Ash? Residue Management: An
Engineering Perspective. (Noyes Publication, Park Ridge, NJ), pp. 28-3 1.
6. Finch, R.C., Salladay, D.G. and Weiss, S.T. (1987). The Proposed
Utilization of Atmospheric Fluidized Bed Combustion Waste in the
Production of Portland Cement and Sulfuric Acid. In Proceedings: Eighth
International Ash Utilization Symposium, EPRI, Vol. II, 40- 1-12.
7. Jiang, W. and Roy, D.M. (1993). New Utilization of Fluidized Bed
Combution Ash with Hvdrothermal Processing, in Proceedings of American
Coal Ash Association 10th International Coal Ash Symposium, Orlando,
Florida, USA, January 17-23, 1993, Vol.I1,74-1-74-11. published by the
Electric Power Research Institute (EPRI).
8. Mather, B. (1980). The Future of Expansive Cement. In Cedric Willson
Symposium On Expansive Cement, SP-64, ACI, Detroit, pp.6.
9. Mikhailov, V.V. and Litver, S.L. (1975). Expansive and Stressing
Cements and Self-stressed Reinforced-Concrete Elements of Construction.
(Russian) Stroiizdat, Moscow, USSR, pp. 5.
10. Lobo, C. and Cohen, M.D.( 199i). Pore Structure Development in Type
K Expansive Cement Pastes," Cement Concrete Research, Vol. 21, pp. 229-
241.
1 1 . Liu, Z., Cui, X. and Tang, M. (1991). Mp.0-Tvpe Delayed Expansive
Cement. Cement Concrete Research, Vol. 2 1, pp. 1049-1057.

A C 1 SP-153 V O L X I 95 E 0662949 0521LbL 359
12. Mehta, P.K. (1973). Mechanism of Expansion Associated with Ettringite

Formation. Cement Concrete Research, Vol. 3, pp. 1-6.
13. Ogawa, K. and Roy, D.M., CdA3S Hydration, Ettringite Formation, and
its Expansion Mechanism: I. Expansion; Ettringite Stability. Cement Concrete
Research, Vol. 11, pp. 741-750, (1981); II. Microstructural Observation of
Expansion. Cement Concrete Research, Vol. 12, pp. 101-109, (1982); III.
Effect of Cao, NaC1; Conclusions. Cement Concrete Research, Vol. 12, pp.
247-256, (1982).
14. Malhotra, V.M. ( 1983). Sulphur concrete and Sulphur-infiltrated
Concrete. In New Concrete Materials, edited by Swamy, R.N. (Surrey
University Press, London), pp. 1-40.
15. Swamy, R.N. and Jurjees, T.A.R. (1986). Stability of Sulphur
Concrete Beams with Steel Reinforcement, J. of Materials and Structure,
Vol. 19, pp. 351-360.
16. Samarai, M.A., Laquerbe, Al-Hadithi, A.( 1965). Sulfur sand mixes
as Building Material. J. of Materials and Structure, Vol. 18, pp. 57-65.
17. Wang, Y. and Su. M. (1993). Third Series Cement in China. In
Proceedings of 3rd Beijing International Symposium on Cement and
Concrete. (Intemational Academic Publishers, Beijing), Vol. III, pp. 116-
121.
18. Brooks, S.A. and Sharp, J.H. (1990). Ettrinizite-based Cements, In
Calcium Aluminate Cement, edited by Mangabhai, R.J. (Chapman and Hall,
London), pp. 335-349.
19. Wu, Z.D. (1993). Sulphoaluminate Cement Hvdrate-Tubular EttrinPite. In
Proceedings of 3rd Beijing International Symposium on Cement and
Concrete. (International Academic Publishers, Beijing), Vol. I, pp. 297-301.
20. Sabatelli, V. and Valenti, G.L. (1980). Influence of Alkali Sulphates
on Setting and Hardening of Pozzolanic Cements. In Proceedings of the 7th
InternatiÖnal Congress on the Chemistry of Cement. Paris, Vol. IV, pp. 256-
260.
21. Yang, R. and Scrivener, K.L. (1993). The Effect of Sulphate Addition
on the Microstructural and Exaansion of Cement Paste. Poster in Conference
on Chemistry and Microstructure of Cement & Concrete, the Institute of
Materials, University of Aberdeen, 13th 8~14thSeptember.
22. Manzoori, A.R. Lindner, E.R. and Agrawal, P.K. ( 1992).
Inorganic Transformation During the Circulatinp Fluidized Bed Combustion
of Low-Rank Coals With High Content of Sodium and Sulphur, in Inorganic
Transformations and Ash Deposition During Combustion, edited by Bensin,
S.A. (United Engineering Trustees, New York), pp. 735-762.
23. Jakob, M. and Mortel, H. (1992). Ashes from Fluidized Bed
Combustion Power Plants as a Potential Raw Material for the Production of
Autoclaved Aerated Concrete. In Advances in Autoclaved Aerated Concrete,
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 PI Obb2949 0521162 295 D
204 Jiang and Roy
edited by Wittmann, F.H. (A.A. Balkema, Rotterdam, Netherlands), pp.

305-3 10.
24. Luxan, M.P., Sanchez deRojas, M.I., Saavedra, J. (1989). Rapid
Evaluation of Pozzolanic Activitv of Natural Products by Conductivity
Measurement. Cement Concrete Research, Vol. 19, pp. 63-68.
25. Jiang, W. and Roy, D.M. (1992). Hvdrothermal Processing of New Fly
Ash Cement, Am.Ceramic Bulletin, Vol. 71, NO. 4.
26. Wu, X., Jiang, W., and Roy, D.M. (1990). Earlv Activation and
Prouerties of Slag Cement, Cement Concrete Research, Vol. 20, pp. 961-
974.
27. Bland, A.E., Jones, C.E., Rose, J.G., and Jarret, M.N. ( 1987).
Production of No-Cement Concretes Utilizing FBC Waste and Power plant
Flyash. In Proc. 9th International1 FBC Conference, (The American Socity of
Mechanical Engineers, New York), Vol. 2, pp. 947-953.
27. Roy, D.M., Gouda, G.R., and Bobrowsky, A. (1972). Very High
Strength Cement Paste PreDared by Hot Pressing and Other High Pressure
Techniaues, Cement Concrete Research, Vol. 2, pp. 375-386.
28. Hansson, C.M. and Berke, N.S. (1989). Chlorides in Concrete. In
Pore Structure and Permeability of CementitiousMaterials, edited by
Roberts, L.R. and Skalny, J.P. (Mater. Res. Soc. Proc. 137,
Pittsburgh, PA), pp. 253-270.
29. Roy, D.M. and Jiang, W. (1994). High-Derformance Cement-Based
Nuclear Waste Forms. In Proceedings of Scientific Basis for Nuclear Waste
Management XVIII, Kyoto, Japan, Octerober, 1994 (in progress).
30. Sugita, S., Shoya, M., and Tokuda, H. (1992). Evaluation of
Pozzolanic Activitv of Rice Husk Ash. In 4th Intl. Conference On the Use of
Fly Ash, Silica Fume, Slag and Natural Pozzolan in Concrete, edited by
Malhotra, V.M. (ACI, SP-132, Detroit), Vol. I, pp. 495-512.
31. You, B.K. and Liu, J. N. (1993). A Studv on Design Parameters of

ExDansive Concrete. In Proceedings of 3rd Beijing International Symposium
on Cement and Concrete. (International Academic Publishers, Beijing), Vol.
III, pp. 803-807.
32. Roy, D.M. (1989). Hvdration. Microstructure, and Chloride Diffusion of
Slag-Cement Paste and MortarsProc. In 3rd Intl. Conference. On the Use of
Fly Ash, Silica Fume, Slag and Natural Pozzolan in Concrete, edited by
Malhotra, V.M. (ACI, SP114, Detroit), Vol. II, pp. 1266-1281.
33. Atkinson, A., Everitt, N.M., and Guppy, R.M.(1989). Time
deDendence of uH in a Cementitious ReDository. In Scient@ Basisfor
Nuclear Waste Management XIZ, edited by Lutze, W. and Ewing, R.C.
(Mater. Res. Soc. Proc. 127, Pittsburgh, PA, 1989) pp.439-446.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 75 Obb2949 0521163 121
TABLE 1 - ELEMENTAL ANALYSIS (WT., PERCENT OXIDES) OF

ASH SUPPLIED BY FORT DRUM
A1203 Ca0 Fe203 K20 MgO Na20 SO3 Si02
12.5 38 6.77 1.13 0.72 0.29 16 23.9
TABLE 2 - CHEMICAL COMPOSITION OF CALCIUM ALUMINATE
CEMENT AND SLAG (PERCENT. WT.)
Si02 Al203 Ca0 Fe203 M& K2O 'Na2Ó so3 LOI
AC 3.28 39.63 37.36 12.79 0.97 --- --- ___ 1.54
Slag 34.70 10.70 39.37 0.41 11.90 0.50 0.25 --- 1.34
TABLE 3 - MIX PROPORTIONS (WT.,

. . PERCENT)
Mix1 Mix2 Mix3 Mix4 Mix5 Mix6 Mix7
AFBC 50 40 50 40 30 20 10
ash
AC* 10.5 10.5 10.5 20.5 30.5 40.5 50.5
Slag 33 30 30 30 30 30 30
Ca0 5 15 5 5 5 5 5
Na2S04 - 2.0 2.0 2.0 2.0 2.0 2.0
Alum - 1 .o 1.o 1 .o 1 .o 1 .o 1.o
MgO 1.5 1.5 1.5 1.5 1 ..5 1.5 1 .s
* AC = high-alumina cement
TABLE 4 - TOTAL POROSITY (PERCENT) OF MORTAR
EXPANSIVE CEMENT AND CONTROL
Sample AFBC expansive cement Ordinary Portland
Cement
--``,`,-`-`,,`,,`,`,,`---
2-dim restrained 14.55 14.28

unrestrained 16.68 14.93
TABLE 5 - PROPERTIES OF EXPANSIVE CEMENT

Specific Fineness Time (hrmin) Comp. Strength (MPa)"
gravity cmUg Setting 3days 7days 28days
Intitial Final
3.17 3500 3:37 5:34 33.2 36.7 42.6
* Standard devation f 8.7 %
TABLE 6 - PROPERTIES OF WARM-PRESSED SAMPLES FOR
VARIOUS MIXES
h4k Bulk density Total pore volumecompressive strength
(gícm3) ("/.I mean (Mpa) range (MPa)
No. 4 2.67 12.23 374 331-393
No. 5 2.75 9.67 427 385-448
No. 6 2.55 10.41 41 1 380-423
No. 7 2.81 10.92 4.5s 438-48 1

A C 1 SP-153 V O L * I 95 06629'49 052Llb4 Ob8
206 Jiang and Roy
--``,`,-`-`,,`,,`,`,,`---
Limestone Feed
Transfer Tubes
Fluidinng Air
Fig. l-Typical atmospheric fluidized-bed combustor (AFBC)

after Pitroio et ai.' redrawn
@ pressure gage
O 0 O 0
sampl inch
0.75~0.75~2.75
Mix 1: at 200 OC,10,000 psi, 1 hour
Fig. 2-Warm pressing experimental setup

A C 1 SP-153 VOL*I 95 Ba 0662949 0521165 T T 4
cement + AFBC ash water mighty 150

--``,`,-`-`,,`,,`,`,,`---
solid:water = 3:l 5% by weight of cement
Fig. &Modified formulation of Mixture 1
'O0 1
0.0 0.5 1 .o 1.5 2.0

variation in conductivity (mS/cm)
Fig. 4-Pozzolanic activity index versus variation in conductivity

A C 1 SP-153 V O L m I 95 0662949 0 5 2 3 3 6 6 930
208 Jiang and Roy
CPS
Ah Ah Anhydrite
CA Tricalcium Aluminate
Hm Hematite
Lm Ca0
41.
20 30 $0 50 SO
20 (CuKa)
(Anhydrite-CaS04, Tricalcium Aluminate-Ca3Al206, Hematite-FezO3)
Fig. 5-XRD pattern of AFBC ash
.-
8
g
v>
0.2
- expansion of AFBC
X
a
ma
-
.-8 -0.2
-0.4
O 60 120 180 240 300 360
age (day)
Fig. €+Effect of expansion of AFBC ash
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 B 0 6 6 2 9 4 9 052LLb7 877
0.8
8
.-O
v)
c
m
a
0.6
0.4
I44
4I
- avg. 10.7 micrometer
lI
X
a,
-
Y avg. 25.2 micrometer
2a, -
c Y 11
-
._
70 -
-m activated mix 2
--``,`,-`-`,,`,,`,`,,`---
i cetav¡ \ \ mix 3
5. 5o -
f?? 60
I
v>
$ 40-
._
fn
u>
W
30 -
Eo 63
20 I
mercury pore vol. (O/., log scale)
Fig. &Mercury pore volume versus compressive

strength

A C 1 SP-153 V O L M I 95 0662949 0521168 703
210 Jiang and Roy
15
t .................... cpc
K
.-
+
O
-
3
O
> 5
a,
O
O 12 24 36 48
time (hour)
Fig. &Heat evolution curves of cements (expansive and ordinary)
before after
sodium sulfate acid solution

-8
v
1O0
srn
C
L
c
v)
a,
>
._
<I>
v>
L
E
O
--``,`,-`-`,,`,,`,`,,`---
Expansive control expansive control
Fig. 1O-Chemical resistance of cement to sodium sulfate and

acetic acid

A C 1 SP-353 VOL*I 75 I0662947 0523367 647'
--``,`,-`-`,,`,,`,`,,`---
13
12
11
10
10 1O0 1 O00 1 O000 100000

VMO
Total volume of water per unit mass of anhydrous cement (literlkg)
Fig. Il-pH of aqueous phase in contact with alkali-activated

AFBC expansive paste leaching with water (Mix No. 4)
300
non-activated
EI activated
o ! I I 1 I
O 10 20 30 40 50
AFBC ash (%)
Fig. 12-Effective diffusion coefficient (De) of paste plotted

as function of content of AFBC additive (Mixes No. 4 through 8)

A C 1 SP-153 VOL*I 75 I0662949 0 5 2 3 3 7 0 363
212 Jiang and Roy
Fig. 1%Photo of warm-pressing experimental setup
Fig. 1&Photo of warm-pressing AFBC expansive cement sample

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 9 Ob62949 0521171 2 T ô
SP 153-12
Active /3-C,S Cement from

Fly Ash and Kiln Dust
by A. Xu and S. L. Sarkar
SvnoDsis: As focus increasingly shifts to protecting the environment through

recycling of industrial by-products and wastes as well as conserving energy and
resources, corresponding restructuring of conventional production technology
and practices has became imperative, In this light, mixtures of kiln dust and fly
ash were hydrothermally treated and calcined to produce a new type of ß-C,S
rich cement.
Fly ash, which is the most abundantly generated industrial by-product is

still largely disposed of as a waste, while kiln dust is the waste product of the
cement industry, vast quantities of which are discarded due to its high alkali
content. The former is composed of alumino-silicate glass, and the latter has a
composition similar to that of partially calcined cement raw-meal.
This study demonstrates that it is possible to produce C,S cement of

adequate 28-day strength by suitably proportioning fly ash and kiln dust. The
results of variations in factors such as the CaO:SiO, ratio and two different
precalcination treatments are presented. Prehydration-dehydration (sintering at
950°C) processes were specially applied for the production of this cement, in
contrast to the direct calcination method in the presence of a mineralizer.
The cement was constituted of ß-GS and calcium aluminates. The

formation of these minerals in relation to the clinkering sequence is discussed.
The cement is sufficiently hydraulic, and its strength development largely
depended on the CaO:Si02 ratio of the raw mix and the precalcination process.
Keywords: Clinker; CS; u;gypsum; strength
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 0662949 0523372 134 D
214 Xu and Sarkar
Aimin Xu is a Research Associate in the Department of Building Materials,

Chaimers University of Technology, Gothenburg, Sweden. He specializes in
waste utilization, particularly fly ash, in the construction industry. He has
published a number of papers on fly ash hydration and high volume fly ash
concrete.
Shondeep L. Sarkar is the Vice President, SECA, Inc., Houston, TX.Formerly

--``,`,-`-`,,`,,`,`,,`---
he was a faculty member in the Department of Civil Engineering, Université de

Sherbrooke, Canada. He is a microstructural scientist specializing in HPC,
concrete durability/deterioration, high early strength cement, and waste
utilization. He is the author of many papers, and has edited a number of books
and proceedings.
INTRODUCTION
Kiln dust is the dust generated by the cement kiln during clinker
production. Usually its composition is similar to partially calcined cement raw-
meal; thus as much of it as possible is reinjected into the kiln. Nevertheless, the
dust often contains a high concentration of chloride, aikali and sulfate salts
which renders its unsuitable for reinjection. Moranville-Re ourd and Boikova
f
[i] stated that the alkalies lead to the substitution of one Ca+ by two aikali ions
in alite (C3S), which strongly distorts its crystal structure, and consequently
makes it unstable and difficult to form. Additionally, the increasing use of
alternative fuels has altered the kiln dust chemical composition through
incorporation of increased levels of leachable heavy metais, which has caused
concern for its disposal.
Fly ash, on the other hand, is produced in vast quantities in coal-burning

thermal power plants in several countries. As a matter of fact, more fly ash is
produced globally than any other industrial by-product. Despite over four
decades of efforts to use it in concrete, nearly 80% of it is still disposed of as
waste [2].
It was demonstrated by Fraay et al. [3] that in a strong alkaiine solution

@H > 13) the solubility of silica and alumina significantly increases, and
consequently the dissociation of fly ash glass (composed of alumina and silica)
is accelerated. Since this enhances the pozzolanic reaction of fly ash, it follows
that appropriate technology based on fly ash - kiln dust combination holds
potential for making cementitious materials.
From the viewpoint of chemical compositions of kiln dust and fly ash,
one can foresee that by adjusting the CaO:(Si02 +
Aì2O,) ratio, that is, by
varying the proportions of these two by-products, it is possible to produce a

A C 1 SP-153 VOL*I 75 0662947 0521173 070 m
cementing material although it may not lie in the exact compositional range of
conventional portland cement.
Efforts have indeed been made earlier to use kiln dust in combination
with other industrial by-products such as fly ash and slag in concrete.
Reportedly this had no significant negative effect on concrete properties [4, 51,
but the amount of kiln dust thus used had to be limited as it does not possess any
cementitious properties by itself.
--``,`,-`-`,,`,,`,`,,`---
Kihara [6] noted that the presence of coal ash caused a decrease in the
softening point of clinker, and its interaction produced C2S and some gehlenite
(C,AS) by absorbing free C a 0 released from C3S [7]. Although these studies
were conducted at 1400°C and 1500°C respectively, C,S formation in the binary
C a 0 - SiO, system at lower temperatures ( < 1000°C) is preferable, due to its
thermal stability in this temperature range [8].
In the ternary C a c o 3 - SiO, - Al,O, system, C,S begins to form at about

800"C, and forms abundantly at higher temperatures ( 2 1000°C); C12A7 and
C3A starts to form at 800" - 900°C. Thus, it is clear that C$S cement can be
produced at a fairly low temperature. which translates into energy savings. For
example, Zhu [9] reported on the production of a C,S - C,,A7 cement by
calcining limestone powder and fly ash at 960°C in the presence of a
mineralizer. The cement was easier to grind and showed a 28-day strength
comparable to that of normal portland cement.
In recent years, making active B - q S at low temperature (< 1000°C) by

hydration - dehydration method has been studied [ 10, 1i]. Here, active ß-C$
refers to a type which is more reactive than belite in normal portland cement.
Jiang and Roy [ 1i] produced this C,S by hydrothermal treatment of lime and fly
ash, followed by ignition at 900°C; the product developed satisfactory strength.
The procedure can be briefed as: the pozzolanic reaction between fly ash and
lime produces C-S-H, C3AH6 and other mineral species which when heated at
500" to 900°C results in a cementitious product composed predominantly of
active ß-C,S and Cl2A,. According to Yang et a1.[10], this active C2S combines
with 12% gel water at 28 days age compared to 3 % by conventionally produced
C,S. They postulated that when ß-C,S forms at a lower burning temperature,
it is poorly crystalline, containing more lattice defects, and also has a higher
specific surface area, consequently its activity at early hydration stage increases.
The authors conceived that using kiln dust to react with fly ash will also
produce belite - C12A7.cement at a low temperature. It should be noted that the
mineralogical composition of kiln dust strongly depends on the clinkering
process, fuel, raw materials, etc. The C a 0 in the dust may either be combined
in C a c o 3 or may be present in the form of free lime, as illustrated in the XRD
patterns in Figure 1. It is therefore, possible to approach the production process
from two different angles; the dust rich in free lime is suitable for the

A C 1 SP-153 VOL*I 95 H Ob62949 0521174 T O 7
216 Xu and Sarkat
hydrothermal-dehydration process, whereas CaC03-rich dust for clinkering with

flux and mineralizer.
In the present work, active B - q S cement was made from a lime-rich kiln
dust and a low Ca-fly ash by a two-stage process, namely hydrothermal
treatment or precalcination followed by dehydration (sintering). The effects of
varying the C:S ratio, and the result of using two different precalcination
treatments were also investigated.
EXPERIMENTAL
Both the kiln dust and the fly ash used in this study are from Swedish
sources. Their chemical analyses are shown in Table 1. Although XRD analysis
(Figure 1) reveals that the C a 0 in the kiln dust is mainly in the form of free
lime, a preliminary test showed that simple mixing of this fly ash with kiln dust
produced very limited reaction, and therefore, no appreciable strength gain
occurred.
Raw-mix proportioning schemes are presented in Table 2. Aimed at

obtaining C,S after burning, the mixes were proportioned at a C:S mole ratio
of about 2. This ratio was varied åeliberately because complete conversion to
C,S was not anticipated at C:S = 2.0. The formation of calcium aluminates
also consumes Ca from this system, and there was no certaînty about the final
products. For each mix, a batch with 1 % (by weight) additional gypsum was
prepared. This was expected to increase the fly ash pozzolanic reaction [12],
as well as enhance the hydraulic property of cement by the inclusion of Sa, in
--``,`,-`-`,,`,,`,`,,`---
the belite structure [13].
The mixtures (except No. 8) were thoroughly mixed with water at water-
to-solid ratio of 0.70 and cast into 2 cm thick discs. One series of mixes was
hydrothermally treated at 90°C for 8 hours, and the other at 200°C for 4 hours.
After these two special treatments, they were ground and pressed into 4x2 cm
circular pellets. The pellets were then heated in a furnace at the rate of
10"C/min up to 95OoC, where they were kept for 4 hours. Then the materials
were removed and air cooled.
The burned mixes were mineralogically analyzed by XRD. Scanning

electron microscopy/energy dispersive X-ray analysis (SEM/EDXA) was also
performed to study the morphology and elemental composition of selected
samples.
Preliminary test showed that this cement sets very rapidly due to the
presence of C,,A7. To control the setting, 3 % SO, by weight of cement as
gypsumíhemihydrate and 1 % naphthalene-based superplasticizer were added
during grinding. Each clinker was ball milled for 10 min and the Blaine specifk

A C 1 SP-153 VOL*I 95 = 0662949 0521175 943
surface area was determined.
The compressive strength of cement pastes of 0.30 water-to-cement ratio

was measured on $I 16 mm x 20 mm cylinders [9] after 3, 10 and 28 days
moist curing. The residues after strength test were analyzed by XRD to
determine the mineralogical changes that occur as a function of hydration time.
Products of Hydrothermal Treatments
XRD analysis revealed considerable amount of Ca(OH)2 in both series of

specimens after the first stage (hydrothermal treatment). but it was less in the
200°C treated samples, indicating more hydration of fly ash glass. It appears
that the constituent minerals of fly ash. namely quartz and mullite in the 200°C
treated samples decreased, though quartz content was still appreciable. The
reaction products were mainly different types of calcium silicate hydrates. The
formation of crystalline varieties of C-S-H was confirmed, and is in agreement
with the compatibility diagrams presented by Roy and Harker [14]. The
morphology of this C-S-H is typical of heat treated C2S, with longer fibers than
at room temperature (Figure 2). The raw material components are rich in K 2 0 ,
therefore, a greater part of it combined with SO, to form sulfate salts, whereas
some of the K 2 0 was incorporated into the C-S-H. The 90°C treated mixes
formed substantial amount of ettnngite. Its absence in the counterpart 200°C
treated mixes can be attributed to its thermal instability at higher temperature.
Clinkering Products
XRD analysis reveals that the principal products after calcination at

--``,`,-`-`,,`,,`,`,,`---
950°C are O-C2S, CI2A7, gehlenite (C2AS), C,A and small amount of C,A3;
free lime was not detected from XRDA in any of the samples. The Fe-bearing
phases include some C,F and C,M, but their amounts are too small to account
for the total Fe content of the raw materials. The relative proportions of the
main compounds formed are shown in Figure 3. A q S content of 40% to 55 %
was estimated from a calculation similar to the Bogue’s formula.
In brief, the mixes with C:S=2.0 contain considerably more q S but less
C2AS than those with C:S=1.8; this trend holds when C:S is increased to 2.2.
As the formation of calcium aluminates also consumes Ca, higher C:S ratios
produce more C2S. Regourd and Boikova [i] postulated that in silica-rich
samples gehlenite formation is more likely, whereas in calcium-rich samples C3S
can be produced in the presence of K20. Thus, it is evident that the initiai
C:S:A balance is the very factor influencing the final products.

A C 1 SP-I53 V O L X I 95 = 0bb2949 0.521176 8 8 T
218 Xu and Sarkar
The two hydrothermal processes produce some mineralogical differences

in the clinkers. For example, C,S is higher in the 90°C treated mixes with C:S
< 2.0, whereas there is slightly more C12A7 in the 200°C treated ones.
The effect of additional gypsum appears to produce a lower amount of
C,S and higher C2AS in the 200°C treated mixes. The major calcium sulfate
products are CaSO, and K2Ca, (SO4)3. The small amount of C4A3 detected may
be due to the fact that it just starts to form at the temperature studied. It is,
however, a major phase in a similar system undergoing higher synthesis
temperature reported by Beretka et al. [15] and summarized by Majling and Roy
[161.
According to Babuskin et al. [8] thermodynamically C12A7, C,A and CA

are the most probable products in the C a 0 - A1203 system. Though the system
C a 0 - SiO, - Al,03 is more complicated, a similar trend can be expected with
preferential formation of Cl2A7 and C,S, as proved by the present results.
Besides solid-solid reaction, some calcium silicates can also form due to
transformation of their hydrates during heating [17], and CI2A7 is known to
form readily through the dehydration of C3AH6 at atmospheric pressure [lo].
Figure 4 shows that 200°C hydrothermal treatment produced higher

specific surface area cements with the same grinding time. It should also be
noted that in general the surface areas are much higher than that of normal
portland cement. This is due to the comparatively lower sintering temperature
used.
SEM/EDXA of selected burned mixes confirmed their small crystal size

(Figure 5). The 200°C pretreated mixes appear to be better sintered: the
crystals grow epitaxially, and are purer in composition (Figures 5 and 6).
Aluminium-rich phases often contain higher quantity of impurities, such as K ,
Mg, S and C1 (Figure 7).
Even when interground with gypsum, the cements set very rapidly, within
20 min at W/C = 0.40 due to presence of CI2A, which reacts very fast [18].
In a separate test it was observed that hemihydrate (Caso, '15 H,O) addition
proves more effective in controlling the setting, while intergrinding with 1 %
superplasticizer was still more effective. At W/C = 0.30, the pastes started to
set at 1 hour, and final setting occurred 30 min later. Products calcinated at
very low temperature, for example 950"C, tend to be unsintered and dusty; there
is no melt formation similar to portland cement clinker. Only with the help of
a superplasticizer was it possible to produce 0.3 w/c paste and get reasonable
strength [191.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L U I 95 I0662947 0523377 73b I
Strength Development
Compressive strength development of these cements is shown in Figure

8. Corresponding to the content of the main hydraulic component, ß-qS,
different strength gain patterns are observed. In general, those with C:S > 2
attain distinctly higher strength than those with C:S = 1.8.
As shown in Figure 8, the 28-day strength, except for some cements

made from lower C:S ratio mixes, reaches 40 MPa or even higher (60 MPa).
Considering the fact that there is very little C,S in these cements, the strength
is mainly derived from the hydration OP calcium aluminate phases at early ages,
and by the belite thereafter.
XRD analysis of pastes at different hydration ages showed a profusion of

ettnngite, calcium aluminosilicate hydrates and a small amount of Ca(OH),;
C12A7 was consumed in the reaction at an early age, whereas ß-C,S gradually
decreased with age.
Pastes 2 and 2a (C:S = 1.8 with 1% extra gypsum in the raw mix) when
cured in water exhibits volume expansion at î day. For pastes 7 and 7a
(C:S = 2 . 2 , 6% gypsum), the expansion created cracks and consequent
reduction in strength. It is suggested that massive generation of ettn'ngite may
be cause for this volume instability.
Mix 8. which was not hydrothermally treated but contains a mineralizer.

developed a rather high 3-day strength (24 MPa), but thereafter the strength
development was low.
CONCLUSIONS
Cements composed of active ß-C2S, Cl2A7 and C,AS were produced

using different proportions of a low-Ca0 fly ash and a lime-rich cement kiln
dust as raw materials. For the raw meals used, the Ca:Si mole ratio higher than
2.0 is essential for producing more ß-C,S and less C,AS, and consequently
adequate strength. The setting of this type of cement is comparatively fast, but
it can be controlled by adding a small amount superplasticizer in addition to
gypsum or hemihydrate.
Raw meal pretreatments included hydrothermal curing at 90°C and 200°C

for the purpose of comparison. The 200°C treated mixes appeared to have a
better sintered clinker morphology, lower alkali content, and were easier to
grind; their specific surface areas were also relatively higher.
The samples with additional gypsum did not demonstrate any superior
performance, and for the mixes with a low C:S ratio (1.80) and 1 % additional
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L m I 95 0662949 0521178 b 5 2 =
220 Xu and Sarkar
gypsum, water curing caused volume expansion at an early age, most likely due
to ettringite formation. More work, however, is needed to explairi this
behaviour, that is, the function of sulfate in this system.
Although this type of cement can also be produced by direct calcination,

using a mineralizer, the strength development was lower than by hydrothermal
treatment.
The strength achieved by the cement pastes with w/c 0.30, was about 40
MPa and can be as high as 60 MPa at 28 days after optimization of the Ca:Si
mole ratio and the choice of the appropríate hydrothermal treatment.
As this cement sets rapidly, it can be used as a rapid hardening cement.

Additionally, its high C,S content estimated to be 40-55 % , holds potential for
long term strength development.
REFERENCES
1. Moranville-Regourd, M. and Boikova, A.I., "Chemistry, Structure,

Properties and Quality of Clinker," Proc. 9th Int. Cong. Chem. Cem..
New Delhi, 1992, Vol. I, p p ~3-45.
2. Mehta, P.K., "Pozzolanic and Cementitious By-products in Concrete -

Another Look," Proc. 3rd Int. Conf. Fly Ash, Slag, Silica Fume and
Natural Pozzolans in Concrete, Trondheim, 1989, pp. 1-43.
3. Fmy, A.L.A., Bijen, J.M. and de Haan, Y .M. "Reactions of Fly Ash
~
in Concrete, A Critical Examination," Cem. Concr. Res., Vol. 19,

1989, p ~ 235-246.
.
4. Bhatty, M.S.Y., "Properties of Blended Cements Made with Portland

--``,`,-`-`,,`,,`,`,,`---
Cement, Kiln Dust, Fly Ash and Slag," Proc. 8th Int. Cong. Chem.
Cem., Rio de Janeiro, 1986, Vol. II, pp. 118-127.
5. Ramahishnan, V., "Evaluation of Kiln Dust in Concrete," Proc. 2nd

Int. Conf. Fly Ash, Silica Fume, Slag and Natural Pozzolans in
Concrete, Madrid, 1986, pp. 821-839.
6. Kihara, Y., "Influence of High Ash Content Mineral Coal in Portland

Cement Clinker Characteristics," Proc. 8th Int. Cong. Chem. Cem., Rio
de Janeiro, 1986, Vol. II, pp. 105-110.
7. Heilmann, T., "Reaction of Coal Ash with Portland Cement Clinker

During the Burning Process," Proc. 4th Int. Symp. Chem. Cem.,
Washington, DC, 1960, Vol. I, pp. 87-98.

A C 1 SP-253 V O L t I 95 a 0662949 0522179 599 a
8. Babuskin, V.J., Matveev, G.M. and Mchedlov-Petrosyan, O.P.

"Thermal Dynamics of Silicate," 3rd ed. (in Russian), Moscow, 1972.
9. Zhu, Y., "Denaturation of Fly Ash and Denaturated Fly Ash Cement."
Arb. 425, Div. Bldg. Mats., Chalmers Univ. Tech., Gothenburg, 1986.
10. Yang, N., Zhong, B and Wang, Z.. "An Active &Dicalcium Silicate
Preparation and Hydration," Proc. 8th Int. Cong. Chem. Cem., Rio de
Janeiro, 1986, Vol. III, pp. 22-27.
11. Jiang, W. and Roy, D.M., "Hydrothermal Processing of New Fly Ash
Cement," Am. Ceram. Soc. Bull.. 1992, Vol. 71, pp. 642-647.
12. Aimin, X. and Sarkar, S.L.. "Microstructural Study of Gypsum

Activated Fly Ash Hydration in Cement Paste," Cem. Concr. Res.,
1991, Vol. 21, pp. 1137-1147
13. Mieke, I., Muller, A. and Stark, J. "Active Belite Cement," Proc. 9th
~
Int. Cong. Chem. Cem., New Delhi, 1992, Vol. II, pp. 399-405.
14. Roy, D.M. and Harker, R.L., "Discussion" of [17], Proc. 4th Int.
Symp. Chem. Cem.. Washington, D.C.. 1960. Vol. I. pp. 196-201.
15. Beretka, J., Santoro, L.. Sherman. N. and Valenti, G.L., "Synthesis
and Properties of Low Energy Cements Based on C,A,," Proc. 9th Int.
Cong. Chem. Cem., New Delhi, 1992. Vol. III, pp. 195-200.
16. Majlïng, J. and Roy. D.M.. "The Potential of Fly Ash for Cement
Manufacture," Am. Ceram. Soc. Bull., 1993, Vol. 72, pp. 77-80.
--``,`,-`-`,,`,,`,`,,`---
17. Taylor, H.F. W., "Hydrothermal Reactions in the System CaO-Si02-

H,O and the Steam Curing of Cement and Cement-Silica Products,"
Proc. 4th Int. Symp. @hem. Cem.. Washington, DC, 1960, Vol. I, pp.
167-190.
18. George, C.M., "Aluminous Cements - A Review of Recent Literature

(1974-1979)," Proc. 7th Int. Cong. Chem. Cem., Paris, 1980, Vol. I,
pp. V-1/3-26.
19. Mehta, P.K., Private Communication, 1994.

A C 1 SP-153 V O L * I 95 O662949 052LLBO 2 0 0 m
222 Xu and Sarkar
Ca0 SiO, A1203 Fq03 MgO SO, K20 Na20 Cl

KD 54.8 18.5 4.2 1.8 3.6 4.5 4.0 0.47 2.3
FA 8.0 48.6 22.0 11.0 4.0 0.8 2.0 0.2 -
TABLE 2 - MIX PROPORTIONS OF RAW-MEAL AND

PRETREATMENT CONDITIONS
No CaO/Si02 Gpsum KD FA Pre-treatment

KD+FA wt R wt 76
_____
1 1.80 O 75 25 at 90°C
2 1.80 0.01 75 25 ...
3 2.00 O 80 20 ...
--``,`,-`-`,,`,,`,`,,`---
4 2.00 0.01 80 20 ...

5 2.20 O 85 15 ...
6 2.20 0.01 85 15 ...
7 2.20 0.06 85 15 ...
la 1.80 O 75 25 at 200°C
2a 1.80 0.01 75 25 ...
3a 2.00 o 80 20 ...
4a 2.00 0.01 80 20 ...
5a 2.20 O 85 15 ...
6a 2.20 0.01 85 15 ...
7a 2.20 0.06 85 15 ...
8 2.20 O 85 15 *
No.8 was mixed R rlimnm minedizer; it w s not hydrothem4 treated.

A C 1 SP-153 V O L X I 95 0662949 0 5 2 L L ô L 147 H
dh
5 ' ~27 29 31 33 35 37 39
w e , CU KUI
Fig. 1-XRD patterns of some cement kiln dusts.

Top one was used in this study
--``,`,-`-`,,`,,`,`,,`---
Fig. 24rystalline C-S-H in a 200 C treated sample

A C 1 SP-153 V O L * I 95 IO662949 052LL82 O83
224 Xu and Sarkar
Selected XRD pean area, 1O counts

25
1200"C.treatedmixesi
20 -
15 -
-
10
2
5-
0-
C12A7 C2AS
--``,`,-`-`,,`,,`,`,,`---
(a)
Selected XRD peak area, lo3 counts

90°C treated mixes: 1-7
<I
5
Fig. 3-XRD peak areas showing relative

content of main compounds formed in
calcined mixes. No. 2, 4, and 6 represent
mixes with 1 percent additional gypsum,
and No. 7 with 6 percent gypsum

~
A C 1 SP-153 VOL*I 95 I0bb2947 0521183 T I T

Specific Surface Area (m'Ikg)

800 -
la
600 3a
5a
6a
1
7a
400
200
O
--``,`,-`-`,,`,,`,`,,`---
Fig. 4-Specific surface area of cements
Fig. 5-Epitaxial growth of minute C,S crystals in 200 C

treated sample No. 5
A C 1 SP-153 V O L X I 95 W 0662949 0523384 9 5 6
226 Xu and Sarkar
--``,`,-`-`,,`,,`,`,,`---
Fig. 6-EDX spectrum of these crystals suggesting

C,S composition
Fig. 7-EDX spectrum of an Al-bearing phase containing Mg,

S, K, CI as impurities

A C 1 SP-153 VOL*I 95 = 0662949 0521185 892
Strength (MPa)
"2 3 5 10 20 30 50
Age (day)
(4
-
5a
4a
3a
40~ 6a
2a
30 - la
7a
20
10
Fig. €+Strength development of cement pastes

made from 90 and 200 C treated mixes
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 IOb62949 05211ôb 7 2 9 I
SP 153-13
The Influence of High Early-Strength

(HES) Mineralized Clinker on the
Strength Development of Blended
Cements Containing Fly Ash, Slag,
or Ground Limestone
by S. Kelham, J. S. Damtoft, and B. L. O. Talling
Svnopsis: The strength development of blends of five cements with various levels
of a fly ash, two blastfurnace slags, a ground limestone and a dried chalk dust has
been determined using EN 196 mortars and, for selected materials, concretes.
Three of the cements were based on normal portland cement (OPC) clinkers and
two on a High Early Strength (HES) mineralised clinker. At the same specific
surface area and SO, content the HES clinker gave cements with strengths 5 - 10
MPa higher than those based on equivalent normal clinker at all ages from 1 to 56
days. This allows the use of significant levels of fly ash, slag or other less reactive
materials in blends giving similar early strengths to normal portland cements. The
early strengths of the blends with the ground limestone (-9OYo < 45 pm) and the
lower surface area HES cement were higher than expected. The finer chalk dust
(-50% < 2 pm) gave significant contributions to strengths with all the base
cements, particularly at early ages. The effect was greater with the lower surface
area cements and those based on HES clinker. It is concluded that the acceleration
of hydration by the fine calcium carbonate is particularly strong with cements
based on the mineralised clinker.
Keywords: Blended cements; clinker; concretes; flv ash; limestone; w;

strength; water content; workability
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOL*I 95 m Obb2949 052LLBï 6 6 5
230 Kelham, Damtoft, and Talling
Stephen Kelham is a senior scientist in the Blue Circle Technical Centre, UK. He
received his D.Phi1. in physics from Oxford University and has been employed by
Blue Circle since 1978. He has studied the influence of portland cement chemistry
and fineness on the workability, strength development and durability of concrete
and the performance of blended cements.
Jesper Sand Damtoft is manager of the Department of Alternative Raw Materials,

Aalborg Portland cement works, Denmark. He received his MSc. in geology from
the University of h h u s . Since 1985 he has been engaged in development of
advanced technical ceramics, advanced concretes, blended cements and the
application of industrial waste and by-products in cement production.
Bob Talling is manager of Cement R&D at Finnsementti Oy cement works,

Finland, where he has been employed since 1983. He received his M.Sc. in
--``,`,-`-`,,`,,`,`,,`---
chemical engineering from Abo Akademi University. He is responsible for the
evaluation of secondary raw materials, physical testing and development of new
binders and systems for solidification of hazardous wastes.
INTRODUCTION
The basic requirement for a cement is that it should be capable of

producing grouts, mortars, concretes etc., which remain workable for the time
necessary for placement and compaction and then develop and retain the necessary
strength. Cement standards around the world therefore spec@ setting times and
strengths of standard mortars or concretes. The European pre-standard ENV
197-1 (Cement - Composition, specifications and conformity criteria - Part i :
Common cements) includes 3 main strength classes based on the 28 day strength
of a standard mortar with normal and rapid early strength sub-classes based on 2
or 7 day strengths. These strength classes apply to all the cement types covered by
the standard which can incorporate a wide range of materials in addition to normal
portland cement clinker [slag, fly ash (calcareous and siliceous), pozzolanas
(natural and industrial), burnt shale, limestone, silica fume and filler].
The linked pressures of economics and environmental concerns tend to

favour cements with high contents of materials which are wastes or by-products
from other processes or are inherently low cost, both economically and
environmentally (1,2). Producing clinker is an energy intensive process and
generally involves considerable CO, emissions associated with fuel combustion
and de-carbonation of limestone or chalk. The use of mineralisers and fluxes in the
clinkering process to reduce kiln temperatures gives only small energy savings in

A C 1 SP-153 V O L X I 75 = Obb2949 0521188 5TL D
modem efficient kilns (3). The replacement of clinker by low environmental cost
materials is therefore the easiest way to reduce the environmental cost of cement
production.
Of course, the replacement of clinker by other materials changes the

properties of the cement. The main materials used to replace clinker, such as slag
and fly ash, do not contribute to strength at early ages and early strength is
therefore reduced in standard tests. Some materials may improve concrete
workability enabling water content to be reduced, partially offsetting the strength
reduction. In concretes designed to a target 28 day strength the early strength will
be the same as with normal portland cement when inert or slowly reacting
replacements are used but in slag concretes the early strength will be lower
because slag contributes significant strength at 28 days. Limestone and filler may
give no direct contribution to strength but they allow the clinker content to be
finer without increasing the strength, thus improving the efficiency of use of the
hydraulic potential (2). The alternative method of producing lower strength class
cements is to grind the clinker more coarsely, which can result in a significant
--``,`,-`-`,,`,,`,`,,`---
proportion of the clinker never hydrating and workability problems.
In order to maximise the use of other materials in cements while

maintaining strength properties similar to those of normal portland cements it is
obviously desirable to use a clinker which gives high strengths, particularly at early
ages. HES (High Early Strength) clinker is a mineralised portland cement clinker
containing increased levels of SO, and fluoride (4). It allows lower kiln
temperatures and hence reduces fuel consumption and NO, emissions. Emissions
of SO, are not normally increased because the kiln is operated so as to retain the
sulfate in the clinker. Initial work concentrated on high early strength properties
and employed high alkali contents which tend to limit the 28 day strength. Long
term (up to 15 years) strength development was similar to that for normal portland
cements. The present work has shown that low alkali HES can be produced with
high early and 28 day strengths. A modified C,S structure is believed to contribute
to the high performance (3). The mineralising and fluxing action of the
sulfatehluoride combination also facilitates the production of high silica ratio
clinkers without the high kiln temperatures normally required. This paper
compares the strength development of blended cements based on normal and HES
clinkers in mortars and concretes in order to determine whether the use of HES
clinker can reduce the environmental costs of concrete production.
MATERIALS
Three clinkers were used, 2 production normal portland cement clinkers

and one trial HES clinker. The chemical analyses are given in Table 1 . The main
difference between the normal clinkers is the higher alkali content of PC2. The

A C 1 SP-1.53 VOL*I 95 I0662949 052111189 438 I
HES clinker has typically high SO, arid F contents and a high silica ratio. The high
silica ratio is not a necessity for HES clinker but the mineraiising and fluxing
action of the SO, and F allow high silica ratio clinkers to be produced without the
excessively hard burning normally required. The mineraiising action leads to a
modified C,S structure, with apparent trigonal symmetry, the presence of which
was detected by XRD.
Five base cements were ground in a pilot scale rotary ball mill operated in
a closed circuit with a high efficiency separator. Sufficient natural gypsum was
interground with the clinker to give a cement SO, content of 3.5%. Specific
surface areas were targeted at 400 or 550 m2kg . The grinding was carried out
cold and the cements subsequently heat treated at 10S°C for four hours to
simulate normal production conditions leading to partial gypsum dehydration.
Table 2 gives the measured SO, and fineness data.
Five other materials were used to prepare blends with the base cements.
These were two ground granulated blastfumace slags of different reactivities, a
siliceous fly ash, a ground limestone and a product from a cement works which
consisted mainly of dried ground chalk with small quantities of fly ash and ground
silica sand. The basic properties of these materials are given in Table 3.
Each base cement was blended with each other material at three levels (by
weight) :-Slags 1 and 2 - 30,40, 50 %, Fly ash - 20, 30,40 %, Limestone and
chalk - 15, 25, 35 %. Some mixed, 3 component, blends were also prepared.
Using a = slag 1, b = slag 2, c = limestone, d = chalk, r = fly ash, the mixed blends
were :- a20c15, b20cl5, a20d15, a30r30, a50r30, b20r20, b30r30, c15r20, d15r20
where the figures give the percentages of the various components,
TEST METHODS
All the base cements and blends were characterised using test methods in
EN 196 Part 1 (mortar strengths at 1, 2, 7,28 and 56 days), EN 196 Part 3 (paste
water demand and setting time) and PR ENV 413 Part 2 (mortar workability by
the plunger method).
The base cements and selected blends were also tested in concrete
mixtures. Each cement was used to produce grade 30 (34 MPa at 28 days) and 45
(48 MPa at 28 days) concretes with 100 mm slumps. Strengths of 100 m m cubes
were measured at i , 7 and 28 days. The blends tested were H4b30, H4cl5,
H4c25, H4d25, H4cl5r20, H5r30, HSr40 where H4 and H5 indicate the 400 and
550 mZkgHES base cements respectively (Table 2). No admixtures were used.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 0662949 0521190 1 5 T =
PASTE AND MORTAR RESULTS
The paste water demands and setting times of all the cements were within
normal ranges and will not be discussed here. The mortar strengths of the base
--``,`,-`-`,,`,,`,`,,`---
cements are shown in Fig. 1. Comparison of the 0 4 and H4 (400 m2kg) cements
indicates that the HES cement gives higher strengths at all ages. The same is true
for the 550 m2kg cements, 0 5 , US and HS. The cement containing the high alkali
clinker, US,gives significantly lower late strengths.
Fig. 2 shows the mortar strength development data for a selection of

cements based on cement 04 (PCl clinker, 400 m'kg). Limestone reduces the
strength at all ages by a value close to the replacement level. The slag gives a
similar pro rata reduction at early ages but makes a significant contribution to the
strength at 7 days and later, giving a higher strength than the base cement at 56
days. The fly ash gives a larger reduction at early ages and contributes to strength
only at ages greater than 28 days. The mixed slag and fly ash blend shows the
expected combination of effects.
Fig. 3 shows similar data for the blends based on cement H4 (HES clinker,
400 m2kg). The strengths are generally higher because of the higher base cement
strength. The early strengths of the limestone blend are particularly high, being
very close to those of the base cement. The blends containing slag and fly ash
show similar early strength reductions to those in Fig. 2 but the contribution from
the slag at later ages appears to be lower.
By comparing the strength results for all the cements with the EN 197-1
requirements the strength class for each cement was determined and these are
given in Table 4.In general the high strengths of the HES cements allow an
increased range of blends giving compliance with the standard or give blends in
higher strength classes.
Figures 4 and 5 show the dependences of 28 day strength on the

proportion of 'other components' in blends based on 0 4 and H4 respectively. They
include indications of the strength ranges satisfying the main strength classes in
EN 197-1. It can be seen that for the limestone, chalk and fly ash blends the
strength relative to the base cement is equal to the proportion of clinker in the
blend. The slags, however, give significant contributions to the strength. The
apparent reactivity, or strength contribution, of the slags is lower with the HES
than with the normal PC. In general the performance of the mixed blends reflects
the performance of the individual components present.
Figures 6 and 7 are the 2 day equivalents of Figures 4 and 5. They include
indications of the EN 197-1 early strength requirements. In these plots it is the
chalk blends which have higher strengths than expected from the clinker content.

A C 1 SP-II53 V O L X I 95 0662949 052119L O96 9
The apparent strength contribution is greater with the HES base cement and with
this cement the limestone also gives higher than expected strengths. The effect is
smaller with the high surface area base cements. As with the 28 day strengths, the
performance of the mixed blends was as expected from the contribution of the
individual components.
By using these and similar plots for the other base cements estimates have
been made of the maximum contents of other cofinonents that could be
accommodated to give blends satisfying the requirements of the important
strength classes 42.5R and 52.5R. These are given in Table 5. It can be seen that
the HES base cements allow higher contents of the other components than the
equivalent normal Portland cements.
CONCRETE RESULTS
The concrete mixture data are summarised in Table 6. The tabulated data
are estimates of the values required to give the specified workability and strengths,
based on the performance of the actual mixtures. The relationships between the
W/C required to obtain the target strength and the 28 day mortar strength of the
cement are shown in Fig. 8. The lines show the values of the expression
w/c = 0 . 6 + 0 . 0 6 ~ ( 0 . 8 x M - C ) / / whereMis
~ the measured mortar
strength and C the required concrete strength. This expression was used to
estimate the w/c for the concrete mixtures. The required w/c for the U5 cement in
the lower strength concrete mixture is higher than predicted, probably indicating
the influence of cement alkali content on the strength v w/c behaviour.
The water requirements are generally slightly higher for the K45 mixtures
and slightly lower for the blended cements, particularly those containing fly ash.
The H4d25 blend containing the chalk dust is notable in having one of the lowest
water requirements in the K30 mixture but the highest water requirement in the
K45 mixture. This is a clear demonstration of the well known interdependence of
cement fineness, cement content and water requirement,
The cement contents are low for the HES base cements as expected from
their high strengths. Excluding the 40% fly ash blend, the cement contents for the
blends are not very different from those for the OPCs. However, the clinker
contents of the concretes are significantly lower for the blended cements than for
any of the base cements.
The estimated 1 day strengths of the concrete mixtures given above are
plotted in Fig. 9. The lower surface area HES base cement gives the lowest early
strength for both concrete grades. In the K30 mixtures the high surface area HES
base cement gives the highest early strength but the range is quite limited. The
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 H 0 6 6 2 9 4 9 0521192 T 2 2
high alkali base cement gives the highest early strength in the K45 mixture and the
blend containing the chalk dust also gave a significantly higher strength than the
other cements. Comparing the performance of the HES base cements with the
blends indicates that the limestone and chalk fillers increase the early strengths
while the slag and fly ash have little effect.
DISCUSSION
The effect of the presence fine particles of various materials on the

hydration of cement or its constituent phases has been studied by a number of
workers using a range of techniques. Soroka and Setter (5) studied the effect of
limestone, dolomite and basalt on mortar strengths and degree of hydration,
estimated from the quantity of 'bound' water. They concluded that hydration was
accelerated by the presence of a fine filler, independent of any pozzolanic reaction,
through the nucleation of hydration products, since the acceleration increased with
increasing filler surface area. Strength increases were observed because the filler
was used to replace an equal volume of sand in the mortar mixtures tested. Most
other investigators have used fillers to replace clinker or cement on a weight basis,
as in the present work. Gegout et al. ( 6 ) studied blends containing up to 60% of
quartz or limestone fillers, mainly in 0.3 w/c pastes. With OPC as the base cement
the limestone blends gave higher strengths than the quartz blends at the same filler
fineness. Except at early ages both fillers gave higher strengths than predicted
using Ferets law. With a low C,A sulfate resistant base cement the strengths for
both fillers were generally close to the Feret predictions. The relationship between
porosity and degree of hydration estimated by XRD was the same for all the
cements, suggesting little influence of the fillers on the nature of the hydration
products. The early age results indicate a retardation of the hydration with the
OPC and some acceleration with the low C,A cement. Paste porosities were also
measured by Guyot et al. (7). The relationship between the porosity of 0.5w/c
pastes and the strengths of 0.5 w/c mortars was shown to be the same for plain
and limestone filled cements. Results for CH and bound water, determined by
thermal analysis, degrees of hydration of C,S and C,A by XRD, and pore size
distributions all indicated that the presence of limestone did not significantly
change the nature or quantities of the hydration products. After 7 days the
presence of monocarboaluminate in the limestone filled cement pastes was
detected but this appeared to have no effect on the physical properties.
Ramachandran and Zhang Chun-me¡ (8) studied the hydration of C,S, C,A
and cement in blends containing up to 50% by weight of a very fine calcium
carbonate. In all cases the presence of the filler accelerated the hydration as
--``,`,-`-`,,`,,`,`,,`---
measured by exotherm and CH production. The calcium carbonate content of the

C,S blend pastes decreased with time, although to a lesser degree than in pastes
containing cement. This suggests that the formation of carboaluminate is not the

A C 1 SP-153 VOL*I 95 W 0662749 0521173 9b9
only chemical interaction. Monteiro and Mehta (9) proposed a 'basic' calcium
carbonate (C~(OH),(CO,),xH,O) to explain microscopical and XRD studies of
limestone aggregate / paste interfaces using cement and C,S. The calcium
hydroxide crystals near to the interface were smaller and less oriented with the
surface when limestone aggregate was used than is normally observed with
siliceous aggregate.
C,S pastes were also studied by Beedle et al. (IO) using conduction
calorimetry, thermogravimetnc analysis and electron microscopy. The influence of
a range of fine particles on hydration was determined. Graphite and a-alumina had
no effect and titania (both rutile and anatase) only a small effect. Amorphous
silica, clays and y-alumina, however, gave large effects. The amorphous silica
accelerated hydration and reduced the CH content. The acceleration was
independent of the fineness of the silica but the pozzolanic reaction increased with
decreasing particle size. Clay particles caused less acceleration and showed no
pozzolanic reaction. After certain heat treatments the y-alumina retarded the C,S
--``,`,-`-`,,`,,`,`,,`---
hydration. The independence of the hydration with respect to particle fineness and
the dependence on particle chemistry led these authors to conclude that the
influence of the particles on hydration was through the ionic content of the liquid
phase. The results are consistent with models of hydration (1 1) in which changes
in CdSi ion ratios alter the type of C-S-H formed. In contrast, Gutteridge and
Dalziel (12) found that rutile of a similar fineness (0.5 pm) accelerated the
hydration of ail the main phases of a Portland cement. Larbi and Bijen (13)
demonstrated that increasing w/c, increasing sand content and increasing sand
fineness ail gave increases in the CH content of Portland cement mortars. This is
consistent with the sand surface acting as nucleation sites for CH crystal growth.
It seems clear that particles of a range of materials act as nucleation sites

for CH and lead to acceleration of hydration. Calcium carbonate in various forms
is particularly effective, with some chemical interaction taking place leading to
smaller less oriented CH crystals. The removal of Ca from the liquid phase would
be expected to accelerate hydration directly and by reducing the CaíSi ratio may
also affect the nature of hydration products. This ratio may also be reduced by
particles containing soluble Si or increased by particles containing soluble Al
(which reduces the solubility of Si).
In the present work the combination of the high SR of the HES clinker and
the fineness and nature of the chalk dust would appear to give a particularly strong
interaction. This could be associated with the high C,S content of the HES, the
hydration of which involves the production of high quantities of CH.
The relatively poor performance of the slags with the HES cements is not
easy to explain. The alkali content of the HES clinker is not significantly different
fi-om that of the normal clinker and the highedearlier CH production associated
with the high C,S content would be expected to improve the slag reactivity. It is

A C 1 SP-153 VOL*I 95 Ob62949 0521L74 8T5 W
possible that the low C,A content of the HES clinker is significant. Fluorine is
known to retard cement hydration, probably through the formation of insoluble
CaF, (3) and may be effective in retarding the slag hydration.
The concrete results demonstrate a number of the difficulties encountered

in predicting the performance of cements in concrete mixtures from standard
mortar tests. The dependence of strength at any age on w/c varies with cement
properties, notably alkali contents. The water required to give the target
workability is influenced by cement properties such as fineness, cement content
and the nature and relative amounts of the fine and coarse aggregates. The high
strengths of the HES cements enable lower cement contents to be used but for
significant reductions in clinker contents cements containing additional main
constituents are required.
Obviously the environmental 'cost' of a m3 of concrete is not only that

associated with clinker production. The granulation and grinding of slag have
waste disposal and energy consumption requirements while the production of fly
ash is based on coal fired boilers with their own SO, and NO, emission problems
Transport and quarrying costs must also be taken into account. However, it is
clear that a significant environmental benefit would be obtained by replacing
current Portland cements by HES blends which can provide similar strength
growth characteristics.
CONCLUSIONS
HES technology can produce low alkali cements with high early and late
strengths.
The production of HES clinker is associated with reduced energy requirements
and reduced emissions of NO, .
The high strengths of HES cements allow lower cement contents in concretes
of a given strength.
Blending HES cements with other materials can produce cements with similar
strength growth behaviour to current normal portland cements.
The use of such cements could lead to a significant reduction in the
environmental cost of a m3 of concrete.
A chalk dust, a by-product of cement manufacture in certain kiln systems,
accelerates strength development in standard mortar tests with cements based
on both normal and HES clinkers.
Acceleration of the strength development of HES cements by limestone and
chalk fillers was greater than that of cements based on normal clinkers.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L I I 75 0662949 0521195 731 W
REFERENCES
1 . Schmidt, M. "Cement with interground additives - Capabilities and

environmental relief" Zement Kalk Gips, Part 1 vol. 2 pp 64-69, Part 2 vol. 6 pp
296-301, (In English Part 1 vol. 4 pp 87-92, Part 2 vol. 8 pp 216-220.), 1992.
2. Baron, J. and Douve, C. "Technical and economical aspects of the use of
limestone filler additions in cement", World Cement, April, 1987.
3. Moir, G.K. and Glasser, F.P. "Mineralisers, modifiers and activators in the
clinkering process", 9th. Int. Congress on the Chemistry of Cement, (Delhi)
1992, vol. 1, pp 125-152.
4. Moir, G.K. "Improvements in the early strength properties of Portland cement",
Phil. Trans. Roy. Soc., A 310, pp 127-138, 1983
5. Soroka, I. and Setter, N. "The effect of fillers on the strength of cement
mortars", Cement and Concrete Research, vol. 7, pp 449-456, 1977.
6. Gegout, P., Homain, H., Thuret, B., Mortureux, B., Volant, J. and Regourd, M.
"Texture and performance of filler cements", 8th. Int. Congress on the
Chemistry of Cement, (Rio de Janeiro) 1986, vol. 4, pp 197-203.
7. Guyot, R., Ranc, R. and Cariou, B., "Development of hydraulic activity of
clinker in Portland cements containing calcareous filler addition", ibid., vol. 6,
pp 198-203.
8. Ramachandran, V.S. and Zhang Chun-mei "Cement with calcium carbonate
additions", ibid., vol. 6, pp 178- 183
9. Monteiro, P.J.M. and Mehta, P.K. "Improvement of the aggregate-cement paste
transition zone by grain refinement of hydration products" ibid., vol. 3, pp
433-437.
lO.Beedh, S.S.,Groves, G.W. and Rodger, S.A. "The effect of fine pozzolanic
and other particles on the hydration of C,S", Advances in Cement Research,
vol. 2, no. 5, pp 3-8, 1989.
1 1 .Gamer, E.M. and Jennings, H.M. "Thermodynamics of calcium silicate
hydrates and their solutions". J. Am. Ceram. Soc. vol. 70, no. 10, pp 743-749,
1987.
12.Gutteridge, W.A. and Dalziel, J.A. "Filler cement: The effect of the secondary
--``,`,-`-`,,`,,`,`,,`---
component on the hydration of Portland cement". Cement and Concrete

Research, vol. 20, pp 778-782, 1990.
13.Larbi, J.A. and Bijen, J.M.J.M. "Effects of water-cement ratio, quantity and
fineness of sand on the evolution of lime in set Portland cement systems",
Cement and Concrete Research, vol. 20, pp 783-794, 1990.

A C 1 SP-153 VOL81 75 0662749 0521196 678 I
TABLE 1 - CHEMICAL ANALYSES AND PHASE COMPOSITIONS OF

CLINKERS
PC 1 PC 2 HES
SiO, 21.9 21.7 22.6
%O3 4.9 4.2 2.2
3.2 2.6 0.8
Mn203 0.03 0.30 0.02
p205 0.17 0.07 0.15
Tio2 0.26 0.19 0.11
Ca0 67.0 64.2 70.0
MgO 0.7 3.1 0.6
so3 0.48 1.30 2.60
LOI 0.5 0.5 0.3
K,O 0.49 0.96 0.3 1
Na20 0.25 0.63 0.22
Eq Na,O 0.57 1.26 0.42
wls K20 0.35 0.83 0.26
wfs Na,O 0.08 0.34 0.15
wls Eq Na,O 0.31 0.89 0.32
F 0.27
Free Lime 1.o 0.7 1.2
LSF~'][%I 96.7 95.1 105.4
SR 2.70 3.19 7.53
m 1.53 1.62 2.75
Bogue analysis
c3s 64.8 61.7 85.0
c2s 14.0 15.7 0.7
C3A 7.6 6.7 4.5
c4AF 9.7 7.9 2.4
CaS0,12' 4.4
QXRD
c3s 59 59 84
c2s 20 14 1
C3A 9 6 2
c4AF 8 8 1
11 Ignoring SO3
21 Ignoring SO, for PCl and PC2. Ail SO, assumed to be CaSO, in HES.
--``,`,-`-`,,`,,`,`,,`---

A C I SP-153 V O L X I 75 m ~ 7m
O ~ L Z W0 ~ 5 ~ 1 504
TABLE 2 - BASE CEMENT SO, CONTENTS AND FINENESSES

I Cement I 04 o5 u5 H4 H5
Clinker PC 1 PC 1 PC 2 HES HES
so, [%I 3.5 3.6 3.4 3.5 3.5
Density [kg/m3] 3130 3130 3160 3 100 3100
SSA [m2/kg] 400 547 548 400 542
< 45 pm [%] 99.7 99.9 99.9 99.9 99.8
< 10 pm [%I 62 63 41 57
< 2 pm [%I 12 12 7 8
TABLE 3 - CHEMICAL ANALYSES AND FINENESSES OF OTHER

MATERIALS (PERCENT BY WEIGHT UNLESS SPECIFIED OTHERWISE)
Material Slag 1 (a) Slag 2 (b) Fly ash (r) Limestone (c) Chalk (d)
SiO, 33.8 36.5 54.2 2.4 10.7
A1203 11.2 9.7 21.2 o. 1 2.3
Fe203 1.3 0.26 10.7 o. 1 1.5
Mn203 0.24 0.78 0.06
p205 0.01 0.02 0.3 1 0.02
Tio2 0.48 1.O3 1.10 0.04 0.13
Ca0 41.9 39.4 3.1 54.2 47.2
Mg0 9.2 10.7 1.9 0.2 0.4
so3 o. 1 0.6 o. 1 0.4
LOI 0.4 3.2 42.7 35.8
K2O 0.29 0.58 2.10 0.02 0.68
Na20 0.30 0.44 0.8 0.01 0.21
Eq Na20 0.49 0.82 2.16 0.02 0.66
w/s Eq Na,O 0.01 0.02 0.03 0.23
S 0.94 1.18 0.01
CO2 42.7 35.0
TOC 0.06 0.61
Carbon 2.6
glass 83
lenity [kg/m3 2950 2930 2260 2682 2706
SSA [m2/kgl 426 412 270 536 1235
< 4 5 pm 99.4 1O0 71.5 86.7 1O0
< 10 pm 48 48 27 58 97
< 2 um 8 7 3 20 49
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 Ob62949 0521198 440 M
TABLE 4 - STRENGTH CLASSES FOR ALL BLENDS

Other component Base cement
TvDe % 04 05 u5 H4 H5
O 52.5 52.5R 52.5R 52.5R 52.5R
slag 1 (a) 30 52.5 52.5 52.5 52.5
40 52.5
50 42.5 42.5 42.5
slag 2 (b) 30 52.5 42.5 52.5 52.5R
40 42.5 42.5 42.5R 52.5
50 42.5 42.5 32.5R 42.5 42.5R
imestone (c) 15 42.5R 52.5R 42.5R 52.5R 52.5R
25 42.5R 42.5R 32.5R 52.5R 52.5R
35 32.5R 32.5R 32.5R 42.5R 42.5R
chalk (d) 15 52.5 52.5R 42.5R 52.5R 52.5R
25 42.5R 52.5R 32.5R 52.5R 52.5R
35 32.5R 42.5R * 42.5R 42.5R
fly ash (r) 20 42.5R 52.5 42.5R 52.5 52.5R
30 32.5R 42.5 32.5R 42.5R 42.5R
40 32.5R 32.5R 32.5R 32.5R
a20cl5 35 42.5 42.5R 42.5R 52.5 52.5
b20c 15 35 42.5 42.5R 42.5R 52.5 52.5R
a20d 15 35 42.5 52.5 42.5R 52.5R 52.5R
a30r30 60 32.5 32.5 32.5 32.5 32.5
a50r30 80
b20r20 40 42.5 42.5 32.5R 42.5 42.5R
b30r30 60 32.5R 32.5
cl Sr20 35 32.5R 32.5R 32.5R 42.5R 42.5R
d15r20 35 32.5R 42.5R 32.5R 42.5R 42.5R
- Does not meet the requirements of any strength class
* Not tested
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 V O L W I 95 W Ob62949 052LI199 387
TABLE 5 - MAXIMUM PROPORTIONS OF OTHER COMPONENTS

(PERCENT BY WEIGHT) TO SATISFY ENV 197-1 STRENGTH
CLASSES 42.R AND 52.5R
Strength Other Base cement
class component o4 05 u5 H4 H5
42.5R a 34* 47*
b 30* 46* 51*
C 26* 32 23 36 35
d 32* 38 23 43 42
r 22 * 30* 23 31* 36
52.5R a 18* i 6* 14* 28*
b 14* 14* 16* 31*
C 20 * 8 26 26
d 27* 8 30 31
r 16* 8 11* 24 *
rnm DIN FLOW

K30 28d=34MPa K45 28d=48MPa
--``,`,-`-`,,`,,`,`,,`---
w/c water cement clinker w/c water cement clinker

04 0.80 193 249 237 0.59 186 315 299
05 0.88 196 223 212 0.69 196 286 272
u5 0.87 187 215 205 0.61 196 320 304
H4 0.90 187 211 205 0.72 187 262 254
H5 0.90 190 212 205 0.76 197 260 252
H4b30 0.76 187 246 167 0.60 193 322 218
H4cl5 0.80 182 228 188 0.63 183 290 239
H4c25 0.72 183 256 186 0.55 183 331 241
H4d25 0.77 178 231 168 0.58 200 345 251
34c15r20 0.69 177 258 163 0.51 181 355 224
H5r30 0.70 182 261 177 0.56 188 334 227
H5r40 0.61 179 292 170 0.48 185 385 224

A C 1 SP-L53 VOL*I 95 Obb2949 0521200 929
80
70
-B 60
350
I
8
$40
U
I-
V>
30
20
I I I I I I I I
10
1 2 7 28 56
AGE [days]
Fig. l - s t r e n g t h development of base cements
--``,`,-`-`,,`,,`,`,,`---
80
70
25% limestone
-.+-.
60 I- I 50% slag 1
-..*-..
_.-..- I 40% Ry ash
50% slag 1
+ 30% fly ash
..-. _...
20
10
-.- I I 1 I 1
O
1 2 7 28 56
AGE [days]
Fig. 2-Typical strength development data for blends based on 0 4

A C 1 SP-153 V O L S I 75 H 0662947 0521201 665 H
25% limestone
-.+-.
50% slag 1
-..**..
40% fly ash
50% slag 1
+ 30% fly ash
.....
.+._._
Fig. &Typical strength development data for blends based on H4
80
--``,`,-`-`,,`,,`,`,,`---
pro rata
70
60
n
Q,
E. limestone
5 40 --e--
c
E30 -..... -
;; mixed
20
fly ash
10 --.c
n
O 10 20 30 40 50 60 70 80 90 100
Filler content Ml
Fig. 4-28-day strengths of blends based on 0 4 (PC 1 clinker, 400

m2/kg)

A C 1 SP-1.53 VOL81 95 Obb2949 0 5 2 3 2 0 2 7 T l
80
H4
pro raia
70
slag 1
60 -.....e
CI
8 50 slag 2
---e.....
E, limestone
--Q--
chalk
- ...-..-
.<
mixed
20
fly ash
10 A
O
O 10 20 30 40 50 60 70 80 90 100
Filler content [%I
--``,`,-`-`,,`,,`,`,,`---
Fig. 5-28-day strengths of blends based on H4 (HES clinker, 400
m2/kg)
40 I l I l I I I I I
I l I I I I I l I o4
I I l I I I I
pro rata
slag 1
30 .-""a..-.-
CI
P slag 2
.-"..D...-
E, limestone
5 20 - - Q - -
ul
C
e
Y;
chalk
.
-..-.. ..- ..-
mixed
10 4
fly a s h
+
O
O 10 20 30 40 50 60 70 80 90 100
Filler content [%I
Fig. 6-2-day strengths of blends based on 0 4

A C 1 SP-153 V O L * I 95 = 0662749 0523203 b38
c i I I I I l lI I
I
I H4
pro rata
slag 1
slag 2
D.....
limestone
--+--
chalk
_.._....
< -
mixed
fly ash
+
--``,`,-`-`,,`,,`,`,,`---
O 10 20 30 40 50 60 70 80 90 100
Filler content [%I
Fig. 7-2-day strengths of blends based on H4
1
K30 data
0.9
K45 data
$ 0.8
p>
model
c,
0.7
0
c
8 0.6
0.5
0.4
40
’ 50
I
60
I
70
1 I
80 90
Mortar 28 day strength [MPa]
Fig. 8-Influence of mortar strength on concrete WIC requirement

A C 1 SP-153 VOL*I 95 Obb2949 0521204 574
cement
O4 (OPC 1 400)
O5 (OPC 1 550)
u5 ( O X2 550)
H4 (HES 400)
H4cl 5 (1 SohUstone)
H4c25 (25% Ustone)
H4d25 (25% Chalk)
H4b30 (30% Slag 2)
H4cl 5RO (1 5%+
l20FA)
H5 (HES 550)
H5r30 (30% Fly Ash)
H5r40 (40% Fly Ash)
O 5 10 15 20 25
1 day Strength [MPa]
Fig. 9-l-day strengths of K30 and K45 concretes
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 E Ob62949 0523205 400 E
SP 153-14
Mixture Proportioning for Highly-

Flowable Concrete Incorporating
Limestone Powder
by K. Sakata, T. Ayano, and A. Ogawa
Synopsis: T h e c o n c e p t of h i g h l y - f l o w a b l e c o n c r e t e w a s
d e v e l o p e d f r o m t h e t r a n s f o r m a t i o n of u n d e r w a t e r c o n c r e t i n g
ideas t o t h e c o n c r e t i n g s t r u c t u r e s on l a n d . T h e r e f o r e ,
t h e g e n e r a l p r o p e r t i e s of highly-flowable c o n c r e t e are
similar t o t h o s e f o r c o n c r e t i n g u n d e r w a t e r . The
v i s c o s i t y o f h i g h l y - f l o w a b l e c o n c r e t e i s h i g h so t h a t
s e g r e g a t i o n o f t h e coarse a g g r e g a t e f r o m t h e c o n c r e t e
--``,`,-`-`,,`,,`,`,,`---
c a n be e l i m i n a t e d . T h e s l u m p f l o w o f h i g h l y - f l o w a b l e
c o n c r e t e i s g r e a t e r t h a n 600mm so a s t o i n c r e a s e i t s
f l o w a b i l i t y . T h e s l u m p f l o w i s d e f i n e d a s t h e diameter
of s l u m p e d c o n c r e t e . T h e d i s t i n c t i v e f e a t u r e of t h e
m i x t u r e is t h a t a l a r g e r p r o p o r t i o n of f i n e m a t e r i a l is
u s e d i n i t . T h e h i g h v i s c o s i t y a n d l a r g e a m o u n t of
fines increases its resistance to segregation.
I n t h e m e t h o d of m i x t u r e p r o p o r t i o n i n g of h i g h l y -
flowable c o n c r e t e p r o p o s e d by t h e a u t h o r s , a h i g h - r a n g e
w a t e r - r e d u c i n g a d m i x t u r e (HRWRA) i s u s e d i n order t o
i n c r e a s e t h e slump flow. Furthermore, a s e g r e g a t i o n -
reducing a g e n t is used t o minimize t h e s e g r e g a t i o n
a l t h o u g h a l a r g e p r o p o r t i o n of f i n e s s o m e w h a t i n c r e a s e s
t h e v i s c o s i t y o f c o n c r e t e . L i m e s t o n e powder, w h i c h i s a
r e l a t i v e l y l o w reactive material, i s u s e d t o r e d u c e t h e
h e a t of h y d r a t i o n and s h r i n k a g e . I n t h e p r o p o s e d m e t h o d
of m i x t u r e p r o p o r t i o n i n g , it i s p o s s i b l e t o c h o o s e t h e
r e q u i r e d a v e r a g e s t r e n g t h , water c o n t e n t a n d f i n e
aggregate-total aggregate ratio to s u i t s p e c i a l and
p a r t i c u l a r c o n d i t i o n s of c o n c r e t e s t r u c t u r e s u n d e r
various environmental conditions.
Keywords: Aggregate; flowabilitv; limestone; mix proportionin%;

segregation; slump; viscosity; water content

A C 1 SP-153 V O L * I 95 E 0662949 0523206 347 m
250 Sakata, Ayano, and Ogawa
AC1 Member K e n j i S a k a t a i s professor, d e p a r t m e n t o f

environmental and civil engineering, faculty of
e n v i r o n m e n t a l s c i e n c e a n d t e c h n o l o g y , Okayama u n i v e r s i t y ,
Okayama, J a p a n
T o s h i k i Ayano i s l e c t u r e r , d e p a r t m e n t o f e n v i r o n m e n t a l
a n d c i v i l e n g i n e e r i n g , f a c u l t y of e n v i r o n m e n t a l s c i e n c e
a n d t e c h n o l o g y , Okayama u n i v e r s i t y , Okayama, J a p a n
A k i r a Ogawa i s g e n e r a l m a n a g e r , t e c h n o l o g y d e v e l o p m e n t
d i v i s i o n , t e c h n o l o g y d e p a r t m e n t , Ohmoto-Gumi C o . L t d . ,
Okayama , J a p a n
INTRODUCTION
The method f o r m i x t u r e p r o p o r t i o n i n g o f h i g h l y -
f l o w a b l e c o n c r e t e , w h i c h c a n be p o u r e d i n t h e c a s t i n g
forms without any compaction, i s presented i n t h i s
p a p e r . T h i s t y p e of c o n c r e t e i s of i m p o r t a n c e t o many
e n g i n e e r s b e c a u s e of t h e r e l i a b i l i t y o f e c o n o m i c a n d
--``,`,-`-`,,`,,`,`,,`---
e f f i c i e n t c o n s t r u c t i o n of c o n c r e t e s t r u c t u r e s by u s i n g
v e r y l i t t l e manpower f o r p l a c i n g o f v o i d - f r e e c o n c r e t e .
V a r i o u s t y p e s of m i x t u r e p r o p o r t i o n s o f h i g h l y - f l o w a b l e
c o n c r e t e h a v e b e e n p r o p o s e d b y some J a p a n e s e r e s e a r c h
o r g a n i z a t i o n s . Some o f t h e m h a v e been a p p l i e d i n a c t u a l
c o n s t r u c t i o n . It i s a p p a r e n t t h a t t h e p r a c t i c a l u s e of
h i g h l y - f l o w a b l e c o n c r e t e w i l l be a d o p t e d f o r o r d i n a r y
c o n s t r u c t i o n a l t h o u g h some p r o b l e m s s t i l l r e m a i n y e t .
The r e s e a r c h a n d d e v e l o p m e n t o n h i g h l y - f l o w a b l e
c o n c r e t e w e r e s t a r t e d e a r l y i n t h e 1 9 8 0 ' s by Okamura e t
a l ( 1 ) . And now, v a r i o u s t y p e s o f h i g h l y - f l o w a b l e
c o n c r e t e h a v e b e e n d e v e l o p e d a n d some of t h e m h a v e b e e n
u s e d i n actualconstruction. Suchhighly-flowable concrete
h a s been v a r i o u s l y called "High Performance C o n c r e t e "
or " H i g h l y - F l o w a b l e C o n c r e t e " o r " H i g h l y S u p e r p l a s t i c i z e d
C o n c r e t e " ( 2 ,3 , 4 ) . B u t , t h i s t y p e o f c o n c r e t e h a s n o t
been p r o p e r l y d e f i n e d y e t .
I n t h i s paper, t h e a u t h o r s have d e f i n e d highly-

f l o w a b l e c o n c r e t e a s concrete w h o s e s l u m p i s g r e a t e r
t h a n 250mm a n d w h o s e s l u m p f l o w i s b e t w e e n 6 0 0 a n d
700mm o n c o n d i t i o n t h a t t h e water does n o t bleed f r o m
t h e e d g e of t h e e x p a n d e d f r e s h concrete and t h a t t h e
coarse a g g r e g a t e does n o t a c c u m u l a t e a t t h e c e n t e r o f
expanded f r e s h c o n c r e t e . F u r t h e r m o r e , c o n c r e t e whose
s l u m p and s l u m p f l o w are l a r g e i s d e f i n e d as c o n c r e t e
of h i g h v a r i a b i l i t y . T h e c o n c r e t e , w h i c h t a k e s less

A C 1 SP-153 V O L * I 95 0662949 0521207 283
time t o p a s s t h r o u g h t h e f u n n e l o r h a s h i g h s e l f - r i s i n g
c a p a c i t y i n t h e b o x c u l v e r t c a s t i n g f o r m , i s d e f i n e d as
t h e c o n c r e t e of high f l o w a b i l i t y .
The p u r p o s e o f t h i s p a p e r i s t o p r e s e n t a m i x t u r e
proportioning method for highly-flowable concrete
i n c o r p o r a t i n g l i m e s t o n e powder f o r o r d i n a r y r e i n f o r c e d
c o n c r e t e i n w h i c h maximum s i z e o f a g g r e g a t e i s 20mm.
The r e q u i r e d a v e r a g e s t r e n g t h , t h e f l o w a b i l i t y a n d t h e
r e s i s t a n c e t o s e g r e g a t i o n can be c h o s e n e a s i l y b y u s i n g
t h e p r o p o s e d method.
CONCRETE MATERIALS
The method p r o p o s e d by t h e a u t h o r s has been

e s t a b l i s h e d by u s i n g t h e f o l l o w i n g m a t e r i a l s :
Cement
--``,`,-`-`,,`,,`,`,,`---
Normal p o r t l a n d c e m e n t t y p e - I was u s e d .
Limestone Powder
T h e s p e c i f i c g r a v i t y , a n d s p e c i f i c s u r f a c e area
o f l i m e s t o n e p o w d e r by t h e B l a i n e m e t h o d were 2 . 7 3 a n d
3,ûû0cm2/g, r e s p e c t i v e l y .
Aggregate
T h e coarse a g g r e g a t e w a s c r u s h e d s t o n e w i t h n o m i n a l
maximum s i z e o f 2Om. T h e f i n e a g g r e g a t e was r i v e r s a n d
a n d sea s a n d .
Hiah-Rancie Water-Reducinci Admixture
A naphthalene formaldehyde condensate was used.
Segregation-Reducing Agent
An a c r y l a m i d e a d m i x t u r e w a s u s e d .
APPARATUS AND T E S T PROCEDURE
T e s t €or F l o w a b i l i t y
I n order t o e x a m i n e t h e f l o w a b i l i t y o f h i g h l y -
f l o w a b l e c o n c r e t e , t h e s e l f - r i s i n g c a p a c i t y of h i g h l y -
flowable c o n c r e t e and t h e t i m e t o p a s s through t h e
f u n n e l were m e a s u r e d . T h e s e l f - r i s i n g c a p a c i t y i s t h e
h e i g h t o f r i s e o f h i g h l y - f l o w a b l e c o n c r e t e on t h e side

A C 1 SP-353 VOL*I 95 W O662949 0523208 33T m
o p p o s i t e t o t h e c a s t i n g s i d e of t h e b o x c u l v e r t f o r m
shown i n Fig.1 o r t h e U - t e s t a p p a r a t u s shown i n F i g . 2 .
The c o n c e p t of U - t e s t a p p a r a t u s h a s been d e v e l o p e d by
t h e a u t h o r s . T h e s i z e and s h a p e o f f u n n e l u s e d i s shown
i n Fig.3.
Evaluation of Resistance to Segregation
I n order t o e x a m i n e t h e r e s i s t a n c e t o s e g r e g a t i o n
of highly-flowable concrete, t h e ' r e s i s t a n c e index t o
s e g r e g a t i o n ' o b t a i n e d f r o m E q u a t i o n ( 1 ) was m e a s u r e d .
The r e s i s t a n c e i n d e x t o s e g r e g a t i o n is t h e r a t i o o f
coarse a g g r e g a t e (c-a) area i n t h e s q u a r e " B " t o t h a t
i n t h e s q u a r e " A " o n a c e n t e r s e c t i o n of b o x c u l v e r t a s
shown i n Fig.1. However, t h e h i g h l y - f l o w a b l e c o n c r e t e
w a s p l a c e d from o n l y one side t h a t i n v o l v e s s q u a r e " A " .
When t h e resistance i n d e x t o s e g r e g a t i o n i s h i g h , it
i n d i c a t e s t h a t t h e s e g r e g a t i o n of coarse a g g r e g a t e f r o m
c o n c r e t e is least.
--``,`,-`-`,,`,,`,`,,`---
c-a area i n t h e square "B"
R e s i s t a n c e index t o s e g r e g a t i o n - (1)
c-a area i n t h e square "A"
PROPOSED MIXTURE PROPORTIONING METHOD
Outline of the Promrtionina Method for K i U N V - F l a w a b l e Concrete
Fig.4 s h o w s a f l o w c h a r t u s e d i n t h e p r o p o r t i o n i n g
of t h e h i g h l y - f l o w a b l e c o n c r e t e i n c o r p o r a t i n g l i m e s t o n e
powder as p r o p o s e d by t h e a u t h o r s . The f i r s t s p e c i a l
f e a t u r e i s t h a t t h e q u a n t i t y of a g g r e g a t e i s same e v e n
i f t h e w a t e r - c e m e n t r a t i o (W/C), water c o n t e n t o r f i n e
a g g r e g a t e - t o t a l a g g r e g a t e r a t i o i s d i f f e r e n t . T h e HRWRA-
c e m e n t c o n t e n t r a t i o i s decided b y m i x e r c a p a c i t y a n d
t y p e of f i n e a g g r e g a t e as shown i n Table 1. However, it
i s n o t n e c e s s a r y t o a d j u s t f o r t h e e f f e c t of p i t s a n d
or c r u s h e d f i n e a g g r e g a t e u s e d f o r t h e a d j u s t m e n t o f
g r a d i n g . The q u a n t i t y o f s e g r e g a t i o n - r e d u c i n g a g e n t i s
decided b y W / C , water c o n t e n t and f i n e a g g r e g a t e - t o t a l
a g g r e g a t e r a t i o as shown i n T a b l e 2 . B o t h t h e q u a n t i t i e s
of t h e HRWRA a n d t h e s e g r e g a t i o n - r e d u c i n g a g e n t a r e n o t
i n v o l v e d i n t h e p r o p o r t i o n i n g of t h e u n i t c o n t e n t o f
concrete. T h e m i x i n g p r o c e d u r e o f c o n c r e t e i s a s
f o l l o w s : C e m e n t , l i m e s t o n e powder, f i n e a g g r e g a t e a n d
s e g r e g a t i o n - r e d u c i n g a g e n t a r e m i x e d f o r 30 s e c o n d s a t
d r y i n g c o n d i t i o n , a n d a f t e r t h a t , HRWRA, w a t e r a n d
coarse a g g r e g a t e a r e added a n d m i x e d f o r 2 m i n u t e s .

A C 1 SP-153 V O L + I 95 E 0662949 O521209 O56
Choice of W/C
The average strength of highly-flowable concrete

proportioned in accordance with Fig.4 is linear to
cement-water ratio as shown in Fig.5. Therefore, in
accordance with the same manner by which W/C of
ordinary concrete is decided, W/C for highly-flowable
concrete can be selected by using the relation between
28-day strength and cement-water ratio. The relation
between 28-day strength (f'c in MPa) and cement-water
ratio (C/W in % ) shown in Fig.5 can be expressed by
Equation ( 2 ) .
--``,`,-`-`,,`,,`,`,,`---
f'c=19.2XC/W+5.80 (2)
Choice of Water c o n t e n t
Fig.6 shows the relation between water content

and the time to pass through the funnel shown in Fig.3.
These results were obtained from the experiment of
highly-flowable concrete whose W/C was 0.5. Fig.7 shows
the relation between water content and the self-rising
capacity. The results shown in Fig.7 are measured by
the box culvert form shown in Fig.1. The symbols and
0 represent the results of highly-flowable concrete of
fine aggregate-total aggregate ratio 42.5% and W/C of
0.4 and 0.5, respectively. The symbols 0 and 0
represent the results of highly-flowable concrete of
fine aggregate-total aggregate ratio 52.5% and W/C of
0.4 and 0.5, respectively. A s shown in Fig.6 and Fig.7,
the higher the water content, the shorter the time
required to pass through the funnel and the higher the
self-rising capacity. Therefore, the higher the water
content, the better the flowability of highly-flowable
concrete proportioned in accordance with Fig.4.
Fig.8 shows the relation between water content
and resistance to segregation. The resistance index to
segregation shown in Fig.8 is obtained from Equation
(1). As shown in this figure, the resistance to
segregation of the highly-flowable concrete proportioned
by our method is high when the water content is least.
Fig.9 shows the ratio of bug holes to the area of
finished surface of highly-flowable concrete structure
with the concrete of water-cement ratio=0.4. A s is
evident from this figure, the more the water content of
highly-flowable concrete, the smaller the area occupied
by bug holes. So, the finishability of highly-flowable
concrete is better in case of higher water content.
Therefore, when thewater content of highly-flowable

c o n c r e t e i s chosen, t h e f l o w a b i l i t y shown i n Fig.6 and

F i g . 7 , r e s i s t a n c e t o s e g r e g a t i o n shown i n Fig.8 and
f i n i s h a b i l i t y shown i n Fig.9 a r e t a k e n i n t o c o n s i d e r a t i o n .
Furthermore, a s shown i n Fig.10 and Fig.11, when t h e
water c o n t e n t i s very low, t h e slump and slump flow a r e
small so t h a t t h e highly-flowable c o n c r e t e can n o t be
made w i t h very small amounts of water. On t h e o t h e r
hand, when water c o n t e n t i s very h i g h , l a r g e amounts of
segregation-reducing a g e n t a r e r e q u i r e d i n o r d e r t o
make t h e highly-flowable c o n c r e t e . Such a highly-flowable
c o n c r e t e can n o t s a t i s f y economic c o n s i d e r a t i o n s .
Determination of Limestone Powder Content
I n o r d e r t o o b t a i n t h e limestone powder c o n t e n t ,
t h e base f i n e aggregate c o n t e n t S , and t h e base c o a r s e
aggregate c o n t e n t G, should be decided. The t o t a l
volume of t h e base mixture c o n t a i n i n g S,, G,, cement
c o n t e n t , water c o n t e n t and a i r c o n t e n t b u t n o t limestone
powder i s l m 3 . The G, i s o b t a i n e d by m u l t i p l y i n g t h e
mass of u n i t volume of oven-dry c o a r s e aggregate by t h e
--``,`,-`-`,,`,,`,`,,`---
c o e f f i c i e n t shown i n Table 3 r e l a t e d t o f i n e n e s s
modulus of f i n e aggregate. T h e S, i s o b t a i n e d by
m u l t i p l y i n g t h e volume, t h a t i s found by s u b t r a c t i n g
a l l components except f o r f i n e aggregate and limestone
powder from lm3, by t h e d e n s i t y of f i n e aggregate.
Fig.12 shows t h e r e l a t i o n between t h e q u a n t i t y of
limestone powder and slump flow. The symbols 0 and 0
r e p r e s e n t t h e r e s u l t s of t h e c o n c r e t e o b t a i n e d from
r e p l a c i n g a p a r t of f i n e aggregate and c o a r s e aggregate
c o n t e n t of base c o n c r e t e mixture shown i n Table 4 w i t h
limestone powder. The symbol A r e p r e s e n t s t h e r e s u l t s
of t h e c o n c r e t e o b t a i n e d from r e p l a c i n g a p a r t of
a g g r e g a t e c o n t e n t w i t h limestone powder keeping t h e
f i n e a g g r e g a t e - t o t a l aggregate r a t i o a t 4 7 . 5 % t h a t i s
same a s t h a t of base c o n c r e t e . The f i n e a g g r e g a t e
c o n t e n t and c o a r s e aggregate c o n t e n t of base c o n c r e t e
shown i n Table 4 correspond t o S, and G,, r e s p e c t i v e l y .
I t i s c l e a r t h a t slump flow of c o n c r e t e i s more t h a n
600mm when a p a r t of f i n e or c o a r s e aggregate i s
r e p l a c e d w i t h t h e limestone powder by 2 0 % of S,.
Whereas, when a p a r t of t h e c o a r s e a g g r e g a t e i s
r e p l a c e d w i t h t h e limestone powder, t h e slump flow of
c o n c r e t e w i t h limestone powder r e p l a c i n g 3 0 % of S, i s
s m a l l e r t h a n t h a t of c o n c r e t e w i t h limestone powder
r e p l a c i n g 2 0 % of S,. When a p a r t of f i n e aggregate i s
r e p l a c e d w i t h t h e limestone powder, t h e slump flow of
c o n c r e t e w i t h limestone powder r e p l a c i n g 3 0 % of S, i s
l a r g e r t h a n t h a t of c o n c r e t e w i t h limestone powder
r e p l a c i n g 2 0 % . B u t , it i s observed experimentally t h a t
t h e r e i s bleeding water a t t h e p e r i p h e r y of expanded
f r e s h c o n c r e t e and accumulation of c o a r s e aggregate a t

A C 1 SP-153 VOL*I 95 0 6 6 2 9 4 9 0521211 704
the center of expanded fresh concrete in which a part

of fine aggregate is replaced with limestone powder at
30% S,. Furthermore, it is obvious that the slump flow
of concrete is smaller than 6 0 0 m when a part of total
aggregate content is replaced with limestone powder
without any change in fine aggregate-total aggregate
ratio of the base concrete.
Therefore, in o u r proportioning method of highly-
flowable concrete, the limestone powder content is
obtained by multiplying the 20% volume of the S , by the
density of limestone powder in accordance with the
result shown in Fig.12. The limestone powder content
obtained by above procedure is increased when the
amount of fine particles involved in fine aggregate is
small. The above procedure to select the limestone
--``,`,-`-`,,`,,`,`,,`---
powder content can adjust the quantity of fine particles

of fine aggregate by a part of limestone powder,
automatically.
Choice of Fine Aggregate and Coarse Aggregate Content
Fig.13 shows the relationship between slump flow

and fine aggregate-total aggregate ratio of concrete
with limestone powder replacing 20% Ss for mixture
shown in Table 4. A s is evident from Fig.13 for fine
aggregate-total aggregate ratio is lower than 47.5%,
the smaller fine aggregate-total aggregate ratio, the
larger the slump flow. But, it should be further
confirmed from bleeding of paste at the tip of expanded
fresh concrete and accumulation of the coarse aggregate
at the center of expanded fresh concrete when fine
aggregate-total aggregate ratio is smaller than 42.5%.
when fine aggregate-total aggregate ratio is larger
than 52.5%, the largerthe fine aggregate-total aggregate
ratio is, the smaller the slump flow. And, when fine
aggregate-total aggregate ratio is same as 47.5% as
that of proportions of base concrete, the slump flow is
not larger than 600mm.
Therefore, in our proportioning method for highly-
flowable concrete, the fine aggregate-total aggregate
ratio, which is 42.5% or 52.5%, should be chosen,
alternatively. The choice of fine aggregate-total
aggregate ratio between 42.5% and 52.5% should be
decided according to the scheme and condition of
concrete structure while referring to the results shown
in Fig.6, 7, 8 and 9.
Change of Flowability with T h and Maintaining Flowability
When a construction site is far from a concrete

mixing plant, or when conveying a large amount of

A C 1 SP-153 VOLaI 95 0662947 0521212 640 =
concrete is restricted, one should keep the flowability

of highly-flowable concrete f o r a long period after
mixing. However, onecannot expectto keepthe flowability,
especially when the ambient temperature rises very much
in the summer, o r when the start of casting is delayed
for certain reasons for the progress of work. T o know
the change of flowability with time and keeping the
expected flowability after mixing is very important in
order to use the highly-flowable concrete in concrete
construction. That is why one should know the effect of
time-dependent change of slump flow on the flowability
of highly-flowable concrete.
--``,`,-`-`,,`,,`,`,,`---
The proportions of the highly-flowable concrete
used in this investigation are shown in Table 5. These
proportions have been selected in accordance with
Fig.4. The experimental data are obtained in the laboratory
and have been obtained by using a forced mixer with a
capacity 40 litre and slump flow is controlled by the
addition of a HRWRA.
Fig.14 shows the change of slump flow with time,
and Fig.15 shows the change of flowability with time
which was measured by the U-test apparatus shown in
Fig.2. The positive values of vertical axis represent
the height of rise of highly-flowable concrete on
opposite to the casting side of the apparatus. The
negative values on vertical axis in Fig.15 represent
the distance from the tip of stationary highly-flowable
concrete after placing to the bottom corner of opposite
to casting side. The symbols and represent the
results of highly-flowable concrete whose fine aggregate-
total aggregate ratios are 42.5% and 52.5%, respectively.
These concretes, having 650*50mm slump flow immediately
after mixing, contain 8.46kg/m3 ( C X2.35%) of HRWRA.
The symbols 0 and 0 represent the results of highly-
flowable concrete whose fine aggregate-total aggregate
ratios are 42.5% and 52.5%, respectively. Theseconcretes,
having 75Ok50mm slump flow immediately after mixing,
contain 10.3kg/m3 (CX2.85%) of HRWRA. It is apparent
from the above that the time-dependent change of slump
flow of highly-flowable concrete is closely related
with that of flowabilitymeasuredby theU-test apparatus.
The flowability of the concrete deteriorates with the
decreasing of slump flow. And, when the change of slump
flow is small, the change of flowability is also small.
On the other hand, with a slump flow 650k50mm immediately
after mixing, the flowability immediately after mixing
of the concrete of fine aggregate-total aggregate ratio
52.5% is higher than that of fine aggregate-total
aggregate ratio 42.5%; and, the time-dependent change
of the flowability of concrete of fine aggregate-total

A C 1 SP-153 V O L * I 95 0bb2947 0521213 5 8 7 W
a g g r e g a t e r a t i o 5 2 . 5 % i s a l s o much h i g h e r t h a n t h a t o f
f i n e aggregate-total aggregate ratio 42.5%.
Fig.16 s h o w s t h e t i m e - d e p e n d e n t c h a n g e of s l u m p
f l o w recovered a t 40 o r 8 0 m i n . a f t e r m i x i n g . T h e
r e s u l t s shown i n t h i s f i g u r e a r e o b t a i n e d f r o m t h e
experiment of highly-flowable concrete with fine
a g g r e g a t e - t o t a l aggregate ratio of 52.5% and w i t h a
s l u m p f l o w o f 6 5 0 k 5 0 m m . T h e s y m b o l b, r e p r e s e n t s t h e
r e s u l t f o r c o n c r e t e i n which slump f l o w had never been
r e c o v e r e d . The symbols and 0 represent t h e r e s u l t s
o f c o n c r e t e w h o s e s l u m p f l o w w a s recovered a t 4 0 m i n .
a f t e r m i x i n g t o 6 5 0 k 5 0 m m a n d 750 *50mm, r e s p e c t i v e l y .
And, t h e s y m b o l s and 0 r e p r e s e n t t h e r e s u l t s of
c o n c r e t e w h o s e s l u m p f l o w w a s recovered a t 8 0 m i n .
a f t e r m i x i n g t o 6 5 0 1 5 0 m m a n d 7 5 0 &50mm, r e s p e c t i v e l y .
I t i s c o n c l u d e d from t h e d a t a i n F i g . 1 6 t h a t t h e s l u m p
f l o w i s decreased a g a i n when t h e s l u m p f l o w i s recovered
by 6 5 0 i 5 0 m m a n d t h a t t h e s l u m p f l o w n e v e r c h a n g e s
a f t e r t h e r e c o v e r y of s l u m p f l o w by 7 5 0 k 5 0 m m . I n o t h e r
words, t h e e f f e c t o f t h e s i z e o f recovered s l u m p f l o w
o n t h e t i m e - d e p e n d e n t c h a n g e o f s l u m p f l o w i s same a s
t h a t o f t h e s i z e i m m e d i a t e l y a f t e r m i x i n g shown i n
Fig. 14.
Fig.17 s h o w s t h e f l o w a b i l i t y of t h e c o n c r e t e
whose slump f l o w i s r e c o v e r e d a t 4 0 o r 8 0 m i n . af.ter
mixing. It is e v i d e n t from t h i s f i g u r e t h a t t h e
flowability o f t h e concrete c a n be a l w a y s r e c o v e r e d u p
t o t h a t of immediately a f t e r mixing i f t h e s i z e of
slump f l o w can be recovered i s t h e same a s t h a t
immediately a f t e r mixing.
--``,`,-`-`,,`,,`,`,,`---
CONCLUS IONS
A method of proportioning for highly-flowable

c o n c r e t e w i t h l i m e s t o n e powder h a s b e e n p r o p o s e d . I n
t h i s method, t h e r e q u i r e d a v e r a g e s t r e n g t h , water
c o n t e n t a n d f i n e a g g r e g a t e - t o t a l a g g r e g a t e r a t i o c a n be
p r e s e l e c t e d or c h o s e n a c c o r d i n g t o t h e scheme a n d
c o n d i t i o n of c o n c r e t e s t r u c t u r e w h i l e r e f e r r i n g t o t h e
f l o w a b i l i t y , r e s i s t a n c e t o s e g r e g a t i o n and f i n i s h a b i l i t y
a s d e f i n e d i n t h i s p a p e r . F u r t h e r m o r e , it i s c l e a r l y
i n d i c a t e d t h a t t h e f l o w a b i l i t y of h i g h l y - f l o w a b l e c o n c r e t e
c a n be r e c o v e r e d b y r e c o v e r i n g t h e s i z e o f s l u m p f l o w
w h i c h i s t h e same as t h a t i m m e d i a t e l y a f t e r m i x i n g . I t
i s h o p e d t h a t t h i s t y p e o f concrete w i l l b e u s e d i n t h e
f i e l d f o r a v a r i e t y of p r o j e c t s t o p r o d u c e r e l i a b l e a n d
d u r a b l e concrete s t r u c t u r e s .

A C 1 S P - 1 5 3 V O L * I 95 I0662949 0521214 913 m
REFERENCES
1. I z u m i , T . , Maekawa, K., Ozawa, M . , a n d K u n i j i m a M.

" T h e E f f e c t of C e m e n t P a s t e o n F r i c t i o n R e s i s t a n c e
between S o l i d M a t t e r s " , P r o c e e d i n g of t h e J a p a n
C o n c r e t e I n s t i t u t e , Vol.10, 1 9 8 8 , p p . 3 0 9 - 314 ( i n
JapaneSe).
2. Okamura, H . , M a e k a w a , K., a n d O z a w a , M. " H i g h
P e r f o r m a n c e C o n c r e t e " , Gihohdoh P u b l i s h i n g Co. l t d . ,
1993 ( i n J a p a n e s e ) .
3. " S y m p o s i u m o n H i g h l y - f l o w a b l e c o n c r e t e " , t h e J a p a n
Concrete I n s t i t u t e , 1993 ( i n J a p a n e s e ) .
4 . O h a s h i , J. , T a m a i , S . , a n d Maeda T. " B a s i c P h y s i c a l
Properties of Highly Super-Plasticized Concrete" ,
C o n c r e t e R e s e a r c h a n d T e c h n o l o g y , Vo1.2, No.2, I s s u e
4 , 1 9 9 3 , pp.13 - 2 3 ( i n J a p a n e s e ) .
--``,`,-`-`,,`,,`,`,,`---
TABLE 1 - QUANTITY OF HRWRA
I Type of mixer I
(mixer volume)
Forced mixing type Tilting mixer
(40Q) (1.6d) (1d)
Zi
.-> 2.4% 1.2% 1.5%
U
a
a,
CI) 3.6% 1.8% 2.2%

A C 1 SP-II53 V O L X I 95 I Obb274q 0521215 3 5 T m
TABLE 2 - QUANTITY OF SEGREGATION-REDUCING AGENT
II I 0.4
%I 0.0 kg
?
Water-Cement ratio
1.5 kg 8 3.0 kg 8
Y-
0.5
1.5 kg :1
I
O1
0.6
5.0 kg
7.0 kg
I
50
io 7 7
io
P-
- 3.0 kq E 4.5 kq
O
8 9.0 k q
%I1.5 kg 3.0 kg Iml 7.0 k g l
2 3.0 kg 4.5 kg 7 o 9.0 kg
a 11.0 kg
v-
2 4.5 kg
7
6.0 kg
TABLE 3 - UNIT COARSE AGGREGATE RATIO
F.M. of fine aggregate 2.40 2.60 2.80 3.00

Coefficient 0.65 0.63 0.61 0.59
TABLE 4 - PROPORTIONS OF BASE CONCRETE
Unit weight (kg/m3)

W C Lf s G HRWRA S.R.
2.0 0.5 47.5 170 340 - 867 1006 7.99 3.00
S.R.: Segregation-reducingagent
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L + I 95 IObb29Vq 052123b 296 =
TABLE 5 - PROPORTIONS OF CONCRETE WITH LIMESTONE

POWDER
Air s'a Unit weight (kg/m3)

% % W C Lf s G HWRA S.R.
42.5 703 1010 4.50
2.0 0.5 - 180 360 135 variable
52.5 868 834 3 .O0
~~
S.R ,: S e g regation-reducing age nt
r
Placing of concreie Placing of concrele
I
--``,`,-`-`,,`,,`,`,,`---
2000mmL
Fig. 1-- F.ig. l-Size and shape of box culvert
(All measurements in mrn)
Fig. 2-U-test apparatus

A C 1 SP-353 V O L + I 95 0662949 0523237 1 2 2 H
(Al measurements in mm)
Fig. &Size and shape of funnel

--``,`,-`-`,,`,,`,`,,`---
Flowability
Segregation
Finishability
F.M. of
I-.’
f i n e aggregate
Gg -b S g - W Lf
W e i g h t of u n i t v o l u m e
of coarse a g g r e g a t e
Fig. &Procedure of proportioning of highly flowable concrete

incorporating limestone powder

A C 1 SP-153 VOL81 95 E O662949 0521218 O69 =
--``,`,-`-`,,`,,`,`,,`---
Cement /water ratio % -

Fig. 5-Compressive strength at 28 days
170 180 190

Water content - kg / m3
Fig. &Time to pass through funnel

A C 1 SP-153 V O L X I 95 I0662947 0521219 TT5 I
Water content kg / m3 -
Fig. 74elf-rising capacity
8
hoo'
.-0 1
ci
m
80
L.
a
a
*O 60
ci
x
%c 40
.-
al
20
Y
a
--``,`,-`-`,,`,,`,`,,`---
Fig. &Degree of segregation of highly flowable concrete

6.q i
8 I Form size = 70x 70x 100cm
I
.-
O
ci 5.0 ..........
2
a .........
o 4.0
m
rc
L
3
v) 3.0
ci, ',
-a
0 2.0
*.
c
1.0
155 165 175
-
Water content kg / m
Fig. %Bug holes on concrete surface
21 .o'
140 160 180 200 220
Fig. 10-Relation between slump and unit water content
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I
No reproduction or networking permitted without license from IHS 95 E NotObb2949
for Resale 0523220 717 m
30.0'
140 160 180 200 220
Fig. 11-Relation between slump flow and unit water content
70.0- l . .
i
COarse aggregat e re piacernent
........................................
................ ................. ................................... .......................... ..........

- e - - - -
\
Q
\ *\,
E
-3 55 o ...i.. aggregate replacement
................
\
................ >.%..
v) * '
I 8
50.0'
O 90 180 27O
Limestone powder content kg/m3 -

Fig. 12-Effect of limestone powder quantity on slump flow
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 75
Obb2ïi.19
Not for Resale
0521221 653 I
E o
6
=I
50.0
--``,`,-`-`,,`,,`,`,,`---
40.0
40.0 45.0 50.0 55.0 60.0 65.0
d a - %
Fig. 13-Relation between slump flow and fine aggregate-total
ratio
s / a.= 52.5 %
-
tñ 5n (.-mixing= 65050mm
40.0
I w=l80,kg/m,
' 3
, , / , , ,
O 40 80 120
Time after mixing min. -

Fig. 14-Change of slump flow with time

A C 1 SP-153 VOL*I
No reproduction or networking permitted without license from IHS 95 O662949
Not for Resale 0521222 5 9 T
A C 1 SP-353 VOL*I 95 IB 0662949 0523223 426
s I a =52.5 %
Slump flow jukt after mixing
i+50mrn,750+50mm '
L
/ : I sja=42.5% I
--``,`,-`-`,,`,,`,`,,`---
Q)
S
L
O
o
E
L
yl
.-O
a
-40.0' ' ' '

O 40 80 120
Time after mixing min. -
Fig. 15-Change of self-rising capacity with time
O 40 80 120
Time after mixing - min.

Fig. 1GChange of slump flow with time

A C 1 SP-I153 VOL+I 95 IOb62747 0 5 2 3 2 2 4 3 6 2 =
E
o
I
L
Q)
E
O
o
E
2 HRWRA = ..........
............................................................................ 75060mrn
.
--.
ic
-
Q) -10.0 _.
i *.
o 's/a=52.5%
c
Cu
ci -20.0
.-
..............................
.'slump flow just --
.! ................
after
...* .
I........... No addition
.-G,.-,
....
--``,`,-`-`,,`,,`,`,,`---
:
?I*--
v)
mixing = 650fiOmm :
n
'
Fig. 1/-Recovery of self-rising capacity

A C 1 SP-153 VOL*I 95 8. Obb2949 0523225 2 T î
SP 153-15
Properties of Lightweight
Aggregate Produced from a
High Calcium Fly Ash
by G. Baykal, T. Özturan,
--``,`,-`-`,,`,,`,`,,`---
M. Savaz, and K. Z. Ramadan
Svnousis : Because of increasing annual production volumes of fly ash,

large volume applications such as aggregate production are beneficial in
solving the disposal problem of fly ash while making economical use of a
mineral resource. Aggregates have been produced from high calcium fly
ash of Soma Theimal Power Plant and their engineering properties have
been measured. For high volume utilization of fly ash, aggregate
production involving pelletization and pressing into specially designed
molds has been carried out successfully. Mechanical propeity and
durabiliiy tests were conducted on the cured lightweight fly ash
aggregates; five per cent by weight lime addition to fly ash showed the
best performance. It is also shown that different shapes of aggregates can
be produced using the pressing technique.
Kevwords: Aggregates; durability; fly ash; lightweight aggregates; lime fly

ash; mechanical properties; pelleting

269
A C 1 SP-153 V O L * I 95 I0662747 0 5 2 1 2 2 b 135 I
270 Baykal et al
Gökhan Baykal is an associate professor at the Department of Civil

Engineering, Bogaziçi University, Istanbul, Turkey. He is the director of
“Center for Industrial By-products Utilization”. His research interests
include environmental geotechnics, fly ash utilization, microanalysis
techniques and aggregate production.
Turan Özturan is an associate professor at the Civil Engineering
Department, Bogaziçi University, Istanbul, Turkey. His research interests
include utilization of mineral by-products in concrete, high strength
concrete and durability of cement composites.
Mahmut Savas is an associate professor at the Department of Mechanical
Engineering, Bogaziçi University, Istanbul, Turkey. His main research
interest is in crystal growth and manufacturing processes which involve
a phase change.
Khaled Z. Ramadan is a PhD Candidate at the Department of Civil
Engineering, Bogaziçi University, Istanbul, Turkey.
INTRODUCTION
Annual fly ash production in Turkey has reached approximately 15

million tons. Only a few per cent of it is utilized. Among the various
methods of using fly ash in different areas of civil engineering is
lightweight aggregate production ( 1-7 ). Production of aggregates from
fly ash will create a huge mineral source for the construction industry and
at the same time handling of fly ash will be easier and environmentally
safer.
Granulating or pelletizing of the fly ash is the basic step in the

--``,`,-`-`,,`,,`,`,,`---
technology of lightweight aggregate production. Binding of the fly ash

particles in pellets can be accomplished by using either a cold- binding or
sintering technique ( 5-6 ). Binding materials such as portland cement,
lime, gypsum, aluminium powder are used within this process. The final
step in the production method is the curing of the fly ash aggregates. The
temperature, humidity and pressure applied during the curing process and
the duration of curing are the most important parameters.
Lightweight fly ash aggregates thus obtained find many

applications in the civil engineering industry as other natural and
manufactured lightweight aggregates do. Beneficial properties of
lightweight aggregate concrete include lightness and heat insulation.
Construction of highway base and subbase layers using fly ash aggregates

A C 1 SP-153 V O L U I 95 0662949 0523227 071
with good drainage and durability properties is one applicatioin example.

The engineering properties of these aggregates , however, determine the
limitations for their use . The parameters involved in mixing, pelletizing,
curing and binding procedures are the prime factors affecting these
properties.
In this study, the production of lightweight fly ash aggregates

through the cold binding method with the aid of lime in v a ~ i o u s
percentages as a binder is considered. The effect of lime content on
various engineering properties has been investigated. Further
investigations are directed towards surface treatment of the lightweight
pellets with water glass.
METHODOLOGY
Materials Used
The fly ash was sampled from Soma Thermal Power Plant which is
located in the West region of Turkey. Lignite ( 2100-2400 kCal) is used in
this power plant for energy production. Presently the fly ash produced in
this unit is mixed with water and pumped to a dam for disposal. The fly
ash was sampled from the central compartment of the electrostatic
precipitator. Approximately 1 ton of fly ash was used in this study. After
sampling, the fly ash was sealed to prevent carbonation and any increase
in its moisture content. The physical and chemical properties of the fly ash
are given in Tablel. The Blaine fineness is 382 m”kg, and the mean
diameter is 17.7 pm, and the specific gravity of the fly ash is 2.22. This
is a high calcium fly ash, with self cementitious properties. The SO3
content is less than 5 YOand the loss on ignition is 1.1 YO.
Lightweight Flv Ash AggrePate Production Technique
The flow diagram of the aggregate production technique used in this

study is given in Fig. l a , lb. Five per cent, 10% and 20 % by weight of
hydrated lime are mixed with fly ash at a water content to the wet side of
the optimum water content obtained from Standard Proctor test (ASTM
D698). By continuous manual mixing pellets are formed. The pellets are
coated with dry fly ash and are sieved through different size sieves. The
aggregates produced are placed into sealed bags and are cured for 28 days
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 œ Obb29LI9 0521228 TO8 œ
272 Baykal et al
at 21OC in the curing room. After the completion of curing time, bulk unit
weight , specific gravity, water absorption (ASTM C127), Los Angeles
abrasion test (ASTM C13 i), sodium sulphate durabiliîy (S), crushing
value (BS 812) and California Bearing Ratio (AASHTO T 193) and point
load tests were conducted . Radiographic pictures of the cured and
uncured aggregates were taken to observe any density change and cracks
in the aggregates and it was observed that the pelletization technique used
was adequate. Finally, to improve the properties of the aggregates
produced, surface treatment was done by using water glass. Some of the
aggregates were immersed in water glass for ten minutes and then dried
with air pressure, before being heat treated in an oven for 12 hours at 110
O C . The aggregates with surface treatment were then tested for water
absorption, Los Angeles abrasion, crushing value and freeze-thaw

durability. In addition to pelletization technique, pressing technique for
aggregate production was investigated using specially designed steel
molds.
RESULTS and DISCUSSION
--``,`,-`-`,,`,,`,`,,`---
The experimental results are summarized in Table 2.
Phvsical Propeities
Bulk Unit Weight Tests -- The unit weights of different size ranges
of aggregates and the effect of adding lime to fly ash on bulk unit weight
is given in Fig. 2. The bulk unit weights range between 6.8 - 9.3 kN/m3
with the lower values for the larger aggregate sizes. Addition of lime to
fly ash reduces the bulk unit weight. This reduction is more prominent for
large size ranges as compared to that of the finer aggregates. For use in
concrete, backfill, fill and block making the light weight of the produced
aggregates will result in economical implications.
Specific Gravity -- The specific gravity of the lime-added

aggregates range between 1.51 and 2.00 (Fig. 3) . The specific gravity of
the aggregates produced with 5% lime addition is the highest. Although
the specific gravity of the aggregates were expected to decrease with
increasing lime content due to the low unit weight of lime, an increase in
specific gravity for 5% lime addition is observed, which suggests that the

A C 1 SP-153 VOL*I 95 9 Obb2747 0523229 944 9
pelletization procedure is most efficient for this percentage. Higher lime

contents decrease the specific gravity to 1.52.
Water Absorption of Aggregates -- Water absorption values are

around 30 % , which is high but typical for this type of lightweight
aggregate. An increase in lime content does not affect the water absorption
of the aggregates significantly. It can be concluded that the void ratio of
the aggregates are not affected from lime addition. These aggregates are
appropriate for structural and sub structural unit production however the
high water absorption property should be considered during mixture
design.
Mechanical Properiies
The effect of lime content on the mechanical properties and durability of

fly ash aggregates are given in Figure 4.
Los Angeles Abrasion -- TestsTo investigate the potential use of the

aggregates produced in highway pavements, abrasion properties are
measured by Los Angeles Abrasion Test. The abrasion loss for the 5%
lime added aggregates decreases to 44.7% fiom the abrasion loss of
4’7.8% for fly ash aggregates with no lime addition. The specifications
allow aggregates up to 50% abrasion loss, which states that the produced
aggregates are suitable in this regard for pavement wearing surface.
Crushing Value Tests -- The crushing value test i s an indication of

the aggregate strength. The crushing values of the lime-added fly ash
aggregates range between 32% and 46% . The lowest value is obtained for
5% by weight lime addition. For comparision, limestone aggregate of
similar grain size is also tested and the crushing value is found to be
around 22%.
California Bearing Ratio Test -- For the investigation of potential

use of lightweight fly ash aggregates as base and subbase materials for
highway pavements CBR tests are conducted. The CBR value increases
--``,`,-`-`,,`,,`,`,,`---
fiom 71% for no lime addition to 83% for 5% lime added fly ash
aggregates. The minimum value for CBR is given as 80% for bases and

A C 1 SP-153 V O L S I 95 W 0662949 0523230 666 =
274 Baykal et al
subbases in the specifications (AASHTO T 193). Lime addition to fly ash

has increased the CBR values over the specified limits. The fly ash
aggregates with 5% lime addition can be used as base and subbase
material in highway pavements.
Point Load Tests -- The point load values for 0% and 5% by weight
lime added fly ash aggregates are around 200 kg (Figure 5). Further
increase in lime content decreases the point load values to less than half of
the values obtained for 0% and 5% lime added aggregates. This suggests
that high lime contents are not desirable for high particle strength.
Durability
Freezing and Thawing Tests -- The indirect measurement of

freezing and thawing durability is made by using sodium sulphate solution
(8). The fly ash aggregates with no lime addition have the best durability
--``,`,-`-`,,`,,`,`,,`---
(7% weight loss after treatment). With lime addition the losses after
sodium sulphate treatment increases to 14-16% by weight. The weight
losses after freezing and thawing greater than 12% is an indication of
poor quality. Special precautions should be taken if the aggregates are to
be used in areas where excessive freezing and thawing cycles are
expected.
The Effect of Freezing and thawing Cycles on Crushing Value and Point
Load Value
The aggregates with 5% lime were subjected to direct freezing and

thawing cycles. The aggregates were placed in a deep-freezer for 48 hours
at -20°C and then thawed at 21°C for 48 hours. Ten cycles were
completed for each set of aggregates. Crushing value tests and point load
tests were then conducted on these samples. The crushing value
increased from 32% to 39%, and the point load value decreased from 1.94
kN to 1.19 kN after freezing and thawing cycles are applied to the
aggregates. The fly ash aggregates were adversely affected by freezing
and thawing cycles. This is an important consideration if these aggregates
are to be used in areas with extreme weather conditions.

A C 1 SP-153 V O L J I 95 Obb29LI9 0523233 5T2
The Effect of Surface Treatment
The aggregates with 5% lime were treated with water glass and
cured at 110°C for 24 hours. The surface treated aggregates were
subjected to physical and mechanical property tests (Table 3). The water
absorption values of the aggregates decreased from 32% to 18.8%. This
shows that water glass helped to seal pores on the surface. Freezing and
thawing loss decreased from 15.4% to 11.8%. The crushing value was not
affected much with surface treatment. The abrasion ratio decreased from
45% to 37% with surface treatment.
Pressing. Technique
Fly ash mixtures with 25% by weight of water were prepared and
pressed into circular and rectangular cross sectioned steel molds under 800
kPa pressure. The pressed specimens were exti-uded from the mold, sealed
and cured for 28 days at 21°C. The compressive strength of the cured
specimens reached 15 MPa. In the beginning many problems were
encountered in sample preparation. Later with the experiences gained, the
production of the pressed aggregates became easier. Finally a very
complex aggregate shape was also produced by the pressing technique
which (to be reported later). The feasibility of producing special shaped
aggregates at the industrial production level is being investigated.
CONCLUSIONS
1- Different size aggregates are produced from fly ash by using

pelletization technique. The optimum lime addition for pelletization was
found to be 5% by weight.. Five percent lime addition increased the
strength of fly ash aggregates while decreasing the freezing and thawing
durability of the aggregates when compared to fly ash aggregates with no
lime addition. Optimum lime content should be selected so that while
increasing the strength of the aggregates the durability should not decrease
to values lower than the specified limits.
2- The fly ash aggregates produced comply with common specifications

and have potential for use as lightweight aggregate in different areas of
civil engineering such as: lightweight concrete, highway base, subbase and
wearing courses, embankment fill, and backfill materials.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I 95 I0662949 0523232 439 W
276 Baykal et al
--``,`,-`-`,,`,,`,`,,`---
3- Special shaped aggregate production is tried using pressing technique

into specially designed molds. The compressive strength of pressed fly ash
has reached 15 MPa after 28 days of curing at 21" C. Feasibility of
aggregate production using pressing technique at the industrial level
should be investigated further.
4- Surface treatment using water glass and curing produced a glassy film
on the surface of aggregates which has improved the crushing value,
water absorption, and abrasion values. However this technique is
expensive and other surface treatment methods should be tried.
ACKNOWLEDGEMENTS
We would like to express our gratitude to Turkish Scientific

Research Institution for their financial support for this research project.
REFERENCES
1. Beny, E., Malhotra, V.M., " Fly Ash for Use in Concrete - A Critical
Review AC1 Journal, V.77., N.2, pp. 59 - 73, 1980.
'I,
2. Swamy, R.N. ( Editor ), " Cement Replacement Materials ", Surrey

University Press, 1986.
3. Naik, T.R., Wei, L., and Golden, D.M., Application of Good I'
Combustion By-products Utilization EPRI Report No: 104, 1992. 'I,
4. Baykal, G., Köprülü, K., Rubber Added Fly Ash Base and Subbase in
'I
Highway Construction 10th Fly Ash Utilization Symposium,

I',
Orlando, Florida, USA, 1993.

5 . Hwang, C.L., Lin, R.Y., Hsu, K.M., and Chan, J.F., Granulation of I'
Fly Ash Lightweight Aggregate and Accelerated Curing Technology I',

Proceedings of the 4th International Conference on Fly Ash, Silica
Fume, Slag, and Natural Pozzolans in Concrete, Istanbul, Turkey, V. 1.,
P.P. 419 438, 1992. -
6. Yamashita, T., Yamane, R., Kohata, H., Sera, S., Kasami, H., Izumi, I.,
and Yonezawa, T., Fly Ash Lightweight Aggregate Sintered in a
'I
Circular Grate Kiln ",Proceedings of the 4th Intemational Conference

on Fly Ash, Silica Fume, Slag, and Natural Pozzolans in Concrete,
Istanbul, Turkey, Supplementary Papers, p.p. 895 915, 1992. -

A C 1 SP-it53 V O L * I 95 Obb29Ll9 0521233 375 E
7. Baykal, G., Savas,M., Özturan,T., and Ramadan, K., “Aggregate and

Composite Production Using Fly Ash “TUBITAK, INTAG 606
Research Report, Istanbul, Turkey, 1994.
8. Postacioglu, B. “ Concrete”, (in Turkish), Matbaa Teknisyenleri
Publishers, Istanbul, Turkey, 1987.

OF FLY ASH
Chemical Analysis Fly Ash (%)
Silicon dioxide, SiO- 47.20

Aluminum oxide, A1203 25.56
Iron oxide, Fez03 5.64
Calcium oxide, Ca0 14.49
Magnesium oxide, MgO 2.04
Sulphur trioxide, SO3 2.74
Loss on ignition 1.10
--``,`,-`-`,,`,,`,`,,`---
Physical Properties
Blain finenss, m’Ag 382

Relative density 3 33
I.--

A C 1 SP-153 VOLrI 95 W Obb2949 0523234 203 W
278 Baykal et al
--``,`,-`-`,,`,,`,`,,`---
ir!
r

A C 1 SP-153 VOL*I 9 5 IObb29Ltï 0523235 L 4 â
Absorption Loss Angeles Crushing Value Sodium Sulphate

Po) Abrasion @) Soundness
( /O/
O) (“A)
18.8 37.0 30.1 11.8
1 Mixing Fly Ash At Different Lime Contents I
Testing the Pellets For,
Unit weight
Specific Gravity
Absorption
Los Angeles Abrasion
Soundness
Crushing Value
--``,`,-`-`,,`,,`,`,,`---
California Bearing Ratio
Point Load Test
L
Aggregate Production At
Selected Lime Content
Performance Tests;
Crushing
Point Load
Performance Tesis,
Abrasion
Soundness
Crushing Value
L.A. Abrasion Test
Fig. 1(a)--Outline of aggregate testing program

A C 1 SP-I153 V O L X I 95 I0662949 0521236 084
280 Baykal et al
I Adding 25% by Weight Water and

Pelletizing By Continuous Mixing I
Adding Dry Fly
--``,`,-`-`,,`,,`,`,,`---
Screening of Different
Sizes by Sieving
I
Curing for 78 Days at 21°C
Fig. 1(b)-Flow chart of fly ash aggregate

production technique
unit
2,54crn 2.26-1.25 1.25-0,48 0.48-0,20

aggregate size cm
Fig. 2-Unit weight of fly ash aggregates versus lime content

A C 1 SP-353 V O L X I 95 I0662949 0523237 T L O I
SPECIFIC
GRAVITY
O 5 . 10 20
LIME %
Fig. 3-Specific gravity of fly ash aggregates versus lime content
Abrasion Frz-Thaw Crushing CBR

Test type
Fig. &Fly ash aggregate properties versus lime content

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 V O L * I 75 E 0662949 0523238 957
282 Baykal et al
POINT LOAD KO
O 5 10
LIME %
Fig. %Point load values of fly ash aggregates versus lime content
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 V O L * I 75 = Obb2749 0523237 8 9 3
SP 153-16
Five-Year Exposure Test on

Long-Term Properties of
Concretes Containing Fly Ash,
Blast-Furnace Slag, and Silica Fume
by T. Sasatani, K. Torii, and M. Kawamura
Synopsis: This report presents the results of 5-year exposure test on the long-term
properties of concretes containing fly ash ( FA ), blast-fumace slag ( BFS ) and
silica fume ( SF ). Four kinds of concretes with and without a mineral admixture,
i.e. OPC concrete, FA 30 % concrete, BFS 50 % concrete and SF 10 % concrete,
were prepared. After 28 days of the initial curing, they were exposed to different
environments for 5 years. The compressive strength, pulse velocity, depth of
carbonation and chloride ion penetration of concrete were determined at various
intervals of exposure time. From the results, it was found that under the indoor
exposure condition, influences of initial curing condition on the long-term strength
development of concrete were especially pronounced for FA 30 % concrete and
BFS 50 % concrete, but that under the outdoor exposure condition, its influence
was considerably reduced due to the supply of rainfall during the outdoor exposure.
On the other hand, SF 10 % concretes showed some reduction in compressive
strength when they were initially cured in water for 7 days and then continuously
air-dried indoors for a long period. The depth of carbonation of BFS 50 %
concrete and FA 30% concrete was much greater than that of the corresponding
OPC concrete and SF 10 % concrete when they were exposed indoors or outdoors
for 5 years. Furthermore, all mineral admixtures used in this study were found to
be equally efficient in preventing chloride ions from inuuding into concretes under a
--``,`,-`-`,,`,,`,`,,`---
marine environment.
Keywords: Blast furnace slag; carbonation; chloride ions; compressive

strength; environments; exposure; fly ash; penetration tests; silica fume;
tests; velocity

283 Not for Resale
A C 1 S P - 1 5 3 V O L * I 95 IOb62949 05212LiO 505 =
284 Sasatani, Torii, and Kawamura
Teruhiko Sasatani is a civil engineer, Kokudo Kaihatsu Center Co. Ltd.,

Nonoichi, Ishikawa, Japan. His main research activities involve effective
utilization of fly ash and blast-furnace slag in concrete and protective measures for
steel corrosion in concrete structura.
AC1 member Kazuyuki Torii, Dr. Eng., is an associate professor of Civil
Engineering at Kanazawa University, Kanazawa, Ishikawa 920, Japan. He
received his Dr. Eng. degree from Kyoto University in 1986. His current
research has been on chloride ion permeability of concrete, chloride-induced
corrosion of steel reinforcement in concrete, and properties of high performance
concrete.
AC1 member Mitsunori Kawamura, Dr. Eng., is a professor of Civil
received his Dr. Eng. degree from Kyoto University in 1971. He has been active
in research on alkali-aggregate reaction.
INTRODUCTION
It is weil known that the long-term properties of concretes with a mineral
admixture vary widely depending on the initiai curing regime and subsequent
environmental conditions. When concretes with a mineral admixture are exposed
to a dry environment, the removal of water will considerably depress the progress
of hydration of the cement and the pozzolanic reaction of the mineral admixture, its
adverse effect on the strength or durability of concrete being more significant
especially i n poorly cured concretes with a high replacement by a minerai
admixture. The authors suggest that the chloride ion permeability of concretes
containing a minerai admixture is more sensitive to the curing regime and
subsequent environmental conditions compared to ordinary portland cement
concretes (1). Recently, controversial results have been reported with respect to
the long-term strength of silica fume concrete ; some researchers reported the
decrease in compressive strength for air-dried silica fume concretes, while others
did not find any strength loss (2). Larrard et ai. have pointed out that decreases in
strength in air-dried silica fume concretes may result from the occurrence of internal
stresses being induced by a strong moisture gradient in cross section of concrete
cylinders (3). Furthermore, it should be noted that the self-desiccation as well
as drying shrinkage and plastic shrinkage can possibly influence the long-term
properties of silica fume concretes, which may also develop the micro-cracks in
concrete under a dry environment (4). Laboratory tests may not always be
appropriate to predict the properties of concrete in the structure, and field exposure
tests are more preferable. However, there are few studies concerning the long-
term properties of concretes with a mineral admixture which were exposed to
different environments.
The objective of this study is to investigate the long-term properties of
concretes with and without a mineral admixture when exposed to different
environments. Four kinds of concretes, i.e. OPC concrete, FA 30% concrete,
BFS 50% concrete and SF 10% concrete, were prepared and then exposed to four
different environments. The compressive strength, pulse velocity, depth of
carbonation and chloride ion penetration of concretes with and without a minerai
admixture were investigated during the periods up to 5 years.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 0662949 0523241 441
EXPERIMENTAL DETAILS
Materials and Mixture Proportions
Physical properties of fly ash ( FA ), blast-fumace slag ( BFS ) and silica
fume ( SF ) used in this study are presented in Table 1. An ordinary portland
cement ( OPC ) was used : its specific gravity and Blaine fineness being 3.13 and
3230 cm2/g respectively. The fine and coarse aggregate used were river sand (
specific gravity : 2.61, absorption : 1.3 %, fineness modulus : 2.46 ) and crushed
stone ( specific gravity : 2.69, absorption : 0.8 %, maximum size of aggregate : 25
mm ) respectively. A vinsol-resin type air-entraining admixture was also used.
Mixture proportions of concretes with and without a mineral admixture are
presented in Table 2. OPC concretes as the control were prepared with the water
to cement ratio of 0.45, 0.55 and 0.65, whereas mineral admixture-containing
concretes for preliminary tests were made with the water to cementitious material
ratio of 0.55 only. The air content of fresh concretes was maintained at 5 k 1 % ;
the content of total cementitious materials was kept at 300 kgIm3. The
replacements of OPC by fly ash, blast-fumace slag and silica fume were 30 %, 50
% and 10 % by weight respectively.
Preparation and Testing of Specimens

Cylindrical specimens of 100 mm in diameter and 200 mm in height were
prepared for the exposure test. Chloride permeability and pore size distribution
of concrete were measured around 28 days after the initiation of the exposure test ;
chloride permeability was evaluated according to the Rapid Chloride Permeability
Test described in AASHTO Standard T 277-831 and pore size dismbutions were
determined using a mercury intrusion porosimeter with intrusion pressures up to
400 MPa (60,000 psi). At the exposure time of 1 year, 3 years and 5 years, the
compressive strength, pulse velocity, depth of carbonation and chloride ion
penetration of concretes with and without a mineral admixture were measured.
The depth of carbonation was measured by spraying a 1 % phenolphthalein ethanol
solution containing 10 % water on fractured surfaces of the specimens, and the
penetration depth of chloride ion was determined only for concrete exposed to a
marine environment by measuring the colored depth after spraying O. 1 N AgN03
--``,`,-`-`,,`,,`,`,,`---
solution on fractured surfaces of the specimens. All experimental data are the
average value of three specimens.
EXDOSUE
Condition
The specimens were demolded one day after casting and then cured in two
different ways ; the continuous curing regime in water at 20 OC for 28 days, which
is labeled W, and the other regime of curing in water at 20 OC for 7 days, and then
in a dry environment of 60 % R.H. up to 28 days, which is labeled A. After
28 days of the initial curing, all specimens were divided and exposed to four
different environmental conditions : in water at 20 OC ( successive wet condition,
indoors) ; in a room at 20 OC and 60 % R.H. ( successive dry condition, indoors )
; on the roof of a building in Kanazawa University which is 15 km from the sea (
repeated wet and dry condition, outdoors ) and on the tidal zone at Matsuto beach
facing the Sea of Japan near Kanazawa city ( repeated wet and dry condition,
marine environment ). The location of exposure sites is illustrated in Fig.1.
The exposure site located at the Matsuto beach is often attacked by great waves
especially during the winter. Also, the climate of Kanazawa city is normally mild

A C 1 SP-153 V O L S I 95 W 0662949 0523242 3 8 8 W
286 Sacatani, Torii, and Kawamura
but humid, the average temperature and relative humidity of Kanazawa city in the
last decade being 14.1 OC and 74 % respectively. The average freezing and
thawing cycles which the specimens underwent during the winter was 10 to 20.

Total Pore Volume and AASHTO T 277-831 Chloride Permeability
Compressive strength, total pore volume and chloride permeability of 28-
day old concretes with and without a minerai admixture are summarized in Table 3.
For OPC concretes, both total pore volume and volume of pores larger than 0.1
pm increased with increasing water to cement ratio and decreased with increasing
curing time in water. FA 30 % concretes showed a little greater total pore volume
than BFS 50 96 and SF 10 % concretes. Interestingly, the addition of a mineral
admixture effectively reduced more markedly the volume of coarse pores larger
than O. 1 pm than the total pore volume even at 28 days. This may be atmbuted
to the pore refinement and the reduced calcium hydroxide content in the process of
pozzolanic reaction of mineral admixtures. Similarly, the chloride permeability of
OPC concretes increased with increasing the water to cement ratio, but no
substantial difference in chloride permeability between OPC concretes cured in
water and in air was found. Also, FA 30 9% and BFS 50 % concretes showed a
slightly lower chloride permeability than OPC concretes, and the chloride
permeability of SF 10 % concretes was the lowest among them for both curing
conditions. It appears that concretes with a mineral admixture have already been
less permeable than OPC concretes with the same water to cement ratio at the
starting point of exposure test.
Comuressive StrenPth
Figs. 2 through 4 show changes in compressive strength of concretes with
and without a mineral admixture when exposed indoors for 5 years. As shown in
Fig. 3 and 4, when the concrete was successively stored in a dry environment, its
adverse effect on the strength development of conmte was more significant for FA
--``,`,-`-`,,`,,`,`,,`---
30 % and BFS 50 % concretes than for OPC and SF 10 % concretes.

Furthermore, especially when the initial curing time in water was only 7 day, all
concretes with a mineral admixture reached the maximum strength at 28 days and
showed little strength gain beyond 28 days. Prolonged water curing from 7
days to 28 days improved the strength development between 28 days and 1 year in
a dry environment, but their strength gain almost ceased after 1 year of exposure
time. On the other hand, SF 10%concretes showed the decrease in compressive
strength with exposure time when they were initially cured in water for 7 days and
then continuously air-dried indoors for a long period. Carette et al. have also
observed a reduction in long-term strength for air-dried silica fume concrete (5).
Such a phenomenon may possibly be explained by internal stresses being induced
by a non homogenous drying in the surface and inner portion of concrete cylinders
since the pore structure of silica fume concrete is dense and discontinuous. The
authors have recently found out from fluorescence microscopic observations of air-
dried silica fume high-strength concrete that the micro-cracks with the width of 10
pm to 20 pm develop at regular intervals from the surface of concrete due to
tension stresses built up in the surface skin of concrete specimens (6).
Figs. 5 through 8 show changes in compressive strength of concretes with
and without a mineral admixture when exposed outdoors for 5 years. The trends

A C 1 SP-353 VOL*I 95 W 0662949 0523243 214
of strength development of concretes with and without a mineral admixture were

found to be very similar both in outdoor exposure conditions at seaside and
Kanazawa University. Under an outdoor environment, the gain of compressive
strength was also significant up to 1 year of the exposure time regardless of
whether mineral admixture had been used or not, but subsequently there was hardly
any increase of compressive strength up to 5 years, In some cases, the
compressive strength of concrete was decreased after 1 year of the exposure time
due to the detrimental effect of wetting and drying repetitions, and freezing and
thawing repetitions, especially for OPC concretes with the water to cement ratio of
0.65 and FA 30 % concretes in the exposure at seaside. It is likely that when
concretes are exposed outdoors, the influence of the curing condition on the
subsequent strength development of concrete becomes small since the hydration of
the cement or the pozzolanic reaction of the mineral admixture can sucessively
proceed due to the supply of rainfall (7).
Depth of Carbonation
Depths of carbonation of concretes with and without a mineral admixture
exposed indoors and outdoors are presented in Table 4. As shown in Fig. 9,
there was a relation between the 28-day old compressive strength and the depth of
carbonation in concretes both with and without a mineral admixture exposed
indoors and outdoors for 5 years. Depths of carbonation of all concretes with and
without a mineral admixture increased in the following order of the environmental
exposure condition ; the 60 % R.H. indoor storage > the outdoor exposure at
seaside > the outdoor exposure in Kanazawa University. The depth of
carbonation of OPC concretes increased with increasing the water to cement ratio
and decreased with the period of initial water curing. It is also evident that in all
environmental conditions, the depth of carbonation of FA 30 % and BFS 50 95
concretes is much higher than that of the corresponding OPC concretes and SF 10
% concretes. The depth of carbonation of concrete is known to be related not
only to the porosity of concrete and its degree of saturation but also to the residual
amount of remnant Ca(OH)2 in concrete. Therefore, as shown in Fig. 10, a
linear relationship between depth of carbonation and volume of pores larger than
0.1 pm was found for OPC and SF 10 % concretes, but their plots in FA 30 % and
BFS 50 % concretes were not consistent with the line obtained in OPC concretes.
It was confirmed that the influence of curing and subsequent enviromental
condition on the depth of carbonation of concrete became more significant for
concretes with a mineral admixture than for the corresponding OPC concretes.
Chloride Ion Penetration
Fig. 11 shows depths of chloride ion penetration into concretes exposed to
a marine environment for 3 years and 5 years. OPC concretes with the water to
cement ratio of 0.45 reduced the chloride ion penetration to some extent, while
those with water to cement ratios of 0.55 and 0.65 showed a thorough penetration
of chloride ion in the splitted cross section of cylinders after 5 years of exposure.
On the other hand, all mineral admixtures effectively reduced the chloride ion
penetration into concrete. That is to say, chloride ion penetration profiles were
very similar to one another regardless of the type of mineral admixture used, their
depths of chloride ion penetration being surpressed within 25 mm from the surface
of concrete even at 5 years of exposure. Furthermore, in the long-term
exposure to a marine environment, the influence of curing on the depth of chloride
ion penetration of concretes with and without a mineral admixture also became
negligible. These results somewhat correspond to AASHTO T 277-831 chloride
permeability data shown in Table 3. For OPC concretes, the protective ability of
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153
288
VOL*I 95
Sasatani, Torii, and Kawamura
Obb2949 0 5 2 1 2 4 4 150 =
concrete to resist chloride ion penetration was very poor at water to cement ratios of
0.55 and 0.65, in which their charge passed of 28-day old OPC concretes was
more than 5000 coulombs, while its relationship was not clear for concretes with a
mineral admixture. It should be noted that although FA 30 % and BFS 50 %
concretes had relatively high coulomb ratings their chloride ion penetration was
equal to or less than SF 50 % concretes. Although the AASHTO T 277-831 test
is primarily a conductivity measurement, it is considered that the test can give a
reasonable estimate of chloride permeability of OPC concretes in service (8,9).
CONCLUSIONS
The 5-year exposure test in different environments was carried out in order
to evaluate the influence of curing and enviromental condition on the long-term
properties of concretes with and without a mineral admixture. From experimental
results, it was found that under an indoor exposure condition, the influence of
initial curing condition on the long-term strength of concrete became more
pronounced especially for FA 30% concrete and BFS 50% concrete, but that under
the outdoor exposure condition, its influence was considerably reduced during the
outdoor exposure. On the other hand, SF 10% concretes showed some reduction
in compressive strength when it was initially cured in water for 7 days and then
continuously air-dried indoors for a long period. With respect to the carbonation
of concrete, the depth of carbonation of BFS 50% concrete and FA 30%concrete
was much higher than that of the corresponding OPC and SF 10 % concrete when
they were exposed indoors or outdoors for 5 years. Furthermore, all mineral
admixtures were found to be equally efficient in preventing the ingress of chloride
ion into concrete under a marine environment although FA 30 % and BFS 50 %
concretes had relatively high coulomb ratings compared with SF 10 % concretes.
ACKNOWLEDGMENTS
The authors are grateful to Dr. Y. Kajikawa, Prof. of Civil Engineering at

Kanazawa University, for his advice and encouragement. The authors also thank
M. Miyoshi, graduate student of Kanazawa University, for his expenmental work.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 Obb2949 0521245 0 9 7
REFERENCES
1. Toni, K. and Kawamura, M., " Pore Structure and Chloride Permeability of
Concretes Containing Fly Ash, Blast-fumace Slag and Silica Fume Proc. of I',
4th Int'l Conf. on Fly Ash, Silica Fume, Slag and Natural Pozzolans in
Concrete, AC1 SP-132, Istanbul, Vol.1, 1992, pp.135-150.
2. Larrard, F.D. and Bostvironnois, J.L., " On the Long-term Losses of Silica
Fume High-strength Concretes ", Magazine of Concrete Research, Vo1.43,
N0.155, 1991, pp.109-119.
3. Larrard, F.D. and Aitcin, P.C., Apparent Strength Retrogression of Silica-
"
Fume Concrete ",AC1 Materials Journal, Vo1.90, No.6, 1993, pp.581-585.

4. Atlassi, E., " The Influence of Silica Fume and Some Other Parameters on the
Compressive Strength of Concrete ", Blended Cements in Construction,
Elsevier Applied Science, 1991, pp.248-262.
5. Carette, G.G., Malhotora, V.M. and Aitcin, P.C., " Preliminary Data on Long-
term Strength Development of Condensed Silica Fume Concrete ",Proc. of 3rd
Int'l Conf. on Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete,
Trondheim, Supplementary Papers, 1989, pp.597-617.
6. Torii, K., Satoh, K. and Kawamura, M., Strength Development and "
Microstructure of Ultra High-strength Concretes Exposed to High Temperature

at Early Ages Proc. of the 49th Annual Conference of the Japan Society of
I',
Civil Engineers, 5, 1994, pp.1024-1025 (in Japanese).

7. Ewertson, C. and Petersson, P.E., The Influence of Curing Conditions on the
"
Permeability and Durability of Concrete, Results from a Field Exposure Test I',
Cement & Concrete Research, Vo1.23, 1993, pp.683-692.

8. Torii, K., Sasatani, T. and Kawamura, M., " Carbonation and Steel Corrosion
in Concretes Containing Mineral Admixtures under Different Environments I',
Proc.of Int'l Conf. on Corrosion and Corrosion Protection of Steel in Concrete,

Sheffield, 1994, pp.658-667.
9. Toni, K. and Kawamura, M., " Pore Structure and Chloride Ion Permeability of
Mortars Containing Silica Fume Cement & Concrete Composites, 16, 1994
I',
(in press).
TABLE 1 - PHYSICAL PROPERTIES OF FLY ASH, BLAST-FURNACE

SLAG, AND SILICA FUME USED
Blast-furnace slag
Silica fume Specific gravity : 2.33,

BET specific surface area : 24.2 m2/g
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L + I 95 I0662949 052124b T 2 3 I
TABLE 2 - MIXTURE PROPORTIONS OF CONCRETES WITH AND

WITHOUT MINERAL ADMIXTURE
O K : Ordinary portland cement, FA : Fly ash, BFS : Blast-furnace slag, SF : Silica fume
Compressive Total pore Chloride.

strength volume permeability
(ma) (1 0-3 '(coulombsj
OPC 45A 35.3 24.5 ( 2.7) 2640 [ M l
OFT 45w 36.0 18.3 ( 3.4 } 2990 1 M 1
O K 55A 27.7 53.5 í. 15.0), 5230 r H I
OPC 55w 26.2 40.7 (11.2) i
5270 H j
OFT 65A 23.9 64.9 (25.9 ) 7790 [ H ]
OFT 65W 20.9 73.7 (20.5) 6210 [ H ]
FA 55A 20.4 85.1 ( 43.5 ) 5560 [ H I
FA 55W 20.0 72.2 ( 30.0) 3160 [ Ml
BFS 55A 21.2 42.5 ( 14.0) 3850 [ MI
BFS 55W 24.1 19.9 ( 9.7) 2760 [ M l
SF 55A 31.3 55.7 ( 22.4) 1340 [ L I
SF 55W 27.9 58.4 ( 6.9) 920 [ VL ]
air up to 28 days
W :Continuously cured in water for 28 days
( ) : pore volume larger than 0.1 p n ,10-3cc/g
[ I : Evaluation according to AASHTO T277-831
( H : High, M : Moderate, L : Low, VL : Very Low )
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 = 0662949 0523247 9bT
TABLE 4 - DEPTHS OF CARBONATION OF CONCRETES WITH AND

WITHOUT MINERAL ADMXTURE EXPOSED INDOORS AND
OUTDOORS, mm
--``,`,-`-`,,`,,`,`,,`---
_ * The Soto Peninsula
+
The Sea of Japan
I"--) The Mat sut o beach
a azawa University
8 2
The Pacific Ocean
Fig. l-Location of exposure sites in field exposure test

50 k
m
n
I
40
5
m
C
a,
L
30
c
-
v)
al
>
._
v)
v)
L OPC55W
a
o
* OPC65W
10 - -It FA55W
BFS55W
+ SF55W
Or ' I ' I , I , , . ,
Fig. 2-Compressive strength of concretes with

and without mineral admxiture cured in water at
20 c
m i
a
40-1 4
o
.-
--``,`,-`-`,,`,,`,`,,`---
ln
ln
L
a
E
--a-- OPC45W
-
u
O
* OPC55A
10 - --t- OPC55W
OPC65A
-t- OPC65W
O , ' I I , . ,
Fig. 3-Compressive strength of OPC concretes

stored indoors at 20 C and 60 percent R H

A C 1 SP-153 V O L t I 95 0662949 0 5 2 3 2 4 9 732
--O-- FA55W
* BFS55A
+ BFS55W
U SF55A
--t- SF55W
0 8 ' 1 ' I " ' " I
O 1 2 24 36 48 60
--``,`,-`-`,,`,,`,`,,`---
Exposure t i m e , months
50 >
5
40 I l
m
S
2 30
L
VI
al
.->
2 20 U OPC45A
L + OPC45W
5
0 10- --+-
u
OPC55W
OPC55A
U OPC65A
-t- OPC65W
O
O 12 24 36 48 60
Exposure t i m e , months
Fig. S o m p r e s s i v e strength of OPC concretes

exposed outdoors at Kanazawa University

A C 1 SP-153 V O L * I 95 W 0bb2949 0523250 4 5 4 W
40
30
+ FA55W
* BFS55A
10 - -t- BFS55W
-D- SF55A
--t- SF55W
O I . , . , . ,
Exposure time, months
Fig. 6-Compressive strength of concretes with mineral

admxiture exposed outdoors at Kanazawa University
OPC45A
+ OPC45W
* OPC55A
-t- OPC55W
-[I- OPC65A
--``,`,-`-`,,`,,`,`,,`---
--#--- OPC65W
O 12 24 36 48 60
Exposure time, months
Fig. 7-Compressive strength of OPC concretes

exposed outdoors at seaside

A C 1 SP-153 V O L X I 95 W Obb2949 052I125L 390
= 295
50
v)
2 + FA55W
n
+ BFS55A
D
o 10-
--A-- BFS55W
U SF55A
SF55W
O I ' I ' I ' I ' '
Fig. ô-compressive strength of concretes with

mineral admixture exposed outdoors at seaside
20 r Correlaiion lactor ' O 694 0 Indoors at 60 yo RH

E A At seaside
E
O In university campus
15
fP
al
U
.-o 10 O O
\
w
m \
c Correlation factor O 832
O \
2rn
0 5
Correlation factor O 739

--``,`,-`-`,,`,,`,`,,`---
C
1 5 20 25 30 35 40
C o m p r e s s i v e strength of 28-day old concrete, MPa
Fig. 9-Relations between compressive strength of 28-

day-old concrete and depth of carbonation in concretes
with and without mineral admxiture exposed indoors
and outdoors for 5 years

A C 1 SP-153 V O L X I 95
296
0 6 6 2 9 4 9 0521252 227
Sasatani, Torii, and Kawamura
=
SF55
0.00 0.01 0.02 0.03 0.04 0.05
Volume of pores larger than 0.1 ,um, cc/g
Fig. ICI-Relation between volume of pores larger than

0.1 pm of 28-day-old concrete and depth of carbonation
in concretes with and without mineral admixture exposed
indoors for 5 years
E
E Ï I
=- 50
-O
I-
L
40
C
W
R
C 30
.-
.c
10
O
5a 0
o
Fig. 11-Depths of chloride ion penetration into concretes

with and without mineral admixture exposed at seaside for
3 and 5 years
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 W Ob62949 0523253 3 6 3
SP 153-17
Movement of Ions through Mortar

Mixed with Mineral Admixtures
by N. Otsuki, S. Nagataki, and M. Hisada
Synopsis : It is ncccssary for concrctc cnginccrs to gct morc information

on thc ion movcmcnt through and in concrctc. Thc rcason is the dcvcl-
opmcnt of ncw tcchnologics such as cathodic protcction, dcsalination
and rc-alkalization for rcinforccd concrctc mcmbcrs. I n concrctc
mcmbcrs with thcsc trcatmcnts, various ions should be moved through
and in concrctc mcmbcrs. Thc movcmcnts of ions could influcncc thc
concrctc propcrtics and stccl rcinforcing bars. Ground granulated blast-
furnace slag, fly ash, and silica fumc havc bccn rccognizcd as high quali-
t y mincral admixturcs for concrctc. Siricc structurcs built with thcsc
matcrials might cvcntually bc subjccted to clcctro migration processcs a
sct of cxprirncnts to asscss thc cffccts of thcsc pozzolans wcre dcviscd.
I n this study, considcring t h e conditions mcntioncd abovc,
movcmcnt of scvcral kinds of ions through hardcncd mortar with mineral
admixtures are invcstigatcd. As ions, Na+, I(+ and C1- wcrc sclcctcd
bccaiisc thc ions wcrc closcly rclatcd to alkali-aggrcgatc rcaction or
chloridc attack. As mincral admixturcs, ground graiiulatcd blast-furnacc
slag, fly ash, and silica fumc wcrc uscd. Also, the influcnccs of watcr to
bindcr ratio on the movcmcnt of ions wcrc invcstigatcd.
Elcctrochcmical cclls wcrc uscd for thc cxpcrimcntal work, and
thc currcnt was applicd to a ccll i n thc range bctwccn 0.1A/m2 and
ill.0A/ni2. Analyzing thc data from tlic cxpcrimcntal work, the follow-
ing conclusions wcrc obtaincd:
(1) Thc clcctromigration of ions through mortar arc rcduccd with the
addition of admixturcs.
(2) Thc clcctromigration of ions incrcascs with thc watcr to bindcr ratio.
( 3 ) Thc clcctromigration of thc ions is closcly rclatcd to the porc size
distribution of mortar and paste.
Keywords: Blast furnace slag; chloride ions; fly ash; mineral admixtures;
mortars (material); porosity; potassium ions; silica fume; sodium ions
--``,`,-`-`,,`,,`,`,,`---

297
298 Otsuki, Nagataki, and Hisada
Dr. Otsuki is a mcmbcr of ACI. He is an Associate Profcssor in Dcpart-

ment of Civil Enginccring, Tokyo Institute of Technology, Tokyo,
Japan.
Dr. Nagataki, FACI, is a profcssor in Dcpartment of Civil Engineering,

Tokyo Institutc of Technology, Tokyo, Japan
Mr.Hisada is a Research Associate in Department of Civil Engineering,

Tokyo Institute of Tcchnology, Tokyo, Japan
INTRODUCTION
Many concretc structurcs arc scvcrcly damagcd bcforc their

expccted service lives. They arc damagcd by numcrous causes. Among
the causes, especially in Japan, chloridc attack, carbonation and alkali-
silica reaction arc widely rccognizcd phcnomcna for concrete structures.
These three phcnomcna arc closcly rclatcd to the movcment of ions
through and in concrctc. Thc prescncc of C1- plays a very important
role in the corrosion of embcddcd stccl bars, so thc movement of this
ion is closcly related to the dctcrioration of concrctc structurcs or
mcmbers attacked by chloride attack. Also, the prcsence of Na+ and K+
arc the main factors for thc alkali-silica reaction, the movement of thcse
ions is vcry important.
Rccently, through electrochcmistry, some methods have becn

dcsigncd to rehabilitate concrctc mcmbcrs damagcd by thcsc phcnomc-
na. The methods are known as dcsalination, rc-alkalization, and cathod-
ic protection. Desalination and cathodic protcction arc mainly for pro-
tection against chloridc attack, and re-alkalization is to protcct against
carbonation. Also, thc effect of taking out Na+ and K+from mortar bars
damagcd by alkali-silica rcaction (A.S.R.) was shown by the authors( 1).
However, neithcr the mechanism nor the influcntial factors on the
movemcnt of ions are fully undcrstood. Thcre arc only fcw studies on
the quantitative cvaluation of the movement of ions.
In this study, the authors intcndcd to get some quantitative

information on the movement of ions from an clcctrochemical basis.
Then, the authors would like to relate the elcctromigration of ions to
somc basic properties of hardened mortar, namely, pore size distribution.
--``,`,-`-`,,`,,`,`,,`---
Also, from a practical point of view, it is important to clarify the influ-

ential factors on the electromigration of ions, For this purpose, the influ-
ences of mineral admixturcs, water to bindcr ratio and current densities
werc invcstigated.

A C 1 SP-153 VOLaI 95
Obb2949 0521254 O T T
Not for Resale
A C 1 SP-153 V O L * I 95 E 0662947 0521255 T3b m
Milwaukee C o n f e r e n c e 299
--``,`,-`-`,,`,,`,`,,`---
SCOPE OF INVESTIGATION
Mortar of pastc disk 100mm in diamctcr by IOmm thick wcrc sct

i n clcctrochcmical cclls with the following solutions (Ccll typc A: NaCl
solution II mortar (pastc) disk II Ca(OH)2 solution, or, Ccll typc B:
distillcd watcr II mortar (pastc) disk II distillcd watcr). I n thcsc cclls,
contri~llcdclcctrical currcnts wcrc imprcsscd to pass through thc mortar
(pastc) disk, and ions wcrc forccd to movc through and/or in mortar
disks. Aftcr thc current was imprcsscd, thc conccntrations of ions in
solutions wcrc mcasurcd, and flux, vclocity of ions, transport numbcr
and mobility wcrc calculatcd. Also, thc total porosity and porc sizc dis-
tributions wcrc mcasurcd for cach plates. T h c influcncc of mincral
adniixturcs, watcr to bindcr ratio and porc size distribution on flux,
transport nunibcr and mobility arc discusscd.
MATERIALS
Thc mortar and pastc mixturcs wcrc madc at thc concrctc labora-
tory i n Tokyo Institute of Tcchnology in thc fall of 1993 using thc fol-
lowing niatcrials.
Cement: Normal portland ccmcnt, was uscd. Its physical propcrtics and
chcmical analysis arc givcn in Tdblc 1.
Silica Fume: Undcnsificd typc silica fumc' was uscd. Its physical
propcrtics and chcmical analysis arc givcn in Tablc 1.
Fly Ash: Thc physical propcrtics and chcmical analysis of thc fly ash
iiscd arc givcn in Tablc 1.
Ground Granulated Blast-Furnace Slag: Thc physical propcrtics

and chcmical analysis of thc ground granulatcd blast-furnacc slag uscd
arc givcn i i i Tdbk 1.
Superplasticizer: A naphtharcnc sulphonatc typc high range watcr

rcduccr**was uscd.
Anti-washout admixtures: To control against scgrcgation of mortar

with thc watcr ccmcnt ratio 1.0, mcthyl ccllulasc typc anti-washout
adniixturc was uscd.
Fine APgregates: As the finc aggrcgatc, local natural sand was uscd.
Thc EM., arc and absorption capacity of the sand wcrc 2.20, 2.62 and
1.17% rcspcctivcly.
*: Elkcm 940U
**: Kao Mighty 150

A C 1 SP-153 V O L U I 95 Obb29Ll7 0 5 2 L 2 5 b 9 7 2
300 Otsuki, Nagataki, and Hicada
MIXTURE PROPORTIONS
The proportions of thc mortar and pastc mixturc arc sumrncrizcd

in Tablc 2. The water to bindcr (ccmcnt + admixture) ratios uscd wcre
0.3, 0.5, 0.7 and 1.0. In the casc of watcr to binder ratio 1.0, an anti-
washout admixture was added (1.0% wcight pcrccntage of watcr). Thc
rcplacemcnt ratios of silica fumc, fly ash and ground granulatc blast-
furnacc slag wcrc kcpt constant, 10931, 30% and 50% by wcight rcspcc-
iively .
TESTING METHODS
Movement of CI-
The clcctromigration tcst was donc iii cc11 typc A (iiegativc polc
II 5 % NaCl solution II spccimcn II Ca(OH), saturated solution II
positive polc). Thc spccimcns wcrc madc using ali of thc mixture propor-
tions in Table 2 . Aftcr setting a specimen in a ccll, a constant currcnt
density was applied to the ccll for a schcdulcd timc pcriod.
For each of the mixture proportions, 1.0A/m2 was applied as a

constant currcnt density on a t lcast onc spccimcn. For thc spccimcns,
whose W/C = 0.5 and S/C =2.5, 0.1A/m2 and 10A/m2wcrc also applied
--``,`,-`-`,,`,,`,`,,`---
as constant currcnt dcnsitics. Aftcr thc currcnt was loadcd, a sct of solu-
tion samplcs was takcn from each sidc of cclls at schcdulcd times and the
conccntrations of CI- ion in the solution samplcs wcrc mcasurcd. Thcn,
thc amounts of CI- which passcd from the ncgative sidc of spccimcn to
thc positivc side wcrc calculatcd. With thcsc data, transport mcrnbcr and
mobility of CI- for each spccimcn wcrc also calculatcd.
In thcsc cases, ihc amounts of ions forced come out from the
spccimcns by the currcnt wcrc mcasurcd. Bccausc thc authors wcrc vcry
interested in the mitigation of ASR by this principle, this typc cell B was
adopted for thcse ions. Thc spccimcns, the mixture proportions and the
currcnt dcnsitics uscd werc same as in thc casc for Cl-.
MOVEMENT OF CHLORIDE ION
1) Basic Parameters for the movement of CI- -

To evaluate the movcmcnt of the ion in mortar specimens, basic

A C 1 SP-353 VOL*I 95 Ob62949 0523257 ô09 =
parameters as follows were measured, calculated, and/or evaluated. Thc

basic theory followcd was from a textbook(2).
a. Measurement of the amount of the ion that passed through the

specimen (denoted Q: moi)
Thc concentrations of the ion in the solution of positivc sidc wcrc
mcasured, and the amounts of the ion that passcd through the spccimen
were calculated.
b. Calculation of the flux of CI- (J: mol/s.m2)

The flux was calculated as Q dividcd by duration and cross section
of the specimen.
c. Measurement of the concentration of CI- in mortar (C: mol/m3)

After thc current was chargcd, a mortar spccimcn was crushed
and ground to fine particlcs under 105pm. log of thc powder was mixed
into the 1OOg of distilled water and kept 24 hours, thcn the conccntration
of the C1- ion of the solution was mcasurcd, and the concentration of thc
ion against unit volume of mortar was calculatcd.
d. Calculation of the velocity of CI- (v: m/s)

Thcre is a relation bctwcen flux, conccntration in a spccimcn,
and velocity, narncly, J=Cv. So, v can be calculatcd.
e. Calculation of the mobility (u: m2/(\?S))

--``,`,-`-`,,`,,`,`,,`---
T h e mobility (u) can bc calculatcd as thc velocity of ion (v)

divided by the slope of thc potcntial (E/cm), Namcly, u = v / E.
f. Calculation of the transport number

The fraction of thc total clcctric currcnt carricd by a single spc-
cics (in this casc Ci-) in a solution is called thc transport nunibcr. Hcrc,
the transport number of C1- ( t ,-) can bc calculatcd by the amount of
current carricd by C1- dividcd i y thc total amount of applicd current.
Namcl y,
whcre, Q: thc amount of chloride ion passcd through the

spccimcn
M: molccular weight of CI- (35.5)
F: Faraday?s numbcr
I: current
t: duration of applying current
2) Results and Discussions

a. Influence of the current density on the electromigration of CI-
In Fig. 1, the influencc of the currcnt density on the total elcc-
tromigration of C1- is shown. Thc watcr to binder ratio and sand to

A C 1 SP-153 V O L X I 95 0 b b 2 9 4 9 0521258 7 4 5 =
binder ratio of the mortar are 0.5 and 2.5 rcspectivcly. Also, from this
figure after C1- passed through the spccimen, the flux can be assumcd
constant. So, we can calculate, flux, vclocity, mobility and transport
number with the measured valucs of concentration and potential differ-
ence, as shown in Table 3.
The fluxes of the CI- are 4.43 x 10-7mol/s.m2, 5.27 x 10-6mol

/s.m2 and 5.01 x 10-5mol/s~rn2for current dcnsities 0.1A/m2, 1.0A/m2
and 10.0A/m2, respectively, so the ratios of the flux arc 0.84: 1 .OO: 0.95.
So, w e can say thc flux is roughly proportional to the currcnt dcnsitics
especially in thc range bctwccn 1.0 N m 2 and 10.0A/m2. Also, from this
figure, the amount of electromigration of 0 . 1 N m 2 is vcry closc to that of
natural diffusion only.
b. Influence of water to binder ratio on the eiectromigration of CI-

Thc influence of W/C on thc clcctromigration of CI- is shown in
Table 4. In this table, the watcr to bindcr ratios rangc from 0.3 to 1.0,
and the sand to bindcr ratios are O, 2.5 and 3.0. It can bc sccn from this
table that as thc water to bindcr ratio is incrcascd, thc f l u x and thc
mobility are also larger and thc resistivity is smallcr. Also, it is clcar that
the transport numbcr is larger when thc watcr to bindcr ratio is highcr.
Thc comparison of the rcsults bctwccn pastc and mortar shows

that the flux and the mobility of thc CI- arc grcatcr in mortar than in
paste. Thc reason may be the prcscnce of the poor iiitcrfacc of sand and
pastc in mortar, Also, the influcncc of thc sand to bindcr ratio can not be
recognized from this table.
c. Influence ofthe mineral admixtures on the electromigration of CI-

The influcnccs of the mincral adrnixturcs arc summcrizcd in
Tablc 5. Thc rcsistivity of the spccimcns mixcd with B.F.S. and S.F. arc
highcr than thc others'. Rclatcd to thc rcsistivity, thc mobility of thosc
mixcd with B.F.S. and S.F. are lowcr than thc othcrs'. Also, thcrc is not
so much diffcrcnce bctwccn the valucs of W/C = 0.5 and thosc of W/C =
0.7. Howcvcr, the valucs of W/C = 0.3 clcarly show highcr resistivity
and lower mobility of Ci-. From this tablc, thc mixturc proportion which
has the highest rcsistivity and lowcst mobility is thc mortar with B.F.S.
having W/C = 0.3.
--``,`,-`-`,,`,,`,`,,`---
MOVEMENT OF SODIUM AND POTASSIUM ION
In this section, Cell t pc B (ncgative polc II distilled watcr II

spccimcn I
distillcd watcr positivc pole) was uscd. In this 1x11, from
thc positive pole to the ncgative polc, the currcnts (O.lA, 1.0A and
10A/m2) were chargcd. Mtcr schcdulcd pcriods, thc conccntrations of
the ions on the ncgative side solution wcre mcasurcd. Also, thc concen-
trations of ions in spccimcns aftcr thc currcnt charge and thosc without
currcnt charge wcrc mcasurcd.

A C 1 SP-353 V O L * I 95 0 6 6 2 9 4 9 0523259 b ö 3
1) Measurement of the electromigration of Na+ and K+

a. Assessment of the electromigration by measuring the increase of
the concentrations of the negative side solution
After the constant current (0.1, 1.0 or 10A/m2) charged, the
concentrations of Na+ and K+ ion in the negative sidc solution were
--``,`,-`-`,,`,,`,`,,`---
measurcd a t the scheduled time. Then, with the conditions that the
volumes of negativc side cell and mortar spccimen are 9.3 x 10-4m3 and
7.85 x 10-5m3 respcctively, the rcduction of thc ions in mortar spccimens
was calculated.
b. Assessment of the electromigration by measuring the ion concen-

trations in pore solutions of the specimen
Samples from the spccimens that are just after the current charge
and those with no current charge were taken by a prcssout method and
the ion concentrations of pore solution were measured. Then, consider-
ing the volume of the specimen (7.85 x lO-'rn3), the rcduction of the ions
pcr unit volume (m2) was calculatcd.
2) Results and Discussions

a. Influence of the current densities on the electromigration of Na+
and K+
In Figs. 2 and 3 , the influcncc of the current dcnsities on the
elcctromigration of Naf and K' arc shown respectively. In these cases,
the mixture proportion of the mortar was W/C = 0.5 and S/C = 2.5, and
thcse data were obtaincd based on the mcthod describcd at 1) a, In thcse
figures, it is obvious that the largcr the current density, the larger the
rcduction of the ions from the specimens. The amounts of reduction are
however, not proportional to currcnt dcnsitics. Comparcd to the theoret-
ical concentrations of Na+ (5.1 x 10t'mol/m3) and K+ (7.2 x 10+'mol/m3)
which are calculated with the assumption that thcse ions come only from
cement, the amounts of reduction are still smallcr and even in the case
of 10A/m2, we cannot reduce the ion concentration any morc. Also, we
can say that Na+ can be rcduccd easier than Kt.
In Fig. 4 and 5 , the reductions of ion concentrations which are

measured by the method dcscribcd in l)b, arc shown. From these figures,
w e can reduce the concentrations of Na+ and K+ to less than 1.0 x
10t1mol/m3, or we can take out 80% Na+ and 70% K+ from the mortar
specirncn.
b. Influence of mineral admixtures on the electromigration of Na+

and K+
In Figs 6 and 7 the influences of mincral admixturcs on the elec-
troniigration of Na+ and K+ are shown respcctively. It is clear that the
migration of ions mixed with B.F.S. is smaller than those of the others'.
One reason can bc that the replaccment ratio of B.F.S. is 50% and the
total amounts of ions are smallcr. However, this reason does not com-
pletely explain the rcsult. Also, the influences of S.F. and E A . are not
clcar, and the reduction rates are vcry closc to that of plain mortar. The

A C 1 SP-153 V O L t I 95 Obb2747 0521260 3T3 = w
pore size distribution in mortars may be an influential factor as well as the

replacement ratio.
In Fig. 4 and 5, the reduction of ion concentrations which are

measured by the method described in 1) b. are shown. Compared to that
of plain mortar specimens, the rcduction of B.F.S. spccimcn is very slow
and can not be reduced smaller than 2.0 x lOf'mol/m3. In the cases of
S.F. and EA. the ion concentrations can be reduced to less than or equal
to those of plain mortar.
INFLUENCE OF PORE SIZE DISTRIBUTION
1)Parameters for Pore Size Distribution

In this study, we used three parameters for reprcscnting pore size
distributions of mortar specirncns.
a. Absorption capacity
b. Total porc volumc bctween 0.006pm and 30pm measurcd by mercury
porosimetry (Hcreafter dcnoted by total pore volumc)
c. Pore volume between O.1pm to 360pm (Hereafter denotcd by C. type
pore volume)
2) Influence of three parameters on the electromigration of CI-

In Figs 8, 9 and 10, the influences of three parameters on the
mobility of C1- are shown respcctivcly. It is confirmed that loose micro-
structure makes the mobility largcr. The total pore volume and C-type
porc volume have much clearer influence on the mobility than absorp-
tion capacity. This means that pores, between 0.006pm to 360pm con-
tribute the electromigration of CI-. Howcvcr, we cannot say C-type
pore volume is a better parametcr for the mobility. Wc tried to find out
the better parameters for mobility and couldn't find out a better one yet.
--``,`,-`-`,,`,,`,`,,`---
Regarding the influence of the admixtures, mortars mixed with S.F. or

B.F.S show smaller mobility than those without admixture in thc condi-
tion of the same pore volume.
CONCLUSIONS
Based upon the results of this study the following conclusions are made;
1. The electromigration of ions (CI-, Na+ and K+) through and in

hardened mortar is reduced with the addition of mineral admix-
tures.
2. The electromigration of ions increases increased the water to

binder ratio.

A C 1 SP-153 V O L X I 95 I0662949 0 5 2 3 2 b 1 23T I
3. The electromigration of ions is closely rclatcd to the pore size

distribution.
4. The clectromigration of ions through mortar is largcr than that in

pastc.
5. A simple resistivity measurcmcnt givcs a vcry good approxima-

tion as to the electric migration mobilitics of Cl-, Na+, and K+
ratio ions in ccmcnt mortars and pastcs.
6. The transort numbcr of CI- is largcr when thc watcr to bindcr

ratio is largcr.
REFERENCES
1) S. Nagataki, N. Otsuki, T. Yamamoto: Influcncc of Environmcn

tal Condition on thc Expansion Rcsulting from AAR, Durability
of Building Materials and Componcnts 6, Volumc 1, pp. 363-
372, 1993.
2) G. Kortum, J. O. M. Bockris: Tcxtbook of clcctrochcmistry,

Vol. 1, Elscvicr Publishing Co., pp. 30-41, 1951.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 Ob62949 0523262 L 7 b I
TABLE 1 - PHYSICAL AND CHEMICAL PROPERTIES OF CEMENT

AND CEMENTITIOUS MATERIALS
--
Phvsical Properties Unit OPC SF FA BFS
Specific Graviiy 3.17 2.1 2.18 2 91

Fineness (Blaine) mZ/g 0.3270 0.3210 0.8070
(BET) mz/g 20.2
Moisture Content % 0.6 0.13
Compressive Strength* 7days HPa 26.7
28days 12.5
Bcnding Stress* 7days (Pa 5.5
28days 7.4
--
Chemical Composition Unit OPC SF
-
FA BFS
LOI YO 06 36 1.7 0.4

si0 2 % 21 3 92.6 50.7 13.7
Alzo3 % 53 06 21. I 13 4
Feio3 % 26 0.6 5.5
Ca0 % 64 1 0.2 10.0 4l.Y
Mg0 Yo 22 06 2.2 7.1
so 3 % 19 o0 0.3
CI % 0 007
Nat0 % 0 28 0.28 2. I 0.2
KzO % 0 60 0 80 I .2 0.3
C %
--1.29 0.6
*JIS (Japan Industrial Standard) R 5201
TABLE 2 - MIXTURE PROPORTIONS OF MORTAR AND PASTE
WIC SIC
0.50 2.5
0.1, 1.0, and i0.0A/m2
0.50 30
70-3 .o
100-3.O
0.30 0.83
PE 50 0.50 1.0
0.70 I 13
I
PEIOO 1.00 1.33
SF 30 Silica Fume
SF 50 Replacement ratio 10%
SF70 0.70
FA 30 Fly Ash 0.30

FA 50
FA70 1 Replacement ratio 30%
BFS 30
BFS 50
BFS 70
Ground granulated
blast-fumace slag
Replacement ratio 50%
0.30
0.50
0.70
I 2.5
2.5
2.5
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I 95 I0662949 0523263 002 W
w o-N
"ci+
a -? v! w.
O 0 0 0
1
1 o
o
6
8
Z
z O
O F
F d
d L?
!2 2
2
2I- I-
L!
L!
J
-I
W
W z
z O
O 0
Er I-
s
¿ñ
z I-
W Z
n W
I-
z 5
--``,`,-`-`,,`,,`,`,,`---
W
U 9
U
U W
3
o à
LL
O
3
W
o
8
W
Z o
W Z
3 W
u.
z 3
LL
I z
m I
Ym d
!? -
2 m C
B
- o c
5 8 .2
;e m. '" P.c
0 0 0 -
" T C
oo-
0 -
5
s

A C 1 SP-153 VOL+I 95 0662949 0523264 T 4 9
W W n W o - w - w - - o w -
N W P N " O N 0 rnr4-t-m
a r???
O 0 0 0
??\o?? ? -. ? -. ?
0 0 0 0 0 0 0 0 0 0
o 000
n m w
0 0 0 0 0
O m P "
m - o m W N - W W
N O O W " " ~ t - ~
- U m m
0 C t R r - m
m w m - w
*?O.??
0 0 - 0 -
m m m m m
I , # , ,
00000
x x x x x
PNNU\D
??N?
O-"-
--``,`,-`-`,,`,,`,`,,`---
iz

A C 1 SP-353 V O L * I 95 W 0662749 0523265 985
4.0 !i / O:
w
: Natur I Diffusion
0.1 A/m2
: 1.ûA/rn2
O : 10.0 Aim2
0.0 10 20 30
Charging Time (days)
Fig. 1-Influence of current density on electromigration

of CI-
'"1 ___ ..__ ..

................. ... .......................................................
Initial Amount of Na+ (Calculated

o: 0.1 Aim2
p"" H : i.ûAim2
O : íû.ûAirn*
--``,`,-`-`,,`,,`,`,,`---
K I I I I I I
0.0 10 20 30
Fig. 2-Influence of current density on electromigration

of Na+ [Method l(a)]

A C 1 SP-L53 V O L X I 95 0662749 0523266 811 M
5.01f
4.0
3 4 I
I
tI I
initial Amount of
K+ (Calculated): 7 . 1 ~ 1 -5rnol/crn3
0
I I l I l
0.0 10 20 30
Fig. %Influence of current density on electro-

migration of '
K [Method l(a)]
O : 0.1 A/m2 Without Admixture

--``,`,-`-`,,`,,`,`,,`---
O : 1.O A/m2 Without Acmixture
: 1.O A/m2 With SF
: 1.0 A/m2 With FA
O : 1.O A/m2 With BFS
0.0 10 20 30
Fig. &Reduction of Na' contents in specimen

A C 1 SP-153 V O L X I 75 W 0662947 0523267 758
O : 0.1 Alm2 Without Admixture

5.0 - 0 : 1.O A h 2 Without Acrnixture
4 : 1.0 Aim2 With SF
--``,`,-`-`,,`,,`,`,,`---
Fig. 5-Reduction of K+ contents in specimen
...................................................... -.-............
Initial Amount of Na+ (Calculated)
4.0
Ø
3.0
e : Without
2.0 Admixture
O :SF
.FA
:
1.o U : BFS
Current Density : 1.O Aim2
Y I I I I 1 I
0.0 10 20 30
Fig. &Influence of mineral admixtures on electro-

migration of Na'

A C 1 SP-153 V O L * I 75 Obb2947 0 5 2 L 2 b ô b 7 4
0 : Without Admixture
O : SF
1 : FA
O : BFS
4.0
Initial Amount of
K+ (Calculated): 7.1~1O-~rnolicrn3
3.0
2.0
1.o
I .O A/m*
I I I I I I
0.0 10 20 30
Fig. 7-Influence of mineral admxitures on electro-

migration of K+
(B
5.0
>
---
E
9 4.0
1+ 0 : Without Admixture
1 : With SF
A : With FA
: With BFS
O
8
7 Current Density:
A
X i .O A/m2
I- O
O A
1;
a, 00 O
.=
O 2.0
t
Y-
1.0
+
-
o
h
.-
.- ', lAo,;i
++ I ,
n '
=O
0.0 ,o
--``,`,-`-`,,`,,`,`,,`---
20 30 40
Adsorption Capacity (%)
Fig. &Influence of absorption capacity on mobility

of CI-

A C 1 SP-L53 V O L X I 95 m Obb2949 0 5 2 3 2 6 9 5 2 0 m
5.0
O : Without Admixture
H : With SF O
A : With FA
+ : With BFS
Current Density:
A
1.O Aim
3.0 O 0
A
8 O
2.0
1.01 , ~ I Ao,: , . ',
o.05 10 15 20 L 5
Pore Volume between 0.006 and 360 y m (Yo)
Fig. %Influence of pore volume, between 0.006

and 360 pm, on the mobility of CI'
--``,`,-`-`,,`,,`,`,,`---
(B
: With SF
+ : With BFS
7
X
v O O
S A
-O 0 O
-
..
"
O
+
O 1 .o- A i
O+
1 I I l
0.0 0.05 0.10 0.1 5
Pore Volume Between 0.1 and 360 ,u m ( c d g )
Fig. 10-Influence of pore volume, between 0.1

and 360 Fm, on the mobility

A C 1 SP-353 VOL*I 95 = Ob62949 0523270 242
SP 153-18
Properties of Concrete with Bagasse

Ash as Fine Aggregate
by B. K. Baguant
Abstract : Bagasse is the fibrous residue of sugar cane, which is burnt for
energy leaving various t-pes of ashes as waste residue. of which grate ash
--``,`,-`-`,,`,,`,`,,`---
is found to be the most suitable for use in concrete. Grate ash shows poor
chemical reactivity with portland cement. making it not very effective as a
pozzolan. It can. however, be used as a fine aggregate constituent of
concrete.
Five grades of concrete were tested. ranging from 20 to 60 MPa, in
order to compare the performance of grate ash concrete with that of normal
concrete. The use of the ash alone as fine aggregate gave harsh concrete
with low workability and poor cohesion. This was improved b} blending
about 25O.o normal concrete sand with the ash. Bleeding was comparable
with, if not generally less than in normal concrete.
Grate ash concrete, in particular the lower strength mixes, liad 10 -
1890higher initial drying rates, and would therefore require niore stringent
curing precautions than normal concrete. Rates of strength developnient
were comparable in the two concretes. Compressive strengths of over 80
hlPa were achieved after 1 year with the high-strength ash c o n m t e
mixmres. But, for a givsn strengtk the grate ash concrete requircs more
cement than normal concrete.
In comparison with iiornial concrete. grate ash concrete had similar
shrinkages. slightlv lower modulus of elasticity, and about 4Ooó lower
creep defonnations. For equivalent strengths. the two concretes shokked
similar durability properties. in terms of their resistances to mechanical
abrasion. to u ater absorption, to chloride difhsion. and to carbonation.
However, due to the porosity of the grate ash particles: the concrete liad a
much better resistance to freezing and thawing attack than normal
conuete, even though all concretes were non-air etitrainzd.
Keywords: Abrasion resistance; absorption; bagasse; bleeding (concrete);

carbonation; chloride ions; creep properties; deformation; drying
shrinkage; freeze thaw durability; modulus of elasticity; moisture content;
strength; workability
315 Not for Resale
A C 1 SP-153 VOL*I 95 0662949 0521271 189
316 Baguant
B.K. Baguant is Senior Lecturer in Civil Engineering at the Universitv of

Mauritius. He obtained his Ph.D from the same institution.
INTRODC'CTION
The economy of Mauritius, a small 1800 km'Indian Ocean island.

has heen fòr many years and is still dependent on the cultivation of sugar
cane ( a production of about 5.6 s 106 tons per y a r ) [ l ] . Bagasse. the
fibrous residue of sugar cane after crushing and estraction ofjuice. consists
of water (about 5 0 O 0 ) . fibres (about 48%) and relatively small amounts of
soluble solids. Kearly all bagasse produced in Mauritius is ciirrmtl? burnt
for energy needed for sugar processing. Any surplus steam is converted
into electricit?. Only a very small amount is used for niaking resiii-bonded
bagasse fibre boards.
Bagasse ash is considered to be a waste product with little or no use.

It has negative va1112 in that the sugar factories have to spend money to
dispose of some 20,000 tons per year [Z]. The ash represents about 0.30,0
of cane cnished or about 2.89.0 ofthe d q . weight of bagasse. The fiimaces
have bagasse fed from the sides. which is then distributed by a spreader-
stoker on to the plan area of the combustion chamber. while primary air is
blown upwards through a grate, enabling the fibres to bum in suspensioti in
air. The typical firing temperature of bagasse in the furnaces is 1000-
1100°C [2]. Three types ofash are produced in this process:
(a) Grate ash - accumulates on the grate and is removed by

tilting the grate h m time to time (about 1 1,000 tons):
(b) Hopper ash - blown into hoppers by secondary air fed from
the side ofthe fiirnace (about 3.000 tons): and.
(c) Fly ash - carried up the chinme? (about 4,000 tons).
Photographs of the ashes taken through a scanning electron

microscope (Fig. 1,2 and 3) reveal that the grate ash hiis ven fe\\ spherical
particles of the type seen in coal flv ash. Most of the particles are rough
and angular. The hopper ash also has u feu spherical particles. while îhz
rest of the particles are less angular and generally more rounded (Fig 2).
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 m Obb2949 0521272 015 m
The fly ash on the other hand clearly shows fibrous unbumt particles with
a few spherical particles (Fig.3).
The bagasse fly ash has a high carbon content (70-80%), is soft and
compressible, making it unsuitable as a constituent of concrete and has
therefore been excluded from this study. The grate and hopper ashes have
a high silica content, low lime content and a small amount of unburnt
material (Table 1). They are granular. rou& porous particles with
relative densities of 1.90 - 2.12 on a saturated surface d q basis. The ashes
also have high absorption values of 2 to 6% and their grading is generally
coarse (Table 2). [2].
The prime use of grate ash in concrete would be as partial

replacement of cement, all of which is imported in Mauritius. However,
this will require grinding of the ash to a fineness which would be
compatible with that of cement, which means additional cost. The other
possibility is to use bagasse ash in its as-produced state as fine aggregate,
for example, in the making of concrete blocks which are widely used in
building construction. The fine aggregates used in Mauritius are crushed
basalt sand, which is expensive, and a lagoonal coral sand which is
becoming scarce.
Tests camed out in accordance with BS 3892:1982 showed rather

poor reactivity of grate ash with cement. The water requirement was 104 -
1 10% and the pozzolanic activity index was 65 - 68% even after grinding
to a fmeness of less than 45 pm [3]. This is not too surprising in view of
the relative porous structure and absence of spherical particles as revealed
by the SEM photographs. However, many pozzolanas are known to
exhibit low reactivities at early ages and yet develop significantly higher
strength at later ages. Therefore. the strength development with time of
concrete containing ground grate and hopper ashes was investigated. The
strengths of both grate ash and hopper ash mixtures were found to be
comparable with those of the control mixture at all ages up to 1 year[4].
There was, therefore, no evidence of any significant additional strength
due to pozzolanic activity. This paper evaluates the possibility of using
grate ash as fine aggregate in concrete. The results obtained are compared
with those of concrete normally used.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 V O L + I 95 B 0662747 0523273 T5L B
318 Baguant
--``,`,-`-`,,`,,`,`,,`---
Grate ash was selected for the overall investigations of the use of
bagasse ash in concrete because of its granular nature requiring no further
grinding for use as sand. Hopper ash usually contains agglomerated lumps
which must be broken down. Also, grate ash is available in larger
quantitiesthan hopper ash. Grats ash obtained &om a single factory (Von
Desert Alma) was oven-dried and passed through a 4.75 mm test sieve to
remove about 8Oó of the coarser particles. Crushed basalt coarse aggregate
(20,14. and 10 mm single sizes) and a medium grade natural sand (Table
2) were used in the control mixtures. The same coarse aggregate was used
in the bagasse ash mixtures.
Initial trial mixtures with bagasse ash alone as fine aggregate gave
very harsh concrete, whose workability could not be improved significantly
by increasing water content. This was thought to be due to the coarse
grading of the bagasse ash. It was, therefore decided to m o d e the grading
by blending in 25% crushed basait sand with the grate ash (Table 2). Also,
since the purpose of the investigation was to evaluate the mechanical
strength characteristics of the material in concrete, it was decided to use a
superplasticiser (Cormix SP5 at a dosage of 1.25% by weight of cement) to
reduce the water and produce reasonably high-strength concrete. '4range
of equivalent mixtures were proportioned in accordance with the
DOE/DOT method [5] for the normal and bagasse ash concretes. Table 3
shows details of the mixture proportions used. The properties investigated,
the test specimens, testing environments and procedure are outlined in
Table 4.
FRESH CONCRETE
Plastic Densitv, Workabilitv and Bleeding
The plastic density of grate ash concrete was lower than that of
normal concrete because of the lower relative density of grate ash (2.1)
compared with natural sand (2.6) (Table 5 ) . Had it not been for the
presence of the crushed sand (relative density 2.86) in the grate ash
mixtures, this difference would have been greater.
Slump was slightly lower and cohesion was generally more lacking
in the bagasse ash concrete mixtures. Bleeding in the nomai concrete
decreased with increase in strength while the workability remained more or

A C 1 SP-153 V O L * I 95 I Obb2949 0523274 998
less constant (Table 4). But in the bagasse ash concrete, bleeding did not
seem to be influenced by concrete strmgth and fluctuated near an average
value of about 3O/Ó of water in the mixtures. From Fig. 4 it can be seen that
the lower strength concrete had a tendency to bleed faster. For example, in
the Grade 20 ash mixtures, most of the bleeding occurred during the f r s t
-
40 50 minutes, whereas in the higher strength concretes the corresponding
time was at least 100 minutes. This was due to the higher cement content
which tended to make the tugher strength concretes more plastic and
cohesive.
HARDENED CONCRETE
Moisture Loss
The results (Table 6) show that more than half of tlie ultimate
moisture loss occurred during the first day of exposure to the atmosphere.
--``,`,-`-`,,`,,`,`,,`---
The low strength concretes lost niore moisture than tlie higher streiigth
grades and this was apparent Com the firstday. It appears from the results
that bagasse ash concrete ultimately lost i0 - l 8 O 0 more moisture than
normal concrete. However. a closer look at the results (Fig.5) reveals that
this difierence had set in from the first day. Subsequent to the first day.
there was little difference in the moisture loss characteristics between
bagasse. ash concrete and nornial concrete. 'ïhe practical significance of
the faster iniìial drying rate of bagasse ash concrete is that it may require
more protection against early drying, for example in terms of adequate
curing. in order to ensure satisfactory strength development.
Strength development
Bagasse ash concrete showed the same trend for A b r a m Law's

strength vs. waterkement relationship as for normal concrete (Fig.6).
However? for the same watw'cement, bagasse ash concrete had lower
strength than normal concrete at all ages up to one year. The diflerent set
of relationships for bagasse ash concrete indicates that bagasse ash is a
different material from natural sands. It also means that for a given target
strength. more cement than that for a iionnal concrete will be required for
the bagasse ash concrete niih?ure. Strength values in excess of 8 0 s 'nm2
were obtained indicating that there should tie little or no strength liniitation
in practice wiih the use of bagasse ash in concrete for nornial eiigiiiccriiig
applicrttions.

A C 1 SP-153 V O L X I 95 Obb2949 0521275 ô 2 4 9
320 Baguant
Strength development rate in bagasse ash concrete was comparable

with that of normal concrete at corresponding ages for both water curing
and air curing. This is shown in Table 7 in terms of actual strzngths
achieved. It can also be seen. as would be expected, that inadequate curing
such as air curing slows down strength development quite significantly.
Elastic deformation
The modiilus ofelasticity ofbagasse ash concrete was slightly lower

than that of normal concrete at corresponding strengths (Fig.7). Also
plotted on the Fig. is Equation 17 &om BS 8 110 : Part 2 : 1985, which is
given as
Es.28 = i- o.2 fcu28
where KOhas been taken as 20 kNimm2for normal aggregates.
It can be seen that for normal concrete there is a perfect agreement

between the E-values given by Equation 17 and the experimental values.
But for bagasse ash concrete, Equation 17 overestimates the E-values by 4
--``,`,-`-`,,`,,`,`,,`---
to 89’0 (Table 8). However. if, as for lightweight concrete. the E-values
prcdicted by Equation 17 are multiplied by (WBWs)z, where W, is the
density of bagasse ash concrete and W, that of normal concrete (in kg/m3).
the dotted curve is obtained. There is very good agreement betwezn the
dotted curve and the experimental E-values for bagasse ash concrete.
Thus, the lower density of bagasse ash concrete must be taken into account
for the purpose of estimating its modulus of elasticity from its cube
strength. Typical stress-strain relationships for the two concretes are
illustrated in Fig.8.
Creep deformation
Contrary to what would have been expected from the observed

differences in strength and modulus of elasticity between the two types of
concrete. creep deformation in bagasse ash concrete was significantly less
than in normal concrete at a stress/strength ratio of 3Ooo (Fig. 9). For
example. at 110 days, the total strains in the Grade 40 specimens tested
under load were 1900 x 10-6 and 1300 x 10-6 in normal and bagasse ash
concretes respectively. The corresponding strains in the unloaded
specimens were 520 x 10-6and 460 x 10-6 respectively. Even if the
shrinkage of the bagasse ash concrete cplindzr specimens had been q u a l to
or slightly higher than that of normal concrete, as was observed in the

A C 1 SP-1.53 VOL*I 75 Obb2947 0523276 760 =
siiiallcr prisni specimens, the diRerence in creep deformation between the

two concretes would still be significant. The creep strain in bagasse ash
concrete was only about 6Ooo of that of normal concrete‘. although the
strength oftlid bagasse ash concrete (38.3MPa.) was lower than that of tlic
nomal concrete (47.5MPa.). The creep deformation behavior of bagasse
ash concrete probably requires further investigation. but at least it is not an
adverse or liiiiiting factor in thc use of bagass2 ash in concrete in
accordance with data obtained in this project. At best it would be an
advantage.
Slirinkage
The two tvpes of concrete show- coniparable ultimate drying

shrinkage strains for all grades of concrete (Table 9). This is compatible
with the fact that the two concretes lost more or less the sanie aiiiouiits of
nioisture from tlie first day onwards as discussed earlier. The lean concrzte
tnistures had loner slirinkagz while the higher strength concretes had
lii&er but similar sliriiikage values. Fig. 10 shows t y i c a l shrinkage strain
YS, time rrllationsliips for the two concretes. Tlic drying sliriiiliage values
ineasured in the cylinder specimens used as control in the creep tests were
also similar for the two types of concrete. Ilonever. the shrinhags of thc
cylinder speciniens (500 N 1 0 - 0 ) was 1oif.erthan that of the prisms (700 s
lO-’j)).MWst this niay be due to diITercnt datuni age (28 days for cllinder
specimens rind 7 dn>s for the prisni specimens) or to different shapes and
\ d u m e to surfaGc ratios o1 the t m speciiiiciis, it clearly demonstrates the
iniportaiice of considering such factors when interpreting sliririliage data.
particularl’, when t q i n g to predict shrinkage in fi111 scale structural
nienibers.
In general. tlie deformation behavior (elastic, creep aiid shrinkage)

of bagasse asli concrete is similar to that of normal concrete, except for
creep which was found to be about 4O0o lower in the ash concrete.
Homever. when estimating the niodiilus of elasticity of bagasse ash
concrete from its strength if the correction factor for density of concrete
suggested bv BS 81 10 is applied, close agreenient is obtained betueen the
estimated and espenmental E-values.
Durability
Initial surface absorption -- Durability of concrete is considered to

depend closely on its surface absorption characteristics or the ability of
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L S I 95 m Obb29Y9 0523277 bT7 m
322 Baguant
materials in solution or in a gaseous state to penetrate the concrete surface.

.An indirect measure of this is the Initial Surface Absorption test (ISAT)
[6,7] which measures the rate offlow ofwater under a sniall constant head,
into ovendried concrete per unit surface area after a stated interval of time
h m the beginning of the test. The initial surface absorption of concrete
dzc-reasrs with time until eventually the surface becomes saturated and no
more water is absorbed. Bagasse ash concrete and normal concrete seem
to have similar surface absorption values which decrease with increase in
strength of concrete (Fig. 1 I).
Carbonation -- Carbonation reduces alkalinity in concrete and

thereby increases the risk of reinforcement corrosion due to the reduction
in passivation of steel as a result of reduced pH. The test results (Table
10) show that depth of carbonation increases with exposure tinit. and
decreases with increase in strength of concrete. These are illustrated in
Fig. 12(a) and 12(b). Depth of carbonation does not increase linearly with
time as is the case with difñision type mass transfers in solid media, and,
also because of strength and weight changes that occur in the concrete
during the period of exposure to carbon dioxide. However, depth of
carbonation vs. square root of tinie relatioiiships are found to be generally
linear (see Fig. 12(a)). As with initial surface absorption, bagasse ash
concrete and normal concrete seem to have similar resistances to
--``,`,-`-`,,`,,`,`,,`---
carbonation (Fig. 12(b)). Weight inueases occur as a result of carbon

dioxide absorption while moisture loss produces weight reductions. In the
weaker concretes carbonation occurs faster, while moisture loss also
occurs faster, so that their net weight increases are less than those of the
stronger concretes.
Chloride penetration -- Chloride penetration tests are another

measure of durability of concrete in terms of its resistance to penetration of
solutes by diffusion. Chlorides are particularly known to reduce the
electrical resistivity of concrete cover thereby promoting electrochemical
corrosion of steel, especially under hot humid conditions. The tests were
carried out on Grade 40 mixtures only, with 3 cubes specimens of each
type of concrete. After curing under water for 28 days, the cubes were
allowed to surface &-y before applying a sealant primer on 4 faces, leaving
2 opposite faces unsealed followed by a paraffin wax coating on the 4
sealed surfaces. After conditioning under water for 1 day, the specimens
were transferred to the chloride tank. At the test age, the cube specimen
was split into 2 halves and the fmctured faces wcre sprayed with Silver
Nitrate Solution followed by fluorosodium. The chloride ion invaded

region showed a paler color. After 3 months in a 5M chloride solutioit

cliloride ions had penetrated to depths of 28 nun and 27.5 mm in the
normal and bagasse ash concretes, thus showing no significant difkrence in
the chloride penetration resistance of the tv,o concretes. M e r 6 nionths,
chlorides had invaded the whole section of the 100 mm cubes in both
concretes. as they were penetration íiom two opposite faces of the cube
specimens.
.%rasion resistance --
Abrasion resistance was assessed using
concrete slabs made with Cirade 40 mixtures. which were water-cured for
28 days. allowed to surfice dry for 2 days and tested on both faces. The
mean abrasion depths of the two concretes \ w e 1.23 mm for the normal
concrete and 1.66 mm for the bagasse ash concrete, which may be
attributable to the dserence in strengths of 47.5MPa for the normal
concrete and 38.3MPa for the bagasse ash concrete. For practical
purposes there does not seem to be an appreciably signifcant dserence in
the mechanical abrasion resistance of the two concretes, perhaps, because
the same coarse aggregate was used and because the bagasse ash has a low
content of fine particles. Abrasion resistance is known to be influenced by
factors such as concrete strength nature and content of coarse aggregate,
and fines content [7].
Freezin~-thawiiig,resistance -- Although frezzing and thawing is not

a problem in Mauritius, it was thought worthwhile to c a r y out freezing-
thawing tests in order to understand the behavior of bagasse ash concrete
--``,`,-`-`,,`,,`,`,,`---
under tlie action of internal stresses. Ail concretes were non-air entrained.
The results (Fig. 13) show a marked departure in the behavior of bagasse
ash concrete from normal concrete in terms of a much better resistance to
freezing-thawing attack of the bagasse ash concrete. Changes started
occurring in the normal concrete in terms of change in lengtk pulse
velocity, and dynamic modulus of elasticity after only 20 cycles of fieezing
and thawing. Similar changes started occurring in the bagasse ash concrete
after about 230 freezing-thawing cycles or higher. The durability factors
calculated in accordance with ASTM (2-666 were found to be about 1890
(passing)for the normal concrete and 80% (passing) for the bagasse ash
concrete. Whiie it may be argued that the superplasticiser may have
entrained some air in the bagasse ash mises. thus improving its fieezing-
thawing resistance, this factor alone cannot explain the large diffaences
observed in the behavior of the two concretes. it appears that the porous
nature of the bagasse ash particles is the single most important dif3erence
= 0bb2949 O523278 5 3 3
A C 1 SP-153 VOL>wI 95
A C 1 SP-153 V O L * I 95 m Ob62949 0521277 4 7 T m
324 Baguant
iron1 natural sand which can account for the greatly d a n c e d freezing-
thawing resistance of the bagasse ash concrete.
Comparing thc. durability properties of the two concretes. it appears

that for eqiiivalent strength they have similar resistance to water
absorption to chloride ion diffiision and to carbonation. For equivalent
strengths they could also be espected to have comparable resistance to
mechanical abrasion. But the major difference appears in a much
enhanced resistance to internal pressurzs arising from constituents that
expand. (such as those due to ice during freezing-thawing cycles), for
bagasse ash concrete in comparison with normal concrete.
CONCLUSIONS
The objective of this investigation was to evaluate the possibility of

using bagasse ash, in particular grate ash a waste product of the sugar
cane industn;. as a fine aggregate in concrete and to coiiipare its
performance with that ofconcrete normally used. Grate ash showed poor
chemical reactivity with cement with a pozzolanic activity indes of 65-
68Oh and is, thus. not very effective as a pozzolan. It can, however, be
used as frne aggregate constituent of concrete.
Because of its coarse grading, the use of grate ash alone as fine
aggregate gave harsh concrete with low workability and poor cohesion.
This was improved by blending about 25 Ojo normal concrete sand
containing sufficient filler, with the ash. Bleeding was comparable with if
not generally less than in normal concrete.
Five grades of concrete were tested. ranging from 20 to 60 MPa.

Grate ash concrete. in particular the lower strength mixtures. had 10-18O.9
higher initial drying rates, and would therefore require greater care during
curing than normal concrete.
Compressive strstigths in excess of 80 MPa were achieved after 1

year with the high-strength ash conmetes. Kates of strength development
were comparable in the two concretes. But for the given strength, the grate
--``,`,-`-`,,`,,`,`,,`---
ash concrete requires more cement than normal concrete; that is. the
strengtyh vs. watercement relationship for the ash concrete is diffetent
fiom that for normal concrete.

A C 1 SP-153 V O L t I 95 H Ob62949 O523280 371
Grate ash concrete had slightly lower modulus of elasticity, similar

shrinkages, and about 40% lower creep deformations in comparison with
n o m a l concrete. For equivalent strengîhs, the two concretes showed
similar durability properties, in terms of their resistances to mechanical
abrasion, to water absorption to chloride diffusion and to carbonation.
However, due to the porosity of the grate ash particles, the concrete had a
much better resistance to freezing and thawing attack than normal
concrete. even though all concretes were non-air entrained.
ACKYOWLEDGEMENTS
The author gratefùlly acho-ledges the invaluable support of the

British Council for having funded visits to Ihiversity of Dundee. where
some of the tests were carried out, and of the C'niversitj of Mauritius.
REFEREYCES
1. hlohamedbhai, G.T.G., & Baguant. B.K.. "Possibility of Using

Bagasse Ash and other Furnace Residues as Partial Substitutes for
Cement in hlauritiiis", Reku-uz Agricole et Sumide de ïIlz Maurice 0,
3. Sept-Dec 1985.
2. Li Pin Yuen, L.Y.Y.G., "L4vailability of Bagasse .kli and its

Characteristics in hlauritius". H.Tech Final ì e a r Pro-iect. Lhiversit!? of
Mauritius. 1986.
3. Choollun, V.K.. "Pozzolanic Activity of Bagasse .-ish and its

Characteristics in Mauritius", J3.Tech Final Year Projsct, Cniversity of
Mauritius. 1986.
4. Kim Curnint G.S.. "The Effects of Plasticiser on Bagasse

Concrete", B.Tech Final i e a r Project, Lni\:enity of hlauritiiis. 1988.
5 . Teychennk. D.C.. Franklin. R.E.. Erntroy, H.C., "Design of Normal

Concrete
Mixes", Department of the Environment. Department of Transport.
Revised Edition
1988.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 = 0662949 05232811 O28
326 Baguant
6. Leviti, M., "Non-DestnicîiveTesting of Concrete by ISA Method",

Proceeáings of the Symposium on Non-Destructive Testing of
Concrete and Timber, London, 1 1-12 July 1969, ICE, 1970, pp 23-28.
7. BS 1881: Part 5: 1970, "Methods of Testing Hardened Concrete for

other than strength".
8. Dhir, R.K., Hewletî, P.C., & Chan, S.Y.,

"Near-SurfaceCharacteristics
of Concrete: Abrasion Resistance", RILEM, Materiaus et
Constructions, Vo1.24, March 1991. pp 122-128.
TABLE 1 - TYPICAL CHEMICAL CONSTITUENTS OF
BAGASSEASH
Grate Ash
C m ~ t s 36 by weighî
Si02 73.1 20.2
Ii
--``,`,-`-`,,`,,`,`,,`---
I
A1203 6.9 2.0
Fe203
Ca0
Mgo
U0
Na20
I 5.1
4.3
2.7
2.7
0.2
1.4
i
P205
SO3
2.6
0.2
Ii
Cl2 0.01
L.O.I. 1.3 71 .o
TABLE 2 - GRADATION OF GRATE ASH, NATURAL SAND,

CRUSHED BASALT SAND, AND MODIFIED GRATE ASH
r I I
I
I
Particle Size Distribution ("/o passing) I
I
J
Sieve Size Grate Naturai Crushed 75% Grate A h

Ash Sand W t Sand + 25% Crushed Sand
100.0 99.6 99.8
83.0
68.0
90.5
82.8 ' 93.4
82.4
85.6
71.6 i
I
0.60
0.2 12
17.1
7.2
0.3
60.6
51.1
55.8
47.3
26.3
1 26.8
17.2
6.8
I
I
i
o. 150
0.075 0.06 1 1.1 4.3 1.1 I
GRADE
-__ sand ash =ta I n,uwi(B ccme- j
20
30 275 224 671 1 1050 1 165
165
1 623
40 333 6(xi 1077
50 388 564 ! 1083 I I63 1 025
60
___-
__ --I
20 224 1 %
--``,`,-`-`,,`,,`,`,,`---
30
40
50
275
333
338
i
I
778
717
660
60 - 452 I 6 2
= Ob62949
A C 1 S P - I 1 5 3 V O L X I 95
No reproduction or networking permitted without license from IHS Not for Resale 0521282 Tb4 m
328 Baguant
TABLE 4 - TEST DETAILS

Pro(wrty I Spslmcn$/test detau1 I Procedure-
Plastic density i ' BC 1881
i
Workablty Slump test I BSIUû1
I
I
Blerdmg
.Moisture loss After demouìdurg c u b s afta 24 ius III an at Z ~ C i I

WAR H, and w a r n cubes with tune I
!
Shengihdevelopmmt IOOmm cubes tested up to 1 year, two ninng regimes, BS 1881
,
ather water at 2U'C or an at 200C óO%R H Part 110 lu83
I
Elastic deformation 15Omm e x 3OOmm cyhnden tested at the age of 28 ES 1881
days for moduìus of elast~ntyand shes-straui cume Part5 1970
creep 1 LOO mm0 x 300 mm cyhnder, stressistrcngrh rano of i

I
I
l
30% of cube strength under sustained load ûom the
age of 28 days
l 50 x 50 x 200 mm pnsm piacedmauat 20°C WAR H BS 1881
i attfieageof7days
Exposure to vanous enwonments starts at the age of
parts 1970 i
i
l
28 days
l
i -inibaiSurface I 100 mm cubes BS 1881 ~
1
I
AbsotphonTest Part5 1370
i
I -carboMhOn 100 mm cuba water-cured for 14 days, air-dned for
14 days before bemg -sed to 4% Co;! at 2U'C,
~
1
I
Sû% R H
' -Chhide peneûation 100 mm cubes sealed on four f a a s and m e r s e d at l

l
M days III 534 NaCI + saturatedC a ( 0 a solmon for l
up to 1 year l
- Freeze-thaw resistance 200 mm pnsms subjected to up to 300 ASTU '2-666,
1 80cycles80ofx ûeeze-thaw
x l
I
1
between -2U'C and + 5°C Method B
I
I !
- Abrasion resistance I Mo x 300 x lûûmm thick slabs testedm a modbed Reference 8
I accelerated abrasion resistance machine I
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 75 O Obb2749 0 5 2 3 2 8 4 837 O
1
Normal Concreîe Bagasse Ash Concreîc
Grade Plastlc Slump ' Piastic Siump Bleed@* 1
--``,`,-`-`,,`,,`,`,,`---
(mm) (mm) (YO)
20 2453 45 5 53 2346 I 30 3 27
30 2480 45 4 52 2394 35 1 280 ,
40
-50
60
2483
2503
2503
1
1
50
50
55
3 23
2 95
240
2430
2411
2462 I
30
4 0 1
292
3 12
TABLE 6 - MOISTURE LOSS WITH TIME

-
M d s h v e lors YO oftotal mix water I
Grade NoniralCo~~~reîe Bagasse Ash Concrete
1 1 4 10 140 1 '
lj 20 I 47
I
i
I
61 i 67
days
74 64
47 152 65 45
4 4 1 4 9 5 8 \ 3 1 44150 6 7 1
39 45 55 I 36 47 I 57 69
1
~
1 60 30 1 39 44 54 1 40 1 49 1 55 65
TABLE 7 - STRENGTH DEVELOPMENT WITH TIME

CUBE STRENGTH - MPa I
WIC AIR-CURING l
I WATEE 1-
7 1281365) 190 7 I 2 8 90 1 365 I
- BAGASSE ASH CONCRETE

0.74
0.60
0.49
0.42
0.36
27.5
37.4
18.1
10.4
32.7
41.9
1
8.0 ! 10.0 I 11 3
16.2
30.9
30.5
45.7
10.6
22.1
36.9
33.1
43.6
I1 ,1
I days !
I
1
1 7.8
15.4
27.6
27.1
43.0
1
12.9
127.1
38.3
44.2
61.8
458
53.0 1'51.0
62.0
72.7 1 886 i
1
NORMAL CONCRETE I
0.80 I 11 5 I 12.4 I 17.1 I
308

330 Baguant
TABLE 8 - MODULUS OF ELASTICITY
- ._ . --
stren8t i Erperimeitsi Estimated
ai 28 day$ E-value E-vaiue
(BS 8 110,
Equ. 17)
W?)- @"mm*) C!!Nlmr-
30.9 26.0 26.2
47.5 29.7 29.5
5tl.3 . 30.1 -. - - 31.7 -
TABLE 9 - DRYING SHRINKAGE
--``,`,-`-`,,`,,`,`,,`---
GRADE «)
O 49.2 O O 48.3 I O I O
5 0.408 1 1
10
I5
1 59.4
63.0
10.0
14.0 0.343
49.7
54.1
13.1
16.3
0.391
0.0% 1
20
65.8
60.0
16.0
18.0
0.483
0.541
56.8
57.2
19.3
24.5 0.257 I
GRADE 50
O
5
10
70.5
73.0
74.0
O
7.5
10.1
O
0.374
0.298
54.8
62.0
60.0
O
10.8
15.0
I
I
O
0.681
0.771
15 74.7 13.4 0.2% 61.3 17.5 I 0.945 i
20 I

A C 1 SP-353 VOL*I
No reproduction or networking permitted without license from IHS 95 0 Ob62949
Not for Resale 0523285 7 7 3
A C 1 SP-153 VOL*I 95 IObb2949 0521286 bOT m
--``,`,-`-`,,`,,`,`,,`---
Fig. l - G r a t e ash (1 lox)
Fig. 2-Hopper ash (46x)

A C 1 SP-153 V O L W I 95 0662949 0523287 546
332 Baguant
Fig. %Fly ash (60x)

--``,`,-`-`,,`,,`,`,,`---
I
O 50 100 I50 200
TIME (mins.)
Fig. &Bleeding of fresh concrete with time

A C I S P - 1 5 3 VOL*I 95 n o b b z w q 0 5 z ~ z a a482 n
.
Grade
..... 20
....................-o
Normal Concrete
--``,`,-`-`,,`,,`,`,,`---
1 4 140
'O DAYS
Fig. &Moisture loss with time
I
O30 O40 0.50 0.60 O 70 0.80 O90
WATEWCEMENT
Fig. 6-Compressive strength versus water-cement ratio

A C 1 SP-153 VOL*I 95 I0 6 6 2 9 4 9 0521289 319 I
334 Baguant
8s 811O:Part2:1985(Eqn.17)
I'y621 -
[29.5]
29.7
131.7)
._____.....--
[i::]
,_.._...--,-
U
u---....~----~
23.5 [:i:;]
y71 - - - - O - - -Bagasse
- Ach
\
Concrete
Eqn.17 x(WwWs)2
J Normal Concrete
=
8
=
5L
0
20 25 30 35
" Experimental values[*]Calculated values
40 45 50 55 60
i
CUBE CRUSHING STRENGTH (MPa.)
Fig. 7-Modulus of elasticity versus strength
--``,`,-`-`,,`,,`,`,,`---
,..... u
u-----.-.
1 +Normal Concrete
- - - - O - - -Bagasse
- Ash
Concrete
1
0.00 5.00 10.00 15.00 20.00 25.00
COMPRESSIVE STRAIN (X 1O E -4)
Fig. &-Typical stress versus strain

A C 1 SP-153 VOL*I 95 I
I 0662949 0523290 030
O 20 40 BO 80 1aJ 120 140

AGE ( d w )
Fig. 9-Deformation under sustained load with time
80 T Normal Concrete
q? 70
LU 60
50
V 40
04 : -- I
O 20 40 60 80 1O0 120 140
AGE (days)
Fig. 1&Typical shrinkage versus time
2 Bagasse Ash Concrete

& trnT .k e o C.I A b +O
O 10 mins 30 mins 60 m i n s l 2 0 mins
5 íûmins
O
e 1 e
O
n o
I
O A A
-
A A
I
O 4 4
6
t
E 10
Oi
20 25
Normal Concrete
30 35 40 45 50 56 60
I
CUBE m u s w STRENGTH (MPa.)
Fig. 1I-Initial surface absorption versus strength

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 Obb2949 0521291 T77
336 Baguant
Fig. 12(a)-Depth of carbonation with time

--``,`,-`-`,,`,,`,`,,`---
Fig. 12(b)-Effect of strength on carbonation depth

A C 1 SP-I153 V O L * I 95 Ob62949 0523292 903
-
Bagasse Ash Concrete

..o
...u
....o ! . . o ~ ~ . . . u -I- - ~ " ~
200 250 300 350
NUMBER O F FREEZING - THAWING CYCLES
Fig. 13(a)-Change in length with freezing-thawing cycles
- Bagasse Ash
Normal Concrete
I
O 50 1 O0 150 200 250 300 350
NUMBER OF FREEZING - THAWING CYCLES
Fig. 13(b)-Change in pulse velocity with freezing-thawing cycles
Q --u.
Bagasse Ash Concrete u
--``,`,-`-`,,`,,`,`,,`---
O 50 100 150 200 250 300 350

NUMBER OF FREEZING - THAWING CYCLES
Fig. 13(c)-Change in dynamic modulus with freezing-thawing cycles

A C 1 SP-I53 VOL*I 95 m Obb2949 0523293 8 4 T m
SP 153-19
Mechanical Treatment of Fly Ashes:

Strength Development and
Workability of Mortars Containing
Ground Fly Ashes
by J. Monzó, J. Payá,
E. Peris-Mora, and M. V. Borrathero
Svnomis: This paper presents the results of a study of the influence

of ground fly ashes on workability and strength of mortars. Fly ash
(TO) was obtained from the thermoelectric power plant of Andorra-
Teruel (Spain). Samples of TO fly ash were ground using a laboratory
ball-mill for 10, 40 and 60 minutes (T10, T40 and T60). This
process crushed spherical or spheroidal fly ash particles so that the
morphology of the particles was substantially modified and the
fineness notably increased. Mortars were prepared by replacing from
15 to 60% of cement by fly ash. Curing time, curing temperature and
fly ash amount influenced the strength of mortars. Curing times
longer than 7 days showed significative differences among fly ashes,
with compressive and flexural strengths decreasing in the order
T60>T40>T10>TO. Increasing the curing temperature from 20' to 40
*C produces a rise of compressive strength that exceeds control
mortars when T60 and T40 fly ashes were used. It is concluded that
the use of ground fly ashes improves the strength of mortars
compared with strengths obtained with normal fly ash, but high
replacement percentages of ground fly ash adversing affect
workability.
Keywords: Compressive strength; flexural strength; flow table tests; f i

-
ash; mortars (material); particle size distribution; specific surface;
strength; workability
--``,`,-`-`,,`,,`,`,,`---

339Not for Resale
A C 1 SP-153 V O L * I 95 0 6 6 2 9 4 9 0521294 7 8 b =
340 Monzó et ai
José Monzó is an Assistant Professor of chemistry of materials and

environmental chemistry in the Polytechnical University of Valencia
(Spain). He received his Ph.D. thesis degree from the University of
Valencia. His research activities and publications are in the fields of
analytical chemistry, bulding materials and recycling.
Jordi Payá is an Assistant Professor at the Departament of

Construction Engineering, Universidad Politécnica de Valencia, and
he obtained his Ph.D. degree from Universitat de Valencia in 1990.
His main research interest is the use of solid industrial by-products
and wastes in cements, mortars and concrete production.
E. Peris-Mora is Professor of chemistry of materials and

environmental chemistry and head of "oficina verde" in the Poly
technical University of Valencia. He received his Ph.D. thesis degree
from the University of Sevilla. Has published books and papers about
water pollution and waste materials
M.V. Borrachero is an Associate Professor in the Departament of

Construction Engineering at the Polytechnical University of Valencia
(Spain). She obtained her Ph.D. thesis from the University of Murcia
in 1990. Her research interest includes industrial by-products used as
replacement of portland cement.
INTRODUCTION
It is generally accepted that: a) shape morphology and size of

fly ash particles strongly affect the properties of freshly mixed pastes,
mortars and concretes, due to lubricant and filler effect; and b)
--``,`,-`-`,,`,,`,`,,`---
chemical composition, vitreous character and specific surface of fly

ash modify hardened paste, mortar and concrete properties, due to
pozzolanic reaction with calcium hydroxide during cement hydration.
The performance properties of fly ashes can be changed by means
several procedures (1-4) the most frequent being the classification of
an original fly ash into several fractions with different fineness
(sieving, flotation or air separation), or blending of successive size
fractions (mechanical and electrostatic separators) in the
thermoelectric power plant. In these cases, removal of coarse particles

A C 1 SP-I153 V O L * I 95 m 0662949 0523295 bb2 m
improves fly ash quality, due to the removal of the less reactive and
irregular shaped particles. In the processes mentioned above fineness
is increased and the spherical or spheroidal shape morphology of the
particles is maintained. Grinding is an alternative process method for
increasing the fineness of a fly ash, although the shape and texture
of the particles is substantially modified.
The objective of the investigation was to provide data about the

behavior of fresh and hardened mortars containing ground fly ashes,
and explore, in a preliminary way, the possibility for using them in
mortar and concrete production so that a significant improvement of
some properties is obtained. Several samples of an original fly ash
were ground using a laboratory mill, varying the grinding time from
10 to 60 minutes. Workability of mortars was studied by means flow
spread measurements on mortars containing fly ash (original or
ground samples) replacing mass of cement from 15 to 60 %. Early-
strength development of mortars containing fly ashes (original or
ground samples) was studied at several curing temperatures (from 20
to 80 *C) for compressive arid flexural strength.
EXPERIMENTAL SECTION
--``,`,-`-`,,`,,`,`,,`---
Materials
Mortar mixtures were prepared using a commercial Spanish

cement II-F/35A which consists of a mixture of an ASTM Type I
portland cement with a finely ground inert limestone (13% by mass).
This cement is considered as Type II/A-L in the European Prenorm
PRENV 197-1. An original low-calcium fly ash (namely TO) from
the thermoelectric power plant of Andorra-Teruel (Spain) was used
as received with natural sand, of fineness modulus 2.93. Analytical
data for clinker and original fly ash are presented in Table 1.

A C 1 SP-I153 V O L * I 95 D 0662949 0523296 5 5 9 D
342 Monzó et al
Fly Ash Preparation and Examination
Samples of TO fly ash were ground using laboratory ball-mill

(Gabbrielli Mill-2) for different times: 450 g of original fly ash TO
were introduced into the ball-mill containing 98 balls of alumina (2
cm diameter) and were ground for periods of 10, 40 and 60 minutes,
yielding the ground fly ashes namely T10, T40 and T60 respectively.
Particle size distributions were performed using a Sympatec Helos
Particle Size Analyzer.
Mortar Preparation and Testing
Control mortars were prepared by mixing 450 g of cement, 1350

g of fine aggregate and 200 mL of water. The rest of mortars were
prepared with various replacement pecentages of cement by original
or ground fly ash. Workability was determined as flow table spread
according to ASTM C-109 and UNE-83.425 standars.For strength
tests, mortars were put in a mold for obtaining 1 6 x 4 ~ cm
4 specimens,
which were stored in a moisture room (2011~C) for 24 hours. After
demoulding, specimens were stored under water at temperatures
between 2 0 d *C and 8011 *C until the test age of 3 to 28 days.

--``,`,-`-`,,`,,`,`,,`---
Particle Characteristics of Ground Fly Ashes
Grinding process crushed spherical or spheroidal fly ash

particles such that the morphology of particles was substantially
modified and fineness notably increased. Fig.1 shows particle size
distribution curves for original fly ash (TO) and ground samples
(T10,T40 and T60). Interestingly, when the original fly ash is ground
for only 10 minutes, particle size distribution curve is notably
modified. Greater grinding times also produced important particle
size distribution modifications, but grinding effect diminished with
time. In the same way, the mean particle diameter (dm) decreased
and the calculated specific surface (Sc) increased with grinding time

A C 1 SP-153 VOL*I 95 W Obb2949 0523297 495 =
(Fig.2). The fineness determined using the Blaine air permeability

apparatus (Sb) were compared with values calculated from particle
size (Sc). Sc values were generally slighty less than Sb values.
Workability of Mortars ContaininE Ground Fly Ashes
Flow table spread values, (FTS), are given in Table 2 and are
compared with the value of 126.5 mm for the control mortar FL'
Fig.3 plots flow table spread difference, d(FTS), [that is (FTS)i minus
(FT'S),] versus fly ash replacing percentage. For the lowest fly ash
content in mortars, 15%, no difference was observed. For higher
percentages, from 30 to 60 %, two clear tendencies can be noticed.
First d(FTS) values increased with fly ash percentage. This indicates
that despite the shape of part of the particles having been changed,
the workability of mortars is enhanced when ground fly ash partially
replaces cement. Second the workability of mortars is reduced when
the grinding time is increased, showing that although the number of
fly ash particles is raised, their shape morphology significantly
worsen the workability.
The influence of fly ash fineness on the workability of mortars

can be compared (see Fig.4) with fly ash fineness obtained by means
air separation method (S), where shape morphology of particles was
--``,`,-`-`,,`,,`,`,,`---
not altered in the Classification process. For a given mean diameter,
d(FT'S) value fall drastically when ground fly ash is used.
Compressive and Flexural StrenEths of Mortars ContaininP Ground

Fly Ashes
Compressive strength values of mortars are given in Table 3.

Fig.5 shows the variation of Rci/Rcl ratio with curing times from 3
to 28 days Rci being the compressive strength of mortars containing
fly ashes and Rcl the compressive strength of control mortars. In this
figure a Rci/Rcl ratio increase with curing time can be observed.
Except at age 3 days when no very well established differences
among fly ashes were observed, the rest of the curing times (7, 14,
28 days) show important differences among fly ashes. Clearly,
pozzolanic reaction rate increases when grinding time of fly ash

A C 1 SP-L53 VOL*I 95 Obb2949 052L29ô 321
344 Monzó et al
--``,`,-`-`,,`,,`,`,,`---
increases. However, the trends were slighty different for both

percentages: while 30% test presents a non linear correlation, 60%
substitution test shows a linear correlation between RciíRcl and
curing time (3-28 days). This linear correlation is probably due to
the high fly ash content (higher reactive silica), that permits increased
pozzolanic activity as the curing period increases. When fly ash
content is lower (30%) curing times larger than 7 days produces an
increase of Rci/Rcl but no linear increase, probably due to decrease
of active silica content.
Flexural strength values of mortars are given in Table 4. Fig.6

shows the results obtained for flexural strengths. The tendency
observed is almost the same that observed for compressive strength,
but in this case Rfi/Rfl ratios are larger and TO (30%) is almost the
same as T60 (60%) for 28 days curing time. This agreement between
30% and 60% replacement levels makes clear the crucial importance
of grinding fly ash in order to obtain larger flexural strengths.
Compressive strengths at 28 days for mortars cured at various

temperatures are given in Table 5. Fig.7 illustres the variation of
compressive strength when curing temperature is raised from 20" to
80°C. First, it shows that at 20 QCthere are a significative differences
in compressive strength between control mortar and mortars
containing fly ashes and also significative differences among mortars
containing fly ashes with different grinding times (T60 > T40 >T10
>TO). Among mortars containing fly ash higher compressive strength
values were obtained when grinding time increased.
A similar trend was observed for the 40 QCcuring, although in

this case no differences were observed between T40 and T60 ground
fly ashes. Increasing temperature from 20" to 40°C produces a rise
of compressive strength that exceeds the control mortar strength when
T60 and T40 fly ashes were used. In general, this increase obtained
for mortars containing fly ash when temperature is raised from 20"
to 40°C is probably due to modification in a positive sense of the
kinetic of pozzolanic reaction. When temperature is raised to 60"C,
a significative decrease of compressive strength is observed for
mortars containing fly ash, and similar results were observed for
80°C. This phenomenon makes clear that 40°C is an optimum

A C 1 SP-I153 V O L X I 95 Obb29Li9 0521299 268
temperature for pozzolanic reaction development in the experimental

conditions studied. It is curious that the compressive strength of the
control mortar is not affected when curing temperature increases from
20" to 60"C, decreasing markedly at 80°C.
Flexural strength values of mortars are given in Table 6. Fig.8

shows the variation of flexural strength when curing temperature is
increased from 20" to 80°C. Variable behavior is observed for
mortars containing fly ash when the temperature is increased and no
defined tendency is observed with mortars containing fly ash with
different grinding times. In ali cases mortars containing fly ash
produced higher flexural strength than control mortars except for
20°C experiments that produced similar strength.
CONCLUDING REMARKS
1. Grinding fly ashes produces a drastic modification in their

nature: fineness is increased, mean diameter is decreased and
--``,`,-`-`,,`,,`,`,,`---
shape morphology of part of the particles is altered to a more
angular forms.
2. Substitution of part of cement by fly ash (original or ground
samples) produces mortar mixtures with greater workability than
"only cement" mortars as measured by the flow test.
3. When the percentage is low (15%), use of ground fly ashes in
mortar do not greatly influence the workability.
4. For higher replacement percentages (230%) the workability of
mortars is reduced as grinding time is increased.
5. Crushing spherical or spheroidal fly ash particles contributed
significantly to lessen at the workability of mortars containing
ground fly ashes, due to loss of lubricant effect.
6 For a given curing time, when fly ash grinding time increases
Rci/Rcl and Rfi/Rfl ratios increase. This phenomenon is more
evident at 28 days of curing time.
7 Increasing curing temperature from 20" to 40°C produces a
increase in compressive strength that surpasses control mortar
when T60 and T40 fly ashes were used.

A C 1 SP-153 V O L * I 95 O b b 2 î L i î 0521300 B O T =
346 Monzó et al
8 20"C, 60°C and 80°C curing temperatures tests produce almost

the same compressive strength for mortars containing fly ashes.
9 40°C and 80°C curing temperature tests produce almost the
same flexural strength of specimens containing fly ashes. In all
cases mortars containing fly ashes produced higher flexural
strength than control mortars, except for 20°C test that produced
similar strength.
As a final conclusion we can establish that the use of ground fly

ashes improves the strength of mortars containing non mechanically
treated fly ashes, but high grinding time decrease mortar workability.
--``,`,-`-`,,`,,`,`,,`---
We can state that the best conbination for parameters studied are:
4 0 T curing temperature (optimun respect 20,60 and 80QC),30% fly
ash substitution, 40 minutes of grinding time (increase markedly
stregth and increase workability slighty compared to only cement
mortar) and 28 days curing time (produces a Rci/Rcl= 0.85 and
Rfi/Rfl= 1)
REFERENCES
1 W.B. Butler, M.C. Mearing, MRS Symposia Proceedings: Fly

Ash and Coal Conversion By-products; Characterization,
Utilization and Disposal II, 65 (1986) pp.11
2 E. Peris Mora, J. Payá, J. Monzó. Materiales de Construcción 41

(19Y1) 29.
3 R. Hiirdtl, Studies in Environmental Science 48, Waste Materials

in Construction Proceedings: Environmental Implications of
Construction with waste materials, Maastricht (1991) 399.
4 E. Anakura, H. Fujinawa, T. Nishida, Y. Fukada. Jpn. Kokai

Tokkyo Koho,41,137,1991
5 E. Peris-Mora, J. Payá and J. Monzó, Cement and Concrete

Research, 23 (1993) 917.

A C 1 SP-353 V O L * I 95 I0662949 0523303 746 I
TABLE 1 - CHEMICAL ANALYSES OF CLINKER AND FLY ASH
Clinker Fly ash

Chemical Analysis
Sulphur trioxide (SO,),% 1.7 1.0
Ferric oxide (Fe,O,),% 4.8 16.0
Aluminum oxide (A1203),% 4.6 26.2
Silicon dioxide (SiO,),% 20.8 41.4
Calcium oxide (Cao) total,% 65.6 6.1
Magnesium oxide (MgO),% 1.2 1.1
Sodium oxide (Na,O),% o,1 o. 1
Potassium oxide &O),% 1.0 0.5
Loss on Ignition,% 0.2 2.1
Bogue Potential
Compounds Composition
GS 66.5 -
GS 9.5 -
GA 3.9 -
C,AF 14.7 -
TABLE 2 - FLOW TABLE SPREAD FOR VARIOUS GRINDING TIMES

AND FLY ASH PERCENTAGE
Flow Table Spread

mm
15% 30% 45 % 60%
~~ ~ ~~ ~~
TO 133.5 149 155 169.5

T10 134 142.5 146.5 160.5
T40 130 134.5 138.5 148.5
T60 139 132.5 133.5 141.5
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I 95 W 0bb2949 0523302 682
348 MonzÓ et al
TABLE 3 - COMPRESSIVE STRENGTH VARIATION WITH CURING

TIME AND GRINDING TIME FOR MORTARS CONTAINING 30 AND 60
PERCENT REPLACEMENT WITH FLY ASH
MPa
3-d 7-d 14-d 28-d
30%
TO 15.9 21.4 26.5 34.4
T10 17.3 23.7 29.2 38.3
T40 18.2 25.2 32.2 41.5
T60 18.2 25.9 33.1 43.0
60%
TO 6.0 7.0 11.2 17.1
T10 6.5 8.4 12.2 20.0
T40 7.9 10.6 16.0 23.6
T60 7.7 11.2 16.7 25.4
TABLE 4 - FLEXURAL STRENGTH VARIATION WITH CURING TIME

AND GRINDING TIME FOR MORTARS CONTAINING 30 AND 60
REPLACEMENT WITH FLY ASH
Flexural Strength
MPa
3-d 7-d 14-d 28-d
1
T40 1.8 2.4 3.5 6.1
--``,`,-`-`,,`,,`,`,,`---
T60 1.8 2.5 3.5 6.1

A C 1 SP-I153 V O L X I 95 W 0662949 0523303 539
TABLE 5 - COMPRESSIVE STRENGTH VARIATION WITH CURING

TEMPERATURE AND GRINDING TIME OF FLY ASH (30 PERCENT
REPLAC EMENT)
MPa
20QC 40QC 60QC 80QC
Cement 49.4 48.1 48.7 33.3
TO 34.4 47.3 37.2 31.9
T10 38.3 49.5 36.8 36.4
T40 41.6 51.5 38.0 37.7
T60 43.0 51.2 39.0 37.9
TABLE 6 - FLEXURAL STRENGTH VARIATION WITH CURING

TEMPERATURE AND GRINDING TIME OF FLY ASH (30 PERCENT
REPLACEMENT)
Flexural Strength
MPa
20QC 40T 6OQC 80QC
Cement 7.5 7.3 5.2 3.4
TO 6.5 10.1 6.5 7.2
T10 7 9.7 6.6 8.5
T40 7.5 8.7 7.5 9.3
T60 7.7 9.9 7.4 9.0
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I53 VOL*I 95 0 0662949 0521304 455 M
350 MonzÓ et al
accumulated volume (%)

1O0
80
* TO
60
+T10
40 * T40
20
*T60
O
1 10 1O0
diameter (um)
Fig. 1-Particle-size distribution curves for original fly
ash (TO) and ground fly ashes (TlO, T40, and T60)
Specific Surf.* lo9 (cm2/g)

7
..................... 6
. . . . . . ,.
35
5
h
30
.............. ndm
sc
.,.......
HSb
TO T10 T40 T60

FLY ASH
Fig. 2-Mean diameter (drn) and specific surface (calculated

S,, and Blaine S,) for original (TO) and ground (T10, T40,
and T60) fly ashes
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L t I 75 0662949 0523305 391 m
d (FTS)
I I
15 30 45 60
fly ash percentage
Fig. %Flow table spread difference d(FTS) for mortars containing fly
ashes versus percentage of fly ash replacement
TO
\
40- +30% ground

-O- 60% ground
30-
"-30% air clas.
20-
+ 60% air clas.
10-
O 10 20 30 40 50 60
mean diameter Olm)
Fig. 4-Comparison between ground- (solid lines) and air-classified

(dashed lines) fly ashes and their influence on workability of mortars
containing 30 percent (wide lines) and 60 percent (thin lines) fly ash
replacement --``,`,-`-`,,`,,`,`,,`---

A C 1 SP-lt53 VOL81 95 = 0662949 0523306 228
352 Monzó et al
Rci/Rcl i \
* TO(30%)
+ T10(30%)
++ T40(30%)
+ T60(30%)
* TO(60%)
* T10(60%)
-T40(60%)
O 7 14
days
21 28 -* T60(60%)
Fig. &Relative early compressive strength development for mortars

containing original (TO) and ground (TlO, T40, and T60) fly ashes: 30
percent replacement percentage, wide lines; 60 percent replacement
percentage, thin lines
.
--``,`,-`-`,,`,,`,`,,`---
Rfi/Rfl
+- T0(30%)
+ T10(30%)
-R T40(30%)
- T60(30%)
* T0(60%)
* T10(60%)
-T40(60%)
* T60(60%)
O 7 14 21 28 /
days
Fig. &Relative early flexural strength development for mortars

containing original (TO)and ground (T10, T40, and T60) fly ashes: 30
percent replacement percentage, wide lines; 60 percent replacement
percentage, thin lines

A C 1 SP-I153 V O L X I 95
5
50
45
40
35
30
12
--``,`,-`-`,,`,,`,`,,`---
20 40
m
60
Temperature (OC)
0662949 0523307 3b4
Fig. 74ompressive strength variation with curing temperature for

mortars containing 30 percent fly ash replacement
Rfi
80
,-
* Cement
m
353
10
6
- T60
*Cement
4
2
20 40 60 80
Temperature (OC)
Fig. &Flexural strength variation with curing temperature for mortars

containing 30 percent fly ash replacement

A C 1 SP-153 VOL*I 95 I0662949 0521308 O T O
SP 153-20
Influence of Fineness and Soluble

Silica Content of Fly Ashes on
Their Strength Development with
Respect to Age
by R. V. Ranganath, R. C. Sharma,
and S. Krishnamoorthy
Synopsis : In this paper the authors have examined the liine-reactivity

strength data of fourteen samples of fly ash obtained from different Thermal
Power Plants of India. The sand-lime-fly ash mortars cured at 50°C and
relative humidity of 90% were tested in compression at different ages up to 90
days. It is found that lime reactivity is best correlated with combined parameter
of fineness and soluble silica content rather than with each individually. Also
examined are the strength of concrete mixtures in which part of cement is
replaced by a low reactive fly ash. Fineness of fly ash and testing ages for
strength were the variables. It is concluded that the soluble silica content was
related later-age strengths, whereas the early-age strength correlated better with
fineness of fly ash. The mechanism for the later may not be chemical but
physical such as dispersion of cement particles or micro-filler effect.
Kevwords: Cements; concretes; fineness; flv ash; lime; silica; solubility;

strength
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOL*I 95 W 0662949 0523309 T37 W
356 Ranganath, Sharma, and Krishnamoorthy
Ranganath R.V. is a research fellow at the Department of Civil Engineering

of Indian Institute of Technology, New Delhi. He received his M.Tech degree
from the same Institute. He is preparing a Ph.D thesis on Characterization and
Utilization of Ponded Fly Ash in Concrete Mixture.
Rakesh Chandra Sharma obtained his M.Sc. degree in chemistry from Meerut
University and Ph.D degree from IIT Delhi. He worked for eight years as a
scientist at the National Council for Cement and Building Materials, Delhi.
Presently, he is employed as Assistant Manager (Chem) in Regional Testing
Laboratory, Ministry of Industries, Bombay.
Krishanmoorthy, S. is professor of Civil Engineering at IIT Delhi. He received

his Ph.D. degree from Imperial College, London. His research activities are
--``,`,-`-`,,`,,`,`,,`---
in the fields of Concrete Technology, Construction Management, Durability of

Concrete and Building Science.
INTRODUCTION
Fly ash is an industrial waste and its use as a building material gains
importance because of its pozzolanicity. Most reviewers agree that it is not yet
possible to predict the reactivity from any known combination of physical and
chemical measurements on the fly ash alone: thus, direct tests of strength
development with lime or portland cement are still necessary in order to
evaluate fly ashes for use in blended cement or concrete.
Sersale(1) examined different types of fly ash for their pozzolanic

activity and stated that this activity is due to the chemical composition, quantity
of active phases, fineness, structure, morphology of the fly ash etc. Puri(2)
considered that the fineness is one of the principal parameters which defines
the rate of development of mechanical strength when fly ash is added to
cement. Ravina(3), i n particular evaluated the size distribution and specific
surface methods for determining fineness of fly ash and he found a linear
relationship between the fineness and pozzolanic activity of the ash obtained
from a single power station.
Richartz(4) explained that pozzolanic reaction is to be expected from

only those mineral phases in which silica dissolves with sufficient rapidity in
an alkaline environment, since, only after such a dissolution, the silica would
react with lime to form the strength-giving calcium silicate hydrates. He

A C 1 S P - I 1 5 3 V O L U I 95 E 0 b b 2 9 4 9 0521310 759
considered that the percentage of soluble silica of a fly ash should be a

principal criterion for evaluating its potential reactivity. It is generally accepted
that such soluble silica is predominantly present in the amorphous, vitreous
parts of the fly ash.
Hubbard and Dhir(5) proposed an empirical parameter, Pozzolanic

Potential Index (PPI) which is the molar ratio of potash to alumina (KIA), as
a means of assessment of the chemical nature of the pozzolanicity of an ash.
According to them, PPI is an indicator of the long term pozzolanic reactivity
potential of fly ash. They reasoned that the formation of a glassy phase is
related to the presence of K,O through an involved petrological and chemical
analysis. Yuan et d ( 6 ) proposed that the adsorption of enough micro-particles
of fly ash on cement particles will result in dispersion of the cement particles
in suspension, this in turn, helps the cement particles to hydrate at a faster
rate.
A recent study conducted by Sharma(7) with twenty five samples of fly

ash obtained from eight different thermal power stations showed that a
correlation existed between the lime reactivity and a combined parameter of
fineness and soluble silica content of the fly ashes. For strength at 10 days of
curing at 50+2"C and a relative humidity of 90% as per IS 1727-1967, the
correlation is
--``,`,-`-`,,`,,`,`,,`---
L = (F/1500)O.XS * sO.8" ___________(1)

where
L = Lime Reactivity strength at 10 days (MPa)
F = Fineness (Blaine's) (sq.m/Kg)
S = Soluble silica content(%)
The correlation was obtained through a standard regression model which

could handle two variables simultaneously. The coefficient of correlation is as
high as 0.94.
In this paper the authors have reported the effect of fineness and soluble
silica content of fourteen fly ashes on the strength development of sand-lime-fly
ash mortar specimens for 90 days as well as cement concrete cubes in which
a part of the cement was replaced with fly ash.

A C 1 SP-153 V O L * I 95 0662949 0521311 695 =
EXPERIMENTAL
Fourteen samples of fly ash were obtained from thermal power stations
located in different parts of India, and their principal characteristics are given
in Table 1. Principally, these could be differentiated as low, medium and high
reactive ashes. Lime of reagent grade (96&0.5%)purity was used for lime
reactivity test. The chemical analyses of the samples was determined by
complexometric (largely EDTA) and flame photometer methods. Soluble silica
content was taken as the difference between total silica and free silica.
Lime-fly ash mortar cubes of 50mm size were cast and cured for 48
hours in the laboratory at 27°C and at a RH which exceeded 90%. The
specimens were then cured at 50°C and a similar high humidity till the time of
testing. The age of the specimens ranged from 3 to 90 days.
A second series of tests were conducted with one of the fly ashes,
which had been found to have relatively low reactivity. This fly ash was
further classified into three different grades, A, B and C such that the
maximum size of the particles were restricted to 45pm, 75pm & 150pm
respectively. The results of the lime reactivity test at 10 and 28 days, as per
IS 1727-1967, and fineness (Blaine) for these three grades are shown in Table
2. Table 3 presents the results of chemical analysis. For strength tests in
concrete, part of the cement, 10% & 20% was replaced with fly ash and
compressive strength tests on standard cubes (100mm) were performed at
laboratory temperature, which ranged from 26 to 30°C during the period of
curing. The specimens were cured by immersion in water tanks until before the
test. Mixture proportions are shown in Table 4. The proportions had been
obtained following the current British Method of concrete mixture design(8).
A constant W/C+F, 0.55, was used for all the concrete mixtures.
RJSULTS AND DISCUSSION
In Fig.1 the strength of mortar specimens made with different fly ash
samples is plotted against fineness (Blaine) for testing done at different ages.
It is seen that the values exhibit a smaller scatter for early age 3, 7 days
strengths and a larger scatter for 28 and 90 days strength. Fig.2 shows the
relationship of strength of mortar specimens to soluble silica content at
different ages. There is little increase in strength when soluble silica content
increases from 20%to 30% but when the soluble silica content is greater than
30% there is a good dependence between the soluble silica content and
strength. Fig.3 shows the lime reactivity strengths against an empirical ,
I
--``,`,-`-`,,`,,`,`,,`---

parameter obtained as the product of soluble silica and fineness divided by 100.
There seems to exist a good correlation over a large range of this value, from
about 70 to over 200.
Fig 5 plots the co-efficient of correlation of the curves which had been
obtained by regression analysis from Fig. 1, 2 & 3. The degree of correlation
for strength (at different ages) with only fineness is decreasing while that for
soluble silica alone increases with age. The combined parameter maintains a
very high co-efficient of correlation throughout at all ages. Fig.4 shows the
lime reactivity strength plotted against the right hand side of Eq.1. The
correlation coefficients of plots shown in Fig.4 have been plotted in Fig.5 for
comparison. It appears that for strength at various ages, the combined
parameter of FXS gives a better representation than that given in Eq.1.
Table 2 contains the results of lime reactivity strength of the three

grades of fly ash, A, B, C cured for 10 and 28 days. the table also shows the
fineness of the three grades of fly ashes. The grade-A fly ash which was the
finest showed about three and half times the lime reactivity strength, at 10
days, compared to grade-C fly ash, which was the coarsest. However, at 28
days the ratio of the strengths of grade-A to grade-l was only about 1.6. This
indicated that a significant cause of the high early strength of grade-A of fly
ash in mortar, was its fineness. It has to be noted that all the three grades of
fly ash had been obtained from the same fly ash of dyke-1 of Badarpur thermal
power plant (Delhi) and have nearly the same chemical composition (Table 3)
and without much variation in the soluble silica content. It is possible that the
fine particles contribute to early high strength predominantly due to micro-filler
effect.
Fig 6 and 7 show the compressive strength ratios of concrete cubes

plotted against the fineness of the three grades of the fly ash. The strength
ratios are obtained by dividing the strength of fly ash cement concrete cubes
(fly ash as part replacement of cement) by the strength of control concrete
cubes (0% fly ash) both obtained at the same age. Different curves have been
plotted for strength at different ages.
For 10% replacement of cement with fly ash (Fig 6) the strength ratios
show that there is a substantial correlation between strength and fineness at
early ages while the 28 day strength was considerably higher at the fineness
290 sq.m/Kg Blaine and 312 sq.m/Kg Blaine, at low fineness the strength of
fly ash cement concrete was lower than that of control concrete. It is proposed
that up to age 14 days the principal source of strength in the fly ash concrete
was the pore-filling effect of finer particles of fly ash and the dispersal caused
to cement particles.
--``,`,-`-`,,`,,`,`,,`---
=
A C 1 SP-153 VOL*I
No reproduction or networking permitted without license from IHS 95 Ob62949 0523332 5 2 1
Not for Resale
However, at 28 days there is distinct increment in the strength ratio

which indicates pozzolanic activity as well. This confirms the postulate that fly
ash when added to mortars and concretes contributes to strength due to the
soluble silica content of the fly ash at later ages. Fig 7, which refers to the
situation wherein a larger amount of cement is replaced by fly ash (20%)
shows similar trends. However, the amount of cement replaced was probably
more than what could be optimally done, and strength ratios are greater than
unity only for higher fineness and that too after 14 days of curing.
CONCLUSIONS
The study shows that the fineness of fly ash plays an important role in
the strength of mortars and concretes at early ages, probably via a micro-filler
or a cement dispersion effect or both, At the later ages the soluble silica
content of the fly ash or its pozzolanicity becomes more significant. Since the
mechanism and rate of formation of calcium silicate gel are both physical and
chemical, the combined parameter of fineness and soluble silica content of fly
ash is probably a more appropriate factor in assessing the potential strength
contribution of a fly ash.
REFERENCES
1. Sersale, R., “Aspects of Chemistry of Additions”, Advances in Cement

Technology, Ed: by S.N. Gosh, Pergamon Press, Oxford, pp 537-567
(1983)
2. Puri, A.M., “Aspects concernant l’utilisation de Cendres de Centrala

Thermique Comme Addition lors d u Gryoage du ciment”, Materials de
Constructii, 5 , 1, pp 27-30 (1975)
3. Ravina, D., “Optimized Determination of PFA fineness with reference

to pozzolanic activity”, Cement and Concrete Research, Vol. 10, No.4,
pp 573-580 (1980)
4. Richartz, W., “Composition and Properties of Fly Ashes“, ZKG 284,

pp 62-70 (1984)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I
Not for Resale
75 W Ob62949 0521313 468 m
A C 1 S P - I 1 5 3 VOL*I 95 M Obb2949 0521314 3T4 =
Hubbard, F.H., Dhir, R.K. and Ellis, M.S., "Pulvensed Fuel Ash for
concrete: compositional characterisation of United Kingdom PFA" ,
Cement and Concrete Research 15, pp 185-198 (1985)
Yuan, R.J., Jin, S.X. and Qiam, J.C., "Effects of Fly Ash on the
Rheology of Fresh Cement", Skanly, J.P., Ed., Effect of Surface and
Colloid Phenomena on Properties of Fresh Concrete, Proc. Symp.
Mater. Res. Soc., Annual Meeting, Nov. 1982, Univ. Park, PA, pp
182-191 (1982)
Sharma, R.C., Jain, N.K. and Ghosh, S.N., "Semi-Theoretical Method

for the Assessment of Reactivity of Fly Ashes", Cement and Concrete
Research 23, pp 41-45 (1993)
Teychenne, D.C., Franklin, R.E. and Erntroy, H., "Design of Normal

Concrete Mixes", pp 31 (Department of the Environment, London,
H.M.S.O., 1975).
Sample Silica Alumina Iron Calcium Soluble Fineness

No. Oxide Oxide silica (Blaine)
sq.m/Kg
1 FI 1 56.30 I 24.38 I 4.70 1 2.06 I 27.50 I 460 1

--``,`,-`-`,,`,,`,`,,`---
F2 63.52 25.57 2.64 0.79 32.60 470
F3 63.04 28.40 5.12 0.50 34.39 396
F4 60.18 19.63 8.76 1S O 24.07 389
F5 55.53 21.39 12.06 1.98 34.69 536
F6 52.65 19.49 5.81 2.96 19.28 390
F7 58.78 31.08 4.69 1.51 30.00 573
F8 59.21 23.53 5.40 1.86 28.50 318
F9 58.66 29.26 4.92 1.67 32.06 341
FIO 56.61 27.16 3.35 0.81 27.28 363
FI1 60.11 26.16 5.39 2.82 38.02 516
F12 59.96 24.17 5.23 1.12 31.05 386

F13 50.58 25.15 4.84 1.18 20.00 411
FI4 64.31 25.59 4.45 1.03 25.2 425

TABLE 2 - LIME REACTIVITY STRENGTH AND FINENESS DATA OF

DIFFERENT GRADES OF FLY ASH
Samples Lime Reactivity Finenzss Sp. Gravity

(MP4 (Blaine)
' sq.m/Kg
10 Days 28 Days
-
Grade-A (0-45pm) 4.5 5.9 312 2.23

Grade-B (0-75pm) 2.9 4.8 290 2.19
Grade-C (O-i5Opm) 1.3 3.6 230 2.12
TABLE 3 - CHEMICAL COMPOSITION OF DIFFERENT GRADES OF

FLY ASH (PERCENT)
I Chemical
Analysis
*
6.89
--``,`,-`-`,,`,,`,`,,`---
sio, 58.16 58.23 56.85

28.14 26.67 28.54
6.41 1 5.35 1
0.07
~~ ~
Soluble Silica 26.21 20.60 21.97

A C 1 SP-153 VOL*I 95 0662949 052131b 177 m
TABLE 4 - MIXTURE PROPORTIONS USED FOR MAKING

CONCRETE
Relative Batch Quantities (kglm')
I I i
Cement
Control 100
I 1
Concrete
2 10% Fly 90
I I
Ash
3 20% Fly 80
Ash
* Badarpur natural sand

** Crushed aggregate of maximum size 20mm
a
--``,`,-`-`,,`,,`,`,,`---
T
5
m
C
g 5.
v)
I
MO
1
300
I
400
1
500 6
Fineness i m2/kg 1
Fig. l-Influence of fly ash fineness on lime reactivity strengths at

various ages

A C 1 S P - 1 5 3 V O L * I 75 Ob62949 0521317 003 = w
10- 0 3 days
x 7 doys
0 28doys
90doys
O
4
5
ct 5-
G
I I I I I
10 20 30 LO 50
Soluble Silica i%)
Fig. 2-Influence of soluble silica contgents of fly ash on lime reactivity

strengths at various ages
10 - 0 3 days
X 7 doys
0 28doys
9odoys
q
5-
lñ
I I I I
O'
50 100 150 200
Fineness x S S
100
Fig. 3-Influence of product of fineness and soluble silica contents on

lime reactivity strengths of fly ashes at various ages
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 V O L * I 95 = 0662949 052L3LB T 4 T 9
--``,`,-`-`,,`,,`,`,,`---
Fig. 4-Influence of right-hand side of Eq. (1) on lime reactivity

strengths of fly ashes at various ages
0 Fineness
x Soluble Silica
1.0
D Combind
w
A Cornbind (&f.85x(s)0.8
.-
C
O
.-
o
-Y -
8 0.5
.- C
.-
-..-+
U
al
u
I l I I
0.c 90
3 7 28
Age idoys)
Fig. 5-Relationship between coefficient of correlation versus age

A C 1 SP-153 V O L r I 95 I0662949 0521319 9 8 b
366 Ranganath, Sharma, and Krichnamoorthy
130 -
x 3 days
120- O 7 days
0 1Cdays
28days
110-
O
.-
c
O
100-
5
0
C
L
Ülw-
80 -
70 I I 1
200 230 290 312
Fig. U t r e n g t h ratios at different ages for 10 percent

replacement of cement with fly ash
120 -
110 -
-0
c
100-
L
5
c2 90-
,
3i
60-
702 0 0 230 290 312

Fineness .(m%g)
Fig. 7 4 t r e n g t h ratios at different ages for 20 percent

replacement of cement with fly ash
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 IOb62949 0521320 bTB I
SP 153-21
Improvement of Characteristics
of Roller Compacted Concrete by
Classified Fly Ash
by T. Fukute, K. Nakano, and M. Ishii
Synopsis : Classified fly ash (CFA) is produced by separating the fine components
of fly ash by mcans of air classification. CFA is made of fine particles of
micro-meter size and spherical shape, and is expected to improve the consistency
of fresh concrete and the durability of hardened concrete. The use of CFA in roller
compacted concrete (RCC) pavement has the effect of reducing the water content of
RCC mixtures, and thcreforc the drying shrinkagc and the number of joints in
pavement.RCC pavements havc becomc popular for roads and streets in Japan.
The maximum thickncss of RCC slabs that may be placed in one layer is limited
to 25cm because of limitations in the compactibility of the concrete and control of
the pavernent surface profile. To increase the slab thickness of RCC placeable in
one layer, an improved concrctc that requires minimal energy for obtaining a high
filled-volume ratio is desirable.
In this paper, the effects of CFA additions to cement on the compactibility and
water content of RCC mixture were studicd.
--``,`,-`-`,,`,,`,`,,`---
Kevwords: Compaction; compaction tests; flv ash; particle size

distribution; pavements; roller comDacted concrete

A C 1 S P - 1 5 3 V O L r I 95 I0662949 0521321 534
368 Fukute, Nakano, and Ishii
Tsutomu Fukute is the chief of thc Matcnals Laboratory at the Port and Harbour
Research Institute, Ministry of Transport, Japan. He rcccivcd his Doctor of
Engineering Degree from Nagoya University in 1985. His research interest covers
the durability of concrcte, new construction materials and airport pavemcnt
engineering. He is a member of JSCE and JCI.
Kin-ichi Nakano is the managing director of Sumitomo-Osaka Ccment Co.,Ltd.,

Tokyo, Japan. He reccivcd his Doctor of Enginccring Degree from Kyoto
Univcrsity in 1985. He is a member of JSCE, JCI and JSMS.
Mitsuhiro Ishii is gcncral deputy manager of Techno-Resource Company,

Inc.,Takamatsu, Japan. He receivcd his Dr. Eng. from The Univcrsity of
Tokushima in 1 9 9 4 . H ~has bcen engaging in research and dcvclopment of thc use
of cou1 ash and construction materials. Hc is a member of JSCE, JCI and JSMS.
--``,`,-`-`,,`,,`,`,,`---
INTRODUCTION
Fly ash produced in recent years has a lower quality for use as an
admixture in concrete, bccause of changes in the combustion systcm of power
plants and use of more diversificd brands of coal. For this reason, it is nccessary to
reduce the fluctuation of physical propertics of fly ash for gcncral use.
Classified fly ash (CFA) is produccd by separating the fine components of raw
fly ash by means of air classification and is more uniform in quality than the raw
fly ash. CFA is made of fine particles of micro-meter size and spherical shape, and
is expected to improve the consistency of fresh concrctc and the durability of
hardened concrete.
Roller compacted concrete (RCC) pavemcnt is expected to be an economical

and rational concrete pavemcnt system and to becomc increasingly popular in
Japan. RCC pavement can reduce labor through mechanization during
construction, and it can be opened to traffic in a short timc after construction. Thc
use of CFA in roller compacted concrctc (RCC) pavcmcnt should have beneficial
effects in reducing the water content of RCC mixtures, drying shrinkage and the
number of joints in the pavement. Although slabs highly compacted with surface
vibrating equipment are desired, the rclationship between the consistency of RCC
and the equipment wight, amplitude, frequency, and acceleration of vibration has
not been fully asscsscd.
A high stiffness of RCC is preferred for operating the vibrating rollers,

although less stiffness is appropriate to attain full consolidation. Thus, the mixture
proportions of RCC should be designed to obtain the proper consistency to satisfy
both requircmcnts. In Japan, the consistency of RCC is dctcrmincd by thc Marshall

A C 1 SP-153 V O L t I 75 IO662747 0521322 470
compaction test. This methods are convenient and popular for practical use but
provide little information for improving the construction procedurc of RCC
pavements.
Vibrating accelerationdecreases downward within the slab during compaction,

and the density of compacted material in the lower laycr is less than that in the
upper layer. This shortcoming requires the compaction of RCC slab in two layers
for thicker pavements for heavy loads and is an engineering problem that must be
solved before RCC pavements can be used for hcavy traffic such as major airports
and seciports. To increase the RCC slab thickness that can be consolidated in one
layer, concrete materials with improved compactibility should be developed.
In this paper, the improvement of the consistency of RCC mixed with CFA
was studied. The consistency of RCC was evaluatcd using the compactibility tcst
apparatus proposed by Dr. Kokubu et al (l),from the vicw point of not only fillcd
volume ratio alone but also the process of compaction, that is the trend of the fillcd
volume ratio curve versus supply of vibratory energy.
THE EFFECTS ON IMPROVEMENT OF COMPACTIBILITY USING

CLASSIFIED FLY ASH IN LABORATORY TESTS
MATERIALS
1. CEMENT, JIS STANDARDIZED FLY ASH AND CLASSIFIED FLY ASH

Physical and chemical propcrtics of thc normal portland ccmcnt (NPC), JIS
standardized fly ash ( JFA) and classificd fly ash (CFA) used in the cxperimcnts
are summarized in Talde 1. CFA was classified to conform with the regulation of
blaine value,JTS and CFA was classified with JFA to have more small size particles
( 5 2 0 y m ,diameter).
2. AGGREGATES
Pit sand was used as the fine aggregate, and crushcd stonc with a maximum
size of 20mm was used as the coarse aggrcgatc. Physical propcrtics of thc fine and
coarse aggregatcs arc summarized in Table 2.
MIXTURE PROPORTIONS OF RCC
In this experiment, thrcc scrics of mixture proportions were employed. In

series 1, the unit water content, unit aggregate content, bindcr volume and
replacement ratio 20%(in weight) of JFA or CFA were kept constant. In series 2 ,
the unit watcr content was varied from 90 to 120 kg/m3on the conditions of
constant unit binder content (320 kg/m3)and sand percentage (s/a=40%). In series
3, thc sand percentage was varied from 36 to 46% on the condition of constant unit
water content and unit binder content (320 kg/m3). These mixture proportions are
summarized in Tablc 3.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153
370
VOL*I
Fukute, Nakano, and Ishii
95 0662749 0521323 307 -
TEST METHODS
1. COMPACTIBILITY TEST
The apparatus for compactibility test (i)uscd in this study is composed of an
electromagnetic table vibrator, and measuring unit as shown in Photo-1. The
change in the filled volume ratio during vibration is alculatcd from the settlement
of the concrete sample in the cylinder (diametcr :15cm, hcight :30cm).
Experiments were performed under the vibration at frequency of 6OHz. The

amleration was measured by an acceleration sensor during vibration. The
settlement of concrete was measured on the top surfacc of concrctc by a
displacement apparatus cvery 0.3 sec. The data wcre input into a personal
computer, and the displacement data werc convertcd to the fillcd volurne ratio, with
which a consolidation curve was displayed on the cathodc-ray tube. Thc fillcd
volume ratio was defined as that concretc sample density dividcd by theoretical
density at the zero void on the specified mix (%). Concrctc samplcs were prcparcd
by precisely weighing the amount cquivalcnt to 100 pcrccnt fillcd volurne ratio
based on the unit weight of the specified mixture proportions without any void.
Concrete was cast into a cylinder in three layers, being roddcd in twenty-two
strokes on each layer.
2. MARSHALL COMPACTION TEST

The Marshall compaction tcst was carricd out according to thc appendix in
Technical Guidc for Rollcr Compactcd Concrctc Pavement ; the Road Association
of Japan.
3 . PARTICLE SIZE DISTRIBUTION OF CEMENT AND FLY ASH

The particle size distribution of cement, fly ash, and ccmcnt partially replaccd
with fly ash was measured by a lascr granulomctcr.
4. MICROSTRUCRJRE OF FLY ASH

Microstructures of fly ash were obscrvcd with a scanning clcctron microscope.
From the results of the compactibility tcst, consolidation curvcs were drawn for
the relationship between fillcd volume ratio and vibrating energy. E is the total
vibrating cncrgy on a unit mass of concrctc givcn during thc vibrating time o f t scc
and is espresscd as Eq. 1.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I 95 0662949 0523324 243
where
E : vibrating energy per unit mass of concrete ( J/ e)
p : weight of unit volume of concrete (kg/ 4 )
n : frequency (Hz)
a maT : maximum acceicration (cm/scc?
t : vibrating time (sec) .
1. THE EFFECTS OF THE REPLACEMENT OF NPC BY CFA ON

COMPACTIBTLITY (SERIES 1)
Fig.1 shows thc cffcct of the replaccmcnt of NPC by JFA and CFA on
compactibility under conditions whcrc thc unit watcr content, unit aggregate
content, binder volumc and rcplacemcnt ratio 20% wcrc kept constant. As can bc
seen in Fig.1, the compactibility is incrcascd by CFA rcplaccmcnt. This may be
due to the ball-bcanng effcct of CFA, ùccausc this concrcte has the same volumc of
mixing water, binder and aggregates as concrctc without CFA. JFA docsn't havc
any significant cffccts on compactibility of RCC with such littlc water
(W=100kg/m3).
--``,`,-`-`,,`,,`,`,,`---
2. THE EFFECTS OF CFA ON REDUCING UNIT WATER CONTENT

(SERIES 2)
Fig2 shows thc rclationship lxtwccn unit wafcr content and fillcd volumc ratio
at a vibrating encrgy 7000 J/ t . Fillcd volumc ntio at 2000 J/ t was uscd in this
figurc bccause thc fillcd volume ratio of cach mixture is constant Ilcyond 2000 J/ e
as shown in Fig.1.
In the case of RCC without fly ash, thc fillcd volumc ratio incrcascd with
increasing unit watcr content and thc highcst ratio is shown in thc condition of unit
watcr content of 115kg/m3. In the case of RCC with JFA and CFA, the optimum
unit watcr contcnt was 110 kg/m3 and IOOkgirn', rcspcctivcly.
As this rcsults shows, rcplaccmcnt of NPC by 20 wcight pcrccnt of JFA in

RCC can reduce the unit water contcnt by 5kg/m3 and, that rcplaccmcnt by CFA in
RCC can reduce thc unit water content by 15kg/m3.Thc usc of CFA as admixture
in RCC appears to bc superior to that of JFA to reduce unit watcr contcnt. It is
therefore expected to be cffcctive for incrcnsing thc strcngth, minimizing the drying
shrinkage and cnhancing the durability.
The unit aggregate contcnt and particle sizc distributions should bc considered
for RCC compactibility. In recent years, thc ratio of pastc volumc to thc void
volumc formcd by finc aggregates (Kp) and thc ratio of mortar volumc to thc void
volume formed by coarse aggregates (Km) havc bccn studied for RCC mix design
( 2 ) . Kp and Km arc cxpressed as Eq.2 and Eq.3.

A C 1 SP-353 V O L * I 95 = 0662949 0523325 38T
Wlp, + C l p , + F/p,
Kp =
( l / T s - lips) S
--``,`,-`-`,,`,,`,`,,`---
where
W: unit water content (kg/m3), C: unit cement content (kg/m')
S: unit fine aggregate content (kg/m3)
G: unit coarse aggregate content (kg/m3)
F unit fly ash content (kg/m3)
p w: specific gravity of water, p specific gravity of cement,
p 2 specific gravity of fine aggregate
p G: specific gravity of coarse aggregate
p F: specific gravity of fly ash
T,: unit mass of fine aggregate (kg/ t )
TG:unit mass of coarse aggregate (kg/ t )
When Kp=l, the volume of cement paste is equal to the void volume formcd by
fine aggregates.
Fig.3 shows the relationship between Kp and filled volume ratio for the same
mixtures as in Fig.2. The highest fiilcd volume ratio appears bctwcen 1.00 and
1.10 of Kp for these mixturcs. RCC with CFA shows the lowest value of Kp in
these mixtures. In other words, the void formed by fine aggregates in RCC with
CFA can be filled up with less amount of ccmcnt paste in compnrison with RCC
without fly ash and RCC with JFA.
Fig.4 shows the relationship between Km and filled volume ratio for the same
mixtures as in Fig.2.RCC with CFA shows the lowest value of Km in these
mixtures. The void formed by coarse aggregates in RCC with CFA can filled up I
I
with less amount of mortar in comparison with RCC without fly ash and RCC with
JFA.
I
From these results, it can be concluded that the rcplacemcnt of NPC by CFA in l
,
I
RCC increases the workability and the void volume formed by fine and coarse l
aggregates can be filled more rcadily.

A C 1 SP-153 V O L J I 95 0662949 052132b 016
Fig5 shows the Marshall compaction test results for the same mixtures as in
Fig.2 . In the case of RCC with CFA, the filled volume ratio was higher than that
of RCC without fly ash at the same unit water content. In the case of RCC with
JFA, the filled \,ohme ratio was also higher than that of RCC without fly ash for
the same unit water content, but, the gradient was steeper. This indicated that it is
easier to control the RCC qualities using CFA in RCC mixture at concrete plants,
because the surface water of aggregates sometimcs varies widely and is unstable.
Consequently, the use of CFA as an admixture of NPC appears to be superior to
that of JFA in view of the effect of reducing unit water content and quality control
of RCC.
3. THE EFFECTS OF CFA ON INCREASING SAND PERCENTAGE

(SERIES 3)
Fig.6 shows the compactibility test results for different sand percentages,
constant unit water content and constant binder content. In the case of RCC without
fly ash, the level of compactibility is constant in the range of sand percentage from
36 to 40% , and it decreases with increasing sand percentage over 40%.
In a recent study, the increase of sand percentage without loss of compactibility

of RCC and flexural strength was confirmcd to be effective in reducing the
difference of filled volume ratio behveen the upper and lower layer on RCC
paverncnt (3). The increase of sand percentage is considered cffcctive,especially for
thick RCC pavement for heavy traffic such as major airports and seaports. As
mentioned above, the optimum sand percentage for RCC without fly ash was 40
pcrccnt .In the case of RCC with JFA or CFA, the same Icvcl of compactibility was
shown bchveen a sand percentage of 40 and 42%. The optimum sand percentage
in both mixtures was 42%.
These findings indicated that the use of JFA or CFA as an admixture for RCC
results in a high optimum sand percentage. That is, the void space between fine
aggregate particles increases with increasing sand percentage, but fly ash particles
fill these voids. This is one of the reasons why the final filled volume ratio does not
drop even at a higher sand percentage as compared with the optimum sand
percentage of RCC without fly ash.
As mentioned above, the use of fly ash as an admixture in cement is effective

for increasing the slab thickness placeable at one time.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L r I 95 IOb62949 0521327 T52 I
4. PARTICLE SIZE DISTRIBUTION OF CEMENT AND FLY ASH

Fig.7 and Fig.8 show the results of particle size distribution measured by a
laser granulometer. As shown in thcse figures, the particle size of CFA is finer
than that of NPC or JFA. NPC partially rcplaced by fly ash shows particle size
distribution curves similar to NPC without fly ash, because the replacement ratio
of 20% is not large enough to affect the size distribution of NPC. These findings
indicate that the reduction of unit water content and the increase of optimum sand
percentage by the replacement with CFA or JFA are not due to particle size
distribution.
5. MICROSTRUCTURES OF NPC AND FLY ASH

The microstructures of NPC,JFA and CFA observed through a scanning
electron microscope (SEM) are shown in Photo-2(a)(b)(c). As shown in
Photo-2(a), the particles of NPC have an irregular and angular shape with no
spheres. As shown in Photo-2 (b), some of thc particles of JFA have irregular and
crushcd shape, while the finer particlcs are smooth-surfaced spheres. As shown in
--``,`,-`-`,,`,,`,`,,`---
Photo-2(c), on the other hand, almost all particles in CFA are smooth-surfaced
spheres. Based on the visual evidcncc in the photos, the ability of the fly ashes to
reduce the unit water content may tx attributed mainly to the surface texture and
shape of particles.
However, concerning the optimum sand pcrcentage, the effect of surface
texture and shape of particles on mmpactiliility is not clear, because both RCC
incorporated with CFA and JFA show the same value of optimum sand percentage
in spite of the difference in surface texture and shape of particlcs(Fig.6). The
effccts of surface texture and shape of particles in increasing the optimum sand
percentage may not be so strong as the effect in reducing the unit water contcnt.
CONCLUSIONS
In this paper, the effect of classified fly ash on improving the consistency and
compactibility of RCC for pavement was examined in laboratory tests. As the
result of three series of tests, the following conclusions were dcrivcd.
1. The compactibility of RCC was increased by replacement of NPC by CFA.

This may be due to the ball-bearing effcct of CFA.
2. Replacement of 20 percent by weight of NPC by CFA in RCC reduced the
unit water content by 15kg/m3. In the case of JFA, the unit water content was
I
reduced by 5kg/m3. Therefore, the use of CFA as an admixture was more I
effective than the use of JFA in reducing the unit water content for RCC.
3. In the case of RCC with CFA, less paste and mortar were needed to fill the
void space than in RCC without fly ash and with JFA.
4. The use of CFA as an admixture of RCC was effective for the quality control
of RCC.

A C 1 SP-353 VOL*I 95 a Obb2949 O523328 9 9 9 D
5. The optimum sand percentage of RCC mixed with JFA or CFA was higher
than that of RCC without fly ash. This effect will contribute to increase the
slab thickness which can be placed in one layer.
6. The particles of CFA were almost completely smooth-surfaced spheres.
This might be one of the reasons why the partial replacement of NPC by CFA
can reduce the unit water content in RCC more than replacement by JFA.
From the results mentioned above, it was confirmed that CFA can improve
thc compactibility of RCC and can achieve a high level of filled volume ratio in
concrete. Thc authors will continue further research to increase placeable slab
thickness and improve the surface profilc for practical use of CFA in RCC for
heavy duty pavements.
REFERENCES
I . Kokubu K,Ucno A and Kondoh T, "Studies on Compactihility and Its Test

Method of Extremely Dry Concrete Used for Roller Compacted Concrete
Pavement", Fifth International Conference on Concretc Pavement Dcsign and
Rehabilitation, 1993, vol.?, pp771-280
2. Nakahara Y, Yokota S, Hirata S, Mix Design and Consistency of Roller

'I
Compactcd Concrete Pavement", 1979, No.384, pp12-18 (in Japanese)
3.Kagata M, Fuchigami M and Saknta K: A Study of Mix Design Procedure for

Roller Compacted Concrete Pavement, Ccment Association of Japan 43th
conference, 1989, pp812-817 (in Japanese)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 I0662949 0521329 825 I
376 Fukute, Nakano, and ishii
TABLE 1 - PHYSICAL AND CHEMICAL PROPERTIES OF NPC, JFA,

AND CFA
--``,`,-`-`,,`,,`,`,,`---
TABLE 2 - PHYSICAL AND CHEMICAL PROPERTIES OF FINE AND

COARSE AGGREGATES
maximum
Specific Absorption Fineness
size gravity (%) modulus
(mm)
Fine
5 2.58 1.58 2.63
aggregate
Coarse
20 2.69 0.79 6.78
aggregate

A C 1 SP-I153 V O L X I 95 I0662747 0521330 5 4 7 I
TABLE 3 - MIXTURE PROPORTIONS OF RCC
NPC
I
Series I perceniage
Sand
W C
Unit weight (kg/m3)
342 -
F S G
EA 40 1O0 252 63 817 1278

CFA 256 64
Sand Unit weight (kgim3)

Series 3 percentage
C F S G
NPC
+ll 40 115 320
-
SOY 1265
42 849 1223
44 s90 1180
40 so5 125Y
845 1217
JFA 42 110 256 64
44 886 1175
46 926 1133
I 1
40 817 1278
CFA 100 356 64

8YY 1193
I 46 I 940 1150
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 9 5 E 0 b b 2 9 4 9 0521331 483 =
--``,`,-`-`,,`,,`,`,,`---
1O0
n
8
W
O
95
'
.Y
4
2
90
3
-3 0 RCC without fly ash
o 85 A RCC with JFA
>
-u 0 RCC with CFA
-
i
0
.r(
80
W,S,G = const (in weight)
Binder = const (in volumeì
Replacement ratio = const (in w e g h t , 2 0 % )
L4
75 ' " 1 ' 1 ' 1 ' 1 ' 1 ' ' I I
O 500 100015002000 2500 3000 35004000
Vibrating energy (J/ f )
Fig. 1-Effects of replacement of NPC by CFA
5 98 i
ash
I HRCC with CFA

I
._
LL
I I
I
I
90 95 100 105 110 115 120 125

Water con tent (kg/m3)
Fig. 2-Compactibility test results on different unit
water content

A C 1 SP-153 V O L U I 75 S 0662749 0523332 3LT
'' I
I
O R C C without fly ash
A R C C with JFA
I I BRCCwithCFA
0.90 1.o0 1.10 1.20

KP
Fig. 3-Relationship between Kp and filled volume ratio
t
E 94t
-f
92 ash
I A R C C with JFA
I .RCC with CFA
1.40 1.45 1.50 1.55

Km
Fig. 4-Relationship between Km and filled volume ratio
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 W 0662949 0523333 256 W
98 /
W i /
O
*
U e
96 -
1
294 -
O
>
'c3 -
4
Q) 92
.A
4
ru
d
O RCC without fly ash
';d 90 - A RCCwithJFA
7l RCCwithCFA
b
5 88.' I - I ' I a I 1 1 1 I I I
Fig. %Marshall compaction test results
98 I
ORCC without fly ash

ARCC with JFA
B R C C with CFA
I I
I I
I I I I I < I d
93
34 36 38 40 42 44 46 48
Sand percentage (%)
--``,`,-`-`,,`,,`,`,,`---
Fig. 6-Compactibility test results on different

sand percentage

A C 1 SP-153 VOL*I 95 I0662949 0523334 192
0
1 10 100 1000
Particle diameter ( y m)
Fig. 7-Particle-size distribution
--``,`,-`-`,,`,,`,`,,`---
1 10 100 1000
Particle diameter ( y m)
Fig. 8-Particle-size distribution

A C 1 SP-153 VOL*I 95 0662949 0523335 O29
Photo l-Compactibility test apparatus
Photo 2(a)-Micrograph of NPC
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 75 0662747 0 5 2 3 3 3 6 Tb5
Photo 2(b)-Micrograph of JFA
Photo 2(c)-Micrograph of CFA
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 m 0662’349 0523337 9TL m
SP 153-22
Class C Fly Ash as a Shrinkage

Reducer for Cement Paste
by S. Tangtermsirikul, T. Sudsangiam,
T. Deesawangnade, and P. Nimityongskul
Svnoosis : This paper introduces some experimental results on the application

of ASTM Class C (high-lime) fly ash from Thailand to reduce shrinkage of
cement paste. Measurement of both autogeneous and drying shrinkage were
conducted on cement paste samples. Parameters varied in the autogeneous
shrinkage test are type of fly ash (two samples of Class C fly ash, from the same
source. with different chemical composition, and a sample of Class F fly ash),
cement replacement percentage (O%, 30% and 50%). curing condition (seal and
submerged). and curing period. For drying shrinkage, the primary parameter was
curing period. For autogeneous shrinkage specimens. flexural strength.
compressive strength. and setting time, were tested to compare the mixtures
containing Class C fly ash with those containing Class F fly ash and with those
without my fly ash, in order to derive some basic information for judging the
suitability of the Class C fly ash as a pozzolan.
From the test results. it was found that Class C fly ash was effective for
reducing autogeneous shrinkage. and improving flexural strength. The effect was
due to expansion which occurred in the samples containing Class C fly ash. For
the tested range. the higher the replacement percentage, the more effective the tly
ash becomes. Class C fly ash which contained higher SO, content was more
effective than that with the lower SO, content for reducing shrinkage. Water
--``,`,-`-`,,`,,`,`,,`---
curing was more effective than sealed curing since the expansion process required
water and specimens with longer water curing period showed smaller shrinkages.
The pozzolanic activity index of the tested Class C fly ashes was higher than that
of the tested Class F fly ash (see Table i). therefore, higher 28-day compressive
strength in paste with the Class C fly ash than in paste with the class F fly ash was
observed. Setting times of pastes with the Class C fly ash were generally shorter
than that o f ihr paste with the Class F fly ash.
The Class C fly ash also proved to be effective for reducing drying
shrinkage. ;IS indicated by comparison of specimens made with and without Class
C fly ash. Longer curing period reduced the drying shrinkage of specimens with
and without tly dsh
Kevwords: Cement Dastes; drying shrinkage; durability; expansion;

flexural strength; fly ash; lime fly ash; shrinkaee; strength

A C 1 SP-353 V O L * I 95 0662949 0523338 838
386 Tangtermsirikul et al
S. Tangtermsirikul is an assistant professor of civil engineering at the Engineering

(English) Program, Thammasat University, Thailand. He received his D.Eng.
from the University of Tokyo in 1989. His research activities include high
performance concrete, use of waste materials in concrete, mathematical
simulation and durability of concrete.
T. Sudsangiam is an engineer at the Concrete Products and Aggregate Co.,Ltd.

(CPAC), Thailand. He received his M.Eng. from the Asian Institute of
Technology, Thailand in 1993. His research interests are in the fields of concrete
technology and products.
T. Deesawangnade is an engineer at the Thai Master Builders Co.,Ltd., Thailand.
--``,`,-`-`,,`,,`,`,,`---
He obtained his M.Eng. from the Asian Institute of Technology, Thailand in
1994. His research fields are admixtures for concrete and shrinkage simulation of
concrete.
P. Nimityongskul is an associate professor at the Asian Institute of Technology,

Thailand. He obtained his D.Eng. from the same institution. His research areas
are durability of concrete, high strength concrete, ferro cement, rice husk ash and
natural fibres.
INTRODUCTION
As modem technology aims toward concrete with high filling ability and
strength, there is a tendency to increase the amount of cementitious material. An
example of modem concrete is high performance concrete which needs no
vibration [i]. Durability of the concrete also becomes a very important issue to
be considered. Shrinkage affects not only durability but also mechanical
properties, tensile and flexural strengths in particular. Shrinkage of concrete can
be categorized into two types, autogeneous and drying shrinkage. The
mechanism of autogeneous shrinkage was reported to be the volume reduction of
cementitious matrix due to hydration [ 2 ] . When water is consumed in the
hydration reaction, voids are created, leading to negative pressure causing

A C 1 SP-153 VOL*I 95 I0662997 0521339 7 7 4
shrinkage in the matrix. Autogeneous shrinkage has been neglected since it was
measured to be small in conventional concrete. However, as water content is
small and the amount of paste is large, it becomes essential to consider this
shrinkage in the mixture proportioning. Also it is relevant to find an efficient
method to reduce the shrinkage when it becomes serious. Drying shrinkage has
been known to cause cracks in concrete. The effect is serious when water
content in the concrete becomes higher which is opposite to the case of
autogeneous shrinkage. It is then clear that the problem of cracking due to both
kinds of shrinkage can hardly be solved simultaneously by only adjusting the mix
proportion of the concrete without adding some costly admixtures such as an
expansive agent.
The demand of energy in Thailand has been rising sharply during recent
years due to industry expansion. This leads to the increase in coal utilization to
produce electricity, thus increasing the amount of coal ash. Mae-Moh electricity
plant has been producing a huge amount of fly ash each year. However, the plant
has been facing problem of controlling the quality of the fly ash. The fly ash was
also found to cause expansion when used as a pozzolan.
This paper proposes a solution to reduce both autogeneous and drying

shrinkages simultaneously by applying Class C (high-lime) fly ash from Mae-Moh
as a pozzolanic material, taking advantage from its chemical expansion. It also
clarifies the mechanisms of autogeneous shrinkage and its effect on some
mechanical properties of concrete, especially flexural strength. The influence of
curing condition on shrinkages was also studied. This paper shows the potential
to bring this fly ash into the construction industry in Thailand.
EXPERIMENTS
Material Used and Mix Proportion
The materials used in this experiment were ordinary portland cement, a

sample of ASTM Class F (low-lime) fly ash imported from Hong Kong, and three
samples of Class C fly ash obtained from Mae-Moh power plant. The physical
properties and chemical composition of the materials are shown in Table 1 and
Table 2, respectively. The results of the chemical analysis in Table 2 verify that
fly ashes from Mae-Moh and fly ash from Hong Kong are of Class C and Class F,
respectively, in accordance with the ASTM Test Designation C-618. Tap water
was used as mixing water. Mixture condition of specimens tested in this study are
listed in Table 3. The mixtures for testing autogeneous shrinkage were
proportioned with w/(c+f) of 0.3. This is because autogeneous shrinkage was
reported to be highest when cement paste had w/c equal to 0.3 [2]. This was not
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 m 0 b b 2 9 4 9 0523340 496 m
confirmed in this study, however. it is considered a reasonable value to be used

for comparison of various cement paste mixtures. Mixtures for testing drying
shrinkage were designed with w/(c+f) of 0.5. Actually, the higher w/(c+f) is
considered better for drying shrinkage test, since effect of drying shrinkage will be
more dominant. However. the value of 0.5 was selected to avoid bleeding of the
paste samples.
Specimen Preparation and Test Procedure
In the autogeneous shrinkage test, specimens were prepared for 3

purposes for: measuring length change (1 5 x 4 0 160mm);
~ measuring flexural
strength (40x40~ I60mm); and measuring compressive strength (50x50x50mm).
One average test result was obtained from the average of results of three
specimens. In the drying shrinkage test, specimens were prepared for measuring
length change only.
The parameters considered for autogeneous shrinkage test were type of

fly ash (two samples of Class C fly ash from Mae-Moh and a sample of Class F fly
ash), SO? content in Class C fly ashes (1.64% and 4.87%), fly ash content (O%,
30% and50% by weight of the total cementitious content) and submerged curing
period (3 and 7 days). In drying shrinkage test, the parameters varied were fly
ash content (0 and 50% by weight of the total cementitious content) and
submerged curing period (2.6 and 28 days).
Specimens were subjected to two kinds of curing conditions, sealed curing

and submerged curing. Sealed curing was done by wrapping the specimen with
vinyl sheet so that no moisture exchange could occur between the specimen and
its environment. Sealed curing condition, in which there was no moisture
exchange between the specimens and their environment, was considered proper
for observing autogeneous shrinkage. This is because drying shrinkage will be
involved if the specimens were allowed to loose moisture. On the contrary,
autogeneous shrinkage will not occur if water is sufficiently supplied to the test
specimens. Submerged curing was performed by submerging the specimens in
water so that water would be sufficiently supplied to the specimen. Both curing
conditions were conducted under room temperature of 2511°C. For drying
shrinkage tests after the submerged curing period, the specimens were put in the
room with constant temperature and humidity of 2511°C and 6012%RH,
respectively.
The measured data were linear strain, flexural strength, compressive

strength, and setting time for autogeneous shrinkage specimens; and, only linear
strain for drying shrinkage specimens. Fig.1 shows the arrangement of specimens
for length change measurement. Linear strain was examined by fixing two
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 Ob62747 0523343 3 2 2 =
measuring points on each 40x 160mm face of the specimens and measured with a
demounted mechanical strain gauge (conformed to ASTM C490-89). The 28-day
flexural strength was tested using a third-point loading test as shown in Fig.2.
The 28-day compressive strength was measured using the 50xSOxSOcm
specimens. Setting time of the paste was measured by the Vicat needle method in
accordance with ASTM C 19 1-92.
Autogeneous Shrinkage
Fig.3 and Fig.4 show the comparison of length change of paste specimens
containing 30% and 50% fly ash. respectively, with that of cement. It is shown
that all specimens with fly ash exhibit smaller autogeneous shrinkage than the
cenient paste did. Specimens contarning the Class C fly ashes expressed a smaller
autogeneous shrinkage than those containing the Class F fly ash, especially when
the replacement percentage was large and when the SO, content in fly ash was
high (compare mixtures containing FMI with those containing FM2). It can be
seen from these figures that the higher the fly ash content. the more the
autogeneous shrinkage is reduced. However, increasing the content of the Class
F fly ash did not affect the amount of autogeneous shrinkage. This can be
explained based on two mechanisms of autogeneous reduction. The first, which
occurs in both the Class C and Class F fly ashes. was the result of particle shape
of fly ash. Fly ash particles were spherical, as verified by the electron microscope
photo. Therefore they retained less water than cement particles which were
--``,`,-`-`,,`,,`,`,,`---
irregular. This resulted in a larger free water content in the mixture with fly ash
than in mixture without fly ash when prepared with the same w/c. As
autogeneous shrinkage is the result of water consumption in the hydration
process. larger free water content can, therefore, reduce the shrinkage. The
second. which is the special characteristics of Class C fly ash from Mae-Moh, is
the chemical expansion which compensates the autogeneous shrinkage. This
expansion will be discussed in the next section. As a consequence, the tested
Class C fly ashes are considered more effective than the Class F fly ash for the
autogeneous shrinkage reduction.
ExDansion -- Expansion can be considered to consist of two components

namely swelling due to water absorption and chemical expansion. In this study,
only the chemical expansion, which is the major component of expansion, will be
concentrated on, since swelling is a recoverable process which is considered not
effective for autogeneous shrinkage reduction. The submerged curing condition
was designed for the study of expansion because it was found that the chemical
expansion requires water [ 3 ] . It was found [3] that chemical expansion occurs ÙI

A C 1 SP-353 V O L * I 95 I0662949 O523342 267 =
the Class C fly ashes because they contain high SO, content. This was supported
by the author's results which show higher chemical expansion in specimens
containing high SO, fly ash (FM2) than in the specimen with low SO, fly ash
(FMI) when they are compared by the same fly ash replacement percentage, as
shown in Fig.5. The results of chemical expansion in Fig.5 were obtained by
subtracting the expansion of the Class F specimens, which is considered to be
swelling, from the total expansion of the specimens with the Class C fly ash by
assuming that swelling of specimens with the Class F fly ash are similar, even not
exactly equivalent, to those with the class C fly ash. This was assumed because
both swelling and chemical expansion occured in pastes with Class C fly ash, and
there was no method for measuring swelling by prohibiting chemical expansion of
the pastes with Class C fly ash. This problem can be solved by using Class C fly
ash with very small SO3 content. Unfortunately, it was not possible to obtained
from the Mae-Moh source. Nevertheless, the assumption is considered
reasonable in the light that the value of swelling is small when compared with that
of the chemical expansion. It can be seen from Fig.5 that not only the SO3
content in the Class C fly ash but also the fly ash replacement percentage have
effect on chemical expansion. The more the Class C fly ash from Mae-Moh in the
mixture is, the larger the chemical expansion can be obtained.
7-day submerged curing have lower autogeneous shrinkage than those with 3-day I
submerged curing. This is because larger expansion is to be expected when
submerged curing period is longer.
Compressive and Flexural Strength -- Fig.7 to Fig.10 are the results of

compressive and flexural strength in submerged and sealed curing conditions of
mix 1 to mix 7. It can be seen that in the case of submerged condition, which is
the standard condition for strength test, compressive and flexural strengths of
specimens with fly ashes are lower than those of the control mixture which is
cement paste, and both compressive and flexural strengths have the same
tendency.
For the case of sealed curing, the same tendency as in the submerged
condition was obtained for the compressive strength. However, higher flexural
strength was obtained in the specimens containing fly ashes than in the cement
paste specimens. This is opposite to the case of submerged condition. The
increase of flexural strength in the case of sealed curing was considered to be due
to the reduction of autogeneous shrinkage when the specimens incorporate fly
ashes. It is also obvious that the Class C fly ashes are more effective for
improving the flexural strength. Therefore, it can be proposed that the evaluation
of flexural strength from compressive strength, should take into account the
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L S 1 95 I0662949 0521343 L T 5 I
environmental condition of the actual structure, especially when autogeneous

shrinkage is involved and fly ash is used.
Setting Time -- Fig.11 and Fig.12 show the results of initial and final
setting times, respectively, of Mix 1 to Mix 7. It can be seen that ail of the paste
mixtures with fly ash have longer setting times than that of the cement paste (0%
fly ash). For initial setting time of mixtures with the same fly ash content, FM2
(Class C) mixture has the shortest initial setting time among the mixtures with fly
ashes, followed by FM1 (Class C) mixture and FHK (Class F) mixture,
respectively. Considering the final setting time of paste mixtures with same fly
ash content, FM2 (Class C) has the shortest final setting time when compared
with the other two. Mixtures with FMI (Class C) and FHK (Class F) have almost
equivalent final setting time. It was found by Carles-Gibergues and Husson [4]
that calcium sulfite fly ash delayed the initial setting of the cement-fly ash. On the
other hand, Dodson [5] reported that incoporating a high calcium fly ash at a high
cement replacement level reduced setting time. These findings indicate that high
sulfate content delay the setting time but high calcium content reduces the setting
time. The Class C fly ashes used in this study are rich in calcium but have not so
high sulfate content, resulting in a tendency of reduction of setting time. These
results indicate that the tested Class C fly ash is more suitable than the tested
Class F fly ash to be pozzolanic material regarding the setting properties.
Drving Shrinkage
Effect of Class C Fly Ash -- Fig.13 to Fig.15 show that for all conditions
of submerged curing period of 2 days, 6 days, and 21 days, the pastes with F M 3
(Class C) display smaller drying shrinkage than the cement pastes. It can be
noticed that the water to cementitious ratios of the specimens with and without
Class C fly ash in the experiments were the same. However, the application of fly
ash reduces the water requirement of the mixture. Therefore, drying shrinkage
can be reduced even further in actual practice.
Effect of Submerged CurinP Period -- Fig. 16 and Fig.17 show that both
specimens with and without Class C fly ash exhibit smaller drying shrinkage when
the submerged curing periods are longer. However, the results of drying
shrinkage are not different when the submerged periods are longer than 6 days.
The tendency is the same for specimens with and without Class C fly ash. The
results also show that the specimens with Class C fly ash are less sensitive to the
--``,`,-`-`,,`,,`,`,,`---
submerged curing period than those without fly ash. This is rather peculiar since
concrete with fly ash is usually known to be sensitive to curing condition. This
may be caused by the effect of chemical expansion of the utilized Class C fly ash
as a cementitious reaction. Mechanisms of chemical expansion need to be
clarified in future studies.

A C 1 SP-153 V O L S I 95 0662949 0521344 0 3 1 =
CONCLUSIONS
Based on the test results in this paper, the following conclusions can be
drawn to express the potential for introducing Class C fly ash from Mae-Moh as a
pozzolanic material.
1. Both samples of the Class C fly ash are more effective for reducing
autogeneous shrinkage than the sample of Class F fly ash. The Class C fly ash
with higher SO, content is more effective than that with lower SO, content.
Increased fly ash content in the mixture results in smaller autogeneous shrinkage.
2 . The autogeneous shrinkage reduction of the Class C fly ashes used in this
project is due to chemical expansion. For the same Class C fly ash content,
higher expansion is obtained in the mixture containing Class C fly ash with higher
SO, content. Considering same Class C fly ash sample, higher expansion occurs
in the mixture with greater fly ash content. Expansion of specimens with Class C
fly ashes is much larger than that of the specimen with the Class F fly ash.
3. Longer submerged curing period leads to lower autogeneous shrinkage.
4. In sealed curing condition, where autogeneous shrinkage occurs, paste

specimens with fly ash have higher flexural strength than the cement paste
specimen. The tested Class C fly ashes are more effective than the tested Class F
fly ash for improving flexural strength. The improvement of flexural strength was
considered to be due to the reduction of autogeneous shrinkage.
5. Both initial and final setting times of paste mixtures with fly ashes are longer I
than those of the cement paste. However, the tested Class C fly ashes are
superior to the tested Class F fly ash in term of setting properties.
6. The pastes with Class C fly ash exhibit smaller drying shrinkage than the I
--``,`,-`-`,,`,,`,`,,`---
I
cement pastes, for all submerged curing period conditions. l
7. Longer submerged curing period gives rise to smaller drying shrinkage for I
pastes with and without Class C fly ash. However the effect does not improve
when curing period is longer than 6 days.
REFERENCES
1. Ozawa, K., Maekawa, K. and Okamura, H. "Development of High

Performance Concrete", Journal of the Faculty of Engineering, The University
of Tokyo, Vol.XL1, No.3, pp.381-439, 1992.

A C 1 SP-153 V O L * I 95 0662949 0523345 T 7 ô
2. Tazawa, E. and Miyazawa, S. "Autogeneous Shrinkage of Concrete",

Proceeding of Japan Concrete Institute, Vol. 14. No. 1, pp.561-566, 1992.
3. Raksasataya, B. "Influence of Rice Husk Ash on Volume Changes and

Compressive Strength of Fly Ash-Portland Cement Mortar", A master thesis
submitted to Asian Institute of Technology, Bangkok, Thailand, Thesis No.
ST-90- 13, April, 1990.
4. Carles-Gibergues, A. and Husson, B. "Effect of the Use of Sulfitic Fly Ash in

Mortars and Concretes", Proceeding of the 4th CANMET/ACI International
Conference on Fly Ash. Silica Fume, Slag and Natural Pozzolans in Concrete,
Vol. 1 , pp.67 1-692, 1992.
5. Dodson, V.H., "The Effect of Fly Ash on the Setting Time of Concrete
Chemical or Physical", Proceedings of the Symposium on Fly Ash
Incorporation in Hydrated Cement Systems, S . Diamond, Ed., Material
Research Society, Boston. 1981, pp.166-171.
TABLE 1 - PHYSICAL PROPERTIES OF CEMENT AND FLY ASHES

Source of Fly Ash
Physical property Portland Class C Class C Class C Class F
Cement Mae-Moh Mae-Moh Mae-Moh Hong
Type I (FM1) (FM2) (FM3) Kong
FHK)
Specific Gravity 3.15 2.41 2.64 2.21 2.26
Blaine Fineness (cm2/g) 3461 2,739 2,845 2,151 3,926
Bulk Density (gll) 1 .o2 1.O6 1.16 i .O7 0.85
Moisture Content (%) 0.06 0.06 0.1 1 0.13 0.18
Loss on Ignition (%) 1 .O3 0.21 0.11 0.65 2.59
Pozzolanic Activitv Index 86 91 73
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 V O L X I 95 0662949 0523396 904
TABLE 2 - CHEMICAL COMPOSITION OF CEMENT AND FLY ASHES
I
Chemical Composition Portland Class C Class F
(%) Cement Mae-Moh Mae-Moh Mae-Moh Hong
TY Pe 1 (FMI) 0342) (FM3) Kong
(FHK)
Silicon Dioxide (Si02) 21.14 33.62 45.48
Aluminium Oxide 5.52 15.08 30.36
(A1203) 3.25 11.27 5 07
Ferric Oxide (Fe2O3) 65.93 23.96 6.41
Calcium Oxide (Cao) 1.41 3.52 1 .o1
Magnesium Oxide (MgO) 2.48 I .64 0.34
Sulphur Trioxide 6 0 3 ) O. I 1.12 0.20
Sodium Oxide (Na20) 0.37 I .93 2.32 0.73
Potasium Oxide (K20) 0.0 0.12 0.1 1 0.09 0.05
Manganese Oxide (MnO)
Loss on Ignition I .O3
emark : FM i , FM2 and FHIK were US
I 0.27 0.1 1 0.65 2.59
in autogeneous shrinkage test FM3 was
used in drying shrinkage test
TABLE 3 - MIXTURE CONDITION OF TESTED CEMENT PASTE
Compressive Flexural Setting time

f/(c+f) Designations Strength (MPa) Strength (MPa) (min)
(I) (2) (i) (2) initiai final
O CTA 90.2 117.1 4.2 10.4 182 290
0.3 FHK 72.8 84.9 4.6 7.7 245 325
0.5 FHK 63.0 63.4 4.7 5.2 295 385
0.3 FM 1 83.1 100.9 4.8 8.0 205 325
0.5 FM 1 64.9 71.7 5.7 6.3 263 390
0.3 0.3 FM2 87.6 106.4 4.8 9.4 187 300
0.3 0.5 FM2 69.8 86.3 5.8 7.1 235 380
0.5 O CTD
0.5 0.5 FM3
w : water, c : cement, f : fly ash * mixtures for testing drying shrinkage
( i ) : sealed curing (2) : submerged curing
CTA. CTD : cement pastes for testing autogeneous and drying shrinkages. respectively
FHK : Class F fly ash from Hong Kong (see Table 1 and Table 2)
FMI, FM2, FM3 :Class C fly ashes from Mae-Moh (see Table I and Table 2)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 I0662947 0523347 ô40 I
Gauge
length 4 ,spimen
Load
5.
--``,`,-`-`,,`,,`,`,,`---
Gauge points
Fig. l - L e n g t h change Fig. 2-Flexurai strength by

measurement third-point loading
0.2
T9 Specimen age (days)
-s o -0.2 10 20 30 40 50 60
I
80 Mix 2 (FHK, Class F)
4 -0.4 Mix 4 (FMI, Class C)
3 -0.6 Mix 6 (FM2, Class C)
Y
8E -0.8 /
8 -1
B -1.2
-1.4 1
Fig. 3-Autogeneous shrinkage of cement paste
and pastes with 30 percent fly ash

A C 1 S P - 1 5 3 V O L X I 95 = Obb2949 0521348 787
06
Specimen age (days)

I
30 40 so 60
MIX7 (FM2, Class C)
E n o L\ MIX5 (FMI, Class C)
----_ Mix
_ 3 (FHK. Class F)
-1.4
'>
\
,
, - ,- _ -, -_-_ li
Mix 1 (no fly ash)
Fig. 4-Autogeneous shrinkage of cement paste

and pastes with 50 percent fly ash
0.9 ,&- *-- - *-----

Mix 7 (50%FM2, Class C )
-$ 0.8
0.7
'(>------o
v
3
8
.-
rn
5
a
0.6
0.5
'
,.' ;__
> - - % I - - - -
MIXS (SO%FMl. Class C)
--------_ ________.
Mix 6 (3A%FM2, Class c)
-b: 0.4 il
-- -- ?\
.zz 0.3 ,^.-i\-
4- - - - - A
Mix 4 (30%FMI, Class C)
2 0.2
u
o. 1
O i
O 5 10 15 20 25 30
Specimen age (days)
Fig. 5-Chemical expansion of paste specimens with

Class C fly ashes
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLaI 95 = Ob62949 0523349 bL3 =
0.6 T
[ ] : Submerged curing period
o----.-----
-1.2 1
--``,`,-`-`,,`,,`,`,,`---
Fig. ô-Effect of submerged curing period on autogeneous
shrinkage of paste specimens for Mix 6 (30 percent
Class C fly ash, FM2)
[ ] : Fly ash percentage

u I
O-
Fig. 74ompressive strength of submerged specimens

A C 1 SP-153 V O L X I 95 M 0662749 0521350 335 M
Fig. 8-Compressive strength of sealed specimens
l2 T
4t
2 [ ] : Fly ash percentage
Fig. +Flexural strength of submerged specimens
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 Ob62949 0521351 271
[ ] : Fiy ash percentage
Fig. 1&Flexural strength of sealed specimens
-
_ - - -O - - - - FHK
(Class F)
FM1
'.i
(Class C )
3
100
: : , i -----E:sc)
~-
O 20 40 60
Fly ash percentage (a)
Fig. I l - R e c u l t s of initial setting time of paste
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 m 0662949 0523352 104 m
400 T 8 , I
3 - - - - FHK
(Class F)
-i+FMI
(Class C)
C 280 --fi-- FM2

Y T (Class C)
I
240 4
O 20 40 60
Fly ash percentage (%)
Fig. 12-Results of final setting time of paste
3.5
I MIX8 (0% fly ash)
Mix
E- 3
2.5
M MIX9 (50%Class C)
3 2
5 1.5
M
c
.* 1
--``,`,-`-`,,`,,`,`,,`---
0.5
Y Submerged curing period 2 days
I
O 10 20 30 40 50 60 70 80
Drying period (days)
Fig. 13-Drying shrinkage of pastes with and without

Class C fly ash (specimens with 2 days' submerged
curing condition)

A C 1 SP-153 V O L t I 95 M 0662949 0521353 O44
Mix 8 (0% fly ash)
fi Mix 9 (50%Class C)
$ 1.5
ci 0.5 'li
O@
Submerged curing period 6 days
I
O 10 20 30 40 50 60 70 80
--``,`,-`-`,,`,,`,`,,`---
curing condition)
O 10 20 30 40 50 60 70 80

curing condition)

A C 1 SP-153 V O L X I 95 0662747 052l135q T B O
6;3 2.5
O0
1 2
8 1.5
2 1
5
n 0.5
O
O 10 20 30 40 50 60 70 80
Fig. 16-Drying shrinkage of cement pastes with

different submerged curing condition
--``,`,-`-`,,`,,`,`,,`---
6; t 3
2.5
$ 2
$ 1.5
O
O 10 20 30 40 50 60 70 80
Fig. 17-Drying shrinkage of pastes with 50 percent

Class C fly ash with different submerged curing
condition

A C 1 SP-353 VOL*I 95 Obb2949 0523355 917
SP 153-23
Construction Experience with CLSM Fly

Ash Slurry for Underground Facilities
by B. W. Ramme, T. R. Naik, and H. J. Kolbeck
Svnoosis: This paper presents the results of research performed in

developing and using flowable fly ash slurry which is classified as a
Controlled L o w Strength Material (CLSM) as defined by AC1 Committee 229
for underground facility construction and abandonment.
The mixture proportions for the CLSM described in this paper used f l y ash
as a primary ingredient. The fly ash w a s produced at Wisconsin Electric's
--``,`,-`-`,,`,,`,`,,`---
Port Washington Power Plant as a by-product of burning coal from
Pennsylvania. Port Washington Power Plant has four 80 M W electric
generating units that were brought in service between 1935 and 1949.
Additional ingredients included portland cement, water and conventional
fine and coarse aggregates.
Information is also included on the compressive strength, electrical

resistivity, thermal conductivity and compatibility w i t h plastics used in the
manufacture of underground electric cable jackets and natural gas lines.
The results indicate that CLSM fly ash slurry is an excellent material for
backfilling trenches and filling abandoned underground facilities.
Kewords: Backfilling; compaction; compressive strength; electrical

resistance; flowability; fly ash; slurries; subsurface structures; thermal
conductivity

A C 1 SP-153 V O L X I 95 IObb2949 0521356 853 =
404 Ramme, Naik, and Koibeck
Bruce W . Ramme is Operations Manager, Port Washington Power Plant,

Fossil Operations Department, Wisconsin Electric Power Company, 333 ,
West Everett Street, Milwaukee, W I 53201. He received his BS and M S
degrees in structural engineering from the University of Wisconsin,
Milwaukee.
Tarun R. Naik is Associate Professor of Civil Engineering, Director, Center

for By-products Utilization, Department of Civil Engineering and Mechanics,
The University of Wisconsin-Milwaukee, P.O. Box 784, Milwaukee, WI
53201. He received his BE degree from the Gujarat University, India. and
M S and PhD degrees from the University of Wisconsin, Madison.
Henry J. Kolbeck is Assistant Director, Center for By-products Utilization,

Department of Civil Engineering and Mechanics, The University of
Wisconsin-Milwaukee, P.O. Box 784, Milwaukee, WI 53201. He is
engaged in research on the use of such by-products as coal ashes in
concrete construction materials and products.
INTRODUCTION
The objective of this project was t o expand the existing use of CLSM f l y
ash slurry being produced at Wisconsin Electric power plants. Projects
using flowable fly ash slurry produced at the company's Valley Power
Plant, located in d o w n t o w n Milwaukee, date back t o 1 9 8 3 . It was used
a t that time for the abandonment of underground steam tunnels, shafts,
vaults and pipelines ( 1 ) . Production of CLSM at Valley Power Plant was
accomplished by loading the fly ash directly into ready-mix trucks from the
w e t unloaders located under the ash storage silos that are routinely used
for loading open dump trucks. The ready mix trucks would arrive loaded
w i t h the required amount of portland cement and water; the desired I
amount of f l y ash would be batched by timed filling and then the truck
would proceed t o a scale. Additional ash or water were then added t o
achieve the desired mixture proportions and flowability. This process
involved some spillage of fly ash when loading the trucks and required
close control by an operator.
Port Washington Power Plant is located in the City of Port Washington,

Wisconsin, approximately 40 kilometers north of Milwaukee and is
undergoing a major renovation t o significantly extend the plants life. A
n e w fly ash collection, handling and mixer unloading system is being added
as part of this renovation. This presented an opportunity t o incorporate a
portland cement silo and batching equipment to simplify the CLSM
production process. This equipment became operational in May of 1 9 9 3 .
Trial batches were produced by the Valley Power Plant method t o
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 m 0662947 0521357 79T m
demonstrate the feasibility of using Port Washington Power Plant fly ash
for the production of CLSM. T w o construction projects were also supplied
w i t h CLCM material t o further demonstrate it’s practical capabilities.
Initial CLSM fly ash slurry applications in Wisconsin were limited t o the
abandonment of underground facility voids such as tunnels, manholes,
vaults, underground storage tanks, sewers and pipelines. Another obvious
utility application is the backfilling of trenches for underground lines. In
these applications, it is imperative that the material be excavatable,
compatible w i t h the underground line materials and provide the required
thermal properties of a backfill for underground high voltage transmission
lines. Results of these studies were positive and CLCM fly ash slurry has
been used t o backfill trenches for various steam and electric utility lines.
LITERATURE REVIEW
A comprehensive bibliography on the use of controlled l o w strength

materials was recently published in Concrete International magazine ( 2 )and
therefore will not be repeated here. T w o additional papers on medium t o
high strength CLSM fly ash slurry work a t Wisconsin Electric Power
Company using ASTM C 61 8, (Standard Specification for Fly Ash and Raw
or Calcined Natural Pozzolan for Use as a Mineral Admixture in Portland
Cement Concrete) Class C or F fly ash for sub-structural and backfill
applications have also been reported.i3)(4) Three papers were also found
on the thermal properties of backfill for underground cables.(5)(6)(7)
MATERIALS
Fly ash produced a t Port Washington Power Plant, ASTM C 150,

(Specification for Portland Cement) Type 1 cement and the local municipal
drinking water supply were used in all mixtures. No admixtures were used.
A S T M C 618 chemical test results are not available for the Port
Washington fly ash because it is not normally used in concrete. The loss
on ignition of the fly ash was 10.9%. Physical tests were performed and
are shown in Table 1. ASTM C 618 test data is available for the Valley
Power Plant fly ash which uses the same coal source as Port Washington
Power Plant and is shown in Table 2. Concrete sand and 19 m m maximum
size coarse aggregate were used in some trial mixtures. N o admixtures
were used.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 E 0bb2949 0523358 626
406 Ramme, Naik, and Kolbeck
EXPERIMENTAL
Mixture Prooortions
A small laboratory scale mixture w a s made a t the Center for By-products

Utilization at the University of Wisconsin-Milwaukee in November, 1 9 9 1 .
Four trial batches were made w i t h and without aggregates in a local ready
mixed concrete supplier’s mixers in July, 1 9 9 2 in nominal five cubic yard
batches. These mixtures and compressive strength results are s h o w n on
Tables 3 and 4 respectively.
Mixture # I contains no aggregates and the largest quantity of fly ash.

Mixture #2 contains sand while Mixture # 3 contains 1 9 mm coarse
aggregate. Mixture # 4 w i t h both sand and 19 m m coarse aggregates w a s
proportioned t o meet the Wisconsin Department of Natural Resources
exemption for maximum permissible quantities of fly ash used in ready
mixed concrete.
The electrical resistivity, thermal conductivity and plastics compatibility

testing w a s performed on solid CLSM fly ash slurry material made from a
mixture containing 5 7 8 kg. of Valley Power Plant fly ash, 6 8 kg. of Type
1 Portland Cement and 4 7 6 kg. of water per cubic yard.
--``,`,-`-`,,`,,`,`,,`---
Soecimen Preparation and Testinq
Standard 1 5 0 mm diameter by 3 0 0 mm long cylindrical specimens were

prepared for tests of compressive strength. Typically, t w o cylinders were
tested a t ages of 1, 3, 7 and 2 8 day ages in accordance w i t h ASTM test
procedure C 39, (Standard Test Method for Compressive Strength of
Cylindrical Concrete Specimens). Additional cylinders that had been buried
below frost and some that had been stored dry in the laboratory, were
tested a t an age of t w o years. Results are s h o w n in the bottom half of
Table 4.
Electrical resistivity tests were performed in the laboratory on six samples

prepared in accordance with California Test 643-1 9 7 8 , (Method for
Estimating the Service Life of Steel Culverts). The moisture content of the
samples varied from 2 0 % t o 100%. The results of these tests are s h o w n
on Table 5.
Thermal conductivity tests were conducted on six samples using the

thermal needle test method(8). The moisture content of the samples
ranged from O t o 7 7 percent and the dry density varied from 800 t o 9 0 0
kg/m3. The results of these tests are shown on Table 6.

A C 1 SP-153 VOL*I 45 0662949 0521357 562
The compressive strength results of mixtures 1 through 3 were very

comparable and followed k n o w n patterns. The 0.27-0.43 MPa strength a t
2 8 days is quite comparable t o many undisturbed or re-compacted soils and
makes it suitable as a backfill material. Although these materials will
continue t o gain some strength they should be easily excavatable w i t h
conventional equipment. The fourth mixture w i t h mixture proportions
similar t o a conventional ready mixed concrete w i t h l o w cement content
produced a 28 day strength of 1.9 MPa. This mixture will also continue t o
gain strength and can be used in higher strength applications such as below
foundations where future excavatability concerns are n o t important.
Additional comparison strength tests were conducted at the age of t w o
years. The t w o year strength results in both a buried (below frost) and dry
(ambient temperature) environment did not show significant strength
changes as shown in Table 4.
Electrical resistivity measurements are useful in predicting the corrosiveness

of soils. The list below provides a rough indication of Soil Corrosivity vs.
Resistivity.
Resistivity
(ohm-cm) Description
Below 500 Very corrosive
500- 1,000 Corrosive
1,000-2,000 Moderately corrosive
2,000-1 0,000 Mildly corrosive
Above 10,000 Progressively less corrosive
The electrical resistivity measurements on the CLSM fly ash slurry ranged
from a high of approximately 21 4,000 ohm-cm at 20 percent moisture t o
a l o w of approximately 60,000 ohm-cm at moisture contents of 60% and
higher as shown on Table 5. These values are all well above the values
s h o w n above; indicating the CLSM fly ash slurry is not considered t o be
corrosive.
The thermal conductivity results exhibited a near linear relationship w i t h

moisture content. Values ranged from a l o w of 0.08 (BTU/hr-ft-F) at 0%
moisture t o 0.53 at 63% moisture. As the moisture content and dry
density increase, so does the CLSM's thermal conductivity. Thermal
conductivity values of the fly ash slurry are typically lower than sands, silts
and clays, and higher than peat. Where high thermal conductivity is
desired, such as backfill for underground power cables, high density and
very l o w porosity (maximum surface contact area between aggregate
particles) are desirable.
A plastics compatibility study (9) w a s performed by Dr. Henry E. Haxo, Jr.

of Matrecon, Inc. of Alameda, California for Wisconsin Electric Power
Company. Samples of polyethylene pipe and polyethylene coated steel pipe
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 = Ob62949 0521360 2 8 4
used for natural gas lines were analyzed and found t o have densities of
0.935 and 0.949 g/cm3 which were medium and high densities
respectively. A sample of electric power cable jacket w a s identified as
linear l o w density polyethylene. The l o w permeability of the polyetheylenes
t h a t were used t o manufacture these pipes and cable jackets would
minimize the entrance of water and ionic species into the cable or pipe per
Dr. Haxo. The basic conclusion of his report is that the polyethylene pipe
and jacketed cable would not be adversely affected by the CLSM fly ash
slurry. Dr. Haxo did express some concern regarding possible damage t o
the coated steel pipe during installation from aggregate. A n inadequate
coating, particularly at the joints, could expose the steel t o liquids in the
backfill. This is an application and installation issue which is present
regardless of the type of backfill. It would seem the fine gradation of the
fly ash slurry and it’s flowable nature would aid in minimizing scratching
and nicking the polyethylene surface.
CONSTRUCTION
Construction experience w i t h Port Washington flowable fly ash CLSM has

been limited t o t w o projects during the 1 9 9 2 construction season. The
first project involved the abandonment of a 76.2 c m diameter natural gas
main in St. Francis, Wisconsin associated w i t h the Lake Arterial highway
--``,`,-`-`,,`,,`,`,,`---
project. Approximately 5 7 cu.m. of material were successfully used on this
abandonment project in August of 1 9 9 2 . The second project involved
backfilling an underground electric cable trench adjacent t o the fire
department building in d o w n t o w n Cedarburg, Wisconsin. Approximately
73 cu.m. of material were used on this project during November of 1 9 9 2 .
A f e w practical construction considerations must be remembered when

using these CLSM materials. Flowable fly ash CLSM is a liquid when
poured into an excavation. This material exerts a hydrostatic pressure that
needs t o be considered when placing it along basement walls or similar
structures. Multiple lifts after setting and hardening has occurred may be
required. The mixture ingredients and amount of water used will affect the
time of set. Many CLSMs require 8 - 2 4 hours t o harden. Trenches of liquid
CLSM material must also be covered or otherwise protected t o prevent
accidental entry by the public. Another consideration when backfilling
around pipes, conduits and power lines is that they may float while placing
CLSM if not secured.
NEW EQUIPMENT
A n e w fly ash handling, storage and unloading system w a s installed a t Port

Washington Power Plant as part of a larger plant renovation project. The
system consists of a vacuum transportation system that sends the fly ash
collected by electrostatic precipitators t o t w o 4 2 5 cu.m. storage silos. One
silo has been equipped w i t h an internal 20 cu.m. capacity cement silo and

A C 1 SP-1.53 V O L * I 95 0662949 0 5 2 1 3 6 1 110
a batching system t o accurately measure the quantity of cement, fly ash

and water that is placed into a 4 cu.m. batch mixer. This system
becameoperational in May 1993 and has significantly reduced the
production cost of flowable fly ash CLSM by eliminating the double
handling of it's main ingredient. The system also provides dust free, spill
free and accurate batching of the component materials.
CONCLUSIONS
The following conclusions may be drawn from the executed tests:
- CLSM flowable fly ash slurry can be successfully produced for trench
backfill and underground facility abandonment w i t h Port Washington Power
Plant's fly ash.
- The addition of a cement silo and batching system t o a plant fly ash
unloading system simplifies the mixing of CLSM flowable fly ash slurry and
eliminates double handling of the mixtures main ingredient, fly ash.
- The corrosion potential of CLSM flowable fly ash slurry produced w i t h fly
ash derived from the combustion of the Pennsylvania coal used at Port
Washington Power Plant is significantly less than that of typical soils used
for trench backfill.
--``,`,-`-`,,`,,`,`,,`---
- CLSM fly ash slurry is not expected t o adversely affect polyethylene

natural gas lines or polyethylene jacketed power cables due t o its high
impermeability. Care must be exercised when backfilling polyethylene
coated steel natural gas pipelines w i t h all backfill materials t o prohibit
scratching or damage t o the coating.
- High density very l o w porosity CLSM should be used where high thermal
conductivity is desired such as backfill around underground power cables.
ACKNOWLEDGEMENTS
The work described was carried out in cooperation w i t h several

consultants, researchers and material suppliers. The authors are grateful
t o the following individuals and corporations for their participation: Schmitz
Ready Mixed Concrete, Inc., Dan Large, EWI Engineering Associates, inc.,
Mike Marlin, Dr. Henry E. Haxo, Jr., John Tews, Tom Jansen, Wisconsin
Electric Power Company, Wisconsin Natural Gas Company, Center for By-
Products Utilization at the University of Wisconsin-Milwaukee and Amr
Hasballah.

A C 1 SP-153 V O L a I 95 Obb29Li9 05213b2 057 M
REFERENCES
1. Naik, T.R., Ramme, B.W. and Kolbeck, H.J., "Filling Abandoned

Underground Facilities w i t h CLSM Fly Ash Slurry," Concrete
International, July 1990, pp 19-25.
2. Adaska, W.S. and Krell, W.C., "Bibliography on Controlled Low

Strength Materials (CLSM)," Concrete International, October 1 9 9 2 ,
pp. 42-43.
3. Naik, T.R.. Ramme, B.W. and Kolbeck, H.J., "Controlled Low

Strength Material (CLSM) Produced w i t h High-Lime Fly Ash,"
Proceedinqs: Shanahai 1 9 9 1 Ash Utilization Conference, Electric
Power Research Institute Project 2422, G S - 7 3 8 8 , Volume 3, pp
110-1 through 110-1 1 .
4. Naik, T.R. and Ramme, B.W., "Low Strength Concrete and

Controlled L o w Strength Material (CLSM) Produced w i t h Class F Fly
Ash," presented a t the 1 9 9 2 AC1 Spring Convention held in
Washington, D.C., March 14-20, 1992.
5. Parmar, D., "Current Practices for Underground Cable Thermal

Backfill," UTTF Meeting, Montreal, Canada, September 1 9 9 1 ,
6. Parmar, D., "Optimizing the Use of Controlled Backfill t o Achieve

High Ampacities on Transmission Cable," Proceedinqs of Power
Enaineerina Societv Insulated Conductors Committee, 1992.
7. Steinmanis, J.E., "Underground Cable Thermal Backfill,"

Proceedinas of the SvmDosium on Underaround Cable Thermal
Backfill, Toronto, Canada, September 1 9 8 1 .
8. Mitchell, J.K. and Kao, T.C., "Measurement of Soil Thermal

Resistivity," ASCE Journal of Geotechnical Enqineerina Division,
October 1978.
9. Haxo, Jr., H.E., "Compatibility of Utility Polyethylene Pipe and

Polyethylene Jacketed Cable w i t h Flowable Fly Ash Slurry,"
Matrecon, Inc., 8 1 5 Atlantic Avenue, Alameda, CA 9 4 5 0 1 , August
29, 1 9 9 0 .
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L + I 95 Obb2949 O523363 T93
Milwaukee Conference 41 1
TABLE 1 - PHYSICAL PROPERTIES OF PORT WASHINGTON

POWER PLANT CLASS F FLY ASH
--``,`,-`-`,,`,,`,`,,`---
Class F
Fly Ash
I I
I I
Fineness,
% retained on #325 sieve
Pozzolanic Activity Index
With Cement (28 days),
%
With Lime (7d a w ) , MPa
Water Requirement,
% of Control
Autoclave Expansion, YO 0.05 I - I 0.8
Specific Gravity
Variation from Mean

Specific Gravity, % 0.214 5
Fineness, % 2.290 5
* Not enough material was available to perfo I this test.

A C 1 SP-153 VOLII 95 m Ob62949 052L3b4 92T
TABLE 2 - CHEMICAL AND PHYSICAL TEST DATA FOR CLASS F

FLY ASH FROM VALLEY POWER PLANT
Number of Range Average ASTM C

Chemical Composition Samples Percent Percent 61 8
Silicon Oxide, SiO, 4 50.06-50.20 50.14 ___
Aluminum Oxide, AI,O,
Iron Oxide, Fe,O,
Total, SiO,+AI,O,+ Fe,O,
4
4
4
25.24-25.36
14.66-15.39
89.96-90.82
25.27
14.93
90.36
...
---
5 0 Min.
I
Sulfur Trioxide, SO, 4 0.20-0.33 0.26 5 . 0 Max
II
Calcium Oxide, C a 0
Magnesium Oxide, MgO
Carbon
4
4
4
1.18-1.44
0.70-0.74
3.59-6.94 I
1.27
0.71
5.08
5 . 0---Max
I 6 . 0 Max
I
Available Alkalis as Na,O 4 1.61-1.70 I 1.65 I
u suifur 0.22
--``,`,-`-`,,`,,`,`,,`---
Fineness, % Retained on 1 25 25 3 4 . 0 Max

#325 W e t Sieve
Ingredient Actual Weight Cubic Yard Basis

Cement ( T w e 1) 1 kq 31 kci
20 kg 6 3 0 kg
Water 15.4 kci 4 8 5 kg
W a t e r K e m e n t Ratio 15.4
WaterKementitious 0.73
Materials Ratio
Compressive
Test Age Max Load, kg Strength, MPa
7 day 290 0.16
28 day 5 20 0.28
5 6 day 490 0.26

A C 1 SP-153 V O L X I 75 W Obb2747 0523365 8bb W
Mix Number: 1 2 3 4
Cement (Type l ) , kg 43 43 43 43
Fly Ash', kg 785 603 523 31 7
Water, kg 387 292 280 169
Sand (SSD), kg 454 544
3 i 4 " Aggregate SSD, kg 454 77 1
Slump, mm 229 229 254 222
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L * I 95 0662949 0523366 7 T 2 =
TABLE 5 - RESISTIVITY TEST RESULTS CLSM FLY ASH SLURRY
Resistivity
(Ohm-cm)
Moisture
Content
(%I
20
Sample 1
213606
I I I
Sample 2 Sample 3 Sample 4 Sample 5 Sample 6
30 133504
40 13478
50 73427 150859 173555 106803
60 60077 140847 94788 134171 146854 101463
70 56739 1261 61 120821 108138 140179 100128
80 60077 108138 118151 97458 132169 92118
90 60077 95455 120154 86778 120154 86778
100 60077 941 20 120154 87445 120154 86778
Dry 81 3 878 813 837 893 1094

Weight
íkglm,
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L Z I 95 I0662949 0523367 639
TABLE 6 - THERMAL CONDUCTIVITY TEST RESULTS CLSM FLY

ASH SLURRY
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 IO662949 0523368 575 I
SP 153-24
A Strength Definition for the Water

to Cementitious Materials Ratio
by A. Hassaballah and T. H. Wenzel
Synopsis: The water to cementitious materials ratio (W/CM) is recognized as an

important variable in understanding and controlling the quality of concretes
containing pozzolan powder additives, such as fly ash. This paper presents part
of a study to determine a correct way to evaluate the contribution of fly ash to
concrete strength as is usually indicated by the W/CM ratio. A rational
mathematical model of the form W/CM = W/(C K * F.A.) is presented, +
where W, C and F.A. are water, cement and fly ash contents per m3 of concrete
respectively. K is a pozzolan efficiency factor based on comparing the
compressive strength of two concretes having the same workability and the same
amount of cement.
An experimental program was conducted to demonstrate the use of the proposed

W/CM ratio inodel and corresponding K values. The variables studied were
class and addition level of fly ash and slump, strength and age of concrete.
Results show that the model describes and considers the influence of fly ash on
the rheological properties of fresh concrete and on the strength of hardened
concrete. The model is also suitable for use as an equivalent to Abram’s law to
account for rnodern-day powder additives.
Kevwords: Concretes; fly ash; pozzolan cements; strength; water-

cementitious ratio
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - I 1 5 3 V O L * I 95 = 0662949 0521369 YO1
418 Hassaballah and Wenzel
Amr Hassaballah is an Assistant Professor in the Department of Civil

Engineering at United Arab Emirates University, AI Ain, U.A.E. He has
worked as a structural engineer with the city of Milwaukee, U.S.A. He received
his Ph.D. degree from Marquette University, Milwaukee, Wisconsin.
Thomas H. Wenzel is Associate Professor and Chairman of the Department of

Civil and Environmental Engineering at Marquette University, Milwaukee,
Wisconsin. He is a member of several AC1 committees. He received his Ph.D.
degree froin Northwestern University, Evanston, Illinois.
INTRODUCTION
In the past it has become evident that the addition of fly ash, or other powder
siliceous additives, to concrete, imparts significant enhancements to many of it’s
properties. Currently, research efforts are directed to understanding the
durability aspects and deterioration mechanisms of concrete. Structures required
to perform under adverse conditions, such as offshore gravity towers and parking
structures, have necessitated the development of high performance concrete. It
is now recognized that high strength alone is not always sufficient to achieve high
performance. Among the desirable high performance effects achieved by fly ash
addition are: improved rheological behavior, strength, permeability, resistance
to thermal cracking, sulfate attack and alkali-silica reaction.
In North America, fly ash concretes with compressive strengths of 50 - 60 MPa

at 28 days are commercially available and find applications in fast-track projects.
However, there is a lack of a unified approach to a correct evaluation of the
contributions of powder additives to concrete properties. This diversity in
approach, has resulted in three different mixture proportioning methods for fly
ash concrete. As Berry and Malhotra [ 11 categorized them, they are: (I) simple
replacement method, (2) addition method and (3) rational proportioning. The
water to cementitious ratio (W/CM) is generally recognized as a fundamental
variable in understanding and proportioning concrete. Some codes, specifications
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 0662749 0521370 123 I
75 I I
and guides in the industry [2, 3, 41 have already converted from W/C ratios to
W/CM ratios. Since ali proportioning methods center around the W/CM ratio,
its definition in these codes is crucial to future fly ash utilization and to the
quality of concrete. The W/C and W/CM ratios, referred to in this paper, are
weight ratios of free water to cement or cementitious materiais in concrete
mixtures.
This paper reports part of an experimental study to evaluate the contribution of

pozzolans to the strength and quality of concrete as indicated by the W/CM ratio.
--``,`,-`-`,,`,,`,`,,`---
A rational strength-based definition for the W/CM ratio is proposed. First, a

brief review of different W/CM ratio models available in the literature is
presented. Then the proposed definition of the W/CM ratio is introduced and
is followed by a discussion of the experimental results and final conclusions.
REVIEW OF W/CM RATIO MODELS
Many researchers have studied the relation between the W/CM ratio and fly ash
concrete strength. The W/CM ratio models utilized in such studies are quite
different. Smith [5] was the first to propose a rational model for the water to
cementitious ratio through the introduction of a "fly ash cementing efficiency
factor" (K). It was defined such that a mass of fly ash (F.A.) was equivalent to
a mass (K * F . A . ) of cement. The model was of the form W/CM = W/(C +
K * F.A.), where K was assumed to be unique for each fly ash. The K factor
is calculated by equating the W/C of portland cement concrete to the W/CM of
portland cement/fly ash concrete, provided the two concretes have the same
workability and the same 28-day compressive strength. Results from Smith's
experiment indicated that K is not constant for a particular fly ash, but a value
of 0.25 for K was suitable for use in preliminary mixture proportioning. For
practical applications, the method is reported to be complex [i].
In 1968, Cannon [6] introduced a factor that took into account the relative costs
of fly ash and cement. This approach does not consider workability and did not
find acceptance in practice. Later, Ghosh [7] equated the strength of cement and
cementMy ash concretes in the form of W/(C F.A.) = M +
N * (WE), +

A C 1 SP-153 V O L * I 95 I0662949 052L37L ObT =
where M and N are constants. Using laboratory measurements and linear

regression, the empirical constants M and N were calculated and found to vary
with the level of fly ash replacement.
Warriss [8] has proposed an efficiency factor based on the rate at which calcium
hydroxide released by the cement is bound by the pozzolan used. This approach
is only suitable for laboratory applications. To include curing conditions, Mills
[9] introduced an efficiency factor based on the equivalent maturity of concrete.
His model assumes that the W/C of portland cement concrete is equal to W/(C
+ K * F . A . ) of it’s fly ash counterpart provided that both concretes have equal
maturity. This maturity efficiency factor (K) can be used to characterize portland
cementlfly ash mixtures in terms of their response to different curing regimes.
In 1988, the Building Research Establishment (BRE) [4]in the United Kingdom
adopted Smith’s definition of K, the cementing efficiency factor, in their guide
to design of concrete mixtures. It assumes that a portland cementMy ash
concrete will have the same strength as a portland cement concrete of similar
workability if W/(C +
K * F) = W,/CI, where W, C, and F are the weights of
the free water, cement and fly ash respectively, and W, and Cl are the weights
of the free water and cement in the portland cement concrete. The guide
recognizes that this K factor may vary from 0.2 to 0.45 for most European fly
ashes, which are mostly Class F.
Recently, Hedegaard and Hansen [IO] proposed a model relating the strength of
fly ash concrete to a cement to water ratio and a fly ash to water ratio: Sf =
A(C/W) +
B(F/W) + E. This equation is a modified form of the equation
introduced by Bolomey [i 11 many years earlier. Bolomey related the strength
of concrete to its water to cement ratio through the equation, Sr = A(C/W) +
E, where S, = strength of concrete, C, F and W are the cement, fly ash and the
free water content of concrete respectively and A , B and E are constants for
given materials, age and curing conditions in both equations. Hedegaard and
Hansen’s equation can be rearranged in a format similar to that of Smith [ 5 ] :
S, = A ( (‘ +FF)) + E, where K = -
A
B
Using A and B values generated from their experiment, the pozzolan efficiency
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 V O L * I 95 I0662747 0523372 TTb
factor K was calculated to be O. 18. This is lower than suggested by BRE [4] and
later on by Comite Euro International DuEton [12].
In 1992, AC1 published a revised AC1 318 report [13] which replaced the
traditional W/C values with W/CM ratios, without changing numerical values of
the two ratios. However, the corresponding 28 day compressive strengths were
increased by only 6%. AC1 defined the W/CM ratio as W/(C F.A.). +
Recently in their guide for selecting proportions for high strength concrete with
cernent and fly ash, AC1 Committee 211 [14] presents a proportioning method
that utilizes W/CM ratios. The resulting concrete is essentially proportioned by
the simple replacement method. As for ASTM standards covering the use of fly
ash, there has been no major change in recent years. ASTM 618 [15] still
classifies fly ash based on its source and physical or chemical characteristics
rather than its perforinance in concrete, while ASTM C 31 1 [I61 is still missing
a strength evaluation test to judge the quality of fly ash. The only test that
attempts to ineasure the strength potential of fly ash is the pozzolanic activity
index test. Helinuth [17] questions the pozzolanic activity test and its
applicability to concrete.
PROPOSED STRENGTH-BASED METHOD TO

EVALUATE POZZOLAN EFFICIENCY
The proposed research approach is based on two fundamental principles: First,

for a particular set of materials, a property of concrete is a unique function of its
W/CM ratio. Second, a property of concrete, i.e., compressive strength,
permeability, workability, etc. is a result of contributions made by cement as
well as pozzolans such as fly ash. These contributions will vary froin one set of
inaterials to another. Within a given set of materials, these and other properties
are also dependent upon curing conditions, age and other factors. As seen from
the preceding review, the rational model introduced by Smith, W/CM = W/(C
+ K * F.A.), is the most widely accepted model. Despite this fact, researchers
approach K, the efficiency factor, from different views, i.e. based on maturity,
litne combustion, strength or workability. Some scholars and codes substitute
a value of 1.0 for K. In Smith’s model, K is simply a reduction factor to
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOLtI 95 m Obb2949 0523373 932 m
account for the lower cementing ability of fly ash as compared to portland
cemen t.
In this research, a strength-based method to obtain K values is proposed. This

method is based on comparing the compressive strengths of two concrete
mixtures having the same workability. The first mixture contains portland
cement and fly ash. The second mixture has the same amount of cement as the
first mixture, but no fly ash. If the two mixtures have the same workability, it
is expected that the 28-day compressive strength of the first mixture (fC’),,will
be more than that of the second mixture (fe’)*. The total contribution of fly ash
--``,`,-`-`,,`,,`,`,,`---
to the compressive strength of concrete is then the difference between (fc’)i and
The ratio of this difference to the compressive strength of the second
mixture (f,’)2 is, by definition, the pozzolan efficiency factor. The importance
of workability is widely recognized and is affected by the W/CM ratio. The
method recognizes and evaluates the ability of a fly ash to reduce or increase the
water demand for a given workability, depending on fly ash type, amount and
physical characteristics.
It is generally accepted that high strength concrete does not necessarily mean
high performance concrete. In the latter, durability aspects, such as low
permeability, are of greater concern. The aforementioned efficiency factor K can
measure the relative contribution of pozzolans to any particular concrete
property, but will vary with property considered. For example, K values may
relate to fresh concrete, i.e. reduced bleeding and heat of hydration, or hardened
concrete, i.e. higher strength and less permeability. K values with positive signs
indicate improvement while negative signs indicate detraction, as in the case of
Class F fly ash and early age concrete strength.
RESEARCH OBJECTIVES AND SCOPE
The objective of this research is to evaluate if the proposed model is suitable as

a substitute for Abram’s law to account for modern-day powder additives. In
addition, the objective includes generating K values and corresponding W/CM
ratios versus f,’ curves and identifying factors affecting them.

A C 1 SP-153 V O L X I 95 0662949 0523374 8 7 9
Unfortunately, the number of variables involved in studying modern concrete,

especially the number of ingredients, is too large to examine in one laboratory
study. The scope of this research was limited to studying the efficiency of Class
C and Class F fly ashes. Among all pozzolans, fly ash was chosen because of
its high production rate and availability worldwide, especially in North America.
Usually chemical admixtures, water reducers and superplasticizers are used in
concretes with low W/CM ratios. Because superplasticizers were not included
as a part of this project, low to normal W/CM ratios were the focus of this
program. This study focused on the compressive strength (fc’) for concrete
because it is an industry standard that can be related to the quality, durability and
performance of concrete. The proposed definition of K is based on comparing
two concretes with the same workability but different strength. The importance
of workability is well recognized since the cost of placing concrete is dependent
on it. The slump test is a way to quantify workability. The slump test has been
criticized for many years, but it will endure until a practical replacement is
found. Because of its importance in this research, the slump was measured three
times for each concrete in accordance with ASTM C143 [18].
EXPERIMENTAL DESIGN AND TEST RESULTS
To achieve the objectives of this research, four concrete slump categories were .
considered; 50 inin, 75 inin, 100 min, 125 mm (k 5 mm). To cover a larger

range of WICM ratios, the cement content was varied between slump categories.
It increased as the slump decreased and varied from 300 kg for 50 mm slump to
200 kg for 125 m m slump concretes. For each slump category, one reference
concrete with only cement was prepared. In addition, for both fly ashes, three
fly ash addition levels of lo%, 20% and 30% by weight of cement were
considered for each slump category. For the seven concretes within each slump
category the amounts of cement, aggregates, sand and slump were kept the same,
--``,`,-`-`,,`,,`,`,,`---
while the water content was varied as needed to achieve the desired slump.
Table 1 shows the concrete mixture proportioning. Three cylindrical specimens
were tested at the ages of 3, 7, 14, 28 and 91 days. ASTM designations C192
[19] and C39 [20] were followed to prepare, cure and test the specimens.

The test program described herein is designed as a multi-way factorial

experiment. A factorial experiment is one in which the response, K values, is
observed at all factor-level or variable-level combinations of the independent
variables. Thus, this experiment is a 4-way factorial design with 2(F.A. types)
X 4(slumps) x 3 (addition levels) X S(ages) = 120 different variable
combinations. This permits studying the statistical dependency of K, the
efficiency factor, on the chosen variables.
The chemical composition and physical properties of the cement and fly ashes
used were found to be within the limits of ASTM CI50 [21] and C618 [15]
respectively. This test data is published elsewhere [22]. Figures 1 and 2 show
the standard cured cylinder compressive strength versus age for Class C and
Class F fly ash concretes, respectively. Each graph contains four curves
representing the three fly ash addition levels and the corresponding reference
concrete for each slump category.
--``,`,-`-`,,`,,`,`,,`---
A strength definition was proposed for W/CM ratio of the form W(C + K *
I
F.A.), where K is a factor that measures the efficiency of fly ash. This
efficiency factor is defined as the ratio between total fly ash contributions to
compressive strength and the compressive strength of a counterpart portland
cement concrete of equal workability. To assess the effect of the studied
variables on K and all interactions among them, a detailed analysis of variance
was conducted for the measured f,’ and corresponding K values. Table 2 reports
the results of this analysis. The first column identifies the source of variation
and the second column gives the sum of the squared differences between the
observed and the mean values. The third column lists the degrees of freedom
considered for each case. The fourth column gives the mean squares which is
the sum of squares divided the degrees of freedom. The fifth column contains
the F-ratio which is the ratio of corresponding mean squares to total mean square
due to error. This ratio is an appropriate test statistic to measure the
corresponding effect of each combination on the K value. The last column
provides the P-value which is the confidence interval level at which the

hypothesis test procedure changes conclusions. In this analysis, the research

hypothesis is that the effect of a variable or combination of variables will not
significantly affect the fly ash contribution as measured by K. This analysis of
variance showed that K values are significantly dependent on the studied
variables for any confidence interval. Therefore, it can be concluded that the
concept of a single K value even for a specific cement fly ash combination is not
valid. This is expected since K measures the relative change in strength due to
fly ash addition. This change in compressive strength is dependent on; (1) class
of fly ash, i.e. fly ash reactivity, (2) water content i.e. slump, ( 3 ) addition level,
i.e. the amount of ceinentitious materials, and (4) on the age of concrete, i.e. its
strength level.
It is evident from Figures 1 and 2 that the addition of fly ash increases the 28-
day strength of ail concretes. In general, these strength development curves
show higher strength values with an increase in fly ash addition level, up to 30%.
From Figures 1 and 2 , K values were calculated and are shown in Figures 3 and
4 for classes C and F concretes respectively. Each graph represents three
mixtures with l o % , 20% and 30% addition levels. In general, the highest K
values were associated with 30% fly ash addition level. This observation is more
evident for Class C fly ash. Compressive strength at 28 days ranged from 24
MPa to 42.7 MPa for 125 min and 100 mm slump concretes respectively, while
it ranged from 41.4 MPa to 58.7 MPa for concretes with 75 mm and 50 m m
slumps respectively. The 125 mm and 100 mm slump concretes are essentially
normal strength concretes while the 75 mm and 50 mm represent high strength
concretes. From Figures 3 and 4 it can be seen that K values for 125 mm and
100 mm slump concretes increase with time and K values for 75 mm and 50 mm
slump concretes peak at about 10 days of age. In general, higher K values were
associated with higher slump or normal strength concretes. The K values at 28
days ranged from 0.4 to 0.6 for normal strength concretes and from 0.1 to 0.4
for high strength concretes. Since the amount of cement increased as the slump
decreased, one can state that the relative contribution of fly ash to concrete
strength, K , decreases with an increasing amount of cement and visa versa.
Figure 5 shows the W/CM ratio versus concrete compressive strength for all fly
ash and control concretes. Only the 7, 28 and 91 day results are presented.
Graphs for W/CM versus f,’ at 3 and 14 days followed a similar trend. It is
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-Il53
V O L X I 95
No reproduction or networking permitted without license from IHS œ 0662949 0523376 641 m
Not for Resale
noted that the curves for W/CM versus f,? are similar to the curves of W/C
versus f,? ratio. Both curves can be approximated by an exponential function
similar to that introduced by Abrams. Although the two curves behave similarly
with respect to fc?, the W/CM ratio curves are shifted upwards relative to their
W/C ratio counterparts. In practice this can be viewed in two ways: (1) for a
given f,? the required W/CM ratio is greater than the corresponding W/C ratio
or (2) if both ratios are numerically equal then the fly ash concrete will give
higher strength.
As shown in Figure 5 , W/CM versus f,? ratio curves representing fly ash addition
levels tend to forin a family of curves above the control. These curves converge
to the control curve as the W/CM ratio increases. This observation implies that
the differences in strength between fly ash and control concretes increase as the
+
W/(C K * F.A.) ratio decreases. It is then concluded that the highest fly ash
contributions are associated with the lowest possible W/CM ratio. For optimum
use of fly ash the W/CM ratio should be reduced by increasing the fly ash or
reducing the water content, and not by increasing the cement content. The latter
option only increases the cost.
--``,`,-`-`,,`,,`,`,,`---
Because of the steeper slope of the W/CM ratio strength curves, i.e. converging
to control, the relation between fly ash concrete and it?s f,? is perceived to be
more sensitive to reduction in water content. This implies that if the W/CM ratio
for a fly ash concrete and W/C of a counterpart portland cement concrete were
reduced by the same amount, the fly ash concrete is expected to produce larger
gains in compressive strength. Similar results were reported by other researchers
[17]. By studying Figure 5 it is realized that the fly ash family of curves shift
upwards away from the control curves as concrete ages. This indicates that fly
ash contributions to concrete increase with time. Other researchers have obtained
similar conclusions [4, 171.
Although the objectives of this research did not include formulation of a new
mixtures proportioning method, it can provide a starting point for more efficient
proportioning of fly ash concretes. If one can measure the total increase in 28-
day compressive strength due to fly ash addition, then there is a ratio between
this change in strength and the weight of fly ash in a cubic meter of concrete.
The unit of this ratio is (MPa/kg per m3), and the authors choose to name it ?the

A C 1 SP-353
V O L * I 95 0 b b 2 9 4 9 0523377 588 W
Not for Resale
A C 1 SP-I153 VOL*I 95 I0662949 0523378 414 9
efficiency index". This index assigns a strength contribution, or addition, to a

unit weight of fly ash. The major assumption here is that the interaction between
the amount of fly ash and its strength contributions is linear. This assumption
is correct when narrow ranges of fly ash addition levels are employed. One
could argue in favor of a mixture proportioning method that assigns an additional
strength value for a given fly ash addition level. In such a case, a fly ash
concrete may be designed as a regular portland cement concrete with an average
28-day strength that is equal to f,' * (I-K) where f,' is the required design
strength for the fly ash concrete and K is the previously defined efficiency factor.
The amount of fly ash per m3 of concrete that is required can then be calculated
as the division of the strength balance (f,' * K) by the efficiency index. It is
expected that proportioning fly ash concrete based on assigning additional
strength value due to fly ash addition, will result in a greater utilization of fly
ash. More importantly, this may allow utilization of ashes that are currently
outside ASTM standards, but can produce durable concretes.
CONCLUSIONS AND REMARKS

--``,`,-`-`,,`,,`,`,,`---
For concretes that have the same workability and amount of cement but different
strengths, the following conclusions can be reached;
From the analysis of variance Table 2, it is clear that K is dependent on

all variables considered. Since K measures the contribution of fly ash to
concrete strength it is concluded that all studied variables significantly
affect fly ash contributions to concrete strength. Furthermore, we believe
that the concept of a single K value, even for a specific fly ash cement
combination, is not valid.
Fly ash strength contributions to concrete increase with time. The ratio
of this contribution to the strength of a counterpart control concrete, Le.,
K values, may increase or decrease with time. As seen in Figure 3, high
strength fly ash concrete achieves most of its strength contributions during
the first ten days while the contributions of the fly ash in normal strength
concrete extend for a much longer period of time.

A C 1 SP-153 V O L + I 95 = 0662747 0523377 350
(3) The relative contribution of fly ash to concrete strength (K), increased
with a decreasing amount of cement. Based on this observation one can
conclude that reducing the amount of cement in a mixture will result in
higher relative contributions of fly ash to concrete strength.
(4) Figure 4 shows that the difference in strength between fly ash and control
concretes increase as the W/CM ratio decreases. Therefore it is
concluded that the highest fly ash contributions are associated with the
lowest W/CM ratio that is practical. Lowering the W/CM ratio should
be achieved by reducing the water content and adding a water reducer
admixture, if need be, or by increasing the quantity or quality, i.e. K, of
fly ash.
(5) Because of the steeper slope of the W/CM ratio strength curve, the
relation between fly ash concrete and its f,' is perceived to be more
sensitive to a reduction in water.
(6) Curves representing the relationship between the proposed W/CM ratio
model and fc', for various fly ash concretes, are similar to those
representing the relationship between W/C and f,'. Both relationships can
be expressed as exponential functions.
(7) The proposed definition of K should not be used to transform an amount

of fly ash to an equivalent amount of cement, but it can be used to assign
--``,`,-`-`,,`,,`,`,,`---
a strength value for a unit weight of fly ash.
REFERENCES
1. Berry, E.E., Malhotra, V.M., "Fly Ash in Concrete," CANMET, SP85-

3, 1986, Ottawa, Canada.
2. Design and Control of Concrete Mixtures, Editions 11, 12, 13, Portland
Cement Association, Skokie, IL, 1968, 1979, 1988.

A C 1 SP-353 VOLaI 95 0 6 6 2 9 4 9 0523380 0 7 2
3. AC1 Committee 21 1 , "Recommended Practice for Selecting Proportions

for Normal Weight Concrete", AC1 211.1-92, ACI, Detroit, MI, 1992,
16 pages.
4. BRE 106, "Design of Normal Concrete Mixes", Building Research

Establishment, Watford, United Kingdom, 1988, pp. 42.
--``,`,-`-`,,`,,`,`,,`---
5. Smith, I.A., "The Design of Fly Ash Concrete," Proceedings, Institute

of Civil Engineers, London, Vol. 36, 1967, pp. 769-790.
6. Cannon, R., "Proportioning Fly Ash Concrete Mixes for Strength and
Economy", AC1 Journal, November 1968, pp. 969-979.
7. Ghosh, R., "Proportioning Concrete Mixes Incorporating Fly Ash",

Canadian Journal of Civil Engineering, Ottawa, Vol. 3, 1976, pp. 68-82.
8. Warriss, B., "Strength of Concrete Containing Secondary Cementing

Materials", ACI, SP 79-28, Detroit, Michigan, 1983, pp. 5389-5557.
9. Mills, R., "Evaluation of the Performance of Blast-Furnace Slag and Fly

Ash when Blended or Mixed with Portland Cement", ASTM, STP 897,
Ed. Frohnsdorf, G . , Philadelphia, Pennsylvania, 1984, pp. 89-105.
10. Hedegaard, S.E., and Hansen, T.C., "Modified WaterKement Ratio Law
for Compressive Strength of Fly Ash Concrete", Rilem, Materials and
Structures, Vol. 25, No. 149, June, 1992, pp. 273-283.
1 1. Boloiny, J., "Dureis.wmcnt des mortiers er bétons ", Bull. Tech. Suisse
Romunde, Nos. 16, 22, 24, 1927.
12. CEB-FIP Model Code, chapters 1 to 14, Comite-International Du Béton,

CEB, Lausanne, Switzerland, 1990.
13. AC1 Committee 3 18, "Building Code Requirements for Reinforced

Concrete", AC1 318R-92, ACI, Detroit, MI, 1993, 353 pages.

A C 1 SP-LS3 V O L X I 75 M Obb2949 0523383 T O 9 W
14. AC1 Committee 211.4R "Guide for Selecting Proportions for High-
Strength Concrete with Portland Cement and Fly Ash", AC1 Materials
Journal, Vol. 90, No. 3, May-June 1993, Detroit, Michigan, pp. 272-
283.
15. ASTM C618-91 "Standard Specification for Fly Ash and Raw or Calcined
Natural Pozzolan for Use as a Mineral Admixture in Portland Cement
Concrete", Vol. 4.02, Philadelphia, PA, Amencan Society for Testing
and Materials, 1991, pp. 291-293.
16. ASTM 3 11-9 1, "Standard Test Methods for Sampling and Testing Fly
Ash or Natural Pozzolans for use as Mineral Admixture in Portland
Cement Concrete", Vol. 4.02, Philadelphia, PA, American Society of
Testing and Materials, 1991, pp. 182-186.
17. Helmuth, R., Flv Ash in Cement and Concrete, Portland Cement
Association, Skokie, Illinois, 1987, 202 pages.
18. ASTM C143-78 "Standard Test Method for Slump of Portland Cement
Concrete" Vol. 4.02, Philadelphia, PA, American Society for Testing and
Materials.
19. ASTM C192-90 "Standard Practice for Making and Curing Concrete Test
Specimens in the Laboratory", Vol. 4.02, Philadelphia, PA, American
Society for Testing and Materials.
20. ASTM C39-86 "Standard Test Method for Compressive Strength of

Cylindrical Concrete Specimens", Vol. 4.02, Philadelphia, PA, American
Society of Testing and Materials.
21. ASTM C 150-92 "Standard Specification for Portland Cement", Vol. 4.02,
Philadelphia, PA, American Society for Testing and Materials, 1991. 1
I
22. Hassaballah, A., Wenzel, T.H., "Defining the Water to Cementitious
Ratio in Fly Ash Concrete", Concrete 2000 Economic and Durable
Construction Through Excellence, Ed. Dhir, R.K. and Jones, M.R.,
E&FN SPON, Dundee, Scotland, 1993, p. 541-558.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 I0662949 0523382 945
TABLE 1 - CONCRETE MIX PROPORTIONS PER YD3

Class C Fly Ash
Mix No. * 5 c 5 c 5 c 5 c 4 c 4 c 4 c 4 c
O 10 20 30 O 10 20 30
Cement, Lbs' 450 450 450 450 550 550 550 550
Fly Ash, Lbs O 45 90 135 O 55 110 165
Water, Lbs 227 227 231 232 240.5 216 217 220
Sand, Lbs 1610 1610 1610 1610 1550 1550 1550 1550
Coarse,Lbs 1810 1810 1810 1810 1810 1810 1810 1810
Mix No.' 3 c 3 c 3 c 3 c 2 c 2 c 2 c 2 c
O 10 20 30 O 10 20 30
Cement, Lbs' 611 611 611 611 650 650 650 650
Fly Ash, Lbs O 61.1 122.2 183.3 O 65 130 195

Water, Lbs 201.4 221 222 225 244.4 218 21 5 201
Sand, Lbs 1450 1450 1450 1450 1400 1400 1400 1400
Coarse. Lbs 1810 1810 1810 1810 1810 1810 1810 1810
--``,`,-`-`,,`,,`,`,,`---
+ (5 C 1O. 5-slump lin), C-Class C Fly Ash, 1O - Addition Levell

Mix Designation
(5 F 10, 5-slump (in), F-Class F Fly Ash, 1 0 - Addition Level)
1 Ib = 0.454 Kg, 1 in. - 25.4 mm
Class F Fly Ash
Mix No.+ 5F 5F 5F 5F 4F 4F 4F 4F
O 10 20 30 O 10 20 30
Cement, a s ' 450 450 450 450 550 550 550 550
Fly Ash, Lbs O 45 90 135 O 55 110 165

Water, Lbs 227 227 224 238 240.5 248 237 24 1
Sand, Lbs 1610 1610 1610 1610 1550 1550 1550 1550
Coarse,Lbs 1810 1810 1810 1810 1810 1810 1810 1810
Mix No.+ 3F 3F 3F 3F ZF 2F 2F 2F
O 10 20 30 O 10 20 30
Cement, Lbs' 611 611 611 611 650 650 650 650
Fly Ash, Lbs O 61.1 122.2 183 O 65 130 195
Water, Lbs 201.4 236 236 260 244.4 217 280 219
Sand, Lbs 1470 1470 1470 1470 1400 1400 1400 1400
Coarse,Lbs 1810 1810 1810 1810 1810 1810 1810 1810

A C 1 SP-153 V O L X I 95 Obb2949 0523383 881
TABLE 2 - ANALYSIS OF VARIANCE
Siiin of Degrees of Mean

Soiircc of Squares Freedom Square F-Ratio P-Valut
Variation*
Maiii Eífcci? 7.966 IO 0.797 665.864 .O00
A 3.493 1 3.493 2919.460 .O00
II 2.712 3 0.914 763.967 .O00
c 0.458 2 0.229 191.391 .O00
D 1.274 4 0.318 266.123 .O00
2-Way Interactions 1.718 35 0.049 41.031 .o00
A I3 0.084 3 0.028 23.478 .O00
AC 0.348 2 0.171 143.237 .O00
AD 0.341 4 0.085 71.291 .o00
nc 0. I35 6 0.022 18.745 .000
131) 0.735 12 0.061 51.180 .O00
CD 0.08 I 8 0.010 8.423 .o00
~~
1- Way I II tcrac Lions 0.464 50 0.009 7.751 .O00

ABC O. 109 6 0.018 15.228 .O00
ARD o. 120 12 0.010 8.345 .o00
AC11 0.084 8 0.01 I 8.801 .000
I3CD o. I50 24 0.006 5.235 ,000
LWay Iiitcractiotis O. 114 24 0.005 3.968 .O00
ADCD 0.1 14 24 o. 00s 3.968 ,000
Ex plaincd 10.262 1 I9 0.086 72.080 .O00
Rcsidiial 0.287 240 0.001
Total 10.549 359 0.029
* A = Clms ofJy ash

B = Slitnip category
C = Adliliorr level
U = Cotrcreíe age
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 I0662749 0523384 718 I
135 m m SLUMP 100 m m SLUMP
6e I
a ao 40 LI U 20 4@ LI 60 100
TIM8 (DAïW TIME (DAW
CONTROL
+ ASH 10%
ASH 2 0 2
60 - b@
O . .. .---
c II- c II-
M Y
S
S
s
4b-
E
O
Y
30 30
15 21
O 20 40 LO 80 100 o ZI 40 60 io ln
TIYE (DAYS) TIME (MYS)
Fig. l-compressive strength versus age of Class C and control

concretes
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOL+I 95 O662949 0521385 654
60
D
75 m m SLUMP
1 +
Q
ASH 10%
ASH 20%
ASH30% 1 50 m m SLUMP
m 10 40 LO 8O 100 O 1, 40 O 80 I##
TIYB (DAYS) TIYB (Oual
Fig. 24ompressive strength versus age of Class F and control

concretes
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 IObb2949 0523386 5 9 0
0.1 O.(
x
r
0.1
0.i
K * 0.4
0.6
V V
A A o1
L L
U U
E OA E
S s o.:
0.3
o. i
0.2 a
20 40 do O0 WO o 20 . «I LO LO mo
AGE (DAYS) AGE (DAYS)
CLASS C ACH 2OU
75 m m SLUMP
O. 0.0
+ *
I 0.6 - ;* -
O.
*
--``,`,-`-`,,`,,`,`,,`---
0.4 - -
K K
-
V
; I +
U
E
9
o.
1
O.
0.2 - --
0.1
20 40 do LO (o( D
AO€ (DAYS)
Fig. 3-K-value versus age for Class C fly ash concretes

A C 1 SP-353 V O L X I 95 m Obb2949 0523387 427 m
O 0.1
O 0.4
o..
K O *
V V
A o. A o.:
L L
U U
E E
s o I s 0.1
O. ** a
c-
-0.1
20 40 Bo 80 i00
L CLASS F ASH IOU

-I- CLASSFASHZO’L
75 m m SLUMP
0.16, 1
-0.161 I -0.16
O 20 40 û0 80 100 O 2û 40 M 8 O í O O
Fig. 4-4-value versus age for Class F fly ash concretes
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 IObb29Li9 0523388 363 m
CLASS C ASH CLASS F ASH

7 DAYS 7 MYS
--``,`,-`-`,,`,,`,`,,`---
28 MYS 28 DAYS
4.
* CONTROL
+ ASH IOI
4- ASH 101
71 ASH JO-
O1 MYS 01 DAYS
0,
I
g 001
Y
L eo- m-
:- -
:m -
i
L --
E .o-
,
" ao-
II
:.o-
Fig. 5-Compressive strength versus water-to-cementitious ratio =

+
W/(C K * F.A.) for fly ash and control concretes

A C 1 SP-153 V O L J I 95 = ûbb2949 0521389 2 T T
SP 153-25
Utilization of Fly Ash in

the Development of a Cost-
Effective Cementitious Product
by S. L. Sarkar, A. Kumar,
D. K. Das, and G. Banerjee
w:The individual binding capacity of fly ash in lime bearing systems and
gypsum on its own is well established. This study was aimed at utilizing gypsum as
phosphogypsum and industrial lime in conjunction with high volume fly ash to
develop a cost-effective cementitious binder product by advantageously utilizing the
individual binding capacity of the materials.
The materials were first fully characterized chemically and mineralogically to

evaluate their potential as building material components. Different mixture
proportions were tested. Compressive strength data of different mixtures at 1 day, 3,
7, 14, 21 md 28 days x e presented. These are correlated with the hydration
properties at corresponding ages studied by means of XRD, SEM/EDXA, and DTA.
The discussion relates to the roles of the individual components in the development
of strength properties. Products with an interlocking microstnicture and compressive
strengths of over 12 MPa after 28 days of hydration are described. The cost-
effectiveness and the possible applications of cementious products that can be
developed with such a system are also described.
Kevwords: Binders (materials); C-S-H; ettringite; fly ash; hydration; lime;

--``,`,-`-`,,`,,`,`,,`---
phosuhoevpsum; strength; wastes

A C 1 SP-353 VOL*I 95 IObb2949 0523390 T I L =
440 Sarkar et al
Shondeep L. Sarkar obtained his doctoral degrec in Crystallography from the

University of London, U.K. He is Vice-president, SECA, Inc., Consulting
Engineers, Houston, Texas. He specializes in high performance concretes,
optimization of cement properties, and waste remediation. The author of several
papers on cement and concrete, he has also co-edited a number of booh and
conference proceedings on cement and concrete.
Amitabha Kumar obtained his doctorate in Solid State Science from the
Pennsylvania State University. He was engaged in research on the utilisation of
waste and alternate materials for building application and in materials for high
temperature applications at the time of writing this paper. He is presently with E.
Khashoggi Industries, Santa Barbara, CA, USA.
Dinah K. Das obtained his Post-graduate Degree in Civil Engineering from

Jadavpur University, Calcutta, India. He is presently conducting research on ways to
develop low cost alternate building materials preferably through utilisation of waste
materials at the Central Glass and Ceramic Research Institute, Calcutta, India.
Gautam Banerjee holds a doctorate in Ceramic Technology from the Calcutta

University, India and presently heads the Refractory Division of the Central Glass
and Ceramic Research Institute, Calcutta, India. His research interests include
refractory materiais and synnthetic aggregates for high temperature application and
building materials. He is an expert in steel plant refractories.
--``,`,-`-`,,`,,`,`,,`---
INTRODUCTION
I
Generation of industrial by-products has been receiving considerable public
attention because modern society has become increasingly environmentally I
conscious, and demands that special attention be paid either to their proper disposal
or utilization in order to reduce pollution. It is me to say that these by-products are
being produced in large quantities all throughout the world and that their disposal has
become a major issue of concern.
Among a l l the industrial by-products produced worldwide, fly ash is

generated in the largest quantity. Despite over six decades of fly ash use in the
construction industry, more than 80% ash generated globally is still disposed of as
waste [i]. Research has provided viable avenues for utilization of fly ash in cement
and concrete; for example, as a blending component in cement [2], and raw material
and fuel in the kiln for cement clinker production [3]. Malhotra [4] has demonstrated
structural advantages and economic benefits of using high-volume fly ash in

A C 1 SP-353 VOL+I 95 = 0662949 0 5 2 3 3 9 3 958
concrete. Nevertheless, further research to find ways for economic yet mass
utilimtion of fly ash continues all over thc world.
Fly ash brick is considered to be one of the most effective means to utilize
large tonnage of ash without much concern about the physical and chemical
properties of the fly ash. As early ils in 1964, Shafer and Cockrell developed a
process l'or manufacturing dry-pressed fly ash bricks 151. Day and Bergman 161
tested several fly aih fired bricks, and Slonaker [7] reported the production of 40%
core-area fired structural producLs made from 758 fly ash, 22% bottom slag and 3L7
sodium silicate (N-SO,).
Phusphogypsum, on the other hand, is a by-product in the manufacture of

phosphoric acid (H,PO,) by the wet process. Although exact figures are not
available, several million tons of phosphogypsum are produced in the world
annually. The calcium sulfate ohtaintxi as a by-product of phosphoric acid is
crystallized in one of the three forms: anhydrite (CaSO,), hemihydrate (CaSO, . 1/2
H,O) or gypsum (Caso, . 2-0) or us a combination thereof, depending on the
temperature and concentrations invoivcd in the processing of the acid. The most
significant contaminants are phosphates (0.5 to 1.5%) and fluoridcs: hence the term
phosphogypsum. Chemically, the process can be represented as follows:
The most convenient means of disposal of this by-product is to dump it on
--``,`,-`-`,,`,,`,`,,`---
dry land. into the sea, or estuarine waters. Since gypsum is soluble, and causes
permanent hardness of water, it dws not affect the potability. The insoiuhle residues
of the phosphate rock, however, can be problematic. Therefore, in some countries
like South Africa and Australia. it is mandatory to dispose phosphogypsum in
properly designed lagoons.
Phosphogypsum has been proved to be an effective set retarder for cement

[ 81. A study by Olmez and Erdem [9] has shown that untreated phosphogypsum can
be used as a set retarder directly in 'trass' cement, whereas portland cement requires
the purified form. According to Mehta and Brady [ IO], not only can it bc used as a
set-retarder, but when added to the cement raw meal. it also acts us a minerdim for
clinker.
However, at present there is no effecctive utilization of this by-product. A

small amount is used in the manufacture of gypsum piaster. plasterboard and glass-
reinforced gypsum.
Since pollution of streams and water reserves by lhe phosphogypsum-ric.h

liquor can be troublesome, there is mounting pressure from environmentalists, arid
therefore, considerable effort is now being directed towards utilihon of
phosphogypsum.

A C 1 SP-153 V O L * I 95 IO662949 0521392 894
442 Sarkar et al
Basic research investigations of Lin et al. [ i i ] has shown thiit

phosphogypsum when subjected 10 high compaction pressure can attain considerable
compressive strength. The compaction force can either be applied dynamically, Le.,
by dropping a weight or vibration roller, for road base applications, or statically
(pressing) for making building products. Nanni et al. [i21 developed an
experimental moulding press for this purpose. Both these studies exploited the
binding property of gypsum.
It is well known that portland cement activates fly ash reaction with calcium
oxide. Lime and gypsum are two other useful calcium-karing binders that are uscd
as primary cementitiou mater& in building applicaticins. Recently, the activation
mechanism of fly ash by gypsum was described by Xu and Sarkar [13]. The
beneficial properties of lime in pozzolans system are well established, and have been
used with a measure of success in the prcxluction of cost-effective fly ash-based
construction products. Donelly and Jons have produced a synthetic gravel from a
mixture of fly ash-lime-gypsum [ 141.
Based c n this background infcrmation, *is study, in general terms, was

aimed at joining these approaches to prtduce a cost-effective cementitious prrduct
from fly ash-lime-phosphogypsum.
The process conceived was economical in the sense that it did not involve the
use of expensive chemicals such as sodium silicate, and no thermal treatment like
autoclaving, gelling or steam curing was applied. Besides, among all the
applications, block manufacturing appeared the most promising because of the
limited dimensions of the masonry block, as large-size expensive equipment is not
essential. Scientifically, the investigation was an attempt to utilize the binding
abilities of lime and phosphogypsum, and activate fly ash in a high volume fly ash-
based binder. The hydration behavior was studied in order to understand the
sequence of reactions and correlate this with the strength development pattern in the
selected system. The addition of phosphogypsum to the lime-fly ash system was
anticipated to play an important role in the early activation of fly ash and possibly in
the formation of etuingite-bused bonding [ 151.
In the first phase of the study, after some trials, a selected mixture of fly ash,
hydrated lime, and phosphogypsum were mixed with water and pressed into
cylinders for study after curing. In the second stage, samples were made by vibration
casting in moulds, using beneficiated phosphogypsum.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0662749 0523393 720
EXPERIMENTAL METHODS
Phosphogypsum was obtained from an industry producing phosphoric acid.

In the first stage of experiments, phosphogypsum was used as-received. whereas in
the second stage, beneficiated phosphogypsum was used. Several methods have been
suggested for removing the impurities within phosphogypsum 1 161. The beneficiated
phosphogypsum used in the study was obtained from a source utiliAng a proprictwy
developed at the Central Glass and Ceramic Research Institute, Calcutta, India [ 171.
The process involves the separation of impurities of phosphates and fluorides through
a series of water washing and clarification steps similar to the purification and
winning of China clay. Surface active agents are used in the multi-step washing
process to fl«cculate and dcflocculate the phosphogypsum during the washing.
Commercial quicklime was slaked to produce hydrated lime which was dewatered to
a water content of 50 c/c by weight. The same batch of lime was used throughout the
--``,`,-`-`,,`,,`,`,,`---
study. Fly ash was obtained from the electrostatic precipitator zone of two thermal
power plants using Indian coal from the Eastern region of the country.
In the first stage of experiments, the phosphogypsum, wet hydrated lime and
fly ash were mixed in the weight ratio of 1316. The dry mars was mixed with
13.5% wate: by weight md tie mass w u pressed into cylindcn 5 0 min diamctcr. SO
mm high using a hydraulic press at a pressing pressure of SO MPa. The cylinders
were moist cured under wet burlap for 24 hours and then cured under water lor the
remaining time until the test date. Samples were removd for compressive strength
measurement and microstructural studies at 1 day, 7, and 28 days.
Since the as-received phosphogypsum was found to contain all the three
calcium sulfate forms (gypsum. hemihydrate and anhydrite), this series was selected
for microstructural analysis. It was surmised that because of the presence of the
more soluble types of calcium sulfate, the activation effect would be amplified, and
therefore would be more prominently reflected on the microstructure. Samples were
prepared by immersing small crushed picces in acetone for 2 hours li,llowcd by
drying at 6o"C for 3 days. Powder XRDA, SEMEDXA, and DTA/TG were carried
out on them.
In the second series, beneficiated phosphogypsum. lime and lly ash were
mixeú together in a planetary mixer with necessary water to provide a flow of about
75%, using the procedure described in ASTM C- IOY on a flow table conforming to
ASTM C-230. The fly ash content was kept constant at 80% by weight. The limc-
to-phosphogypsum ratio wils varied and the mixture was added to make-up uie
remaining 20% of the mix. The batch compositions of all the mixtures studied are
given in Table I, and their percentage cornpositions are given in Table II. The pastes

A C 1 SP-153 V O L * I 95 m Obb2949 0521394 bb7 m
444 Sarkar et al
were cast into 50 mm cubes using about 2000 vpm vibration and demolded after 24
hours moist curing. The same wet curing procedure as the first series was used.
Char-tends
The chemical composition of the two fly ashes and the as-received and
beneficiated phosphogypsum used in the study are given in Table III. As observcd
from the table, the two fly ashes differ in their alkali and alkaline earth oxide
contents. Fly ash II was relatively free of unburnt carbon, though fly ash I with
3.2841 LOI was reasonably low in unburnt carbon for the application in this study.
--``,`,-`-`,,`,,`,`,,`---
The silica and alumina contents of the two fly ashes were similar. Beneiïciation t)f
phosphogypsum resulted in higher gypsum content, reduced soluble sulfates,
decreased phosphate, flouride and other impurities as detailcd in Table III.
The particle size distributions of the three raw materials used (after dry
sieving through a 150 pm sieve) in the second stage of the study are given in Fig. 1.
The phosphogypsums used in both stages were similar in terms of particle s i 7 the~
mean puticle sim: (d5,,)king about SO pm.
Fly ash from both sources had sirnilar particle size distributions. As shown in
Fig. 1, the d,, was about 1 0 pm und over 10’3 particles were below 1 pm. The
hydrated lime was very fine with a d,,, of about 3 pm. However, in actual use, since
wet lime with about 50% water wus used, the hydrated lime was agglomerated. nie
hydrated lime was sieved through a mesh with an opening of 6(M) pm and then mixecl
into the batch.
XRD powder patterns of these IWO ashes arc presented in Fig. 2. Qum7,
feldspar and mullite were found to k the major crystalline pha.cs with an
amorphous mass due to the glassy component in fly ash. Some hematite and
magnetite were also present. The two ily ash samples were similar mineralogically,
except that fly ash II contained no feldspar. This difference was not anticipated to
affect their behavior in the systems being studied.
Powder XRD patterns of the phosphogypsum samples are reproduced in Fig.

3. The major phases present are gypsum along with soluble calcium sulfate,
hemihydrate, and brushite with extremely minor amounts of quart/.. The
beneficiated phosphogypsum does not have any soluble calcium sulphate aiid
hemihydrate. These phases were removed during the knefïciation process. The
hydrated lime was almost entirely composed of portlandite. There wus a small
amount (about 2%) of calcite, probably relics of the limestone which was used to

A C 1 SP-353 V O L X I 95 0662949 0523395 5T3
produce the quicklime. Care w i s taken to store the hydrated lime under water to
prevent carbonation, though this source of contamination cannot be entirely
prevented.
Strength cain in relation to phase Chang=
It was observed that the compressive strength upto 7 days in the pressed
samples was quite low after which the system began to improve in strength except in
the case of samples of Series 2, Batch No. 4 and 5, given in Table IV. The cast
samples did not disintegrate upon being immersed in water after 24 hours. The
difference in the strength development pattern before and after 7 days of hydration
was investigated by monitoring the phase changes in the system. XRD patterns of
hydrated pastes, at 1 day, 7, and 28 days of hydration, Fig. 4 show that hydrated h e
was consumed to a large extent within the first week of hydration. Yet, strength was
not generated through this consumption as observed in Table IV. The soluble part of
phosphogypsum, Le., soluble calcium sulfate and hemihydrate in the unbeneficiated
phosphogypsum, began to react from the first day, but gypsum which remained intact
up to the seventh day was consumed by the twenty eighth day of hydration. The
major reaction products that were observed are ettringite and calcium silicate hydrate.
DTA resu!& shown in Fig. 5 cor,firm the XP93 rcsults. Unreactd pmlandite
was observed at the 1 day stage but none was detected at 7 and 28 days. Gypsum
increased during the fist 7 days but there was a considerable decrease thereafter.
This increase in gypsum is attributed to recrystallisation of soluble calcium sulfate in
this unbeneficiated phosphogypsum. It is considered that when 15% lime and 5%
phosphogypsum are used, a molar equilibrium between Ca and SO, is established
which allows for gypsum recrystailisation in this particular system. The decrease in
lime at the 7-day’s level is linked to this phenomenon (see DTA in Fig. 5) with some
lime being consumed for the fly ash hydration.
This provided further motivation for a study in lime-rich and lime-deficient

systems with beneficiated phosphogypsum which does not contain this soluble
component of calcium sulfate. The authors believe that a two-stage reaction is in
progress wherein Ca and soluble SO, react and recrystallise to form gypsum, and this
recrysîailised gypsum is a source for fly ash activation at a later stage to form
ettringite. Fig. 5 shows the formation of ettringite in the system at the 28 day stage
as confirmed by DTA. Phase analysis data in Fig. 4 also indicates the same
information. Some carbonation in the original lime was observed by DTA study of
the samples and this increased with age of hydration.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL+I 95 I0662749 0523396 4 3 T
446 Sarkar et al
The typical microstructure of hydrated sample of Seriesl, Batch 1, at one day

age comprising mostly unreacted fly ash, a few short fibers, and gypsum, is shown in
Fig. 6. The short fibers were found to develop on the fly ash and phosphogypsum
particles. There was evidence of lime and sulfate reaction. The CdSi ratio obtained
from probe analysis indcated some C-S-H formation, which was found to
incorporate Al, Mg and S. The adsorption of C a 0 by the fly ash particles was
evident from the lime coated fly ash particles. The gypsum showed split partings
along clevage planes, possibly due to dissolution of the soluble calcium sulfate
fraction(s). Needles of AFt phase were observed, but the amount was extremely
small and scattered.
The microstructure at 7 days was more well developed (see Fig. 7).
Corroded glassy fly ash surfaces with a reticular network were evident. The needies
on the fly ash grains were larger (@ 10 pm) and distinct. They were identified as
ettringite. The phosphogypsum had reacted to a small extent (Fig.8). The gel
formation was higher, but the composition was mostly C-A-S-H with some S
suggesting reaction with fly ash glass. Though there was some evidence of ettringite
from SEM, it was not detected at this stage by XRû.
--``,`,-`-`,,`,,`,`,,`---
At 28 days of hydratioii theie was a significant diange in the microstructure,

Fig. 9. Radiating bundles of AFt needles were found in parts. Though gypsum was
detected, its corrosion was more pronounced. The general feature was one with
distinct reaction products. C-S-H incorporated some Al and S as shown in Fig. 10.
Some evidence of Type I fibrous C-S-H on fly ash particles was observed with low
S content, distinguishing it from ettringite (Fig. 9). However, the reticular box work
(Type II) C-S-H was more prevalent, known to form in iime-pozzolana systems [ 171.
Following this detailed investigation, a study was carried out in the second
stage to assess the effect of the iime-to-phosphogypsum ratio on the strength
characteristics of such a high volume fly ash system. in addition, the
phosphogypsum was beneficiated to remove soluble sulfate as given in Table IIï.
This was anticipated to reduce the recombination effect of Ca with the soluble sulfate
and thus provide more lime for the fly ash activation process to promote strength
gain. The batch and percentage compositions are described in Tables I and II
respectively. The results of this part of the study are summanzed in Fig. 11. As
noted from this figure, when fly ash was activated only by lime in these vibrocast
samples, the strength gain up to the first 7 days was rather small (1.2 Mpa), and the
28 day compressive strength was only about 6 Mpa (Series 2, Batch 1). When it was

A C 1 SP-153 V O L X I 95 111 0662949 0523397 37b 111
activated by phosphogypsum alone, the result was disastrous (Series 2, Batch 5 ) .

There was virtually no strength gain over the fmt four weeks.
At lime-to-phosphogypsum ratios of 3:l and 1:l (Series 2, Batch 2 and 3),

the 28 day strength was about 12 MPa. When this ratio was decreased to 1:3 (Series
2, Batch 4) the system became lime deficient and lower 28-day strength w a
observed. in all, it was concluded that phosphogypsum and lime with a 1:l weight
proportion (Senes 2, Batch 3) can be used along with 80% fly ash by weight to
activate a system capable of providing strength above 10 MPa.
According to Bijen et al. [18], the amount of lime plus gypsum required to
achieve a specified strength depends on the amount of available lime. They have
classified 'safe' and 'non-safe' areas as a function of mixture proportions. In parallel,
they have drawn attention to the destructive formation of expanding AFt when lime
and gypsum are used. In the 'safe' area, the expansion lies within acceptable limits,
while the 'non-safe' area depicts considerable expansion, but products in this region
can still be used for certain applications.
In the present study, no visible evidence of expansion, however, was

encountered since no cracking was observed. Cubes were found to be strong even
after 12 months. According to the authors the calcium sulfate helps to activate the fiy
ash, i.e., to break up the glassy phase: the hydration products formed thereafter
depend on the calcium available. If the amount of lime in the fly ash - lime -
phosphogypsum can be optimijsed, C-S-H is the principal phase that will contribute
to the strength. The delayed strength gain in such a system can basically be related to
the dissolution of fly ash. The bridging action of ettringite, proposed by Zmachinsky
[ 151 did not seem to appear very convincing in the fly ash: lime: phosphogypsum
mixtures of weight ratio 80:20 studied.
CONCLUSIONS
High-volume fly ash based binders can be formulated with mixtures of

phosphogypsum and hydrated lime to provide cementitious properties. The fly ash
content was maintained at 80% and lime-to-phosphogypsum ratios between 3: 1 and
--``,`,-`-`,,`,,`,`,,`---
1:3 were found to yield moderate strength. Within this range, higher lime ratios are
preferred. Compressive strengths of about 12 to 14 MPa are achievable through
pressing or vibrocasting of paste/wet mixtures. In general, most applications for this
type of binder is for low strength products that range from 5 to 20 MPa.
Additionally, since this type of product is made from industrial by-products, and the
process technology is economical, it holds promise as building bricks/blocks for cost-
effective housing programs, artificial aggregates, road construction, masonry mortars
and renderings, especially in hot climate countries.

A C 1 Sp-153 VOL*I 95 I0662949 0521398 202
448 Sarkar et al
Pliase clieniistiy and niicrostructural arialysis Ieveded the forniatioii of

calcium silicate phases dong with ettriiigite to form the cementitious body. The
presence of soluble calcium sulfate plays a dominant role in controlling the release of
calcium and this can be improved through the use of beneficiated phosphogypsum.
A two-stage mechanism was proposed for fly ash reaction.
ACKNOWLEDGMENTS
The authors of the Central Glass and Ceramic Research Institute, Calcutta,
India, thank their Director, Dr. B.K. Sarkar, for permission to publish the findings
presented in the paper. The authors are thankful to UNDP for providing necessaiy
financial assistance to S. L. Sarkar under the Transfer of Knowledge Through
Expatriate Nationals Programme in collaboration with the Council of Scientific and
Industrial Research under which the study was conducted.
REFERENCES
1. Mehta, P.K., "Pozzolanic and Cementitious By-products in Concrete-Another

Look," Proc. 3rd Int. Conf. Fly Ash, Slag, Silica Fume, and Natural
Pozzolans in Concrete, Trondheim, Norway, Ed. V.M. Malhotra, 1989, pp.
1-43.
2. Frohnsdorff, G., "Blended Cements," ASTM STP 897, American Society for
--``,`,-`-`,,`,,`,`,,`---
Testing and Materials, Philadelphia, PA, 1986.
3. Bijen, J. and Wal!ie, H., "Alternative Raw Materials and Bonding Materials
for Portland Cement, Part IV: Slag-Fly Ash Cement," Ministry of Housing,
Physical Planning and Environment, Leidschendam, Holland, 1985.
4. Malhotra, V.M., "High Volume Fly Ash Concrete for Structural
Applications," CANMET Sem. Nova Scotia Fly Ashes, Canada Center for
Mineral and Energy Technology, Ottawa, Canada, 1986.
5. Shafer, H.E. Jr., and Cockrell, C.F., "A New Approach to the Production of
Fly Ash Based Structural Materials,'' Coal Research Bureau Report No. I l ,
Morganlown, W. Va., 1964, 8 pp.
6. Day, R.L. and Bergman, J.W., "Fly Ash as a Substitute for Clay in Brick
Manufacture," Proc. 8th. Inti. BricWBlock Masonry Conf., Dublin, Ireland,
1988, Elsevier Science Publ. Co.. London, U.K., Vol 1, pp 14-25.
7. Slonacker, J.F., "Production of Forty Percent Core-Area Brick Using
Selected Fly Ashes," 4th Int. Ash Utilis. Symp., Morgantown, W. Va.,1976.
8. Mukarami, K., "Utilizationof Chemical Gypsum for Portland Cement," Proc.
5th Int. Cong. Chem. Cem., Vol. IV, Tokyo, Japan, Cement Association of
Japan, Tokyo, 1969, pp. 459-463. I
9. Olmez, H. and Erdem, E., "The Effects of Phosphogypsum on the Setting I
and Mechanical Properties of Portland Cement and Trass Cement," Cem. l
Concr. Res., Pergamon Press, New York, Vol. 19, 1989, pp. 377-384. l

A C 1 SP-I153 V O L S 1 75 IO662949 0521399 1 4 9 m
IO. Mehia, P.K. and Brady, J.R., "Utilization of Phosphogypsum in Portland

--``,`,-`-`,,`,,`,`,,`---
Cernent Industry," Ccm. Concr. Res.. Pcrgamon Press, New York, Vol. 7,
1Y77. pp. 537-544.
I I. Lin, K.T.. Nanni, A. and Chang, W.F., "Compressive Strength of Compacted
Portland Cement Mixtures Using Phosphogypsum", Present& at the Symp.
Consolidation of Concr., AC1 Annual Convention, San Francisco, 1986.
12. Nanni, A., Swain, M.R., Ahmadi, B.H. and Chang, W.F., "Bench Model
Production and Uses of Phosphogypsum Bricks," Proc. 2nd Int. Symp.
Phosphogyps., Miami, FL, Vol. II. IYXX, pp. 385-395.
13. A. Xu and Sarkar, S.L., "Microstructural Study of Gypsum Activated Fly
Ash Hydration in Cement Paste, Cem. Concr. Res., Pergamon Press, New
York, Vol. 21, lYYl, pp. 1137-1147.
13. Donelly, J.R. and Jons, E., "Synthetic Gravel from Dry Flue Gas
Desulphurization End Products," Presented at the 6th Int. Ash Utilis. Symp.,
Reno, NV, 1962.
IS. Zmachinsky, A.E., Lyashkcvich. I.M. and Chemaya, L.G., "Production of
Gypsum Concrete with PFA Ingredicnlst" Proc. Int. Symp. Use of PFA in
Concrete, Ed. J.G. Cabrera and A.R. Cusens, UK, Vol. 1, 1982, pp. 273-276.
16. Singh. M., Garg, M. and Rchsi, S.S., "Purifying Phosphogypsum for
Cement Manufacture," Construc. Bldg. Mats., Butterworth-Heincman Lu.,
London. U.K., Vol. 7, lYY3, pp. 3-7.
17. Aïtcin, P.C., Sarkar, S.L. and Diatta, Y., "Microstructural Study of Different
Types c)í' Very High Strecgth Concrelcs," Mat. Rcs. Six.. Synp. Roc., Vol.
85,Materials Research Society, Pittsburgh, PA, 1987, pp. 261-272.
18. Bijen, J., Skalny, J.P. and Vazquez, E., "Other Uses of Fly Ash" in Fly Ash
in Concrete, Ed. K. Wesche, E&FN Spon, London, UK, 1991, pp. 160-177.

A C 1 SP-153 VOL*I 95 D 0662949 0523400 790 D
450 Sarkar et al
TABLE 1 - BATCH COMPOSITION OF SAMPLES
Series Butch Materials (g)
Hydrated Phospho- Fly Ash Total

*
Lime gypsum Water
1 1 750 250 4m) 625

~
2 1 1000 o 4Ooo 2550

2 2 750 250 4” 2250
2 3 soo 500 4000 2000
2 4 250 750 4Ooo 1800
2 5 o lo00 4000 1500
* : Dry Basis; Actual hydrated lime contained 50% water included in total water.
TABLE 2 - PERCENTAGE COMPOSITIONS OF SAMPLES STUDIED
Series Batch Hydrated Phospho- Fly Ash Total Water*

#
Lime gypsum FA + HL + PG
(Wt%) Wt%) Oxlt%’.)
1 1 15 5 80 O. 125
2 1 20 O 80 0.5 10
2 2 15 5 80 0.450
2 3 10 10 80 0.400
2 4 5 15 80 0.360
2 5 O 20 80 0.300
~ ~
# : Dry Basis; * : Includes water present in hydrated lime.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 95 m Obb29Y9 0523403 b 2 7 m
TABLE 3 - CHEMICAL COMPOSITION OF FLY ASHES AND

PHOSPHOGYPSUMS USED IN THE STUDY
:hemical Fly Ash I Fly Ash I1 As-received Beneficiated

:onsti tuent (Wt%) (Wt%o) Wt%) (Wt%)
60.16 55.90 1S O 0.20

23.83 27.50 0.40 O. 15
4.53 5.20 O. 17 0.12
1.30 3.0 NE NE
32.52
--``,`,-`-`,,`,,`,`,,`---
3.65 1.o0 30.40
I .23 0.70 0.58 0.40
0.20 0.06 0.20 o.10
1.82 0.87 NE NE
3.28 0.20 19.00* 20.55'
NE NE 1.61 O. 30
NE NE 0.28 0.18
NE NE 45.82 44.80
NE NE 90.80 98.20
* :Combined water released at 250°C: NE : Not Estimated.
*
Series Batch Compressive Strength (Mpa) at Age
1 day 3days 7 days 14days 2ldays 28days
1 1 1.8 _____ 3.5 _____ _____ 13.7

2 1 0.1 0.5 1.2 3.0 5.3 6.4
2 2 0.7 4.0 8.2 13.5 12.4 12.5
2 3 0.6 2.6 8.3 11.2 14.6 11.8
2 4 0.7 3.3 5.9 4.7 5.1 6.1
2 5 0.3 0.3 0.2 o. 1 0.0 0.0
* : Average of six cubes, each 50 m m side; in case of Series 1,50 m m dia cylinder.

A C 1 SP-153 V O L X I 95 m Obb2949 0523402 563 m
452 Sarkar et al
I I I I
--
-
-
--
-
Equivalent Spherical Diameter, prn
Fig. l-Particle-size distributions of fly ash, phosphogypsum,

and hydrated lime used for Series 2 samples in the study
1
I
-JA
i'
4
45 5 5 5
5
4
o I'_"___F_r__'"'''"'''I''''I''''
Lo. 15 20. 2s. 30. 35. 40. 45. 50 55. 6 0 .
o
10.
I
*S.
, P, I , ,
BO. 25. 30. 35. 40.
I , I ' ' ' ' I
45. 50
"-
,
55.
I ' ' ' '
60.
Fig. 2-Powder XRD patterns of two fly ashes, where 1 =

mullite, 2 = hematite, 3 = magnetite, 4 = anorthite
feldspar, and 5 = quartz
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL21 95 0bb2749 0523403 4 T T
Fig. %Powder XRD patterns of as-received and benefi-

ciated phosphogypsum, where 1 = soluble anhydrite, 2 =
gypsum, 3 = hemihydrate, 4 = brushite, and 5 = quartz
10 I5 10 25 JO 30 40
Fig. &Phases developed in hydrated pressed samples of Series 1,

Batch 1, of fly ash, phosphogypsum, and lime with 16:1:3 weight ratio
after curing for 1, 7, and 28 days (1 = gypsum, 2 = portlandite, 3 =
hemihydrate, and 4 = ettringite)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 m Ob62947 0523404 3 3 b m
454 Sarkar et al
I I
IOpV
i doy
I 1 I
-50 250 550 850 il50
Temperature
Fig. 5-DTA data for three corresponding

curing ages of hydrated pressed sample
of Series 1, Batch 1, with fly ash:phospho-
gypsum:lime weight ratio of 16:1:3. E =
ettringite, G = gypsum, CH = Ca(OH),, and
Q = quartz (The consumption of gypsum and
formation of ettringite and hydrated phases
can be seen from these data.)
Fig. &Typical microstructure of 1-day hydrated sample

of Series 1, Batch 1 mix with fly ash:phosphogypsum:lime
weight ratio of 16:1:3, indicating low degree of hydration
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0662949 0521405 272 9
Fig. 7-Reticular network and short fibers on fly ash and

phosphogypsum at 7 days. Hydrated sample of Series 1,
Batch 1 mix with fly ash:phosphogypsum:lime weight
ratio of 16:1:3
--``,`,-`-`,,`,,`,`,,`---
Fig. &Hydrated sample of Series 1, Batch 1 mix with fly

ash:phosphogypsum:lime weight ratio of 16:1:3 at 7 days’ age
showing one portion of phosphogypsum to be intact, whereas
other parts are corroded, showing partial reaction of
phosphogypsum

A C 1 S P - 1 5 3 V O L U I 95 Obb2949 0 5 2 1 4 0 6 L O 9
456 Sarkar et al
Fig. 9-28-day hydrated sample of Series 1, Batch 1 mix

with fly ash:phosphogypsum:lime weight ratio of 16:1:3
showing abundant radiating ettringite needles and C-S-H
in the paste
Fig. 1û-EDX spectrum of C-S-H containing AI, S, and P in

28-day hydrated sample of Series 1, Batch 1 mix with fly
ash:phosphogypsum:lime weight ratio of 16:1:3
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 75 = Obb2747 0521407 045
7 14 21 28
Curing Time (day)
Fig. 1l-Compressive strength gain in

vibrocast fly ash:phosphogypsum: lime
samples of Series 2, Batches 1 through
5, as function of lime (L) to phospho-
gypsum (P) ratio and curing time. Fly
ash loading was maintained at 80 percent
by weight in this series of samples
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0662949 0521408 T B L
SP 153-26
Morphology and Selected Properties

of Fly Ash
by P. K. Rohatgi, P. Huang, R. Guo,
B. N. Keshavaram, and D. Golden
Svnomis: Fly ash is finding a variety of new applications. It is increasingly

important to determine the structural properties of fly ash particles, especially
for increasing use in composites. such as polymer matrix and cast metal
matrix composites. In this paper selected properties of precipitator fly ash
and cenosphere fly ash were directly measured, and other properties were
indirectly estimated from the experïmental measurements on the properties of
composites incorporating fly ash. The properties studied included sphericity
of fly ash particles, wall thickness, the ratio of wall thickness to diameter and
modulus. The data generated on properties of fly ash have been compared
with other filler or reinforcement materials. such as glass microspheres,
AI,O,, SiO, and Sic particles. The results show that the deviation of
cenospheres from sphericity is virtually independent of diameter. The ratio
of wall thickness to the diameter of cenospheres is about O. 1 and it tends to
decrease with increasing particle diameter. The calculated values of effective
modulus of fly ash from the property measurements on metal matrix-fly ash
composites are in the range 140 to 310 GPa which are of the same order of
magnitude as of general ceramics and glasses. The morphology of
precipitator and cenosphere fly ash particles studied using scanning electron
microscope is discussed. The implications of the morphology and properties
--``,`,-`-`,,`,,`,`,,`---
of fly ash on its utilization, specially in micro and macrocomposites, including

cements is also discussed.
Keywords: Aluminum; composite materials; flv ash; matrix; morphoIo@;

placing; thickness; walls

A C 1 SP-153 V O L * I 95 m 0662747 0523407 718 m
460 Rohatgi et al
Pradeep K. Rohatgi is Ford/Briggs and Stratton Professor and Director of the

Center for Composites in the Materials Department at the University of
Wisconsin Milwaukee, P.O. Box 784, Milwaukee, Wi 5321 1. He received
his doctorate degree from Massachusetts Institute of Technology.
Ping Huang is a Ph.D. student in the Materials Department at the University

of Wisconsin Milwaukee,
Riqiang Guo is a Ph.D. student in the Materials Department at the University

of Wisconsin Milwaukee.
B. N. Keshavaram is a Research Associate in the Materials Department at the

University of Wisconsin Milwaukee
D. Golden is a Project Manager at the Electric Power Research Institute, Palo

Alto, CA 94303.
INTRODUCTION
--``,`,-`-`,,`,,`,`,,`---
Fly ash from coal-fired power plants has been used in varieties of
applications during the last several decades. such as in construction, plant
growth and mineral resource. Its chemical and physical characteristics have
been studied by a number of investigators [1,2]. Recently, fly ash has
received attention in some high value applications such as metal matrix
composites [3,4] and polymer matrix composites [5,6].In these composites,
fly ash generally acts as a filler replacing energy intensive metal or polymer.
In certain cases, the properties of metal or polymer are also improved as a
result of addition of fly ash.
A complete characterization of fly ash particles is very difficult due to

the large number of variables involved. In this paper, specific characteristics
of fly ash are being reported which are essential for applications of fly ash
as reinforcements or dispersoids in composites. The characterization has been
focused on shape of fly ash particles, wall thickness, the ratio of wall
thickness to diameter, density and modulus. Moreover, morphologies of fly
ash particles as received have been studied. An attempt has been made to
compare the properties of fly ash with other reinforcements and dispersoids
used in composites, to assess their relative merits as an additive to
composites. With increasing interest in using fly ash as a reinforcement and
filler in composites, the effective mechanical property contribution of fly ash
dispersions has been indirectly calculated from measurements of properties of
metal matrix-fly ash composites.

A C 1 SP-153 V O L + I 95 m O662949 05214LO b3T m
CHARACTERIZATION PROCEDURES
SDhericitv and Wall Thickness
In the present work, sphericity of particles of cenosphere fly ash was

determined by measurements of out-of-roundness. This involved measuring
the four diagonals d,, d,, d, and d4, as shown in Fig. 1. This was carried
out on optical or scanning electron micrographs of individual fly ash particles,
and in some cases, in aluminum alloy-fly ash composites. The smaller the
deviation between d,, d2, d, and å4* the higher the sphericity. As an
empirical measure, the formulae (1-3) indicate the differences in diameters
as a percent of the average diameter, and the smaller the value, the higher
will be the sphericity. Zero percent deviation indicates true sphere.
Id, - d3 ~
Deviation A = x 100%
I
Id, - d4 I
Deviation B =
-
(d2 dd
2
x 100%
Sphericity deviation = ~
(A + B) (zero percent deviation
2 (3)
Indicates true sphere)
The wall thickness of fly ash particles was also measured at four
locations on the particles at 90 degree angles, and was represented as t, , i,,
t3s and t,, as shown in Fig. 1. The average of these values was taken for
each particle. The normalized average wall thickness can also be expressed
as a percent of the average diameter of the cenosphere as shown in formulas
(4-5).
(ti t2 lg 14)
The average wall thickness i
+ + +
=
4
-
4 x 100 t
= x 100%
Wall thickness percentage = =
(d, + 4 + d, + d4) d (5)
4
(normalized with respect to diameter)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 M 0662947 0521411 576 =
462 Rohatgi et al
Densitv of Flv Ash
The density of fly ash is primarily a function of chemical composition,

crystal structure, diameter, wail thickness and porosity of particles. Two ways
were used to obtained the density of the fly ash: (i) measured by means of
AccuPyc 1330 Pycnometer; (ii) estimated theoretically following the relation
as Equation(6), if the information on the parameters are available. Assuming
the average outside diameter of a cenosphere is dout,and the average inside
diameter is 4,. We have:
where: pcenosphereis the true density of the cenospheres, m is the mass, V is

volume, do,, and 4, are the outside and inside diameters, Voutand Vi, are
the outside and interior volumes, pflyashis the true density of solid fly ash, or
the material which constitutes the solid part of fly ash.
MorDhology
The scanning electron microscope (SEM) has proved to be a very

important tool for study of size, size distribution and shape of fly ash particles
due to its high magnifying power (30,OOOX) and very large depth of focus.
Surfacecontour, topography and agglomeration or adherenceof finer particles
on the surface of larger particles can be readily revealed under SEM. As-
received fly ash particles were observed very carefully under SEM after Au-
Pd sputter coating.
Modulus
It is very difficult to directly measure the modulus of individual fly ash

particles, due to their small size. However, the effective modulus of fly ash
dispersions in different matrix materials may be indirectly calculated from the
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L U I 95 B 0 6 6 2 9 4 9 0521412 4 0 2 =
measured modulus of the composite and the matrix, the volume percentage
of fly ash and the volume percentage of the matrix, according to the rule of
the mixtures [ 7 ] :
Ecomposite = %yash'flyash + Ematrixvmatrix (7)
'flyash = Ecomposite - Ematrixvmatrix

(8)
'fly ash
where: Ecowosite is modulus of the composite, Efiy ash is modulus of the fly
ash, Emah, is modulus of the matrix, Vmhx is volume of matrix, Vflyash is
volume of fly ash.
However, the rule of mixtures expression is more appropriate for

continuous reinforcements, and it has been modified for discontinuous
reinforcements according to the Hdpin-Tsai equation 181,
where:
and s = particle aspect ratio. For spherical fly ash particles, s = 1.
By measuring the modulus of the composite, the modulus of the matrix

and the volume percentage of fly ash, the effective modulus of fly ash can be
calculated using either the rule of mixtures or the Halpin-Tsai equation.
Since the measurement of modulus of individual particle is difficult, thus
effective modulus of dispersions of fly ash in different matrix materials, can
be used to make predictions of properties of composites containing fly ash.
In fact it is this effective moåulus of fly ash dispersions, more than the
modulus of individual particles, which influences the properties of composites
containing fly ash.
RESULTS AND DISCUSSIONS
SDhericitv and Wall Thickness
The wail thickness and sphericity of cenospheres calculated as per the

procedure described before are given in Table 1. Deviations from sphericity
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0662949 0521413 349
464 Rohatgi et al
of the particles and ratios of wall thickness to diameter as a function of

cenosphere diameter are plotted in Fig. 2.
Table 1 and Fig. 2 indicate that for the cenosphere the deviations from
sphericity, and the ratios of wall thickness to diameter are less than 12% and
16% , respectively, for most of the particles. The average values of deviation
from sphericity and t/d ratio are 2.5% and 8.4%, respectively. Wall
thickness ranges from 4 to 21 pm. The tld ratio ranges from 3.1-16.0%.
In general, ehe deviation from sphericity virtually shows no obvious
relationship with the diameter of the cenospheres. The ratio of wall thickness
to diameter shows a tendency to decrease with diameter of fly ash despite the
wide scatter in the data, Le., as the cenosphere becomes larger. the ratio of
wall thickness to diameter becomes smaller. This information will be
important in calculating the properties of individual particles of fly ash,
specially their mechanical behavior..
Densitv of Flv Ash
The density of individual fly ash particles is very important since it will
directly influence the density of composites according to the rule of mixtures.
The experimental measurement shows that the density of the precipitator fly
ash (solid fly ash) ranges from 2.2 g/cc to 2.45 g/cc, the density of the
cenosphere fly ash(hol1ow fly ash) ranges from 0.45 g/cc to 0.58 glcc.
We also may do some estimation of the density of the cenospheres from

the Equation (6) if we know the density of the solid fly ash, say 2.2 g/cc.
According to Equation (6), if we take dJdout = 0.9, t/dout = 0.1 the
density of the cenosphere particle should be close to 0.596 g/cc, which is
quite close bo the experimental measurements of 0.45-0.58 g/cc. The
estimated data values are thus in conformity with the measure value of the
cenospheres. A more general cdcuîation was done by taking into account the
fraction of porosity of the wall of cenospheres which often contains spherical
cavities. The result is shown in Table 2. It I s obvious that as the ratio of the
wall thickness and outside diameter will increase, the true åensity of
individual cenosphere particle will increase; as the porosity fraction of the
wall increases, the true density of the cenosphere decreases. In general the
density of the cenosphere of the morphologies selected in Table 2 ranges from
0.28 to 0.81 g/cc.
Momhology
The SEM photographs of fly ash particles are shown in Figs. 3 and 4.
A typical collection of cenospheres are shown in Fig. 3. From many

such collections, the size of the cenosphere particles was estimated to range
from 30-250 pm. Most particles are very close to perfect spherical shape.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL81 95 Obb29Li9 0521414 285 W
Surfaces of cenospheres are generally clean and wrinkle free. No

agglomeration of the cenosphere particles were seen. From the morphology
of the broken particles, it appears that there is frequently substantial porosity
in the walls of the cenosphere particles. The porosity occurs in the walls in
form of spherical cavities of the size range from 1 to 13 ym. The broken
cenospheres particles could be formed during the process of formation,
collection, handling and sampling. This porosity in the wall of cenosphere
will influence the properties of the cenospheres and the properties of
composite materials using these cenospheres; specially density, thermal and
electrical resistance and damping property
SEM pictures of precipitator fly ash are shown in Fig. 4. It is illustrated

that the precipitator particles are finer compared to cenosphere particles,
which are in the range of 2-75pm. The surface is not clean and has a lot of
attachments, including small particles and bridges, as in Fig. 4(a). Crystals
of some unidentified phases appear on the surface of precipitator ash
particles. There are generally no broken precipitator fly ash particles which
is indication of its high strength. The cross section of the precipitator fly ash
could be seen in the polished sample of the metal matrix-fly ash composite.
Fig. 4(b) shows that the precipitator fly ash particles are not completely solid
and they also have a certain amount of porosity.
Figure 5 shows the distribution of fly ash particles in a metal matrix

composite W C ) . It I S indicated from Fig. 5(a) that some of the
cenospheres are filled with the AI alloy during the liquid state processing of
metal matrix composites. This could be due to the defects on the surface of
the wall of the cenospheres. However, for precipitator fly ash as shown in
Fig. 5(b) and 4(b), filling of fly ash particles by metal matrix is less
--``,`,-`-`,,`,,`,`,,`---
frequently found, apparently there i s less porosity and enough strength in

precipitator fly ash particles to withstand the thermal force and strain
distortion during the solidificationprocess. This character of precipitator fly
ash particles may result in improved properties of MMC such as wear
resistance and hardness [9] because the precipitator fly ash is a very hard
material. Another important factor for the properties of composites is the
bonding between the fly ash and the matrix alloy which is also related the
compounds formed at the interface between the fly ash and the Al alloy
matrix. Some of the likely reactions between the fly ash and Al alloy are as
follows :

A C 1 SP-153 V O L * I 95 m Obb2949 0523435 333 m
466 Rohatgi et al
However, the extent to which these reactions actually proceeded in the

composites were not analyzed.
Estimation of Modulus
Modulus of fly ash is one of the most important properties for the use
of fly ash in the synthesis of composites. It is difficult to measure the
modulus of individual fly ash particles due to their small size. The modulus
of fly ash is a function of chemical composition, particle size, shape and test
conditions. In the present work, the modulus of fly ash is indirectly
calculated from the measurements of modulus of composites containing fly
ash as one of the constituents.
The quantitative value of the elastic modulus is somewhat dependent on

the method of measurement, with dynamic measuring methods tending to give
larger values than static measurements obtained from the elastic portion of the
tensile stress-strain curve. Static values may also depend on whether the
measurements are made in tension or compression.
The experimental measurements of the modulus Al alloy-fly ash

composites (Ashalloy) containing different volume percentages of fly ash
( 5 % , 10% and 15%), are listed in the Table 3, According to the rule OP
mixtures (Equation 7), the modulus of' fly ash was calculated from the
measured modulus of the Ashalloy composites to be in the range of
18.6 X lo6 to 28.6 x lo6 psi (128 to 197 GPa), as shown in Table 3.
However, if one uses the Halpin-Tsai equation [8] to calculate the modulus
of fly ash, the values are in the range 20.8 x io6 psi to 44.9 X lo6 psi (137
to 310 GPa). The effective modulus of fly ash appears to decrease with
volume percentage of fly ash in the range investigated.
A comparison of the moduli of fly ash calculated from the measurement

moduli of metal matrix composites, with the moduli of other materials such
as SiO,, A1203, solid glass spheres. mullite and Sic, is given in Table 4. The
effective modulus of fly ash in metal matrix examined in the present study is
in the same range with SiO, and mullite, however, is lower than Sic and
AI20, [lo].
CornDarison of Properties of Flv Ash with Other Filler Materials or

Related Materials
Fly ash may be used as a particle filler or reinforcement in polymer

matrix composite, metal matrix composite and ceramic matrix composite.
Selected published values of chemical, physical and mechanical properties
of fly ash and other materials are listed in Table 5 and 6, and compared
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - I 1 5 3 V O L X I 95 M 0 6 6 2 9 4 9 05214Lb O58
with the properties of several fillers, reinforcements and matrix materials used
in the composites.
It is indicated in Table 5 that the main constituents of typical fly ash are
SiO,, A1,0,, F%O, and C a 0 [i]. However, the principal constituents of 3M
glass sphere are SiO,, Na,O and C a 0 [i i]. It i s shown from Table 5 that the
chemical composition of fly ash is more complex compared to the chemical
composition of glass spheres and other fillers.
Comparing the physical and mechanical properties of fly ash with other
related materials (as shown in Table 6), it 1s illustrated that the densities of
fly ash (2.1-2.6 g/cc for precipitator. 0.4.0 6 glcc for cenosphere) [IO] are
lower than most other materials except hollow glass sphere (0. 15-0.4 glcc)
[12, 131. The melting temperature of fly ash 1s generally greater than 1200
C [13] which is high enough tor it to act as a filler or reinforcement in
several nonferrous metal matrices. The estimated modulus of fly ash is also
quite high ranging from 143 to 310 GPa. which is in the same order of
magnitude as the moduli of SiO, and mullite, but lower than the moduli of
Al,O, and S i c [lo]. The thermal conductivity of fly ash IS quite low ranging
between 0.06-0.35 W/m.K [13], compared to the thermal conductivity of 3M
glass spheres [ l i ] and S i c [IO]. which are 1.5 W/m.K and 4-20 W/m.K,
respectively. This could be mainly due io the typical porous structure of fly
ash which frequently has porosity in the wall. The low thermal conductivity
of fly ash may be useful to make composites with low thermal conductivity.
The electrical resistance of fly ash is very high between the order of 109-1012
Clcm [14] similar to the electrical resistance of glass spheres [i i]. The high
electrical resistance of fly ash may be useful in making electrically insulating
composites.
Our initial studies indicate that the low density, spherical shape, low
--``,`,-`-`,,`,,`,`,,`---
cost, large volumes. hollow and porous structure of fly ash make it very
attractive for dispersion in MMC. Also the electrical, heat, and sound
insulating properties and wear resistance as well as resistance KO bulk
compression and to deformation of composites may be improved by the
distribution of fly ash particles. It is possible to make specific components
of MMC with fly ash dispersions which require high wear resistance.
However the variable composition (Table 5 ) and variable complex mineral
structure (Table 7) [i] will be the disadvantages of the fly ash as dispersions
in MMC, since it could lead to random variations in the properties of
composites. This will require establishing effective property ranges for fly ash
(as has been in this paper) and the ranges of properties expected in
composites.

A C 1 SP-153 VOLSI 95 Obb2949 0521417 T 9 4
Rohatgi e t al
CONCLUSIONS
The ratio of wall thickness to diameter for fly ash cenospheres is in the
range from 3.1 % to 16.0% The average ratio of wall thickness to
I
diameter of cenospheres is in the order of 10%. Most cenospheres are

close to perfect spherical shape with the average deviations from
sphericity of 2.5%. The spherical shape of fly ash will prove to be an
advantage in both the processing as well as the properties of the
composites containing fly ash, compared to other reinforcements and
fillers which are angular.
Compared to other particle reinforcements or fillers, fly ash is lighter

having a density of 2.1-2.6 glcc for precipitator ash, and a density of
0.4-0.6 g/cc for the cenospheres mainly due to the porosity in the preci-
pitators and the cenospheres. The lower density of fly ash, specially of
cenospheres, will be an advantage in making lighter weight composites.
The effective modulus of fly ash indirectly calculated from the

measured modulus of aluminum alloy-fly ash composites is in the range
of 140-310 GPa which is in the same order of magnitude as several
ceramics but is lower than the moduli of Sic and Alzo,.
The thermal Conductivity of fly ash is quite low, of the order of 0.06-
0.35 W/m.K compared to the thermal conductivity of other materials
such as 5-30 W/m.K for M,O, and 4-20 W1m.K for Sic. The low
thermai conductivity of fly ash will be an advantage in the synthesis of
thermally insulating composites.
The electrical resistance of fly ash is of the order of lo9-" ohm cm, and
this would be of advantage in the synthesis of electrically insulating
composites.
--``,`,-`-`,,`,,`,`,,`---
The chemical composition and structure of fly ash are variable compared
to synthetic fillers or reinforcements. This would require establishing
ranges of effective properties of fly ash and the properties that can be
expected in composites containing fly ash.
REFERENCES
Roy, D.M., Luke, K. and Diamond, S . , "Characterization of Fly Ash

and Its Reactions in Concrete, " Mat. Res. Soc. Symp. Proc., Materials
Research Society, Vol. 43, p. 3, 1985.
Findelman, R.N., "Characterization of the Inorganic Constituents in

Coal, " Fly Ash and Coal Conversion By-products: Characterization,
Utilization and Disposai II, Vol 65, MRS, p. 71, 1985.

A C 1 SP-153 V O L + I 95 m 0662949 05214L8 920 m
3. Rohatgi, P.K., Keshavaram, B.N., Asthana, R and Golden, D.M.,

"Cast Al-alloy Fly Ash Composite A Material Conserving Abrasion
Resistant Alloy, " Proceedings Ninth international Alloy Symposium,
American Coal Ash Association, Vol. 3, pp. 75-1 to 75-23, 1991.
4. Rohatgi, P.K., Keshavaram, B.N., Huang, P., Guo, R. and Golden

D.M., "Microstructure and Properties of Cast Aluminum-Fly Ash
Particle Composites, '' Proceedings Tenth International Ash Use
Symposium, American Coal Ash Association, Vol. 2, pp. 76-1 to 76-22,
1993 I
5 . Berry, E.E., Hemmings, R.T. and Leidner, J., "Investigation of Some

New Spherical Fillers. " Plastic Compounding, NovembedDecember,
p. 12, 1986.
6. Chaná, N., "SEM Observation of Fractured Fly Ash-Polyester

Composites," Journal of Materials Science Letters, Vol. 7, p. 36-38,
1988.
7. Chawla, K.K., CompositeMatenais, Science andEngineering, Springer-

Verlag, New York, 1987, p. 179.
8. Chawla, K.K. Composite Matenals, Scïence andEngineenng, Springer-

~
Verlag, New York. 1987, p. 408.
9. Huang, P. and Rohatgi, P.K., "AbrasiveWear Behavior of Al Alloy-Fly

Ash Composites," to be published in Proceedings: ASTM Conference,
Chicago, 1994.
10. Lloyd, D.J., "Particle Reinforced Aluminum and Magnesium Matrix

Composites," International Marerials Revìews, 1994, 39, No. 1, p. 1.
11. User's Menu of 3M Products.
12. Cheremisinoff, P., "Coal Fly Ash: Power Plant Waste or By-product?"
Power Engineering, July, 1988, p. 40.
13. Keeffe, J., "The Use of Cenosphere in Composite Materials," Ash Tech
'84, p. 86.
14. Environmental Protection Agency, "A Technique for Predicting Fly Ash
Resistivity, " Interagency Energy/EnvironmentR & D Program Report,
August, 1979.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOL*I 95 D 0662949 0521419 867 D
470 Rohatgi et al
TABLE 1 - DIAMETER, WALL THICKNESS, DEVIATION FROM

SPHERICITY, AND RATIO OF WALL THICKNESS TO DIAMETER OF
FLY ASH CENOSPHERES
pee - 1 .
i E
--``,`,-`-`,,`,,`,`,,`---
4 h 5 t t
run run
- run em lun
-
156 I56 156 156 I56 22 21 22 19 21
99 98 100 100 99 II 13 6 2 8
131 I22 1 I3 III I I9 33 20 11 II 19
67 68 61 67 67 Il IO 9 3 8
100 103 100 100 101 6 4 2 5 4
106 103 101 106 104 3 6 6 1 4
100 106 103 95 101 6 3 6 1 4
84 89 86 88 87 5 3 11 7 7
77 12 I2 72 73 6 6 7 3 6
39 40 39 39 39 6 9 II 11 9
102 105 102 105 104 I 7 7 7 I
70 68 68 68 61 3 5 4 5 4
55 55 54 55 55 5 5 2 3 4
47 48 46 48 47 7 5 5 5 6
109 111 I10 109 I10 Il II 4 7 8
---- --
98
85
97
86
III
85
III
84
104
85
1
2 3
1 5
6
1
6
4
4
-
3p iI II
Averwe: 89 7.5
-
TABLE 2 - THEORETICAL ESTIMATION OF DENSITY OF

CENOSPHERES
Ratio of Wall Density Porosity Density of

di,
- Thickness of in Cenosphere
do,,
and Outside Fly Ash the Waii g/w
Diameter g/w %
0.95 0.05 2.2 O 0.313

0.90 o. 10 O. 596
O. 85 O. 15 O. 848
0.95 0.05 2.0 O 0.285
0.90 o. 10 0.542
0.85 O. 15 0.771
0.95 0.05 2.2 5 O. 297

0.90 o. 10 0.566
O. 85 O. 15 0.806

A C 1 SP-153 VOL*I 95 m Obb2949 0523420 589 m
TABLE 3 - MODULUS OF AL ALLOY-FLY ASH COMPOSITES AND

FLY ASH
P
Composite Emapix> Efl sh, sh,
x10 psi xid'psi x1B'psi
A356-5% fly ash I 11.5 I 10.6 I 28.6 I 44.9
A356-10% fly ash 11.4 10.6 18.6 20.9

A356-15% fly ash 11.8 10.6 15.5 20.8
TABLE 4 - COMPARISON OF EFFECTIVE MODULUS OF FLY ASH

WITH OTHER MATERIALS
1 Materials I Modulus, psi

~
(GPa) --``,`,-`-`,,`,,`,`,,`---
SiO, 13.6 X lo6 (94)

56 X IO6 (390)
Solid glass sphere 10 x 106 (69)
Mullite 31 x lo6 (215)
61 x lo6 (4201
Fly ash 20.8-44.9 X lo6 (143-310)
'Calculated from metal matrix composites by Halpin-Tsai equation.

A C 1 SP-153 VOLrI 95 = 0662999 O523921 415 W
472 Rohatgi et al
TABLE 5 - CHEMICAL COMPOSITION OF FLY ASH AND GLASS

SPHERE, W., PERCENT
TABLE 6 - PHYSICAL AND MECHANICAL PROPERTIES OF FLY ASH

AND OTHER MATERIALS
Thermal
True
Density
fw
Melting
Point
'C
Poisson's
Ratio 1 Modulus
GPa 1 Conducîivity
IR%=" Electrical
Fly Ash
0.06-0.16
A20' I 3.9 I 2250
sic 3.2
II
I
420 I
I
'Od
4-2d
I
l
lo00
SiO, 2.6 1580' 94 I

Mullite 3.2 1850 0.25 I 140 I c5.9 I
Glass-sphere (3M) 589'
I 1:; I
Hollow 0.15-0.4
Solid 2.45-2.5
SWnGiass 0.23 I
I
60-70 I
I I
2.5 X lo6
at 250 O C
0.33 I 69-79 I 237 I 3.15X10-6
--``,`,-`-`,,`,,`,`,,`---
'soft point
%ingle crystal
'Polycrystal
4Maximum service temperature

A C 1 SP-153 V O L + I 75 I0662947 0523422 351 M
Items Compositions
Mullite 3A1,03.2Si0,
Quartz si02
Magnetite-ferrite Fe@, - (Mg,Fe)(Fe,Mg),O4
Hematite Fe203
--``,`,-`-`,,`,,`,`,,`---
Anhydrite CaSO,
Class C fly ash primary crystalline phases

Items I Comaositions
Militate Ca,Mg,A1(Si207)
(gehlenite-akermanite)
Ferrite spinel (Mg~Fe)(Fe,M&04
Merwinite Ca3Mg(SiO&
Bredigite, iarnïte Ca2Si O, ~
Lime Ca0
* Cement nomenclature: C=CaO, A=Al,03, S=SiO,, S = S 0 3

474 Rohatgi et al
--``,`,-`-`,,`,,`,`,,`---
Fig. l-Sphericity and wall thickness

measurements on fly ash cenospheres
[Eq. (1) through (5) in text]

A C 1 SP-353 V O L X I 95
No reproduction or networking permitted without license from IHS 0662949 0523423 298
Not for Resale m
A C 1 SP-353 VOLSI 95 I0 6 6 2 9 4 9 0523424 124 I
20 40 60 80 100 120 140 160
Cenosphere diameter, pm
(a)
--``,`,-`-`,,`,,`,`,,`---
20 40 60 80 100 120 140 160
Cenosphere diameter, pn
(b)
Fig. 2-(a) Variation of sphericity deviation as

function of cenosphere diameter; (b) variation of
ratio of wall thickness to diameter as function
of cenosphere diameter

A C 1 SP-153 V O L S I 95 Ob62947 0523425 Ob0
476 Rohatgi et al
--``,`,-`-`,,`,,`,`,,`---
Fig. M r o s s section of cenospheres: (a) broken

cenospheres; (b) porosity in wall of cenospheres

A C 1 SP-153 V O L X I 95 = 0662949 052142b TT7
--``,`,-`-`,,`,,`,`,,`---
Fig. 4-SEM photomicrographs of fly ash

precipitators: (a) whole view; (b) cross
section in metal matrix-fly ash composite
A C 1 SP-153 VOL*I 95 0662949 0523427 933
478 Rohatgi et al
Fig. +Fly ash particles in Al-alloy matrix-fly ash composite:

(a) intersection of cenospheres, some cenospheres filled
with metal; (b) SEM photograph of fly ash on fracture surface
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 Obb2949 0521428 8 ï T
SP 153-27
Comparative Testing of PortIand

Cement, Fly Ash, Ground Granulated
Blast Furnace Slag and Silica Fume
Concretes for Potential Durability
by P. C. Taylor, P. E. Streicher, G. Goch, and L. Fliss
Synopsis: A test programme was conducted to establish criteria for a

performance based specification of concrete quality, as opposed to a prescriptive
specification, for a major project in South Africa.
Concretes containing different combinations of portland cement, fly ash, ground

granulated blastfurnace slag and silica fume were prepared over a range of
waterbinder (W/Cm) ratios. The samples were stored in water for three days
to simulate the probable effects of site curing practice. Each concrete was then
subjected to three different tests: air permeability and water sorptivity, both
conducted in an "Autoclam", and a rapid chloride conductivity test.
Time constraints prevented the preparation of a performance specification, but

the results were used to prescribe a W/Cm ratio and binder type. The results of
the investigation also provide the basis for future evaluation of the site concrete
by conducting similar tests on cores extracted from the smcture.
It was established that specifying only on the basis of concrete strength is

insufficient to ensure a high potential durability.
--``,`,-`-`,,`,,`,`,,`---
Keywords: Blast furnace slag; chlorides; conductivity; diffusivity;

durability; fly ash; permeability; silica fume; specifications; &
&

A C 1 S P - 1 5 3 V O L * I 95 = Obb2949 0523429 706 W
480 Taylor et al
Peter Taylor is an Engineer at the Portland Cement Institute in South Africa and
a graduate of the University of Cape Town. His current research interests are
in the measurement and specification of durable concrete. His doctoral thesis
(in preparation) is on the topic of fatigue mechanisms in mortars containing fly
ash.
Pieter Streicher is a postgraduate student at the University of Cape Town, South

Africa. He received his BSc degree from the University of the Witwatersrand.
His research activities are in the fields of chloride diffusion through concrete,
and rapid chloride test methods.
Gregory Goch is an area manager on Alusaf's R7 billion Hillside Smelter project
--``,`,-`-`,,`,,`,`,,`---
presently under construction. He has a BSc (Civil Engineering) from the
University of Cape Town and has completed a management development
programme (Project Management) from UNISA. He has been involved in the
problem of concrete spalling at Alusaf since 1986.
Lyonelì Fiiss is chief civil engineer with Engineering Management Services in

Johannesburg, South Africa. He received his MSc degree from the Institute of
Civil Engineering of Bucharest. His activities are mainly in the areas of
reinforced concrete structures and concrete technology for industrial
developments.
INTRODUCIION
Those involved in the specification, construction and supervision of structural

concrete are increasingly aware of the need for specifications that are
performance based rather than simply prescriptive.(1) There is a need to be able
to demand a durable concrete, and assess whether that demand has been met,
rather than to lay down guidelines for methods and materials and hope that they
are not abused.
It was with this view that a test programme was carried out to establish
performance criteria for a major new smelter project in South Africa in which
durability, and in particular resistance to chloride attack, was essential. A
variety of concretes were prepared using several binders over a range of
waterbinder (W/Cm) ratios. Each combination was then subjected to several
durability indicator tests, and the data used to generate families of curves of
"durability index" versus W/Cm.
This paper describes the concretes that were made, the work that was carried out
on them, and presents the results and conclusions drawn.

A C 1 SP-153 V O L X I 95 O662949 0521430 428 =
MATERIALS
A number of concretes were made using a fine river sand, a 19-mm granite stone
and Lhe following binders:
normal portland cement (Type I)(OPC),
rapid hardening portland cement (Type III)(RHPC),
ground granulated blastfumace slag (GGBS),
fly ash (Type FWA),
and silica fume in slurry form (SFS) and powder form (SFP).
Properties of the materials are given in Tables 1 and 2.
A matrix of 24 mixtures was made using six binder combinations, as shown in

Table 3, each at four W/Cm ratios of 0,40,0,46, 0,5 and 056. The fist four
mixtures (OPC, OPCFA, OPC/GGBS, OPC/SFS) were selected as reasonable
combinations of the binders freely available in South Africa. An
OPC/GGBS/SFS mixture was tested to evaluate the combined impermeability of
silica fume concretes and the apparent chloride binding ability of slag. A
RHPC/GGBS mixme was tested to compensate for the slow rate of cementing
reaction of the 50/50 OPC/GGBS blend.
A single mixture (OPUSFP) was made, at W/Cm = 0,46, using silica fume in
powder form along with a plasticiser, in order to observe if there was any
difference in the potential durability as a result of using silica fume in slurry or
in powder form.
Proportions were selected on the basis of achieving similar workabilities (slump

75 I 25 mm) and are given in Table 4. The water contents were not the same,
and the OPC/SFS and OPC/SFP mixes were the only ones that contained a
plasticiser. This was considered preferable to using mixtures with similar water
contents but a wide range in consistence.
SAMPLE PREF'ARATiON
100-mm cube samples for the different tests were preparexi as described below
from 20 litre concrete batches made in a pan mixer.
After casting, all of the cubes were stored in a chamber with 90% relative
--``,`,-`-`,,`,,`,`,,`---
humidity at 23°C until they were demoulded the 5 - l ' -wing day.
Cubes for compressive strength testing were cured, after demoulding, in lime
saturated water at 23 "C until they were tested.

A C 1 S P - 1 5 3 V O L * I 95 = 0662949 0521431 3 6 4
482 Taylor et al
Cubes for durability testing (Autoclam(2) and chloride conductivity(3)) were

demoulded after one day and placed into lime saturated water at 23 “C for a
further two days. This regime, equivalent to approximately three days of water
curing, was selected on the basis that it would simulate the effects of site
practice.
The samples to be iised in the Autoclam were then epoxy coated on four faces
such that two opposite faces were left exposed, and placed in a drying oven at
a temperature of 50 f 5 “C for at least seven days.
One core was drilled from each of the cubes for chloride conductivity testing,
and each core was cut into three discs, two from the cast faces and one from the
centre. The discs were approximately 30 mm thick and 68 mm in diameter.
They were placed in the oven for at least seven days. The initial tests were
inconclusive and further discs for repeat tests of the OPC, OPC/FA, OPC/GGBS
and OPC/SFS mixes were cut from the cubes already used for some of the
Autoclam tests (air-permeability), and re-conditioned in the oven. These discs
were therefore approximately four weeks old before they were cut from the
cubes. in contrast, the OPC/GGBS/SFS and RHPC/GGBS discs had been cut
from the cubes after three days. The implications of this difference in age are
covered in the discussion.
TESTS
The compressive strength of the concretes was determined by means of crushing

sets of cubes at seven and 28 days.
Three different tests were used to provide a measure of potential durability as

follows.
The first test was the measurement of air permeability by means of measuring a
falling head from an initially applied 500-mbar head in the Autoclam. The
change in Fressure, plotted on a log scale against time, gave a straight line, the
slope of which (in log(nbar)/minute) provided an index of air permeability.
The second test was the determination of water sorptivity (ie, the rate of water
absorption) by means of measuring the volume of water drawn into the sample
under a nominal head of 20 mbar, also using the Autoclam. The volume of water
absorbed, plotted against the square root of time, gave a straight line, the slope
(in m3/minute”) of which provided an index of sorptivity.
The third test was for assessing the chloride diffusivity of the concretes by the
rapid determination of the conductivity of pre-saturated samples. The test was
based on the principle that the rate of diffusion is proportional to the conduction
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 0662949 0523432 2 T O
under an imposed elecmc potential. The theoretical basis and validation of this
principle may be found in reference 3. The test, using a system devised at the
University of Cape Town(3) and derived from the Dundee University test(4),
consisted of presaturating a disc-shaped sample in 2,5 molar calcium chloride
solution in a low-grade vacuum for a period of eight hours. The sample was
then secured in a cell (Fig. i) with 2,5 molar calcium chloride solution at each
face. A potential difference of 10 volts was applied across the specimen, and the
current and the voltage in the solutions were recorded. The current, normalised
for the voltage and the specimen thickness, gave an index of the chloride
conductivity of the concrete.
RESULTS
The cube strengths of the various concretes at seven and 28 days are given in
Fig. 2,3.
The air permeability results are shown in Fig. 4. Limits of "very good',"good',
"poor" and "very poor", based on values given in reference 2, are marked on the
figure.
The tests for water sorptivity are summarised in Fig. 5 . Limits are from
reference 2.
Chloride conductivity test results are given in Fig. 6,7. Fig. 6 gives results from
discs cut from the scïfaces of the cubes. The results in Fig. 7 relate to discs
from the centre of the cubes, which had effectively 30-mm cover during the
period before they were cut from the cubes.
All of the results of the single OPC/SFP mixture were very similar to those of
the equivalent OPC/SFS concrete, showing that there was no significant
difference between the two forms of silica fume in terns of potential durability.
DISCUSSION
The air permeability results indicated that the OPC/FA and OPC/GGBS blends
were adversely effected by the poor curing that they received. The plots of the
other four blends flattened out at W/Cm ratios of 0,46 and below. The OPC/SFS
blend was relatively unaffected by changes in W/Cm.
For the sorptivity tests, only the OPC at W/Cm = 0,4 gave a result that was
bettier than "very poor". It is probable that this was due to the poor curing,
particularly for the OPC/GGBS blend.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 V O L X I 95 = Ob62949 0523433 337
484 Taylor et al
--``,`,-`-`,,`,,`,`,,`---
In the chloride conductivity tests, the OPC/SFS mixture outperformed the other
blends, the OPC/GGBS/SFS mixture proved disappointing and there was little
difference between the other mixtures.
The chloride conductivity of the internal discs was lower than that of the external
for the OPC, OPC/FA, OPC/GGBS and OPC/SFS samples, indicating that the
protection given by the cover concrete was beneficial. The OPC/GGBS showed
the greatest difference between the external and internal slices. This was
probably due to the inner slices continuing to hydrate in the period before the
samples were cored and sliced, whilst the outer slices had dried out. i n the case
of the OPC/GGBS/SFS and RHPC/GGBS samples, the discs were cut out after
only three days under water, and so there was only a short period of protection
and accordingly little difference between the external and internal slices. This
supports the concept that curing only affects the "covercrete" (3, or the outer
layer of a concrete which is roughly the same depth as the distance from the
surface to the steel.
A different curing regime would probably have resulted in a different ranking of

the various binders. Ideally a more extensive test programme should be carried
out to c o n f i this. The selection of a binder would then also be influenced by
its relative cost against the cost of additional curing.
Fig. 8 to 10 show the durability index results plotted against strength instead of
against W/Cm. They show that if a concrete is specified simply on the basis of
strength, there could be a wide range in potential durability. For example, 50
MPa concrete using txe OPC/GGBS mixture would be potentially less durable,
in terms of air permeability, than the OPC mixture of the same strength.
However in terms of chloride conductivity it would be more durable, which
agrees with other published work.(ó)
The durability index plots, against W/Cm, provide the basis of specifying the
performance of a concrete, with limits set from laboratory trials using the site
materiais proposed. The mals should also take into account the type and amount
of curing to be carried out because differing curing regimes may influence the
selection of binder types. The site concrete could be monitored by the testing of
samples cored from the in situ concrete. Should the samples fail, then the
contractor wodd have the choice of applying extra curing (which may or may
not be effective;, or repiacing the concrete under consideration. Additionally, the
onus is then placed on the contractor to select binder type, binder content and
curing regime to meet the requirements, and on the basis of cost and his
experience.

A C 1 SP-153 VOL+I 95 = 0662949 0 5 2 3 4 3 4 073 M
CONCLUSIONS
The following conclusions can be drawn:
Test methods are available to act as the basis for writing performance
specifications.
Effective early curing contributes markedly to potential durability of the
covercrete.
Silica fume enhances the durability of concrete, by making the concrete
less permeable in general and more resistant to the passage of chlorides
in particular.
Differences between concrete made with silica fume in slurry or densified
powdered form are not measurable by the techniques used in this test
programme.
Thanks go to ALUSAF and ALPROM (Pty) Ltd for the vision to initiate and
sponsor this work, and for permission to publish this paper. Thanks also to
University of Cape Town, Department of Civil Engineering for the chloride
conductivity rig design, and Portland Cement Institute for the backing in carrying
out the work.
REFERENCES
--``,`,-`-`,,`,,`,`,,`---
1. Armaghani J.M. and Bloomquist, D.G. Durability specification and ratings

. gs of the International Conferenœ,
for concrete, Concrete 2000, proceedui
Dundee, Scotland, Sept.1992, vol.1, pp.23-36.
2. Basheer, P.A.M. A brief review of methods for measuring the permeation

properties of concrete in situ. proceedings of the Institution of C i d
Engineers: Strucaires & Buildings, Feb.1993, vo1.99, pp.74-83.
3. Streicher, P.E. and Alexander, M.G. A critical evaluation of chloride

diffusion test methods for concrete, 3rd Internationai conference on the
durability of concrete, Nice, France, CANMET/ACI, 1994.
4. Dhir, R.K. et al. Rapid estimation of chloride diffusion coefficient in

concrete, MagazineofConmteResearch,Sept.1990,no.152,pp.177-185.

A C 1 SP-153 VOLL1 95 0662949 0523435 T O T D
486 Taylor et ai
5. Dhir, R.K.,Jones, M.R., Green, J.W., Protection of Structural Concrete,

Protection of concrete, Pmceedm . gs of the International &nfen=aœ,
Dundee, Scotland, Sept.1990, pp.331-346.
6. Peters, A.G.E. A comparison of permeability characteristics of blended

cement mixes for marine exposure conditions in the Cape Town area,
Advanced concrete Technology Course: Individual pmject, Cape Town:
Portland Cement Institute, 1993.
TABLE 1 - MATERIAL PROPERTIES-CEMENTS AND EXTENDERS

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*I 75 m 0662747 0523436 746 m
River sand Granite stone
26,5 mm 100
19,O mm
-
79
13,2 mm 4
I 935 I 1
6,7 mm
4750 pm
600 pm 97
300 pm 58
150 pm 5
75 pm 13 03
Fineness modulus 1,41
- Relative density 2,66 2,63

Loose bulk 1380 1360
density (kg/m3)
Compacted b u k 1530 1450
density (ks/m3)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 IObb2949 0523437 8 8 2
488 Taylor et al
TABLE 3 - BINDER COMBINATIONS
(sluny powder
form) with
plastic-
ox I loo I I I I I
OPWA 70 30
OPCKiGBS 50 50
OPUSFS 94 6
OPUGGBS/SFS 70 25 5
RHF'UGGBS 70
OPUSFP 94 6
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 Ob62949 052LL-138 7 1 9
TABLE 4 - MIXTURE PROPORTIONS

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 I0662947 0523439 655
490 Taylor et al
TABLE 4 (CONT’D.) - MIXTURE PROPORTIONS
1OV DC power source

I
--``,`,-`-`,,`,,`,`,,`---
A I
Rubber collar
2,5M CaCI, solutio 2,5M CaCi, solution
Fig. l-Layout of chloride conductivity test rig (section)

A C 1 SP-153 VOL*I 75 IOb62947 0521440 377
I
50
30
20
10 I I I I I I I
0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 C 56
W/Cm
--``,`,-`-`,,`,,`,`,,`---
-m- OPC
--a- OPC/SFS
-- OPCIFA
RHPC/GGBS
-)t OPC/GGBS
+-OPC/GGBS/SFS
Fig. 2-7-day compressive strength results
-
-8-
OPC
OPC/SFS
-- OPC/FA
RHPC/GGBS
* OPC/GGES
-t OPC/GGBS/SFS
Fig. 3-28-day compressive strength results

A C 1 SP-153 VOL*I 95 m 0662949 0521441 203 m
492 Taylor et al
1.6
1.4
1.2
C
.E
.1.0
h
% 0.8
II
E
0.6
0.4
0.2
0.0
0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 0.56
--``,`,-`-`,,`,,`,`,,`---
w/c
-
++
OPC
OPC/SFS
- OPC/FA
+RHPC/GGBS
- OPC/GGBS
+OPC/GGBS/SFS
Fig. &Air permeability results

1.2E-06
I .I E-06
1 .OE-O6
7 9.OE-07
'
v
C
8.OE-07
Eo 7.OE-07
6.OE-07
5.OE-07
4.OE-07
3.OE-07
0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 0.56
W/Cm
-
-E-
OPC
OPC/SFS
- OPC/FA
+RHPC/GGBS
* OPC/GGBS
+OPC/GGBS/SFS
-
Fig. >Water sorptivity results

A C 1 SP-I153 V O L X I 95 Obb2949 0 5 2 3 4 4 2 3 4 T W
W/Cm
-
++ OPC/SFS
OPC -
-t
OPC/FA
RHPC/GGBS
* OPC/GGBS
+OPC/GGBS/SFS
Fig. &-Chloride conductivity results for external samples
180
160
140
120
E 100
U
E 80
60
40
20
O
0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 0.56
W/Cm
-
* OPC/SFS
OPC ++ OPC/FA
+ RHPC/GGBS
* OPC/GGBS
+OPC/GGBS/SFS
Fig. 7-Chloride conductivity results for internal samples
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 = Obb2949 0523443 O86 =
494 Taylor et al
I .6
1.4
1.2
.E 1.0
E
2
m 0.8
a
E
v
-
c 0.6
0.4
0.2
0.0
30 35 40 45 50 55 60 65 70 75 80
28 day strength (MPa)
-
-e-
OPC
OPC/SFS
-
-+-
OPC/FA
RHPC/GGBS
++ OPC/GGBS
-t OPC/GGBS/CFS
Fig. &Air permeability results plotted against strength
1.2E-06
1 .I E-06
-
r!
1 .OE-O6
9.OE-07
l-
Y
8.OE-07
'SI 7.OE-07
m
<
E 6.OE-07
5.OE-07
4.OE-07
3.OE-07
30 35 40 45 50 55 60 65 70 75 t
- OPC
OPC/SFS
OPC/FA
-)lt
+ RHPC/GGBS
-OPC/GGBS
+OPC/GGBS/SFS
Fig. %Water sorptivity results plotted against strength
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I 95 I0662949 0523444 T L 2
180
160
140
120
aE" 100
E
80
60
40
--``,`,-`-`,,`,,`,`,,`---
20
30 35 40 45 50 55 60 65 70 75 80
- OPC
-8- OPC/SFS
OPC/FA
-++
+ RHPC/GGBS
* OPC/GGBS
-+OPC/GGBS/SFS
Fig. 1M h l o r i d e conductivity (external) plotted against strength

A C 1 SP-153 VOL*I 95 W Ob62949 0523445 959 W
SP 153-28
--``,`,-`-`,,`,,`,`,,`---
Heat Treatment of Fine-Grained

Cementless Concrete Based on
High-Calcium Fly Ash and Slag
from Thermal Power Plants
by S. I. Pavlenko
SvnoDsis: Cementless fine-grained concrete based on

high-calcium fly ash and slag from thermal power plants
was developed by the Siberian Metallurgical Institute in
1990.
This paper presents the results of a study of

schedules of heat treatment of the cementless concrete
aimed at the improvement of the quality and durability
of concrete.
Prior to heat treatment, concrete was cured for 12,
6 , and 3 hours at 60, 80, and 100°C. The temperature rise
and cooling took 3 hours each. This cycle was provided
by an automatic steam-curing chamber.
After moist curing at high temperature using the
above cycle, the specimens were tested for compressive
strength immediately after c o o l i n g to room temperature
and at the age of 28 days.
I t was found that the temperature of the isothermal
heating should be in the range of 80 to 100°C. The best
results were obtained with 100°C, though i t is difficult
to achieve this temperature, especially in cast in-place
construction: besides, i t demands great amount of an
electric energy. Therefore, 8 O - 9 O 0 C should be acceptable
as the optimum temperature range. The optimum time of
the isothermal heating is 9 to 1 2 hours. However, the
computer processing of the results of the investigation
showed that the optimum time of curing was 6 to 7 hours.
The technology and recommendations for heating of
cementless slag ash concrete, by means of heating wires
used in the construction of low-rise houses both in
summer and winter periods, have been developed.
Kewords: Curing; durability; flv ash; heating; moist curing; slags;

thermal gradient

A C 1 SP-L53 V O L M I 95 m 0 6 6 2 9 4 9 0521446 895 m
498 Pavlenko
‘Professor of the department of Civil Engineering,

Siberian State Mining and Metallurgical Academy,
academic adviser of the Russian Engineering Academy
INTRODUCTION
Results of the research of the optimum time and

temperature conditions f o r heat treatment of fine-
grained cementless slag ash concrete (SAC), carried out
by the Department of Civil Engineering of the Siberian
Metallurgical Institute, are presented in this paper.
High-calcium ash ( 1 , 2 ) has good binding properties,
but i t affects concrete adversely in the presence of
free calcium oxide (irregular volume change in the
presence o f moisture in concrete ) . This drawback can be
eliminated by binding free lime with silica fume at
specified temperatures.
Previous investigations ( 3 , 4 ) showed that the best
results of binding of free lime in a cementless concrete
was obtained by double heat treatment of its components:
by hot water (60 to 8 0 ° C ) while making concrete mixture,
and by heating the concrete after placing and compacting
at 8 0 to 90°C according to the methods given below.
--``,`,-`-`,,`,,`,`,,`---
Optimum composition of the cementless fine-grained

SAC was determined in a laboratory. The components of
the concrete were by-products from a thermal power plant
( T P P ) and a ferroalloy plant. These were high-calcium
ash from the Novosibirskaya TPP-3, slag sand with a
particle size distribution of O to 5 mm from the same
source, and silica fume. Natural o r artificial coarse
aggregates were not used. Methods o f heat treatment,
providing the binding of free calcium oxide by silica
fume into cementitious materials, and to accelerate the
hardening of concrete, in construction of cast in-place
apartment buildings were studied on the optimum
composition of the concrete developed.
MATER IALS
The concrete mixtures were made in a laboratory of

the Institute using the following materials.
Fly Ash
The fly ash from the Novosibiskaya TPP-3 was a fine-
dispersed powder of light brown color. The average
characteristics of the fly ash were determined by a
computer using 120 samples of ash taken at a different

A C 1 SP-153 VOL*I 95 = 0662947 05211447 721
time during charging of ash into a motor transport. Its

physical properties and chemical analysis are given in
Tables 1 and 2.
To evaluate binding properties of the high-calcium
fly ash produced by burning of brown coals, the Siberian
Zone Research Institute of the Experimental Design
(SibZNIIEP) suggested the use of coefficient of quality
according to GOST 3 7 4 6 - 8 4 ( 5 ) :
CaO+Al,03+Mg0
C
@
'
sío2
Ash having C 2 1 has good binding properties.

--``,`,-`-`,,`,,`,`,,`---
According to the aberage data (Table 2 ) , Cq was 1 . 5 1 , and

according to the chemical analysis of the sample used in
this investigation, i t was 1 . 4 8 (Table 3 ) .
Granulated Slag
Granulated slag from the Novosibirskaya TPP-3
consists of glossy particles mostly black in color and
having uneven edges. The fineness modulus of the slag
was 3 . 7 - 3 . 8 which is an equivalent to a coarse sand.
Its physical properties and chemical analysis are given
in Table 3 . To improve the physical characteristics of
the slag ( to eliminate microcracks produced by
granulation, to reduce the fineness modulus and to
break-up agglomerated particles ) i t i s advisable to
grind the slag in a roller-crusher. In this study, the
slag sand with the fineness modulus of 2 . 7 ( instead of
3 . 8 ) and with a particle size distribution of O to 5 mm
( medium sands for concretes ) was used.
A s can be seen from Table 3 , the granulated slag.

compared t o the fly ash, had a higher contents of
silicon oxide ( by 6 P, ) and iron oxides ( by 6 X ) but
a lower content of total calcium oxide (by l o % ) , and i t
contained negligible amounts of free calcium oxides
( O . S 3 % ) , sulfur trioxide ( 0 . 5 9 % ) and unburnt particles
of coal (0.51%). The chemical analysis shows that the
ash and the slag can be used in concrete.
X-ray analysis o f the granulated slag showed the
prevalence in i t of a X-ray amorphous substance and a
small content of a quartz with various impurities.
Silica Fume
Silica fume i s a waste product o f the Kuznetsky
Ferroalloy Plant ( about 1 2 0 0 0 tons are collected per
year 1 . Its characteristics are given in Table 3 . I t i s

A C 1 SP-153 VOL*I 95 = 0662949 0521448 668
500 Pavlenko
a superdispersed powder of a light grey color. mostly in

the amorphous state. I t becomes hydraulically active
when mixed with lime. Testing f o r the hydraulic activity
at 85'C ( 102 mg/g Ca0 ) showed that the active free
silica available from this silica fume with the free
lime present in the high-calcium ash from the
Novosibirskaya TPP-3.
OPTIMUM COMPOSITION OF
CEMENTLESS FINE-GRAINED SAC
The design of mixture was determined experimentally

on the basis of previous investigations (3, 4. 5 ) .
Mixture Proportions
High-calcium ash and silica fume were used as
cementitious materials and slag sand was taken as fine
aggregates. The slag sand content in the combination of
cementitious materials plus slag sand was in the range
of 3 0 . 4 0 , S O and 6 0 /ó by weight of a dry mixture, and
the silica fume content in the cementitious materials
(ash plus silica fume) was in the range of O , 1 0 , 2 0 ,
3 0 , 4 0 and 50%.
3 6 preliminary mixture proportions were used. The

temperature of the mixing water was +60°C. The mixtures
were made in a laboratory rotary-drum mixer. Cube
specimens, 7 0 x 70 x 7 0 mm in size, were cured foi- 6
hours in the laboratory at 20°C and then placed in the
laboratory steam-curing chamber where they were cured at
60°C using the 3 + 6 + 3 hours cycle (heating + holding
+ cooling cycle).
The data on the compressive strength and density of
concrete a r e given in Fig.1.
After processing of these data, i t was found that
the optimum mixture proportions f o r the fine-grained
cementless SAC( eased upon high compressive strength at
the 28-day age) were as fo l o w s :
fly ash - ? 2 1 kg/ml, f
slag sand - 7 2 1 kg/ml,
silica fume - 160 kg/m,
water - 2 9 2 kg/ml.
Further testing was conducted using these mixture
proportions, Table 4.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 Obb2949 052LYi19 5 T 4
EFFECT OF HEAT TREATMENT SCHEDULE

ON PHYSICO-MECHANICAL PROPERTIES OF CONCRETE
The schedule o f the experiment, Table 4 , was as

follows: curing before heat treatment for 3 , 6 and 12
hours, temperature rise period of 3 hours, isothermal
curing f o r 6, 9 and 1 2 hours, and cooling period of 3
hours. The temperature of the isothermal curing was 6 0 ,
80 and 1 0 0 ° C .
The effects of 2 7 schedules ( 3 x 3 x 3 ) of the heat

treatment on a compressive strength and density of
concrete were investigated. The specimens were tested
for the compressive strength and density in three
periods: after heat treatment when cooled to a room
temperature (24 h), at 7 and 28 days.
A summary of the test results is given in Table 4
and the compressive strength of concrete at different
schedules of heat treatment are given in Figs 2 to 6 .
DISCUSSION
A s can be observed from the data given in Table 4
and Figs. 2 to 10, the optimum temperature for the
isothermal heating of the cementless fine-grained SAC
was in the range of + 8 0 to 1 0 0 ° C . The best results were
obtained at 100°C. However, to obtain this temperature
on a construction site is a difficult and expensive
task. Besides, this high temperature affects hardening
only during the first 2 4 hours. At 7 days and especially
at 28 days, the strength development slows down. I t is
more economical to heat concrete at 8 O o C . This
--``,`,-`-`,,`,,`,`,,`---
temperature was used in the construction of a cast in-

place 6-storey apartment buildings using the cementless
fine-grained S A C .
The optimum time of the isothermal heating at 8OoC
was 9 hours. An increase in the time of heating gave
some strength gain but with a 3 3 % increase in the cost
of energy. Six hours curing of the SAC before heat
treatment generally provided optimum results.
The results of the investigation of physico-

mechanical and deformation properties o f the cementless
fine-grained concrete for a 1-year period show that the
concrete made from these industrial by-products and the
technology of its mixing, placing and heat treatment
produced satisfactory performance.

A C 1 S P - I 5 3 VOL*I 95 = O662949 0521450 216
502 Pavlenko
CONCLUSIONS
1 . High-calcium fly ash produced by burning brown coals

of KATEC had good binding properties and can be used in
the production of the cementless fine-grained SAC of the
strength classes of 5 to 20 MPa for the construction of
single, two-storey buildings.
2 . The optimum silica fume content introduced into
concrete for binding free lime and improving other
properties o f concrete was in the range of 2 0 X of the
ash content.
3 . The slag sand content was 4 0 to 50% by the weight of
the blended cementitious materials which provided the
maximum strength of the S A C . Grains of the slag sand
were floating and they, in the main, compensated for
internal stresses arisen in the process of hydration of
the cementitious materials and at high temperature of
heat treatment of concrete.
4 . T o achieve high efficiency and eliminate an irregular
volume change of concrete, double heat treatment is
advisable: the first heat treatment is provided by using
hot mixing water (60 t o 8 O o C ) and the second one is
performed in the structural elements ( e.g., by means of
heating insulated wires in cast in-placr structure o r by
heating units in precast structures ) .
5 . The desirable heat treatment schedule for concrete in
structures was a s follows: previous curing after casting
befaïe heat treatment of 6 hours, rise of temperature
for 3 hours, isothermal curing f o r 9 hours and three
hours cooling.
6 . Silica fume should be fed into a concrete mixer a s an
aqueous emulsion.
ACKNOWLEDGEMENTS
The author would like to thank professors

B.A.Krylov, A.V.Lagodina, S.D.Vitko, the Laboratory of
Accelerated Hardening of Concrete, NIIZhB, Gosstroy of
Russia, for their help in the development o f the heat
treatment schedule for cementless fine-grained SAC.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 m Ob62747 0523453 152 m
--``,`,-`-`,,`,,`,`,,`---
REFERENCES
1. Savinkina, M.A., and Logvinenko, A.T., "Ashes
Produced from the Kansko-Achinsky Brown Coal",
Novosibirsk, Nauka, 1 9 7 9 , p.83.
2. Papayianni, I., High-Calcium Fly Ash Grants",
I'
Concrete 2 0 0 0 , Economic and Durable Construction

through Excellence, Proceedings of the International
Conference held at the [Jniversity of Dundee
Scotland, on 7 - 9 September 1 9 9 3 . Volume Two.
Infrastructure, Research,New Applications. pp. 1 3 0 8 -
1 3 0 9 (Edited by R.K. Dhir and M.R. Jones).
3. Pavienko. S.I., " Fine-Grained Cementless Concrete

Made with High-Calcium Fly Ash and Slag Sand from
Thermal Power Plants". Fourth CANMET/ACI
International Conference on Fly Ash, Silica Fume,
S l a g and Natural Pozzolans in Concrete.
Supplementary P a p e r s , pp. 7 4 9 - 7 6 4 , Istanbul, Turkey.
1992.
4. Pavlenko, S.I., and Oreshkin, A.B.. "Structure

Formation of Cementless Concrete Made with Slag Sand
and High-Calcium Ash from Thermal Power Plants",
Proceedings o f 9th International Congress on the
Chemistry of Cement. pp.647-652, New Delhi. India,
1992.
5. Ignatova, O . A . , "Study of the Homogeneity of High-

Calcium Ashes from Kansko-Achinsky Coal and
Development of Standard Requirements for Use in
Concretes", Proceedings o f the All-Union Conference
on Concrete Containing A s h and Slag Sand from TPP
and their Use in Construction, Edited by S.I.
Pavlenko, V o l . 1 , 1 9 9 0 , pp. 1 4 6 - 1 4 7 .

A C 1 SP-153 VOL*I 95 0662949 0.521452 O99 M
504 Pavlenko
TABLE 1 - AVERAGE STATISTICAL DATA ON PHYSICO-

MECHANICAL PROPERTIES OF HIGH-CALCIUM ASH FROM
NOVOSIBIRSKAYATPP-3
~~
I Ave- Coeff i - Mini- Maxi-
II
cient of mum mum
Var i a- Value Value
rage t ion
I
R e s i d u e on S i e v e 7.4 3.7
008 m m , %
Sp cific S u r f a c e , 2940 21.7
f
cm / g
Coefficient of 19.6 7.6
Normal Consistency
C", % .
Initial S e t , m i n 40 56.4
Irregular Volume 46.3 1 1 6

C h a n g e IVC, d a y s
Compressive 31.7
S t r e n g t h of A s h
C l i n k e r , MPa
TABLE 2 - AVERAGE DATA ON CHEMICAL ANALYSIS OF HIGH-

CALCIUM ASH FROM NOVOSIBIRSKAYA TPP-3
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+I 95 06b2949 0 5 2 3 4 5 3 T25 w
--``,`,-`-`,,`,,`,`,,`---

FLY ASH, GRANULATED SLAG FROM NOVOSIBIRSKAYA TPP-3, AND
SILICA FUME FROM KUZNETSKY FERROALLOY PLANT
High- Crushed Si1 ica

Calcium Granulated Fume
Fly Ash Slag,
Physica I Tests 0.5 mm
Fineness - passing 4 g pm, % 92.20 0.20 1O0
- Blaine, m/kg 322 - 2900
Specific Gravity 2.85 2.75 2.20
Bulk Density, kg/m3 1180 1590
Setting Time, h : mm
- Initial O . 58
- Final 5.46 -
C o lor 1 ight black 1 ight
brown brown
II Chemical Analyses I I I I
IlSilicon dioxide (SiO,), % I 32.33 I 37.98 188.9011
Aluminium oxide (A1201),Ir, 7.94
Ferric oxide (Fe,O,), % 12.05 18.32 3.71
Calcium oxide ( C a o ) total, % 36.92 26.91
Calcium oxide (Cao) free, % 7.59 0.83
Magnesium oxide ( M g O ) . % 2.98
Sulfur trioxide ( S O , ) , X 2.65 0.59 1.15
Sodium oxide (NalO),% 0.51 3.36 1.04
Potassium oxide ( & O ) , % 0.36 0.92 0.76
Manganese dioxide ( M n O Z ) , % 0.31 0.46 0.20
Phosphorus oxide ( P I O 5 ) , X 0.03 1.03 0.19

Loss on ignition, % 2.73 0.51 1.71

A C 1 SP-I153 VOL*I 95 m Ob62949 0521454 961 m
506 Pavlenko
--``,`,-`-`,,`,,`,`,,`---
TABLE 4 - EFFECT OF HEAT TREATMENT SCHEDULE ON

PHYSICO-MECHANICALPROPERTIES OF CEMENTLESS FINE-
GRAINED SAC
Ho Heat Treat- 'empera- Densi-

ment Schedule: ure of Slump. ty of Dens i t v , Compressive
Curing before sother- cm Conc- ks/r3 Strength,
H . T t i Tempe- I YPa
rature Rise t
I bot hermal At 1 At Aftei At 7 A t
Heat ingt days 28 Heat days 28
Coolins).hour Treat days Treaí day 6
-ment -meni
1 12t(3t6t3) 60 3.1 1990 1916 1843 1890 9.2 12.6 17.4

2 6tt3t6t3) 60 3.0 1980 1929 1892 1903 8.5 13.2 16.9
3 3+(3tOt3) GO 2.9 1965 1955 i887 1916 5.3 9.5 16.8
4 12+(3tG+3) 80 2.8 1955 1895 1880 1956 11.2 15.7 20.7
5 6t(3+6t3) 80 2.0 i980 1945 1892 1955 10.2 15.2 16.4
6 3+(3+6+3) 80 2.6 1975 1971 1887 1925 10.0 12.9 19.7
7 12+(3+6t3) 100 3.6 1987 1920 1890 1942 16.5 20.0 23.1
8 6+(3tot3) 100 3.4 1995 1950 1903 1856 13.8 19.4 25.5
9 3ti3t6t3) 100 3.5 1990 1913 1915 1923 13.0 16.3 23.2
10 12ti3t9t3) 60 3.8 1985 1873 1922 1880 11.2 13.4 17.2
il 6ti3t9t3) 60 3.2 1975 i877 1905 i910 11.5 16.4 19.7
12 3*(3t9t3) 60 3.4 1910 1824 1899 1910 9.4 11.7 17.R
13 12+(3t9+3) 80 3.8 1995 1817 1915 1879 12.0 18.2 22.1
14 Gt(3t9t3) 80 3.8 1995 i883 1929 1938 13.9 17.4 19.0
1s 3t(3+9*3) 80 3.5 1980 1894 1901 1892 13.2 14.9 19.8
16 12+(3+9+3) 1 O0 3.7 1960 1929 1910 1950 21.8 22.0 22.4
17 6+(3t9t3) 1 O0 3.3 1985 1905 1902 1940 20.4 21.5 22.7
18 3*(3*9+3) 100 3.5 1986 1938 1897 1882 19.7 22.4 22.7
19 12+(3+12+3) GO 3.0 1990 1982 1913 1929 10.3 19.8 23.2
20 6t(3+12+3) 60 2.7 1985 1940 1918 1935 10.2 14.9 20.2
21 3tt3t12t3) GO 2.9 1990 1950 1903 1940 9.2 14.8 21.9
22 12t(3*12t3) so 3.5 2006 1970 1920 1930 14.3 17.2 21.8
23 6t(3t12t3) 80 3.9 1996 1938 1906 1937 13.2 17.3 20.2
24 3+(3+12+3) 80 3.6 2026 19SO 1913 1932 13.1 15.2 17.8
25 12ti3t12t3) 1O 0 3.7 1997 1915 1889 1905 19.9 24.5 27.2
26 6+(3+12+3) 100 3.4 1985 1958 1892 1909 22.8 22.4 25.1
27 3+(3+12+3) 1O0 3.3 1995 1920 1902 1903 22.4 21.7 23.7
Notes: 1. Mixture P r o p o r t i o n s , kg/m3: Slag Sand - 7 2 1 ,

Fly A s h - 7 2 1 , Silica Fume - 160, Water -292.
2. Workability o f Concrete was determined by a
"Mortar" Cone.
3 . The Temperature o f Mixing Water is +60°C.

A C 1 SP-L53 V O L X I 95 IObb2949 0521455 8 T 8 =
400 90 80 70 60 5 0 FLY ASH,%

Cre
Fig. l-Density and compressive strength at 28-day age of fine-

grained cementless SAC versus fly ash-to-silica fume-to-slag
sand ratio
--``,`,-`-`,,`,,`,`,,`---
Fig. 2-Compressive strength of cementless concrete after

heat treatment at 60 C

A C 1 S P - 1 5 3 V O L S I 95 m 0662949 0 5 2 3 4 5 6 734 m
508 Pavlenko
--``,`,-`-`,,`,,`,`,,`---
Fig. 3-Compressive strength of cementless concrete after
Fig. M o m p r e s s i v e strength of cementless concrete after


A C 1 SP-353 VOL*I 95 W 0 b b 2 9 4 9 0523457 6 7 0
--``,`,-`-`,,`,,`,`,,`---
Fig. e o m p r e s s i v e strength of cementless concrete at 7

days after heat treatment at 60 C
Fig. M o m p r e s s i v e strength of cementless concrete at 7


A C 1 SP-353 V O L X I 95 m Obb2949 0523458 507 m
510 Pavlenko
--``,`,-`-`,,`,,`,`,,`---
Fig. 74ompressive strength of cementless concrete at 7
days after heat treatement at 100 C
Fig. 8-Compressive strength of cementless concrete at 28


A C 1 SP-153 VOL*I 95 Obb2949 0523459 443
Milwaukee Conference 51 1
--``,`,-`-`,,`,,`,`,,`---
Fig. 9-Compressive strength of cementless concrete at 28

Fig. 10-Comprescive strength of cementless concrete at 28


A C 1 SP-153 V O L X I 95 0 b b 2 9 4 9 05214b0 Lb5
SP 153-29
Use of Fly Ash, Blast Furnace Slag,

and Chemical Gypsum for the
Synthesis of Ca I cium Su Ifoa Iuminate-
Based Cements
by G. Belz, J. Beretka, M. Marroccoli, L. Santoro,
N. Sherman, and G. L. Valenti
Svnopsis: This paper presents a study on high early strength cements based on
calcium sulfoaluminate, C4A3S. These cements can be produced at temperatures
-300°C lower than normal portland cement and they also can be synthesized using
industrial process wastes and by-products such as fly ash, blast furnace slag, chem-
ical gypsums and other waste materials containing reactive sulfate and alumina.
Cements designed to contain C4A3s, Beta-C2S and Cs, or C4A$ calcium

sulfosilicate, C,S2s, and C s have been synthesized using (a) pure analytical reagent
(AR) calcium carbonate or commercial limestone as the source of CaO; (b) fly ash,
blast furnace slag, bauxite, clay or alumina as the source of A1203 and SO,; and
(c) natural gypsum, phosphogypsum or desulfogypsum as the source of sulfate.
Ettringite, C6AS3H32, generated by the hydration of C4A3S and CS is

responsible for the high early strength of these cements. The hydration of the
silicate phase and the presence of C5S$ contribute to the ultimate strength. These
ettringite-containing cements do not expand, and in fact they have dimensional
stabilities similar to portland cement.
In these types of cements durability problems may arise from the poor
resistance of ettringite to carbonation. Due to the higher resistance to carbonation
of another calcium sulfoaluminate hydrate, monosulfate (C4AsH12), the investigation
has been extended to a composition which included brownmillerite, C4AF, whose
presence promotes the conversion of ettringite to monosulfate during hydration.
Kevwords: Blast furnace slag; calcium sulfoaluminates; cements;

compressive strength; C,AF, eîtringite; expansion; flv ash; hivh early
streneth cements; hydration; industrial wastes; shrinkage; supersulfated
cement
--``,`,-`-`,,`,,`,`,,`---

513
A C 1 SP-I153 VOL*I 95 0662949 0521461 U T 1
514 Belz et al
G . Belz is a Researcher at the Research Centre for the Valorization and Treatment
of Byproducts, ENEL (the Italian Electricity Board), Brindisi, Italy. He obtained
his Masters Degree is Mechanical Engineering from the University of Bari in
1990. His research activity mainly deals with the re-use of industrial wastes and
by-products
J. Beretka is a Principal Research Scientist at the CSIRO Division of Building,

--``,`,-`-`,,`,,`,`,,`---
Construction and Engineering, Melbourne, Australia. He holds a Dip.Chem.Eng.

from the Technical University of Budapest and an MSc. from the University of
Adelaide. He has published over 70 papers on solid state chemistry, ceramics,
the chemistry of calcium sulfate, and the use of industrial wastes and by-products
in the building, construction, cement and ceramic industries.
M. Marroccoli is Assistant Professor at the Department of Environmental Engin-

eering and Physics, University of Potenza, Italy. She obtained her Masters Degree
in Chemical Engineering from the University of Napes in 1986. Her research
interests are in cement chemistry and the utilization of industrial by-products.
L. Santoro is Professor of Chemical Plants at the Department of Chemistry,

University of Naples, Italy. Since he obtained his Masters Degree in Chemical
Engineering in 1971, he has been involved in studies on heterogeneous reactions
and the utilization of industrial solid wastes.
N. Sherman obtained her Dip.Chem.Eng. and B.Sc. in Silicate Technology at the

Leningrad Institute of Technology, specialising in ceramic binders for abrasives.
Currently she is a ceramicist at the CSIRO Division of Building, Construction and
Engineering, Melbourne, Australia, where her main interest is the development
of special cements.
G.L. Valenti is Professor of Materials Technology and Applied Chemistry at the

Department of Environmental Engineering and Physics, University of Potenza,
Italy. Since 1970, when he obtained his Masters Degree in Chemical Engineering,
he has been engaged in research concerning chemistry of cement and the utiliza-
tion of industrial by-products.
INTRODUCTION
Calcium sulfoaluminate (C4A3$)* based cements are characterized by high

early strength, high ultimate strength and dimensional stability similar to that of
normal portland cement (1,2). In the literature they are also referred to as super-
sulfated alumina-belite cements (3), rapid hardening or high early strength
cements (4), non-alitic cements (5) and low energy cements (6,7). Their early
strength is due to the formation of non-expansive ettringite, C6AS3H32. generated
by the hydration reaction of C4A3s and anhydrite, Cs; and their later strength to
~~ ~~
* In this paper the notation adopted in cement chemistry, viz. C = Cao, A = A1203
s
S = Si02, = SO,, H = H 2 0 etc., has been used.

A C 1 SP-153 V O L b I 95 I0662749 05214b2 T 3 ö
ettringite and to the foimation of calcium silicate hydrates, CSH. These cements
can be produced at temperatures -3OOOC lower than OPCs using not only natural
materials but particularly industrial wastes and by-products such as chemical
gypsums, fly ash, blast furnace slag and other waste materials containing reactive
sulfate and alumina (8,9). After firing, the resulting clinkers are relatively soft and
friable and require little energy to grind. Consequently these cements contribute
to the saving of natural resources and energy.
This paper desciibes experiments on the synthesis and hydration of C4A3S-

based cement systems with a planned composition of C4A3S-C2S-CS in the
weight ratio of 1.5:1:1. These cements were made from mixtures of pure analyt-
ical reagent (AR) and commercial materials (limestone, bauxite) and also from
industrial process wastes, particularly fly ash, blast furnace slag and phospho-
gypsum. The compounds of the above systems were synthesized separately.
With the above planned composition synthesized in a single firing (“ternary

-
system”), the fired product (at 1200°C) containes calcium sulfosilicate, CsS2S,
instead of Beta-C2S (7,9). Therefore, the systems of C4A3S-CsS2S-C.S- with the
--``,`,-`-`,,`,,`,`,,`---
newly obtained weight ratio of 1.5: 1.4:O.h was investigated. Experiments were
also conducted on the above system in which the ratios of C4A38 to C,S$ were
varied from 1/3 to 3/1.
Due to the problems associated with the poor resistance of ettringite to

carbonation (10,11,12), carbonation studies were also carried out on some of the
above-mentioned systems.
Furthermore, due to the higher resistance of calcium monosulfate hydrate,

C4ASH12, to CO2 attack, the experiments were extended to the system including
brownmilleiite, C4AF, whose presence promotes the conversion of freshly formed
ettnngite to monosulfate during hydration. Thus, the high early strength provided
by cttringite can he utili7,ed and the resistance of cements to carbonation can be
improved.
EXPERIMENTAL
Raw Materials and Procedures
The principal chemical constituents of the commercial and industry-derived

raw materials used for the experiments are shown in Table 1. The pure AR
materials were not analysed. The planned compositions of the various systems
investigated are given in Table 2.
The compositions with the individually synthesized components C4A3S,

C2S and CS were marked with the symbol 101; and those in which the synthesized
compounds were blended with blast furnace slag, or blast furnace slag and fly

A C 1 SP-353 V O L t I 95 m Ob62949 O523463 974 m
516 Belz et al
--``,`,-`-`,,`,,`,`,,`---
ash, were marked with the symbols 102 and 103, respectively. The compositions
in which the above components were synthesized in a single firing (“ternary
systems”) and contained fly ash, blast furnace slag or clay as the source of alumina
and silica were identified with the symbols FA, BS and CL. With composition
FA, in which the weight ratio of C4A$ to C5S2S was varied from 113 to 311, the
numerical symbols reflect the relevant ratios of C4A&C5S2s in the compositions
accordingly. The system containing brownmilleiite, C4AF, designed to facilitate
the conversion of ettringite to monosulfate during hydration, was identified with
the symbol EM.
For the experiments on the compositions marked 101, 102 and 103, the
C4A$, C2S and C s were synthesized at different temperatures, either from (a)
pure AR materials; (b) from commercial materials; or from (c) commercial and
waste materials as described previously (7). The compositions of the ternary
sytsems marked FA, BS and CL were synthesized from mixtures of pure AR
materials, commercial materials and industrial process wastes, fired at 1200°C -
in a single firing and the method adopted previously for processing the cements
has been used (9).
The system with brownmillerite, EM, was prepared from individually
synthesized components of C4A$, C s and C4AF in a stoichiometric ratio
suitable for ettringite-monosulfate transformation (weight ratio, 1:0.45:1.6). AR
materials were used for these experiments.
Hydration studies on system EM were carried out as before (7,9). In
particular, small (2 g) specimens were mixed with water (w/s = O S ) , placed in a
plastic envelope, and hydrated for various time intervals at either 23 or 55°C.
100% RH. At the end of the hydration period the specimens were removed, the
reaction stopped with acetone, the material dried with ether, then analysed by
XRD and TGA/DTA.
The testing of cements was carried out by conventional methods. In
particular, 25 mm cube specimens and 100 x 12.5 x 12.5 mm expansion bars
were cast at the wls of 0.5 (unless stated otherwise), which were cured at 23”C,
100% RH for various time intervals, and their compressive strength, density and
shrinkage/expansion were determined. The cured specimens were also analysed
by TGA/DTA and XRD.
Carbonation Studies
For the determination of atmospheric carbonation, 25 mm cubes were cast

at wls, 0.5 (unless stated otherwise), cured for 28 days at 23OC, 100% RH. The
cubes were then dried for 21 d in a constant temperature room (CTR) set at 2loC,
67% RH, then carbonated in a CTR for 1 year and tested for compressive strength
and density. Accelerated carbonation was camed out on specimens which were
placed in a carbonation chamber (4% C02, 60% RH) for up to 28 days before
testing. The changes in the mineralogical composition of the specimens during
carbonation were determined by -XRD and TGA/DTA.

A C 1 SP-353 VOL*I 95 0662949 0523464 ô00
Individuallv Svnthesized and Blended Compositions,

System C&S-C,S-CS
Figure 1 shows the compressive strengths of compositions 101, 102 and 103,
prepared from pure AR materials (Fig. l(a)), commercial materials (Fig. l(b))
and commercial materials with phosphogypsum (Fig. l(c)).
The results indicate that composition 101 had the highest early (1 d) strength,
particularly with pure AR materials, but the later (28 d) strengths were about the
same as with commercial materials and with commercial materials and phospho-
gypsum. With composition 102 (blended with blast furnace slag) and 103 (blended
with blast furnace slag and fly ash), the following observations can be deduced. In
the case of using pure AR materials (Fig. l(a)), the addition of blast furnace slag
alone (102) has a large negative effect on 1 d strength. However, the 28 d strength
of the specimens containing either blast furnace slag (102) or both blast furnace
slag and fly ash (103), markedly increased as compared with the pure system of
composition 101. With the compositions synthesized from commercial materials
(Fig. l(b)), and from commercial materials with phosphogypsum (Fig. l(c)),
somewhat similar findings were obtained at early ages. However, at 28 d curing,
only the results for Composition 102 were similar to those of composition 101,
while for composition 103 the compressive strength was lower for cornmercial
materials (cf. Fig. I@)) and higher for the composition containing commercial
materials and phosphogypsum (cf. Fig. l(c)).
XRD examination revealed that ettiingite formed rapidly (in 1 day) and its
content gradually increased with cuiing time (9).
The densities of the specimens of composition 101 diied to constant weight

were of the order of 1720 kg/m3. The specimens tended to expand between 1 and
7 days (0.08%),then shrink (0.1% at 28 d and 0.2% at 90 d), similar to normal
portland cement pastes.
Ternary System CAAS-C5S2S-CS
After the exploratory experiments on the system CqA3s-Beta-C~S-Cs

(planned weight ratio, 1S:l:l) described previously, attempts were made to
synthesize the above compounds in a single firing at -120O0C, using pure AR
materials, commercial materials and industrial process wastes (fly ash, blast
furnace slag and phosphogypsum). It was found that in these experiments, the
fired product did not contain C2S, but it consisted mainly of C4A3S. and another
solid phase identified as calcium sulfosilicate, C5S2s, and C s ; in the weight
ratio of about 1.5:1.4:0.6 (7,8,9).
--``,`,-`-`,,`,,`,`,,`---

518 Belz et al
The physico-mechanical properties of these cement compositions, contain-

ing fly ash (FA), blast furnace slag (BS) and clay (CL), respectively, were most
promising, as shown in Fig. 2. It can be seen that all three compositions had very
good early (1 d) strength (49 MPa for compositions FA and CL, and 35 MPa for
BS), high 28 d strength, which camed on increasing to -90 d; after this time some
retrogression of strength was observed with composition FA. At the end of 1 year,
--``,`,-`-`,,`,,`,`,,`---
however, their compressive strengths were all in the range 72-76 MPa.
XRD examination of the hydrated specimens after 1 d curing indicated that

they consisted of C6AS3H32, C5S2S, and some unhydrated C4A3s and Cs. After
28 d the latter two reactants were almost fully consumed. The content of C5S2S
remained fairly constant (9).
The dimensional stabilities of compositions FA, BS, and CL were similar

to OPC. In particular, at the end of 1 year curing they shrank 0.255, 0.171 and
0.298%, respectively.
Hvdraulic Properties of C&
According to the literature, CsS2s is a non-hydrating or very slowly

hydrating mineral phase (3,4,7,9,13). Scanning electrom microscopy (SEM) (9)
and hydration experiments cairied out at elevated temperatures confirmed that the
material hydrated at a very slow rate, without any major changes in its mineral-
ogical composition. C5S2S obviously contributes to the mechanical strength of
the systems at later ages.
Compositions FA, BS and CL
In order to verify the contribution of C5S$ to the physico-mechanical

properties of the cements studied here, additional experiments were conducted
on compositions designed to contain C4A3S and CsS$ in weight ratios of 1:1,
1:2 and 1:3. The findings are illustrated on composition FA and the results are
shown in Fig. 3. It can be observed that the composition containing C4A$ and
C5S2S in the weight ratio of 1:l (FA-l/l), and consequently having the highest
ettringite content, also had the highest mechanical strength at early ages. The other
two compositions, containing lower ratios of C4A3S and C5S2S (weight ratios of
1:2 and 1:3, respectively), i.e. containing less ettringite and more C5S2s, had
lower mechanical strength, as expected.
While the mechanical strengths of compositions FA-1/2 and FA-1/3 were

relatively constant at later ages, composition FA- 1/1, which contained the highest
amount of ettringite phase, reached a maximum at 28 d curing, after which time
its strength was gradually reduced. This was probably due to the commencement
of carbonation of the ettringite phase in this particular composition (10,11,12).
Therefore, additional experiments were conducted to investigate the potential
carbonation of the C4A3S-C5S2S-Cs system.

A C 1 SP-353 V O L X I 95 = 0662949 0523465
Not for Resale
747 m
A C 1 SP-153 V O L X I 95 0662949 0521466 683
46 MPa). Industrial wastes and by-products can be used for the synthesis
of this cement.
9. In addition to commercial materials, industrial wastes and by-products (fly
ash, blast furnace slag, chemical gypsums, etc.) can be utilized as sources of
silica, lime, alumina and sulfate, for synthesizing calcium sulfoaluminate-
based cements; and also for blending them with the above clinkers.
REFERENCES
1. Kurdowsky, W., George, C.M., and Sorrentino, F.P. “Special Cements”, Proc.
8th Int. Congr. Chem. Cement, Rio de Janeiro, Volume 1, pp. 292-318, 1986.
2. Muzhen, S., Kurdowsky, W., and Sorrentino, E “Development in Non-
Portland Cements”, Proc. 9th Int. Congr. Chem. Cement, New Delhi,
Volume 1, pp. 317-354, 1992.
3. Ikeda, K. “Cements Along the Join C4A$-C2S”, Proc. 7th Int. Congr.
Chem. Cement, Paris, Volume 2, Theme III, pp. 31-36, 1980.
4. Sudoh, G., Ohta, T., and Harada, H. “High Strength Cement in the CaO-
A1203-Si02-SO3 System and Its Applications”, Proc. 7th Int. Congr. Chem.
Cement, Paris, Volume 2, Theme III, pp. 31-36, 1980.
5. Mudbhatkal, G.A., Parmeswaran, P.S., Heble, A.S., Pat, B.V.B., and
Chatterjee, A.K. “Non-alitic Cement from Calcium Sulfoaluminate Clinker:
Optimisation for High-strength and Low-temperature Applications”, Proc.
8th Int. Congr. Chem. Cement, Rio de Janeiro, Volume 4, pp. 364-370, 1986.
6. Mehta, P.K. “Investigations on Energy-saving Cements”, World Cement
Technol., May, pp. 166-177, 1980.
7. Beretka, J., Santoro, L., Sherman, N., and Valenti, G.L. “Synthesis and
Properties of Low Energy Cements Based on C4A$’’, Proc. 9th Int. Congr.
Chem. Cement, New Delhi, Volume 3, pp. 195-200, 1992.
8. Beretka, J.. de Vito, B., Santoro, L., Sherman, N., and Valenti, G.L.
“Utilisation of Industrial Wastes and By-products for the Synthesis of
Special Cements”, Resources. Conservation and Recycling, Volume 9, pp.
179-190. 1993.
9. Beretka, J., de Vito, B., Santoro, L., Sherman, N., and Valenti, G.L.
“Hydraulic Behaviour of Calcium Sulfoaluminate-based Cements Derived
from Industrial Process Wastes”, Cement and Concrete Research, Volume
23, No. 5 , pp. 1205-1214, 1993.
10. D’Ans, J., and Eick, H., “Investigations on the Setting Process of Blast
Furnace Slag”, Zement-Kalk-Gips, Volume 7, pp. 449-459, 1954.
11. Grounds, T., Midgley, H.G., and Novell, D.V. “Carbonation of Ettnngite
by Atmospheric Carbon Dioxide”, Thermochimica Acta, Volume 135, pp.
347-352,1988.
12. Nishikawa, T., Suzuki, K., Ito, S., and Takabe, T. “Decomposition of
Synthesized Ettringite by Carbonation”, Cement and Concrete Research,
Volume 22, pp. 6-14, 1992.
13. Nakamura, T., Sudoh, G., and Akaiwa, S., “Mineralogical Composition of
Expansive Cement Clinker Rich in Si02 and Its Expansibility”, Proc. 5th
Int. Congr. Chem. Cement, Tokyo, Volume 4, pp. 351-365, 1968.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 V O L + I 95 m 0662749 052L467 5LT m
520 Belz et al
The preliminary results of the mechanical properties of the above system

are shown in Fig. 8. The results indicate that this system also has reasonably good
early (1 d) and 28 d mechanical strength. However, the shrinkage of the specimens
was a little higher than normal portland cement or the systems studied above
(-0.59% in 28 d).
The resistance to carbonation of this monosulfate system is superior to those

studied previously (cf. FA, BS, etc.), as shown in Table 5. During 6 months of
atmospheric carbonation in a CTR the mechanical strength of the EM specimens
increased about 20%. Furtheimore, even under accelerated conditions in a car-
bonation chamber, after a slight decrease in 1 and 3 d, the mechanical strength of
the specimens increased, and at 28 d the strength was about 5% higher than the
uncarbonated specimens.
During accelerated carbonation the densities of the carbonated specimens

remained about the same, -1930 kg/m3.
The above results clearly indicate that it is possible to design C4A3S-based

cementitious sytems which are resistant to carbonation. Such experiments are in
hand and the results will be published at a later date.
CONCLUSIONS
1. High early strength cements of the separately synthesized system C4A3S-

Beta-C2S-CS, at the weight ratio of 1.5:1:1, were made from commercial
materials and industrial wastes and by-products. The cements hydrated
rapidly to ettnngite and developed high early (1 d) and later (28 d) strengths.
2. The blending of fly ash or blast furnace slag with the above composition
reduces the quantity of ettringite in the systems, and consequently reduces
the early (1 d) strength, but the later (28 d) strength in general is retained.
3. The synthesis of the above three component system (C4A3S-C+CS) was
not possible in a single firing at temperatures -120O0C, because of the
formation of C5S2S hstead of Beta-C2S in the system.
4. The resulting C4A$-C5S2S-CS cement could be produced at 12OO0C, -
which is about 250-300°C lower than used for the clinkering of OPC. The
clinkers produced are soft and friable and require little energy to grind.
5. The cements are reactive, hydraulic and rapid hardening, and develop high
mechanical strength at early (1 d, 35-49 MPa) and later ages (28 d, 58-76
MPa). They also have good dimensional stabilities, similar to OPC.
6. The cements had good resistance to atmospheric carbonation to 1 year, but
they carbonated under severe exposure to CO2 in a carbonation chamber.
In spite of extensive carbonation in a carbonation chamber, about 70% of
the original-mechanical strength of the specimens was retained.
7. By altering the C4A3S-C5S2S-CS ratios of the system, cements with
different mechanical properties can be obtained.
8. A system moi= resistant to carbonation was designed by converting ettringite
to monosulfate using brownmillerite. The system C4A3S-CS-C4AF pro-
vided good mechanical strength at early (1 d, 26 MPa) and later ages (28 d,
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L t I 95 Obb2949 052LYb8 Y5b =
Carbonation of Compositions FA, BS and CL
Table 3 shows the results of atmospheric carbonation of specimens of

compositions FA, BS and CL, which were cured for 28 d at 23OC, 100% RH,
then dried for 21d at 2loC, 67% RH in a CTR. It can be seen that the mechanical
strength of all the specimens increased to 180 d aging, after which time the
strength slightly decreased to 1 year. All the compositions retained their original
mechanical strength at 1 year. The strength of the carbonated specimens BS and
CL were even higher than for the uncarbonated ones. The decrease in strength
for FA between 180 and 365 d can be attributed to the carbonation (partial decom-
position) of the ettringite component of the specimens by CO2 The carbonation
of the above specimens was verified by XRD and TGNDTA analyses. Figure 4
shows the XRD trace of the initial specimen (Fig. 4(a)), then the sample after 1
year carbonation in a CTR (Fig. 4(b)). It can be seen that the ettringite in the
specimen slightly carbonated, and some small quantities of carbonation products
(calcite, vaterite (p-CaCO,) and hemihydrate) were present in the specimens
(Fig. 4(b)).
The results of accelerated carbonation in a carbonation chamber (4% COZ)

camed out on composition FA only are shown in Table 4. It can be observed that
the specimens carbonate with time and their mechanical strength is gradually
reduced. XRD examination of the carbonated specimens after 28 d exposure to
CO2 is shown in Fig. 4(c). It is evident that most of the ettringite in the specimens
carbonated to calcite and vaterite, gypsum and hemihydrate. Alumina gel was also
present in the specimens as determined by TGNDTA. Although the ettringite
present in the specimen at the end of 28 d exposure to COZwas about 40% of the
original, the percentage of strength retained was still relatively high, about 70%.
Svstem CnA2S-CS-CnAF(Monosulfate Svstem)
Due to the potential carbonation of ettringite (11,12) and subsequent loss

of mechanical strength of ettringite-containing systems, it was decided to design
systems in which the ettringite in the specimens would be converted to mono-
sulfate, C4ASH 12, duiing hydration; since this compound has better resistance to
Carbonation. This is illustrated in Fig. 5 , which shows XRD results of synthetic
monosulfate (Fig. 5(a)), and that carbonated in a carbonation chamber for 28 d
(Fig. 5(b)). The results clearly indicate that under the conditions of the experiments
the monosulfate did not carbonate. The traces of carbonation products shown in
Fig. 5(b) are due to the traces of ettiingite which was present in the synthesized
monosulfate used for these experiments.
Hydration experiments on pastes of the system C4A$-CS-C4AF, in which

C4AF was used to promote the conversion of ettiingite to monosulfate, are shown
in Figs 6 and 7. At the ambient temperature of 23OC (Fig. 6) the hydration takes
place relatively fast, ettringite forms rapidly in 1 d, and gradually transfoims to
monosulfate. At 55°C (Fig. 7), transformation of ettringite to monosulfate is
more rapid.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L S I 75 m Obb2747 0521467 372 m
522 Belr et al
TABLE 1 - MAJOR CHEMICAL COMPONENTS (WT., PERCENT) OF

RAW MATERIALS USED
Mateiial Ca0 Si02 Al203 FqO3 MgO SO3 P2O5 H20

1 Bauxite 0.02 4.70 51.50 15.30 0.04 n.a. 0.04 25.40
Blast furnace
slag 41.10 33.20 14.20 1.57 7.00 2.58 n.a. 0.15
Clay 1.30 46.80 34.50 1.33 0.12 0.10 n.a. 14.69
Fly ash 4.80 56.80 25.50 4.20 1.50 0.40 n.a. 0.40
Limestone 54.10 1.57 0.38 0.40 0.61 0.05 0.01 42.92*
Naturd gyp. 32.60 3.33 0.35 0.22 0.06 43.40 0.0 1 20.70
Phosphogyp. 32.60 0.05 0.23 0.02 0.22 44.90 0.47 20.50
--``,`,-`-`,,`,,`,`,,`---
~ Silica n.a. 99.00 0.37 0.06 n.a n.a. n.a. 0.28

* CO,; n.a.= not analysed
TABLE 2 - COMPOSITIONS (WT., PERCENT) OF SYSTEMS

INVESTIGATED
Individually Synthesized and Blended System
(wt ratio, C,A$-C,S-CS, 1S:l: 1)
......................................................
101 102 103
.................................
C4A3S 43.0 30.0 30.0
Beta-C2S 28.5 20.0 20.0
CS 28.5 20.0 20.0
Blast furnace slag - 30.0 20.0
Fly ash - - 10.0
Ternary System (wt ratio, C ~ A ~ S - C S S ~ S -1.5:C S 1.4:0.6)
,
......................................................
. FA,
. . . .BS,
. . . .CL
..
C4"3! 42.9
c5s2s 40.0
CS 17.1
Systems with Different C4A,s-C5S2S Weight Ratios (wt ratios in parentheses)
......................................................
FA- 113 FA- 112 FA-111
.....................................
C4A3S 22.2 (1) 28.6 (1) 40.0 (1)
C5S2S 66.7 (3) 57.1 (2) 40.0 (1)
CS 11.1 (0.5) 14.3 (0.5) 20.0 (0.5)
System with Brownmillerite (wt ratio, C4A$-CS-C4AF, 1:0.45: 1.6)
________________________________________--------------
. .EM
.....
C4A3S 32.8
CS 14.7
C4AF 52.5

A C 1 SP-153 V O L X I 95 0662949 0521470 O04
TABLE 3 - COMPRESSIVE STRENGTH (MPa) OF COMPOSITIONS

FA, BS, AND CL CURED AT (A) 23 C, 100 PERCENT RH FOR 28
DAYS, TESTED WET AND DRY; THEN AFTER 180 AND 365 DAYS OF
ATMOSPHERIC CARBONATION; W/S FOR FA, 0.5; FOR BS AND CL, 0.4
-1 FA BS c n
I WET DRY WET DRY WET DRY11
28(fog) 50.4 66.3 55.4 64.3 62.0 72.2
180(CTR) - 73.1 - 75.8 - 86.0
365(CTR) - 60.8 - 71.8 - 76.6
TABLE 4 - COMPRESSIVE STRENGTH AND DENSITY OF

COMPOSITION FA CURED FOR 28 DAYS AT 23 C, 100 PERCENT
RH, TESTED WET AND DRY; FOLLOWED BY ACCELERATED
CARBONATION IN CARBONATION CHAMBER CONTAINING 4
PERCENT CO,. ETTRINGITE CONTENT ALSO SHOWN BEFORE AND
AFTER 28-DAY ACCELERATED CARBONATION; W/S, 04
Compr. strength Ettringite Strength Density

(MW content retained Wm3)
WET DRY
("/.I WET DRY
Before carbonation
75.3 102 47.9 100* 1929 1850
Days in carbonation chamber
1 - 102.6 100.6 - 1827
2 - 89.6 87.8 - 1820
7 - 80.0 78.4 - 1828
28 - 67.8 -18.5 66.5 - n.d.
*Dry strength, loo%, nominal
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L + I 95 W Obb291r9 0521471 T 4 0 W
524 Belz et al
r
Days Compressive strength Density
(time) (MW (kdm3)
Atmospheric carbonation (w/s, 0.45)
28 d DRY (control) 48.2 1951
.......................................................
6 month 57.7 1892
--``,`,-`-`,,`,,`,`,,`---
1 year n.a.*
2 years n.a.
Accelerated carbonation (w/s, 0.4)
28 d DRY (control) 66.7 1926
.......................................................
1 day 58.9 1923
3 days 57.6 1935
7 days 63.7 1921
28 days 70.2 1923

A C 1 S P - I 1 5 3 V O L X I 95 m 0662949 0523472 9 8 7 m
60
40
20
-2 0
E 60
I
l-
u
5cf 40
+
LB
1 20
LB
LB
w
r r o
a
g 60
40
20
O
1 7 28
DAYS CURING (square root scale)
Fig. l-Compressive strength (MPa) for

compositions 101, 102, and 103 with
components synthesized separately;
cured at 23 C, 100 percent RH; w/s, 0.5.
Components synthesized from (a) pure
AR materials; (b) commercial materials;
and (c) commercial materials and
industrial process wastes and by-products
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 W 0662949 0521473 813 W
526 Belz et al
-m 80
a
70
40
cn
m
W
--``,`,-`-`,,`,,`,`,,`---
K 30
a
2
8 20 I II
10
A
OBF *S
o CL
1
L I I I I I I l
O
1 3 7 14 28 56 90 180 365
Fig. 2-Relationship between compressive strength

(MPa) and days of curing for compositions FA, BS,
and CL cured at 23 C, 100 percent RH; wls, 0.4
80
1
m
70
5
60
E 50
+
m
w 40
2
m
30
K
a
20
o 10
n"
1 3 7 28 56 90 180 365
Fig. 3-Relationship between compressive strength

(MPa) and days of curing for compositions FA-1/1,
1/2, and 1/3; cured at 23 C, 100 percent RH; wls, 0.4

A C 1 SP-353 VOL*I 95 I0662949 0523474 7 5 T I
A
l
A
--``,`,-`-`,,`,,`,`,,`---
. .
I I I I I I I I I
50 45 40 35 30 25 20 15 10
20 Co K u
Fig. 4-XRD diagrams of Specimen FA (a) uncarbonated;

(b) carbonated for 1 year in a CTR; and (c) after 28 days'
exposure to 4 percent CO, in carbonation chamber: A =
C,AS3H,,; B = C4A3S; C = C,S,S; D = CS; E = calcium carbonates; F
= CSH,,5; G = CSH,

A C 1 SP-153 V O L U I 95 m Ob62949 0523475 b9b m
528 Belz et al
I II
Y
1 B
I I I I I I I I l
50 45 40 35 30 25 20 15 10
Fig. 5-XRD diagrams for: (a) monosulfate before

carbonation; and (b) monosulfate after 28 days’
exposure to CO, in carbonation chamber (4 percent
CO,); A = C,AS,H,; B = C,ASH,,; C = calcium
carbonates
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 I0662949 0521476 522 =
J I I I I I I
20 100 200 300 400 500 600 700 800

TEMPERATURE ( O C )
Fig. &DTA traces for composition EM (system

C,A,S-CS-C,AF) (monosulfate system) after 1
to 70 days’ hydration at 23 C; wls, 0.5: A =
C,AS,H,; B = C,ASH,,; C = alumina gel
--``,`,-`-`,,`,,`,`,,`---

I I I I I I I l
20 100 200 300 400 500 600 700

TEMPERATURE (OC)
Fig. 7-DTA traces for composition EM (system

C,A,S-CS-C,AF) after 1, 7, and 14 days’
hydration at 55 C; wls, 0.5: A = C,AS,H,;
B = C,ASH,,; C = alumina gel
m
a
z
I
l-
c7
Z
W
U
l-
(B
W
2
(B
2
U
a
I
o
1 3 7 14 21 2a
DAYS CURING
Fig. &Relationship between compressive strength

and days’ curing for composition EM (system
C,A,S-CS-C,AF) cured at 23 C, 100 percent RH;
wIs, 0.4 --``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 I0662949 052LY78 3T5
SP 153-30
Mexican Natural Pozzolans and the

Evaluation of the Specifications
Related to Their Use
by R. Uribe-Afif and R. E. Rodriguez-Camacho
SvnoDsis : The geological characteristics of Mexico

permit an important number of materials to be considered
for use as pozzolans in the construction industry.
--``,`,-`-`,,`,,`,`,,`---
These materials have great importance, due to their
relevance to problems of concrete durability. This
situation has provoked an increase in the use of
pozzolanic cement.
This increase of use of pozzolanic cement, creates

a need for characterization of these products, and
evaluation of their performance, based on the
specifications related on their use in concrete. Mexican
natural pozzolans meet the requirements of the
specification, with some deficiencies in some pozzolans.
The objective of this work is a detailed

characterization of all pozzolans actually used in
Mexico, their evaluation for use as an admixture in
concrete, using for this purpose the ASTM C 311 and C
618. Those particular points of the specifications that
are not satisfied completely and the elements that
contribute to the fact are discussed.
Keywords: Chemical analysis; compressive strength; glass; petrography;

pozzolan cements; pozzolanic reactions; pumice; specifications; tests

A C 1 SP-153 V O L * I 95 Obb2949 0521479 231
532 Uribe-Afif and Rodriguez-Camacho
R. Uribe Afif is professor of earth sciencies at the

National University of Mexico. He received his bachelor
degree from same institution. He is member of AC1 Mexico
South-Central Chapter.
R.E. Rodriguez Camacho obtained her bachelor degree in

chemistry from the National University of Mexico. She
has worked for five years in cement industry. She is
preparing her master thesis on pozzolans of Mexico.
INTRODUCTION
Requirements of quality assurance in the production

of cement to world level have encouraged research on
pozzolans used by themselves or combined with cement.
Different types of cement can be made to produce
concrete that meets severe quality controls now in
effect.
The use of pozzolanic materials in the construction

industry has been a common practice for many years ( i ) .
Mexico has not been an exception to this, and the use of
these materials have been a wide spread practice for
many decades. Materials with the best pozzolanic
characteristics have not always been used. Rocks of
volcanic origin like tuff are the principal form of
natural pozzolans. It is logical to believe that there
are many of these deposits and that they can replace
the pozzolans actually developed.
The importance of using natural pozzolans in the

cement industry in Mexico, encouraged the need to carry
out this study and their evaluation.
The objective of this study is to present the

results of a classification of the main natural
pozzolans used in the production of cement in Mexico.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 IObb2949 0521480 T53 I
The classification of each pozzolan includes its

mineralogical-petrological characteristics, chemical
composition, pozzolanic activity index with lime and
portland cement and available alkalies.
The characterization of these materials must give

a basis for appropriate ptechniques to locate, explore,
and classifly them, and to evaluate them according to
specifications related to their use.
EXPERIMENTAL METHODS
Materials
As shown in Fig.1, representative samples of 16

natural pozzolanic deposits located in six different
states of the Mexican Republic (Sonora, Sinaloa,
Jalisco, Hidalgo, Veracruz and Oaxaca) were obtained.
These materials were dried at a temperature of 100

'C. They were ground and the fineness was determined
(amount of material retained on 45-pm sieve) according
to ASTM C 430 (2).
PetroqraDhic Examination
In order to make the petrographic identification,

thin sections of each sample were prepared and observed
under the petrographic microscope.
X-Ray Diffraction
The identification of the clay fraction was done

using a Siemens X-ray diffractometer, using the powder
method and radiation Cu . K Q ~were used.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+I 95 Obb2949 0521481 99T m
Chemical Analysis
The chemical composition was determined by wet

chemical methods according t.0 ASTM C 114 (3).
Pozzolanic Activity with Lime
The compressive strength of cubes of mortars

prepared with lime+pozzolan and an inert material like
quartz, cured at temperature of 55 OC and tested at an
age of 7 days was determined according to ASTM C 311
( 4 ) . In order to consider the tested material as a

satisfactory pozzolan, the average strength of cubes of
mortar at 7 days, must not be lower than 5.39 MPa
according to ASTM C 618 (5).
Pozzolanic Activity with Portland Cement
The pozzolanic activity with portland cement is

determined from the compressive strength of mortar
cubes, prepared with a control mixture of portland
cement alone and a test mixture with a 20% by mass of
pozzolan in substitution of cement. The specimens are
cured at 23 f 2 OC and are tested in compression at 7
and 28 days.
The activity index was determined in according to

ASTM C 311. The strength of the test cubes as a percent
of the average strength of the control mixture, is
considered the pozzolanic activity index with portland
cement.
Available Alkalies
The available alkalies were determined by ASTM C

311 Method. 5.0 g of the sample (pozzolanic material
powder) and 2.0 g of hydrated lime were carefully mixed
and transfered to a small plastic vial of aproximally
25-mL capacity. 10 mL of water was added to this
mixture. The vials were sealed and the material was
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+I 95 Obb2949 0523482 8 2 6
blended by shaking and they were stored at 38 -+ 2 OC for

2 8 days.
The material was broken up and formed into a

uniform slurry by adding water and stirring by 1 hour.
The slurry was filtered onto a 500 mL volumetric flask
and the filtrate was neutralized with diluite HC1 ( 1 + 3 )
and 5 mL in excess. The solution was filled to the mark
with distilled water. The amount of sodium and potassium
were determined by ASTM C 114.
PetrosraDhic Characteristics
Natural pozzolans in Mexico are materials of

pyroclastic origin as a result of explosive volcanic
eruptions, where eruptive fragments are transported by
air to be finally deposit on the ground or in water.
Once deposited as incoherent materials they can be
subjected to diagenetic processes transforming them into
compacted rocks called tuffs.
In the case of Mexican pozzolans, they are

exploited as incoherent materials or as compact rocks.
In the incoherent pozzolans, these correspond to similar
deposits (like in the state of Hidalgo where they are
close to each other) with very little lithological
variations causing small changes in the chemical
composition. The products show an evident acid
composition. In relation with this aspect the pozzolan
--``,`,-`-`,,`,,`,`,,`---
of El Zapote which is in another region, shows a low

content of Si02 which classifies as a basic material
but this is not a detriment to the pozzolanic activity
index.
It is very common that these materials are found

partially cemented with a vitreous binder with several
degrees of alteration. The mineralogical-petrological
characteristics and the diagenetic processes affecting
each deposit, in particular are shown in Table 1.
Mexican tuffs (compacted materials) used as

pozzolans have as components pyroclastic and matrix
zeolites produced by diagenetic transformation (6).

A C 1 SP-153 V O L * I 95 m Obb2949 0523483 7 6 2 W
Zeolitic minerals identified by XRD in nine of these

pozzolans are clinoptilolite, heulandite and gmelinite.
It is clear that there exists an important association
between the alteration of the vitreous matrix of these
tuffs with the presence of two mineral species of
diagenetic origin, evidence that has been proved in
laboratory tests by Sersale ( 7 ) . As in the case of
incoherent materials, their characteristics are shown in
Table 1.
X-Ray Diffraction
By means of the X-ray diffraction patterns, the

following constituents were identified: feldspar,
quartz, cristobalite, tridimite, clay minerals as
chlorite-montmorillonite and the zeolites
clinoptilolite, heulandite, and gmelinite. Results are
given in table 2.
Chemical Analysis
There are easily measurable characteristics of

pozzolans that are correlatable with their activity.
Among these characteristics, the chemical composition
plays an important part. In Table 3 it can be seen the
chemical composition of Mexican natural pozzolans have
a strong acid character, having a high (Si0 + A1203)
content ranging around 73 to 87% of the totai. Between
the two oxides, silica prevails in all cases, it reaches
percentages greater than 52%. The importance of the
content (Sioz + Alzo3) is clearly emphasized by the fact
that the active vitreous phases of pozzolans generally
are richer in silica and alumina content. Chemical
composition of Mexican natural pozzolans either
incoherent and tuffs are rich in silica. It is important
to emphasize that the total alkali content in Mexican
pozzolans, is lower than 6.2%, whereas the loss on
ignition is between 3-14% and the content of other
elements like lime is lower than 7%.
--``,`,-`-`,,`,,`,`,,`---
Pozzolanic Activity with Lime
I
The evaluation of pozzolanic activity is essential l
to consider and use a material as a pozzolan. Lea (8)
has proposed different methods to evaluate it.

A C 1 SP-153 V O L 8 1 95 0662949 0521qö4 b T 9
Mechanical strength tests nowadays are a basic

complement to the petrographic and chemical methods.
--``,`,-`-`,,`,,`,`,,`---
Besides, the two fundamental pozzolan

characteristics are: a) ability to react with lime and
b) ability to form products with binding properties (6).
According to results shown in Table 4, compressive

strength of Mexican natural pozzolans ranged between
5.46 to 8.64 MPa which is over 5.39 MPa specified by the
ASSM Standard C 618.
It is well known that one of the fundamental

conditions for a rapid zeolitization is the structure of
finely subdivided volcanic glass ( 9 ) . In fact most
easily zeolitizable pozzolans are those which have a
more marked hydraulic activity as those presented mainly
in San José and Chiguitan deposits. This reaction
produces new hydrated phases (hydrated calcium silicates
and aluminates in excess of lime) which are important to
form binding compounds, which is very advantageous when
the material contains silica and alumina easy mobilized,
this is typical of amorphous structures and particulary
of acid glasses (9).
Materials were detected in this study that

containing zeolites which presented more reactivity than
those containing vitreous constituents, this confirms
what R. Sersale found ( 9 ) . This is due to probably to
the more open porous structure of the zeolites,
therefore more likely to react. Indeed these pores allow
chemical agents to penetrate, destroying their
crystalline structure, liberating silica, alumina and
alkalies, the first of which combine with lime.
Pozzolanic Activity with Portland Cement
Although the principal pozzolanic reaction is the

chemical reaction involving lime and silica,
cementitious products are also formed as a result of the
chemical reactions between lime and alumina. The
essential difference between the pozzolanic reactions
and the reactions involving the hydration of portland
cement alone is not in the composition of the hydration
products but the rate at which these are formed ( 1 ) .

The behavior of the Mexican natural pozzolans can

show different compressive strength of pozzolan-portland
cement mortars compared to those with portland cement
alone. Mechanical strength tests are still today the
indispensable complement to chemical and physical
methods. According to Table 5 strength activity index
with portland cement ranging of 79-114% at 7 days old
and 88.4-149.8% at 28 days o l d , which exceeds the 75%
specified by ASTM Standard C 618. The pozzolans which
contain zeolitic minerals present an marked increase
hydraulic activity as these from San José and Chiguitan
with presence of cìinoptilolite.
Available Alkalies
The chemical interaction of certain siliceous

mineral constituents of aggregate with the alkalies in
portland cement is known to cause expansion and cracking
of concrete. The commonly practised method of reducing
the risk of such expansion involves the use of a low-
alkali cement. When the use of a high-alkali portland
cement ( 5 0.6% Na20 equivalent) in combination with an
aggregate containing alkali-reactive constituents seems
unavoidable the expansion phenomenon may be controlled
by incorporating in the concrete mixture a pozzolanic
material that has proven in laboratory tests to be
effective in reducing the alkali-aggregate expansion
(1).
All natural pozzolans are not equally effective in

combating alkali-silica expansion. It is important to
consider the available alkalies to prevent this
expansion although many natural pozzolans themselves
contain a high alkali content. Most of the Mexican
natural pozzolans present a high content of alkalies (up
to 6.18% Na20 equivalent), however the available
alkalies content ranging between 0.09-1.22% Na20
equivalent that is less than 1.5% specified by ASTM C
618. Results are given in Table 6. The most of Mexican
pozzolans which contain zeolitic minerals present less
than 1% Na20 equivalent as available alkalies.
CONCLUDING REMARKS
The Mexican natural pozzolans are characterized to

be of pyroclastic origin, with diagenetic processes in
different degrees; these processes were identified as:
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 IObb2949 0523486 473 =
devitrification, sericitization, chloritization,

oxidation, and zeolitization.
Representative minerals of these lithological

groups are: glass, oligoclase, andesine, quartz, pumice
and volcanic lithics mainly of acid composition.
Chemical analysis show that these materials are

very rich in acid components, having values over 52% in
Si02 and up to 73% of (SiO2 + Also3) content which is an
essential characteristic for products having a good
pozzolanic activity. It was found that total alkalies is
under 6.2% (Na20 equivalent), which is different to the
--``,`,-`-`,,`,,`,`,,`---
values reported by Massazza (6) for pozzolanic
materials. Besides, these alkalies have values under 5%
(Na20 equivalent) for pozzolanic products obtained from
compact materials, having an approximate relation of 2 :1
of total alkalies of incoherent materials vs coherent
materials.
Mineralogical zeolitic species identified by X-ray

represent zeolitic materials not previously identified
in Mexican natural pozzolans. New species identified
are: clinoptilolite, heulandite and gmelinite; whereas
those found in other pozzolans are: herschellite,
analcime, phillipsite, and chabazite. The identified
mineralogical species were found associated to those
pozzolans obtained from compact materials with different
diagenetic processes.
In order to emphasize the characterization of

natural pozzolans it is advisable to evaluate their
pozzolanic activity index taking advantage that they
are able to combine with lime and form compounds of low
solubility showing mechanical strength after hardening.
This index of pozzolanic activity with lime and portland
cement complemented with the chemical analysis,
petrographic analysis and XRD clearly indicates when a
material is behaving as a pozzolan. This knowledge of
the essential characteristics of pozzolans may have a
positive influence on the techniques used for its
location, exploration, and classification.
According to standard specification ASTM C 618, to

evaluate pozzolanic materials class N the maximum limit
on loss ignition must be 10%. The objective of these
requirements is to ensure that the pozzolan is in dry
state use. Nevertheless, some Mexican natural pozzolans

A C 1 SP-153 V O L X I 95 0662949 0 5 2 3 4 8 7 308
containing zeolitic minerals (San José, Chiguitan and

Cajón de Felix) surpass this value. It can be
interpreted due to the presence of crystallization water
in these minerals. It is important to point out that
these cases on loss on ignition determined do not
decrease their pozzolanic activity so this requirement
must be reconsidered to evaluate the natural pozzolans,
due to this group of zeolitic minerals act in favour to
the pozzolanic reaction, containing in its structure
crystallization water that is liberated during ignition.
Class N pozzolans must meet in the sum of three

oxides (SiOs + Al O + Fe203) have a minimum limit of
70%. When present? 'in a non-crystalline (glassy) or
poorly crystalline state, these constituents participate
in pozzolanic activity reactions. In the case of Mexican
natural pozzolans, all meet with this value.
Nevertheless, as it can be seen in Table 2, it
identified crystalline phases of minerals as: quartz,
feldspars, chlorite-motmorillonite, cristobalite and
tridimite, which contain in their structure Si02 and
A1203.
REFERENCES
1. "Supplementary Cementing Materials", CANMET Special

Publication SP 86-83 (Editor: V.M. Malhotra),
Energy, Mines & Resources Canada, Ottawa, Canada,
pp 15, 19, 1987.
2. ASTM Standard C 430. Test Method for Fineness of

Hydraulic Cement by the 45 pm (No. 325) sieve.
3. ASTM Standard C 114. Test Methods for Chemical

Analysis of Hydraulic Cement.
4. ASTM Standard C 311. Tests Methods for Sampling and

Testing Fly Ash or Natural POZZOlanS for Use as a
--``,`,-`-`,,`,,`,`,,`---
Mineral Admixture in Portland Cement Concrete.
5. ASTM Standard C 618. Fly Ash and Raw or Calcined

Natural Pozzolan for Use as a Mineral Admixture in
Portland Cement Concrete.

A C 1 SP-153 VOL*I 95 W 0662949 0521488 244
6. Massazza, F. Chemistry of Pozzolanic Additions and

Mixed Cements. The VI International Congress on the
Chemistry of Cement. Volume I. Moscow. September
1974.
7. Sersale, R. The Constitution, Genesis and Chemical

Behaviour of Volcanic Tuffs. Rend. Soc. Min. Ital.,
1 7 . 499-536. 1961.
8. Lea, F.M. The Chemistry of Cement and Concrete.

3rd. ed., 414-453. E. Arnold Publ. LTD. pp 727.
London 1970.
9. Sersale, R. Structure and Characterisation of

Pozzolans and Fly Ashes. 7th. International
Congress of the Chemistry of Cement. Volume I.
Paris, 1980.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-253 V O L X I 95 0662747 0 5 2 3 4 8 9 I180 =
TABLE 1 - MINERALOGICAL AND PETROLOGICAL

CHARACTERISTICSOF NATURAL POZZOLANS
CLASSIFICATICN
w
TUFFVITREOUS ANDESITE -VOIDS STRUCTURE
RWO-DACITIC(R) D A C EAND -DMTRIFICAllON LESS THAN 30%
PUMICE -umics ALTERED OF DACITEAND
umics ANDESITE
LAS PLACiiAS/ OLAN,GAND -PïRûCLASliCTEXTURE
TUFFCRYSTAL- VOLCANICS -VOIDSAM CRACKEDSTRUCTURE
vImEous-umic umics -DMTRIFICATICN 100%
ANDESITIC@) -SOME CRYSTALS mssownm
-MATRU( QUARTZ-FMESPATIC
-MAFICS ALTEREDTO CLAY
W NDE FELIN 0LAN.Q.G -pyRocmsnc TEXTURE
TUFFVITREOUS AND DACITE. -VOIDS STRUCTURE
DACmCg) ANDESITE -umics srnicimm 50-60%
umics
HUICHAPAN/ G.Q.S AND -PYROCLASllCTEXTURE
TUFFVITRYS OL -VOIDSAND FLUID STRUCTWE
Rwounc( ) -DMTRIFICATION 10%
TLAUTW AN.Q - usnc TEXTURE p w u n c )
TUFFVITREOU~ %-PUMICE -MAFICS ALTERED BY CHLORITE
RHY- DACITIC(')
LA CAPILUTAI N. -mocusnc I LXTURE
TUFF vImEous-
umic
%&& -VOIDS STRUCTURE
-UMICS SWICTIZEDANDOMDED
Rmounc(*) LESS TW\N 10%
TEQUEQUWAN/ GAND -wRocLAsnc ~ R E
TUFFVITREOUS PUMICE -VOIDS AND FLUID STRUCTCRE
ACID(') umics -uTHICS ALTERED 100%
LAUW 3LQ.GAND - ocusnc iWRE
TUFFVITREOUS- PUMICE -umics ALTERED BY swianzm
umic DACITAAND AND OMOES80%
DACITICCì) GNEISS
umics
CHIGUTTAN/ 0LAN.Q.G -PYROCLASTiC 1 W R E
TUFF VITREOUS- AND PUMICE - u m i c s ~ ~ mBY
mCHLORITE
CRYSTALLINE AND DACITE AND SWICITE
--``,`,-`-`,,`,,`,`,,`---
DACITICfii) umics -DMTRIFICATICN 80%
BOJAYI G.Q.M. AND -PYRCCLASTICrrXniRE
TUFFVITREOUS- uma -umics 100% ALTERED BY SE-
umic RICITEAND CO(1DES
Rtwounc(*)
MESARWONON QOLGANO - P w c c u s n c m ~ ~
TUFFVITREOUS ANDESITE -DMTRIFKXTION 100%
RWO-DACITIC(*) umics -SERICITIZED umics
ELZAPOTE/ AN.Q.G AND -PYROCLASllCTEXlURE
TUFFCRYSTAL- ANDESITE -DMTRIFICATION xix
VITREWS AND DACITA -ANDESITE AND DACE umm
Dncmcy) umics ALTERED By SERICITE10%
CHOCAMAN/ AN ANDG -PYROCLASTIC TEXTURE
TUFF umic
ANDESITIC(.)
M. ESMBEDOI ANAND G -lR4CHYnClDílWE
TUFF CRYSTAL- -VOIDS STRUCTURE
ANDESITIC(*)
CHOLUW G. AN AND -wRccmncm~~
TUFFCFIYSTAL- umics -VOIDS STRUCTURE
umic -DEVITRIFICATION 25%
ANDESITIC(*)
ATOTONILCO/ GLASS -GLASS TMTURE
TUFFVITREOUS -Fe-Mg INCLUSIONS.
JPUMICE') - W I D STRUCTURE
NOTAS a=wacu~~ c=cuARTz
AN=ANDESINE S=SANIUNE
G=GLASS R=ROCK
'=INCOHWENl MATWIAL

TABLE 2 - MINERALOGICAL IDENTIFICATION BY X-RAY

DIFFRACTION OF NATURAL POZZOLANS
I DEPOSIT MINERALS
IDENTIFIED
SAN JOSE CL-M, Q, Clp and F IDENTIFICATION
LAS PLACITAS Q, Crt, F and Clp

CAJON DE FELIX H, C L - M , F a n d O CL: CHLORITE
HUICHAPAN Crtand F M: MONTMORILLONITE

TLAUTLA Fand CL Crt: CRISTOBALITE
LA CAPILLITA F Q: QUARTZ
TEQUEQUEXPAN F, Q and Crt F: FELDSPAR
LA OLLAGA F, Q, Clp and CL H: HEULANDITE

CHIGUITAN H, Clp, F and C L - M G: GMELINITE
BOJAY Fand G Clp: CLINOPTILOUTE
MESA REDONDA Fand Q T r y TRIDYMITE
EL ZAPOTE F a n d Crt
CHOCAMAN F, H a n d Crt
MARIAN0 ESCOBEDO F, H a n d C r l
CHOLULA F, Try, Crt and Q
ATOTONILCO F. Crt, Try a n d Clp
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L U I 95 E
No reproduction or networking permitted without license from IHS Not for Obb2949
Resale 0523490 9T2
A C 1 SP-153 V O L * I 95 m 0662949 052L49L 839 m
TABLE 3 - CHEMICAL ANALYSIS OF NATURAL POZZOLANS

-
S.JOSE P LAC ITA >AJON DI
-
s i 0 2 (S)
---
63.82 55 60
FELIX
61.80
HUICHAPAN-
68.35
TLAUTLA
70.62
CHOCAMAP
59 13
A1203 (A) 14.14 1 7 79 15.90 15.58 15.03 20 68
Fe203 (F) 1.64 5 89 1.72 2.54 2.05 4 96
S+A+F 79.60 78 88 79.42 86.47 87.70 84 77
Ca0 3.83 7 06 5.00 1.61 0.91 6 15
MgO 1.10 2 60 1.30 0.90 0.50 3 10
SO3 0.44 o 47 0.10 0.20 0.16 o 23
L. I. 11.66 7 81 14.36 3.01 2.71 122
ALKALIES
Na20 1.24 144 0.22 2.92 2.84 3 46
K20 2.32 2 04 0.50
---
4.96 4.96 156
TOTAL (Na201 2.77
LA
2 78
TEQUE-
0.55
LA
6.18
CHIGUITAN
- 6.10
:HO LU LA
4 51
MARIAN0
:APILLITP VJEXPAN OLLAGA iSCOBEDO
--``,`,-`-`,,`,,`,`,,`---
s i 0 2 (S) 71.60 70 20 67.22 65.20 61.72 60 27

Al203 (A) 15.06 15 28 13.29 13.88 19.14 19 70
Fe203 (F) 1.72 2 62 4.59 1.80 5.28 4 96
S+A+F 88.38 88 10 85 10 80.88 86.14 84 93
Ca0 1.01 O 50 2.24 2.82 5.75 5 73
M9O 0.40 O 40 0.80 1.10 3.40 3 10
SO3 0.16 o 12 0.12 0.07 0.18 o 25
L. I. 2.64 3 34 5.89 10.95 1.56 o 91
ALKALIES
Na20 2.84 3 60 1.72 1.o0 2.25 3 48
K20 5.04 3 92 3.40
--
2.96 1.o2 2 O0
TOTAL (Na20) 6.16
BOJAY
6 18
MESA
3.96
EL
2.95
ATOTONILCO
- 2.92
;PEC. AS 1
4 80
C 618
s i 0 2 (S)
-69.60
EDONDP
68 70
ZAPOTE
52.04 68.56
CLASS N. %
A1203 (A) 14.59 16 O0 21.20 14.58

Fe203 (F) 2.05 2 38 7.38 2.56
S+A+F 86.24 87 O8 80.62 85 70 70.00 MIN
Ca0 1.61 1 o1 6.46 1.92
MgO 0.60 o 80 4.50 0.40
SO3 0.12 O 07 0.19 0.28 4.0 MAX.
L. I. 3.76 3 80 3.70 3.91 10.0 MAX
ALKALIES
Na20 2.64 2 56 3.24 2.52
K20 5.20 4 72 1 .O8 4.96
TOTAL (Na20) 6.06 5 66 3.95 5.78
L.I.: LOSS ON I ITION

A C 1 SP-353 V O L X I 95 0662949 0523492 775
TABLE 4 - POZZOLANIC ACTIVITY WITH LIME (SELECTIVE TEST)

OF NATURAL POZZOLANS
FINENESS DENSITY 'OUOLANIC ACTIVITY

RET 45-,m INDEX WITH LIME
SIEVE, (%) (MgIrn3) (MPa)
SAN JOSE 42 2.27 864

I A S PLACITAS 34 2.45 622
CAJON DE FELIX 40 2.19 736
HUICHAPAN 47 2.30 546
TLAUTLA 37 2.26 584

LA CAPILLITA 35 2.22 569
TEQUEOUEXPAN 47 2.27 6 15
LA OLLAGA 47 2.29 557
CHIGUITAN 44 2.12 8 o1
BOJAY 41 2.28 5 47
MESA REDONDA 52 2.28 726

EL ZAPOTE 72 2.42 6 61
CHOCAMAN 35 2.49 6 70
M. ESCOBEDO 35 2.40 6 51
CHOLULA 20 2.48 734
ATOTONILCO 27 2.31 846
SPECIFICATION
ASTM C 618 340MAX 5.39 MIN
CLASS N
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L r I 95 = Obb2949 0521493 bO1i
TABLE 5 - ACTIVITY POZZOLANIC INDEX WITH PORTLAND

CEMENT (SELECTIVE TEST) OF NATURAL POZZOLANS
I I ACTIVITY POZZOLANIC INDEX WITH
%) CONTROL AT
DEPOSIT
20 DAYS
SAN JOSE 114.0 137.0
LAS PIACITAS 105.O 114.6
CAJON DE FELIX 97.0 97.6
HUICHAPAN 92.6 1028
TLAUTU4 90.5 97.6
LA CAPILLITA 90.5 100.0
TEQUEQUEXPAN 68.0 101.6
LA OLIAGA 90.6 111.1
CHIGUITAN 96.5 149.8
BOJAY 89.6 95.0
MESA REDONDA 89.1 101.1
EL ZAPOTE 92.2 101.3
CHOCAMAN 66.0 90.3
MARIAN0 ESCOBEDO 81 .O 00.8
CHOLULA 79.0 00.4
ATOTONILCO 91 .o 94.3
I SPECIFICATIONASTM C 618 I 75 MIN. 75 MIN.
--``,`,-`-`,,`,,`,`,,`---

TABLE 6 - AVAILABLE ALKALIES OF NATURAL POZZOLANS
I SAN JOSE
DEPOSIT Na20, %
O. 26
K20, %
0.13
TOTAL ALKAUES.
%
0.34
LAS PLACITAS 0.12 0.54 0.47
CAJON DE FELIX 0.09 0.15 0.09
HUICHAPAN 0.43 1.10 1.15
TLAUTLA 0.44 1.12 1.18
LA CAPILLITA 0.42 1 .o2 1 .o9
TEQUEQUEXPAN O. 55 0.94 1.17
LA O L i A G A O. 74 0.23 0.89
CHIGUITAN O. 07 0.22 0.21
BOJAY 0.41 1.12 1.15
MESA REDONDA 0.42 1 .o6 1.12
--``,`,-`-`,,`,,`,`,,`---
EL ZAPOTE 0.24 0.22 O. 38

CHOCAMAN 0.41 0.43 0.69
MARIAN0 ESCOBEDO 0.37 0.45 0.67
CHOLULA 0.40 O. 29 0.59
ATOTON ILCO 0.47 1.14 1.22
I SPECIFICATION ASTM C 616 1.50

CLASS N, MAX.
I

A C 1 SP-153 VOL*I 75 IObb2747 0523495 484
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL*I 95 IObb2949 0523496 3 L O
SP 153-31
Rubber Added Fly Ash for

Underground Petroleum Tanks
by G. Baykal and K. Köprülü
Synopsis : Due to increasing volumes of fly ash production each year, new
utilization areas must be found. A new application has been developed at
Bogaziçi University. Fly ash with various weight percentages of rubber
tire chips were mixed and compacted at a water content wet side of
optimum. Sealed single ring infltrometer and falling head permeability
tests were conducted on these specimens with water and gasoline as the
permeants. Unconfined compression and split tensile strength tests were
conducted to evaluate the mechanical behavior of the proposed liner
material. When gasoline was permeated through rubber-fly ash specimens
a decrease was observed in the permeability as compared to that of
measured during water permeation. This decrease is due to the physical
characteristic of rubber; expansion upon contact with gasoline. The
expanded rubber holds some portion of the gasoline in itself while sealing
the voids and blocking the pascageways for further leakage. For the above
mentioned technique patent protection has been applied and this technique
has a good application potential in the field because the liability for the
underground petroleum storage tanks will decrease considerably when this
technique is used.
Keywords: Fly ash; permeability; rubber; seepage; subsurface structures;

tanks (containers); wastes
--``,`,-`-`,,`,,`,`,,`---

Gökhan Baykal is an associate professor at the Department of Civil
Engineering, Bogaziçi University, Istanbul, Turkey. He is the director of
"Center for Industrial By-products Utilization". His research interests
include environmental g e o t e c h c s , fly ash utilization, microanalysis
techniques and aggregate production.
Kahraman Köprülü, is a former graduate student at the Department of
Civil Engineering, Bogaziçi University.
INTRODUCTION
Fly ash alone can be used successfully for several applications. Due
to increasing annual production volumes of fly ash, newly emerging
application areas must be found. When fly ash is used as a fill material
especially around tanks, its permeability characteristics become very
important. The rigidity of fly ash makes it prone to cracking when it is
strained due to differential settlements expected in the liner. Cracks in the
liner will cause a large increase in the hydraulic conductivity.
Generally the strength, deformation and durability properties of fly

ash and additives like cement or lime are studied. Permeability studies are
fewer as compared to strength studies. The permeability of compacted fly
ash was studied by various researchers (1,2,3,4,5,6) and they have
concluded that fly ash with some additives can be used as a liner material .
Every new application favors large volume utilization that will decrease
the increasing disposal problem of fly ash. Beyond just decreasing the
disposal problem, in some cases fly ash itself behaves as a superior
material. This increases its economic value. An innovative technology has
been developed in Bogaziçi University which involves mixing fly ash with
waste rubber tire chips and compacting it around underground petroleum
storage tanks as a fill material. In case of a leak from the petroleum tank,
the rubber chips expand and seal the pores of fly ash decreasing the
overall permeability (7). Another positive contribution of fly ash in
decreasing the permeability is sealing of existing cracks in fly ash which is
very likely due to the rigid behavior of fly ash. Normally these cracks
would have been easy passageways for the permeant which would have
then contaminated the environment. The fiber shapes of the rubber chips
act as a reinforcing element which decrease the propagation of cracks.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 Ob62949 0.523498 1 9 3
METHODOLOGY
Materials Used
-
Flv Ash The fly ash used in this study is a high calcium type fly
ash and is obtained from Soma Thermal Power Plant located in Turkey.
Five hundred kilograms of fly ash was sampled from electrofilters. The
physical and chemical properties of fly ash are given in Table 1. The total
amount of Sioz, Fe203, and A 1 2 0 3 is 65.03 %. The C a 0 content of 26.3
% states that this fly ash is high calcium type. The SO, amount is less than
5 Yo.
Rubber -- The rubber chips were supplied by a tire re-tread

company. The outermost layer of the tires are scraped of with rotating
steel nails and fiber shaped rubber chips with various sizes are obtained.
Rubbers belong to polymer group which are high molecular weight
compounds, predominantly organic, consisting of long chain molecules
made up of repeating units (8). These crosslinked, long flexible molecules
form a three dimensional network. Elasticity and stiffness are the major
properties of rubbers (9). Rubbers are able to undergo large elastic
deformations. Strength is another important property of the rubber. When
crosslinked, rubbers will have tensile strengths in the range of 10 - 30
MPa which is much higher than that of fly ash. All the rubbers have to be
crosslinked which is accomplished by the vulcanization of rubber by
--``,`,-`-`,,`,,`,`,,`---
heating it with sulfur and other chemicals. Mineral fillers are added to
harden and cheapen the product. The rubber was sieved through standard
sieves and a controlled gradation was used throughout the study (Figure
1). The specific gravity of the rubber was 1.1 . To be able to prepare a
standard size gradation to be used throughout the study, rubber chips were
sieved through standard sieves ASTM 4, 10, 20, 40, 60, 70. The onginal
sample was poorly graded. A new well graded mixture of grain sizes have
been achieved by re-mixing different size ranges.
Mixture Proportioninq
Three, 6 and 9 per cent of rubber by weight were mixed with fly ash
and the optimum water contents were determined using Standard Proctor
Tests (Figure 2). For all rubber contents the optimum water contents

A C 1 SP-153 V O L * I 95 W Obb2949 0521499 0 2 T D
552 Baykal and Köprülü
were within a narrow range thus 19 % water content which is slightly at

the wet of optimum was selected to compact all specimens for the
permeability test. Fly ash and rubber was mixed frrst and then water was
added. After the mixtures were thoroughly mixed, they were immediately
compacted into special molds using Standard Proctor procedure (ASTM
D-698).
Swelling Tests
Free swell tests were conducted in the consolidation device. To

determine the swelling pressures ASTM D4546-87 Method C was used.
Permeabilitv Testing
Sealed Single Ring Infiltrometers (SSRI) and Falling Head (FHP)

Permeability Tests were conducted. A typical set up for Sealed Single
Ring Infiltrometer is given in Figure 3. Sealed Single-Ring Infiltrometers
(SSRI) used in this study were constructed of sheet metal with 200 mm
diameter and 160 mm height. The rings were sealed with transparent
Plexiglas lids and the burettes used for applying the hydraulic gradient and
monitoring the permeant flow were fixed to these lids. The samples were
mixed in boxes of 320mnur320mmx160mm. The ring was placed in a 110
mm deep circular trench excavated previously in compacted soil. The
rings were sealed with a chemical grout. The ring and the burette was
filled with permeant which was maintained at a constant head. The
volume of the permeant infiltrating the sample was measured periodically.
Two rigid wall falling head permeability apparatus with different
diameters were used. After the compaction, the samples were connected to
the apparatus and vacuum was applied in order to saturate the samples.
The results of the infiltrometer tests were analyzed by using the

Green-Ampt wetting front model (10) which simplifies the actual
behavior of the soil moisture profile. The infiltration rate versus time
curves were used to calculate the wetting front depth (b),
and hydraulic
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 Ob62949 0521500 671
conductivities were calculated using Darcy's Law :
ks=i[ l+(h+@ )$]-I
ks : hydraulic conductivity,
i : the steady infiltration rate read fi-om the plotted infiltrometer graphs,
h : the depth of the water column above the liner,
Q> maîtric potential at the wetting fiont.
Falling head tests were analyzed using Darcy's Law. The results of
kaolinite-mbber and fly ash-rubber mixtures are presented separately.
Free Swell and Swellincr Pressures of Rubber and Sand-Rubber
Rubber particles were placed in the consolidation ring and immersed

in gasoline and their swelling behavior was observed (1 1). The major
portion of swelling of rubber has occurred during the first half hour after
being immersed in the gasoline and subsequently the swelling rate
decreased (Figure 4). The swelling of rubber is a physical reversible
process. The ultimate swell of rubber after one week of immersion was
found to be approximately 7.5 times its original volume. Samples were
prepared by mixing sand, rubber and water or gasoline and compacting
them into consolidation rings and resulting swelling pressures due to the
expansion of rubber were measured (Figure 5 ) . In twenty five to fifty
minutes major portion of the swelling pressures has developed. The
swelling pressure measured for water compacted sample was 353 kPa and
for gasoline compacted sand-rubber mixture the swelling pressure was
854 kPa. These high swelling pressures are the key point to the principie
of the technique developed. The rigid pore walls of the compacted fly ash
are strong enough not to crack under these pressures, however they
provide a strong foundation for the sealing effect of rubber when it
expands.
Mechanical Properties of Rubber Added Fly Ash
Unconfined compressive strength and split tensile strength tests were

conducted on specimens which were sealed and cured at 21OC for 28 days.
The test results are given in Fig. 6 , 7. The unconfined compressive
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I 95 Ob62949 0521501 508
strength decreased from 12 MPa for fly ash to 7 MPa for 9% rubber added
fly ash. The decrease in compressive strength for this fill application is not
important because even a compressive strength of 7 MPa is still much
more than required. However an interesting observation was made when
the results of the split tensile strength tests were analyzed. An increase in
the split tensile strength was observed at a rubber content of 3%. At higher
rubber contents the split tensile strength decreased. When the optimum
rubber content is determined this fact should be taken into account. The
physical observations made on the broken specimens showed that
although large cracks have occurred the samples did not fail apart and the
rubber chips hold the pieces together. The rubber chips with their higher
tensile strengths (10-30 MPa) have a reinforcing effect on fly ash.
Permeabilitv of Rubber Added Flv Ash
When the permeant was water, no significant change was observed in

the hydraulic conductivity values of samples with pure fly ash and rubber
added fly ash (Table 2). The values obtained for nine per cent rubber were
approximately three and four times larger than those of pure fly ash for
falling head and SSRI apparatus respectively.With gasoline permeation
the hydraulic conductivities of rubber added mixtures decreased upto one
sixth of the values obtained for pure fly ash. The higher the rubber
content, the lower was the observed hydraulic conductivity value (Fig. 8).
CONCLUSIONS
--``,`,-`-`,,`,,`,`,,`---
1- Compacted fly ash - waste rubber mixtures can be used as a liner

material for the underground petroleum storage tanks. The expansion of
rubber upon contact with gasoline seals the pores and decreases the
amount of permeant passing through these voids.
2- The rubber chips hold leaking petroleum physically roughly upto 1.6
times its volume which states that in case of a leak there will be a
warning period before the petroleum pollutes the environment.
3- The proposed technique works well with even for fly ash that has
cracks in it. The rubber chips act as reinforcing elements and decrease the
potential for crack propagation.
4- The compressive strength and split tensile strength tests show that
rubber- fly ash interface is adequate.

A C 1 SP-1.53 V O L * I 95 IO662949 0523502 4 4 4
5- The ease of mixing and compacting of rubber and fly ash makes it a
promising material for field applications.
6-When the huge number of underground petroleum tanks are considered
throughout the world, the use of the above mentioned technology will
create large volume utilization of both fly ash and waste rubber.
REFERENCES
1- Bowders, J., Üsmen, M.,A., and Gidley, J.,S., "Stabilized Fly Ash for
use as Low-Permeability Barriers", Geotechnical Practice for Waste
Disposal 87, (Editor R.D. Woods), ASCE, N.Y., pp. 320-333, 1987.
2- Edil, T.,B., Berthouex, P.,M., and K.,D., Vesperman, "Fly Ash as a
Potential Waste Liner", Geotechnical Practice for Waste Disposal 87,
(Editor R.D. Woods), ASCE, N.Y., pp. 447-461, 1987.
3- Janardanan, R.," Mix-Design of Soil-Fly Ash for Canal Lining",
Proceedings, 7th International Ash Utilization Symposium, Orlando,
Florida, Vol 1, pp. 372-380, 1985.
4- Parker, D.,G., Permeability of Fly Ash Stabilized Soils", Poceedings,
'I
ASCE Speciality Conference on Geotechnical Disposal of Solid Waste,

Ann Arbor, MI, pp. 63-70, 1977.
5- Usmen, M.A., Bowders,J.,J., and Gidley, J.,S., "Low Permeability
--``,`,-`-`,,`,,`,`,,`---
Liners Incorporating Fly Ash, Disposal and Utilization of Electric Utility

Wastes, ASCE, Tennessee, pp. 50-65, 1988.
6- Vesperman, K.,D., Edil, T.,B., and Berthouex, P.,M., "Permeability of
Fly Ash and Fly Ash Sand Mixtures", ASTM STP 874, pp.389-398,
1985.
7- Köprülü, K., " Hydraulic Conductivity and Strength Properties of
Rubber Reinforced Fly Ash as a Liner Material.", M.Sc. Thesis, Bogazici
University, Turkey, 199 1.
8- Blow, C.,M., "An Outline of Rubber Technology", Rubber Technology
and Manufacture, (Editor C.,M.,Blow), Institution of the Rubber Industry,
London, pp.20-53, 1971.
9- Allen- P.,W., Natural Rubber and the Synthetics", Granada
'I
Publishing Limited, London, 1972.

10- Green, W.,H., and Ampt, G.,A., " Studies on soil physics: 1. Flow of
air and water through soils", Journal of Agricultural Science, 4: pp.1-
24, 1911.
11- Alpatli, H.,M., "The Effect of Vertical Confinement on the Hydraulic
Conductivity of Rubber Clay Liners", MSc Thesis, Bogaziçi University,
1994.

A C 1 S P - 1 5 3 VOLUI 95 W Obb2747 0523503 380 W
556 Baykal and Köprulu
TABLE 1 - CHEMICAL COMPOSITION

AND PHYSICAL PROPERTIES OF SOMA
FLY ASH
Chemical Comuocition ph)

26.3
2.34
0.27
2.38
4.75
38.9
4.79
--``,`,-`-`,,`,,`,`,,`---
0.65
21.3
0.30
Phvsical Properties
Specific G r a v i s 2.45
Optimum Moisture Content % 19.00
Maximum Dry Density kN/m’ 15.00
Loss On Ignition % 2.71

A C 1 SP-153 V O L + I 95 = Obb2949 0523504 2 1 7 m
TABLE 2 - PERMEABILITY TEST RESULTS OF FLY ASH-RUBBER

MIXTURES
RUBBER PERMEANT TEST TYPE ksx10-7

(“A) (cmísec)
O water ssRI* 2.00

3 water SSRI 4.17
6 water SSRI 6.43
9 water SSRI 8.75
O gasoline FHP** 8.84
9 gasoline FHP 1.44
O water FHP 1.04
9 water FHP 3.12
O water FHP 1.45
9 water FHP 4.60
* Sealed single-ring infiltrometer

** Falling head permeability apparatus
sieve number
4 10 20 40 70 IO0 200
1 O0
.-01
C
v1
U
v1
a
50
U
p>
L
4,
n
Fig. l-Gradation curve of rubber
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOLJI 95 m 0662949 0523505 153 m
5.50
1
>-
5.00
4.50 -
I 3.00
':n
I
L--------
IO 14 I& -22
21
3
4
m\
-
-- &A
5x
I l y ash odded fly ash
38 rubber
pure
rubber added Ilv ash
rubber odded li; osh
MOISTURE CONTENT
26
(IF)
Fig. 2-Moisture density curves for rubber-

added fly ash
--``,`,-`-`,,`,,`,`,,`---
chemical
grout
Fig. e e a l e d single ring infiltrorneter

A C 1 SP-I153 V O L * I 95 I0662949 052150b 09T W
1401
60
1 Reslroined Under 5 kPo

. -* 2 Completely Free Swell
TIME (min)
Fig. 4-Swelling behavior of rubber immersed in gasoline
2
. .
ea o 0 j *.
Y
W 700$ SAND + 10% RUBBER
.....
--``,`,-`-`,,`,,`,`,,`---
LI ___ 1 Compacted w i t h Woter

..... 2 Compacted with Gasoline
w
1
1 O0
o1 - Ö ' TIME'460'
(min)
'580' ' '6Ói' '7ÒO' I 'SÓ0
Fig. 5-!3welling pressures of sand-rubber mixtures immersed

in gasoline
A C 1 SP-153 VOLaI 95 W ObbZqqq 0521507 T2b W
I I I
O 4 8 12
Percent Rubber
Fig. &Unconfined compressive strength versus rubber content
--``,`,-`-`,,`,,`,`,,`---
O 4 8 12
Per Cent Rubber
Fig. 7-Split tensile strength versus rubber content

A C 1 SP-153 V O L X I 95 I0662949 0521508 962 I
SP 153-32
Effectiveness of Fly Ash in

Reducing Expansion of Concrete
Made with Reactive Aggregates
from New Brunswick, Canada
by B. Fournier, W. S. Langley, and V. M. Malhotra
Synopsis - Three reactive aggregates from N e w Brunswick,

Canada, a greywacke, a gneiss, and a meta-volcanic rock were
evaluated for their potential alkali-reactivity (AAR) in concrete
mixtures incorporating 420 kg / m 3 of cementitious materials. The
concrete mixtures consisted of the control made with CSA Type 10
low- a n d high-alkali cements, and mixtures incorporating ASTM
Class F fly ash at 20, 30, and 56% replacement levels of the high-alkali
cement. The susceptibility of the concretes to AAR was evaluated by
casting test prisms, and subjecting these to various accelerated curing
conditions in the laboratory, For comparison purposes, mortar bars
were also made, and tested according to the ASTM C 1260-94
Accelerated Mortar Bar Test procedure.
The AAR concrete prism tests performed in this study have

s h o w n that none of the test prisms cast from concrete mixtures
incorporating 20, 30, and 56% fly ash showed significant expansion
--``,`,-`-`,,`,,`,`,,`---
after two years of testing at 38°C and relative humidity > 95%. These
results were in g o o d accordance with those obtained in t h e
accelerated mortar bar test. Some alkaline immersion test results
would indicate, however, that concrete incorporating 20% fly ash
might not offer adequate protection against potential deleterious
expansions with highly-reactive aggregates.
Kevwords: Accelerated tests; alkali aggregate reactions; cement aggregate

reactions; concretes; expansion; fly ash; tests

561
A C 1 S P - 1 5 3 V O L * I 95 m 0 6 6 2 9 4 9 0 5 2 3 5 0 9 8 T 9 m
562 Fournier, Langley, and Malhotra
B. Fournier is a research scientist with CANMET, Department of

Natural Resources Canada, Ottawa, Canada. He is a member of the
CSA A5 committee on Hydraulic cements and of the Board of
Directors of the Eastern Ontario and Quebec Chapter of ACI. His
current research interests are in the areas of durability of concrete,
and in particular the prediction and the control of alkali-reactivity
reactivity in concrete.
AC1 Fellow W.S. Langley is President of W.S. Langley and Associates

Limited, Dartmouth, Nova Scotia, Canada. The firm is engaged in
concrete consulting and research in supplementary cementing
materials and alkali-aggregate reactivity. He is a member of several
CSA committees, AC1 and the Canadian Construction Research
Board and has authored numerous papers on various aspects of
concrete technology.
AC1 Honorary Member V.M. Malhotra is Program Principal of the

Advanced Concrete technology Program of CANMET, Department of
Natural Resources Canada, Ottawa, Canada. He is a former member
of the AC1 Board of Direction, and has served on numerous AC1 and
ASTM committees. He is a prolific author, editor, and researcher, and
has received many awards and honors from AC1 and other
institutions throughout the world.
INTRODUCTION
ee - ate Reactivitv in New Brunswick
Since the late 1960s, a number of studies have been conducted

in New Brunswick to explain the premature deterioration of concrete
structures in various parts of the province. Many of these structures
were showing defects such as surface map cracking, pop outs,
efflorescence and closure of expansion joints with extrusion of joint
--``,`,-`-`,,`,,`,`,,`---
filling materials, some of which are commonly associated with alkali-

aggregate reactivity (AAR) [l]. In addition to the visual survey of
highway bridges, the above studies included the petrographic
examination of samples cored from selected deteriorated concrete
structures, and the testing in the laboratory of aggregate samples from
aggregate sources throughout the province. Potentially reactive rock
types in New Brunswick include greywackes, argillites (slates),
Phyllites, some quartzites, schists, and some fine-grained volcanic
rocks such as rhyolites. The most common constituent contributing
to alkali-silica reactivity in the rocks is believed to be microcrystalline
quartz, with a grain size in the range of 100 pm and less [2].

A C 1 SP-153 VOL*I 95 Ob62949 0523530 5 3 0
In 1992, the Canada Centre for Mineral and Energy Technology

(CANMET) awarded a contract to Jacques, Whitford, and Associates
Limited, St. John, New Brunswick, for evaluating the effectiveness of
fly ash to control the expansion of concrete m a d e with selected New
Brunswick reactive aggregates. This paper presents the results of this
study.
SCOPE
The scope of this study is shown in Table 1. Three aggregates

from N e w Brunswick showing various degrees of alkali-aggregate
reactivity, a greywacke, a gneiss, and a meta-volcanic rock, were used
in control concrete mixtures m a d e with low- and high-alkali
cements, a n d in fly-ash concrete mixtures at a 20, 30, a n d 56%
replacement level, by mass, of the high-alkali cement. The nominal
cementitious material content of both the control and the fly-ash
concrete mixtures was 420 kg/m3. For acceleration of the reaction,
concrete mixtures were also made where the alkali content was raised
by adding NaOH to the mixture water.
The properties of freshly-mixed concrete were determined.

Concrete cylinders were cast for compressive-strength determination
at various ages. The susceptibility of the coarse aggregates to AAR,
a n d the effectiveness of the fly-ash concretes in controlling the
expansion of concrete prisms were evaluated using two accelerated
storage conditions in the laboratory, i.e. at 38OC and R.H. > 95% and
38OC i n 1N N a O H solution. Mortar bars w e r e also m a d e
incorporating the above aggregates, and tested according to ACTM C
1260-94 Accelerated Mortar Bar Test procedure [31.
CONCRETE MIXTURES
The petrography and the physical properties of the three

quarried coarse aggregates from N e w Brunswick selected for this
program are given in Table 2. These included a greywacke (Spi), a
gneiss (Gn), and a meta-volcanic rock (Dg). Table 3 gives the grading
of the coarse aggregates used in the concrete mixtures.
Tables 2 a n d 3 also give the petrography, t h e physical

properties and the grading of the non-reactive fine aggregate from
N e w Brunswick that was selected for use in the control and fly-ash
concrete mixtures.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*I 95 m Obb2949 0521511 457 m
Portland Cements and Flv Ash
The physical properties and the chemical composition of the

CSA* Type 10 low- and high-alkali cements and the ASTM Type F fly
ash from Nova Scotia used in this program are given in Table 4.
Chemical Admixtures
A commercially available modified naphthalene sulfonate

--``,`,-`-`,,`,,`,`,,`---
superplasticizer meeting t h e CSA r e q u i r e m e n t s for chemical

admixtures for concrete w a s used in the high-volume fly-ash
concretes.
MIXTURE PROPORTIONS
All concrete mixtures in this study were made in a counter-

current laboratory pan mixer.
The concrete mixture proportions used are shown in Tables 5,

7, and 9, for Spl, Gn, and Dg aggregates, respectively. Control mixtures
incorporating the low- and high-alkali cements were made according
to CSA A23.2-14A Concrete Prism Test [4] using a cement content of
420 kg/m3. In one of the control mixtures, the total alkali content was
raised to 1.25% N a 2 0 equivalent, by cement mass, by adding NaOH to
the mixture water (Table 1). The water-to-cement ratio of the control
mixtures varied from 0.42 to 0.51.
Fly-ash concrete mixtures having a nominal cementitious

material content of 420 k g / m 3 were made at a 20, 30, and 56%
replacement level, by mass, of the high-alkali cement. Duplicate
series of these mixtures were made where the alkali content of the
system was raised by adding NaOH to the mixing water (Table 1). In
addition, the water-to-cementitious materials ratio of the mixtures
incorporating 20 a n d 30% fly ash varied from 0.42 to 0.51; this ratio
was kept at about 0.30 for the high-volume fly-ash mixtures.
In this study, representative sub-samples of the three coarse

aggregates were ground such as to pass the 4.75 mm sieve. The
material thus obtained was then sieved and the various size fractions
re-proportioned according to the ASTM C 1260-94 test requirements
[3]. Control a n d fly-ash mortar mixtures were then made with the
* Canadian Standards Association, Rexdale, Ontario, Canada

A C 1 SP-253 VOL*I 95 0662949 05225L2 393
three aggregates investigated using a cementitious materials to

aggregate ratio of 1 : 2.25, and a fixed water-to-cementitious materials
ratio of 0.50.
CASTING A N D INITIAL CONDITIONING

OF TEST SPECIMENS
For each concrete mixture made in this study, ten cylinders, 150
x 300 mm in size, were cast for compressive-strength determination
at 7,28,91,365, and 730 days and three to six prisms, 75 x 75 x 405 mm
in size, were cast for AAR testing. Cylinders and prisms were cast,
consolidated, and finished using the procedures specified in CSA
A23.2-3C. Immediately after casting, all concrete specimens were
covered with wet burlap and plastic sheets, and were kept in their
molds for the first 24 hours. After this initial conditioning period, the
specimens were demolded, and placed in their specific storage
conditions as described later in this paper.
Mortar bars, 25 by 25 by 285 mm in size, were made as specified

in ASTM C 1260-94 [31. The bars were kept in their molds for 24
hours. After this initial conditioning period, the specimens were
demolded, and immediately subjected to the test procedure described
below.
--``,`,-`-`,,`,,`,`,,`---
STORAGE OF TEST SPECIMENS
Test SDech e n s for Strenpth Determination
All test specimens for compressive-strength determination

were stored in the moist curing room at 23 I 1°C until required for
strength testing.
Concrete Prisms for AAR Testing
As indicated in Table 1, the concrete-prism and mortar-bar

expansion tests were used for evaluating the effectiveness of fly ash
in reducing the expansion of concrete specimens incorporating the
three reactive aggregates. Concrete prisms, in sets of three, were
stored in the following conditions:

A C 1 S P - 1 5 3 V O L * I 95 0662949 052L5L3 22T= =
Storage Condition Description

A 38°C and relative humidity > 95%
B Immersion in 1N NaOH at 38OC
The prisms subjected to the condition "A" were placed

horizontally inside a 36L plastic container. Spacers consisting of
pieces of pvc tubing cut lengthway were placed transversally at the
bottom of the container for the prisms to be approximately 50 mm
above the bottom. The height of the water was maintained at 25 mm
at the bottom of the container. A wick was placed around the inside
wall of each container to assure proper humidity conditions. All
prisms for condition "8"were stored in similar containers but
immersed in the 1N NaOH storage solution. The containers were
kept on shelves in the same 38°C temperature-controled room.
Mortar Bars for AAR Testing
Immediately after demolding, the mortar bars were put in a

plastic container filled with water at 23OC, which was then placed in
an oven at 8OOC. After 24 hours, an initial measurement was taken
--``,`,-`-`,,`,,`,`,,`---
(zero reading), and then the bars were transferred to 1N NaOH
solution at 80°C.
TEST RESULTS
Properties of Freshlv Mixed Concrete
The properties of the freshly mixed concrete are given in

Tables 6, 8, and 10 for Spl, Gn, and Dg aggregates, respectively. The
slump, air content, and the density of the concrete were determined
for all concrete mixtures. As far as possible, all tests were performed
in accordance with the CSA standards. For control concrete mixtures
and those incorporating 20 and 30% fly ash, the slumps ranged from
70 to 100 mm; for the high-volume fly-ash (HVFA) concretes, the
slumps ranged from 150 to 200 mm. For ail the concrete mixtures, the
entrapped air content was < 2% (Tables 6, 8 and 10); the only
exception was high-volume fly-ash mixtures incorporating Dg
aggregate for which the entrapped air content was about 2.6%.
Compressive Strenpth of Concrete
The 7-, 28-, 91-, and 365-day compressive strengths of the

concretes are also given in Tables 6, 8, and 10. For the control

A C 1 SP-153 VOL*I 95 Obb2949 0 5 2 3 5 3 4 I b b =
mixtures, higher compressive- strength values were obtained with

the low-alkali cement (LA) than with the high-alkali cement (HA).
The highest 28-day and one-year compressive strengths of 44.7 and
57.2 MPa were achieved by concretes Spl LA and Dg LA, respectively.
Control concrete mixtures made with the added alkalies (HA+) gave
somewhat lower compressive strengths than the companion concrete
mixtures without added alkalies (HA).
Concrete mixtures incorporating 20 and 30% fly ash generally

gave lower 7- and 28-day compressive strenghts than the
corresponding control mixtures made with the high-alkali cement;
however, the strengths obtained after 91 and 365 days were
comparable (Fig. i).High-volume fly-ash concrete mixtures generally
gave compressive strengths higher than the control mixture made
with the high-alkali cement at the ages of 28/91, and 365 days (Fig. i).
The highest one-year compressive strength of 70.0 MPa was achieved
by concrete Gn FA 56. The fly-ash concrete mixtures made with added
alkalies (FA 20+, 30+, 56+) gave significantly lower compressive
strengths than the companion concrete mixtures without added
alkalies (FA 20,30,56).
Alkali-Aaaegate Reactivitv Testing
Tables il and 12 give the length changes of the concrete prisms

stored for two years at 38°C and 100% R.H. and in a 1N NaOH
solution at 38"C, respectively. Figures 2 and 3 present the plots of
expansion versus time for selected series of these prisms.
--``,`,-`-`,,`,,`,`,,`---
Table 13 gives the length changes of mortar bars immersed for

56 days in 1N NaOH solution at 80°C. Figure 4 presents the plots of
expansion versus time for mortar bars made with the Spl and Dg
aggregates.
DISCUSSION
Alkali Cements
According to Appendix B of CSA A23.1-M94 [51, an aggregate is

to be considered potentially alkali-reactive if it produces an expansion
> 0.04% after one year in the CSA A23.2-14A Concrete Prism Test.
This test uses a concrete mixtures incorporating 420 kg of high-alkali
cement per m3 of concrete with a total alkali content of the mixture
raised to 1.25%, by cement mass, expressed as Na20 equivalent; such
mixtures have been designated as "HA+" in this study.

A C 1 S P - 1 5 3 V O L * I 75 W 0662949 0521515 O T Z
The immersion testing in the 1N NaOH solution at 38°C was

introduced to accelerate the expansion and, to some extent, to verify
if better control during storage could be achieved by using an
immersion test procedure [6,7]. It is suggested that the 0.04%
expansion level be used also as a limit for this immersion test;
however, no time limit criterion is currently available.
Concrete test prisms stored at 38'C and R.H. > 95% - Table 22 and
Fig. 2 indicate that both Spl and Dg aggregates are sensitive to the
alkali content of the concrete mixture. None of the test prisms cast
from the control mixtures incorporating these aggregates and the
low-alkali cement (i.e. LA series) or the high-alkali cement without
added alkalies (i.e. HA series) expanded significantly during the first
two years of testing at 38OC and R.H. > 95% (Table 11); however, test
prisms cast from concrete mixture Dg HA (and also Gn HA) showed a
trend for increasing expansion that has not stabilized at the end of the
above testing period. Test prisms cast from concrete mixtures Spl
HA+ and Dg HA+ expanded extensively over this two-year period.
Prisms made with the greywacke aggregate Spl expanded in excess of
0.04% after only 13 weeks of testing at 38°C and R.H. > 95% (Fig. 2A).
The expansion trend was characterized by a main phase of expansion
that started after the 12-week measurement, and which levelled off
after about nine months of testing at an expansion value of about
0.270% (Fig. 2A). Test prisms made from mixture Dg HA+ showed a
slower onset of expansion than the prisms incorporating Spl
aggregate. A steady expansion rate was observed between the 26 and
the 52 weeks; the 0.04% expansion level was reached after 32 weeks of
testing at 38°C and R.H. > 95% (Fig. 2B).
Only one series of test prisms incorporating the Gn aggregate,

Le. those made from mixtures Gn HA+, expanded in excess of 0.04%
--``,`,-`-`,,`,,`,`,,`---
during the two-year testing period at 38°C and R.H. > 95% (Table 11);
these prisms reached the 0.04% expansion level after about 92 weeks,
and resulted in a total expansion of 0.045% at the end of the two-year
testing period in the above storage condition (Table 11).
Concrete test prisms immersed in 1N NaOH at 38°C - The

expansions obtained under this storage condition were found to be a
function of the alkali content the concrete mixture (Table 12). Test
prisms made from control mixtures Spl HA+, Spi H A and Spl LA
expanded over 0.04% after approximately 13, 42 and 54 weeks of
storage in the above condition, respectively (Fig. 3A). For test prisms
made from concrete mixtures Gn HA+, Gn HA and Gn LA,
expansions in excess of 0.04% were obtained after approximately 40,
47 and 60 weeks of testing, respectively (Fig. 3B).

A C 1 SP-I153 VOL*I 95 m 0662749 0523536 T37
Mortar bars immersed in I N NaOH a t 80°C - The mortar bars made

from the control mixtures Spl HA and Dg HA showed a rapid and
steady expansion rate up to the end of the 56-day testing period (Table
.13; Fig. 4). The expansions were largely over the limits of 0.15% at 14
days and 0.33% at 28 days suggested by numerous investigators [8-11].
Mortar bars made with the Gn showed relatively low expansion
values, i.e. 0.049% at 14 days and 0.082% at 28 days, both of these
values suggesting that this aggregate is non-reactive (Table 13).
Interaretation of the fest data for control mixtures - The concrete

prism and accelerated mortar bar test results confirmed the potential
for deleterious alkali-reactivity of the Spl and Dg aggregates. The
concrete prism expansion test results indicated that these aggregates
are, however, sensitive to the alkali content of the concrete mixture.
The use of the immersion procedure in 1N NaOH solution at

38°C makes the interpretation of the test results of control mixtures
rather difficult. First, the immersion testing in I N NaOH is not
adequate for evaluating the effectiveness of a low-alkali cement to
reduce or control expansion due to AAR because of the infinite
availability of alkalies from the NaOH solution. Secondly, much
faster and/or higher test prism expansions are obtained in the NaOH
solution than in the control condition, Le. 38°C and R.H. > 95%. For
example, even if test prisms Spl HA+ reached the 0.04% expansion
level after about 13 to 14 weeks in both storage conditions at 38°C (Fig.
2A and 3A), the two-year expansion obtained in the 1N NaOH was
about twice that obtained at R.H. > 95%. Thirdly, control test prisms
eventually expand > 0.04% in 1N NaOH at 38"C, even those that do
not expand significantly at 38OC and R.H. > 95%.This last observation
may be significant for aggregates such as the Gn aggregate. The
limited but steady trend for increasing expansion observed for test
prisms Gn HA+ at 38°C and R.H. > 95%, but especially the relatively
high expansions obtained for test prisms in the 1N NaOH at 38"C,
may suggest that this aggregate is potentially reactive. Such a
potential for deleterious expansion had not been identified
previously in the accelerated mortar bar test; actually, the results of
this test, which is recommanded for use as a screening test for
determining the potential alkali-reactivity of concrete aggregates [51,
would have probably led to the acceptance of this aggregate in a
normal testing program for AAR. A s no conclusive field
performance record is available for the Gn aggregate, it is
consequently difficult to conclude that the data obtained from the test
prisms immersed in 1N NaOH at 38°C are definitively indicative of a
potential for deleterious reaction and expansion in field concretes.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 95 Ob62949 0521517 975 W
Despite the difficulties associated with the interpretation of the

test results obtained in the IN NaOH concrete prism immersion test,
it may point towards the necessity of specifying preventive measures
when using marginally reactive aggregates in critical concrete
structures such as dams and some highway bridges. Indeed, long-
term contribution of additional alkalies to the concrete pore fluid by
sources other than the cement, such as the coarse and fine aggregates,
may, in some cases, increase the total alkali content of the concrete
mixture incorporating such aggregates to levels that may, in turn,
lead to deleterious reaction and concrete distress in the long term
[12,13].
Performance of Flv Ash Concretes and mortars
The Appendix B of CSA A23.1-M94 [51 states that "at present,

the most suitable method for assessing the efficacy of supplementary
cementing materials in reducing expansion due t o AAR is the
concrete prism expansion test". When conducting the test for this
purpose, CSA recommandations are that "the cernent be replaced at
the level proposed for construction and that additional alkali be
added, in the form of NaOH, to bring the c e m e n t alkali content to
--``,`,-`-`,,`,,`,`,,`---
1.25% N a 2 0 equivalent for acceleration purposes. Current experience
is that a testing period of two wears is sufficient for the evaluation of
concrete containing fly ash or slag but particular attention should be
paid to the rate of expansion toward the end of the testing period".
ASTM C 1260 Accelerated Mortar Bar Test, with an expansion

limit criterion of 0.10% at 14 days, has often been used for evaluating
the effectiveness of pozzolans and slags in reducing expansion due to
AAR [14,15].
Test prisms stored at 38°C and R.H. 95% - Table I l indicates that
none of the test prisms made from the fly-ash concrete mixtures
incorporating Spl, Dg, and Gn aggregates showed expansion values in
excess of 0.04% after two years of testing in the above condition.
However, a slow but a steady increasing expansion trend was noticed
for concrete mixtures incorporating 20% fly ash and Spl aggregate
(Table 11; Fig. 2A). Expansion values of 0.022 and 0.035% were
obtained after two years of testing in the above condition for test
prisms cast from mixtures Spl FA 20 and Spl FA 20+, respectively,
and the expansion trend has not stabilized at this age.
Test prisms immersed in I N NaOH at 38°C -- The expansions

measured for test prisms cast from fly-ash concrete mixtures
incorporating Spi aggregate and tested in 1N NaOH were found to be
influenced by the alkali content of the concrete mixture. Test prisms

A C 1 SP-153 VOL*I 95 0662949 052L5Lô B O L
cast from concrete mixtures Spl FA 20+ and Spl FA 20 expanded over
0.04% after approximately 50 weeks and 83 weeks of immersion in 1N
NaOH at 38OC, respectively (Fig. 38). Test prisms cast from mixtures
Spl FA 30+ expanded > 0.04% after about 85 weeks of testing in the
above storage condition (Fig. 3A, Table 12).
None of the fly-ash concretes incorporating Gn aggregate

showed expansion values in excess of 0.04% after two years of testing
in 1N NaOH at 38°C. This represent significant reduction of the
expansions compared to those obtained with the control concrete
mixtures made with the high-alkali cement when tested under this
condition (Gn HA+) (Table 12; Fig. 38).
Mortar Ear Testing - Ears Immersed in 1N NaOH at 80°C - None of

the test bars incorporating the aggregates under study and cast from
the fly-ash mortar mixtures expanded in excess of 0.10% after 14 days
of storage in 1N NaOH at 8OoC (Fig. 4). The above expansion level
was reached between 21- and 49-day measurements for mortar bars
Spl, Gn and Dg FA 20, and Dg FA 30.
Interaretafion of the test dafa - The results of the various series of

mortar-bar and concrete-prism tests performed in this study indicate
that the use of cementitious systems incorporating 20, 30, or 56% fly
ash is effective in reducing significantly the expansions of test
specimens made with the selected alkali-silica reactive aggregates as
compared with those obtained for the control mixtures made with
the high-alkali cement (Le. series HA+). In fact, none of the concrete
prisms made from fly-ash mixtures incorporating the Spl, Gn and Dg
aggregates resulted in expansion > 0.04% after two years of testing at
38°C and R.H. > 95%.
A slow but a steady increasing expansion trend was noticed for

test prisms made from mixtures Spl FA 20 and Spl FA 20+ when
tested at 38OC and R.H. > 95% (Table Il; Fig. 2A). The relatively high
expansions obtained for the companion concrete prisms immersed in
the 1N NaOH at 38°C also suggest that the cementitious system
--``,`,-`-`,,`,,`,`,,`---
incorporating 20% fly ash might not offer adequate protection against
potential deleterious expansions with the highly-reactive Spl
aggregate (Table 12; Fig. 3A). Such a risk for potential deleterious
alkali-reactivity was not apparent from the results obtained in the
accelerated mortar-bar test. None of the mortar bars incorporating fly
ash expanded more than the suggested limit of 0.10% expansion at 14
days. In fact, only one series of mortar bars, i.e. Dg FA 20, exceeded the
0.10% expansion level during the first 28 days of immersion in TN
NaOH at 80°C (Table 13; Fig. 48); however, none of the test prisms

A C 1 SP-153 V O L X I 95 Obb2949 052L5L9 7 Y B
cast from concrete mixtures Dg FA 20 or Dg FA 20+ expanded

significantly after two years of testing at 38OC and R.H. > 95%.
The results presented above would suggest that, according to

Appendix B of CSA A23.1-M94, concrete systems incorporating 20, 30
or 56% fly ash would generally prevent potential deleterious
expansions with the aggregates investigated in this study. It is
difficult to state at this stage if the risk for long-term distress as
apparent from some concrete prism immersion test results for
concretes incorporating 20% fly ash and the highly-reactive Spl
aggregate is real for concrete structures subjected to natural
environmental conditions. A more detailed investigation, which is
currently in progress in CANMET laboratories may provide data as to
the reliability of the laboratory test results.
CONCLUSIONS
1) The 7- and 28-day compressive strengths of concretes
incorporating 20 and 30% fly ash as replacement for portland
cement were lower than the corresponding strength of the control
concrete made with the high-alkali cement; however, the later age
strength of the concretes were comparable. The compressive
--``,`,-`-`,,`,,`,`,,`---
strength of the high-volume fly-ash concretes at ages > 28 days
were higher than those of the control concretes made with high-
alkali cement. The compressive strength of control and fly ash
concretes incorporating additional alkalies were somewhat lower
than the corresponding concretes made without additional
alkalies.
2) The expansion test results obtained for the control concrete prisms
and mortar bars made with the high-alkali cement confirmed the
potential alkali-reactivity of Spl and Dg aggregates investigated in
this study. The Gn aggregate did not result in significant concrete-
prism expansion after two years of testing at 38°C and R.H. > 95%;
however, test prisms stored in 1N NaOH at 38OC showed
significant expansions after various periods of testing. The latter
test results suggest a potential for deleterious alkali-reactivity for
Gn aggregate that had not been identified for test prisms stored at
38OC and R.H. > 95%. As no conclusive field performance data are
currently available for the Gn aggregate, it is difficult to conclude
that the data obtained from the immersion testing in 1N NaOH at
38OC are indicative of a potential for deleterious
reaction/expansion in field concretes. The relatively low

A C 1 SP-153 VOL*I 95 I0bb2749 0521520 4bT m
expansion values obtained in the accelerated mortar bar test with

Gn aggregate also suggested that this aggregate is non-reactive.
3) None of the concrete prisms made from fìy-ash concrete mixtures

incorporating Spl, Dg and Gn aggregates expanded more than
0.04% after two years of testing at 38°C and R.H. > 95%.However,
concrete p r i s m e x p a n s i o n test r e s u l t s s u g g e s t t h a t t h e
cementitious system incorporating 20% fly ash might not offer a n
a d e q u a t e long-term protection against potential deleterious
expansions with the highly-reactive Spl aggregate. It is difficult to
conclude that these laboratory test data are indicative of a real risk
of failure of a 20% fly-ash concrete system in preventing
expansion in field concretes incorporating the Spl aggregate.
4) The concrete prism and mortar bar test results suggest that the fly
ash concrete systems investigated would adequately prevent
potential deleterious expansions with aggregates Dg and Gn.
ACKNOWLEDGMENTS
This s t u d y was funded through the Mineral Development

Agreement (MDA) between the Federal Government of Canada and
the Provincial Government of New Brunswick.
--``,`,-`-`,,`,,`,`,,`---
REFERENCES
AD1 Limited, "A Study of the Alkali-Reactivity of Potential

Concrete Aggregates of N e w Bunswick", Final Report of a
Contractual Study Funded Under the MDA Program in N e w
Brunswick, File 1264-30, November 1989.
G r o u n d Engineering a n d Materials Technology (Gemtec),

"Alkali-Aggregate Reactions in Concrete", Final Report of a
Contractual Study Funded Under the MDA Program in N e w
Brunswick, Contract no. SSC No. 039 SQ.23440.1-9025, 1993.
ASTM C 1260-94, "Standard Test Method for Potential Alkali

Reactivity of Aggregates (Mortar-Bar Method)", Annual Book of
ASTM Standards, 04.02, Concrete and Mineral Aggregates,
American Society for Testing and Materials, Philadelphia, U.S.A.,
1994, p. 648-651.

A C 1 S P - 5 5 3 V O L * I 95 Ob62749 0521521 3Tb
4. Methods of Test for Concrete, "A23.2-14A - Potential Expansivity

of Aggregates (Procedure for Length Change Due to Alkali-
Aggregate Reaction in Concrete Prisms)", In A23.2-M94, Methods
of Test for Concrete, Canadian Standards Association, ISSN 0317-
5669, Rexdale, Ontario, June 1994, p. 205-214.
5. CSA A23.1-Appendix B, "Alkali-Aggregate Reaction", In A23.1-

14A, Concrete Materials and Methods of Concrete Construction,
Canadian Standards Association, ISSN 0317-5669, Rexdale,
Ontario, June 1994, p. 112-135.
6. Fournier, B., Malhotra, V.M., Langley, W.S. and Hoff, G.C.,

"Alkali-Aggregate Reactivity (AAR) Potential of Selected
Canadian Aggregates for Use in Offshore Concrete Structures",
Proceedings of the Third CANMET/ACI International
Conference on the Durability of Concrete, Nice, France, May 1994,
V.M. Malhotra Editor, AC1 publication SP 145-35, pp. 657-686.
7. Fournier, B. and Malhotra, V.M., "Effectiveness of

Supplementary Cementing Materials in Reducing Expansion Due
to Alkali-Aggregate Reaction in High-Performance Concrete",
Proceedings of the AC1 International Conference on High-
Performance Concrete, Singapore, November 1994, V.M.
Malhotra Editor, AC1 publication SP-149, pp. 729-751.
8. Hooton, R.D., "New Aggregate Alkali-Reactivity Test Methods",

Ministry of Transportation of Ontario, Research & Development
Branch, Report MAT-91-14.
9. Fournier, B. and Bérubé, M.A. "A Comparison of Laboratory

Testing Methods for Evaluating Potential Alkali-Reactivity in the
St. Lawrence Lowlands (Quebec, Canada)", Proceedings, Ninth
International Conference on AAR in Concrete, London, U.K.,
July 1992, Concrete Society (U.K.)
Publication CS.104, pp. 327-337.
10. Grattan-Bellew, P.E., "Canadian Experience with Mortar Bar

--``,`,-`-`,,`,,`,`,,`---
Rapid Tests for AAR, Canadian Developments in Testing

Concrete Aggregates for Alkali-Aggregate Reactivity, Ministry of
Transportation of Ontario, C.A. Rogers Editor, Report EM-92, pp.
17-34.
11. Bérubé, M.A. and Fournier, B., "Accelerated Test Methods for
Alkali-Aggregate Reactivity", In Advances in Concrete
Technology, CANMET publication MSL 94-1(lR), Natural
Resources Canada, Second Edition, V.M. Malhotra Editor, pp. 991-
1044.

A C 1 SP-153 V O L * I 95 I0662749 0521522 232
12. Thompson, G.A., "Alkali-Aggregate Reactivity Remedial

Measures - Mactaquac Intake Structures", Proceedings, CANMET
International Workshop on Alkali-Aggregate Reactions in
Concrete: Occurences, Testing and Control, Halifax, Nova Scotia,
May 1990, J.A. Soles Editor, paper no. 16.
13. Grattan-Bellew, P.E., "Alkali Contribution from Limestone

Aggregate to Pore Solution", AC1 Materials Journal, Vol. 91, No.
2,1994, pp. 173-177.
14. Davies, G. and Oberholster, R.E., "Use of the NBRI Accelerated

Test to Evaluate the Effectiveness of Mineral Admixtures in
Preventing the Alkali-Silica Reaction", Cement and Concrete
Research, Vol. 17, No. 1, pp. 97-107.
15. Bérubé, M.A., and Duchesne, J., "Evaluation of Testing Methods

Used for Assessing the Effectiveness of Mineral Admixtures in
Suppressing Expansion Due to Alkali-Aggregate Reaction",
Proceedings, Fourth International Conference on Fly Ash, Silica
Fume, Slag, and Natural Pozzolans in Concrete, Istanbul, Turkey,
May 1992, V.M. Malhotra Editor, AC1 SP-132, American Concrete
Institute, Detroit, Michigan, Paper no. 31, pp. 549-575.
--``,`,-`-`,,`,,`,`,,`---

-
... ... .. ..
. <
..
. <
..
:Ni
3
. ..
..
-
< .
< .
..
t
<.. .
.
.
. .
..
. ...
... ...
. <
N jm
.
<
... .
....
... ....
-
.. ..
<
. <
.
.. .
.
.
<
<
. .
. ..
..... ....
. .
...
.
.
<
..
.
.
.
<
<
.
<
<
.
...
..
I
. .
.
.
. <
...
.
.
<
< ...
. .
... ...
- <
.. ..
I
.
... ..
. ..
.... ....
. .
M
Y
00
M
4
I l l N N n
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153
V O L + I 95 I
0662949 0523523 379
Not for Resale
A C 1 SP-I153 V O L X I 95 Ob62949 0521524 005 W
--``,`,-`-`,,`,,`,`,,`---
TABLE 2 - PETROGRAPHY AND PHYSICAL PROPERTIES OF

COARSE AND FINE AGGREGATES USED IN THIS STUDY
Density Absorption
Aggregate Type Rock Type1 SCD (g/crn3) (%)
Quarried
SPI sedi ment a ry Greywacke 2.69 0.78
rock
Quarried
To granitic Gneiss 2.70 0.57
rock
Quarried Meta basaltic tuff (63%),
D& meta-volcanic rhyolite (35%)and 2.68 1.20
rock rhyolitic tuff (2%)
Quartz, feldspar (-KI%),
Fine aggregate Natural sand (-'"%)i 2.52 1.o0
argillite, greywacke and
meta-argillite (-10%)
Information from DeMerchant 1993 [XI
TABLE 3 - GRADING OF AGGREGATES USED IN THIS STUDY
Coarse aggregates Fine aggregate

Size
ímm)
Cumulative % retained
Spl, Gn & Dg
Size
ímm)
(~~xn)
4.75
I Cumulative
70 re;ined
20 O 2.36 I 7
14 33 1.18 I 23
10 66 0.600
I 52
5
Pan
100
1o0
o.30o
0.300
0.150
Dan
I E
I
76
91
i00
100

A C 1 SP-153 VOL*I 95 = 0662949 0521525 T41 M
--``,`,-`-`,,`,,`,`,,`---

CEMENTS AND ASTM CLASS F FLY ASH USED IN THIS STUDY
Ma terials Characteristics
A PhvsicalT-
1- CSA T
Low-alkali
e 101 Cements
High-alkali
Fly Ash
ASTM Class I
(FA)
Fineness passing 45 p,%

Blaine, m2/kg
Specific gravity
Compressive strength
on 50.8 mm cubes, MPa
3days
7days
28days
Pozzolanic Activity Index
B. Chemical Analvsis
Silicon dioxide (Si@>, %
Calcium oxide total (Cao), %
Aluminum oxide (Ai@& %
Ferric oxide (F4031, %
Magnesium oxide (MgO), %
Sulphur oxide (SO& %
Free calcium oxide, %
Loss on ignition, %
Sodium oxide (NaiO), %
Potassium oxide &O), %
Total alkalies, (Na20 equiv.), %
C. Bogue compounds
c3s 58.9 52.4 __
czs 18.1 18.0 --
C3A 4.4 10.3 _-
CAAF 10.7 6.0 I
* This is equivalent to ASTM Type I cement.

A C 1 SP-353 VOL*I 95 0662949 0 5 2 3 5 2 6 988
--``,`,-`-`,,`,,`,`,,`---
L -
u c -
2 .M .$
3
53
2+ h h h m a r n - a r < r <
V
i 7 7 7 t Y
O
7
0
7
0
cO? c0?
3 0 0 O 0
\

A C 1 SP-353 VOL81 95 I0 6 6 2 9 4 9 0523527 834
W
I-
a
w
IT
c3
2-
Q
c3
z
m
3
W
I-
W
II
o
z
O
o
n
w
Z
W
n
IT
a
I
n E Ë
Z 3
m -
6
a
I
m
w
LT
LL
LL
O
m
!
t-
:/4 u
LT
W
Q
a
LL
O
--``,`,-`-`,,`,,`,`,,`---
>
CE
a
2
r
2
m
I
CD
!!m
2

A C 1 SP-I153 V O L * I 95 m 0662949 0 5 2 3 5 2 8 750 m
2+
V
\
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL+I 95 =
0662949 0 5 2 3 5 2 9 fa97 =
.-L -g E
Li
E -
u
E2
3 E
m -
--``,`,-`-`,,`,,`,`,,`---
51;u

1
A C 1 SP-153 VOL*I 95 I0662949 0523530 309
il'-
U
O M
\
2i
U
\
1
--``,`,-`-`,,`,,`,`,,`---
Y -
5 *€
5%
us

A C 1 SP-153 V O L t I 95 m Obb2949 0521531 245 m
LL
I-
U
L?
U
u
u
a
U
p
u
z
u3
3
W
I-
w
a
o
Z
O
o
n
W
z
W
n
a
a
I
n E Ê
z I E
a m -
I
(B
W
[r
LL
LL
O
(B
W
i=
LT
--``,`,-`-`,,`,,`,`,,`---
w
a
$
a
LL
O
>.
a
a
5
5
z)
0
I
O
7
W
-I
m
a
t-

TABLE 11 - CONCRETE PRISM EXPANSION TEST RESULTS

Mixtures Control and fly ash conaete mixtures
Aggregate Spi, Gn, and Dg
Testing condition Concrete Prisms at 38°C and R.H. > 95%
Concrete Expansion (%I vs Time (weeks)

mixture 1 2 4 8 12 16 24 32 40 52 79 104
identificatior ~~ ~ ~~~~ ~ ~~
CplM 0.004 0.000 0.002 0.008 -0.003 0.002 0.003 -0.005 0.002 0.003 0.003 0.011
%A HA 0.004 -0.007 0.003 0.003 0.004 0.005 0.001 0.OOO 0.009 0.012 0.007 0.010
Spi HA+ 0.004 0.001 0.015 0.017 0.023 0.067 0.163 0.230 0.258 0.271 0.264 0.267
Spi FA 20 0.000 0.002 0.007 0.006 0.001 0.004 0.000 0.002 0.009 0.017 0.013 0.022
Spi FA 20+ 0.006 0.008 -0.002 -0.003 -0.005 -0.004 -0.007 -0.007 0.007 0.018 0.022 0.035
Spi FA 30 0.014 0.000 0.003 0.005 -0.004 -0.003 -0.004 -0.003 0.001 0.010 0.004 0.013
Spi FA 30+ 0.014 0.017 0.011 0.019 0.008 0.012 0.007 0.004 0.013 0.024 0.019 0.029
Spi FA 30++ 0.000 -0.004 -0.004 -0.009 0.000 -0.007 -0.008 -0.008 0.001 0.011 0.010 0.017
Spi FA 56 __ -0.002 -- -0.006 0.001 -0.004 -0.004 -0.011 0.002 0.006 0.002 0.009
Spi FA 56+ -0.031 -0.001 -0.001 -0.004 0.002 -0.001 -0.005 -0.005 0.000 0.005 0.005 0.01C
GnLA 0.007 0.010 0.008 0.005 0.013 0.013 0.008 0.006 0.009 0.012 0.012 0.017
Gn HA -0.015 -- 0.007 0.002 0.013 0.009 0.003 0.003 0.009 0.012 0.017 0.024
Gn HA+ 0.001 -0.018 -0.009 0.010 0.008 0.011 0.013 0.018 0.017 0.032 0.036 0.045
Gn FA 20 0.002 --- 0.001 0.002 --- 0.001 -0.007 -0.007 -0.001 0.002 0.007 0.011
Gn FA 20+ -0.002 -0.015 -- -0.006 -0.008 -0.002 -0.006 -0.003 -0.003 0.006 0.005 0.01C
Gn FA 30 -0.012 - - - -0.005 0.000 -0.006 -0.006 -0.010 -0.013 -0.007 -0.006 -0.003 0.OOC
Gn FA 30+ 0.001 -0.024 - - -0.006 -0.012 -0,008 -0.009 -0.007 -0.006 -0.002 -0.004 0.001
Gn FA 30++ .0.015 :.. 0.001 0.004 0.006 -0.004 0.001 -0.001 0.004 0.005 0.009 0.015
Gn FA 56 ___ _ _ .-0.020 0.000 0.003 -0.004 -0.006 -0,008 -0.002 0.001 0.001 0.OE
--``,`,-`-`,,`,,`,`,,`---
Gn FA 56+ .0.005 -0.024 -0.012 0.001 -0.003 0.000 -0.006 -0.001 0.001 0.006 0.001 0.002
DgLA 0.008 0.006 0.006 0.001 -0.001 -0.002 -0.001 -0.009 -0.002 0.006 -0.001 0.W
Dg HA 0.006 0.001 0.001 0.001 0.000 0.001 -0.001 -0.002 0.002 0.013 0.010 0.02;
ng HA+ 0,010 0.003 0.003 0.005 0.002 0.006 0.015 0.040 0.084 0.136 0.169 0.202
Dg FA 20 -0.006 0.003 0.000 -0.006 -0.007 -0.010 -0.008 -0.009 -0.005 0.006 -0.003 O.O@
Dg FA 20+ -0.001 -0.001 -0.005 -0.006 -0.007 -0.009 -0.009 -0.011 -0.003 0,005 -0.001 0.00;
Dg FA 30 -0.010 -0.012 -0.013 -0.014 -0.017 -0.017 -0.019 -0.019 -0.016 -0.008 -0.015 -0.00,
Dg FA 30+ 0.002 0.002 -0.001 -0.001 -0.007 -0.007 -0.006 -0.010 0.001 0.005 0.001 0.01(
Dg FA 30++ -0.000 -0.002 -0.006 -0.005 -0.020 -0.005 -0.012 -0.013 -0.006 0.001 -0.003 O.O@
Dg FA 56 -0.002 -0.003 -0.003 -0.001 -0.010 -0.002 -0.006 -0.008 -0.002 0.003 -0.003 0.00;
De FA 56+ -0,005 0,002 -0.001 0.001 -0.010 -0.002 -0.004 -0.007 -0.004 0.001 -0.004 0.OW

A C 1 SP-353 V O L + I 95 U Obb2949
No reproduction or networking permitted without license from IHSNot for Resale 0523532 L B 3 =
A C 1 SP-153 V O L U I 95 = 0662949 0521533 018
TABLE 12 - CONCRETE PRISM EXPANSION TEST RESULTS

Mixtures
Aggregak
Testing condition
I Control and fly ash concrete mixtures
[ Spi, Gn, and Dg
IConcrete Prisms immersed in 1N NaOH at 38°C
II
Concrete Expansion (%I YS Time (weeks)
mixture 1 2 4 8 12 16 24 32 40 52 79 1M
ientificatio1
CplM -0.001 -0.007 -0.003 0.009 0.013 0.013 0.013 0.014 0.024 0.036 0.074 0.119
cpl HA -0.005 0.007 0.006 0.011 0.010 0.013 0.007 0.009 0.021 0.119 0.288 0367
Spi HA+ 0.001 0.004 0.011 0.018 0.027 0.054 0.146 0.wB 0.320 0.407 0.474 0.511
Spl FA 20 0.000 0.013 0.001 -0.001 O.OO0 -0.001 -0.004 -0.002 0.007 0.015 0.034 0.063
Spi FA 20+ -0.003 -0.004 -0.002 -0.002 0.001 0.000 0.001 0.001 0.015 0.042 0.084 0.119
Spi FA 30 -0.005 -0.006 -0.008 -0.003 -0.014 -0.010 -0.010 -0.010 -0.008 0.003 0.006 0.027
Spi FA 30+ 0.005 0.006 0.004 0.006 0.004 0.005 -0.002 0.001 0.011 0.015 0.031 0.057
Gn LA 0.004 0.061 0.001 0.001 0.002 0.003 0.003 0.009 0.011 0.027 0.072 0.132
GnHA 0.000 0.002 0.002 0.002 0.000 0.003 0.003 0.009 0.022 0.050 0.123 0.182
Gn HA+ 0.001 0.004 0.002 0.008 0.007 0.003 0.008 0.020 0.039 0.081 0.175 0.246
Gn FA 20 0.004 -0.001 -0.006 -0.005 -0.006 -0.008 -0.008 -0.004 -0.003 0.001 0.000 0.024
Gn FA 20+ -0.003 -0.002 -0.007 -0.004 -0.010 -0.006 -0.010 -0.005 -0.004 0.004 0.004 0.024
Gn FA 30 0.004 0.002 -0.004 -0.008 -0.010 -0.011 -0.012 -0.009 -0.002 0.000 -0.003 0.008
Gn FA 30+ 0.000 -0.002 -0.005 -0.006 -0.008 -0.008 -0.011 -0.008 -0.005 -0.002 -0.003 0.006
TABLE 13 - ACCELERATED MORTAR BAR TEST RESULTS

~-
Mixtures Contra1and fly ash mortar mixtures
Aggregate Spl, Gn, and Dg
Testing condition Mortar bars immersed in 1N NaOH solution at 80°C
Concrete Expansion (a) vs Time (weeks)

mixture 1 3 5 7 10 12 14 21 28 35 42 49 56
identification
spi HA -0.001 0.047 0.137 0.201 0.255 0.290 0.314 0.393 0.466 0.442 0.610 0.615 0.701
Spi FA 20 -0.002 0.008 0.028 0.024 0.032 0.042 0.045 0.070 0.092 0.098 0.150 0.159 0.192
Spi FA 30 0.W 0.010 0.017 0.017 0.021 0.020 0.030 0.023 0.039 0.051 0.061 0.071 0.086
--``,`,-`-`,,`,,`,`,,`---
Spl FA 56 0.006 0.010 0.013 0.006 0.018 0.017 0.027 - 0.026 0.030 0.034 -- 0.038
Gn HA 0.W 0.003 0.020 0.023 0.032 0.045 0.049 0.072 0.082 0.089 0.117 0.128 0.142
Gn FA 20 0.m 0.004 0.013 0.011 0.021 0.022 0.032 0.055 0.071 0.070 0.117 0.132 0.152
Gn FA 30 4.012 -0.013 -0.002 -0.007 -0.006 0.004 0.010 0.018 0.024 0.039 0.053 0.062 0.080
Gn FA 56 4.004 4.005 0.002 0.001 0.005 0.W 0.006 0.007 0.011 0.016 0.020 0.024 0.034
Dp HA 4.001 0.044 0.149 0.217 0305 0.335 0.378 0.485 0.575 0.645 0.750 0.791 0.826
DgFA20 0.001 0.004 0.018 0.024 0.034 0.046 0.060 0.085 0.139 0.179 0.227 O 2 6 8 0.303
DgFA30 4.005 0.003 O.Oo0 0.006 0.010 0.011 0.017 0.019 0.M9 0.046 0.083 0.104 0.123
DgFA56 4.0024.001 O.Oo0 O.Oo0 0.002 O.Oo0 0.003 0.001 0.009 0.010 0.016 0.016 0.029

70
h
m
v5 60
--``,`,-`-`,,`,,`,`,,`---
sbo
5
CI
50
3;
o)
.?
v)
40
v)
E!
3 30
8
20
Fig. 1-Typical evolution in compressive strength values against

time for fly ash and control concretes made in this study

-
0.28
0.20
1 -1 -
f-
- [ 38"C, R.H. > 95%
v SplHA
SplLA
A
/
SplHA+
+ SplFA20+
5 0.12 + CplFA30++
--t- SplFA56+
n,
x . 0.08
W
0.04
0.0
-0.04p . , , , . , . , , ,I . ,
O 20 40 60 80 100 120
Time (weeks)
E
O 20 40 60 80 700 120
Time (weeks)
Fig. 2-Expansion test results for test prisms cast from

control and fly ash concrete mixtures and stored for 2
years at 38 C and RH > 95 percent
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 75 ENot0662947
No reproduction or networking permitted without license from IHS for Resale O523535 990
A C 1 SP-353 VOL+I 95 IPI O662949 0523536 8 2 7 IPI
- A
0.32
0.28 -
,
p
0.511% at
0.367% at 104 weeks
[38"C,1N NaOH
SplHA
SplHA+
-t-
+ CplFA20
+ SplFA20+
e SplFA30
-0.04! . , . , . , . I . ,' . I
O 20 40 60 80 100 120
Time (weeks)
B
--``,`,-`-`,,`,,`,`,,`---
O 20 40 60 80 100 120
Time (weeks)
Fig. 3-Expansion test results for test prisms cast from control and fly
ash concrete mixtures and immersed for 2 years in I N NaOH at 38 C

A C 1 Sp-153 V O L t I 95 0662949 0523537 763
1 Accelerated Mortar Bar Test I A

0.75
0.65
0.55
s
W
0.45
c;
O
.d
m 0.35
52 0.25 posed expansion limit at 14 days
w 0.15
0.05
4.051
O
. 8
IO
'. 20
. I
30
.
40
I . ,
50
.
t 3
Time (days)
Accelerated Mortar Bar Test

0.95
0.85
- 0.75 0.65
-i
-t- DgFA56
/
W
G 0.55
O
'g 0.45
5 0.35
Proposed expansion limit at 14 days
0.25
0.15
0.05
--``,`,-`-`,,`,,`,`,,`---
O 10 20 30 40 50 60
Time (days)
Fig. +Expansion test results for mortar bars cast

from control and fly ash mortar mixtures and immersed
for 56 days in 1N NaOH solution at 80 C

I SP-153 vo
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 0662949 0521560 046
Fly Ash, Silica Fume, Slag, and

Natural Pozzolans in Concrete
Proceedings
Milwaukee, Wisconsin, USA, 1995
--``,`,-`-`,,`,,`,`,,`---
Editor
V.M. Malhotra
Volume 2 SP-153
1 No reproduction or networking permitted without license from IHS Not for Resale
A C 1 SP-II53 VOLJII 95 Ob62949 052II5bII T ö 2 W
DISCUSSION of individual papers in this symposium may be submitted in

accordance with general requirements of the AC1 Publication Policy to AC1
headquarters at the address given below. Closing date for submission of
discussion is January 1, 1996. All discussion approved by the Technical
Activities Committee along with closing remarks by the authors will be
published in the May/June 1996 issue of either AC1 Structural Journal or
--``,`,-`-`,,`,,`,`,,`---
AC1 Materials Journal depending on the subject emphasis of the indi-vidual

paper.
The Institute is not responsible for the statements or opinions expressed in

its publications. Institute publications are not able to, nor intended to,
supplant individual training, responsibility, or judgment of the user, or the
supplier, of the information presented.
The papers in this volume have been reviewed under Institute publication
procedures by individuals expert in the subject areas of the papers.
Copyright O 1995
AMERICAN CONCRETE INSTITUTE
P.O. Box 19150, Redford Station
Detroit, Michigan 48219
Ail rights reserved including rights of reproduction and use in any form or
by any means, including the making of copies by any photo process, or by any
electronic or mechanical device, printed or written or oral, or recording for
sound or visual reproduction or for use in any knowledge or retrieval system
o r device, unless permission in writing is obtained from the copyright
proprietors.
Printed in the United States of America
Editorial production Victoria Lunick
Library of Congress catalog card number 95-76270

PREFACE
The Canadian Centre for Mineral and Energy Technology

(CANMET) of Natural Resources Canada, Ottawa, has played a significant
role in Canada for over twenty-eight years in research on fly ashes, ferrous
and nonferrous slags, and silica fumes, in order to conserve both resources
and energy. In July-August 1983, CANMET, in association with the Ameri-
can Concrete Institute and the U.S. Corps of Engineers, sponsored a five
day international conference at Montebello, Quebec, Canada, on the Use
of Fly Ash, Silica Fume, Slag and Other Mineral By-products in Concrete.
The main purpose of the conference was to bring together representatives
from industries, universities, and government agencies to present the latest
information on these materials and to explore new areas of needed re-
search. The two volume proceedings of the conference containing 62 papers
from 15 countries were published as AC1 Special Publication SP-79.
tute, the Canadian Society for Civil Engineering, and a number of organ-
izations in Spain, sponsored the Second International Conference on the
subject of Fly Ash, Silica Fume, Slag, and Natural Pozzolans in Concrete.
The conference was held April 21-25, 1986, in Madrid, Spain. The two
volume proceedings of the conference containing 72 papers from more than
20 countries were published as AC1 Special Publication SP-91.
tute, Norwegian Institute of Technology, and several other organizations in
Canada and Norway, sponsored the Third International Conference on the
above subject. The conference was held June 18-23, 1989, in Trondheim,
Norway. The two volume proceedings of the conference containing 83
papers from more than 25 countries were published as AC1 Special Publi-
cation SP-114.
tute, Electric Power Research Institute, U.S.A., and several other or-
ganizations in Canada and Turkey, sponsored the Fourth International
Conference on the subject. The conference was held May 3-8, 1992, in
Istanbul, Turkey. More than 130 papers from 32 countries were received
and reviewed in accordance with the policies of the American Concrete
Institute; 89 papers were accepted for publication as AC1 Special Publi-
cation SP-132.
tute, Electric Power Research Institute, U.S.A., Canadian Electrical
--``,`,-`-`,,`,,`,`,,`---

iii
A C 1 SP-153 V O L U I I 95 E 0662949 0521563 855 E
Association, Montreal, and several other organizations in Canada and the

United States, sponsored the Fifth International Conference on the subject.
The conference was held June 4-9,1995, in Milwaukee, U.S.A. The two vol-
ume proceedings of the conference containing 62 papers from 23 countries
were published as AC1 Special Publication SP-153.
--``,`,-`-`,,`,,`,`,,`---
To all those whose submissions could not be included in the confer-

ence volumes, the Institute and the Conference Organizing Committee ex-
tend their appreciation for their interest and hard work. The accepted
papers have been published in two volumes. The first volume contains
papers dealing with fly ash and natural pozzolans, and the second volume
consists of papers dealing with silica fume, slag, and other materials. Some
papers could have been published in either volume because the material
covered more than one subject.
In addition to the papers which have been published in these vol-
umes, more than 20 other papers were presented. Most of these papers
were published as supplementary papers, and the authors have been
encouraged to publish them in technical journals of their choice.
Thanks are extended to the members of the "Paper Review Panel"
which met as Cascais, Portugal, June 5-9, 1994, to review the papers.
Without their dedicated effort it would not have been possible to publish
these volumes before the conference. The cooperation of the authors in
accepting reviewers' suggestions and revising their manuscripts accordingly
is greatly appreciated.
The help and assistance of Mr. H. S . Wilson, Consultant, Ottawa,
Gordon D. Brearly and Maria Venturino of CANMET are gratefully ac-
knowledged in the administrative work associated with the conference, and
in processing of the manuscripts both for AC1 proceedings and the supple-
mentary volume. Thanks are also extended to A. Bilodeau (Chairman) and
Messrs. B. Fournier and R. Chevrier (Members) of the Slide Review Panel
for their services to ensure that the slides meet the CANMET/ACI cri-
terion.
As an integral part of the conference, a special symposium to honor
Dr. Narayan Swamy, Prof. Dept of Civil Engineering, University of Shef-
field, U.K., was held during the conference. The papers presented at this
symposium have been published in a separate volume.
V. M. Malhotra, Editor
Chairman, CANMET/ACI Fifth International
Conference on Fïy Ash, Silica Fume, Slag
June 1995

iv
A C 1 SP-153 V O L S 1 1 95 E 0662949 0521564 791
Organizing Committee
on
Fly Ash, Silica Fume, Slag
Milwaukee, Wisconsin
1995
V. M. Malhotra H. S. Wilson
Chairman Secretary-Treasurer
Members
T. W. Bremner
H. L. Isabelle
W. S. Langley
V. S . Ramachandran
--``,`,-`-`,,`,,`,`,,`---
Dedicated to Members of the "Paper Review Panel" who assisted in the

review of the manuscripts.
Copyright American Concrete Institute V

A C 1 SP-153 VOLXII 95 S 0662947 O523565 628
CONTENTS
...
PREFACE ........................................... 111
PERFORMANCE O F CONCRETES INCORPORATING

VARIOUS FORMS O F SILICA FUME
by J. Wolsiefer, Sr., V. Sivasundaram, V. M. Malhotra,
--``,`,-`-`,,`,,`,`,,`---
a n d G . G. C a r e t t e . . ................................... 591
EFFECTIVENESS O F SUPPLEMENTARY CEMENTING

MATERIALS IN CONTROLLING CHLORIDE PENETRATION
INTO CONCRETE
by R. N. Swamy and J. C. Laiw ........................... 657
ENSURING HIGH QUALITY SILICA FUME CONCRETE

OVERLAYS
by C. Ozyildirim . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
STRAIN RATE SENSITIVITIES OF STRENGTH AND

DEFORMATION O F HIGH-STRENGTH SILICA FUME
CONCRETE
by N. Han and J. C. Walraven . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
NONEVAPORABLE WATER AND DEGREE O F CEMENT

HYDRATION IN SILICA FUME - CEMENT SYSTEMS
by E. H. Atlassi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703
SURFACE AND COLLOIDAL PROPERTIES O F SILICA FUMES

IN AQUEOUS MEDIUM
by Q. Chu, S. Bonnamy, and H. Van D a m m e . . . . . . . . . . . . . . . . .719
INFLUENCE O F HIGH SILICA FUME AND HIGH FLY ASH

CONTENTS ON ALJWLINITY O F PORE SOLUTION AND
PROTECTION OF STEEL AGAINST CORROSION
by U. Wiens, W. Breit, and P. Schiessl ...................... 741

MOISTURE DIFFUSIVITY OF FIBER REINFORCED SILICA
FUME MORTARS
by E. Danarié and Y. F. Houst ........................... 763
MANUFACTURE O F HIGH-STRENGTH AERATED

--``,`,-`-`,,`,,`,`,,`---
CONCRETE CONTAINING SILICA FUME

by H. Fujiwara, E. Sawada, and Y. Ishikawa . . . . . . . . . . . . . . . . . .779
SULFATE RESISTANCE O F MORTARS CONTAINING

SILICA FUMES AS EVALUATED BY DIFFERENT METHODS
by A. Yeginobali and F. T. Dilek .......................... 795
HIGH REACTIVITY METAKAOLIN (HRM) FOR HIGH

PERFORMANCE CONCRETE
by M. A. Caldarone and K. A. Gruber ...................... 815
T H E INFLUENCE O F SILICA FUME ON T H E HEAT O F

HYDRATION OF PORTLAND CEMENT
by M. I. Sánchez de Rojas and M. Frías ..................... 829
STUDIES ON FERROCEMENT CONTAINING SILICA FUME

by M. Tamai and T. Takaya ............................. 845
LONG-TERM PERFORMANCE O F SILICA FUME CONCRETES

IN THE USA EXPOSED TO ABRASION-EROSION OR
CAVITATION - WITH 10-YEAR RESULTS FOR KINZUA
DAM AND LOS ANGELES RIVER
by M. D. Luther and W. Halczak .......................... 863
T H E DURABILITY OF CONCRETES MADE WITH BLENDS OF

HIGH-ALUMINA CEMENT AND GROUND GRANULATED
BLAST FURNACE SLAG
by G. J. Osborne and B. Singh ........................... 885
BLAST FURNACE SLAG AGGREGATE IN T H E PRODUCTION

O F HIGH-PERFORMANCE CONCRETE
by M. N. Haque, O. A. Kayyali, and B. M. Joynes . . . . . . . . . . . . . 911
EFFECTS O F FLY ASH, BLAST FURNACE SLAG AND

SILICA FUME ON RESISTANCE O F MORTAR TO CALCIUM
CHLORIDE AïTACK
by K. Torii, T. Sasatani, and M. Kawamura . . . . . . . . . . . . . . . . . . 931

viii
A C 1 SP-153 VOL*II 95 0662947 0 5 2 2 5 b 7 4 T 0
EFFECTS O F HIGH FINENESS AND LARGE AMOUNTS O F

GROUND GRANULATED BLAST FURNACE SLAG ON
PROPERTIES AND MICROSTRUCTURE OF SLAG CEMENTS
by T. Tomisawa and M. Fujii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
EFFECT O F TEST PROCEDURES ON THE ASSESSMENT

O F THE SULFATE RESISTANCE OF SLAG CEMENTS
by J, P. H. Frearson and D. D. Higgins . . . . . . . . . . . . . . . . . . . . . 975
UTILIZATION O F LOW HEAT CEMENT WITH HIGH CONTENT

OF FINELY GROUND BLAST FURNACE SLAG FOR HIGH
STRENGTH CONCRETE
by M. Iwai, A. Takagi, T. Mizobuchi, and Y. Nobuta . . . . . . . . . . .995
EFFECTIVENESS OF GRANULATED BLAST FURNACE SLAG

IN PREVENTING ALKALI-SILICA REACTION
by D. D. Higgins and M. D. Conne11 ...................... 1017
--``,`,-`-`,,`,,`,`,,`---
EFFICIENCY O F FINELY GROUND BLAST FURNACE SLAGS
IN HIGH-STRENGTH MORTARS
by Y. Ohama, J. Madej, and R. Demura . . . . . . . . . . . . . . . . . . . 1031
A STUDY OF T H E PROPERTIES O F PORTLAND CEMENT

INCORPORATING SILICA FUME A N D BLAST FURNACE
SLAG
by S. Nagataki and C. Wu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1051
EFFECT O F BLAST FURNACE SLAG IN REDUCING

EXPANSION D U E TO ALKALI-SILICA REACTION
IN CONCRETE
by T. Wang, S. Nishibayashi, K. Nakano, and Q. Bian . . . . . . . . . 1069
EFFECT OF HEAVY METALS IMMOBILIZATION ON THE

PROPERTIES O F ALKALI ACTIVATED SLAG MORTARS
by J. Malolepszy and J. Deja ............................ 1087
PROPERTIES O F MORTAR AND CONCRETE USING RED

MUD A N D FINELY GROUND SILICA
by K. Kohno, K. Amo, Y. Ogawa, and M. Gyotoku . . . . . . . . . . . 1103
A STUDY O F STRENGTH DEVELOPMENT AND

CARBONATION O F CONCRETE INCORPORATING
HIGH VOLUME BLAST FURNACE SLAG
by J. Nakamoto and K.Togawa ...................... 1121

ix
A C 1 SP-153 VOLtII 95 D 0662949 0 5 2 3 5 6 8 337
--``,`,-`-`,,`,,`,`,,`---
FLY ASH AND SLAG JET-BLAST RESISTANT CONCRETES

by P. J. Robins and S. A. Austin ......................... 1141
CHEMICAL ACTIVATION OF LIME-SLAG BLENDS

by C. Shi and R. L. Day ............................... 1165
SMALL-ANGLE SCATIERING STUDY O F CONCRETE

MICROSTRUCTURE AS A FUNCTION OF SILICA FUME,
FLY ASH OR OTHER POZZOLANIC ADDITIONS
by A. J. Allen and R. A. Livingston ....................... 1179
SI (Metric) TABLES. ................................. 1201
INDEX ........................................... 1203

X
A C 1 SP-153 VOLaJ.1 75 W 0662749 0523567 273
SP 153-33
Performance of Concretes
Incorporating Various Forms
of Silica Fume
by J. Wolsiefer, Sr., Y. Sivasundaram,
V. M. Malhotra, and G. G. Carette
Synopsis: This paper presents the results of a joint
--``,`,-`-`,,`,,`,`,,`---
project between CANMET, Ottawa, Canada and NORCHEM
Concrete Products, Inc., Hauppauye, New York, on the
performance of concretes incorporating various forms of
silica fume. Eleven different product forms of silica
fume were used in four series of concretes with water-to-
cementitious materials ratio of 0.40, 0.35, 0.30, and
0.22. Test specimens from the above concretes were
subjected to varying curing conditions, and were tested
for compressive and flexural strengths, drying shrinkage,
and rapid chloride permeability. It was found that, in
general, the performance of the silica fume concretes in
terms of mechanical properties was comparable, regardless
of the silica fume product form used and the SiO, content
of the fumes. The Rapid Chloride Permeability values, in
coulombs at 41 days, a measure of the resistance of
concrete to the penetration of chloride ions (AASHTO
T277) for all the silica fume concretes tested, except
those made with silica fume blended cements, ranged from
9 4 to 3 4 6 coulombs indicating very low permeability of
the concretes. The values for concretes made with the
blended silica fume cements were slightly higher.
Keywords: Blended cements; chlorides; compaction; compressive

strength; drying shrinkage; flexural strength; mix proportioning;
permeability; silica fume; slurries

59 1
A C 1 SP-153 VOL811 95 0662949 0523570 T95 =
592 Wolsiefer et al
John Wolsiefer Sr. is President of Norchem Concrete

Products, a silica fume manufacturer. He has a B.S.
Applied Physics, an M.S. Engineering and is serving on
many AC1 and ASTM committees. He has given numerous
presentations, authored papers and received an
international award in the field of silica fume concrete
technology.
Vasanthy Sivasundaram was a Research Engineer with
Canada Centre for Mineral and Energy Technology (CANMET),
Energy, Mines and Resources Canada, Ottawa, Canada. She
received her S.Sc. in Civil Engineering from the
--``,`,-`-`,,`,,`,`,,`---
University of Sri Lanka and an SM degree from MIT. She
worked in the area of durability of concretes
incorporating supplementary cementing materials. She
left CANMET in 1994.
AC1 Honorary Member V. Mohan Malhotra is Program
Principal, Advanced Concrete Technology Program, CANMET,
Ottawa, Canada. He is a former member of the AC1 Board
of Direction and has served on numerous AC1 committees.
He is a prolific author, editor, and researcher, and has
received many awards and honours from AC1 and other
institutions throughout the world.
George C. Carette was a Senior Materials Engineer
with Canada Centre for Mineral and Energy Technology
(CANMET), Energy, Mines and Resources Canada. He had
been engaged in applied research in the field of cement
and concrete technology for over 25 years, and had
authored a number of technical publications related to
the use of supplementary cementing materials in concrete.
He passed away in 1993.
INTRODUCTION
In 1991, CANMET initiated a joint program with
NORCHEM Concrete Products, Inc., Hauppauge, New York, on
the performance of concretes incorporating various
product forms of silica fume. The main objective of this
program was to determine the effects of chemical and
physical variations in the different product forms of
silica fume on the mechanical properties and durability
aspects of the resultant silica fume concrete.
Representative product forms of silica fume obtained from
silica fume suppliers, ready-mixed concrete plants,
precast plants, and job sites in Canada and the United
States were used in this investigation. A total of
eleven different silica fume product forms, from ten
different sources, were used in the silica fume
concretes. These included dry uncompacted silica fume
from two sources, dry compacted silica fume from five
sources, water-based slurry from one source, and blended
silica fume cement from two sources. This report gives

A C 1 SP-153 voL*II 95 m Obb29i.19 0521571 921 m
the findings of the above investigation.

SCOPE
Thirty-four concrete mixtures involving sixteen

different silica fume samples and seventy-six 0.06 m3
batches were made in this program. The concrete mixtures
were proportioned to match those utilized in the concrete
industry in North America. Specifically, these mixture
proportions were selected to conform to the concrete
durability improvement criteria used for parking garages,
highway bridges, marine construction, and high-strength
concrete columns in high-rise buildings. The cement
content, silica fume as a percentage of cement, and
water-to-cementitious materials ratio (W/C+SF) in the
three concrete series were fixed at: a) 360kg/m3*,8.5%
and 0.35; b) 385 kg/m3", 12% and 0.30; and c) 5 2 0
kg/m3"*, 15% and 0.22, respectively. A fourth series,
with reduced variables was made at a W/C+SF of 0.40 in
order to compare its performance with the concretes
having the lower W/C+SF 0.22, 0.30 and 0.35.
All concretes incorporated a superplasticizer and an
ordinary water reducer-retarder, and all the concretes,
except those with a W/C+SF of 0.22, were air entrained.
The properties of the fresh concretes were determined,
and a number of specimens were cast for the determination
of compressive and flexural strength at various ages,
drying shrinkage, air void parameters and rapid chloride
permeability on the specimens subjected to moist, field
and accelerated curing.
SILICA FUME PRODUCT FORMS
The different product forms of silica fumes
available in North America can be classified as follows:
Dry, Uncompacted Silica Fume
This form of silica fume is sold "as produced" from
the ferrosilicon or silicon metal bag house, generally in
bags. In North America, the fume is marketed in bulk.
The uncompacted fume may be slightly agglomerated and
densified due to pneumatic handling, de-aeration in
packaging, in addition to pressure and vibration caused
during shipping.
Dry, Compacted Silica Fume
In order to improve the bulk material handling

characteristics and transportation economics, this fume
'605 lb/yd3 "650 lb/yd3 "'875 lb/yd3
--``,`,-`-`,,`,,`,`,,`---

594 Wolsiefer et al
is agglomerated and densified by air or by pressure, and

is supplied in bags, super sack, and bulk. The air
densified silica fume is processed by air injection into
the bottom of steel storage silos creating turbulence and
collision between silica fume particles. This causes
weak agglomerate or clusters of particles held together
loosely by molecular forces between the submicron
particles. The pressure densified material is obtained
by passing the uncompacted fume through a device that
compresses the individual particles together, which
remain attached through the same molecular force of
attraction. Both compacted forms are easily reversed and
separated back to individual particles by the shearing
forces generated in concrete mixing.
Blended Silica Fume Cement
Typically, the blended silica fume cement is

--``,`,-`-`,,`,,`,`,,`---
manufactured by two methods and incorporates 7 . 5 to 8.5

percent silica fume. In the first method, silica fume in
pelletized form is interground with cement clinker and in
the second method, uncompacted silica fume is blended
with cement.+
Silica Fume Slurrv
Water-based silica fume slurry products are 45 to 50

percent dry solids manufactured with and without a
superplasticizer; this product is available in drums and
bulk.
CONCRETE MATERIALS
The concrete mixtures were made at CANMET

laboratories in the winter of 1991 using the following
materials.
Cement
Normal portland cement, ASTM Type I, was used in all

concrete mixtures. Its physical properties and chemical
analyses are given in Table 1 .
‘The pelletized silica fume form is processed by the

injection of uncompacted, as produced silica fume, along
with water and heat, into an inclined rotary disk. The
silica fume pellet formed is fairly hard, and cannot be
broken down to its original particle size with the forces
generated by concrete mixing. This product form can be
interground with cement to form a blended pozzolanic
cement. The resultant particle size is not as small as
the original, but more typically the size of a cement
particle.

A C 1 SP-153 V O L X I I 95 IOb62949 0521573 i T 4 I
S i l i c a Fume
Sixteen silica fume samples from ten different
sources were used in the concrete mixtures. They are
listed as follows:
SF-1 Uncompacted silica fume from a Canadian silicon
metal manufacturing source (SiO, level 93.6%).
SF-2 üncompacted silica fume from a concrete
contracting source in the U.S.A. (SiO, level
94.1%).
SF-3 Compacted air densified silica fume from a ready
--``,`,-`-`,,`,,`,`,,`---
mixed concrete source in the U.S.A. (SiO, level
79.9%).
SF-4 Compacted air densified silica fume from a
silicon metal manufacturing source in the U.S.A.
(SiO, level 89.6%).
shotcrete contracting source in the U.S.A. (SiO,
level 79.7%).
SF-6 Silica fume slurry from an admixture
manufacturing source in the U.S.A. This slurry
incorporated 50% water with dry uncompacted
silica fume (SiO, level 94.95%).
SF-7 The same silica fume slurry, as used in SF-6, at
6 months age. After the first set of concrete
mixtures, the remaining slurry was left
undisturbed in the storage drum for 6 months
before use in the concrete mixture.
SF-8 Sample A from the production plant of a silica
fume blended cement manufacturer. This blended
cement from a Canadian source is said to contain
8.5% uncompacted silica fume by weight.
SF-9 Sample B from the above blended cement, SF-8.
SF-10 Sample A from the production plant of another
Canadian silica fume b l e n d e d c e m e n t m a n u f a c t u r e r .
This blended cement is said to contain 7.5%
interground pelletized silica fume by weight.
SF-11 Sample B from the above blended cement, SF-10.
contracting source in the U.S.A. (SiO, level
95.35%).

A C 1 SP-153 V O L J I I 95 m Obb2949 0521574 b 3 0 m
596 Wolsiefer et al
SF-13 High density, compacted air densified silica fume

from a shotcrete contracting source in the U.S.A.
(SiO, level 80.1%).
SF-14 Compacted, pressure densified silica fume from an
admixture company in the U.S.A. (SiO, level
94.3%).
SF-1 5 Sample A of blended, uncompacted silica fume
cement from the manufacturer of SF-8 and SF-9,
however, this sample was said to have been
obtained from a field silo in a construction
area.
SF-16 Sample B, taken at the same time from the source
mentioned, in SF-15 above.
The physical properties and the chemical analyses of
the above silica fumes are given in Table 1.
Aqqreqates
The coarse aggregate was crushed limestone with a
nominal maximum size of 19.0 mm, except for the mixtures
made with 0.22 W/C+SF; in the latter case, the limestone
used had a maximum size of 12.7 mm. Local natural sand
was used as the fine aggregate. Both aggregates were
separated into different size fractions, and then
combined to a specified uniform grading. The grading and
physical properties of the coarse and fine aggregates are
given in Tables 2 and 3.
Superplasticizer
A commercially available sulphonated, naphthalene-

formaldehyde condensate superplasticizer was used.
Air-Entraininq Admixture
A synthetic resin type air-entraining admixture was

used in all the concrete mixtures, except the concretes
with 0.22 W/C+SF, which were made without the air-
entrained admixture.
Water Reducer/Retarder
A commercially available water reducer/retarder was

used in all the concrete mixtures.
MIXTURE PROPORTIONS
The proportioning of the concrete mixtures is

summarized in Table 4 . For all mixtures, the graded
coarse and fine aggregates were weighed in the room-dry
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL*II 95 m 0662949 0523575 577 m
condition. The coarse aggregate was then immersed in

water for 24 hours, the excess water decanted, and the
water retained by the aggregate determined by the weight
difference. A predetermined amount of water was added to
the sand and then allowed to stand for 24 hours.
Four series of concrete mixtures were made with
cement contents of 360, 385, and 520 kg/m3. In the first
series incorporating 360 kg/m3 cement, the W/C+SF was
kept at 0.35, and the silica fume replacement was 8.5% by
weight of the total cementitious material. This mixture
proportioning is normally used to produce durable
concrete in a less aggressive environment. In the second
series, the cement factor was 385 kg/m3, the W/C+SF was
0.30 and the silica fume replacement was 12%. This
mixture proportioning would normally be used in a more
aggressive environment that has high chloride exposure.
In the third series incorporating 520 kg/m3 of cement,
the W/C+SF was 0.22, and the silica fume replacement was
15%. This mixture proportioning is typically used to
produce very high strength concrete. The last series was
used to obtain comparative perf ormance at a higher W/C+SF
(0.40). However, this series was conducted using only
two silica fume forms and the same cement factor (385
Kg/m3) and silica fume percentage (12%) as the second
series.
PROPERTIES OF FRESH CONCRETE
The properties of the fresh concrete, that is,

temperature, slump, air content, unit weight, and setting
time are shown in Table 5.
Batch A
Thirty-three 102x203 mm' cylinders were cast from
Batch A of each mixture for the determination of
compressive strengths from the ages of 1 day to 2 years.
These cylinders were cast in two layers and compacted on
a vibrating table. After casting, all the molded
specimens were left, covered by a saturated burlap, in
the casting room at 20 ? 2" C and 50% relative humidity
for 24 hours. They were then demolded, weighed, and
transferred to the moist curing room at 100% relative
humidity until required for testing. Nine of the
cylinders were taken out of the moist room at the age of
7 days and were left to cure in the laboratory atmosphere
until tested in compression.
'4x8 in.
--``,`,-`-`,,`,,`,`,,`---

598 Wolsiefer et al
Batch B
Typically, ten 102x203-mm cylinders and twelve
75x100~400mm' prisms were cast from Batch B of each
mixture. These specimens were cast and cured in the same
manner as described in Batch A. Three of the cylinders
were used for the determination of the 28-day compressive
strength, and three prisms each were tested in flexure at
the ages of 28 and 91 days. The other six prisms were
used for drying shrinkage measurements. The remaining
seven 102x203 mm cylinders were used for determining the
rapid chloride permeability (RCP) after 28, 42, and 91
days of moist curing. Except for this RCP phase of the
testing which was jointly carried out in both a U.S.A.
laboratory and CANMET, all the testing was performed at
CANMET. In a few selected concrete mixtures, two more
102x203 mm cylinders were cast for the purpose of RCP
measurement following accelerated curing of test
cylinders.
Batch C
Two 458x356~127mm" concrete slabs and nine 102x203

mm cylinders were cast from Batch C of the concretes.
This batch was made only with three selected silica fume
samples, i.e. two compacted fumes and one slurry form.
In each mixture, one slab was moist-cured after 24 hours
of initial curing under a wet burlap cover, while the
companion slab was moved to the basement immediately
after casting, and kept beside an open window. After the
initial set, a curing compound was applied to the exposed
surface of the slab. At one day, the forms were removed
and the slab was completely coated with the curing
compound and was moved outdoors and left to cure. The
mixing and casting of the slabs were done during February
and March 1992, when the average day and night time
temperatures were about 1°C and -10°C. This curing
method was utilized to simulate actual project curing
conditions in cold climates, and their potential effect
on RCP results. Six of the 102x203-mm cylinders were
also kept under the same curing conditions after casting,
and were treated with curing compound as for the slabs
and left outdoors. These cylinders were tested in
compression at the ages of 28, 42, and 91 days.
Specimens for the RCP measurements were cored from the
moist-cured and outdoor cured slabs at 42 and 91 days.
The testing schedule is shown in Table 6. All
'3x4~6 in. *'18xl4x5 in.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L m I I 95
0662949 0523576 403
Not for Resale
A C 1 SP-353 VOL*II 75 E 0662949 0523577 3 4 T m
specimens for the compression testing were capped with a

sulphur and flint mixture before testing. Test prisms
for flexural strength were tested at third point loading
at 2 8 and 9 1 days. The prisms for drying shrinkage
measurements were stored in lime-saturated water at 2 3 k
1.7"C; at 7 and 2 8 days, two prisms were transferred to
the drying chamber maintained at 2 3 f 1.7"C and 5 0 %
relative humidity. The remaining two prisms were kept in
lime-saturated water as the reference specimens. The
length and weight changes of the drying shrinkage
specimens and the reference specimens were determined at
regular intervals until 4 4 8 days, and then the prisms
were tested in flexure.
The specimens for the RCP testing of the concrete
were conditioned as specified in AASHTO T 2 7 7 . Two
slices, each with a thickness of 5 0 mm, were cut from the
1 0 2 x 2 0 3 mm cylinders or cores, and their circumferences
were coated with fiberglass and resin. After an hour of
air drying, they were kept under vacuum (pressure < 1 mm
Hg) for 3 hours, 1 hour more under vacuum with the
specimens in de-aerated water, and then left for 1 8 hours
soaking in water at the atmospheric pressure. After this
conditioning, the specimens were placed in the testing
cells. The testing consisted of monitoring the amount of
electrical current passed through the specimen, when a
potential difference of 60V dc is maintained across the
specimen for a period of 6 hours. In this test, chloride
ions are forced to migrate out of a NaC1 solution
subjected to a negative charge, through the concrete,
into a NaOH solution maintained at a positive potential.
The total charge passed, in coulombs, is used as an
indicator of the resistance of the concrete to the
penetration of chloride ions.
Approximately seven days after casting, 5 0 mm thick
discs were cut from the top ends of seven 1 0 2 x 2 0 3 mm
cylinders from all Batch B concretes, and some of the
specimens were shipped in a saturated condition to a
commercial laboratory in the U.S.A. to determine
laboratory to laboratory variation. The balance of the
specimens, which were mostly generated in the later
testing stages, were tested at the CANMET laboratory. Of
the above specimens, two each were tested at 2 8 and 9 1
days, and three were tested at 42 days. In ten of the
concrete mixtures made towards the end of the mixing
phase, the RCP testing followed the accelerated curing of
the test cylinders. In this accelerated procedure, 5 to
6 hours after casting, two 1 0 2 , 2 0 3 mm concrete
cylinders, still in their molds, were immersed in a warm
water bath and cured for 1 6 f 1 hour in an oven
maintained at 7 1 ? 1°C. Afterwards, the cylinders were
unmolded, air cooled, and 50 mm slices were cut from the
top surface of the cylinders and tested for RCP.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 Obb29Y9 052L57B 286 W
600 Wolsiefer et al
Moist and outdoor-cured slabs made from Batch C of

the three concrete mixtures were cored at the ages of 42
and 91 days. After removing 6 mm from both ends to
remove the curing compound from the outdoor cured slabs,
50 mm thick discs were cut from the top and bottom of the
cores. Two top 50 mm discs from each moist and outdoor-
cured slabs were tested for RCP at each age. The two
bottom 50 mm discs taken from each outdoor-cured slab
were subjected to warm-water accelerated curing before
being tested for RCP. This procedure was utilized to
determine the effect of low temperature retardation of
cement hydration on the RCP values.
TEST RESULTS
Compressive strength results at the ages of 1, 3 , 7 ,

28, 42 and 91 days are given in Table 7. The flexural
strengths at the ages of 28 and 91 days are also shown in
Table 7. The RCP results obtained from the tests carried
out at the ages of 28, 42, and 91 days on the moist-cured
specimens and the results of the RCP tests on specimens
subjected to warm-water accelerated curing are shown in
Table 7 as well. The compressive strength results of
moist and field-cured cylinders, and the RCP results on
moist and field-cured slabs cores are given in Table 8.
The drying shrinkage results, up to 448 days of air-
--``,`,-`-`,,`,,`,`,,`---
drying, are'given in Tables 9 and 10 for prisms subjected

to initial moist curing of 7 and 28 days, respectively.
Table 11 shows a comparison of the compressive strength
results obtained from moist-cured as well as laboratory-
cured specimens. Table 12 shows the results of the
flexural strength and carbonation tests done on the
drying shrinkage prisms at the end of 448 days of drying.
The air-void parameters of the hardened concrete
specimens are given in Table 13.
DISCUSSION
Characterization of Silica Fumes
Sixteen different samples of silica fume were
investigated in this program. Only SF-1 and SF-2 were
uncompacted, with bulk densities of 282' and 200" kg/m3.
The compacted silica fume samples were gathered from
field and warehouse sources, representing both air and
pressure densification product forms for four different
compaction plants. Among the remaining silica fumes, SF-
3, SF-4, SF-12 and SF-14 were compacted silica fumes
having normal bulk densities of 641'*', 641, 614 and 666
kg/m3; SF-3, SF-5 and SF-13 were compacted fumes from the
same source; however, SF-3 and SF-5 were normal density
'17.6 lb/ft3 *'12.5 lb/ft3 "'40 lb/ft'

A C 1 SP-153 V O L a I I 95 I 0 6 6 2 9 4 9 0523579 3 3 2 =
fumes and SF-13 was a high density fume with a bulk

density of 923 kg/m”. The measurement of the bulk
density, although conducted, was not applicable for the
blended silica fume cements, and was not measured for the
silica fume slurry used at two ages. In the determina-
tion of the fineness by 45 pm sieve, neither the
compacted fumes nor the two slurries gave any useful
results. The wet sieve method of fineness measurement
was found not to be suitable for these fumes. The
fineness values of SF-1 and SF-2 were determined as 96.9
and 97.7% passing the 45 pm sieve. The surface area of
the fumes measured by the nitrogen absorption method
ranged from 17,890 to 26,430 m2/kg. The silica fume
slurry at both ages was evaporated, and the residual
ground before being subjected to the nitrogen absorption
tests; however, the results were not found to be useful.
The physical tests were not done on SF-12, as there was
barely enough material for the chemical analysis, and for
making the concrete.
From the silica fume chemical analyses the highest
SiO, contents of 95.4, 95.0, 94.3, 94.1, and 93.6% were
found in SF-12, SF-6, SF-14, SF-2, and SF-1, respec-
tively. The lowest SiO, contents of 79.7, 79.9, and
80.1% were obtained for SF-3, SF-5, and SF-13. respec-
tively. The Ca0 content of SF-3 was fairly high at
12.8%. The MgO content of SF-5 and SF-13 was fairly high
in comparison with the other fumes, 12.0% for SF-5 and
12.3% for SF-13. The chemical analyses of the blended
silica fume cement samples were similar. Blended silica
fume cement samples SF-8, SF-9, SF-15, and SF-16,
received from one source, were supposed to contain 8.5%
silica fume by weight of the cement; samples SF-8 and SF-
9 were received from a cement production plant, whereas,
SF-15 and SF-16 were received from a field silo at a
construction site. SF-10 and SF-11, which were sapples
taken from another blended cement were supposed to
contain 7.5% silica fume by weight of cement. There is
no test method available to measure and separate out the
SiO, percentage in the blended cement, which is
contributed by the silica fume. This does not allow an
accurate determination of SiO, level or variation, with
the blended silica fume cement product form. The blended
cement SiO, level reported in Table 2 is the total S i O ,
as a percentage of the blended cement which includes the
Cio, present in the cement before blending.
--``,`,-`-`,,`,,`,`,,`---
Concrete Mixtures
In proportioning the concrete mixtures, the three
basic mixtures were used, with silica fume at 8.5, 12,
*57.6 lb/ft3

A C 1 SP-153 VOL*II 95 = 0662949 0521580 934
602 Wolsiefer et ai
15% by weight of cement and W/C+SF of 0.35, 0.30, and

0.22, respectively. In mixing with blended cements, the
silica fume percentage had to be kept at one proportion
for all three concrete mixtures, i.e. 8.5% by weight of
the blended cement for mixtures with SF-8, SF-9 SF-15,
and SF-16, and 7.5% by weight of blended cement for SF-10
and SF-11. The effect of the stated lower silica fume
percentage (1%) for the one blended silica fume cement
was not capable of being measured or evaluated, and as
such the final test data w e o n l y able to be compared to
its nearest product form. In these instances the blended
cement quantities used were equal to the total
cementitious material content of the three basic
mixtures, at 390, 430, and 600 kg/m3. The air-entraining
admixture was not used in the mixtures with W/C+SF of
0.22. The concrete mixtures made with the silica fume
slurry having W/C+SF of 0.35 and 0.22 were repeated
(mixtures SC22D and SC23D), due to the slight differences
in the silica fume percentage in the earlier mixtures.
Superplasticizer Docaqe and Slump
In all of the silica fume concrete mixtures with a
W/C+SF of 0.35, the superplasticizer dosage ranged from
3.3 kg/m3 for SF-6 to 6.8 kg/m3 for SF-2, with most of
the mixtures having the superplasticizer content of about
5.0 kg/m3. The amount of water reducer-retarder added
was kept constant at 0.7 kg/m3 in the above mixtures.
The slumps obtained were in the range of 100-200 mm. In
the mixtures with W/C+SF of 0.30, the superplasticizer
dosage needed to obtain slumps of 90-200 mm ranged from
4 . 4 kg/m3 for SF-10 to 1 0 . 3 kg/m3 for SF-12. The amount
of water reducer/retarder added to the mixtures in this
series was 0.8 kg/m3. In concretes with W/C+SF of 0.22,
the superplasticizer addition ranged from 8.5 kg/m3 for
SF-10 to 33.8 kg/m3 for SF-12. The amount of the water
reducer/retarder added to mixtures in this series was 1.1
kg/m3. In this series, SF-2, SF-3, and SF-12 concretes
--``,`,-`-`,,`,,`,`,,`---
also showed higher superplasticizer demand.

In the silica fume slurry concretes, the water in
the slurry was taken into account as part of the mixing
water. Although it is known that superplasticizer is
used in the process of making the slurry, the amount
utilized was not determinable. Thus, the total amounts
of superplasticizer reported in Table 4; mixtures
incorporating slurry, for SF-6 and SF-7 are understated
by the amount of the superplasticizer contained in the
slurry material.
The concretes made with a W/C+SF of 0.40, utilized
only the slurry form (SF-6) and one compacted silica fume
(SF-12). Superplasticizer addition, over and above that
already contained in the slurry (SF-6) itself, was not
necessary as slumps of 80 and 130 mm were obtained with

A C 1 SP-153 V O L S 1 1 95 Obb2949 0521581 8 7 0
ordinary water reducer/retarder addition alone. With

concretes made using SF-12, 3.0 kg/m3 of superplasticizer
was added to produce slumps of 115 and 165 mm.
Air-Entrainment
The air-entraining admixture (AEA) required to
produce air contents of 4 to 6 % in concretes with a
W/C+SF of 0.35 was in the range of 50-100 mL/m3. In case
of concretes with a W/C+SF of 0.30, to obtain 5+1% air in
the fresh concrete, 50 to 75 mL/m3 of AEA was needed in
concretes made with the blended cements and the silica
fume slurry; whereas, the AEA requirement in concretes
made with uncompacted and compacted fumes ranged from 100
to 150 mL/m3. For the concretes having a W/C+SF of 0.40,
and made with the SF-6 slurry and SF-12 dry compacted
fume, the AEA required was about the same, at about 100
mL/m3. The concretes with W/C+SF of 0.22 were made
without air entrainment, and the air content measured in
the fresh concretes ranged from 2 to 3%; the exceptions
were concretes made with the two blended cements (SF-9
and SF-10) and compacted silica fumes SF-3 and SF-5,
which showed rather high air contents of 3 to 4%.
Densitv of Hardened Concrete
The one-day density of the concretes with W/C+SF of
0.35 and 0.30 were in the order of 2400 kg/m3'. For the
concretes with a W/C+SF of 0.22, the density was about
2460 kg/m3. These values measured on the hardened
concretes were slightly higher than those measured on the
fresh concrete. The loss of air in concrete with time
could have been one possible cause.
Compressive Strenqth of Moist-Cured Specimens
The compressive strength results are given in Table
7. In addition, the compressive strength data are
organized by silica fume percentage and W/C+SF ratio in
Appendix B, Tables B1 to B4. The results are illustrated
in Figures 1 to 3, summarized on a silica fume product
form basis. The silica fume product form average data
are shown in Tables Bla to B3a. The data from the
strength tables was averaged by silica fume product form
for uncompacted, compacted, slurry and blended cement.
Figure 1 shows the compressive strength development
for concrete ages, ranging from one day to two years.
The W/C+SF is 0.30 and 12% silica fume dosage. Figure 2
--``,`,-`-`,,`,,`,`,,`---
shows the same compressive strength development for the

W/C+SF of 0.35 and 8.5% silica fume. Figure 3, in turn,
shows the compressive strength development for W/C+SF of
0.22 and 15% silica fume. The 42-day strength of the
*150 lb/ft3

604 Wolsiefer et al
specimens was found to be very close to either the 28 or

the 91-day value in most cases. The product form
strengths are very similar, in all the series. In fact,
for the high strength series, with 15% silica fume and a
W/C+SF of 0.22, the compressive strength data at 2 years
ranges from 97.6 to 100.6 MPa only. In this series, the
concretes incorporating the SF-3 and SF-5 compacted
silica fume forms and SF-6 (slurry) had the highest 2
year strengths of 100.4, 102.2 and 100.6 MPa,
respectively, of all the silica fume product forms.
A comparison of W/C+SF versus compressive strength
development for the 0.40 and 0.30 W/C+SF series, at the
12% silica fume dosage, is shown in Fig. 4. The
comparison is shown for both the compacted and slurry
silica fume forms. The results show a 18% difference at
2 years, in compressive strength when decreasing W/C+SF
ratio from 0.40 to 0.30.
The variation in the air contents of the concretes
was not taken into account in comparing the compressive
strength results. In addition, the cement used in all
the test series was the same for all silica fume forms.
The only exception was the concrete made using the
blended silica fume cement. A review of the data seems
to indicate that the cements used in the blended cements
are of high strength, because the performance was good
despite the lower silica fume percentage. In view of the
above potential adjustments to the data and the
differences attributable to the variations in the
specimen preparation and testing, the comparable strength
results for all the product forms are considered to be
very similar.
Compressive Strenqth of t h e Field-Cured Specimens
The compressive strengths of field-cured concrete
specimens for two compacted silica fumes SF-3, SF-12 and
one slurry SF-6 are shown in Table 8 , and illustrated in
Fig. 5 . The concretes were cast in the winter, as
described previously, and left outdoors after the initial
set following the application of a curing compound on the
exposed surfaces. The 28-day strengths of the field-
cured specimens are much lower than that of the companion
moist-cured specimens, because of the colder curing
temperature. The increase in strength from 28 to 42-days
is not very high as the weather did not get much warmer
duringthis period. However, the 91-day strength is much
higher than the 42-day strength, as this was in warmer
late spring. For comparison purposes, the 91-day strength
of the moist-cured specimens from Batch A of the
respective concretes are also shown in Fig. 5. The 91-
day strength of the field-cured specimens are almost
equivalent to that of the moist-cured specimens. Once
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 E 0662949 0523583 643 =
the concrete is sealed from drying, it reaches its

strength potential, irrespective of the early cold
weather curing. This aspect needs to be confirmed with
additional investigations.
Compressive Strenqth of the Air-Cured Specimens
FromBatch Aconcrete specimens, nine cylinders were
removed from the moist room at 7-days and left to cure in
the laboratory atmosphere at about 23°C and 50% R.H.
Three cylinders each were tested at gl-day, one and two
years, and the results are shown in Table 9, together
with that of the companion moist-cured specimens. The
results at W/C+SF of 0.30 are illustrated in Fig. 6. The
91-day strengths of the air-cured cylinders are lower
than that of the moist-cured cylinders. The drop in
strength, on the average, is about 5 MPa. At one year,
the strengths of the air-cured specimens were observed to
drop further; on the average, a 10 MPa drop in strength
is seen between the 1-year moist-cured and laboratory-
cured specimens for concrete with a W/C+SF of 0.30.
After one year of air-curing, the strengths of almost all
the concrete specimens lie somewhere in between their
respective 7 and 28-day most-cured strengths. In this
investigation, the specimen size is also a factor
affecting the drying of the concretes, as the 102x203 mm
cylinders were used in the study. In a companion
investigation carried out at CANMET, this phenomenon was
observed with normal portland cement concretes as well.
Flexural Strenqth
The 28 and 91-day flexural strength results of the
moist cured 75x100~400-mmconcrete prisms are shown in
Table 7. The average strength results for each product
form concrete, with a W/C+SF of 0.30 are illustrated in
Fig. 7. The data variation was small, ranges from 9.1 to
9.3 MPa at 91-days. Regardless of the type of silica
fume used, there were no significant differences between
the flexural strengths of the concretes within each
series. Furthermore, the flexural strengths do not show
any increase from 28 to 91-days. For the concretes with
a W/C+SF of 0.35, 0.30, and 0.22, the flexural strengths
were of the order of 8, 9 and 10 MPa respectively.
Rapid Chloride Permeabilitv (RCP) Test Results
The RCP test results obtained at the ages of 28, 42
and 92 days on the moist cured concrete specimens are
shown in Table 7. Most of the values shown are the
average of results taken from three specimens and in the
beginning of the program, two laboratories were
conducting the tests, with very good "laboratory to
laboratory" test data correlation. All of the silica
fume forms were utilized in the concrete mixtures having
--``,`,-`-`,,`,,`,`,,`---

606 Wolsiefer et al
a W/C+SF of 0.30. The concrete mixtures with W/C+SF of

0.22, and 0.35 were made with selected silica fumes
representingthe uncompacted, compacted, slurry and blend
cement product forms. In addition, the RCP data shown in
Table 7, was further organized by silica fume percentage
and W/C+SF ratio; in Tables B1 through B6, which are
given in Appendix B. Figures 8 and 9 present the
performance data summarized on a silica fume product form
basis; the silica fume product form data averages for
these figures are shown in Tables B3a and B6a.
Figure 8 , presents RCP results versus W/C+SF ratio.
The data, for concretes made with all the product forms,
show the RCP values improving as the W/C+SF ratio
decreases and the silica fume dosage increases. The data
grouping is very tightly spaced with uncompacted,
compacted and slurry silica fume forms almost equal , with
the values for the blended cement form, slightly higher
at all W/C+SF ratios. However, the silica fume content
for the blended cements was only equal to the other
product forms at the 0.35 W/C+SF, which explains the
higher values at the other W/C+SF ratios. Because the
nature of the blended cement product is a fixed
--``,`,-`-`,,`,,`,`,,`---
percentage, the silica fume dosage level was less for the
W/C+SF ratios of 0.30 and 0.22.
Figure 9, RCP Values versus Silica Fume Product Form
shows data, for one of the mixture series (15% SF, W/C+SF
0.22) at ages of 28, 42 and 91 days. The RCP back-up
data are shown in Tables B3 and B3a. Again, the RCP data
are in a narrow range, with values of 82, 65, 4 9 and 135
coulombs for the uncompacted, compacted, slurry and
blended cement forms, respectively.
Figure 10, RCP Values versus W/C+SF of 0.30 and 0 . 4 0
(12% SF), shows the effect of decreasing the W/C+SF at 41
and 91 days curing age. The mixture series was conducted
for the one slurry form (SF-6) and one compacted silica
fume form (SF-12). The RCP data (Table B4) at both ages
are very similar with 137 coulombs for SF-6 and 159
coulombs, for SF-12.
Additional RCP test results, using warm-water
accelerated concrete curing on the day of mixing, are
shown in Table 7. This testing was carried out on a few
of the concretes made at the end of the mixing phase.
Figure 11 shows a comparison of the RCP values obtained
on the specimens subjected to the accelerated curing and
on the specimens moist cured for 91-days, for concretes
with a 0.30 W/C+SF. The RCP values of the accelerated
cured specimens and 91-day moist-cured specimens are
nearly the same (Table 7, Fig.11). This is also true for
the SF-6 and SF-12 concretes with W/C+SF of 0.22, 0.35,

A C 1 SP-153 VOLxII 95 NotE
No reproduction or networking permitted without license from IHS 0bb2949 0 5 2 1 5 8 4 58T
for Resale
~
0.40. Therefore, it appears possible to predict the 91-

day RCP values of silica fume concretes after one to two
days by using the accelerated curing method.
The RCP results from the test on the cores taken out
of the moist-cured and field-cured slabs are shown in
Table 8. The RCP tests were conducted on the cores
drilled from the slabs at 42 and 91 days. At these ages,
some of the cores taken from the field-cured slabs were
also subjected to the warm water accelerated curing
and tested for RCP afterwards. Figure 12 shows the RCP
results on the cores subjected to the various curing
regimes. The effect of the curing temperature on the RCP
results is evident from the data, as the silica fume
concrete slabs were cast in the winter, and the field-
cured slabs subjected to very cold temperatures. For
example the 42-day RCP value for a core taken from a
compacted silica fume concrete specimen cast in mid-
winter was 4,425 coulombs; however, when another portion
of the core was cured in warm water, the RCP value
obtained was 279 coulombs. Table 8, shows repeatedly of
the same retarding effect the winter curing conditions
had on the field-cured slabs. As another example, the
RCP of SF-3 concrete core with W/C+SF of 0.35 at the age
of 42 days measured 2,145 and 2,071 coulombs, whereas, in
the moist-cured condition the RCP values were 1 0 0 and 259
coulombs, respectively. The reason for this anomaly is
that the 0.22 W/C+SF concrete was left to cure in mid-
winter and the 0.35 W/C+SF concrete was made and cured
three weeks later in the beginning of spring, thus, the
latter had more warm curing weather. The RCP results for
the cores drilled from the field-cured concrete were of
the same order as for the cores drilled from the moist-
cured slabs, except for the concretes cast early in the
winter, which did not have enough warm-curing weather.
More significantly, the RCP results obtained following
the accelerated curing of the cores drilled at 42 and 91-
days from the field cured slabs were quite similar, and
a fairly accurate predictor of the 91-day moist-cured
values. In general, these results were marginally lower
than the RCP results obtained on the specimens after warm
-water curing on the day of mixing.
Performance Measurements with respect to Silica Fume
Chemical and Phvsical Variations
As discussed earlier, the silica fume samples used
in this program had variations in the chemical and
physical characteristics (Table 1) as they are by-
--``,`,-`-`,,`,,`,`,,`---
products of silicon, 75% ferrosilicon alloy, and 50%

ferrosilicon metal alloy production. Different metal
alloy furnace configurations and raw materials, produce
variations in the Cio2, MgO, LOI, particle size, bulk
density and surface area. In addition, as silica fume
particles are under one pm in diameter, they are
VOL*II 95 m Obb29V9 0523585 43b m

A C 1 SP-353
608 Wolsiefer et al
naturally agglomerative and form random agglomeration

even in their as-produced uncompacted form. Further
silica fume processing such as material handling,
compaction densification, slurry making, pelletization
and silica fume cement blending produces more
agglomeration. However, in general all the agglomeration
characteristics of these silica fume forms, except that
of pelletization, are normally reversible, due to the
shearing forces generated during concrete mixing. This
test program evaluated the technical performance of
concretes incorporating different silica fume forms,
along with the variations in SiO,, MgO, LOI, bulk density
and surface area and found the resultant concretes to be
comparable in performance.
Table B5, A test data comparison of compacted
silica fume concretes, from silicon and ferrosilicon
metal production, shows compressive strength, flexural
strength, RCP and autoclave expansion for six compacted
silica fumes with SiO, levels ranging from 79.7% to 95.4%
and bulk densities 6 1 4 to 9 2 3 kg/m3. The performance
varLation is remarkably small for all these concretes
( 1 2 % SF, W/C+SF 0 . 3 0 ) . The compressive strength at 1
year ranges from 7 1 . 6 to 7 5 . 6 MPa, flexural strength at
9 1 d ranges 8.0 to 9 . 9 MPa and RCP values from 1 4 5 to 2 3 9
coulombs. Silica fumes SF-3 and SF-5 which had the
lowest SiO, contents of 7 9 . 9 and 79.7% performed well in
the high strength concrete mixtures ( 1 5 % S F , 0 . 2 2
W/(C+SF), with the highesttwo-year cornpressive strengths
of 1 0 0 . 2 and 1 0 2 . 2 MPa, respectively.
The high MgO contents, of silica fumes S F - 5 and SF-
13 did not affect the mechanical or durability
performance of their respective concretes. ASTM C 151
autoclave expansion tests were conducted for these two
compacted silica fumes at O, 8.5, 12 and 1 5 % silica fume
dosages. The test results showed the expansion ranging
--``,`,-`-`,,`,,`,`,,`---
from 0 . 0 1 5 to 0 . 0 2 2 % , with the expansion decreasing as

the silica fume percentage increased. The autoclave
expansion test results fall below the limits of ASTM C
151 (1%maximum) for delayed expansion. The above
results are due to the fact that the MgO was not in the
periclase form (Appendix C).
The agglomeration characteristics of the compacted
silica fumes tested were assumed to have been broken down
and dispersed when subjected to the normal shearing
forces generated by the laboratory concrete mixer, as the
technical performance was comparable to the other product
forms .
The silica fume slurry was tested at two ages six
months apart, and was thoroughly agitated before its use
= 0662749 05221b9 537 =

A C 1 SP-153 VOL*II 75
~-
in mixing. Before mixing, the slurry samples were

evaporated to determine the water content, 49.5% at age
1 and 49.2% at age 2. There were no significant
differences observed in the strength characteristics of
the concretes made with the slurry at both ages.
Therefore, the possible agglomeration of silica fume
particles in the aged slurry appears to be reversible if
the aged slurry is vigorously agitated before use.
Silica fume surface area was measured utilizing the
nitrogen absorption method, for the uncompacted and
compacted silica fumes. The surface area range was
17,890 (SF-5) to 26,430 m2/kg (SF-2). For the silica
fume product forms (SF-1, SF-2, SF-3, SF-4, SF-5, SF-13
and SF-14), the variation in the surface area produced no
discernible influence on the admixture dosage or the
concrete performance.
Drvinq Shrinkaqe
The drying shrinkage strains are given in Tables 10
and 11, and the results obtained for the concretes with
a W/C+SF of 0.30 are illustrated in Fig. 13 and 14.
Among the silica fume concrete specimens with a W/C+SF of
0.35 and subjected to drying shrinkage after 7 days of
moist curing, the strains after 448 days ranged from
5 1 8 ~ 1 0 -for
~ SF-2 concrete to 6 6 0 ~ 1 0 -for
~ SF-6 concrete.
For the concretes with a W/C+SF of 0.30 and subjected to
the same curing regime as above, the strains ranged from
475 to 557x10-', except for the SF-10 and SF-3 concretes;
the values for the latter were 599 and 4 3 3 ~ 1 0 - after
~ 448
days of drying. For the concretes with a W/C+SF of 0.22,
the strains measured after 448 days ranged, from 472 to
628~10-~.
When subjected to drying after 28 days of moist
curing, the drying shrinkage strains, after 448 days
ranged from 418 to 5 5 0 ~ 1 0 -for
~ the concretes with a
W/C+SF of 0.35. In the series with a W/C+SF of 0.30, the
shrinkage strains, after 448 days ranged from 365 to
4 8 2 ~ 1 0 - ~and
, for concretes with a W/C+SF of 0.22, the
values ranged from 383 to 504~10-~.
In general, regardless of the initial moist curing
period, the drying shrinkage strains for concretes with
W/C+SF of 0.30 and 0.22 were similar, but were slightly
higher in concretes with W/C+SF of 0.35. Nevertheless,
the strains of most of the silica fume concretes were
about 5 0 0 ~ 1 0 - ~which
, for any type of concrete is
considered low.
--``,`,-`-`,,`,,`,`,,`---
After 448 days of drying, the air-dried as well as

tHe water-cured reference prisms were tested in flexure
at third point loading, and the broken pieces were tested

A C 1 SP-153 V O L * I I
No reproduction or networking permitted without license from IHS 95 0662949 052158b 352
Not for Resale
610 Wolsiefer et al
for carbonation using phenolphthalein spray (Table 1 2 ) .

The concretes with a W/C+SF of 0.22 did not exhibit any
carbonation. Some carbonation was observed in the other
concretes; 4 to 5 mm in the concretes with a W/C+SF of
0 . 4 0 , 1 to 3 mm in the concretes with a W/C+SF of 0.35,
and 1 to 2 mm in concretes with a W/C+SF of 0.30. These
carbonation values, measured after 4 4 8 days of air
drying, are not considered significant.
Air-Void Parameters in Hardened Concrete
Air-void analysis by the modified point count method
was carried out on polished sections of the hardened
concretes. This determination was done on selected
concretes with a W/C+SF of 0 . 3 0 (Table 1 3 ) . In general,
the air content in the hardened concrete were lower than
in the fresh concrete. This loss of air in the concrete
was seen in the density values of the fresh and hardened
state as well. Although the air content was lower, the
spacing factor values of most of the silica fume
concretes were about 0.2 mm, which is the general
limiting value for good freezing and thawing durability.
The exceptions were the blended cements ( S F - 9 , S F - 1 0 , SF-
11, S F - 1 2 ) concretes (mixtures SC5B, S C ï B , SC12B and
S C 1 4 B ) , which showed higher values of the spacing factor,
0.321, 0.311, 0.353 and 0 . 2 6 5 mm, respectively,
Therefore, the silica fume blended cement concretes,
could require more air entrainment in the fresh condition
to ensure sufficient air in the hardened concrete.
CONCLUSIONS
1. The results of this investigation show that,

regardless of the product form, the mechanical
properties and durability characteristics of the
silica fume concretes, were comparable.
2. There was no significant difference in the
mechanical properties a n d d u r a b i l i t y c h a r a c t e r i s t i c s
of concretes incorporating different product forms
of silica fume with Cio, ranging from 7 9 to 9 5 % .
Lower SiO, levels did not require higher silica fume
dosages for comparable performance.
3. The agglomeration characteristics of the compacted
silica fumes tested were assumed to have been
sufficiently broken down and dispersed when
subjected to the normal shearing forces
generated by the laboratory concrete mixer, as the
technical performance was comparable to the other
product forms and in particular to the uncompacted
silica fume.
--``,`,-`-`,,`,,`,`,,`---
4. The possible agglomeration of the aged slurry does

A C 1 SP-153 V O L X I 1 95 m 0662949 0521588 125 m
not appear to affect its performance in concrete, as

long as it is agitated thoroughly prior to mixing.
5. The RCP test results obtained on the specimens
subjected to the warm water accelerated curing on
the day of mixing were found to be of the same
magnitude as those obtained on 91-day moist cured
specimens. Thus, it appears possible to predict the
91-day RCP values from the accelerated test-results
at less than two days.
6. The variation in higher than normal bulk density of
the dry compacted form of silica fume did not affect
the performance of the silica fumes in concretes.
7. The RCP values of all the silica fume concretes
tested, (12% SF and 0.30 W/C+SF) were below 300
coulombs, indicating very low permeability of the
concretes.
8. Test results, on the field-cured concrete specimens,
showed that once the silica fume concrete is sealed
from drying, the initial cold curing weather did not
prevent the concrete from reaching its strength
potential in the long term. This was even more
evident in the tests for determining the rapid
chlorid permeability.
9. Variation in surface area of different product forms
(19,620 to 26,430 m2/kg) had no measurable effect on
their performance in the concrete.
10 Higher than normal MgO contents for the silica fumes
from ferrosilicon metal production had no measurable
effect on their performance in the concrete.
Autoclave expansion test results fall below the
limits of ASTM C 151 for producing delayed
expansion.
11. Decreasing the water-to-cementitious materials ratio
and increasing the silica fume percentage decreased
the RCP values.
12. The drying shrinkage strains of the silica fume
concretes made with the different product forms of
the fumes were low, at about 5 0 0 ~ 1 0 -after
~ 448 days
of air drying.
13. The air-void spacing factors for concretes
incorporating 8.5, 12 and 15% silica fume were at or
below 0.2 mm, the limiting value for excellent
resistance to freezing and thawing durability. The
spacing factors for the blended silica fume cements
--``,`,-`-`,,`,,`,`,,`---

612 Wolsiefer et al
were somewhat higher.

--``,`,-`-`,,`,,`,`,,`---
14. The silica fume blended cement sample tested in the

laboratory may or may not represent the true bulk
blended cement product available in the field.
Thus, due to the potential for silica fume and
cement segregation during bulk material handling,
conclusions cannot be drawn, that the potential
field perf ormance will be comparable to the
laboratory data. This is an area that should be
evaluated under a future study.
15. Almost all silica fume concretes exhibited no
carbonation, after 28 days of moist curing and 448
days of air drying.

OC1 SP-353 VOL*II 95 0662949 0523590 883
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 = 0662949 0521591 7LT
614 Wolsiefer et al
Coarse Aggregate Fine Aggregate

Sieve Size Cumulative Sieve size Cumulative
Percentage mm Percentage
mm Retained Retained
19.0 0.0 4.75 0.0
12.7 40.0 2.36 10.0
9.5 65.0 1.18 32.5
4.75 100.0 0.600 57.5
0.300 80.0
0.150 94.0
pan 100.0
TABLE 3 - PROPERTIES OF AGGREGATES

Coarse Aggregate' Fine Aggregate"
Specific Gravity 2.69 2.70
Absorption,% 0.82 1.1
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L W I I 95 0662949 0521592 656
W
I-
W
ar
o
z
O
o
W
2
3
u.
fA
CI)
I-
LL
O
CI)
Z
0
I-
ar
a
2
R
W
a:
3
I-
s
vim
mt?SX.Tc!
0 0 0 0 0 0
35
r
I
d
w
-I
m
3
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 Obb2949 0521593 5 9 2 =
616 Wolsiefer et al
45
I I
c
W
E
U
-
--``,`,-`-`,,`,,`,`,,`---
LI 2
L4
M
w
íj 8 :ac
5:

A C 1 SP-153 VOL+II 95 m O662949 0523594 429 m
--``,`,-`-`,,`,,`,`,,`---
o
&
Z
O
2
W
t-
W
CK Ë
o M
\
Z X
O M
o .-
.-
.
d
I
W
H
2
8
a
L?
4
m
u-
O
m
Z
0
F
I-
CK
a
a
W
cc 31
3
t-
5
z
I
d
W
A
m
2

A C 1 SP-353 V O L * I I 95 m 0662949 0523595 3b5 m
618 Wolsiefer et al
--``,`,-`-`,,`,,`,`,,`---
W
I-
W
[r
o
z
o
W
2
3
U

A C 1 SP-153 VOL*II 95 m 0 b b 2 9 4 9 052159b 2Tl1 =
?
n
i-
Z
O
2-
W
+
W
rx
1 q
KK
g
O 0
o
z
O
o
W
2
i?
a
Q
=!
(B
LL
O
(B
z
--``,`,-`-`,,`,,`,`,,`---
O
F
K
a
2a 31
ra.
2
W
rx
3
-I
25
z
I
d
W
-I
m
2

A C 1 SP-153 VOL*II 95 = Obb2949 0521597 1 3 8
620 Wolsiefer et al
W
I-
w
tc
o
z
O
o
I
m
W
tc
LL
LL
O
m
E
i-
[r
w
a
a
I
0
!m
2
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0662949 0523598 074
-?
n
i-
Z
O
2
w
I-
w
a:
o
Z
O
o
I
m
W
I
T
U
LL
O
(B
4
I-
a:
W
a
?La
I
Lo
3
m
5
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I I 95 = 0662949 0523599 TOO
622 Wolsiefer et al
U
--``,`,-`-`,,`,,`,`,,`---
c
n
L
z
O
9.
W
I-
w
a
o
z W
Li
O I
c,
o m
I Ktk)
(o
w
[r
o,
LL
LL
O
(o
;
I-
LT
w L
a
3æ 8o 8ö qo qo qo .o aaq3.q
2a 4 f
tB
0 0 0 0 0 0
I
ln
W
-I
m
5 .ï o
2 2
.*9
iij

A C 1 SP-153 VOL*II 95 I0662749 0523600 5 5 2
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 VOLaII 95 = 0662949 052LbOL 499
624 Wolsiefer et al
O 0
22
--``,`,-`-`,,`,,`,`,,`---
N N m *
N N
LL
16
3
cn 8
O
:
s!
\
o :
c
\o
h
N
%
:y
;?
1
üi

A C 1 SP-I153 VOL*II 95 0662947 0523602 325
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL811 95 = 0662747 0521603 261
626 Wolsiefer et al
(o
W
I-
W
LT
o
Z
O
o
W
2
?i
a
2
1
v)
LL
O
v)
W
3
%
a
o
LT
n
z
a
(o
5
3
(o
W
I I
I-
(o
W
I-
--``,`,-`-`,,`,,`,`,,`---
I
bZ
W
[r
I-
(o
I
b
!m?
2

A C 1 SP-153 VOL*II 95 O662949 0521604 L T ô
--``,`,-`-`,,`,,`,`,,`---
LL
O
v)
W
3
%
I ! I 1 1

A C 1 SP-153 VOL*II 95 m 0 b b 2 7 4 9 052Lb05 034 m
628 Wolsiefer et al
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 V O L * I I 95 0662949 0523606 T70 m
--``,`,-`-`,,`,,`,`,,`---

630 Wolsiefer et al
a
>
I-
V)
W
I-
F
u
Z
w
a
I-
V)
I
IC
I-
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L x I I 95
No reproduction or networking permitted without license from IHS - Obb2949 0521b07 907
Not for Resale m
A C 1 SP-353 V O L X I I 75 M 0 6 6 2 7 4 7 0523608 843
I
. -
--``,`,-`-`,,`,,`,`,,`---
U
31 $
-
;xi
.-
P

632 Wolsiefer et al
TABLE 9 - COMPRESSIVE STRENGTH RESULTS OF MOIST-CURED

AND LABORATORY AIR-CURED SPECIMENS
Compressive Strength measured on 102x203-mm Cylinders ( m a )
(1
Moi pJ
I
Id 3d 7d 2 2
30.4 37.2 46.0 60.1 49.9
35.7 47.3 51.6 68.3 57.8
54.3 65.6 77.0 94.5 n.2
- -
30.0 42.1 51.0 65.7 54.9
39.6 50.1 565 75.8 69.0
SF-8 (A)
56.8
37.5
64.6
50.1
728
56.9
93.1
- -
84.9 78.2
-
82.4
-
75.5
!E
33.1 40.6 48.2 70.8 58.4
36.8 44.8 527 76.0 63.4 60.4
54.1 65.6 702 100.1 79.5
- - n.5
24.5 37.6 43.2 64.2 56.8
SF-10 33.7 46.5 53.8 78.5 68.0 70.1
47.5 59.1 67.4
1 SC14AI
q
SF-11 (B) 0.30 35.0 48.4 55.8
SF4 ISC15AI 0.30 373 46.7 57.1
I SF-3
SC16A 0.30
(SCZOAI 0.35
ISC21AI 0.22
38.9
322
46.3
40.2
58.1 68.1
55.5
47.3
77.1
54.4
(SC17AI 0.30 37.2 445 53.1

I SF-5 ISC18AI 0.35 29.1 37.9 46.1
--``,`,-`-`,,`,,`,`,,`---
CC19A 0.22 56.4 65.8 735

ISC22AI 0.36 34.5 43.4 521
0.35 35.3 44.3 54.7
0.24 55.7 66.3 77.1
0.23 53.7 63.9 78.7
(Age 1) 0.30 395 50.4 627
SC25A - 28.9
0.40 37.4 45.1
0.30 40.1 48.8 58.2
0.35 322 39.7 48.4
] S C B A I 0.40 -
56.9
SF-13 ISC3OAl 0.30
-
71.6
-
74.5
-
78.2
44.5 I 53.3 I 64.5 -
78.3
*AU cured after I days of moi curing

A C 1 SP-353
No reproduction or networking permitted without license from IHS V O L r I I 95 m Obb2îi.19 0523b09 78T
Not for Resale m
~~
A C 1 SP-153 V O L X I I 95 W 0662949 0 5 2 L b L O 4TL
TABLE! 10 - RESULTS OF DRYING SHRINKAGE OF PRISMS AFTER

7 DAYS OF MOIST CURING
-
Silica K
-
Gzz kY cF/c hying Shrinkage Strain, x i0 -6
Fume NO. C+SF - - 28day 56day E
Frcent
-
SF-1
-
SCIB
-
0.35
- E$?
8.4 2% 408 450 507 628
SCZB 0.30 12 206 273 354 379 408 457 514
CWB 0.23 15 220 298 348 379 411 475 546
SF-9 SC4B 035 8.5 262 330 390 415 440 486 539
(8) SC5B 0.30 8.5 220 291 351 372 418 475 511
SC6B 0.22 8.5 195 280 337 348 387 436 472
jF-8 (A) sc7B 0.30 8.5 270 312 376 411 472 507 532
SF-2 SC8B 0.35 8.4 230 294 340 390 454 500 518
Sî9B 0.30 12 230 316 355 408 472 525 557
SCIOB 0.22 15 234 355 397 454 528 589 628
SF-10 SCIIB 0.35 7.5 238 348 411 465 528 582 589
(A) SC12B 0.30 7.5 238 316 349 426 504 546 599
SC13B 0.22 7.5 280 326 383 454 514 560 589
iF-i1 (BI SC14B 0.30 7.5 184 277 323 372 443 479 489
SF-4 SC15B O30 12 234 298 355 401 486 514 550
SF-3 SC16B 0.30 12 167 241 298 348 401 418 433
SF-5 SC178 0.30 12 220 291 355 390 443 468 539
SC18B 0.35 8.5 202 273 362 418 461 504 560
SC19B 0.22 15 181 252 319 365 401 454 521
SF-6 SC228 0.35 8.5 238 305 358 422 479 567 660
Slurry Sî23B 0.23 15 227 273 348 394 454 543 511
(Age i) X24B 0.30 12 202 280 344 397 443 525 539
X25B 0.40 12 245 333 411 472 525 582 613
--``,`,-`-`,,`,,`,`,,`---
SF-12 SC26B 0.30 12 184 241 305 342 418 482 475
x27B 0.35 8.5 238 353 379 447 486 528 617
Sî28B 0.40 12 223 326 411 486 553 645 652
SF-13 CWOB 0.30 12 252 298 372 433 479 500 546
SF-14 SC31B 0.30 12 195 230 330 340 379 457 521
CF-7 CW2B 0.30 12 I74 270 362 390 415 500 560
(Age 2)
iF-15(Al X33B 0.30 8.5 199 24.5 301 337 397 443 493
jF-160 CC34B
ùote: :
0.30 8.5
drying especi;
209
NWer
-
#tored
-209
ime-sa
351
ratedu &
401 422
-
ays.
-
479
d on 76x102x390-mm prisms.

A C 1 S P - 1 5 3 VOL*II 75 = Obb2747 0 5 2 1 b 1 1 338
634 Wolsiefer et al
TABLE 11 - RESULTS OF DRYING SHRINKAGE OF PRISMS AFTER

28 DAYS OF MOIST CURING
- vlixhir -
Silica -
W Wr Drying Shrinkage Strain, x 10 4
Fume No. C+SF xrcen - - --
-
SF-I
-
SCIB
-
0.35
-
8.4
EgY 112da]
351 411 468
SC2B 0.30 12 121 209 273 312 358 429 468
CWB 0.23 15 117 i77 230 248 326 397 443
SF-9 SC4B 0.35 8.5 149 220 273 284 348 390 418
(B) SC5B 0.30 8.5 I35 188 223 255 312 362 387
SC6B 0.22 8.5 138 i77 209 238 301 337 383
jF-8 (A) SC7B 0.30 8.5 117 184 223 280 337 379 401
SF-2 SC8B 0.35 8.4 138 206 266 333 415 468 511
SC9B 0.30 12 121 170 255 323 387 436 472
XIOB 0.22 15 135 174 262 337 418 468 504
SF-10 Sî11B 0.35 7.5 163 234 298 390 468 507 550
(A) SC12B 0.30 7.5 124 188 270 333 383 457 472
SC13B 0.22 7.5 138 174 270 333 383 447 468
iF-11 (BI SCI4B 0.30 7.5 145 209 270 337 394 461 482
SF-4 SC15B 0.30 12 142 216 255 344 397 461 472
SF-3 X16B 0.30 12 117 199 245 333 367 447 457
SF-5 SC17B 0.30 12 I52 230 291 337 394 383
SCl8B 0.35 8.5 163 230 287 355 394 489 479
SC19B 0.22 15 131 163 209 262 305 387 383
SF-6 SC22B 0.35 8.5 117 223 312 387 457 504 535
Slurry SC23B 0.23 15 106 191 273 344 426 475 482
(Age i) SC24B 0.30 12 142 174 241 301 348 372 418
SC25B 0.40 12 145 195 277 348 411 433 571
SF-12 K26B 0.30 12 152 202 277 330 397 447 445
x27B 0.35 8.5 1% 227 301 358 411 461 486
K28B 0.40 12 160 230 333 408 489 553 578
SF-13 K30B 0.30 12 135 202 266 319 365 394 429
SF-14 iC-31B 0.30 12 142 184 223 273 348 408 461
SF-7 iC-32B 0.30 12 152 223 262 337 408 454 535
[Age 2)
F-15 (A) k-33B 0.30 8.5 128 184 238 287 355 390 436
F-16(B) 0.30 8.5 89 -- -
113
ote: 1 ior io i dryinp, ! Speci N Wei 8tom.I
i77 213
ime-sa ateà H
- erfor: 284 316
days.
-
365
2 rains were mea&red o n 76x102x390-mm prisms.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0662949 0521612 274 =
TABLE 12 - FLEXURAL STRENGTH AND CARBONATION DEPTH

DETERMINED AT END OF DRYING SHRINKAGE MEASUREMENTS
Silica
Fume
K
C+SF
1 SF/C
7day moistare
befmdrying
Flexural Carbonation
nation detem
%day I
M
Flexural
OI
1
1 after 448 days of drying
st-cure
yyig
Carbonation
Flexure of
wa tercured
--``,`,-`-`,,`,,`,`,,`---
Ref. prisms,
-
SF-I
trength, MPa depth, mm strength, MPa
5.7 2.0 5.9
depth,mm
0.0
MPa
7.4
6.9 1.0 75 0.0 93
8.6 0.0 9.0 0.0 10.7
SF-9 035 85 7.4 1.0 7.6 0.0 8.8

(B) O30 85 73 0.0 7.0 0.0 78
o22 85 9.0 o .o 8.1 0.0 10.7
iF8 (A) o30 8.5 7.5 75 0.0 8.5
SF-2 0.35 8.4 6.8 1.o 7.4 2.0 7.9

O30 12 7.7 0.0 8.2 1.O 8.9
0.22 15 9.0 0.0 8.7 0.0 10.0
SF-IO 7.0 1a 7.5 1.o 8.7

(A) 7.1 1.0 72 0.0 8.4
8.7 1.o 82 0.0 10.6
8-11 (B: o30 7.5 7.1 1.o 7.1 1.o 8.4
SF4 0.30 12 63 1.0 6.6 1.o 7.9
CF-3 OJO 12 6.7 1.o 7.4 1.o 8.4
SF-5 OJO 12 7.1 1.o 7.1 1.O 7a

0.35 85 6.4 2.0 6.4 2.0 7.7
o22 15 9.0 0.0 5.1 2.0 10.9
SFd o35 85 62 3.0 7.6 2.0 7.9
Slurry O23 15 9.1 0.0 9.1 0.0 10.8
(Age 1) 0.30 12 7.8 2.0 8.0 0.0 9.4
0.40 12 5.0 4.0 5.6 2.o 73
SF-12 o30 12 6.9 2.0 72 0.0 8.8

o35 8.5 6.3 2.0 72 1a 8.0
0.40 12 4.4 5.0 5.1 2.0 6.7
CF-13 0 3 12 65 3.0 7.1 0.0 8.1
CF-14 o30 12 7.9 0.0 7.9 0.0 9.0
SF-7 o30 12 7.7 0.0 7.9 0.0 8.3

(Age 2)
iF-I5(A: o30 85 8.1 oa 75 0.0 93
jF-160 O30 8.5 8.5 0.0 8.5 0.0 8.4

A C 1 SP-153 V O L X I I 95
636 Wolsiefer et al
= 0662949 0523633 L O O
TABLE 13 - AIR-VOID PARAMETERS DETERMINED IN HARDENED

CONCRETE WITH W/(C SF) OF 0.30 +
- -- Air Harde I concrete p meters
Silica dixture W S/C content Specific
Fume No. CZF percent in fresh Air surface Spacing
- - - :oncrete,I :ontent, I mm2/mm3 actor, mm
SF-l X2B 0.30 12 52 3.8 28.6 0.191
SF-9 SC5B 0.30 8.5 5.0 4.2 16.1 0.321
CF-8 X7B 0.30 8.5 5.2 4.0 16.9 0.311
SF-2 X9B 0.30 12 4.7 5.0 20.9 0.222

CF-10 92128 0.30 7.5 4.5 3.2 15.6 0.353
CF-1 1 X14B 0.30 7.5 4.9 4.3 18.6 0.265
CF-4 X15B 0.30 12 6.2 5.5 28.7 0.154
CF-3 X16B 0.30 12 5.6 4.6 23.8 0.184
CF-5 X17B 0.30 12 5.6 3.5 28.4 0.179
CF-6 SC24B 0.30 12 4.4 3.9 23.4 0.223
SF-12 CU6B 0.30 12 4.8 3.6 24.1 0.222
-
CF-13 -
X30B -
0.30 -
12 5.7 4.7 22.4 0.21 1
--``,`,-`-`,,`,,`,`,,`---
Q 100 W Uncompacted
o Compacted
I
Slurry
Ed Blended Cement
" Id 28d 91d lyr 2yr

Age
Fig. l-Compressive strength development: for 12 percent SF,

with W/C + SF = 0.30

A C 1 SP-153 V O L X I 1 95 m 0662949 052LbL4 0 4 7
Uncompacted
Compacted
gE
80 Slurry
E l BlendedCement
60
v)
.s!
v)
40
p. 20
" "
Q n
id 28d 91d lyr 2yr
Age
Fig. 24ompressive strength development: for 8.5 percent SF,

with W/C SF = 0.35 +
--``,`,-`-`,,`,,`,`,,`---
100 - Uncompacted
Compacted
S Slurry
2 80- E# Blended Cement
r
5
o)
!!! 60-
tj
.-a>l
$ 40-
Ep.
0
E 20-
ni
u
id 28d 91d lyr 2yr
Age
Fig. 3-Compressive strength development: for 15 percent SF,

+
with WIC SF = 0.22
Copyright American Concrete Institute 6'

A C 1 SP-II53 V O L 8 1 1 75 m Obb2ïY9 052IIbII5 Tô3 =
638 Wolsiefer et ai
90
80
-
SF6 Slurry
SF6 Slurry
6c 70 *
SFI2 Compacted
2 60
yj
- -* -
SF12 Compacted
.-9 50
v)
- -+ -
v)
40
o
5 30
Fig. 4-Compressive strength development comparison: with 12

percent SF for W/C SF = 0.30 and 0.40 +
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m Obb2949 052LbLb 91T 9
I c.
.-v)
E
U
5
.c
O
O
-
a
a,
>
a,
W
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 m 0662949 0523617 856 W
640 Wolsiefer et al
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0662749 0521bLB 7 9 2
10 I
--``,`,-`-`,,`,,`,`,,`---
u
Uncompact Compact Slurry Blnd Cement
Fig. 7-Flexural strength (12 percent SF, WIC + SF) = 0.30

A C 1 SP-153 V O L * I I 95 W 0662949 0 5 2 1 b L 9 629 W
642 Wolsiefer et al
W Uncompacted
Compacted
0 O ,
400 Slurry
- Blended Cement
300
2L 200
1O0
n
"
0.40 0.35 0.30 0.22
WIC+SF
Fig. &Rapid chloride permeability versus W/C + SF ratio
---
7nn I
28d
250 41d
- 200 H 91d
150
o
u 100
50
n
" Uncompacted Compacted Slurry Blended Cement
Fig. %Rapid chloride permeability versus silica fume

product form for 12 percent silica fume and W/C + SF
= 0.30
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 Ob62749 052Lb20 340
400 I W 42d
91d
" SF6 (0.40) SF6 (0.30) SF12 (0.40) SF12 (0.30)

Curing Age
Fig. 1C-Rapid chloride permeability comaprison at WIC +

SF of 0.30 and 0.40 with 12 percent silica fume
4 0
Aoielerated cure by wann watera h initial Jet ofconcrete

' 9l-daymoistcum
--``,`,-`-`,,`,,`,`,,`---
CF-3 SF-6 SF-7 CF-12 SF-13 SF-14 SF-15 SF-16

Silica fume commies
Fig. 11-Rapid chloride permeability results of 91-day moist-cured

same-day accelerated-cured concretes

A C 1 SP-153 V O L 8 1 1 95 m 0662949 0521621 287 m
644 Wolsiefer et al
I42dmoistcure
9ldmoislcure
I42dfddwre
9ldïdwre
O 42dñsid cure and warm water w n
9idFsidwnandwarmwaterwrn
(0.35)
SF-3
__...__.._._
(0.30)
____________
(022)
1..
(0.35) (0.30) (0.22)
____________SF.6 ____________
Fig. 12-Rapid chloride permeability results of moist-cured and field-

cured silica fume concrete cores
(0.35) (0.30) (0.22)
____________SF.12 ____________
Fig. 13-Drying shrinkage of concrete prisms after 7 days

of moist cure: W/C S f = 0.30 drying +
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 = 0662949 OSE'Lb22 lL3
Fig. 1LCDrying shrinkage of concrete prisms after 28 days

of moist cure: W/C + SF = 0.30
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL*II 95 m 0662949 0521623 05T m
646 Wolsiefer et al
APPENDIX A: SUMMARY OF RESULTS OF PREVIOUS RCP

INVESTIGATION AT CANMET
TABLE A l - TEST PROGRAM-RCP EVALUATION OF WARM

WATER AND BOIL CURE PROCEDURE
Mix & Air Cement Silica Comp. Chloride-ion
No. (C+SD content, content, hime, strength‘ Curing conditions permeability,
96 kg/m3 k g / d MPaípsi) coulombs
--``,`,-`-`,,`,,`,`,,`---
ab/yd3) Wyd3) (“1

CPl 0.31 6.2 394 43.5 48.1 Warm water, 71°C
(661) (73) (6980) for 16h (after ñnal set)
47.3 7-day Moist cured (Lab)

(6860)
60.6 W a y Moist cured (Lab)

(8790)
46.5 M a y Field cured
(6745)
61.5 42-day Moist cured (Lab)

(8920)
55.2 42day field cured
(8005)
56.5 42-day Core (field slab)
(8195)
59.4 91day Moist cured (Lab)

(861s)
57.4 91day Field cured
(832.9
58.2 91-äay Cored
(8440)
Strength values are determined using two cylinders.
*N~unbersin brackets represent the permeability cell wd.

A C 1 SP-ri53 VOL*II 95 W 0662949 0521624 T9b
=
647
TABLE A l - TEST PROGRAM-RCP EVALUATION OF WARM

WATER AND BOIL CURE PROCEDURE (CONT'D.)
Mix W Air Cement Silica Comp. Chloride-ion
No. (C+CF) content, content, fume, strength' Curing conditions permeability,
96 kg/m3 k g / d MPa(psi) coulombs
(Ib/yd? (Ib/yd3) (")
CP2 0.31 5.9 397 43.8 51.2 l d a y m.c.+3.5 h boiùing Y31 (i)
(669) (74) (7525) 143 (2)
49.8 2 d a y m.c.+3.5 h boiling 115(1)

(7220) faulty cell
52.5 7 d a y n c . +3.5 h boiling 156 (1)

(7615) 170 (2)
50.2 7 d a y Moist cured (Lab) 1366 (1)
(7280) 1344 (2)
63.8 m a y Moist cured (Lab) 275 (1)

9250 306 (2)
56.3 28-day Field cured 328 (1)
(8165) 328 (2)
65.0 42day Moist cured (Lab) 250 (3)

(9430) 262 (4)
56.7 42day Field cured 293 (i )
(8225) 263 (2)
64.5 91day Moist cured (Lab) 177 (1)

(9355) 186 (2)
57.2 91-day Field cured 103 (3)
(8295) 11s (4)
Strength values are determined using two cylinders.
"Numbers in brackets represent the permeability cell used.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 V O L U I I 95 O662949 0521625 922
648 Wolsiefer et al
TABLE A l - TEST PROGRAM-RCP EVALAUTION OF WARM

WATER AND BOIL CURE PROCEDURE (CONT'D.)
Mix Air Cement Silica Comp. Chloride-ion
No. ( C + W content, content, fume, strength' Curing conditions permeability,
% kg/m3 k g / d MPa(psi) coulombs
ab/ydJ) ab/ydq ("1
cp3 0.31 8.0 383 42.2 44.6 Warm water, 71°C for 1410)
(646) (71) (6170) 16 h (after final set) 136 (2)
41.7 Iday m.c.+3.5 h boiling 162(I)

(6050) 165(2)
42.3 2day m.c.+3.5 h boiling 137(I)

(6135) 164 (2)
45.0 74ay m.c.+3.5 h boiling 139 (i)
(6525) 145 (2)
43.2 7day Moist cured (Lab) 771 ( i )

(6265) 861 (2)
52.3 B d a y Moist cured 301 (1)
(7585) 297 (2)
53.9 91d a y Moist cured 209 (1)

(7820) 185 (2)
'Strength values are determined using two cylinders.
"Numbers in brackets represent the permeability cell used.
--``,`,-`-`,,`,,`,`,,`---

APPENDIX B: TEST RESULTS SUMMARIZED BY PRODUCT FORM,

W/C + SF AND SILICA FUME PERCENTAGE
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLaII 95 IOb62949 0 5 2 L b 2 b 8 6 9
A C 1 SP-153 VOL*II 95 9 0 b b 2 9 4 9 052Lb27 7T5
650 Wolsiefer et al
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L l i t I I 95 E 0662949 0521628 631 m
Cu
Cu
o
II
4
v,
+
o
2
LL-
V)
I-
z
W
W
Q
2
U
V)
W
3
a
>
Q
--``,`,-`-`,,`,,`,`,,`---
n
z
a
0
5
3
V)
w
a:
I-
V)
w
I-
I
I-
za:
W
I-
V)
I
o
m
W
-I
m
5

A C 1 SP-153 VOL*II 95 W 0662949 0521629 578 W
652 Wolsiefer et al
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 VOLtII 95 0662949 052IIb30 29T W
TABLE 136 - RAPID CHLORIDE PERMEABILITY VERSUS W/C + SF
I
Silica Fume Form 0.40 0.35 0.30 0.22
N/A 231 143 83
SF2 Uncompacted N/A 239 130 81
SFS Compacted ( S i 0 79.7%) N/A 290 161 66
SF6 Slurry 297 233 137 67
SF 9 Blended Cement (Pellet) N/A 238 I98 103
SF 1O Blended Cement (Uncornpacted) N/A 404 274 166
PF! 2 Comnacted ( S i 0 95.4%) 324 246 159 76
TABLE BS(a) - RAPID CHLORIDE PERMEABILITY VERSUS W/C + SF*

[ilka Fume Product Form
Uncornpacted
Compacted
Sluny
Blended Cement
1 1 1 1
0,4:/j
324
2 97
N/
0.3z35
268
233
321
03.;:
137
236
0.22;;
67
135
Averaged by Silica Fume Product Form

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 V O L X I I 95 = Ob62949 0521ib31 II26 =
654 Wolsiefer et al
APPENDIX C
AUTOCLAVE EXPANSION OF SILICA FUME/CEMENT PASTE

INCORPORATING SILICA FUME CONTAINING ABOUT 12 PERCENT
MgO
In the NORCHEM/CANMET work on “Performance of Concrete

Incorporating Various Forms of Silica Fume“I the chemical analysis
of silica fume samples SF-5 [normal density compacted air-densified
fume (43.2 lbs/ft’ and SiO, 7 9 . 9 % ) ] and SF-13 [high density
compacted air-densified fumes (57.6 lbs/ft’ and S i O , 80.1%) ]
indicated that the MgO contents of these fumes were higher than
usual, at 12.0% and 12.3%, respectively. There was concern that,
these magnesium oxide might be in the form of periclase, which has
the potential for high delayed expansions in concretes. To verify
--``,`,-`-`,,`,,`,`,,`---
this, autoclave expansion tests were carried out on cement paste
incorporating both silica fume samples. The ASTM Type I cement
used was the same cement used in the NORCHEM silica fume
investigation. The percentage replacement of cement by silica fume
was kept at 8.5%, 12% and 15%.
The attached data sheet gives the ASTM C 187 normal consistency
test results and the ASTM C 151 autoclave expansion test results.
The mixture proportions of the control and silica fume/cement
pastes are given in the normal consistency test results. Two
control portland cement pastes and six silica fume/cement pastes
were made and subjected to the autoclave expansion testing
according to the standard. Two specimens were tested from each
paste, and average expansion results are lower than 0.025%. A l s o ,
with the increase in silica fume in the paste, from 8.5% to 15%,
there was a trend of reduction in the expansion. The limiting
value for autoclave expansion according to the standard is 1.0% for
a sound paste. Therefore, it is concluded that there is no delayed
expansion caused by the higher than usual amount of magnesium oxide
in the silica fume SF-5 and SF-13.

A C 1 SmP-L53 V O L m I I 95 m 0662949 0521632 Ob2 m
AUTOCLAVE EXPANSION OF SILICA FUME PASTES
Normal Consistency ASTM C187

SF5
Control 650 g cement (CT45). 165 mL water = 25.5 %
8.5 % 595 g cement, 55 g SF, 180 mL water = 28.0 %
12 % 572 g cement, 78 g SF, 190 mL water = 29.0 %
SF13
Control 650 g cement (CT45), 165 mL water = 25.5 %
8.5 % 595 g cement, 55 g SF, 180 mL water = 28.0 %
Autoclave ExpansionASTM C151
Gauge Reading
Initial Final
SF5
Control #1 0.0506 0.0497
#2 0.0374 0.0365 Expansion = 0.009 %
8.5 % #1 0.0620 0.0600
#2 0.0290 0.0267 Expansion = 0.022 %
12 % #1 0.0286 0.0265
#2 0.0196 0.0173 Expansion = 0.022 %
15 % #1 0.2427 0.2414
#2 0.0205 0.0189 Expansion = 0.015 %
Gauge Reading
Initial Final
SF13
Control #1 0.2346 0.2338
#2 0.0017 0.0008 Expansion= 0.009 %
8.5 % #1 0.2463 0.2441
#2 0.0027 0.0005 Expansion= 0.022 %
12 % #1 0.0018 0.2498
#2 0.0173 0.0152 Expansion = 0.021 %
15 % #1 0.0322 0.0303
#2 0.0443 0.0424 Expansion = 0.019 %
CSA-A25-M88 : 1.O0M a .
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 IObb2949 0521633 T T î m
Effectiveness of Supplementary
Cementing Materials in Controlling
Chloride Penetration into Concrete
by R. N. Swamy and J. C. Laiw
Synopsis: This paper presents the results of a study to investigate the

effectiveness of ground granulated blastfurnace slag, fly ash and silica fume in
controlling chloride penetration into concrete of high water-binder ratio. To
simulate field conditions, the tests were carried out on 1000 x 500 x 150 mm
reinforced concrete slabs. To understand the basic roles of mineral admixtures
in controlling chloride penetration, the cement was replaced, mass for mass, by
65'% slag, 30% fly ash and 10% silica furne without modifying either the water-
binder ratio or using a water-reducer or superplasticizer. A constant and high
water-binder ratio was deliberately used for all the concrete mixtures, and the
results are compared, where appropriate, with mixtures of lower w h . The
effects on workability, compressive strength and chloride penetration were then
evaluated, the latter two properties ovtr a period of 18 months through cyclic
exposure to 4% sodium chloride solution. Irrespective of their effects on
workability and cornpressive strength, all the cement replacement materials
reduced both the depth of penetration and the chloride concentration at a given
depth from the concrete surface. Silica fume was the most effective and fly ash
the least. Even at a very high wh of 0.75, slag concrete showed a consistently
lower chloride concentration for all exposure levels up to 50 cycles, and at all
depths from the concrete surface compared to that of portland cement concrete.
Both the type of supplementary cementing material and the period of exposure
influenced chloride penetration, but the water-binder ratio also had a significant
effect at ail ages.
Keywords: Blast furnace slag; chlorides; compressive strength; drying;

durability; fly ash; ponding; silica fume; slabs; tests; water binder ratio;
workability
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-253 VOL+II 75 = Obb2949 0.522634 935 =
658 Swamy and Laiw
AC‘I inombsr Prof. R. Narayan S\$am\i is at the Structural Integrity Research

Institute, Uni\ ersity of Sheffield, England. His research interests are in concrete
materials and concrete structures. He received the George Stephenson gold
Medal of the Institution of Civil Engineers and the Henry Adams Diploma from
the Institution of Structural Engineers. He is Editor of Cement and Concrete
(‘omposites and the Book Series on Concrete Technology and Design. He
recently reczik ed the CANMETI’ACI Award for contributions to Durability of
Concrete.
Dr. Tony Laiw took his PhD degree from Sheffield and is currently Head of the
Research and Development Section of the Taiwan Area National Expressway
Engineering Bureau, Ministry of Transportation and Communications, Taiwan.
His major research interests are in concrete materials, durability and concrete
structures.
INTRODUCTION
Corrosion of reinforcing bars associated with the ingress into concrete of

chloride ions from de-icing salts and sea water is now universally recognized te
have contributed to the most prevalent form of destructive mechanism foi.
bridge decks and marine structures. Chloride ions are thus considered to be the
major cause of premature corrosion of rebars in reinforced concrete structures
that affect the integ-ity and long-term service life of structures. Many
laboratory and field investigations show that chloride intrusion into concrete
appears to be just a question of time before detrimental amounts of chloride
reach the rebars, even when the concrete has been proportioned, mixed and
placed in accordance with specifications ( 1,2).
Chloride ions can only be transported into concrete or diffuse through it ir.
liquid-phase water, and the mechanism of their intrusion is a combined effect of
physical and chemical reactions. The paths that provide chloride intrusion
depend on the pore structure of the concrete. These paths consist of micropores
and microcracks on the surface of the concrete and the inter-connected internal
pores that form a permeable continuous pore channel which may arise from high
waterhinder ratio (wh) or inadequate curing or internal microcracking. The
characteristics of these channels are determined by the total porosity, pore size
distribution and the chemical nature of the surfaces of the pores (3,4).
The properties of concrete and its exposure environment (including the

characteristics of chloride solution) are the two major factors influencing the
intrusion of chloride. Composite cements with different percentages of silica
fume (SF), bg-ound granulated blastfurnace slag (GGBFS) and fly ash (FA) have
proved to have better resistance to chloride intrusion than ordinary portland
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L U I I 95 m 0bb2949 0521635 8 7 1 m
cement ( 5 - 8 ) . It is generally concluded that when considering long-term

durations of exposure, both the nature of the cement matrix and the w/t:
influence the depth of chloride penetration, although if the w/b is low enough tc
provide a discontinuous pore structure, the cement matrix can be more critical
than the w/b (9).
*
Much of the published data on chloride intrusion into concrete are,
however, based on tests on cement pastes or cubes and prisms of concrete. To
obtain a better understanding of the chloride penetration process in practice, and
the role and effectiveness of the incorporation of mineral admixtures in concrete
and to develop desi@ parameters, the data presented in this paper are based on
some carefully chosen features in the test program. Firstly, the data presented
are based on fairly large-sized reinforced concrete slabs, 1 O00 x 500 x 1SO mm,
simulating structurai elements such as pavements and bridge decks. Secondly, a
fairly high water-binder ratio was used, quite deliberately, partly in order to
obtain a good amount of experimental data in a reasonable time and partly to
examine if the supplementary cementing materials can be effective at high water
--``,`,-`-`,,`,,`,`,,`---
contents. In practice, there are many situations where concrete mixtures with
w/b in excess of 0.50 to 0.55 are used; one of the aims of this project was to
examine if the incorporation o f , mineral admixtures in such mixtures was
beneficial or not. Further, the concrete mixtures were proportioned in such a
way to replace cement, mass for mass, by GGBFS , FA or SF without the use of
a water-reducer or superplasticizer. The effects of these variables were then
directly observed on workability, compressive strength development and
chloride intrusion, and the results are compared with comparable concrete
mixtures containing portland cement alone. The data reported here form part of
a major study, and therefore only results relevant to the above are presented
here.
The experimental programme consisted of the exposure of seyera!

reinforced concrete slabs to 4'X, sodium chloride solution on the top surface.
The slabs used in the tests were 1000 x SOO x 150 mm, reinforced with high
tensile steel (Table i). The concrete mixtures used in the slabs contained total
cementitious content of 350 kgim3. Ground granulated blast-furnace slag, fly
ash and silica fume were used as cement replacement materials, mass for mass,
at levels of 65o/u, 30%~and 10% respectively as shown in Table I . A high water-
binder ra.tio of 0.60 was used partly to simulate the concrete mixtures often usee
in practice, and partly to highlight the benefits of supplementary cementing
material:; even at high water contents. ( I t is emphasized that 0.6 w:% is not
recommended for severe chloride exposures - the ability to develop B
discontinuous pore distribution is a key component for reducing chloridr
ingress). Some additional tests were carried out at a w:% of 0.75 with concrete
mixtures containing GGBFS; several tests wzre also camcd out at 0.45 ar,%, bu:

A C 1 SP-153 VOLS11 95 = Obb2949 0521b3b 708 =
660 Swamy and Laiw
--``,`,-`-`,,`,,`,`,,`---
these are not reported here. The slabs were exposed to cyclic ponding for 7
days with the 4% sodium chloride solution on the top surface and subsequent
drying for 3 days. The chloride content in the concrete was determined by
chemical analysis.
The slabs were all cast individually with 20 mm diameter high tensile
reinforcing bars. Each slab had a rectangular acrylic frame embedded into the
concrete during the fabrication of the slabs: these frames formed an
embankment on the top surface for later salt solution ponding.
Concrete Mixture Proportions
The total cementitious content was kept constant in all the slabs at 350
kg/m3. The mineral admixtures were used to replace the cement, mass for mass.
The total aggregate-cementitious ratio was kept constant at 5.26:l and the
percentage of sand in the total aggegate was kept constant at 32% for al!
mixtures. The aggegates for the concrete mixtures were used in an air dry
condition: the water content was then checked, and adjusted before concrete
mixing. To obtain a uniform and cohesive mixture, and to reduce bleeding, the
mixing water was added in two stages (lo), and this ensured that there was
practically no observed bleeding of the concrete mixtures.
Concrete Materials
Normal portland cement, ASTM Type J was used throughout. The cement
had a specific surface of 345 mz,'kg, and a total equivalent sodium oxide alkali
content of 0.82%. The Bogue composition of the portland cement consisted of
C3S 54%, C2S 19%, C3A 9% and CJAF 10%.
Both the GGBFS and fly ash satisfied the current BS specifications. The
slag had a fineness of 4 17 m2/'kg, whilst the fineness of the fly ash expressed as
the mass proportion of the ash retained on a 45 pm mesh was 7.6%. The silica
fume was in powder form, and contained 97% silicon dioxide.
The fine and coarse aggregates used were washed natural aggregates, The
fine agbTegate had a fineness modulus of 2.1 ; the coarse aggregate consisting of
a mixture of rounded and crushed gavel with 10 mm maximum particle size
had a fineness modulus of 1.84. The aggregates contained very little chloride
(less than 0.1'%) and were innocuous so far as alkali-aggregate reactivity was
concerned.

A C 1 SP-353 VOL411 95 0662949 0523637 644
Test Del ails
The slabs and the cubes for compressive strength tests were subjected tc)
similar curing conditions. Both were initially covered by polythene sheets for
24 hr immediately after casting. After 24 hr, the slabs were cured by water
ponding on the top surface for 6 days, then sponge dried, demolded and exposed
to ambient conditions for 21 days further air curing. The cubes werz demolded
at 24 hr, and stored in water at 20°C for 6 days and then moved into ambient
conditions for air curing near the slabs.
The slabs were exposed to 4%) sodium chloride ponding from 28 days.
Each cycle consisted of ponding for 7 days, then removal of the solution and the
surface dried at ambient condition for 3 days. During each cycle a new solution
with the same concentration was used in ponding, and the depth of ponding was
kept at 1O mm depth.
Chloride Concentration Profiles
The chloride analysis was carried out according to BS 1881: Part 124:
1988. ?Method for Analysis of Hardened Concrete?. The chloride content is
expressed as acid-soluble chloride content by weight of cement, and each
chloride concentration shown in the results was obtained from the average of
two analysis results.
Samples for chloride content analysis were taken by a rotary hammer dril;
uith a 20 mm diameter bit. The samples were taken from six different positions
over the depth of the slab, and exactly above the rebars. Each sampling position
was divided into five different depths from the top surface of the slab, the
sampling depths being 5-25.25-45,45-65, 65-85 and 85-105 mm. The concrete
powder drilled from the top 0-5 mm was discarded to avoid the discrepancies
and variations associated uith top weak surface layers. The powders obtained
from each position at the same depth were then combined to b? ?ive 2
representative sample for later analysis. The weight of powder obtained from
six 20 m m diameter x 20 mm depth holes was sieved through a 150 pm sieve,
and the sample thus obtained was adequate for chloride and cement content
analysis. The sampling interval on the slabs was after 10, 20 and 50 cycles or
exposure.
The holes left after sampling were filled with mortars having the same
water-binder ratio as the original concrete, and carefully sealed. The salt
exposure tests were then continued. The interval between sampling the slabs,
then filling the holes and re-exposure to sait solution varied from about 7 to 14
days.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 0bb2949 052l1638 580 =
662 Swamy and Laiw
TEST RESULTS AND DISCUSSION
Concrete Workability
The workability of the concrete mixtures used in the slabs was expressed
by its slump. The slump test was performed immediately after mixing the
concrete. The results of the slump test are shown in Table 1. Both GGBFS and
fly ash enhanced the workability properties of the concrete mixture, confirming
that at these high water-binder ratios a reduction in the amount of water required
--``,`,-`-`,,`,,`,`,,`---
for a given degree of workability can be effected from that required for an
equivalent concrete mixture without the mineral admixture. Concrete
containing 10% SF, on the other hand, had its slump decreased by about 70%
compared to portland cement concrete.
The compressive strength of the concretes containing the different mineral

admixtures was determined on 100 mtn cubes at various ages up to about 18
months. The results of these tests are shown in Table 2.
The portland cement concrete showed little increase in strength betweer.

28 days and about 4 months; at about eight months, the strength increase
compared to that at 28 days varied between O and IO'%, whilst at about 18
months, the strength increase beyond 28 days was between 10% and 20%. Ali
the concretes with mineral admixtures registered substantial strength increases
with age compared to their 28 day strength: at 8 months, this strength increase
varied between 15% and 50'!/0, whilst at 18 months this ranged between 25%
and 85% Concretes with W B F S and fly ash registered low early strength: at
both w/b ratios of 0.60 and 0.75 it took CiCiBFS about 8 months to reach the
same compressive strength as portland cement concrete. The fly ash concrete,
on the other hand, never caught up in strength with portland cement concrete;
even at 18 months it had nearly 20% less strength compared to portland cement
concrete. The concrete with silica furne registered higher strength at all ages
from 7 days onwards, and this varied from about 10')/0to 30% between 28 days
and 18 months.
Table 3 and Fig. 1 compare the strength development of concrete

containing GGBFS. fly ash and SF with that of the control concrete. It is clear
that at a fairly high water-binder ratio, fly ash concrete needs a longer we;
curing period than GGBFS and SF in order to de\,elop an equal or higher
strength than control concrete.
Chloride Concentration Profiles
The chloride concentration profiles in the concretes in the slabs containing

GGBFS, fly ash and SF after 10 ( 100 days), 20 (700 days) and 50 (500 daysi

A C 1 SP-153 V O L S 1 1 95 0662949 0521637 417
--``,`,-`-`,,`,,`,`,,`---
C>C!CE iif sxpnsure tu 4% sodium chloride solution are presented in Table 4 and
Fig. 2 to 5 . Although ths general shape of the chloride concentration profiles
appears to be similar in all the cases sholtn, these data have some interesting
differences. .At \v!b = 0.60, there is clear indication that the depth of chloride
penetration is initially small and increases only with time and continued
exposurz to cycles of \vetting and drying. At the high wíb of 0.75, on the other
hand, the depth of penetration is very high even after the first 10 cycles; after
these number of cycles, the depth of chloride penetration is about 100 mm at
w,'b = 0.75, cornpared to about 50 mm a t 0.60 w h .
With continued exposure to chloride solution,' the chloride ions penetrated

deeper into the concrete, and the amount of chloride concentration at a given
depth also increased. This trend continued as the concrete continued to be
exposed further to chlorides.
l h e data in 'Table 4 and Fig. 2 to 5 also clearly indicate the effectiveness

of the different mineral admixtures and the watec'binder ratio. 'To give a better
understanding of the influence of these parameters in resisting chloride intrusion
in relation to the control portland cement concrete, the results are further
clarified in Fig. 6 to 9. Fig. 6 to 8 compare the effectiveness of GGBFS, fly ash
and SF at a \v;b of 0.60 after IO, 20 and 50 cycles, whilst Fig. 9 compares the
chloride intrusion into concretes with CiGBFS and portland cement at a \v/b of
0.75.
The data in Fig. 6 to 8 show that the depth of penetration of chloride ions
depends very much on the number of cycles of exposure and the type of minera:
admixture. Thus, up to 10 cycles of chloride exposure, concretes with all
mineral admixtures show a much reduced depth of chloride penetratiori
compared to portland cement concrete. At 20 cycles of repeated ponding and
drying, chloride ions penetrate fly ash concrete to the same depth as portland
cement concrete, whereas it takes about 50 cycles for chloride ions to reach the
same depth in slag concrete as in portland cement concrete. In concrete with
SF, on the other hand, the depth of chloride penetration was still very much less
than that in portland cement concrete even after 50 cycles of exposure.
The results of Fig. 6 to 8 also show that the presence of mineral

admixtiires substantially reduces the amount .of chlorides present at a givefi
depth from the surface of the slabs. concrete with SF is seen to give the best
performance at all levels of exposure. It exhibits the lowest chloride
concentration at all depths compared to portland cement concrete and concrete
with G B F S and fly ash. Concrete with GGBFS also shows better performance
in resisting chloride intrusion than fly ash concrete, particularly after the initia!
I 0 cycles of exposure.
Fly ash concrete is clearly seen to be less resistant to chloride penetratiori

than concretes with slag and SF, but it must be emphasized that it shows a much

A C 1 SP-153 VOL+II 95 m 0662949 0523b40 139 m
664 Swamy and Laiw
reduced chloride concentration at depths beyond about 25 mm depth compared

to that in portland cement concrete. One particular disadvantage of fly ash
concrete is that it appears to be very susceptible to chloride penetration just
below the external surface, and levels of chloride concentration above that of
portland cement concrete were observed in the region of 5-25 mm from the
concrete surface. Similar phenomenon has been observed by other investigators
( 1 1 ) and also explains why fly ash concrete near the top exposed surfaces have
been found susceptible to greater erosion, scaling etc.
The results presented here generally confirm the greater effectiveness of

SF in reducing the intrusion of chloride ions into concrete than GGBFS and fly
ash. The ultra fine particles comprising SF (0.1 to 0.2 pm) and the high Si02
content result in the formation of a large C-S-H phase in capillary pores which
refines the pore structure and leads to reduced permeability.
--``,`,-`-`,,`,,`,`,,`---
Fig. 9 shows the effectiveness of GGBFS in reducing chloride penetration
into concrete even at as high a wib as 0.75. At all exposure levels up to 5G
cycles, the slag concrete shows a lower chloride concentration at all depths from
the concrete surface compared to that of portland cement concrete. The
differences in chloride concentration at all depths increase with increased
exposure to chlorides, and this suggests an increasingly better performance with
time of slag concrete than portland cement concrete when exposed to a chloride
environment.
A quantitative comparison of the reduction in chloride concentratiofi

achieved by the incorporation of mineral admixtures in concretes with wíb of
0.60 and 0.75 and after 50 cycles of exposure to chlorides is shown in Table 5
The results show that the percentage reduction in chloride concentration
compared to the control portland cement concrete increased with the depth of
the concrete in the slab. Silica fume is seen to be the most effective; followed
by GGBFS and then by fly ash. Comparing slabs S7 (w:b = 0.60) and slab SI0
(w/b = 0.75) containing GGBFS, it can be readily seen that mineral admixtures
are most effective in reducing chloride intrusion in concretes with lower w/t?
than concretes with higher wib, as indeed would be expected.
The superior nature of SF compared to GGBFS and fly ash can be seen
from Table 6 in which the chloride concentration in slab S9 with SF is
compared with those in portland cement concretes with wíb = 0.60 (slab S2) and
wíb = 0.45 (slab SI). It is seen that concrete at a wib = 0.60 and containing
10% cement replacement with SF is far more effective in resisting chloride
intrusion than by reducing the wíb ratio from 0.60 to 0.45 in portland cemen:
concrete. On the other hand, the 0.45 wíb (slab S1) out performed GGBFS
(slab 7) and FA (slab 8) at w/b = 0.60. If early strength was important, the 0.45
portland cement concrete might be one choice compared to GGBFS and FA,
although high early strength can also be obtained with GGBFS and FA if
appropriate mixture proportioning methods are used ( 12, 13).

A C 1 SP-153 VOLL11 95 I0662949 0 5 2 3 6 4 3 075
CONCLUS1ON S
The important conclusions derived from this investigation are summarised

below.
1. Both GGBFS and fly ash enhanced the workability properties of the
concrete mixture as measured by the slump test. Incorporating MS, on the
other hand, reduced slump by about 70%.
2. At w/b ratios of 0.60 and 0.75, it took GGBFS (at 65'% replacement level)
about 8 months to reach the same compressive strength as portland cement
concrete. Fly ash concrete reached only about 80% of the strength of
portland cement concrete after 18 months. Microsilica concrete registered
higher strengths at all ages beyond 7 days varying from 10% to 30%.
3. The water-binder ratio had a clear and significant influence on the depth of
chloride penetration after the first 10 cycles of exposure to chlorides.
4. The depth of penetration of chloride ions at any given time depended very
much on the number of cycles of exposure and the type of mineral
admixture. After 10 cycles of exposure concretes with all mineral
admixtures showed reduced depth of chloride penetration.
5. The presence of mineral admixtures substantially reduced the amount of

chlorides present at a given depth from the concrete surface. Chlorides
reached the same depth in fly ash concrete as in portland cement concrete
after 20 cycles of exposure. it took about 50 cycles of exposure for
chloride ions to reach the same depth in slag concrete as in portland
cement concrete. In SF concrete, on the other hand, the depth of chloride
penetration was still very much less than that in portland cement concrete
even after 50 cycles of exposure.
6. Concrete with SF showed the best resistance to chloride penetration at all

depths from the concrete surface. Fly ash concrete was less resistant than
both slag and silica fume.
7. Fly ash concrete was particularly susceptible to chloride penetration just

below the external surface, and showed levels of chloride concentration
above that of portland cement concrete, although beyond about 25 mrn
depth, it showed a much reduced chloride concentration.
8. Slag was effective even at w/b = 0.75, and showed reduced chloride
penetration at all exposure levels up to 50 cycles. These differences in
chloride content at all depths increased with increased exposure to
chlorides.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLJII 95 Obb2949 0523642 T O 1 9
666 Swamy and Laiw
9, At both w'b of0.60 and 0.75. the percentage reduction in chloride content,
after 50 cycles of exposure, increased with the depth of the concrete from
the surface. Microsilica was the most effective, followed by slag; fly ash
was the least effective of all the three materials. The incorporation of
mineral admixtures can thus bring tangible technical benefits even in
concretes with high wÍb.
10. The effectiveness of SF was such that concrete at w'b = 0.60 and
containing 10'%,cement replacement was far more effective in resisting
chloride penetration than by reducing the w!'b ratio from 0.60 to 0.45 in
portland cement concrete.
REFERENCES
1. Mehta, P.K., "Durability of Concrete - Fifty Years of Progress":

Proceedincs 2nd Int. Conf., Durability of Concrete, AC[ Publ. SP-126,
Editor V . M . Malhotra, 1991, pp.1-31.
--``,`,-`-`,,`,,`,`,,`---
2. Gjorv, O.E., "Durability of Concrete Structures in the Ocean

Environment", &. FIP Symposium on Concrete Sea Structures, Sept.
1972, London, pp.141-145.
3. Li, S. and Roy, D.M., "investigation of Relations Between Porosity, Pore

Structure and Chloride Diffusion of Fly ,4sh and Blended Cement Paste",
Journal of the American Ceramic Societv, Vol. 16, No. 5 , Sept. 1086.
pp. 749-756.
4. Collepardi, M., et ai, "Penetration of Chloride Ions into Cement Paste and
Concrete", Journal of the American Ceramic Society, Vol. 55, No. 10,
1972, pp.534-535.
5. Page, C.L., Short, N.R., and Tarras, A. El, "Diffusion of Chloride ions ir!
Hardened Cement Pastes", Cement and Concrete Research, Vol. 1 1, No. 3,
May 198 I , pp.395-406.
6. Byfors, K., "Influence of Silica Fume and Fly Ash on Chloride DiYfusion
and PH values in Cement Paste", Cement and Concrete Research, Vol. 17,
No. 1, Jan 1987, pp.115-130.
7. Luping, T., and Nilsson, L-O, "Chloride Binding Capacity, Penetration

and Pore Structures of Blended Cement Pastes with Slag and Fly Ash",
Proceedings, Int. Conf. on Blended Cements in Construction, Editor R.N.
Swamy, Sept. 1991, pp.377-388.

A C 1 SP-153 VOL*II 95 M Obb291r9 0521643 9 4 8 M
8. Arya, C., et al, "Factors Influencing Chloride Binding in Concrete"

-
Cement and Concrete Research, Vol. 20, No. 2, March 1990. pp.291-300.
9. Gjorv, O. and Vennesland. O., "Evaluation and Control of Steel Corrosion

in Offshore Concrete Structures", Proceedings, Concrete Durability,
Katherine and Bryant Mather Int. Conf., AC1 SP-100, 1988, pp.1575-
1602.
10. Swamy, R.N., and Falih, F.M., "Development of a Small Aggregate

Concrete for Structural Similitude of Slab-Column Connections", Design
-
of Concrete Structures: The Use of Model Analvsis. Elsevier Applied
Science Publishers, 1985, pp.25-34.
11. Mangat, P.S., El-Hatib, J.M. and Molloy, B.T., "Microstructure, Chloride
Diffusion and Reinforcement Corrosion in Blended Cement Paste and
Concrete", Proceedings, Int. Conf. on Blended Cements in Construction,
Sept. 1991.
12. Suamy, R.N. and Bouikni, A., "Some Engineering Properties of Slag
Concrete as Influenced by Mix Proportioning and Curing", AC1 Materials
Journal,
- - Vol. 87, No.3. May-June 1990, pp.2 10-220.
13. Swamy, R.N., "Fly Ash Concrete - Potential Without Misuse, RILEM
Materials and Structures, Vol. 23, No. 138, 1900, pp.397-411.
-
TABLE 1 - SLUMP OF CONCRETE MIXTURES USED IN SLABS

Mineral Slump
admixture mm
- 30
I Li2 I 0.60 - 80
I S3 I 0.75 - 165
I S7 I 0.60 65% GGBFS I 115
30% FA I 160
10% SF I 25
I s10 I 0.75 '65%GGBFS I 200
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*II 95 = Obb2949 0523644 884
668 Swamy and Laiw
GGBFS (52%) (100%) (106%) (142u/) (161%)

S8 0.60 30% 17 26 33 33 42
FA (65%) (100%) (127%) (127%) (161%)
s9 0.60 10% 35 50 55 61 65
SF (66%) (100%) (104%) (115%) (123%)
SI0 0.75 65% 15 23 29 35 43
GGBFS (65%) (100%) (126%) (152%) (187%)
--``,`,-`-`,,`,,`,`,,`---
s3 0.75 - 100 100 100 100 100

S10 0.75 65% 68 74 88 103 116
GGBFS

A C 1 SP-153 VOLXI1 95 Ob62949 0521645 710 M
TABLE 4 - CHLORIDE PROFILES IN SLABS WITH MINERAL

ADMIXTURES (UNIT: PERCENT CEMENT WEIGHT)
TABL.E 5 - COMPARISON OF CHLORIDE CONCENTRATION IN

SLABS WITH MINERAL ADMIXTURES AFTER 50 CYCLES OF
EXPOSURE (UNIT: PERCENT OF CEMENT WEIGHT)
* Ratio of chloride concentration in slab divided by concentration in S2 at the same depth.

+ Ratio of chloride concentration in slab S10 divided by concentration in slab S3 at the
same depth.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 75 0662747 0523646 657
670 Swamy and Laiw
TABLE 6 - COMPARISON OF CHLORIDE CONTENTS IN PORTLAND

CEMENT AND SF CONCRETE AFTER 50 CYCLES OF EXPOSURE
(UNIT: PERCENT OF CEMENT WEIGHT)
Slab Wh Depth from concrete surface, m m

No. ratio 5-25 25-45 45-65 65-85 85-105
SI 0.45 2.98 0.72 0.32 0.09 0.00
s2 0.60 4.52 2.32 1.39 0.87 0.47
s9 0.60 2.05 0.20 o. 10 0.00 0.00
70
60
50
40
30
20
10
O
O 100 200 300 400 500 600
Fig. l-Strength development of concrete without and with mineral

admixtures
--``,`,-`-`,,`,,`,`,,`---

+ 10 cycles
oi 1.5 -
1.2 -
0.9 -
\
0.6 -
0.3 -
'E3 - --_
__
Ly-7: ~,, , ,
-1-7
O 15 30 45 60 75 90 105 120 135 150

Distance from concrete surface, mm.
Fig. :&Chloride profiles in slag concrete after different cycles of

exposure (wlb = 0.60)
O 15 30 45 60 75 90 105 120 135 150

Fig. %-Effect of fly ash on chloride penetration into concrete (wlb =

0.60)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L J I I 95
No reproduction or networking permitted without license from IHS Ob62947 0521647 573
Not for Resale
~~
672 Swamy and Laiw
i0
Fig. 4-Chloride intrusion in SF concrete with exposure cycles (wlb =

0.60)
--``,`,-`-`,,`,,`,`,,`---
Fig. 5-Chloride intrusion in slag concretes with wlb = 0.75

3.0 .
2.7 1 8 GGBFS OPC
Y €- YS O P C _
f
6
B
2 2.1
O
3' 1.84
1.5;
r-
o
$ 1.2:
E:
O
0 0.9 -
.-
a"
k 0.6
I
O
6 i 0.3
0.0 --
O 15 30 45 60 75 90 105 120 135 O
Fig. &-Comparison of chloride profiles after 1O cycles of exposure

(wlb = 0.60)
3.5
X PFA OPC
8GGBFS OPC
' 1 ~ ' I ' ' l ' ~

O 15 30 45 60 75 90 105 120 135 1 i0
Fig. 7-Chloride profiles in concretes after 20 cycles of expsoure (wlb

= 0.60)
--``,`,-`-`,,`,,`,`,,`---
=
A C 1 SP-153 V O L X I I 95 I0662949 0522649 366
Not for Resale
~~
674 Swamy and Laiw
Fig. &Influence of mineral admxitures on chloride profiles after 50

cycles of expsoure (wlb = 0.60)
--``,`,-`-`,,`,,`,`,,`---
O 15 30 45 60 75 90 105 120 135 1

Fig. *Effect of slab on chloride penetration at wlb = 0.75

A C I SP-153 V O L * I I 95 0662949 0521650 0 8 8 W
ACI SP-153 V O L a I I 95 Ob62949 0521651 T L 4
SP 153-35
Ensuring High Quality

Silica Fume Concrete Overlays
by C. Ozyildirim
--``,`,-`-`,,`,,`,`,,`---
Synopsis: Thin concrete overlays are widely used for protection against corrosion
during the rehabilitation of concrete bridge decks. These overlays protect the
reinforcing steel from the ingress of chlorides from deicing salts or the marine
environment.
The Virginia Department of Transportation (VDOT) has successfully used

thin concrete overlays containing silica fume (minimum thickness 1 i14 in [32
mm]) to provide a high resistance to the penetration of chlorides into the concrete.
Silica fume concrete (SFC) overlays are now an acceptable alternative to other
rehabilitation procedures. In the development of SFC overlays, certain problems
were encountered at different phases of production and construction, including
proportioning, mixing, bonding, consolidation and curing. These probleins and
their solutions are discussed and recommendations are made for minimizing
problems in future installation.
Kevwords: Chlorides; curing; permeability; placing; ponding; resurfacing;

silica f u n s
Copyright American Concrete Institute 675

A C 1 SP-153 VOL*II 95 H 0662949 0523652 950
676 Ozyildirim
Celik Ozyildirim is a principal research scientist with the Virginia Transportation

Research Council in Charlottesville, Virginia. Dr. Ozyildirim is a Fellow of AC1
and is active in ACI, TRB, and ASTM. He has specialized in, research on concrete
properties with emphasis on the issue of long-term durability.
NTRODUCTION
Bndge deck overlays with low permeability concretes are widely used in
rehabilitation projects in the United States to prevent chlorides from penetrating to
the level of the reinforcing steel (1). Latex-modified concrete (LMC) has been
widely used to provide low permeability. Recently, silica fume concrete (SFC) has
been used as a successful alternative to LMC (2). The chlorides come mainly from
deicing salts or seawater, causing corrosion of the reinforcing steel if the concrete
is highly permeable and the reinforcing steel is not protected (3). While measures
are often taken to protect the reinforcing steel in present construction practices
involving concretes exposed to salt, the reinforcing steel in older structures is
uncoated. A protective oxide layer forms on the steel in the high alkaline
environment of concrete, but this layer can be destroyed by chlorides or low pH
values in the liquid filling the concrete pores. In many new structures epoxy-
--``,`,-`-`,,`,,`,`,,`---
coated reinforcing steel (ECR) is used, and the epoxy coating is expected to isolate
the steel from the corrosive environment. The Virginia Department of
Transportation (VDOT) has been using ECR since the mid ~ O ' S ,and the
experience to date has been positive. However, the complete effectiveness of the
epoxy coatings in isolating the steel from its environment over the full lifetime of
the concrete structure has recently been questioned (4). Instances have been
reported in which ECR was corroding in moist environments in the presence of
chlorides. In such cases, the epoxy debonded from the steel, allowing corrosion to
take place.
A common repair method used by VDOT for reinforced concrete subjected

to corrosion is to remove the top 1/2 in (13 mm) of concrete If the deterioration
is deeper, further removal is made until sound concrete is reached. In reinforced
concrete with a chloride content exceeding 2 Ib/yd3 (1.2 kg/m3) at the level of the
steel, removal of contaminated concrete to a depth at least I in (25 mm) below the
steel is required. A thin low-permeability overlay of LMC or SFC concrete with a
minimum thickness of 1 1/4 in (32 mm) is placed to extend the life of the structure.
Both types of concrete can provide good protection, but the use of SFC as an
alternative to LMC provides cost benefits and enhances strength and resistance to
sulfates, chlorides, and alkali-silica reactivity (ASR).
SFC, LMC, or any other quality concrete with a low water-cementitious

material ratio (W/CM) requires extra care and attention compared to ordinary
concretes during production and construction. In particular, proper proportioning,
mixing, consolidation, and curing are essential to obtain the expected high
performance.

A C 1 SI3-153 VOL*II 95 111 0662949 052Lb53 897 111
This paper summarizes methods developed or followed by VDOT for

achieving high quality SFC overlays. The tests used to measure permeability are
described, and the production of low permeability SFC and the successful
construction of SFC overlays in the field are discussed, under the headings of
proportioning, mixing, surface preparation, placing, consolidation and finishing,
and curing.
PERMEABILITY
One effective way to achieve long-lasting reinforced-concrete structures in

an aggressive environment is to construct them with low permeability concrete.
Such concretes provide high resistance to the penetration of chlorides or other
aggressive solutions that can cause concrete deterioration.
The Virginia Transportation Research Council (VTRC) conducts two

concrete permeability tests. One is the rapid chloride permeability test, AASHTO
T 277 and ASTM C 1202, which determines the electric current passing through a
saturated specimen subjected to 60 V dc in a 6 hour period. The corresponding
coulomb value (product of current and time) is then calculated. Concretes are
rated for their relative chloride permeability by the magnitude of the coulomb
values. Above 4,000 coulombs, the chloride permeability is considered to be high;
from 2,000 to 4,000, it is moderate; from 1,000 to 2,000, it is low, from 100 to
1,000, it is very low; and below 100 it is negligible. This electrical test is rapid and
convenient, and in the absence of interference, gives a good indication of the
permeability of concretes at the time the test is made. However, the permeability
of a concrete will decrease with time and the amount of decrease varies depending
on the curing conditions, its composition and the temperature to which it is
exposed. VTRC studies have shown that bridge deck concrete at a water-cement
ratio (W/C) of 0.45, tested at 28 days, exhibits coulomb values exceeding 4,000
which indicates high chloride permeability (5). At later ages ( I 1 to 30 years) deck
concretes with a maximum W/C of 0.49 had coulomb values generally in the 2,000
to 3,000 range. Laboratory studies of portland cement concretes with a low W/C
of 0.35 havi: shown 28-day coulomb values close to 3,000 ( 5 ) . SFC used in
overlays by VDOT containing 7 to 8% silica fume by weight of portland cement
and having a maximum W/CM of 0.40 exhibits coulomb values about i ,000
coulombs or less at 28 days. Further reduction in values occurs with age (6).
The other permeability test is the ponding test, AASHTO T 259, a more
direct way of determining the chloride permeability. In this test, the slabs are
--``,`,-`-`,,`,,`,`,,`---
ponded with 3% sodium chloride solution, and the chloride content at different
depths within the concrete is determined. For bridge deck concretes it has been
determined that about 1.3 Ib/yd3 (0.77 kg/m3) of chlorides at the level of
reinforcing !;teel is sufficient to initiate corrosion (7). This is known as the
corrosion threshold value. Evaluation of chloride content obtained from
laboratory and field specimens, including control and silica fume concretes, has

A C 1 SP-153 V O L X I I 95 M 0662949 0 5 2 L b 5 4 723
678 Ozyildirirn
shown that SFC is more resistant to the penetration of chlorides than control
concretes, and the differences noted were consistent with the results of the rapid
permeability test (coulomb values). After extended periods of ponding (1 5 to 30
months) chloride content at the i .5 to 2.0 in (38 to 5 i min) depth was small or
negligible in SFC, but was above the threshold value in the controls (8).
The results of both permeability tests have shown that SFC provides the
low permeability needed for longevity of a concrete structure exposed to a salt
environment. However, proper proportioning, mixing, consolidation, and curing
procedures must be followed.
PROPORTIONING
The proportion of silica fume in the concrete and the W/CM aKect the
permeability of the concretes (9,lO). VDOT specifications require that the
minimum mass of silica fume added be equal to 7% of the mass of the portland
cement. Silica fume is specified to meet AASHTO M 307 (Microsilica for Use in
Concrete and Mortar) or ASTM C 1240 (Silica Fume for Use in Hydraiilic-
Cement Concrete and Mortar).
It is desirable to keep the amount of cementitious material and the water

content low to minimize volumetric changes and to attain low perineabilities (1 1).
VDOT specifications require a minimum cementitious material (cement plus silica
fume) content of 658 lb/yd3(390 kg/m3). However, in VDOT applications,
producers have chosen to use 635 to 658 Ib/yd3 (377 to 390 kg/m3) of portland
cement and one bag (50 Ib [23 kg]) of dry-densified silica fume except in the first
overlay. In the first overlay, a silica fume slurry was used, and silica fiime was
added at 2 rates, 7% and 1O%, by mass of portland cement ( 12). The portland
cement content was 658 Ib/yd3 (390 kg/m3). In small and isolated jobs, as in the
overlays, use of dry-densified silica fume appears to be more convenient and
economical than using the slurry. The maximum W/CM is 0.40. The proportions
used by VDOT are expected to result in permeability values at or close to the very
low range (<1,000 coulombs) at 28 days, with compressive strengths exceeding
3,500 psi (24 MPa) at 1 day, and 7,500 psi (52 MPa) at 28 days. Table i
illustrates the I-day and 28-day compressive strengths, and the 28-day
permeabilities, of the first 5 SFC overlays in Virginia. In environments outside
Virginia different proportions and performance criteria may be selected.
In some projects, inadvertently high water contents have resulted in higher

coulomb values and lower 1-day compressive strengths than expected. For
example, in the overlay identified as No. 3 in Table 1, half of the deck was first
placed with SFC with a reported W/CM of 0.40 (Table 1 values are an average of
2 batches, and the values for individual batches are given in Table 2). However,
the 1-day strengths were lower than expected and this was brought to the attention
of the producer. The 28-day permeability of this concrete was also high, almost
--``,`,-`-`,,`,,`,`,,`---

double the expected value. In the other half of the deck, the producer lowered the
water conient, and the reported W/CM was 0.36. Test results of concrete from
the second batch were as initially expected; very low permeability (690 coulombs)
and high I-day strengths (4080 psi [28.1 m a ] ) . Both concretes were tested at 1
year using the rapid permeability test. Results showed reductions in coulomb
values as expected (see Table 2). Slabs were prepared fioiii batches of the first
half and subjected to the ponding test. The chloride content in these slabs after 15
months of ponding was negligible at an average depth of i .S in (38 nim) or
greater. Even the concretes with coulomb values higher than expected at 28 days
appear to perform satisfactorily. The coulomb values were in the low or at the low
end of the moderate range at 28 days, and very low or close to very low at i year .
This confirms the high level of performance expected with SFC.
The 5th silica fume overlay in Table 1 had 40% of the portland cement
replaced with ground-granulated blast furnace slag. It was placed in the fall. The
combination of cool weather, slag, and a Type G (retarding) high-range water
reducing admixture (HRWRA) was responsible for the slow strength development
of only 740 psi ( 5 . I MPa) at 1 day. The 28-day strength was very high ( 10,640 psi
[73.4 ma])and permeability was low (710 coulombs). Further woi-k with fly ash
and slag together with silica fume for enhanced properties has been \tiy promising
( 6 ) , and the use of a combination of pozzolanic material (fly ash. silica f h e ) and
slag is encouraged because of the potential cost savings.
--``,`,-`-`,,`,,`,`,,`---
Air entrainment and water-reducing admixtures have been routinely used in

SFC. The low W/CM and the high water demand resulting from the fineness of
silica fume require that HRWRA be used. HRWRA also provides a n efficient
dispersion of fine cementitious particles enabling enhanced properties. I-IRWRA
has been added at the plant, job site or both. Some authorities recuniiiiend
addition of all or part of HRWRA at the plant to achieve the best results Others
prefer to use the HRWRA at the job site, claiming that it is more efficient when
added later, and therefore, that less admixture can be used for ecoiioiny. extended
workabilit:y(less slump loss) and less retardation. Currently, VDOT specifications
permit the use of HRWRA at the plant, job site, or both Evaluation continues.
When HRWRA is added, thorough mixing is required to ensure uniformity.
The miniinum concrete temperature is specified to be 50 F ( I O C), and the

inaxiinum concrete temperature is 85 F (29 C) Maintaining a concrete
temperature close to or lower than the air temperature during placement results in
a reduced rate of evaporation froin the concrete surface High evapor<itionrates
lead to plastic shrinkage cracking. If the ambient air tei-ripei-aturefills below 50 F
( I O C) during the curing period, insulating blankets and, ifiieeded. external heating
should be used to keep the concrete temperature above SO F ( I O Ci
The air content is specified to be 7.5+_2.5%(5 to 10%). In conventional

VDOT concretes, the upper limit on air content is 8% because of concerns about

A C 1 SP-153 VOL*II
No reproduction or networking permitted without license from IHS 95 0 6 6 2 9 4 9 0523655 bbT
Not for Resale
~ _ _ _ _ ~~
680 Ozyildirim
strength. However, the strength of SFC used by VDOT is generally much higher
than the strength required in overlays.
MIXING
Silica fume should be mixed thoroughly with the other ingredients, enabling
uniform distribution of fine silica fume particles throughout the concrete.
Thorough mixing can be achieved by providing extended mixing times and
batching the silica fume with aggregates. Another effective procedure used by
some producers is mixing the dry silica fume with water at the beginning of the
load to form a slurry. SFC is mixed at least 70 revolutions at the plant and at least
30 at the job site if more water is added. After each addition of HRWRA, a
minimum of 70 revolutions is also recommended. Inadequate mixing of SFC may
result in balling of fine cementitious material and variation of properties at the
plastic and hardened states. The importance of clean unworn fins on the drum
blades is also emphasized for thorough mixing.
To test for uniformity in the load of concrete, requirements of ASTM C 94

may be followed. Because of concerns that the addition of extra water would
affect the quality of concrete at different parts of the load, specimens in one of the
projects were prepared at the beginning, middle, and end of a truck load of SFC
for the rapid chloride permeability test. The results given in Table 3 show that
coulomb values are close, indicating uniformity, but higher than expected,
suggesting that more mixing water was added to the batch than desired
--``,`,-`-`,,`,,`,`,,`---
SURFACE PREPARATION
For proper performance, overlay concrete must bond thoroughly to the

underlying base concrete. Any delaminated section would not withstand the heavy
trafic loads and would spall or break off For adequate bonding. the surface of the
base concrete must be clean and have exposed coarse aggregates. I t may be
cleaned by milling, shotblasting, waterblasting, sandblasting. or any combination of
these methods. The cleaning removes contaminated and deteriorated concrete,
exposes the surface coarse aggregate (minimum 25% of the surface area
recommended), and leaves a rough surface texture. Generally, the total deck is
milled prior to placement. Usually, the overlay will be placed on one half of the
deck while trafic continues on the other half. The half of the deck that is milled
and opened to trafic while the other half is being repaired, is generally sandblasted
before the placement of the overlay. During this cleaning. care should be taken to
remove any fine material that may have seeped under the longitudinal form along
the centerline from the repaired section. This hardened fine material may interfere
with bonding.
The surface of the deck is thoroughly and continuously soaked at least 1

hour prior to the placement of the overlay to prevent the absorption of water from

VOL+II 95
A C 1 SP-153 = 0662949 0521656
Not for Resale
5Tb W
A C 1 SP-153 V O L X I I 95 = Obb2949 052Lb57 V32
the 0verla.y concrete, to cool the surface in hot weather, and to wash away any
dust. After wetting, the surface is covered with plastic to retain the moisture and
to keep it clean. When the plastic is removed to apply the bonding layer prior to
the placement of the concrete, the surface should be visibly moist but free of
standing water. Dry areas should be rewetted, and all standing water in
depressions should be removed by brooming or blowing it out with oil-free
compressed air.
To provide the bonding layer, the mortar portion of the SFC is brushed
onto the deck surface. Excess coarse aggregate remaining after brushing is
removed and discarded. Care is taken to ensure that both the vertical and the
horizontal surfaces receive a thorough even coating of mortar about li8 i 1/16 in.
(3 2 2 min) in thickness. The rate of progress should be such that the bonding
layer does not become dry before the overlay is applied (typically 3 to 5 fi [ 1 to 2
m] in frorit of the placement of the SFC). In some states. grout consisting of equal
--``,`,-`-`,,`,,`,`,,`---
amounts of cement and sand mixed with sufficient water to make a mixture of
creamy consistency is used as the bonding material. Bonding material provides a
good transition between the base and the overlay.
Bonding material has been used successfully in Virginia and elsewhere In

well-bonded concretes it is dificult to identi@ the interface, and chipping of the
overlay reveals an interface with broken aggregates contributed from either the
base or the overlay concrete. Petrographic examination of cores taken from
properly bonded overlays reveals an excellent bond and an interface ditlicult to
detect. For example, in a core with a vertical crack from the first overlay. the
crack was found to propagate into the base concrete rather than along the
interface. This indicates a satisfactory bond However, problems have occurred
when the bonding material has been allowed to dry before the placement of the
overlay concrete. When debonded sections have been examined. the presence of a
powdery, dusty surface at the interface has been observed, indicating drying of the
bond mortar.
PLACING, CONSOLIDATION, AND FINISHING
Generally, in overlay applications ready-mixed concrete trucks discharge

concrete on the bridge deck. SFC is cohesive, and therefore higher sliinip values
(about 1 to 2 in [25 to 50 mm]) are needed for workability similar to ordinary
concretes. Finishing machines equipped with an auger strike-oK a vibrating
element with a minimum frequency of 3000 vibrations per minute, roller(s), pan
float, and a burlap drag are found to be satisfactory A vibrating element provides
adequate consolidation. The areas along the edges that the element cannot reach,
and areas deeper than 3 in (75 mm), should be consolidated using sui-face-typeor
immersion-type vibrators
Concretes with slump values exceeding 5 in (125 inin) are found to finish

A C 1 S P - 1 5 3 VOLaII 95 O662949 0523658 3 7 9
682 Ozyildirim
easily with the roller screed without any need for further finishing. Only the areas
where the screed cannot reach are hand-finished. Concretes with high slump
values were found to flow under vibration; therefore VDOT specifications require
a sfuinp o f 4 to 7 in (100 to 180 mm).
In some cases debonding has occurred in areas which were inadequately

consolidated with the immersion type vibrators. Upon the reinoval of the wooden
forms along the center of the roadway. voids resulting from poor consolidation
were evident in some jobs.
CURING
--``,`,-`-`,,`,,`,`,,`---
The proper curing of the concrete is critical to achieving the desired

properties, and for minimizing or eliminating plastic shrinkage cracking. Plastic
shrinkage occurs when the rate of evaporation exceeds the rate of bleeding. SFC
concrete is prone to plastic shrinkage because the low W/CM and the fineness of
SFC result in little or no bleeding. Therefore, immediately after screeding,
precautions must be taken to prevent the loss of moisture from the coiicrete
surface.
Fog misting with pressure sprayers is recommended for overlays, starting

immediately after screeding and continuing over the screeded area until wet burlap
is placed. The wet burlap should be placed as soon as possible after the finishing
operation. Wet burlap must be thoroughly saturated over its entire area, but
should be drained of excess water The burlap should be lapped a ininimum of 12
in (300 inm), covered with plastic sheeting, and kept wet for a ininiinuiii of 72 hr.
After the wet cure, the surface of the concrete should be immediately covered with
liquid membrane-forming curing compound as the burlap is removed Two layers
of curing compound should be applied, one layer perpendicular to the other. The
curing compound should be completely dry before opening the overlay to trafic.
When the evaporation rate is such that the SFC's potential foi. cracking is
high, concrete placement is not recommended unless the contractor ensures that
the necessary precautions (such as fog misting, wind screens, shading devices,
cooling of the concrete, etc.) are taken to reduce the rate of surface evaporation,
and that a crack free overlay is provided. For favorable placement conditions.
some contractors have chosen to place concrete in the evening, early in the
morning, or at night.
In VDOT's first experimental overlay project, constructed in 1987, two

curing methods were tried ( 1 1). One method applied curing compound only, and
the other used wet burlap for one day followed by the curing coinpotind In this
project, the surface was textured by metal tines and fog sprays were not used.
Plastic shrinkage cracks occurred. After that project, VDOT has used saw-cutting
of hardened concrete (at least 14 days later or after 85% of the 28-dny design

A C 1 SP-153 VOL*II 95 0662949 0 5 2 L b 5 9 205
compressive strength is reached) in lieu of tines to achieve the desired deep texture
in the deck for improved water removal and skid resistance. The elimination of
tining has made the immediate application of wet burlap possible. This,
accomparlied by fog misting, reduces plastic shrinkage on the deck surface.
However, at the joint areas where deeper removal of concrete is normally made
because of tying to the reinforcement or due to the extent of deterioration, cracks
perpendicular to the joints have been observed. Placement of concrete in two
layers, enabling a constant thickness overlay throughout, is being tried to eliminate
such cracking.
VDOT requires a strength of 3,500 psi (24 1 MPa) for opening the overlay
to trafic This strength can be achieved in one day by SFC However, where
feasible longer lane closure times are recommended for extended moist curing to
improve durability Suppliers recommend a 7-day moist curing period for SFC,
and VDOT requires a minimum of 72 hr moist curing followed by the application
of curing compound However, sometimes constraints on lane closure times limit
extended moist curing time For example, in one project. closure of any of the two
lanes for periods greater than 2 days was prohibited SFC developed 4,300 psi
(3 O m a ) in 24 hours After 24 hours, a curing compound was applied, and the
bridge was opened to trafic in 36 hours
SUMMARY AND CONCLUSIONS
VDOT's experience with SFC indicates that these concretes provide the
very low permeability needed to reduce the penetration of chlorides into the
concrete. In addition, high early (I-day) and ultimate strengths are attained. High
early strengths are beneficial when there are restrictions on lane closure. However,
early opening to trafic restricts the duration of moist curing. Therefore, when
possible, longer closure times should be required and extended water curing should
be maintained for enhanced durability.
S I T must be correctly proportioned to obtain the desired properties. Trial

--``,`,-`-`,,`,,`,`,,`---
batches and testing to indicate the expected properties and provide familiarity with
the material are recommended. Good construction practices are essential to ensure
that the expected properties are achieved in actual field applications. Proper
attention to construction practices in field applications will ensure the achievement
of high quality overlays containing silica fume, and provide the high level of
performance expected of this material.
ACKNOWLEDGMENTS
The information provided here was gathered from different studies

conducted at the Virginia Transportation Research Council. The opinions,
findings, and conclusions expressed in the paper are those of the author and not
necessarily those of the sponsoring agency.

A C 1 SP-153 VOL+II 95 W Obb2949 0521bb0 T27
684 Ozyildirim
REFERENCES
1. Ozyildirim C., 1992, "Concrete Bridge-Deck Overlays Containing Silica Fume,"

AC1 SP-132. Flv Ash. Silica Fume. Slag and Natural Pozzolans in Concrete,
American Concrete Institute, Detroit, pp. 1287-1302.
2. Sprinkel, M. M., 1992, "Twenty-Year Performance of Latex-Modified Concrete

Overlays, Transportation Research Record 1335, Transportation Research
I'
Board, Washington D. C., pp 27-35.
3. Berke, N. S.; Pfeifer, D. W.; and Weil, T. G., 1988, "Protection Against
Chloride Induced Corrosion," Concrete International: Design and Construction, V.
10, NO. 12, pp. 45-55.
4. Clear, K. C., 1992, "Effectiveness of Epoxy-Coated Reinforcing Steel,"

Concrete International, V. 14, No. 5, May, pp. 58-62.
5. Ozyildirim, C. 1993, "High-Performance Concrete For Transportation

Structures," Concrete International, V. 15, No. 1, Jan., pp. 33-38.
6. Ozyildirim, C., "Resistance to Penetration of Chlorides into Concretes

Containing Latex, Fly Ash, Slag, and Silica Fume," Third CANMET/ACI
International Conference on Durabilitv of Concrete, V. M. Malhotra editor,
France, May, 1994.
7. Clear, K. C., "Time-to-Corrosion of Reinforcing Steel in Concrete Slabs - Vol.

3," Report No. FHWA-RD-76-70, Federal Highway Administration, Washington,
D.C.., 1976, 59 pp.
8. Ozyildirim, C., "Rapid Chloride Permeability Testing of Silica-Fume Concrete,''
Cement, Concrete, and Aggregates, ASTM, Vol. 16, No. 1, 1994, pp. 53-56.
9. Ozyildirim, C., "Laboratory Investigation of Concrete Containing Silica Fume

for Use in Overlays," AC1 Materials Journal, January-February 1987, pp. 3-7.
10. Bunke, D., "ODOT Experience with Silica-Fume Concrete," TRR 1204,
Transportation Research Board, Washington D.C., pp. 27-35
1 1. Hooton, R.D., "High Strength Concrete as a By-product of Design for Low

Permeability," Concrete 2000, Edited by Ravindra K Dhir and M. Roderick Jones,
Published by E & FN Spon., 1993, pp. 1627-1637.
12. Ozyildirim, C., "Experimental Installation of a Concrete Bridge-Deck Overlay

Containing Silica Fume," TRR 1204, Transportation Research Board, Washington
D.C., pp. 36-41.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 0662749 052LbbL 9 b 3 E
TABLE. 1 - STRENGTH AND PERMEABILITY OF FIRST FIVE SFC

OVERLAYS
Overlay i# W/CM SF Strength (ma) Coulombs

1-day 28-day 28-day
1 0.39 710 33.5 55.6 680
0.39 33.1 54. I 400

2 0.39 7.6 ---- 58.5 840
3 0.40 7.9 15.0 46.7 1,970
--``,`,-`-`,,`,,`,`,,`---
0.36 7.9 28.1 59.5 690

0.4 7.9 29 53.4 1260
0.40(S) 7.9 5.1 73.4 710
Note: 1-day strength was between 24 to 30 hours because of time required to

transport the specimens to the VTRC.
In overlay 5,40% of the portland cement by mass was replaced with slag.
TABLE 2 - PERMEABILITY AND CHLORIDE CONTENT FOR 3RD

OVERLAY

A C 1 SP-I153 V O L X I I 7 5 = 0662747 052Lbb2 B T T =
686 Ozyildirim
TABLE 3 - PERMEABILITY TESTS FOR UNIFORMITY IN COULOMBS

--``,`,-`-`,,`,,`,`,,`---
Front 1,903 1,930 1,916
Middle 2,062 2,101 2,08 1
i ,960 2,118 2,039

A C 1 SP-153 V O L X I I 95 0662949 0523663 736
SP 153-36
Strain Rate Sensitivities of

Strength and Deformation of
High-Strength Silica Fume Concrete
by N. Han and J. C. Walraven
Synopsis: The sensitivity of strength and deformation of high strength concrete

incorporating silica fume to the variations in strain rates have been studied
experimentally and have been compared with those of normal strength concrete
(without silica fume). The observed phenomena in the experiments are
qualitatively interpreted according to an assumed mechanism of strain rate
sensitivity of concrete. The differences of the material structure between high
strength concrete with silica fume and normal strength concrete without silica
fume are discussed, where emphasis is placed on the change of the pore structure
and the moisture content due to the incorporation of silica fume for high strength
concrete and its influence on the rate sensitivities to strength and deformation of
concrete. In particular, the Stefan Effect is believed to play a very important role
in the casc of rate sensitivity. In general, it is found that high-strength silica fume
concrete is more sensitive to the variation of the strain rate than normal strength
concrete SIS far as the strength and deformation in compression are concerned.
However, in tension, this rate sensitivity is less pronounced.
--``,`,-`-`,,`,,`,`,,`---
Kevword-: Compression; deformation; hieh strength concretes; porosity;

silica fume; strains; strength; tension

688 Han and Walraven
Ningxu Han is a PhD candidate at the Delft University of Technology, the

Netherlands. His main fields of interest are: material and mechanical properties
of high-StrengtWperformanceconcrete.
Joost C. Walraven is professor of structural engineering and head of the

Department of Mechanics and Structures of the Faculty òf Civil Engineering,
Delft University of Technology, the Netherlands. He is co-chairmen of CEB-
Commission II, 'Modelling of material and structural behaviour' and member of
the CEB-FP Working Group on 'High Strength Concrete'.
INTRODUCTION
It is well known that concrete is a rate-sensitive material. The mechanical

properties of concrete subjected to various loading- or strain-rates have been
investigated for several decades. It has been observed that the behaviour of
concrete is sensitive to the loading history: a higher loading speed or a higher
strain rate results in a higher strength of the concrete.' Therefore, various
research programs on rate sensitivity have been carried out. The used strain rates
ranged from dynamic loading2 to creep 10ading.~The effect of the strain rate is
an aspect to be considered for the design of members loaded in compression,
bending and shear, and it plays as well a role with regard to crack width control
and minimum reinforcement. However, up to now, there is no basic model to
fundamentally describe the mechanism of rate sensitivity of concrete. It was once
assumed by Kaplan4 that the pore water pressure might play a significant role
with regard to the rate sensitivity, but no further description was given. Without
understanding the basic mechanism of rate sensitivity of concrete, it is difficult
to explain a lot of contradictory experimental results. From appearance, this
contradiction can be related to changes in test conditions, such as the moisture
content of specimens, the curing conditions, the strength of the concrete, or the
range of strain rates used. Through further analysis, it seems that the key point
is the variation of the pore structure inside the concrete.
It is now well recognised that high strength concrete (HSC) generally has
a material structure which significantly differs from that of normal strength
concrete (NSC). HSC has a more discontinuous and closed pore structure, smaller
pore sizes, and a more uniform pore distribution. These significant changes of
material structure of HSC can be attributed to the addition of silica fume: the
pozzolanic reaction of silica fume leads to a better bond between aggregate
particles and cement matrix, and the microparticles of silica fume have a filler
function as ell.^,^,' The interface area between the matrix and the aggregate,
which usually contains larger pores and more microcracks even before loading,
becomes very compact by virtue of silica fume.' Fewer flaws and pre-loading
microcracks are found in HSC: possibly due to the difficulty of the moisture
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 75 E 0662747 052Lbb5 507 W
exchange between inside and outside of the concrete," resulting in smaller drying
shrinkage. Furthermore, the stronger bond within the interface area also
contributes to the reduction of the number and the size of the microcracks.
In order to fully understand the strain rate sensitivity of concrete, a

mechanism aiming to qualitatively explain the strain rate sensitivity of concrete
is assume:d. On the basis of this mechanism, the rate sensitivities of HSC and
NSC are discussed, and the differences of the material structure between HSC
and NSCI are emphasized. Furthermore, the observed phenomena in the
experiments for HSC and NSC in uniaxial compression and tension, which were
carried out in the Stevin Laboratory, Delft University of Technology, the
Netherlands, are qualitatively interpreted according to the basic mechanism of
rate sensitivity, whereas emphasis is made on the changes in pore structure and
moisture content due to the incorporation of silica fume for HSC. More details
of this investigation are provided in references.","
ASSUMED MECHANISM OF STRAIN RATE SENSITIVITY
Material ,Structure of Concrete and Classification of Water
The material structure of concrete is very complicated. In general, a

concrete i,s a multi-phase material composed of at least seven components: coarse
aggregate, sand, unhydrated cement particles, cement gel, gel pores, capillary
pores and entrapped air voids along with various states of ~ a t e r . ' ~ Water
. ' ~ in
concrete can be classified into three categories according to the degree of
firmness held by the solid phase. At one extreme, there is free water which is
capillary water or free water inside the air voids or the microcracks. This kind
--``,`,-`-`,,`,,`,`,,`---
of water is beyond the surface forces of the solid phase. At the other extreme,
there is chemically bounded water or water of hydration, forming a definite part
of the hydrated compounds. Between these two categories there is gel water
which consists of adsorbed water, i.e. water held by the surface forces of the gel
particles (van der Waals forces), and interlayer water which is held between the
surfaces of hydrated calcium silicate. (see Fig. 1)
In addition, microcracks existing in the interface area between matrix and

aggregate before and during loading can be regarded as the macropores, which
are several orders larger than the gel pores and Capillary pores. Microcracks
before loading are caused by segregation and by tensile stresses resulting from
early volume changes that are largely associated with hydration and shrinkage of
the cement paste. During loading, these microcracks tend to develop further to
form even larger cracks.

A C 1 SP-153 VOL+II 95 m 0662949 052Lbbb 445 m
Assumed Mechanism of Rate Sensitivity of Concrete
When concrete is subjected to external loading, the water in various voids

and pores behaves in different ways. Here two different loading situations are
considered: compression and tension, which are the general loading cases in
practice. Because of their random orientation in thc concrete (especially gel
pores), voids and pores are generalized, for reasons of simplicity, in two
directions: perpendicular and parallel to the direction of loading. (see Fig. 2)
When a compressive force is applied on a concrete element, the pores

perpendicular to the loading direction tend to close, resulting in a movement of
the water in the pores. Because of the viscosity of the liquid, the movement of
water will go together with a pressure gradient. This hydrostatic pressure (pore
water pressure) Fp depends on the size of the pore, the amount of pore water, and
the closing speed of two opposite pore walls (see Fig. 2 left). The increase of this
pore water pressure can help the solid phase in the concrete to resist the external
force (by adding further resistance to the longitudinal deformation). The
contributions of the pores parallel to the loading direction can be explained on
the basis of the Stefan Effect, well known to physicists, which is described as
follows: the presence of a thin viscous film (for example, water or other liquid
phase) between two perfectly plane and parallel plates, separated by a certain
distance h , creates an opposing force if an attempt is made to separate the two
plates at a velocity dwdt ( 1 3). In a concrete the plates separated by the water can
be considered as an analogy to the walls of pores. If a load is applied, the walls
parallel to the loading direction tcnd to separate from one another, creating an
opposing force F,, which will counteract this separation (see Fig. 2 right). This
will further reduce the development of microcracks and restrict the transverse
deformation, resulting in a higher compressive strength. If the loading speed or
strain rate decreases, the created pore pressure and the Stefan Effect also tend to
decrease. At one extreme, the rate sensitivity disappears, and the concrete only
has its strength from the solid phase.
When a tensile force is applied, it is clear that only the Stefan Effect
plays an important role. In this case, the Stefan Effect will directly restrict the
longitudinal deformation and counteract the development of cracking perpendicu-
lar to the loading direction.
From the above discussion, it can be seen that both the pore water
pressure Fp (in the case of pore-compression) and the opposing force by the
Stefan Effect F,, (in the case of pore-tension) are functions of the following
parameters: a) size of the pores; i.e. the distance between the opposite walls of
a pore; the smaller is the distance, the higher is the pore pressure or the opposing
force; b) the volume of the water; the larger is the volume of the water, the
higher is the pore pressure or the opposing force; c) the velocity of the relative
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 75 m 0662749 0 5 2 L b b ï 381 m
displacement of the pore walls (strain rate); the higher is the velocity, the higher
is the pore pressure or the opposing force.
EXPERIMENTAL PROCEDURES
Materials and Mixture Proportions
All the mixtures for the HSC were prepared with rapid hardening portland
cement (Class C ) . River sand was used as fine aggregate, whereas crushed gravel
was used as coarse aggregate. The fine and coarse aggregates were totally dried
in the air. Therefore, they contained no moisture before mixing. The maximum
size of the coarse aggregate was 16 mm. Silica fume was added in the form of
dry powder. Furthermore, a superplasticizer consisting of lignosulfonate with a
little Na-gluconate, lignosulfonate and naphthalene was added. The percentage
of superplasticizer was referred to the total weight of cement and silica fume. All
the mixtures for the NSC were prepared with blast-furnace slag cement, with the
same river sand and crushed gravel used as fine and coarse aggregates. There
was some water inside the aggregates before they were mixed. The slumps of the
mixtures for HSC were more than 200 mm, and those for NSC were approxi-
mately 160 mm. Mixture proportions are shown in Table i .
Specimens and Curinp,
For the compressive tests, the specimens were cast in horizontal moulds
of 100 x 100 mm in cross-section and 400 mm in length. For the tensile tests,
moulds of 100 x 100 mm in cross-section and 500 mm in length were used.
Before beginning the tensile tests, the specimens were sawn through in the
middle into two parts with a length of 250 mm. All specimens for the tensile
tests were notched on the two opposite sides at the middle. One day after casting,
the specimens were removed from the moulds and immediately wrapped in
plastic foil in order to avoid moisture losses, and were placed in a curing room
with 65% relative humidity and temperature of 20 I 3OC. Threc days before
testing, the plastic foil was removed in order to prepare the specimens. The
measuring devices were glued on the specimens. Afterwards, ali specimens were
put back into the curing room until the tests started. Additionally, three cubes
(150 x 150 x 150 mm) were cast as strength reference specimens. The cubes
were cured in the same condition as the test specimens. For tensile tests, before
testing, the end-faces of specimens with a sawn surface were coated with a
polyester resin. When this coating was sufficiently hardened, the surface was
sandpapered until it looked dull. Then, the end-faces of the specimen were coated
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 VOL*II 95 = Obb29Ll9 0521ibb8 218 =
with glue, and were placed between the loading steel platens. Afterwards, the
specimen was loaded with a small compressive force.
Measurements and Testing Procedure
The loads were measured by means of a load cell with a maximum

capacity of 1600 kN (H.5 kN). All the deformations were measured by means
of LVDT and clip gauges. In the compressive tests (see Fig. 3a), four LVDTs
(Sangamo A65, a range of f 5 mm with an accuracy of 0.00015 mm) were
respectively attached to the four sides of the prismatic specimen to control and
measure the transverse deformations. Meanwhile, the longitudinal deformations
were measured by means of clip gauges (a range o f f 1 mm with an accuracy of
0.0002 mm). In the uniaxial tensile tests (see Fig. 3b), only LVDTs were used
to control and measure the longitudinal deformation. All data (loads and
deformations) were recorded automatically at specified constant time intervals by
means of a computer-controlled datalogger.
Ail the tests were performed in a closed-loop servo-hydraulic machine

with a loading jack with a capacity of 2000 kN. The force is applied by the
upward movement of the loading jack with its own hydraulic servomechanism.
In the compressive tests, the average value of the measurements of the transverse
deformations at the four sides by means of LVDTs was used as a feedback
signal. In the tensile tests, the average value of the longitudinal deformation at
the four sides was used as a control signal. A programmable function equipment
( P E ) was used to realise the expected strain rates (or loading rates). During the
loading period, the average value of the controlling LVDTs (or a loading value)
was calculated by a high speed processor and transferred to the PFE as a
feedback signal. If the difference between the specified value and the feedback
signal exceeds the allowed limit, the machine automatically readjusts the loading
jack at a very high speed to guarantee the expected strain rate.
Strength in Compression
The peak stresses (strength) for both HSC and NSC in uniaxial compres-
sion are shown as a function of the transverse strain rate (Fig. 4).In compression,
two tests for each strain rate were carried out, and in tension, three tests for each
strain rate were carried out. It is clearly indicated that in compression, HSC is
more sensitive to the variation of the strain rate than NSC.'6,'7~'8The reduction
of the peak stress for HSC in compression, if the transverse strain rate decreases
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP,-L53 VOL*II 75 0bb2949 0 5 2 L b b î 1 5 4
from 6.25 x 1Q6 to 2.0 x 1@’, is about 20%. In comparison with HSC, NSC
hardly displays any dependence on the strain rate. After carefully evaluating the
results of Rasch,Ig it was found that these results showed a similar behaviour.
The experimental observations might be possibly explained on the basis

of the previous assumed mechanism: for HSC in compression, at a higher strain
rate, higher pore-water pressure is built up due to the smaller pore size, which
mainly contributes to the restriction of the longitudinal deformation, while the
Stefan Effect explains the delayed development of the transverse deformation;
moreover, because of the difficulty of the movement of free water through the
concrete, less free water could evaporate duiing the periods of curing, thus, more
free water is available in creating pore-water pressure, and the Stefan Effect is
enhanced at loading; at a lower strain rate, the stressed water in the pores will
get enough time to flow through the channels (microcracks and flaws) to the
unstressed regions, causing a relaxation of the pore-water pressure; additionally,
the opposite force produced by the Stefan effect also decreases due to a lower
strain rate; hence, the concrete tends to show the strength values of the solid
phase.”
Ini NSC, even before the load is applied to the concrete, it is found that
about 50% of the total crack length at the peak stress is already present.’l Smadi
and Slate’ also found that for NSC (28-day compressive strength of 102x203 mm
cylinder of 23 N/mm2), cured in water for 28 days, the totally measured crack
length is about three times as large as for HSC (with a 28-day compressive
cylinder strength of 64 N/mmz). If the concrete is cured in air for 30 days, the
totally measured crack length due to shrinkage in NSC is about nine times as
long as that in HSC. In addition, relatively larger pore sizes and more flaws (air
voids) are another characteristic of NSC. Hence, it is very difficult to build up
pore-water pressure in compression (except if a very high strain rate is applied)
during loading because the free water can easily flow through these channels to
the less stressed areas. Furthermore, less free water (or even gel pore water) is
available in NSC to create a significant pore-water pressure and to activate the
Stefan effect due to its open internal structure, resulting in no significant
difference in peak stress if the strain rate varies. The results of the experiments
show that strain rate within the adopted range has little influence on the peak
stress of NSC.
From the above discussion, it can be seen that the strength, which is
generally regarded as a basic material property, is in fact rate sensitive. Along
with the strain rate, any changes related to the pore structure and pore-water
condition may result in different strengths. At an extreme, if there is little or no
free water in the concrete, there will be no change of strength at all.” Concrete
shows the strength of the solid phase. This strength can be called the inherent
strength of concrete. Normally, the strengths obtained from standard tests fall into
the range which is beyond that of the inherent strength. This area can be called
the rate-sensitive area. (see Fig. 5 )
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 V O L * I I 95 m 0662949 052IIb70 976 m
Deformation in Comuression
The transverse and longitudinal strains under the peak stress for HSC and
NSC as a function of the strain rate are shown in Fig. 6. Below a certain strain
rate (about 7 . 5 ~ 1 0 - ~there
) , is a clear increase of all strains at peak stress, both
for HSC and NSC. This is due to the decreasing influence of both pore water
pressure and the Stefan Effect on the longitudinal and transverse deformation if
a lower strain rate is applied. If the strain values at the lowest and the highest
strain rates are taken as the references, it is indicated that the strain rate has
relatively stronger effect on the transverse strain than on the longitudinal strain
for both HSC and NSC. The increase of the transverse strain for HSC is about
115%, whereas the increase of the longitudinal strain is about 35%. For NSC,
this increase is about 100% for the transverse strain and about 30% for the
longitudinal strain. This may imply that pore water pressure and the Stefan Effect
play a very different role as far as the rate sensitivity is concerned. In the case
of compression, the restriction of the transverse deformation due to the Stefan
Effect overshadows the restriction of the longitudinal deformation due to pore
water pressure. This can be confirmed through a further analysis of the deforming
behaviour before the peak stress.
In Fig. 7, the ratios between the transverse strains as well as the

longitudinal strains at the highest and the lowest strain rates versus the various
stress levels (25%, 50%, 75% of the peak stress) are displayed. It is found that
as the stress level increases from 25% to 75% of the peak stress and the strain
--``,`,-`-`,,`,,`,`,,`---
~ to 1 . 0 ~ 1 0(eR6),
rate decreases from 6 . 2 5 ~ 1 0 .(eR,) ~ ~ the relative increase of
transverse and longitudinal strain is about 75% and 30% respectively for HSC,
and 10% and 3% respectively for NSC. From this analysis, it can be clearly seen
that the Stefan Effect plays a dominant role in compression with regard to the
strain rate sensitivity. A higher strain rate results in more restriction in the
transverse direction: consequently, less transverse deformation appears. As the
strain rate decreases, the influence of the Stefan Effect decreases, resulting in less
transverse restriction, i.e. larger transverse deformation.
Strength and Deformation in Tension
The peak stresses (strength) for both HSC and NSC in uniaxial tension
are shown as a function of the longitudinal strain rate (see Fig. 8). At the strain
rates between 2.3 x 1U6 and 1.0 x lo-*, the reduction of the peak stress does not
differ very much for HSC and NSC (I 1% for HSC and 13% for NSC). From the
basic mechanism of rate sensitivity, it is understood that only the Stefan Effect
plays a role as far as the strain rate sensitivity in tension is concerned. For
different loading conditions (compression or tension), the Stefan Effect works out
in a different way. In compression, the Stefan Effect reduces the transverse

A C 1 SP-153 V O L X I 1 75 0bb2747 0521671 802
deformation, in combination with the reduction of the longitudinal deformation

due to the pore water pressure, resulting in an increase of the compressive
strength, whereas in tension, the Stefan Effect is only directly related to the
reduction of the longitudinal deformation. Therefore, it is obvious that the
influence of the Stefan Effect in compression is larger than in tension.
The longitudinal strain at the peak stress for both HSC and NSC in
uniaxial lension are shown as a function of the longitudinal strain rate (see Fig.
9). No significant differences are found for both HSC and NSC with regard to
the strain rate sensitivity. In general, as the strain rate decreases, the longitudinal
strain increases. From the test results, it can be seen that the increase of the
longitudinal strain for HSC seems to be more consistent than that for NSC.
CONCLUSIONS
1. The experimental observations for both HSC and NSC might be explained
on the basis of the contributions of pore water pressure and the Stefan
Effect.
2. The experimental observations show that in compression, HSC is more

sensitive to the strain ratc than'NSC (for both strength and deformation),
whereas in tension, both HSC and NSC show the same rate sensitivity.
--``,`,-`-`,,`,,`,`,,`---
ACKNOWLEDGEMENTS
ï h e research project was made possible by the financial support of the

Dutch Centre for Civil Engineering Research and Codes (CUR), the Professor
Bakkerfonds and MEBIN. Mr. A. van Rhijn and Mr. F. Schilperoort, member of
the technical staff of the Stevin Laboratory, are gratefully acknowledged.
REFERENCES
1. Han, N. "Time-Dependent Behaviour of High Strength Concrete - Part I

Literature Survey", Stevin Laboratory Report, No. 25.5-92- 14, June 1992,
Delft University of Technology, The Netherlands, 35pp.
2. Bischoff, P.H., and Perry, S.H. "Compressive Behaviour of Concrete at

High Strain Rates", Materials and Structures, Vol. 24, 1991, pp. 425-450.

A C 1 SP-I153 V O L + I I 95 0662949 0523672 749 =
3. Neville, A.M., Dilger, W.H., and Brooks, J.J. "Creep of Plain and
Structural Concrete", Construction Press, London and New York, 1983,
361 pp.
4. Kaplan, S.A. "Factors affecting the relationship between rate of loading

and measured compressive strength of concrete", Magazine of Concrete
Research, Vol. 32, No. 11 1, June 1980, pp. 79-88.
5. Sellevold, E.J. "The function of Condensed Silica Fume in High Strength

--``,`,-`-`,,`,,`,`,,`---
Concrete", Proceedings, Symposium on Utilization of High Strength

Concrete, Stavanger, Norway, June 15-18, 1987, pp. 39-49.
6. Sarkar, S.L., and Aïtcin, P.C. "Comparative Study of the Microstructures

of Normal and Very High-Strength Concretes", Cement, Concrete and
Aggregates, CCAGDP, Vol. 9, No. 2, Winter 1987, pp. 57-64.
7. Bentur, A., Goldman, A., and Cohen, M.D. "The Contribution of the
Transition Zone to the Strength of High Quality Silica Fume Concretes",
Bonding in Cementitious Composites, S. Mindess and S.P. Shah, Editors,
Materials Research Society, Boston, 1987, pp. 97-104.
8. Goldman, A., and Bentur, A. "Bond Effects in High-Strength Silica-Fume

Concretes", AC1 Materials Journal, Vol. 86, No. 5, September-October
1989, pp. 440-447.
9. Smadi, M.M., and Slate, F.O. "Microcracking of High and Normal

Strength Concretes under Short- and Long-Term Loadings", AC1
Materials Journal, Vol. 86, No. 2, March-April 1989, pp. 117-127.
1o. Nagataki, S., and Yonekura, A. "Properties of Drying Shrinkage and

Creep of High-Strength Concrete", Transactions of the Japan Concrete
Institute, Vol. 4, 1982, pp. 223-236.
11. Han, N. "Time-Dependent Behaviour of High Strength Concrete - Part II

Experimental Descriptions and Results", Stevin Laboratory Report, No.
25.5-92- 15, August 1992, Delft University of Technology, The Nether-
lands, 230 pp.
12. Han, N. "Time-DependentBehaviour of High Strength Concrete - Part III

Experimental Analysis", Stevin Laboratory Report, No. 25.5-92-16,
October 1992, Delft University of Technology, the Netherlands, 76 pp.
13. Neville, A.M. "Properties of Concrete", 3rd Edition, Longman Scientific

& Technical, 1991.

A C 1 SP-153 VOL+II 95 Obb2949 0523673 685
14. Mindess, S . "Relationships between strength and microstructure for

cement-based materials: an overview", Materials Research Society
Symposia Proceedings, Vol. 42, Pennsylvania, 1984, pp. 53-68.
15. Rossi, P. "A physical phenomenon which can explain the mechanical
behaviour of concrete under high strain rates", Materials and Structures,
Vol. 24, 1991, pp. 422-424.
16. Han, N., and Walraven, J.C. "The Effect of Strain Rate on the
Compressive Properties of High Strength Concrete", Progress in Concrete
Research, Annual Report, Vol. 2, 1991, Delft University of Technology,
pl). 31-43.
17. Han, N., and Walraven, J.C. "Sustained Loading Effects in High-Strength
Concrete", Proceedings, Symposium on Utilization of High Strength
Concrete, Lillehammer, Norway, June 20-23, 1993, pp. 1076-1083.
18. Han, N. "The Behaviour of High-Strength Concrete under Sustained and

Slow Increasing Load", 29. Forschungskolloquium von Deutscher
Ausschuss für Stahlbeton, am 24. und 25. März 1994 an der Technischen
Universität Delft, pp. 13-20. (in German)
19. Rasch, C. "Spannungs-Dehnungs-Linien des Betons und Spannungsverteil-

ung in der Biegedruckzone bei Konstanter Dehngeschwindigkeit",
Deutscher Ausschuss für Stahlbeton, Heft 154, Berlin 1962, 72 pp. (in
German)
20. Han, N., and Walraven, J.C. "Properties of High Strength Concrete
Subjected to Uniaxial Load", This paper will be published in the AC1
Special Publication for the AC1 1994 International Conference on High
Performance Concrete, November 15-18, Singapore.
21. Stroeven, P. "Some Aspects of the Micromechanics of Concrete", PhD

Thesis, Delft University of Technology, The Netherlands, 1973, 323 pp.
22. Spooner, D.C. "Stress-strain-time relationships for concrete", Magazine

of Concrete Research, Vol. 23, No. 75-76, June-September 1971, pp. 127-
131.
--``,`,-`-`,,`,,`,`,,`---

TABLE 1 - MIXTURE PROPORTIONS FOR HSC AND NSC
Mixture Unit HSC NSC Note
Silica fume kg/m3 25 O dry powder

W/(C+SF) 0.30 0.50 Water/(Cement+Silica Fume)
Agkmate kg/m’ 1796 1816 total weight of aggregate
0-4mm kg/m’ 718 726 Fine aggregate
4-16mm kdm’ 1078 1090 Coarse aggregate
--``,`,-`-`,,`,,`,`,,`---
superplasticizer: percentage of weight of cement
lignosulfonate 0.2 with a little Na-gluconate

Lignosulfonate % 0.6 0.2 W¡thOüt Na-gluconate
Naphtalene 2.2-2.5 (40% solid)
AU content % I I I****
Cubic N/lNll2 113.8 42.3 Cube strcnpth (28 days) is deta-

compressive mined at a constant loading rate of
strength 13.5 kN/s
SD 4.1 1.4
15Ox150x150mm
~ ~~
RisIllatic N/& IM) 29.4 Rismatic strength (28 days) is

compressive detamineci at a constant longitudi-
strength SD 3.3 1.4 nai suain rate
1~x100x400mm of 7.3 x 10-6 s-’
Cement paste
gel pore
I
interlayer water
Fig. l-Pore structure inside concrete

A C 1 SP-lu53 V O L S 1 1 95 = 0662949 0 5 2 L b 7 5 458
pore water pressure the Stefan Effect
--``,`,-`-`,,`,,`,`,,`---
Fig. 2-Basic mechanism of strain-rate sensitivity
LVDT
I
CLIP GAUGE
r LvDT
LVDT
CLIP GAUGE
LVDT f' i
J4
70
r 110 250
12s
80 1.
Fig. 3-Experimental setup for compressive and tensile tests

A C 1 S P - 1 5 3 V O L X I I 95 = 0662949 0521676 394 M
120 -
HSC A NSC
100 -
80-
80-
40-
A A A
b
A
20 -
Linear regression
o , I
Fig. &Peak stress versus transverse strain rates in

compression
intrinsic area (solid phase feature)
I
1
rate sensitive area

I
--``,`,-`-`,,`,,`,`,,`---
'cd Eih
Fig. %Rate-sensitive area in stress-strain curve

A C 1 SP-153 VOL*II 95 IObb29LI9 O521677 220 I
4 +
o HSC transverse strain
3 -
o
/
NSC transverse strain
2 -
..............
/ A ............ ........... 0..........
1 - ei ................. ,,CL................
,@...........
q::""""' .................................
.............. 4
4
O
--``,`,-`-`,,`,,`,`,,`---
Fig. 7-Strain ratio versus various stress levels in compression

A C 1 SP-153 VOL*II 95 m 0662949 0523678 167 m
6
o HSC x NSC
5 - o
U
o u Q o n
U Y a
4 - o
LI
3 -
X
It
X
x Y
Y
2 -
E x X
1 -
- Linear regression
O
Fig. &Peak stress versus longitudinal strain rates in tension
0.1 -
/
A
Linear regression
lo3 10'~ 10-9 [ s-'1

Longitudinalstrain rate
Fig. -train versus longitudinal strain rates in tension
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L a I I 95 m 0bb2949 0 5 2 L b 7 9 O T 3
SP 153-37
Nonevaporable Water and Degree

of Cement Hydration in Silica
Fume-ce ment Systems
by E. H. Atlassi
Synopsis: The most common way of estimating the degree of hydration of

cement (a)in practice has been to measure the nonevaporable water
content (W,) using the relation W, = 0.25aC.
However when silica fume is incorporated in a mixture, some of

the nonevaporable water is converted to evaporable water. More
specifically, the water originally bound in the Ca(OH)? which reacts with
the amorphous silica is released in a polymerization process. This was
shown in a study of mature cement-silica fume systems where a new
quantitative thermogravimetric method was used. Thus, for the same
degree of hydration of the cement the total nonevaporable water content
is lower in a mixture with reacted silica fume than in one without.
Moreover, the degree of hydration of the cement is slightly

increased when moderate amounts of silica fume are added, provided
sufficient water is present in the pore system, either by water curing or a
high initial water-to-cement ratio. In mixtures with low w/c, tile faster self-
--``,`,-`-`,,`,,`,`,,`---
desiccation and the reduced permeability caused by silica additions affect

the moisture state in a larger specimen (even if it is water cured) and
consequently the degree of hydration of the cement.
Keywords: Hvdration; microsilica; pozzolanic reactions; silica fume; water

of hydration

703
A C 1 SP-153 VOL*II 95 W 0662749 0521b8O 815 W
704 Atlassi
E. Helsing Atlassi has obtained her M.Sc. degree in civil engineering and
Ph.D. degree at Chalmers University of Technology in Göteborg, Sweden
where she at present works as a researcher at the Department of Building
Materials. Her research activities and publications concern the influence
of silica fume on the chemical, physical and mechanical properties of
concrete, with a special interest in high performance concrete.
INTKODUCTION
The relation between the total amount of nonevaporable water

(W,) and the degree of hydration (a)in pure cement systems is fairly well
known (W, = 0.25aC) and this is the most common way of estimating, in
practice, the degree of hydration of the cement (see for example [l]).
However, the nonevaporable water is not a homogenous phase but

consists of water bound in different compounds. It may be present as
hydroxyl ions bound in calcium hydroxide (CH) or other hydroxides, or as
hydrate water fixed in several different compounds such as calcium-
silicate-hydrates (CSH), calcium-aluminate-(sulphate)-hydrates(CAH) and
calcium-ferrite-(sulphate)-hydrates (CFH).
Silica fume (SF) is a pozzolanic material i.e., it reacts with the CH

released during hydration of cement, possibly together with H,O, and an
additional amount of CSH is formed. However, the composition of the
pozzolanic reaction product and, more specifically, its nonevaporable
water content is still an undecided issue among researchers. Most
researchers assume that all the hydroxyl water is preserved as hydrate
water [2,3] but other possibilities have also been put forward (e.g. [4]).
The reaction can be generalized as follows:
xSi0, + yCa(OH), + zH,O = > yCaO .xSiO,. (k.y+z)H,O + (1-k)-yH,O
where OIk11 and z=O if k < 1.
The question then arises as to whether the hydroxyl water is partly

or fully integrated in the CSH structure (O< k < 1 and k = 1 respectively) or
is it released as evaporable water (k=O)? Or is it possible that even more
water than the hydroxyl water is incorporated in the reaction product
(z>O)?
--``,`,-`-`,,`,,`,`,,`---

Since the nature of the pozzolanic reaction product is not entirely

established, the relevance of the traditional relation between
nonevaporable water content and degree of hydration of the cement
mentioned above may also be questioned when silica fume is incorporated
in the mixture.
Another matter in dispute is how the addition of silica fume affects

the cement hydration process. Since the nonevaporable water content per
binder is less in a mixture with silica fume than in a comparable mixture
without (e.g.[5]) it has been assumed that silica fume obstructs the cement
hydration (idxef.). In other investigations, for example [6] where X-ray
diffraction was used, silica fume did not affect the cement hydration.
These aspects, together with several others such as the influence of

relative humidity and carbonation, have been studied in an extensive
investigation of both the nonevaporable and evaporable water in cement-
silica fume blends [7,8]. The part presented in this paper is concerned
with the influence of silica fume on the nonevaporable water content in
two year old, water cured mortar specimens.
METHODS
A detailed description of the experiments; methods, materials,

results and analysis methods can be found in [7].
A new thermogravimetric method, which makes it possible to

separate and quantify the decornposition of different types of compounds
in the nonevaporable water range (105-975°C); hydrates, calcium
hydroxide and carbonation products, was developed and used in this study.
The temperature was gradually raised to fKed temperature levels. At each
fixed temperature level the temperature was kept constant until a relative
weight equilibrium was achieved.
The temperature steps used and the corresponding decomposing

components were:
Temperature
- interval Decomposing component
- 105°C Evaporable water
105 - 380°C Hydrate water from CSH and CAH
380 - 600°C Ca(OH), + CFH + Carbonation products
other than calcite
600 - 750°C Calcite
750 - 975°C Some secondary hydration products
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L J I I 95
No reproduction or networking permitted without license from IHS e 0662949 0521b8L 751
Not for Resale
A C 1 SP-153 VOLrII 95 0662949 0521682 698
706 Atlassi
The analyses were carried out on a LEC0 Mac-500

thermogravimetric analyzer. The equipment could analyze 19 specimens,
as large as 5-6 grams, simultaneously. A mixture of about 50% nitrogen
and 50% air was used as a thermogravimetric atmosphere.
The thermogravimetric results are presented as retained weight at

the fiied temperature levels per ignited cement weight, which in this case
is called a weight loss curve (see Figure 1).
MATERIALS
--``,`,-`-`,,`,,`,`,,`---
The thermogravimetric experiments reported here were carried out

on samples from the interior of mortar prisms with an inert aggregate
(quartz sand). Only well cured specimens (minimum 2 years of water
curing) were used, where the hydration process and the pozzolanic
reactions could be assumed to be close to being terminated, either due to
lack of space or lack of unhydrated cement.
The tests were carried out on specimens with a normal portland

cement with 5% limestone filler (ASTM Type I). The silica fume was in
powder form with 87% pure SiO,. Data on the cement and the silica fume
are given in Table 1. A constant dose (0.4% dry weight per cement
weight) of a naphthalene based superplasticizer was used in all mixtures.
The compositional parameters were chosen to cover ranges in

which silica fume is normally used in structural concrete; w/c = 0.30 -
0.60 and SF additions lower than 15% (SF/C by weight). One mixture
with a higher silica fume addition, 25%, was also included. The
compositions of the mixtures are given in Table 2. The denomination of
the mixtures are designed to give a rapid comprehension of the
compositional parameters without having to refer to Table 2; the first
number comes from w/c and the two last from SF/C.
Chemical Influence of Silica Fume on the NonevaDorable Wat2r Content
The pozzolanic reaction product can be characterized by its molar

ratio [C/SI, = y/x and [H/S], = ( k -y t z)/y. This pozzolanic product does
not necessarily have to be a real existing compound. It may be an
imaginary product which can be considered as additional CSH and
represents the changes induced on the hydrating system.

A C 1 SP-153 V O L a I I 95 Obb29Y9 0521683 524 =
If the nature of the cement hydration products does not change

when silica fume is added, the difference between the TG results from
mixtures containing silica fume and those which don’t must be due to the
pozzolanic reaction and a possible variation in the degree of cement
hydration. As expected, the most prominent difference between a weight
loss curve from a mixture with silica fume and one without is a
diminishing weight loss in the temperature interval where CH is released;
380 to 600°C.
However, when samples (previously untouched by detrimental

environmental factors such as carbonation) with pure cement as a binder
were analyzed with T G the proportions between the weight losses in the
different temperature intervals were constant (Figure i). When samples
incorporating silica fume were analyzed this proportionality disappeared.
The recorded weight loss in the step between 105 and 380°C varied
considerably, even if the samples were taken at the same time from the
same prism, while the weight losses in the other steps were almost the
same, as can be seen in Figure 1.
What may then be the explanation of this deviation in weight loss

between 105 and 380°C in most of the silica fume mixtures? Either the
pozzolanic reaction creates hydrate water, but the decomposition
temperature of this hydrate is lower than in ordinary CSH-gel, or this is
really evaporable water that is more difficult to evacuate than evaporable
water in a hydrated mixture without silica fume. In both cases the
conclusion must be that the nature and/or the structure of the pozzolanic
--``,`,-`-`,,`,,`,`,,`---
product is not the same as that of the CSH-gel formed when pure cement
hydrates.
With a mathematical method where the weight loss curves from the
mixtures with silica fume are compared quantitatively to the curve of a
reference mixture without silica fume, all the theoretically possible [C/SI,
and corresponding [H/S], and degrees of hydration of the cement were
determined for each silica fume mixture. The degree of hydration of the
reference mix is known and the molar weights of Cao, SiO, and H,O are
used. Together with several additional factors, such as comparison to
results obtained by other researchers and with other methods, this analysis
leads to the conclusion that the most stable condition of a hydrated silica
fume mixture is achieved when all the reacted hydroxyl water is converted
into evaporable water, i.e. z=O, k=O and [H/S],=O. If moderate amounts
of silica fume were added, the [C/SI, ratio was then around 1.15 in all
cases. However, if more silica fume than could be consumed by the
calcium hydroxide formed during the cement hydration was added, the
stoichiornetry of the cement hydration was influenced and the method
would not give conclusive results. The mathematical method, the
theoretical analysis as well as the results are presented in detail in [7].

A C 1 SP-I153 V O L X I I 95 Obb2949 0523684 4 6 0
708 Atlassi
Thus, the nonevaporable water content of a hydrated cement-silica

fume mixture decreases with the amount of water initially bound in the
CH that has reacted with the silica fume. This implies that the
nonevaporable water content is not a univocal function of the degree of
hydration of the cement when silica fume is incorporated in the mixture;
the amount and the degree of reaction of the silica fume also have to be
considered.
As long as no more silica fume is added than can be consumed by

the formed CH, the relation between the degree of hydration and
nonevaporable water content in a mixture with silica fume becomes:
--``,`,-`-`,,`,,`,`,,`---
(SaF is the amount of pure amorphous silica in the condensed silica fume
and a, and as are the degree of reaction of the cement and silica fume
respectively)
Consequently, different amounts of nonevaporable water per

cement or binder content can appear in mixtures with the same degrees of
hydration of the cement if the degree of reaction of the silica fume differs,
even if the SF/C ratio is the same.
Structural Influence of Silica Fume on the NonevaDorable Water Content
The explanation of the varying weight loss between 105 and 380°C
recorded in samples from the silica fume mixtures could be that some of
the evaporable water is present in pores with extremely small pore
openings. The gel water then has to be removed to open up channels for
this evaporable water. The closed pores must then have been created
during the pozzolanic reaction, since this kind of behaviour is not
experienced even in very dense pure cement mixtures.
The varying weight loss is then an equilibrium problem and the

constant weight criterion used in the TG-analysis was not sufficiently
severe to clearly distinguish between evaporable and nonevaporable water
in a silica fume modified CSH-gel. This hypothesis is supported by the fact
that a clear influence of specimen size on the weight loss in the
temperature interval in question was also noted; the larger and more
spherical the sample used in the thermogravimetrical analysis the greater
the weight loss between 105 and 380°C. Similar observations about the
influence of specimen size have been made by Sellevold [9].

A C 1 SP-153 VOLtII 95 Ob62949 0521685 3T7 m
The theory that a conversion of nonevaporable water to evaporable

water takes place and that closed pores are formed is further supported by
the acquired water vapour sorption isotherms of the mixtures. One
example can be seen in Figure 2. The maximum evaporable water
content or total pore volume per cement content is higher in the silica
fume blended mixture. It is probable that this additional pore volume
cannot become drained until the relative humidity falls below 43%, since
a sudden drop that is about equal to the increase in total pore volume
occurs in the first desorption isotherm between 33 and 43% RH of the
silica fume mixture. As can be seen in the absorption isotherms the
capillary pore structure is refined, probably due to the filler effect of the
silica fume, but the specific extra pore volume is not filled until between
94 and 98% RH. This type of hysteresis effect is typical for 'ink bottle'
pores, i.e. large pores with small openings.
Even if the pore volume increases when silica fume is added, the
connected capillary pore system becomes refined and blocked, which
reduces the permeability.
The origin of these relatively large pores may be discussed. They

may be hollow shells of the hydrating alite grains, so called 'Hadley grains'
[lo] or spaces originally occupied by CH crystals [li].But it is also
possible that these pores, which occur only in silica fume systems, are
--``,`,-`-`,,`,,`,`,,`---
spaces originally occupied by the silica fume grains, which in the beginning
of the hydration process become surrounded by precipitated Ca(OH),. In
a humid environment the silica fume and the CH gradually react with one
another and combine by polymerization with the existing surrounding CSH
(see Figure 3), liberating free water molecules. The CSH structure around
the original particles then becomes densified. Since the volume of the
reaction products is less than the volume of the reactants the volume of
the original particles will not be filled, but leaves a pore. The size of the
pores deduced from the sorption isotherms corresponds well with the size
of the silica fume particles [7].
Influence of Silica Fume on the Degree of Hvdration of the Cement
The degree of hydration of the cement in this study is not greatly

influenced by the silica addition, except when very high doses of silica
fume are used (Figure 4). Though, it must be noted that these results
were obtained on specimens from prisms that have been continuously
water cured for two years, and with, in some cases, higher water-to-binder
ratios than in other investigations. Therefore the conclusion is valid
provided sufficient water is not only supplied but also accessible to the
system. In. silica fume mixtures with very low water-to-binder ratios the

A C 1 SP-153 VOL*II 95 Obb2949 0523686 233
710 Atlassi
self-desiccation will be .substantial,which reduces the internal moisture

content of the specimen, and the permeability will be so low that water
cannot easily penetrate from the outside. As pointed out by Sellevold et
al. [2] the influence of silica fume on the cement hydration process is due
to a difference in availability of 'free' water, which will be more
pronounced in low water-to-binder ratios.
However, if more silica fume than can be consumed by the CH

that is released during hydration is added the cement hydration process is
affected; both its stoichiometry and degree. The critical dosage of silica
fume will then depend on:
* cement type (amount of CH released)
* w/c (maximum degree of cement hydration)
*
--``,`,-`-`,,`,,`,`,,`---
curing conditions (virtual degree of hydration)

* amorphous silica content of the silica fume (capable of consuming
the CH released during cement hydration)
If a molar ratio C/S= 1.2 for the pozzolanic product is used (on the
safe side) the maximum silica addition for a mixture with w/c=O.3, with
the materials and curing used in this study, should be:
Pure SiO,/C = aC [CH-max/C] / (1.2.74).60 =

= 0.6 *0.27/(1.2.74). 60 = 0.11
Le. as a maximum 13% of the SF used in this study (pure Si0,=87%)

should be added to a mixture with this cement when w/c=0.3.
Nonevaoocable Water Develouments in Cement - Silica Fume Svsterns

It is well known that the development of the degree of hydration of
cement ( a C )is greatly influenced by several circumstantial factors, such as
w/c and moisture conditions, see for example [ll].
It does not seem as though the development of the pozzolanic

reaction is influenced to the same extent by these factors [12], probably
due to the fact that the volume of the reaction product from the
pozzolanic reaction is less than the volume of the reactants and that the
amount of physically bound water increases in the reaction.
The difference in reaction developments of the silica fume and the

cement under varying circumstances gives rise to an infinite number of
possible nonevaporable water developments with curing time when these
two components are combined.

A C 1 SP-153 VOL*II 95 6 Obb27Ll7 0521687 1 7 T 6
If :i certain amount of silica fume (below the critical dosage) is

added to a mixture with such a high w/c that hydration may continue for
a long time the pozzolanic reaction will only be seen as a temporarily
decreasing rate of nonevaporable water development, often interpreted as
a decreasing rate of cement hydration. See Figure 5.
If the same amount of silica fume is added to a mixture with such a

low w/c that the cement hydration is virtually stopped or slowed down
significantly at an early age due to lack of space, it is possible to record an
actual decrease in nonevaporable water content after the initial rapid
cement hydration period (Figure 6). This has also been experienced by
Radocea (reported in [7]) and Zhang & Gjorv [12]. The phenomenon will
be more pronounced with a rapid hardening cement than with a cement
with a slower initial hardening.
CONCLUSIONS
Water from the Ca(OH), involved in the pozzolanic reaction is

released as evaporable water, lowering the total amount of nonevaporable
--``,`,-`-`,,`,,`,`,,`---
water per hydrated cement content in silica fume blends.
If sufficient water is supplied to a system, either by water

curing or a high initial w/c, with no more silica fume than can be
consumed by the CH the cement hydration of a normal portland cement
will not be greatly influenced, neither its stoichiometry nor its degree. In
very dense systems with low water-to-cement ratios the hydration may be
obstructed by the lack of free water, caused by an increased self-
desiccation.
Pores of a certain size (diameter about 1000 A) embedded in the

CSH gel are created during the pozzolanic reaction.
When silica fume is incorporated a more severe equilibrium

criterion for the weight loss at 105" has to be used to differentiate
between nonevaporable and evaporable water than that which was
necessary with pure cement systems.

A C 1 SP-153 VOL*II 95 I0662999 05216ôô OOb W
712 Atlassi
REFERENCES
1. Neville A., "Properties of concrete", 3rd Edition, Longman

Scientific & Technical, London, 1981
2. Sellevold E.J. and Justnes H., "High strength concrete binders part
B: Nonevaporable water, self-desiccation and porosity of cement
pastes with and without condensed silica fume", 4th Canmet/ACI
Int. Conf. on Fly Ash, Silica Fume, Slag and Natural Pozzolans in
Concrete, Istanbul 1992, Vol 2, pp 891-902.
Huang C. and Feldman R.F., "Hydration reactions in portland

cement - silica fume blends", Cement and Concrete Research, Vol
15, 1985, pp 585-592.
Justnes H., "Hydraulic binders based on condensed silica fume and

slaked lime", 9th Int. Conf. on the Chemistry of Cement, New
Delhi, 1992, Vol III, pp 284-290
Batrakov U.G., Kaprielov S.S.and Sheinfeld A.V., "Influence of

different types of silica fume having various silica content on the
microstructure and properties of cement, 4th Canmet/ACI Int.
Conf.on Fly Ash, Silica Fume, Slag and Natural Pozzolans in
--``,`,-`-`,,`,,`,`,,`---
Concrete, Istanbul, Vol 2, 1992, pp 943-963.
6. Helsing Atlassi, E., "A quantitative thermogravimetric study on the

nonevaporable water in mature silica fume concrete", Thesis, Publ.
93:6, Department of Building Materials, Chalmers University of
Technology, S-412 96 Göteborg, Sweden, 1993.
7. Helsing Atlassi, E., 1994 "Water vapour sorption isotherms and

related properties of cement - silica fume systems. Experimentals
and results", Publ. 94:6, Dep. of Building Materials, Chalmers
University of Technology, S-412 96 Göteborg, Sweden
8. Sellevold E.J., "Bestemmelse af luft/makro og gel/kapillaer

porositet samt relativt bindemiddelinnhold", Norwegian Building
Research Institute, Report 01731, 1986, (in Norwegian).
9. Hadley D N, "The nature of the paste-aggregate interface", PhD

Thesis, School of Civil Engineering, Purdue University, West
Lafayette, IN, 1972.

A C 1 SP-II53 V O L X I I 95 m 0662949 0523689 T 4 2 m
10. Buil M & Delage P, "Some further evidence on the specific effect
of :dica fume on the pore structure of portland cement mortars",
Cernent and Concrete Research vol. 17, pp 65-69, 1987
11. Copeland L.E. and Kantro D.L., "Chemistry of hydration of

portland cement at ordinary temperature", in The Chemistry of
Cement, Ed. Taylor H F W, 1964, pp 313-370.
12. Justnes H., Sellevold E.J. and Lundevall G., "High strength
coricrete binders part A: Reactivity and composition of cement
pastes with and without condensed silica fume",
--``,`,-`-`,,`,,`,`,,`---
13. Zhang M.-H. and Gjorv O.E., "Effect of silica fume on cement
hydration in low porosity cement pastes", Cement and Concrete
Research Vol. 21, 1991, pp 800-808.
Ca0 SO, N,O, Fe,O, MgO K,O SO, Loi' Spec

surf.
m2/Q
Cernent 63.5 19.3 5.2 3.0 1.3 1.3 3.3 2.3 380
Blaine
0.4 85.7 0.5 1.2 2.7 1.6 0.8 3.8 19550

BET

A C 1 S P - 1 5 3 VOL*II 95 = O662949 0523690 764
714 Atlassi
TABLE 2 - COMPOSITION OF MIXTURES
Aggr-lC
0.50 0.05 2.94 0.48

510 0.50 0.10 2.88 0.46
5 15 0.50 O. 15 2.82 0.44
525 0.50 0.25 2.70 0.40
310 0.30 0.10 1.35 0.27
410 0.40 0.10 2.11 0.36
610 0.60 0.10 3.65 0.54
Retained weight per ignited cement weight
O0
Temperature, "C
Fig. 1-TG weight loss curves for water-cured samples of mortar with
and without silica fume
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 V O L X I I 95 = Obb2949 0521671 bTO
We/Cign
First desorption
SF/C=O
+
SF/C=O.l O
0.:3
t ............................... ,
Absorption
SF/C=O
+
SF/C =O. 1O
-8-
...............
W/C =O.50
O 20 40 60 80 100
RH %
Fig. 2-Water vapor sorption isotherms for water-cured

rriortars with and without silica fume
Fig. 3-Principles of possible mechanism of creation of pores due to

pozzolanic reaction
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 V O L X I I 95 W Obb27LI9 O523692 537
716 Atlassi
Degree of hydrationof the cement Degree of hydrationof the cement

1
w/c =0.5 SF/C =O.1 O

0.9
0.8
1 -+.- . ._-..-J..
\.
...............................................
i..
x... ....
0.8
..................................................
c
._
iii
._
L
m
0.7 0.7
I
0.6 0.6
O 5 10 15 25 0.3 0.4 0.5 0.6
--``,`,-`-`,,`,,`,`,,`---
SF/C, % w/c
Fig. &Degree of hydration of cement in silica fume-blended mortar

prisms water-cured for 2 years
C..I-.'C"
&e* A
-
-
0.15 Wn development in a
t - silica fume system
SF/C=O. 1 O
Awn from the pozzolanic reaction

O
--_--------**---.
I I l I I I I
-0.05
Fig. 5-Nonevaporable water development in silica fume-blended

mixture with water-cement ratio higher than about 0.4

A C 1 SP-153 V O L U I I 75 U Obb2747 0523673 473
Nonevaporable water content per cement weight

0.25
sI=/c=o.l
o
,.’
aual Wn development in a
0.05
cement - silica fume system
O -------__
-0.05
0.3 1 3 10 30 100 300 1,000
Time, days
Fig. 6-Nonevaporable water development in silica fume-blended

mixture with water-cement ratio lower than about 0.4
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0662947 0521674 30T
Surface and Colloidal Properties

of Silica Fumes in Aqueous Medium
by Q. Chu, S. Bonnamy, and H. Van Damme
Synopsis: In order to understand better the behaviour of silica fumes (SF) in

fresh mortar and concrete, four French silica fumes, with different chemical and
textural properties (cf. M. Lajnef et al., this conference), were characterized with
respect to their surface properties and their behaviour in aqueous dispersion. Zeta
potential ineasurements were performed as a function of pH and ionic strength.
Below about pH=4, all materials behave similarly, whereas at higher pH, the
electrochemical potential was found to be related to the Ca content. In suspension,
the decrease of the average particle size (bimodal distribution) is directly related to
the power input (ultrasonic treatment) and to the intragranular compactness, mass-
fractal dimension and densification treatment. With Ca-rich SF, sedimentation
volumes and velocities were found to increase as dispersion proceeds, which
suggests that the elementary sub-micrometric silica spheres re-agglomerate after
the dispersion treatment, probably due to bridging by calcium silicate hydrates.
Kevwords: Agglomeration; bleeding (concrete); particle size distribution;

silica fu-; Zeta potential
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOLxII 95 0662949 05211695 246
720 Chu, Bonnamy, and Van Damme
Q. Chu is graduate student preparing a Ph.D at the "Center de Recherche sur la

Matière Divisée", C.N.R.S., Orléans, France. He holds his Master's degree from
Chongqing Institute of Architecture and Engineering in China in 1984, and was
teaching as an Associate Professor in the Dept. Building Materials of this institute
till 1991. He is the author of a few papers on mechanical properties of cement and
concrete.
Dr S. Bonnamy, Ph. D in Physical Science, is senior researcher" at the

C.R.M.D.K.N.R.S. in Orléans, France. Her research activities focus on the
studies by optical and electron microscopy of the multi-scale organisation of
materials. Most of her work was devoted to carbon-based materials including
fibres, pitches and carbon blacks. In the last year, she became interested in
cements, mortars and silica fumes.
H. Van Damme is senior researcher of the C.N.R.S and head of the C.R.M.D.
centre. He is a physical chemist and has been working in the field of surface and
colloidal properties of finely divided materials since 1974.
INTRODUCTION
--``,`,-`-`,,`,,`,`,,`---
Silica fume is known to be a pozzolanic material which can contribute

unique properties to portland cement products, and which can modify
characteristics of fresh cement paste as well as the microstructureof the paste after
hardening.
There are various mechanisms of action of SF which cause physical and

chemical changes in cement paste or concrete. The beneficial action of SF has
been attributed generally (1) to the extremely small size of SF particles, the
pozzolanic properties of SF, and the great improvement in the microstructure of
the hydrated cement paste in the vicinity of coarse aggregate particles, called
transition zone in concrete. Bache (2) explained the gain in workability obtained in
concrete with low W/C ratios by the fact that the small size of SF particles can
displace some of the water present between flocculated cement particles. De
Larrard (3) showed how the small size of SF particles results in densification of

A C 1 SP-153 V O L * I I 75 m Ob62949 0 5 2 L b 9 b 182 m
the fresh cement paste, and that the small SF spheres fill some of the voids
between the much coarser cement particles which otherwise can be occupied by
water. Detweiler and Mehta (4) discovered that carbon black, a non-pozzolanic
powder that has an average particle size similar to that of SF, played a similar role
in improving the mechanical properties of cement paste as that caused by SF.
After comparing the effects of SF and carbon black, Goldman and Bentur (5)
suggested that the modification of the concrete strength and microstructure by the
presence of SF, is due to a large extent to filler effect, rather than pozzolanic
reactivity. So the small size of SF elementary particles with respect to cement
grains appears to be the key factor of their activity.
Unfortunately, SF powder and commercial slurry are all in fact large

aggregates of elementary submicrometric spheres. Deagglomeration of the grains
in the fresh mortar, concrete or slurry is of primary importance to reach a good
--``,`,-`-`,,`,,`,`,,`---
dispersion of the elementary particles in the cementitious matrix. i t has been fund
(6) that the effect of SFs dispersivity on the viscosity-reducing of high strength
concrete. We can expect that well dispersion of silica fume would improve greater
the microijtructure, and so the properties of concrete.
As the first part of our project, this paper will address some colloidal
behaviours of the aqueous dispersion of SF, with particular reference to their
agglomeration and deagglomeration behaviours in terms of surface and textural
properties. This is basic to investigate the dispersion statement of SF in cement
paste or iconcrete and the effect of this dispersion statement on properties of
concrete, and to make SF slurries more available for concrete. It will present the
results of granulometric, electrophoretic and sedimentation measurements as a
function of ionic strength, pH or dispersion treatment.
EXPERIMENTAL
Silica f u m
Four French silica fumes were used in our experiments. Some physical
parameters are given in Table 1. They are all grey powders with specific surface
areas froin 14,500to 24,640 m2/kg.

A C 1 SP-153 VOL*II 95 m 0662749 0523697 O39 m
Table 2 gives the elemental composition of our SF. Calcium contents in

C 1 and C2 are much higher than in the others. A2 has more Fe and K.
Transmission Electron Microscopy
The TEM technique was used for the calculation of the particle size
distribution. The samples for TEM were prepared in very dilute suspensions with
a concentration of about 0.005% by weight, and ultrasonically dispersed for five
minutes with a 600 Watt sonotrode. Then a small drop of this suspension was put
carefully on a grid and it was allowed to dry slowly. Using the samples prepared
--``,`,-`-`,,`,,`,`,,`---
with this method, we could obtain images, as in Fig. 1, on which the profile of the
individual particles could be easily recognized.
Granulometric Measurement in Aqueous Medium
Deagglomeration of the SF?s grains (aggregates) was followed with a

COULTER-LS laser-granulometer. The samples were sonicated for five minutes
with the sonotrode, with increasing input powers. After sonication, the samples
were poured into the granulometer?ssample holder and the size distribution was
immediately measured.
Sedimentation
Measurements of the sedimentation rate and volume were carried out in

tubes of $ 1 6 ~ 1 5 0mm, by observing the evolution of the height of the interface
between the settling suspension and its supernatant. The suspensions were treated
by ultrasound with a given power for two minutes, then poured in the tubes. In
most cases the supernatant was clear, but in very diluted suspensions or in
suspensions with low pH or certain dilute concentration, the supernatant was
cloudy.
Electrokinetic Potential
Electrokinetic potentials (6 potential) were obtained with a Zetasizer4

(Malvern Instruments Ltd) laser-zetameter. The concentration of the suspension
samples for measurements was 5 mg silica fume in 150 ml distilled water or

A C 1 SP-153 V O L X I 1 95 E 0662949 0521698 T55
solution. The samples were dispersed by a two-minute ultrasound treatment at

360 W. The determinations of electrokinetic potential were carried out after
adjusting the pH by dropwise addition of HCI or NaOH solutions. Each sample
was measured more than three times and the results averaged.
Particle Size Distribution
The transmission electron microscopy image show that the SF is indeed a

very fine material. The elementary particles appear to be almost perfect spheres
with a diameter spreading from about 0.01 pm to 0.5 pm.
Three methods are generally used to evaluate the fineness of SF. The first
is the residue by sieving on a 45 pm sieve. This method can not provide any
information on the particle size distribution of SF, but rather on the amount of the
impurities it contains. The second is an indirect calculation of the fineness from
specific area measurement, but this method can only give an average size of
material, not the size distribution. The third method is by direct measurement. For
--``,`,-`-`,,`,,`,`,,`---
instance, Aitcin (7) performed measurements of the diameter of about 200 SF
particles. A special technique (8) was developed at the Pennsylvania State
University, by which the size distribution of SF was determined using an electron
microscope. ELKEM (9) has published a mean diameter values of SF between
0. 18 pm and 0.26 pm, but their method of determination was not indicated.
By computerized image analysis (Optilab software), we measured about

300 particles for each sample from TEM micrographs as shown in Fig.1. The
particles projection images were individually copied on a tracing paper. These
pictures were then fed into computer by a HP scanner, and processed. The
calculation results are given in Fig.2.
From the curves in Fig.2, one can see that the CI sample has coarser
particles as compared with the three others which have similar size distributions.
This conc iusion can be related to the specific surface area data presented in Tab. 1.

A C 1 SP-153 V O L S 1 1 95 m Ob62949 052Lb99 991 m
C1 is indeed found to have a specific surface area smaller than that of the other
three SF.
From the results of Fig.2, calculation can be made for the maximum
diameter (0.38pm to 0.54pm), the minimum diameter (0.014ym to 0.020pm) and
the mean diameter (0.17pm to 0.24ym). All these values are given in Table 3.
DisDersivitv of the Silica Fumes
The main parameters expected to control the dispersivity of SF are the

grain (aggregate) density and the strength of the bonding between elementary
particles. The chemical composition of the alloy produced in the furnace, the
temperature, the redox conditions and a post-production densification treatment
may be ultimately involved. Following the average size evolution by laser-
granulometry after ultrasound treatment is a simple way to estimate the
dispersivity, provided one can avoid re-agglomeration of the dispersed fragments.
We may consider that this is the case in the very dilute conditions of the
COULTER cell. Fig.3 gives typical COULTER curves.
The relationships between the mean diameter of the SF aggregates and the
input power is shown in Fig.4. It is clear that the average size in very dilute
suspension is related to the input power of ultrasound treatment. Rising the input
power can effectively decrease the average size. In the condition of the maximum
power of our sonotrode, all four SF reached a similar size. However, the rate of
the decrease is highly non linear and depends very much on the sample.
We can give the following order for the SF dispersivity:
Al +C 1 + A2, C2
Al is the most difficult to disperse, as compared to the two undensified samples,

A2 and C2 which were relatively easy to disperse, as expected. The sequence of
dispersivity that we obtain is the same as the decreasing order of intragrain
compactness obtained by LAJNEF (10) on the same samples:
0.29(A1) + 0.28(Cl) + 0.26(A2) + 0.1 l(C2).
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I53 V O L X I I 95 Obb2949 0523700 433 W
Compactriess is defined as the fraction of grain (aggregate) volume occupied by

the elementary spherical particles.
Sedimentation and Agglomeration in Aaueous Medium
Sedimentation rate and volume measurements are classical and rather

quantitative methods to determine the stability, which depends on the interaction
of the particles, of colloidal systems and, ultimately, the agglomeration state of the
solid particles dispersed in the liquid.
The four silica fumes used in our experiment gave different results when
they were dispersed in distilled water. The settling of C1 and C2 could be
observed immediately from the beginning of the experiment, and was finished in
24 hours as shown in Fig.5. But Al and A2 were found to settle very slowly (see
Fig.ó), and we have only got a relatively clear and stable supernatant after 4 to 5
months (Fig.7).
In order to account for these differences, it is essential to consider the

possible role of the impurities in SF which could cause re-agglomeration in the
suspensions of C1 and C2, but not that of Al and A2. Indeed, the dramatic
difference between A and C samples cannot stem from the densification treatment.
On the other hand, the elementary particle sizes are close to each other in all
samples and are in any case too small to account for the large difference in
sedimentation rate. All elementary particles are within the colloidal range and after
high power ultrasonication, all suspensions are expected to be stable, if no re-
agglomeration occurred. So in the case of SF dispersed in distilled water, there
are good reasons to attribute the rapid settling of the suspensions to the impurities
--``,`,-`-`,,`,,`,`,,`---
of SF. In order to verify the effect of impurities, we measured the pH of SF

suspensions (Fig.8). The suspension pH of C1 and C2, which are also the
samples with the highest calcium content, was found to be much higher than that
of the two other SFs. This result gave a possibility of re-agglomeration in higher
pH medium which caused them to settle.
order to verify the relationship between re-agglomeration, high pH and

Iri
Ca content, we dispersed Al and A2 in a solution of calcium oxide at different

concentrations. This is a media similar with that of C1 and C2 dispersed in

distilled water, and the suspensions of A 1 and A2 were expected to settle in this
case. The result was satisfactory, as shown in Fig.6, suggesting that the re-
agglomeration occurred due to interparticle bonding through the cations, mainly
through Ca cations, or bridging by calcium silicate hydrates.
More information about the structure of the secondary agglomerates (those

formed by re-agglomeration) may be obtained from the sedimentation volume and
rate. Fig.7 gives the final settling volume at the end of sedimentation. In distilled
water, the settling volume of A2 remains constant, whatever the input of
ultrasound power. This can be explained with the results in Fig.4 where A2 was
found to be always weil dispersed and to have a similar mean size (less than 1pm)
in the whole range of ultrasonic power.
With A I , the settling volume increased slightly with input power while,
simultaneously, the aggregate size was diminishing (Fig.4) in the COULTER
laser-granulometric measurement. This can be explained by considering the
difference between the sedimentation and the granulometric measurements. In the
later case, the medium is very dilute and little re-agglomeration is expected to
occur, contrary to the former case where the concentration is high and re-
agglomeration likely. Thus the increase of sedimentation volume with input power
suggests that, as the original and rather compact aggregates are destroyed, new --``,`,-`-`,,`,,`,`,,`---
(secondary) aggregates with a larger apparent volume are formed by re-

agglomeration. In terms of fractal dimension, the secondary aggregates are
expected to have a lower fractal dimension than the primary aggregates.
The case of CI and C2 is more complex because of the additional effect of

calcium. The presence of divalent ions may considerably modify the surface
charge of the particles at the solid-solution interface and this may in turn modify
(increase) the sticking probability as two particles encounter each other. In this
case also, a more open secondary aggregate structure would be associated with a
larger settling volume.
A larger volume of sedimentation means a larger porosity and larger

agglomerates. We used Richardson and Zaki equation ( i 1) for the group settling
rate of uniform, spherical particles:

A C 1 SP-353 VOL+II 75 W Obb2947 0523703 37T W
~
A C 1 SP-153 V O L * I I 95 IOb62949 0523702 206 I
V - settling rate of slurry-Supernatant interface, cmíhr.

V,, - Stokes' velocity for single agglomerate, c d h r .
3 - void fraction
--``,`,-`-`,,`,,`,`,,`---
If one assumes that the average (equivalent) agglomerate radius aa is

relatively independent of SF fraction over the dilute range, and that it does not
change once settling has begun, the settling rate should be given by Stokes' law:
a, - mean radius of agglomerates

pa - density of agglomerates
pN - density of water
@a - volume fraction of agglomerates
From mxterial balance:
pi - density of experimental suspension

p .;t' - density of SF
asisf - volume fraction of SF in suspension
Thus we have the following equation with Cas = 4>$4>,f:
Then the Stokes' settling velocity for a single agglomerate, V,,, is given by, if a,
is expressed in pm:
Therefore equation (III) can be written as:

I
- -
I
v465 =V"~(I-C
\" 0s
@ )
>f

A C 1 SP-353 VOL*II 95 0662949 0523703 I142 =
The curve of VI14.65 versus @,f, should be a straight line from which VCa and Cas
--``,`,-`-`,,`,,`,`,,`---
can be obtained. Then from the equation (IV), we have the formula of the
equivalent agglomerate radius:
Where the value of constant A depends on SFs density. For our silica fumes:
AA,=1.073; A A ~1.167;
=
Acizl.2 12; AC^= I . 195.
The curves of ViJ4.65 versus Qsf are given in Fig. 9 and the equivalent
diameter of agglomerate is the following (Ci):
Ultrasonic power (W): 180, 360, 540,

D (w): 165, 256, 300.
The question remaining is why the rise of input power changes the
aggregate size. In absence of flocculation or coagulating agent, it could be due to a
increased dissolution of impurities electrolytes (especially divalent cations) as the
power increases.
Surface of Silica Fumes
Fig.10 shows the variation of Zeta potential with the pH of the

suspensions. The study of the influence of this parameter is of a great interest in
the analysis of the electrokinetic properties of SF due to its effect on the charge
distribution on the particle surface. It can be observed that the negative potentials
increase monotonously (in absolute value) as the pH is raised for all four silica
fumes.
Because the Zeta potential is measured by electrophoretic effect, it is

considered to be the potential between the slipping plane at the outer boundary of
the Stern layer (outer Helmholtz plane), which moves with the particle, and the
dispersion media at an infinite distance. The negative charge on the surface of
amorphous silica has been shown in many papers. It may be assumed (12) that

A C 1 SP-353 V O L X I 1 95 0662949 0523704 089 m
the silica structure is sufficiently open that the co-ordination number of each
adjacent silicon atom is increased by a fractional amount. Bolt (13) showed that
hydroxyl ions are adsorbed by the silica surface in amounts increasing with pH,
in the pH range from 3.5 to 10.5. So the increase in ICI with the pH of
suspensions is probably due to adsorption of OH- ions on the surface of SF
particles, On the other hand we noticed that, in the case of C 1, ici is lower than
with the other samples. This may be correlated to the dissolution of impurities
which are more abundant than in the three other SF, especially for the divalent
cations.
From Fig. 1 I , evaluation can be made of the influence of electrolytes on

the surface charge of SF particles, which can be used also to explain the settling
experimental results. When SF particles are in solution of electrolyte, the cations
are adsorbed on the surface of this amorphous silica, so the negative charge is
neutralized to different levels. From Fig. 1I(b), one can see that the Ca cations are
more efficient to diminish the Zeta potential at the same ionic strength. In the
solution of CaC12 (O. 1N) with pH about 9, the negative potential is completely
saturated, and above this pH the Zeta potential becomes positive.
CONCLUSION
--``,`,-`-`,,`,,`,`,,`---
ï h e filling effects of silica fume have been known important, so the

dispersion statement of SFs particles can be expected to effect on the structure of
fresh and hardened concrete, and on the concrete properties related from this
structure. This study based on the surface and colloidal properties of silica fumes
in water with or without the cations (Ca++, Na'+) can derive the following
conclusions:
- All the four French silica fumes used in this paper are polydispersed
aggregai.es of small, sub-micrometric spheres. The diameter of these elementary
spheres is in the range of 0.014 pm - 0.54 pm. The mean diameters are
respectively O. 17 pm for A 1, O. 18 pm for A2 and C2 and 0.24 pm for C 1.
- When silica fume was dispersed in water by ultrasound, it can be broken

with the grain size spreading over a wide range. The mean size of the aggregate

A C 1 SP-353 VOL*II 95 m 0662949 0523705 TI5 m
decreases to less than one micron with rise of input power. The undensified SFs
can be dispersed in water more easily than the densified samples.
- With Ca-rich SF (Ci and C2), the sedimentation volume and velocities
increase as dispersion proceeds in distilled water. The suspensions of Ca-poor SF
are stable during several months. The fact that all SFs settle in the presence of Ca
cations suggests that the elementary sub-micrometric silica spheres could re-
agglomerate in presence of Ca cations after the dispersion treatment. This is
caused by electrochemical reactions on the particle surface.
- The surface of SF particles presents a negative Zeta potential in aqueous
--``,`,-`-`,,`,,`,`,,`---
medium, and their Zeta potential varies with pH of the suspensions and increases
monotonously as the pH is increased. In the presence of electrolyte, which results
in a compression of the double layers, the values of ICI is diminished with increase
of the ionic strength. Divalent cations like Ca++ are more effective for the Zeta
potential diminution. At the pH 9 the later may even become positive.
REFERENCES
1. Khayat, K. H. and A k i n , P. C., "Silica fume in concrete -An overview",

Proceedings of the 4th CANMETIACI International Conference on Fly Ash,
Silica Fume, Slag and Natural Pozzolans in Concrete, V. 2, pp.835-872,
Istanbul, 1992.
2. Bache, H. H., "Densified cement-based / ultrafine particles-based materials",

Proceedings of the Second International Conference on Superplastizer in
Concrete, pp. 185-2 13, Ottawa, 1981.
3. De Larrard, F., "Ultrafine particles for the making of very high-strength

concrete", Cement & Concrete Research, Jan.-Feb. 1989, V.19, pp.161-172.
4. Detweiler, R. J. and Mehta, P. K., "Chemical and physical effects of

condensed silica fume in concrete", Supplementary paper of the Third
International Conference on Fly Ash, Silica Fume, Slag and Natural Pozzolans
in Concrete, pp.295-306, Trondheim , June 1989).

A C 1 SP-153 VOL*II 95 IObb2949 052170b 951 D
5. Goldman,A. and Bentur, A., "Effects of pozzolanic and non-reactive

microfillers on the transition zone in high strength concretes", Proceedings of
the RILEM International Conference: Interfaces in Cementitious Composites,
pp.53-61, Toulouse, 1992.
6. Yonezawa, T., Izumi, I., Okuno, T., Sugimoto, M., Shimono, T. and
Asakma, E., "Reducing viscosity of high strength concrete using silica fume",
Supplementary papers of the 4th International Conference on Fly Ash, Silica
Fume, Slag and Natural Pozzolans in Concrete, pp.765-780, Istanbul, 1992.
--``,`,-`-`,,`,,`,`,,`---
7. Aitcin, P. C., Pinsonneault, P. and Roy, D. M., "Physical and chemical

characterization of condensed silica fume", Am. Ceram. Bull., V. 63,
pp. 1487, 1984.
8. Malhotra, V. M., Rarnachandran, V. S., Feldman, R. F. and Aitcin, P. C.,

"Condensed Silica Fume in Concrete", CRC Press, Inc. pp.12, 1987.
9. ELKEM silica Technical Bulltin, ELKEM - SPIGERVERKET als, Fiskaa

Verk, P. O. Box 40,4620 Vaayobygd, Norway, 1980.
10. Lajnef, M., "Etude des fumées de silice: microstructure, microtexture et

influence sur mortier", Thèse de l'université Paris VI, Université Pierre &
Marrie Curie, 1993.
11. Richardson, J. F. and Zaki, W. N., Trans. Inst. Chem. Engrs. V.32, 35,
1954.
12. Iler, R. K., "The chemistry of silica", John Wiley & Sons, pp.355, 1979.
13. Bolt, G . H., J. Phys. Chem. V.61, 1166, 1957

A C 1 S P - I 5 3 VOL+II 95 0662949 0523707 898 =
TABLE 1 - PHYSICAL PARAMETERS OF SILICA FUMES
Al A2 c1 c2
__________~
Color grey grey grey grey

Treatment densified undensified densified undensified
Spec. Surface
22,560 24,640 14,500 20,500
(mk)
Appar. 638 I83
520 110
Density
Wm3)
p (kg/m3) 12214 2321 2372 2352
--``,`,-`-`,,`,,`,`,,`---
TABLE 2 - ELEMENTAL COMPOSITION (PERCENT) OF SILICA

FUMES
I
Si Fe Ca Mn Mg Na K Ai Ti CI LOSS
Al 43.70 0.11 0.70 0.02 0.20 0.09 0.37 0.14 0.02 0.09 4.20
A2 46.30 1.00 0.30 0.03 0.12 0.56 1.10 0.36 0.02 0.81 4.20
c 1 38.20 0.63 7.40 0.06 0.91 0.09 0.49 0.52 0.02 0.1 1 2.95
c 2 40.79 1.99 2.20 1.08 0.31 1.08 0.30 <0.005 0.47 2.77
TABLE 3 - DIAMETERS (pm)OF SF ELEMENTARY PARTICLES

FROM TEM IMAGES
Dmax Dmin D50
Al 0.48 0.0 I5 0.17
A2 0.43 0.017 0.18
c1 0.54 0.020 0.24
c2 0.38 0.014 0.18

A C 1 SP-1511 VOLXII 95 I0662949 0521708 724 I
Fig. '1-Typical transmission electron microscopy image of SF

particles
I o0
7
!',./ ~
se
u
L
a
5
2
u
80
60 .... . . -
... ... ...
.. ... ...
.. .. ..
. .
.. .... .. : .........................
i
i /
: .
il
. .I. . . . . .
* ...............
.............
:
,........
Z
.- 40 .. .. ..
u . . .
L ... .. .. . .
<
, . .
.
a .. .. .. . . : :.
........ .
20
e
.
.. .. ..
<
!g
. . . : . . . :...
.... .... ....
,.. .. ..
.. .. ..
. . ,.:...
I
. * .
)
,.
_
.
. .. .
,
ku J
................. 1 ........
O
0.01 o. 1
Diameter (pm)
Fig. 2-Elementary particle-size distribution obtained

from TEM images
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOLaII 95 m 0662949 0521709 660 m
o. I I IO I O0 IO00
Diameter ( p m)
Fig. 3 - S i z e distribution of SF particles (Al) in

suspension measured by COULTER laser-granulometry,
after different ultrasound input power
50
40
E 30
J
o
ci 20
IO
O
O 60 120 240 360 480 600 720
Ultrasound Power (Watt)
Fig. &Variation of mean aggregate size of silica

fumes versus input power
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0662949 0521710 382
I20
--420 W, 2rnin
U-
h
E 100 360 W. 2rnin

f
v
42
$*
-
-
300 W. 2iniii
240 W, h i n
*
a>
80
-
-
I80 W. 2rnin
I20 W. 2min
60 W,2min
560
c
æ
._
M
40
20
0.01 0. 1 I IO IO0
Time (hr)
Fig. 5-Settling curves of SF in distilled water,

treated at different ultrasound power (Sample C1,
1 percent by volume)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 75 0bb2747 0521711 219
80
60
40
20
0.01 0.1 1 10 1no
Time (hr)
i on
80
60
t
I
40
I I A2, 1%)
20 I ' ' """I ' ' """I ' ' " ' ' 7 ' 1 ' ' ""'
o.ni 0.1 1 in 100
Time (hr)
Fig. U e d i m e n t a t i o n of SF in solution of Ca0

(dispersed by ultrasound, 360 watt, 2 min)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLrII 95 e O662949 0521712 155
50
--``,`,-`-`,,`,,`,`,,`---
O
O 120 240 360 480 600 720
ULTRASOUND POWER (W)
Fig. 7-Final sedimentation volume of SF suspensions

(Cv: 1 percent) versus ultrasound power (watt)
12
10 1 SF: 2% I
a
l a 6
O
Al A2 c1 c2
SF SAMPLES
Fig. 8-pH values of SF suspensions (dispersed

by ultrasound, 360 watt, 2 min)

A C 1 SP-153 V O L X I I 95
738
0662949 0521713 091 D =
Chu, Bonnamy, and Van Damme
0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016

Cvll O0
Fig. 9-Settling velocity versus SF (Cl) fraction in

dilute suspensions (dispersed by ultrasound at
different power, 2 min)
--``,`,-`-`,,`,,`,`,,`---

A C 1 XP-153 V O L X I I 95 m 0662949 0523734 T28 m
h
>
v
E
m
Y
0
N
O 2 4 6 8 10 12 14
PH
-10
-20
h
>
v
E
-30
Ym
0
N
-40
-50
-60
O 2 4 6 8 10 12 14
PH
Fig. 1&Electrokinetic potential of SF particles in

distilled water (dispersed by ultrasound, 360 watt,
2 min)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 W 0662949 0521715 964 W
10
-1 o
-20
-30
-40
-50
-60
O 2 4 6 8 10 12 14
PH
--``,`,-`-`,,`,,`,`,,`---
10
-10
>
5
-
-20
m
fi -30
-40
-50
-60
O 2 4 6 8 10 12 14
PH
Fig. 1 l-Electrokinetic potential of SF (Al) particles

in solutions of electrolytes (dispersed by ultrasound,
360 watt, 2 min)

A C 1 SP-153 VOL*II 95 Ob62949 05217Lb B T O
SP 153-39
Influence of High Silica Fume

and High Fly Ash Contents on
Alkalinity of Pore Solution and
Protection of Steel against Corrosion
by U. Kens, W. Breit, and P. Sthiessl
Svnotxis: In order to assess risk of corrosion due to high silica fume or fly ash
content, hardened cement paste and concrete tests were performed at the Institute
for Building Materials Research (ibac) at the Aachen University of Technology
(RWTH Aachen) to determine the influence of these concrete admixtures on the
alkalinity of the pore solution and on chloride-induced corrosion of the
reinforcing steel in the concrete. The fly ash content in the tests was up to 60
mass-%, the silica fume content up to 25 mass-% of total binder content. The
mixtures were made up with a portland cement and a portland blast-furnace slag
cement (50 mass-% blast-furnace slag) at varying waterhinder. A combination of
45 mass-% portland cement, 15 mass-% silica fume and 40 mass-% fly ash was
also included in the test programme.
Redwings the portland cement clinker content in mixtures with high silica fume
contents by the use of blast-furnace slag or by the substitution of high amounts of
fly ash leads to a rapid exhaustion of calcium hydroxide. Substantial quantities of
alkalies are bound to reaction products resulting in a dramatic drop of pH value in
pore solution (below pH = 12,O) and hence increasing the risk of depassivation of
the steel surface. The reduced alkalinity must be weighed against a significant
refinement of pore structure through the rapid pozzolanic reaction of silica fume,
clearly increasi g the electrolytic resistance of concrete and reducing the
corrosion rates to possibly negligible values.
Kevword-: Alkalinity; blast furnace slag; chlorides; corrosion; electrolytic

resistance; flv ash; high strength concretes; portland cement; silica fume;
steels
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L J I I 95 = 0662949 05211737 737 =
742 Wiens, Breit, and Schiessl
Ud0 Wiens has been a Research Engineer at the Institute for Building Research
(Institut f i r Bauforschung, ibac) of the Aachen University of Technology (RWTH
Aachen), Germany, since 1991. His field of activity includes research work on
reaction mechanisms of silica fume and fly ash in concrete and the effect of these
admixtures on chloride induced corrosion.
Wolfgang Breit is a Research Engineer at the ibac. His current research interests
are primarily in the areas of corrosion of steel in concrete and the electrochemical
monitoring of corrosion as well as the repair of concrete structures.
AC1 member Peter Schiessl has a Ph. D. in civil engineering from Technical
University in Munich and is Director of the ibac. Key research topics include
concrete technology, utilization of industrial by-products, operational
performance and durability of reinforced and prestressed concrete, corrosion,
corrosion protection and repair.
INTRODUCTION
Together with strength properties, durability is of decisive importance for

the quality of concrete. Alkalinity in the concrete generally protects the
reinforcement satisfactorily against corrosion. The high alkalinity of the pore
solution is governed chiefly by the soluble alkalies of the cement [i]. This
alkalinity is maintained by the calcium hydroxide Ca(OH)2 formed during cement
hydration, which is present mainly as an undissolved precipitate in the pore
solution of the hardened cement paste.
The alkali reserve is consumed during pozzolanic reaction of concrete
admixtures like fly ash and silica fume. The extent of the reduction depends
mainly on the type of cement, the amount of admixture added and the type of
pozzolan [2,3]. According to Sellevold et al. [3], the use of some 20 mass-%
silica fÙme in relation to (c+s) in portland cement mixtures at a w/(c+s) of 0.60
leads to complete exhaustion of the calcium hydroxide reserve. Research by
Huang and Feldman [4] with 30 mass-% silica fume in relation to (c+s) indicate
that no more Ca(OH)2 is present in the hardened portland cement paste after a
period of 3 days at a w/(c+s) of 0.45 or 14 days at a w/(c+s) of 0.60. According
to Zhang and Cj0rv [5], 16 mass-% silica fume in relation to (c+s) are already
sufficient to consume all the Ca(OH)2 in hardened cement pastes with low
w/(c+s) of between 0.20 and 0.40. Irrespective of the w/(c+s), the time for total
--``,`,-`-`,,`,,`,`,,`---
exhaustion of calcium hydroxide according to Zhang’s and G~0rv’sstudies was

550 days.
It is known from several investigations that in mixtures with silica fume
and portland cement alkalies continue to be incorporated in reaction products due
to the pozzolanic reaction [5,6], leading to a drop of pH value in pore solution.
The passivity of mild steel in aqueous alkaline solutions is ensured at pH values in

A C 1 SP-1.53 VOL*II 75 Obb2947 0521718 b73 W
excess of 11.5 [7]. Lower pH values may lead to depassivation of the steel
surface, increasing the risk of corrosion to the reinforcement.
While a number of authors describe the influence of high silica fume
contents on the alkalinity of pore solution in portland cement mixtures, less is
known about the action of silica fume in mixtures with blast-furnace slag cements.
Moreover., only a small number of investigations about the influence of a
combination of fly ash and silica fume on the alkalinity of pore solution have been
available. 'In Germany the use of combined admixtures of fly ash and silica fume in
concrete generally is prohibited, although e. g. in Scandinavian countries the
combination of both admixtures has proved successful in practice. The purpose of
this paper is to examine the influence of high amounts of silica fume and fly ash
and a combination of both in portland cement and blast-furnace slag cement
mixtures on the alkalinity of pore solution and the chloride-induced steel
corrosion.
MATERIALS AND MIXTURES
Materials
The chemical and physical properties of the selected base materials are
given in Table 1. In order to achieve the lowest possible initial pH value for the
pore solution, an ordinary portland cement (PC) with a low alkali content
(Na20equi = 0.59 mass-%) was chosen. A portland blast-furnace slag cement
(BFSC) with a slag content of roughly 50 mass-% was also used. Both cements --``,`,-`-`,,`,,`,`,,`---
comply with the German cement standard DIN 1164 and conform with DIN-
strength class 3 5 .
On the basis of previous tests [SI, a medium-fine German bituminous fly
ash (D) from a dry-bottom furnace was chosen for the tests (D2 in [SI). An
uncompacted silica fume occurring as a by-product of ferrosilicon manufacture
was used as a high-reactivity pozzolan. The fly ash and silica fume beaf a mark of
conformit:y from the German Institute for Construction Engineering (DIBt) in
Berlin for use as concrete admixtures according to German standard for design of
concrete structures DIN1 1045. A sand-gravel mixture was used in the concrete
tests (max. grain size 16 mm). The grading curve of all concretes corresponded to
A 16 / B 16 according to German standard DIN1045.
Mixture Prooortions
Tables 2 and 3 review the compositions of the hardened cement pastes

and concretes in the tests and summarize the fresh concrete properties. Concrete

A C 1 SP-I153 V O L r I I 95 0662949 0521719 50T
consistencies according to German standard DIN 1045 ranged from KP (plastic

consistency) to KR (sofì consistency). Where necessary, superplasticizer was
added.
In order to ensure comparability of the hardened cement paste and
concrete tests, identical waterhinder and admixturekement were chosen for the
hardened cement paste and concrete mixture. The wlc for the two reference
mixtures (PC) and (BC) was established at the maximum w/c of 0.60 for exterior
component concretes specified in German standard DIN 1045. The comparatively
lower w/c and w/(c+f) used in the mixtures with high fly ash content (PD) and
(ED) were entailed by planning for the concrete tests; the compressive strengths
at 28 days of mixtures (PD) and (BD) were to be roughly equivalent to those of
the relevant reference mixtures (PC) and (BC) (Table 4).
Moreover, up to 25 mass-% of either portland or blast-furnace slag
cement were replaced by the same quantity of silica fume at high and low w/(c+s)
(Table2). The (PDSF) mixture was used to establish the extent to which a
combination of 40 mass-% fly ash (D) and 15 mass-% silica fume (SF) at low
w/(c+s+f) causes fly ash mixed with silica fume to intervene in reaction processes.
EXPERIMENTAL
Hardened Cement Paste
The calcium hydroxide content of the hardened cement paste specimens

was determined over a hydration period of 730 days, and the pore solution
composition of the hardened cement pastes was analyzed. After mixing, the
cement pastes were poured into plastic bottles (50 and 250 mL) and airtight
sealed. To prevent segregation of the cement paste, the plastic bottles for all
mixtures were rotated in the longitudinal axis for 24 h at a temperature of 20 "C.
The airtight sealed plastic bottles were then stored at a temperature of 20 OC until
the date of testing.
Calcium hydroxide -- The calcium hydroxide content was determined

using thermogravimetric analysis (TGA) in accordance with the method described
in [9]. Immediately prior to testing, the hardened cement specimens were
removed from the 50 mL plastic bottles, crushed coarsely and stored in
isopropanol for 1 day to stop hydration. The hardened cement paste fragments
were then ground in a disc pulverizer until there was no more residue on a O. 125
mesh sieve. A review of the calcium hydroxide contents is given in Table 5.
Pore Solution Composition -- To determine ion concentrations in the pore

solution, the hardened cement paste specimens were cut out o f the plastic bottles
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L S 1 1 75 Obb2747 0523720 2 2 1 W
(250 mL) at the time of testing, placed in a test set-up for pore solution
expression and subjected up to a stress of 520 MPa. The expressed pore solution
was recovered without air contact. Using the pore solution obtained in this way,
Na+, K+ and Ca++ ion concentrations were determined by means of flame
photometiy and S042- and C1- ion concentrations by means of ion
chromatography. OH- ion concentrations in the pore solution were determined by
potentiometric titration. The results of the pore solution tests are summarized in
the Tables 6a and 6b.
Concrete
Compressive Strength -- Specimen storage and compressive strength

-
testing were according to German concrete standard DIN 1048: 150 mm-cubes -
7 days urider water, aRer that storing under laboratory conditions at 20 "C and
65 % R.H. until testing. The concrete compressive strength was tested at ages of
7,28,91, 182, 365 and 730 days.
Corrosion Cell -- The (PDSF) and (BSF2) concrete formulations were

selected for corrosion behavior tests. Amounts of 1.5, 3.0 and 5.0 mass-%
'
chloride in relation to cement content was added to the fresh concrete of these
two mixtures. The specimen set-up for the corrosion tests is shown in Fig. 1. The
electrodes were an St-37 stnictural steel (material no. 1.0038) and a platinum-
coated titanium rod (fully-coated with a 2.5 pm platinum film). The platinum-
coated rod exhibits no corrosion under the given conditions with a maximum of
5.0 YOchloride, allowing specimens to be fabricated in a single step. Cables were
connected to the electrodes so that an electrical contact could be established
between them after concreting. It is possible to infer the macro-cell corrosion
behavior of the steel from the electrical currents measured between the
electrodes. The cell currents in the specimens are recorded continuously using an
automatic logging unit. The electrolytic resistance of the concrete is determined at
regular intervals by AC resistance measurements (measuring frequency 1O8 Hz)
between the electrodes. The specimens were cured for 4 days in a vapour
chamber and subsequently stored in a climate with 20 "C/80 % R.H.
Hardened Cement Paste
Calcium hydroxide -- The calcium hydroxide content of the hardened

cement paste specimens is shown in Fig. 2 and 3. The reference mixture (PC)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 1 95 E 0662749 0521721 1b8 E
reveals the rise to values above 20 mass-% after 28 days which is customary with
portland cements. When discussing alkalinity of pore solution only absolute
calcium hydroxide content is of interest. The calcium hydroxide content in the
mixture with 60 mass-% fly ash (PD) is roughly 3 mass-% in relation to (c+Q
after 730 days. One significant reason for the low calcium hydroxide content is
the dilution effect caused by the substitution of fly ash for cement, which is not
taken into account when referring the values to the solids content (c+f). Owing to
the significant reduction in cement content, less calcium hydroxide is available to
the fly ash as a reaction counterpart. On the other hand significant amounts of
Ca(OH)2 have been consumed by the pozzolanic reaction of the fly ash. As is also
apparent from Fig. 2, the reaction rate slows considerably as the age of the
specimens increases, i.e. lime binding and hence consumption of the alkali buffer
become slower. This probably is due to refinement of the pore structure through
the formation of hydration products on the fly ash surface. Ion exchange between
the fly ash and the pore solution takes place through extremly slow difision
processes.
Since silica fume is more reactive than fly ash, due to its greater fineness
and higher glass content, the reaction with calcium hydroxide must also occur at a
faster rate and must bind larger quantities of Ca(OH)2. As a result of replacing
cement with 25 mass-% silica fume (PSF) or a combination of 15 mass-% silica
fume and 40 mass-% fly ash (PDSF), the entire Ca(OH)2 buffer is consumed.
Due to low cement content at low w/(c+s+f) in the (PDSF) mixture no calcium
hydroxide was found after about 28 d, whereas in the (PSF) mixture calcium
hydroxide was detected up to 365 days (Fig. 2).
Fig. 3 shows the development of calcium hydroxide content for mixtures
with blast-furnace slag cement, In line with the blast-furnace slag content
(50 mass-%), the Ca(OH)2 content in reference mixture (BC) is some 50 % lower
than that in reference mixture (PC) made up with portland cement, i.e. there is
fundamentally less calcium hydroxide available for pozzolanic reaction of the
admixtures in blast-furnace slag cements. In a mixture with blast-furnace slag
--``,`,-`-`,,`,,`,`,,`---
cement and 40 mass-% fly ash (BD), the absolute calcium hydroxide content is
roughly as high as in the (PD) mixture. The amount of Ca(OH)2 in mixtures with
blast-furnace slag cements and fly ash is reduced due to dilution by the slag and
the fly ash. Moreover, the use of blast-furnace slag cement produces a significant
refinement of the pore structure in the hardened cement paste. Both effects lead
to a decrease in Ca(OH)2-binding by the fly ash and a significant reduction in rate
of pozzolanic reaction. As compared to the mixture (PD) the pozzolanic reaction
of the fly ash in the mixture (BD) is slower; hence, a complete loss of alkali
reserve in this mixture is unlikely over a long hydration period.
A silica fume content of 15 mass-% combined with blast-furnace slag
cement is insufficient to bind all the Ca(OH)2 content during the test period. If
the silica fume content is increased to 25 mass-% and the w/(c+s) reduced to
0.34, however, no more calcium hydroxide is detectable after 28 days.
In order to consider the question of durability, it is now necessary to
establish the extent to which a reduced calcium hydroxide content affects the

A C 1 SP-353 V O L + I I 95 Ob62949 0523722 O T 4 =
composition of the pore solution.
&re Solution Composition -- In order to assess and compare the ion

concentrations of pore solutions expressed from hardened cement paste, it is
usually necessary to take account of the quantity of free water in the paste. Given
a constant soluble alkali content, the ion concentration in the solution varies
inversely with the w/c, Le. it increases when there is a smaller quantity of pore
water as solution liquid. For considerations about alkalinity of pore solution only
actual concentrations are of interest. Hence, the differences in water-binding of
the different mixtures are neglected.
Whereas in the early stage of hydration the alkalinity of the pore solution
is governed mainly by the hydroxides of the calcium and by the soluble alkalies, it
depends almost exclusively on the sodium and potassium hydroxide content from
an age of 28 days onwards [lo]. The calcium hydroxide has scarcely any
remaining influence on the pore solution alkalinity, as the solubility of Ca(OH)2 in
--``,`,-`-`,,`,,`,`,,`---
alkaline kydroxide solutions is very low (200 m a ) . The calcium concentrations
of the pore solutions were very low as compared to the other ion Concentrations.
The undissolved Ca(OH)2 present as a precipitate in the pore water acts as an
alkali reserve. As long as calcium hydroxide is available as a buffer, the pH value
of the pore solution cannot fall below about 12.5 (pH value for saturated
Ca(OH)2 solutions).
Fig. 4 and 5 indicate the total alkali concentrations in the pore solutions of
hardened cement pastes made up with portland cement and blast-furnace slag
cement. The mixtures with 60 mass-% fly ash in portland cement (PD) and
40 mass-% in blast-furnace slag cement (BD) have a somewhat lower alkali
concentration than the reference mixtures (PC) and (BC) but the ion
concentrations remain nearly constant at all test dates. One reason for the lower
alkali concentrations in the mixtures with fly ash is due to the dilution effect
caused by the substitution of 60 respectively 40 mass-% fly ash for cement. This
effect is partly compensated by the lower w/(c+f) and the surrendering of alkalies
to the pore solution during dissolution of the amorphous fly ash constituents in
the alkaline medium.
The lowest absolute alkali concentrations were found for both cements in
the mixtures with high silica fume contents (Fig. 4 and 5). The very low total
alkali contents already encountered in the pore solution of these mixtures at an
age of 28 days indicate that large amounts of alkali are incorporated in reaction
products by this point. With increasing age, there is a tendency to hrther
reduction of the ion concentrations in the (F'SF) mixture. Given the same
wateríbintler as for the mixtures (PC) and (BC), the substitution of 25 and 15
mass-% of silica fume for portland cement and blast-furnace slag cement
respectively in mixtures (PSF) and (BSF1) entails a mean reduction in ion
concentration by a factor of roughly 10 for total alkali concentration.
The alkali concentration of the mixture with 15 mass-% silica fbme
(BSF1) remains consistently below the total alkali concentration of the mixture

A C 1 SP-153 V O L X I I 75 B 0662949 0523723 T30
with 25 mass-% (BSF2). This is probably due to the significantly higher w/(c+s)
in the (BSF1) mixture.
Fig. 6 and 7 show the time curve for the pH value of the portland cement
and blast-furnace slag cement pore solutions calculated fiom the OH- ion
concentrations. Up to an age of 730 d, the pH value of the pore solution is
significantly higher than 13.5 in the reference mixture (PC) and about 13.5 in the
mixture with 60 mass-% fly ash.
Due to the binding of alkalies in reaction products in mixtures with high
silica fume contents (PSF), already referred to in Fig. 4 and 5, the pH value
decreases significantly during the course of hydration. As long as calcium
hydroxide is available as a precipitate in the pore solution, the pH value cannot
fall below about 12.5. After 365 d, the entire Ca(OH)2 stock in the (F'SF) mixture
has been consumed (Fig. 2); the pH value falls to slightly below 12.5.
Owing to the small quantity of expressed pore solution for the (PDSF)
mixture, it was possible to determine the pH value only at an age of 28 days. At
12.6, it is roughly in the range for a saturated calcium hydroxide solution. No
further Ca(OH)2 was detected in this mixture &er 28 days (Fig. 2).
Substitution of 40 mass-% of fly ash for the same quantity of cement (BD)
also causes only a slight reduction in the pH value as compared to the reference
mixture (BC) (Fig. 7). While the pH value in the reference mixture may be given
as a roughly constant 13.6, it is only slightly lower in the (BD) mixture with 40
mass-% fly ash. If 15 mass-% of silica fume is used, there is a distinct fall in the
pH value between 28 and 91 days (BSF1). Large amounts of alkali are also bound
in this mixture, and are no longer available to maintain a high alkalinity in the pore
solution. After 365 d, the pH value stabilizes at about 12.7. The Ca(OH)2 content
at this time is approximately 2 mass-% in relation to the total binder content, i.e.
an adequate alkalinity reserve is still available in the pore solution at this point.
If the silica fume content in the blast-furnace slag cement is increased to
25 mass-% in the (BSF2) mixture, the pH value of the pore solution falls very
rapidly to 11.7 after 730 days. The entire stock of calcium hydroxide in this
mixture had already been consumed after 28 d, i.e. the alkalinity reserve had been
exhausted (Fig. 2). It is evident that the pH value of the pore solution falls very
rapidly if a reduction in the alkali content of the pore solution and an exhaustion
of the Ca(OH)2 occur simultaneously.
On the basis of these results, depassivation of the steel surface is unlikely
in the mixtures with high fly ash contents but can occur in mixtures with high
silica fume contents after a long hydration period, especially in mixtures with
blast-furnace slag cements at low w/(c+s+f).
Concrete
Compressive Strength -- Table 4 gives the compressive strengths of the

concretes in the test up to a test age of 730 days. At the selected w/(c+f), the
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0 Ob62949 0523724 9 7 7
compressive strengths of the two concretes with 60 or 40 mass-% fly ash in

relation to total binder content P D and HD) are of roughly the same order as
those of tlie reference concretes (PC and BC). They can be assigned to DIN 1045
strength dass 25. The pozzolanic reaction of the fly ash is, however, still
incomplete after 730 d; a further increase in strength may be anticipated.
The two concretes with a combination of 15 mass-% silica fume and 40
mass-% fly ash in the portland (PDSF) and 25 mass-% silica fume in the portland
blast-furnace cement (BSF2) are high-strength concretes according to the
RILEM/CEB/FIP classification. Their compressive strength curves are virtually
identical (Table 4).
-~
Corrosion -- At the very high pH values prevailing in the pore solution of
hardened cement pastes, a dense, continuous oxide film (passive film) is formed
on the surface of the reinforcing steel in the presence of oxygen, almost
completely preventing corrosion of the steel. Destruction of the passive film is
referred to as depassivation. After depassivation, the steel is active, i.e.
susceptible to corrosion. Depassivation of the steel surface occurs e.g. if the
chloride content exceeds a critical limit. As indicated, the pH value of the pore
solution decreases in concretes with high silica fume contents. If chloride is
added, the ratio of free chloride content to inhibiting hydroxile ion content in the
pore solution may exceed a critical limit. This effect may be compensated by the
refinement of pore structure during pozzolanic reaction of the silica fume in high
strength concretes, leading to increased electrolytic resistance.
In order to quant@ the influence of electrolytic resistance on cell current,
the cell currents for the geometries of the concrete corrosion cells in the tests
(Fig. 1) and for cell voltages between 50 and 300 mV were calculated as a
function of electrolytic resistance. To simpliQ the computation method according --``,`,-`-`,,`,,`,`,,`---
to [i i], the influence of the anodic reaction was not taken into account. For the
purposes of computation, a free corrosion potential of 200 mV/H was assumed
for the cathode (platinum-coated titanium rod, surface area 150 cmz). The
remaining description of the cathode according to [ 11J is defined by the exchange
current density io = -0.10 pA/cm*and the penetration factor a = 0.20.
The result for the range of resistances fiom 10 R to 100 kt2 is shown
logarithmically in Fig. 8. As expected, the cell currents fall significantly as the
electrolytic resistance increases. Due to the effect of the electrolytic resistance, a
voltage drop occurs between the anode and the cathode in the concrete (Fig. 8,
centre). At extremely high electrolytic resistances in the 10 kR range almost the
entire voltage drop occurs in the concrete, with negligibly small cell currents,
virtually ruling out corrosion. If the voltage drop in the concrete is related to the
cell voltage, a so-called resistance control, i.e. the influence of electrolyte
resistance on cell current, is obtained (Fig. 8, bottom). According to [i 11, these
values apply solely to non-polarizable anodes and consequently represent upper
limits. If the anode is taken into account, resistance control values decrease
accordingly.

A C 1 SP-353 V O L X I I 95 = 0662949 0523725 803
To control this theoretical computation, test specimens with different

electrolytic resistances should be prepared. Due to the fact that increasing
chloride contents lead to a significant decrease in electrolytic resistance chloride
content was chosen 1.5, 3.0 and 5.0 mass-% related to cement content. To
indicate the range in which the tested corrosion cells lie, the determined
electrolytic resistances and associated chloride contents have been plotted in Fig.
8. This result signifies that the cell current for the tested high strength mixtures is
controlled chiefly by electrolytic resistance. The electrolytic resistance drops
sharply with increasing chloride content. Addition of 1.5 % chloride in relation to
cement content already means a 90 % resistance control. Assuming a resistance of
roughly 100 kR for a chloride-free mixture with pozzolanic admixtures, a cell
current of between 0.5 and 1.0 pA may be calculated. Mainly because of their
pozzolanic reaction, the addition of fly ash and silica fume produces a finer pore
structure in hardened cement pastes, significantly diminishing the transportation
rates of the ions involved in the corrosion processes.
The relationship between cell current and the electrolytic resistance of the
concrete as a function of its chloride content is depicted in Fig. 9. It is apparent
that only very small cell currents are detected from a chloride content of 1.5
mass-% downwards. A comparison of the calculated cell currents (Fig. 8, top)
with the measured values in Fig. 9 indicates good agreement between the two.
The associated corrosion process is controlled largely by the electrolytic
resistance of the concrete. A further reduction in chloride content, to values
below 1.0 %, cannot be regarded as useful with the present test Set-up, since the
available measuring equipment would no longer be able to detect the expected
cell currents with sufficient accuracy.
--``,`,-`-`,,`,,`,`,,`---
CONCLUSIONS
The results of the test series may be summarized as follows:

The absolute Ca(OH)2 content is reduced significantly by the lower
cement content in mixtures with high fly ash contents and by the pozzolanic
reaction. The pozzolanic reaction rate falls as the pore structure becomes finer
due to newly-created reaction products, greatly slowing the consumption of
calcium hydroxide. The replacement of 60 mass-% of portland or 40 mass-% of
blast-furnace slag cement by the same amount of fly ash leads to no significant
change in the alkalinity of the pore solution over the test period of 730 days. The
pH value is about 13.5, excluding depassivation of the steel.
The point of time when no calcium hydroxide is found in mixtures with
silica fume strongly depends on the waterhinder, silica fume content and type of
cement. Reducing the portland cement clinker content in mixtures with high silica
fume contents by the use of blast-furnace slag or by the substitution of high
amounts of fly ash leads to a rapid exhaustion of Ca(0H)z. Substantial quantities
of alkali are bound in reaction products, pH values fall below 12.0. A tendency

A C 1 SP-153 V O L + I I 95 E 0662949 0523726 7 4 T
towards further reduction of pH values with increasing hydration time is to be

expected; hence depassivation of the steel surface may occur without adding
chloride.
The corrosion risk may increase because of the reduced amounts of
alkalies in the pore solution and the complete exhaustion of the alkalinity reserve
in hardened cement paste with high silica fume contents. The theoretical
computation of the corrosion process corresponds well with the measured values
of corrosion current. Neglecting the anode polarization, it was shown that with
such high electrolytic resistances the corrosion process is already 90 YOresistance-
controlled at a chloride addition of 1.5 %.
The reduced alkalinity in silica fume concretes must be weighed against a
significant refinement of pore structure through the rapid pozzolanic reaction of
the silica fume, increasing the electrolytic resistance of the concrete and hence
reducing corrosion rates to possibly negligible values.
FURTHER INVESTIGATIONS
Ac the pozzolanic reaction rate of fly ash falls degressively with increasing
hydration time, long-term tests will be necessary in order to determine whether
and if so at what point the alkalinity reserve of Ca(OH)2 in the pore solutions of
--``,`,-`-`,,`,,`,`,,`---
hardened cement pastes with high fly ash contents is exhausted. It will also be
necessary to determine whether alkalies are bound by reaction products at a later
stage, reducing the pH value of the pore solution.
In tests so far carried out on the corrosion behavior of the reinforcement
in concrete with high pozzolana contents, it was not possible to clarifi the critical
chloride content using the chosen test set-up for the concrete corrosion cells. A
further reduction of chloride content to values below 1.0 % is not useful with the
present Set-up, since the equipment is not capable of detecting the cell currents
with sufficient accuracy.
Current-voltage curves could help to answer the question of critical
chloride content. Preliminary tests on the existing specimens indicate that the
method is fundamentally feasible. Owing to the high electrolytic resistances
concerned there will, however, be polarization problems. Further investigations
along these lines are in preparation.
ACKNOWLEDGEMENT
The authors wish to express their appreciation of the financial support received
from the German Institute for Construction Engineering (DIBt) in Berlin in
carrying lout their research.

A C 1 SP-153 VOL*II 95 I0662749 0521727 686 9
REFERENCES
1. Page, C.L.: Nature and Properties of Concrete in Relation to Reinforced

Corrosion. Aachen : Institut f i r Bauforschung, Ibac, 1992 - In: The
Corrsion of Steel in Concrete - A Short Course to be Offered at two
Locations, 7- 19 February 1992 in Aachen, 26 Seiten
Härdtl, R.: Effect of the Combination of Slag Cements and Fly Ash on the
Pore Structure of Cement Mortars. Istanbul : Canmet/ACI International
Conference, 1992.- In: Fourth Canmet/ACI International Conference on
Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete. Suppl.
Papers, Istanbul, May 1992, S. 1005-1022 (Editor: V. M. Malhotra)
Sellevold, E.J. ;Bager, D.H. ;Klitgaard Jensen, E. ;Knudsen, T.: Silica

Fume - Cement Pastes : Hydration and Pore Structure. Trondheim : The
Norwegian Institute of Technology, NTH. - In: Division of Building
Materials, Report No. 82.610 (1982), S. 19-50
4. Huang, Cheng-Yi ; Feldman, R.F.: Influence of Silica Fume on the

Microstructural Development in Cement Mortars. In: Cement and
Concrete Research 15 (1985), S. 285-294
--``,`,-`-`,,`,,`,`,,`---
5. Zhang, M.-H. ; Gj0rv, O.E.: Effect of Silica Fume on Cement Hydration

in Low Porosity Cement Pastes. In: Cement and Concrete Research 21
(1991), Nr. 5, S. 800-808
6. Page, C.L. ;Vennesland, O.: Pore Solution Composition and Chloride

Binding Capacity of Silica-Fume Cement Pastes. In: Materiaux et
Construction 16 (1983), Nr. 91, S. 19-25
7. Gouda, V.K. ; Halaka, W.Y.: Corrosion and Corrosion Inhibition of

Reinforcing Steel - I: Immersed in Alkaline Solutions. II: Embedded in
Concrete. In: British Corrosion Journal 5 (1970), Nr. 5, S. 198-208
8. Sybertz, F. ; Wiens, U.: Effect of fly Ash Fineness on Hydration

Characteristics and Strength Development. London : Elsevier Applied
Science, 1991.- In: International Conference on Blended Cements in
Construction, Held at The University of Sheffield 9-12 September 1991
(Swamy, R.N. (Ed)), S. 152-165
9. Marsh, B.K.: Relatationships Between Engineering Properties and

MicrosttucturalCharacteristics of Hardened Cement Paste Containing
Pulverized-Fuel Ash as a Partial Cement Replacement. Phd Thesis the
Hatfield Polytechnic ;Cement and Concrete Association, 1984

A C 1 SF’-153 VOL*II 95 0662949 0521728 512
10. Gunkel, P.: Die Zusammensetzung der flüssigen Phase erstarrender und
erhärtender Zemente. In: Beton-Informationen 23 (1983), Nr. 1, S. 3-8
1 1. Raupach, M.: Zur chioridinduzierten Makroelementkorrosion von Stahl in

Beton. Berlin : Beuth. - In: Schrifienreihe des Deutschen Ausschusses fur
Stahlbeton (1992), Nr. 433, Dissertation
TABLE! 1 - CHEMICAL AND GRANULOMETRIC PROPERTIES OF

BASE MATERIALS
Item Unit Ce ent
PC BFSC7)
- Si02 25.9 47.1 91.1

- A1203 7.03 26.9 0.14
- Fe203 1.99 9.26 3.65
- Ca0 53.6 4.26 1.09
- MgO 3.77 2.28 1.02
- K20 0.74 3.31 0.60
- Na70 O. 19 1.19 0.42
0.68 3.37 0.8 1
2.25 1.77 0.53
- Ckbon Content n. d. 0.80 1.25
1.89 1.93 1.96
Granuloinetq
- Density 3050
384
- Specific Surface, BET n. d. n. d.
n. d.: not determined

1) 5 0 Mass-% Blast-Fumace Slag
2) Fly Ash fiom Dry Bottom Fumace
3) Data Related to LOI-Containing Substances
4) Test Results fiom Quality Control
Clinker Compositionof PC (Bogue): C3S = 62,3 Mass-%

c2s = 9,6 Mass-%
C3A = 8,8 Mass-%
c4AF = 9,5 MES-%
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLxII 95 0662949 0523729 459 m
TABLE 2 - MIXTURE COMPOSITION AND ABBREVIATIONS FOR

HARDENED CEMENT PASTES
--``,`,-`-`,,`,,`,`,,`---
1O0
PD PC
PSF PC 75 O
PDSF I PC x x 40 I 15 I I
0.23 0.50
BC I BFSC I - I - 100 I 0 1 O 1 0.60 I 0.60
1) D: Fly Ash
3ì qF. Ciliri Riirne
TABLE 3 - MIXTURE COMPOSITION AND FRESH CONCRETE

PROPERTIES OF CONCRETES
1) SF: SilicaFume
2) D: Fly Ash
3) Liquid Content of Superplasticizer included
4) A Aggregate: Sand-Gravel Mixture
TABLE 4 - COMPRESSIVE STRENGTH OF CONCRETES

(CUBES, 150 mm)
Mixture Compressive strength at
No. (c+s+f) 7d I 28d I 91d I 182d I365d I730d
i) n. d.: not determined

A C 1 SP-253 VOL*II 95 0662949 0521730 2 7 0
TABLE 5 - CALCIUM HYDROXIDE CONTENT IN HARDENED

CEMENT PASTE
Calcium hydroxide Content
2d I 7d I 28d 156d I 91d I 182d I365d 1730d
I
14.21 18.6s 21.59

-
5.90
3.14
PDSF 1.82 1.12 -0.09
8.70 8.67 11.37 10.76
BD 5.07
BSF 1 4.56
BSF2 1.47 0.98 -0.00 0.00
1) I): Fly Ash

2) S: SilicaFume
TABLE: 6(a) - PORE SOLUTION COMPOSITION OF HARDENED

CEMENT PASTE
Mixt. C/D1)/S2) y Age pH- Ion Concentration in Pore Solution
NO. (c+s+f) d Value Na+ I K+ I Ca" I S042- I OH- I CI-
11.1
5.8 I 332
346 I 1.9
1.9 I
3.8 325
n. d. n.d.

1) D: Fly Ash
2) S: SilicaFume
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m 0 b b 2 9 4 9 0 5 2 1 7 3 1 007 W
TABLE 6(b) - PORE SOLUTION COMPOSITION OF HARDENED

CEMENT PASTE (CONTINUATION)
Mixt. C I DI)I S2)
No.
Mass-%
BC 100 I o I o
BD 60 I40 I O
BSFI 8510115
BSF2 7510125 0.34 12.73

23.9

1) D: Fly Ash
2) S: SilicaFume
iside view
q.-o
front view
S?f 16 St-37, i = 300 mrn

16 platinized titanium, I = 300 mrn
top view
50 I 300 I 50
400 all dimensions in mm
Fig. 1-Test setup for reinforcement corrosion tests
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-,353 VOLaII 95 O 0662949 0523732 T 4 3 O
CaiOH), in g/lOOg solids (c+s+f)

25
20
15
10
O . .
O 2 7 28 56 91 182 365 730
age in days (-/I
Fig. 2-Development of calcium hydroxide content Ca(OH), for

hardened portland cement paste with high pozzolan contents
Ca(OH)2 in g/lOOg solids (c+s+f)
--``,`,-`-`,,`,,`,`,,`---
BC 0.60 100 O 0
BO 0.48 60 40 O
BSFl 0.60 85 0 15
0SF2 0.34 75 O 25
O 27 28 56 91 182 365 730
age in days (4)
Fig. 3-Development of calcium hydroxide content Ca(OH), for

hardened blast furnace slag cement paste with high pozzolan contents

A C 1 SP-I153 V O L X I I 95 0662949 0 5 2 3 7 3 3 98T D
concentr. 'of total alkali (Na' and K') in mmol/l
400 - 20 OC
350 i
A A
300 - -
L
250 -
I
-
50 - 0.60 1 75 I O I25
" 8
O 28 91 365 730
age in days (4)
Fig. &Total alkali concentration (Na' and K') in pore solutions from
--``,`,-`-`,,`,,`,`,,`---
hardened portland cement paste with high pozzolan contents
concentr. of total alkali [Na' and Ki) in mmol/l

450
400
350
300
250
addition
200 No.
C+S+f pfa sf
150
- i-] im.%l Im.%l
100 BC
BO
50 BSF1 0.60 85 O 15
O -
BSF2 0.34 O 25
Fig. +Total alkali concentration (Na+ and )

'K in pore solutions from
hardened blast furnace slag cement paste with high pozzolan contents

A C 1 SP-L53 V O L J I I 95 B Obb29Y9 0523734 8 L b =
calculated pH
14.0
W addition
-____
-
C+S+f
-
1-1
0.60
11.5 o. L2
PSF 0.60
11.0 -
v PDSF 0.23
O 28 91 365 730
age in days [JI
--``,`,-`-`,,`,,`,`,,`---
Fig. 6-pH-value of pore solution from hardened portland cement

paste; calculated from measured OH- ion concentration
calcvlated pH
14.0
13.5
13.0
12.5
12.0
11.5
11.0
O 28 91 365 730
age in days I-/)
Fig. 7-pH-value of pore solution from hardened blast furnace slag

cement paste; calculated from measured OH- ion concentration

A C 1 SP-153 voL*II 75 Obb2749 0523735 752
760 Wiens, Breit, and Schieccl
macrocell current in VA
500
400 area =
300
200
1O 0
potential drop in concrete in mV

300
250
200
150
1O0
50
resistance control in YO
IO0
90
--``,`,-`-`,,`,,`,`,,`---
80
70
60
50
40
30
O 0 o
20
N
10
O
io 1O 0 I000 1O000 100000
electrolytic resistance in ohm [log]
Fig. 8-Relationships between electrolytic resistance and cell current

calculated for geometry of concrete corrosion cell

A C 1 SP-I153 VOL*II 95 0662749 0523736 699
macrocell current in FA
t rn PDSF
20 i,
5.0 % chloride
BSF2
3.0 % chloride
5 .- I.5% chloride -
O- I
IO00 IO000 100000

electrolytic resistance in ohm
Fig. &Results of cell current measurements as function of electrolytic
resistance at age of 350 days
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 75 0662949 0523737 525
SP 153-40
Moisture Diffusivity of Fiber

Reinforced Silica Fume Mortars
by E. Denarié and Y. F. Houst
Synousii :The moisture diffusivity is of considerable importance for quantitative

assessments of creep and shrinkage as well as durability of cementitious material.
For this reason, the influence of the composition of repair mortars on their
effective: moisture diffusivity as a function of the relative humidity of the
surrounding air has been investigated. Silica fume, superplasticizer and
polypropylene fibers have been added in order to reduce the permeability and to
control (cracking induced by drying shrinkage. It has been shown that the
moisture transport in cementitious materials can be realistically described by a
non-lineiu diffusion process governed by Fick's law. A computer program based
on the finite volume method has been used in order to get the best effective
moisture diffusivity by comparing experimental results (moisture losses of
drying mortar cylinders) with the numerical solution. The applicability of a
combined experimental-numerical approach to characterize repair mortars
regarding their moisture diffusivity has been demonstrated. The material
properties necessary for the characterization and qualification O€ new materials
can be found numerically. Moreover, the diffusivities obtained provide useful
input data for further numerical calculations. The positive effect o€ the addition of
silica fume on the moisture diffusivity was clearly shown. The positive
combined effect of polypropylene fibers and silica fume with increasing entrained
air content was observed. Finally, no significant detrimental effect on the
addition of fibers (even at relatively high volumes) has been observed for
materials cast under shrinkage free conditions.
Keywords: Diffusivity; drying; moisture content; mortars (material);

polpropvlene fibers; repairs; silica fume
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L * I I 95 0662949 0523738 461
764 Danarié and Houct
Emmanuel Denarié, a civil engineer, is research engineer at the Laboratory for

Building Materials, Federal Institute of Technology, Lausanne, Switzerland.He
is currently working on the development of new testing methods for fiber
reinforced cementitious materials.
AC1 member Yves F. Houst, a chemist, dr. ès sciences, is the Head of the
Cement Group of the Laboratory for Powder Technology, Federal Institute of
Technology, Lausanne, Switzerland (EPFL). He is involved in various research
programs related to properties of cement, suspensions, admixtures and durability
of cementitious materials. He is also a lecturer at the EPFL.
INTRODUCTION
--``,`,-`-`,,`,,`,`,,`---
The number of defects detected on concrete surfaces in buildings or

highway bridges has increased dramatically in the last few years. Most often,
these defects are due to spalling of the concrete cover produced by the corrosion
of the reinforcement. As a consequence, the demand for repair mortars able to
restore the protection of the reinforcement and give a second life to the damaged
structures is growing significantly. The properties required for these materials are
somewhat contradictory such as a very high compactness (to limit the penetration
of aggressive substances like water, COZ,0 2 . chlorides..) and at the same time
the ability to withstand thermal stresses and to provide sufficient bonding to the
old concrete without cracking (which means for instance a low elastic modulus,
i.e. a good strain compatibility with the base concrete).
Beside the use of polymer modified mortars, the addition of very fine
pozzolanic-fillers such as silica fume has proven to be highly efficient in reducing
the moisture diffusivity and the penetration of dangerous substances.
It has been shown in a previous study (1) that tensile stresses higher than
the intrinsic strength of the material could appear in the neighborhood of the
concrete-mortar interface, depending on drying conditions. In that same study, it
was also shown that the first week after the application of a repair mortar, is
critical for the risk of cracking due to drying shrinkage. Thus, the curing
conditions are particularly important and the drying shrinkage is partially
dependent on the moisture diffusivity.
From the law of mixtures, one possible solution to decrease the elastic
modulus and thus increase the elasticity is to add low or zero modulus materials
such as entrained air or polypropylene fibers. Unfortunately, due to the relatively
low quantities that can be added to normal mortars, the fibers cannot contribute in
a significant way to the decrease of the elastic modulus. Nevertheless, synthetic
fibers are known to act as a reinforcement of the microstructure of the cement
paste at early ages by preventing and distributing internal stresses (due to plastic
shrinkage, to bleeding, etc.), thus decreasing the permeability of concrete
surfaces.
Consequently, it appears that a suitable mix for repair mortars could be
sought in the mixture of silica fume + synthetic fibers + entrained air.

A C 1 SP-353 V O L X I I 95 m 0662947 0523739 3T8 m
The aim of this study was to investigate the effect of the addition of silica
fume with or without synthetic fibers on the moisture diffusivity for several
repair mortars including air-entrained ones. It is part of an ongoing research
program on repair mortars for concrete ( 1,2).
--``,`,-`-`,,`,,`,`,,`---
MOISTURE DIFFUSION IN CEMENTITIOUS MATERIALS
Theory
In cementitious materials, there is continuous transfer in the form of water

vapor arid condensed water. The transport of liquid water is slow enough to be
purely laminar and can be described by Hagen-Poiseuille’s law. In the general
case, the porous materials are not saturated and several mechanisms can take
place sirnultaneously.If the pore dimensions are smaller than the mean free pathi
of water molecules, Knudsen’s diffusion takes place. In larger pores, where the
mean free path of gas molecules is smaller than the pore diameter, normal gas
diffusion predominates. In pores of intermediate size, Knudsen and normal
diffusion occur at the same time. In addition to these two mechanisms, surface
diffusion also can occur at the same time. But, there are some indications that
surface diffusion is a mechanism of only secondary importance in inorganic
building materials (3).
Despite the complicated transport mechanisms which occur in materials
such as cement paste or mortar, moisture diffusion can be described by Fick’s
second law which describes the continuity of the moisture flow through an
infinitely small material layer. In the unidirectional case with w being the local
water content and D(w) the corresponding effective diffusion coefficient or
diffusivity, one gets:
The diffusivity D is an unknown function of the water content w and thus

equation (1) has to be solved numerically in the general case.
For concrete-like materials, the diffusivity can be dramatically modified
by the porosity (size and distribution of the pores and of the microcracks) of the
cement paste and of the interfacial zones. The addition of silica fume reduces the
porosity in several ways. Firstly, the silica particles are on average ten to twenty
times smaller than the cement grains and thus they extend the particle size
distribution of cement in the range of very fine grains providing a better
geometrical packing. Secondly, their very high specific surface (almost one
hundred times that of cement) and their high content in amorphous Si02 make
them a very reactive pozzolan. Finally, these two effects are combined during the
formation of the microstructure of hydrated cement paste (hcp), where the
1 The distance a molecule travels between collisions. This distance is 1.7.10-7 m at 20°C and
1 atm for a water molecule.

A C 1 SP-153 VOL*II 95 0 b b 2 9 4 9 0523740 OLT 9
766 Danarie and Houst
pozzolanic reaction fills voids with dense C-S-H gel and consumes the porous
calcium hydroxide.
Synthetic fibers such as polypropylene have a lower elastic modulus than
--``,`,-`-`,,`,,`,`,,`---
hcp. For this reason, their action on the control and redistribution of internal
stresses is mostly limited to early ages, when their modulus is still higher than
that of the cementitious matrix. Nevertheless, many phenomena such as plastic
shrinkage, bleeding, autogeneous shrinkage, occur during this period which can
dramatically influence the physical and mechanical properties of the material
surface and especially the moisture diffusivity . Provided that the specimens are
submitted to restrained shrinkage, several authors have shown the positive'effect
of polypropylene fibers on the crack distribution and width (4).
Numerical Simulation
Various forms of the diffusivity have been found to be realistic; for instance the
exponential type used by Mensi et al ( 5 ) , described by two parameters or the S
shape type from Bazant and Najjar (6) which better describes the moisture flow
at high water contents but includes four parameters.
One possible approach to get an estimation of the diffusion coefficient is
to use a numerical simulation of drying experiments where D(w) is assumed to
follow a simple function (for instance exponential) completely defined by a set of
parameters (pi, p2, ...). These parameters are determined by fitting the numerical
drying results to the measured drying data (7). The best fit is obtained by
successive iterations.
The code used for the simulation of the drying experiments was
developed by Sadouki (8). It calculates, by means of the finite volume method,
the drying of cylindrical specimens with any boundary conditions. In this case,
the perimeter of the cores was sealed and drying occurred only uniaxially.
The transport driving force is input by means of the initial water content
(at saturated state) wo and the final water content (at equilibrium with the external
relative humidity RH)wb.
wb was determined through extrapolation of the experimental drying
curves (by fitting to a bi-hyperbolic function of time, see 4.2). The diffusion
coefficient can be any differentiable function. For this simulation, the following
function was chosen:

A C 1 SP-153 V O L X I I 95 Ob62949 0523743 T5b
EXPERIMENTAL
.-Materiais
Normal portland cement (PC) from the plant at Eclépens (Switzerland)

was of ASTM C150 type I, with fineness defined by specific surface area 290
m2kg (Blaine). The silica fume (SF) was imported from Germany2 in a gray
powder form slightly densified. The silica content was 96.5 % of amorphous
silica, the BET specific surface area was 20'000 to 22'000 m2/kg, and the
density :!'200 kg/m3.
The sand (0-3 mm) from a glacial moraine was composed of 80 % of
rounded shape particles and 20 % crushed. Mineralogically, this sand was
composed of 40 to 46 % calcite, 29 to 32 % quartz, 8 to 13 % residue of
crystalline rocks of multimineral composition, predominantly quartzitic, and 12
to 18 % of composite grains, essentially quartzitic. The grading curve of the sand
was already given in (2).
For all the mortars, one superpla~ticizer~,
consisting of sulfonated
melamine formaldehyde condensate, has been used. For certain mortars, one air-
entraining admixture4, has also been used.
ï h e collated fibrillated polypropylene fibers5 were 19 mm long. The
density was 920 kg/m3, the elastic modulus was 5 GPa and the tensile strength at
least 0.5 GPa.
Mortars
The cement content of the mortars varied from 468 to 556 kg/m3 with
C+SF ranging from 515 to 556 kg/m3. W/(C+SF) was kept constant at 0.41 and
C/A at 0.37 to 0.38 (W, C, SF and A being respectively the water, cement, silica
fume and aggregate content by mass). The consistency, defined by the spread
value, was about the same, i.e. between 120 and 150 mm. The composition of
the mortars is given in Table 1. Nine different mortars were prepared. The
mortars 1 to 3 contained 10 % silica fume relative to the mass of cement. These
mortars differed only from one another in the quantity of the superplasticizer and
the air-entraining admixture. The mortars 4 to 6 had the same composition as the
mortars 1 to 3, except a fiber content of O. 1 % by volume. The mortars 7 to 9 do
not contain any silica fume. In order to keep the volume of binder constant, the
silica fu:me was replaced by an equivalent volume of cement. The fiber content
was varied from O to 0.6 % by volume (which is the practical limit from the
point of view of the workability of the fresh mix for this type of fiber). It was not
possible to increase this amount and maintain a constant consistency. The
consistency of these mortars was regulated by using the superplasticizer only.
Trademark: V.A.W. RW Füller.

Trademark: Sikament 320.
Trademark: Sika Fro V5.
Trademark: Forta, type AS.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 0662747 0521742 992
The binder content was chosen according to Caquot’s formula6, which relates the
minimum cement content to the maximum grain size of the aggregate, necessary
to give a compact mortar or concrete. For a Dm,, of 3 mm, the calculated
minimum cement content Cmin is 482 kg/m3.
The total mass of ingredients for a batch was 26.7 kg. The preparation of
a fiber reinforced mortar was carried as follows:
- mixing of sand, cement, and silica fume if used, for 2 min.
- addition of water.
- addition of admixtures.
- addition of fibers (if needed) and final mixing for 3 to 7 min, depending
on the fiber content.
--``,`,-`-`,,`,,`,`,,`---
The mortars were cast into molds to prepare slabs 500x400~40mm3. The
slabs were cured at RH > 95 % and 20°C for 28 days. The slabs were free to
deform (except for friction at the mold surfaces), in order to test the pure material
behavior of the mortars independently of the structural related cracking due to
restrained shrinkage. The aim was to evaluate the possible detrimental effect of
the fibers added as an inclusion on the diffusivity and see how it was affected by
the addition of silica fume and/or entrained air.
Phvsical and Mechanical Properties of the Mortars
The bulk density of the fresh mortar was calculated after having measured
the mass of one liter of mortar.
The air content was measured by the pressure method which allowed us,
after calibration of the apparatus, to read the percentage of air directly.
The consistency of the mortar was measured with a flow table in
accordance with Swiss Standard SIA 115. This equipment is close to that
described in ASTM Standard C 230. The mean diameter of the mortar specimen
measured in two perpendicular positions, after it has been spread by the
operation of the table, represents the spread value.
Three prisms 40x40~160mm3, which had been sawn from the slabs,
were used to determine the flexural strength. They were tested in 3 points
bending with a span of 100 mm. After the tests, the two parts of the prisms were
used for the determination of the compressive strength.
Drying Experiments
For these experiments, cores of mortars of 50 mm diameter and 38 mm

length drilled from the slabs were used. Then, these cores were saturated with
water under vacuum and their mass measured by weighing. The cores were

A C 1 SP-I153 VOL*II 95 0662949 0523743 829
placed into synthetic rubber tubes so that the cylinders of mortar could dry only
axially. They were immediately transferred into a glove box at 55 % RH and
2OOC. The mass of the specimens was recorded as a function of time. After the
measurements, the tubes were removed and the cylinders of mortar dried at
105°C and weighed in order to calculate their maximum water content, Le. their
open porosity which corresponds to water saturation data.
Phvsical and Mechanical ProDerties
The compressive and flexural strengths as well as the bulk densities are
given in Table 1.
The addition of fibers has only a slightly detrimental effect on the flexural
strength. This is probably due to additional defects introduced by the air-
entraining admixture together with fibers.
The adjunction of entrained air at high content decreases in a significant
way the compressive strength (mortars 1, 2, 3 and 4, 5 , 6), but not the flexural
strength. This could be expected as the flexural strength is mostly determined by
a very srnall zone where stresses are maximum (outer border of the specimen),
the compressive strength however is measured on almost the whole volume of
the specimen.
The positive effect of silica fume on compressive and flexural strengths is
all the same very clear as expected.
Drying Curves
The drying of 4 specimens of each mortar has been recorded as a function

of time. The results are represented graphically in Fig. 1 to 5. Each experimental
point of the curve is the mean value of 4 measurements. In order to estimate the
asymptotic value of the water loss, which is required as an input value for the
numerical simulation, the following function was fitted to experimental data:
Am
-=- alt I agt
(3)
m a2+t a4+t
were Andm is the water loss, t the time and al, as, a3, aq parameters. The sum of
parameters ai and a3 is equal to the final water loss (t=-), Le. the equilibrium
water content. The parameters al to aq are given in table 2 and the corresponding
calculated curves are represented by solid lines in Fig. 1 to 5.
?'he presence of fibers always reduces the water loss as a function of
time. That means that the evaporable water at 55% RH of saturated mortars, the
sum of ;a1 and a3, is always lower for mortars with fibers (Fig. 1 and 2). The
effect of silica fume is the same with or without fibers (Fig. 3 and 4). The
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 m O662747 0523744 765 m
770 Danarié and Houst
evaporable water of mortar 1 (with silica fume) is hardly higher than that of
mortar 7 (without silica fume). This could be an inaccuracy due to the
extrapolation of the asymptote of the drying curve. On the other hand, one can
see that the bi-hyperbolic function of equation 3, represented by solid lines in
Fig. 1 to 5, fits the experimental data very well. This indicates that the choice of
the function, which is purely empirical, was adequate. Therefore, a better
evaluation of the asymptotic value could be obtained by measuring the drying
loss for a longer time.
Diffusivity
The diffusivity was obtained by means of numerical simulation of the

--``,`,-`-`,,`,,`,`,,`---
drying experiment. The fit was performed iteratively by slightly changing the
parameters pl and pz of the diffusivity function, until a satisfactory visual
matching of the numerical results with the experimental data was reached. The
procedure was the same for the nine mortars. An example of a typical fit obtained
is given in Fig. 6.
Table 3 summarizes the values of the parameters pl and p2 which gave
the closest fit while Fig. 7 shows the diffusivity obtained by the numerical
simulation for all the mortas tested.
From these curves, several trends can be distinguished. First, the addition
of silica fume has a marked effect in reducing the diffusivity for all the mixes.
Secondly, the addition of fibers together with silica fume shows very small
(mortars 1 and 4) or no differences (mortars 2 and 5 ) in the moisture diffusivity
of zero to medium content of entrained air. Conversely, a maximum effect in the
case of the highest content of entrained air (mortar 3 and 6 ) is observed. In fact,
with increasing entrained air content, the effect of the addition of fibers together
with silica fume on the diffusivity changes gradually from slightly detrimental to
no effect and finally a very clear positive effect, even providing the lowest
diffusion coefficient of all the tested mixes. This effect cannot be explained by
existing results. Further investigations are necessary to confirm this trend.
Finally, the effect of the addition of fibers to mortars without silica fume
is slightly detrimental on the diffusivity. More important, no difference can be
observed between the usual fiber content (O. 1 vol. % ) and the maximal one (0.6
vol. %). This tends to suggest that the difference is more likely to come from the
mixing and casting operations, which are less easy with high fiber content, than
from a detrimental effect of the supplementary interfacial zones introduced by the
fibers.
CONCLUSIONS
In this study, the applicability of a combined experimental-numerical

approach to characterize repair mortars regarding their diffusivity has been
demonstrated.
Besides standard drying experiments, the numerical simulation enables
one to determine a diffusivity by fitting calculated drying results to the

A C 1 SP-153 VOL*II 95 m Obb2949 0 5 2 3 7 4 5 bTZ m
experimental data. In this way, the material properties necessary for the
characterization and qualification of new materials can be found numerically.
Moreover, the diffusivities obtained provide useful input data for further
numerical calculations.
The positive effect of the addition of silica fume on the moisture
diffusivity was clearly shown.
--``,`,-`-`,,`,,`,`,,`---
The positive combined effect of polypropylene fibers and silica fume with
increasing entrained air content was observed.
Finally, no significant detrimental effect of the addition of fibers (even at
relatively high volumes) has been observed for materials cast under shrinkage
free conditions.
REFERENCES
1. Jaquerod, C., Alou, F., and Houst Y.F. Nondestructive testing of Repair
“
Mortars for Concrete”, Proceedings of the 3rd International Colloquium on

Materials Science and Restoration, (F.H. Wittmann, Ed.), Expert Verlag,
1993. Vol. 1, pp. 872-888.
2. Alou, F., and Houst, Y.F. “ Repair Mortars for Concrete Exposed to Freeze-
Thaw and Deicer Salts”, 4th CANMET/ACI InternationalConference on Fly
Ash, Silica Fume, Slag and Natural Pozzolans in Concrete“,Istanbul,
Turkey, 1992, Supplementary Papers, pp. 33 1-350.
3. Quenaxd, D., and Sallée, H. “Water Vapour Adsorption and Transfer in
Cement-Based Materials: a Network Simulation”,Materials and Structures,
Vol. 25, 1992, pp. 515-522.
4. Bentur, A., and Mindess, S. “Fiber Reinforced Cementitious Composites”,
Elsevier Applied Science, London and New-York, 1990, pp. 334.
5. Mensi, R., Acker, P., and Attolou, A. “ Séchage du béton: analyse et
modélisation”, Materials and Structure, Vol. 21, 1988, pp. 3-12.
6. Bazant, Z.P., and Najjar, L.J. “Non Linear Water Diffusion in Non Saturated
Concrete”, Materials and Structures, Vol. 5, Number 25, 1972, pp. 3-20.
7. Wittmann, X., Sadouki, H., and Wittmann F.H. “Numerical Evaluation of
Drying Test Data”, Trans. 10th SMIRT (A.H. Hadjan, Ed.), Anaheim, CA,
USA, 1989, Vol. H, pp. 71-79.
8. Sadouki, H., Personal Communication, 1994.
ACKNOWLEDGMENT
The authors wish to thank dr. H. Sadouki for having provided them with
a part of his computer code and for his valuable advice on numerical problems.

A C 1 SP-1-53 VOL*II 95 m Obb2949 0 5 2 L 7 4 b 538 =
TABLE 1 - COMPOSITION AND CHARACTERISTICS OF MORTARS
Mortar No 1 2 3
Sand [kg/m3] 1443 1421 1405
Cement [kg/m3]
Silica fume [kg/m3]
Water [kg/m3]
48 1
48
216
474
47
213
1 468
47
21 1
I
Superplasticizer [kg/m3] 12 8
Air-entr. adm. [kg/m3]
~- ~
O 1
Fibers [L/m3] O
Bulk dens. ikg/m31 2200
Air [vol. %j
Spread [mm] 140 140
W/(C + SF) 0.41 0.4 1
59.2 56.0 49.2
F. strength ïMPal** 9.7 8.4
Mortar No 4 5 6
Sand [kg/m3] 1443 1421 1405
Cement [kg/m3] 48 1 474 468
Silica fume [kg/m3] 48 47 47
Water [kg/m3] 216 213 21 1
Superplasticizer [kg/m3] 12 8 7
Air-entr. adm. [kg/m3] O 1 2
Fibers [Um31 1 1 1
Bulk dens. [kg/m3] 220 1 2165 2141
Air [vol. %] 6.4 7.9 8.9
spread [mml 135 135 135
W/(C + SF) 0.41 0.41 0.4 1
C. strength [MPa]* 62.2 59.2 50.7
F. strength [MPa]** 9.0 9.3 9.1
Mortar No 7 8 9
Sand [kg/m3] 1444 1445 1464
Cement [kg/m3] 549 549 556
Silica fume [kg/m3] O O O
Water [kg/m3] 225 225 228
Superplasticizer [kg/m3]
Air-entr. adm. [kg/m3]
Fibers [L/m3]
Bulk dens. [kg/m3]
Air [vol. %]
Spread [mm]
W/(C + SF)
6 10
i:
n
-1 15
i ?n
C. strength iMPal** 51.9 52.0 55.5

F. strength [MPaj**
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I I 95 = 0662747 0523747 474
TABLE 2 - PARAMETERS a, TO a4 OBTAINED BY FITTING EQ. (3)

TO EXPERIMENTAL DATA
Mortar No 1 2 3 4 5 6 7 8 9
4.41 1.41 7.09 3.10 3.83 1.83 1.20 1.51 4.40
58.10 0.82 61.34 43.58 50.72 1.31 1.04 0.89 24.23
1.33 4.96 2.60 1.06 1.26 7.39 4.22 4.71 1.50
aq 0.890 59.72 1.91 0.680 0.800 65.68 30.57 28.78 0.887
-
Mortar No 1 2 3 4 5
pl [m%] 3.61.10-12 5.09.10-12 6.36.10-12 3.47.10-12 5.09*10-12
P2 [-I 4.4 4.0 4.1 4.5 4.0
pi [m2/c] 6.36.10-i2 1.04.10-11 1.27.10-11 1.27.10-11
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL811 95 O 0662949 0 5 2 1 7 4 8 300
- A 1: no fibers, 1 admix.
A 4: 0.1 vol. % fibers, 1 admix.
-Y 4-
O 10 20 30 40 50 60
time [days]
Fig. 1-Drying curves of Mortars 1 and 4. Solid line was fitted using
Eq. (3)
0 10 20 30 40 50 60
time [days]
Fig. 2-Drying curves of Mortars 2, 3, 5, and 6. Solid line was fitted

using Eq. (3)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL211 95 = 0662949 0523749 2 4 7
1: silica fume, no fibers, 1 admix.
o 10 20 30 40 50 60
--``,`,-`-`,,`,,`,`,,`---
time [days]
Fig. %Drying curves of Mortars 1 and 7. Solid was fitted using Eq.
(3)
vol. % fibers 1 admix.

4: silica fume, 0.1 vol,
8: no silica fume, 0.1 vol. % fibers, 1 admix.
o+
o
- I
10 20
I I
30
I
40
I
50 60
time [days]
Fig. &Drying curves of Mortars 4 and 8. Solid line was fitted using
Eq. (3)

A C 1 SP-353 VOL*II 95 IObb2749 O523750 Tb7 I
776 Danarié and Haust
--``,`,-`-`,,`,,`,`,,`---
I I I I I
O 10 20 30 40 50 60
time [days]
Fig. %Drying curves of Mortars 7 , 8, and 9. Solid line was fitted using
Eq. (3)
O 10 20 30 40 50 60
time [days]
Fig. &Moisture loss as function of time for Mortar 1. Solid line was
fitted and corresponds to best fit obtained by numerical simulation

A C 1 SP-153 VOL*II 95 U ûbb2749 0521751 9T5 I
--``,`,-`-`,,`,,`,`,,`---
----- elllca fume and fibers
.............,.,. no silica fume, no fibers 3
_.._._..-.._
~
fibers and no silica fume 4
1
W
6
ci
l i l l l i l l i ” i i l ’ l i l ’ l l
O 0.2 0.4 0.6 0.8 1
ûegree oí saturation [%]
Fig. 7-Moisture diffusivity of mortars as function of degree of

saturation

A C 1 SP-153 V O L X I 1 95 e 0bb2949 0521752 831
SP 153-41
Manufacture of High-Strength Aerated

Concrete Containing Silica Fume
by H. Fujiwara, E. Sawada, and Y. Ishikawa
Srnopsisi : The increasing construction of high-rise buildings in

recent years has led to a demand for lightweight, high-strength
concrete. In this study, the compositions of the matrix a n d the
air void structure of aerated mortar containing silica fume were
investigated as the basis for manufacturing lightweight, high-
strength concrete. Mortars made with cement containing silica
fume and fine or ultra-fine silica stone powder, having a particle
size between that of cement and silica fume, were tested and the
properties of cement paste in fresh and hardened conditions were
improved. The compressive strength and the air void structure of
prefoamed aerated mortars were determined and their relationship
was stu.died. Based on the results, it was confirmed that
lightweight. high-strength concrete could be made with a n
effective combination of aerated mortar containing silica fume
and lightweight coarse aggregate.
Kevwordii: Air entrainment; cellular concretes; compressive strength;

strength
- concretes; lightweight aggregates; lightweight concretes; silica
--``,`,-`-`,,`,,`,`,,`---
fume

A C 1 SP-153 V O L X I I 95 m 0662949 0521753 778 m
780 Fujiwara, Sawada, and Ishikawa
Hiromi Fujiwara is a n Assistant Senior Research Engineer,

Central Research Laboratory, Nihon Cement Co., Ltd.. Tokyo,
Japan. He has been engaged in fundamental research in the field
of cement and admixtures for concrete. He qualified as a n
authorized consulting engineer in the field of construction in
1990, and is a member of JSCE and JCI.
Eiji Sawada is a Chief Research Engineer, Central Research
Laboratov, Nihon Cement Co., Ltd., Tokyo, Japan. He received
his degree of M. Eng. from Hokkaido University in 1974. He has
been engaged in research and development of construction
materiais. He qualified as a n authorized consulting engineer in
the field of construction in 1992, and is a member of AIJ and JCI.
Yuko Ishikawa is a n Assistant Senior Research Engineer, Central
Research Laboratory, Nihon Cement Co., Ltd., Tokyo, Japan. He
received his degree of M. Eng. from Kagoshima University in 1984.
He has been engaged in research and development of construction
materiais. He qualified as a n authorized consulting engineer in
the field of construction in 1992. and is a member of AIJ.
INTRODUCTION
The increasing construction of high-rise buildings in recent

years has led to a demand for development of lightweight, high-
strength concrete to improve the structure a n d rationalize
construction work. In the past, the weight of concrete was
reduced by the use of lightweight aggregate, or by entraining foam
into the concrete. Concrete containing lightweight aggregate
provides sufficient strength to permit its use as a structural
material: However, as the specific gravity often exceeds 1.5, the
material is still relatively heavier than foamed concrete. The
specific gravity of foamed concrete can be is lower at less than
1.0, but its strength is not sufficient to permit its use as a
structural material. Therefore, if the m a n u f a c t u r e of a
lightweight, high-strength concrete having a specific gravity of
less than 1.5, but still providing sufficient strength to permit its
use as a structural material could be realized, the benefits could
be considerable.
In this study, the following investigations were carried out to
establish a basis for manufacture of a lightweight concrete which
is lighter and stronger than conventional Iightweight concrete:
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL*II 95 0662749 0523754 604
( i ) increasing the strength of cement paste containing silica

fumle;
(2) decreasing the specific gravity of mortar containing high-
strength paste:
(3) evaluating lightweight, high-strength concrete containing
lightweight aerated mortar and lightweight coarse aggregate.
INCREASING STRENGTH OF CEMENT PASTE

CONTAINING SILICA FUME
Outline of test
In order to obtain high-strength concrete, the ratio of water
to cement is generally kept low. However, the reduction of the
water/cement adversely affects the workability of the paste.
Therefore, in order to obtain high-strength concrete, it is
important to use a paste with good workability despite the low
water/cement. In recent years, the focus has been on technology
in which a paste having high-fluidity and a low water/cement is
obtained using silica fume and a superplasticizer. Silica fume is
a powder with spherical particles having a diameter approximately
1 / 2 0 0 that of cement particles, t h u s providing high density:
--``,`,-`-`,,`,,`,`,,`---
Further, the spherical shape of the particles c a u s e s them to
reduce viscosity. We investigated various paste compositions to
find one providing favorable strength and workability properties
for use i n the above lightweight concrete technology.
Based on the density theory of particle technology, the
average particle size ratio of 1:SOO is not necessarily a n effective
ratio. Furnad 1 ) revealed that, when mixing a powder containing
particle sizes in this ratio, the further addition of a third power
having a n intermediate particle size increases the densification
effect. ?'he optimum particle size of the third powder is calculated
as the square root of the product of the mean particle size of the
silica fume. O.lpm, a n d that of cernent, 20pm. as d m=
1.4pm. Powders having a mean particle size near the above value
are blast furnace slag and ultra-fine silica stone powder. In this
investigation, ultra-fine silica stone powder having a mean
particle size of 2.4pm was used to study the workability a n d
strength of paste containing three components: cement, silica
fume and ultra-fine silica stone powder.
Test materiais
Materials used for the test are as follows.

A C 1 SP-153 VOLaII 95 I0662947 0523755 540 =
Cement: high-early-strength portland c e m e n t [C;

specific gravity, 3.13; specific surface area,
4,400cmz /g)
Admixtures: silica fume [SF: specific gravity; 2.19, specific
surface area, 200,000cm2 /g);
ultra-fine silica stone powder (UFS; specific
gravity, 2 . 6 5 ; specific s u r f a c e a r e a ,
13,000cm2/g)
Superplasticizer: naphthalene sulfonate
Mixture proportions
The mixture proportions of C. S F and UFS used in the test is
shown in Figure 1. Figures in circles indicate the number of the
blended powder. In order to increase paste density, the amount of
superplasticizer was 3% by weight of the blended powder. the
value at which t h e greatest water-reducing effect h a s been
confirmed: and the water! blended powder ratio was O. 19.
Casting method
Using the mixture proportions described above, measured
materials were fed into a n omni-mixer [ 10-liter capacity) and
--``,`,-`-`,,`,,`,`,,`---
mixed for five minutes to produce a paste. The paste was formed
into a '2 X 2 X 8cm test specimen using a form on a vibratory
table (1OOHz). The paste was cured for one day in moist air (20°C.
lOO%R.H.) and then in water (20°C) for a further six days.
Test Parameters
Paste flow value was measured in accordance with JIS
R520 1. In this method the diameter of the paste is measured after
it has been spread by the operation of flow table. The value is
defined as flow value which is employed for estimation of
flowability. A higher value indicates to be superior in flowability.
Compressive strength was measured in accordance with
ASTM C116. Six portions of three 2 0 by 20 by 80-mm beams
broken in flexure were used for determining t h e 28-day
compressive strength.
Analysis of test results

Figure 2 shows the flow value and compressive strength of a
hardened paste cured for seven days after placement. I t was
found that the addition of ultra-fine silica stone powder causes
the flow value to increase considerably. Further, strength did not

A C 1 SP-153 V O L X I I 95 I 0662949 0523756 487 m
decrease although the ultra-fine silica stone powder itself did not
display hydraulic properties. It is thought that these phenomena
result from the addition of ultra-fine silica stone powder, which
increases the density.
REDUCING WEIGHT OF MORTAR CONTAINING

HIGH-STRENGTH PASTE
Description of tests
Generally, lightweight aggregate is used in mortar to decrease
its weiglht a n d a n aggregate strength index is employed for
estimation of aggregate strength. To determine the index
lightweight aggregate is packed in a vessel and covered with a rigid
plate as :shown Figure 3: Deformation is measured while load was
applied. A load-displacement curve is drawn and the slope of the
linear portion of the curve is defined as the aggregate strength
index [P/d(N/mm)l.The curve shows that a higher index indicates
a stronger aggregate. Several types of lightweight fine aggregate
having different strengths were mixed with the paste of the
mixture proportion @ without using foaming agent to obtain a
mortar having a specific gravity of 1.5 a n d the compressive
strength of each mixture was measured.
Figure 4 shows the relationship among paste strength,
aggregate strength and compressive strength of mortar at that
point. Figure 4 also shows that addition of strong aggregates
causes mortar strength to increase considerably, particularly
when the strength of the paste is high. Therefore, in order to
make the most of the properties of the aggregate, use of the above
high-strength paste of the mixture proportion @ is considered
--``,`,-`-`,,`,,`,`,,`---
effective..
However, when mortar is made with only lightweight fine
aggregai.e, workability decreases in proportion to the amount of
aggregate used to reduce weight. Therefore, in order to reduce the
weight of the mortar while maintaining good workability, we
investigated the strength characteristics of aerated mortar made
by mixing air voids into the above high-strength paste using the
prefoaming method.
Test materials
The foaming agent used for this test is an animal protein
(prefoamed type). Cement and other admixtures are the same as
those used for the previous test.

A C 1 SP-153 VOL+II 95 W 0662949 0523757 3 3 3 W
Mixture Drooortions
The same materials and ratios as for the previous test were
used, and air voids were created in the mixture by prefoaming.
The air void content was adjusted to keep the specific gravity of
fresh aerated mortar between 1.O +O. 1 or 1.5 +O. 1.
Casting method
The paste was mixed for two minutes in a n omni-mixer (10-
liter capacity), then air was introduced and mixing was continued
for one minute. The test specimen for t h e strength test was
formed by pouring the aerated mortar into a 5Ø x 10cm cylindrical
form. It was cured for one day in moist air and further cured in
steam [temperature increase 20°C/ hr. maintained at 65°C for four
hours, then cooled naturally).
Test Parameters
After curing, the weight and volume of the test specimen were
measured to calculate its specific gravity: this value was then
used to calculate the ratio of voids in the hardened mortar.
Compressive strength was measured in accordance with ASTM
c39.
Analvsis of test results

Figure 5 shows the relationship between the air void ratio
[the ratio of air voids volume to total volume of solids and air)
and compressive strength of the mortar. Since the existence of
air voids leads to a loss of cross-section, it was thought that a n
increase the air void ratio would result in a n equivalent reduction
in compressive strength: however, the decrease in mortar strength
was much greater than expected. This is thought to be due to the
increased ratio of coarse air voids accompanying the increase in
the air void ratio.
Figure 6 shows the relationship between the air void ratio
and mean air void size. Thus it can be seen that this method is
not effective, since the presence of a large number of air voids
causes a remarkable loss of mortar strength. Therefore, we
decided to make lightweight mortar containing both lightweight
fìne aggregate and prefoamed air.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL*II 95 0662949 0521758 25T W
LIGHTWIGHT, HIGH-STRENGTH CONCRETE MADE

BY MIXING LIGHTWEIGHT AERATED MORTAR
AND LIGHTWEIGHT COARSE AGGREGATE
Outline of test
Lightweight concrete is considered to be a combination of
--``,`,-`-`,,`,,`,`,,`---
lightweight mortar and lightweight coarse aggregate, and the most

effective combination of these components was investigated. For
this test, two kinds of lightweight coarse aggregate were selected
and their strength characteristics evaluated. Those aggregates
were then combined with several types of lightweight mortar
having different specific gravity a n d strength levels to produce
lightweight concrete, and the specific gravity and strength of the
resulting lightweight concrete were measured.
Test materials
The two kinds of lightweight coarse aggregate described in
Table 1 were used for this test: granulated pumice stone
lightweight aggregate: a n d “Asano Lite”, a n ungranulated
expansive shale lightweight aggregate. The type of fine aggregate
used was varied in accordance with the specific gravity level of the
particular mortar. For mortar with a specific gravity between 0.5
and 1 .6, expanded silica fine aggregate [specific gravity saturated
surface-dry, 0.24: particle size, 0.5-1.5mml was used: for a specific
gravity of 1.6 to 2.0, expansive shale fine aggregate [specific
gravity under oven-dry, 1.70; particle size, 0.5-5mm) was used:
and for i i specific gravity of more than 2.0, mixed sand (specific
gravity saturated surface-dry, 2.60, FM=2.65) consisting of river
sand from the Fuji River and mountain sand from Kisarazu was
used. Cement and admixtures used for this test were the same as
those used for the previous tests.
Evaluation of strength of coarse aggregate

__
The strength of coarse aggregate was evaluated in accordance
with the method described by H. H. Bache(21, in which the
strength of the coarse aggregate (aalis calculated by the following
formula.
= al/n am ( l - l / n l
am
However: approx. 2 c -< approx. 15. O c n < approx. 0.5
aa

A C 1 SP-153 V O L X I I 95 0662949 0523759 396 W
Where, a,: strength of coarse aggregate

om: compressive strength of mortar
u : compressive strength of concrete
n : absolute volume ratio of coarse aggregate in concrete
Mixture Proportions
Table 2 shows the specific gravity of each mortar used in
combination with the coarse aggregate. No.@ mixed powder (60%
cement, 10% silica fume, 30% ultra-fine silica stone powder) was
used for the paste: the water/ blended powder and superplasticizer
amounts were 19% and 3%. respectively. The specific gravity of
each mortar was adjusted by controlling the volume of aggregate
and air voids. In this case, the ratio of fine aggregate to air voids
was 1: 1 by volume. Mortar and coarse aggregate in the ratio of
6:4 by volume were mixed to produce concrete.
Casting method
The paste was mixed for two minutes in a n omni-mixer: the
fine aggregate and air were introduced and mixing was continued
for one more minute to make the mortar. The mortar was poured
into a 50 x 10cm cylindrical form to make the test specimen.
--``,`,-`-`,,`,,`,`,,`---
Next, coarse aggregate was added and the material mixed for
another two minutes to produce concrete. The concrete was
poured into a 100 x 20cm cylindrical form to make the test
specimen. Three specimen per mixture proportion were used for
each test. The test specimen was cured for one day in moist air
and further cured in steam (temperature increase 20"C/hr,
maintained at 65°C for four hours, then cooled naturally).
Test Parameters
After curing, the weight and volume of the test specimen were
measured to calculate its specific gravity: compressive strength
was measured in accordance with ASTM C39. Following the load
test, a fractured face of the concrete test specimen was examined
in order to confirm whether failure was due to rupture of the
mortar or of the aggregate.
Analvsis of test results

Figure 7 shows the relationship between the specific gravity
and compressive strength of mortar and concrete, when pumice

A C 1 XP-I153 V O L X I I 95 m 0662949 0523760 9 0 8 m
stone lightweight aggregate was used. Figure 8 shows the

relatiomhip when expansive shale aggregate was used. The
figures indicate that the strengths of both mortar and concrete
increase as specific gravity increases. However, when specific
gravity is in the range of 0.8- I . 1 for fire-resistant lightweight
aggregate and 1.4- 1.8 for expansive shale aggregate, the strength
of the concrete is greater t h a n t h a t of the mortar: This
relationship is reversed in other specific gravity ranges.
In order to explain these phenomena, mortar and coarse
aggregate were mixed in the ratio of 1: 1 by volume and as a result
concrete having a specific gravity between those of mortar and
--``,`,-`-`,,`,,`,`,,`---
coarse aggregate was obtained. Figure 9 shows the conceptual

relationship between the specific gravity a n d strength of the
mortar and concrete. When aggregate having a predetermined
specific gravity and aggregate strength ( in this Figure, which is
calculated by Bache’s formula) and mortar whose compressive
strength increases as its specific gravity increases were mixed to
produce concrete. it was found that the relationship between the
specific gravity a n d the strength of the concrete shows the
following tendencies.
When concrete is made with mortar having a specific gravity
and a compressive strength lower than those of the aggregate
it is mixed with (Figure 9,AL the compressive strength of
concrete varies with the strength of the mortar a n d the
specific gravity of the concrete becomes larger than t h a t of
the mortar (0).
When concrete is made with mortar having t h e s a m e
compressive strength as the aggregate but greater specific
gravity (Figure 9,& the compressive strength of the concrete
is equal to that of the mortar but specific gravity becomes
smaller than that of the mortar (0).
When concrete is made with mortar having a specific gravity
and a compressive strength greater t h a n those of t h e
aggregate it is mixed with (Figure 9,A),the specific gravity of
the concrete is lower than that of the mortar: compressive
strength is also lower t h a n that of the mortar due to the
great influence of the strength of the aggregate (0).In this
case, however, the strength of the aggregate does not
imrnediately determine the compressive strength of the
concrete as indicated in (1): the compressive strength of the
concrete increases more or less as the strength of the mortar
incl-eases. This is because the mortar exists as a continuous
body in the concrete, while the coarse aggregate exists as a
discontinuous body.

A C 1 SP-I453 V O L * I I 95 m 0662749 0521761 ô44 m
Although the above phenomena were observed when the

coarse aggregate strength symbol (0)was located above t h e
specific gravity-compressive strength line for the mortar, it is
thought that the specific gravity and compressive strength of the
concrete would show a similar tendency when t h e symbol is
located below the line. Photo 1 shows t h e r u p t u r e face of
concrete made with pumice stone lightweight aggregate a n d
mortar whose specific gravity and compressive strength are lower
than those of the aggregate: Photo 2 shows the rupture face of
concrete made with pumice stone lightweight aggregate a n d
mortar whose specific gravity and compressive strength are higher
than those of the aggregate. Photo 1 indicates that rupture of the
mortar led to rupture of the concrete, while Photo 2 indicates t h a t
rupture of the aggregate led to rupture of the concrete: this seems
to confirm the above hypotheses.
On the basis of the above study it was found that, when
lightweight concrete is made with lightweight coarse aggregate,
the use of mortar whose strength is greater t h a n t h a t of the
aggregate produces concrete having acceptable specific gravity and
compressive strength. Therefore, as shown in Figures 7 a n d 8,
when pumice stone aggregate is used, it is effective to combine it
with mortar whose compressive strength is between about 12MPa.
or equal to that of the aggregate, and 24MPa. or twice that of the
aggregate: when expansive shale aggregate is used, it is effective to
combine it with mortar whose compressive strength is between 40
--``,`,-`-`,,`,,`,`,,`---
and 80MPa. Even if the aggregate is mixed with mortar whose
strength is higher than twice that of the aggregate, the influence
of the strength of the aggregate will prevent the strength of the
concrete from increasing any further.
CONCLUSION
A basic study was carried out fo5 the purpose of obtaining

lightweight, high-strength concrete and the following results were
obtained.
( 1) A high-strength, high-fluidity paste was used to obtain high-
strength concrete by blending powders having different
particle sizessuch as cement.silica fume and ultra-fine silica
stone powder, in an appropriate ratio (60C/ IOSF /3OUFS).
(2) When air voids are incorporated into the paste used to make
aerated concrete, a n excessive volume of incorporated air
generates very large air voids, resulting in a considerable
lowering of the compressive strength of the concrete.

A C 1 SP-353 VOLtII 95 W 0662949 0523762 7 8 0
m
=
(3) When lightweight coarse aggregate and mortar are mixed to

make concrete, concrete having suitable specific gravity and
compressive strength can be obtained with the use of mortar
whose strength is 100-200%that of the coarse aggregate.
REFERENCES
1) C.C. Furnas: Industrial and Engineering Chemistry, 23(91,

(19311
2) H.H. Bache: Strength of Structural Lightweight Aggregate
--``,`,-`-`,,`,,`,`,,`---
Concrete, Proceeding of RILEM Symposium on Testing a n d
Design Methods of Lightweight Aggregate Concrete, ( 1967)
TABLE 1 - LIGHTWEIGHT COARSE AGGREGATE
Shape Specific Strength

size(mm) gravity (MPa)
Granulated 0.80 12.0
Asano Lite Ungranulated 1.28 39.4
TABLE 2 - SPECIFIC GRAVITY OF MORTAR AND CONCRETE
Type of coarse
aggregate
Type of fine
aggregate
SG of inortar
SG oí concrete

A C 1 SP-153
790
VOL+II 95
Fujiwara, Sawada, and Ishikawa
= 0662949 052L7b3 bL7 F
O
o 10 20 30 40
Ultra-fine silica stone powder
Fig. 1-Powder blending ratio (e.g., 0 is 70C/2OUFS/lOSF)
200
150
125 --
No. 0 0
L
80 --
120
140
Fig. =-Flow value and compressive strength of paste

--``,`,-`-`,,`,,`,`,,`---

~ ~~
A C 1 SP-lu53 V O L X I I 95 M Obb2949 0523764 553 M
O Vessel
Q Plate
0 Dial gauge
Displacement d(mm)
Fig. &Measurement of aggregate strength index
Estimated equivalent mortar strength line
--``,`,-`-`,,`,,`,`,,`---
I
Numbers indicate mortar I
compressive strength ( M h ) I
l
I I
I I
I
l I
0.1 I
O 50 1O0 150
Paste compressive strength (MPa)
Fig. 4-Relationship among compressive strength of mortar,

compressive strength of paste, and aggregate strength index

A C 1 SP-I153 V O L U I I 95 = Obb2949 0523765 49T
Air void ratio (P)
Fig. 5-Relationship between air-void ratio

and compressive strength
200 i O
50
o'
t 0.1 0.2 0.3 0.4 0.5 0.6
Fig. 6-Relationship between air-void ratio

and mean air-void size
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 V O L X I I 95 IObb29Y9 0 5 2 I I i b b 32b I
.
:Concrete
.
:Concrete 0.Mortar IO
O: Mortar i3 Coarse aggregate
I
I
O: C»am aggregate l
I 9'
I
i
. .
'0.5 1.0 1.5 o "1:o 1.5 2.0
Spcciftcgravliy Spccific graviiy
Fig. 7-Relationship between specific Fig. 8-Relationship between specific

gravity and compressive strength of gravity and compressive strength of
mortar arid concrete containing mortar and concrete containing
pumice stone expansive shale aggregate
U Concrete
---A--- Moriar
o : Coarse aggregate
SO lower
-I-
SG higher
thancoarse ! thancoarse
--``,`,-`-`,,`,,`,`,,`---
specific gravity
Fig. 9-Conceptual relationship between

specific gravity and compressive strength
of mortar and concrete
A C 1 SP-I153 V O L X I I 95 0662949 0523767 262
It--------- 20cm
Ta
O
c=,
h
i
Photo l-Rupture face of concrete made with pumice stone and low
specific gravity, low-strength mortar
--``,`,-`-`,,`,,`,`,,`---
Photo 2-Rupture face of concrete made with pumice stone and high
specific gravity, high-strength mortar

A C 1 SP-153 V O L U I I 95 = 0662949 052L7b8 L T 9
SP 153-42
Sulfate Resistance of Mortars

Containing Silica Fumes as
Evaluated by Different Methods
by A. Yeginobali and F. T. Dilek
svnoDsls.Sulfate resistance of two types of silica fumes from ferrosilicon (FeSi)

and silicoferrochromium (SiFeCr) m e s has been evaluated using ASTM
C452 and ,4STM CI 012 test procedures. Cubic mortar specimens have also been
immersed separately in 10% Na2S04 and 8.4% MgSOq solutions. After being
subjected to periodic mass change and "visual durability index" determinations
they were tested for compressive strength at the age of 60 weeks to assess their
relative deterioration with respect to specimens stored in water.
In the test program two normal, two pozzolan modified and one sulfate
resisting portland cement were used together with standard sand in preparing the
moríar specimens. Silica fume replacement levels were O, 8, and 15 percent by
mass of cement. Mixing water content was kepi constant within a group and a
superplasticizing admixture was used to maintain comparable mortar flows.
According to the results available at this time silica fume addition

reduced the mortar bar expansions through the age of 41 weeks in both ASTM
tests. Different meawrement techniques used to evaluate the detenoration of
mortar cubes in concentrated sulfate solutions indicated that the addition of
silica fume was benefical to the sodium sulfate resistance and detrimental io the
magnesium sulfate resistancc of the mortars.
In general, addition of silica fume to replace 15% of cement by mass

seemed to be more effective. SiFeCr fume with lower Si02 content and smaller
water demand performed slightly better than FeSi fume in controlling the mortar
expansions. Cements used in the study showed comparable sulfate resistance.
Keywordsi: Compressive strength; corrosion; durability; magnesium

sulfates; mortars (material); uortland cement; silica fume; sodium sulfate;
sulfate resistance
--``,`,-`-`,,`,,`,`,,`---

795
A C 1 SP-153 VOL*II 95 9 0 b b 2 9 4 9 0 5 2 3 7 6 9 035
796 Yeginobali and Dilek
him Ye$nobali is professor of civil engineering at the Middle East Technical

University in Ankara, Turkey. He is a graduate of the Ohio Staîe University and
is member of AC1 and RILEM. His research activities and publications are
mainly in the field of cement and concrete technology.
F a d Tuncer Dilek is an assistant inspector in Ministry of Public Works and

Settlement in Ankara. He is currently studyrng for his Ph.D degree in the civil
engineering department of the Middle East Technical University.
INTRODUCTION
The deterioration of concrete by aggressive chemicals is a complex

process. Despite extensive research, the reactions between such chemicals and
constituents of concrete are not clearly understood and a good correlation
between laboratory findings and field performances is still missing. To solve the
problem systematic approaches are proposed which would use appropriate
testing techniques and integrate the measurement of various material properties
(1).
Silica fume has become a popular admixture for cement and concrete
during the past 15 years. Most of the research has been conducted on the strength
development of silica fume concretes and only limited data has become
available regarding the durability aspects. Furthermore, the findings on the role
of silica finne in sulfate resisiance of cements and concretes are not conclusive
and there are indicationsthat the behavior of this new material may be different
from the other pomlans in this respect (2,3).
With such considerations, a research study was undertaken to investigate

the sulfate resistance of mortars made with different cements and incorporating
two types of silica fumes by using different test methods and property
measurements. The experiments are being conducted in the Materials of
construCtion Laboratory of the Middle East Technical University. The project is
sponsored by the Turkish Scientific and Technical Research Council.
At the time of this presentation all test results were not available. Also,
because of limited space, complete test data from different phases of the study
could not be included. Instead,typical results from selected observation periods
are tabulated for each test.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-It53 VOL*II 95 IOb62949 0 5 2 3 7 7 0 ô57 I
SCOPE OF THE STUDY
in the experimental program two wrmai and two pozzolan modified

portiami cements and a sulfate resistlligportlaad cement were us6d together with
a local standard sand in preparing the mortarmixturts. Two types of silica fumes
coiiecîeú from îbe fmsilicon and silicoferrocromiian funraces of the same
plant were used as mineral admurtures in mortars.The expimentai program
consistecl of three phases involving the tests jmformed according to ASTM
C452 "Standard Test Method for Potential Expansion of Portland Cement
Mortars Exposed to Sulfate", ASTM C1012 "Standard Test Method for Length
Change of Hydraulic Cement Mortars Exposed to a Sulfate Solution" and the
experimenîs coiaducted with 50 mm cubic moriar specimens s t
ored separately in
IO?! sodium sulfate and 8.4% magnesium sulfate solutions. The deterioration of
the cubic specimens were studied by visual observations and by determiningthe
changes in their mass and compressive strength.
In all phases of the study the proportioniag of the mortar mixtures

remainedconstantasl~Ofcem~tand2.75partsOfstandardsand~water
content was determined for the oontrol mixture of each cement type to produOe a
flow of around 1 IO?? and was kept constant for tbe blended mixtures. The flow
test was perfomed as described in ASTM C1W "Standard Test Method for
Compressive Sîrengtb of Hydraulic Cement MorEars". The silica fume addition
was ûieú at two levels, correspondingto 8% and 15% of the cement mass in the
mixture.
In mortar mixaires prepared for ASTM C1012 tests aná for making the
cubic specimens, small amounts of superplasticizing admixture were also useá
together with silica fume to maintaincomparable flow values.
Two normal portland cements (NPC1 andNPC2), two pozzolan modified

cements (PMC1 and PMC2) and a sulíàtemsisîingportland cement (SRC) were
used pMc2 contained around 15% trass, a natural pozzolan. PMC1 was an
imported cement and contained less pozzolan than PMCî. AU cements complied
with the relevant Turkish Standards. "2beloaged to a slightly higher strength
grade as compared with the otbers.The physical and chemical properties of the
cements are given in Table 1.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 0662949 0521771 793
The standard sand used in making the mortar mixtures complied with the
relevant Turkish sîandard It had slightly higher water requirement for a given
flow as compared with ASTM graded standrud sand.
The silica fumes were obtained from the plant of E t i W

Electrometallurgy Industry in Antalya One was from the ferrosilicon funiace
(SFl) and the other one was from the silicoferrochromium furnace (SE). Their
properties are shown in Table 1.
A high range water reducing admixture* complying with Type F

admixture in ASTM CY94 "Standard Specification for Chemical Admixtures for
Concrete" was used in some of the mortar mixtures.
TESTS PERFORMED ACCORDING TO ASTM (352 METHOD
ASTM 0 5 2 standard test methud determines the potential expansion of

portland cement mortars exposed to suifate. Sulfate exposure is provideú by
mixing the portland cement with gypsum in such proportions that final mixture
has an SO3 content of 7% by mass. The mortar mixture, proportioned as 1
of cement plus gypsum, 2.75 parts of standard sand and 0.485 parts of water, is
used to cast25 by 25 by 285 mm prisms. Aíkr initial curing the specimens are
stored in water and changes in their lengths are determined at the age of 14 days.
In the experimental program the method was applied with some

modifications. In addition to the control mixture without silica h e , test mortar
mixtures conîaining silica fume at levels corresponding to 8% and 15% of the
cement mass were prepared. "he quantity of gypsum was adjusted for each mix
so that the SO3 content remained constant as 1.87% of the toial dry material
mass as well as 7% of the cement plus gypsum.
(*) Trade name Meiment L10133

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 Obb2949 0523772 b2T
In one series of mixtures, volume of the sîandard sand was reduced

accordingly, as silica fume partiaiiy replaced the sand. The water content of the
control mixture was determined to have a flow of around 100% and was kept
constant for a given set of materials. The tests were repeated using both silica
fumes and different cements. The results as expansions of mortar bars at 2 weeks
and 4 I weeks of age are shown in Table 2a. In another group of mortar mixtures
the cement was replaced with silica fume at 8% and 15% levels by mass. Again
the water content was kept constant. Both silica fumes were used together with
PMC2. The results as expansions of mortar bars at 2 weeks and 4 1 weeks of age
are shown in Table 2b.
TESTS PERFORMED ACCORDING TO ASTM C 1O12 METHOD
ASTM CI012 standard test method covers the determination of the

length change of mortar bars stored in 5% sodium sulfate solution. Mortar
mixtures proportioned as 1 part of cement, 2.75 paris of sand and 0.485 parts of
water, were used to cast prismatic specimens 25 by 25 by 285 mm in size and 50
mm cubic: specimens. If mineral admixtures were used, the water content was
adjusted to keep flow of the mortar within 55% of that obtained with W/C of
0.485. Specimens were cured in water until the mortar cube strength reached a
value of 20 MPa. At this time prismatic specimens were stored in sulfate
solution for periodic length-change measurements at the ages of 1 week to 15
weeks.
--``,`,-`-`,,`,,`,`,,`---
In the experimental program, for a given cement and silica fume

combination, one control mixture without silica h e and two test mixtures were
prepared. The test mixtures contained silica fume at 8% and 15% levels of
cement replacement by mass.The water content was determined to give a flow
of I10+_5% for the control mixture and it was kept constant for the test mixtures
with the help of the superplasticizing admixture. The sulfate solutions in
specimen containers were replenished at regular intervals. The results as
expansions of mortar bars at the ages of 15 weeks and 41 weeks are shown in
Table 3. Complete test daîa obtained through 65 weeks on (PMCl+SF2) is
plotted in Figure I .
OTHER TESTS PERFORMED ON MORTAR SPECIMENS STORED IN

SULFATE SOLUTIONS
Effects of silica fumes on sulfate resistance of cements have been also

investigaied using 10% sodium sulfate and comparable magnesium sulfate
solutions as the aggressive mediums. Relative deteriorations of the mortar

A C 1 S P - 1 5 3 V O L * I I 95 W Obb27LI9 0523773 5 6 6
specimens were determined by visual evaluations, and by recording the changes

in the mass and compressive strength.
The mortar mixtures used in this phase of the experimental program were
identical with those produced for ASTM C1012 tests. From each mixture twelve
50 mm cubic specimens were cast following the ASTM Cl09 standard
procedure. AAer an initial curing period of 28 days in lime-saturated water, nine
of the specimens were removed from the water. Of these, three were tested to
determine the compressive strength of the mixture, three were immersed inside a
lû?! sodium sulfate solution and the remaining three were immersed in 8.4%
magnesium sulfate solution. Both solutions had the same SO4 ion concentration
of 67.6 gíl. The solutions were replenished at 8 week intervals and the liquid
level over the top surface of the specimens were kept constant.
Mortar specimens stored in sulfate solutions undergo progressive

deterioration accompanied by typical cracking and erosion patterns over their
surfaces.Based on previous experiences with such patterns, a numbering system
was developed to identie specimens at various stages of deterioration. A visual
durability index (VDI) of 10 was assigned to a perfect specimen and zero was
assigned to a completely destroyed specimen. During their storage in sulfate
solutions cubic mortar specimens were periodically examined and rateù for
visual durability index values. Figure 2 shows the appearance of the specimens
from the same mortar mixture group after 60 weeks in sulfate solution together
with their VDI ratings. The variations in index value of the specimens from
another group of mixtures through the test period are plotted in Figure 3. The
values are the averages of the observations on three specimens belonging to the
same mixture.
The mass change of the specimens stored in sulfate solutions were

determined periodically. The specimens were brought to a surface dry condition
before weighing over a balance with 0.1 g sensitivity.Average values obtained
from three specimens were recorded for each mixture. These values were used to
plot diagrams such as the ones shown in Figure 4.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 = 0662949 0523774 4T2 =
The effect of sulfate exposure on the strength development of mortars

with and without silica fume could be studied by testing the specimens stored in
the sulfate solutions and in the lime saturated water at the end of the
experimeritai program and comparing the results with each other and with the
2S-day strength of the mixture. During the laboratory studies, this phase of the
test pro- was planned to terminate for each mixture when the specimens
reached an age of 60 weeks in sulfate solution. The results available at this time
are presented in Table 4.
DISCUSSION
All cements used in the experiments seemed to have good sulfate

resistance as determined by the ASTh4 C452 method. As shown in Table 2, the
I4-day expansion of the control mixtures were similar to each other and
remained below the 0.04% limit. However, according to the results at 41 weeks
PMC2 and SRC were performing better at later ages. At constant water content,
partial replacement of sand with silica fume decreased the W/(C+SF) while
partial replacement of cement with silica fume increased the W/C. In both cases
flow values were decreasedand the effect of silica fume addition on mortar bar
expansions were similar. At 14 days the effect was not significant, silica fume
--``,`,-`-`,,`,,`,`,,`---
even causing some increase in the expansion of mortars made with PMC2 and
mortars with 15% cement replacement. On the other hand, silica fume addition
caused a sharp decrease in all 41-week expansions. Silica fume additions at 15%
level wert: more effective. Of the two silica fumes SF2 caused smaller decreases
in flow and seemed to perform slightly better.
Although ASTM 0452 method is recommended only for portland

cements it seems that it may be a useful supplementary method to evaluate the
effect of the silica fumes on long-term sulfate resistance of cements.
cio17 ~ e s t s
Acxording to the results of the ASTM CIO12 test at 15 and 41 weeks the
cements wed in the test again showed similar sulfate resistance. One exception
was PMCi1 whose control mixture exceeded 0.1% expansion at the age of 41

A C 1 SP-153 VOLJII 95 m Ob62949 0523775 339 m
weeks in the sulfate solutions as shown in Figure 1 and Table 2. Addition of

silica fume was beneficial in reducing the expansions both at 15 and 4 1 weeks of
age. In general 15% addition was more effective although mixtures with 8%
addition could also perform well occasionally during the test period. Again SF2
seemed to be slighîly more effective than SFl in reducing the expansions at
these observation periods.
Findings mentioned above are in agreement with the results of the

previous work where the expansion of the portland cement mortars in 5%
sodium sulfate solution and in ASTM Cl012 test could be effectively controlled
by the addition of silica fume (4,5).
The visual durability index concept was developed and successfully

--``,`,-`-`,,`,,`,`,,`---
applied in a previous research program (6). In the current study it was again
useful as an additional method to assess the gradual deterioration of the
specimens by quantifj4ng the subjective observations. The six specimens shown
in Figure 2 clearly illustrate the different corrosion patterns of mortar specimens
in different sulfate solutions, the effects of silica h e addition and the VDI
rating system.
The deterioration of the cubic mortar specimens in concentrated sodium

sulfate solutions progressed with the formation and growth of circumferential
cracks along the edges of the faces. In such solutions the gypsum and ettringite
formations can be considered as corrosive mechanisms. The expansive nature of
gypsum formation is questioned (1). The results of this study indicated the
occurence of expansions in the specimens which could be effectively controlled
by the addition of silica h e .
The behaviour of the mortar specimens in concenúated nagnesium

sulfate solutions was completely different. The deterioration progressed by
softening and uniform erosion of the specimen surfaces. The corrosive
mechanism is the magnesium attack, which decomposes the cementitious
calcium silicate hydrate gel (CSH) into noncementitious magnesium silicate
hydrate ( 1,2). Addition of silica fume to the mortar was detrimental as seen from
Figure 2. This could be explained by the pozzolanic action of the silica fume
resulting in the elimination of protective magnesium hydroxide layer and by the
formation of a lower quality CSH gel (2).
The relative deterioration of the mortar specimens belonging to the same

mixture group could be studied by plotting the VDI values as shown in Figure 3.

A C 1 SP-153 VOL*II 75 0662747 0523’7’76 275
Mass change of the mortar specimens stored in sodium and magnesium

sulfate solutions followed different patterns, in line with the possible corrosive
mechanisms mentioned above. As seen fiom Figure 4, the mass of the specimens
stored in rmíium sulfate solution initially showed an increase before beginning
to decrease . Specimens containing silica fume had smaller mass change. In
specimens: stored in magnesium sulfate solution mass loss occured almost fiom
the beginning. Addition of silica fume increased the magnitude of the mass
losses. The findings were consis2ent with the results of a previous work
performedon paste specimens in sulfate solutions of similar concentrations(2).
The test data presented in Table 4 on compressive strength of the

mixtures made with “(21 supported the results of the VDI and mass change
studies. A.ccording to the 60-week strength values of the specimens stored in
water and in sulfate solutions, silica fume again had beneficial effect in sodium
sulfate and detrimental effect in magnesium sulfate solutions. SF1 seemed to be
more effective than SF2. Contribution of silica fumes to strength development
seemed to diminish at the later ages.
CONCLUSIONS
Blending with silica fume improved the sulfate resistance of cements as

determined by ASTM C1012 and ASTM C452 methods.
ASTM 0452 method could be useful in studying the effect of silica fume
on sulfate resistance of cements and mortars at later ages.
Addition of silica fume improved the durability of mortars in
concentrated sodium sulfate solution. However it had a detrimental effect
on mortars stored in magnesium sulfate solution of similar
concentration.
in general, addition of silica fume to replace 15% of the cement by mass
prave-d to be more effective than the 8% level.
Ofthe two silica fumes, the one from SiFeCr funuices had lower water
demand and Si02 content. Most of the time it performed better in
controlling mortar expansions.
Cements used in the study so far had comparable sulfate resistance and
the test results did not seem to be significantly affected by the type of
cement.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L W I I 95 = Obb2949 0521777 101 =
o Visual durability index concept and measurement of mass changes were

very useful in studying the deterioration of mortar specimens in sulfate
solutions.
1. Cohen, M.D. and Mather, B. "Sulfate Attack on Concrete-Research

Needs",AC1 Materials J o d , Vo1.88, No. 1, January-February
1991, pp.62-69.
2. Cohen, M.D. and Bentur, A. "Durabilityof Portland Cement Silica

Fume Pastes in Magnesium Sulfate and Sodium Sulfate Solutions",
AC1 Materials J o d , Vo1.85, No.3, May-June 1988, pp.148-157.
3. Khayat, K.H. and Aitein, P.C. "Silica Fume in Concrete An

ûverwiew", AC1 Special Publication SP 13246, 1992, pp.835-872
(Editor: V.M. Maihoîra).
4. Maâej, J. "Corrosion Resistance of Normal and Silica Fume Modified

Mortars Made from Different Types of Cement", AC1 Special
Publication SP 13244,1992, pp.1189-1207 (Editor: V.M. Malhoîra).
5. Hooton, R.D. "Influence of Silica Fume Replacement of Cement on

Physical Properties and Resistance to Sulfate Attack, Freezing and
Thawing and Aikali-Silica Reactivity", AC1 Materials J o d ,
V01.90, N0.2, March-April 1993, pp.143-151.
6. Yehoball, A. and Al-Hadrami, N. "Sulfate Resistance of Jordanian

Cements as Evaluated by Different Methods", Proceedings of the
Fourth international Conference on Durability of Building
Materiais and Components, Singapore 1987, V01.2, pp.762-769.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 B Obb27Y7 0523778 0 4 8 E
I
'
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 75 0662947 0 5 2 3 7 7 9 T & 4
o>
I-
o> O O O O C
W
I-
c\I I
rn
o2 momomoooomoooo
NmmmmmP4NP4N
k 9 9 99999
0000000000
I- I
(B I
I
a
LL
O
c
-I
n
-I
3
o>
W
U
1 :
cut:
w t
-1 .!
P
c
-i
d4
f
6
..!
.I
c
U
,
-
I I I I I IC
--``,`,-`-`,,`,,`,`,,`---

A C 1 SI3-153 VOLXII 75 E Obb27V9 0 5 2 3 7 8 0 7Tb
I 1 I
(B
I-
(B
W
I-
I I I
--``,`,-`-`,,`,,`,`,,`---
i
t

A C 1 SP-153 V O L + I I 95 = 0662747 0521'78l b32 m
I I I
m
+
0)
W
I-
c\I
8
r
o
z
m
a
LL
O
m
5
3
m
w
[r
I
m
w
J
m
5
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 O662949 0521782 5 7 9
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*II 95 m Ob62949 0523783 405 m
--``,`,-`-`,,`,,`,`,,`---
0.250 1
$ 0.200
.g 0.150
9B 0.100
0.050
Fig. 1-ASTM C1012 test results on (PMC1 + SF2) mortar mixtures

A C 1 SP-$53 VOL+II 95 0662949 052L784 341
Fig. 2-Mortar specimens from (PMCl + SF2) mixtures after 60 weeks

in sulfate solutions
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I I 95 = Obb29Y9 0523785 288 =
1 3 5 7 9 II 13
MOnttis
1-7 controi 8?!SF II5%SF
in 10% Na2S04 Solution
10
9
8 -1 ri
7
6
--``,`,-`-`,,`,,`,`,,`---
V
D 5
' 4
3.
2.
1.
O
1 3 5 7 9 11 13 15
Months
O control
in 8.4% WSO4 Solution
Fig. 3-Variations in visual durability index values of mortar specimens

from (NPCI + SF1) mixtures stored in sulfate solutions

A C 1 SP-153 VOL*II 95 0 b b 2 9 4 9 0 5 2 1 7 ô b 114
2.00-
1.80.
a 1.60
S
1.40-
1.20
C
11
.. 13 15
3 5 7 9
Months
¡-.-I Control 8%SF 115% SF
In 10%Na2SO4
3 5 7 9 11 13 15
Months
LJ control R 8%SF 15%SP
In 8.4% MgSO4
Fig. +Mass change of mortar specimens from (NPC1 + SF2)

mixtures stored in sulfate solutions
--``,`,-`-`,,`,,`,`,,`---

A C 1 SF?-153 VOL*II 95 m 0662949 0523787 050 m
SP 153-43
High Reactivity Metakaolin (HRM)

for High Performance Concrete
by M. A. Caldarone and K. A. Gruber
Synopsis: High Reactivity Metakaolin (HRM) is produced by

controlled thermal activation of purified kaolinite, an
aluminosilicate mineral, to a reactive, amorphous state. HRM,
being pozzolanic, reacts with free lime (Ca(OH),), a by-product
of portland cement hydration.
In this investigation, two high performance concrete

mixtures containing HRM were studied. In the first mixture
proportion, HRM was formulated as an addition to the cement.
--``,`,-`-`,,`,,`,`,,`---
In the second mixture, HRM was used as a cement replacement.

The compressive strength and rapid chloride permeability of the
HRM concretes was compared to non-pozzolanic concrete
controls and concretes that contained equal amounts of silica
fume,
The results of this study show that the strength and

impermeability of HRM concrete is significantly higher than
non-poz:zolanic concrete. The HRM concrete showed properties
equivalent to similar silica fume (SF) concretes, while using
significantly less superplasticizer to reach an equivalent
consistency.
Kewords: Chlorides; compressive strength; high performance concretes;

metakaoh; permeability; pozzolans; silica fume

815
A C 1 SP-153 V O L X I I 95 0bb2949 0521788 T97
816 Caldarone and Gruber
Michael A. Caldarone is a former Assistant Manager of Technical

Service for Material Service Corporation, Chicago, Illinois. He is
currently Materials Engineer for Dolese Bros. Co., Oklahoma
City, Oklahoma and has over 10 years of experience in the
production and testing of high-strength concrete.
Karen A. Gruber, a Chemist and Chemical Engineer, is a

Technical Service Engineer for Engelhard Corporation, Iselin,
New Jersey. She is a member of the ACI.
INTRODUCTION
Previous studies indicate that kaolinite, after calcination at

specific temperatures and under controlled conditions, forms
--``,`,-`-`,,`,,`,`,,`---
metakaolin, which exhibits pozzolanic properties (1-4).
Metakaolin in the form of unpurified calcined clays, trass and
volcanic ashes were used earlier for improving the durability of
concrete in marine, hydraulic and underground structures and for
preventing expansion from alkali-aggregate reaction (5).
The purpose of this study was to evaluate the pozzolanic

property of a high reactivity metakaolin (HRM). HRM, an
almost 100% reactive material, was manufactured in a controlled
environment to achieve optimum pozzolanic performance.
Compressive strength and rapid chloride permeability were
measured. Two mixture proportions containing HRM were
studied. One mixture incorporated additions of the pozzolans and
the other used pozzolans as replacements of cement. Silica fume
was included in the study as a reference of a highly pozzolanic
admixture.

A C 1 XP-153 VOL+II 95 Obb2949 0523789 923
MATERIALS
--``,`,-`-`,,`,,`,`,,`---
The following materials were used during the preparation of

the concrete samples.
Cement
General purpose, Type I portland cement (ASTM C150)

was used for all of the concrete mixtures.
High Reactivitv Metakaolin
The High Reactivity Metakaolin (HRM) used in this study

was a Commercially available product that is classified under
ASTM C618 as a Class N pozzolan. The average particle size of
the HRM used in this study (approximately 2 pm) is significantly
smaller f.han the cement particles, but larger than silica fume
particles (approximately O. 1 pm). HRM, a white, maniifactured
product, is produced using statistical process-control. HRM is an
aluminosilicate which is approximately 44% Alzo, and 54% SO,.
Silica Fume
The silica fume (SF) used in Mixture Proportion #1 of this

study was a commercially available pre-dispersed slurry. The SF
in Mixture Proportion #2 was a commercially available, densified
product.

A C 1 SP-153 VOL*II 95 = Obb2949 0523790 645 =
Azzregates
The fine and coarse aggregate both originated in the

Midwestern region of the United States of Am*erica. The fine
aggregate was a manufactured blend of natural sand and limestone
crusher screenings which meet ASTM C33 grading reqriirements.
The coarse aggregate was crushed dolomitic limestone, 1-inch
maximum size (ASTM #57 grading).
Water-reducing Admixture
A commercially available naphthalene-based condensate,

high-range water reducer (HRWR) was added to Mixture
Proportions #I and #2. The HRWR conforms to Type F
classifications according to ASTM C494.
A commercially available water reducer (ASTM C494,

Type A) was added to Mixture Proportion #2.
Air Entraining Admixture
In Mixture Proportion #1, a neutralized vinsol resin (ASTM

C260), a commercial air-entraining admixture, was used. No air
entraining agent was used in Mixture Proportion #2.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 Ob62949 0 5 2 1 7 9 1 5 ô L m
MIXTURE PROPORTIONS
Mixture Prouortion #1 (Pozzolans used as an Addition)
Thie concretes were prepared to a target slump of 102-152

mm. The water-to-cement ratio was maintained at 0.40. Air
entraining agent was adjusted to produce an air content of 5 to 7
percent. The pozzolanic materials, HRM and SF, were included as
additions, to the concrete. In this formulation, the SF was added as
a pre-dispersed slurry to the mix water during batching. The HRM
was added to the mixer in powdered form after the concrete had
been batched.
Fiine aggregate weight adjustments were made to maintain the

yield. Adjustments were made in the high range water reducer
(HRWR) to achieve the desired slump. Except for the concrete
prepared with SF slurry, no HRWR was added until the concrete
had been batched. The actual mixture proportions of the concretes
with pozzolans used as addition are summarized in Table 1.
Mixture Proportion #2 (Pozzolan used as Cement Replacement)
For these mixtures, the portland cement was replaced with

either HRM or SF. Unlike Mixture Proportion #1, the SF in this
formulation was a densified powder. Both the HRM and the SF
were added in conjunction with the cement during the batching
process.
No air entraining agents added to these concretes. Two

types of water reducers, ASTM C494 Type A and Type F, were
added. Adjustments were made in the Type F HRWR to maintain
a desired slump of 200-250 mm. The water-to-cementitious ratio
was maintained at 0.40. The mixture proportions of the concretes
with pozzolans as cement replacements are summarized in Table 2.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLrII 95 = 0bb2949 0.521792 4Lô M
PROPERTIES O F FRESH CONCRETE
The properties of the freshly mixed concretes for Mixture

Proportion #1 and #2 are shown in Table 3 and 4, respectively.
--``,`,-`-`,,`,,`,`,,`---
PROPERTIES OF HARDENED CONCRETE
For Mixture Proportion #1, the addition of pozzolans, the

compressive strength measurements are averages of three moist-
cured 152 x 305-mm cylinders. These results are listed in
Table 5.
For Mixture Proportion #2, replacement of cement with

pozzolans, the compressive strength measurement were an average
of two moist-cured 102,x 203-mm cylinders. Compressive
strength test results are summarized in Table 6.
Durability of the Mixture Proportion #1 concretes to

freezing and thawing was measured by the ASTM C666 Type A
method. The results of the testing appear in Table 7.
Rapid chloride permeability measurements were made in

accordance with AASHTO T-277. The test results are based upon
the average data of two 102 x 203-mm cylinders that had been
moist-cured for 56 days. Tables 8 and 9 show the permeability
results and ratings (according to AASHTO T-277) for Mixture
Proportion #1 and #2, respectively.

A C 1 SP-153 V O L X I 1 9s m 0662949 0523793 354 m
DISCUSSION OF TEST RESULTS
Water-R.educina Admixture Requirements
-
Mixture Proportion #1--The superplasticizer (HRWR)
dosage required for the control concrete was approximately 0.8 %
based upon the cement weight. As expected, because of the
addition of extra cementitious material of fine particle size, the
HRM required approximately 1.2 % based upon the weight of
cementitious material. However, the SF concrete required almost
1.9% based upon the total cementitious material.
T:he HRM concrete required significantly less (almost 50%)

HRWR (superplasticizer) than the concrete containing the SF
addition.
Mixture
Proportion #2--When cement replacement by HRM
-
was made, the amount of Type A water reducer was held constant
on the basis of portland cement only. Based upon the cementitious
weight, the total water reducer requirement was 1.3%, 1.7% and
2.4%, for the control, the 8.5% HRM replacement, and the
8.5 % S:F replacement concretes, respectively.
In this study, the HRM concrete required approximately

40% less HRWR (superplasticizer) than the SF concrete to achieve
an equal consistency.
-Compressive Strength Development
Mixture ProDortion #1--As shown in Table 5 , the strength

-
development of the concrete when HRM was used as an addition,
was significantly greater than that of the control concrete. The
strength development of the HRM concrete was similar to, or
slightly better than the concrete with the SF addition.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L b I I 95 M Ob62949 0523794 290 M
Mixture Proportion #2--The strength development of the

concrete in which portland cement was replaced with HRM was
significantly greater than the control concrete which contained only
portland cement (Table 6). The compressive strength of the
concrete containing HRM was similar to, or slightly better than the
concrete with the SF replacement of the concrete.
Freezing and Thawing Durability
Mixture Proportion #1--Because Mixture Proportion #1

contained entrained air, was tested for freezing and thawing
durability. Because the mixture was a high performance concrete,
all of the mixtures passed the freezing and thawing test (Table 7).
Mixture Proportion #2--No freezing and thawing durability

was tested, since no air entrainment was used.
Rapid Chloride Permeability
Mixture Proportion #1 --The addition of the pozzolanic

materials, either HRM or SF, reduced the chloride permeability of
the control concrete from an AASHTO T-277 rating of high to
very low (Table 8). The rapid chloride of the HRM concrete was
similar to that of the SF concrete.
Mixture Proportion #2--The replacement of cement with

pozzolans reduced the permeability rating of the concrete from an
AASHTO T-277 rating of low to a rating of very low (Table 9).
The rapid chloride permeability rating of the HRM concrete was
similar to that of the SF concrete,
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L Z I I 95 0662949 0523795 327
CONCLUSIONS
This study indicates that the inclusion of High Reactivity

Metakaolin (HRM) in portland cement-based concretes increased
the compressive strength and decreased the permeability without
affecting the durability to freezing and thawing. The HRM
improved the performance of the concrete both when used as an
addition and when added to the concrete as a cement replacement.
The improvement in the concrete performance with the HRM was
similar to the improvements obtained by the use of silica fume,
although the HRM required significantly less HRWR
(superplasticizer) than the mixtures containing silica fume.
REFERENCES
1. Ambroise, J., Martin-Calle, S. and Pera, J., "Pozzolanic Behavior of

Thermally Activated Kaolin", Proceedings of the 4th International Conference
on Flv Ash. Silica Fume. Slap.. and Natural Pozzolans in Concrete, Istanbul,
Turkey, 1992, AC1 SP-132, Volume I, pp. 731-748. Editor: V.M.
Mal hotra.
2. Larbi, J.A. and Bijen, J.M., "Effect of Mineral Admixtures on the

Cement F'aste-Aggregate Interface", Pr0ceedinp.s of the 4th International
Conference on Flv Ash, Silica Fume. Slae. and Natural Pozzolans in --``,`,-`-`,,`,,`,`,,`---
Concrete., Istanbul, Turkey, 1992, AC1 SP-132, Volume I, pp. 655-669.

Editor: V.M. Malhotra.
3. Bredy, P., Chabannet, M. and Pera, J., "Microstructure and Porosity of

Metakaolin Blended Cements", Mat. Res. Soc. SvmD. Proc., 1989, Materials
Research Society, Volume 136.
4. de Silva, P.S. and Classer, F.P., "Hydration of Cements Based on

Metakaolin : Thermochemistry", Advances in Cement Research, 1990, 3,
NO. 12, Oct., 167-177.
5. Lea, F.M., The Chemistrv of Cement and Concrete, 3rd Edition, New
York, N'Y, 1970, Chemical Publishing Company, Inc., pp. 414-453.

TABLE 1 - MIXTURE PROPORTION #1 PER CUBIC METER

(POZZOLANIC ADDITIONS)
10% SF
390
O
39
1035
686
6.9**
522
157
0.40
Water-To-Cementitious 0.41 0.36 0.36
--``,`,-`-`,,`,,`,`,,`---
Ratio
= 0662949 0523796 063

A C 1 SP-153 VOL*II
95 Not for Resale
A C 1 SP-I153 V O L X I I 95 m 0662749 0521797 TTT m
TABLE 2 - MIXTURE PROPORTION #2 PER CUBIC METER

(REPLACEMENT OF CEMENT WITH POZZOLANS)
I CONTROL I 8.5% HRM I 8.5% SF

--``,`,-`-`,,`,,`,`,,`---
Type I Cement (kg) 386 353 353

High Reactivity O 33 O
Metakaolin (HRM) (kg)
Densified Silica Fume O O 33
(SF) (k:g)
Coarse Aggregate (kg) 1032 1032 1032
Fine Aggregate (kg) 872 872 I 872
Type A Water Reducer 0.75
(1)
Type E: HRWR (1) 3.5
Water (kg) 154 154 154
~~
Water-To-Cement Ratio I 0.40 ~~
0.44 I 0.44
W ater-To-Cementi tious 0.40 0.40 I 0.40
Ratio
TABLE 3 - FRESH CONCRETE PROPERTIES OF MIXTURE
+
PROPORTION #1
CONTROL 10% HRM 10% SF

Slump (mm) 159
I
6.3
1
Air Content (%)
~ ~
6.2 6.2
Concrete Temperature 23 27 27
(“C)
1 Unit Weight (kg/m3) 2310
Initial Set (hrs.) 4.8

A C 1 SP-153 VOLaII 95 m Obb2949 0521798 93b m
CONTROL 8.5% HRM 8.5% SF

Slump (mm) 216 248 248
Air Content (%) 2.3 2.8 3.5
Concrete Temperature 20 21 22
(“Cl
Unit Weight (kg/m3) 2420 2410 2380
TABLE 5 - COMPRESSIVE STRENGTH DEVELOPMENT (MPa) OF

MIXTURE PROPORTION #1
COMPRESSIVE STRENGTH (MPa)

TESTING AGE
(DAYS)
7 1 33.1 I 52.5 I 44.0

1 I I
~~
28 41.0 63.0 57.7

90 I 51.4 I 64.2 I 63.7
360 I 59.2 I 72.1 I 68.3
TESTING AGE COMPRESSIVE STRENGTH (MPa)

(DAYS)
CONTROL 8.5% HRM 8.5% SF
7 59.0 72.8 66.0
28 68.9 85.8 84.2
56 78.0 94.2 93.5
90 83.8 112.7 105.7
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 Ob62949 0523799 872
CONTROL 10% HRM 10% SF

Dynamic Modulus, % 102 104 97
0.07 -0.59 -0.39
0.018 -0.043 0.034
TABLE 8 - RAPID CHLORIDE PERMEABILITY FOR MIXTURE
1 1 1 1
PROPORTION #1
1 Chloride Ion
Permeability,
Coulombs
. :Y
OC 1 0 8 r 1OG;F
TABLE 9 - RAPID CHLORIDE PERMEABILITY FOR MIXTURE

PROPORTION #2
CONTROL I 8.5% HRM I 8.5% SF I

Chloride Ion 1800 1O00 900
Permeability,
Coulombs
--``,`,-`-`,,`,,`,`,,`---

A C 1 SF’-353 V O L * I I 95 I0662949 0523800 3 3 4
SP 153-44
The Influence of Silica Fume on the

Heat of Hydration of Portland Cement
by M. I. Sánchez de Roias and M. Frías
S v p n o s i - Exothermal reactions take place during cement

hydration and heat the cement mass. This temperature
increase, from the initial moment of setting until the
hardening of the cement, causes shrinkage which
contributes to the cracks that can be seen in some
constriictions that are made of large masses of concrete
or cement rich mixtures.
The use of pozzolans reduces the heat given off by the
cemente during hydration. However, the reactions of the
pozzolanic materials with the lime also produce heat and
the decrease should not be proportional to the level of
clinker substitution in the mixed cements. The first
hours show that most of the additions, which present
higher activity at early stages, increase the hydration
heat of the mixed cements in relation to the control
cement,,
The effect of different silica fumes on the hydration
heat with respect to a control cement and other
pozzolanic materials was studied in this paper.
Kevwords: Cements; fly ash; heating; heat of hvdration; portland cement;

silica fun-
--``,`,-`-`,,`,,`,`,,`---

829
A C 1 SP-153 V O L U I I 95 0662949 052180I1 250 9 =
830 Sanchez de Rojas and Frias
M.I. Sanchez de Rojas, PhD in Chemical Sciences.

Researcher of the Instituto de Ciencias de la
Construcción Eduardo Torroja (CSIC). Her reseach work
deals with the characterization of pozzolanic materials.
M. Frías, Ph. D in Chemical Sciences. Researcher of
Instituto de Ciencias de la Construcción Eduardo Torroja
(CSIC). His reseach work focused on the use of by-
products in cements and concretes.
INTRODUCTION
Mineral additions generally help to decrease the heat of

hydration of cement ( 1 ) ( 2 ) ( 3 ) and therefore, in massive
concrete constructions, pozzolanic materials and
particularly fly ash are incorporated in portland
cements. Therefore, pozzolanic materials were studied,
particularly the control and quantification of the heat
of hydration (4)(5)(6)( 7 ) .
The results obtained in the previous work using the
--``,`,-`-`,,`,,`,`,,`---
Langavant Calorimeter method (8) on the hydration of

portland cements with different mineral additions show
that in cements with fly ash the evolution of the heat
of hydration is principally influenced by the dilution
of cement in the mixture. The proportionality between
the decrease of the heat of hydration and the percentage
of addition is greater when natural additions, with a
greater reactivity at earlier ages, are used.
This paper presents the results obtained using the
Langavant Calorimeter on portland cements with different
proportions of silica fume with respect to a control
cement. The effects of silica fumes from different
sources on the heat of hydration were studied too. At
the same time, a comparative study was made between
these results and those corresponding to a fly ash with
a low lime content.
Mixed cements were designed with different percentages

of cement and silica fume (SF1): 100/0, 9 5 / 5 , 90/10,
85/15 and 7 0 / 3 0 . Measurements of the heat of hydration
of these blended cements were given using the Langavant
Calorimeter ( 9 ) , in order to establish the influence the
silica fume content.

A C 1 SP-153 VOL*II 95 0662949 0523802 1 9 7
A study was also made on the effect of different silica

fumes ( S F 2 , SF3, SF4, SF5, SF6 and SF7) on the evolution
of the heat of hydration given, in cements with 1 0 %
silica fume.
A comparative study was also carried out between silica
fume arid fly ash in mortars produced with the same base
cement, in relation to the variations observed in the
heat of hydration.
EXPERIMENTAL
Materi-2
* Base Cement: According to the Spanish UNE 8 0 301

standard ( 1 0 ) , the base cement is a Type Il45 A cement
with at: least 95% of clinker.
* Si1ic:a Fume: The silica fumes used in this study were
obtained from different countries. Their chemical
characteristics followed Spanish experimental standard
UNE 8 3 460 ( l l ) , given in Table I.
X-Ray Diffraction patterns showed the low crystallinity
nature of silica fumes, with low intensity peaks
corresponding mainly to quartz, silicon carbide and
silicon.
The granulometric distribution was given by a Laser
Diffraction method ( 1 2 ) . Fig. 1 shows the particle size
distribution curves for each of the silica fumes
considered; similar particle size intervals are observed
in all of them except for silica fume SF2. These silica
fumes appear coarser than usual.
* Fly Ash: This is generated in a power plant that uses
bituminous and anthracite coal as a power source. The
loss on ignition value ( 0 . 9 % ) reflects its low unburned
content, of which the main constituents are silicon,
aluminium and iron, so that it is a fly ash with a low
calcium content ( 2 . 9 % ) . The main crystalline components
are quartz, mullite and hematite (13).
* Sand: The sand used is of siliceous origin with a
silica content of more than 9 8 % and maximum particle
size of less than 2 mm.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m 0 6 6 2 9 4 9 0523803 023 m
Mixture Proportions
The mixtures were prepared in a high speed powder mixer

. to guarantee their perfect homogeneity and safeguard
their granulometry.
In this way the mixed cements prepared are formed by
cement and the addition of the following percentages,
referring to the weight of the materials:
* Base CementISilica Fume (SF1): 100/0, 9515, 90/10,
85/15, 70130
* Base cementlsilica Fume (SF2, SF3, SF4, SF5, SF6,

SF7): 90/10
* Base Cement/Fly Ash: 7 0 1 3 0
These mixed cements are used to prepare mortars, whose
sandlcement proportion is 3/1 and the W/C is 0.5.
Method
The method given for determining hydration heat in the

Spanish standard (9) is based on the Langavant
Calorimeter (14) .
The semi-adiabatic method consists in quantifying the
heat generated during cement hydration using a Dewar
flask, or, more exactly, a thermally isolated bottle.
Since the exterior conditions are very influential, the
test is carried out in a climatized room at 2OoC f 2OC.
For this purpose the cement under study is used to make
up a test mortar that is placed in a closed vessel which
in turn is placed within the isolated bottle. The mortar
temperature during the course of hydration is compared
with that of a thermally inert mortar (one which was
mixed up earlier, at least three months before testing,
following the same standard).
Heating is the name given to the difference between the
heat given off by the mortar tested and the heat from
the control mortar. This value of heating is used to
calculate of the heat of hydration developed by the test
sample.
The measurements were made during five days as indicated
by the standard (9). The heat increase is very low at
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-:L53 VOL*II 75 0662949 052LB04 T b T
later t.imes, and the relative error of the measurement

increases beyond that time.

--``,`,-`-`,,`,,`,`,,`---
The study includes the following aspects:

- The influence of the silica fume percentage on the
heat of hydration on blended cements.
- The effect of different silica fumes on the heat of
hydration.
- The comparison with a fly ash.
I. =ifluence of the silica fume percentaqe on the heat

of hvdration on blended cements
-
Fig. 2 shows the evolution of the heat of hydration over

time, i~pto an age of 5 days (120 hours) , in blended
cements prepared with different percentages of silica
fume ( S F 1 ) .
This graph shows that, in general, the cements in which
silica fume is included, show that greater heat is given
off, in comparison with the control cement.
The effect is also observed in Fig. 3 which shows the
evolution of heating with the different mixtures
analyzed. Figure shows that the maximum heat given off
occurred approximately 18 hours after the commencement
o f the test. The appearance of this maximum is slightly
earlier when silica fume is added, although the .greatest
differences occur in the intensity of the peak.
These results indicate that there are two different
effects to be considered regarding the behaviour of
silica fume: on the one hand its pozzolanic activity,
and on the other the influence of substituting portland
cement by silica fume (effect of dilution).
Thus, in the mixed cement prepared in a proportion of
9515, the addition of silica fume and its pozzolanic
activity increase the heat developed during hydration
compared to the base cement; however, this increase is
not so noticeable as it is in the case of mixed cement
preparsed with percentages of 9 0 1 10, where the greater
silica fume content causes the pozzolanic reaction to

A C 1 SP-353 V O L X I I 95
834
Obb2949 O523805 9Tb =
Sanchez de Rojas and Frias
occur to a greater extent, therefore causing greater

heat of hydration.
However, when the 85/15 dosage is analyzed, a similar
hydration heat is found to that of the control cement.
This may be due to 15% silica fume being excessive for
reaction with the calcium hydroxide available at these
ages; therefore, the larger substitution of cement
counteracts the heat arising from the pozzolanic
reaction.
This fact is much more evident in the case of the 7 0 1 3 0
proportion where the predominant effect is that of
substituting cement by a large amount of silica fume,
which, due to the lack of portlandite available, acts as
filler as shown by less heat being given off than in the
base cement.
Fig. 4 shows the evolution of the heat of hydration
during the first 12 hours of the test. It is observed
here the important activity of the silica fume which is
able to react with the calcium hydroxide given off
during the hydration of the portland cement at very
early stages, since during the first hours all the mixed
cements give off greater heat than the control cement,
including those made up with a 7 0 1 3 0 proportion,
although after 10 hours, and due to the effect indicated
above, the latter is below the curve corresponding to
--``,`,-`-`,,`,,`,`,,`---
the 100/0 proportion.

The increase in hydration heat caused by the
incorporation of silica fume may reach 80 J/g, Fig. 5,
where zero is given for the hydration heat developed by
the base portland cement and the differences (positive
and negative) found for each of the mixed cements
tested.
In the case of mixed cement with a proportion of 7 0 1 3 0 ,
the decrease in heat after 10 hours is 20 J/g,
representing less than 10 % of the decrease against the
control cement. Therefore, no correlation is observed
between the decrease in heat and the degree of
substitution of cement due to the pozzolanic reaction
that takes place (15).
II Effect of different silica fumes on the heat of

hydration
In order to carry out this test, silica fumes from

different countries were selected; their characteristics

A C 1 SP-153 V O L X I 1 95 IOb62949 05218Ob 832 D
are shown in Table I.

Mixed cements were prepared with percentages of 10% in
each of these silica fumes: SF1, SF2, S F 3 , S F 4 , SF5 and
SF6.
Fig. 6 , 7 show the evolution of the heat of hydration

and heating respectively. In both cases it can be seen
that a11 the silica fumes tested showed similar
behaviour, with higher and earlier heat of hydration and
heating compared with the base cement.
At the end of the first 12 hours, Figure 8 , it can be
seen that all mixed cements behave in a similar manner
and no significant differences exist between them.
III G)mparative studv with flv ash
This comparative study was carried out with mixed

cements; made from 70% base cement and 3 0 % mineral
add ition.
The materials added to these mixed cements were silica
fume (SF1) and a fly ash with a low lime content.
As can be observed in Figure 9 , where the heat of the
hydrati-oncontrol cement is taken as zero, the increase
in hydration heat (positive values) is due to the
incorporation of silica fume and not to the fly ash,
which always decreases the hydration heat with respect
to the control cement ( 8 ) . This is because fly ash is
slower in its pozzolanic activity and therefore the
dilution effect is predominant. However, the silica
fume, with greater early activity, increases the heat
during the first hours of the test. Although beginning
--``,`,-`-`,,`,,`,`,,`---
at 10 hours the effect can be seen clearly.
CONCLUSIONS
* Silica fume increases the heat of hydration of

blended cements due to the pozzolanic reaction with the
calcium hydroxide liberated in the hydration of the
port land cement.
* This increase in the heat of hydration is found to a
greater degree in mixed cement made with 10% silica
fume, :Ln which the predominant effect is the pozzolanic
reaction. On the contrary, when 3 0 % silica fume is

A C 1 SP-153 VOLUII 95 m Obb2949 0523807 7 7 9 m
836 Sáncher de Rojas and Frias
incorporated, dilution effect is predominant.

* Maximum heating takes place slightly earlier in mixed
cements with silica fume, than in portland cement
without additions.
* The behaviour of different silica fumes in blended
cement is very similar.
The pozzolanic activity in these materials, and
particularly in the early stages, plays an important
role in the heat of hydration. Thus when low heat
cements are required for a construction, this must be
taken into consideration, since the dilution of
portland cement by additions is not the sole factor to
be considered.
In cements containing fly ash, the evolution of
hydration heat will be mainly influenced by the decrease
in the proportion of cement within the mixture. The
ratio between the decrease in hydration heat and the
percentage of mineral addition incorporated will be
larger in cements which have additions with higher
reactivity at early ages ( 8 ) .
--``,`,-`-`,,`,,`,`,,`---
When using fly ash, the advantages of low heat of

hydration have to be considered in relation to the
possible reduction of strenght. This is not the case
with silica fume cements which result in higher heat of
hydration and higher strenght.
The data offered by this paper indicate that a
correlation exists between the results obtained for
hydration heat, using the Langavant calorimeter method,
and the activity of silica fume. This allows to select
the appropiate percent of silica fume for a particular
application.
REFERENCES
1.- SPRINGENSCHMID, R.: Ilcracks in Concrete Caused by

the Heat of Hidration". Zement Kalk Gips, N. 3,
1991, 132-138.
2.- MASSAZZA, F. : "Structure of Pozzolan and Fly Ash

and the Hydratation of Pozzolanic and Fly Ash
cements". 7th Int. Congress on the Chemistry of
Cement. Paris, 1980,IV, 85-96.

A C 1 SP-153 V O L X I I 95 = 0662947 0521ô08 605 =
3.- UCHIKAWA, H.: IIEffect of Blending Components on

hydration and Structure Formationt1, 8th Int.
Congress on The Chemistry of Cement. Rio de
Janeiro, 1986, I, 249-280.
4.- RIO, A.; CELANI, A.; MIELE, A.: llSulla
Determinazione del Calore di Idratazione dei
Cementi Pozzolanici con il Metodo del Calore di
SoluzioneI1. L'Ind. Ital. Cem., 1964, N.4, 223-232.
5.- KOKUBU, K. ; TAKASHASHI , S. ; ANZAI, H. : "Effect of
Curing Temperature on the Hydration and Adiabatic
Temperature Characteristics of Portland cement
Blast Furnace Slag Concreteq1.3th CANMETIACI Int.
Conference on Fly Ash, Silica Fume, Slag, and
Natural Pozzolans in Concrete. Trondheim, 1989, 2,
1361-1376.
6.- DOUGLAS, E.; ELOLA, A.; MALHOTRA, V.M.:

"Characterization, conduction Calorimetry,
Microstructure and properties of Ground Granulated
Blast Furnace Slags and Fly Ashesll. 3th CANMET/ACI
Int. Conference on Fly ash, Silica Fume, Slag, and
Natural Pozzolans in Concrete. Trondheim, 1989,
Supplementary Papers, 618-640.
7.- COSTA, U.: "A simplified Model of Adiabatic
Calorimeter1#.I1 Cemento, 2, 1979, 75- 91.
8.- SANCHEZ DE ROJAS, M.I.; LUXAN, M.P.; FRIAS, M . ;
GARCIA, N. : "The Influence of Different Additions
on Portland Cement Hydration Heat". Cement and
Concrete Research, 1993, 2 3 , N . 1 , 46-54.
9.- Norma UNE 80 118 86: "Métodos de Ensayo de
Cementos. Ensayos Físicos: Determinación del Calor
de HidrataciÓn por Calorimetria Semi-adiabática
(Método del Calorimetro de Langavant)Il.
10.- Norma UNE 80 301 88: IlCementos. Definiciones,
Clasificación y Especificacionest1.
11.- Norma UNE 83 460 94: "Adiciones al hormigón. Humo
de sílice. Recomendaciones generales para la
utilización del humo de siliceIl.
12.- FRIAS, M.; LUXAN, M.P.; SANCHEZ DE ROJAS, M . I . ;
GARCIA,N.: IIGranulometric analysis of fly ashes by
laser diffractionIl. Advances in Cement Research,
1990, 3 , n.10, Apr, 47-54.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 W Obb2949 0523809 541 W
13.- LUXAN, M.P.; SANCHEZ DE ROJAS, M.I.; FRIASIM.:

I1Investigationson the Fly Ash - Calcium hydroxide
.
Reactionsll Cement and Concrete Research, 1989 , 19,
69-80.
14.- ALEGRE, R.: IlLa Calorimétrie des Ciments au

CERILH". Revue des Matériaux, (547) 1961, 218-229.
(548) 1961, 247-26.
15.- LESSARD, S.; AITCIN, P.C.; REGOURD, M.:

"Development of a l o w heat of hydration blended
cement". proceedings of the CANMET/ACI First Inter.
Conference on the use of fly ash, silica fume, slag
and other mineral by-products in concrete,
Montebello, 1983, 2 , 747-763.
TABLE 1 - CHEMICAL CHARACTERISTICS OF SILICA FUMES
Silica Fume I LOI(%) CL- (%) s i 0 2 (%)

SF1 6,60 oro1 91,22
SF2 2,94 0,16 93,30
SF3 1,13 0,06 92,ll
SF 4 1,67 0,07 92,46
SF5 2,03 Oto4 90,35
S F6 234 0,03 96,08
SF7 6,30 O 80,85
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 Obb2949 0521810 2b3 =
Volume distribution
A- SF3
0- SF4
0.9 +- SFI
O- SF5
pr) 0.8 a- SF6
o O- SF2
f 0.7
.-c
-- SF7
-3
O
O. 6
5
o 0.5
L
o
?3 0.4
0.3
(L
o. 2
o. 1
O
10-1 10' 102
loo x-microns
--``,`,-`-`,,`,,`,`,,`---
Fig. l-Granulometric distribution curves of silica fumes (laser

diffraction)
...
...
...
...
...
...
...
I I I I 1 I I I I I l
O 10 20 30 40 50 60 70 80 90 100110120130
Age, hours
Q- 10010 * 95/5 +e 9011O f 85/15 * 70130

Fig. 2-Heat of hydration over time. Base and mixed cements

A C 1 SP-I153 VOLL11 95 W 0662949 0 5 2 1 8 1 1 LTT W
....................................
.........................
.............
10
II ‘‘‘sa, ........................
O
O 10 20 30 40 50 60 70 80 90 100110120130
Age, hours
-0.10010 * 95/5 * 90110 * 85/15 * 70130
--``,`,-`-`,,`,,`,`,,`---
Fig. %Heating over time. Base and mixed cements
...............
fl
uI-I ...............................................................
I
...... ....................
c,
L 200 ... ......... ... .......................
‘E!
................................ ...............
y.
O
.......................... .......................
c,
o
Q
50 . . . . . . . . . . . . . . .............................
I I l I I I I l I 1 I
O 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2
Age, hours
* 10010 * 9515 90110 f 85/15 * 70/30

Fig. &Heat hydration (12 hr). Base and mixed cements

A C 1 SP-153 VOL*II 95 Obb29Y9 0.521812 036
-? 80- ..................... ............................

7
--``,`,-`-`,,`,,`,`,,`---
..........................................
r
-40-. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
O, 1 2 3 4 5 6 7 8 9 1011 1213141516
Age, hours
* 95/5 CI- 90110 + 85/15 * 70130

Fig. %Ratio between additions percentage and base cement
......................................................
O 10 20 30 40 50 60 70 80 90 100110120130
Age, hours
+Base Cement *SF1 *SF2 +SF3 *SF4 *SF5 *SF6 *SF7
Fig. &-Heat hydration over time. Effect of different silica fumes

A C 1 SP-153 V O L X I I 95 O662949 0521813 T i 2 = m
. . . . . . . . . . . . . . . . . . . . . ..................
. . . . . . . . . . .
. . . . . . . . . . . ...................................
--``,`,-`-`,,`,,`,`,,`---
............
10
O
O 10 20 30 40 50 60 70 80 90 100110120130
Age. hours
"Base Cement * SFI +e SF2 * SF3

* SF4 -+- SF5 * SF6 * SF7
Fig. -/-Heating over time. Effect of different silica fumes
m
350 1 I
O 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2
Age, hours
Q Base Cement *-SF1 * SF2 + SF3 * SF4 * SF5 * SF6 * SF7

Fig. &Heat of hydration (12 hr). Effect of different silica fumes

A C 1 SP-153 V Ò L * I I 95 0662949 052LBL4 909
40
F
7
20
E a
.-O
tr
-20
U
2-40 ..............................................................
w-
O
c,
m
I -80
-60
-1O0
O 1 2 3 4 6
1
..............................................................
..............................................................
5 7
Age, hours
8 9 1011121314
*FLY ASH e SILICA FUME
Fig. %Heat of hydration: Fly ash and silica fume
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 Obb2947 0521815 8 4 5
SP 153-45
Studies on Ferrocement
Containing Silica Fume
by M. Tamai and T. Takaya
Synopsis: Ferrocement is a form of reinforced concrete using closely

spaced multiple layers o i mesh and/or smail-diameter rods completely
infiltrated w i t h , or encapsulated, in mortar. The presence of wire
mesh reinîorcernent in ferrocement improves crack resistance, iiltimate
strength and toughness. In recent years, due t o increased awareness
of the need f o r conservation of ncm-renewable t o p i c a l f o r e s t r e s a r c e s ,
increased consideration is being given t o the use of ferrocement as a
substitute for wood.
In this paper, mechanicai properties of t h i n ferrocement plôtes
(thickness:lOmm) made of cement mortar ríixed with silica fume as a
mat,rix and two kinds of wire mesh as reinforcement were investigated.
The effects of the reinforcement a.rrangerneriis on strength and
--``,`,-`-`,,`,,`,`,,`---
defornialional characteristics of ferrocement in direct tension and
simple bending were studied experimentally. Test results indicate
that ferrocement containing silica fume has higher workabj lity,and did
not segregate iii fresh state. Rietests show higher ultimate strength
as well as toughness compared with the normal ferrocement.
Kevwords: Concretes; ferrocement; modulus of elasticity; silica fume;

strength:, superplasticizer; tensile strength; toughness; welded wire fabric

A C 1 SP-153 V O L U I I 75 m Obb2747 052181b 7 8 1 m
846 Tamai and Takaya
M.Tamai, Dr.Eng. is a professor of constructional materials a t the

Civil Engineering Dept., Kinki iJni-Jersi ty, Osaka 577, Japan.
He i s a member of JSCE, JCI and ACI. His main interests are related t o
functional cement concrete and iiti!isiation of poder wastes as
construct ion mater ia 1.
T.Takaya i s a research engineer of Hirose Co., Ltd., Osaka 550, Japan.
His main interest i s related to concrete tecnology, especiaiy design
and construct ion of underground concrete structure.
INTRODUCTION
Composite materials arc: produced from a t least two kinds of

materials in combination so as t o have desired fuiictions. World-
wide>a variety of composite materials, including rubbers, plastics,
metals, ceramics, c0ncret.e. aspha.1t, etc. are !inder investigation.
In the f i e l d of construction materials. concrete reirif'orced with
steel i s a popular composite material, and it, use has rapidiy
expanded since 1867. Recently, continuous fiber reinforcing materials
including fibers of carbon, Aramide etc., which are light.--weight and
anti-corrosive, have been investigated. However, a reinforcing
material, which has a low elongation ratio a t fracture and exhibits no
yield, tends to be fractured abruptly. Therefore, composite materials
ccntaining chemicai fibers f o r major reinforcement tend t o suffer
b r i t t l e fracture. This is unfavorable property f o r their application
in structurai concrete. For the purpose of eliminating the above
shortcoming, it i s proposed i o use, as reinforcing material, wire-net
shape steel fibers having a high shear strength, a high elongation
capability. and a yield range. Such composite material i s ferro-
cement which has been used in the production of water tanks and canoes
et.c. in Cceania for a very long time.
This study aims a t developing high strength, thin ferrocement
materials for use in pernianent molds, utilizing the following
approach :
(1) In order to enhance the strength of cement mortar matrix, which
is one of the coristituents of the furrocement, s i l i c a fume and a
superplasticizer are used as admixtures (1).
(2) The effect of the different types of wire-mesh steel fibers as a
reinforcing material and their arrangement in ferrocement, on
the tensi le strength, bending strength and toughness are empiri-
cally investigated. The bending moments are calculated by the
AC1 method (2).
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 IObb2747 0523837 bL8 I
NATERIALS AKD MIXTURE PROPORTIURS ÛF MORYAK

Cement aiid Si 1i r a FE
Normal portland cement was utilized. The s i l i c a fiime used was of
the powder type. Physical properties and chemical analysis are given
i n Tôble 1.
Superphjt icizec
The :';üpXplasticilier used was h naphthalenebased product.
Fine Aggregate
A fine aggregate with a 0.6 - 0.15 rnm s i z e range and a specific
gravity of 2.58 was used.
Reinforcing Batur ia-

A square wire mesh and three kind of expan<i.ed metal mesh were used
f o r reinforcement.Their shapes and physical properties are shown i n
Tabie 2.
Hixture Proport.ions of Mortar
The proportioning of the mortars are summarized in Table 3.
FABRICATION AND CURING OF SPECIMENS

The flow values of mortar were controlled a t 210I10mm. The fabri-
a t i o n of cement mortar was carried ont as shown i n the flow chart of
Big.1. Reinfurcing materials were arranged t o be i n the center of
ferrocenient specimen. The specimens were relezsed from the mold at
an age i,f 1 day and i;iired i n water at. 2OiZC until age 28 days.
A tensile test. specimen is iiliistrated in Fig. 2, and a bending
test specimen i n Pig. 3 (33. Different types of wire mesh were
arrarrgerl in t h e specimens.
EXPERIMENTAL PROCEDURES
The strength test of the cernent mortar was carried out according
t o JIS li 5201. The tensile test was conducted as illustrated in Fig.2.
w i t h 0.2 MPa/s loading rate. The bending t e s t was conducted by the
three-points loading method Using a span of 33 cm, as shown i n Fig.3.
The loading r a t e was lEPa/gin. For strain measuremect, a wirc strain
gauge was attached t o the upper and lower surfaces of the test
speciriien. The deflection of the t e s t specimen was measured with
a dial Fauge.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 = Obb2949 0521818 554
EXPERIMENTAL RESC'LTS AND DISCUSSION

Strength Test of Cement Mortal:
Fig. 4 shows stress-strain curves given by the compressive strength
t.est of cylinder test specimens. The comparison of the mixture types
A and B show that the inclination of the curves,(i.e., the elastic
modulus) are nearly equal to each other. C h the other hand, the
mixture type B exhibits a higher cornpressive strength. reflecting the
effect of the added superplasticizer. The mortar mixed with silica
funie exhibits a strength about 1.2-1.4 times higher that t.he mortar
without t h e silica fume. In the case of the silica fume containing
nortar, the gozzoimic reaction and the microfi Iler eifect ma& the
mortar matrix denser. The highest strength was obtained by the mortar
containing a silica fume substitution ratio of 20%.
Tensi le Strength Test

1. Effect. of Mortar Mixture Type
Pig. 5 illustrates the load-strain relations of the test specimens
containing WH-5 as reinforcing materiai a i d mixtiire type A-1). I t is
generally known that mortar tias an elongation ratio of 200 t o 300 c.
This means that the initial cracking is caused near the elongation
ratio. The elastic modulus is enhanced by the incorporation of silica
firne. This causes the load a t cracking t o increase t o some degree.
2. Effect of the Number of WM Sheets
Fig. 6 shows the load-strain relations of specimens produced from
the mortar mixture type D and uire meshs WH-3 t o WH-5. With the
amount of the reinforcing materials, the final fracture strengths are
increased, and also the ferrocement modulus of elasticity are enhanced
with the load a t cracking.
3. Effects of Types of Reinforcing MaLerials
Fig. 7 illustrates the load-strain relations of specimens prduced
from the mortar mixture type D, with parameters of EM-S, EM-M. and
EM-L. The ratio (Vf) of the reinforcing materials were calculated
by the equation (1) and are shown i n Table 2. Though the Vf of EM-S,
M-M are nearly equal to those of WM-3, WM-4, the specimens are
deformed in different ways (2).
Vf = Vs/Vfc ._,._.____.____._..........._..._.........._.*...
(%)....__.___..__......... (1)
where, Vf: volume fraction of reinforcement
Vs: volume of reinforcing material
Vfc: volume of specimen
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-It53 V O L * I I 95 I0 b b 2 9 4 9 052LBL9 490
4. Effects on Cracking and Fracture States

A comparison of the cracking p a t t e r n shows t h a t the s p e c i m e n s u s i n g WM
as reinforcing material are cracked in the perpendicular direction t o
the load axes, and the cracks are favorably distributed. The use of
E3 causes a different cracking p a t t e r n ; the tens ion force
i s applied in such a direction that the mesh openings are closed, and
the cracking tends t o occur i n the axial direction. The tension of
ferrocement i s greatly infjiienced with the shearing force acting at
the interface between the reinforcing material and the matrix. The
tension properties of the ferrocement specimens are different, depend-
ing on the contact areas per a unit volume, even a t same Vf. The
surface areas per a unit length(%) were calculated by the equation
(2) according t a the AC1 method(2). and are shown in Table 3. As seen
from these values, Sr of the specimen using WM, hac an effect on the
adhesive properties of the specimens. That is, the WN with t h e sur-
face area i s ePfective in improving the distribution of cracks and
the fracture state.
Si-=C __
......_...._________
_______......_..___.____._______________.....
(2)
Where, Sr: specific surface of reinforcement
Co: total siirface area of bonded reinforcement per unit
length
h: width of ferrocement section
n: thickness of ferrocement section
Beiiding :Strength Test of Ferrocement

I . Effect -
of Mortar Mixture Type
Fig. 8 shows the load-deflection relations of the specimens produced

from the mixture types A, E and C. using WN-3 for the three mortars.
Each curve shown in the figure has two point of inflection, which are
caused by the generation of the i n i t i a l cracking and t h e yield of the
wire mesh, respectively. The incorporation of s i l i c a fume makes the
--``,`,-`-`,,`,,`,`,,`---
mdiilus of e l a s t i c i t y of ferrccement higher, and increases the load

rwuired t o cause the same deformation. That is, the load a t cracking
and t h e load a t fracture are enhanced. The cracks were distributed
discretely in correspondence t o the mesh openings. The speciinens
were broken and led to the final fracture, without being peeled.
The specimens mixed with s i l i c a fume exhibited a high adhesion to the
wire meshs.
2. Effects of Number of Wire Mesh Layers
Fig. 9 j llustrates the load-def lection relations of the specimens
produced from the mixture type D, employing different wire mesh
arrangements, WM-3 t o WM-5. As the weight of the inserted wire mesh
is higher, the load i s increased. However, i n the case of five sheets
of wire meshs inserted, the coverage of the mortar is relatively thin,
and the increase of ihe load tends to be minimized. When the ferro-

A C 1 SP-153 VOL*II 95 S 0 6 6 2 9 4 9 0523820 L O 2 =
cernent specimen uses a plural-layer reinforcing material of WH type,

the load applied t o the specimen continues t o increase even after it
begins t o be cracked, and the tecoiiics constônt afterthe îeinforcing
material begins t o yieid, while the deformation continues.
3. Effects of Reinforcing Material Types
Fig. 10 illustrates the load-deflectien rerations of the specimens
produced from the mixture type D, employing different types of wire
meshs, EK-S te EA-L. Table 4 tabulates t.he ratios Vf of the wire
nìesh reinforcing materiais and the ratios Sr of the surface areas.
EM has properties different from UM, and has a higiier stiffness(Ei1)
and a lower surface areaiSr) than WM. Therefore, the specimens using
EM tend t o reach the aaximcn load with relat.iveiy small deformation,
and the mortar is peeled and abruptly fractured sincr the adhssiori
area of EB t o the mortar is small.
4. Effect of Composite Reinforcing Materia!
Fig. 11 shows the load-defrectÄon i elations of the specirsns

produced from the type D mortar and the wire meshs of types MH-X and
NM-Y. The sire mesh of MM is so designed io have a higher stiffness
from EH, WM and improved adhesive properties for mortar on the tension
side. The loads and defrections ofthe specimens after yielding are
enhanced. The specimens were prevented fror being fractured abrUptly.
and cracks were favorably distributed.
Considerat ion of Balanced Reinforcement Ratio
As t o the consideration of the fracture state, the ferrocement
using a reinforcing material concentrically, first the mortar was
crushed. Such fractures are caused abruptly and ara very undesirilble.
The wire mesh of EM-L, correspondent to. the above ferrocement, using
the wire nesh inserted only i n the center. The balanced reinforcement
ratio suggests the abrupt occurrence of the fracture. As seen in the
--``,`,-`-`,,`,,`,`,,`---
above description, the incorporation of silica fume enhanced the

cracking strengtli and the tiltimate strength and improved the adhesion
of the mortar t o the reinforcing material. Also, i t is shown that the
cracking state and the fracture-form are different, depending 3n the
types of the reinforcing materials and the differeat arrangements.
Calculation of Ultimate Moment Strength
The fracture bemiirqy moment was examined according t o the guide of
AC1 Committee Guide 549. The nomene values were calculated by the
equation (3). Table 5 tabulates t h e experimental values of the
ultimate moment and the calculation values obtained by the AC1 method
when the mixture D was used as Lhe matrix and ferrocement of M-3 t o
WM-5 Fias done. The test specimens were thin. with a thichess of 10
rom, making i t difficult t o calculate the areas of cross-sectioris.
Due t o such difficulties, the calculat.ed values were approximated.

A C 1 SP-153 V O L * I I 95 M 0662747 0521821 047
Where, Csi=(fsi-O.%f’ c)Asi, Tsi=fsi-Asi,

Mn: nominal momeiit strength
f’c: spscified compressive strength of mortar
f s i : stress in reinforcing layer i
di: distance from e x t r e k compression f i b e r t o centroid of
reinforcing layer i
C : distance from extreme compression f i b e r toneutral axis
8 : : factor defining depth of rectangular stress block
Asi: effective cross-sectional area of reinforcement of
mesh layer i in the direct.ion considered
Toughness Evaluation by Bending Test
Conventionally, the fracture of t h e c o n c r e t e and mortar has been
investigated, based on strength. In recent. investigations of iracture
behavior, not only its strength but its toughness at. fracture is
considered. In the case of concrete mixed with short fibers, some
--``,`,-`-`,,`,,`,`,,`---
evaluation methods f o r toughness have been investigated, (the degree
how the concrete durability changes with the progress o í the deforma--
tion.) For example, according t o the AC1 inethod, t,he toughness of
a specimen where the s i z e is 10XlOX40 cm is evaluated based on the
area definedby the load-displacement curve. By the JSCE method
for toughness estimation. the area defined by the load-deflection
curve of a specimen i s processed according t o the calculation formula
considering the s i z e of the specimen. In addition, Kodulus Of
Toughness(HOT1 has been proposed for tho estimation of the deformation
capability and strengths of a specimen a f t e r i t begins t o crack.
This aethod is assumed t o be most adaptable t o ferrocement. Accnrdiw
t o t h i s method, the toughness of a specimen is evaluated based on the
range of’ energy of thc specimen, since the basic load(ioad applied a t
the s t a r t of cracking! is applied. MOT value i s obtained by
caìcuiat.ion using equation (4).
In principie, MOT is used for the evaluation of the toughness of
a specimen when the deflection is 1/150 tims of its span :ength(L=
300 mm). In t h i s study, the toughness a t a deflection of U 2 0 times
of the span length was evaliia.ted, since ferrocement exhibits a
relatively high deflection. Table 6 shows the HOT values calciilated
using equation (4). The specimen containing silica fume had an
increased HOT, in addition t o a higher ultimate bending load, as
comparecl with those excluding s i l i c a fume. The MOT values are higher
in the order of E#, WM, and MM. In the case of E E L haviiig a high
ultimate bciiding load, but it c a n n o t be stated that EM-L has a higher
toughness than any other wire msh.
fiOT-100.2s/ (Pc.K)+200 .................................................................... (4)
Where, MOT: Modulus of toughness
S : area of triangle xyz
Pc: cracking load
K : increasing value of deflection from cracking load

A C 1 SP-153 V O L S 1 1 95 m Obb2947 0523822 T ô 5
CONCLUSION
1. The types of cement mortar nixed w i t h siiperpiasticizer and silica
fume present an improved workalility while in their fresh stage so
that they can flown even through narrow mesh openings t o produce
homgeneous ferrocement. The use of superplasticizer with silica
fume and helps facilitate the production o f high strength ferro-
cement of which the strength after hardening is increased by 50 t o
60% as compareà t o that of normal mortar.
2. As revealed by the tensile test, the cement mortar with silica
fime exhibited an enhanced modulus of elasticity and an increased
cracking strength. Moreover, the silica fume mortar had high
bonding properties with reinforcing materials. I t has been
shown that the loads a t fracture are different depending on the
reinforcing material utilirjsed, especially w i t h respect to the
different surface areas, even when the voliimes of the reinfocing
materials were equal.
3. The bending test of‘ ferrocemerit. has shown that the cracking loads
are influenced with the strengt.h of the matrixes and the thickness
of the matrix coverings n f the reinforcing materials on the
tension side, i n addition t o Lile type of the reinforcing materiais
--``,`,-`-`,,`,,`,`,,`---
4. The results of the ultimate bending ionen!. test calculated by the

AC1 method show that, for the reiforcin! materials of WM type, the
calculated values are substantial iy equal t o the experimental
values.
5. The different toughness evalliation methods were exmined based on
the deflection properties of the fiber reinforced materials given
by the be:idiiig test. The experimental results show that, MOT
method is a proper evaluation method. Moreover, silica fume is
shown t o have a great effect on the enhancement of the toughness
of ferrocement.
6. Tne addition of silica fiime t o ferracement can help the production

of high strength, thin ferrocement materials.
REFERENCES
1. Malhotra, V. H., Carette, G. G., and Sivasundarani, V. ”Role of Silica
Fume in C o n c r e t e : A R e v i e w ” , A d v a n c e s i n C o n c r e t e T e c h n o l o q-.
y,
Editqr: V.M. Malhotra, CANMET, R e p o r t MS.L 9 4 - 1 ( I R ) , pp. 915-9
1994.
2. AC1 Committee 549, “Guide For the Desig,i, Construction, and Repair
of Ferrocement” AC1 Structural Jour. /Hay-Jme, pp. 325-353, 1988
3. TABAI, M., and TAKAYA, T. Studies on the Properties of Ferro-
”
cement Mixed with Silica Fuine”, ,Journal of the Facuity of Science

and Technology Kiriki Universitj, Vol. 29, pp. i05-11!, 1333

A C 1 SP-153 VOL*II 95 m Obb2949 0523823 9 3 3 m
Chemical Analysis
CN" SF*' CN' SF"
Fineness-Blaine m2/kg 335 2-10'' Insoluble residue O. 20 --
Silicon dioxide(SiO2) 22.2 95.8
Specific gravity 3.16 2.21 Aluminum oxide (A1203) 5.5 --
Setting time, min Ferric oxide (Fezos) 3.1 --
- Initial 162 - Calcium oxide (Cao) 63.6 0.14
- Final 260 - Magnesium oxide (BgO) 1.6 --
Compressive strength Sulphur trioxide ( S o n ) 1.9 -
MPa: 7-day 24.5 - Sodium oxide (Na201 - O. 13
28-day 41.2 - Potassium oxide (KA)) -_-- 0.12
Flexural strength Carbon (C) 1.6
MPa: 7-day 5.4 - Phosphorus ox!de(PZO5) -- O. 16
28-day 7.4 - Loss on ignition 0.7 1.8
f l CIY: Normal portland cement
I2 SB: Silica fume
TABLE 2 - PROPERTIES OF REINFORCING MATERIALS

--``,`,-`-`,,`,,`,`,,`---
Modulus of elasticity: 2O0X1O3 MPa

O X @

A C 1 SP-153 V O L J I I 95 W Obb2949 052182Y 858 W
TABLE 3 - MIXTURE PROPORTIONS OF MORTAR

--``,`,-`-`,,`,,`,`,,`---
W: Water, C: Cement. S: Fine aggregate,

SF: Silica fume, Sp: Superplasticizer
TABLE 4 - VOLUME FRACTION OF REINFORCE-

MENT 0/9 IN TENSILE SPECIMEN
Wire
mesh
1.96
I $-Layers I 2.69 I M-type I 2.86 1
I 5-Layers I 3.36 I L-type I 6.66 [
TABLE 5 - SPECIFIC SURFACE OF REINFORCE-

MENT (Sr) IN TENSILE SPECIMEN
Wire Sr Sxpanded Sr
mesh (%) metal mesh (%)

A C 1 Sip-153 V O L X I I 95 0662949 0523825 794
TABLE 6 -VOLUME FRACTION OF REINFORCEMENT (V9 AND

SPECIFIC SURFACE OF REINFORCEMENT (Sr) IN FLEXURAL
SPECIMEN
TABLE 7 - ULTIMATE MOMENT STRENGTH

IN FLEXURAL SPECIMEN
3-layers
I 4-layers 1 12.6 I 12.3 I
5-yayers 14.2 14,7
TABLE 8 - EVALUATION OF TOUGHNESS BY MOT METHOD
Mixture
type o!'
A
B
I C 1 2 . 2 8 1 3 . 0 6 1 3 . 0 6 11.85 12.75 16.40 1 2 . 0 0 13.16 I
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 W 0662949 0523826 620 W
SF+W +Sp
I
Mixinp for 2 min.
Fast 3min.
24 hours
7 &)o and 20 days
Fig. l-Mixing and fabrication

of specimens
P D
i
1
Fig. 2-Tensile test specimen and testing

arrangement
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 O662949 O523827 567
-I I
1- - 1
Dimension :cm
Fig. &Bending test specimen and testing
arrangement
Strain ( X io-")
Fig. -tress-strain curves of mortar by

compression test
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 W Obb2949 0 5 2 3 8 2 8 4 T 3
! - ? - ? - v .
............; .... ....<<..;.............. ............................
'0 1000 2000 3000 4000 5000

S t r a i n ( X lo-')
Fig. 5-Load-strain curves of tensile test

specimen
O 1000 2000 3000 4000 5000

Strain (X io-")
Fig. &Load-strain curves of tensile test

specimen
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-253 V O L X I I 95 m 0662947 052382q 337' m
O 1000 2000 3000 4 0 0 0 5000

S t r a i n ( X io-")
Fig. 7-Load-strain curves of tensile test

specimen
--``,`,-`-`,,`,,`,`,,`---
Def 1ec t ion (mm)
Fig. 8-Load-deflection curves of bending

test specimen

A C 1 SP-153 VOL*II 95 = Ob62949 0521830 051
'0 5 10 15 20 25 30 35 40
Deflection (mm)
Fig. Road-deflection curves of bending

test specimen
a
m
O
a
.
Def 1 ec t ion (mm)
Fig. 1O-Load-deflection curves of bending

test specimen
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 I0662949 0521831 T98
--``,`,-`-`,,`,,`,`,,`---
Def 1ec t ion (mm)
Fig. 1 l-Load-deflection curves of bending

test specimen
Deflection ( 6 1
Fig. 12-Evaluation method of toughness

AC]: SP-353 VOL*II 95 0662949 0523832 924 W
SP 153-46
Long-Term Performance of Silica

Fume Concretes in the USA Exposed
to Abrasion-Erosion or Cavitation -
With 10-Year Results for Kinzua Dam
and Los Angeles River
--``,`,-`-`,,`,,`,`,,`---
by M. D. Luther and W. Halaok
Synops&: The first two abrasion-erosion concrete repair

projects in the United States that used silica fume (SF)
concrete started in 1983. One was the stilling basin
rehabilitation of the Kinzua Dam, in northwestern
Pennsylvania. The other was the L o s Angeles river low-
flow channel rehabilitation project (completed in 1985).
The first known application of S F concrete (SFC)
addressing cavitation resistance occurred in 1985, also
at the Kinzua Dam, but for a sluice repair.
This paper largely summarizes long-term performance
information relating to the 1983-1985 SFC placements.
Other more recent S F C projects where abrasion-erosion or
cavitation was a concern are mentioned. Also presented
are two mixtures featuring portland cement with ground
granulated blast-furnace slag and SF and that were
recently used in a very severe environment.
Overall, after up to 10-1/2 years in service, the
various S F C s are performing very well. The 1983 Kinzua
Dam stilling basin SFC wear after 1 0 - 1 / 2 years is only a
small fraction of that seen in previously utilized
concretes. For the Los Angeles River S F C s , all of the
three different SFC mixtures that were employed are
performing comparably as of March, 1994. Overall
erosion was uniform and to an estimated 4-12 mm depth.
The 1985 Kinzua Dam sluice repair concrete showed no
evidence of cavitation damage by 1994.
Keywords: Abrasion; blast furnace slag; cavitation; compressive strength;

dams; durabiliíy; erosion; fly ash; high performance concretes;
performance; proportioning; repairs; silica fume

863
A C 1 SP-153 V O L X I 1 95 D 0662949 0 5 2 3 8 3 3 860
864 Luther and Halczak
Mark D. Luther is the Manager of Technical Services for

Koch Minerals Company, Wichita, Kansas - working out of
the Weirton, West Virginia ground granulated blast-
furnace slag grinding plant office. He received h i s
M.S. in civil engineering materials from Purdue
University in 1981.
William Halczak, P.E., is a Senior Materials Engineer
for the United States Army Corps of Engineers, Los
Angeles District, L o s Angeles, California.
INTRODUCTION
The long-term performances of the first two abrasion-
erosion application projects featuring silica fume (SF)
concrete in the United States - the 1983 Kinzua Dam
stilling basin rehabilitation (Fig. i), and the 1983-
1985 L o s Angeles River low-flow channel rehabilitation
(Fig. 2) - are discussed in this paper. The first knowr
SF concrete (SFC) use for cavitation resistance also
occurred at the Kinzua Dam, involving a sluice repair ir
1985 (Fig. 3).
--``,`,-`-`,,`,,`,`,,`---
To facilitate continued monitoring of SFC projects, this

paper also lists other SFC projects where abrasion-
erosion or cavitation was the main concern. A l s o ,
ground granulated blast-furnace (GGBF) slag is not knowr
to have been used before in abrasion-erosion or
cavitation resistance applications. Two mixtures
containing GGBF slag are presented.
Terminoloav and Conventions
The American Concrete Institute Committee 116 defines

several wear-related terms as follows (1):
abrasion damage - wearing away of a s u r f a c e b y r u b b i n g and
f r i ct i on
erosion - p r o g r e s s i v e d i s i n t e g r a t i o n o f a s o l i d b y t h e
a b r a s i v e o r c a v i t a t i o n a c t i o n of g a s s e s , f l u i d s , o r
s o l i d s i n motion
cavitation damage - p i t t i n g of c o n c r e t e caused b y
imp1o s i o n ,
i . e . , t h e c o l l a p s e of vapor bubbles i n f l o w i n g w a t e r
which forins i n a r e a s of l o w p r e s s u r e and c o l l a p s e a s t h e l
e n t e r a r e a s of h i g h e r p r e s s u r e
Combining these definitions, in this paper the term

abrasion-erosion is used to describe forms of underwatex

A C 1 SP-II53 VOL*II '75 811 Obb29Y9 052IIB3Y 7 T 7
wear except cavitation [damage], which is aptly defined

above.
Throughout this paper, portland cement (PC), fly ash,
ground granulated blast-furnace ( G G B F ) slag, and silica
fume ( S F ) are considered cementitious materials Ic+m).
Also, f l y ash or GGBF slag amounts are expressed as a
percent, by mass, replacing the PC, and SF is expressed
as a percent, by mass, in addition to the combined other
cementitious materials.
KINZUA DAM STILLING BASIN REHABILITATION

(ABRASION-EROSION 1983) -
The 1983 U.S. Army Corps of Engineers (Corps) Kinzua Dam
stilling basin rehabilitation project and the SFC used
in it have been described in detail (Table 1)(2,3). In
addition to the bi-yearly (more or less) diver
inspections commissioned by the Corps, information about
the ongoing performance of the S F C in the basin was
published after the five year age (4,5,6). For the nine
year and 10-1/2-year performance results, the diver
rep0rt.s were again consulted, and this new information
is presented below.
History and Wear Mechanism
Kinzua Dam became operational in 1965, and it employed

21 MPei PC concrete in the 1.2 m-thick stilling basin
floor. Abrasion-erosion damage necessitated the first
floor repair, which occurred in 1973 and 1974. At that
time, the floor elevation was raised another 300 mm with
steel-fiber-reinforced 28 MPa PC concrete. Within two
years, one abrasion-erosion cavity was already 420 dgep.
The 1983 work replaced all the earlier repair concrete
and restored the floor to the 1973-1974 elevation.
The wear mechanism in the Kinzua Dam stilling basin
originally (before 1983) involved eddy currents
transporting debris into the basin from downstream.
Then rocks and other material larger than about 150 mm
diameter would dwell in the basin and be lifted and
pounded into the concrete repeatedly - driven by water
velocities approaching 27 m/sec. Smaller material would
move downstream again. Any unbalanced sluice operation
would generally cause even more debris to enter the
basin.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 3 5 3 VOL*II 95 E O b b i 7 4 9 0523835 633
The 1983 Repair

For the 1983 repair, a second end sill wall was
constructed to capture and trap debris (Fig. 4). This
worked imperfectly (due in part to continued unbalanced
sluice operation) until the river bed just downstream of
the end sills was lined with concrete-filled bags and an
"even" sluice operation was achieved (around 1985)(Fig.
4). Also, approximately 1700 m3 (2200 yd3) of SFC were
placed in the stilling basin floor and parts of the
baffles (Fig. 5). The SFC in the new basin floor
averaged about 0.6 m thick, and nearly twice that in
some locations. The SFC proportions and performance
information is presented in Table 1.
Early Post-1983 Rer>air Stillina Basin Floor Wear
In 1984 and 1985, large amounts of material (more than

seen before the 1983 repair) were pulled from the basin
and the end sill trap. During this period, the wear in
the stilling basin was concentrated at cracks and slab
joints (Fig. 6). By 1985, wear was still limited to a
nominal 100 mm-wide band along some cracks and joints,
and the maximum wear depth along these features was an
estimated 12 mm, and the maximum depth was 30 mm.
Subsequent to the 1985 river bed improvements, the basin
retained relatively small amounts of debris. By 1989,
wear along some cracks and joints had feathered out at
the edges, with an estimated average depth under 25 mm
and occasional places around 40 mm deep. These
observations led to speculation that the small amount of
wear seen resulted from silt-sized material suspended in
the water. It should be noted that, early on, concern
had been expressed about the cracks. After several years
in service, however, these did not appear to be
seriously affecting the durability of the SFC (7).
wear at Nine Years
The September 16, 1992 diver inspection (nine years

after the silica fume concrete floor was cast) indicated
the following (Fig. 6): About two-thirds of the basin
--``,`,-`-`,,`,,`,`,,`---
floor was covered with gravel up to an i00 mm diameter.

One eroded area along the left (looking downstream
[typical]) training wall was 50 mm deep. Another area to
the right of the center of the basin about 20 m from the
dam toe was 100 mm deep. The baffles showed two small
eroded areas 50 mm deep. One spa11 was 8 0 mm deep and
exposed five reinforcing bars. Three other small spalls
were as deep as 7 mm.
After the debris was removed, the basin floor was again
inspected. Across the basin at the toe (where the dam

A C 1 SP-153 V O L X I I 95 U 0662949 0.523836 5 7 T U
meets t h e basin floor) contraction joint, there was an

average 80 mm wear associated with this joint. One
location was 150 mm deep. Most of the wear here
apparently progressed into the conventional concrete of
the darn itself, which, in turn, exposed the SFC in the
basin floor to more aggressive action. No progressive
erosion (relative to previous inspections where up to 40
mm erosion was noted along some cracks and joints) was
reported in the basin floor. The joints in the floor
were tight, and the basin floor was characterized as
being in good condition.
At nine years, the overall volume loss in the stilling
basin :€loorwas estimated to be less than 1/24th, and
the maximum depth at any one location was estimated to
be about 1/8th as deep, as that of the 1973 repair
concrete when it was only seven years old.
Wear at 10-1/2 Years
The 1994 diver inspection was conducted on June 7-8, and
it showed the following (refer to Fig. 4)(9): Gravel up
to 100 mm diameter was found in the debris trap at the
downstream end of the stilling basin, although there was
somewhat less than seen in 1992. The basin floor was
free of debris with the exception of two irregular-
shaped (suggesting they were new in the basin) 150 mm-
diameter stones.
10-1/2 Year Wear in the Baffles: Portions of some
baffles received SFC repairs in 1983, so it is not clear
whether wear seen in the baffles relates to SFC or PC --``,`,-`-`,,`,,`,`,,`---
concrete. Baffle No. 8 (Fig.6) showed light spalling on

the downstream face and right corner. Baffle No. 6
showed the same wear pattern, and it also had a two
spalls: one 75 mm wide by 300 mm high; the other 760 mm
long by 75 mm wide by 3 0 0 mm high.
Baffle No. 5 showed spalling on the left face, but this
may have been delaminated repair material. At the base
of the right side was a 3 m-long by 4 6 0 mm-high [high on
one end and tapering down to the base at the other] by
75 mm-deep spall that exposed five reinforcing bars.
Baffle No. 4 had one 760 mm-diameter by 50 mm-deep
circular spall at the base of the right side just past
the upstream corner. Baffle No. 3 had a triangular 760
mm-long by 320 mm-high by 5 0 mm-deep spall on the right
side, and there was a 510 mm-long by 460 mm-high by 50
mm-deep spall on the left.
10-1/2 Year Wear in the Stillinq Basin Floor: Only
"minimal" additional wear was found in the basin floor
relative to 1992 (Fig. 4). As in 1992, greatest mass
loss occurred at the dam toe. Here, wear in the PC

A C 1 SP-153 VOL*II 95 O662949 0523837 YOb m
concrete in the dam itself averaged about 150 mm and was

as deep as 300 mm. The edge of SFC abutting the toe had
become more rounded than seen in 1992.
Construction joints between the floor slabs were
characterized as Ittightat.
Along the first construction
joint from the left training wall, in the second and
third rows of slabs from the dam toe, was a 640 mm-long
by 910 mm-wide by 130 mm-deep void. Several other
smaller voids were noted (Fig. 4). The so-called
hairline cracks mentioned in the diver report were
present even before the SFC was placed into service in
1983 (Fig. 6). The small number of voids were mainly
concentrated along joints.
Wear reported before 1990 mentioned volume loss
concentration about 40 mm deep along some joints and
cracks, and feathering out at the top more and more from
inspection to inspection. No mention of this feature was
noted in the 1994 diver report. Therefore, the
feathering out at most of the joint and crack tops may
have proceeded to the extent that the wear was not
easily recognizable.
Kinzua Dam Stillins Basin Performance Assessment
The 1983 Kinzua Dam SFC is outperforming previously used

PC concretes by a wide margin. For example, neither of
the previously used PC concretes cast in the Kinzua Dam
stilling basin floor lasted longer than about seven
years. For both the original and the 1973-1974 repair PC
concretes, by the time repairs had been effected, the
loss of concrete was widespread, it was measured in feet
(maximum of 1.2 m (4 ft)) - not inches, and it was most
severe along the joints.
Discussion during the 1983 Kinzua Dam repair led to an
informal consensus that the SFC would last over 20 years
before needing repair. Based upon the current
performance of the 1983 Kinzua Dam stilling basin floor
SFC, it now appears that this expectation is
conservative.
LOS ANGELES RIVER LOW-WATER CHANNEL REHABILITATION

(ABRASION-EROSION 1983-1985) -
The portion of the L o s Angeles river discussed in this
report was authorized by the Flood Control Act of 1936,
and it was constructed by the Corps from 1939 to 1942.
Some portions of the channel bottom were lined with PC
concrete as late as 1959.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L r < I I 95 P Ob62949 0523838 342
Performance of Orisinal PC Concrete

By 1966 the amount of abrasion-erosion necessitated
removal and replacement of some invert segments, while
others received a 75 mm overlay - all employing PC
concrete. Additional PC concrete overlays were cast in
1973. Again, by 1977 the nominal 300 mm-thick channel
invert had been worn completely through in some
locations. From 1983 to 1985, 20,600 m3 (27,000 yd3) of
SFC were cast in 300 mm-thick overlays using a different
SFC mixture each year (Table 1).
Wear Mechanism
At the mid point of the S F C liner section, the low
channel flow continuously conveys approximately 1.7
m3/sec of water at a velocity of approximately 1.5
m/sec. During peak flows at this same location, the
entire river cross section conveys approximately 2900
m3/sec (104,000 ft3/sec) of water at a velocity of 11
m/sec. Therefore, the channel may swell to thousands of
times the low-flow flow rate after rain. Carried in the
flow is debris comprised largely of earth, sand, gravel,
cobbles, occasional boulders (Fig. 7), and man-made
objects. A significant portion of the total abrasion-
erosion is caused by the smaller particles, which are
carried continuously by the low-flow.
inspection
On March 18, 1994, the authors inspected the SFC segment

of the L o s Angeles river low-flow channel (Fig. 8 ) .
Four visual reviews were made of the concrete, inspected
only from the right-hand edge of the low flow channel.
Having rained the previous evening, the low-flow channel
was brim-full of water at the beginning of the viewing.
Flow was higher in the upstream one-third of the SFC-
lined part of the channel and lower in some places. The
water level dropped about 50 mm over the course of the
inspection, thereby exposing more S F C . During viewing,
the water velocity was estimated at 2.2-2.6 m/sec (5-6
m.p.h.).
On March 18th, assorted reinforcing steel bars
(including one of 38 mm-diameter (No. 12 size)),
shopping carts, car parts, and other metal items were
seen in the channel in addition to a small amount of
large rocks (Fig. 7) and other natural debris.
The three different SFC mixtures were evident, judging
from the aggregate types, sizes, and distribution seen
at the concrete surfaces (Table 1). Among these, no
differences in wear depth or pattern were seen.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL111 95 m 0662949 0523839 289 m
Transverse cracks known to have occurred soon after

placement, at nominal 1.2 m intervals (with great
variation), showed no evidence of increasing in number
or - unlike at Kinzua Dam - in focusing the wear.
Basically, there was no apparent consequence to the
cracks.
Nearly all the visible SFC - whether seen directly or
viewed through water to about one meter from the water's
edge - had worn such that at least the very top of the
coarse aggregate was visible (Fig. 9). Some other areas
showed more of the coarse aggregate, but seldom as much
as a full cross-section. The amount of coarse aggregate
visible and the position of the top of the SFC relative
to other structures allowed for an estimation of the
depth of wear. This was between three and 10 mm.
In an occasional location - always no more than the full
cross section of the specific piece of coarse aggregate
- an individual piece of soft coarse aggregate had
eroded mostly away, usually to about 5 mm deeper than
the surrounding concrete.
The far end of a hand-held 2.3 m-long, 16 mm- diameter
(No. 5) steel reinforcing bar was repeatedly dragged
underwater, and above the water's edge, against and
across visible SFC (Fig. 10, Fig. 11). The sound and
feel of the rod was noted. Then the rod was used to
gauge the condition of the SFC that was out of sight,
--``,`,-`-`,,`,,`,`,,`---
often by dragging the far end of the rod directly from

visible concrete and into deeper water. No changes in
feel or sound were noticed. There was, however, no way
of knowing whether the wear in the center of the
channel, although still relatively smooth, was overall
deeper than along the edges. Special attention was given
to concrete under or just upstream of the occasionally
seen strongly rippled water. The rationale here was that
the ripples may have been caused by uneven concrete.
However, no other notable concrete surface features were
ever found.
L o s Anqeles Channel Nominal 10-Year Performance
Assessment
In the case of the L o s Angeles River channel lining SFCs

placed in 1983-1985, all the three different SFC appear
to be performing comparably as of March, 1994. Overall,
the concretes were wearing more or less evenly to an
estimated 3-10 mm depth, and the SFCs appeared to have
performed very well.

A C 1 SP-153 VOL*II 95 H O662949 0521840 T T O
KINPUA DAM SLUICE NO. 4 REPAIR

(CAVITATION 1985) -
In April, 1985, 0.54 m3 (19 ft3) of a proprietary very-
high strength SFC (Table 1) were cast into a prepared
notch in the right wall of Kinzua Dam sluice No. 4, just
below the gate (Fig. 3). This area had been damaged by
cavitation. Not only the original PC concrete was
affected in the sluice, but two stainless steel plates
(one was 16 by 3 0 0 by 460 mm-long) installed to protect
against cavitation at this location had been ripped from
the wall. Incidentally, this plate had been worn to an
oval from impacts with the SFC placed in the stilling
basin in 1983. The cavitation was detected by unusual
vibration from within the dam, and it had been confirmed
during an inspection. Thereafter, reduced use of sluice
No. 4 created more eddy currents in the basin until the
1985 repair.
The SFC was inspected at three years, and it was then
unchanged since installation. By March, 1994, after
nearly nine years, the SFC remained unchanged.
OTHER PROJECTS; CONCRETE MIXTURE CONSIDERATIONS
SFCs have been used in many other abrasion-erosion or

cavitation applications (Table 2)(9). Some of the mid-
1980s 'concreteswere patterned more or less after the
Kinzua Dam stilling basin mixture, which employed 18%
SF. Other projects employed lower SF contents in
conjunction with fly ash, like two of the L o s Angeles
river :mixtures (Table 1). Perhaps the most recent
application of this cementitious materials scheme was
for the Corps Seven Oaks Dam Diversion Tunnel project
(1993-1994) in southern California, specifically for the
tunnel invert concrete (Table 2).
GGBF Slaq
Very recently, GGBF slag has also been used in SFC for
abrasion-resistant applications. In 1993 a PC-GGBF
slag-SF combination was employed in a cavitation and
abrasion-erosion application in Weirton, West Virginia
(Table 1). Here, exposure temperatures range from 90°C
on most days to below freezing, intermittently, in
winter. The typical exposure environment may be
represented as follows: For at least four hours per day
a water stream of 38,000 l/sec travels at a velocity
of 16 .m/sec while transporting a 50 kg/sec amount of
fine aggregate (Moh's hardness = 7). The stream impacted
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL811 95 Obb2949 052Lô4L 937
18 mni-thick flat hardened steel plates. The plates

required replacement every three months, on average.
The very high-strength concrete panel (1500 mm-wide by
1200 mm-high by 300 mm-thick)(properties in Table 1)
that replaced the steel plates showed a volume loss of
only about 0.04 m3 (1.4 ft3) after 4-1/2 months, located
in the impact zone. The wear crater was, and continues
to be, repaired easily with a proprietary prepackaged
nominal 170 MPa calcium aluminate-based high-SF dose
concrete. The performance of the concrete panel is
considered to be very successful. Based upon this
favorable showing, in September, 1994, 0.85 m3 (1.1 yd3)
of another PC-GGBF slag-SF concrete (Table 1) was cast
into the floor below the panel.
E f f e c t of w/(c+m) and Assresate

For the 1983 Kinzua Dam rehabilitation SFC mixture, the
combination of limestone (relative soft: Mob's hardness
3.7) and natural aggregate in conjunction with low
w/(c+m) (at 0.28) has proven to be an effective
combination for resisting abrasion-erosion. Harder
aggregate, less SF, and higher w/(c+m) was employed for
the L o s Angeles channel work in 1983-1985 (Table 1).
This combination also has performed well. All the
cavitation SFCs also featured very low w/(c+m) and at
least some very hard aggregate, like calcined bauxite.
Of interest is the solitary PC concrete slab (slab No.
52) cast in the Kinzua Dam stilling basin floor on
November 8, 1983 (Fig. 6). This mixture employed the
same aggregates as the SFC, 415 kg/m3 PC, a 0.45 w / c ,
and achieved 43 MPa at 28 days. Although no SF was
employed, this concrete is also performing favorably.
Although using harder aggregate, lowered w / ( c + m ) , and SF
in concrete are features associated with improving
underwater durability, exceptions have occurred (above)
in abrasion-erosion environments. These exceptions
suggest that a broad array of materials combinations may
be used successfully in abrasion-erosion environments.
Viable concrete mixtures have featured a wide assortment
of combinations of PC and SF, either with or without fly
ash or GGBF slag.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I 1 95 0 6 6 2 9 4 9 0521842 8 7 3 9
CONCLUSIONS
After up to 10-1/2 years in service, all the silica fume

concretes (SFCs) are performing very well. Where
comparison can be made, the SFCs are far outperforming
previously-used materials or systems. There is an
expectation that the SFC used in the 1983 Kinzua Dam
stilling basin repair will not need significant repair
until after 2 0 years in service.
One observation in the area of abrasion-erosion
resistant concretes is that the incorporation of fly ash
or GGBF slag into the mixtures has proven to be a viable
option.
ACKNOWLEDGMENTS
--``,`,-`-`,,`,,`,`,,`---
The authors express their gratitude to Anton Krysa,

structural engineer for the United States Army Corps of
Engineers, Pittsburgh District. Mr. Krysa provided
Kinzua Dam diver inspection information. Appreciation
is also extended to Steve Tatro, R.A. Gutschow, Larry
Mondak, Tony Liu and many others in the Corps and to
Koch Minerals Company for providing information and
resources toward enabling this paper to be written. The
opinions and conclusions presented in this paper are
those of the authors and do not necessarily reflect
those of other people or organizations.
REFERENCES
1. AC1 Committee l16,ttCement

and Concrete Terminology"
Committee 116, Terminology for Concrete, (AC1 116R-
9O)Il American Concrete Institute, Detroit, Michigan,
U.S.A., 68 pp.
2. Holland, T.C., Krysa, A, Luther, M.D., and Liu, T.C.,
"Use of Silica Fume Concrete to Repair Abrasion-
Erosion Damage in the Kinzua Dam Stilling Basin,"
Proceedinqs, CANMET/ACI Second International
Conference on the Use of Fly Ash, Silica Fume, Slag,
and Natural Pozzolans in Concrete, edited by V.M.
Malhotra, Madrid, Spain, April, 1986, V.2, pp. 841-
864.
3. Hol.land, T.C. and Gutschow, R.A.,~~ErosionResistance

Wit.h Silica Fume Concrete," Concrete International,
V.9, No.3, March, 1987, pp. 32-40.

A C 1 SP-353 V O L X I I 95 m 0662949 0523843 70T m
4. Luther, M.D.,IISilica Fume (Microsilica) Production,

Materials, and Action in Concretell, Proceedinqs,
Advancements in Concrete Materials, edited by Z.
Bayasi and R. Bhatacharya, Bradley University,
Peoria, Illinois, U.S.A., March, 1989, pp. 18.1-
18.21.
5. Luther, M.D.,IlMicrosilica (Silica Fume) Concrete

Durability In Severe Environmentst1,Proceedinqs, San
Francisco Structural Materials Congress, edited by
J.F. Orofino, American Society of Civil Engineers,
New York, New York, U.S.A., May 1-5, 1989, pp. 9 5 -
105.
6. Luther, M.D.,llCase Studies of Microsilica (Silica

Fume) Concrete Repair Projects," Structures Congress
Abstracts, Baltimore, Maryland, edited by R.B.
Corotis and B. Ellingwood, American Society of
Civil Engineers, New York, New York, U.S.A., April
30-May 3 , 1990, pp. 533-534.
--``,`,-`-`,,`,,`,`,,`---
7. Luther, M.D. and Lopez-Flores, F., Discussion of

paper entitled "Effect of Fiber Addition on the
Autogenous Shrinkage of Silica Fume Concretellnby
Paillere, Buil, and Serrano, Materials Journal, V.87,
No.1, American Concrete Institute, Detroit, Michigan,
U.S.A., January-February, 1990, pp. 81-83.
Goodboy, S.L.,Wnderwater Diving Inspection of
Stilling Basin and Downstream Area at Kinzua Dam,
Warren, Pa", Memorandum For The Files, CEORP-OR-R,
U.S. Army Corps of Engineers, Pittsburgh District,
Pittsburgh, Pennsylvania, June, 1994, 9 pp.
Luther, M.D.,llHigh-PerformanceSilica Fume
(Microsilica)-Modified Cementitious Repair
Materials," Cement, Admixtures and Concrete,
Transportation Research Record, No. 1284,
Transportation Research Board, National Research
Council, Washington, D.C., U.S.A., 1990, pp. 88-94.
10. Mattingly, S . and Smoak, G., Repair of
Abrasion/Erosion Damage to Vallecito Dam with Silica
Fume Concretenn,American Society of Civil Engineers,
NY, N.Y., September, 1994.

A C 1 SP-1-53 VOL*II 95 W 0662949 0523844 b 4 b
r -
u&
$2
t-z Y
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L J I I 95 = 0662947 0523845 582 m
m
c
U
h
fa
a
a,
E
8
u)
rl
91
k
7
U
uI
k
U
u)
a,
e .
+u)
a
-Ll
a
a,
u 0
m
C
d
-I
Ll
.u
-a,
m u)c
h IJ aci
a k
E O h
3'9
m
C 0)
U u)c
k k
IJ a o
4 m a
C
C -lm
O mL4
rl em
U 4
u u)
H U
a>
ci Du)
O O
Ll m u
4 a
4 0
o u
vik J G
m
hC
Eai
4u
.?
n a
ucr n
v u
c i l
a n
--``,`,-`-`,,`,,`,`,,`---
/E
3 -
?r"
-lu)
cm
-
3rl
4
-lu
O
na,
!%
3ci
4 m

A C 1 SP-153 VOL+II 95 E 0662949 0523846 4 3 9 W
--``,`,-`-`,,`,,`,`,,`---
Fig. l--Kinzua Dam stilling basin, northwestern Pennsylvania, as it

appeared during 1983 rehabilitation with silica fume concrete (photo
courtesy U.S. Army Corps of Engineers, Pittsburgh -transmitted by
Larry Mondak)
Fig. 2--1983-1985 Los Angeles rehabilitation: Silica fume concrete

low-flow channel liner being cast (photo courtesy of R. A. Gutschow,
U.S. Army Corps of Engineers, Los Angeles)
A C 1 S P - 1 5 3 VOLaII 95 Obb2947 0521847 355 W
Fig. 3-1985 Kinzua Dam sluice No. 4 cavitation repair (very high
strength silica fume concrete being placed behind form)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m Obb2949 0523848 2 9 1 m
Legend: A = 25 m deep x 50 mm wide x 460 mm long;

B = 5 0 mm deep x 180 x 460 nm; C = 50 nun deep; toe area -
--``,`,-`-`,,`,,`,`,,`---
D = dimensions not noted, E = 150 nun deep, F = 100 nun deep,

G = 100 mm deep, H = 125 nun deep, I = 100 mm deep;
J = 150 mm deep; K = 75 mm deep x 180 x 610 mm long;
L = 7 5 mm deep x 200 x 330 mm long wlth a stone found;
M = depression; N = debris to wlthin 610 nun o f top of wall [end silll;
O = concrete-filled bag from 1985 - only concrete remains; P = no
debris; Q = 50 nun deep x 200 mm by 460 mm long.
Fig. M i a g r a m of Kinzua Dam stilling basin showing wear noted in

1994 diver report. Silica fume concrete in basin floor was placed in
Fall 1983

A C 1 SP-153 VOL*II 95 Ob62949 052Lô49 126
Fig. 5-1983 Kinzua Dam: Placing silica fume concrete in stilling basin
floor slab using tandem vibratory screed
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLrII 95 m Obb2949 0521850 V Y T m
-
ALLEGHENY RIVER BED
70 M
DEBRIS TRAP I
--``,`,-`-`,,`,,`,`,,`---
Legend: A = silica fume slab reinforced with 16 nun (No. 5)

reinforcing steel bars in 150 by 150 nun grid with 75 nun cover; B
= portland cement concrete slab -
one of the latest cast in
1983; C = 50-75 mm deep saw-cur joints; D = 50 nun deep x 900 nun
wide x 1500 nun long; E = 100 nun deep x 200 by 480 nun, not
specifically located; F = eroded area not dimensioned; G =
typical silica fume c o n c r e t e slab dimensions were 18 by 30 m; H
= even 8 0 nun deep wear along toe with one 160 nun deep spot.
Fig. 6-Kinzua Dam stilling basin: Location of cracks and joints in

floor, as mapped in Nov. 14-16, 1983, before the basin was flooded
(Nov. 17). Also, abrasion-erosion features noted from 1992 diver
inspection

A C 1 SP-1153 V O L * I I 95 m O662949 052118511 88b m
Fig. 7-Los Angeles River channel: Boulder and other debris seen
during Mar. 18, 1994 inspection of silica fume concrete channel liner
3.7 M
4
-1
/
3.1M
SILICA FUME CONCRETE>
PORTLAND CEMENT
Fig. &Los Angeles River: Typical low-flow channel silica fume

concrete overlay for 1984. Some geometry variation was employed in
other years. A 300-mm portland cement concrete overlay (Location A)
was cast in upper two-thirds of silica fume concrete overlay
construction (1 983-1~185)~
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLXII 95 = 0bb2949 0.523852 712
Fig. +-Los Angeles channel: Typical wear seen in silica fume

concrete (left two-thirds of picture) liner during inspection on Mar. 18,
1994 (riominal 10 years in service)
--``,`,-`-`,,`,,`,`,,`---
Fig. 1@-Los Angeles channel: Co-author Bill Halczak calibrating the

"feel" of steel sounding rod against visible silica fume concrete along
edge of low-flow channel

A C 1 SP-1.53 V O L X I I 95 Obb2949 0523853 659
--``,`,-`-`,,`,,`,`,,`---
Fig. 1 l-Los Angeles channel: Co-author Halczak using sounding rod
to locate voids and determine surface texture condition of silica fume
concrete that is not visible

A C 1 SP-153 V O L X I 1 95 = Obb2949 0 5 2 3 8 5 4 595 =
SP 153-47
The Durability of Concretes Made with

Blends of High-Alumina Cement and
Ground Granulated Blast Furnace Slag
--``,`,-`-`,,`,,`,`,,`---
by G. J. Osborne and B. Singh
Svnopsis. : A rapid-hardening cement has been made by blending mixtures of

high-aluinina cement (HAC) and ground granulated blast-fumace slag
(GGBS)’*. The addition of slag alters the course of hydration reactions in
HAC. A chemical compound 2Ca0.A1,0,.Si02.8H,0 (gehlenite hydrate or
strätlingite), only seen in plain HAC in small amounts, readily forms and
becomes the main stable hydrate in the blended-cement concretes in the
temperature range 5 3 8 ° C replacing the metastable hydrates which lead to loss
of strength in HAC through the conversion reaction.
The properties of mortars and concretes made with this cement have
been assessed in u series of durability studies carried out by the Building
Research Establishment. Mortars made with the blend have shown excellent
sulfate resistance. Concrete specimens have been compared with those from
HAC concretes of similar proportions, following exposure for 2 years in
aggressive sulfate, marine, and soft acid water environments. The findings, at
this relatively early stage. are very encouraging and longer term tests will be
carried out at 5 and 10 years. Concretes made with the blend have shown a
greater tolerance of high water - to - cement ratio mixtures in forming stable
products with reduced temperature rises, enhanced durability in terms of their
excellent sulfate, seawater, and soft acid water resistance.
Keywords: Acid resistance; adiabatic conditions; blast furnace slag;

blended cements; concretes; durability; high alumina cements; seawater;
sulfates
*This product has been given the trademark name ‘Brecem’(1)

885
A C 1 SP-353 V O L X I I 95 M Ob62949 0 5 2 3 8 5 5 4 2 1 m
886 Osborne and Singh
Geoffrey Osborne is a Principal Scientific Officer and Head of Concrete

Durability Section at the Building Research Establishment, UK. Main
research interests include; studies on properties of portland and high-alumina
cements, their use with blast-furnace slag and pozzolans and long-term
durability of concrete. He is the author of many papers and a member of a
CEN committee on methods of test for cements.
Bahadur Singh is a Higher Scientific Officer in the Concrete Durability

Section at the Building Research Establishment, UK. He was involved with
the original development studies on ‘Brecem’ and has worked extensively on
the hydration of calcium aluminate cement and its blends and on the
durability of concretes using these cements.
INTRODUCTION
The Building Research Establishment (BRE) in the United Kingdom

has developed a blended cement based on high-alumina cement (HAC) and
ground granulated blast-furnace slag (GGBS)*. The properties of concrete
made from the new cement are being studied at BRE in collaboration with
the industry. The reasons for the development of the cement and how it
differs from HAC, in terms of the hydrate formation and stability, have been
fully described in a recent paper (2).
Calcium-aluminate or high-alumina cement is not used in structural

applications in the UK at the present time, as concrete made from such
cement shows reduction in strength with time under hot and humid
--``,`,-`-`,,`,,`,`,,`---
conditions. This reduction in strength is associated with chemical reactions,

often referred to as ‘conversion’, that produce an increase in porosity of the
concrete (3). The addition of slag alters the course of hydration reactions in
HAC. A chemical compound, gehlenite hydrate (strätlingite), not seen in
HAC in significant amounts, forms readily and becomes the major hydrate
constituent in due course, and is thought to provide a more stable phase
assemblage (4).
Studies to determine the chemical and physical properties of mortars

and concretes using the blend over a range of temperatures and storage
conditions have been set up at BRE and previously reported (2, 5, 6). This
*This cement has been given the trademark ‘Brecem’ (1)

A C 1 SP-I153 V O L X I 1 95 0662949 0521856 368
paper gives the results of tests carried out on concrete durability specimens
made with the blend and HAC concretes of similar mixture proportions,
following storage for 2 years in aggressive sulfate, marine, and soft acid
water environments. Daia are also presented on temperature rise produced
in near adiabatic conditions for a series of metre cubes using similar
concretes, with cores being subsequently taken to assess strength
development and hydrate formation. Practical trials were carried out on
precast concrete blocks for application purposes.
Development of blended HAC and GGBFS cement
Before the collapse of a roof in Stepney, London, in 1974(7), when

HAC was written out of the British Standard Code for structural concrete
(AMD1553 in CPllO : 1972), HAC* had been used in many structural
applicaiions where concrete needed rapid strength development or good
chemical resistance or both. One of the principal causes of failure of HAC
concrete units was the reduction in compressive strength with time, a
condition which is accelerated in certain environments where hot and humid
conditions prevail. Majumdar et al (4) showed that the effects of conversion
in HAC concrete could be sufficiently counteracted, if not eliminated, by
mixing a large proportion (typically 40-60 %) of GGBS with the HAC.
They observed that in wet environments, the hydration of calcium aluminates
in HAC produced gehlenite hydrate (strätlingite), C,ASH, or
2Ca0.A1,0,.Si0,.8H20 in the presence of GGBS, and that at temperatures
higher than the ambient this phase became a major constituent of the
hydrated cement in a matter of months. With HAC alone a number of
different metastable hydrates form with water which convert rapidly at
higher than ambient temperatures, typically above 25°C to form stable
hydrates of increased porosity (3). It should be noted though, that whilst
associated with large strength losses converted HAC* was found to be no
more porous than ordinary portland cement (OPC) of equal water-cement
ratio QVv/c, (8).
The formation and stability of gehlenite hydrate and the calcium

aluminate hydrates have been discussed in relation to the physical and
chemical properties of blended-cement and HAC concretes (2). Blended-
cement mortars and concretes have been shown to have a greater tolerance
to high w/c's in forming stable assemblages with reduced temperature rises
and enhanced durability, and there could be cost savings compared with
HAC concretes for a number of potential applications (2).
* also known as Ciment Fondu
--``,`,-`-`,,`,,`,`,,`---

Concrete Durability Studies
Long term durability studies have been started to determine the

--``,`,-`-`,,`,,`,`,,`---
performance of concretes made with different mixture proportions of HAC,

in the range O, 40, 50 and 60% by mass replacement of two GGBFS’s.
Concrete specimens stored in a number of internal and external aggressive
environments have been assessed up to 2 years of age.
Adiabatic Temperature Rise of Concretes
The temperature rise characteristics of a similar series of concretes,

to those used in the durability programme, were determined using 150-mm
and I-m cube moulds insulated with 100-mm thick Styrofoam. Near
adiabatic temperature conditions were achieved using this technique. 100-
mm diameter cores were cut through the metre cubes at ages of about 7, 28
and 180 days and 100-mm sections were tested for compressive strength
development and the hydration products examined (2).
Precast Concrete Blocks
The use of blended cement in precast concrete blocks was also

investigated, with potential applications in mind. Precast blocks, 300 by 500
by 500 mm in size, were manufactured using the same series of concrete
mixture proportions as employed in the metre cubes. The slabs were
demolded at early ages of 4 or 5 hours, and measurements of temperature
rise, hydrate formation, and compressive strength were made at 1, 3, 7, 28,
and 180 days. The data are discussed with a view to the possible use of
blends in structural concrete elements.
CONCRETE MATERIALS
The high-alumina cement (HAC) was supplied by Lafarge Special

Cements in the UK and the two ground granulated blast-furnace slags
(GGBS), one British and the other French, originated from the Appleby
Frodingham Cement and Civil and Marine Slag companies and these sources
are designated B and A respectively in the Tables. These three companies
were industrial sponsors and contributed to the funding of this research. The
chemical analysis of these cementitious materials and their surface areas are

A C 1 SP-153 VOLrII 95 Obb27i.19 052Lô58 130 m
given in Table 1. Thames Valley gravel coarse and fine sand aggregates
were used for all the concrete mixtures which are described in Table 2.
Chemical Analysis
The HAC and slags were analysed by X-ray fluorescence (main

oxides), flame emission (alkalies) and by using the LeCo apparatus for total
sulfur. These commercially available materials had fairly low loss on
ignition values and were approximately of the same surface area at about
400 mZ/kg. There were minor differences in the chemical analyses of the
two slags, with the UK sample having a slightly lower CaO/SiO, ratio, a
smaller SO, content (0.15 cf 1.90%),and higher Alzo,. than the French slag.
CONCRETE DURABILITI' STUDIES

--``,`,-`-`,,`,,`,`,,`---
A comprehensive program of durability studies was set up at BRE to

investigate the performance in a variety of aggressive environments of
concretes made with the blend, in comparison with those made using HAC,
with variations in mixture proportions. 100-mm concrete cubes cured in
water at different temperatures for up to 28 days, prior to storage in a
number of sulfate, marine, and acidic water environments, were assessed
after 1 and 2 years and specimens remain for testing at 5 and 10 years. The
visual a.ppearance, attack ratings, and retention of compressive strength of
the concrete cubes were determined by an established BRE method (9).
Concrete Mixtures
There are presently no recommended concrete mixtures in the UK for

the use of calcium-aluminate cements in structural concrete. Concretes were
therefore prepared to the appropriate mixture proportions which either
satisfied; (a) the minimum requirements of BS 5328, Part 1, 1990 for the
"Guide to specifying concrete", when placed in exposure conditions
classified as most severe or (b) the recommendations for concrete exposed to
sulfate and acid attack in classes 3-4 conditions of sulfate according to BRE
Digest 363 (10). It should be stressed that the HAC and slag cement
concretes were proportioned to provide equal cement content and workability
rather than equal 28 day strength.
Concretes in which one or other of the two blast-furnace slags

replaced HAC in the proportions O, 40, 50 and 60% were prepared as 100-
mm cubes. The concrete mixture proportions and fresh properties are
given in Table 2. These showed that (a) the marine and acid water
specimens, of 380 kg/m3 total cementitious content, were prepared from

A C 1 SP-153 VOL*II 95 m Ob62949 0523859 O77 m
moderate slump concretes (60 - 100 mm) with compacting factors between
0.90-0.96, and (b) the 335 kg/m3 specimens, for testing over a range of
temperatures and in sulfate solutions, were from lower slump (25 - 55 mm)
concretes, with compacting factors in the range 0.86-0.91. These data are
given in Tables 3 and 4 respectively. Both series of concretes were deemed
to have reasonably good workability and no problems were experienced in
their preparation and placing in molds, although the GGBS originating from
the UK gave slightly more workable concretes than did the French slag
when blended with the same HAC.
The concretes were vibrated in 100-mm cube molds and stored below
a cover of damp hessian and polythene sheet to maintain an initial curing
condition close to 100% relative humidity. The concrete cubes were then
demolded, numbered, and pre-cured in water at 5"C, 20°C. or 38°C or in air
at 20°C and 65% RH for a further 27 days, to attain their characteristic 28-
day strength, prior to placing randomly in the different aggressive storage
environments for testing at 1, 2, 5 and 10 years.
Aggressive Storage Environments
The three main aggressive storage environments, namely sulfate

solutions, seawater and, soft acid-water have been described in detail
previously( 1i), however a brief description is given below:
i) Laboratoiy storage in medium and strong, sodium, and magnesium

sulphate solutions, containing the equivalent of 0.35% SO, (medium)
and 1.5% SO, (strong), which represents respectively Class 4 and
three times the lower limit of Class 5 conditions of sulphate as
classified by BRE Digest 363 (10).
--``,`,-`-`,,`,,`,`,,`---
ii) The BRE'manne exposure site, with spray, tidal, and full immersion
zones, is situated at Shoeburyness, 4 miles east of Southend on the
River Thames estuary in the UK( 12).
iii) The BRE soft acid-water site is at Butterley reservoir in Yorkshire in

the UK(13), and the water has a pH of 3.5 to 4.5 due to the humic
acid from the peaty soils.
Methods of Test and Assessment
Concrete cubes (100 mm) stored in water at 2 0 T , (as controls), in

the four sulfate solutions at 20°C and those from the seawater and soft acid-
water environments were collected in batches of three at the different ages
of test for assessment in the laboratory. The physical appearance was
determined visually and by measuring the "attack rating" (9). One of the

A C 1 SP-153 VOL*II 95 W Ob62949 05218b0 8 9 9 W
cubes from each environment was photographed prior to the determination

of the compressive strength in accordance with BS 1881 : Part 116 (BSI
1983) (1~4).
Sulphate Tank Test
The sulfate resistance of the 100-mm concrete cubes was measured

according to the method established at BRE following procedures described
by Steele and Harrison (15). Cubes were stored at 20°C in tanks of medium
and strong sodium and magnesium sulfate solutions containing the
equivalent of 0.35 and 1.5% SO, (designated D ,C, I, and E respectively)
and in water as control. The normal pre-cure for the BRE tank test is 27
days in water at 20°C after demolding at 24 hours. This provides a severe
test, a deliberate choice as the test was intended as a relatively short-term
performance test (2-3 years) for appraising and comparing concretes
--``,`,-`-`,,`,,`,`,,`---
containing different cements to determine whether the concretes were

generally sulfate resistant or not. The comparative assessment involved the
visual appearancc (photographs), measurement of sulfate "attack rating'' and
95 compressive strength retention in comparison with that of the water-stored
control specimens at the same age and storage temperature (9). The mean
results for 3 cubes tested at 1 and 2 years arc given in Table 5.
The use of 100-mm concrete cubes as a research facility for

durability studies has sometimes been criticised, as not providing realistic
data, as the specimens are quite small compared with concrete of larger
dimensions in real structures. However, the outer 50-100 mm of reinforced
concrete is that which protects the steel reinforcemcnt and it may not behave
too differently from the concrete cubes used in the present study.
'The main object of the durability study is to obtain a comparative

assessment of the range of HAC and blended-cement concretcs, with similar
mixture proportions, following storage in the different aggressive
environments. This paper gives some I-ycar results but deals mainly with
the 2-ycar data (See Tables 5 and 6 and Figure 2).
'The metre blocks of concrete were used in order to obtain realistic

data on temperature rises, strength development and information on
hydration products for concretes which could be esscntially considered as
'heart' (concrete. The temperature achieved in the near adiabatic conditions,
within the fully insulated metre cubes, can reasonably be assumed to
represent the maximum temperature profile in a massive floor slab or
concrete dam construction. The comparative data from both 150-mm and
l-m insulated blocks and the precast concrete slabs should provide useful

A C 1 SP-1.53 VOL*II 95
0662747 0521861 725 =
information relevant to actual concrete elements used in practice (See Tables
7 and 8).
CONCRETE DURABILITY STUDIES
The effect of water temperature on blended-cement concrete
The compressive strength tests of 100-mm concrete cubes with HAC

and 60/40, 50/50 and 40/60 blends of HAC/GGBS (A) and stored in water at
20°C and 38°C have been completed up to two years and for those stored in
water at 60°C have been completed up to 1 year and the results are given in
Figure 1, (a), (b) and (c) respectively.
It is clear from Figure l(a) that the concrete cubes made with
different blends of HAWGGBS (A) and stored in water at 20°C showed
continuous increases in strength up to 2 years, whereas those made with
HAC typically showed increases up to 90 days and then started to show
slight decreases in strength.
At 38°C in water (Figure l(b)) HAC concrete cubes showed

decreased strength from 3 days to 90 days followed by a small increase in
strength up to 2 years. On the other hand the strength results of concrete
cubes made with the different blended-cement proportions showed
continuous increases, except when the water temperature in the tank rose to
boiling point duc to thermostat failure and even then the strength started to
increase once temperature control was resumed. The compressive strength
of concrete cubes at 2 years increases with increased slag content and those
containing 60% GGBS gave highest compressive strength.
The compressive strengths of concrete cubes made with HAC and

blends of 60/40 HAC/GGBS(A) and stored in water at 60°C (Figure l(c))
showed a decrease at 7 days compared to that at 24 hours. This reduction
in strength was not apparent for the blends with increased slag content. The
concretes containing more slag gave better performance and the concrete
containing 60% GGBS again gave highest compressive strength at 1 year.
It can therefore be concluded that the strength development of the

blended-cement concrete is improved with increased slag content when
stored in water at higher temperatures of 38 and 60°C.
Sulfate resistance of blended-cement concrete
The assessment of sulfate resistance of 1 and 2-year old concrete

cubes made with HAC and different blends of HAC/GGBS (A) and
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 VOL*II 95 W 0 b b 2 9 4 9 052Lôb2 bbL W
HAC/GGBS (B) is given in Table 5. The visual examination of concrete

cubes stored in four different solutions of sodium and magnesium sulphate
revealed no signs of attack for any of the concrete specimens. The 2-year
old concretes made with HAC showed a slight loss in compressive strength,
while those made with blended-cement mixtures generally showed small
increases. These results graphically presented in Figure 2 indicated that the
sulfate resistance of concrete made from blended cement was marginally
better than that of HAC and was also improved with increased slag content
when stored in either sodium or magnesium sulfate solutions. The results
for blends using GGBS (A) were very similar to those using slag (B).
Effect of aggressive environments on concrete
1100-mm cubes made with neat HAC and 60/40, 50/50 and 40/60
blends of HAC/GGBS in the mixture proportions 1:1.75:2.91 and total w/c
of 0.50, had been pre-cured for 27 days in water at 20", 38" and 5°C and in
air at 20°C, 65% RH prior to placing at BRE's marine site at Shoeburyness,
in soft acid-water at Butterley reservoir, Yorkshire and at the Garston
exposure site.
'The collection, visual examination, photography, assessment of wear

ratings, and compressive strength tests were carried out on the 2-year old
100-mtri concrete cubes made with HAC and different blends using slag (A)
from the above mentioned aggressive environments. The 2-year tests for the
blends using slag (B) are in hand and the results for blends with slag (A)
are presented in Table 6 and the main findings were as below:-
- -
HAC concretes
Good strength development was achieved with cubes pre-cured in

water ai 20°C, or 5°C and in air at 20°C 65% RH followed by storage in the
full immersion and tidal zone marine waters and in soft acid-water. The
concrete cubes pre-cured in water at 38°C and with the lower 28-day
strength showed signs of attack when stored in full immersion and tidal
zones of the marine exposure site and in soft acid water. There was slight
spalling of concrete at the corners and edges with cracks appearing at the
edges of some of the marine-stored cubes. Slight softening of edges and
corners had also occurred in some cubes following 2 year's storage in soft
acid-wa ter.
Blended cement concretes
Concrete made with different blends of HAC/GGBS(A) showed no

signs of attack in any of the above aggressive environments and were in
excellent condition at two years. Those stored at the BRE Garston exposure
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - I 1 5 3 VOL311 95 I0662949 052l1863 5 T 8 m
site and the manne site spray zone gave the best durability results. The
concretes with 50/50 and 40/60 blends of HAC and GGBS, pre-cured in air
at 20°C 65% RH had increased strengths at 2 years in these aggressive
environments, although somewhat less than their water-stored controls at
20°C.
The collection, visual examination, photography, assessment of wear

rating, and compressive strength tests were also carried out on the 1-year old
100-mm concrete cubes from the above BRE aggressive environment sites
which were made from 60/40, 50/50 and 40/60 mixtures of HAC and GGBS
(B). These concrete cubes also showed no signs of attack and the results of
assessment were very similar to those made using blends containing slag (A)
and will be published with the 2-year data in due course.
These results show that the performance of blended cement concrete

cubes is somewhat better than those of HAC cubes when stored in the above
aggressive environments, although the HAC concretes have generally
performed well.
ADIABATIC TEMPERATURE RISE MEASUREMENT OF CONCRETE
Adiabatic temperature rises of concretes made with HAC, 60/40 and

50/50 and 40/60 mixtures of HAC/GGBS using a total w/c of 0.45 (free
w/c 0.36) were measured using one metre cube and 150-mm cube molds
both insulated with 100-mm thick Styrofoam. The concretes were made
using a mixture proportion 1:1.75:2.91, poured and compacted in six layers
in the metre cubes using a vibrating poker. The temperatures at the centre
and at one quarter length from the edges of the metre cubes and at the
centre of the 150-mm cubes were recorded using an electronic data logger
and embedded thermistors. Six 100-mm cubes were also made from the
same mixes and stored under damp hessian for 24 hours, demolded and
placed in air near to the metre cube and were tested for compressive strength
at the age of 7 and 28 days for purposes of comparison with the
strength of the cores taken from the metre cubes. The metre cube and the
150-mm cube were demolded at 7 days and a 100-mm core was taken
through the metre cube. Cores were also drilled at 28 days and 180 days,
tested for compressive strength( 16) and the nature of the hydrated phases
determined by XRD. The properties of these metre cubes are given in Table
7 and the temperature profiles are shown in Figure 3.
The maximum temperatures and times to reach those temperatures for

the near adiabatic metre cubes of concrete made from HAC, 60/40, 50/50
and 40/60 mixtures of HAC and GGBS are given in Table 7. They show a
pronounced decrease in temperature maxima and corresponding increases in
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 m Obb2949 052LBb4 4 3 4 m
time to reach these temperatures as the proportion of slag increases. For the
50/50 and 40/60 HAC: GGBS concretes there were initial maxima at 15-18
hours, followed by more sustained higher maximum temperatures at about
42 hours. Fully insulated 150-mm concrete cubes of the same mixture
proportions showed a similar trend, decreasing from 75°C for plain HAC to
42°C for 40/60 HAC: GGBS concretes. These data corresponded very well
with the temperature maxima achieved in the one-metre cubes, and indicates
that the use of the smaller 150-mm size cube would provide meaningful heat
release data, as a diagnostic technique, in the comparison of different cement
types.
The compressive strength data from 100-mm core sections revealed

some differences in strength development between the plain HAC concrete
and the 60/40, 50/50 and 40/60 HAC: GGBS, blended cement concretes.
The HAC concrete achieved its highest strength of 41 MPa at 8 days,
whereas the blended cement concretes tended to have lower early strengths
of 25-38 MPa rising to a high of 47.5 MPa for the 60/40, HAC: GGBS
concrete at about 6 months.
The hydrated compounds found in the 100-mm cores of the metre

cubes taken at different ages are presented in Table 7 and clearly show that
for the HAC concrete, only C,AH, and some AH, are present. However, as
the level of slag in the blended cement mixes increases from 40 to 6096, the
principal hydrated compound C,ASH, (Strätlingite) was progressively
formed.
PRECAST CONCRETE BLOCKS
Two concrete blocks 300 by 500 by 500-mm were made from HAC,
60/40, 50/50 and 40/60 mixtures of HAC and GGBS using mix proportions
1: 1.75:2.91 and total w/c of 0.45.. The temperatures at the centre of the
blocks were recorded using a data logger and embedded thermistors. The
physical properties and the hydrated phases found in the precast blocks are
given in Table 8.
The first block was demolded after 5 hours and the second one after
4 hours of casting. Soon after demolding, the first block was transferred to '
an open store, where there was no control for air temperature, and the
second block to a constant humidity room at 20°C, 90% RH. Both blocks
were sprayed with water for 24 hours, to reduce or control the temperature
rise during early curing.
100-mm cores were taken from the blocks at 24 hours, 3, 7, 28, and
180 days and tested for compressive strength (16) and one of the sections of
the core was examined by XRD to. detect the hydrated phases. There was
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L a I I 95 = 0662949 0522865 370 M
no problem in demolding the blocks which had attained a reasonable

strength within 4-5 hours of casting and for moving them to different places
of storage. The equivalent cube compressive strength calculated from the
100-mm cores taken from the concrete blocks containing 50/50 and 40í60
mixtures of HAC and GGBS were 23 and 14 MPa respectively at 24 hours
which increased to 53 and 48 MPa after 28 days.
The maximum temperature recorded for HAC alone and for 60/40,
50/50 and 40/60 mixtures of HAC and GGBS were 63", 56", 50", and 45°C
respectively. The maximum temperatures of < 50°C for both 50/50 and
40/60 mixtures of HAC and GGBS were good.
The hydrated phases present in the core samples drilled after 24

hours, 3, 7, and 28 days from HAC blocks were CAH,,,.C2AH8and C,AH,
and were converted to C,AH, and AH, after 180 days. The cores taken
from the block made with 60/40 blend of HAC/GGBS showed the presence
of CAH,, and C,AH8 24 hours after casting and the hydrated phase found at
3 days was the stable hydrate C2ASH, and remained the principal phase
thereafter. In the precast units made with 50/50 and 40/60 blends of HAC
and GGBS, the principal phase formed was C2ASH8. After 7 days very
small amounts of hydrogarnet (C,AH,) and AH, (gibbsite) were also found
in the 50/50 blend and remained up to 180 days.
CONCLUSIONS
1. Blended-cement concretes with of 0.45 to 0.525, showed no

signs of strength loss at temperatures from 5" to 38°C whereas HAC
concretes with w/c greater than 0.45 and cured at 38°C showed
considerably reduced strength due to the effects of "conversion".
HAC concretes were also less tolerant to the effects of water content
than blended-cement concretes.
2. The continuing strength gain of the blended-cement concretes is due

to the formation of the stable gehlenite hydrate which replaces the
metastable hydrates.
3. Two year old blended-cement concrete specimens contained large

quantities of gehlenite hydrate, when pre-cured over the temperature
range of 5" to 38°C. This compound is stable and is responsible for
more consistent performance and improved strength characteristics of
this cement when stored in water.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 Ob62949 05218bb 207 =
4. HAC and especially blended-cement concretes performed very well

after 2 year's storage in sodium and magnesium sulfate solutions.
5. All blended-cement concretes, with w/c of 0.45, showed excellent

durability in both marine and soft acid-water environments with no
signs of attack at 2 years. Equivalent HAC concretes also performed
very well with high strength retention and increased strength
development up to 2 years in ail aggressive environments, even
though there was some slight softening and spalling at edges of some
HAC concrete cubes.
6. Both of the GGBS materials when used as the blended-cement in

concrete mixtures gave similar performances.
7. The 2-year durability results for the range of blended-cement

, concretes assessed in the different aggressive environments are
promising for their prospective use as repair materiais or for tiles and
pipes. However, longer-term studies are necessary before the
commercial application of this material can be recommended with
confidence.
8. The use of 50% slag as replacement for HAC in the fully insulated
metre-sized concrete cubes resulted in a considerable reduction in
maximum achievable temperature which dropped from 91°C to 64°C.
9. The precast concrete blocks made with 50/50 and 40/60 blends of
HAC and GGBS gave very encouraging results as far as temperature
rise 'and hydrate formation were concerned. The practical
significance for the use of the blended cement in structurai concrete
applications, in comparison with existing HAC concrete structures
(17, is), will be investigated further.
ACKNOWLEDGEMENT
The work described has been carried out as part of the strategic research
programme of the Building Research Establishment of the Department of the
Environment and this paper is published by permission of the Chief
Executive. The authors thank Dr A J Majumdar for his earlier involvement
with this project and Mrs J L Hardcastle and the Concrete Laboratory staff
for carrying out the experimental work.
--``,`,-`-`,,`,,`,`,,`---

-
A C 1 SP-353 V O L S 1 1 95 Obb2949 0523867 I143
REFERENCES
1. Majumdar, A.J: and Singh, B. "Cement Compositions", UK. Patent

GB 2211 182 B. 1991.
2. Osborne, G.J. "BRECEM: A Rapid Hardening Cement Based on

High Alumina Cement". Proceedings of Institution of Civil
Engineers, Structures and Buildings, 104, pp 93-100, February, 1994.
3. Midgley, H.G. and Midgley, A. "The Conversion of High Alumina

Cement". Magazine of Concrete Research, 27, pp 59-77, 1975.
4. Majumdar, et al. "Blended High Alumina Cements", Proceedings of

International Conference on Advances in Cementitious Materials
Gaithersburg. Ceramic Transactions, 16, pp 661-678, July, 1991.
5. Quillin, K.C. and Majumdar, A.J. "Phase Equilibria in the CaO-

Alzo3 - SiO, - H,O System at 5°C 20°C and 38°C". Advances in
Cement Research, 6 No 22, pp 47-56, 1994.
6. Majumdar, A.J. and Singh, B. "Properties of Some Blended High-

Alumina Cements". Cement and Concrete Research, 22, pp 101-114,
1992.
7. Bate, S.C.C. "Report on the Failure of Roof Beams at Sir John

Cass's Foundation and Red Coat Church of England Secondary
--``,`,-`-`,,`,,`,`,,`---
School, Stepney". Building Research Establishment, Garston, BRE.

Current Paper, CP 58/74, p 18, 1974.
8. George, C.M. (Mangabhai, R.J. (ED)). "Manufacture and

Performance of Aluminous Cement; a New Perspective". Calcium
Aluminate Cements, E and F.N. Spon, London, pp 181-207, 1990.
9. Osborne, G.J. "The Sulphate Resistance of Portland and Blastfurnace

Slag Cement Concretes". Proceedings of Second CANMET/ACI
International Conference on the Durability of Concrete, Montreal, II,
AC1 SP-126, pp 1047-1071, August 1991, Detroit MI.
10. Building Research Establishment, BRE Digest 363. "Sulphate and

Acid Resistance of Concrete in the Ground". BRE, Garston, UK.
1991.
11. Osborne, G.J. "The Durability of Concretes Made with Gasifier Slag
Cement". Durability of Building Materials, 4, pp 151-177, Elsevier
Science Publishers. 1986.

A C 1 SP-153 V O L X I I 75 = 0662947 052Lôbô OBT
12. Osborne, G.J. "Concrete Durability Studies at the Building Research

Establishment Marine Exposure Site, Shoeburyness". Proceedings of
Marine Concrete 1986. The Concrete Society, London, pp 157-164,
1986.
13. Matthews, J.D. "The Resistance of PFA Concrete in Acid Ground

Waters". Proceedings of the Ninth International Congress on the
Chemistry of Cement, New Delhi, India, Vol V, pp 355-362,
November, 1992.
14. British Standards Institution, BS 1881, Part 116, "Method for

Determination of Compressive Strength of Concrete Cubes", BSI,
--``,`,-`-`,,`,,`,`,,`---
London, 1983.
15. Steele, B.R. and Harrison, W.H. "Immersion Tests on the Sulphate
Resistance of Concrete". Proceedings of a RILEM International
Symposium on Durability of Concrete, Prague, Academia,
Preliminary report, Part II, pp C163-Cl86, 1969.
16. British Standards Institution, BS 1881, Part 120, "Method for

Determination of Compressive Strength of Concrete Cores". BSI,
London, 1983.
17. BRE Digest 392, "Assessment of Existing High Alumina Cement

Concrete Construction in the UK". Building Research Establishment,
Garston, UK, March 1994.
18. Montgomery, R.G.J., Rashid, S., Capmas, A. and Woolley, W.B.

"Calcium Aluminates and their Derivatives: New Applications and
-Technologies". Proceedings of Concrete 2000, E. and F.N. Spon,
Dundee, Vol 2, pp 1857-1879, September 1993.

A C 1 SP-153 VOL+II 95 = Ob62949 0523ôb9 T l b W
TABLE 1 - CHEMICAL ANALYSIS OF HAC AND

GGBS (PERCENT BY MASS)
Oxides HAC GGBS (A) GGBS (B)

SiO, 3.64 34.20 35.56
A1,0, 39.62 11.30 13.08
Fe203 16.12 1.17 0.64

Ca0 37.66 41.60 39.39
MgO 0.67 8.21 9.37

Na0 0.0 1 0.26 O. 27
KIO 0.08 0.40 0.46
mo, 0.05 0.25 0.48
Tio, 1.94 0.77 0.7 1
ZrO, 0.03
Ba 0 0.04 0.06
SO, I 0.08 I 1.90 I 0.15
P,O, I 0.03 I - 1 -
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L 8 1 1 75 = 0662747 0523870 738
in O in
3 I
(B
!
! 2
c1 0
v3 $3
I-
LT
w
a
2a
W
I-
W
U
o
Z
8 in
m
m
zm Q:
m
I
(B
W
U in
u-
n
z
N
?
O
O
7
O x
in
a
(B
Z 9 9 9
0
I-
+ + 4
U
2
2a O
?
4
in
Y
i
W
(r
3
I-
3
2
w
I- O
W
CT
o
m
Z
8
I
01
5
rn
2
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 H 0662949 0521871 674
Cements Workability 28 Day Compressive Strength

íMPa)
Slump Vebe CF Water Water
(mm) time 38°C
65% rh
HAC I 80 I 3 I 0.95 I 83 26
GGB S
(A)
60140 60 4 0.91 50 56
HAC+
GGBS
50150 75 4 0.94 52 59
HAC+
GGBS
40160 ' 55 4 0.90 39 51
HAC+
GGBS
GGBS
(BI
60140 90 2 0.96 50 46
HAC+
GGBS
50150 100 2 0.96 44 48
HAC+
GGB S
40160 70 2 0.93 31 42
HAC+
GGBS
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 H Ob62949 0523872 500 D
vi
a
00
h
CI
&
vi
1
O
W E
v3 s E vi
u
d
z
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOL*II 95 0662949 0521873 447 =
TABLE 5 - COMPRESSIVE STRENGTH DATA (MPa) FOR HAC/GGBS

100-rnrn CONCRETE CUBES STORED IN SULFATE SOLUTIONS
Cements
Magnesium sulfate Water Sodium sulfate
Soin. c I SoIn. E (20 C) Soln. D ISoin. I
I
I(0.35% SO31 (1.5: -
2 Yr
-
i yr I
I
2yr j
1
i yr
CGM (A)
64.0
73.0
65.5
67.0
67.0
76.0
65.0
I I 70.0 74.5
65.0 64.0
71.0
65.0
61.5 64.0 65.0 62.5 66.0 64.5 66.0
56.5 63.0 59.0 64.0 64.0 63.0
71.0 66.5 63.0 70.0 65.0 68.0

64.0 61.0 64.0 61.0 62.0 65.0
--``,`,-`-`,,`,,`,`,,`---
49.0 55.0 47.5 53.0 50.0 55.0
Data Expresse as %
- -L-
'ength of the Water ored ubes at 2ot= (Cont D
- -
'(AC
loo I o , loo 100 103 99 100
SGBS (A)
6 0 1 40 loo i00 100 95 100
50 1 5 0 Iioolioo 96 102 99
108 1oó
93 98
94 95
108 123
-

A C 1 SP-153 VOLmII 95 0662749 0523874 3 8 3
TABLE 6 - COMPRESSIVE STRENGTH DATA (MPa)

FOR HAC/GGBS(A) CONCRETES STORED IN AGGRESSIVE
ENVIRONMENTS AT 2 YEARS
Storage Environments
-
I COMROL I MARINE
--
son
ACID
,LllDOOR
2fZlL WATER GOntOn
Water 80.5 79.0 70.0 78.0 66.0

34.0 34.0 40.0 33.0 38.0
71.0 71.0 52.0 76.5 45.0
67.5 70.0 47.0 72.0 44.0
65.0 69.5 74.0 65.0 71.0

61.0 64.0 74.0 61.0 67.0
68.0 69.5 75.0 64.0 74.0
67.0 67.0 69.0 60.0 63.0
67.0 65.0 73.5 63.5 73.0

62.5 61.O 69.0 56.0 68.5
64.0 65.0 69.0 64.0 68.0
59.0 57.0 61.O 54.0 61.0
59.0 58.0 63.0 54.0 61.O
--``,`,-`-`,,`,,`,`,,`---
59.0 57.0 65.0 53.0 65.0
57.0 57.0 59.0 56.0 59.0
51.0 51.0 51.O 47.0 50.0
, --
Data Eroresseda s S rengih ( he Waii itored C les
,trol>
126 123 109 122 103

103 103 121 la, 115
158 158 115 170 100
159 165 111 169 103
98 105 111 98 107

95 100 116 95 105
96 98 105 90 104
104 104 107 93 98
50150 HACIGGBS
Water 104 101 114 98 113
119 116 131 107 130
94 96 101 94 1M)
91 88 94 83 94
40160 HACIGGBS
Water 94 92 100 86 97
Water 92 89 102 83 102
92 92 95 90 95
91 91 91 84 89
I __.

A C 1 S P - 1 5 3 VOLrII 95 IObb2949 052187.5 2 L T I
TABLE 7 - PROPERTIES OF 1-m CONCRETE CUBES MADE WITH

DIFFERENT BLENDS OF HAC AND GGBS (1:1.75:2.91:0.45)
I
l
Properties
I Cement content (kg/m’)

i
HAC
390
60140
HAC:
GGBS
390
50150
HAC:
GGBS
390
40160
HAC:G
GBS
390
U Slump (mm) 25 10
Maximum temperature 91.2 (58.4) (52.4)

reached (“C) 61.6
Time to reach maximum 9.0 (15.5) (18.0)

temperature (hour) 43.0 42.0
Compressive strength of
100- mm cores (MPa)
41.0 38
29-32 days 36.5 41
--``,`,-`-`,,`,,`,`,,`---
180-190 days 36.9 47
II
I Hydrated phases ’
I
8-9 days C3AH6
AH3
C2ASH,
29-32 days
AH3
180-190 days C3AH6 C3AH6

AH3 AH,
C,ASH,
Maximum temperature 75.0 42.0

reached in an adiabatic 150-
mm concrete cube (“C)

A C 1 SP-153 VOL*II 95 E Obb2949 052187b 156 E
TABLE 8 - PROPERTIES OF PRECAST CONCRETE BLOCKS (300 x

500 x 500 mm) MADE WITH DIFFERENT MIXTURES OF HAC AND
GGBS (1:1.75:2.91:0.45)
60140 50150 40160

Properties HAC: HAC: HAC:
GGBS GGBS
Cement content (kg/m3) 390 390
Slump (mm) 30-40 I 40-60 50 35-40
Maximum temperature
reached (OC)
62.8 I 55.5 49.6 45.2
~~
Time to reach maximum
temperature (hr)
Compressive strength of
100 mm cores (MPa)
1 dav
3 days
t 5.0
23
24
5.0
14
15
7 days 29 23
28 days 53 48
180 days 65 59
Hydrated phases CAHI,
1 day C,ASH,
3 days C,ASH, C,ASH,
7 days C2AH8 C3ASH8

AH3
C,ASH,
28 days CAH,, C3AH, C3AH6 C,ASH,

C,AH, AH, AH3
C3AH6 C,ASH, C,ASH,
180 days C,ASH,

AH3
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLXII 95 m 0662949 0523877 O92 m
"T
Bo
{ 70
--``,`,-`-`,,`,,`,`,,`---
lo
O J
t 4
1 10 la, lmi
A g . h day.t!w scab)
Fig. l-Compressive strength development of concretes at

different temperatures

A C 1 SP-I153 V O L t I I 95 Obb2949 0 5 2 3 8 7 8 T 2 9
B.-c
ea,
u
--``,`,-`-`,,`,,`,`,,`---
L I
Sulfate Solution E
Fig. 2-Percentage strength retained of concretes stored in sulfate

solutions for 2 years
90
---- *-
-- --i.
=,, - e . - y . . -
.............-. ......~,
+
,
....-,b
p 'i%
O 25 50 75 103 125 150

Tirne (Houn)
Fig. 3-Adiabatic temperature rise in metre-cube concrete blocks (wIc

= 0.45)

A C 1 SP-153 V O L * I I 95 m Obb2îi.19 0523879 965 m
SP 153-48
Blast Furance Slag Aggregate in

the Production of High-
Performance Concrete
by M. N. Haque, O. A. Kayyali, and B. M. Joynes
Synopsis: The use of blast-fumace slag aggregate (BFSA) is not new, but
its application in the production of high-performance concrete (HPC) is
nonexistent at least, in Australia. This paper presents the results of a
preliminary optimization of the high-strength concretes made using BFSA,
normal sand, portland cement, ground, granulated blast-furnaceslag (GGBFS),
condensed silica fume (CSF) and a proprietary superplasticiser. The paper also
describes some additional characteristics of the optimized concretes. In all,
fifteen types of concretes were made and the properties examined were:
workability, density, compressive strength, elastic modulus, shrinkage and
water penetration.
The maximum strength achieved using the slag aggregate was 107 M a
which placed the slag aggregate concrete well into the very high-strength range
of concretes. The workability was found IO be unaffected by the use of the
slag aggregate. The tensile strength of the concrete was relatively high (5.4
m a ) , and the shrinkage was found to be lower than concretes produced with
normal aggregates, as was the water penetration and absorption. of particular
importance, the elastic modulus was found to be markedly lower than that of
concretes made with normal aggregates. It is concluded that the slag
aggregate can be used successfully in the production of high performance, high
strength concrete.
Kevwords: Aggregates; blast furnace slag; compressive strength;

1 performance concretes; shrinkage; silica fume
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L X I I 95 Obb29V9 0 5 2 3 8 8 0 687 =
912 Haque, Kayyali, and Joynec
AC1 member M.N. Haque is a senior lecturer in the Department of Civil

Engineering, Australian Defence Force Academy (ADFA), Australia. His
special research interests are durability of concrete, utilization of marginal
aggregates and the use of additional cementitious materials.
Dr O.A. Kayyali lectures in the Department of Civil Engineering, ADFA. His

research interests include design of reinforced concrete and the durability of
concrete structures.
B.M. Joynes graduated in Civil Engineering from ADFA in 1993.
INTRODUCTION
High-strength concrete (HSC) is a very valuable and high quality
The HSC, of course, has obvious advantages of
material of constr~ction('-~).
fast track construction, more rentable area, longer maintenance free service life
and overall reduction in the self weight of the structure as a whole. The
production of HSC has been made possible because of the availability of the
high range water reducers (chemical admixtures) and the additional
cementitious materials such as condensed silica fume (CSF) ground granulated
blast furnace slag (GGBFS) and an abundance of the highly effective and
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I I 95 M 0662949 0523881 513
dependable classified fly ache^(^-^). Now the ready mix concrete producers are
capable of supplying a 120 MPa specified compressive strength concrete.
Obviously, an ongoing supply of very high quality aggregates is an

essential requirement for the production of the HSC. It is essential that the fast
depleting sources of good quality aggregates should be supplanted. One
possible source of aggregates is the use of some indusmal by-products. The
use of by-products in concrete making has an additional advantage of the
enhancement of the environment in a dual way@).
The study reported in this paper forms a preliminary part of a

comprehensive research plan to characterise and evaluate the production of
HSC using blast furnace slag aggregates (BFSA). This paper reports the
optimization of the concrete mixtures using the BFSA in conjunction with
normal portland cement, CSF and GGBFS. The preliminary results reported
here suggest that the use of BFSA can produce a good workable concrete of
about 100 MPa compressive strength. Some other Characteristics which are
indicative of the ductility and the durability of the BFSA concrete are also very
encouraging.
Materials Used
Type A cement, similar to ASTM Type 1, was used and its' chemical
composition and other characteristics are included in Table 1. The properties
of the GGBFS and CSF used are also included in Table 1.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 =
0662949 0523882 45T =
914 Haque, Kayyali, and Joynes
A proprietary superplasticiser was used at a dosage of 1 litre per 100
kg of the total cementitious materials. The coarse aggregate used was 10 mm

air-cooled blast furnace slag"', and its chemical and physical characteristics are
included in Table 1.
Concrete Cast
The BFSA has not been used previously to produce HSC, so no prior
information was available on the mix proportioning. The main objective was to
produce a good workable and economical mixtures of the maximum possible
strength("). Initial trials suggested that for the given coarse and f í e
aggregates used, 30% sand of the weight of the total aggregates will have
minimum void contents and hence would be economical. To limit shrinkage of
the concretes it was also decided that the total cementitious contents of the
concretes will preferably be in the range of 500 to 550kg/m3of concrete. In aU

fifteen mixes were cast and tested. The mixture designation used was:
WC-CC-SF-GS(*)
where WC = nominal water to cementitious ratio

CC = total cementitious contents
SF = % cement replaced by the CSF (by weight)
GS = % cement replaced by the GGBFS
(*) = indicates crushed granite (lûmm) aggregate

instead of the
BFSA
The characteristics of the fresh concretes cast are included in Table 2.

From each mixture, 12 - 100 x 200mm cylinders were cast and the final two
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*II 95 œ ! ü b b 2 9 4 9 0 5 2 3 8 8 3 39b
i Milwaukee Conference 915
mixes (mix 14 and 15) had, in addition, three extra cylinders and two prisms of
285 x 85 x 85 mm size for shrinkage.
--``,`,-`-`,,`,,`,`,,`---
- S
After casting the specimens were stored for 24 hours in the laboratory
environment and then demoulded and stored in a fog room (at 21 & 2C" and 95
+ 3 % R.H.). The tests(") performed were slump test for workability, density
-
of the fresh concrete, air content, compressive and indirect tensile strength,
shrinkage, elastic modulus and water penetration. The curing regime used for
the water absorption test and Shrinkage monitoring was 23 2 2C" and 40 2 5%,
relative humidity in a control room.
The compressive strength of the cylinders was determined at 7, 28, 56

and 91 days. The modulus of elasticity of the cylinders was determined after
91 days. The results included in Table 3 are the average of 3 specimens. The
shrinkage tests were performed on the test specimens from mixtures 14 and 15
only. The shrinkage prisms were fog cured for 7 days and then transferred to
control room where readings were taken after O, 1, 3, 7, 14, 28 and 56 days.
The results are included in Table 4.
The two hour water penetration and absorption test was performed on
the test specimens from mixtures 14 and 15 only. For each mix 3 cylinders
were cured for the duration of 56 days in the control room. The depth of
water penetration and the amount of water absorbed in the cylinders after 2

A C 1 SP-153 V O L X I I 95 I0662749 0523884 222 I
hours of soaking under a constant head were determined. The results are
included in Table 4.
RESULTS
As mentioned earlier, no prior information was available for the mix
design of concrete using BFSA. Accordingly, an iterative approach was
adopted to maximize the strength of the concrete containing the slag
aggregate. That is basically for a given cement content, watedcement was
varied, while keeping all other factors constant, to maximise the strength. This
procedure was repeated for differing cement contents and differing cement
replacements with CSF, GGBFS or both.
First, mixtures 1-4 were cast with a total cement content of 500 kg/m3
and the nominal w/c ratios of 0.35, 0.3, 0.25 and 0.23 respectively. The 7 and
28 days compressive strength of the mixtures 1-4 are included in Fig. 1.
Three other mixes were cast at water/cenient of 0.25 and cement

contents of 450, 500 and 600 kgJni3. The results are included in Fig. 2. The
results suggest that cement content of 550 kg/m3 of concrete at a waterhement
ratio 0.25 is optimal although a slump of 40 mm is not indicative of a workable
concrete.
In order to find optimal cementitious contents, two additional mixes

were cast. the waterkement was kept constant at 0.3 and the cenientitious
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L * I I 95 M 0662949 0523885 L b 9 m
content at 500 kg/m3. These additional mixes had 10% silica fume, and 10%
silica fume plus 30% GGBFS respectively. The results are included in Fig. 3.
As given in Fig. 3, 10% silica fume concrete gave a 28 day compressive

strength of 80 MPa and a good workability of 125 mm slump (see Table 2).
However, when the mix was recast with a water/cement of 0.23 (mixture 10) it
gave a 28 day strength of 97 MPa but very low workability (O slump). So to
get a better workable concrete, mix 10 was recast with w/c of 0.25 with a .
slump of 35 mm and 28 day strength of 94-MPa. Mixtures 10 and 11 were the
mixtures with the highest 28 day strength and accordingly were recognised as
the optimal laboratory concretes. To record the strength level which could be
achieved using crushed granite of 10 mm nomial size aggregate instead of the
BFSA, mixes 12 and 13 were made which were replica of the mixes 10 and 11,
respectively (except the aggregate type). The characteristics of these concretes
are included in Tables 2 and 3.
The field placeable concretes were considered to require at least a

slump of 100 mm and extrapolation of slump vs w/c ratio plot of the concretes
(see Fig. 4) led to making mixes 14 and 15 using the previously optimised
concretes with a view to attaining 100 mm slump. Accordingly, mixes 14 and
15 were cast with a desired slump (Workability) and the characteristics of these
concretes are included in Tables 2 and 3.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 D Obb2949 052LBBb OT5 D
Dying Shrinkage Strain

The drying-shrinkage of the blast furnace slag concretes was only
monitored for the two optimized mixtures ie. 14 and 15. The shrinkage results
are included in Table 4.
Two Hour Water Penetration and Absorption

The test was conducted after 56 days of control room curing (20 2°C
and 40% R.H.). The test cylinders were immersed in water for two hours and
thereafter the depth of water penetration and the increase in weight of the
cylinders were measured. The results of water penetration and absorption test
are included in Table 4.
.
I
DISCUSSION
Characteristics of Fresh Concrete
--``,`,-`-`,,`,,`,`,,`---
The concretes made with BFSA were as workable as those made with
good quality crushed aggregates. Accordingly, no extra effort was required to
compact the BFSA concretes. The amount and rate of slump loss were also
similar. Of course, all the concretes manufactured had high total cementitious
contents, and contained superplasiticiser. So rate of slump loss was higher but
no different to comparable high strength concretes. As shown in Tables 2 and
3, concretes 10 and 1 1 were comparable to concretes 12 and 13 respectively
but were not workable as measured by slump test.

A C 1 SP-353 V O L + I I 95 Obb2949 0523887 T3L
As shown in Table 2, slag concretes are about 1.5% lighter than the
concretes produced using normal aggregates. This marginally increased the
strength/weight ratio of the BFSA concretes.
Characteristics qf Hardened Concrete

As discussed earlier the use of BFSA in conjunction with CSF andlor
GGBFS produced high strength field placeable concretes of 90 & 3 MPa.
Further a comparison of mixtures 10 and 12, and 11 and 13, indicates that the
use of good quality crushed aggregate (granite) produced concrete strength
almost similar to those using BFSA (see Table 3). From the standpoint of
strength BFSA are as good as any good quality aggregate. The cost
comparison, based on information in Table 5 , as included in Table 6 also
suggests that the high strength BFSA concretes are somewhat cheaper, both in
terms of per cubic meter and per cubic meter per MPa. From these
comparisons, it is concluded that the use of BFSA in the manufacture of high-
strength concrete is equally feasible and more economical than the high-
strength concretes produced with the conventional good quality aggregates.
--``,`,-`-`,,`,,`,`,,`---
Some additional characterisitics of these concretes are:
Young's Modulus of Elastici@ "E"
The Young's modulus of the mixtures 10 to 15 are somewhat similar

i.e. 40 & 5 GPa with BFSA concretes slightly less stiff. The modulus of the
various concretes cast is plotted against their compressive strength as shown in
Fig. 5 and is approximating linear relationship. The relationship is:
E = 0.165 (f,) + 25.5

A C 1 SP-153 V O L * I I 95
O662949 0521888 978 = =
where E = elastic modulus (GPa)

f, = compressive strength (MPa)
Using AS 3600 (12) recommended expression for the calculation of the

E value:
E = 45 GPa, where the experimental value is 40 GPa, a variation of
12.5%.
Drvinp Shrinkape
The 56 day shrinkage results of the two field pbceabie BFSA concretes
as shown in Table 4 are 452 and 570 pm which seem low and permissible
although the total cementitious content of 550 kg/m3 is very high i.e. high
strength concretes of reasonable volume stability can be produced using BFSA.
In an earlier investigation@),a concrete comparable to mixture 14 with normal
quality aggregates resulted in a 56 day shrinkage of 490 microstrain.
Two hours water penetration and absorption values are, to some

extent, indicative of permeability of the concrete. Again, these values are
somewhat similar to those obtained with nomal aggregated'). The
expectation was that the porous and vesicular nature of the BFSA would result
in a greater depth of water penetration and a high value of water absorption.
One of the reasons for a low water penetration is that concretes with a high
cementitious content are normally highly impervious.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I 1 95 = Ob62949 0 5 2 3 8 8 9 804
Indirect Tensile Strength

The tensile strength of the two field placeable concretes of 5.1 and 5.4
MPa are again marginally higher than those tested by Sharp"' for similar
concretes with normal aggregates of 4.8 to 4.9 MPa.
In summary, most of the characteristics of the field placeable concretes

manufactured using BFSA are, if not superior, in no way inferior to the high
strength concretes produced using normal good quality aggregates.
CONCLUSIONS
1. The slag aggregates used resulted in a good workable and compactable
concrete. The maximum compressive strength achieved using slag
aggregate and 10% CSF of a total cementitious contents of 550 kg/m3
was 107 MPa and a comparable mix using normal (granite) aggregates
resulted in compressive strength of 111 MPa. This strength differential
seems nominal. The maximum compressive strength of a field
placeable slag concrete (100 mm slump), however, was 97 MPa.
2. Some other characteristics of the field placeable slag concretes (mixes

14 and 15) like drying shrinkage, modulus of elasticity, indirect tensile
strength and two hours water penetration and water absorption all
suggest that the use of BFSA can produce both high strength and high
performance concretes.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 V O L X I I 95 =
Obb2949 05Z3890 5 2 6
922 Haque, Kayyaii, and Joynes
REFERENCES
1. Aitcin, P.C. and Neville, A.M. "High Performance Concrete

Demystified", AC1 Concrete International, Vol. 15, No. 1, pp. 21-26,
1993.
2. Collins, M.P., Mitchell, D. and MacGregor, J.G. "Structural Design

Considerations for High Strength Concrete", AC1 Concrete
International, Vol. 15, No. 5 , pp. 22-34, 1993.
3. MacGregor, J.G. "Canadian Network of Centres of Excellence on High

Performance Concrete", AC1 Concrete International, Vol. 15, No. 2,
pp. 60-61, 1993.
--``,`,-`-`,,`,,`,`,,`---
4. Ozyildirim, C. "High Performance Concrete for Transport Structure",

AC1 Concrete International, Vol. 15, No. 1, pp. 33-38, 1993.
5. Webb, J. "High Strength Concrete: Economics, Design and Ductility",

AC1 Concrete International, Vol. 15, No. 1, pp. 27-32, 1993.
6. Hester, W.T. Ed; "High-Strength Concrete", Second International

Symposium, ACI, SP- 121, p. 786, 1990.
7. Malhotra, V.M., Ed; "Fly Ash, Silica Fume, Slag and Other Minerai
By-products i n Concrete", Vol. 2, SP-79, pp. 1143-1150, 1979.
8. Sharp, D.J. "The Production and Properties of High Strength

Concrete", Final Year Project, University College, ADFA, Australia, p.
84. 1989.
9. ASMS, "I0mm Slag Aggregate Product Data Sheets", Supplied by the

Australian Steel Milling Services (ASMS), May 1993.
10. Joynes, B.M. "Blast Furnace Slag Aggregate in the Production of High
Performance High Strength Concrete" Final Year Project, University
College, ADFA, Austrdkì, p. 102, 1993.
11. Australian Standard - AS 1012 "Standard Methods of Sampling and

Testing Concrete - 18 Parts", 1973,
12. Australian Standard - AS 3600 "Concrete Structures", 1988.

A C 1 SP-153 V O L U I I 95 m Obb2949 0521891 462 m
13. Australian Standard - As 2758.1 "Aggregates and Rock for

Engineering Purposes - Pari I - Concrete Aggregates", 1985.
TABLE 1 - CHARACTERISTICS OF CEMENT, GGBFS, CSF, AND

BFSA
Percentage
- Composition
Chemical (%
Cement GGBFS CSF BFSA"
SiO, 20.6 32.6 93 32-37
A1203 4.6 12.8 0.6 13-16
Fe203 5.0 1.3 1.o d.3
Ca0 64.7 4.10 0.2 38-43
Mg0 1.1 7.2 1.2 5-8

Na,O, 0.53 1.1 <1 .5
K20 2.4 2.6 0.3 <1
so, < 1000pp
c1- 2.0 0.2 2.0 m
L on I
Specific 3.16 2.93 2.33 2.65
Gravity
* Meets the requirements of AS 2758.1'13'.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLJII 95 Obb2949 O523892 3 T 9
TABLE 2 - MIX DESIGNATION AND PROPERTIES OF FRESH

CONCRETE
Mix No. Mix Density Slump Air content wtc
Designation (kdm3) (mm)
1 0.35-500-00-00 2340 170 O. 60 0.37
2 0.30-500-00-00 2380 135 0.69 0.32
3 0.25-500-00-00 2413 30 1.65 0.27
4 0.23-500-00-00 2409 O 2.11 0.25
5 .30-500-10-00 2384 125 O. 89 0.32
6 0.30-500-10-30 2355 130 0.98 0.32
7 0.25-550-00-00 2411 40 1.72 0.27
8 0.25-600-00-00 2414 40 1.92 0.27
9 0.25-450-00-00 2401 35 1.46 0.27
10 0.23-550-10-00 240 1 O 2.20 0.25
11 0.25-550-10-00 2407 35 2.03 0.27
12" D.23-550-10-00* 2438 O 2.17 0.25
13* 3.25-550- 10-00* 2443 30 1.98 0.27
14 0.27-550-10-00 2399 100 0.88 0.29
15 3.27-550- 10-300 2323 105 0.96 0.29
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOL*II 95 m 0662949 0 5 2 3 8 9 3 235 m
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 Obb2949 0521894 171 =
TABLE 4 - SHRINKAGE AND SORPTIVITY CHARACTERISTICSOF

FIELD PLACEABLE CONCRETES
Tensile
Designation Drying Shrinkage Strain, x10' strength
(No.) (MPa)
0.27-550- 10-0 5.4

(14)
0.27-550-10-30 I I I I 1
22 79 125 570 12 I 1.7 5.1
Material Used cost

Cement $157 tonne
10 mrn Crushed Granite $18 tonne
10 mm Air Cooled Slag $13.50 tonne (ASMS-iOOkm from Sydney)
Washed River Sand $17 tonne
Silica Fume $550 tonne (CSR Humes)

--``,`,-`-`,,`,,`,`,,`---
GGBFS $.i4 tonne (ASMS-100km from Sydney)
Superplasticiser (Rheobuild 1000) $3.50 litre (CE Industries)

A C 1 SP-153 V O L X I 1 95 Obb2949 0521895 O08
--``,`,-`-`,,`,,`,`,,`---
TABLE 6 - COST COMPARISONS OF MIXES BASED ON 28-DAY

COMPRESSIVE STRENGTH
Mix Number Mix Designation Cost per Cost per m3 per

cubic metre MPa obtained at
($1 28 days ($1
1 .35-500-00-00 106 i .61
2 . .30-500-0()-0() 114 1.58
3 .25-5ot)-o()-00 124 1.55
4 .2 3-500-00-00 129 1.49
5 .30-500- 10-00 1 47 1.84
6 .30-5oO-10-30 125 1.66
7 .25-550-o()-00 126 1.52
8 .25-6oo-oo-~x) 132 1.61
9 .25-450-00-00 113 1.42
10 .23-550- 10-00 160 1. 64
11 .25-550-10-00 159 1.69
12* .23-550- 10-00* 167 1.66
13* .25-550- 10-00* 166 1.73
14 .27-550-10-00 160 1.80
15 .27-550-10-30 137 1.69

A C 1 SP-153 V O L X I I 95 = 0662949 052189b T44
87
90
80
w 70
2
v3
60
v3 I 50
üb
az
L
40
E 30
o2
o t- 20
03
10
O
WIC
0.3
0.25 0,23 ’
Duyc
Fig. l-ûptimizing of wlc
90.0
80.0
c!J
Z 70.0
W
K 60.0
c
50.0
--``,`,-`-`,,`,,`,`,,`---
40.0
u#
W 30.0
a
I
a
20.0
u 10.0
0.0
Days
CEMENT CONTENT (kg/m3)
Fig. 2-ûptimizing of cement content

A C 1 SP-353 V O L * I I 95 H 0662949 O523897 980 W
n I
--``,`,-`-`,,`,,`,`,,`---
Fig. 3-Optimizing of cementitious combination

A C 1 SP-153 VOL*II 75 Obb27q7 0521878 AL7 =
--``,`,-`-`,,`,,`,`,,`---
-
180 -,-
160 0H
02
# /
NH
140
/E’ ’/
//
%/
-/-
// /; I
/L
// ;
// I
/f./ 1
//
0
- , :__f__l
0.2 0.22 0.24 0.26 0.28 0.3 0.32 0.34 0.36 0.38 0.4
WIC
Fig. &Variation of slump with w/c
37
I---+
70 75 80 85 90 95 100 i05 110 115
COMPRESSIVESTRENGTH (MPa)
Fig. &Variation of Young’s modulus with compressive strength

A C 1 SP-153 VOL*II 95 W Ob62949 0521B99 753 W
SP 153-49
Effects of Fly Ash, Blast Furnace Slag,

and Silica Fume on Resistance of
Mortar to Calcium Chloride Attack
by K. Torii, T. Sasatani, and M. Kawarnura
Svnogsis : Chemical attack caused by a high concentration CaC12 solution and its
preventive measures by the addition of a mineral admixture are described.
Changes which occur in mechanical strengths and chemical properties in mortars
with and without fly ash, blast-furnace slag and silica fume when immersed in a
30 % CaC12 solution at different temperatures were investigated. Portland
cement mortars seriously deteriorated at early ages of exposure to a high
concentration CaC12 solution, its deterioration being associated with the cracking
and spalling on the surfaces of specimens. On the other hand, 10 % silica fume
and 50 % blast-furnace slag mortars showed a good resistance to calcium chloride
attack, although 30 % fly ash mortars slightly deteriorated at late ages of exposure.
X-ray diffraction and differential thermal analysis indicated that the deterioration of
portland cement mortars caused by the chemical attack of a high concentration
CaC12 solution was attributed primarily to both the dissolution of calcium
hydroxide and the simultaneous formation of a complex salt in the mortar. Thus,
the combined effect of a decrease in calcium hydroxide content and a reduced
chloride ion permeability by the addition of a mineral admixture effectively
improved the resistance of mortar to calcium chloride attack.
--``,`,-`-`,,`,,`,`,,`---
Kevwords: Blast furnace slag; calcium chlorides; chloride ions;

compressive strength; deicers; deterioration; differential thermal analysis;
flv ash; mortars (material); silica fume; x-ray diffraction

A C 1 SP-153 V O L X I I 95 E 0662949 0523900 2T5 E
932 Torii, Sasatani, and Kawamura
AC1 member Kazuyuki Torii, Dr. Eng., is an associate professor of Civil

received his Dr. Eng. degree from Kyoto University in 1986. His current
research has been on chloride ion permeability of concrete, chloride-induced
corrosion of steel reinforcement in concrete, and durability related properties of
high performance concrete.
Teruhiko Sasatani is a civil engineer, Kokudo Kaihatsu Center Co. Ltd.,
Nonoichi, Ishikawa 921, Japan. His main research activities involve effective
utilization of industrial by-products in concrete and chloride-induced corrosion of
--``,`,-`-`,,`,,`,`,,`---
steel reinforcement in concrete.

AC1 member Mitsunori Kawamura, Dr. Eng., is a professor of Civil
Engineering at Kanazawa University, Kanazawa, Tshikawa 920, Japan. He
received his Dr.Eng. degree from Kyoto University in 1971. He has been active
in research on alkali-aggregate reaction and fracture mechanisms of SFRC.
INTRODUCTION
In Japan, it is becoming common to keep main roads free of ice and snow
during the winter season by using de-icing salts since the use of studded tires was
prohibited all over the country in 1991. The most popular de-icing salts used in
Japan are sodium chloride (NaCl) and calcium chloride (CaC12) ;calcium chloride
is used especially in cold districts of Hokkaido and Tohoku or in a mountainous
region. It is well known that de-icing salts can penetrate into concrete smctures
and accelerate the corrosion of steel reinforcement in concrete. In some cases,
deicing-salts also promote the expansion of concrete due to the alkali-silica reaction
or the scaling of surface layers of concrete in the freezing-thawing cycles. In
addition, some researchers have pointed out that a high-concentration CaC12
solution is particularly aggressive even towards the concrete itself (1,2,3).
In recent work camed out by the authors, it has been found that severe
deterioration occurs in mortars immersed in CaC12 solution if the temperature of
solution is below 20 "C and the concentration of solution is 30 %, but that no sign
of deterioration is observed in mortars immersed in NaCl solution independently of
the concentration and temperature of solution (4). From visual observations of
deteriorated mortars, it is inferred that the deterioration caused by a 30 % CaC12
solution is associated with the scaling and/or softening on surface layers of mortar,
which might be attributed mainly to both the dissolution of Ca(OH)2 and the
simultaneous formation of a complex salt of 3CaO*CaClz.l5H20. The
mechanism of deterioration of concrete caused by chemical attack of a high
concentration CaC12 solution is not still fully understood. However, taking into
considerations the mechanism of calcium chloride attack, the addition of a minerai
admixture such as fly ash, blast-furnace slag and silica fume may be effective in
preventing the calcium chloride attack on portland cement concrete.
This study aims at evaluating the effects of fly ash, blast-furnace slag and
silica fume on the resistance of mortar to the calcium chloride attack. Portland
cement mortars with and without a mineral admixture were exposed to a 30 %
CaC12 solution at 5 "C, 20 "C and 40 "C. Changes in length, compressive
strength and dynamic modulus of elasticity in mortars immersed in a 30 % CaC12
solution were examined. The effects of mineral admixtures on the calcium

A C 1 SP-353 V O L W I I 95 066291.17 0523903 333
chloride attack were discussed based on the measurements of the chloride ion
penetration into mortar and the characterization of reaction products and
microstructural features.
EXPERIMENTAL
Materials and Mixtures Promrtions
Two types of portland cement were used ; an ordinary portland cement
(OPC) with a specific gravity of 3.16 and a Blaine fineness of 3300 cm2/g and a
high early strength portland cement (HPC) with a specific gravity of 3.11 and a
Blaine finehess of 0.433 m2/g. Mineral admixtures used were as follows ; fly
ash (FA) with a specific gravity of 2.40 and with a BET specific surface of 1.17
m2/g, blast-furnace slag (BFS) with a specific gravity of 2.94 and with a BET
specific surface of 1.O4 m2/g and silica fume (SF) with a specific gravity of 2.23
and with a BET specific surface of 22.4 m2/g. Chemical compositions of
portland cements and mineral admixtures used in this study are given in Table 1.
Fine aggregate used was a good-quality river sand with a specific gravity of 2.61
and with a water absorption of 1.3 % , which was supplied from the Hayatsuki
river in Toyama prefecture in Japan. The mixtures with and without a mineral
admixture were prepared with a sand : cementitious materials ratio of 2 according to
JIS R 5201. Portland cement mixtures using an ordinary portland cement and a
high early strength portland cement were made with a water : cement ratio of 0.3
and 0.5. A naphthalene-based superplasticizer was added for some mixtures with
a low consistency to give the same flow value as portland cement mixtures with a
water : cement ratio of 0.5. The water : cementitious materials ratio of the
mixtures with a mineral admixture was selected at 0.5 and replacement percentages
of ordinary portland cement by fly ash, blast-furnace slag and silica fume were 30
%, 50 % and 10 %, respectively.
--``,`,-`-`,,`,,`,`,,`---
Experimental Procedures
The prismatic specimens, 40 mm by 40 mm by 160 mm, were prepared for
the measurements of the resistance of mortar to calcium chloride attack. A 30 %
CaC12 solution was made from a reagent-grade calcium chloride (CaClp2H20) and
distilled water. At 1 day, the specimens were demolded and cured in water at 20
OC until 7 days or 28 days. After the initial curing period of 7 days or 28
days, the specimens were immersed in a 30 % CaC12 solution for 3 months, where
the temperature of solution was kept at 5 OC, 20 OC and 40 OC. Changes in
length, compressive strength and dynamic modulus of elasticity of the specimens
were measured at regular intervals for 3 months. The depth of chloride ion
penetration into the mortar was measured by calculating the colored depth by means
of an image analyzer after spraying a 0.1 N AgN03 solution on the fractured
surfaces of prismatic specimens. Otsuki et al. have pointed out that the soluble
chloride content of cement paste at the colored and discolored boundary determined
by this method is about 0.15 % by weight of cement (5). Furthermore, in order
to investigate changes in microstructural features and reaction products in the
deteriorated portion of mortar, X-ray diffraction analysis, DSC-TG analysis and
SEM observations were carried out at selected stages. Control specimens were
stored in water at 5 "C, 20 OC and 40 OC, and tested by the same method.

A C 1 SP-I153 VOL*II 95 0662949 0523902 0 7 8 =

Chloride Ion Penetration
The depths of chloride ion penetration into the mixtures with and without a
mineral admixture are presented in Table 2. As shown in Table 2, the chloride
ion penetration into the mortar varied significantly depending on the type of cement
and mineral admixture used, and the water : cement ratio. Furthermore, the
influence of the temperature of CaC12 solution on the chloride ion penetration was
not so significant as expected, although a high temperature of solution beyond 20
"C tended to slightly accelerate the chloride ion penetration into portland cement
mixtures. The depth of chloride ion penetration of portland cement mixtures was
almost the same for both ordinary portland cement and high early strength portland
cement independently of the initial curing period. The portland cement mixtures
with a low water : cement ratio of 0.3 significantly reduced the chloride ion
penetration, while those with a high water : cement ratio of 0.5 showed a thorough
penetration of chloride ion in the cross section of prismatic specimens at 28 days of
immersion. On the other hand, the addition of a mineral admixture effectively
reduced the chloride ion penetration into the mortar. That is to say, the depth of
chloride ion penetration in 50 % blast-furnace slag and 10 % silica fume mixtures
was less than 10 mm even at 91 days. However, 30 % fly ash mixtures showed
a little greater chloride penetration depth than 50 % blast-furnace slag and 10 %
silica fume mixtures, although prolonging the curing period from 7 days to 28 days
reduced their chloride ion penetration to some degree. Silica fume at 10 % and
blast-furnace slag at 50 % replacement in mixtures seem to be more effective in
reducing the chloride ion penetration than fly ash at 30 % in mortar mixtures.
D e m of Deterioration
--``,`,-`-`,,`,,`,`,,`---
Figs.1, 2 and 3 show the external appearance of the specimens from each
mixture with and without a mineral admixture after 91 days of immersion in a 30 9%
CaC12 solution. It was found from visual observations of deteriorated portland
cement mixtures with a water :cement ratio of 0.5 (OPCo.5 & HPC0.5) that visible
small cracks occurred first along the corners of specimens at 2 weeks of immersion
in a 30 % CaC12 solution, and was followed by swelling and spalling of the
surfaces of specimens in an "onion-skin"type failure. In the comparison among
portland cement mixtures successively stored in a CaC12 solution at different
temperatures, the aggressiveness of a 30 % CaC12 solution was highest at 20 OC,
second highest at 5 OC and lowest at 40 OC. Similar results are reported by
Chatterji and Collepardi (I, 3). It was observed that at early stages of calcium
chloride attack, the portion of breakdown is limited on surfaces in which the
chloride ion has already penetrated, and the inner portion of specimens still remains
unaffected. On the other hand, portland cement mixtures with a water : cement
ratio of 0.3 (OPC0.3 & HF'C0.3) and 30 % fly ash mixtures showed a scaling and
cracking on the surfaces of specimen after 1 month of the immersion in a 30 %
CaC12 solution. However, no visible evidence of deterioration was observed in
50 % blast-furnace slag and 10 % silica fume mixtures independent of the
temperature of CaC12 solution. It is apparent that the degree of deterioration of
the mixtures with and without a mineral admixture is related primarily to their
chloride ion penetration into mortar as described above.

A C 1 SP-153 V O L * I I 95 H 0662949 0521i903 T O 4 =
Change in Length
Figs.4 and 5 show changes in length of specimens made from mixtures
with and without a mineral admixture stored in a 30 % CaC12 solution. It can be
characterized from the results of length change that a large expansion of the
specimens does not usually occur in the process of calcium chloride attack, and in
some cases the specimens shrink to a considerable extent at early stages of
immersion in a 30 % CaC12 solution. An overall expansion was observed just
before the failure only in severely damaged specimens. These results indicate
that the calcium chloride attack is quite different in the mechanism of deterioration
from the alkali-silica reaction or sulfate attack in which the expansive nature
associated with the development of internal cracks is observed. It is considered a
strange phenomenon that the specimens shrink in the CaC12 solution and this may
result from either thermal shock or osmotic pressure. Furthermore, an
accelerated expansion behavior occurred only in the specimens stored at 40 OC, and
it may be attributed to the re-crystallization of a complex salt when the temperature
falls down from 40 OC to 20 "C since changes in length of the specimens were
measured in the atmosphere at 20 OC. Chatterji has pointed out that a complex
salt containing both Ca(OH)2 and CaC12 is soluble at 40 OC, but precipitated out at
20 OC or lower temperature, which generates a crystallization pressure (1).
Comuressive Strength
Compressive strengths measured on specimens from each mixture with and
without a mineral admixture stored in a 30 % CaC12 solution are summarized in
Table 3 and 4. As shown in Fig.6, the portland cement mixtures with a water :
cement ratio of 0.5 stored in a 30 % CaC12 solution at 5 OC and 20 OC showed a
decrease of more than 50 % in compressive strength, while the decrease in
compressive strength of those stored in a 30 % CaC12 solution at 40 "C was very
little. Portland cement mixtures using high early strength portland cement
showed a larger strength reduction at 5 OC and 20 OC than those using ordinary
portland cement, and more interestingly prolonging curing time from 7 days to 28
days adversely influenced it. The reason for this is probably that the high early
strength cement liberates more calcium hydroxide in a longer curing time than
ordinary portland cement does. On the other hand, portland cement mixtures
with a water cement of 0.3 kept their initial compressive strength except for
OPC0.3 stored at 5 OC due to the small chloride ion penetration into mortar.
Again, as shown in Fig.7,50 3'6 blast-furnace slag and 10 % silica fume mixtures
showed a progressive strength development even in a 30 % CaC12 solution, while
30 % fly ash mixtures gradually decreased in the compressive strength especially
when the curing time was only 7 days. This result is in good agreement with the
recent work by Monosi et al. (6). A good resistance of blended cement mixtures
to calcium chloride attack, results from both effects of the low calcium hydroxide
--``,`,-`-`,,`,,`,`,,`---
content and the pore refinement in the process of pozzolanic reaction of mineral
admixtures. Accordingly, the long curing time before the exposure to a CaC12
solution is also essential in the mixtures with a mineral admixture to prevent
calcium chloride attack.

A C 1 SP-I153 VOL811 95 IObb2949 0523904 940 I
Reaction Products Formed bv Calcium Chloride Attack

F i g 8 shows DSC-TG curves for high early strength portland cement
mixtures with a water : cement ratio of 0.3 and 0.5 at 91 days of immersion. In
DSC-TG curves for portland cement mixtures with a water : cement ratio of 0.5,
there was a small endothermic peak of Friedel's salt at 280 OC, a small endothermic
peak of Ca(OH)2 at 460 OC and a large endothermic peak around 570 "C which
seems to result from the decomposition of a complex salt of 3CaO*CaCl2*15H20.
Chatteji and Collepardi have pointed out that this complex salt is the main product
responsible for the deterioration of portland cement mortar, which is formed by the
reaction of CaC12 with Ca(OH)2 in the mortar (2,3). Thus, a 30 % CaC12
solution which had penetrated into mortar dissolved away Ca(OH)2 completely by
forming a complex salt involving Ca(0H)z and CaC12.
Peak heights of Ca(OH)2 and a complex salt determined by X-ray
diffraction diagrams for the mixtures with and without a mineral admixture after 91
days of immersion in a 30 % CaC12 solution are presented in Table 5. In the
deteriorated portland cement only mortars, a complex salt of 3CaO*CaClp15H20
with its characteristic peak of 8.3 A was observed, while the peak of Ca(OH)2 was
almost absent. XRD data of a complex salt obtained in this study are in good
agreement with recent works by Monosi and Yang (3,7). It is also confirmed
from XRD analysis that the breakdown of the mortar in a 30 % CaC12 solution is
due to the leaching out of Ca(OH)2 and the simultaneous formation of a complex
salt. It can be concluded that in blended cement mixtures, the reactions
responsible for the deterioration of mortar in a 30 % CaCli solution are effectively
controlled by both effects of the low calcium hydroxide content and the reduced
chloride ion penetration into mortar.
CONCLUSIONS
A high concentration CaC12 solution at 20 OC or lower temperature was very

aggressive on portland cement mixtures, which was associated with the cracking
and scaling on the surfaces of specimens. On the other hand, 10 % silica fume
and 50 % blast-furnace slag mixtures showed a good resistance to the calcium
chloride attack compared with 30 76 fly ash mixtures, since 10 % silica fume and
50 % blast-furnace slag mixtures were more effective in reducing the chloride ion
penemation into mortar. X-ray diffraction and differential thermal analysis
indicated that the deterioration of portland cement mixtures was awibuted primarily
to both the dissolution of calcium hydroxide and the formation of a complex salt in
the mortar. In blended cement mixtures, the reactions responsible for the
deterioration of mortar were effectively controlled due to the low calcium hydroxide
content and the reduced chloride ion penetration into mortar. From the results, it
can be concluded that the partial replacement of portland cement by a mineral
admixture as well as a low water : cement ratio is essential to prevent the chemical
attack caused by a high concentration CaC12 solution.
ACKNOWLEDGMENTS
The authors would like to thank Dr.S . Chatterji, Tecknologisk Institute in
Denmark, for his useful guidance in carrying out the experiment, and also to thank
M. Yamada, Kajima Co Ltd., for his help in the experimental work.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 O662949 0523905 8 8 7 0
REFERENCES
1. Chatterji, S . and Jensen, A.D. " Studies of the Mechanism Calcium Chloride
Attack on Portland Cement Nordisk Beton, Vo1.5, 1975, pp.5-6.
I',
2. Chatterji, S., " Mechanism of the CaC12 Attack on Portland Cement Concrete I',
Cement & Concrete Research, Vo1.8, 1978, pp.461-468.

3. Monosi, S . and Collepardi, M., " Chemical Attack of Calcium Chloride on the
Portland Cement Paste iL Cement, Vol.86, 1989, pp.97-104.
I',
4. Torii, K., Kawamura, M., Yamada, M. and Chatterji, S., " Deterioration of
Cement Mortars in NaCl and CaC12 Solution ",JCA Proceedings of Cement &
Concrete, No.42, 1992, pp.504-509 (in Japanese).
5 . Otsuki, N., Nagataki, S . and Nakashita, K.," Evaluation of AgN03 Spray
method for Measurement of Chloride Penetration into Hardened Cementitious
--``,`,-`-`,,`,,`,`,,`---
matrix Materials AC1 Material Journal, No.89-M64, 1992, pp.587-592.

I',
6. Monosi, S., Longhi, M. and Collepardi, M., " The Influence of Pozzolanic
Additions on the Concrete Resistance to CaC12 Attack Compilation of I',
Research Papers of CANMET / AC1 Conference on Advances in Concrete

Technology, 1992, pp.251-260.
7. Yang, Q.B., Wu, X.L. and Huang, S.Y., " Mechanisms of Deicer Scaling of
Concrete ", Proc. of 9th Int. Congress on the Chemistry of Cement, Vo1.4,
pp.282-288, 1992.

A C 1 SP-153 V O L r < I I 95 Obb29q9 052190b 713 W
TABLE 1 - CHEMICAL COMPOSITIONS OF CEMENTS AND

MINERAL ADMIXTURES USED, PERCENT
OPC : Ordinary portland cement,

HPC : High early strength portland cement,
FA : Fly ash, BFS : Blast-furnace slag, SF : Silica fume
TABLE 2 - DEPTHS OF CHLORIDE ION PENETRATION INTO

MORTARS WITH AND WITHOUT MINERAL ADMIXTURE AT
IMMERSION TIME OF 28 AND 91 DAYS, mm
--``,`,-`-`,,`,,`,`,,`---
* The value of 20 mm (shading) shows a thorough penetration of

chloride ion in the cross section of prismatic specimens of
40 mm by 40 mm.

A C 1 SP-153 VOL*II 95 I0662747 0523707 b5T
TABLE 3 - COMPRESSIVE STRENGTH OF MORTARS WITH AND

WITHOUT MINERAL ADMIXTURE EXPOSED TO 30 PERCENT
CALCIUM CHLORIDE SOLUTION (INITIAL CURING TIME IN WATER: 7
DAYS)
Shading : Ratio of compressive strength of the specimens immersed in a 30 %

CaCl2 solution to that of the specimens immersed in water at same
--``,`,-`-`,,`,,`,`,,`---
temperature is less than 70 %.

A C 1 SP-153 V O L X I I 95 0662747 0521708 5 9 6
TABLE 4 - COMPRESSIVE STRENGTH OF MORTARS WITH AND

WITHOUT MINERAL ADMIXTURE EXPOSED TO 30 PERCENT
CALCIUM CHLORIDE SOLUTION (INITIAL CURING TIME IN WATER:
28 DAYS)
Shading : Ratio of compressive strength of the specimens immersed in a 30 %

CaC12 solution to that of the specimens immersed in water at same
temperature is less than 70 %.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 S 0662949 0523909 422
TABLE 5 - PEAK HEIGHTS OF CALCIUM HYDROXIDE AT 18.1 DEG

AND COMPLEX SALT AT 10.6 DEG DETERMINED BY X-RAY
DIFFRACTION ANALYSIS AFTER 91 DAYS OF IMMERSION IN 30
PERCENT CALCIUM CHLORIDE SOLUTION (C.P.S)
--``,`,-`-`,,`,,`,`,,`---
* X-raydiffraction analysis : Cu-Ka(40kV-20mA), Ni-filter

ND : not-detected(1essthan 50 C.P.S.) ,OS : over-scaled (more than 500 C.P.S.)

A C 1 S P - 3 5 3 VOL*II 95 W Obb2949 0523930 I144
--``,`,-`-`,,`,,`,`,,`---
Fig. l-External appearance of OPC mortars aiter 91 days of

immersion in 30 percent CaCI, solution

A C 1 SP-153 VOL*II 95 I0662949 052191L 080 I
--``,`,-`-`,,`,,`,`,,`---
Fig. 2-External appearance of HPC mortars after 91 days of

immersion in 30 percent CaCI, solution

A C 1 SP-II53 VOLrII 95 = 0662949 052L9L2 T L ?
Fig. %External appearance of mortars with mineral admxiture aller 91

days of immersion in 30 percent CaCI, solution
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 VOL*II 95 I0662949 0.521713 953
0.2 0 OPC0.3
( 5 "Cl A HPC0.3
o OPCO.5
A HPC0.5
0.0
-0*1*
--``,`,-`-`,,`,,`,`,,`---
-0.2
( 2 0°C)
0.11
-0.2 I I I I I I I I I I I
0.2
O*Ol
( 4 0°C)
o. 1
-0.1
Immersion time, days
Fig. 4-Changes in length of OPC and HPC mortars with

immersion time in 30 percent CaCI, solution (initiai
curing time in water: 7 days)

A C 1 SP-253 V O L U I I 95 m Ob62949 0 5 2 2 9 2 4 ô 9 T m
0 FAO.5
- (5°C) A BFS0.S
0.1 - ü SF0.5
t
-0.1
O*OI
0.0
-0.1
-0.2
O 20 40 60 80 100
Fig. 5-Changes in length of mortars with mineral admixture

with immersion time in 30 percent CaCI, solution (initial
curing time in water: 7 days)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1-53 V O L + I I 95 B 0662949 052L9L5 726
80
1' (5°C)
A
7 ,.
o OPCO.3
A HPC0.3
O OPCO.5
O z
Fig. ô-changes in compressive strength of OPC and HPC

mortars with immersion time in 30 percent CaCI, solution
(initial curing time in water: 7 days)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L U I I 95 IObb2949 052191b 662 I
- o FAü.5
80 - ( 5 "Cl A BFS0.S
- u SFü.5
60 -
-
40 -
-
20 -
-
= o l i i i i i i i i i l i
3 - (20°C)
f* 80-
a -
l i i i i i i i i i l i
0 0
40 1
2 o
--``,`,-`-`,,`,,`,`,,`---
o O 20 40 60 80 100
Immresion time, days
Fig. 7 4 h a n g e s in compressive strength of mortars with

mineral admixture with immersion time in 30 percent
CaCI, solution (initial curing time in water: 7 days)

A C 1 SP-153 VOL*II 75 W 0662747 0521717 5 T 9 W
Temperature ( O C )
u
CH
cs
CH
) HPCO.5( W28)
Et : Ettringite
Fr : Friedel' salt
CH: Ca(OH)2
Et CS: Complex salt
Fig. ô-DSC-TG curves for HPC mortars after 91 days

of immersion in 30 percent CaCI, solution
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 W 0662949 OC21918 435 H I
SP 153-50
Effects of High Fineness and Large

Amounts of Ground Granulated Blast
Furnace Slag on Properties and
Microstructure of Slag Cements
by T. Tomisawa and M. Fujii
Synopsis : This paper describes the test results obtained on the heat of
hydration, strength development, hydration products, pore structure and
combined water of blended cements with high fineness and large amounts of
GGBS and discusses the relationship between them, comparing them with
ordinary portland cement(OPC1 and blended cement with smaller amounts of
GGBS.The following conclusions can be drawn from this study:(l) The heat
of hydration of blended cement with over 70 % content of CGBS reduces
significantly. The blended cement incorporating a large amount of GGBS
with high fineness can have the properties of lower heat of hydration and
relatively high compressive strength required for massive concrete
generally used in Japan;(B)The blended cement with high fineness and high
content of GGBC results in a more compact pore structure than OPC due t o
the formation of finer hydration products.
Kevwords: Blast furnace slag; blended cements; compressive strength;

fineness; heat of hydration; microstructure; porosity; slap;s; strength
--``,`,-`-`,,`,,`,`,,`---

95 1
A C 1 S P - 1 5 3 VOLJII 95 0662949 O52L9L9 371
952 Tomisawa and Fujii
Toshimichi Tomisawa is a senior research engineer of the Slag Cement

Technologies,Nippon Steel Chemical Co., Ltd., Japan. He has been involved
in the research and development of blastfurnace slag cement for about
thirty years.
Manabu Fujii is a professor,Department o f Civil Engineering,Kyoto
University. He received his doctor of engineering degree from the
University of kyoto.He has carried out on the research and development of
--``,`,-`-`,,`,,`,`,,`---
prestressed concrete, and the repair and reinforcement of concrete for
over thirty years.
i NTROWCTi ON
ln Europe, s l a g cement with ground granulated blastfurnace slag

(GGBS) content of over 70 % has been standarized in the Industrial
Standards and used to construct massive concrete structures such as dams
for a long time (1,2).
So far in Japan,as the maximum content of GGBS in slag cement used
in public construction works has been limited to l e s s than 70% by
Japanese Industrial Standards(J1S R 52111, few researchers have
investigated the properties of slag cements with GGBS contents over 70% .
Several years ago. in order t o restrain the thermal cracking of mass
concrete, the blended cement with over 70% cementitious materials of GGBS
or CCBS and fly ash have been developed and practically used.
This paper describes the test results obtained on the heat of
hydration, strength development, hydration products, pore structure and
combined water of blended cements with high fineness and large amounts of
CGBS and discusses the relationship between them, comparing them with
ordinary portland cement(0PC) and blended cement with smaller amounts of
GGBS.

A C 1 SP-353 VOL*II 95 0662949 0523920 093
--``,`,-`-`,,`,,`,`,,`---
EXPERIENTAL PROGRAMME
Mater i a I s
In this work, the following materials were used:
Ordinary portland cement was made in a cement plant.The GGBS ground in a
plant mill had three levels of Blaine fineness of 330,400 and 600 m2/kg,
and the GGBS of Blaine fineness of 800 m2/kg was ground in a test mill.The
GGBS and OPC were mixed in a V-type blender.The content of gypsum in the
blended cement was prepared to be 2.0 % as SO3. The chemical analyses and
physical properties of the OPC and GGBS are given in Tables 1 and 2.
The combinations of blended cements investigated were as follows :
A Series : In order to study on the effects of GGBS content, using GGBS
of Blaine fineness of 400 and 600 m2/kg, on the properties of the blended
cement, the combination shown in Table 3 were used.
B Series : For the 85 % GGBS content, the effects of GGBS fineness on
the properties of the blended cements, were examined using the mixture
combination also given in Table 3 .
Test Methods
In this study, tests for compressive strength, heat of hydration,
XRD, pore structure, combined water and SEM observation were carried
out.The compressive strength and heat of hydration were complied with J I S
R 5201(W/C = 0.65, C/S = 1:21 and 5203(W/C = 0.401,respectively. The test
samples for XRD, pore structure, combined water and SEM observation were
prepared from the cement paste with 40 96 water-cement ratio. To determine
the amount of combined water in hardened paste, after pre-preparation to
stop the hydration progress, the weight loss at temperatures of 40, 150,
400 and 550 were measured, taking into consideration the dehydration
O C
temperatures of ettringite, CSH and Ca(OHI2, respectively. The hardened

paste o f GGBS and Ca(OHI2 was made using the mixing water with
concentration of 2 % Ca(OHI2, as described by Coale et al. (31.

A C 1 S P - 1 5 3 V O L X I I 95 Obb2949 0521921 T 2 T
954 Tomisawa and Fuji¡
RESULTS AND D i SCUSS ION
1. Compressi ve Strength
The compressive strengths of A series and B series mixtures are
given in Figs 1 and 2. With the 400 m'/kg Blaine fineness of A series, the
compressive strength at earlier ages decreases proportionally with the
increase in GGBS content . The compressive strength of blended cement with
400 m'/kg Blaine fineness and about 50 % content of GGBS is comparable t o
OPC at 28-day. whereas the compressive strength of blended cement with
over 80 % GGBS content decreases remarkably. Using slag with 600 m'/kg
Blaine fineness increases the compressive strength at all ages(Figure 1)
due to the finer GGBS particles. For the 85 % GGBS content of B series,
strength increases with fineness at all test ages(Figure 2 ) .
2. Heat of Hydration
The relationship between the heat of hydration of b ended cements
and GGBS contents or GGBS fineness is shown in Figs 3 and 4, respectively.
In Fig.3, the effects of GGBS contents on the heat of hydration can be
seen to be similar to those on the compressive strength; This trend has
been observed before (4). For the 85 % GGBS content of Fig.4, the heat of
hydration of blended cements with not less than 400 m'/kg Blaine fineness
does not increase with the increase of Blaine fineness . On the other hand
as previously described , the compressive strength increases with
increasing GGBS fineness. Therefore, tests were carried out on the heat of
hydration of blended cements with higher water-cement ratios, and the
results are given in Fig. 5. It is found that the heat of hydration of
blended cements with higher GGBS fineness increases with the increase in
water-cement ratio at all ages, and with increasing finenesses. In JIS R
5203, the water-cement ratio of the cement paste used for testing for heat
of hydration is 0.4. It seems that this 0.4 value may not be suitable for
blended cements with large amounts of high fineness GGBS. The phenomenon
might be resulted in the " self-desiccation " as described by A.M.NeviIle
(5).
--``,`,-`-`,,`,,`,`,,`---

3.The Ratio of Compressive Strength t o Heat of Hydration ( o , / O 1

Figs 6 and Ï show the relationship between GGBS fineness and o c /
Q of blended cement with 85 % GCBS content. The u c / Q of the blended
cement with 85 % GGBS content is seen to increase with GGBS fineness for
both O. 40 and O. 60 water-cement ratios, though more so with water-cement
--``,`,-`-`,,`,,`,`,,`---
ratio of 0.60. As C.cerareni at al (6) have previously observed, blended

cements with large amounts of high fineness GGBS can have the properties
of lower heat of hydration and relatively high compressive strength
required for use in mass concrete generally used in Japan.
4.Pore Structure
Figs 8.9, 10 and 11 show the total pore volume and average pore
radius of series A and B cements, respectively. Regardless of GGBS
content and GGBS fineness, the total pore volume and average pore radius
decrease with the progress of age, reflecting the development of
hydration in blended cements. In Figs 8 and 9, the total pore volumes of
blended cements of 4A70 and 4A85 are larger than that of 4AO(OPC) at each
age, whereas the average pore radius of blended cements of 4AÏ0 and 4A85
are almost the same as 4AO(OPC) or less. In Figs 10 and 11, the total pore
volume and average pore radius of the 6B85 blended cement are somewhat
less than those of the 4885 blended cement. Therefore, i t may be concluded
that blended cement with large amounts of high fineness GGBS produce a
finer pore structure with large amounts of smaller radius but more pore
volume, compared to those of 4AO(OPC). This is more clearly seen in Figs.
12 and 13.
Mehta at a l ( 7 ) presented a correlation between the permeability of
cement paste and the volume of pores greater than 132x1111 diameter.
Irrespective of the age of hydration and water-cement ratio, as long as a
specimen of hardened paste did not contain pores greater than 132nm. its
permeability remained low. Figs. 14 and 15 give the relationship between
the pore volume of >75nm pore radius and GGBS content and fineness. The
>75nm pore volume of blended cement of 4AÏ0, 4A85 and 6A85 is less than
that of 4AO(OPC).
5. Hydrat ion Products

The hydration products identified by XRD are given in Table 4. The
hydration products formed in the blended cement are ettringite, Ca(OH)e,

A C 1 SP-153 V O L * I I 95
No reproduction or networking permitted without license from IHS Obb2949 0523922 966
Not for Resale
A C 1 S P - 1 5 3 VOLaII 95
= 0662949 0521923 A T 2 W
hydrated aluminate (C4A HI^). monosulfate (AFm) and hydrated silicate

(CSH) as same as those in OPC.
6.SEM Observation
Figure 16(a)-(f) show the hydration products in hardened pastes. AS
Regourd at al (8) have previously reported, the size and shape of
ettringite in 6A85 blended cement are a little smaller than that in
4AO (OPC).
7. Combined Water
The test results of the combined water in hardened paste determined
are given in Figs.17 and 18. From the 40-550°C combined water given in
Figs. 16 and 17, it can be seen that the development of hydration reduces
with increasing GGBS content in blended cement and increases with increase
in GGBS fineness. In Fig. 17, as the combined water of 400-550°Cdecreases
with the increase o f GGBS content, one can see that the amount of
ettringite reduces with the increase of GGBS content. On the other hand,
--``,`,-`-`,,`,,`,`,,`---
the 40-150 combined water of 4A100(GGBStCa(OH~z) was determined as 3 96

O C
or less. Ettringite can not be formed without gypsum in the hydration of

GGBS and Ca(OH)2, although the hydration product of 40-150°C was regarded
as ettringite. Accordingly, the combined water from other hydration
products may be included in the combined water of 40-150°C.
As the calcium hydroxide formed in OPC and blended cement is thought
almost not to contribute to the development of compressive strength(9)
, the combined water of 40-400°C can be considered to be related to the
development of compressive strength of OPC and blended cement and is named
"effective combined water" in this paper.
Fig. 19 gives the relationship between the effective combined water
and compressive strength of OPC and blended cements, and Fig.20 shows the
relationship between the total pore volume and compressive strength of
OPC and blended cements. I t is clearly seen that, regardless of GGBS
content and GGBS fineness, there is a good correlation between the
effective combined water and compressive strength of both cements, and the
correlation with the combined water is better than that with the total
pore volume.

A C 1 SP-I53 VOLrII 95 H Obb2949 0521924 739 a
The reasons why the blended cement with a large amount and high
fineness of GGBS, in spite of a small amount of OPC content, is able to
develop the compressive strength required and to evolve lower heat of
hydration is discussed below, with reference to Table 5 which compares the
characteristic values of OPC and 6885 as an example.
(1) The ratio of 6B85/OPC is 0.80 for compressive strength and 0.51 for
heat of hydration, the value for compressive strength being larger than
that for heat of hydration.
(2) The u / Q value of 6B85 is 1.56 for OPC. This means that the
compressive strength to the unit amount of heat of hydration of 6885 is
higher than OPC.
(3) The amount of hydration products of 6B85 identified by XRD is nearly
the same as OPC, excluding Ca(OHI2.
(4) The total pore volume of 6B85 is about 1.8 times larger than OPC
whereas the average pore radius of 6885 is the same as OPC. The >750 A
pore volume of 6B85 is nearly a half smaller than OPC. Accordingly, the
pore structure of 6885 is finer than that of OPC. This seems to be
attributed to the formation of finer hydration products in the 6B85
blended cement.
CONCLUS I ON --``,`,-`-`,,`,,`,`,,`---
The following conclusions are drawn from the study :

1. The compressive strength of blended cement with 400 m2/kg Blaine
fineness and about 70 % content of GGBS is comparable to OPC at 28-day
whereas the compressive strength of blended cement with 400 m2/kg
Blaine fineness and over 80 % content of GGBS decreases remarkably. In
case of 85 % GGBS content, the higher GGBS Blaine fineness effectively
increases the compressive strength with ages.
2. The heat of hydration of blended cement with over 70 % content of GCBS
reduces significantly. The blended cement incorporating a large amount
of GGBS with high fineness can have the properties of lower heat of
hydration and necessary compressive strength to practically use for
mass concrete generally used in Japan.

A C 1 SP-I53 VOL*II 95 m 0662949 0521925 675 m
3. The heat of hydration of 85 % GGBS blended cement determined complying

to JIS R 5203 (W/C=0.40) does not increase with raising the Blaine
fineness. This may be due to self-desiccation. A water-cement ratio of
0.50 or more should be employed to properly appreciate the heat of
hydration of blended cement with high fineness and high content of GGBS.
4. The blended cement with high fineness and high content of GGBS results
in a more compact pore structure than OPC due to the formation of finer
hydration products.
5. The effective combined water and compressive strength of OPC and
blended cement have a better correlation than the total pore volume and
compress ive strength.
6. The hydration products of blended cement with high fineness and high
content of GCBS are almost the same t o those of OPC, except for Ca(OH)
B,which is lower in GGBS cement.
REFERENCES
1. Pirette,P.. Huttenzemente und Ihre Anwendung in Belgien, Tonind. -Ztg.

89 Nr. 7/8, 1965. pp. 155-158
2 . Swarmy, R. N . , Concrete Technology and Design, Vol. 3, Cement
Replacement Materials, Serrey University Press, 1986. PP. 97
3. Coals, R. D.. Wonlhuter, C. W., Jochens, P. R. and Howat, D. D.,
Cement it ious Properties of Metarurgical Slags, Cement and Concrete
Research, Vol. 3, 1973, pp.81-92
4. Tomisawa,T., Chikada,T. and Nagao,Y., Properties of Super Low Heat
Cement Incorporating Large amounts of Ground Granulated
Blastfurnace Slag of High Fineness, Proceedings of The Forth
International Conference, Istanbul, AC1 SP-132, May 1992, pp. 1385-
1399
5. NeviIle,A.M, Properties of Comcrete, Sir Isaac Pitman and Sons LTD,
. London, 1965, pp.22-24
6. Cesareni,C., and Frigione, G., A contribution to The Study of
Physical Properties of Hardened Paste of Portland Cements Containing
Ground Granulated Blast-Furnace Slag, Proceedings of The Fifth
Internat ional Symposium on The Chemistry of Cement, Vol. IV, Tokyo,
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 = 0662949 0521926 501
1968, pp. 237-247

7. Mehta,P.K. and Monmohan, Pore Size Distribution and Permiability of
Hardened Cement Paste, 7th International Congress on The Chemistry
of Cement, Vol. III, Paris, 1980, pp.W-1-5
8. Reg0urd.M.. Structure and Behavior of Slag Portland Cement
Hydrates,7th International Congress on The Chemistry of Cement, Vol.
I , Paris, 1980, PP. III-2/1-2/26
9 . Mehta, P . K . , Pozzolanic and Cementitious Byproducts as Minara1
Admixtures f o r Concrete -A Critical Review, AC1 SP-79, Vol. I ,
pp/l-46
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 75 m O b b 2 7 4 7 O523727 448 m
960 Tomisawa and Fuji
Igloss SiOe Alzo3 Fe203 Ca0 MgO MnO SOa S

OPC 2.3 30.3 5.0 2.7 63.7 2.0 0.18 2.1 ~
GCBS 0.2 33.7 14.0 0.9 43.8 4.9 0.37 - O. 8
TABLE 2 - PHYSICAL PROPERTIES OF OPC
Compressive Str. (Wa)

Grabity Fineness
,~
OPC 3.14 370 1 :40 2:40
--``,`,-`-`,,`,,`,`,,`---
TABLE 3 - COMBINATIONS OF GGBS CONTENT AND FINENESS

02 Series) (B Series)
GGBS s : ~(rn2/kg)
iF GGBS Fineness XBS Content
Content
(9 (rn2/kg> 85 %
O 330 33B85
50 4A50 6A50 400 4B85
70 4A70 6A70 600 6B85
80 4A80 6A80 800 8B85
85 4A85 6A85
90 4A90 6A90
100 4AIOO 6A100

A C 1 SP-153 V O L * I I 95 IObb2949 0521928 344 H
--``,`,-`-`,,`,,`,`,,`---
TABLE 4 - HYDRATION PRODUCTS
I I Hydrat ion Products I

1 OPC I Ettringite Ca(OH):! (C4AHia) (AFm) (CSH) U.C. I
B i ended Cement /I ( ( 1 ( 1 u. s.
GGBS+Ca(OHIe ~
~
( '
I __ ( - u. s.
1. ( 1: minor or undistinctly observed products
2. U. C. :unhydrated cement, U. S. :unhydrated slag
1 Compressive St r. (MPa)
Heat of Hydration (kj/kg)
oc/ Q (MPa)/(kj/kg)
Total Pore Vol. ( X10-2cc/g)
~
OPC
44.4
376
0.118
7.53
1
I
6 B 8 5 6B85/OPC
35.5
193
O. 184
13.49
1 1
O. 80
1.79
>75nm Pore vol. ( x10-2cc/g) I 1.62 I 0.80 I 0.49 1
Average Pore Radius ( nm ) I 11.4 I 11.4 I 1.00 1
Effective Combined Wat. ( %1
Et t ringi te
Hydration Ca (OH)
Products Same
AFm Same
Same

A C 1 SP-353 V O L X I 1 95 m 0662949 0523929 210 m
.................
<.I..<. I
I O-- 600 m2/kg YI

"
O 50 70 80 90 100
GGBS content (96)
Fig. l-Relationship between compressive strength

and GGBS contents (blended cement with 400
and 600 m*/kg GGBS fineness)
--``,`,-`-`,,`,,`,`,,`---
330 400 600 800

GGBS fineness (m2/kg)
Fig. 2-Relationship between

compressive strength and GGBS
fineness (blended cement with
85 percent GGBS contents)
A C 1 SP-353 VOL*II 95 I0662749 0523930 T I 2 I
500
M
..................................................................
Q>
m
@-- 400 m2/kg

0.- 600 m2/kg o
nl ’ I
1 1 1 1
O 50 70 80 90 100
GGBC content (90)
Fig. 3-Relationship between heat of hydration
and GGBS contents (blended cement with 400
and 600 m2/kg GGBS fineness)
--``,`,-`-`,,`,,`,`,,`---
3-day
o’ I
I
330 400 600 800

GGBC fineness (m2/kg)
Fig. 4-Relationship between heat of
hydration and GGBS fineness (blended
cement with 85 percent GGBS contents)
A C 1 SP-153 VOLrII 95 = Obb2949 0521931 9 7 9
300
28 days
2 5 0 .......................................
200
50 GGBS finenei c
24
\ A 800 m'/kg
2 150
O 400
E O 330
2
c>
100
a 7 days
Li
-d
2 250
,-I4
O
4
+
2 200 ....................................................................
"
150
100
3 days
250
2 0 0 .......................... ". ................
d
+
--``,`,-`-`,,`,,`,`,,`---
150 ................................. ."............

"
100
40 50 60
Water cement ratio (%I
Fig. 5-Relationship between
water-cement ratio and heat
of hydration (85 percent GGBS
content)

A C 1 SP-153 V O L X I 1 95 E Ob62949 0521932 805 E
30
33
5a
20
N
I
O
,-I
G+
‘10 ........
S Y S
b
O ~~
330 400 600 800

CCBS fineness (m’/kg)
Fig. 6-u, /Qversus GGBS
fineness of blended cement
with 85 percent GGBS content
--``,`,-`-`,,`,,`,`,,`---
(W/C = 0.40)
30
>
3
A
5-
a
20
N
I 28 days
O
@
4
X
W
‘10 ....................................................................................
O
330 400 600 800
GGBS fineness (m2/kg)
Fig. 7 - 0 , /Qversus GGBS
fineness of blended cement
with 85 percent GGBS content
(W/C = 0.60)
A C 1 SP-353 VOLtII 95 Obb29r19 0 5 2 3 9 3 3 743
. .
v
0
0
I
2 3 0 ......................................................................................................................................................... t
N
I
O
4
x 2 0 ................ " ..............................

a,
6
3
,-l
*O
t: 1 0 ...............
a
Co
OI I I I I I
O 50 70 85 100
GEBS Content (%)
Fig. &Total pore volume versus GGBS content

(GGBS fineness, 400 m2/kg)
--``,`,-`-`,,`,,`,`,,`---
o
3
.rl
S 300
ffi
t ..........................................................................................................................................
t: ............
a 2 0 0 ................ ................. ................ k.
a,
50
t. "
?4
8 100 ............... ;,
o' ' I I I 1
O 50 70 85 100
GGBS Content (%)
Fig. %Average pore radius versus GGBS content


A C 1 SP-153 VOLXII 95 Obb2949 052193Y 688
X
e, 28-day
4
4
O
--``,`,-`-`,,`,,`,`,,`---
€$ 2$ 0
330 400 600 800
Fig. lû-Total pore volume versus GGBS fineness

(GGBS content, 85 percent)
u
4 0 0 1.................. .........
ffi I \
k
8 200
a
3
8 100
>
4 91-day
O : 330 400 600 800
Fig. 11-Average pore radius versus GGBS fineness


A C 1 SP-153 V O L X I I 95 m Ob62949 0523935 534 m
20
3-day OPC :370 mz/k
GGBS:400 n2/k
15
10
- 5
2o 0
u
o
2 15
X
- 10
4J 5
Eo
o>
L-i
a
0 0
28-day
\!
15
10
15
10
O
2.5 7.5 24 240 750 2400
75
l l l l l i i
7.5 24 75 240 750 2400 7500
Pore Radius (nm)
Fig. 1 2 4 0 r e structure versus GGBS content

--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 = Obb2949 0523936 4 5 0
20 I I
I 3-day OPC :370 m2/kg 1
Fineness (m2/kg)
-*-a- 800
...... GOO
-1-1
--``,`,-`-`,,`,,`,`,,`---
400
- 330
28-day
15
10
O
91-day
15
10
O
2.5 7.5 24 75 240 750 2400
2 1 1 ì ì 1 ì
7.5 24 75 240 750 2400 7500
Pore Radius (nm)
Fig. 13-Pore structure versus GGBS fineness


A C 1 SP-353 VOL*II
75 m 0662747 0 5 2 3 7 3 7 377 m
970 Tornisawa and Fuji
158.5 129.1
100
i
I i
\
h
IPC :370m2/kg OPC :370mz/kg
-bo
o OPC :15%
o XBS: 400m2/kg
GGBS :85%
\\
y 80
O
4
X
0 3-dt
9>
60
4 28-dt
O
g 40
2
a
LrJ
?A 20
O
O 50 70 85 100 330 400 600
CCBS Fineness(m?/kg)
8( ,
CCBS Content (%I I
Fig. 14->75-nm pore volume versus Fig. 1!5->75-nm pore volume ver
GGBS content GGBS fineness
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLIII 95 m 06629i49 0523938 223 m
I I
10um a OPC 3-day x 1000 10um ' d 4A85 3-day ~1000
I l I I
b OPC 3-day X8000 e 4A85 3-day X8000
1 um 1um
I I I I
c OPC 28-day X8000 f 4A85 28-day X8000
1f i m
1um
Fig. 16-Hydration product
--``,`,-`-`,,`,,`,`,,`---

AGI SP-353 VOL*II 95 = 0bb2949 0523939 LbT m
22 22
20 91-day
o 20
18 18
PIG %-day P16
.
-._
3-day
8 8
G G
4 4
2 2
e .e
1G 16
a P1.2 P14
91 day
e
’-o
--
*A/, .
c
-0 Zf day
O
b
3 day
O
P 8
0 6
lm
A 4
O
- 2
O
8
PG
o
z4
o
03 2
O
Pl0
8
O
3 6
O
* 4
3-day
2
O
O 50 ’i0 85 100 330 400 600 800
CCHS Cniilenl (X) CCBS Fineness (m2/kg)
Fig. 174ornbined water versus Fig. 1€&Combined water versus

GGBS content (GGBS fineness, GGBS fineness (GGBS content,
400 m2/kg) 85 percent)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 m Obb2949 0523940 981 m
70
e AO
4A50
53 6 0 A 4A70
+ 4A85
4A100 * o
5 50 X .
2 O 33885
Q)
k O 6885
t; 40
0
.?I
VI
30
VI
'
X 4 $
a 20 *Q'=
2 Y=-318t53.4X
10
x
X
o
3 r =O. 960
(except X 4A100
O
O 5 10 15 20
--``,`,-`-`,,`,,`,`,,`---
Effective Combined Water (%I
Fig. 19-Compressive strength versus effective

combined water
e AO
4A50
I Ä 4A70
5 50
2 A n
+4A85
X 4A100
Q)
t; 40
m O* O 33985
k
06985
a) A o A 8885
e x
.s
rn
VI
30
Q)
k em x
a 20
E Y~629-24.6X
=Ir ;
10 A
7 =O. 906 * x
(except X 4A100) O _.
Y
I I I I
O' I I
O 5 1 0 1 5 2 0 2 5 30 35
Total Pore Volume (XlO-' c c / d
Fig. PO-Compressive strength versus total

pore volume

A C 1 SP-153 VOL*II 95 Obb2949 0521941 ô 1 ô
SP 153-51
Effect of Test Procedures on the

Assessment of the Sulfate
Resistance of Slag Cements
by J. P. H. Frearson and D. D. Higgins
SYNOPSIS: Various accelerated test methods have been proposed for the
assessment of sulfate resistance of cements. A majority of these methods measure
the expansion of mortar prisms in sulfate solution.
Differences in test procedure can have a significant effect on the expansion

observed, and may possibly affect the ranking of cement types.
The different performance in sulfate solutions of cements containing different slag

percentages and water cement ratios and the lesser influence of different slag
alumina contents have been reported previously.
This paper summarises data from various test work, which demonstrate the effect
on expansion of variations in the following test parameters:
- aggregate cement ratio (at constant water cement ratio)
specimen shape
initial curing period
specimen compaction
initial curing deficiencies
early carbonation
concentration of sulfate solution
type of sulfate solution
The first three had comparatively little influence on expansion; the remainder had
more significant influences on expansion
Sieving mortar for test specimens from production concrete provided a useful and
comparable method of assessment.
The test programmes were principally concerned with slag cement blends but as
any test method has to be applicable to all types of cement, a number of sulfate
--``,`,-`-`,,`,,`,`,,`---
resisting portland cements were tested and the wide range of expansion
characteristics suggest that a "typical" control SRPC may not be easily defined.
Kevwords: Aggregates; blast furnace slag; compaction; curing; expansion;

mortars (material); slags; sulfate resistance; water cement ratio m;
975
A C 1 SP-153 VOL*II 95 m 0662949 0523942 754 m
976 Frearson and Higgins
John Frearson is an Associate with the Consultancy Group of Messrs Sandberg,

Consulting, Inspecting, Testing and Quality Assurance Engineers, London, UK.
He has been concerned with investigationsinto concrete performance and durability
for some 20 years and has been involved with a number of litigations concerning
defective concrete performance.
Denis Higgins is Business Development Director of Civil and Marine Slag Cement
Ltd, a major UK producer of ground granulated blastfurnace slag. He was
formerly senior materials advisor with the UK Cement and Concrete Association.
INTRODUCTION
A number of different test methods have been proposed and used to assess the
potential sulfate resistance properties of cements, cement blends and indeed actual
concretes. A range of earlier test methods were reviewed by Locher [i] and
Wittekindt [2], and more recently by Calleja [3], Mehta [4] and Osborne [5J.
Lawrence [6] in addition to reviewing test methods, has also reviewed a number
of factors that can influence the test results, and Cohen and Mather [7] have
reviewed "research needs".
This paper does not attempt to review the considerable literature but considers
those methods of test which have survived the test of time and are in current usage.
These generally involve immersion of specimens in sulfate solutions of various
concentrations, and comparison of their performance with that of control specimens
immersed in water. The mixes tested and the immersion solutions vary
considerably. The parameters compared are typically either strength or, more
commonly, expansion. Appearance, "weathering", and loss of weight or dimension
may also be taken into account.
Strength Methods
Strength methods can range from compressive tests on 1OOmm concrete cubes, as
described by Osborne [ 5 ] , to flexural strength tests on small (10xlOx80mm)mortar
prisms, as described by Koch and Steinegger [8]and Locher [9].
A disadvantage of strength tests is that at each age of test, both test and control
specimens are destroyed, and a large number of specimens are required for tests
carried out over a prolonged period; extended testing is not possible unless
sufficient specimens have been provided at the outset.
Expansion Melainas
Measurement of expansion has the considerable advantage that the testing is
ongoing: the same specimens can be remeasured at many ages and the tests can
continue until disruption. Measurement frequency can be varied to suit the rate of
expansion.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0662947 0523943 690
A range of procedures and specimen types have been used for expansion testing,
by various researchers, and more recently in inter-laboratory tests intended to
establish a European test method. A summary of test methods indicating the
various prism types, mixtures and pre-immersion curing periods and temperatures,
also the different concentrations of sulfate solutions, is given in Table 1.
Only one test method appears to have been standardised, the ASTM C1012 method
[ 101. Uniquely, this requires the mortar to have achieved a minimum strength, of
20.7MPa (3OOOpsi), before immersion of the prisms in sulfate solution.
s -moC
The differences in the test procedures mean that test data cannot be readily
compared. The requirement to compare results obtained using other test
procedures with existing data, led to initiation of some of the testing described in
this paper and over the last twelve years investigations to examine the sulfate
resistance of slag cement blends and other cements have included various studies
on the effect of test method variation on sulfate expansion. Whilst these were not
designed as a fully integrated trials, the data provide an insight into the extent that
various parameters affected expansion results.
Subsequently, participation in a European inter-laboratory testing exerciseprovided
a further opportunity to compare existing procedures, as did several projects
initiated to investigate test variables.
Particular attention was given to the expansion characteristics of low C,A, sulfate
resisting portland cements (SRPC), as any test procedure has to be applicable to all
types of cement, and SRPCs are often used as controls.
THE SANDBERG TEST METHOD
The main test method used in the investigations described in this paper is based on
the German flat prism test, described by Smolczyk and Blunk [ 111 in 1972. The
test has been further modified and is described in detail by Frearson [12] and
Frearson and Higgins [13].
The basic test procedure involves casting sets of 3: 1 sand:cement mortar prisms
(160x10x40mm) which on stripping after 24 hours are water cured to an age of 14
days. During this period measurement points are fixed to the prism sides. Care
is needed to prevent the body of the prism drying out during this operation.
Alternatively small measurement studs can be cast into the ends of the prisms, but
--``,`,-`-`,,`,,`,`,,`---
there was initially concern that these would not be stable in a 1Omm prism.
The prisms are then immersed in a 0.31 molar Na,SO, solution (Na,SO, content
44g/l; SO., content 30g/l i.e. 3%) [other solutions can be used]. For each set of
three prisms in sulfate solution, control prisms are stored at the same temperature
(normally 20°C) in ordinary tap water. The prisms expansions are measured after
various time intervals and the mean expansion calculated after correction for the
expansion of the water cured control prisms.

A C 1 Sp-353 V O L X I 1 95 Obb2949 0523944 527 M
978 Frearson and Hlggins
The mortars are made using UK cement test sand as defined in BS 4550:Part
5 : 1978 [ 141 blended to give a grading similar to that of the DIN testing sands used
for the original German test. The grading used is given in Table 2 .
As originally described, the test mortar for the German test used a water cement
ratio of 0.60. In subsequent work, in particular that reported by Frearson [12],
and Frearson and Higgins [13], mortars have been produced with lower water
cement ratios more typical of those normally used, or specified, for concretes
designed to combat sulfate ground conditions.
These lower water cement ratios were produced by increasing the cement content
of the mortar, whilst retaining a constant water content to ensure full compaction
of the specimens. This procedure is reported by Frearson [12] to provide a more
representative response to changes in water cement ratio than reductions in the
water content, and better represents the concrete production. The various mortar
mixes used are detailed in Table 3.
EFFECT OF SLAG ON SULFATE EXPANSION
It is well established that increased ggbs content can reduce sulfate expansion.
Frearson and Higgins [13] tested four slags of different alumina content and
confirmed the well established increase in resistance to expansion as the ggbs
content is increased from 30% to 70%. The alumina content of the slags over the
range exarniaed (11.7 - 15.5. % A1,OJ had little effect on expansion.
Frearson and Higgins [13] also provided data for slag cement blend mortars
produced at both 0.60 and 0.45 water cement ratio which confirmed that the 0.45
water cement ratio prisms had consistently lower expansion than the 0.60 water
cement ratio prisms, in mixtures containing 30%, 50% and 70% ggbs.
THE TEST PROGRAMMES
The test programmes described in this paper, provide an insight into the effect of
test procedure variables upon expansion characteristics.
&regate:Cement Ratio
The effects of aggregate:cement ratio (at constant water cement ratio) on the
expansions of mortars made from a slag cement blend and several SRPC mortars
are shown in Table 4.
The prism expansions are fairly similar. Whilst expansion of the higher cement
content mixes are slightly greater at 1 year, there is no such definite trend after 3
years immersion. It appears that a higher cement content, in itself, will not
significantly reduce sulfate expansion; indeed, at a constant water cement ratio
there will be both more reactive medium and a greater amount of capillary voidage
to promote sulfate ingress, reaction and subsequent expansion.
The aggregate:cement ratios for the various test methods listed in Table 1 range
from 2.75:l [li] to 4:l [15]. However, the effect of these differing cement
contents upon expansion may have to be considered when comparing shorter term
--``,`,-`-`,,`,,`,`,,`---
test data.

A C 1 SP-153 V O L b I I 95 9 0662949 0523945 463
Specimen Shape
The expansions of flat prisms made with graded sand mortars have been compared
with those for conventional square section ASTM type prisms made with mortars
incorporating a single sized sand as described by Kollek and Lumley [ 161.
The test results are given in Table 5. The expansions given by the two test
methods were all within 0.015% after three years, and whilst the flat prisms
generally show greater expansion, the magnitude of the difference suggests that in
this case the prism geometry may be less significant than commonly supposed.
al Water Ciiring Period
Different periods of water curing (7, 14 and 28 days) were used prior to immersion
in sulfate solution, for a series of 70% slag: 30% cement and SRPC mortars
produced at 0.60waterkement ratio and at both 3:l and 4:l aggregate cement
ratio. The prisms used in this case were 285 x 25 x 25mm "square" ASTM CI012
[lo]prisms but made with single sized sand as described by Kollek and Lumley
1161.
The expansion results are given in Table 6 and suggest that whilst the time of
initial curing has some influence upon the early expansion, over the longer term
this effect is very much reduced. Further tests on less sulfate resistant mixtures
might show different influences.
Prisms having different periods of water curing will have differing strength and
permeability on immersion. This effect might have been expected to be greater for
the 70% slag mixtures, but could have been masked by their greater resistance to
sulfates. Only the ASTM C1012 [lo]procedure requires test mortars to have
reached a specified strength before immersion.
Specimen Compaction
The effect of compaction has been considered previously by Frearson [12].

Reduction of the water content to achieve lower (0.45)water cement ratio test
mortars resulted in greater expansion and it was postulated that this was due to
inferior compaction, even though the prisms appeared satisfactory.
A more detailed study of compaction effects has been started recently. A series of
70% ggbs mixtures were produced with a range of compactions achieved by using
different aggregate cement ratio mixes at constant water cement ratio. The
mixtures used are also detailed in Table 3.
The test results are given in Table 7. The densities of the prisms ranged down to
90% of the calculated values for the mixes and show good correlation between
under-compaction and increased expansion, confirming the importance of full
compaction of test mortars used to assess the resistance of cement materials to
sulfate expansion.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L X I I 95 W 0662949 0 5 2 3 9 4 6 3 T T W
--``,`,-`-`,,`,,`,`,,`---
Effect of Early Drying

Trials were carried out to examine the sensitivity of the test procedure to any
accidental exposure to air during the curing period. The test results for an SRPC
are summarised in Table 8.
It is apparent that if the prisms are exposed to air and dry during the initial curing
period, even for a short time, then this can affect the test results. The extent to
which this would be significant for other cement types requires further
investigation.
Effect of Carbomkm
One set of prisms was exposed to a carbon-dioxide atmosphere for 16%hours prior
to immersion in sulfate solution. The test results, which are also given in Table
8, show that the surface carbonation provided considerable resistance to expansion,
and confirmed the findings of Osborne [ 171.
th of S0Iut.u
Flat-prism tests were undertaken on normal portland cement mortars using both the
-
normal solution of 44g/l Na,SO, and the weaker test solution of 23.66gA Na,SO,
used in the European inter-laboratory trials.
The test results are summarised in Table 9, and as might be expected, the prisms
in the more concentrated solution expanded at a faster rate.
Typically sodium sulfate has been used for testing purposes (see Table 1).
Magnesium sulfate solutions are generally considered to provide a more severe test
environment, although the two types of attack should possibly be considered as
very different.
Tests were carried out on flat prisms made at 0.5 water cement ratio; 2.3:l
aggregate cement ratio mixtures with:
- five different UK sulfate-resisting cements
50% ggbs/50% normal portland cement
70% ggbs/30% normal portland cement
These were immersed in both the standard 0.31 molar Na,SO, solution and in an
equivalent 0.31 molar MgSO, solution.
The results are summarised in Figures 1 and 2. As expected the normal portland
cement (12.2% C,A) was the least resistant to both sodium and magnesium sulfate,
showing very large expansion (greater than 1%) followed by disruption, in under
one year.
The five different sources of SRPC differed significantly in their expansions, and
emphasised the difficulty of trying to compare expansion with a "control" or
"typical" SRPC. Although there was some correlation of expansion with C,A

A C 1 SP-153 V O L + I I 75 0bb2947 0521947 236 M
content, this was not clear-cut. Expansion was invariably greater in magnesium
than sodium sulfate and for one SRPC the expansion in magnesium sulfate was
nearly as rapid as for the normal portland cement.
The 50% ggbs blend showed low expansion in sodium sulfate, comparable with the
best of the SRPCs. In magnesium sulfate, its expansion was less than that of the
normal portland cement on its own and comparable with the higher expansion
SRPCs.
The 70% ggbs blend showed very low expansion in sodium sulfate and initially the
same was the case in magnesium sulfate, however, at about 11 months, rapid
expansion initiated followed by disruption.
Both the 50%and 70% slag blends perform better than normal portland cement and
also better than the majority of the SRPCs, in sodium sulfate. In magnesium
sulfate the performances of slag cements is somewhat different: the 50%slag blend
is equivalent to the inferior SRPCs and the 70% slag is equivalent to the best of the
SRPCs.
PRECISION
Very little work has been undertaken to assess the precision of the flat-prism test,
although an assessment of the test procedures that use smaller size specimens has
been undertaken by Osborne [5]. The individual prisms (typically three) within
each test set typically show remarkably similar expansions.
Where duplicate test sets produced at different times were included within these
present investigations, the results are summarised in Table 10.
Whilst these were not formally constituted as precision trials, the expansion
patterns show good consistency, However, the European inter-laboratory trial is
understood to have shown a much lesser degree of precision. Some of the factors
outlined in this paper may have had an influence.
TESTING OF MORTARS FRACTIONS FROM CONCRETES
The test programmes outlined above have all been undertaken using laboratory
mixed mortars using standard sands to make an assessment of various cement
samples. More recently the test procedure has been adapted to test concretes. The
--``,`,-`-`,,`,,`,`,,`---
mortar fraction was separated from the coarse aggregate using a 2.36mm sieve and
cast into flat prism moulds. The mortar specimens were then tested using the same
procedure as for the laboratory mixes.
The procedure has been used successfully in an assessment of cement, slag, and
silica-fume blend concretes as described by Fidjestd and Frearson [18]. The test
results are summarised in Table 11; the expansion results were sensibly of same
order as would be expected for these cement blends when assessed using the
normal laboratory procedure and the procedure is now being used in further
investigations.

A C 1 SP-153 VOL*II 95 Obb2949 0523948 172
CONCLUSIONS
It is well established that the following factors have a large effect on expansion and
the flat-prism test procedure can thus be used to assess potential performance: -
cement type
ggbs content
watedcement ratio
Mortars containing significant content of ggbs generally show very low expansion
(particularly at 70% ggbs). Mortars containing SRPC appeared to have a larger
capacity for expansion before final disruption, and different SRPCS show very
different expansion characteristics.
However, to ensure consistent testing, various test parameters have to be

controlled. Those which had larger effects on expansion were:-
type of sulfate solution

strength of sulfate solution
specimen compaction
initiai exposure to air
initiai carbonation
Other test parameters which appeared to have relatively lesser effects on expansion
were:-
cement content (at constant water cement ratio)

specimen shape
- period of initial water curing
If consistent test procedures are used, the flat-prisms test can provide a useful
indication of resistance to sulfate expansion of mortars made with different cements
and produced either in the laboratory or by sieving from production concretes.
REFERENCES
1. Locher F.W., 'Die Prüfung der Widerstandsfihigkeit von Zementen', ('Testing the
sulfate resistance of cements'), Zement-Kalk-Gips, 9, 1956, pp 204-210.
2. Wittekindt W., 'Sulfatbeständige Zemente und ihre Prüfung', ('Sulfate-resistant

cements and their testing'), Zement-Kalk-Gips, Vol 13, Nr 12/1960, pp 565-572.
3. Calleja J., 'Durability', Sub-theme VII-2 in Vol 1, Seventh International Congress on

the Chemistry of Cement, Paris, 1980, pp VII-2/1 - 2/48.
4. Mehta P.K., 'Sulfate Resistance of blended portland cements containing pozzolans and
granulated blast-fumace slag', Proc. Fifth International Symp. of Concrete
Technology, Monterrey, Mexico, March 1981, pp 35-50.
5. Osborne G.J., 'Determination of the sulfate resistance of blast-fumace slag cements

using small-scale accelerated methods of test', Advances in Cement Research, No. 5 ,
January 1989, pp 22-27.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m 0662949 0521949 009 m
6. Lawrence C.D., 'Sulfate attack on Concrete', Magazine of Concrete Research,

No.153, Dec 1990, pp 249-264.
7. Cohen M.D. and Mather B., 'Sulfate Attack on Concrete - Research Needs', AC1
Materials Journal, Jan-Feb 1991, pp 62-69.
8. Koch A . and Steinegger H . , 'Ein Schnellprüfverfahren für Zemente auf ihr Verhalten
bei Sulfatangriff', ('A rapid method for testing the resistance of cements to sulfate
attack'), Zement-Kalk-Gips, Vol 13, Nr. 7/1960, pp 317-324.
9. Locher F. W., 'Zur Frage des Sulfatwiderstandes von Huttenzementen', ('The

problem of the Sulfate Resistance of Slag Cements'), Zement-Kalk-Gips, 9, 1966, pp
395-401.
10. American Society for Testing and Materials, ASTM C1012-89, 'Standard Test
Method for Length Change of Hydraulic-Cement Mortars Exposed to a Sulfate
Solution', ASTM, Philadelphia, USA, 1989.
11. Smolczyk H . and Blunk G., 'Zum verhalten von sehr jungem Beton gegen
Sulfatwasser' , ('The behaviour of very young concrete in sulfate solution'), Beton
Information, 1, 1972, pp 2-9.
12. Frearson J. P. H., 'Sulfate Resistance of Combinations of Portland Cement and

Ground Granulated Blast-Furnace Slag', Proceedings of 2nd International Conference
on "Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete", Madrid, Spain,
1986; also American Concrete Institute, Special ?ublication SP-91, 1986.
13. Frearson J. P. H. and Higgins D. D., 'Sulfate Resistance of Mortars containing

Ground Granulated Blast-Furnace Slag with variable Alumina Contents', Proceedings
of 4th International Conference on "Fly Ash, Silica Fume, Slag and Natural Pozzolans
in Concrete", Istanbul, Turkey 1992; also American Concrete Institute, Special
Publication SP-132. 1992.
14. British Standards Institution, BS 4550:Part 5:1978, 'Methods of Testing Cement -

Standard Sand for Concrete Cubes', BSI, London, 1978.
15. Wolochow D., ' A Lean Mortar Bar Expansion Test for Sulfate Resistance of Portland
Cement', 'Determination of the Sulfate Resistance of Portland Cement', Proc.
American Society Testing Materials 52, 1952, pp 250-266.
16. Kollek J.J. and Lumley J.S., 'Comparative Sulfate Resistance of SRPC and Portland
Slag Cements', Blue Circle Technical Services Division Report, May 1990.
--``,`,-`-`,,`,,`,`,,`---
17. Osborne G.J., 'The effectiveness of a carbonated outer layer to concrete in prevention
of sulfate attack', Proceedings of International Conference on 'The protection of
concrete' at University of Dundee, Scotland, 11-13 September 1990, pp 75-91.
18. Fidjestol P. and Frearson J.P.H., 'High Performance Concrete using Blended and
Triple Blend Binders', Proceedings of AC1 conference on High Performance
Concretes, Singapore, November, 1994.

Frearson and Higgins
O
N O m
N N
8 8 8
d e' 5:
d e
O
N
8
3
O
c. O
N
O
'4
O
-
m
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 m 0 6 6 2 7 ~ 70521951 767 m
--``,`,-`-`,,`,,`,`,,`---
TABLE 2 - GRADING OF TEST SAND
SIEVE SIZE % PASSING SIEVE
5 .OOmm 100
2.36mm 1O0
1.18mm 75
600pm 40
300pm 20
150pm 10
75pm
TABLE 3 - MORTAR TEST MIXTURES

A:C Cement Sand Water WIC
g g g
3: 1 200 600 120 0.60

2.6.1 220 580 120 0.55
2.3: 1 240 560 120 0.50
2: 1 266 534 120 0.45
3: 1 200 600 100 0.50

4: 1 160 640 80 0.50
4.7: 1 140 660 70 0.50
The quantities given are sufficient to make a set of six flat prisms

A C 1 SP-153 VOL+II 95 H 0662949 0521952 bT3
TABLE 4 - EFFECT OF AGGREGATE-CEMENT RATIO
1
Expansion (%) at.
Mixture A:C w'c

2years I 3years
70% Slag:30% 3: 1 0.012

OPC 4: 1 -0.003
South Ferriby 2.3: 1 O.070
SRPC (C,A - 0.5%) 3: 1 0.031
Swanscombe SRPC 2.3:l 0.50 O. 029
(C,A - 1.4%) 3: 1 0.50 0.021
3: 1 0.028
4: 1 o.022
Pitstone SRPC 2.3: 1 0.033
(C,A - 1.7%) 0.50 I 0.021 I 0.042 I 0.063
Weardale SRPC 2.3: 1 O. 184
(C,A - 1.7%) O . 163
O. 146
(CXA - 2.9%) o. 121
TABLE 5 - EFFECT OF PRISM SHAPE
Mixhire
0 . 6 0 ~ 1SRPC
~
A:C
3:l
Piismshape
Flat
hl-
1 year
0.028
Expansion (%)
2 years
0.037
3 years
0.059
ex Swanscombe Square 0.021 0.036 0.047
0 . 6 0 ~ SRPC
1~ 4:1 Flat 0.022 0.026 0.039
ex Swanscornbe Square 0.018 0.026 0.025
O. 60wlc 3:l Flat 0.012 0.010 0.020
70% slag:30% OPC Square 0.002 Nil -0.005
O. 60wlc 4:l Flat -0.003 0.002 0.001
70% slag:30% OPC Square -0.003 Nil o.002
Flat prisms 160 x 40 x 10 mm: Square prisms 285 x 20 x 20mm
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 VOL*II 95 m Obb2949 0521953 53T m
TABLE 6 - EFFECT OF INITIAL WATER CURING
Expansion %
Initial
Water (All at
Curing 0.6Owíc) mo* 3 year
~ ~
7 Days 3:l SRPC 0.013 0.022 0.038 0.045

4:l SRPC 0.011 0.018 0.025 0.021
3:l Slag -0.001 0.004 0.010 -0.002
4:l Slag 0,001 0.004 0.004 o.002
14 Days 3:l SRPC 0.012 0.021 0.036 O.047
4:l SRPC 0.013 0.018 0.026 O .025
3:l Slag -0.004 -0.002 Nil -0.005
-41Slag-
Nil -0.003 ~
Nil Nil -
28 Days 3:l SRPC 0.008 0.012 0.025 0.039
4:lSRPC 0.010 0.011 0.017 0.021
3:1 Slag -0.007 -0.006 -0.006 -0.006
--``,`,-`-`,,`,,`,`,,`---
4:l Slag -0.006 Nil -0.005 0.002
I l
Slag* 7 days O. 004 O. 007
14 days
SRPC* 7 days 0.012 o.020 O .032

14 days 0.012 o.020 0.031 0.036
0.030
* Specimens were 'square' prisms [16],single sized sand (see Table I).
SRPC = Swanscombe SRPC (C,A = 1.4%)
+
Slag = 70% ggbs (Alzo, = 11.9%) 30% OPC (C,A = 12.2%)

A C 1 SP-353 VOL*II 95 Obb2949 0523954 476
--``,`,-`-`,,`,,`,`,,`---
z
O
uj
z
2
wz
a
3,
z
0
I-
o
a
3
8
8
I-
w
LL
LL
w
I
r-
Y
m
2

A C 1 SP-153 VOL*II 95 0662949 0521955 302 H
TABLE 8 - EFFECT OF EARLY-AGE DRYING AND CARBONATION
E x m i o n (%) after üme
Exposure
to Air
I .lm
3m I 1 6m 12m
Minimal 0.006 0.018 0.090 0.355

3% hr 0.006 0.018 O.070 0.337
17% hr 0.007 0.018 0.055 0.220
Exposure to Air pius Carbonation

~
--``,`,-`-`,,`,,`,`,,`---
2 % hr plus 0.000 0.000 0.003 o.O08

16% hr CO,
Test specimens: SRPC (C,A 1.6%);2.3:i A/C; 0.50 wlc ratio
TABLE 9 - EFFECT OF SOLUTION STRENGTHS
Immersion Time E x p i o n (%) in N%SO, Solution
23.66gll 44gll
i month 0.010 0.015
3 month O.040 0.052
6 month 0.233 0.738

9 month 0.853 i. 302
1 year D D
Mortar composition:A:C = 3:l; wlc 0.50 with 8.3% C,A Cement

D = Disrupted.

ACI sp-153 VOLS11 95 M O662949 0523956 249
h
,!
-E 3
o
'B
r3
NCI
22 O 0
99
99
O 0 ??
3 -
O 0
99
?? --``,`,-`-`,,`,,`,`,,`---
.u
B
O
'?
O
3
..
c?
CI

A C 1 SP-153 V O L S 1 1 95 0662949 0523957 185
Expansion (%)
Mortar Type *
6 1 2 3
m o b year years Y-
OPC 0.361 32.0

(wlc 0.43)
50% OPC/SO% Slag 0.006 0.014 0.017 0.022
(w/c 0.48)
SRPC 0.032 0.213 0.528 0.602
1 (w/c 0.45)
* Mortars sieved from fresh concrete samples, then tested as per Frearson and
Higgins [13], in sodium sulpate solution.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 VOL*II 75 M Obb2947 0521758 011 H
1.01 : ' ' ' ., 1

C,A Content % Slag
+0.5% *1.4% +1.7% *SO
.. . . . . . . .
0.8 .. . . . ... . . . .... . . . ... . . . .. . . . ., .. . . .. .. .
.
. . . . . . .
I'
. . . . . .
Na,SO,
0.6
5
h
. . (30g/l S O , )
E
.-O
v1 . <
E
m I
a . . . . . . . . . .
. . . . .
0.4 - . .. . . . .. . . . .
< . :../i... . -1..-1..
. .
. . .
. . . . . . .. . . . .. . . . :. . .
. :. .
Time (Months)
Fig. I-Expansion of portland cements and slag-

cement-blend mortars in sodium sulfate solution
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 0bb2949 0523959 T58
2.0
C,A Content % Slag

+0.5% * 1.4% * 1.7% * 50
*17% *29% 8122% '70
1 .s
wzso,
(30g/l S O , )
--``,`,-`-`,,`,,`,`,,`---
5
h
C
O
' Z 1.0
C
d
o.
X
u
0.5
0.0
O 2 4 6 8 IO 12 14 16 18 20 23 74
Time (Months)
Fig. 2-Expansion of portland cements and slag-

cement-blend mortars in magnesium sulfate solution

A C 1 SP-153 V O L X I I 95 Ob62949 0523’360 7 7 T
SP 153-52
Utilization of Low-Heat Cement

with High Content of Finely Ground
Blast Furnace Slag for High-
Strength Concrete
--``,`,-`-`,,`,,`,`,,`---
by M. Iwai, A. Takagi, T. Mizobuchi, and Y. Nobuta
Synopsis: When using high strength concrete in large structures, it is important

to minimize generation of thermal stresses during hydration of cement and the
variation in concrete properties. Also needed for concrete is proper workability.
A research program has been underway with the above aspects in mind to
optimize the requirements of high strength, low heat generation and pumpability
using both the newly developed low heat cement (LSC) with high content of
finely ground blast furnace slag and the high range water reducing admixture.
This paper describes the test results on fundamental properties, pumpability,
and thermal stress reduction effects on high strength concrete of 60 MPa, using
such a low heat ccment. The following results were obtained.
(1) The heat generation of LSC is remarkably lower than conventional low heat
cement (blended cement : FMKC). When using LSC, the thermal stress was
reduced by 60% compared to concrete using normal portland cement.
(2) The quality of concrete manufactured in the concrete plant was comparative-
ly uniform.
(3) Pressure loss during pumping was three to four times larger than ordinary
concrete. However, it was verified that after pumping, the quality of concrete
using LSC showed satisfactory workability and had less variation compared to
the quality of concrete using FMKC.
(4) From results mentioned above, by selecting proper high range water reduc-
ing admixture, use of LSC is considered to be a solution for reducing cracks
due to hydration in high strength concrete while maintaining suitable workabili-
ty and sufficient strength development.
Kevwords: Adiabatic conditions; admixtures; blast furnace slag; fly ash;

hieh strength concretes; low heat cements; mass concrete; pumpability;
thermal cracking; thermal stresses; water reducing agents

995
A C 1 S P - 1 5 3 VOLIII 95 m 0662949 0521961 bob m
996 Iwai et al
I
M.Iwai is a research engineer of Kajima Technical Research Institute (KaTRI),
Kajima Corporation, Tokyo. His main interests are aggregate, admixtures and
high strength concrete. He is a member of Japan Concrete Institute (JCI) and I
Japan Society of Civil Engineers (JSCE). ,
I
A. Takagi is a manager of Plant Engineering Dcpartment, Tokyo Gas Corpora-

tion, Tokyo. He has been involved in construction of many mass concrete struc-
tures associated with gas storage.
T. Mizobuchi is currently a project engineer at Nukui Dam Construction Project
Office, Kajima Corporation, Hiroshima. He is a former research engineer at
KaTRI and attended this research before moving to Hiroshima. He is a member
of JCI and JSCE.
AC1 member Y. Nobuta is a senior rcsearch engineer of KaTRI. His recent
rcsearch work has been on thermal stress analysis? high strength concrete and
precast concrete. He is also a member of JCI and JSCE and has served on sever-
al technical committees of JCI and JSCE..
INTRODUCTION
High strength concrete is being increasingly used in the construction of rein-
forced and prestressed concrete structures. Instances have been reported where
concretes with a characteristic strength of more than 80 MPa has been used in
columns of high rise buildings[l]. However, it is not simply enough for the
concrete to have the required compressive strength, especially when used in
large structures, such as the towers of cable stayed bridges, walls of tanks, etc.
In such applications it is equally important to ensure that :
(1) the generation of thermal stresses during hydration is kept to a minimum,
(2) the variation in properties of fresh concrete, due to changes in tempera-
ture? surface
--``,`,-`-`,,`,,`,`,,`---
water content of the aggregate, etc. be kept to a minimum, and

(3) the concrete can be easily pumped using normally available equipments
over a reasonable
distance.
For controlling temperature rise in concrete, it is effective to combine portland
cement with slag and/or fly ash. However, in order to obtain high strength at the
same time, conventional blended cement with slag andíor fly ash is not neces-
sarily a solution taking into consideration the strength development and the heat
generation characteristics. And, now that there are many types of high range
water reducing admixtures available, the selection of chemical admixture is also
of importance for improving pumpability of concrete with large quantities of
cement.
A research program has been underway with the above aspects in mind to
optimizc the requirements of high strength and low heat generation using both
the newly developed low heat ccment with high content of finely ground blast
furnace slag and the high range water reducing admixture available.
This paper describes the results obtained in the course of the research
carried out to study the application of such materials for high strength con-

A C 1 SP-153 V O L + I I 95 m 0662949 0523962 542 m
Crete with characteristic compressive strength of 60 MPa in the side walls of an

underground storage tank, where one of the requirements was to minimize the
possibility of cracks caused by thermal stresses, in view of the mandatory
water-tightness requirements for the structure.
ACCEPTANCE CRITERIA
From considerations of design, ease of construction, quality control and durabili-
ty, it was required that the concrete satisfy certain criteria for workability (slump
flow), air content, compressive strength, etc. The criteria are briefly summarized
in Table 1.
RESEARCH PROGRAM
The study was dividcd into three parts :
(1) laboratory studies to confirm that the mixtures identified comply with the
basic requirements as described above,
(2) field tests where concrete was pumped using normally available transporta-
tion equipments over' a distance of 50m, including two 90" bends. The variation
in properties such as the slump flow, compressive strength, pressures in
conveying pipe during pumping, etc. was measured and the compliance with
the acceptancc criteria verified
(3) the results of adiabatic temperature rise experiments carried out in the
laboratory were used to accurately estimate the extent of temperature rise in
a concrete wall. Thermal stress analysis was then carried out and the possi-
bility of initiation of a thermal stress induced crack was studied taking into
consideration the actual strength development of concrete.
EXPERIMENTAL
Materials Used
Cements -- In addition to Normal Portland Cement (NPC), two special ce-
--``,`,-`-`,,`,,`,`,,`---
ments were used in this study:

a ) U C : This cement was specially devcloped as a low heat cement for use in
high strength concrete and included finely ground blast furnace slag (fineness
6000cm2/g) with NPC in the ratio of 752.5. Reference [2,3] describes some of
the other preliminary work carried out using this cement.
b)FMKC : This cement had been originally developed for use in mass
concrete[4] and is composed of normally available slag (fineness 4000cm2/g),
NPC and fly ash in the ratio of 5:4:1.
The properties of the cements used are described in Table 2.
Chemical admixtures -- High range water reducing admixtures having air en-
training ability were selected for each cement on the basis of experience taking
into consideration the design criteria laid down in Table 1. High range water
reducing agents with highly condensated aromatic sulfonate compound and
complex of denatured lignin, alkylarysulfonate and newly available polycarbox-
ylic ether complex as the main ingredients were chosen.
Aggregates -- Normally available pit sand and crushed limestone, conforming
to the standard specifications of Japan Society of Civil Engineers (JSCE) were
used throughout the study. Their properties are summarized in Table 3.

A C 1 SP-153 V O L r I . 1 95 0662949 052L9b3 489 W
998 Iwai et al
Mixture Proportions
On the basis of preliminary studies [2,3], the mixture proportions as given in
Table 4 were chosen for the required quality of concrete for the different cement
types. The water-cement ratio was kept constant (30%), and the unit water
content had to be varied for the three mixtures depending upon the type of
cement and the type and dosage of the chemical admixtures used.
Mixing and Curing of Concrete
The concrete was mixed using a forced type mixer with Win shafts. After load-
ing all the materials, mixing was carried out for 120 seconds. Unless otherwise
stated, in the course of this study, all specimens were cast in the chamber at
20°C in disposable molds and stored in a chamber maintained at 2O0C/60%RH
for a day. After demolding, they were cured in water (also at 20°C) until the
time of testing.
--``,`,-`-`,,`,,`,`,,`---
Measurement Items
The following items were basically measured in accordance with relevant
Japanese Industrial Standard (JIS) or JSCE specifications.
Laboratory test;
- Slump flow :JSCE-1990 "Method of slump flow test for concrete"
- Air content : JIS A 1128 "Method of test for air content of fresh concrete
by pressure method"
- Setting time : ASTM C 403 "Test for time of setting"
- Compressive strength : JIS A 1108 "Method of test for compressive
strength of concrete (using 100mm dia x200mm cylinders)
I'
- Splitting tensile strength :JIS A 1113 "Method of test for tensile strength
of concrete" (using 150mm dia x200mm Cylinders)
- Young's modulus : JSCE-1988 "Method of test for Young's modulus of
concrete''
- Adiabatic temperature rise
(using a calorimeter which can measure an adiabatic temperature rise)
- Drying shrinkage : JIS A 1129 "Method of test for length change of mortar
and concrete" (using 100x100x400mmspecimens)
- Freezing and thawing resistance : JSCE-1986 "Method of test for freezing
and thawing resistance of concrete"
(using 100x100x400mmspecimens)
Field test;
- Slump flow : JSCE-1990 (same as the above)
- Compressive strength : JIS A 1108 (using 100mm dia x2OOmm cylinders)
- Loss of head (using pressure gages)
FUNDAMENTAL PROPERTIES
Effects of Differences in Mixing Temperatures on The Properties of Fresh
Concrete
When concretes with large amounts of slag and/or fly ash are used along with
high range water reducing admixtures, an excessive loss in the slump during
summer and a delay in the setting time in the winter are always of concern. A
study on the effect of temperature on the properties of concrete was carried out
by varying the temperature of fresh concrete behveen 10°C and 30°C. In these
experiments, all of the material was previously stored at the required tempera-

A C 1 SP-153 V O L 8 1 1 95 m 0bb2949 0 5 2 3 9 b 4 315 m
ture and the fresh concrete also kept in chambers maintained at that temperature
to study the changes in concrete properties.
Fig.1 and Fig.2 show the variation in slump flow with time for concrete using
LSC and FMKC, when the mixing temperature was varied from 10°C to
30°C. In case of LSC, there was practically no effect of temperature on the
slump flow immediately after mixing. Comparison of flows at 10°C and
20°C showed that the retention of flow improved until 90 minutes at 20°C.
However, at 30°C and higher temperatures, the flow reduction was large,
and after 90 minutes, results indicated a reduction in flow by about 200 mm.
For FMKC on the other hand, the slump flow immediately after mixing in-
creased with the increase in temperature, and when the mixing temperature
was 30"C, there was practically no flow reduction, in contrast to LSC. As
shown in Figs.l,2, the effect of temperature on variation of slump flow with
time varies with the combination of the type of cement and high range water
reducing admixture and dosage of high range water reducing admixture. The
reason for this is not clearly understood at present. Precise adjusting of the
dosage of high range water reducing admixture is required to keep this effect to
a minimum in concrete manufacturing.
Air content was uniform and in the target range for all concrete mixtures
throughout this research.
Fig.3 and Fig.4 show the test results for the setting time. From Fig.3 it is seen
that in the mixing temperature range of 10°C to 30"C,the initial setting time of
FMKC is about 1 to 3 hours later, compared to LSC. The results indicate that
the condition for the initial setting time of less than 10 hours is not satisfied at
low temperatures. As shown in Fig.4, the maturity [5] until the initial setting
remains almost constant. This shows that the initial setting time can be predict-
ed to some degree from the results of the temperature measurements of the
actual construction.
Hardened Concrete
Fig.5 shows the increase in compressive strength by age. The results indicate
that the target strength at 91 days is almost satisfied for all the cements used in
the tests. NPC at an age of 7 days has
75% the strength at 91 days, demonstrating good strength at a relatively early
age. In contrast, the strength develops gradually in LSC and FMKC, with the
increase in strength distributed over a longer period.
As stated at the outset, one of the main objectives of the study was to reduce the
possibility of occurrence of thermal cracks. This necessitates a better under-
standing of the development of not only the compressive but also the tensile
strength. Fig.6 shows the relationship between splitting tensile strength and
compressive strength. The relationship between these two strengths could be
expressed by approximately the same curve for concrete using any type of
cement.
Test results on the Young's modulus of the concrete were shown in Fig.7. The
Young's modulus for concrete using LSC and FMKC at the same compressive
strength is larger than that of NPC. The relationships among the Young's
modulus, splitting tensile strength and compressive strength can be expressed by
two equations proposed previously [6] in Fig.6 and Fig.7.
Adiabatic Temperature Rise
Table 5 and Fig.8 show the results of adiabatic temperature rise tests. The
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-It53 V O L * I I 95 = Obb29Y9 0523965 2 5 1
1000 Iwai et al
adiabatic temperature rise (Q ) for FMKC and LSC is 10 to 20°C lower com-
pared to NPC. Since the cement content at each mixture proportion varies,
comparison of the temperature rise per kg of unit quantity of cement (Q /C)
shows that the temperature rise for FMKC is about 5% less, and for LSC is
about 45% less compared to the temperature rise value of 0.123"C/kg for NPC.
Also, a comparison of the temperature-strength ratio (Q /fc') shows that this
value for FMKC is about 9% less, and for LSC is about 35% less than the
temperature-strength ratio of 0.824"ChíPa for NPC. From these results, using
LSC which has a high content of fine blast furnace slag, is effective in control-
ling the heat liberated from high strength concrete. Table 5 also shows the
measurement results of specific heat and thermal conductivity. The specific heat
and thermal conductivity values when using LSC and FMKC are almost the
same as the normal values when NPC is used.
Drying Shrinkage
The results of drying shrinkage tests of concrete using LSC and FMKC of age
to 1year are shown in Fig. 9. It is seen from Fig. 9 that the drying shrinkage
for LSC of age up to 6 months was 2 9 0 ~ 1 0 -and
~ , for FMKC was 3 1 0 ~ 1 0 - ~In.
the documents [7,8], related to drying shrinkage of high strength concrete in the
past, the shrinkage at age 6 months for concrete using NPC with the same
mixture proportion conditions is 700 to 8 0 0 ~ 1 0 - ~The
. numbers for the both
--``,`,-`-`,,`,,`,`,,`---
high strength concrete with LSC and FMKC were considerably reduced
compared to concrete using NPC.
Freezing and Thawing Resistance

Fig.10 shows the results of freezing and thawing tests of concrete using LSC and
FMKC. For concrete with LSC as well as FMKC, the relative dynamic modu-
lus of elasticity up to 300 freezing and thawing cycles, was more than 95%.
It was confirmed that both concretes with LSC and FMKC had sufficient dura-
bility against freezing and thawing action.
PUMPABILITY
Concrete has often got ton be pumped to the actual site of placement. A study
was carried out to verify if the high strength concrete described in the above
section could be successfully pumped using normally available equipmcnt and if
the pumping causes any significant changes in the variation of slump flow,
segregation, compressive strength etc. More than 100 cubic meters of concrete
using both LSC and FMKC was pumped over a distance of 50 m including two
90 degree bends using a 150mm diameter pipe as shown in Fig.11. Thc pressure
head at points of PO to P4 was measured using pressure gages to study the loss
of head over the distance and concrete samples were collected from points of
leaving plant, arriving at site and after pumping and tested for slump flow and
compressive strength. The results are briefly discussed below.
Slump Flow of Fresh Concrete
Fig.12 shows the results of slump flow tests at the time of leaving the plant.
ar&al on site and after pumping.' About 20 minutes were required-to traisport
the concrete from the mixing plant to the construction site, and the concrete
was pumped immediately after arrival on site.
Though there was a slight variation in the slump flow when leaving the plant,
both LSC and FMKC satisfied the target value (550 50mm) almost completely.
The slump flow at the arrival on site showed a tendency to be greater than the

A C 1 SP-153 VOL+II 95 m 0662949 0523’366 398 m
flow when leaving the plant by 50 to 100 mm. This is attributed to the action of
the high range water reducing admixture, similar to the results obtained in the
laboratory tests. However, even when the slump flow became greater than
700 mm, segregation of coarse aggregate did not occur because of the high
viscosity of mortar.
As can be seen from Fig.12, pumping causes an appreciable slump loss in the
case of concrete using FMKC, but the flow remains more or less constant for
--``,`,-`-`,,`,,`,`,,`---
LSC. Though the reason for the effect of cement type on slump loss is not clear-
ly understood, the variation could be attributed to the segregation of water that
occurs during pumping of the concrete under pressure and the problem is
compounded in the case of FMKC with the lower unit water content (130kg/m3)
compared to the LSC (160kg/m3). The water content should not be too small
even when satisfying the required slump flow value at the mixing. This may
result in the increase in cement content for FMKC.
Fig.13 shows the results of comtxessive strength tests. The variation in strength
atihe time of leaving the plait, arrival on &e and after pumping, is small &d
the average value of compressive strength of LSC almost satisfied the mixture
proportion strength of 72 MPa. The tendency for a slight reduction in
strength after pumping was observed but the number never dropped below the
characteristic strength of 60 MPa. The results of the tests showed that the
compressive strength of FMKC had a larger variation compared to LSC. This
resulted from the lower unit water content used in the FMKC.
Loss of Head
The results of measurement of pressure in pipes during pumping are shown in
Table &The pressure a t the pump was about 50% the limiting value of the
pumping equipment (4.5 MPa) during the test this time. There was no blockage,
and pumping of both concrete using LSC and FMKC was smooth. However,
since both concretes are more viscous than ordinary concrete, it is important to
choose proper equipments having enough capacity of pumping. The loss of head
was highest in the horizontal pump piping sections, with an average value of
0.047 MPa/m for LSC and 0.079 MPdm for FMKC. These values are almost
the same as the pressure resistance of anti-washout underwater concrete with
slump flow of 500 to 550 mm and about 4 to 5 times the pumping resistance of
ordinary concrete [9].
THERMAL STRESS
The temperature measurement values in the actual structure in the field and the
values predicted by analysis were compared, and the validity of heat character-
istics obtained in laboratory tests were investigated. In the field tests, the LSC
concrete shown in Table 1 was placed in the wall structure shown in Fig.14,
and the temperature history at the central portion of the wall was measured using
thermocouples. The materials used in the concrete were the same as the
materials used in the laboratory tests.
The thermal stress analysis of concrete using various types of cements shown
in Table 5 was then carried out to investigate the thermal stress reduction
effects of low heat type high strength concrete using LSC, and the tempera-
tures and stresses were compared. The structure analyzed was a wall-shaped
structure modeling the underground storage wall shown in Fig.15. Tempera-
ture analysis was carried out by two-dimensional Finite Element Method and

A C 1 SP-153
1002 Iwai et al
VOL*II 95 W 0662949 0521967 024 =
the Compensation Plane Method was used for thermal stress analysis.
Comparison of Measured and Calculated Temperature
Fig.16 shows the comparison of measured and analyzed values of temperature
in the field tests. The field tests were carried out in the middle of October, the
concrete placing temperature was about 23°C and the average air temperature
was about 16°C. The temperature rise of concrete in the analysis was about
35°C in the central part of the wall and about 25°C on the wall surface. The
time taken for the temperature to reach the maximum value was about 40 hours.
The measured values at the central part and on the surface coincided with the
calculated values. It was verified that the temperature history of the actual
structure could be accurately analyzed by using the heat characteristic
values obtained in laboratory tests.
Analytical Case Study
The results of temperature and stress analyses assuming a wall-shaped struc-
ture were compared according to the type of cement. The comparison is shown
in Fig.17 and Fig.18. The temperature and stress history showed that the
maximum temperature rise and the maximum temperature stress occurred at
the central part of the wall. The maximum temperature of concrete was about
70°C for NPC. In comparison, the maximum temperature for FMKC was about
56"C, for LSC about 50"C, indicating that the temperature rise for the latter is
smaller compared to NPC. The maximum value of tensile stress for NPC was
about 6.8 MPa. The results also showed that the corresponding values were
lower for FMKC and LSC, about 80% and 60% respectively.
CONCLUSION
The fundamental properties, pumpability, and thermal stress reduction effects of
high strength concrete of characteristic strength 60 MPa, using two types of low
heat cement -- LSC and FMKC, were investigated. The results are summarized
below.
(1) Comparison of the results of adiabatic temperature rise for the different
types of concrete at the same strength level showed that concrete using LSC
generated the minimum amount of heat. Results of analysis of temperature
stresses showed that in concrete using LSC, the thermal stress was reduced by
60% compared to concrete using NPC.
(2) Quality of concrete manufactured in the concrete plant was comparatively
uniform. It was confirmed that the properties and compressive strength of fresh
concrete almost satisfied the required conditions.
(3) Pressure loss during pumping was three to four times larger than ordinary
concrete. It was verified that after pumping, the quality of concrete using LSC
--``,`,-`-`,,`,,`,`,,`---
showed satisfactory workability and had lesser variation compared to the quali-
ty of concrete using FMKC.
(4) Properties of fresh concrete showed large variation depending on the tem-
perature conditions. The cause may be attributed to the properties of the high
range water reducing agent. For stable quality, proper selection of admixtures to
suit the type of cement and temperature conditions is considered necessary.
(5) From results mentioned above, by selecting proper high range water reduc-
ing admixture, use of LSC is considered to be one of solutions for reducing
cracks due to hydration in high strength concrete while maintaining suitable
workability and sufficient strength development.

A C 1 SP-353 VOL*II 95 Ob62949 0523968 TbO m
REFERENCES
[l]Iwashimizu,T.; "Ultra High Strength Concrete", Sekoh, No.291, pp.126-129,
1990.1
(in Japanese)
[2]Yurugi,M., Mizobuchi,T. and Terauchi,T.; "Development of Low Heat High
Strength Concrete", Annual Report of Kajima Technical Research Institute,
V01.39, pp.17-26, 1991.10
[3]Yurugi,M., Mizobuchi,T., and Terauchi,T.; "Utilization of Blast-Furnace
Slag and Silica Fumc for Concrete Temperature Rise in High-Strength Con-
crete", Proceedings o€ Fourth International Conference of Fly Ash,Silica
Fume,Slag and Natural Pozzolans in Concrete, pp.1433 -1450, 1992.5
[4]Sugi,t.; "Measures for Mass Concrete in LNG Tanks", Concrete Journal,
Japan Concrete Institute, V01.22, No.3, pp.81-86, 1984.3
[SIJapan Society of Civil Engineers, "Standard Specification for Design and
Construction of Concrete Structures -1986, Part2 [Construction]".
[6]Tomozawa,F.,et al; "Fundamental Mechanical Properties of High Strength
Concrete",Proceedings of Annual Conference of Architectural Institute of Japan,
1990.10
[7]Nagataki,S., and Yonekura,A.; "Drying Shrinkage and Creep Characteristics
of High Strength Concrete", Concrete Journal, Japan Concrete Institute, V01.20,
No.4, pp.75-87, 1982.4
[8]Fukushi,I., "Experimental Study on Strength Properties and Durability of
High strength Concrete", Annual Report of Housing and Urban Development
Research Institute, No.90, pp.293-301, 1989
[9]Kashima,H.,et al; "Construction of Underwater Concrete of Akashi Kaikyo
Bridge", Cement and Concrete, The Cement Association of Japan, No.508,
pp.6-14 1989.6 (in Japanese)
Henry, G.R., Steven, H.G. and David, W. ;"High Strength Concrete", Civil
Engineering, Vo1.59, No.11, pp.59-61, 1989.11
TABLE 1 - REQUIRED PROPERTIES
I Item ITarget Value I Comments 1

Characteristic Strength 6OMPa At 91 days. Considering the Variation in qUal¡tY,
etc. a 20%higher strength
Target Strength 72MPa (than characteristic strength) is targeted.
Slump ~ 1 0 5 5 0 ~ 5 0 m mThe values chosen for easy constructionand

~
. durability. Also, consideringthe transportation,
Retention Time ZgOmin a retention time of 90min on these is imposed.
Air Content 4 I 1Yo
initiai Setting Time SlOhr To minimize the lateral pressure on the formwork.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 = Obb2949 05219bî î T 7
1004 Iwai et al
TABLE 2 - PROPERTIES OF CEMENTS
Material Comments
Pit Sand ; Density = 2.60

Fine Aggregate Fineness modulus = 2.47
~~ ~ ~
Crushed Limestone ; Density = 2.70

Coarse Aggregate Fineness modulus = 6.58
Maximum size = 20mm
TABLE 4 - MIXTURE PROPORTIONS OF CONCRETE
Unit Quantity (kgíd)
FMKC I 30.0 I 39.6 130 I 433 I 717 I 1081 I 14.72 I

OPC 30.0 36.7 145 483 636 1107 7.37
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 75 E Ob62747 0523970 bL7
TABLE 5 - ADIABATIC TEMPERATURE RISE
LSC 533 68.8 36.5 1.41 0.068 0.531 1.10 2.24

FMKC 433 67.1 50.8 0.62 0.117 0.756 1.12 2.54
I NPC I 483 I 72.2 I 59.5 I 1.08 1 0.123- 1 0.824 I 1.15 I 2.67
Equation of Adiabatic Temperature Rise

Q (t) = L(i-exp(-rt))
TABLE 6 - PUMPABILITY TEST RESULTS
LSC FMKC I
Type of Cement
Average I
Number of Data 21
Slump Flow before Pumping
535 66 563 110
írnrnl ~~
Concrete Temperature
16.3 1.3 24.2 0.5
(“C)
Pumping Rate
(rn3Br)
43.3 5.5 51.5 4.3
--``,`,-`-`,,`,,`,`,,`---
Pumping Pressure [PO]

(MPa)
2.35 0.80 2.04 0.69
2.15 0.80 1.65 0.69
0.0470 I 0.0294 0.0794 I 0.0255 I

Vertical
Pressure [P2]
1.73 I 0.75 1.08 I 0.73 I
(MPa/m) 0.0096 I 0.0061 0.0094 I 0.0082 I
I Pressure [ P ~ I
(MPa)
0.86 I 0.47 I
Tapering Pipe
Loss of Head
(MPa)
0.255 0.245 0.206 I 0.137 I
A C 1 SP-153 VOL*II 95 W 0662949 052l197L 555
1006 Iwai et ai
n
E 700 1
I
L
E
W
b
600 - 'Acceptable
O range
-
+ 500
1
0. -
E 400
300 -
200' o 30
I
60
I I
90
I
Elapsed Time ( m i n )
--``,`,-`-`,,`,,`,`,,`---
Fig. l - C h a n g e in slump flow values with time (LSC)
800 I 1
p
3
-
L
E 700 - -
M 30°C
E
W3 600 -. .................................................... .2OoC...................
Acrptable
i
O range
,
+
Y-
500 _ ............................................................................................ ....,.......
E
3
400 -
.
s:-003200 o
30
60 90
Elapsed Time ( m i n )
Fig. 2-Change in slump flow values with time (FMKC)

A C 1 SP-153 V O L X I I 95 M Ob62949 0521972 491 M
\
\
I I
4' 10 20 30
Concrete temperature ("Cl
Fig. 3-Variation of initial setting time

with concrete temperature
-I
m
2601
I I I
10 20 30
Concrete temperature ("Cl
Fig. &Variation of maturity until intial

setting with concrete temperature
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOLS11 95 m Obb2949 0 5 2 3 7 7 3 328
1008 Iwai et al
--``,`,-`-`,,`,,`,`,,`---
'LL
2 80
x
v
5
03
60
S
W
L
cn 40
W
>
.rl
2W 20
L
Q
E
OO 0
1 3 7 28 91
Fig. 5-Relationship between age and

compressive strength
LF I
5. o
4. o
3.0 -
2.0 -
0.566
f t =o. 391 x ( f cl
9
03
= 1.01
*rl
+->
* [6] --
4
Q
"'"O 20 40 60 80
cn
Compressive Strength (MPa)
Fig. &Relationship between splitting tensile
strength and compressive strength

A C 1 SP-153 VOL*II 95 m 0662949 052197Y 264 m
4-0
3. o
2.0
1
- Ec=1811 X ( f c ) 0.3 x r 2
r
n r : Unit weight of concrete
**.[6]
3
O
t
o. oO 20 40 60 80
Fig. 7-Relationship between Young’s modulus
o n c r e t e temperature
O 2 4 6 8 1 0 1 2 1 4
--``,`,-`-`,,`,,`,`,,`---
Elapsed Time (days)
Fig. &Adiabatic temperature rise

A C 1 SP-153 VOL*II 95 0662949 0521975 L T O
1010 Iwai et al
O
100
v
Q) 200
07
3
c
300
o
c
500 1
--``,`,-`-`,,`,,`,`,,`---
.rl
2 600 I I I I
o 0 1O0 200 300 400

Drying Period (days)
Fig. %Drying shrinkage
W I
't
3
A
-0
O
= 94
..
z 90' I I I
I I I I I I
2
I1I
O 30 60 90 120 150 180 210 240 270 300
Number of Freezing and Thawing Cycles
Fig. 1û-Freezing and thawing resistance

A C 1 SP-153 VOL*II 95 0662949 0521976 037
Bending pipe Concrete pump[Po]
P1-P4: Pressure Gage
Vertical conveying pipe

[150mmG. 42m] -
[l mR, 90'1
Fig. 11-Location of pressure gages
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 75 0662949 0523977 T73
1012 Iwai et al
4
2
O
,--.
O
c (B
'c
4-
Q
d
.. .. .. Cu
CIX D
O
.
I
I
d
I
.
I
E € '
zr
g gEmE - 2
II Il II h
CIX ü o
-0 v)
J
v
+
-03 r m
C
o 4
c
al a
L -
-0 U
3
al
L
LL m
- d C
-
- N
I ' I '
-0
0 0 0 0 0
0 0 0 0 0
r - a l n l f c >
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 e 0bb2949 0523978 ï 0 T =
-
O
cn h
h
u
_J æ
æ
w
v
x o
A
o c
a,
c
W 3
U
3 U
al
L
al
L
U
L
U al
+->
Le
a
.. .. ..
KIX O
h
O
cn
h u
æ
w
x o
x
o
S 8
al
W
3 c U
3
O
U al
L
W
L -i
Lu
U
U
>
.-i
L
Y-
L O
4
n
æ
v
x
0
L3
W
3
D
W
L
L
u m U
c
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 0662947 0523979 846
1014 Iwai et al
Steel
-G;
100 650
Measurement point
I
& 1,500 [unit :mm1
Fig. 14-Model of concrete tem-

perature measurement
Existing concrete I 1F-l

[unit :mm]
--``,`,-`-`,,`,,`,`,,`---
Fig. 15-Model of thermal stress analysis for walls

of tank

A C 1 SP-153 VOL*II 95 m 0662949 0523980 568
o o Measuremant
-
Calculation
"0 5 10 15 20 25 30
Elapsed t i m e (days)
Fig. 1&-Comparison of measured and calculated

temperatures
8o c
o
'O t I
O' 10 20 30 40 50 60
Elapsed time (days)
--``,`,-`-`,,`,,`,`,,`---
Fig. 17-Type of cement and concrete temperature rise

A C 1 SP-153 VOL*II 95 W 0662949 0521981 4 T 4
1016 Iwai et al
3 4 **.,.........................
Ea,
E 2
--``,`,-`-`,,`,,`,`,,`---
O I
40 50 60
-4
-2 t ***:
Elapsed time (days)
Fig. 18-Calculated thermal stress

A C 1 SP-153 VOL*II 95 0 b b 2 9 4 9 0 5 2 3 9 8 2 330
SP 153-53
Effectiveness of Granulated
Blast Furnace Slag in Preventing
Alkali-Silica Reaction
by D. D. Higgins and M. D. Connell
Synopsis : In a programme covering a wide range of mixtures, three

portland cements and two ground granulated blastfurnace slags
have been used to investigate the relationship between alkali-
content and ASK expansion. Length changes were monitored, for
several years, on concrete prisms made with a reactive natural
aggregate; the prisms were moist stored at 2OoC and 38OC.
Storage at 38OC was found to be an accelerated test which
correlated well with storage at 2OoC. At 2OoC the rate of
expansion was some four times slower than at 38OC. Nonetheless,
there was very good consistency between the two temperatures in
classifying mixtures as either 'expanding' o r 'non-expanding' .
Current indications are that the magnitudes of ultimate expansions
are independent of temperature.
The mixtures containing ggbs, tolerated much greater alkali
contents in the concrete, without expansion. This effect was more
pronounced for higher proportions of ggbs. The results of the
programme are discussed in relation to various rules which have
been proposed to take advantage of the effectiveness of ggbs in
preventing ASR.
Keywords: Accelerated tests; alkali aggrep;ate reactions; blast furnace

slag; expansion; slags; specifications
--``,`,-`-`,,`,,`,`,,`---
Copyright American Concrete Institute I

A C 1 SP-153 VOL+II 95 Obb29V9 0521983 2 7 7 =
1018 Higgins and Connell
Denis Higgins i s a D i r e c t o r o f C i v i l and Marine S l a g Cement Ltd,

London Road, Grays, Essex, England.
Mike Connell i s Group Technical Manager f o r t h e Appleby Group Ltd,

Brigg Road, Scunthorpe, South Humberside, England.
INTROWCTION
Ground g r a n u l a t e d b l a s t f u r n a c e s l a g (ggbs) i s used a s a

within-mixer a d d i t i o n or as a component of a factory-blended
p o r t l a n d b l a s t f u r n a c e cement. Its a b i l i t y t o prevent Alkali-
S i l i c a Reaction i s w e l l e s t a b l i s h e d worldwide (1). Evidence of
t h e e f f e c t i v e n e s s o f ggbs i n preventing ASR h a s come from
numerous l a b o r a t o r y i n v e s t i g a t i o n s which, almost without
e x c e p t i o n , have confirmed its a b i l i t y t o prevent d e l e t e r i o u s
expansion. I n g e n e r a l t h e tendency f o r expansion reduces with
i n c r e a s i n g ggbs c o n t e n t . Additional and p o s s i b l y even more
--``,`,-`-`,,`,,`,`,,`---
convincing e v i d e n c e , h a s come from experience o f a c t u a l
structures. Countless s t r u c t u r e s throughout t h e world have been
c o n s t r u c t e d u s i n g p o r t l a n d b l a s t f u r n a c e cement. It i s t h e
w o r l d ' s second most commonly used cement t y p e and h a s been
e x t e n s i v e l y employed f o r o v e r one hundred y e a r s . However, ASR
i n c o n c r e t e c o n t a i n i n g ggbs i s v i r t u a l l y unknown.
Regulations and a d v i c e on t h e avoidance of ASR vary from

country t o country ( 2 ) . I n those countries with relevant
r e g u l a t i o n s and where s l a g cements are a v a i l a b l e , r u l e s have
evolved f o r t h e use o f ggbs a s a p r e v e n t a t i v e measure a g a i n s t ASR.
Table 1 summarises t h e s e . The common f a c t o r of t h e s e approaches
is t h a t , a t s l a g percentages g r e a t e r t h a n about 502, more a l k a l i
i s permitted i n a s l a g cement t h a n i s a l l o w a b l e i n a p o r t l a n d
cement ( t y p i c a l l y n e a r l y twice as much).
Recommendations f o r s l a g l e v e l s lower t h a n about 50%are less

w e l l developed. I n t h e üK, t h e approach i s based on l i m i t i n g t h e
a l k a l i content i n t h e concrete. T h i s approach p a r a l l e l s a
procedure f o r normal p o r t l a n d cement c o n c r e t e s , which l i m i t s t h
c a l c u l a t e d a l k a l i c o n t e n t o f t h e c o n c r e t e t o less t h a n 3.0 kg/m 5.
(It should be noted t h a t c a l c u l a t i o n s are based on average a l k a l i
c o n t e n t s and s t a t i s t ' c a l f l u c t u a t i o n s may l e a d t o a c t u a l c o n t e n t s
up t o about 3 . 5 kg/m 3 ). For normal p o r t l a n d cement, t h e f u l l
a l k a l i c o n t e n t (expressed a s t h e sodium o x i d e e q d v a l e n t ) is
included i n the c a l c u l a t i o n , b u t f o r any s l a g p r e s e n t , o n l y a
p r o p o r t i o n of its a l k a l i is i n c l u d e d . There are two v i e w s i n t h e
UK on t h e a p p r o p r i a t e proportion of t h e s l a g a l k a l i t o i n c l u d e ,
A Concrete S o c i e t y Technical Report ( 3 ) recommends t h a t o n l y

t h e water-soluble a l k a l i c o n t e n t of t h e ggbs need be counted as
t h e r e a c t i v e a l k a l i contribution. The water-soluble alkali i n

A C 1 SP-153 VOLrII 95 W Obb29Y9 052L984 L O 3
ggbs i s normally v e r y small, t y p i c a l l y less t h a n 0.05%, and t h e

c a l c u l a t e d c o n t r i b u t i o n from t h i s i s o f l i t t l e s i g n i f i c a n c e .
However, Building Research Establishment Digest 330 ( 4 ) recommends
t h a t t h e c o n t r i b u t i o n should b e one h a l f of t h e acid-soluble
a l k a l i c o n t e n t of t h e ggbs. The acid-soluble a l k a l i c o n t e n t o f
ggbs i s e s s e n t i a l l y t h e t o t a l a l k a l i c o n t e n t , and one h a l f of t h i s
is s i g n i f i c a n t ( t y p i c a l l y 0.3%, expressed as sodium o x i d e
equivalent).
The p r e s e n t programme of r e s e a r c h was designed t o t r y t o

r e s o l v e t h i s c o n f l i c t of advice. Expansion measurements are
being c a r r i e d o u t on c o n c r e t e prisms c o n t a i n i n g n a t u r a l UK
aggregates. The chosen a g g r e g a t e s were a combination of f l i n t -
bearing sand and crushed limestone coarse a g g r e g a t e ; t h e s e were
s e l e c t e d because ASR damage i n UK s t r u c t u r e s h a s o c c a s i o n a l l y
r e s u l t e d when high-alkali p o r t l a n d cement h a s been used w i t h s u c h
a combination. The following parameters have been v a r i e d :
1) c e m e n t i t i o u s c o n t e n t (420 kg/m3 t o 1000 kg/rn3)

2) percentage ggbs (0% t o 70%)
3) a l k a l i c o n t e n t of p o r t l a n d cement (0.54% t o 1.15%)
(0.58% and 0.8 %)
4)
5)
a l k a l i c o n t e n t of ggbs
added a l k a l i 3
(O t o 3.8 kg/m )
6) s t o r a g e temperature (2OoC and 3 8 O C )
Nearly t h r e e hundred specimens, corresponding t o 136 d i f f e r e n t

combinations o f t h e above are being monitored
S i n c e a priinary aim of t h e programme was t o t e s t t h e
--``,`,-`-`,,`,,`,`,,`---
h y p o t h e s i s t h a t ggbs c o n t r i b u t e s one h a l f of ts t o t a l a c i d -
s o l u b l e a l k l a i t o t h e a l k a l i - s i l i c a r e a c t i o n , t h e matrix of
mixture d e s i g n s was based on t h i s assumption. Xowever, a
s u f f i c i e n t l y wide range of mixtures was included t o e n a b l e
a l t e r n a t i v e hypotheses t o be t e s t e d .
METHOD OF TEST
Prisms (75 x 75 x 250 mm) were cast with s t a i n l e s s steel

i n s e r t s € o r l e n g t h measurement. Expansion t e s t i n g followed t h e
method given i n t h e d r a f t B r i t i s h Standard ( 5 ) , with t h e following
e x c e p t i o n s and a d d i t i o n s :
Two p a i r s of specimens were cast from each combination; one

p a i r was s t o r e d a t 20 2 2OC and t h e o t h e r a t 38 2 2OC.
The specimens were wrapped i n moist t o w e l l i n g o r c l o t h , and

t h e n placed i n s i d e 500 gauge polythene t u b i n g which was s e a l e d a t
each end; t h i s was t h e n placed i n t o a p r o t e c t i v e n e t and t h e
specimens were s t o r e d h o r i z o n t a l l y .

A C 1 SP-153 VOL*II 95 IOlala2949 0521985 0 4 T
The specimens were i n i t i a l l y measured and weighed a t 1 and 28

days. For t h e . f i r s t two y e a r s t h e 3 8 O C specimens were measured
a t monthly intervals and t h e 20bC specimens a t 3 monthly
intervals. Subsequently t h e time span between measurements has
been i n c r e a s e d .
The c o n c r e t e m i x t u r e s were designed t o produce nominal

r e a c t i v e alkali c o n t e n t s g e n e r a l l y e i t h e r 5, 6 , 7 o r 8 kg/m 3 ,
u s i n g 3 combinations of p o r t l a n d cement alkali c o n t e n t s and 2 ggbs
a l k a l i contents. It w a s assumed f o r t h e purpose o f c a l c u l a t i o n
t h a t 50%of t h e a c i d - s o l u b l e alkali i n t h e ggbs was a v a i l a b l e f o r
reaction. Details of t h e materials are g i v e n i n Table 2 and t h e
c o n c r e t e mix propor i o n s i n Table 3. Mixtures t h a t r e q u i r e d i n
5
e x c e s s of 1000 kg/m of cement used a t o t a l cement c o n t e n t of
--``,`,-`-`,,`,,`,`,,`---
1000 kg/m3 cement, and potassium s u l p h a t e w a s added t o b r i n g t h e
t o t a l a l k a l i t o t h e required level. After t h e programme had
commenced, i t was found t h a t t h e measured alkali c o n t e n t o f some
of t h e c e m e n t i t i o u s m a t e r i a l s d i d n o t c o i n c i d e e x a c t l y w i t h t h e
v a l u e s o r i g i n a l l y i n d i c a t e d by t h e manufacturers. It is f o r t h i s
r e a s o n t h a t t h e a c t u a l a l k a l i c o n t e n t s of t h e m i x t u r e s do n o t
always p r e c i s e l y a l i g n w i t h t h e nominal values.
I n a l l t h e c o n c r e t e s , 25% o f t h e f l i n t - b e a r i n g sand (ex
on a m i x t u r e w i t h a cement c o n t e n t of 700 kg/m s.

Thames V a l l e y ) w a s i n c l u d e d by volume of t h e t t a l a g g r e g a t e based
The combination
of a g g r e g a t e s chosen h a s a wide 'pessimum' and i t h a s been
r e p o r t e d t h a t similar expansions are o b t a i n e d w i t h between 20
and 40% Thames Valley ( 6 ) sand and w i t h between 15 and 35%Thames
Valley sand (7).
T a b l e 4 r e c o r d s t h e r e s u l t s f o r t h e m i x t u r e s which have shown

any s i g n i f i c a n t expansion ( g r e a t e r t h a n 0.05%).
Expansion C r i t e r i o n
An expansion of 0.1% was t a k e n as a l i m i t , above which t h e

specimen was c o n s i d e r e d t o have expanded, I n t h e 3 8 O C specimens
t h e s h o r t e s t t i m e t o r e a c h t h i s expansion was 2 months, t h e l o n g e s t
t i m e t o d a t e i s 45 months. I n t h e 2OoC specimens, t h e s h o r t e s t
t i m e t o r e a c h 0.1% expansion w a s 9 months. The Specimens were
cast o v e r a p e r i o d of t i m e and are c u r r e n t l y between 3 and 4.5
years old.
E f f e c t o f Temperature
S t o r a g e a t 38OC accelerates ASR expansion and is advantageous

f o r o b t a i n i n g r e s u l t s w i t h i n a r e a l i s t i c timescale i n a
laboratory. Fig.1 compares t e s t i n g a t 3 8 O C w i t h r e s u l t s f o r
2OoC, which is more r e p r e s e n t a t i v e of normal ambient temperature.

A C 1 SP-II53 V O L * I I 95 0662949 052II986 TBb D
For t h e m i x t u r e s which have expanded, t h e a g e a t which t h e y

a c h i e v e 0.1% expansion a t 38OC i s p l o t t e d a g a i n s t t h e age t o
a c h i e v e t h i s expansion a t 2OoC. The p o i n t s w i t h a n arrow are
m i x t u r e s which have achieved 0.1% a t 3 8 O C b u t n o t as y e t a t 2OoC.
It c a n be s e e n t h a t t h e r e i s good c o r r e l a t i o n between 20°C

and 3 8 O C ; t h e specimens a t 2OoC t a k e about f o u r times l o n g e r t o
r e a c h 0.1% t h a n t h o s e a t 3 8 O C and t h e m i x t u r e s which have n o t
expanded a t 3 8 O C have n o t expanded a t 2OoC.
The magnitudes of u l t i m a t e expansion (see Table 4 ) vary.

However, f o r a given mix, c u r r e n t i n d i c a t i o n s are t h a t t h e
u l t i m a t e expansion a t 3 8 O C is similar t o t h a t a t 20°C.
Cementitious Content and A l k a l i Level r e q u i r e d f o r Expansion
Of t h e m i x t u r e s which expanded, t h e one with t h e l o w e s t

c e m e n t i t ' o u s c o n t e n t was a mixture without ggbs, c o n t a i n i n g
458 kg/mS of h i g h - a l k a l i (1.15%) cement. It is worthy of n o t e ,
t h a t i n terms of cement c o n t e n t , cement a l k a l i and a g g r e g a t e
combination, t h i s mixture is similar t o c o n c r e t e m i x t u r e s known t o
have s u f f e r e d ACR damage i n a c t u a l UK s t r u c t u r e s . For t h e
m i x t u r e s without ggbs, t h e lowest a l k a l i l e v e l f o r expansion was
5. O kg/m3.
The m i x t u r e s w i t h 25% ggbs had i n c r e a s e d r e s i s t a n c e t o

expansion The l o w e s t c e m e n t i t i o u s c o n t e n t t o expand was
595 kg/$ and t h e lowest c o n c r e t e t o t a l - a l k a l i c o n t e n t was
5.6 kg/m .
Even g r e a t e r r e s i s t a n c e was shown by t h e 50% ggbs mixtures.
The l o w e s t c e m e n t i t i o u s c o n t e n t t o expand was 856 kg/m3 and t h e
l o w e s t c o n c r e t e t o t a l - a l k a l i c o n t e n t w a s 8.5 kg/m 3 .
None of t h e 70% ggbs m i x t u r e s have expanded, even w i t h
c e m e n t i t i o u s c o n t e n t s of 1000 kg/m 3 and c o n c r e t e t o t a l - a l k a l i
c o n t e n t s over 10 kg/m 3 .
Reactive P r o p o r t i o n of S l a g A l k a l i
The r e s u l t s were used t o t e s t t h e h y p o t h e s i s t h a t a f i x e d

p r o p o r t i o n of t h e t o t a l a l k a l i i n t h e ggbs might be t a k e n as i t s
contribution t o t h e 'reactive' a l k a l i i n concrete.
F i g . 2 , 3 and 4 are graphs of c a l c u l a t e d ' r e a c t i v e ' alkali

c o n t e n t of c o n c r e t e a g a i n s t % ggbs and t h e s q u a r e s i n d i c a t e
specimens which have n o t expanded and t h e c r o s s e s , i n d i c a t e
specimens which have expanded. The ' r e a c t i v e ' a l k a l i c o n t e n t
--``,`,-`-`,,`,,`,`,,`---
i s the sodium o x i d e e q u i v a l e n t i n kg/m 3 and was c a l c u l a t e d

assuming: F i g u r e 2 : f u l l c o n t r i b u t i o n from ggbs
F i g u r e 3 : ' h a l f ' c o n t r i b u t i o n from ggbs
F i g u r e 4 : no c o n t r i b u t i o n from ggbs

A C 1 SP-153 VOLaII 95 m Ob62949 0523987 912 =
I f t h e 'reactive' a l k a l i c o n t e n t i s a c t u a l l y t h a t c a l c u l a t e d , t h e n
i t should be p o s s i b l e t o draw a s t r a i g h t v e r t i c a l l i n e s e p a r a t i n g
t h e expanding from t h e non-expanding specimens. T h i s is n o t
p o s s i b l e on any of t h e t h r e e g r a p h s which s u g g e s t s t h a t t h e
concept of t a k i n g a f i x e d p r o p o r t i o n of t h e a l k a l i i n t h e ggbs as
r e a c t i v e , is not valid. The assumption o f a full c o n t r i b u t i o n
from t h e ggbs underestimates t h e e f f e c t i v e n e s s o f ggbs i n a l l
cases. The assumption o f a h a l f - c o n t r i b u t i o n from t h e ggbs
underestimates t h e e f f e c t i v e n e s s of ggbs a t a l l replacement l e v e l s
o v e r 25%. The assumption of no-contribution from t h e ggbs
underestimates t h e e f f e c t i v e n e s s a t ggbs l e v e l s above 35%; a t 25%
t h e r e c a n be a s l i g h t overestimate. However, i t should be noted
t h a t t h i s s l i g h t o v e r e s t i m a t e i s of t h e same o r d e r as t h e
r e p r o d u c i b i l i t y i n measuring t h e a l k a l i c o n t e n t o f OPC combined
with t h e u n c e r t a i n t y i n d e f i n i n g t h e c r i t i c a l a l k a l i c o n t e n t f o r
t h e normal p o r t l a n d cement mixes.
B e n e f i t of ggbs
A s h a s been d i s c u s s e d elsewhere ( 6 ) , i t i s u n l i k e l y t h a t t h e
b e n e f i t s of ggbs are simply due t o a r e s t r i c t e d a v a i l a b i l i t y of
its a l k a l i . Indeed, when ggbs h y d r a t e s , i t s a l b l i w i l l
i n e v i t a b l y be r e l e a s e d i n t o t h e p o r e s o l u t i o n and t h e r e a f t e r be
i n d i s t i n g u i s h a b l e from t h a t r e l e a s e d from p o r t l a n d cement.
S e v e r a l i n v e s t i g a t o r s have a t t r i b u t e d t h e reduced ASR-

s u s c e p t i b i l i t y of ggbs c o n c r e t e , t o m o d i f i c a t i o n s i n t h e chemistry
and permeability of t h e c e m e n t i t i o u s p a s t e . They s u g g e s t (1)
t h a t t h e reduced permeability t o a l k a l i and/or t h e i n c r e a s e d
a b i l i t y of t h e c e m e n t i t i o u s p a s t e t o bind a l k a l i , r e s u l t i n ggbs
c o n c r e t e s being a b l e t o t o l e r a t e high l e v e l s of a l k a l i without
expansion. As shown i n T a b l e 2 t h i s i s a n approach t a k e n by
Germany, Belgium and France i n t h e i r Regulations.
Fig.2, which t a k e s i n t o account t h e f u l l c o n t r i b u t i o n o f

a l k a l i from a l l s o u r c e s ( i n c l u d i n g t h e g g b s ) , demonstrates t h i s
i n c r e a s e d t o l e r a n c e t o a l k a l i . A t 50% ggbs, no exp n s i o n has
occurred with mixtures c o n t a i n i n g as much a s 8 kg/m o f a l k a l i . 9
At 70% ggbs, no expansion h a s occurred even with approaching
11 kg/m3 of a l k a l i . By comparison, normal p o r t l a n d cement
mixtures expanded w i t h a s l i t t l e a s 5 kg/m 3 o f a l k a l i .
UK Rules f o r t h e Avoidance of ASR
It a p p e a r s t h a t t h e concept o f t a k i n g a proportion of t h e
ggbs alkali as r e a c t i v e , i s n o t v a l i d . This being t h e case, i t
w i l l never be p o s s i b l e t o s e n s i b l y determine t h e correct
p r o p o r t i o n t o c o n s i d e r as r e a c t i v e . The b a s i c philosophy of UK
rules, t h e r e f o r e , needs t o be r e c o n s i d e r e d . Nonetheless f o r UK
materials, t h e assumption of a z e r o (or water-soluble o n l y )
c o n t r i b u t i o n of a l k a l i from t h e ggbs a p p e a r s t o err on t h e s a f e
s i d e , p a r t i c u l a r l y f o r a ggbs p e r c e n t of 35% o r more.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 Obb2949 0521988 ô59
Milwaukee conference 1023
CONCLUSIONS
1. The c o n c r e t e prism t e s t produced expansion i n t h e l a b o r a t o r y
with a mixture similar t o t h a t known t o have s u f f e r e d
ASR damage i n t h e UK, i n a c t u a l s t r u c t u r e s .
2. S t o r a g e of prisms a t 38'C gave similar expansion behaviour

t o s t o r a g e a t 2OoC b u t i n a s h o r t e r timescale (about f o u r
times f a s t e r ) .
3. S t o r a g e of c o n c r e t e prisms a t 3 8 O C i s a n a c c e l e r a t e d test
which a p p e a r s t o c o r r e l a t e well w i t h p r a c t i c a l s i t u a t i o n s .
4. The r e s u l t s are n o t c o n s i s t e n t w i t h t h e concept of t a k i n g a

f i x e d proportion of t h e alkali i n t h e ggbs as r e a c t i v e ,
A t 25% ggbs, a n assumed c o n t r i b u t i o n o f e i t h e r 0% or 50% of
ggbs a l k a l i would f i t w i t h i n t h e accuracy of t h e results.
A t 35% and 50% ggbs, an assumed c o n t r i b u t i o n of 0% of ggbs
a l k a l i is more a p p r o p r i a t e . A t 70% ggbs t h e r e i s a n
apparently negative contribution.
5. The c o n c r e t e s c o n t a i n h g ggbs, t o l e r a t e d g r e a t e r a l k a l i
c o n t e n t s without expanding. T h i s e f f e c t was inore
--``,`,-`-`,,`,,`,`,,`---
pronounced f o r h i g h e r p r o p o r t i o n s of ggbs.
6. UK Design Rules f o r t h e u s e o f ggbs t o avoid ASR, appear

t o be based on a n i n c o r r e c t h y p o t h e s i s , and underestimate
t h e e f f e c t i v e n e s s of g g b s , p a r t i c u l a r l y a t h i g h e r
replacement p e r c e n t a g e s .
1. Hogan, F.J., "The E f f e c t o f B l a s t f u r n a c e S l a g Cement on

A l k a l i Aggregate R e a c t i v i t y : A L i t e r a t u r e Review", Cement
Concrete and Aggregates, Vol 7 , No.2, pp 100-107, 1983.
2. Nixon, P.J. and Sims, I., "RILEM TC106 A l k a l i Aggregate

Reaction-Accelerated T e s t s , I n t e r i m Report and Survey of
National S p e c i f i c a t i o n s " , Proceedings of t h e Ninth
I n t e r n a t i o n a l Conference on Alkali-aggregate Reaction i n
Concrete, pp 731-738, 1992.
3. UK Concrete S o c i e t y , "Alkali-Silica Reaction : Miniinising

t h e Risk of Damage", Technical Report No.30, 1987.
4. UK Building Research Establishment, "Alkali Aggregate

Reactions i n Concrete", Digest 330, 1988.
5. B r i t i s h Standards I n s t i t u t i o n , "Testing Aggregates : Alkali-

S i l i c a R e a c t i v i t y : Concrete Prism Method", D r a f t f o r p u b l i c
comment, 88/11922DC, 1988.

A C 1 SP-153 VOL+II 95 W 0662949 0523989 795 W
6. Sims, I., and Higgins, D.D., "The Use of GGBS to prevent ASR
Expansion caused by üK Flint Aggregates",Proceedings of the
Ninth International Conference on Alkali-aggregate Reaction
in Concrete, pp 175-183, 1992.
7. Thomas, M.D.A., private communication 1992.
TABLE 1 - REQUIREMENTS UNDER WHICH SLAG CEMENTS CAN

BE USED AS A PRECAUTION AGAINST ASR (EQUIVALENT TO LOW-
ALKALI CEMENT)
- Maximum sodium Maximum sodium
I_-
% ggbs oxide equivalent oxide equivalent

of cementitious of Portland cement
~-
-___ component only
Germany > 50 1.1%
> 65 2.0%
Belgium < 50 0.9%

> 50 1.1%
France
UK
>
>
>
60
80
50
II 1.1%
2.0%
1.1% I -
Japan
South Africa
I- I --
'-I indicates:no requirement
--``,`,-`-`,,`,,`,`,,`---
TABLE 2 - ALKALI CONTENT OF CEMENTITIOUS MATERIALS

--
I
I Sodium oxide eqi ,alent content
I
l
Nominal Measured
Portland cement 'H' 1.20% 1.15%

Portland cement ' M i O. 87% 0.87%
Portland cement 'L' 0.60% 0.54%
GGBS 0.87% O. 83%

GGBS 0.45% 0.58%

A C 1 SP-I153 VOL*II 95 m Ob62949 0523990 407
TABLE 3 -CONCRETE MIXES

a l k a l i from
total alkali total PC and K SO
Mix PC
used
ggbc
used
% ggbs cementitious from K2SO4 alkali plus bal$ 04
a l k a l i from
ggbs
(kg/m3) (kg/m3) (Kg/m3) (Kg/m3)
5HO H - O 417 O 4.8 4.8

5Hh25 H h 25 496 O 5.3 4.8
58125 H 1 25 523 O 5.2 4.9
5Hh50 H h 50 612 O 6.1 4.8
5H150 H 1 50 702 O 5.9 5
5Hh70 H h 70 752 O 7 4.8
5H170 H 1 70 966 O 7 5.2
6H0 H - O 500 O 5.8 5.8
6Hh25 H h 25 595 O 6.4 5.7
68125 H 1 25 627 O 6.3 5.8
6Hh50 H h 50 7 34 O 7.3 5.7
--``,`,-`-`,,`,,`,`,,`---
6H150 ti 1 50 842 O 7.1 6
6Hh70 H h 70 903 O 8.4 5.7
6H170 H 1 70 1000 O. 8 8 6.1
7H0 H - O 583 O 6.7 6.7
7Hh25 H h 25 694 O 7.4 6.7
7H125 H 1 25 732 O 7.3 6.8
7Hh50 H h 50 856 O 8.5 6.7
7Hl50 H 1 50 982 O 8.3 7
7Hh70 H h 70 1000 0.4 9.7 6.8
7H170 H 1 70 1000 1.8 9 7.1
8HO H - O 667 O 7.7 7.7
8Hh25 H h 25 793 O 8.5 7.7
88125 H 1 25 837 O 8.3 7.8
8Hh50 H h 50 979 O 9.7 7.7
8H150 H 1 50 1000 0.9 9.4 8
8Hh70 H h 70 1O00 1.4 10.7 7.8
8H170 H 1 70 1000 2.8 10 8.1
5MO M - O 575 O 5 5
5Mh25 M h 25 657 O 5.7 5
5M125 M 1 25 705 O 5.6 5.1
5mSO M h 50 766 O 6.5 4.9
SM150 M 1 50 913 O 6.4 5.2
5Mh70 M h 70 884 O 7.4 4.9
5M170 M 1 70 1000. O. 8 7.2 5.3
6MO M - O 690 O 6 6
6Mh25 M h 25 788 O 6.8 6
6M125 M 1 25 847 O 6.7 6.1
6Fíl-150 M h 50 920 O 7.8 5.9
6x150 M 1 50 1000 0.5 7.6 6.2
6Mh70 M h 70 1O00 0.3 8.7 5.8
6Ml70 M 1 70 1000 1.8 8.2 6.3

A C 1 S P - 1 5 3 VOLrII 95 0662947 052l199L 3 4 3
TABLE 3 - CONCRETE MIXES (CONT’D.)

a l k a l i from
total alkali total PC and K SO
41ix
used
PC ggbs
used
% ggbs cementitious from K2S04 a l k a l i p l u s halg 04
a l k a l i from
7MO M - O 805 O 7 7
7Mh25 M h 25 920 O 7.9 7
7M125 M 1 25 988 O 7.8 7.1
7Mh50 M h 50 1000 0.5 9 6.9
7m50 M 1 50 1O00 1.5 8.6 7.2
7Mh70 M h 70 1000 1.3 9.7 6.8
7Mi70 M 1 70 1000 2.8 9.2 7.3
8MO M - O 920 O 8 8
8Mh25 M h 25 1O00 0.4 9 8
8M125 M 1 25 1O00 0.9 8.8 8.1
8Mh50 M h 50 1000 1.5 10 7.9
8M150 M 1 50 1000 2.5 9.6 8.2
8Mh70 M h 70 1000 2.3 10.7 7.8
8Mi70 M 1 70 1000 3.8 10.2 8.3
5LO L - o 833 O 4.5 4.5
5Lh50 L h 50 966 O 6.6 4.6
6LO L - o 1000 O 5.4 5.4
6Lh50 L h 50 1000 0.8 7.7 5.6
7LO L - o 1000 1.0 6.4 6.4
7Lh25 L h 25 1000 1.4 7.5 6.5
7Lh50 L h 50 1O00 1.8 8.7 6.6
7Lh70 L h 70 1000 2.2 9.6 6.7
5.5HO H - O 458 O 5.3 5.3
5.75HO H - O 479 O 5.5 5.5
5.5Hh25 H h 25 545 O 5.8 5.3
6Hh35 H h 35 644 O 6.7 5.7
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 V O L J I I 95 0 0662949 0523992 2ôT O
TABLE 4 - EXPANSION (PERCENT) OF MIXES THAT HAVE

EXPANDED MORE THAN 0.05 PERCENT
1 0.5 1
STORED AT 38OC
2
YEARS
3 3.5 4 0.5 1
CMRED AT 20°C
2
YEARS
3 3.5 4
5MO 0.08 0.02 0.23 0.34 0.01 0.02 0.07 0.09

5Mh25 0.03 0.13 0.13 0.18 Below .O4
5M125 0.02 0.14 0.2 0.23 O 0.02 0.06 0.06
5M150 0.02 0.03 0.07 0.05 Below .O4
5Lh25 O 0.02 0.06 0.06 Below .O2
680 0.3 0.33 0.36 0.33 0.36 0.35 0.02 0.1 0.17 0.19 0.29 0.28
6Hh25 0.1 0.21 0.23 0.22 0.27 0.26 O O 0.08 0.13 0.15 0.17
68125 0.02 0.07 0.12 0.11 0.14 0.15 O O 0.02 0.03 0.04 0.05
6MO 0.26 0.36 0.39 0.41 0.46 0.47 O 0.6 0.23 0.32 0.34 0.34
6Mh25 0.01 0.07 0.23 0.26 0.28 0.27 O 0.01 0.03 0.07 0.09 0.11
6M125 0.03 0.19 0.29 0.33 0.34 O 0.01 0.04 0.13 0.15
6Mi.50 O 0.03 0.07 0.09 0.12 O 0.01 0.02 0.02 0.04
6Mh70 O 0.02 0.06 0.06 0.07 O 0.01 0.02 0.03 0.03
780 0.36 0.38 0.37 0.38 0.39 0.38 0.03 0.08 0.24 0.3 0.34 0.34
7Hh25 0.19 0.32 0.37 0.37 0.33 0.37 0.02 0.03 0.19 0.21 0.24 0.28
78125 0.17 0.32 0.33 0.33 0.33 0.37 0.02 0.03 0.25 0.22 0.23 0.24
7Hh50 0.01 0.03 0.04 0.08 0.09 0.11 0.01 0.02 0.04 0.04 0.04 0.05
7H150 0.02 0.03 0.06 0.03 0.04 0.09 0.01 0.02 0.02 0.04 0.03 0.04
7670 0.01 0.02 0.06 0.06 0.05 0.01 0.01 0.02 0.01 0.01
7MO 0.46 0.52 0.5 0.53 0.54 0.61 0.06 0.17 0.42 0.5 0.59 0.59
7Mh25 0.27 0.37 0.48 0.47 0.5 0.5 0.03 0.05 0.14 0.21 0.31 0.32
7Ml25 0.08 0.22 0.39 0.41 0.47 0.42 0.02 0.03 0.05 0.11 0.14 0.16
7LO 0.04 0.2 0.23 0.26 O 0.03 0.14 0.2
7Lh25 0.01 0.04 0.08 0.08 Below .O3
8HO 0.38 0.39 0.4 0.44 0.43 0.02 0.11 0.25 0.43 0.46 0.46
8Hh25 0.18 0.32 0.4 0.38 0.38 0.41 0.02 0.04 0.18 0.29 0.33 0.37
ßH125
. ~~. 0.1 0.22 0.32 0.33 0.36 0.02 0.03 0.08 0.15 0.18
8Hh50 O 0.03 0.11 0.1 0.1 O 0.02 0.03 0.03 0.05 0.05
8MO 0.4 0.52 0.57 0.53 0.52 0.04 0.1 0.29 0.38 0.41 0.42
8Mh25 0.03 0.25 0.29 0.3 0.02 0.03 0.1 0.13 0.19
8M125 0.03 0.15 0.3 0.32 0.28 O 0.04 0.08 0.13 0.16
1
--``,`,-`-`,,`,,`,`,,`---
8Mh50 0.01 0.02 0.08 0.08 Below .O5

8Ml50 O 0.02 0.08 0.08 0.1 Below .O3
5.7580 0.15 0.23 0.29 0.29 O 0.01 0.14 .I4
5.5HO 0.11 0.28 0.21 0.23 O 0.01 0.10 .I4
5.5Hh25 O 0.05 0.08 0.07 -.o1 o o o

A C 1 SP-153 V O L * I I 95 W 0662747 0523993 116 W
c
U
Fig. 1-Months to 0.1 percent expansion
100
I NOT EXPANDINQ x EXPANüINQ
00
ao
70
eo
L
so
40
i ,-e
.c,
. I
,. j
30
>Q<ix x x x
I :
jare,&j >o(>o(j >o(
20 . /
i’
: I
I:
10 <:
I:
--``,`,-`-`,,`,,`,`,,`---
O ”.”. I
Y “
T
“ Y ”
r
3
‘’ T I I
1 5 6 7 8 9 io li
Fig. 2-Reactive alkali calculated assuming full contribution

from GGBS

A C 1 SP-153 VOL+II 95 II 0662949 0523994 052 H
100
90
80
v) ?O
--``,`,-`-`,,`,,`,`,,`---
8
U 60
5 so
YU 40
w 30
n.
20
lo
O
3 4 5 0 7 8 9
CALCULATED ALKALI (0.5 OF QGBS)
Fig. %Reactive alkali calculated assuming half contribution

from GGBS
lWL 1 NOT EXPANDINQ x EXPANDING

@o
80
?O
80
50
-
I:
O 1 I
P
".Y
71 * "
"Td '.
" U
'\
*
T "'-*T
2 3 4 5 0 7 8 I
ALKALI FROM OPC AND K2S04 ONLY

Fig. &Reactive alkali calculated assuming no contribution
from GGBS
A C 1 SP-153 VOLaII 95 IObb2949 0523995 T 9 î m
SP 153-54
Efficiency of Finely Ground

Blast Furnace Slags in
High-Strength Mortars
by Y. Ohama, J. Madei, and K. Demura
Synopsis: The efficiency of finely ground blast-furnace slags (BFS) is studied in

relation to the fundamental physico-mechanical and structural properties of
cement mortars. A positive effect of BFS fineness on the workability of fresh
mortars is proved. Due to a small water content (20 % by mass of the
cementitious material) when combined with a high-range water-reducing
admixture (HRWRA), the compressive strengths of mortars ranging between 80
and 100 MPa are ascertained at normal curing conditions. Special curing
conditions such as autoclaving or hot water curing produce the specimens with
compressive strengths in the range of 1 O0 to 130 MPa, depending on the grading
of BFS and the compositions of the binder. With additional heat curing, the
compressive strength of the mortars increase, in general, by about 10 to 50 %
over that of either autoclaved or hot water cured mortars. In the paper, some
other properties of high-strength mortars incorporated finely ground BFS are
discussed, including porosity and durability investigations. The efficiency of BFS
addition is compared with other fine mineral powders such as silica fume and fine
silica powder, with special attention paid to binder compositions and curing
conditions.
--``,`,-`-`,,`,,`,`,,`---
Kevwords: Binders (material); blast furnace slag; compressive strength;

curing; durability; high strength mortars; porosity; silica fume; workability

A C 1 SP-153 V O L M I 1 95 W Obb2949 052199b 925 m
1032 Ohama, Madej, and Demura
AC1 member Yoshihiko Ohama is a professor of architecture at the College of

Engineering, Nihon University, Koriyama, Japan. He is a chairman at the
Department of Architecture. He has actively been involved in the research and
development of concrete-polymer composites for over 3O years. He is specialized
in fiber-reinforced and superhigh-strength concrete. He is vice-president of ICPIC
and a member of RILEM, ASTM, AIJ, JSMS, SAMPE, JCI and JTTAS
Committees.
Jan Madej is a senior research engineer at BETON W I S Co., Ltd., Bratislava,

Slovakia. He is specialized in the chemical aspects of building materials and
industrial by-products considered for use in concrete. He has ben involved with
research on durability and deterioration of concrete with mineral additives and
artificial aggregates.
AC1 member Katsunori Demura is a lecturer of architecture at the College of

Engineering, Nihon University, Koriyama, Japan. He has been involved with
research on concrete-polymer composites, fiber-reinforced concrete and
superdurable concrete for about 15 years. He is a member of RILEM, AIJ, JSMS,
JCI and JTTAS Committees.
INTRODUCTION
Materials such as fly ash, silica fume and blast-furnace slags are produced
in huge quantities all over the world. Long-term laboratory investigation and
testing have proved the suitability and efficiency of such materials as the
ingredients in cement manufacture or concrete production [i].
In recent years, much attention has been drawn to a development of

high-strength, high-performance, or "super" high-strength cement-based materials
[2-71. The high strengths, however, are closely related to the materials of high
--``,`,-`-`,,`,,`,`,,`---
quality, using fine mineral powders such as silica fume, and taking into
consideration the mixture proportions, mixing process, curing conditions, etc.
Some data obtained for high-strength concrete using finely ground blast-furnace
slags have also been published [S-121.
In the Laboratories of Nihon University in Koriyama, attempts have been

made on basic investigations of process technology for superhigh-strength
mortars using silica fume. The mortars were prepared using portland cement, fine
aggregates such as silica sands and stainless steel particles, high-purity silica,
silica fume and various HRWRA. It was proved by experiments that
compressive strengths 200 MPa or higher can be obtained under appropriate
process conditions by using these materials [ 13,141.
The present paper deals with the investigation of the suitability of ground
granulated blast-furnace slags of different finenesses for the preparation of
high-strength mortars, applying similar experimental conditions to those in the
above-mentioned laboratory investigation.

i
A C 1 SP-153 VOLS11 45 a Obb2949 0523997 8bL
MATERIALS
The mortars were made at Nihon University laboratories in the summer

of i 992 by using the following materials:
Cement and Silica Sand

Portland cement (PC) and silica sand (1 : 1 silica sand No.4- No.7 mixture)
were used for the preparation of mortars. The producer of cement, ASTM Type
I, was Onoda Cement Co., Ltd., Japan.
Blast-Furnace Slap
The slag of Japanese origin, "Himent", was ground to ifferent finenesses:
4000, 8000 and 15000 cm2/g, respectively.
Silica Fume and Fine Silica Powder

The silica fume (SF) and high-purity silica powder Si-powder), were
used as pozzolanic materials.
Superplasticizer
A commercial HRWRA Mighty 2000 WH was used for mortars
The chemical compositions and fundamental physical properties of

cement and mineral powders used for the experiments, are given in Table I . The
particle size distribution curves for the blast-furnace slags are seen in Fig. 1.
MIXTURE PROPORTIONS
The plain cement mortar (1 00% PC), considered as a control mixture, and the
mortars with a partial cement replacement with either blast-furnace slag (60%
PC + 40% BFS) or with slag and silica fume (60% PC + 30% BFS + 10%
SF) were prepared with a binder to sand ratio of 1: 1. In addition, two mixtures - a
combination of fine silica powder and silica fume (60% PC + 30% Si-Powder +
10% SF) and cement replacement with the silica fume (90% PC + 10% SF) were
prepared. The proportioning of the mixtures is summarized in Table 2 .
PREPARATION OF SPECIMENS
The mortars were prepared using a laboratory Omni mixer. In the mixing
process, particle being mixed are tossed upwards from the bottom of the drum by
cyclic rebound of the rubber bowl. As a result, the Omni mixer increases
efficiency and ensures a homogeneous mixture.
The fine mineral powders were added with cement and sand, and
homogenized in the mixer for 3 minutes. The HRWRA was added to the mixing
water. The total mixing time was 6 minutes.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOLtII 95 0662949 052L998 7 T ô
The mortar specimens for compressive and flexural strengths and for the
additional tests (for carbonation and chloride-ion penetration) were cast in
two layers, and compacted on a vibration table with a vibration of 25 Hz. The
specimens in the molds were then cured in a moist room, maintained at 20" C
and 80% R.H. for 48 hours. After demolding, the mortar specimens were
subjected to the following different curing conditions:
a) normal curing, cured in water at 20" C for 7, 28 and 90 days;

b) autoclave curing, cured in an autoclave at a maximum temperature of 180" C,
under a pressure of 1MPa for 3 hours;
c) hot water curing;, cured in hot water at 70" C for 24 hours.
--``,`,-`-`,,`,,`,`,,`---
Additionally, in the case of autoclave curing and hot water curing, separate
specimens were subjected to heat curing at 200" C for 24 hours.
Several testing methods were used
-comoressive and flexural strenpth tests, using mortar specimens 4 0 x 4 0 160

~ mm;
-accelerated carbonation test ; two opposite faces of the mortar specimens

40x40~160mm were coated with an epoxy-resin paint, placed in a sealed
pressurized vessel, evacuated to 667 Pa or less at ambient temperature for
30 minutes, and then exposed to CO, gas with a pressure of 1MPa for 7
and 14 days, respectively. After accelerated carbonation, the mortar
specimens were split, and the split crosssections were sprayed with a 1%
phenolphthalein alcoholic solution. The depth of rim of each crosssection
without color change after spraying with phenolphthalein solution was
measured with slide calipers as a carbonation depth as shown in Figure 7;
- chloride-ion penetration test; two opposite faces of the mortar specimens

40x40~160mm were coated with an epoxy-resin paint by using the same
procedure as in the case of the mortar specimens for the carbonation test, and
immersed in a 3.5% NaCI solution at 20" C for different periods. After
immersion, the specimens were split, and the split crosssections were
sprayed with a 0.1% sodium fluorescein solution and a O.1N silver nitrate
solution as prescribed in UNI 7928 (Concrete- Determination of the
Chloride Ion Penetration). The depth of the rim of each crosssection that
changed to white color was measured with slide calipers as a chloride-ion
penetration depth as shown in Fig.2;
- determination of the pore-size distribution was made on selected mortar

specimens, using a Carlo Erba Mercury porosimeter serie 700, supplied
with a computer program for analyzing the data obtained. The hydration
process of the specimens was stopped by the acetone;

A C 1 SP-153 V O L X I 1 95 E Ob62949 0523999 b3Y M
- investigation of the morpholosy was made on selected mortar specimens,

using a model S-5 1O HITACHI Scanning electron microscope.
TEST RESULTS AND DISCUSSION
Workability
Fresh mortars were proportioned to have a constant water-cementitious

material ratio (w/c=0.70) and a constant content of HRWRA (3.0 % by
mass). Fig.3 shows the influence of the fineness of blast-furnace slag on the
workability of the fresh mortars. The flow of the mortars was improved by
partial cement replacement with finely ground BFS, being positively affected by
--``,`,-`-`,,`,,`,`,,`---
the fineness of BFS. Except for plain mortar, all the mortars give a good
workability, even at relatively low wic.
A combination of BFS with SF provides a positive effect on the

workability of fresh mortars (compared to BFS replacement) only when using
BFS with a specific surface of 4000 cm2/g. The fì-esh mortars composed of ves.
fine slag (S15)either alone (Mixture No.4) or combined with SF (Mixture No.7)
were thixotropic. In this case, the flow measurements are not considered by the
authors to be an appropriate test for the measurement of the workability of the
fresh mortars.
It is assumed that, besides the positive effect of fine mineral powders

(concerned also with their excellent redispersion in the mortars), the special
mixing procedure by using Omni mixer had a decisive influence on the
workability of the mortars.
Compressive Strength of Mortars Cured in Normal Curing Conditions
The compressive strengths of mortars after demolding and after curing in

normal conditions are given in Table 3 .
The early-age (Le., 2- and 7- day) strengths of the mortars with BFS are
either lower than or comparable with those of plain mortar. An increase in the
curing period proves to have a positive effect on the strength development.
This increase is higher for the mixtures containing BFS with higher specific
surface.
The compressive strength results obtained are in an agreement with many

other reported test results on the mechanical properties of mortars or concretes
with slags or pozzolans. It is well known that in the course of pozzolanic reaction
the cement hydration, the pore structure formation and, subsequently, the
fundamental physico-mechanical and structural properties of cement-based
materials are positively influenced by the fineness of the slags or pozzolans,

A C 1 SP-153 V O L a I I 95 m Obb2949 0522000 T 5 4 m
depending on the hydration time, the curing conditions, the mixture proportions,
etc. [14-161. A densification of the structure due to the mixing process, a
dispersion of fine particles, and a low amount of water, respectively, are
considered to be the main reasons of the high strength obtained.
Compressive StrenMh of Mortars Cured at Elevated Temperatures
From Table 4 and Fig.4, it is seen that special curing conditions such as
autoclave curing or hot water curing result in an increase in the compressive
--``,`,-`-`,,`,,`,`,,`---
strength on a level comparable or higher as' for the corresponding mortars
cured in water for 28 days. The strength obtained is markedly influenced by the
slag fineness: the finer slag used as partial cement replacement, the higher the
strength is obtained.
The compressive strength gain (expressed as the percentage of the plain

mortar) for individual mortars with addition of finely ground BFS is illustrated in
Fig.5. While the strength gains of autoclave-cured mortars seem to be
comparable for both BFS and BFS-SF blends, hot water curing is considered
to be preferable in the case of BFS-SF combination as shown in Fig.5. A similar
effect is seen for the flexural strength in Fig.6.
With additional heat curing (200O C for 24 hours) the compressive

strength of autoclaved or hot water cured mortars increases to the level ranging
between 104 and 156 MPa as shown in Table 4 and Fig.4. The use of very fine
BFS with the specific surface 15000 cm2/g shows that the compressive and
flexural strengths are comparable with SF or its combination with Si-Powder as
seen in Fig.7.
The test results obtained are in good agreement with the earlier results
obtained by Ohama et al. [13,14], Wise et al. [18] and Roy et al.[l9]. In some
other references (e.g.,[20]), however, a decrease in the mechanical properties of
the concretes subjected to elevated temperatures is reported. It is supposed that
a positive change in the phase compositions and pore-structure formation has a
decisive influence on the strengths achieved.
It is proved by the experiments, that under some conditions very finely

ground BFS might be used for the preparation of very high-strength
cement-based materials.
fi
The distribution of micropores in the plain mortar and the mortars with
partial cement replacement with BFS with different fineness (surface area
4000, 8000, and 15000 cm2/g), cured in water for 7 and 28 days, respectively,
is represented in Fig. 8. The pore-size distribution curves of the mortars clearly
show a decrease in the volume of the micropores (i.e., the pores with diameter

A C 1 SP-153 VOL*II 95 m Ob62949 0522001 990 m
in the range 3.75 to 7500 nm) with hydration time. Due to a relatively small
w/c (0.20), the volume of microporès is extremely low compared to other data.
With BFS addition the pore volume of the mortars decreases in comparison to
the pore volume of the plain mortar at the same curing period. The role of BFS
addition in the process of portland cement hydration, being influenced markedly
by the grain size of BFS, is well known and thus, many earlier results are
confirmed.
Presence of unhydrated grains of cement were observed in the structures

of the mortars by scanning electron microscopy. The structures were dense,
composed dominantly of calcium silicate hydrates, corresponding to the Type III
--``,`,-`-`,,`,,`,`,,`---
of Diamond’s classification [21]. The unreacted particles of cement or BFS were
well visible after 2 days and 28 days of hydration, respectively. After 28 days of
hydration, the fibrous products appeared visible inside the pores.
Carbonation
The results of the carbonation depth measurements show an extremely

high resistance of the mortars specimens to CO, difision. Even in the case that
a pressurizing method was applied for a relatively long period (7 and 14
days), the carbonation rim in all mortars did not reach a level of 2-4 mm. It is
considered that relatively low diffisivity of CO, is influenced positively by the high
density of the mortars as well as a relatively small amount of calcium hydroxide
available, even in the plain mortar.
Chloride-Ion Penetration
The results of the chlorideion penetration of mortars through

immersion in a 2.5% NaCl solution are summarized in Table 5. Though the
results showed a relatively small diffusion of chloride ions into the mortars
cured before immersion in water, the chloride-ion penetration was well visible
for the heat-cured mortars. It is proposed that a lack of water due to the drying
of the mortars and thus, a relatively high water absorption, are the main
reasons for the higher chloride penetration depth of the heat-cured mortars
compared to the mortars cured in water. Supplementary tests provided in a
more comprehensive research program confirmed the effect of additional heat
curing on water absorption, caused also by some defects at the cement paste
aggregate interface [22].
Nevertheless, the results obtained show the strong positive effect of the
addition of fine BFS on the chloride-ion penetration. Long term laboratory
investigations and a more comprehensive analysis related to the phase
compositions and the pore structure formation are expected to provide a
better knowledge and explanation of the results obtained.

A C 1 SP-153 VOLtII 95 M Obb2949 0522002 8 2 7 =
CONCLUSIONS
1. The workability of fresh mortars with a low w/c (0.20) is improved by the
partial replacement of cement with finely ground BFS. The positive effect of
BFS fineness under experimental conditions is obvious in this respect.
2. The early-age compressive and flexural strength of mortars are influenced

negatively by partial cement replacement either with BFS or BFS-SF
combination. The late-age compressive and flexural strengths, however, are
comparable or higher for blended mortars. A saving of cement is possible
even in high- strength mortars. The positive improvement due to the use of
fine BFS is clear. The strength gain obtained using very fine BFS with a
specific surface of 15000 cm2/g is considered to have comparable effects to
the fine mineral powders such as SF and Si-Powder.
3 . Special curing conditions such as autoclave curing and hot water curing
gives the mortars with compressive strengths in the range of 100 to 130
m a , depending on the grading of BFS and the compositions of the binder.
With additional heat curing, the compressive strength of the mortars
increases by about 10 to 50% over that of either autoclave- or hot water-
cured mortars.
--``,`,-`-`,,`,,`,`,,`---
4. The characteristics of microstructure and pore stnicture formations in
mortars are influenced markedly by the addition of finely ground BFS. The
finer the BFS used as a partial cement replacement, the denser the
structur achieved. This structure is composed predominantly of calcium
silicate hydrates.
5 . The high-strength mortars exhibit high density and an extremely low difisivity
to CO, . Additional heat curing, though resulting in very high strength
(compressive strength ranging between 135 and 155 m a ) , causes higher
water absorption, and thus lower resistance to chloride-ion penetration
compared to normally cured mortars or concretes.
ACKNOWLEDGMENTS
The Authors gratefully acknowledge the support of the Matsumae

International Foundation in Tokyo under MIF fellowship 1993-3 Special
thanks are given to Mr Masanao Kimura from the Hitachi Cement C o , Ltd ,
I
Japan, for his cooperation and assistance in the preparation of the slags used for
the expenments

A C 1 SP-153 VOL*II 95 m 0662'797 0522003 763 m
--``,`,-`-`,,`,,`,`,,`---
REFERENCES
1 . Malhotra, V.M.(Editor) "Fly Ash, Silica Fume, Slag and Natural Pozzolans
in Concrete", Proceedings of the Fourth International Conference, Istanbul,
Turkey, 1992. SP- 132, American Concrete Institute, Detroit, 1993.
3. AC1 Committee 363, State-of-the-Art Report on High-Strength Concrete,

AC1 363R-84. AC1 Journal, Vol. 81, No. 4, July-August 1984, pp. 364-41 1.
3 . Burg, R.C. and Ost, B.W., "Engineering Properties of Commercially

Available High-Strength Concretes", Research and Development Bulletin
RD 104T, Portland Cement Association, Skokie, 1993, 55p.
4. Read, P., Carette, G G. and Malhotra, V.M., "Strength Development

Characteristics of High-Strength Concrete Incorporating Supplementary
Cementing Materials", CANMET/ACI International Workshop on the Use of
Silica Fume in Concrete, CANMET, Ottawa, 1991, pp.83-1 10.
5 Jennings, H M , "Advanced Cement-Based Matrices for Composites", High

Performance Fiber Reinforced Cement Composites (Edited by
H W Reinhardt and A E Naaman), RILEM, Cachan, France, 1992, pp 3-17
6 Bache, H H , "Densified CemenWltrafine Particle - Based Matenals", A

Paper Presented at the Second International Conference on Superplasticizers
in Concrete, Ottawa, June 10-13, 1981
7. Touse, S.A., Bier, T.A., Knepfler, C.A., Young, J.F. and Berger, R.L., "Pore
Structure of Low Porosity DSP Cement Pastes", Materials Research
Society Symposium Proceedings, Vol. 137 (Edited by L.R. Roberts and J.P.
Skalny), Materials Research Society, Pittsburgh 1989, pp.449-456.
8. Baalbaki, M., Sarkar, S.L., Aitcin, P.C., and Isabelle, H., "Properties and
Microstructure of High-Performance Concrete Containing Silica Fume, Slag,
and Fly Ash", Ref.1, pp.931-942.
9. Yurugi, M., Mizobuchi, T. and Terauchi, T., "Utilization of Blast-Furnace

Slag and Silica Fume for Controlling Temperature Rise in High-Strength
Concrete", Ref 1, pp. 1433-1450.
lO.Djellouli, H., Aitcin, P.C., and Chaalal, O.: "Use of Ground Granulated Slag
in High-Performance Concrete", Proceedings of the 2nd Symp. on
High-Strength Concrete, SP- 121, American Concrete Institute, Detroit,
pp.35 1-368.
ll.Sakai, K., Watanabe, H., Suzuki, M. and Hamazaki, K., "Properties of

Granulated Blast-Furnace Slag Cement Concrete", Ref. 1, pp. 1367-1383.

A C 1 SP-153 V O L X I I 95 m 0 6 6 2 9 4 9 0522004 bTT m
12.Nakamura, N., Sakai, M. and Swamy, R.N., "Effect of Slag Fineness on the
Development of Concrete Strength and Microstructure", Ref. 1, pp. 1343-1366.
13.0hama, Y., Demura, K. and Lin, Z., "Effect of Mix Proportions and Curing
Conditions on Strength Properties of SuperHigh-Strength Mortars", (in
Japanese)CAJ Proceedings of Cement and Concrete, No.44,1990,pp.582-587.
14.0hama, Y., Demura, K. and Lin, 2.: "Development of Super-High-Strength

Mortars Using Silica Fume", Proceedings of the Concrete for the Nineties,
International Conference on the Use of Fly Ash, Silica Fume and Other
Siliceous Materials in Concrete (Edited by W.B. Butler and I. Hinczak),
Sydney, Australia, 1990.
15.Uchikawa, H., "Effect of Blending Component on Hydration and

Structure Formation", Principal Report, Proceedings of the 8th
--``,`,-`-`,,`,,`,`,,`---
International Congress on the Chemistry of Cement, Vol. 1, Secretaria Geral

do 82 CIQC, Rio de Janeiro, Brazil, 1986, pp.249-380.
16.ACI Committee 226, "Ground Granulated Blast-Furnace Slag as a

Cementitious Constituent in Concrete", AC1 226.1R-87, AC1
Materials Journal, Vol. 84, No. 4, July -August 1987, pp.327-342.
17.hchardson, I.G., Wilding, C.R. and Dickson, M.J., "The Hydration of

Blastfurnace Slag Cements", Advances in Cement Research, 1987, Vol. 2,
NO. 8, pp.147-157.
18.Wise, S., Satkowski, J.A., Scheetz, B., Ritzer, J.M., Mackenzie, M.L. and
Double, D.D., "The Development of a High Strength Cementitious
ToolingMolding Material", Very High Strength Cement-Based Materials,
Materials Research Symposium Proceedings vo1.42, Materials Research
Society, Pittsburgh, 1985, pp.253-263.
19.Roy, D.M., White, E.L., and Nakagawa, Z., "Effects of Early Heat of
Hydration and Exposure to Elevated Temperatures on Properties of Mortars
and Pastes with Slag Cement", Temperature Effects on Concrete (Edited by
T.R.Naik), STP 858, American Society for Testing and Materials,
Philadelphia, 1985, pp. 150- 167.
20.Nasser, K.W. and Chakraborty, M., "Temperature Effects on Strength and

Elasticity of Concrete Containing Admixtures", Ref. 19, pp. 1 18-123.
21 .Diamond, S., "Cement Paste Microstructure: An Overview at Several

Levels", Proceedings of the Conference on Hydraulic Cement Pastes: ~
Their Structure and Properties, Sheffield, England, 1976, pp. 2-30.
22.Madej, J., "Investigation of Industrial Slags Suitable for Use in High-Strength

Concrete", Technical Report, Fellowship Research Report 1992, The
Matsumae International Foundation, Tokyo, pp.95- 177.

A C 1 SP-153 V O L X I I 95 = 0662949 0522005 536 m
PROPERTIES OF CEMENT AND MINERAL POWDERS USED FOR

EXPERIMENTS
Type of material
Chemical compositions Silica Fine
snd physical property fume silica
powder
I I I I
SF bpowdei
Loss on ignition 0.0

insoluble residue o. 1
21.8 33.9 89 8 99 8
5.2 15.5 02 O0
2.8 0.8 -
64.3 42.5 04 trace
1.6 5.9 - -
2.0 0.0 - -
0.5 0.3 07 trace
0.2 trace
-
2 20 2 60
Surface area (Blaine),
28320* 4620
Average particle size,
0.20 3.50
Note: * Determined by BET method
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 Ob62949 0522006 472
TABLE 2 - MIXTURE PROPORTIONS AND PROPERTIES OF FRESH

MORTARS
IRWRA Composftions of bnder Unit Flow

:onterit Si- weight
PC BFS SF POW-
der
(Y*by mass) kgh'
1:l 20 3.0
TABLE 3 - COMPRESSIVE STRENGTH OF MORTARS CURED IN

NORMAL CURING CONDITIONS
MIX- Curing time

ture Type of mortar BFS /
2 days * ] 7 days 28 days f 90 days
No I
Compressive strength, MPa
--``,`,-`-`,,`,,`,`,,`---
1 Plain (100% PC) 55.5 71.9 81.5 92.8

2 S, 32.1 65.6 85.5 96.6
3 40%BFS 43.0 78.7 96.9 100.2
4 SIS 52.7 81.9 100.7 110.7
5 S, 44.8 70.8 92.3 106.8
6 30% BFS +lo% SF 50.6 77.0 98.3 107.0
7 SM 55.5 83.6 103.2 115.1
8 30% Si-powder+lO% SF - 34.0 76.2 105.4 116.2
9 10%SF 53.4 80.0 101.7 111.4

A C 1 SP-153 VOL*II 75 = Obb2747 0522007 307 =
TABLE 4 - COMPRESSIVE STRENGTH OF MORTARS CURED AT

ELEVATED TEMPERATURES
Plain (I 00% PC) - 42 12 10 7 passing passing

56 13 11 7 passing passing
28 O0 O0 04 O0
S, 42 O0 23 60 O0
56 O0 26 12 6 33
28 O0 O0 O0 O0
--``,`,-`-`,,`,,`,`,,`---
60%PC+40%BFS sa 42 O0 O0 O0 O0
56 O0 O0 23 10
28 O0 O0 O0 O0
SLS 42 0.0 O0 O0 O0
56 O0 O0 O0 O0

A C 1 SP-153 V O L U I I 95 E 0662949 O522008 245
I O0
80
60
40
20
--``,`,-`-`,,`,,`,`,,`---
Diameter of particles, pm
Fig. 1-Particle-size distribution curves for blast furnace slags

used for experiments
(Unit ; mm)
A,B,C,D$ and F:
Measured for Carbonationor Chloride
Ion Penemtion Depth, and Averaged.
Fig. 2-Cross section of specimen after

carbonation or chloride-ion penetration
test

A C 1 SP-I153 V O L X I I 95 E 0662949 0522009 L ô L M
24 0 - 60% PC+30%BFS+lO% SF
-
......................... i ............................ j ....................... i............................

160
1 4 0 (L ........................ :. . . . . . . . . . . . . . . . : ..................... :........................

y ;
Piaini mortar j
I I I
120
Specific surface of BFS, cm*&
Fig. &Influence of fineness of blast furnace slags on

workability of fresh mortars
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L J I I 95 m 0662749 0522030 9T3 I
160
...............................
140
0 120
n
5
f' 100
F
k
0
80
*i
o.
60
ofE 40
20
O
Plain 40% s4 40%S, . 40% S i s
Type of mortar
160
140
--``,`,-`-`,,`,,`,`,,`---
0 120
I
f 100
F
k 80
5
'g 6 0
2
Q
40
o
20
O
Plain 30% S, 30% Se 30% S r s
+lo% *SF +lo% SF +io% SF
Type of mortar
Fig. 4-Compressive strength of mortars cured in different

conditions
A C 1 SP-153 V O L X I I 95 E 0662949 05220LL 83T E
60% PC + 40% BFS
ò? 40
S ..........................................................................................
0 30
m
5 20
W
C
2 10
c
u>
O
->;- 1 0
al
...................................... .............................
1 Before cure 1-1
~
El
I
2 ............................................................................... U 7-day water
......
o
9.-20
0 -30
......................................................................................
El
26-day water
90-day water
Autoclave
Auloclave+heat
.......
-40
1.B ...................................... ...............................................
1 w%+heat l"...I
-50
60% PC + 30% BFS + 10% SF

50
............................................................................... ......................................
8 40
C ............................... ........................................
*i 3o
m4
................................
20
5
-
m4
E 10
v)
O
1"c
al
.->
:- 1 0 ..................................................................................... .....
L ........................................................................................... 0 7-day watet
o
-
a - 2 0 zü-day water ....
H 90-day waler
........................................................................................... Autoclave .....
-30
-40
I
.........................................................................................
0
G]
W
Auloclave+heat
Hol waler
Hol waler+heal I_,__,
-50
Fig. 5-Compreccive strength gain of mortars with different BFS

additions, cured in different conditions
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 Obb2949 0522012 7 7 6
60% PC + 40% BFS

50
................................................................................................................................................
40
ot .......................................................................................
" 30
.-
C
.......................................................................... .....................
20
5
E
10
Ea o
-E - 1 0
a
x
9) -20
iï
-30 0 Hol water
......................................................................................... Hol waler+heal __,_
-40
-50
60% PC + 30% BFS + 10% SF

50
40
Oe
--
........................................ .......................................
30
C
E 20
--``,`,-`-`,,`,,`,`,,`---
G
S
10
$
<n
-2 - 1 0
3
0
-.
-
i ._ 1
......................... El
............................................................
I EI Betore cure I
:- 2 0
iï
..............................................................................................
DB1 9û-day water
..................................... W Autoclave
-30 Auloclavetheal
-40
- .................................................. 8 Hol water
Hot waler+heal ....
-50
Fig. &Flexural strength gain of mortars with different BFS

additions, cured in different conditions

A C 1 SP-353 V O L * I I 95 .
I0662947 0522033 b02
10% SF
30% Si-Powder BFs (s,
+lo% SF
50
$ 40
mE 30
Eo
5Eo 20
g
c.
10
UI
O
-> - 1 0
Q)
U
........................ .......
Before cure
2 0 7-day water
E-20 S 28-day water .......
O 90-day waler
Autoclave .......
-30 Autoclave+heat
Hotwater .......
-40 -............................................................................................. W Hot waler+heat
-50
-
El
U
Lo3 - 1 0 ............................................................................... Q Before cure ......
K El 28-day water
_....................................................................................... ......
al - 2 0 E4 90-day water
-30
_ .............................................................................................. Auloclave ......
--``,`,-`-`,,`,,`,`,,`---
Lz) Auloclave+heal
- 4 0 _. [3 Hot water ......

M Hot water+heal
Fig. 742omparison of strength gain of mortars with different

binder compositions

A C 1 SP-I153 VOL*II 95 W O662949 0522014 549 =
1050 Ohama, Madej, and Demora
7-day water cure

- 7
'O
F
.
"E
' 6
m
o 5
I
a 4
L
O
o.
.-20 3
E
- 2
O
-3
E l
O
' O
28-day water cure

N 7
'O
7
. ' 6
o)
"Eo 5
--``,`,-`-`,,`,,`,`,,`---
t 4
O
o.
.-2Eo 3
- 2
O
-E 13
O
' O 5
Radius of micropore , nm
Fig. &Pore-size distribution of mortars cured in water

A C 1 Sp-153 VOL+II 95 m Ob62949 0522035 485
SP 153-55
A Study of the Properties of Portland

Cement Incorpora tin g SiIica Fume
and Blast Furnace Slag
by S. Nagataki and C. Wu
--``,`,-`-`,,`,,`,`,,`---
Svnomis: The workabilit , strength and durability of concrete arc affectcd by
particle distribution a n i chemical composition of cement. So, a cement
which has ideal particle distribution and chemical composition is needed for
making high-pcrformancc concrctc. This kind of cement can be realized by
blending portland cement, silica furne and blast-fumace slag because they
have different particle distributions and chemical coni ositions. In this ?gee
the triple blended cement was cornposed by 1 % silica fume, B
blast-furnace slag and 60% portland cement as it had suitable chernical
composition and the densest particle distribution in portland cement, portland
cement admixed by silica fume or blast-furnace slag in this research.
Thc hydration process of the triplc blended ccment was similar to the
portland cement but the heat of hydration and Ca(0H)z content in the hydrates
wcrc much lower than that for portland ccmcnt. It was found that thc porosity
of the hardened paste was so low that it was half of that in portland cernent
paste. The RzO in its pore solution was only 88% of that in porc solution of
portland cement paste. This fact means thc triple blended cement may reducc
the alkali-silica reaction of concretc.
The flows of the fresh mortars madc by the triple blended cernent were
higher or lower than the flow of the control mortar depending on the specific
surface area of silica fume uscd. The compressive strengths of the mortar wcrc
higher than that of the control mortar as its denser paste. Because of the low
Ca(0H)z content in the hydrates and R z 0 in the pore solution, the resistance
of the mortars to sulfate attack and alkali-silica reaction was high. However,
thc drying shrinkage of the mortars madc with the triple blended cement was
higher than that of the control mortar.
Kevwords: Alkali aggregate reaction; blast furnace slag; blended cements;

chemical analysis; compressive strength; drying shrinkage; flowability;
hardened paste structure; hieh performance concretes; hydration; mortars
(material); particle size distribution; porosity; silica fume; sulfate attack

A C 1 SP-353 V O L a I I 95 m Obb2949 0522036 313 m
1052 Nagataki and Wu
S Nagaiaki, AC1 Fellow, is a professor, Dcpartmcnt of Civil Enginccring,

Tokyo Institutc of Technology. He rcccivcd his doctor of cnginccring dcgrcc
from University of Tokyo in 1966. Hc has wnttcn many papcrs on
fundamental and applied rcscarch on fly ash, silica furnc, slag and other
pozzolans.
C Wu is a research engineer, Dcpartmcnt of Matcnals and Structures,
Nanjing Hydraulic Rescarch Institutc. Hc rcccivcd his mastcr of cnginccring
dcgree from Nanjing Hydraulic Rcscarch Institute in 1986. His main intcrcsts
are cffccts of chemical and mineral admixturcs on propcrtics of concrctc.
INTRODUCnON
Recently, high performance concrctc is bcing spccificd increasingly for

construction pro.iccts. Whcn portland cement only was uscd as the
ccmentitious matcrial for making concrctc, there were somc problcms. For
cxample, to obtain high-performance concrctc, the W/C had to be vcry low
and the quantity of cement in unit volumc of concrete was so high that the risk
of high heat of hydration, alkali-aggrcgate rcaction and rcaction with
chemical attackers also increascd. For this rcason, silica fumc and
blast-fumace slag can be uscd in high-pcrformancc concrctc. They arc not
only supplementary ccmentitious matcnals but arc also of somc bcncfit as
rcgards to workability, strength and durability ( 1-7 ).
The dcnscr the packing of thc ccrncnt, thc Icss is thc dcmand of
mixing water of thc pastc, and thus thc dcnscr is thc hardcncd pastc. The
dcnscst packing of particles was expresscd in an cquation by Andrcascn as
follows:
Whcrc U( DP ) is thc cumulativc pcrccntagc of passing sicvc sizc, DI)

is thc diamctcr and is the biggcst diameter of particlcs. It is shown in
Fig 1 that particlc s i x distribution of portland ccmcnt diffcrs from that of thc
densest packings. And thc diamctcr of silica fumc and blast-fumacc slag arc
smaller than that of portland ccmcnt. So, it is possiblc that a ccmcntitious
material having thc densest packings is composcd by blcnding portland ccmcnt,
silica fume and blast-furnace slag.
The workability, strength and durability of concrete arc influcnccd by
thc contcnt of C3A in ccmcnt as wcll Ca(0H)z and alkali in hardcncd pastc.
If C3A is rcduccd by some of the portland ccmcnt bcing rcplaccd by silica fumc
and blast-fumacc slag as well as a part of Ca(0H)z and alkali in hardcncd
paste arc consumcd by thc silica fumc and blast-fumace slag, the workability, I
strength and durability of the concrctc can be increascd. According to this, it l
is believed that a ccmentitious matcrial having an ideal chernical composition
l
can be made by blcnding portland ccmcnt, silica fume and blast-fumacc slag
This paper rcports the results of an investigation in which thc triple
blcnded cemcnt madc with portland ccmcnt, silica fumc and blast-fumacc slag
was uscd.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L X I I 95 W 0662949 0522037 2 5 8 W
MATERIALS
Ccmcnt
Normal portland cement madc in Japan was uscd. Its physical

propcrtics and chemical analysis are givc in Table 1.
Silica Furnc
Two kinds of silica fume were used. One was obtaincd from China
( S F ) and another was obtaincd from Japan ( SF-JAN ). Their physical
propcrtics and chcmical analysis arc given in Table 2, 3.
Blast-Furnacc Slag
The blast-furnace slag ( BFS ) was obtaincd from Japan. Its physical
propcrtics and chemical analysis are givcn in Table 2, 3.
The sand uscd in mortar was a mix of the standard Togoura sand
( FM=2. 0 6 ), Soma silica sand spccial No. 4 ( FM=3. 2 4 ) and No. 5
. ). Thc mixture proportion was 1 to 1 to 1. ~ h Pyrex
( F M = ~ 90 c used
in the test of the alkali-silica rcaction was madc in Japan and thc size
distribution accorded with the ASTM C4 11-89.
Air-entraining Superplasticizer
A sulfonated naphthalcnc formaldehyde condcnsatc type air-entraining

superplasticizcr of Japancsc origin was uscd.
Physical Properties and Chemical Analvsis
The specific surface arca of the cemcntitious materials was mcasurcd

with thc BET ( Nitrogen Adsorption Mcthod ).
The density of ccmcntitious matcrials was determined using the ASTM C
188-84, exccpt that the kerosene was replaced by water when density of
silica fume was determined.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L U I I 95 Ob62949 O522038 3 9 4 =
The particle size distribution of the ccmcntitious matcrinls was measured

with iaser Diffraction Particle Size Analyzcr aftcr being dispersed by the
ultrasonic equipment for 20 minutes.
The chcmical compositions of the cementitious matcrials werc analyzed
in accordancc with the ASTM C4 11.
Hydration of Ccmcntitious Material
The evolution of hcat of hydration of the cementitious materials at

2 0 "C was measured with Conductivc Micro-Calorimeter, after sample
( watcr/cemcntitious material = o. 50 ) was stirred for 30 seconds.
The non-evaporable watcr of hardened paste was determined by the
*
difference of its weight at 105 5°C and 950 10°C. *
The relative content of Ca(0H)z in the hardcncd paste was measured by
the Powder X-ray Diffraction Analyzer.
Pore Structure and Solution

--``,`,-`-`,,`,,`,`,,`---
The pore structure in hardened mortar was mcasurcd by the mcrcury

porosimctry. The samples Watcr/Cemcntitiou Materials = o. 32,
Sand/Cemcntitious Material = 8.0 in this tcst were dried at 40°C for 7
days after curing in 20°C water for dl days.
The concentrations of Na20 and KzO in the porc solution of the
hardened paste were analyzed with the method of the ion chromatography. The
pore solution was drawn from the hardcncd paste under high pressurc. In this
test, the spccimcns of hardened paste ( Watcr/Ccmcntitious material = o. 50 )
were curcd in plastic bags at 20°C for 28 days.
Properties of Mortar
The mixture proportions for mortars arc given in Table 4. The flow of
fresh mortar was dctcrmined according to the JIS R 5201. The specimens for
com ressivc strength test wcre 50 by 100 mm cylinders. They wcrc curcd in
20'8 water, as soon as they were dcmodclcd after casting for onc da .
The method tcst for alkali-silica reaction was the ASTM C41'1-89
except that the size of the spccimen was 40 by 4 0 by 160 mm prism, 0: 3
6 % of NazO by the weight of the ccmcntitious materials were introduccd in
the mixing water.
The specimens for determining the resistance to sulfate attack wcrc made
according to the ASTM C1012-89, but the specimens werc 40 by 40 by 160
mm prisms.
The specimens for dryin shrinkage also were 40 by 40 by 160 mm
Eii
prisms They were exposed to 2 "C and R. H. =6 0 2 1096, after being cured
in 2 0 "C water for six days.

RESULIS AND DISCUSSION
Phvsical Propertics and Chemical Composition of the Triplc Blended Cement

--``,`,-`-`,,`,,`,`,,`---
The specific surface areas of portland cement, silica fume

blast-furnace slag and the triple blended cement were given in Table 2. The
specific surface area of the triple blended cement was about four times as much
as that of the portland ccmcnt. The particle sizc distributions of thc portland
cement, silica fume, blast-furnace slag and the triple blended cement arc
given in Fig. 1. It is shown that the triple blended ccmcnt, consisting of 10%
silica fume, 30% blast-fumace slag and 60% portland ccment, has the
particle size distribution to be similar to that of the densest packings. This
means that a denscr hardened paste may bc made by the triple blended cement.
The main chemical compositions of the portland cement, silica fume,
blast-furnace slag and the triple blended cement arc given in Table 3. It is
shown that the Ca0 in the triple blended cement was lower than that in thc
portland ccment and especially the molar ratio of C a 0 to Si02 of the triple
blended cement was much lower than that of portland cement. So, it is
reasonable that the molar ratio of Ca0 to Sioz of C-S-H and the Ca(0H)z
content in hydrates of the triple blended cement would bc lower than those in
the hydrates of portland cement. This fact means that the durability of the
concrete made by the triple blended cement would bc highcr than that of the
portland ccment concrete.
Hvdration of the Triple Blended Cement
The evolution of heat of hydration of the ccmcntitious material is

shown in Fig. 2. It can be found that thc proccss and the rate of hydration of
the triple blended cement were similar to that of the portland cement. but thc
hcat of hydration of the triple blended cement was 83% of that of the portland
cement in thc first two days. This is of benefit for mass concrete or the
concrete having high quantity of cement.
The non-evaporable water in the hardened paste of the triplc blended
ccment in first 3 days was more than that of portland cement (shown in Fig. 3).
According to these results it can be concluded that thc hydration rate of
the triple blended cement is not slower than that of thc portland ccmcnt.
Because in the triple blended cement paste, not only silica fume has a
high activity of pozzolanic reaction with portland cement but also blast-furnacc
slag can react with Ca(OH)2 to form C-S-H gel, the Ca(0H)z in the pastc of
the triple blcndcd cement was consumcd a lot. The Ca(0H)z content in
hardened paste ( W/C=o. 50 cured for 28 days ) of the triple blended cement
was only 10% of that of the portland cement ( shown in Fig. 4 ). It is the
lowest content in hardened pastes of portland ccmcnt and the blended cements,
though it was thought that some of Ca(OH)2 in hardened paste added by silica
fume are poorly crystalline or even noncrystalline to properly diffract the x-rays
( 9 ). The lower content of Ca(0H)z in the hydrates is bclicved to bc of
benefit for the strength and durability of concrete. It is also shown in Fig. 4
that there was relationship between the molar ratio of Ca0 to Si01 of
I
A C 1 SP-153 VOL*II 95 0 0662949 0522039 O20
ccmentitious matcrial and the Ca(0H)z contcnt in its hardcncd pastc. It is
consider that somc of thc calcium ions rclcascd from thc portland ccmcnt wcrc
consumed by silica fumc or blast-fumacc slag to form C-S-H gcl but not to
form Ca(OH)2.
Porc Structurc of Mortars and Porc Solution in Hardcncd Pastc
The porc size distributions in the hardcned mortar ( W/C=o. 32

S/C=2. 0 ) arc given in Fig 5. Apparcntly the porc size distribution in thc
hardened mortar madc with the triple blcndcd cement diffcrcd from that of the
mortar madc with thc silica fumc blcndcd ccmcnt ( only blending 10 5% SF ),
because thc porc volumcs of the mortar madc with thc triplc blcndcd ccmcnt
wcre less than that of thc mortar madc by portland ccmcnt not only in thc rangc
of capillary porc but also in the rangc of gel pore. This suggcsts that the
mortar madc with the triplc blcndcd ccmcnt had quite low pcrmcability, that is,
it had very high resistance to thc pcrmcancc of chemicals.
The R z 0 contents in the porc solution of hardcncd pastc ( W/C=o. 50
cured for 28 days) are given in Fig. 6, 7. It was obscrvcd that thc quantity of
RzO in thc porc solution rclatcd wcll with thc molar ratio of Ca0 to SiOz but
not with thc RzO contcnt of the ccmcntitious matcrial. Thc Icss thc molar ratio
of C a 0 to SiOz, thc Icss was thc R z 0 in porc solution. It suggcsts that thc
silicate in thc ccmcntitious matcrial can rcact with thc R z 0 to form somc of the
hydratcs and rcducc the frcc R z 0 in porc solution. Thc conccntration of R z 0
in thc porc solution of thc paste of thc triplc blcndcd ccmcnt was much lowcr
than that in thc porc solution of thc pastc of thc portland ccmcnt. It is bclicvcd
that the low RzO content in thc porc solution may hclp to rcducc alkali-silica
--``,`,-`-`,,`,,`,`,,`---
reactions.
Properties of Mortar
In ordcr to confirm the propcrtics of thc triplc blcndcd ccmcnt, somc

tcsts on the mortars wcrc carricd out. Thc mixturc proportions of thc mortars
arc given in Tablc 4.
Flow of Fresh Mortar--The influcnccs of the silica fumc and thc blast-fumace
slag on the flow of fresh mortar arc shown in Fig. 8. The addition of SF-JAN
incrcascd thc flow of fresh mortar but the addition of S F dccrcascd the flow.
Bccause sphcrical shape of the silica fumc particles bcncfits thc flow of mortar
but its largc spccific surface arca is harmful to thc flow, thc cffcct of silica
fumc on the flow is dctcrmincd on thcsc two factors. The specific surfricc arca
of SF was so largc ( shown in Tablc 2 ) that much mixing watcr was adsorbcd
by the silica fumc. On othcr hand, undcr the same conditions, thc addition
of the blast-fumacc slag in any proportions incrcascd thc flow of frcsh mortar.
So, the flow of the frcsh mortar mndc with thc triplc blcndcd ccmcnt was
similar to thnt of thc portland ccmcnt.
Compressive Strength--The comprcssivc strcngths of thc hardcncd mortars
shown in Fig. 9. Thc comprcssivc strcngths of hardcncd mortars wcrc lowcr,
as a part of the portland cement was rcplacc by the blast-fumacc slag. But,

A C 1 SP-153 V O L * I I 95 I0662949 0522023 7 8 9
when some of portland cement was replaced by thc silica fume, the
compressive strength of the mortar increased. However, when portland
cement, silica fume and blast-furnace slag were blended in an optimum
proportion, thc highest compressive strcngth could be realized because of its
dcnser micro-structure as described above. The compressive strength of the
hardened mortar of the triplc blendcd cement at the age of 91 days is about as
183% as that of the control mortar.
Alkali-Silica Reaction Resistance--The results of the alkali-silica reaction test
are @ven in Fig. 10. The specimens of the triple blended cement ( cured at
40 C ) almost did not show any expansion for 16 months. Because silica
fume and blast-furnace slag could react with alkali, and thus lowered the RzO
content in thc pore solution ( shown in Fig. 11 ), there werc less of RzO
which could rcact with the active silica aggregates to cause expansion of the
test prism. But the test prisms made with the portland cernent or the slag
blcndcd cernent ( only blended by blast-furnace slag ) had much higher
expansion under the same conditions.
--``,`,-`-`,,`,,`,`,,`---
Sulfntc Rcsistancc--The ex ansion of the mortar bars caused by the sulfate

attack are givcn in Fig I f . Thc spccimcns made with the triple blcndcd
cement did not show any change in length aftcr 16 months but the specimen of
thc portland cement or the slag blended cement (addcd by 30% blast-furnace
slag) had shown dcterioration after six months ( Fig. 13 ). The reason for it is
that the sodium sulfate reacts with the Ca(0H)z and Calcium aluminate in the
hydrates, as follows ( 10 ):
Ca(0H)z t N a s 0 4 t 2Hz0 Cas04 2H20 t 2NaOH
-
--+
2( 3Ca0 Al203 12HzO) t 3 NazS04 1oHzO)

3CaO A1203
*
k
3CaSO4 31HzO t AI(OH)3 t 6NaOH t 17HzO
Because the some of the C3A in the portland cement were replaccd by the silica
fume as well as the Ca(0H)z contcnt in the hydrates of the triplc blcndcd
cement was very low, the mortar specimens made with the triple blcndcd
cement had high durability in 5% NazS04 solution.
Drying Shrinkage-The lengths of spccimens were measured in R. H. =60%
air aftcr 7 days of water curing. The drying shrinkage of specimen made with
the triple blended cement was higher than that of portland cemcnt because the
specific surface area of the triplc blcndcd ccmcnt was much highcr than that of
the portland cement, and the-size of the porcs in the specimen was vcry small
( Fig. 14 ).
CONCLüSIONS
The properties of the triplc blcndcd cement incorporated by portland

cement, silica fume and blast-furnace slag have been researched. According
to the results of the research some conclusions are givcn as below:
The triple blended cement which was composed of 10% silica fume, 3
0% blast-furnace slag and 60% portland cement had suitable chemical

A C 1 SP-153 V O L X I I 95 Obb2949 0522022 b 1 5 m
--``,`,-`-`,,`,,`,`,,`---
composition and the densest particle distribution in the various mixtures of the
portland cement, silica fume and blast-fumace slag used in this research.
Thc hydration rate of the triple blcndcd cernent was similar to that of
the portland cement but its hcat of hydration was lower than that of the portland
cement.
Thcrc is a good relation between the molar ratio of CaO/SiO2 of
cementitious material and the content of Ca(0H)z in its hydrates. &cause the
molar ratio of CaO/SiOz of the triple blended cement is much lower than that
of portland ccment, the Ca(0H)z in the hydrates of the triple blended concrctc
is much less than in the hydrates of portland cement.
The porosity of the hardened mortar of the triple blcndcd ccment was
53% of that of the portland cemcnt in the same conditions. The RZO content
in the pore solution was 88% of that of the portland cement. So, the
hardened mortar or concrete of thc triplc blended cement has highcr strength
and durability.
The compressive strength of the triple blcndcd cement was highcr than
that of the portland cement, as well as that of the silica fume blcndcd cement
or the slag blcndcd cement.
The triple blended cement had high durability in thc situations of the
sulfate attack and alkali-silica reaction.
The disadvantage of the triplc blcndcd cement was its highcr drying
shrinkage.
According to the properties of the triple blcndcd cement, it can bc
used for high performance concrctc.
1. Detwiler, R. J. and Mehta, P. K. "Chemical and Physical

Effects of Silica Fume on the Mechanical Bchaviour of Concrctc" AC1
Material Journal, Vol. 86, 1989, p p 609-614
2. Grutzcck, M. W . , Atkinson, S . and Roy, D. M. " Mechanisms
of Hydration of Condensed Silica Fume in Calcium H rdroxide Solution",

AC1 Special Publication SP-79, 1983, pp. 643-6134.
3. Goldman, A. and Bentur, A, Bond Effects in High-strength Silica
'I
Fume Concretes", AC1 Material Journal, Vol. 86, No. 5,

September-October, 1989, p p 440-447.
4. Torii, K. and Kawamura, M. "Porc Structure and Chloride
Permeability of Concretes Containing Fly Ash, Blast-furnace Slag and
Silica Fume 'I, Fly Ash, Silica Fume Slag and Natural Pozzolans in
Concrete, Proceedings of Fourth International Conference, Istanbul,
Turkcy, May 1992, AC1 Special Publication SP-132, Vol. 1,

A C 1 SP-153 VOL*II 95 Obb2949 0522023 551
pp. 135-150, ( Editor: V. M. Malhotra ).

5. Aitcin, P. C. and Rcgourd, M. " Thc Use of Condcnscd Silica
Fumc to Control Alkali-silica Reaction -- A Field Casc Stud Ccment 'I,
and Concrctc Rcscarch, 1985, Vol. 15, No. 4, pp. 711-!19.

6. Baalbaki, M. , Sarkar, S. L. , Aitcin, P. C. and Isabcllc, H. "
Propcrtics and Microstructurc of High Pcrformance Concrctes Containing

Silica Fume, Slag and Fly Ash Fly Ash, Silica Fumc, Slag and 'I,
Natural Pozzolans in Concrete, Proceedin s of Fourth Intcmational

Conference, Istanbul, Turkey, May. 1f 9 2 , AC1 Spccial Publication
SP-132, Vol. 2, pp. 92 1-942, ( Editor: V. M. Malhotra ).
7. Numata, S. , Koidc, Y. and Shimobayashi, S. " Propcrtics of
Ultra-Highly Pulverized Granulatcd Blast Furnace Slag - Protland Cement
Blends Fly Ash, Silica Fumc. Slag and Natural Pozzolans in
'I,
Concrete, Proceedings of Second International Confcrcnce, Madria,

Spain, 1986, AC1 Special Publication SP-9 1, Vol. 2,
pp. 1341-1360, (Editor: V. M. Malhotra).
8. Andrcasen, A. H. M. , Andcrscn, J. :Kolloid. -Z. , 50, 1930,
DD. 217-228.
9. Khayat, K. H. And Aitcin, P. C. , " Silica Fumc in Concrete--An
Ovewicw Fly Ash, Silica Fumc Slag and Natural Pozzolans in

'I,
Concrcte, Procecdings of Fourth Intcmational Confcrcncc, Istanbul,

Turkc Mai 1992, AC1 Special Publication SP-132, Vol. 1,
pp. ii5-8?2, ( Editor: Malhotra, V. M. ).
10. Neville, A. M. rties of Co crcte ", Third Edition, Pitman
Publishing Limitcd," '[!fi, p p 445.

PORTLAND CEMENT
L O. I. Sim i Al203 Fe203 Ca0 MgO

~~ --,-SO? Na0 U0 Ti02 m'O5 MnO
0.40 21.30 5.00 2.60 65.00 2.001.90 0.21 0.67 0.34 0.14 0.11
OS OS OA c4AF Gypsum Total
60.00 I
I
15.74 I
l
8.84 I
I
7.92 1
I
4.09 1
l
96.59
I Physicid Properties
Density Blaine Fineness Setting Time ( h-mili )

( d h )
~~ Initiai Setting Time Final Setting Time
3.17 323
2 -34 3 - 34
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L * I I 95 m 0662749 0522024 498
TABLE 2 - PHYSICAL PROPERTIES OF CEMENTITIOUS MATERIALS
Blaine Specific Average Diameter ( p m

Ccmcniitious Maierial Density Fineness Surface Area
(dhíg) (nfhíg) BiT Lax1
Portland Cement 3.17 323 O. 806 2.35 19.27
Blast-Furnace Slag I 2.91 I 832 I 2.220 1 0.93 I 3.23
S1: 2.20 __ 32.394 o. 08 o. o9

SF-JAN 2.69 __ 18.986 o. 12 O. 16
1o%SF+9o%PC 3.07 -- 3.965 o. 49 9.22
4oqBFS+6o%PC 3.07 __ 1.372 1.42 7.54

--``,`,-`-`,,`,,`,`,,`---
TABLE 3 - MAIN CHEMICAL COMPOSITIONS OF CEMENTITIOUS

MATERIALS
II I Main Chcmical Analysis ( wt% )

Cementiiious Material
h ~
Na2 O 1ix) CaO/SiO2

'
Portland Cement 21.30 5.00 2.60 65.00 2.00 o. 21 0.67 3.27
Blast-Furnace Slag 34.70 14.20 O. 50 41.70 7.00 o. 20 0.34 1.29
SF 86.50 1.47 0.16 1.48 1.94 O. 61 1.09 --
SF-JAN 91.80 o. 21 3.13 0.21 0.38 O. 13 1.22 --
40%SFS&O mc 26.66 8.68 1.76 55.68 4.00 o. 21 0.54 2.24
5%SF+%%PC 26.75 4.82 2.48 61.83 2.03 O. 23 O. 69 2.47
1o%SFt9o%.PC 27.82 4.65 2.36 58.65 1.99 O. 25 0.71 2.26
5%SFt35%ûFSt60%PC 29.97 8.04 1.74 53.67 3.75 O. 23 0.58 1.92
1O%SFt30%BFS+~O WC 31.84 7.35 1.73 51.66 3.49 O. 25 0.61 1.74

A C 1 SP-153 VOL*II 75 EPI 0662749 0522025 3 2 4 W
Test
Flow of Fresh Mortar 32 2. o 1.2 Blendcd silica sand
Compressive Strength 32 2. o 1.2 Blended silica sand
Alkali-Silica Reaction 50 2.25 __ Pyrex
--``,`,-`-`,,`,,`,`,,`---
Siilfate Attack 50 2.5 I -- ßlended silica sand
_-
Drying Shrinkage 50 2.5 _- ßlended silica sand
Note: W/C=Waicr/Cemcni¡I¡ousmaterial; S/C=SancUCementiiious material;

SP/C=Solid content of air-entraining superplasticizer / Cemeniiiious material
The Densest Packingc --- lO?&SF

--- 1096SF+30?óBFS . - - - - - 40.6 BFS
1O0
80
60
40
20
s
Diameter (,u m)
Fig. l-Diameter distributions of portland cement, SF,BFS, and

blended cements

A C 1 SP-153 VOL+II 95 = Obb2949 0522026 2b0
,5017 -
h
h
Portland Cement 191 .ni/g 4O%BFS 151.5J/g
u7
X .-1O?ÓSF197.2J/g - - - - 103ÓSFt30SÓBFS 157.8J/g
c
v
-3
v
c
.-
O
4-A
-
3
O
>
W
4-A
a
a
I
.4-
O
+-a,
a
U
Hydration Time ( hours )
--``,`,-`-`,,`,,`,`,,`---
Fig. 2-Evolution of heat of hydration of cementitious materials
Lut Curing for 3 Days

i
O Control 1OYÓSF 10YÓSFt30YÓ BFS
Fig. 3-Nonevaporable water in hardened paste

A C 1 SP-153 VOL*II 95 m 0662949 0522027 LT7 m
Molar Ratio of Ca0 to Si02 of Cementitious Material
Fig. 4-C/S of cementitious materials versus Ca(OH), content in

hardened paste
control - -- 10%SFt30?ÓBFS 1OoÓSF
0.0738
h
YE
v
0.0492
E
-3
3c
.!2
v)
0.0246
3
+
-c
L
O biw
1o* 1o4 1o6
Diameter ( Å )
Fig. 5-Pore-size distribution of hardened paste
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 E Ob62949 O522028 033 =
I I
- -
2- 0 Control
-
- -
e 53bSF
- 40?ÓBFS -
- -
1.8 - 5?óSFt35?ÓBFS 0 lO?ÓSF -
- 10?ÓSF+30%BFS
-
- -
- -
I I I I l I I l I I
R 2 0 in cementitious Material ( wt% )
Fig. &R,O in cementitious materials versus R,O in pore solution
--``,`,-`-`,,`,,`,`,,`---
Molar Ratio of Ca0 to SiO2 of Cementitiouc Material
Fig. 7 4 / Sof cementitious materials versus RO

, in pore solution

A C 1 SP-153 V O L W I I 95 IObb2949 0522029 T 7 T
I I I I I I I I
240 - -
-
E - 1O96SF-JAN 536SF-JAN -
E
v
-
-
53bSF
-
u.
.c
O
- -
o
E
12o,r-- -
I
1096SF
I I I I I I I I
BFS Admixed in Cementitious Material ( wt.6 )
Fig. &Flow of fresh mortar
1001 I I I I I I I I
1
t
h
a - -28 Days ---91 Days

a ~
2 --``,`,-`-`,,`,,`,`,,`---
BFS Admixed in Cementitious Materials ( wtYÓ )
Fig. 9-Compressive strength of hardened mortar

A C 1 SP-153 V O L X I I 95 = Obb2949 0 5 2 2 0 3 0 791
Time (months)
--``,`,-`-`,,`,,`,`,,`---
Fig. 1GExpansion of mortar bar caused by ASR
RO
, in Pore Solution ( wt% )
Fig. 11-R,O versus pH in pore solution and expansion of mortar bar

caused by ASR

A C 1 SP-153 VOL*II 95 R 0662949 0522031 628
Control
50
iO%SF+30%BF
-
v v
O 10YóSF
Time (months)
Fig. 12-Expansion of mortar bar caused by sulfate attack
--``,`,-`-`,,`,,`,`,,`---
Fig. 13-Photo of mortar bars in 5 percent Na$O, solution for 16

months

A C 1 SP-I153 V O L m I I 95 m Obb2949 0522032 564 m
20 I I I I I I I
h
P
O
7
X
53 15
10?ÓSF+30?oBFS -
v
30% BFS
(u 103bSF -
B
Y
.s 10
Control -
--``,`,-`-`,,`,,`,`,,`---
2
o
P -
-E
n I I I I I I I
Time (months)
Fig. 14-ûrying shrinkage of mortar bars

A C 1 SP-153 VOL*II 9C Obb2949 0522033 4T0
SP 153-56
Effect of Blast Furnace Slag in

Reducing Expansion Due to Alkali-
Silica Reaction in Concrete
by T. Wang, S. Nishibayashi, K. Nakano, and Q. Bion
Synopsis: In Japan, the use of blast-furnace slag is a specified measure for

reducing alkali silica reaction (ASR) expansion in concrete. Most of the studies on
the effect of blast-furnace slag on reducing ASR expansion have been carried out
with mortar tests and few studies have been carried out on the relationship between
expansions in mortar and concrete. The studies on concrete containing different
contents of reactive aggregate and blast-furnace slag have been very limited and a
proper method for estimating the effect of slag on reducing expansion has not been
established. In this study, the expansion characteristics of mortar made using
reactive aggregate and slag cement and the effect of replacement of portland cement
by slag to reduce the expansion of concrete due to ASR were investigated. The
effect of blast-furnace slag for reducing expansion due to ASR is described from
the viewpoint of dilution,stabilization, and immobilization of alkali. The Pessimum
conditions of expansion in concrete containing different reactive aggregate contents
were studied. The expansion of concrete with 100% reactive fine aggregate was the
largest. In addition, in the concrete with 100% reactive coarse aggregate and 50%
slag, the limit value of total alkali content was estimated, as 8.0 kg/m3 without
considering the alkali content in slag, and 9.0 kg/m3 when the alkali content in
slag is taken into consideration.
Kevwords: Aggregates; alkali content; alkali aggregate reaction; blast

furnace slag; cement aggregate reactions; crack width and spacing;
expansion; modulus of elasticity; slags
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 m Obb2949 0522034 337 m
1070 Wang et al
T. Wang, Dr.Eng., is a chief researcher of Central Research Laboratory of Osaka

Cement CO., LTD., Japan
S. Nishibayashi, Dr. Eng., a member of the ACI, is a professor of Civil
Engineering at Totton University, Japan
K. Nakano, Dr. Eng., is an executive director of Osaka Cement CO., LTD., Japan
Q. Bian, now is a Ph.D. candidate on Material Science, Nanjing Institute of
Chemical Technology, China
INTRODUCTION
Some additions to concrete such as blast-furnace slag, fly ash, or silica fume
have been suggested to be effective in preventing deterioration of concrete due to
alkali-silica reaction (ASR). It is important that the effect of blast-furnace slag
content on reducing expansion, and the expansion characteristics of concrete
caused by some factors such a. types and amount of reactive aggregate, alkali
content and storage conditions are understood.
Two proposals on the mechanism of reducing expansion due to ASR have

been offered which are 1) the diluting, and 2) the physical chemical stabilization
--``,`,-`-`,,`,,`,`,,`---
and immobilization of harmful alkali (1). It has been proposed that the slag can
adsorb some alkali metal ions on its surface due to its capability to combine with
them, thus, the concentration of alkali ions in the pore solution is reduced, and a
nonexpansive gel can be formed. The microstructure of hardened slag cement
paste becomes dense compared to that of ordinary portland cement. The
permeability to water and ions is very small and the rate of diffusion of water and
of Na', K' ions decreases (2),(3). Increase in the amount of the mixing water duo
to the addition of slag increases the porosity of concrete.
In Japan, slag cement such as Types B and C are available. Over 50%
replacement of cement with blast-furnace slag is recommended in view of the effect
of slag on preventing expansion. However, the alkali content in the slag produced
in Japan can be up to 0.7%. Thus, the concentration of alkali ion in the pore
solution of hardened slag cernent paste is almost the same as that in portland
cement (4). The alkali in slag may go into solution over a rather long period.
Therefore, the expansion characteristics of slag concrete should also be studied
over a long term. Most of the previous studies were made using mortar tests, and
only a part used concrete tests. The relationship of expansions between mortar and
concrete has not been studied.
The effect of blast-furnace slag on reducing the expansion of concrete due to

ASR wa. studied by diluting, stabilizing, and immobilizing alkali ion. First, the
expansion characteristics of mortar with reactive aggregate and slag cement were
studied. The effect of blast-furnace slag on the expansion characteristics of
concrete with higher aikali contents and reactive aggregate, and the effect of slag on

A C 1 SP-153 VOL*II 95 I0662949 0522035 273 I
prcvcnting expansion are discussed.
Batch A
In the mortar mixtures, an amount of alkali in the form of NaOH with 1.0,
1.5, 2.0, and 2.5% of NqO equivalent contents were added to the cement material.
The slag contents were O, 33.3 and 100% of the total cement material and 100%
reactive aggregate (Tl). was used. The mortar specimens were 40 by 40 by
100-mm prisms. A cement-sand ratio of 1: 2.25, water cement ratio of 0.5 and
sand size of 2.5 -
5mm, were cast in several mixture conditions.
Batch B
In the concrete mixtures, an amount of alkali in the form of NaOH with 1.0,
1.5, 2.0, and 2.5% N%O equivalent contents were added to the cement material.
The slag content in the binder was 0, 50, and 70%. Reactive aggregate contents of
O, 50, and 100% were used in the total aggregate material. The concrete specimens
had a dimension of 100 by 100 by 400-mm, with 450 kg/m3cement content and a
water cement ratio of 0.45.
--``,`,-`-`,,`,,`,`,,`---
CONCRETE MATERIALS
The concrete mixtures were made at the laboratory of Tottori University using
the following materials.
Cement
Ordinary portland cement (made in Ube, Japan), which has two kinds of alkali
contents (0.42 and 0.50% N%O equivalent) was used. Slag cement (Type C , slag
60-70%, JIS) with an alkali content of 0.44% N 3 0 equivalent was also used in a
mortar test. Table 1. shows the ordinary portland cement and slag cement
described by physical properties and chemical analysis .
Blast-Furnace Slag
Table 2. describes the physical properties and chemical analysis of the

blast-furnace slag.
Aggregates
Two crushed coarse aggregates with a nominal maximum size of 20 mm were

used. One was pyroxene andesite as the reactive aggregate (Type T2) and the other
was a non reactive aggregate (Type NT). The three kinds of fine aggregates were
the pyroxene andesite from crushed reactive aggregate T2 with a F.M.=2.61 and

A C 1 SP-153 V O L m I I 95 m 0bb2949 0522036 10T =
1072 Wang et al
from T1 with a sue of 2.5, -5.0mm and the natural sand NS as the non reactive
aggregate with F.M.=2.79 (Type NS). Table 3 shows the characteristics of these
coarse and fine aggregates.
Added alkali
NaOH (reagent, JIS), dissolved in the mixing water, was used as an

additive.
MIXTURE PROPORTIONS
In the mortar mixture, portland cement and slag cement (Type C) and the
crushed reactive sand (Tl) were used at a content of 100%. Alkali contents of
1.0, 1.5, 2.0, and 2.5% Na,O equivalent were used.
The mixture proportions of the concrete are given in Table 4. For all series, .
the mixtures were proportioned to have a slump of 12-15 cm without the addition
of NaOH and adjustments for variations in slump due to addition of excessive
alkali were not carried out. The coarse and fine aggregates were used in a surface
dry condition. Three series of concrete mixtures were made in which the slag
replaced cement at 0, 50, and 70%. Other parameters were an air content of 2 %,
water cement ratio of 0.45, sand-aggregate ratio of 0.4 and the total cementitious
material content of 450 kg/m3. Like the mortar, the alkali contents were 1.0, 1.5,
2.0, and 2.5% N3O equivalent. The reactive aggregate contents were 0, 50, and
100%.
CASTING AND TESTING OF SPECIMENS
Batch A
In the mortar experiment, sands were wrapped with ordinary cement or with
slag cement at the rate of 1B of the total cement content and were cured in a storage
room (20 "C , R.H.6096 for 24 hours). Next, this aggregate was mixed with
ordinary cement at 2/3 of the total cement content and was cast in 40 by 40 by
160-mm metal forms. Plugs for measuring the change in length were arranged at
the specimens and a strain meter was used to measure length change. The initial
sirain-meter reading of these specimens was taken. Then the specimens were
stripped and immediately autoclaved. The change of length was also measured after
24 hours. Next, these specimens were stored in a curing cabinet (40"C, R.H.
100%). A marking code of mortar specimen was used, for example B-N 1.0,
where B means the kind of cement used in the first step, N means the kind of
cement used in the second step, and 1.0 is the alkali content. The symbol N is
ordinary &ment and B is slag cement.
Batch B
In the concrete experiment, the concrete was mixed in a tilting mixer. The
specimens were consolidated using a vibrator and a shaking table. Plugs for
measuring length change were arranged in the specimens. After taking the initial
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLS11 95 H 0662949 0522037 04b
reading, the specimens were stored in a curing room (40"c, R.H.lOO 96). A
Whittemore strain meter was used to measure length. The dynamic modulus of
elasticity was measured with the sonic method from the flexural resonant
frequency. Cracking by the fractal analysis and the traverse method was estimated.
A marking code of concrete specimens was, for example lOû/lOO 50 2.0, where
100/100 is the iatio of reactive coarse to fine aggregate, 50 is slag content, and
2.0 is the akali content.
The specimens of Batch A and B were measured at the age of 0.5, 1.0, 1.5,
2.0 and 2.5 months and once every month thereafter. The testing plan and
condition of mortar and concrete is given in Table 5 .
DISCUSSION
Results of Mortar Test
Fig. 1. shows the expansion versus time for several alkali contents. The
--``,`,-`-`,,`,,`,`,,`---
expansion increases with the increase in the alkali content, but the expansion is
almost small whcn ordinary cement was used up to alkali content of 1.5%. For an
alkali content of 7.5%, the expansion increases quickly up to 10 weeks with a
small incrcasc occurring after 10 weeks. The greatest expansion is about 0.45%.
Whcn using slag ccment, the alkali content in slag cement is 0.44% and is almost
the same as that in the ordinary cement, but the expansion typically does not occur.
The slag prevents the expansion due to ASR.
The expansion versus time development in which the aggregate is wrapped by

slag cement is shown in Fig.?. The expansion of mortar specimen (B-N2.5) which
has the highest alkali content is small, and is less than 0.1% for all specimens.
The results indicate that slag prevents expansion, even if the slag cement is only
used on the surface of aggregate.
The relationship between expansion and alkali content is shown in Fig.3. As

this figure shows, the expansion of mortar specimen with ordinary cement
increases with the increases in the alkali content and the increase of expansion is
significant when over 1.5% alkali is used. However, the expansion is fairly
suppressed when reactive aggregate is wrapped by slag (B-N). According to the
mortar method standard (JIS) , if the expansion is greater than O. 1% at the age of
12 months, the expansion is harmful. The results of the mortar test by the
wrapping aggregate method shows that the expansion is less than this when slag
cement is used.
Results of Concrete Test
In order to examine the diluting effect of slag which replaces ordinary cement,
when the alkali content in slag is regarded as O%, alkali of 1.0, 1.5, 2.0, 2.5% are
added in the binder, the content of reactive aggregate is O, 50 and 100% and the

A C 1 SP-153 VOL*II 95 D 0662949 O522038 T82 M
1074 Wang et at
replacement rate of slag is O, 50, and 70%, the expansion characteristics depending
on these factors are as follows.
/1) Effect of Slag Content on Expansion
Results of the expansion versus time relation without slag are given in Fig.4.
For an alkali content of 1.5%, it was found that the expansion of concrete
specimens with 100% reactive fine aggregate (0/100) is as large as 0.7% and the
expansions for 50/100, 100/50, 100/0 and 100/100 occurred within the range of
0.1 and 0.3% at the age of 12 months. The Pessimum value for alkali content is
about 2.0% when the 100% reactive fine aggregate is used.
Fig.5. shows the expansion versus time relation for the concrete specimens
with a replacement of cement by 50% slag. In comparison with Fig.4, the
expansion is decreased and is less than 0.3%. The expansion for 0/100 and 50/100
is more than 0.1%, but for 100/100, 100/50 and 100/0 is less than 0.1%.
The expansion versus time relation for the concrete specimens with 100%
reactive fine aggregate and with a O, 50, or 70% replacement rate of cement with
slag is given in Fig.6, and that of 100% reactive coarse aggregate is given in
Fig.7. From these, the expansion becomes higher than 0.1% for all Combinations
and the concrete made with fine reactive aggregate expanded to about 0.7% without
slag, expanded up to 0.25 % (a decrease of 60%) with 50% replacement of cement
with slag, and expanded up to O. 12% (a decrease of KO%) with 70% of slag. For
the concretes using reactive coarse aggregate, the greatest expansion reached about
0.4 5% at 2.0% alkali without slag. This expansion was smaller than that obtained
with the use of reactive fine aggregate. The harmful expansion will occur during a
rather long term, even though reactive coarse aggregate is used.
Fig.8 shows the relationship between expansion and slag content for the
addition of alkali to nonblended cemcnt. The total alkali content in cement and slag
is 4.4 kg/m3 when using 1.5% alkali and replacement of cement with 50 % slag
and is 4.2 kg/m3 when using 2.0% alkali and wiEh 70 % slag. When only
considering the alkali content in cement, the total alkali content is 3.4 k@m3 when
1.5 % alkali and 50% slag were used. A limiting value of 3.0 kg/m3 of total alkali
content for preventing expansion of concrete is specified (JIS A 5308), the above
alkali contents exceed this value, but the expancion did not occur during the testing
period. Therefore, the factors influencing expansion may not only be the level of
alkali ions in the cement / slag combinations, but also in the characteristics of the
slag which stabilize and immobilize akali ions .
12) Relative dynamic modulus of elasticity
Fig.9 shows the relative dynamic modulus of elasticity (RED) with time
relation for reactive aggregate contents. RED is defined as a value relative to the
dynamic modulus of elasticity at the age of 0.5 months. As this figure shows, in
the case without slag, the RED for 0/100 and 100/0 is less than 70 3' 6 and that for
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 m 0 b b 2 9 4 9 0522039 919 m
100/100 is about 95%. With 50% slag, the RED became over 85% and does not
change for 100/0 and 100/100. It was found that the value of RED was less than
80% with expansions up to O. 1 %, which is typically deemed harmful for concrete.
Thus, it is felt that this obtained value is suitable.
(3) Relationship Between Expansion and Alkali Content
Relationship between expansion and alkali content in the concrete specimens

with reactive aggregate is given in the Fig.10 and Fig.11. Fig.10 shows that in
the concrete specimens with reactive coarse aggregate, the expansion increased
with the increase in the alkali content, and decreased with the increases in the
amount of replacement of cement with slag. Fig.11 shows that in the concrete
specimens with reactive f i e aggregate, the expansion increased with the increases
in the alkali content, but the expansion reached the largest value at 2.0% alkali, it
is a Pessimum value for alkali content. On the other hand, the expansion decreased
with the increases in the slag content, but remained higher than 0.1% for all
specimens.
The relationship between expansion and alkali content when ordinary cement
is replaced by 50% slag is given in Fig.12. It can be seen that the expansions for
100/0, 100/100 and 50/50 became less than 0.1 % up to about 1.7% alkali. The
limit-value of total alkali content in concrete for preventing expansion is about 8.0
kdm3 without consideration of alkali content in slag and is about 9.0 kg/m3 when
--``,`,-`-`,,`,,`,`,,`---
considering the alkali content in slag. The expansion for OD00 increased with the
increase in the alkali content and exceeded 0.2%.
(4) Reduction of Expansion when Slag is Used
In order tp clarify the effect of slag on expansion, the rate of reduction (R. R) is
defined as follows.
R.R=-XE,-E2 1006
E*
E, : expansion without slag, E2 : expansion after the replacement by slag.
Fig.13 shows the reduction of expansion versus time in the concrete

specimens with reactive aggregate. This figure shows that the effect of age is very
small with the expansion being reduced to 90% for 100/0 and 50/50 and to 60%
for 100/100, 0/100, 100/50, 50/100. In the concrete specimens with 100% reactive
coarse aggregate, the effect on preventing expansion is significant. Therefore, it is
recommended that ordinary cement should be replaced by about 50% slag. In the
concrete specimens with other ratios of reactive aggregate and high-alkali content,
the expansion after reduction was still higher than 0.1% which is harmful.
An example of the rates of reducing expansion depending on alkali content is

A C 1 S P - L S 3 V O L X I I 95 I0662949 0522040 b30
1076 Wang et al
shown in Table 6. It can be seen that the rate of expansion reduction become large
with the increase in the content of replacement with slag, and decreases with the
increases of added alkali.
( 5 ) Cracking of Concrete Specimen when Slag is Used
For the concrete specimens with 100%reactive fine aggregate, slag contents
of O, 50, 70 % and 2.5% alkali, the crack patterns of the concrete specimens are
illustrated in Fig.14. These crack patterns were analyzed by fractal method ( 5 ) , (6).
D is the fractal dimension which means the similitude characteristic of the crack,
C.D. is the crack degree which means the density of the cracks and N is the
number of the squares having a crack. The number of cracks decreases with
increasing slag content. D is 1.964 with 50% slag, and is 1.901 with 70% slag
and is reduced about 20%. It is found that the number of cracks is decreased with
the reduction of expansion when ordinary cement is replaced by slag.
CONCLUDING REMARKS
1. The results of the mortar tests indicate that slag prevents excessive ASR
expansion. The expansion becomes less than O. 196, even if the slag cement is only
used to coat the surface of the aggregate.
2. The results of the concrete tests indicate that in the concrete specimens with
reactive fine aggregate, the expansion exceeded O. 1%, the largest value being
about 0.7% without slag at 1.5% alkali. The expansion is decreased by 60% when
--``,`,-`-`,,`,,`,`,,`---
50% slag was used, and decreased by 80% when 70% slag was used. The
expansion increases with increases in the alkali content, but the Pessimum value
for alkali content is about 2.0% when the expansion reached the largest value. The
expansion decreased with the increase in the content of slag, but remained over
0.1%.
3. In the concrete specimens with reactive coarse aggregate, the largest

expansion reached about 0.4% without slag and at 2.0% alkali. This expansion is
less than that when using reactive fine aggregate. It is possible that harmful
expansion which will exceed 0.1% will occur-during a rather long term. The
expansion increases with the increase in the alkali content, and decreases with the
increases in the content of slag.
4. In the slag concrete, a total alkali content exceeds 3.0 kg/m3, which is the
control value for preventing expansion according to JIS A 5308. This value does
not result in harmful expansion however, and suggests that the factors influencing
expansion are not only the concentration of alkali.
5. In the concrete specimens with 100% reactive coarse aggregate, the

limit-value of total alkali content above which harmful expansion does not occur is
about 8.0 kg/m3 without consideration of alkali content from slag and is about

A C 1 SP-I153 VOL*II 95 W 0662949 0522043 577 H
9.0 kg/m' when the alkali content from slag is taken into consideration. On the
other hand, for the concrete specimens with 100% reactive fine aggregate, the
expansion increased with the increases in the alkali content and reached over 0.2%,
even when slag is used.
6. The relative dynamic modulus of elasticity became less than 80% when the
expansion reached over 0.1% at 1.5% alkali.
7. Increases in the reduction of expansion occur when increasing the slag

content and decrease with increases in the alkali content. The number of cracks are
reduced when the expansion is decreased by using slag. The effect of slag on
preventing expansion is larger in the concrete specimens with 100% reactive coarse
aggregate. It is recommended that the replacement of cement by 50% slag is
suitable to prevent ASR cracking. In the other ratios of reactive aggregate and
high-alkali amtent, it is possible that the expansion could exceed O. 1% which is a
harmful value for concrete, even though overall reduced expansions occurred.
REFERENCES
--``,`,-`-`,,`,,`,`,,`---
1) Chat&eji,S.and N.F. Clausson-Kaas, " Prevention of Alkali Silica Expansion
by Using Slag-Portland Cement" Cem. and Concr. Rcs.,Vol. 14, No.2,
pp.816-818, 1984.
2) Powers,T.C. and H. H.Stcinour, An Interpretation of Some Published

'I
Researches on the Alkali Aggregate Reaction Part 7", Journal of ACI, Vol. 51,
pp.785-811, 1955.
3) R.F.M. Bakker, " Permeability of Blended Cernent Concrete",Proc.of

CANMET/ AC1 First Intl. Conf. on the use of Fly Ash, Silica Fume, Slag and
other Mineral By-products in Concrete, AC1 SP -79, pp. 589-605, 1983.
4) M.Kawamura, K.Takemot« and Hasaba, " Reduction of Alkali Content in Pore

Solution with Addition and Prevention of Alkali Silica Reaction", Proc. of the
40th Annual Conference of the Japan, pp.181-182, 1985.
5) H.Takayasu , " Fractal Science", Asakura Bookstore, Japan, 1987.
6) SNishibayashi, T.Wang, Y.kawashima and H.Kw»n, " Fractal Analysis and

Evaluation for the Crack of Concrete due to ASR", Proceedings of the Japan
Concrete Institute, Vo1.15, No.1 pp.911-916, 1993.

A C 1 SP-153 VOL811 95 0662949 0522042 403
1078 Wang et al
TABLE 1 - PHYSICAL PROPERTIES OF PORTLAND CEMENT AND

SLAG CEMENT (JIS)
Alkali contents
Type Density Fineness(cm2/g)
Na0 es(%)
Ordinary portland cement 3.15 0.42,0.50 3290
Slag cement (Type C) 2.96 0.44 3660
TABLE 2 - PHYSICAL AND CHEMICAL PROPERTIES OF GROUND

GRANULATED BLAST FURNACE SLAG (JIS)
Fineness Chemical composition ( % ) NazO
Density
(cm2&) SiO, 40, Fe0 Ca0 Mgo So, Na,O K,O eq. (%)
2.89 4540 31.9 13.4 0.2 42.1 6.1 2.0 0.27 0.28 0.45
TABLE 3 - PHYSICAL AND CHEMICAL PROPERTIES OF

AGGREGATE (JCI AAR-1)
JCI chemical method
Kinds and symbols of
--``,`,-`-`,,`,,`,`,,`---
Type F.M. Density W'A. (mmoVL) Sc/Rc

aggregate ("/.I Rc
Sc
Non reactive(coarse)NT Sandstone 6.64 2.7 0.65 21.5 30 1.39
Non reactive(fine) NS Crushed sand 2.79 2.67 1.4 ----- __ ___ _____
Pyroxene
Reactive aggregate T2 6.53 2.64 1.59 67.5 301 4.46
Andesite
Pyroxene
Reactive aggregate T1
Andesite
____ 2.64 1.93 101.0 558 5.53
Note: W.A.- water absorption

Slag Max. size Air Unit weight (kg/m3)
content of aggregate Slump content W/C s/a (%)
series
(%) (m) (ml
(%) W C Slag S G
1 O 20 12-15 2 0.45 40 203 450 O 670 1027
2 50 20 12-15 2 0.45 40 203 225 225 663 1015
3 70 20 12-15 2 0.45 40 203 135 315 660 1010
I
W- Water, C -Cement, S -Fine Aggregate, G -Coarse Aggregate

A C 1 SP-153 VOL*II 95 I0662949 0522043 3 4 T - h
TABLE 5 - TESTING PIAN AND CONDITIONS

Batch A (mortar) Batch B (concrete)
Non reactive coarse aggregate ___ NT
Non reactive f i e aggregate __- NS
Reactive coarse aggregate ___ T2
Reactive fuie aggregate T1 T2
Max.size of aggregate (cm) 5 20
Reactive aggregate contents ( %) 100 o, 50, 100
Cement /sand 1:2.25 --_
Unit weight of cement (kg/m3) --- 450
Blast-furnace slag contents ( %) 60-70 O, 50,70
Alkali contents in cement ( %) 0.42,0.50 0.42,O S O
Kind of added alkali NaOH NaOH
Added alkali contents (Na,Oeq.% ) 1.0,1.5, 2.0,2.5 1.0, 1.5,2.0,2.5
Water cement ratio (a) 50 45
Slump (cm)
___ 12-15
Size of specimen (cm) 4x4~16 10X 10 X 40
Storage condition 4OoC,R.H.100%after 40T,R.H. 100%
autoclave
Items of measurement Length Length, Dynamic modulus
of elasticity, Cracking
TABLE 6 - REDUCTION RATE OF EXPANSION

IN 50, 70 PERCENT SLAG USED
Alkali content (%)
Specimen
1.0 1.5 2.0 2.5
100/0 94 93 46(67) 39(62)
0/1O0 59 63 (78) 59 (66) 37 (59)
100/100 100 62 72 52
50150 100 93 67 54
100/50 --- 65 --- ___
50/100 --- 56 ___ ___
Note: ( ) - in the use of 70 % slag
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOLXII 95 D 0bb2949 0522044 286 m
1080 Wang et al
0.45 1 1
mortar bar, . N0.5
aggregate: T1
ai --f-, NI.0
c
.- 0.25 N1.5
C
m
o.
x N2.5
w 0.15
O 10 20 30 40 50
Age (weeks)
Fig. 1-Expansion versus time depending on alkali

content
0.5
mortar bar.
aggregate: T1
0.4 - --c)- 6-N1.O
E-N1.5
ai
--``,`,-`-`,,`,,`,`,,`---
K 0.3-
.-O
v>
c
m
P 0.2-
x
w
O 10 20 30 40 50
Age (weeks)
Fig. 2-Expansion versus time when slag cement is

used

A C 1 SP-153 VOL*II 95 I0662949 0522045 112 m
MiIwaukee Conference 1081
-op
c
0.3 - age: 24 weeks,
mortar bar,
P
._
O aggregate: T1
v>
C
m 0.2-
P
X
W
o. 1 -’--’
0.0 -
-0.1
0.0 0.5 1.0 1.5 2.0 2.5 3.0
--``,`,-`-`,,`,,`,`,,`---
A l k a l i content (“A)
Fig. 3-Relationship between alkali content and

expansion
0.8 I I
0.6
0.0 7 reactive aaareaate: T2
-0.2; ’ I . I = , . I
--
.
- 1I
O 4 8 12 16 20
Age (months)
Fig. 4-Expansion versus time in concrete specimens

without slag

A C 1 SP-153 V O L X I I 95 W 0662949 052204b 059 =
1082 Wang et al
reactive aggregate: T2
A
-- 1 0 0 / 1 0 0 50 1.5
-I-, 01100 50 1.5
50/100 50 1.5
O 4 8 12 16 20
Age (months)
Fig. &Expansion versus time in concrete with 50

percent slag
0.8 -
alkali: i . 5 % ,
A
0.6-
ac
Y
& 0/100 501.5
LT
.-O
fn
0.4-
n
X
W ,
0.0
O 4 8 12 16 20
Age (months)
--``,`,-`-`,,`,,`,`,,`---
Fig. &Expansion versus time in concrete with different

slag contents

A C 1 SP-153 V O L X I I 95 IObb2749 0522047 T95
+ 100/050 2.0
-- 1 O O / O 70 2.0
-E alkali: 2 . 0 % ,
O 2 4 6 8 10 12 14
Age (months)
Fig. -/-Expansion versus time in concrete with

different slag contents
0.8
1
0.6 -E-- 0/100 O 1 . 5
U 01100 50 1.5
0.4 -
i- 0/100 70 1.5
-.- 0/100 o 2.0

0.2 0 / 1 0 0 50 2.0
+ 01100 70 2.0
0.0
-0.2
4
O 2 4 6 8
!- 10 12 14
Age (months)
Fig. &Expansion versus time (adding alkali to

nonblended cement)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 VOL+II 95 I0662949 0522048 921 I
1084 Wang et al
-2- 10010 o
+
. 10010 50
1 O0
A
-- 100/100 o
Y
8 + 1001100 5 0
o
90
* 0/100 o
W
u 80
concrete,
alkali: 1.5%,
70 reactive aggregate: T2
60
O 4 8 12 16 20
Age (months)
Fig. &Relative dynamic modulus of elasticity versus

time
o'8 I reactive coarse aggregate: T2,100%
1 concrete,
age: 12 months -0- 10010 o
I l I
c
.-Orn
C
m
n
x
w
0.5 1 .o 1.5 2.0 2.5 3.0
Alkali content (%)
Fig. 1&Relationship between alkali content and

expansion
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 E 0662949 0522049 868 E
--``,`,-`-`,,`,,`,`,,`---
0.8
concrete,
. age: 12 months
+ o 0/100
+ 0/100 50
0.6 -t- 0 / 1 0 0 70
pessimurn value for
alkali content reactive fine aggregate: T2.100%
c
0.01 . I . I - 3 I . I
0.5 1.0 1.5 2.0 2.5 3.0
Alkali content (“YO)
Fig. 1 1-Relationship between alkali content and

expansion
concrete,
age: 12 months,
0.5 1 .o 1.5 2.0 2.5 3.0
Alkali content (“YO)
Fig. 124elationship between alkali content and

expansion

A C 1 SP-I153 V O L S 1 1 95 = Obb2947 0522050 5 ô T =
1086 Wang et al
--O- 1 0 0 / 0 50
alkali: 1.5%,
150 50
-8
-c 130
-E- 0 / 1 0 0 50
5 0 / 5 0 50
.-O
I
o -+100/50 50
U 110
-2
O 90
al
70 t
O 2 4 6
- 8 1 0 1 2 1 4
. ~
Age (months)
Fig. 13-Reduction of expansion of concrete with 50

percent slag
o/i O0 N.248. D = l . 981 0/100 N=237. D=1.964

C. D. =O. 465. Exp. =O. 5590 C. D. =O. 431. Exp. =O. 3400
(a) (Slag 0%) (b) (Slag 50%)
O/I O0 N.197. D=1.901

C. D. =O. 354. Exp. =O. 2 137
(c) (Slag 70%)
Fig. 14-Crack patterns of concrete with several slag

contents
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 Obb2949 0 5 2 2 0 5 1 4Lb m
SP 153-57
--``,`,-`-`,,`,,`,`,,`---
Effect of Heavy Metals Immobilization

on the Properties of Alkali
Activated Slag Mortars
by J. Matolepszy and J. Deja
SvnoDsis: The granulated blast furnace slags or nonferrous slags are the main
component of the alkali activated slag cementitious materiais. The calcium
silicate hydrates (C-S-H type) of low basicity, hydrogamets and sodium zeolites
form as the alkali activated slag hydration products. Their structure and
properties indicate that they can play an essential role in the immobilization of
some elements. The microstructure of alkali activated slag pastes shows a higher
gel pores content as compared with normal portland cement pastes and
simultaneously, significantly lower capillary pores fraction.
The properties of alkali activated slag pastes in the presence of Zn, Cå,
Cr and Pb ions were studied. The results of the strength tests as well as the data
relating to the phase composition and microstructure of pastes are presented
hereby.
The mortars containing alkali-activated slag show very high heavy metals
immobilization ratio. Probably it is an effect of phase composition of the mortars
and absence of capillary pores in their structure.
Kevwords: Alkali annrenate reactions; carbonates; compressive strength;

heavv metals; leaching; mortars (material); porosity; scanning electron
microscope; s&p; sodium

1087
A C 1 SP-153 VOL*II 75 IObb27Ll7 0522052 3 5 2
1088 Matolepszy and Deja
Jan Malolepszy is Professor at the Faculty of Material Science and Ceramics of

Univers$y of Mining and Metallurgy in Cracow, Poland. His research activities
are focussed on concrete technology and developing of modem building materials
technologies basing on wastes and secondary raw materials.
Jan Deja is Doctor at the Faculty of Material Science and Ceramics of University
of Mining and Metallurgy in Cracow, Poland. His main research activities are
reusing of waste materials and their application in building materials technolo-
gies. For years he deals with both chemical and physical corrosion of building
materials.
INTRODUCTION
The problem of heavy metals immobilization becomes more and more

significant with increasing contamination of the natural environment. Several
technologies will develop only when heavy metals containing by-products can be
sufficiently and safely well separated. In many research centers the studies are
carried out to solve this problem [l-41.
The cementitious materials play an important role in the heavy metals
immobilization. They can be used not only in the construction of waste dumps
and concrete shields but also as immobilizing agents forming a matrix incorporat-
ing the heavy metais in a physical or chemical way. Cements are particularly
useful in the processing of wet wastes; it is important in view of the fact that the
wastes occur predominantly as slurries (e.g. galvanic wastes containing Cr'".
The efficiency of the heavy metals immobilization is strongly related to the
hardened paste microstructure, particularly to the pore size distribution and
porosity, It is commonly known that the large pores of diameters > 100nm
decisively influence the paste tightness and permeability [5].
The microstructure and properties of hardened paste depend on the C-S-H
phase content and properties [6]. These features, in turn, are often related to the
presence of pozzolanic admixtures. Such materials as silica fume, natural
pozzolans and granulated blast furnace slags produce hydration products as a
result of pozzolanic reaction thus influencing the porosity of paste. The
admixtures listed above bring about a gel pores fraction increase and capillary
pores decrease [5-71. The advantageous changes accompanying the additions of
pozzolans give, as a consequence, the significant decrease of permeability
attributed to the hardened cement matrix in concrete [8].
The pH values in the pastes are very high (about 12) because of the basic
Ca(OH), formation. The heavy metal salts are neutralized at the presence of
Ca(OH), and, as a result, the heavy metals hydroxides of very low solubility
precipitate. The calcium zincates or chromates can also form [9]. Therefore the
immobilization of heavy metals in the hardened cement matrix is the consequence
of the significant C-S-H phase content and high pH value [lo-161. However, a
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 V O L J I I 95 0662749 0522053 299
high concentration of heavy metal ions such as Pb+2,Cd+2,Zn+, and Cr+*brings

about a serious disturbance of cement setting and hardening in some cases.
The properties of alkali activated slag concretes have been studied in our
laboratory for many years [20-241. It has been found that the alkali activated slag
matrix would produce the idealized conditions for immobilization of heavy
metals. The slag hydration products consist mainly of the gel-like C-S-H phase,
zeolites and hydrogarnets [20-24, 271. The pastes are very compact. The pores
of diameters less than 10nm predominate; these pores do not take a part in the
filtration of water throughout the paste. The high pH values resulting from the
presence of alkaline activators, ensure the neutralizing properties of pastes. Such
phases as sodium zeolites and hydrogarnets can incorporate the heavy metals to
the structure [17, 181.
The alkali activated slag cementitious materials have been also applied in
heavy metais immobilization by other authors as it is reported in some works
[25, 26, 311.
CHARACTERISTICS OF STARTING MATERIALS
The following materials have been used to produce pastes and mortars:
Granulated blast furnace slag from a metallurgical plant, ground in a ball mill
to the specific surface of 360+5m2/kg. The chemical analysis and
--``,`,-`-`,,`,,`,`,,`---
physical properties are provided in table 1.

Aggregate. The standard quartz sand of the granulation O to 2mm was used as
aggregate in mortar preparation.
Alkaline activators. The sodium carbonate and water glass have been used as
alkaline activators.
Heavy metals. The following heavy metais containing compounds have been
used: Zn(NO,),, Pb(NO,),, CdCl, and Na,CrO,. Their amounts added to
the hydrating samples are listed in table 2. The samples denoted as I and
J were not doped - only traces of heavy metals have been detected
(originated from slag), as it can be seen in table 2.
PREPARATION OF PASTES AND MORTARS
The mortars were prepared at water to cementitious material ratio equal

to 0.36. The proportion between slag and sand was 1:3. The heavy metals
compounds were dissolved in water. The mortars were mixed in the standard
laboratory mixer, cast into the moulds for I S 0 40 x40x 160mm bars and shaken
in a laboratory shaker.

A C 1 SP-153 V O L I i 1 I I 95 m O662949 0522054 125 W
The mortars denoted as A-I were prepared using sodium carbonate as an

alkaline activator whereas those denoted as J-S were activated by water glass.
The samples denoted as I and J were prepared as reference alkali activated slag
pastes without additions of heavy metal compounds.
The pastes were mixed in the laboratory mixer with water to solid ratio
equal to 0.28 for 180 seconds. The heavy metais compounds were dissolved in
water. The 10XlOxóû mm bars were made with the pastes using a vibrating
table with the frequency of 3000 vibrations per minute.
CURING OF PASTES AND MORTARS
After the preliminary consolidation, all the samples were matured in the
moulds for the first 24 hours, at 20°C and 100% RH. Subsequently, the pastes
and mortars activated by water glass, were stored at 2PC, 100% RH up to 180
days. The mortars and pastes activated by sodium carbonate were subjected to
the steam curing at 85"C, for 4 hours and subsequently stored at 2PC, 100%
RH.
--``,`,-`-`,,`,,`,`,,`---
Mechanical Strength of Mortars
The compressive strength of alkali activated slag mortars was measured

after 3, 7 , 2 8 , 9 0 and 180 days curing. The 40x40~160mm bars were used. The
results are shown in tables 3 and 4.
As it can be seen from the data thus obtained, the lowest compressive
strength values have been measured in the zinc nitrate containing samples
activated with sodium carbonate. Compressive strength loss compared to the
control without heavy metals is also observed when CdC1, is added. At sodium
chromate addition the compressive strength decrease practically does not occur
(less than 10% reference value). The compressive strength results do not change
significantly with the type of activator. As it can be seen, the heavy metals do
not disturb the compressive strength development, which is similar as in
reference samples.
Leaching Tests
The leaching method similar to the German DEV-S4 test was used [28].
The mortars after 28 and 180 days of curing were tested. The following
procedure was applied: 100g samples were ground and the fraction 2 to 4 mm
was selected for the tests. The samples were subsequently treated with 0.5 dm3
distilled water in 1 dm3 polyethylene bottles (mortar to water ratio equal to 1 5 )

A C 1 SP-153 VOL*II 95 m Ob62949 0522055 Ob1 m
and shaken for 24 hours at room temperature. The suspensions were filtered and
the liquids thus obtained were subjected to the chemical analysis.
The chromium (VI) and total chromium content after the Cr(II1) to Cr(V1)
oxidation was analyzed by the following methods:
- spectrophotometrically, as red-violet complex of chromium with
benzocarbazide (A, =545nm at 5cm thick cuvette),
- impulse polarography using sodium hydroxide or sodium hydroxide and
triethanolamine as basic electrolyte [29].
The cadmium, lead and zinc content were determined by the atomic
absorption spectrometry using the air-acetylene flame or by the emission
spectroscopy with the plasma flame. Alternatively, the traces of zinc were
analyzed by derivative impulse polarography in the basic solution of acetate
buffer. The results of leaching tests are presented in table 6 .
At some simplified assumption (among other things that the leaching
process is of linear character, irrespective of the concentration in the solution)
--``,`,-`-`,,`,,`,`,,`---
the following "degree of immobilization" has been found:

a) about 99.9% Zn,
b) about 99.8 Cd at Na2C03activator and about 99.95% Cd at water
glass activator,
c) about 9 9 3 % Cr at 1% Na,CrO, addition and about 95.5% Cr at
2 % Na2Cr0, addition to the slag,
d) about 99.8% Pb.
In the alkali activated slag mortars, the degree of immobilization is not reduced
with time.
Microporositv of Pastes
The microporosity of the pastes after 28 and 180 days of curing was
determined by means of mercury porosimetry. The samples activated by Nazco,
(A to I) as well as those activated by water glass (J to S) were taken into
account. The total porosity and the average pore diameter were determined. The
results are shown in table 5.
The total porosity of the pastes activated by water glass is generally lower
than for samples activated by sodium carbonate. The reduction of the total
porosity with the age of the pastes was also observed. It can be the consequence
of empty spaces being filled by the crystalline hydration products. The influence
of heavy metais addition on the porosity of the pastes was not clearly visible.
On the other hand, the influence of the activator's type on the average
pore diameters reveal remarkable differences. After 180 days of curing the
average pore diameters for the pastes activated by water glass were on the level
4 to 6nm. For the same samples activated by Nazco, the average pore diameters
were in the range 8 to 12nm. Only for samples D and E pore radius was higher
(20 to 25nm). It seems that in ail pastes (especially for those activated by water

A C 1 SP-I153 V O L * I I 75 m 0 6 6 2 9 4 9 0522056 T T B m
glass) small gel pores dominate and the amount of capillary pores is significantly
lower than in typical cement pastes and mortars.
MicroscoDic Observations of Mortars
The microstructure of hardened alkali activated slag mortars was

investigated by SEM. The results are presented in Figures 1-5 . The fractured
samples cured 3, 28 and 180 days were examined. All the samples were very
--``,`,-`-`,,`,,`,`,,`---
compact, with the gel-like CSH phase as a main component, occurring in two
forms: CSH (III) and CSH (IV) respectively, following Diamond's classification
[6]. In some 180 days aged samples, the CSH (I) phase was detected. The
significant differences between the samples doped with heavy metals and
reference samples were not observed. In the samples activated by water glass a
higher amount of gel-like products was detected. In the sodium chromate doped
samples, a CSH I phase increase after 28 days curing was found.
Phase composition of slag pastes
The phase composition of the alkali activated slag pastes was determined
by XRD, after 7, 28 and 180 days storage. The following principal constituents
have been detected: C-S-H, CaCO,, hydrated gehlenite (strätlingite-C2ASH,) and
hydrogarnets (C5AS3H2).First of all, the C-S-H phase content increases with time
has been found. Also it has been found that in the presence of Cd2+ and Zn2+
ions, the C-S-H phase decreased, as compared to reference paste.
Therefore, one can conclude that the Cd2+and Zn2+ ions reduce the rate
of slag hydration. This effect was observed both in the presence of sodium
carbonate and water glass.
REMARKS
The investigations prove that the alkali activated slag cementitious

material can be successfully used as a heavy metals immobilizing agent. High
concentrations of cadmium zinc, lead and chromium were applied (up to 2 % by
weight of binder). In fact, such high concentrations do not occur in practice. It
was found that the degree of Cd2+,Zn2+and Pb2+immobilization was very good,
exceeding 99.8%; only the values for were a little lower (99.5%). The
immobilization seems to be independent on the type of activator. However, one
can notice a higher degree of Cd and Pb immobilization in the mortars activated
by water glass. In the Na2C0, activated mortars, the addition of zinc ions brings
about the compressive strength decrease reaching 30% as compared to the
reference value. The cadmium ions influence is less pronounced - the compres-
sive strength decrease does not exceed 5 %. On the other hand, in the waterglass

A C 1 SP-I153 V O L X I 1 95 IOb62949 0522057 934 m
--``,`,-`-`,,`,,`,`,,`---
activated mortars the cadmium ions reduce the compressive strength most of ail,
while Pb and Cr ions have little effect.
It should be underlined that the strength development takes place in all the
mortars containing heavy metals. It means that the hydration process is not
stopped but only returned. In turn, the hydration of portland cement is strongly
disturbed by zinc and lead compounds - initial and final setting are prolonged as
well as initial compressive strength are reduced [30]. The phase composition
determination confirms these data. The highest C-S-H content was detected in
containing pastes, while the lowest in those prepared with Zn and Cd.
The high level of immobilization can be explained on the basis of
structural data. The hardened pastes of compact microstructure with gel pores
less than 4nm and practically without the capillary pores (10 to 100nm)
immobilize well the heavy metal ions.
Until now it has been difficult to explain the mechanism leading to the
compressive strength decrease. One can presume that the hydroxides precipitating
in the pastes (e.g. cadmium hydroxide) form undissolved films, hindering the
hydration of slag. In the presence of zincates are produced which give the same
effect. These presumptions are based on the data relating to the earlier studies on
cement hydration. The mechanism of heavy metals effect in the alkali activated
slag cementitious materials hydration will be the subject of further investigations.
Acknowledgement
This work is supported by the Polish Scientific Research Committee

under Grant No 18.160.248PB0764/S2/93/05
REFERENCES
1 Jantzen, C.M., Glasser, F.P., Lachowski, E.E, Journ. Amer. Ceram.

Soc., 67 1984, pp. 668.
2 Tashiro, C., Akama, K., Oba, J . , Cement and Concrete Research, 9
1979, pp. 303.
3 Glasser, F.P., Cement and Concrete Research, 22 1979, pp. 201.
4 Kurdowski, W . , Cement Wapno Gips, 6 1992, pp. 185.
5 Mehta, P.K., "Supplementary Cementing Materials for Concrete", Editor
V.M. Malhotra, Canada, 1987.
6 Diamond, S . , 8"' I.C.C.C. Rio de Janeiro 1986, ~01.212pp. 1.
7 Massara, G.F., Obertii, G . , Proc. Durability of Concrete 2ndInt. Conf.,
Montreal 1991, vol.11, pp. 1259.
8 Davis, R.E., Technical Memo, Amer. Concr. Pipe Assoc. 1954.
9 Longuet, P., Bellina, G., '7'" I.C.C.C. Paris 1980, vol.IV, pp. 617.

A C 1 SP-153 V O L * I I 95 0662949 0522058 870
1094 Malolepszy and Deja
10 Roy, D.M., "Cementitious Materials in Nuclear Waste Management", 9"

I.C.C.C. New Delhi 1992, VOLVI, pp. 88-113.
11 Glasser, F.P., "Application of Cements to the Treatment and Condition-
ing of Toxic Wastes", 9" I.C.C.C. New Delhi 1992, vol.VI, pp. 114-
118.
12 Grutzeck, M.W., " Hazardous Waste (Organic, Heavy Metal): Cement
Disposal", 9" I.C.C.C. New Delhi 1992, vol.VI, pp. 119-125.
13 Komarneni, S . , Roy, R., Roy, D.M., "Pseudomorphism in Xonolite and
Tombermorite with Co2+and Ni2+ Exchange for Ca2+ at 25"C", Cem.
Concr. Res., 16 1986, pp. 47-58.
14 Zamorani, E., Sheikh, I.A., Rossa, M.D., Serrini, G., "Physical
Properties and Leachability of MLW Stream Containing Cr, Ni and Cd
--``,`,-`-`,,`,,`,`,,`---
Immobilized in a Cement Matrix, Scientific Basis for Nuclear Waste

Management", XII Mat. Res. Soc. Symp. Proc., 127. pp. 489-494, 1989.
15 Nocuri-Wczelik, W., "Hydrated Calcium Silicates Formation in the
Presence of some additives", 31d Euro-Ceramics 1993, 1, pp. 1041.
16 Plecas, I.B., Peric, A.D., Drijaca, I.D., Kostadinovic, A.M., "Mathe-
matical Modeling of Physico-Chemical Characteristics of Concrete in
Immobilization of Radioactivite Waste", Cement and Concrete Research,
21 1991. pp. 941.
17 Breck, D., "Zeolite Molecular Sieves", New York 1974.
18 Nishi, T., Matsudu, M., Chino, K., Kikuchi, M., "Reduction of Cesium
Leachability from Cementitious Resin Forms Using Natrual Acid Clay
and Zeolite", Cement and Concrete Research, 22 1992, pp. 387.
19 Gluchowski, W.D., "Gruntosilikatni wirobi i konstrukcji", Budiwilnik,
Kiev 1967.
20 Derdacka, A., Malolepszy, J., "Application of Ground Granulated Blast
Furnace Slag in Binding material Production", Cement Wapno Gips 10
1975, pp. 291, (in polish).
21 Malolepszy, J., Deja, J . , "The Influence of Curing on the Mechanical
Properties of Alkali Activated Slag Binders", Silic. Ind. 53, 11-12 1988,
pp. 179.
22 Malolepszy, J., "Activation of Synthetic Melilite Slags by Alkalies", 8"
I.C.C.C. Rio de Janeiro 1986, vol.IV, pp. 104.
23 Malolepszy, J., "Hydration and properties of alkali activated slag
cementitious materials", Zesz. Nauk. Akad. Górn. Hutn., Ceramika 53
1989, (in polish).
24 Malolepszy, J., "The Role of Alkalies in the Hydration of Vitrified
Calcium and Magnesium Silikates", 9" I.C.C.C. New Delhi 1982, vol.IV
pp. 118.
25 Runowa, R.F., "Immobilization of Heavy Metal by the Alkali Activated
Slag Cement", Int. Conf. on Blended Cements in Construction, Sheffield
1991.

A C 1 SP-153 VOLZII 95 .
I0662947 0522059 707 .
I
26 Wu Xuegun, Yen Sheng, Shen Xiaodong, Tang Mingshu, "Alkali

Activated Slag Cement Based Radioactive Waste Forms", Cement and
Concrete Research, 21 1991, pp. 16.
27 Kriwienko, P.W., "Alkaline Cements", 9th I.C.C.C. New Delhi 1992,
vol.IV, pp. 482.
28 Rankers, R.H., Hohberg, I . , "Leaching tests for Concrete Containing fly
ash - evaluation and mechanism", Int. Conf. "Wascon 91" Studies in
Environmental Science, 48 Elsevier 1991, pp. 275.
29 Bobrowski, A., Barchatíska, B.. Chem. Anal., 24 1979, pp. 857, (in
polish) .
30 Leiber, W., "The Influence of Lead and Zinc Compounds on the
Hydration of Portland Cement", 5" I.C.C.C. Tokyo 1968, vol.11, pp.
444.
31 Roy, W.M., "Advanced Cement System Including CBC, DSP, MDF",
9* I.C.C.C. New Delhi 1992, vol.1, pp. 357.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L r I I 95 Obb2949 05220b0 429
Component wt [%]
Ca0 41.10
SiO, 38.10
Al@, 9.60
Mg0 8.40
Fe203 0.40
so3 1.10
Na20 K 2 0 + 1.20
residuum o. 10
glass phase 80 %
specific gravity 2. 95g/cm3
Ions concentration [mg/kg]

Type of
activator Mor Zn Mor Cd
Mor Cr Mor Pb
tar tar tar tar
A 787 C 1384 E 749 G 1432
Na,C03 B 397 D 2767 F 1475 H 2841
I 7 I e2 I e23 I ~ 2 3
K 397 M 1384 O 749 R 1432
Water
glass
,
L 202
7
N
J
2767
<2
P
J
1475
e23
S
J
2841
~ 2 3
TABLE 3 - COMPRESSIVE STRENGTH OF N%CO,-ACTIVATED

SLAG MORTARS PREPARED WITH HEAVY METALS ADDITION
Type of Compressive stren h [MPal

7 days 28 days 90 days 180 days
28.1 32.1 34.1 36.2
27.2 30.1 32.2 34.1
30.4 36.6 40.2 42.1
31.2 33.2 39.7 41.1
27.2 32.8 35.6 44.3 46.1
--``,`,-`-`,,`,,`,`,,`---
28.2 33.8 47.2 46.1 47.2

27.4 30.8 36.2 40.2 42.1
28.5 29.6 34.1 37.8 41.2
28.7 32.3 38.6 41.2 46.3

A C 1 SP-153 V O L * I I 95 e 0662949 0522062 365
TABLE 4 - COMPRESSIVE STRENGTH OF WATER GLASS-

ACTIVATED SLAG MORTARS PREPARED WITH HEAVY METALS
ADDITION
Cornmessive strength IMPal

3 days I 7 days 90 daw I 180 daw
54.5 61.7 76.2 78.3
43.2 40.2 56.2 60. i
41.2 45.3 59.2 63.3
37.2 39.8 43.4 46.1
31.6 34.1 37.1 40.2
53.2 60.2 67.2 69.1
54.1 59.5 69.3 71.5 73.5
52.1 57.2 68.8 70.3 71.2
50.9 55.4 60.2 65.2 65.7
TABLE 5 - POROSITY OF PASTES

Total cumulative vol. Pore radius average
Type of the paste [mm3kl [ 71
-
- 28 days I 180 days 28 days 180 days
A 36.4 20.4 17 12
B 48.5 29.3 i6 10
C 39.5 24.8 13 9
D 47.3 24.9 35 20
Na,CO,
E 44.6 31.0 38 25
activator
F 38.6 25.7 10 9
G 38.2 19.0 20 11
H 38.9 28.2 13 11
I
- 36.4 22.4 12 8
J 29.5 19.3
K 40.1 20.4
L 34.8 21.3
M 31.3 20.8
Water glass
N 29.3 17.9
activator
O 27.1 16.3
P 28.2 17.4
R 30.5 19.3
-S 32.8 20.8
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m Obb2949 05220b2 2 T L m
m m o O 0 0
a ma
m *.~o
6 0 0 0 0
N m O
000 O 0 0
0 0 - 17"
I44i 222
m o o
6 q m
2G;z
7
E
F! ??Y
hl
E
222
L
c
.-cO Wr.4-
E
c>
8
C
3
@g
800
O 0 0
m m m
Z?Z
v1
I
8
va- H Z - va- H Z -
- m o
m o m
-+o E g
O00
0 0 - 447
424 222
ga- xcl-
v)
2
ô e
a9
%
z
Li
a,
Y
P
a,
2 3
00
m
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-1.53 VOL*II 95 W 0662949 0522063 138
--``,`,-`-`,,`,,`,`,,`---
Fig. l-Structure of AASC paste (without addition) after 28

days of curing
Fig. 2 4 t r u c t u r e of AASC paste with Pb ions addition

A C 1 SP-I153 VOL*II 95 Obb2949 0522064 074
11O0 Matolepszy and Deja
--``,`,-`-`,,`,,`,`,,`---
Fig. M t r u c t u r e of AASC paste with Zn ions addition

A C 1 SP-153 V O L X I 1 95 E Ob62949 0522065 T O O I
--``,`,-`-`,,`,,`,`,,`---
Fig. W t r u c t u r e of AASC paste with Cr ions addition

A C 1 SP-153 VOL*II 95 0662949 O522066 947
1102 Ma+olepszy and Deja
Fig. 5-Structut-e of AASC paste wtih Cd ions addition
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 0662947 0522067 883
Properties of Mortar and

Concrete Using Red Mud and
Finely Ground Silica
by K. Kohno, K. Amo, Y. Ogawa, and M. Gyotoku
Synopsis : The properties of mortar and concrete using the mineral admixture
consisting of red mud and finely ground silica were investigated in order to use
effectively an industrial by-product from a chemical factory. It reports on the
effects of five mixing ratios of red mud to finely ground silica on the flow value
and the air content of fresh mortar, the cornpressive strength, the resistance to
chloride penetration and the sulphate resistance of hardened mortar were tested
compared with those of plain mortar. Secondly, the com ressive strength and the
drying shrinkage of concrete specimens cured at 20' in water and a steam
chamber at the maximum temperature of 65-C were investigated on the concrete
using the admixture consisting of 5% red mud and 5% finely ground silica 10%
finely ground silica only. The substitution was 10% of cement.
The flow value of mortars tends to decrease with an increasing rate of red
mud content, when the substitution of the mineral admixture for cement is 50%.
The air content of fresh mortar becomes maximum when the mixing ratio of red
mud and finely ground silica is equal. The compressive strengths of mortars
containing red mud are lower than that of plain mortar at each age. The mortars
containing finely ground silica exhibit higher strength from 7 to 28 days. The
resistance to chloride penetration and the sulphate resistance of the mortars are
clearly improved by the use of this mineral admixture. The compressive strength
of concrete at each age using red mud as a single admixture increases slightly
when compared to concrete using the admixture consisting of red mud and finely
ground silica. The drying shrinkage of the concrete using this admixture is higher
than that of plain concrete, and the shrinkage is slightly reduced by the adoption
of steam curing.
Kevwords: Air entrainment; chloride ions; concretes; drying shrinkage;

fineness; flowability; mortars (material); silica; steam curing; strength;
sulfate resistance
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-L53 VOL+II 95 = Obb2949 0522068 7LT =
1104 Kohno et al
Kiyoshi Kohno, AC1 member, is Professor in the Department of Civil

Engineering, Faculty of Engineering, the University of Tokushima, Tokushima
770. Japan. He is a member of RILEM. He received his Dr. Eng. from Kyoto
University in 1971. He has been studying fibre reinforced concrete, zero-slump
concrete, high volume fly ash concrete and the use of industrial by-products in
concret e.
Kazuo Amo is Associate Professor in the Department of Construction Systems
Engineering, Anan College of Technology, Anan 773, Japan. He has been
studying porous concrete for fish reef and the use of by-products in concrete.
Youji Ogawa is Research Assistant in the Department of Civil Engineering,
Faculty of Engineering, the University of Tokushima, Tokushima 770, Japan. He
received his B. Eng. degree from Tokushima University in 1988. He has been
studying porous concrete absorbing carbon dioxide gas.
Mitsumasa Gyotoku is a Civil Engineer, Department of Civil Engineering, Hyogo
Prefecture, 650 Kobe, Japan. He received his B. Eng. degree from Tokushima
University in 1992, on the study of use of Red Mud and Finely Ground Silica.
INTRODUCTION
Red mud (RM) is an industrial by-product which has been obtained from
aluminum production at a chemical factory. RM has a reddish-blown color and
a superfine particle as the physical characteristics, and has some alkalis in the
--``,`,-`-`,,`,,`,`,,`---
chemical composition. Finely ground silica (FGS) has been produced by grinding
of natural siliceous clay, and has much Si0,as the main chemical component
similar to silica fume(1). The use of RM is considered to be profitable on
ecological and economical points, as it is a low cost industrial by-product. It is
considered that the property of RM having superfine particles is suitable for the
use as an admixture for mortar and concrete. However, it is not expected that the
long-term strength development of mortar and concrete due to low SiO, content.
Therefore, a new admixture consisting of RM and FGS was produced (2),
and the properties of the mortars and concretes mixed with this admixture were
tested. In this study, the effects of the admixture on the flow and the mechanical
properties, sulphate resistance, resistance to chloride penetration, and drying
shrinkage were investigated using mortar or concrete mixtures. The performances
of mortars and concretes have been compared with the results of the specimens
made with portland cement, only.
MATERIALS
Cement
y o r m a l portland cement was used. Its physical properties and chemical
composition are given in Table 1.
Admixtures
RM is an industrial by-product from aluminum production and has a

A C I SP-153 VOLaII 95 m 0662949 0522067 656
superfine particle. FGS was obtained by grinding natural siliceous clay. The
physical properties and chemical composition are shown in Table 2. The
production cost of FGS was about 30% lower than that of silica fume.
-mortar tests, the Toyoura standard sand was used. In the concrete
tests, crushed sandstone with nominal maximum size of 20 mm was used as the
coarse aggregate, and local river sand was used as a fine aggregate. The grading
and physical properties of the coarse and fine aggregates are given in Table 3 and
4, respectively.
Superiastpi
su p onated, naphthalene condensate of non air-entraining type was used
as a superplasticizer .
MIXTURE PROPORTIONS
The proportioning of the mortar and concrete mixtures is summarized in
Table 5 and 6, respectively. For all mixtures, the water cementitious materials
ratio was fixed on 55%. Two series of mortar mixtures were made. In Series 1,
the replacement ratio of admixture for cement was fixed on lo%, and the mixing
ratios of RM to FGS were changed to 5 patterns. The percentage of the
admixture in terms of the cementitious material was (I, 5, 10, 15 and 20% in
Series 2. Three types of concretes were made with cement content of 300 kg/m3,
and the substitution ratio of the admixtures, in which mixing ratios of RM to
FGS were 1:O and 1:1, was 10%. The slump value was controlled at 6*1 cm by
varying the dosages of the superplasticizer. Concrete was mixed in a forced
action type mixer for 3 minutes.

The properties of the fresh mortar such as flow value and air content were
determined immediately after mixing. Then, mortar was cast in 40 X 40 X 160 mm
prism molds. The next day, all specimens were demolded, and cured in a water
tank of 20*2”c until the required ages for testing. The specimens used for
determining the sulphate resistance and the resistance to chloride penetration were
cured in water for 27 days.
For concrete, fresh properties were determined, and then, specimens were
molded in 100X 200 mm cylinder molds and 100X 100 X 400 mm prism molds
cast for the compressive strength and the drying shrinkage, respectively. Partaof
the specimens were cured in a steam chamber at maximum temperature of 65 c.
The next day, all specimens were demolded and cured in water at 20*2%. The
specimens for the drying shrinkage were cured for 28 days after mixing.
The properties of fresh and hardened mortars were determined in
accordance with JIS R 5201. The sulphate resistance monitoring of the mortars
began at 28 days after mixing. Specimens were placed in a 10% solution of
Na,SO, by weight, and the loss weight and the resonant frequency of each
specimen were measured.
The mortar specimens used for the resistance to chloride ion penetration
--``,`,-`-`,,`,,`,`,,`---

A C 1 Sp-153 V O L X I 1 95 W Ob62949 0 5 2 2 0 7 0 378 W
1106 Kohno et al
were cut into two parts after soaking in the chloride solution for 28 days. Then,
the cut sections of every specimen were sprayed by the solutions of 1.5%
dextrin, 0.1% fluorescein sodium and 0.1N AgNO, in that order. After the spray,
the depth of color change from a surface line was measured and used as an
indicator of the resistance to the chloride ion penetration.
The concretes, prisms for drying shrinkage were cured in water at 20 2%
for 28 days after mixing, and then transferred to a drying room under the
conditions at 2 0 I 1°C and 60k5% R.H.. The length and weight changes of the
drying shrinkage specimens were determined every week.
Each result was the average value of tests on three specimens, except the
flexural strength of mortar being performed on six specimens.
DISCUSSION
--``,`,-`-`,,`,,`,`,,`---
Effect of the mixing ratios of RM to FGS

(1) Properties of fresh mortar
The relationship between the flow of the fresh mortars and the mixing
ratios of RM to FGS is shown in Fig.1. The flow value of mortar decreased with
an increasing RM content in the admixture. It was considered that this was due
to the super fineness of the RM particles, and it was noticed that an increase of
the water content and the addition of a superplasticizer became necessary with
increasing RM content to obtain same flow. However, when FCS was only used
in the mortars, it did not appear to reduce the flow value, despite of high fineness
of FGS. Also, the air content was higher when using RM and FGS together (see
Table 5). It was assumcd that the flow value and the air content of fresh mortar
were greatly affected by the different morphology of RM and FGS.
( 2 ) Compressive and flexural strength of mortar
The relationships between the compressive or the flexural strengths and the
mixing ratios of RM to FGS are shown in Fig.2 and 3, respectively. The 3-day
compressive strengths of the specimens using admixtures ranged from 14.5 MPa
to 19.5 MPa, and 28-day strengths ranged from 30.0 MPa to 37.0 MPa. The
compressive strengths of the specimens using mineral admixtures were from 10
to 20 percent lower compared to these of plain mortars at every testing age. The
early compressive strengths of these mortars until 7 days increased with an
increasing the rate of RM in the admixture. This result indicated that the early-
age strength development was improved by the microfillar effect of the RM
particles. The 3-day strength of the specimen using RM only was 20 MPa
compared to 15 MPa for the specimens containing FGS only. However, the rate
of the strengths development from 7 to 28 days increased with an increasing rate
of FGS content. The difference in 28-day strength development of the specimen
using only RM and FGS, respectively, became small. This result showed that
long term strength improvement was possible by the use of FGS. The strength
development was affected by the silicious composite of FGS similar to silica
fume. The early-age strength development resulted from the microfillar effect of
the RM particles, and the later-age strength development was affected by the
silicious composite of FGS. As the cost of admixture could be decreased with
increasing RM content, it was considered that the use of the admixture consisting
of RM and FGS performed effectively, both economically and mechanically
compared to using RM only.
The flexural strengths ranged from 3.2 to 4.5 MPa at the age of 3 days, and

A C 1 SP-153 VOL511 95 0662949 0522073 204
from 6.0 to 7.2 MPa at the age of 28 days. The flexural strength development
was similar to that of the compressive strength.
Effect of substitution ratios of the admixtures
In this study. the admixture, in which the mixture ratio of RM to FGS was
1 : 1, was used.
(1) Properties of fresh mortar

The relationship between the substitution ratios of the admixtures to cement
content and the flow values is shown in Fig.4. The flow values decreased with
increasing the substitution ratios. This result showed that the water-reducing
effect as might be experienced with fly ash could not be expected by the use of
this admixture. The entrained air content was slightly changed with increasing the
substitution ratios from 10 to 20%. The entrained air was affected by the mixing
ratios of the admixture to cement content. (see Table 5)
(2) Compressive strength and flexural strength of mortar
Fig.5 and 6 show the substitution ratios of the admixture versus the
compressive strengths and flexural strength relationship, respectively. The
compressive strengths ranged from 30.5 MPa to 37.0 MPa at 28 days, and
decreased with increasing substitution ratios of the admixture up to 10% of the
cement. The difference of the strength development could not be observed in the
substitution ratios from 10 to 20%. It was considered for this reason that the
entrained air content was not affected by the substitution rates of the admixture,
and that the effects of the microfillar and the pozzolanic reaction of the
admixture controlled the strength development at each age. The flexural strengths
ranged from 6.0 MPa to 7.0 MPa. The flexural strength development was nearly
equal, in spite of the increase of the admixture up to 20% substitution ratios for
cement content. This was due to the bond system of the transition zone being
improved by the addition of the admixture.
Resistance to chloride ion penetration of mortar
The relationship between the penetration depths of the chloride ion and the
substitution rates of the admixture is shown in Fig.7. The penetration depths in
the mortars using the admixture were about 50% lower than that of the plain
mortar, and the resistance to chloride penetration increased slightly with increase
--``,`,-`-`,,`,,`,`,,`---
substitution ratios of admixture up to 20%(3). The same results were obtained

by the addition of a superplasticizer together with the admixture, that is to say,
the incorporation of the admixture in mortars improved the resistance to chloride
penetration. This was due to the improvement in the microstructure of the
mortars by the effects of the microfillar and the pozzolanic reaction of this
admixture.
Sulphate resistance of mortar

The sulphate resistance of the mortar specimens saturated in a solution of
10% by weight of Na,SO, was monitored at one week intervals up to 7 weeks.
The changes of the dynamic modulus of elasticity with test ages are shown in
Fig.8. The dynamic modulus of elasticity increased with age, however, the
differences between specimens could not be determined clearly. Also, the test
results of mortar having the substitution ratios of 10% and 20% showed similar
behavior as shown in Fig.8.

A C 1 SP-I153 V O L * I I 95 0662949 0522072 140
1108 Kohno et al
Effect of superplasticizer
In order to obtain the same flow value, the quantities of the superplasticizer
--``,`,-`-`,,`,,`,`,,`---
increased with increasing substitution ratios of the admixture (see Table 5). The
effect of the superplasticizer on the relationship between the compressive
strengths and the substitution ratios of the admixture compared to that of plain
mortar is shown in Fig.9. These results showed that the use of a superplasticizer
together with this admixture in mortars did not affect the strengths development.
This admixture could be used in concrete together with a superplasticizer.
Effect of mixing ratio on compressive strength of concrete
The relationship between the compressive strength development and the
mixing ratios of the admixture of which the replacement ratio for cement content
was fixed at 10% is shown in Fig.10. The 7-day strengths ranged from 24.3
MPa to 25.5 MPa and the 28-day strengths ranged from 37.1 MPa to 39.5 MPa.
The strength developments of the concretes using admixtures were about 10%
lower at 7 days, and about 5% lower at 28 days compared to those of the plain
concrete. The rate of the strength development of concrete from 7 days to 28
days using the admixture consisting of 1:l in RM and FGS was a little higher
than that of RM only. This tendency on concrete compressive strength was
similar to that of the mortar specimens.
Effect of steam curing on compressive strength and drying shrinkage
The relationship between the compressive strength development and the
mixing ratios of the admixture, when steam curing is used, is shown in Fig.11.
The early-age strengths were improved by steam curing, although the rates of the
strength development after 7 days decreased compared to that of the concretes
under standard curing.
The drying shrinkage strains of the specimens, which had been cured in a
water for 28 days after mixing and cured in a steam chamber before standard
curing, are shown in Fig.12 and 13, respectively. The drying shrinkage strains of
the concretes using admixtures were higher than that of the plain concrete. Also,
the drying shrinkage strains of the concretes tended to increase slightly with an
increasing rate of RM content in the admixture. However, the drying shrinkage
strains of the concretes being cured in a steam chamber reduced significantly
compared to those of the concretes cured by a standard manner. The
improvement of the early-age strength development and the control of the drying
shrinkage strains of the concretes using admixtures could be obtained by the use
of steam curing.
Use of coloring admixture
Photo. 1 showed the effect of the admixture on the surface color of the
concrete. The mixture ratio of the admixture consisting of RM and FGS was
fixed at 1 to 1 in this investigation. In order to obtain the color concrete, the
substitution ratio of RM for cement is at least 5%. It appears that the reddish
color concrete could be obtained by the use of the RM.

A C 1 SP-153 VOL*II 95 m 0662949 0522073 087 m
CONCLUDING REMARKS
The following conclusions were obtained from these investigations of

mortar and concrete.
Mortar
1. The flow value and the entrained air content are affected by the mixing
ratios of the RM and FGS.
2. RM is effective for the early-age strength development, and FGS is
expected to improve the later-age strength development. The use of the
admixture consisting of RM and FGS may be effective from the
mechanical, economical and ecological standpoints.
3. When the admixture having the mixing ratios of RM to FGS of 1:l is used,
the flow value of mortar decreases with an increasing substitution ratio of
--``,`,-`-`,,`,,`,`,,`---
the admixture for cement.

4. The compressive strengths of mortars decrease with increasing replacement
ratios of the admixture until it reaches 10% of cement.
5. The flexural strength developments of mortars are similar in spite of
the increase of the admixture up to 20% substitution for cement.
6. The incorporation of the admixture in mortars improves the resistance to
chloride ion penetration.
7. The use of a superplasticizer together with the admixture in mortars may
not affect the strength development.
Concrete
1. The 28-day compressive strengths of the concretes using the admixture at
the 10% replacement of cement are about 5% lower than the plain
concrete.
2. The drying shrinkage of the concrctes using the admixture is higher than
that of plain concrete. Also, the drying shrinkage seems to increase slightly
with an increasing rate of RM used in the admixture.
3. The adoption of steam curing decreases the drying shrinkage and improves
the early-age strength development of the concrete using the admixture.
4. The reddish color concrete can be obtained by the use of small quantities
of RM in this admixture.
REFERENCES
1. Kohno K., Sugimoto A. and Kashiwai T., " Study of high strength concrete
containing finely ground silica and red mud CAJ REVIEW, pp. I',
112-115, 1988.
2. Kohno K., Amo K., Ogawa Y. and Ikezoe Y., " Effect of Admixture
Consisting of Finely Ground Silica and Red Mud on Properties of High
Strength Concrete for Products" Proceeding of the 4th EASEC, V01.2,
pp.1437-1441, Seoul, Korea, 1993.
3. Kohno K., Aihara F. and Ohno K., Relative Durability Properties and
Strengths of Mortars Containing Finely Ground Silica and Silica
Fume AC1 SP114, V01.2, pp.815-826, June 1989.
'I

A C 1 SP-153 V O L X I I 95 M Obb2949 O522074 T13 M
1110 Kohno et al
i
TABLE 1 - PHYSICAL PROPERTIES AND CHEMICAL COMPOSITION
OF CEMENT
Physical Properties
Density 3.15
Blaine Fineness (m*/g) 3200

Setting Time (h-min)
Initial 2-29
Final 3-33
3day 16.1
7day 26.5
28day 42.3
Chemical Composition
SiO, (%) 20.8
4 0 3 (%I 5.4
Fe203 (%) 1.4

Ca0 (%) 63.8
MgO (%I 2.1
so3 0.63
Cl(%) 0.005
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 75 0662949 0.522075 95T m
TABLE 2 - PHYSICAL PROPERTIES AND CHEMICAL COMPOSITION

OF RED MUD AND FINELY GROUND SILICA
RedMud Rwly Gïvund Silica

Physical Properties
Density 3.35 2.27

Blaine Fineness (m2/g) 21.5 12.0
Average Grain Size ( u m ) 1.5 2.5
Chemical
Composition
SiO, (%) 15.2 86.9
A403 20.3 2.52

--``,`,-`-`,,`,,`,`,,`---
Fe:03 (%I 38.8 1.24
Cao (%) 0.09 0.27
Na20 ("/.I 8.94 0.04
Ignition loss (%) 10.5 6.34

SiO,+Ai,O, +Fe,O, 74.3 90.7

I
C o a r s e . :gregate Fine Aggregate

Sieve Size Cumulative Sicvc Size Cumulative
(mm) percentage (-) percentage
~
retained Maincd
20 0.0 5.0 0.0
10 55.5 2.5 14.4
5.0 99.2 1.2 35.3
2.5 100.0 0.6 64.0

0.3 86.4
0.15 95.7

A C 1 S P - 1 5 3 VOL*II 95 0662949 0522076 896
1112 Kohno et al
TABLE 4 - PHYSICAL PROPERTIES OF AGGREGATES
--``,`,-`-`,,`,,`,`,,`---
Note : A : Admuturc (RM and FGS)

W/C+A :water to cementitious materials ratio
Note : F A and CA. : Fine and Coarse Aggregate, S.P. : Superplasticka

A C 1 SP-153 VOL*II 75 Obb27i.17 0522077 7 2 2
--``,`,-`-`,,`,,`,`,,`---
Plain 1:0 3:l 1:l 1:3 0:l

Mixing ratios of Ri! to FGS
Fig. l - E f f e c t of mixing ratios of RM to FGS on flow

value of mortar
U. 1
Mixing ratios of RM to FGS
Fig. 2-Effect of mixing ratios of RM to FGS on compressive

strength of mortar

A C 1 SP-153 V O L a I I 95 IO b 6 2 7 4 9 0 5 2 2 0 7 8 b b î I
1114 Kohno et al
--``,`,-`-`,,`,,`,`,,`---
. . ....
. ..
.......
: ,
....... ....... ......,...............
,-
............. ...... ,..... ..........
-day
Mixing ratios of RM to FGS
Fig. %Effect of mixing ratios of RM to FGS on flexural

strength of mortar
A
E
E
W
al
3
4
2
5
O
4
LI
Substitution ratios of admixtures
Fig. &Effect of substitution ratios on flow value of mortar

A C 1 SP-153 VOL*II 95 IObb2949 0522079 5T5 I
n
cd
a
r
W
c
c>
M
C
a>
k
+
(o
a>
>
.,-I
(o
(o
a>
k
a
--``,`,-`-`,,`,,`,`,,`---
O
O
u 0% 5% 10% 15% 20%

Fig. &Effect of substitution ratios on 28-day compressive

strength of mortar
Fig. &Effect of substitution ratios on 28-day flexural

strength of mortar

A C 1 S P - 1 5 3 VOL*II 95 m 0 6 6 2 9 4 9 0522080 217 m
1116 Kohno et al
.................................................................................................
--``,`,-`-`,,`,,`,`,,`---
0 % 10% 20%
Substitut ion ratios of admixtures
Fig. 7-Effect of ratios on penetration depths of

chloride ion of mortar
35 ..............................................................................................................
-~
-a- Substitution ~
20%
- - - - Subst
.L.
10%
i tut i o n 1
!
I
-Plain
i
I , I I I
O 1 2 3 4 5 6 7 8
Curing weeks
Fig. M f f e c t of substitution ratios on dynamic

modulus of elasticity of mortar

A C 1 SP-153 V O L U I I 95 Obb2949 O522083 353
I I _ .
40 r
i
35;
30 ~
25
20 -
~
15.
10-
I s. P.
P.
nt
" O % 5% 10% 15% 20%
Fig. %Effect of superplasticizer on compressive strength

of mortar
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 m 0662949 0522082 09T
1118 Kohno et al
50 r'............................................................................................................ :
I 20°C water tank

c
+ 40
M
c
a,
k
f-'
v1 30
O
O 7 14 21 28
Curing days
Fig. 10-Effect of mixing ratios on compressive

strength of concrete with standard curing
40 r
--``,`,-`-`,,`,,`,`,,`---
Y
O
i 7
I
14
Curing days
21 28
i
Fig. 1i-Effect of mixing ratios on compressive

strength of concrete with steam curing

A C 1 SP-153 VOL*II 75 W Obb2747 0522083 T2b
, f '
O 7 i4 21 28 35 42 49
Curing days
Fig. 12-Effect of mixing ratios on drying shrinkage

of concrete with standard curing
............... ...,.. ....................................... ................................................... ...

r""
k6
x
v
e,
M
34
--``,`,-`-`,,`,,`,`,,`---
O
O 7 14 21 28 35 42 49
Curing days
Fig. 13-Effect of mixing ratios on drying shrinkage

of concrete with steam curing

Photo l-Colored concrete
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLXII 95 m Obb2949 0522085 ô T 9 =
A Study of Strength Development and

Carbonation of Concrete Incorporating
High Volume Blast Furnace Slag
by J. Nakamoto and K. Togawa
SYNOPSIS : T h i s p a p e r d e s c r i b e s t h e r e s u l t s o f a n e x p e r i m e n t a l
s t u d y c a r r i e d o u t on c o n c r e t e s i n c o r p o r a t i n g h i g h volume o f
g r o u n d g r a n u l a t e d b l a s t - f u r n a c e s l a g . The s l a g c o n t e n t i n c e m e n t
r a n g e d f r o m 50 t o 95 p e r c e n t b y w e i g h t o f t h e t o t a l c e m e n t i c i o u s
--``,`,-`-`,,`,,`,`,,`---
m a t e r i a l s a n d t h e f i n e n e s s o f s l a g r a n g e d f r o m 4000 t o 8000
cm2/g.
A l a r g e number o f t e s t s p e c i m e n s w e r e s u b j e c t e d t o t h e d e t e r -
m i n a t i o n o f h e a t o f h y d r a t i o n a n d amount o f c h e m i c a l l y c o m b i n e d
w a t e r i n cement paste, t h e a d i a b a t i c temperature r i s e , compres-
s i v e s t r e n g t h , s t a t i c modulus o f e l a s t i c i t y and r a t e o f carbona-
t i o n i n concrete.
The f o l l o w i n g r e s u l t s w e r e o b t a i n e d : ( 1 ) T h e s t r e n g t h d e v e l o p -
ment o f h i g h b l a s t - f u r n a c e s l a g c o n t e n t c o n c r e t e i s more h i g h l y
i n f l u e n c e d by t h e c u r i n g t e m p e r a t u r e t h a n t h a t o f s l a g f r e e con-
c r e t e . ( 2 ) F o r c o m p r e s s i v e s t r e n g t h s b e l o w 5 MPa, t h e c o m p r e s s i v e
strength developed quickly w i t h icncreasing slag content a t
t h e r a n g e o f 70-95%, regardless o f fineness o f slag. (3)The
strength of high blast-furnace slag content concrete i s strongly
r e l a t e d t o t h e amount o f e f f e c t i v e combined water, e s p e c i a l l y a t
t h e e a r l y ages. (4) The c o r r e l a t i o n b e t w e e n t h e c o m p r e s s i v e
s t r e n g t h a n d t h e m a t u r i t y i s h i g h e r on t h e m a t u r i t y o f t h e b a s i c
temperature o f O " G t h a n t h a t o f -1O'C. ( 5 ) T h e maximum a d i a b a t i c
t e m p e r a t u r e r i s e (K) o f c o n c r e t e m i x t u r e d e c r e a s e d w i t h i n c r e a s -
i n g ground b l a s t - f u r n a c e s l a g content, e s p e c i a l l y i n the range
m o r e t h a n 70%. (6) I t i s a v e r y u s e f u l i d e a t o u t i l i z e t h e h i g h
f i n e n e s s s l a g s u c h a s 8000cm2/g, b e c a u s e t h e a d i a b a t i c t e m p e r a -
t u r e r i s e per u n i t compressive strength(k/a)decreases w i t h in-
c r e a s i n g f i n e n e s s o f s l a g . (7) The d e p t h o f c a r b o n a t i o n o f h i g h
blast-furnace s l a g contentconcrete i s p r o p o r t i o n a l t o the square
r o o t o f age s i m i l a r t o t h a t o f o r d i n a r y p o r t l a n d cement c o n c r e t e ,
and u s i n g t h i s r e l a t i o n s h i p , the progress o f carbonation i n
f i e l d e x p o s u r e can be a l s o p r e d i c t e d .
Keywords: Accelerated tests; adiabatic conditions; blast furnace slag;

carbonation; compressive strength; curing; field tests; heat of hydration;
strength; temperature; temperature rise

A C 1 SP-153 VOL*II 95 O662949 0522086 735 =
1122 Nakamoto and Togawa
J u n j i Nakamoto i s a a s s o c i a t e professor i n the Department o f

C i v i l E n g i n e e r i n g a t t h e Wakayama N a t i o n a l C o l l e g e o f T e c h n o l o g y .
K a z u o Togawa i s a p r o f e s s o r i n t h e D e p a r t m e n t o f C i v i l E n g i n e e r -
i n g a t t h e Wakayama N a t i o n a l C o l l e g e o f T e c h n o l o g y . He r e c e i v e d
h i s D.Eng. f r o m t h e U n i v e r s i t y o f K y o t o i n 1982.
I NTRODUCT I ON
R e c e n t l y , i t h a s become m o r e a n d m o r e p o p u l a r t o u t i l i z e t h e
g r o u n d b l a s t f u r n a c e s l a g f o r l o w e r i n g t h e h e a t o f h y d r a t i o n and
f o r i m p r o v i n g t h e r e s i s t a n c e t o c h e m i c a l a t t a c k , and f o r o t h e r
p u r p o s e s . T h e i d e a o f u t i l i z i n g t h e b l a s t - f u r n a c e s l a g , as w e l l
f r o m t h e p o i n t o f v i e w o f e f f e c t i v e use o f i n d u s t r i a l by-prod-
u c t s , seems t o be v e r y u s e f u l i n c o n s e r v i n g energy, r e s o u r c e s
and e a r t h e n v i r o n m e n t a l i n t e g r i t y . The c o n t e n t s o f b l a s t - f u r n a c e
s l a g a r e u s u a l l y u p t o 70 % o f c e m e n t b y w e i g h t i n J a p a n . In
t h i s study,various t e s t s were c a r r i e d o u t f o r t h e h i g h b l a s t -
f u r n a c e s l a g c o n t e n t cement and concrete w i t h ground g r a n u l a t e d
b l a s t - f u r n a c e s l a g u p t o 95% b y w e i g h t .
T h i s paper describes t h e r e s u l t s o f s t r e n g t h development t e s t
w h i c h were c a r r i e d o u t by v a r y i n g t h e f i n e n e s s of s l a g f r o m 4000
c m 2 / g t o 8000cm2/g, s l a g c o n t e n t i n c e m e n t f r o m 5 0 % t o 95%
--``,`,-`-`,,`,,`,`,,`---
a n d c u r i n g t e m p e r a t u r e f r o m 5 ° C t o 30°C. T h e r e s u l t s o f c a r b o n a -
t i o n t e s t s i n t h e a c c e l e r a t i n g t e s t room and i n t h e f i e l d , and
i n a d d i t i o n t h e r e s u l t s o f temperature r i s e t e s t s which were
c a r r i e d o u t w i t h v a r y i n g t h e f i n e n e s s o f s l a g f r o m 4 0 0 0 cm2/g
t o 8000cm2/g a n d s l a g c o n t e n t i n cement f r o m 5 0 % t o 95% a r e
discussed.
CONCRETE MATERIALS
Cement
N o r m a l p b r t l a n d c e m e n t (OPC), h i g h - e a r l y p o r t l a n d c e m e n t
(HEPC) a n d m o d e r a t e h e a t p o r t l a n d c e m e n t (MHPC) m a n u f a c t u r e d a t a
p l a n t o f O s a k a Cement Co., L t d . w e r e used.
Ground Granulated Blast-Furnace Slag
T h e g r o u n d g r a n u l a t e d b l a s t - f u r n a c e s l a g was o b t a i n e d f r o m a
p l a n t o f N i p p o n S t e e l C h e m i c a l Co., L t d . T h e s l a g was g r o u n d i n
a m i l l t o t h r e e l e v e l s o f f i n e n e s s o f 4 0 0 0 , 6 0 0 0 a n d 8000cm2/g
s p e c i f i c s u r f a c e area. The p h y s i c a l p r o p e r t i e s and chemical an
a l y s i s o f t h e s l a g a r e s h o w n i n T a b l e 1.
Aggregates
T h e f i n e a g g r e g a t e was a n a t u r a l r i v e r s a n d w i t h 2 . 5 6 r e l a -
t i v e d e n s i t y a n d 2 . 8 4 f i n e n e s s m o d u l u s . T h e c o a r s e a g g r e g a t e was
a c r u s h e d s a n d s t o n e w i t h 2 0 mm m a x i m u m s i z e a n d 2 . 6 2 r e l a t i v e
d e n s i t y . The c o a r s e a g g r e g a t e s were s e p a r a t e d i n t o d i f f e r e n t
s i z e f r a c t i o n s , and t h e n combined t o a s p e c i f i e d grading.

A C 1 SP-153 V O L * I I 95 m 0662747 0522087 671 m
Admixture
A I i g n i n base a i r - e n t r a i n i n g and water-reducing admixture
was u s e d i n a l I t h e c o n c r e t e m i x t u r e s i n t h e f o r m o f a n aqueous
s o I u t i on.
MIXTURE PROPORT I ONS

The w a t e r / c e m e n t i c i o u s m a t e r i a l s r a t i o was s e t a t t h r e e
l e v e l s : O. 50, O. 5 7 a n d O. 65. S a n d p e r c e n t a g e was k e p t c o n s t a n t
a t 44% T h e a i r c o n t e n t o f a l l m i x t u r e s w e r e c o n t r o l l e d 4+l%
a n d t h e s l u m p o f c o m p a r a b l e c o n t r o l c o n c r e t e w a s 8 0 mm. T h e
c e m e n t c o n t e n t p e r u n i t v o l u m e o f c o n c r e t e was s e t a t t h r e e
l e v e l s : 200kg/m3, 280kg/m3 a n d 360kg/m3. The p r o p o r t i o n o f t h e
s l a g i n t h e c o n c r e t e r a n g e d f r o m 50 t o 9 5 p e r c e n t o f t h e t o t a l
cementicious materials. T e s t c o n d i t i o n i s s h o w n i n T a b l e 2.
CASTING AND CURING OF TEST SPECIMENS

F o r m i x i n g t h e c o n c r e t e , a f o r c e d - m i x i n g t y p e m i x e r was
utilized. When m i x i n g t h e c o n c r e t e , f i r s t , d r y m i x i n g was d o n e
f o r 3 0 s e c o n d s w i t h c e m e n t a n d f i n e a g g r e g a t e s , a n d t h e n i t was
m i x e d f o r a n o t h e r 10 seconds a f t e r a d d i n g water. Finally,
c o a r s e a g g r e g a t e s w e r e p u t in, a n d t h e c o n c r e t e was m i x e d f o r
a n o t h e r 120 s e c o n d s .
I n t e r n a l v i b r a t o r s were used i n c a s t i n g specimens.
The specimens f o r compressive s t r e n g t h t e s t were m o i s t c u r e d
f o r 24 h o u r s a t t h e d e s i g n a t e d c u r i n g temperature, demolded and
t r a n s f e r e d t o t h e m o i s t - c u r i n g room a t 100 r e l a t i v e h u m i d i t y and
a t each c u r i n g temperature u n t i l r e q u i r e d f o r testing.
E a c h s p e c i m e n f o r c a r b o n a t i o n t e s t was m o i s t - c u r e d f o r 24
h o u r s a t 20? C, was t h e n d e m o l d e d , a n d was c u r e d u n d e r w a t e r a t
20°C u n t i l the time f o r testing.
T e s t s f o r heat e v o l u t i o n and c h e m i c a l l y combined w a t e r i n
cement and f o r c o m p r e s s i v e s t r e n g t h , a d i a b a t i c temperature r i s e
and c a r b o n a t i o n i n concretewere c a r r i e d out.
--``,`,-`-`,,`,,`,`,,`---
T h e a d i a b a t i c t e m p e r a t u r e r i s e t e s t i n g a p p a r a t u s was d o u b l e
Ia y e r a i r - c i r c u l ated. T h e d i m e n s i o n s o f c o n c r e t e s p e c ¡men w e r e
@ 3 5 0 X 260mm.
The h e a t e v o l u t i o n curves o f s l a g cement p a s t e were measured
by a conduction calorimeter.
C h e m i c a l l y combined w a t e r i n a cement p a s t e w i t h w a t e r /
c e m e n t r a t i o o f 0 . 5 was o b t a i n e d f r o m t h e i g n i t i o n l o s s o f
weight i n t h e e l e c t r i c m u f f l e furnace.
The d i m e n s i o n s o f specimens f o r compressive s t r e n g t h t e s t s
were @100X200mm. The t e s t s were conducted i n accordance w i t h
P r o c e d u r e A o f ASTM C39.
T h e s p e c i m e n s i n c a r b o n a t i o n t e s t s w e r e p r i s m s o f 100XlOOX
400mm. S u r f a c e s except a s i d e s u r f a c e were coated w i t h epoxy

A C 1 S P - 1 5 3 VOL*II 75 m 0 b b 2 9 4 9 0522088 508 m
r e s i n t o e x c l u d e t h e gas. The specimens were p u t i n s i d e t h e

equipment f o r a c c e l e r a t e d carbonation tests. The a c c e l e r a t e d
c a r b o n a t i o n t e s t s were c a r r i e d out under conditions w i t h a
c a r b o n d i o x i d e c o n c e n t r a t i o n o f 796 r e l a t i v e h u m i d i t y o f 60% a n d
t e m p e r a t u r e a t 20'C. T h e d e p t h o f c a r b o n a t i o n was m e a s u r e d
u s i n g a n a l c o h o l s o l u t i o n o f 1% p h e n o l p h t a l e i n . The a v e r a g e
d e p t h o f c a r b o n a t i o n was c a l c u l a t e d f r o m t h e a r e a o f c a r b o n a t e d
zone w h i c h was u n c o l o u r e d .
HEAT OF HYDRATION
F i g u r e 1 - F i g u r e 3 show t h e h e a t e v o l u t i o n c u r v e s , and
F i g u r e 4 shows t h e t o t a l h e a t o f h y d r a t i o n o f s l a g cement p a s t e
made w i t h d i f f e r e n t f i n e n e s s o f s l a g . S i n c e i n t h e e a r l y s t a g e s
o f h y d r a t i o n t h e d i f f e r e n t compounds h y d r a t e a t d i f f e r e n t r a t e ,
t h e r a t e o f h e a t e v o l u t i o n and t h e t o t a l heat, depends on t h e
c h e m i c a l c o m p o s i t i o n o f cement. I n fact,the heat o f hydration
depends on t h e s l a g content. I t follows t h a t the heat o f hydra-
t i o n d e c r e a s e d b y r e d u c i n g t h e p r o p o r t i o n s o f cement, t h a t i s ,
w i t h i n c r e a s i n g s l a g co-ntent. I n t h e range o f s l a g c o n t e n t o f
70-95%, t h e p e a k o f t h e e v o l u t i o n c u r v e a f t e r t h e d o r m a n t
p e r i o d appears e a r l i e r , and becomes h i g h e r w i t h i n c r e a s i n g s l a g
content. On t h e o t h e r hand, t h e t o t a l h e a t o f h y d r a t i o n d e -
c r e a s e d as t h e s l a g c o n t e n t i n c r e a s e d . The f i n e n e s s o f s l a g
a l s o i n f l u e n c e s t h e r a t e o f h e a t development, and an i n c r e a s e i n
t h e f i n e n e s s o f s l a g makes t h e r e a c t i o n s o f h y d r a t i o n speeding
up, t h e r e f o r e t h e h e a t was e v o l v e d , b u t t h e t o t a l a m o u n t o f h e a t
l i b e r a t e d i s n o t a f f e c t e d s o much b y t h e f i n e n e s s o f s l a g .
COMPRESS I V E STRENGTH
F i g u r e 5 a n d F i g u r e 6 show t h e e f f e c t o f s l a g c o n t e n t o n t h e
c o m p r e s s i v e s t r e n g t h o f c o n c r e t e s made w i t h d i f f e r e n t f i n e n e s s o f
slag. The s t r e n g t h d e v e l o p m e n t o f h i g h b l a s t - f u r n a c e s l a g
c o n t e n t c o n c r e t e i s i n f l u e n c e d more by t h e c u r i n g temperature
than t h a t o f s l a g f r e e concrete. For compressive strengths
b e l o w 5 MPa, a t t h e a g e o f 1 d a y - 3 d a y s , t h e c o m p r e s s i v e
strength developed quickly w i t h increasing slag content i n the
r a n g e o f 70-952, r e g a r d l e s s o f f i n e n e s s o f s l a g . This is
a t t r i b u t e d t o t h e r a t e o f h y d r a t i o n ( F i g u r e I - F i g u r e 3). From
s e v e n d a y s onwards, c o m p r e s s i v e s t r e n g t h d e c r e a s e d as s l a g
content increased. Regardless o f s l a g content, c u r i n g temper-
a t u r e a n d a g e s , c o m p r e s s i v e s t r e n g t h i n c r e a s e d as t h e f i n e n e s s
o f s l a g i n c r e a s e d . [i] I t seems t o b e e f f e c t i v e i n i m p r o v i n g
the compressive strength o f high slag content concrete to
u t i l i z e t h e h i g h f i n e n e s s slag.
MATUR I TY
T a b l e 3 shows t h e equations o f r e g r e s s i o n l i n e between
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L U I I 45 Ob62949 O522089 444
compressive s t r e n g t h ( f c ' ) and maturity(M), which i s g i v e n by

f c ' = a I o g I o M + ß [Z] , w h e r e a a n d ß a r e c o n s t a n t . The c o r -
r e l a t i o n between t h e compressive strength o f high blast-furnace
--``,`,-`-`,,`,,`,`,,`---
s l a g c o n t e n t c o n c r e t e and t h e m a t u r i t y i s h i g h e r on t h e m a t u r i t y
o f t h e b a s i c t e m p e r a t u r e o f O " C t h a n t h a t o f -10°C. The
g r a d i e n t ( a ) o f t h e I ¡ne decreased w i t h i n c r e a s i n g s l a g content,
and d e c r e a s e d w i t h i n c r e a s i n g t h e f i n e n e s s o f slag. As w e l l ,
t h e i n f l u e n c e s o f s l a g c o n t e n t a n d f i n e n e s s o f s l a g o n com-
pressive s t r e n g t h mentioned aboveare reconfirmed from these
e q u a t ions.
A D I A B A T I C TEMPERATURE R I S E / C O M P R E S S I V E STRENGTH R A T I O
The maximum a d i a b a t i c t e m p e r a t u r e r i s e (KI o f c o n c r e t e m i x t u r e

decreased w i t h i n c r e a s i n g ground blast-furnace s l a g content,
e s p e c i a l l y i n t h e r a n g e m o r e t h a n 70%. F i g u r e 7 - F i g u r e 9 show
t h e r e l a t i o n s h i p s b e t w e e n K/o a n d s l a g c o n t e n t a t t h e t e m p e r a -
t u r e o f 2O"C, where K i s t h e u l t i m a t e t e m p e r a t u r e r i s e o f con-
c r e t e under a d i a b a t i c c o n d i t i o n s , and o i s compressive s t r e n g t h .
T h e h e a t o f h y d r a t i o n p e r u n i t o f c o m p r e s s i v e s t r e n g t h de-
c r e a s e d a s s l a g c o n t e n t i n c r e a s e d e s p e c i a l l y a t e a r l y ages. In
a d d i t i o n , t h e i n c r e a s e i n t h e f i n e n e s s o f s l a g was h i g h l y
e f f e c t i v e i n lowering the ratio. T h i s means t h a t t h e i n c r e a s e
i n s l a g c o n t e n t and f i n e n e s s o f s l a g a r e e f f e c t i v e i n c o n t r o l o f
thermal cracking. I t i s a very useful idea t o u t i l i z e the high
f i n e n e s s s l a g s u c h a s 8000cm2/g, b e c a u s e t h e a d i a b a t i c t e m p e r a -
t u r e r i s e per u n i t compressive strength(k/o) decreases w i t h
i n c r e a s i n g f i n e n e s s o f slag.
C H E M I C A L L Y COMB I NED WATER

F i g u r e 10 shows t h e n o n - e v a p o r a b l e w a t e r c o n t e n t i n a c e m e n t
paste. I t may b e r o u g h i d e a , b u t t h e n o n - e v a p o r a b l e w a t e r a n d
C a ( 0 H ) w e r e d e f i n e d a s t h e w e i g h t l o s s f r o m 1 0 5 ' C t o 700'C a n d
f r o m 500'C t o 580"C, r e s p e c t i v e l y . T h e r e w e r e two l a r g e d i f -
f e r e n c e s between s l a g - f r e e cement p a s t e and s l a g cement paste.
One was t h e a m o u n t o f n o n - e v a p o r a b l e w a t e r c o n t e n t a n d t h e o t h e r
was t h e p r e s e n c e o f c a l c i u m h y d r o x i d e . L a r g e amounts were
observed i n the slag-free mixtures. The non-evaporable w a t e r
c o n t e n t increased w i t h i n c r e a s i n g c u r i n g temperature and w i t h
i n c r e a s i n g t h e f i n e n e s s o f slag.
F i g u r e 1 1 s h o w s a t y p i c a l e x p e r i m e n t a l r e l a t i o n s h i p between,.
c o m p r e s s i v e s t r e n g t h and e f f e c t i v e combined water c o n t e n t which
was d e f i n e d i n t h i s s t u d y as t h e w e i g h t l o s s f r o m 1 0 5 ° C t o 700'C
e x c e p t i n g f r o m 500'C t o 580'C, a s s u m i n g t h a t c a l c i u m h y d r o x i d e
does n o t c o n t r i b u t e t h e strengthdevelopment. There i s a d e f i -
n i t e r e l a t i o n b e t w e e n t h e d e g r e e o f h y d r a t i o n a n d s t r e n g t h . [3]
i41

A C 1 SP-153 V O L * I I 95 0662949 0522090 Lbb
STAT I C MODULUS OF ELAST IC I TY
The r e l a t i o n s h i p b e t w e e n t h e s t a t i c m o d u l u s o f e l a s t i c i t y a n d
c o m p r e s s i v e s t r e n g t h f o r a l I t h e c o n c r e t e s i s shown i n F i g u r e l Z .
The s t a t i c modulus o f e l a s t i c i t y o f h i g h b l a s t - f u r n a c e s l a g
content concrete increases approximately w i t h the square r o o t o f
i t s strength, i r r e s p e c t i v e o f s l a g content, the fineness o f s l a g
and c u r i n g temperature.
CARBONAT I ON
F i g u r e 1 3 shows t h e r e l a t i o n s h i p b e t w e e n t h e d e p t h o f c a r b o n -
a t i o n and t h e square r o o t o f t i m e i n t h e a c c e l e r a t e d t e s t . The
depth o f carbonation o f high blast-furnace slag content concrete
i s p r o p o r t i o n a l t o t h e s q u a r e r o o t o f age s i m i l a r t o t h a t o f
o r d i n a r y p o r t l a n d cement c o n c r e t e . The r a t e o f c a r b o n a t i o n
increased w i t h an increase i n s l a g content, especially a t high
water/cement r a t i o s . The t y p e o f c e m e n t a l s o a f f e c t s t h e r a t e
o f carbonation. I n t h e r a n g e o f s l a g c o n t e n t e x c e e d i n g ?O%,
t h e r a t e o f c a r b o n a t i o n showed a much f a s t e r i n c r e a s e . [51
F i g u r e 14 shows t h e r e l a t i o n s h i p b e t w e e n t h e r a t e o f c a r b o n a t i o n
a n d t h e f i n e n e s s o f s l a g , a n d F i g u r e 1 5 - F i g u r e 17 show t h e r e -
l a t i o n s h i p b e t w e e n t h e r a t e o f c a r b o n a t i o n and t h e p e r i o d o f
water curing. I t i s obvious t h a t the increase i n the fineness
o f s l a g was e f f e c t i v e i n l o w e r i n g t h e r a t e o f c a r b o n a t i o n . The
period o f pre-water curing before the carbonation t e s t also
influenced the rate of carbonation of high blast-furnace slag
content concrete. To l o w e r t h e r a t e o f carbonation, i t will
be r e q u i r e d t h e s u f f i c i e n t w a t e r c u r i n g p e r i o d a t l e a s t 3 o r 7
days.
F i g u r e 18 shows r e l a t i o n s h i p b e t w e e n t h e r a t e o f c a r b o n a t i o n
and t h e r e - c i p r o c a l o f s t r e n g t h ( l / a ) . Regardless o f mix pro-
p o r t i o n a n d f a c t o r s , a g o o d c o r r e l a t i o n was o b t a i n e d i n a l l t h e
c o n c r e t e s o f 28 days w a t e r c u r i n g , [ô] b u t t h a t r e l a t i o n was
s t r o n g l y a f f e c t e d by t h e p e r i o d o f w a t e r c u r i n g .
The d e p t h o f c a r b o n a t i o n increases a p p r o x i m a t e l y w i t h t h e
s q u a r e r o o t o f t i m e i n t h e f i e l d t e s t o f a c t u a l e n v i r o m e n t as
we1 I as i n t h e a c c e l e r a t e d t e s t ( S e e F i g u r e 19). F i g u r e 20
shows i n f l u e n c e s o f s l a g c o n t e n t on t h e r a t i o o f t h e r a t e o f
s l a g c o n t e n t c o n c r e t e t o t h a t o f slag-free concrete. I t seems
t h a t a p e r i o d i c w e t t i n g o f t h e c o n c r e t e , ie. by r a i n , i n f l u e n c e
the progress o f carbonation. There i s no l a r g e d i f f e r e n c e s
b e t w e e n a c c e l e r a t e d t e s t and f i e l d t e s t , b u t t h e r a t e i n a c c e l -
erated t e s t i s j u s t a l i t t l e higher in the range o f s l a g content
b e l o w 80%. o n t h e o t h e r hand, i s l o w e r some d e g r e e i n t h e r a n g e
a b o v e 80%. Thus, t h i s m a k e s t h e r e l a t i o n b e t w e e n a c c e l e r a t e d
t e s t and f i e l d t e s t a c u r v e n o t a s t r a i g h t l i n e ( S e e F i g u r e 21).
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L + I I 95 0 0662949 0 5 2 2 0 9 1 OT2 =
CONCLUDING REMARKS
1. The s t r e n g t h d e v e l o p m e n t o f h i g h b l a s t - f u r n a c e s l a g c o n t e n t
concrete i s more h i g h l y influenced by the curing temperature
than t h a t o f s l a g f r e e concrete.
2. F o r c o m p r e s s i v e s t r e n g t h b e l o w 5 MPa, t h e c o m p r e s s i v e
strength developed quickly w i t h increasing slag content i n the
r a n g e o f 70-95% r e g a r d l e s s o f f i n e n e s s o f slag.
3. The s t r e n g t h o f h i g h b l a s t - f u r n a c e s l a g c o n t e n t c o n c r e t e i s
s t r o n g l y r e l a t e d t o t h e amount o f c h e m i c a l l y combined water,
e s p e c i a l l y a t e a r l y ages.
4. The c o r r e l a t i o n between t h e c o m p r e s s i v e s t r e n g t h and t h e
m a t u r i t y o f h i g h b l a s t - f u r n a c e s l a g c o n c r e t e i s h i g h e r on t h e
m a t u r i t y o f t h e b a s i c t e m p e r a t u r e o f O ‘ C t h a n t h a t o f -10°C.
5. The maximum a d i a b a t i c t e m p e r a t u r e r i s e ( K ) o f c o n c r e t e
m i x t u r e decreased w i t h increasing ground blast-furnace slag
--``,`,-`-`,,`,,`,`,,`---
c o n t e n t , e s p e c i a l l y i n t h e r a n g e m o r e t h a n 70%.
6. I t seems t o b e d i f f i c u l t t o k e e p t h e c o m p r e s s i v e s t r e n g t h
o f high slag content concrete equivalent t o that of slag free
m i x t u r e , b u t t h e c o m p r e s s i v e s t r e n g t h can be improved s i g n i f i -
c a n t l y by u t i l i z i n g h i g h f i n e n e s s slag.
7. A d i a b a t i c temperature r i s e per u n i t compressive strength

(k/o) d e c r e a s e s w i t h i n c r e a s i n g f i n e n e s s o f s I ag.
8. The d e p t h o f ’ c a r b o n a t i o n o f h i g h b l a s t - urnace s l a g content
concrete isproportional t o the square r o o t o f age, s i m i l a r t o
t h a t o f o r d i n a r y p o r t l a n d cement c o n c r e t e , and u s i n g t h i s r e -
lationship the progress of carbonation i n f e l d exposure can be
p r e d i c t ed.
9. The r a t e o f c a r b o n a t i o n i s p r o p o t i o n a l t o t h e r e c i p r o c a l o f
s t r e n g t h i n a l l the concretes, but that r e l a t i o n i s strongly
a f f e c t e d by t h e p e r i o d o f w a t e r c u r i n g .
REFERENCES
1. HONDA, K., UECHI,Y.. MOROOKA, H. a n d YASUNAGA. T. ” A S t u d y o n
S t r e n g t h Development o f High Strength M o r t a r Using Ground
G r a n u l a t e d B l a s t F u r n a c e S l a g o f D i f f e r e n t F i n e n e s s e s ” , JCA
P r o c e e d i n g s o f Cement a n d C o n c r e t e , No. 46, pp. 174-179, 1992.
2. PLOWMAN, J. M . ” M a t u r i t y a n d t h e S t r e n g t h o f C o n c r e t e ” , M a g a z i n e
o f Concrete R e s e a r c h , 8, No. 22. pp. 13-22, 1956.

A C 1 SP-153 VOL+II 95 m 0662949 0522092 T39 m
3. TOMISAWA, T., CHIKADA, T., DAN, Y. a n d GOTO, M."A S t u d y o n

t h e H y d r a t i o n and S t r e n g t h Development o f Ground Blast-Furnace
S l a g - R i c h Cements", P r o c e e d i n g s o f t h e J a p a n C o n c r e t e I n s t i t u t e ,
Vol. 14, pp. 251-256, 1992.
4. NAGANUMA, H., HASHIMOTO, T, a n d MAEDA, Y. " I n f l u e n c e o f
Chemical Composition o f Slags o n t h e S t r e n g t h o f B l a s t Furnace
S l a g Cement", JCA P r o c e e d i n g s o f C e m e n t a n d C o n c r e t e , No.44,
pp. 216-221, 1990.
5. YODA, A. " N e u t r a l i z a t i o n o f P o r t l a n d B l a s , t - F u r n a c e S l a g
C e m e n t C o n c r e t e ( R e s u l t s a f t e r T w e n t y Y e a r s ) , JCA J o u r . o f
Cement a n d C o n c r e t e , No. 429, pp. 26-32, 1982.
6. IZUMI, I . , KASAMI, H., OSHIDA. F. a n d NISHIHARA, K. " E f f e c t s

o f Cement, M i x P r o p o r t i o n a n d C u r i n g o n C a r b o n a t i o n o f C o n c r e t e
--``,`,-`-`,,`,,`,`,,`---
" P r o c e e d i n g s o f t h e J a p a n C o n c r e t e I n s t i t u t e , V o l . 7, pp. 117-
ii0. 1985.
TABLE 1 - CHEMICAL ANALYSIS OF GROUND GRANULATED

BLAST FURNACE SLAG
Blaine Spec. Chemical c o m p o s i t i o n (%)
grav. SiO2 Alzo3

A1203 Fe0 Ca0 MgO SOS
4 0 4 0 (abb. 4000) 22.. 9900 32.
3 2 . 77 14.
14.88 0O. . 22 42. 3
42.3 5.5 . 77 22.. 0O
6 1140
4 0 (abb. 6000)
6000) 22.. 9900 32.
32.66 14.
14.33 O.0 . 66 42.
4 2 . 33 5.5 . 99 2.
2 . 0O
-
8 1 6 0 (abb. 8000) 22.. 990
0 32.9
32. 9 14.2
14. 2 O.0 . 22 4 2 . 0O
42. 6.6 . 44 22.. 0O
TABLE 2 - CONDITION OF EXPERIMENT
I Factor I Leve I
I Slag content I O, 50, 70, 75, 80, 85, 90, 95 %
I Fineness o f s l a g I 4000, 6000, 8 0 0 0 cm2/g
W/ (C + B) 50, 57, 65 %
C+B 200, 280, 3 6 0 kg/m3
Cement I OPC, HEPC, MHPC
B: B l a s t - f u r n a c e s l a g

A C 1 SP-153 VOL*II 75 IObb2749 0522093 975
TABLE 3 - ESTIMATION EQUATIONS FOR COMPRESSIVE

STRENGTH
--``,`,-`-`,,`,,`,`,,`---
H y d r a t ion time (hour)
Fig. l-Heat evolution curve (BI.: 4000 cm2/g)

A C 1 SP-153 VOL*II 95 W 0662949 0522094 ô01 W
31
r95 c: OPC
I I I
12 24 36 4
fi y d r a t i o n t i me (hour)
Fig. 2-Heat evolution curve (BI.: 6000 cm2/g)
3
93 c : OPC
li 9? W/’C+B: 50%
OcmZ/g
show B/(C+B:
.-
I 24
I 36
I
12 4
H y d r a t i o n time (hour)
Fig. &Heat evolution curve (BI.: 8000 cm2/g)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L U I I 95 m 0662947 0522095 748 m
m --U--4000cm2/g
W
I
8000cm2/g
__._.._.A...
--``,`,-`-`,,`,,`,`,,`---
O 50 70 85 95
Slag content (%)
Fig. &Heat of hydration of slag cement paste
. ,,
'. ---a--- 4 0 0 0 B l a i n e ; l d a y ;30" C
... --E- 4 0 0 0 B l a i n e ; 3 d a y s ; 5'C
-o- 6 0 0 0 B l a i n e ; 3 d a y s ; 5" C
-n- 8 0 0 0 B I a i n e ; 3 d a y s ; 5'C
*.
'\..'.. . . . A . .8 0 0 0 B l a i n e ; l d a y ; 2 0 ' C
..
O 50
I I
70
1
85
.
95
Slag c o n t e n t (%)
Fig. 5-Relationship between slag content and compressive

strength (Age: 1-3 days)

A C 1 SP-1.53 VOLtII 95 m Ob62747 0522096 b ô 4 m
o 4000 B l a i n e
m 6000 B l a i n e
8000 B l a i n e A-
O' ô l
50
I
70 85
I
95
Slag content (%)
Fig. f3-Relationship between slag content and compressive

strength (Age: 7 days)
_______ -------- -
..............................................
_-._
CtB=280
W/(C+B) :57% B I . :4000cm2/g
O 70 ô5 95
Slag content (%)
Fig. 7-Relationship between K/D and slag content

(BI.: 4000 cm*/g)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 75 m O 6 6 2 9 4 9 0 5 2 2 0 7 7 510 m I
- Age:
Sdays
~
1 I I I
O 50 70 85 95
Slag content (Y),
Fig. &-Relationship between K/D and slag content

(BI.: 6000 cm2/g)
C:OPC Age:
W/ ( C t B ) :57% -o--- Sdays
t->
C t B = 2 8 O k g /m - - - A - - - -/days
B I . :8000cm2/g .-.-..o_____ 2 8 d a v s
--``,`,-`-`,,`,,`,`,,`---
Sldays
\ . a:
.. .;
........ .................. ...........-__---
..----------------- ..... -&-*
..........
Y
1 ---------
I I 1 1
O 70 85 95
Slag content (X)
Fig. 9-Relationship between K/u and slag content
(BI.: 8000 cm2/g)

A C 1 SP-153 V O L S 1 1 95 0662949 0522098 457
0 1 0 0 0 0 1 0 0 0 0 1 0 0 0
0 1 0 0 0 m o o 0 0 1 0 0 0
1000 L O O 0 L O O 0
L C ~ C O O ~ L C ~ W C O
Fig. 1+Nonevaporable water
o Slag free
A 4000 Blaine-85% P
6000 Blaine-85% t
o 8000 Blaine-85% ,,'
I
I
I
I
/
20" c - 3 d a y s f'
I
I
r'
if : P
I 1 I
4 6 a 1
E f f e c t i v e combined water (%)
Fig. 11-Relationship between effective combined

water and compressive strength
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m 0662949 0522099 3 9 3 m
2
,
.I-m
.- L
.-oc3
O
.I--
_z-x P)
3
.t-
O
Co 2
=I
-
3
U
O
E 1
o
.-
.I-
m
G o 5 10 15 20 25
Compress i v e s t r e n g t h (MPa)
Fig. 12-Relationship between static modulus of elasticity

--``,`,-`-`,,`,,`,`,,`---
Ages (v-d a Y)
Fig. 13-Progress of carbonation (accelerated test)

A C 1 SP-153 V O L X I I 95 m 0662949 0522300 935 m
G:OPC
w/ (CtB) :57%
E C t B :28 O k g/m3
\ E / (CtB) :85%
0)
4-
m 01 ' I I
4000 6000 8000

F i n e n e s s o f s l a g (cm'/g)
Fig. 14-Relationship between fineness of slag and rate

of carbonation
--``,`,-`-`,,`,,`,`,,`---
o 3 7 14 28
Water c u r i n g period (day)
Fig. 15-Relationship between rate of carbonation and

water-curing period (BI.: 4000 cm2/g)

A C 1 SP-153 VOL*II 75 0662747 0522303 8 7 3
I
--``,`,-`-`,,`,,`,`,,`---
Fig. 1&Relationship between rate of carbonation and

8
tl C:OPC
\
\
W/(CtB) :57%
'
6 I,..
\
C t B : 2 8 O k g/m
BI. :8000cm2/g
- -u-- - _ _ _ - - - --€I
\\
m.....
4< .m....--............................... I B/ (C+B)
2- L-.
-_ n-
---o---95 %
. . ...... 85 4/
-.~.-7o %
1h y A
-0%
1
Y
Fig. 17-Relationship between rate of carbonation and


A C 1 SP-153 V O L X I I 95 Obb2949 0522302 708
h
=-
c
(D
\
E
v
E
c
O
._
4-
Cu
S
O
n
-
Li
(D
o
aa
4-
m
?
1/a ( X 1 OMPa) -'

Fig. 1&-Relationship between rate of carbonation and l/u
h
E
v
E
c
4-
n
aa
-a
C
O
.-
.w
(D
S
O
n
L
(D
o
Fig. 1Wrogress of carbonation (field test)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L S 1 1 95 I0662949 0522103 i344
--``,`,-`-`,,`,,`,`,,`---
m
<u
m
4- C:OPC
L
*O’ W/ (CtB) :57%

.-O CtB=280kg/m3
4- B I . : ô000cm2/g
E
O
15.
D
L Accelerated test
m
0 10- F ie I d t e s t
Slag content (%)
Fig. 20-Relationship between ratio of carbonation rates

and slag content
-
V
-
.-< u >m
I
+ u
sb
‘E \
O E
.-
w -
E
m1
s o
0-
n
LX
m-
O h
.c -4
0-
<u-
4 - m
m a l
cT4-
Rate o f carbonation (mrn/rday)

in a c c e l e r a t e d t e s t (A)
Fig. 21-Relationship between carbonation rates of

accelerated test and field test

A C 1 SP-153 VOL*II 95 W Ob62949 0522104 580
SP 153-60
Fly Ash and Slag Jet-Blast

Resistant Con[retes
--``,`,-`-`,,`,,`,`,,`---
by P. J. Robins and S. A. Austin
Svnousis : Conventional limestone concrete airfield pavements are

prone to spalling as a result of jet-blast from vertical take-off and
landing aircraft. This paper describes a research programme to develop
jet-blast resistant pavement quality concretes containing alternative
cementitious materials and aggregates. The concretes were evaluated
by subjecting slabs to simulated Harrier jet engine blast, using thermal
imaging and video cameras to record surface temperatures, spa11 times
and spalled areas.
Slag and fly ash as partial cement replacement materials
produced moderate increases in the surface temperature and exposure
time at which spalling initiated. Fly ash aggregates produced
substantial improvements in spalling resistance under simulated
Harrier conditions, particularly when used to replace both the fine and
coarse natural aggregates. The spalling mechanism was associated with
differential thermal expansion, as opposed to the release of water
vapour and the dehydration of cementitious compounds. Spalling
observed during field exposure was attributed to laitance and brushing
of the surface, which also suffered from drying shrinkage cracking.
Kevwords: Airports; fly ash; jet blasts; lightweight aggregates; pavements;

slags; spalling; temperature

A C 1 SP-I153 VOLS11 95 = 0662949 0522105 417 =
1142 Robins and Austin
Simon Austin is a Senior Lecturer in Structural Engineering at

Loughborough University of Technology, with 15 years research
experience in concrete materials and technology and the author/co-
author of over 30 papers on the subject. Dr Austin is a chartered
engineer, Member of the Institution of Civil Engineers and Fellow of
the Concrete Society in the U.K.
Peter Robins is a Senior Lecturer in the Department of Civil

Engineering at Loughborough University. Concrete has been his main
research interest over the last 25 years, including work on deep beams,
NDT, fibre reinforcement cement replacements and concrete repair. Dr
Robins is the author/co-author of over 50 papers, a chartered Member
of the Institution of Civil Engineers and CANMET/ACI reviewer.
INTRODUCTION
--``,`,-`-`,,`,,`,`,,`---
Some aircraft pavements are subjected to high temperatures and
air pressure due to the jet-blast from military aircraft. Two examples
are vertical take-off and landing (VTOL), aircraft, such as the Harrier,
and conventional fixed-wing aircraft during tethered engine testing
and normal take-off with reheat. These extreme conditions can cause
spalling of the concrete surface, resulting not only in pavement
deterioration but also in potential foreign object damage if particles are
subsequently ingested into an aero engine.
This paper describes a research programme which investigated

the benefits of modifying conventional pavement quality concrete
(PQC) by the addition/cubstitution of slag and fly ash products.
Mixtures with 40% cement replacement (by weight) of fly ash and slag
were examined together with three mixtures containing pelletized fly
ash as an aggregate. The evaluation occurred in three phases:
laboratory testing using a simple gas jet to Investigate thermal shock
resistance; jet blast testing with the British Aerospace (Warton) ground
erosion facility, set up to simulate a Harrier aircraft engine; and field
evaluation of three of the special concretes at RAF Wittering.
BACKGROUND
The construction, maintenance and repair of RAF airfield

pavements has been the responsibility of the Property Services Agency
(PSA) for many years. Concrete pavements and landing pads have

VOL*II 95 I0662949 0522106 353 m
~~
A C 1 SP-153
been used extensively in areas where the airfield is subjected to high

temperatures from jet-engine blast. The most severe service condition
occurs with vertical take-Offs and landings by Harrier aircraft.
In the mid 1980s the regular airfield inspections at RAF
Wittering revealed that some concrete pavements laid in 1970 had
begun to show signs of damage. This took the form of shallow sRalls
on the concrete surface. The deterioration raised two problems, one
relating to repair of the pavement and the other to the risk of foreign
object damage to aircraft jet engines.
Published research on the heat resistance of concrete pavements

subjected to jet-engine blast is scarce, al though calcium aluminate
cement (HAC) concretes have been found to be superior to normal
portland cement concretes in resicting erosion by vertical/short take-off
and landing aircraft such as Harriers(l,2). McVay et a1431 have recently
reported on aircraft damage of US Department of Defence airfield
pavements, although this paper is principally concerned with damage
caused by fluid spillage. In 1986 the PSA requested Loughborough
University of Technology's assistance in investigating alternative
materials for VTOL aircraft, there being concern about the durability of
HAC concretes and about difficulties encountered in laying them
within their short setting time. Earlier investigations(4) established
relationships between jet exit temperature, residence time to first spall,
and surface temperature at first spall, showing that under Harrier
aircraft conditions (typically exhaust temperature of 650OC and a
pressure of 1.5 atmospheres) the pavement quality concrete (1) spalled
when its surface temperature reached about 350OC, and that this
occurred after a residence time of around ten seconds. Subsequent
observations at RAF Wittering, using heat sensitive paints, confirmed
that the landing pad concrete attained surface temperatures of up to 300
- 350OC during actual Harrier take-off. It was also confirmed that the
normal take-off time was around 5 to 7 seconds (which would not
result in spalling), whilst prolonged take-Offs resulting from operating
with maximum payloads or by pilots undergoing training could exceed
12 seconds (and thus could heat the concrete enough to cause a spall).
HIGH TEMPERATURE EFFECTS ON CONCRETE
There are two distinct mechanisms associated with the spalling

of concrete caused by rapid heating. Firstly moisture vapour may form
within the matrix at such a rate that resulting pressures fracture the
concrete. In a set cement water may be held in three ways: as
chemically combined water in the cement hydrates, as water adsorbed
in the gel of cement compounds (i.e. in the gel pores), and as water in
--``,`,-`-`,,`,,`,`,,`---

A C 1 Sp-353 V O L * I I 95 = 0662949 0 5 2 2 3 0 7 29T M
the capillary pores of the cement matrix. The effect of increasing

temperature on these different waters is complex, but a simplified view
is that the capillary water will turn to steam at around 1OOOC and the
combined waters (chemically and adsorbed) will form moisture vapour
at higher temperatures, dependent upon the temperature at which the
various compounds dehydrate.
The second mechanism of spalling involves the differential
thermal expansion of the matrix, which subsequently bursts apart the
concrete. This differential movement can be the result of either
different coefficients of thermal expansion of the aggregate and cement
paste or the temperature gradient down through the concrete as the
surface is rapidly heated. Previous work had already shown that
during jet-blast erosion only the top few millimetres experience the
very high temperatures(5).
On heating, a portland cement paste will first lose its capillary
water at around 1OOOC and then its adsorbed and combined water at
higher temperatures before eventually reaching a water-free state
--``,`,-`-`,,`,,`,`,,`---
beyond which new ceramic phases form (around 1OOOOC). Ettringite (if
present) dehydrates at around 150 to 200OC. Hydrogarnet (C3AH6), the
hydrate of tricalcium aluminate and tetracalcium aluminoferrite,
breaks down at around 350OC. At around 500OC calcium hydroxide
breaks down to form free lime, and the calcium silicate hydrates lose
their water at temperatures above 800OC. It is important to note that
the reactions giving off water occur intermittently and this can be
significant in causing cracking. The formation of lime from the
dehydration of calcium hydroxide is a weakness of portland cement
paste, because subsequent wetting can cause severe disruption due to
the large volumetric expansion (44%) as the lime rehydrates to calcium
hydroxide. Thus, though a portland cement concrete can withstand
high temperatures on first heating, it is unsuitable for applications
involving a regime of repeated heating, cooling and exposure to
moisture.
On heating, HAC paste will also lose its capillary water at around
1OOOC. Between room temperature and 300OC adsorbed water is lost
and the calcium aluminate hydrates and alumina gel breakdown; this
process is usually complete by around 400 - 500°C. Unlike OPC, the
hydrates break down in a slower and more controlled manner causing
less internal disruption, and there is also no calcium hydroxide
available to form potentially destructive free lime. At temperatures in
excess of 900OC a refractory HAC concrete will start to increase in
strength again as ceramic phases form within the matrix. Thus,
although an HAC concrete is more spa11 resistant when heated, it can

A C 1 SP-353 VOLaII 95 0662949 0522LOB 126 =
suffer from the disadvantage in ambient structural applications of

conversion of the hydrates with a consequent reduction in strength.
MATERIALS AND MIXTURES
Selection of Materials for Evaluation
A range of materials was selected on the basis of their potentially

beneficial effect on one of the two OPC concrete spalling mechanisms,
namely dehydration and differential thermal expansion. The options
examined in the full investigation included reducing the free-water in
the hardened concrete by lowering the water/cement ratio of the
mixture , and increasing the permeability of the concrete to allow the
water vapour to escape more easily. The data are reported
elsewhere(ó), whilst this paper concentrates on the use of slag and fly
ash both as a cementing material to alter the hydrate compounds of the
mixture and as an aggregate to reduce the effect of differential thermal
expansion within the concrete.
In addition to a conventional PQC mixture, the data for a high
alumina cement (HAC) concrete control mixture are also presented.
Materials
The two cements used in the investigation were: normal
portland cement complying with BS 12 and high alumina cement
(Fondu). The ground granulated blast furnace slag (GGBS) complied
with BS 6699 and the fly ash (FA) with BS 3892; Part 1.
The standard PQ concrete aggregates consisted of washed river

sand fine aggregate and a quartzitic limestone coarse aggregate,
supplied in two maximum aggregate sizes (IOmm and 20mm). The fly
ash aggregate was Lytag, a pelletized and sintered fly ash, used in two
--``,`,-`-`,,`,,`,`,,`---
sizes: a 10mm granular coarse aggregate and a graded fine aggregate

approximate 4mm down.
An air entraining agent was added to all mixtures with the
exception of HAC concrete. A retarding plasticizer was added to the
high alumina cement limestone concrete mixture, to extend its
working time.
Mixture Specification
/
The PSA specification for PQ concrete for airfield construction

contained the following requirements:
(I) maximum aggregate/cement ratio of 5.8;

A C 1 SP-153 V O L * I I 95 = Obb2949 0522309 Ob2 =
(2) maximum water/cement ratio of 0.45;

(3) fine aggregate content to be 32-37% by weight of total aggregate
content;
(4) volume of entrained air to be 5%1: 1%;
(5) slump of 30-60mm; and
(6) a target mean strength of 32.3 MPa at 7 days for trial mixtures.
This specification was generally followed for all the limestone

aggregate/normal portland mixtures. The mixture proportions for the
fly ash aggregate concrete were based on the supplier’s
recommendations and the experience from trial mixes. Throughout
the programme, the requirements for aggregate/cement ratio,
maximum water/cement ratio, fines content and 7 day strength were
met, though workability was principally assessed using the Vebe
method as opposed to the slump test, a time of around 10 seconds
having been found to give satisfactory workability for the method of
slab manufacture used. Mixture proportions are given in Table 1,
together with workability, air content and 7-day compressive strength.
Three of the mixtures were subsequently patented(7).
--``,`,-`-`,,`,,`,`,,`---
Specimen manufacture
In the second stage (for simulated Harrier exposure) three slabs

(600 or 800 x 600 x 100mm) panels were made from each mixture (Table
l), and then (for further simulated Harrier testing) a further nine slabs
were made from three of the most promising mixtures (LAI, LA2 and
GGBS). The compacting and finishing technique was developed to be
representative of site practice and involved internal poker vibration,
removal of excess paste (fat) by scraping, surface closure with a
vibrating beam and hand trowelling to finish. Some slabs were brush
finished as per normal pavement practice. The panels were cured
under plastic sheeting in the laboratory for 3-4 days, or with a sprayed
membrane on site.
OXY-ACETYLENE FLAME TESTING
A series of trial mixtures was chosen to cover the range of

materials identified above. The spall resistance of these concretes was
assessed in the laboratories at Loughborough using an oxy-acetylene
flame, operating at a height of 145mm above the surface. This height
was chosen because it produced a spall in the control OPC mixture in
around 12 seconds, i.e. similar to the time observed previously under
simulated Harrier conditions(4). The performance of these mixtures,
relative to the normal portland cement control, in increasing order of
spalling resistance was:

A C 1 SP-353 VOL+II 95 0662949 0522330 8 8 4
modest improvement:
A lightweight aggregate in combination with limestone sand
fines (mixture LA2) improved spall resistance, as did the HAC
mixture.
large improvement:
A cement replacement material in an otherwise standard PQ
mixture improved spalling resistance, the fly ash (mixture FA)
appearing to be marginally better than the slag (mixture GGBS).
The combination of fly ash and a coarse fly ash aggregate
(mixture FA/LA) also produced a significant improvement.
exceptional improvement:
The use of lightweight fine and coarse aggregates (mixture LA1)
produced a concrete of exceptional spall resistance.
--``,`,-`-`,,`,,`,`,,`---
SIMULATED HARRIER JET-BLAST TESTING
Test Procedures
Slabs were subjected to jet-blast in the ground erosion test facility

at British Aerospace, Warton. For these tests, the rig was initially set up
to simulate current Harrier aircraft jet conditions; this required a
Harrier nozzle configuration with a jet exit temperature of 700OC at a
height of three nozzle diameters above the slab surface and a pressure
of 1.5 atmospheres. Further test runs were conducted at other
temperatures varying from 600 to 1200OC.
Each slab (held in its steel mould) was mounted on the rails of
the ground erosion rig and then positioned centrally under the jet
nozzle, with its surface normal to the axis of the jet and at the specified
height (Fig. 1). Prior to exposure, the test pressure and temperature
were established on a heat shield protecting the specimen. Once the
correct run conditions were achieved, the heat shield was rapidly
removed by a linear-motor powered trolley.
Slabs were tested for a minimum jet residence time of 40
seconds; if no spalling had occurred, the test was continued for up to
120 seconds before shut-down. Complete visual and thermal imaging
data for all test runs was recorded on video tapes for later analysis.
From these recordings the time and surface temperature at the location
of the first spall, together with the maximum surface temperature at 40
seconds were determined for all slabs. Spalled areas were measured on
the cooled slabs.

A C 1 SP-153 VOLJII 95 W 0662949 0522LLl 710 W
Concrete srialling
Spalling was characterised by the progressive ejection of coin-

sized flakes of concrete, which in cases of severe spaliing formed larger
irregularly shaped spalled areas (Fig. 2). The spalling that occurred was
very shallow, typically a few millimetres, and a piece of aggregate was
often visible at the centre of a spall.
A wide range of spalling resistance was. observed. At 700OC the

plain OPC mixtures first spalled after 6 to 18 seconds, the blended
cement mixtures at 11 to 33 seconds, the HAC mixture at 62 to 92
seconds, and the combined limestone and lightweight aggregate
mixtures at 15 seconds to no spall after 120 seconds. The all lightweight
aggregate mixture did not spall during the two minute tests conducted
at 700OC.
Surface temperatures
Under Harrier conditions the surface temperature reached 3OOOC

within a few seconds and had reached a steady-state temperature of
around 500 - 540OC after about ninety seconds. Fig. 3 shows some
typical temperature-time relationships. Little difference was observed
between the OPC control and the blended cement and HAC mixtures.
However, the ail lightweight aggregate mixture (LAI) surface
temperatures increased more rapidly and reached a higher plateau,
whilst the lightweight coarse aggregate/river sand mixtures (FA/LA
and LA2) produced intermediate values. These differences in
behaviour are attributable to the lower thermal conductivity and
diffusivity for the lightweight aggregates and are not due to the
differences in hydrates resulting from the different cementitious
materials. Typical values of thermal conductivity are 0.8 Jm/m2soC for
structural lightweight concrete and around 3 Jm/m2soC for a
limestone concrete.
Occurrence of first wall
The times to first spall for the panels tested at 700°C are shown
in Table 2. The performance of the mixtures; relative to the normal
portland cement control, in increasing order of spaiiing resistance was:
(1) no significant improvement:
The fly ash mixture showed a similar performance to the
normal portland cement control.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L J I I 95 I 0662949 0522112 657 m
(2) modest improvement:

The slag mixture improved average spalling times from 15
seconds to 28 seconds (this average value ignores the one sample
that did not spall).
(3) large improvement:
The HAC mixture produced an average time to first spall of 77
seconds.
(4) exceptional improvement:
No spalling occurred during the 120 second exposure in any of
the panels from the lightweight fine and coarse aggregate
mixture (LAl), the lightweight aggregate in combination with
river sand mixture (LA2) or the lightweight aggregate/sand
mixture containing fly ash (FA/LA).
In the second part of stage two, slabs were exposed to jet

temperatures ranging from 600°C to 1170OC. This allowed a better
comparison of the more resistant materials which did not spall at
700OC (just above current Harrier temperature of 650°C). Fig. 4 plots
first spall time against jet temperature for the GGBS, Lytag/sand and
Lytag mixtures, and all the control PQ concrete mixtures tested during
this and previous programmes. The BAe line represents British
Aerospace's estimate of a lower bound based on their earlier work(5)
on OPC concrete.
It is clear that the all Lytag mixture (LA1) had a greatly superior
blast resistance, spalls only occurring at jet exit temperatures of 1OOOOC
and above, which is well in excess of current Harrier engine jet
conditions. The Lytag/sand mixture (LA2) performed significantly
better than control limestone PQ concrete, with cpalling occurring at jet
temperatures of 700OC and above. The trend of the GGBS modified PQ
mixture is slightly better than that of the standard PQ concrete, though
the spall times were considerably lower than those obtained in the first
part of stage two. The difference in performance cannot be explained
conclusively but it is most likely to be associated with the method of
slab manufacture. More specifically, a greater amount of fat at the
surface may have the effect of burying the potentially disruptive larger
aggregate particles deeper in the surrounding paste and hence reduce
the chance of a particle initiating a spall in the hot zone directly
beneath the engine nozzle.
The most logical relationship between spall time and jet
temperature is one that is asymptotic to a value of jet temperature at
high residence times, and also asymptotic to the temperature axis at
high jet temperatures (when spalling would occur in a very small but
finite time). A curve with an appropriate form is the equation:
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L S 1 1 95 0662949 0522LL3 5 9 3
a
t=- ... (1)
(Ti- b)"
where t is the spall time(s1, Tj the jet temperature (OC), and a, b and n
are constants. For the PQ limestone concrete a value of 450°C for the
temperature asymptote constant b was found to give the best fit with a
correlation coefficient of 0.98. The equation of the curve for the control
PQC is:
2810
t=
(Ti- 450)"06
Corresponding relationships for the three concretes with

slag/OPC cement or fly ash aggregates are:
for the GGBS, (3)
69 1O0
for the Lytag/sand, t= (4)
(Ti - 650)'.87
56
for the Lytag, t= ... (5)
(Ti - 900)0.52
Fig. 4 indicates that under Harrier conditions (650°C) spalling of

a limestone PQ concrete will occur at a residence time of about ten
seconds. This is commensurate with what has been observed in the
field; normal take-Offs taking less than this, and some take-Offs in
training taking longer and thus being likely to produce some cpalling.
The predicted time to first cpall for the GGBS concrete is around 13
seconds, whilst the Lytag/sand mixture did not spall at 650°C and even
at 700°C (where only 1 out of 5 samples failed) the residence time to
first cpall is likely to be well in excess of 20 seconds. The Lytag mixture
did not spall at temperatures of 900°C and below.
--``,`,-`-`,,`,,`,`,,`---
The surface temperatures at first cpall for the slabs tested at

700°C in the second stage of the work are given in Table 3. The OPC PQ
control mixture produced first spall temperatures in the range 320-
370°C, which is very much in line with values observed in previous
work(4) and in the field. The first spall temperatures for the slabs made
with a blended cement (Le. with fly ash or slag) were all in the range
390°C to 425°C. The average first spall temperature for the HAC slabs
was 435°C.
For the second stage work, the surface temperatures at first spall
are shown in Fig. 5 together with the linear regression best-fit line for
PQC(4). Whilst the scatter of results is large, a best-fit straight line

A C 1 SP-153 V O L * I I 95 111 0662949 0522LL4 42T
indicates that the slag mixture spalled at a significantly higher

temperature than control PQ concrete. Under Harrier conditions of
--``,`,-`-`,,`,,`,`,,`---
around 650OC the first spall temperature is around 370oC compared

with 340OC for the PQ concrete. The Lytag/sand mixture (LA2) only
spalled when subjected to jet exit temperatures of 7OOOC and above.
The surface/ jet temperature relationship cannot be defined from the
three data points, but the points lie within the scatter of the GGBS
mixture results. The superior performance of the Lytag mixture (LA1,
coarse and fine aggregates) is again demonstrated by Fig. 5, spalling only
occurring a t surface temperatures above 500OC; such temperatures
cannot be expected to occur with current Harriers.
A general comparison of the spalling performance of the various

mixtures with that of the control OPC PQ concrete shows that whilst
modifying the cementitious matrix (using fly ash or slag) produced
some improvements, by far the most significant increases in spalling
resistance were achieved when the natural aggregates were replaced
with the fly ash Lytag lightweight aggregate. This could be because
these porous aggregates can absorb the released water vapour or,
perhaps more likely, because they induce less differential thermal
expansion (or withstand it better).
It is of interest to note that concretes often exhibit a significant

increase in coefficient of thermal expansion a t temperatures above
32OoC, and this has been attributed to dehydration of the cement paste.
Philleo(8) quotes values of around 8 x 10-6 per O C below this
temperature and 20 x 10-6 per OC above, for a calcareous gravel
aggregate concrete, whilst interestingly an expanded shale aggregate
showed a n increase from only 6.1 to 7.5 x 10-6 per OC. In view of the
fact that the PQ limestone concrete spalled at a temperature of 320 -
370OC (Le. just above the critical transition temperature of 320OC) and
that the fly ash Lytag aggregate concrete (also with a coefficient of
thermal expansion of around 7x10-6 per OC) did not spall, the most
likely principal mechanism causing the spalling is a differential
thermal expansion effect between the top very hot layer of concrete and
the cooler layers below. This effect will be aggravated over any natural
aggregate particles which are close to the surface, as the particles will
have a much lower coefficient of thermal expansion than the paste at
the surface.
Spalled areas
The spalled area of the slabs tested in the second part of the
second stage is plotted against jet exit temperature in Fig. 6 . The spalled
areas (after 40 seconds) of the slag specimens are shown in relation to

A C 1 SP-I453 VOL*II 95 m Ob62949 0522115 3 b b m
the best fit obtained previously for control PQ concrete(3). The spalled
area/jet temperature relationships of the two mixtures are similar,
though the trend for the slag indicates a marginal improvement.
The two Lytag mixtures sustained considerably less damage,

particularly when it is borne in mind that the areas shown are after a
120 second test duration. At Harrier conditions spalling of the
Lytag/sand mixture is minimal (around five square centimetres) and
the all Lytag mixture did not spall at all. Even at jet temperatures of
around 1OOOOC the all Lytag panels suffered only minor damage.
TRIAL AIRCRAFT PAVEMENTS
The slabs tested under simulated Harrier conditions in the

second part of stage two were made from the three concretes used to
construct a trial landing pad (in three bays) in the field at RAF
Wittering. The concretes were the slag mixture (GGBS) with river
sand, the Lytag coarse aggregate with river sand mixture (LA2) and the
Lytag fine and coarse aggregate mixture (LA1).
Two months after construction the trial pad was first subjected to
Harrier vertical take-off and landings. At this time the concretes
looked in good condition. The control over the jet blasting by the
Harriers was limited but the pad withstood the emissions of several
aircraft, including one fully laden with fuel. A few very small spalls
were noticed on the slag trial bay.
--``,`,-`-`,,`,,`,`,,`---
After about six months in service the RAF reported finding

flaws in the trial pad. Subsequent inspections revealed some spalling
on all three concrete bays, together with fine cracking on the surface of
the two concretes containing Lytag lightweight aggregate.
The small spalls were characterized by the loss of material from
the tops of the 'ribs' produced by the brush finish used in construction
of the trial pad. In the case of the slag and Lytag/sand mixtures, small
sand particles were often revealed by the spall, which is consistent with
the previous conclusion that the spalling mechanism is principally the
result of differential thermal expansion between aggregate particles and
the surrounding cement paste. However, differential thermal
properties are unlikely to have been a contributing cause in the all
Lytag mixture. Furthermore, the Lytag panels tested under simulated
Harrier conditions at Warton were totally resistant to normal Harrier
blast temperatures. This suggests a difference in the concretes which,
since the Warton panels were made from the same batch of concrete as

A C 1 SP-153 V O L X I I 95 0662949 0 5 2 2 1 1 b 2 T 2
the Wittering bays, must relate to the placing, finishing and curing, or
perhaps to the exposure to the outside climate.
--``,`,-`-`,,`,,`,`,,`---
Whilst in the earlier development of the mixtures the test

panels had a smooth, trowelled finish, some of the panels made
simultaneously with the trial bays at Wittering were given a brush
finish. The brush finish did not appear to affect the first spall time of
the two Lytag based mixtures but possibly marginally reduced the slag
mixture spall times. Though the use of a brushed finish did not appear
to make the concrete test panels particularly more prone to spalling in
the ground erosion rig tests, the ribs are clearly more susceptible to
damage (both mechanical and thermal) and are perhaps not well suited
to take off and landing pads. Moreover, if the finishing process
produces a weak surface laitance, then brushing will concentrate the
weak material in the ribs. The mixtures required a lot of work when
placed in the field and there was evidence of laitance on the bays. It is
therefore concluded that the spalling of the Lytag mixtures was
associated with the formation of a weak laitance resulting from the
finishing and brushing operations on site, perhaps exacerbated by the .
high cement content of these mixtures. The slag mixture was easier to
lay and did not appear to have significant surface laitance.
The surface cracking appeared on all the Lytag based concrete
exposed at Wittering, namely the pad bays and some test panels left at a
pre-construction area near the landing pad. The cracking was not
visible after two months, was visible at 11 months and had worsened
by 23 months. The cracking was very fine, shallow and of an irregular
pattern. All the indications are that this crazing resulted from drying
out of the surface. The formation of fat and laitance during finishing of
an initially cement rich mixture would produce a surface with
potentially high shrinkage. The exposed situation at the Wittering
airfield, possibly combined with inadequate curing measures, could
easily have induced this shrinkage.
CONCLUSIONS
Based on the tests under simulated Harrier conditions (700OC,

1.5 atmospheres) the tests showed that, whilst modifying the
cementitious matrix (using fly ash or slag) produced some
improvements, by far the most significant improvements in
performance were achieved when the natural aggregates were replaced
with fly ash based artificial lightweight aggregate.
The most likely principal mechanism causing the spalling is the
differential thermal expansion effect between the top very hot layer of

A C 1 SP-I153 V O L * I I 95 m 0662949 0522337 139 m
concrete and the cooler layer below. This effect is clearly aggravated
over any natural aggregate particles which are close to the surface, as
these have a much lower coefficient of thermal expansion than the
paste at the surface.
The portland cement PQ control concrete produced surface
temperatures at first spall in line with values observed in previous
work (i.e. around 340OC). The portland cement/limestone aggregate
mixtures incorporating either the fly ash or slag produced higher first
spall temperatures (around 370OC) and the mixtures containing the fly
ash aggregates were able to sustain surface temperatures of over 5OOOC
without spalling.
The jet-erosion performance of the all fly ash aggregate mixture
was exceptional. This mixture had a greatly superior blast resistance to
that of conventional limestone PQ concrete; no spalling occurred at jet
exit temperatures below lOOOOC, and even at temperatures in the range
1000-1175OC the slabs only suffered minor damage.
The surface cracking observed in the field is thought to result

from restrained drying shrinkage. The crazing and spalling in the
Lytag mixtures are the result of excessive cement paste and laitance
caused by bleeding of water and over working. The latter are probably
the result of the finishing and brushing techniques used on site,
combined with the high cement content of these mixtures.
ACKNOWLEDGEMENTS
The authors acknowledge the PSA's financial support and

technical guidance on airfield pavement design and construction, and
are grateful to British Aerospace for the use of their testing facility and
to the staff of the ground erosion laboratory for their assistance and
advice throughout the testing.
REFERENCES
1. Wu, G.Y.: 'Heat resistant concrete pavements', M i l i t a r y

Engineer, Vo1.509, August 1986, pp 487-489.
2. Fluk, H. and Wu, G.Y.: 'High temperature/pressure testing of
heat resistant runway materials', American Institute of
Aeronautics and Astronautics Aircraft Design, Systems and
Technology Meeting, Texas, USA, October 1983,lO pp.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-II53 VOL*II 95 E 0662949 0522LL8 075
3. McVay, M.C., Smithson, L.D. a n d Manzione, C., 'Chemical

damage to airfield concrete aprons from heat a n d oils', AC1
Materiais Journal, Vo1.90, No.3, May-June 1993, pp.253-258.
4. Robins, PJ., Austin, S.A. and Richards, M.R., 'The resistance of
steel fibre concrete to VTOL engine jet blast', Cement and
Concrete Composites, Vo1.16, in press, 1994.
5. Knott, P.G., 'VTOL aircraft jet exhaust ground erosion - A study
of the behaviour of pavement and platform materials'. British
Aerospace Report No. A I " 535, January 1986.
6. Austin, S.A., Robins, P.J. a n d Richards, M.R., 'Jetblast
temperature-resistant concrete for Harrier aircraft pavements',
Structural Engineer, Vo1.70, No.23/24, December 1692, pp.427-
432.
7. Austin, S.A. and Robins, P.J.: 'Improved pavement material'.
Patent Application No. 9005871.0, 15 March 1990, 23 pp.
8. Philleo, R.: 'Some physical properties of concrete a t high
t e m p e r a t u r e s ' , Journal of the American Concrete Institute,
Vo1.54, April 1958, p p 857-864.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 Obb2949 0522339 TOL
u-
'?
.-
4, so u, ril
a
%G
>-
~ 0 ~ 0 0 0 0
CI
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 W Obb2949 0522320 723 W
TABLE 2 - FIRST SPALL TIMES AT 700 C JET TEMPERATURE
Mixture Description First spall time ts)

Reference
slab 1 slab 2 slab 3 avera e
I
Control OPC 18 14
40% fly ash 17 17
GGBS 40% slag none after 120 22
Fly ash/Lytag none after 120 none after 120 no spall
Lytag none after 120 none after 120 no spall
LA2 Lytag/sand none after 120 none after 120 no spall
HAC HAC 92 62
I
TABLE 3 - SURFACE TEMPERATURE AT FIRST SPALL (700 C JET

TEMPERATURE)
Mixture Description Surface temperature ("C)

Reference
slab 1 slab 2 slab 3
--``,`,-`-`,,`,,`,`,,`---
392 480 435

A C 1 SP-L53 V O L 8 1 1 95 0 6 6 2 9 4 9 05223211 bbT
--``,`,-`-`,,`,,`,`,,`---
Fig. l-Concrete test slab in ground erosion rig

A C 1 SP-153 V O L + I I 95 Obb2949 0522122 5Tb
--``,`,-`-`,,`,,`,`,,`---
Fig. 2-Typical spaiiing of test slab

A C 1 SP-153 VOLlirII 95 = 0662949 0522323 432
2
500
+
ea,
2
E
8
4?
2
-
g 400
5
5
300
O 20 40 60 80 1 DO 120
Residence time (5)
Fig. 3-Sutface temperature/time relationships
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL+II 95 m 0 6 6 2 9 4 9 0 5 2 2 1 2 4 379 m
--``,`,-`-`,,`,,`,`,,`---
O 0
It A
ControlpQc
GGBS
O Lytaglsand
A Lytw
Lylag/sand
o1 I I I 1
400 600 800 1O00 1200
Jet exit temperature (C)
Fig. &Effect of jet temperature on first spall time

A C 1 SP-153 VOLrII 95 W 0662949 0522125 205
700
ControlPQC
GGBC
0 Lytaglsand
-2-
-
600 A Lytw
U
P
c
E
c
c
o
2
a,
L
a,
Q
E
+
a, GGBS
o
3
u)
400
300
400 600 ao0 loo0 1200
Fig. !5-Relationship between jet temperature and surface

temperature at first spall
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L U I I 95 m Obb2949 0522126 141
800
Control PQC (40s)
GGBS(40s)
O Lytaglsand (120s)
A Lytag (120s)
600
iv
E
v
O
o! 400
U
O
-
a>
-
O
Q
cn
200
Lytog/sand
C
400 600 800 1O00 1200
Fig. ô-spalled areas
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 VOLrII 95 m 0662747 0522327 O B B m
SP 153-61
Chemical Activation of
Lime-SI ag Blends
by C. Shi and R. L. Day
Synopsis : Ground granulated blast-furnace slag may show very

high strength in the presence of proper alkaline activators. However,
the high cost and short supply of alkalies restrict the application of such
cementitious materials. This paper reports on an investigation of some
practical ways to increase the reactivity of blast furnace slag.
Experimental results indicate that for moisture curing at 50°C, the
addition of either 4% Na,SO, or 4% flake calcium chloride can
significantly increase the strength of lime-slag mixtures consisting of
80% slag and 20% hydrated lime. The measurements of change in
Ca(OH), content with times in the hardened pastes shows that the
addition of activators accelerates the early reaction, but does not affect
overall reactivity. Strength improvement in Na,SO, pastes is due to the
--``,`,-`-`,,`,,`,`,,`---
formation of ettringite (AFt), while the presence of CaC1, favours the

formation of C3A.Ca(OH),.12H,0. At the same time CaC1, partially
replaces the Ca(OH), in C,A.Ca(OH),. 12H,O and forms a solid solution
of C,A.Ca(OH),. 12H,O - C,A.CaCl,.lOH,O in CaC1, pastes.
Kevwords: Blast furnace slag; chemical analysis; free lime; hydration;

@; porosity; strength

A C 1 SP-353 V O L U I I 95 M 0662949 0522328 "14
1166 Shi and Day
AC1 member Caijun Shi is an environmental process engineer with

Wastewater Technology Centre, Burlington, Ontario, Canada. He
received his Ph.D. from the University of Caigary in 1992. His research
interests include chemical activation and utilization of supplementary
cementing materials and solidificationístabilization of various hazardous
wastes with cementitious materials. He has authored more than 30
technical papers in these areas.
AC1 member Robert L. Day is associate Dean of Engineering Faculty

and professor of Civil Engineering a t the University of Calgary, Calgary,
Canada. His research interests include durability of concrete and the
use of secondary cementing materials to improve durability and
strength. He is a member of AC1 Committee 209 on creep and
shrinkage.
--``,`,-`-`,,`,,`,`,,`---
INTRODUCTION
Ground granulated blast-furnace slag (GBS) has been used widely

in the cement and concrete industry for various purposes [l-21.
Manufacture of cement is an energy-intensive process, requiring 4000
MJ/metric ton. The energy required t o produce GBS is estimated at
only 25 to 33% of that for portland cement. The replacement of portland
cement with blast-furnace slag can result in a considerable saving in
energy 121. At the same time, the presence of blast furnace slag
improves the quality of Lhe transition zone between cement paste and
aggregate, refines the pore structure of hardened pastes and concretes,
and increases impermeability of hardened pastes and concretes.
Because GBS usually hydrates more slowly than portland cement, the
addition of GBS t o concrete may decrease its early strength gain.
However, if GBS is mixed with a suitable activator, such as caustic
alkali or water glass, a higher strength and more durable concrete may
result [3-41. Suitable alkaline activators, however, are not widely
available and may be too expensive for wide-range use.
In previous work [5-71, it was found that the addition of Na,SO, or

CaCl,, which is very inexpensive and widely available, can significantly
increase the strength of lime-natural pozzolan cements. For example,
it was found shown [6] that when pastes are cured at 5O0Cc,the addition
of 4% Na,SO, improved 7-day and 28-day strengths by 80-90%; 4%
CaCl,.ZH,O resulted in 45% improvement of strength a t 7 days and
115%improvement at 28 days. The purpose of the work reported here
was to examine whether the additions of Na,SO, and CaC1, has a
similar effect on the reactivity of lime-GBS cements.

A C 1 SP-353 V O L * I I 95 Ob62949 0522329 950
EXPERIMENTATION
Raw Materials
The chemical composition of the GBS used is presented in Table 1.

The Blaine fineness and density of the ground GBS are 400 m2/kgand
2920 kg/m3. XRD analysis indicates that the slag consists of vitreous
phases and only trace amounts of crystalline substance
(3Ca0.Mg0.2Si02)can be identified. In addition, a commercial hydrated
lime, which meets ASTM C141 specification, was used. Flake
CaC12.2H,0 and anhydrous Na,SO, were used as activators.
Preparation and Testing of Specimens
The lime-slag blends consisted of 20% hydrated lime and 80% GBS
by mass. 4% Na,SO, or CaC12.2H,0 were added based on the mass of
the lime-slag blend. Pastes were cast with a water to solid ratio of 0.45.
Mixing and specimen preparation were carried out at room

temperature; hot raw materials were used to make the initial
temperature of the mixtures close to the curing temperature of 50°C.
After casting into glass vials (925x50 mm), the specimens were placed
into a water bath at 50°C. The glass vials were stripped very quickly
when these specimens had hardened significantly; the demolding process
was very rapid and did not substantially affect the curing process.
At every testing age, four specimens were taken out one hour before
the testing time and cooled. Ends were polished to make the two
bearing surfaces flat and parallel. Three specimens were tested in
compression and the strength results given are an average of the three
specimens. The average coefficient of variation of the strength results
was less than 10%.
Portions of the fourth specimen, which was used for microstructural

analysis, were crashed and then freeze-dried as described previously [81.
The Ca(OH), content in the hardened pastes was determined by thermal
analysis as described previously [9]. X-ray diffraction was used to
identify the hydration products and mercury porosimetry was used to
estimate porosity and pore size distribution of the hardened pastes.
--``,`,-`-`,,`,,`,`,,`---

A C 1 S P - 1 5 3 VOL*II 95 = 0662749 0522130 672
1168 Shi and Day
EXPERIMENTAL RESULTS AND DISCUSSION
Strenah Development
Fig.1 shows the strength development from 3 to 180 days, of the

lime-slag pastes cured at 50°C with and without activators. In the
absence of activators, lime-slag mixtures show low strength ranging
from 6 MPa at 3 days to about 16 MPa at 90 days. The addition of 4%
Na,SO, or 4% CaC1,.2H,O shows a large infiuence on rate of strength
gain. Before 90 days, CaCl, shows a more pronounced activation effect
on the slag than Na,SO, does. Further investigation is required to
reveal the reasons for the apparent strength retrogression of the CaCl,
pastes at 180 days.
Reaction Rate of Ca(OH),
The free Ca(OH), (CH) content in hardened lime-slag mixtures at

ages from 3 to 90 days was measured. Fig. 2 shows the percentage of
CH reacted, calculated from experimental results and the known initial
CH content. Before 3 days, all three pastes show a rapid depletion of
CH; then, the reaction rate of CH slows noticeably. At 3 days, about 12%
more lime in 4% CaCl, pastes is depleted than that in Na,SO, or control
pastes, After 14 days, the rate of reaction of CH in all pastes is slow,
but appears to be more rapid in the control pastes than in the activated
--``,`,-`-`,,`,,`,`,,`---
pastes. The major activation effect of both CaCl, and Na,SO, occurs
before 3 days. After 14 days, control pastes show a CH content similar
to Na,SO, pastes. At 90 days, still more than 10%of the added CH can
be detected in CaC1, pastes.
Pore Structure of Hardened Lime-Slag Pastes
Fig.3 shows the mercury intrusion curves of three types of paste at

3 and 30 days. At 3 days, control pastes exhibit much higher porosity
than CaCl, and Na,SO, pastes. According t o the intrusion curves, this
difference results mainly from the pores in the range of 40 to 100 nm.
Na,SO, pastes also show about 6% higher porosity than the CaCl,
pastes, while this difference is primarily due to the difference of the
pores between 10 and 30 nm. Difference in total porosity at this age is
consistent with compressive strength development and reacted CH
content, as shown in Figures 1 and 2.
At 30 days, the porosity of the three pastes is greatly decreased, and

the main pore size becomes much smaller. CaC1, pastes still have the
lowest porosity among the three pastes, while Na,SO, pastes show a
similar porosity compared to control pastes.

A C 1 SP-153 VOL*II 95 IObb29Y9 0522131 509 I
Hydration Products and Microstructure of Hardened Lime-Slag Pastes
According to the XRD patterns of lime-slag cement pastes (Fig.41,

C-S-H and C,AH,, are the main hydration products in the control paste.
Some C,AH,, exists, but the principal peak is small. When Na,SO, is
added, ettringite (AFt) appears in addition to C4AHI3,but the AFt and
C,AH,, peak heights are also small.
The XRD patterns of lime-slag pastes with 4% CaC1,.2H20 are

similar to those of lime-fly ash pastes with 4% CaCl2.2H,O reported
elsewhere [lo]. Two peaks corresponding to C,A.CaCl,.lOH,O and the
solid solution of C,A.Ca(OH),. 12H,O and C3A.CaC1,. 10H,O appear at 3
and 7 days, but these two peaks form one combined peak at 30 days. I t
appears that more C,AH,, forms at 30 days and the two compounds
develop into a complete solid solution.
Figs.5-7 shows SEM micrographs of three lime-slag pastes at 3

days. In the control pastes, all slag particles are covered by foil-like C-
S-H (Fig.5-a). Fig.5-b shows products in the voids of the control pastes;
the crystalline products are too small to be identified. Fig.6-a indicates
that the pastes with 4% Na,SO, are similar to, but denser than that, of
the control pastes. However, in Na,SO, pastes some needles can be seen
on exposed surfaces. Fig.6-b shows many fine needles in the voids of
Na,SO, pastes; these needles are likely t o be AE't. Although XRD tests
also indicate the presence of C,A.Ca(OH),. 12H,O, no hexagonal plates
were found under SEM observation. The addition of CaC1, to lime-slag
pastes clearly densifies the microstructure (Fig.7-a). Comparison of
Fig.7-b with Fig.5-b shows that the texture inside the voids of CaCl,
pastes is similar to that of control pastes, except for the appearance of
hexagonal plates; X-ray analysis identifies these plates as
C,A.Ca(OH),. 12H,O and C,A.CaCl,. 10H,O.
At 30 days, control pastes show a similar but denser structure than

those at 3 days. A major difference, however, is that many coarse
needles of AFt appear in the voids of the control pastes (Fig.8-a); no
hexagonal plates were observed. N%SO., pastes at 30 days are also
similar to those at 3 days; the slight difference is that the structure is
denser and more needles appear in the voids (Fig.8-b). In addition t o a
denser structure, Fïg.8-c shows that the hexagonal plates in the voids
of CaC1, pastes are definitely larger than those at 3 days.
Hypotheses Concerning: the Activation Mechanism Lime-Slag: Blends
The activation mechanism of lime-slag is roughly similar to that of

lime-natural pozzolan described elsewhere [61. However, some
differences occur because of the high self-cementitious nature of the
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 VOL*II 95 0662949 0522132 445 =
1170 Shi and Day
slag. The slag contains a high content of network modifiers ( C a 0 and

MgO); more network formers are readily dissolved into solution than in
--``,`,-`-`,,`,,`,`,,`---
the lime-natural pozzolan or lime-fly ash systems mixtures when water

is added. Thus hydrated calcium silicates or hydrated calcium
aluminosilicates form quickly in the lime-slag system, and some C&í13
can also be identified. These hydration products cover the surface of the
slag particles. Unlike natural pozzolan and low calcium fly ash, slag
can hydrate by itself in the presence of water. The self-cementitious or
self-hardening properties of slag densifies and strengthens the pastes.
The addition of Na,SO, accelerates the dissolution of slag, but

retards the dissolution of Ca(OH),. The presence of Na,SO, accelerates
early hydration that is controlled by the dissolution of slag and leads to
more C-S-H formed around slag particles. At the same time, the
introduction of Na,SO, leads t o the formation of AE't. Both factors
increase the early strength of lime-slag pastes. However, the formation
of more C-S-H around the slag particles in Na,SO, pastes retards later
hydration of lime-slag mixtures, which is controlled by the diffusion of
water through the hydrated layer on the slag grain surface. This
explains the differences in Ca(OH), depletion and the pore structure
changes between control and Na,SO, pastes. The strength difference
between the control and Na,SO, pastes may be attributed to the
reinforcement effect of AE't.
CaC1, has an opposite action when compared to Na,SO,; it retards

the dissolution of slag and accelerates the dissolution of Ca(OH),. The
addition of CaCl, favours the formation of C3A.Ca(OH),.12H,0. At 3 and
7 days, C,A.Ca(OH),. 12H,O and C3A.CaC1,.10H,0 Co-exist. As more
C,A.Ca(OH),. 12H,O forms, C,A.Ca(OH),. 12H,O and C,A.CaCl,. 10H,O
form a complete solid solution at 30 days. No exposed slag particles can
be observed in lime-slag pastes even at 3 days and there is a high
content of Ca(OH), in CaC1, lime-slag pastes at later ages; this is
attributed to the high self-cementitious properties of the slag.
CONCLUSION
The addition of Na,SO, or CaC1, can substantially increase the

strength of lime-slag pastes. The measurement of CH content vs ages
suggests that the addition of Na,SO, or CaC1, accelerates the reaction
between slag and Ca(OH), at early age, but there is no detectable
difference at later ages.
The hydration products of lime-slag pastes are C-S-H and C,AH,,.

In the presence of Na2S0,, AFt occurs instead of C,AH,,. The presence
of CaC1, accelerates the dissolution of Ca(OH), and favours the

A C 1 SP-153 VOL*II 95 I0662749 0522133 381 M
formation of C,AH,,. At the same time, some CaCl, replaces Ca(OH), in

C,AH,, and forms the solid solution C,A.CaCl,.lOH,O - C,AH,,.
The strengthening mechanism of Na,SO, addition is attributed to

the formation of AFt. The strengthening effect of CaCl, is attributed to
the formation of more C,AH,,.
ACKNOWLEDGEMENT
The financial support from the International Development Research

Centre of Canada and the Natural Science and Engineering Research
Council of Canada is gratefully acknowledged.
REFERENCES
1. Uchikawa, H., Effect of Blending Components on Hydration and
Structure Formation, Proceedings of 8th International Congress
on the Chemistry of Cement, Vol.1, Rio de Janeiro, Brazil, 1986,
pp. 249-280.
2. Malhotra, V. M. Properties of Fresh and Hardened Concrete

Incorporating Ground, Granulated, Blast Furnace Slag, in
Supplementary Cementing Materials for Concrete, ed by V. M.
Malhotra, Minister of Supply and Services Canada, 1987,
pp. 291-336.
--``,`,-`-`,,`,,`,`,,`---
3. Shi,C., Day, R. L., Wu, X. and Tang, M., Comparison of the

Microstructure and Performance of Alkali-slag and Portland
Cement Pastes, Proceedings of 9th International Congress on the
Chemistry of Cement, Vol.3, New Delhi, India, 1992, pp. 298-304.
4. Shi,C., Wu, X. and Tang, M., Hydration of Alkali-Slag Cements

at 150"C, Cement and Concrete Research, V01.21, No.1, 1991,
pp. 91-100.
5. Shi, C. and Day, R. L., Acceleration of Strength Gain of Lime-

Pozzolan Cement Pastes by Thermal Activation, Cement and
Concrete Research, Vo1.23, No.4, 1993, pp. 824-832
6. Shi,C. and Day, R. L., Chemical Activation of Blended Cements

Made With Hydrated Lime and Natural Pozzolan, Cement and
Concrete Research, Vo1.23, No.6, 1993, pp. 1389-1396.

1172 Shi and Day
7. Day, R. L. a n d Shi, C., Relationships Between t h e Strength

Development of Lime-Pozzolan Cement Pastes and the Blaine
Fineness of Natural Pozzolan, submitted to Cement a n d Concrete
Research, 1993.
8. Om, D. M. F., Application of t h e Scanning Electron Microscope to

t h e Study of Initial Hydration of Portland Cement, Cement a n d
Concrete Research, Vo1.13, No.1, 1983, pp. 146-148.
9. Marsh, B. K. a n d Day, R. L., Pozzolanic and Cementitious

Reaction of Fly Ash i n Blended Cement Pastes, Cement a n d
Concrete Research, Vol.18, No.2, 1988, pp. 301-310.
10. Shi, C. a n d Day, R. L., Acceleration of the Reactivity of Fly Ash

by Chemical Activation, Cement a n d Concrete Research (in press),
1994.
--``,`,-`-`,,`,,`,`,,`---

TABLE 1 - CHEMICAL COMPOSITIONS OF GRANULATED BLAST

FURNACE SLAG
SiO, Al,O,Fe,O, Ca0 SO, MgO N q O &O SrO Tio, LOI

35.33 9.94 0.62 34.65 3.97 14.63 0.31 0.44 0.10 0.45 0.00
--``,`,-`-`,,`,,`,`,,`---
Fig. 1-Effect of activators on strength development of lime-slag
pastes
1
r
o
Fig. 2-Effect of activators on degree of reaction of Ca(OH),

A C 1 SP-153 VOL*i<II 75
No reproduction or networking permitted without license from IHS Ob62949 0522135 1 5 4
Not for Resale
A C 1 SP-153 VOL+II 95 0662949 0522136 090
1174 Shi and Day
-c
control
-c
-
4% Na2S04
-*L
4% CaC12.2H20
* ....
1 10 1o00 1O000
Pore Radius (nm)
(a) a t 3 days
--``,`,-`-`,,`,,`,`,,`---
(b) at 30 days
Fig. H o r e structure of hardened lime-slag pastes (contact angle =

140 deg, surface tension of mercury = 480 mN/m)

A C 1 SP-153 VOL+II 95 = Obb2ïit9 0522337 T27
I +4% CaC12.2H20
I
-
Cc C3A.CaC12.1 OH20
-
CH Ca(OH)2
QC - C4AH13
30 d
3d
+4% Na2S04
--``,`,-`-`,,`,,`,`,,`---
7d
3d
_I
30 d
3d
I h i -
I l I I I I
5 15 25 35 45 55 65 75
D i e a c t i o n Angle (20) (cobalt radiation)
Fig. 4-XRD patterns of hardened lime-slag pastes cured at 50 C

A C 1 SP-153 V O L X I I 95 0662949 0522138 963 W
1176 Shi and Day
--``,`,-`-`,,`,,`,`,,`---
(a>‘Fracture Surface (b) Products in Voids
Fig. 5-Microstructure of control pastes cured for 3 days at 50 C
(a) Fracture Surface (b) Products in Voids
Fig. &Microstructure of N%SO, pastes cured for 3 days at 50 C

A C 1 SP-353 VOLrII 95 = Obb2949 0522339 B T T W
(a) Fracture Surface (b) Products in Voids
Fig. 7-Microstructure of CaCI, pastes cured for 3 days at 50 C
(a) Control Pastes (b) Na,SO, Pastes

--``,`,-`-`,,`,,`,`,,`---
(c) CaC1, Pastes
Fig. &Effect of activators on hydration products in voids of hardened

lime-slag pastes cured 30 days at 50 C

A C 1 SP-153 V O L X I I 75 ûbb2747 0522140 511
SP 153-62
Small-Angle Scattering Study of

Concrete Microstructure as a Function
of Silica Fume, Fly Ash, or Other
Pozzolanic Ad ditions
by A. I. Allen and R. A. Livingston
Svnopsis: Small-angle neutron and x-ray scattering techniques are

being used in a systematic study of the development of concrete
microstructure on the nanometer scale (1 1000 nm) as a function of -
the addition of fly ash, silica fume or other pozzolanic materials.
These methods yield direct measures of the fractal aspects of the
material microstructure, including volume- and surface-fractal
exponents, and structure parameters within the calcium-silicate-
h y d r a t e gel. These variables are being evaluated for use i n a
classification system of microstructures. In the first phase of the
program, the emphasis has been on the characterization of silica fume
products both as separate phases and after reaction in concrete. The
combination of small-angle scattering with a fractal interpretation
scheme has been found to provide a resilient and powerful probe of
t h e u n d i s t u r b e d statistically-significant m i c r o s t r u c t u r e s i n
cementitious systems.
Keywords: Fly ash; fractal microstructure; hydration; material properties;

microstructure; pozzolans; silica fume; x-ray diffraction
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L S 1 1 95 W 0662747 0522143 458
1180 Allen and Livingston
A.J. Allen is a Research Associate in the Dept. of Materials and

Nuclear Engineering, University of Maryland, College Park, MD and
also a Guest Researcher in the Materials Science and Engineering
Laboratory, U.S. Department of Commerce, National Institute of
Standards and Technology, Gaithersburg, MD. Current research
interests are in the microstructural characterization of porous
materials, such as advanced ceramics, cement and concrete.
R.A. Livingston is Acting Chief of the Physical Research Division of

the Office of Advanced Research at the Federal Highway
Administration’s, Turner Fairbank Highway Research Center,
McLean, VA. His professional interests concern the materials science
and nondestructive testing of construction materials. During his
career, he has worked in research positions at the U.S. Atomic Energy
Commision, the U.S. Environmental Protection Agency and the U.S.
--``,`,-`-`,,`,,`,`,,`---
Dept. of Commerce’s National Institute of Standards and Technology.
INTRODUCTION
Microstructure is a critical factor in determining the strength

and durability of concrete (1,2). A method for fully classifying and
quantifying characteristic microstructures, representative of
undisturbed concrete morphologies, has not been available, although
the need for one becomes more important as the variety of materials
added to concrete increases. Additions include silica fume and other
pozzolanic materials, which react with the calcium hydroxide in the
cement (31, to enhance production of calcium-silicate-hydrate (C-S-H)
gel, and alter the microstructure in other ways. Besides affecting the
development of strength, fume additions are intended to counter
deterioration processes within concrete, such as alkali-aggregate
reactions or chloride penetration. To date, these effects have*been
determined, largely, by trial and error tests of specific fume/concrete
mixtures. If silica fumes are to be more widely used, it is important to
understand the reasons for their variability (4,5), and a general
classification system is needed, based on the identification of
characteristic microstructures.
While good fume additives are usually distinguished by high
surface areas per unit volume (up to 100 x 106 m-1 (100 m2 cm3)), the
microstructural complexity of hydrating cements and concretes
strongly suggests that the detailed fume microstructures, over the
whole range of length-scales, are significant in determining their
activity. There is also a general need to relate cementitious

A C 1 SP-153 V O L U I I 95 W Ob62949 0522342 3 9 4 W
microstructures to the basic mechanisms governing concrete

performance (6). Therefore, it is of interest to characterize the
statistically-significant microstructures of different silica fumes, and
to quantify their effects on the microstructural evolution across the
whole length-scale range in hydrating cement systems of
technological importance.
Traditional methods for the microstructural characterization of
concretes include desorption studies, mercury intrusion porosimetry
(MIP) and scanning electron microscopy (SEM). Unfortunately, these
methods have had limited success (7-9). This is because they cannot
measure down to the very fine length-scales (1 - 100 nm) that define
critical aspects of the microstructure, and partly because these
methods themselves create changes in the microstructure, either
during drying pre-treatments (SEM), or as a result of hydraulic
pressure and/or their intrusive nature (MIP and desorption). MIP and
desorption studies also involve restrictive assumptions regarding
pore shape and morphology (7). In contrast, small-angle scattering
(SAS) of neutrons (SANS) or x-rays (SAXS) is most effective in this
size range, is non-destructive, and amenable to a range of model
assumptions regarding pore shapes and morphology (7-17). Since SAS
requires no destructive drying pre-treatments, and does not modify
the microstructure itself, it can be used repeatedly in real-time
characterization of the representative microstructural evolution
during cement hydration. SANS can be used to probe a sample
volume several millimeters in diameter and = 1 mm thick, enough
to probe the undisturbed statistically-significant microstructure in
cements and mortars, if not concrete containing full-size aggregates.
Thus, the technique complements methods, such as transmission
electron microscopy (15) (TEM), which give a detailed but highly
localized picture of the microstructure.
It has been demonstrated (15-19) how SAS data yield several
parameters, including particle size, shape, surface area and fractal
exponents, which can provide a concise, quantitative description of
the microstructure. The assumption of approximately fractal
microstructures over appropriate scale-ranges, can form the basis of
stable mathema tical representations for a variety of disordered porous
morphologies, provided three experimental requirements are met.
Firstly, the data must extend over sufficient angular range to
encompass the SAS associated with all significant length-scales.
Secondly, the sample thickness must be sufficiently small so that the
SAS does not suffer from significant multiple scattering effects. In
practice, this means that samples should be no more than 1 - 2 mm
-
thick for neutrons, and 0.1 mm thick for x-rays. Thirdly, the data
must be absolutely calibrated so that the relative strengths of the SAS
arising in different parts of the microstructure can be properly
assessed. This last condition plays an important role in determining
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 M O b b 2 9 4 9 0522343 220 M
that there is no significant multiple scattering, and in eliminating

spurious microstructural interpretations.
In previous SANS studies on hydrating cement systems,
modifications in the microstructural evolution were apparent,
associated with the addition of silica fume, fly ash or blast furnace slag
(12,15-17). The effects of environmental degradation, such as that due
to sulphate attack, were also observed. The present research applies
SANS to the microstructural characterization of different silica fume
(SF) additives in high-performance cements (HPC). The ability of
blended SF/HPC cements to resist microstructural degradation,
associated with alkali-aggregate reactions, freezing and thawing, or
sulphate attack, is also of interest. In this paper we describe a real-time
study of the microstructural evolution during hydration in = 0.4
water-to-cement ratio (w/c) HPC and in one typical = 0.4 water-to-
solids ratio (w/s) SF/HPC blend.
--``,`,-`-`,,`,,`,`,,`---
SCOPE OF STUDY
Small-Anele Scatterino Principles
The small-angle neutron scattering technique takes advantage

of some special properties of the neutron. This atomic particle's
wavelength can be readily adjusted by passing it through materials at
fixed temperatures. With a cold neutron source, chilled to 35 K, the
resulting typical wavelengths range from 0.5 to 2.0 nm. Thus, they
can probe material structure down to the molecular level. Moreover,
neutrons scatter very effectively from hydrogen-bearing materials
such as those found in hydrated cement reaction products. Finally,
compared to other probes of materials such as x-rays, neutrons can
penetrate significant depths. This enables them to measure closed as
well as open porosity.
For SANS the scattering processes involved are essentially
elastic. Consequently, from the laws of conservation of energy and
momentum, the incident and scattered directions, for a neutron of
specified energy, completely define its interaction with a nucleus, as
shown in Fig. 1. In neutron scattering research, it is the practice to use
wavefunctions and wavevectors, derived from quantum mechanics,
to describe the scattering process. Consequently, instead of the
scattering angle, 28, it is customary to use the scattering vector, Q, as
shown in Fig. 2. Its magnitude, Q, is proportional to sine, and has the
dimension of inverse length (nm-1). Note that the direction of Q is
not the same as that of the scattered neutron, and for S A N S where 28
is typically less than 5 O , Q is at approximately 90' to the beam. The Q
range for S A N S studies is typically 0.01 to 10 nm-1, sufficient to

A C 1 SP-II53 VOLXII 95 Obb2949 0522IIYY L b 7 W
characterize features in the size range of 1-100 nm, with the scattering
at the largest accessible Q associated with the smallest part of the size
range.
In SANS studies, a roughly monoenergetic (monochromatic)
beam of neutrons is selected, using a rotating helical velocity-selector.
This beam is highly collimated by a series of neutron wave-guides, 2 -
15 m in length. The beam is then passed through the sample, and the
scattered component is measured with a two-dimensional position-
sensitive neutron detector. For the smallest scattering angles, this
detector array can be located as far as 15 m from the sample.
Fig. 1,2 describe scattering from a single nucleus in the two-
dimensional plane, defined by the incident and scattered neutron
vectors. However, in an actual three-dimensional sample, containing
many nuclei arranged in a heterogeneous microstructure, the
direction of the scattered neutron is not completely described by a
single plane scattering angle, 28, but instead by the probability of
scattering into the solid angle element, da, about a direction defined
by the scattering angle, 28, and the azimuthal angle, cp, as shown in
Fig 3. Thus, dO = d(28)dq . The angular dependence of the scattering
probability for a single neutron is determined by coherent
(interference) summing of the scattered wavefunction amplitudes
arising from the sample's heterogeneous microstructure. The
scattering contributions from different neutrons do not interfere, i.e.,
they sum incoherently. If the sample material's heterogeneous
microstructure is isotropic, the probability of scattering is circularly
symmetric about the incident beam axis. Thus, for a given incident
neutron flux, the probability of scattering is independent of cp ,and
depends only on 28, or Q. This simplification is possible for
cementitous materials, but may not be appropriate for other kinds,
such as geological materials containing laminations with preferred
orientations (18/19].
The raw data are the numbers of scattered neutrons counted at
each detector element in the two-dimensional array. These data are
then normalized to unit sample volume and neutron flux, calibrated
against a standard scatterer, and corrected for background scattering
etc., to give the angular differential macroscopic scattering cross-
section, dI;/dQ. When expressed as a function of Q, dC/dO (with
units: m-1 st-1) is a normalized absolute scattering probability function,
characteristic of the sample material's heterogeneous microstructure,
and not dependent on the particular experimental details or sample
geometry. The interpretation of the SANS data relies on finding an
appropriate physical model that provides a good functional fit to the
experimental variation of dI;/dO with Q. Such models involve a
number of characteristic material microstructure parameters, which
--``,`,-`-`,,`,,`,`,,`---

a r e obtainable from t h e fits. These include particle size, pore-size

distribution, a n d fractal exponents describing b o t h spatial density a n d
surface area. The theory of small-angle scattering is discussed in detail
--``,`,-`-`,,`,,`,`,,`---
elsewhere (20).
Mcrostructural Model
Previous studies of cement paste a n d concrete, b a s e d o n SANS
(13-17,21,22), SAXS (23-25), porosimetry a n d TEM (261, a s well a s SEM
a n d stereology (27), all indicate t h e p r e s e n c e of d i s o r d e r e d o r
heterogeneous p o r o u s microstructures Their prevalence over m a n y
length-scales is itself a defining characteristic of an approximately
scaleinvariant o r fractal solid / p o r e morphology (28).
In real materiais, t w o basic types of fractal microstructure exist:
volume-fractal, a n d surface-fractal. In a t w o - p h a s e volume-fractal
microstructure, the total volume of a given p h a s e included within a
s p h e r e of arbitrary radius, r, centered o n a n y point in the structure,
scales o n average a s rDv, where the volume-fractal exponent, Dv, is
different from 3 (Dv = 3 for a uniformly random structure). Dv can be
between 1 a n d 3, but is usually between 2 a n d 3. A surface-fractal
microstructure is a rough surface structure in which t h e n u m b e r of
surface elements of linear dimension, r, n e e d e d t o cover the surface,
scales o n average a s r-Ds, where the surface-fractal exponent, Ds, is
different from 2. (Ds = 2 for a smooth surface). For the surface-fractals,
o r fractally-rough surfaces, usually encountered in p o r o u s materials,
values of Ds are found between 2 and 3.
Previous SANS studies of c e m e n t s (13-17) have revealed a
volume-fractal structure with Dv = 2.5 - 2.7, depending o n the type of
cement. The emergence of this structure could be correlated with the
time of the main heat output of the hydration reactions, a s measured
by thermal calorimetry, a n d hence with the production of the major
outer C-S-H product gel phase in the o p e n spaces between the original
clinker grains (see Fig. 4). Therefore, it is reasonable t o a s s u m e that
t h e volume-fractal microstructure is the outer C-S-H product phase.
This p h a s e is characterized by a high surface area (up to 200 - 300 x 106
m 11, a fundamental building-block or globule size close t o 5 nm,
which does not s e e m t o vary with hydration time o r between cement
blends, a n d a correlation length, kv SV defines the average upper-limit
length-scale for t h e volume-fractal microstructure. It w a s found to
increase from 5 - 10 nm u p to 100 - 200 nm (depending o n the cement
mix), a s hydration proceeds. This is consistent with a physical model
of colloidal particles of C-S-H o n the order of 5 nm, aggregating into
clusters, which grow t o 100 - 200 nm in size, before growing into o n e
other. In addition t o t h e s e dimensional parameters, t h e s a m p l e
volume fraction of t h e outer C-S-H p r o d u c t phase, $c-H, a n d the

A C 1 SP-153 VOLJII 75 0662949 O522346 T 3 T W
volume fraction occupied by the whole of the volume-fractal

microstructure (solid + open volume), +GEL, could also be determined
and correlated with the hydration reaction heat output. The open
volume associated with the volume-fractal phase should include
much of the open porosity in the cement. However, fine pore spaces,
which are either inside the C-S-H globules themselves or within the
inner C-S-Hproduct gel (formed within the original clinker grains)
--``,`,-`-`,,`,,`,`,,`---
are not included.

At larger length-scales, a surface-fractal structure was revealed
(15-17) in hydrated cement systems, with Ds = 2.5 2.8, depending on -
cement mix and age. This could be associated with the decoration of
the cement grains with a layer of outer C-S-Hproduct. The surface-
fractal microstructure is more difficult to parameterize because its
minimum length-scale is masked by the dominant volume-fractal
structures at smaller length-scales. Also, the average upper-limit
length-scale, tS,is frequently too large (several hundred nanometers)
to parameterize accurately in practical SAS experiments. Moreover, at
early hydration times, the whole surface-fractal effect is masked in
SANS experiments by interface-softening effects as water permeates
into the clinker grains. Nevertheless, tScan be estimated, and it is
expected that the smooth surface, Sor which ignores all roughness on
length-scales less than tS,as well as Eg itself, should be related to the
cement clinker grain dimensions.
Microscopic stereology of fracture surfaces (27) has revealed a
further volume-fractal microstructure in the coarser (1 - 10 pm)
pore/grain morphology, which is the result of different mechanisms
not discussed here. Fig. 4 shows the microstructural model that is
relevant for SAS studies.
Avvlication of Mode1s in SmalbAnde Scattering Experimenb
Come basic points can be made, which are model-independent.

Firstly, a major simplification in interpreting the SAS from
heterogeneous disordered porous materials, such as cement paste, is
that the contribution arising from the pore/solid interface dominates
the scattering. Contributions from other interfaces, such as that
between different hydrated phases, are usually negligible.
Secondly, the total pore/solid interfacial surface area, Sv, can be
determined from the Q-4 Porod scattering at the highest Q values in
the data, using the well-known Porod Law expression (20): dl/dS2 =
2 x I Ap I 2 S, /Q4, where I Ap I2 is the scattering contrast giving a
measure of the strength of the scattering at the solid/pore interface.
The Porod surface, Sv, thus obtained, can be compared with that
determined from other techniques or deduced from applying a

A C 1 SP-153 VOLaII 95 W 0662749 0522147 776
microstructural model.
Thirdly, while the SAS data for different cements vary, the
same generic characteristics are exhibited. Therefore, the
microstructural model, which has been developed for the hydration
of HPC and SF/HPC , should be applicable, in its essential aspects, to
hydration studies of most cementitious systems.
In Fig. 5, the main features in the SAS data, associated with the
microstructural parameters of the model, are shown. These
characteristic hallmarks of SAS from hydrating cementitious
ma terials become pronounced when the incoherent flat-background
scattering is removed (as in Fig. 5) and the data plotted as Q4 dWdQ
--``,`,-`-`,,`,,`,`,,`---
versus Q4, as shown in Fig. 6,7.The model predicts Q-DVscattering (Le.
between Q-1 and 4 3 ) for volume-fractals, and Q+-W scattering (i.e.
between Q-3 and Q-4) for surface-fractals. In the model function for
d Z / d Q as a function of Q, previous work (17) has identified four,
components (see Appendix):
&/dQ = VOLUME-FRACTAL + SINGLE-GLOBULETERM + ...

... + SURFACE-FRACTAL + ...
... + FLAT-BACKGROUND SCATTERING [il
The volume-fractal term contains $CSH, Dv, SV, and the mean
radius, Ror and shape aspect ratio, ß, of the building-block C-S-H gel
globules, here assumed to be spheroids. For a smooth fit, it is also
necessary to include a local packing fraction, q, for near-neighbor gel-
globules, and a correlation-hole radius, R, (not related to SV or {J,
which is the mean nearest-neighbor separation of the individual
globule centers. In fitting the data, the need to incorporate R, with q,
and a well-defined single-globule term, is strong evidence for a solid
volume-fractal phase, composed of globular building-blocks. This is
because nearest-neighbor solid particles cannot exist inside one
another. Thus, unlike the case of fractal pores in clays and porous
rocks (17-19),or eccentrically-shaped solid particles, their centers
cannot approach, on average, to within a well-defined value of R,.
This correlation-hole effect means that, for length-scales of order Ror
the individual particles are seen as distinct objects, even when
incorporated into an aggregated structure. For the single-globule term
itself, satisfactory fits are obtainable with both mildly oblate (ß = 0.5)
and mildly prolate (ß = 2) aspect ratios, giving globule sizes equivalent
to a 5 nm sphere.
The surface-fractal term includes Ds, -$and So. From these
parameters, an estimate can be made of the contribution, made by the
fractally-rough surface, Sf,to the total surface, S., To estimate Sf,a

A C 1 SP-153 V O L * I I 95 Obb29q9 052211tô ô02 =
reasonable assumption can be made that the surface-fractal either

results from the deposition of outer C-S-H product on the clinker
grains, or (possibly) from the independent formation, over longer
hydration times, of inner C-S-H product within the clinker grains (see
Fig. 4). Thus, an acceptable extrapolation might be given by: Sf =
S0(5s/R, I(Ds-2).
The flat-background term in [i] refers to the incoherent flat-
background scattering, and it is usually subtracted out of both data and
fits for convenience.
In recent years, many of the modelling concepts, encompassed
in the above discussion, have become established in the
interpretation of SAS data from disordered porous materials (29).
However, the formulations presented here go further in seeking to
obtain the amounts (volume fractions and surface areas) of each
microstructural component present in cementitious systems. This
fractal approach overcomes many of the problems associated with
more simplistic interpretations, based on determining artificially-
defined pore or particle sizes, where the parameter values determined
are frequently found to vary with the Q-range studied, Le., can
become artefacts of the experimental conditions. In contrast, the
fractal approach has proved both versatile and resilient for a range of
cement studies (13-17), provided that the experimental conditions
discussed previously are satisfied.
Experimental Approach
In the present experiments, two kinds of cement paste samples

were used. Some were hydrated fully prior to the SAS measurements.
For others, hydration took place in real-time during the SANS
experiments. The SANS studies were carried out using the
NIST/Exxon/University of Minnesota 30m SANS instrument at the
Cold Neutron Research Facility (CNRF), National Institute of
Standards and Technology, Gaithersburg, MD (30). A collimated beam
of neutrons, of wavelength, h, 0.55 nm, and A h / h resolution of 15%,
was arranged to impinge on a parallel-sided optical cell containing the
sample. For the pre-hydrated cement pastes, which were kept moist,
sample thicknesses ranged from 0.5 to 0.9 mm. For the real-time
hydration studies, samples were made up and the paste injected into 1
mm thick cells. The diameter of the sampling volume in the incident
beam was 6.35 mm (0.25”). By changing the instrument configuration,
data were obtained over an overall range of the scattering vector, Q, of
0.04 - 1.8 nm-1. In the real-time studies, the instrument configuration
was continually cycled to obtain data over the complete range in
about 2 hours, which was, therefore, the time-resolution for the real-
time experiments.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOLXII 95 m Obb2949 0522349 749 =
For some pre-hydrated samples, the SANS data were

supplemented by ultrahigh resolution SAXS (USAXS)
measurements, which extended the Q range down to 0.003 nm-1. For
the USAXS studies, based on the Bonse-Hart double-crystal diffraction
technique (31), specimens were crushed to give an effective sample
thickness of less than 100 pm, and encapsulated in polyimide plastic
film. These data had to be desmeared to correct for the line-geometry
of the measurement configuration, and, for this instrument, an
absolute geometric calibration was made for each sample. Fig. 5 shows
combined neutron and x-ray dZ/dQ data as a function of Q for HPC.
The x-ray d L / d a data have been normalized to the neutron dZ/dQ
data.
The results presented here are for a comparison of the
microstructure evolution during hydration in a typical SF/HPC
--``,`,-`-`,,`,,`,`,,`---
cement, compared to that in a standard HPC, under the same
conditions. The HPC was made with 0.38 w/c using Type I portland
cement. In the SF/HPC, 10% by weight of the cement solids were
replaced with commercial silica fume. This was supplied in a slurry,
which also contained 28% of the total water weight in the final
hydrated cement mixture. Given the small size of the samples,
ultrasonic mixing, to ensure uniform dispersion of the fume, was not
considered necessary. To prevent the fume from agglomerating
unevenly during cement hydration, small amounts (-1%)of water-
reducer and a superplasticizer were added. To start hydration, these
components were mixed together, and the remaining water added.
The total water-to-solids ratio was 0.38 w/s. By combining studies of
real-time hydration with those using pre-hydrated samples, the data
and results discussed below were obtained.
The internormalized SANS and USAXS data for hydrated 0.38

w/c HPC, shown in Fig. 5, cover an extended range of over three
decades in Q and seven decades in scattering intensity. Fig. 6,7 show
SANS data and model fits for 0.38 w/c HPC and 0.38 w/s SF/HPC,
respectively, at various hydration times, plotted on a log-log scale as
44 dZ/dQ vs Q4. Good microstructural model fits were obtained
almost everywhere, using standard multi-parameter least-squares
fitting techniques. A realistic range of parameter starting values was
probed to ensure stability in the output parameter values. Results are
presented in Tables 1and 2.
For the 0.38 w/c HPC after 11 days hydration, most of the

A C 1 SP-353 VOLXII 95 0662949 0522350 460
characteristics of SAS from fully hydrated cement are apparent.

Application of the model confirms that the C-S-H consists of 5 nm
diameter globules, and indicates that = 10% of the sample volume is
occupied by solid outer C-S-H product and that the total surface area,
C, = 80 x 106 m-1. The total volume of C-S-H plus associated volume-
fractal pores, $GEL, amounts to nearly three quarters of the total
sample volume, occupied by the outer C-S-H product gel phase; but
this includes much of the porosity, as discussed earlier. For the 0.38
w/s SF/HPC, the microstructure after 11 days, as interpreted by the
model, is qualitatively similar to that for 0.38 w/c HPC, although a
marginally smaller solid C-S-H volume fraction, a slightly larger
surface area, and a greater overall volume fraction of the volume-
fractal phase are indicated. Also, while the fits give Dv = 2.6 for both
materials, {v is some 30% larger for SF/HPC, indicating a more
distended volume-fractal phase in this system, and suggesting a less
densely agglomerated long-range microstructure in the outer C-S-H
product.
For the surface-fractal components of the 11-day cement
microstructures, Table 2 shows that the SF/HPC system contains
more surface area in this component than does HPC. For SF/HPC, the
fitted parameter values are consistent both with finer clinker grains
and decorated particle sizes in this system, and with the more
distended volume-fractal phase noted above.
Time-DeDendent Studies of Real-Time Hvdration
Fits for time-dependent studies of 0.38 w/c HPC and 0.38 w/s
SF/HPC are also shown in Fig. 6,7. Tables 1 and 2 present the time-
dependent results for microstructural parameters of interest. For
clarity, only the results for four hydration times are plotted on each
figure. In both cases, hydration changes the SAS from Porod Q4
scattering over much of the range to the more complicated curves
containing the fractal scattering laws discussed earlier. It is of interest
that nowhere is a Q-2 power law behavior observed. This would be a
well-known hallmark (20), indicating the presence of planar or foil-
like C-S-H structures, sometimes seen in TEM studies (26). The
absence of a Q-2 power law indicates that the foil-like structures may
not be statistically-representative (at least in the volume-weighted
sense) of the undisturbed C-S-H gel microstructure.
Comparison of Fig. 6,7 shows that, as expected, there is more
initial high-surface materia1 in the SF/HPC system. At high Q (fine
length-scales), there is increased scattering due to a small amount of
C-S-H gel formation. As hydration progresses, and following the well-
known dormant induction period, the rise in this scattering follows
the time-dependence of the heat output from the main hydration
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L * I I 95 0662949 0522l15L 3T7 =
reactions, as established in earlier work (15). When analyzed using

Guinier plots (8-12) of ln(dZ/dQ) vs Q2 (not discussed in detail here),
this rise in the high-Q scattering at even the earliest hydration times
can be identified with 5 nm diameter features. Experimentation with
the microstructural model reveals the presence of strong correlation-
hole effects, which are consistent with these features being solid
objects, and leads to the conclusion that they are globules of C-S-H.
Recently, this conclusion has been supported both by independent
small-angle scattering studies (21), and by microstructural
characterization studies based on the application of thermodynamic
modelling in nitrogen desorption studies (6). Furthermore, model
fits, which assume that the 5 nm features are pores, do not give
results that are physically meaningful.
--``,`,-`-`,,`,,`,`,,`---
As hydration time progresses, the fit results, presented in

Tables 1 and 2, not only indicate that more C-S-H is formed, but that it
gradually arranges into a volume-fractal aggregate structure. For
SF/HPC, the sequence of fit values in Table 2 shows the complicating
effect of the silica fume microstructure, which masks some of the
early hydrated microstructure development. However, for both
systems, Dv decreases eventually to near 2.6 and increases to more
than 100 nm after 11 days. Fig. 8 shows the rise in volume fraction of
the outer C-S-H product solid phase with time for both cement
systems. The most rapid increase occurs during the first 24 hours’
hydration, although the end of the induction period in SF/HPC is
delayed with respect to that in HPC. This effect is more pronounced
in the rise in total volume fraction of the whole volume-fractal phase
(also shown in Fig. 8). However, it should be noted that, while the
SF/HPC microstructure development is initially delayed with respect
to that in HPC, it tends to catch up as hydration progresses.
While it is not possible to characterize the surface-fractal
microstructure as completely as the volume-fractal microstructure,
some important conclusions can still be drawn. It is evident from a
comparison of Fig. 6,7, and Tables 1 and 2, that the initial fractally-
rough surface area of the grains in the SF/HPC system is two to three
times higher than in HPC. This is to be expected, given the addition of
the finely divided silica fume to this system. Fig. 6,7 also exhibit a
downward slope at intermediate Q and early hydration times, which,
on these plots, is characteristic of an interface-softening effect (17),
probably due to the ingression of water into the anhydrous clinker
grains. Values of Ds less than 2 are obtained, which although not
physically meaningful in terms of a surface-fractal, nevertheless give
an indication of the degree of this interface-softening effect. At later
hydration times, this region develops the surface-fractal
characteristics discussed above.
cs
From the model-fit values of Ds, and So, it is possible to infer

A C 1 SP-I153 VOLXII 95 Obb2949 0 5 2 2 3 5 2 2 3 3
an estimated contribution to the total surface area, S , from the

fractally-rough component, Sf, believed to be the decoration of clinker
grains and other particles with high surface area C-S-H. Fig. 9 shows
both the rise in Sf with hydration time and the variation of S,,
measured from the Porod Q-4 scattering at high Q. Whereas the
growth in Sv seems to be closely related to the amount of the volume-
fractal outer C-S-H product solid phase, @CSH, Sf is more closely
related, at early and intermediate hydration times to the amount of
silica fume present. This increase by a factor of two to three in the
surface area of fine features that decorate the microstructure, appears
to be the largest effect introduced by the addition of this particular
silica fume slurry.
A major point of interest for future studies is the mechanism
by which the silica fume produces the increased surface-fractal
component. This could directly reflect fractal properties in the as-
received silica fume. Alternatively, the higher solubility of silica
fume could produce a greater volume fraction of C-S-H. A third
possibility is that the silica fume has a fractal structure that
encourages the growth of a more distended form of C-S-H.
CONCLUSIONS
In this paper, it has been demonstrated how the application of a

microstructure model, partly based on fractal concepts, can be applied
in small-angle scattering studies to obtain quantitative parameters,
which are representative of the undisturbed microstructures in
hydrating cement and concrete systems. With regard to the objective
of this research, to develop a quantitative description of cement
microstructures, it has been shown' that approximately twelve
parameters (Roy& and q are not presented here) can be obtained or
derived from model fits to SAS data. While considerable more
research is needed, including further validation and calibration of the
model interpretation, it is proposed that SAS could assist in the
development of a broadly applicable classification system of silica
fume and other pozzolanic materials, based on microstructure. By
combining SAS with other methods, and by following changes in
microstructure that take place during microstructural degradation,
due to processes such as alkali-aggregate reactions, freezing and
thawing, or sulphate attack, future research will seek to gain a better
understanding of how mixture proportions may be better optimized
to enhance cement and concrete durability.
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 V O L X I I 95 Obb2949 0 5 2 2 1 5 3 17T
APPENDIX
The components of equation [ i ] are simplified from a

theoretical expression that is based on a derivation in reference (17).
The full expression is given by:
The correlation-hole radius, Rcr is assumed to be weighted over

spheroid surface-contacts, and is given by:
where:
x, = (1/2ß){1 + [ ß ' / . J i - p ' ] l n ( ( l + ~ ~ ) / ß ) ) forß < 1, [A3al
and
x, = (1/2ß){1 + [ ß ' / . J P ' - i ] a r c s i n ( ~ ~ / ß ) ) forß > 1 [A3b]
For a spheroid of aspect ratio, ß, the form-factor for a single globule,
F2(Q), is given by (32):
where V, = (4ßnR,3/3), J33/2(x) denotes a Bessel function of order 3/2,

--``,`,-`-`,,`,,`,`,,`---
and X is an orientational parameter, here integrated over all

orientations of the spheroid with respect to Q. Use of a mildly
spheroidal globule shape avoids the pronounced Bessel function
oscillations for spheres (ß = l),which can perturb the fit at high Q.
All other parameters in [Al] - [A41 are discussed in the text.

A C 1 SP-153 VOL*II 95 B Ob62949 0522154 006 B
REFERENCES
1. Pratt, P. L. “Relationships Between Microstructure and

Engineering Properties”, Mat. Res. Symp. Proc. 85 145-156,
Materials Research Society, Pittsburgh, PA. (1986).
2. Jenning, H. M., Bhatty, J. I. and Hodson, S. K. “Towards
--``,`,-`-`,,`,,`,`,,`---
Establishing a Relationship Between Microstructure and

Properties of Cement-Based Materials”, in Advances in
Cementitious Materials. (Editor: S. Mindess) American
Ceramic Society, Westerville, OH. 289-318 (1991).
Hjorth, L. ”Development and Application of High-Density
Cement-Based Materials”, Philos. Trans. R. Soc. London, Ser.
A, 310 167-173 (1983).
Mehta, P. K. and Gjorv, O. E. “Properties of Portland Cement
Concrete Containing Fly Ash and Condensed Silica Fume”,
Cem. and Conc. Res. 12 587-595 (1982).
Chatterji, S., Thaulow, N. and Christensen, P. “Puzzolanic
Activity of Byproduct Silica Fume from Ferro-Silicon
Production”, Cem. and Conc. Res. 12 781-784 (1982).
Xi, Y. and Jennings, H. M.,”Relationships Between
Microstructure and Creep and Shrinkage of Cement Paste”, in
Materials Science of Concrete III. (Editors: J. P. Skalny and S.
Mindess) American Ceramic Society, Westerville, OH. 37 69 -
(1992).
7. Smith, D. M., Hua, D-W. and Earl, W. L. ”Characterization of
Porous Solids”, MRS Bull. XIX-4 44-48(1994).
8. Allen, A. J.,Windsor, C. G., Rainey, V. S., Pearson, D., Double,
D. D. and Alford, N. McN. “A Small-angle Scattering Study of
Cement Porosities”, J. Phys. D. 15 1817-1833 (1982).
9. Pearson, D., Allen, A. J., Windsor, C. G., Alford, N. McN. and
Double, D. D. “An Investigation on the Nature of Porosity in
Hardened Cement Pastes Using Small-angle Neutron
Scattering”, J. Mater. Sa. 18 430-438 (1983).
10. Allen, A. J. and Pearson, D. “Porosity and Gel Structure of
Cement”, in Proc. 5th Riso Int. Symp. on Metallurgy and
Materials Science: Microstructural Characterization of
Materials by Non-microscopic Techniques, Sept. 1984, Riso
National Lab. Denmark. (Editors: N. H. Anderson, D. J. Jenson,
M. Eldrup, N. Hansen, T.Leffers, H.Lilholt, O. B. Pedersen and
B. N. Singh) Riso National Laboratory, Rosskilde, Denmark.
175-180 (1984).
11. Pearson, D. and Allen, A. J. “A Study of Ultrafine Porosity in
Hydrated Cements using Small-Angle Neutron Scattering”, J.
Mater. S u . 20 303-315 (1985).
12. Pearson, D., Allen, A. J. and Sambeli, R. A. J. “Small-angle
Scattering Data on Cements with Pozzolanic Additives”,

A C 1 SP-3153 V O L * I I 95 = 0662949 0522155 TY2 w
--``,`,-`-`,,`,,`,`,,`---
Harwell Report AERE-R11609 Harwell Laboratory, Didcot, U.K.

(1985).
13. Allen, A. J. and Schofield, P. “Possible Fractal Structure of
Cement Gels“, in Proc. NATO Symp. on Scaling Phenomena in
Disordered Systems, April 1985, Geilo, Norway. (Editors: R.
Pynn and A. Skjeltorp) Plenum Publishing Co., London. 189-
195 (1985).
14. Allen, A. J. and Schofield, P. “Small-angle Scattering from
Fractal Systems”, in Proc. Workshop on Neutron Scattering
Data Analysis, Rutherford Appleton Laboratory, Chilton, U.K.,
March 1986. (Editor: M. W. Johnson) IOP Conf. Ser. 81 97-102
(1986).
15. Allen, A. J., Oberthur, R. C., Pearson, D., Schofield, P. and
Wilding, C. R. “Development of the Fine Porosity and Gel
Structure of Hydrating Cement Systems”, Philos. Mag. B 56 263-
288 (1987).
16. Allen, A. J., Baston, A. H. and Wilding, C. R. ”Small-angle
Neutron Scattering Studies of Pore and Gel Structures,
Diffusivity, Permeability and Damage Effects”, Mat. Res. Symp.
Proc. 137 119-125, Materials Research Society, Pittsburgh, PA
(1989).
17. Allen, A. J. “Time-Resolved Phenomena in Cements, Clays
and Porous Rocks”, J. Appl. Cryst. 24 624-634 (1991).
18. Allen, A. J., Baston, A. H., Bourke, P. J. and Jefferies, N. L.
”Small-Angle Neutron Scattering Studies of Diffusion and
Permeation through Pores in Clays”, Harwell Report AERE-
R13261 Harwell Laboratory, Didcot, U. K.(1988).
19. Allen, A. J., Baston, A. H., Bourke, P. J. and Jefferies, N. L. “The
Application of Small-Angle Neutron Scattering to the Study of
Mass Transfer in Clays”, in Proc. 6th ïnt. Symp. on Water-Rock
Interactions, Malvern, U.K.,August 1989. (Editor: D. L. Miles)
Balkema, Rotterdam, Holland. 9-13 (1989).
20. Porod, G . “General Theory”, in Small-Angle X-ray Scattering
(Editors: O. Glatter and O. Krattky), Academic Press, London,
17-51 (1982).
21. Eichorn, F., Haussler, F. and Baumbach, H.“Structural Studies
on Hydrating Cement Paste”, J. de Physique IV 3 369-372 (1993).
22. Haussler, F., Eichhorn, F. and Baumbach, H. “Small-Angle
Neutron Scattering of Hardened Cement Paste and Various
Substances for Hydration”, Cem. and Conc. Res. 24 514-526
(1994).
23. Vollet, D., Craievich, A. and Regourd, M. “Small-Angle X-ray
Scattering from Hydrating Tricalcium Silicate”, J. Am. Ceram.
SOC. 67 315-318 (1984).
24. Winslow, D. N. “The Fractal Nature of the Surface of Cement
Paste”, Cem. and Conc. Res. 15 817-824 (1985).

A C 1 SP-It53 V O L * I I 95 CB Obb2949 0522356 989 CB
25. Beddoe, R. E. a n d Lang, K. “Effect of Moisture o n Fractal

Dimension and Specific Surface of Hardened Cement Paste by
Small-Angle X-ray Scattering”, Cem. and Conc. Res., 24 605-612
(1994).
26. Groves, G. W. ”Transmission Electron Microscopy of Cements
and Mortars”, Materials Forum 14 1-8 (1990).
27. Lange, D. A., Jennings, H. M., Shah, S. P. and Quenard, D. A. ”A
Fractal A p p r o a c h to U n d e r s t a n d i n g C e m e n t P a s t e
Microstructure”, Ceram. Trans. 16 347-363 (1992).
28. Meakin, P. ”Diffusion-Controlled Cluster Formation in 2-6-
Dimensional Space”, Phys. Rev. A. 27 1495-1507 (1983).
29. Bale, H. D. a n d Schmidt, P. W. ”Small-Angle X-Ray Scattering
Investigation of Submicroscopic Porosity w i t h Fractal
Properties”, Phys. Rev. Lett. 53 596-599 (1984).
30. H a m m o u d a , B., Krueger, S. a n d Glinka, C. J. ”Small-Angle
Neutron Scattering at the National Institute of Standards and
Technology”, J. Res. Nat. Inst. Stand. Tech. 98 31-46 (1993).
31. Long, G. G., Jemian, P. R., Weertman, J. R., Black, D. R.,
Burdette, H. E. and Spal, R. D. ”High-Resolution Small-Angle
X-Ray Scattering Camera for Anomalous Scattering”, J. Appl.
Cryst. 24 30-37 (1991).
32. Roess, L. C. and Shull, C. G. ”X-ray Scattering at Small Angles
by Finely Divided Solids. II. Exact Theory for R a n d o m
Distributions of Spheroidal Particles”, J. Appl. Phys. 18 308-313
(1947).
TABLE 1 - MODEL FIT RESULTS FOR 0.4 W/C HPC (ESTIMATED

STANDARD DNIATIONS, IN LEAST SIGNIFICANT DIGITS, ARE
SHOWN IN BRACKETS AFTER EACH VALUE)
Dv Ds
2.91 (5) 1.91 (5)

2.88 (5) 1.79 (5)
3.08 (5) 2.13 (3)
2.61 (3) 2.27 (3)
3.7 (1) 2.61 (2) 2.33 (2)
4.9 (2) 2.61 (i) 12.61 (2)
2.61 (1)
2.61 (i) 2.610
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-I153 V O L X I I 95 m Ob62949 0522357 8 3 5 W
TABLE 2 - MODEL FIT RESULTS FOR 0.4 W/S SF/HPC (ESTIMATED

STANDARD DEVIATIONS, IN LEAST SIGNIFICANT DIGITS, ARE
SHOWN IN BRACKETS AFTER EACH VALUE)
--``,`,-`-`,,`,,`,`,,`---
NEUTRON TARGET
NUCLEUS
Fig. l-Basic neutron scattering process (for elastic scattering,

velocities v and v' are equal)

A C 1 SP-353 VOL+II 95 0662949 0522358 751 =
k k
I ELASTIC k = k'
Q = 2ksine
Fig. 2-Relationship between scattering angle 26 and scattering vector

Q
dR = dcpd(20) --``,`,-`-`,,`,,`,`,,`---
INCIDENT
NEUTRONS
Fig. 3-Experimental arrangement for small-angle scattering

A C 1 SP-153 VOL*II 95 I0662949 0522359 698 =
CLINKER GRAIN CORES
S-HPRODUCT
PRODUCT
Fig. 4-Schematic of microstructural model assumed for hydrating

cementitious systems (Outer C-S-H product is volume-fractal phase.
Decoration of clinker grains by C-S-H forms suríace-fractal phase)
Q-3’4
power law
surface-fractal
‘+ CEMENT CLINKER
-h
F
\-GRAINS)
‘v; 106
(TOTAL
SURFACE AREA)
MICROSTRUCTURE)
- ,
(C-S-H GLOBULE SIZE)
I , , , ,.,,.I , , , , ,,,,, , , , , ,,,,
1
Fig. +Typical absolute-calibrated radially

summed a / d Q versus Q for hydrated cement,
showing main features associated with micro-
structural model (incoherent flat-background
scattering subtracted, as in Fig. 6 and 7)
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-353 V O L + I I 95 E û b b 2 9 4 9 0522360 30T E
1 o2 ' ' """I ' ' """1 ' '"""1 '~- ' ' ''''"1 ' ' """~ ' ' """' --j
-h
VI
U
'E
?
v
E,
C
?
w
U
5 o 1.8 hrs + 27 hrs
0 9.0 hrs 1 1 days O i
lo-'' ''lllll.l ".'"'l ''"iiiiI ' """" '"""'1 '"""'1 '

1 o-6 1 o-2 1oo 1 o2
' ' 1 * 1 1 1 1 1
1
Q4(nm-4)
Fig. û-Q4 cZ/cfCl versus Q4 for 0.38 w/c HPC,

showing changes in scattering with hydration
time
1 oz 1 ' '"'"'1 ' ''""'1 ' ''""'1 ' ' "'"'1 ' '"""1 ' ' """~ ' ' """I ' ' ""'I
i 0.38 w/s SF/HPC
h
c
4VI
2
10' [ -
c
'€
P
c
v
c: 1
s
*W
loo
1 o-'
1o 6
i
I
0
1
1.6 hrs
13 hrs
1 o-2
+ 31 hrs
11 days
1 oo
1
il
1 o2
Q4 (r~rn-~)
Fig. 7-Q4 dI/dCl versus Q4 for 0.38 w/s SF/HPC,

showing the changes in scattering with hydration
time
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 H Ob62949 0 5 2 2 L b 1 24b
=
--``,`,-`-`,,`,,`,`,,`---
10
c
.-O
w
U
Lm
u- 0.38 w/c HPC
1
0.38 w/s SF/HPC:
-I+ @CS?
- 4GEL
o. 1 I . . . ..... I , , , .,,.,I , , , ,,
0.1 1 10 1O0 1O00

Hydration Time (hours)
Fig. &Volume fractions of solid C-S-H, &SM,

and C-S-H gel, versus hydration time,
for the two cement systems (Determined from
microstructural model fits to SANS data)
-e- -sv
- -SFS
I . I ,, ,..<, , , , , ,,,,, , , ,,
o. 1 1 10 1 O0 1O00
Hydration Time (hours)
Fig. &Total solid/pore surface area per unit

sample volume S,, and fractally rough component
of this surface S, versus hydration time, for the
two cement systems

A C 1 SP-I153 V O L + I I 95 U O662949 05221b2 182
SI (Metric) Tables 1201
CONVERSION FACTOR-INCH-POUND TO SI (METRIC)*
To convert from to multfply by
Length
inch ............................... millimeter(mm) ..................... 25.4Et

foot ................................. meter(m) ......................... 0.304ûE
yard ................................. meter(m) ......................... 0.9144E
mile (statute) ........................ kilometer (km) ....................... 1.609
Area
square in& ..................... square millimeter (mm*) .................. 645.1

square foot ........................ square meter (m2) ...................... 0.093
square yard ........................ square meter (m’) ...................... 0.83151
Volume (capacity)
ounce ............................. milliliters (mL) ...................... 29.57

gallon ............................ cubic meter (m3)$ ...................... O.UT3785
cubic inch ....................... cubic millimeter (mm’) ................ 16390
cubic foot ......................... cubic meter (m3) ...................... 0.02832
cubic yard ......................... cubic meter (III’)$ ...................... 0.7646
Force
kilogram-force ........................ newton (N) ........................ 9.807

kip-force .......................... kilo newton (kN) ...................... 4.448
pound-force .......................... newton(N) ........................ 4.448
Pressure or stress (force per area)
kdogram-fom/square meter . . . . . . . . . . . . . . .paxal (Pa) ........................ 9.807

kip-fom/square inch (ksi) ............. megapascal (MPa) ...................... 6.895
newton/square meter (N/m2) ..............pascal (Pa) ........................ 1.OOOE
pound-force/square foot . . . . . . . . . . . . . . . . . . pascal (Pa) ....................... 47.88
pound-force/square inch (psi) ............ kilopascal ( P a ) ....................... 6.895
Bending moment or torque
inch-pound-force ................... newton-meter (Nem) ..................... 0.1130

foot-pound-force .................... newton-meter (Nem) ..................... 1.356
meter-kilogramforce ................ newton-meter (Nam) ..................... 9.807
--``,`,-`-`,,`,,`,`,,`---

A C 1 SP-153 VOL*II 95 m 0662747 0522163 O17 m
1202 SI (Metric) Tables
To convert from to multiply by
Mass
ounce-mass (avoirdupois) . . . . . . . . . . . . . . . . . . gram (9) ........................ 28.34

pound-mass (avoirdupois) . . . . . . . . . . . . . . .kilogram (kg) ........................ 0.4536
ton (metric) ......................... megagram (mg) ....................... 1.OûûE
ton (short, 2ooo Ibm) . . . . . . . . . . . . . . . . . . . kilogram (kg). ..................... 907.2
Mass per volume
pound-masshbic foot . . . . . . . . . . . . kilogrm/cubic meter (kg/m3) ................. 16.02

pound-mass/cubic yard . . . . . . . . . . . .kilograndcubic meter (kg/m3) . . . . . . . . . . . . . . . . . .0.5933
pound-mass/gallon . . . . . . . . . . . . . . . kilogradcubic meter (kg/m3) . . . . . . . . . . . . . . . . 119.8
Temperalu reg
degrees Fahrenheit (F) . . . . . . . . . . . . . . degrees Celsius (C) . . . . . . . . t = ( t p - 32)/1.8

degrees Celsius (C) . . . . . . . . . . . . . . . . degrees Fahrenheit (F)........ tF = 1.8tc + 32
* This selected list gives practical conversion lactors oí units found in concrete technology. The reference murces for information
on SI units and more exact conversion íactors are ASTM E 380 and E 621. Symbols of metric units are given in pnrrnthesis.
t E Indicates that the factor given is exact.
--``,`,-`-`,,`,,`,`,,`---
$ One liter (cubic decinieter) equals 0.001 m3 or 1000 cm3.

O These equations convert one temperature reading to another and include the necessary scale corrections. To convert a
difference in temperature from Fahrenheit degrees lo Celsius degrees, divide by 1.8 only. ia. a change from 70 to88 Frepresenls
a change of 18 For 1811.8 = 10 C dcg.

A C 1 SP-153 VOL*II 95 M O662949 0522164 T55 =
Index 1203
INDEX
Abrasion, 863 863, 885, 911, 931, 951, 975, 995,

Abrasion resistance, 315 1017, 1031, 1051, 1069, 1121, 1165
Absorption, 315 Bleeding (concrete), 315, 719
Accelerated tests, 177, 561, 1017, 1121 Blended cements, 43, 153, 229, 591, 86, 951,
Acid resistance, 885 1O51
Adiabatic conditions, 885, 995, 1121 Bonding, 25
Admixture, 153, 995 Bonnamy, S., 719
Age, 109 Borrachero, M., 339 c
Agglomeration, 719 Breit, W., 741
Aggregates, 249, 269, 911, 975, 1069
Air entrainment, 779, 1103 Calcium, 81
Airports, 1141 Calcium chlorides, 931
Alkali aggregate reactions, 177, 193, 561, 1017, Calcium sulfoaluminates, 513
--``,`,-`-`,,`,,`,`,,`---
1051, 1069, 1087 Caldarone, M., 815

Alkali content, 1069 Carbonates, 1087
Alkalies, 153 Carbonation, 283, 315
Alkalinity, 741 Carette, G., 591
Allen, A., 1179 Carles-Gibergues, A., 177
Al-Manoseer, A., 109 Carrasquillo, R., 43, 153
Aluminum, 459 Cavitation, 863
Amo, K., 1103 Cellular concretes, 779
Atlassi, E., 703 Cement aggregate reactions, 561, 1069
Austin, S., 1141 Cement pastes, 385
Ayano, T., 249 Cements, 355, 513, 829
Cement types, 125
Backfilling, 403 Chemical analysis, 531, 1051, 1165
Bagasse, 315 Chemical attack, 43, 193
Baguant, B., 315 Chloride ions, 1, 125, 283, 297, 315, 931, 1103
Banerjee, G., 439 Chlorides, 479, 591, 657, 675, 741, 815
Baykol, G., 269, 549 Chu, II.,719
Belz, G., 513 Clinker, 213, 229
Beretka, J., 513 Compaction, 367, 403, 591, 975
Bérubé, M., 177 Compaction tests, 367
Bian, Q., 1069 Composite materials, 459
Bilodeau, A., 1 Compression, 687
Binders (materials), 439, 1031 Compressive strength, 1, 25, 67, 99, 125, 283,
Blast furnace slag, 283, 297, 479,513, 657,741, 339,403,513,531, 591, 657, 779,795,

A C 1 SP-353 V O L * I I 95 0662749 0522365 7 9 1 m
1204 Index
815, 863, 911, 931, 951,'1031, 1051, Expansive cements, 193

--``,`,-`-`,,`,,`,`,,`---
1087, 1121 Exposure, 283

Concretes, 177, 229, 355, 417, 561, 845, 885,
1103 Ferrocement, 845
Conductivity, 479 Field tests, 1121
Connell, M., 1017 Fineness, 355, 951, 1103
Cornelissen, H., 67 Flexurol strength, 1, 25, 81, 339, 385, 591
Corrosion, 741, 795 Fliss, L., 479
Cracking (fracturing), 81 Flowability, 249, 403, 1051, 1103
Crack width and spacing, 1069 Flow table tests, 339
Creep properties, 315 Fly ash, 1, 25, 43, 67, 81, 99, 109, 125, 153,
Curing, 497, 675, 975, 1031, 1121 177,193,213, 229,269,283,297, 339,
C&, 513 355,367,385,403,417,439,459,479,
C+, 213 497,513,549,561, 657,741,829,863,
C-S-Hl 439 931, 995, 1141, 1179
Fournier, B., 561
Dams, 863 Fractal microstructure, 1179
Damtoh, J., 229 Fracture properties, 25
Danarié, E., 763 Frearson, J., 975
Das, D., 439 Free lime, 1165
Day, R., 1165 Freeman, R., 153
Deesawangnade, T., 385 Freeze thaw durability, 1, 25, 315
Deformation, 315, 687 Frías, M., 829
Deicers, 931 Fuji¡, M., 951
Deja, J., 1087 Fujiwara, H., 779
de Larrard, F., 99 Fukute, T., 367
Demura, K., 1031
Deterioration, 931 Galeoto, D., 25
Differential thermal analysis, 931 Giammatteo, M., 25
Diffusivity, 479, 763 Gloss, 531
Dilek, F., 795 Goch, G,. 479
Drying, 657, 763 Golden, D., 459
Drying shrinkage, 1, 25, 315, 385, 591, 1051, Grout, 109
1103 Gruber, K., 815
Duchesne, J., 177 Guo, R., 459
Durability, Z,43, 109, 153, 269, 385, 479, 497, Gyotoku, M., 1103
657, 795, 863, 885, 1031 Gypsum, 213
Electrical resistance, 403 Halaak, W., 863

Electrolytic resistance, 741 Han, N., 687
Environments, 283 Hoque, M., 911
Erosion, 863 Hardened paste structure, 1051
Ettringite, 439, 513 Hossoballah, A., 417
Everitt, M., 81 Haug, M., 109
Expansion, 43, 177, 385, 513, 561, 975, 1017, Heating, 497, 829
1069 Heat of hydration, 81, 829, 951, 1121

A C 1 SP-153 VOL*II 95 Obb2949 0522Lbb ô28
Index 1205
Heavy metals, 1087 Madej, J., 1031

Hellewaard, R., 67 Magnesium sulfates, 795
Higgins, D., 975, 1017 Malhotra, V , 1, 561, 591
High alumina cements, 885 Malolepszy, J., 1087
High early-strength cements, 1, 513 Marchand, J., 125
High performance concretes, 67, 99, 815, 863, Marino, R., 25
911, 1051 Marroccoli, M., 513
--``,`,-`-`,,`,,`,`,,`---
High strength concretes, 687, 741, 779, 995 Mass concrete, 995
High strength mortars, 1031 Material properties, 1179
Hisada, M., 297 Mathematical models, 99
Hornain, H,. 125 Matrix, 459
Houst, Y., 763 Mechanical properties, 269
Huang, P., 459 Metakaolin, 815
Hydration, 125, 193, 439, 513, 703, 1051, 1165, Micronizing, 67
1179 Microsilica, 703
Microstructure, 125, 951, 1179
Industrial wastes, 513 Mineral admixtures, 297
Ishii, M., 367 Mineralogical analysis, 153
Ishikawa, Y., 779
Iwai, M., 995 Mix proportioning, 193, 249, 591
Mizobuchi, T., 995
Jet blasts, 1141 Modulus of elasticity, 1, 25, 315, 845, 1069
Jiang, W., 193 Moist curing, 497
Joynes, B., 911 Moisture content, 315, 763
Monz6, J., 339
Kawamuro, Y., 283, 931 Morphology, 459
Kayyali, O., 911 Mortars (material), 67, 125, 177, 297, 339, 763,
Kelham, S., 229 795, 931, 975, 1051, 1087, 1103
Keshavarom, B., 459 Mukheriee, P., 81
Kohno, K., 1103
Kolbeck, H., 403 Nagataki, S., 297, 1051
Köprülü, K., 549 Naik, T., 403
Krishnamoorthy, S., 355 Nakamoto, J., 1121
Kumar, A., 439 Nakano, K., 367, 1069
Naproux, P., 177
Laiw, J., 657 Nirnityongskul, P., 385
Langley, W., 561 Nishibayashi, S., 1069
Leaching, 1087 Nobuta, Y., 995
Lightweight aggregates, 269, 779, 1141
Lightweight concretes, 779 Ogawa, A., 249
Lime, 355, 439, 1165 Ogawa, Y., 1103
Lime fly ash, 43, 269, 385 Ohama, Y., 1031
Limestone, 177, 229, 249 Osborne, G., 885
Livingston, R., 1179 Otsuki, N., 297
Low heat cements, 995 Özturan, T., 269
Luther, M., 863 Ozyildirim, C., 675

A C 1 SP-1-53 V O L X I I 95 Obb2949 0522167 7b4
1206 Index
--``,`,-`-`,,`,,`,`,,`---
Particle size distribution, 67, 177, 339, 367, 719, Sarkar, S., 213, 439
1051 Sasatani, T., 283, 931
Pastes, 99 Sato, J., 81
Pavements, 367, 1141 Sava$, M., 269
Pavlenko, S., 497 Sawada, E., 779
Payá, J., 339 Scanning electron microscope, 1087
Pelleting, 269 Schiessl, P., 741
Penetration tests, 283 Seawater, 885
Performance, 863 Seepage, 549
Peris-Mora, E., 339 Segregation, 249
Permeability, 125, 479, 549, 591, 675, 815 Sharma, R., 355
Petrography, 531 Sherman, N., 513
Phosphogypsum, 439 Shi, C., 11 65
Pigeon, M., 125 Shrinkage, 385, 513, 91 1
Placing, 459, 675 Silica, 355, 1103
Polypropylene fibers, 763 Silica fume, 67, 283, 297, 479, 591, 657, 675,
Ponding, 657, 675 687, 703,719,741,763,779,795,815,
Porosity, 125, 193, 297, 687, 951, 1031, 1051, 829, 845, 863, 911, 931, 1031, 1051,
1087, 11 65 1179
Portland cement, 741, 795, 829 Singh, B., 885
Potassium ions, 297 Sivasundoram, V., 591
Pozzolan cements, 417, 531 Slabs, 657
Pozzolanic reactions, 193, 531, 703 Slags, 125, 229, 497, 951, 975, 1017, 1069,
Pozzolans, 815, 1179 1087, 1141
Pressure, 109 Slump, 249
Proportioning, 863 Slurries, 403, 591
Prusinski, J., 43 Sodium, 1087
Pumice, 531 Sodium ions, 297
Pumpability, 995 Sodium sulfate, 795
Solubility, 355
Ramadan, K., 269 Spalling, 1141
Ramme, B., 403 Specifications, 479, 531, 1017
Ranganath, R., 355 Specific surfoce, 339
Repairs, 763, 863 Splitting tensile strength, 1, 25
Resurfacing, 675 Steom curing, 11 03
Robins, P., 1141 Steels, 741
Rodriguez-Camacho, R., 531 Strains, 687
Rohatgi, P., 459 Streicher, P., 479
Roller compacted concrete, 367 Strength, 25, 193, 213, 229, 315, 339, 355,385,
Roy, D., 193 417, 439, 687, 845, 951, 1103, 1121,
Rubber, 549 1165
Subsurface structures, 403, 549
Sakata, K., 249 Sudsangiam, T., 385
Salt water, 109 Sulfate attack, 43, 1051
Sónchez de Rojas, M., 829 Sulfate resistance, 43, 153, 795, 975, 1103
Santoro, L., 513 Sulfates, 885

A C 1 SP-153 V O L X I I 95 m Ob62949 0 5 2 2 1 b ô bTO m
Index 1207
Superplasticizer, 1, 845 Volenti, G., 513

Supersulfated cement, 513 Von Damme, H., 719
Swomy, R., 657 Velocity, 283
Viscosity, 249
Takagi, A., 995 Vissers, J., 67
Takayo, T,. 845
Talbot, C., 125 Walls, 459
Tolling, B., 229 Walraven, J., 687
Tomai, M., 845 Wang, T., 1069
Tongtermsirikul, S., 385 Wastes, 439, 549
Tanks (containers), 549 Water binder ratio, 657
Taylor, P., 479 Water-cementitious ratio, 417
Temperature, 67, 1121, 1141 Water cement ratio, 975
Temperature rise, 81, 1121 Water content, 229, 249
Tensile strength, 845 Water of hydration, 703
Tensile stress, 81 Water reducing agents, 995
Tension, 687 Welded wire fabric, 845
Tests, 109, 177, 193, 283, 479, 531, 561, 657, Wenzel, T., 417
975 Wiens, U., 741
Thermal conductivity, 403 Wolsiefer, J., 591
Thermal cracking, 995 Workability, 67, 229, 315, 339, 657, 1031
Thermal gradient, 497 Wu, C., 1051
Thermal stresses, 995
Thickness, 459 X-ray diffraction, 931, 1179
Thomas, M., 81 Xu, A., 213
Togawa, K., 1121
Tomisawa, T., 951 Ye&nobali, A., 795
Torii, K., 283, 931
Toughness, 845 Zeta potential, 719
Uribe-Afif, R., 531

--``,`,-`-`,,`,,`,`,,`---


Aci SP-153 Vol1,2 Book - 1995

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Aci SP-153 Vol1,2 Book - 1995

Caricato da

Copyright:

Formati disponibili

--``,`,-`-`,,`,,`,`,,`---

Copyright American Concrete Institute

DISCUSSION of individual papers in this symposium may be submitted in

The Institute is not responsible for the statements or opinions expressed in

Printed in the United States of America

Editorial production Victoria Lunick

Library of Congress catalog card number 95-76270

Copyright American Concrete Institute

The Canadian Centre for Mineral and Energy Technology

day international conference at Montebello, Quebec, Canada, on the Use

Copyright American Concrete Institute

Association, Montreal, and several other organizations in Canada and the

Copyright American Concrete Institute

Dedicated to Members of the "Paper Review Panel" who assisted in the

Copyright American Concrete Institute

PREFACE ........................................... ...

PROPERTIES O F HIGH-VOLUME FLY ASH CONCRETE MADE

STRUCTURAL CONCRETE INCORPORATING HIGH

USING MEDIUM- T O HIGH-VOLUME FLY ASH BLENDED

PROCESSED FLY ASH FOR HIGH PERFORMANCE

EFFECT O F FLY ASH COMPOSITION ON THERMAL

A MODEL FOR PREDICTING T H E COMPRESSIVE

LONG-TERM PERFORMANCE O F GROUT CONTAINING

Copyright American Concrete Institute

PROPERTIES O F MORTAR MIXTURES CONTAINING

PRODUCTION O F SULFATE-RESISTANT CONCRETE

INFLUENCE O F PARTICLE SIZE DISTRIBUTION ON T H E

EXPANSIVE CEMENT PRODUCED FROM AFBC ASH BY

ACTIVE B - q S CEMENT FROM FLY ASH AND KILN DUST

T H E INFLUENCE O F HIGH EARLY STRENGTH (HES)

MIXTURE PROPORTIONING FOR HIGHLY-FLOWABLE

PROPERTIES O F LIGHTWEIGHT AGGREGATE PRODUCED

FIVE-YEAR EXPOSURE TEST ON LONG-TERM PROPERTIES

MOVEMENT O F IONS THROUGH MORTAR MIXED WITH

Copyright American Concrete Institute

PROPERTIES O F CONCRETE WITH BAGASSE ASH AS FINE

MECHANICAL TREATMENT O F FLY ASHES: STRENGTH

INFLUENCE O F FINENESS AND SOLUBLE SILICA CONTENT

IMPROVEMENT O F CHARACTERISTICS O F ROLLER

CLASS C FLY ASH AS A SHRINKAGE REDUCER FOR

A STRENGTH DEFINITION FOR T H E WATER-TO-CEMENT

UTILIZATION O F FLY ASH IN T H E DEVELOPMENT O F A

MORPHOLOGY AND SELECTED PROPERTIES O F FLY ASH

COMPARATIVE TESTING O F PORTLAND CEMENT, FLY

Copyright American Concrete Institute

HEAT TREATMENT O F FINE-GRAINED CEMENTLESS

USE OF FLY ASH, BLAST FURNACE SLAG AND CHEMICAL

MEXICAN NATURAL POZZOLANS AND THE EVALUATION

RUBBER ADDED FLY ASH FOR UNDERGROUND

EFFECTIVENESS O F FLY ASH IN REDUCING EXPANSION

Copyright American Concrete Institute

Properties of High-Volume Fly Ash

SvnoDsis: Canada Centre for Mineral and Energy Technology (CANMET)

Kevwords: Chloride ions; compressive strength, drying shrinkage; flexural

Copyright American Concrete Institute

AC1 member Alain Bilodeau is a concrete research engineer, Advanced

AC1 honorary member V. Mohan Malhotra is Program Principal, Advanced

In 1990, CANMET undertook a project to develop data base on high-

In spite of the excellent properties shown by the high-volume fly ash

Copyright American Concrete Institute

One way to improve the early-age strength of the concrete is to use

Four air-entrained concrete mixtures involving eight O. 11 m3 batches

The properties of the freshly mixed concrete were determined. These