i

CALCIUM ALUMINATE CEMENTS

Proceedings of the Centenary Conference 2008

ii

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EP71, 798pp, 2006
DURABILITY OF AGEING HIGH ALUMINA CEMENT (HAC) CONCRETE
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BR386, 56pp, 2000
HAC CONCRETE IN THE UK
Assessment, durability management, maintenance and refurbishment
A. Dunster
SD3, 20pp, 2002
HIGH ALUMINA CEMENT CONCRETE BRAC RULES
BR451, 98pp, 2002
HIGH ALUMINA CEMENT CONCRETE IN EXISTING BUILDING SUPERSTRUCTURES
S. C. C. Bate
BR235, 112pp, 1993
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K. Quillin
BR421, 50pp, 2001
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AP147, CD-ROM, 2002
THE PERFORMANCE OF AGEING CAC CONCRETE
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BR353, 30pp, 1998

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iii

CALCIUM ALUMINATE
CEMENTS
Proceedings of the Centenary Conference 2008
Palais des Papes, Avignon, France, 30 June 2 July 2008

Principal Supporter
Kerneos AluminateTechnologies
Co-supporters
Calucem and Cementos Molins
Meeting organised by Cement and Concrete Science

Edited by C. H. Fentiman, R.J. Mangabhai and K.L. Scrivener

iv

Cover photos:
Left: Jules Bied at LeTeil, Ardeche, France, around 1908. Photo: Kerneos
archives Paper 1, page 3.
Top right: CAC concrete piers, Montrose Bridge, Scotland, built in the
1920s Paper 18, page 209, by H. Fryda, S. Lamberet and A. Dunster.
Centre right: SEM image of perovskite-rich manganese cement clinker
Paper 6, page 47, by H. Pllmann, R. Oberste-Padtberg and S. Stber
Bottom right: Concrete pipelines with CAC joints accelerated by lithium
carbonate Paper 30, page 357, by F. A. Orr-Adams.
Details of all publications from IHS BRE Press are available from:
www.ihsbrepress.com or
IHS BRE Press, Willoughby Road, Bracknell RG12 8FB, UK
Tel: 01344 328038, Fax: 01344 328005, [email protected]
Published by IHS BRE Press, 2008
Requests to copy any part of this publication should be made to:
IHS BRE Press, Garston, Watford WD25 9XX, UK
Tel: 01923 664761, Fax: 01923 6642477
EP94
ISBN-13: 978-1-84806-045-6
IHS BRE Press, 2008
The views expressed in the papers in this volume of proceedings are
those of the authors. The editors and IHS BRE Press do not accept any
responsibility for the contents of the papers or for any loss or damage
which might occur as a result of following or using data or advice
given in the papers.

PREFACE

Calcium aluminate cements (CACs), also known as high-alumina cements, are a range
of cements in which calcium aluminates are the principal constituents.
The first industrial process for the production of a cement based on calcium
aluminates was patented in 1908 by Jules Bied and full commercialization took place
shortly thereafter (described in the first paper). Since then, calcium aluminate cements
have become hugely important for a wide range of applications. So it is fitting that we
celebrate the arrival of the centenary of the discovery of CACs with an International
Conference in Avignon, a location that is close to the site of the invention of CACs at
Le Teil, just a few kilometres to the north.
This is the third International Conference on calcium aluminate cements, the first
being at Queen Mary & Westfield College, London, UK in 1990, the second being at
Heriot-Watt University, Edinburgh, UK in 2001. The Proceedings of both previous
meetings are still widely used as standard texts on CACs, and we anticipate that the
same will be true of these Proceedings.
The response to the call for papers for this meeting has been excellent, and these
Proceedings demonstrate a strong continued interest and real progression in the knowledge
and understanding of this important class of cement, demonstrating that CACs are well
placed to continue being an important class of cement for, hopefully, the next hundred
years.
In editing these Proceedings, we have been impressed by the number of papers
dealing with applications of CACs, including a number of diverse uses, such as offshore
applications and encapsulation. Interest in the use of CACs for wastewater treatment has
clearly increased, owing to proven corrosion resistance, and we are able to devote a
whole session to these studies. Refractory applications are still very much an area of
interest, with three papers demonstrating that there is still room for innovation with one
of the oldest applications for these versatile cements.
Various studies also demonstrate the increasing importance of CACs in formulations,
with much interest in blended systems, including applications with fillers and reactive
powders, and especially the ternary system with calcium sulphate and Portland cement.
The prospects for these are demonstrated by a number of papers on self-levelling
flooring applications, which are now very well established.
In addition to these application-oriented papers, we have some very strong contributions related to the phase systems, CAC types, hydration, mechanical properties and
durability.
We would like to thank all the authors for their hard work in preparing their
contributions and for meeting the rather tight deadlines that have enabled these Proceedings
to be ready in time for the conference. The papers included in these Proceedings have all
been reviewed by the Organising Committee, Scientific Advisory Panel and Referee
Panel, all of whom have willingly given up their time to read the manuscripts carefully
and offer the authors valuable assistance in refining their papers. We are profoundly
grateful to them all.

vi

The editors would also like to thank Kerneos Aluminate Technologies, Calucem
and Cementos Molins for their unfailing financial and practical support for this meeting
without their assistance, this Centenary Conference simply would not have been
possible. In particular, we acknowledge Francois Saucier (Kerneos), Christine Alvim
(Kerneos), Frank Michael Kindler (Calucem) and Marieke Van den Berg (Molins), who
have been of particular help with the practicalities of organising this event. We also
wish to thank the Institute of Materials, Minerals and Mining (IOM3) for their support and
assistance in various ways and in particular for promoting the meeting on their website.
Finally, but certainly not least, the Editors would like to extend particular thanks
to Nick Clarke (who worked on the first of these meetings) of IHS BRE Press for all his
hard work in the production of these Proceedings.
The Editors express the wish, on behalf of all authors, that readers find the volume
topical and useful in their work: also, that it stimulates further work on this interesting
and useful class of materials.

Charles Fentiman
Raman Mangabhai
Karen Scrivener
June 2008

Cement and Concrete Science, Horsham, UK

Cement and Concrete Science, London, UK
EPFL, Lausanne, Switzerland

vii

Organising committee
Prof. Karen Scrivener
Raman Mangabhai
Dr Charles Fentiman
Prof. Fred Glasser
Steve Brooks
Christine Alvim

EPFL, Lausanne, Switzerland

Cement and Concrete Science, UK
Cement and Concrete Science, UK
University of Aberdeen, UK
Chair of the Cementitious Materials Group, IOM3, UK
Kerneos, France

Scientific Advisory Panel

Prof. Mark Alexander
Dr Carmen Andrade
Prof. Dr-Ing. Thomas A. Bier
Dr Anjan K. Chatterjee
Prof. Mario Collepardi
Dr Andrew Dunster
Dr Kevin Folliard
Prof. Carolyn Hansson
Dr Dr Rdiger Oberste-Padtberg
Prof. Wang Peiming
Prof. Dr Dr Herbert Pllmann
Prof. Etsuo Sakai
Prof. Michael Thomas

University of Cape Town, South Africa

Instituto Eduardo Torroja of Construction
Sciences, Madrid, Spain,
Technical University Bergakademie Freiberg,
Germany
Conmat Technologies Private Ltd, Calcutta, India
University of Milan, Italy
BRE, Garston, Watford, UK
The University of Texas at Austin, Texas, USA
University of Waterloo, Ontario, Canada
Ardex GmbH, Witten-Annen, Germany
Tongji University, Shanghai, P.R. China
University of Halle, Germany
Tokyo Institute of Technology, Tokyo, Japan
University of New Brunswick, Fredericton, Canada

Referees
Shamshad Ali
Dr Loris Amathieu
Prof. Phil Banfill
Prof. John Bensted
Dr Anjan K Chatterjee
Dr Natasha Constantinou
Dr Alison Crumbie
Dr Charlotte Famy
Dr Ana Fernndes-Jimnez
Dr Sandrine Garrault
Dr Ellis Gartner
Dr Colin Hills
Prof. Harald Justnes
Dr Lars Kraft
Dr Thomas Matschei

Ron Montgomery
Prof. Marcela Muntean
Tony Newton
Dr Kunle Onabolu
Francis Orr-Adams
Geoff Osborne
Dr Angel Paloma
Prof. John Sharp
Dr Francois Sorrentino
Dr Danielle Sorrentino
Bob Viles
Stuart Whittley
Dr Renhe Yang
Prof. Roger Zubriggen.

viii

Glossary of terms and abbreviations

Cement chemists shorthand is widely used in these proceedings wherein the following
abbreviations are used:
C
S
A
F

CaO
SiO2
Al2O3
Fe2O3
SO3

Some examples:
CA
C4AF
C3A.C.H12
AH3
CAH10
CH2

mono calcium aluminate (CaO.Al2O3)

tetracalcium aluminoferrite (4CaO.Al2O3.Fe2O3)
calcium monosulfoaluminate (4CaO.Al2O3. SO3.12H2O),
also called AFm or monosulfate
gibbsite (Al2O3.3H2O)
monocalcium aluminate deca hydrate (CaO.Al2O3.10H2O)
calcium sulfate di hydrate (CaO. SO3.2H2O),
also called gypsum

Some commonly used abbreviations related to cement(s):

AFm
AFt
CA
CAC
HAC
CH
C4AF
ggbs
HAC
LCC
LOI
OPC
pfa
LCC
w/c
w/s

monosulfate
ettringite
mono calcium aluminate
calcium aluminate cement
high alumina cement
calcium hydroxide
tetracalcium aluminoferrite (ferrite)
ground granulated blastfurnace slag
high alumina cement
low cement castables
loss on ignition
ordinary Portland cement
pulverised-fuel ash
low cement castables
water/cement ratio
water/solid ratio

ix

CONTENTS

Preface
Organising Committees

v
vi

PART ONE INTRODUCTION

100 years of calcium aluminate cements

K. L. Scrivener

Quantitative mineralogical, chemical and application investigations of high

alumina cements from different sources
H. Pllmann, R. Oberste-Padberg, S. Stober, J. Gske and B. Raab

Thermodynamic modelling of the system Ca, Al, Si, Fe, O, in the part
relevant to high alumina cement
F. Sorrentino

17

PART TWO CLINKER

31

Compliance of aluminous cements with the European directive regarding chromium

B. Touzo

33

High quality sintered calcium aluminate cement produced in a rotary kiln

G. Liu, J. Zhou, J. Wang and L. Van Nes

39

From calcium aluminate cement to manganese cement

H. Pllmann, R. Oberste-Padtberg and S. Stber

47

Synthesis and crystal chemistry of manganese melilites and related phases

S. Stber and H. Pllmann

59

Structure and properties of hydraulic calcium aluminates modified by

phosphorous and zinc
S. Li and J. Hu

PART THREE HYDRATION STUDIES

9

10

11

69

77

Investigations of the hydration behaviour of pure cement phases by different

synthesis methods
B. Raab, S. Stber and H. Pllmann

79

Hydration behaviour of CAC at various temperatures by isoperibolic heat flow

calorimetry using acetates
M. Schmidt and H. Pllmann

93

Microstructure development of calcium aluminate cements accelerated by

lithium sulfate
C. Gosselin and K. L. Scrivener

109

Contents
x

12

Cryo-SEM-FEG investigations on calcium aluminate cements

H. Pllmann, R. Wenda, M. Fylak and J. Gske

PART FOUR PROPERTIES

13

Early-age properties of calcium aluminate cement concrete with rigid

cracking and free shrinkage frames: isothermal testing
J. H. Ideker, K. J. Folliard and M. D. A. Thomas

123

139
141

14

Accelerated test for conversion of calcium aluminate cement concrete

H. Fryda, E. Charpentier and J.M. Bertino

159

15

Drying and shrinkage of CAC-based concrete

S. Lamberet, H. Fryda, P. Brigandat, F. Saucier and A. Mouchot

171

16

Hydration kinetics of calcium aluminate cement in presence of Li2CO3

F. Goetz-Neunhoeffer

181

17

Synthesis and crystal chemistry of manganese containing perovskites:

phases with brownmillerite structures
S. Stber, O. Prokhnenko, S. Schorr, T. Dring and H. Pllmann

197

PART FIVE LONG TERM PERFORMANCE

207

18

Calcium aluminate cement concrete in old marine structures

H. Fryda, S. Lamberet and A. Dunster

209

19

Carbonation and reinforcement corrosion in CAC concrete

A. Dunster and G. Sergi

221

20

Corrosion of rebar in pore solutions simulating calcium aluminate cement

L. Mammoliti, B. Bergsma and C. M. Hansson

235

21

The durability of CAC concrete exposed to seawater and de-icing salts

M. D. A. Thomas, H. Yi and R. Dhole

249

22

De-icer salt scaling resistance of CAC concretes exposed to various de-icer salts
M. Jolin and F. Gagnon

259

PART SIX WASTEWATER APPLICATIONS

23

24

267

Field investigations of high performance calcium aluminate mortar for

wastewater applications
S. Lamberet, D. Guinot, E. Lempereur, J. Talley and C. Alt

269

Experiences with a full-scale experimental sewer made with CAC and other
cementitious binders in Virginia, South Africa
M. G. Alexander, A. M. Goyns and C. W. Fourie

279

25

Applying experimental data to concrete sewer design and rehabilitation

A. M. Goyns, M. G. Alexander and C. W. Fourie

26

Evaluation of aluminium sensitivity on a biodegrading bacteria Acidithiobacillus

thiooxidans: definition of a specific growth medium
V. A. Geoffroy, M. Bachelet, J-L. Crovisier, G. Aouad and D. Damidot

293

309

Contents

27

Development of CAC concrete jacking pipe for sewer application in Singapore

C. T. Tam, S. S. Hendra, K. C. G. Ong, C. H. Tan, N. K. Lee and C. Hu

28

Sulfate and acid resistance of materials for use in sewage and wastewater
transport systems in Saudi Arabia a review
H. Saricimen

xi

321

331

PART SEVEN SPECIAL APPLICATIONS

343

29

Current calcium aluminate cement applications in well plugging

J. Bensted

345

30

Rapid setting calcium aluminate cement blends for offshore concrete

pipeline applications
F. A. Orr-Adams

357

31

Rapid repair of airfield runway in cold weather using CAC mortar

H. Justnes

32

Non-efflorescing cementitious compositions based on calcium aluminate

technologies
L. Amathieu, S. Lamberet, C. Hu and R. Roesky

373

High alumina cement in low-activation mortar and concrete for use in

nuclear reactor shield walls
T. Mori, T. Higuchi, R. Yoshino, M. Kinno and A. Hasegawa

383

Microstructures and the reaction in autoclaved ordinary Portland cementsilica

powder system with alumina cement and CaSO4
E. Sakai, T. Saito, A. Azuma, M. Daimon, T. Sanda and K. Yamamoto

395

33

34

PART EIGHT REFRACTORY APPLICATIONS

35

36

37

39

403

Comparison of a new temperature independent cement with other 70% Al2O3

cements for low and Ultra low cement refractory castables
A. Buhr, D. Gierisch, H-L. Gro, F. Kraaijenbos, G. Wams and J. Dutton

405

High purity calcium aluminate binders for demanding high temperature

applications
C. Parr, Ch. Whrmeyer, D. Verat and J. P. Letourneux

417

Hydration of calcium aluminates in the presence of yeelenite

M. Muntean, A. Ionescu, I. Ropot and O. Muntean

PART NINE USE OF FILLERS AND REACTIVE POWDERS

38

365

429

435

Mechanical properties and microstructures of calcium aluminate based

ultra high strength cement
E. Sakai, T. Saito, T. Sugiyama and M. Daimon

437

Durability of concrete made with calcium aluminate cement and ground

granulated blastfurnace slag in sulfate and marine environments
A. M. Dunster, F. Moulinier, K. C. Quillin and G. J. Osborne

443

Contents
xii

40

Alkali activation of calcium aluminate cement

C. Pastor, A. Fernndez-Jimnez, T. Vzquez and A. Palomo

455

41

CAC plus metakaolin binders: alkaline hydration

A. Palomo, A. Fernndez-Jimnez and T. Vazquez

465

42

Calcium aluminate cement with supplementary cementitious materials: fly ashes

L. Fernndez-Carrasco and E. Vzquez

475

PART TEN BLENDS OF CEMENTS

43

44

485

Strength development of calcium aluminate cement - Portland cement

blends at different temperatures
. Krca, I. . Yaman and M. Tokyay

487

Microstructure development of ternary binders based on calcium aluminate

cement, calcium sulfate and portland cement
S. Lamberet, L. Amathieu and K. L. Scrivener

501

45

Ternary system: calcium alumina cement portland cement gypsum

S. Maier

511

46

Suitable dispersant for calcium aluminate cement

K. Yamada, K. Tsukada, H. Nakanishi, Hanehara

527

47

Dimensional change of self-levelling materials developed by mixing

aluminous cement, Portland cement and anhydrite
Y. Hirano, K. Makida, R. Komatsu and K. Ikeda

PART ELEVEN BUILDING CHEMISTRY

48

The efficiencies of -, - and -casein fractions for plasticising cement-based

self levelling grouts
C. Winter, J. Plank and R. Sieber

533

541
543

49

Development of self-levelling screed based on calcium aluminate cement

J. Ambroise and J. Pera

557

50

Kinetics of two types of flooring mortar: PC dominated vs CAC dominated

J. Kighelman, K. L. Scrivener and R. Zubriggen

567

51

Mutual influence of additive fractionation and hydration kinetics in self-levelling

flooring mortars
A. De Gasparo, U. M. Herwegh and R. Zubriggen

573

Characterisation of the microstructure of self-levelling compounds (SLC)

using 2-dimensional XRD (GADDS)
S. Seifert, J. Neubauer, F. Goetz-Neunhoeffer and H. Motzet

581

Author Index

593

Subject Index

595

52