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CALCIUM ALUMINATE CEMENTS Proceedings of the Centenary Conference 2008

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ALSO AVAILABLE FROM IHS BRE PRESS AN OVERVIEW OF THE BRAC GUIDANCE IN RELATION TO CURRENT GUIDANCE ON HIGH ALUMINA CEMENT CONCRETE BR429, 140pp on CD-ROM, 2002 CONCRETE: CONSTRUCTIONS SUSTAINABLE OPTION Proceedings of the International Congress, Dundee, July 2008 EP86, 6 volumes, 2008 CONCRETE IN AGGRESSIVE GROUND BRE Special Digest 1, 3rd edition 2005 CONCRETE SOLUTIONS Proceedings of the International Conference, St Malo, June 2006 M. G. Grantham, R. Jauberthie and C. Lanos (Editors) EP71, 798pp, 2006 DURABILITY OF AGEING HIGH ALUMINA CEMENT (HAC) CONCRETE A. Dunster, D. Bigland, I. Holton and B. Reeves 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 LOW ENERGY CEMENTS K. Quillin BR421, 50pp, 2001 THAUMASITE IN CEMENTITOUS MATERIALS I. Holton (editor) AP147, CD-ROM, 2002 THE PERFORMANCE OF AGEING CAC CONCRETE A. M. Dunster, I. R. Holton and A. E. Beadle BR353, 30pp, 1998 Visit www.ihsbrepress.com for details of these and over 1400 other titles for construction professionals

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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

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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, brepress@ihs.com 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.

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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 contri-butions 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.

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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 Cement and Concrete Science, Horsham, UK Raman Mangabhai Cement and Concrete Science, London, UK Karen Scrivener EPFL, Lausanne, Switzerland June 2008

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Organising committee Prof. Karen Scrivener EPFL, Lausanne, Switzerland Raman Mangabhai Cement and Concrete Science, UK Dr Charles Fentiman Cement and Concrete Science, UK Prof. Fred Glasser University of Aberdeen, UK Steve Brooks Chair of the Cementitious Materials Group, IOM3, UK Christine Alvim Kerneos, France Scientific Advisory Panel Prof. Mark Alexander University of Cape Town, South Africa Dr Carmen Andrade Instituto Eduardo Torroja of Construction

Sciences, Madrid, Spain, Prof. Dr-Ing. Thomas A. Bier Technical University Bergakademie Freiberg,

Germany Dr Anjan K. Chatterjee Conmat Technologies Private Ltd, Calcutta, India Prof. Mario Collepardi University of Milan, Italy Dr Andrew Dunster BRE, Garston, Watford, UK Dr Kevin Folliard The University of Texas at Austin, Texas, USA Prof. Carolyn Hansson University of Waterloo, Ontario, Canada Dr Dr Rdiger Oberste-Padtberg Ardex GmbH, Witten-Annen, Germany Prof. Wang Peiming Tongji University, Shanghai, P.R. China Prof. Dr Dr Herbert Pllmann University of Halle, Germany Prof. Etsuo Sakai Tokyo Institute of Technology, Tokyo, Japan Prof. Michael Thomas 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.

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Glossary of terms and abbreviations Cement chemists shorthand is widely used in these proceedings wherein the following abbreviations are used: C CaO S SiO2 A Al2O3 F Fe2O3 SO3 Some examples: CA mono calcium aluminate (CaO.Al2O3) C4AF tetracalcium aluminoferrite (4CaO.Al2O3.Fe2O3) C3A.C.H12 calcium monosulfoaluminate (4CaO.Al2O3. SO3.12H2O), also called AFm or monosulfate AH3 gibbsite (Al2O3.3H2O) CAH10 monocalcium aluminate deca hydrate (CaO.Al2O3.10H2O) CH2 calcium sulfate di hydrate (CaO. SO3.2H2O), also called gypsum Some commonly used abbreviations related to cement(s): AFm monosulfate AFt ettringite CA mono calcium aluminate CAC calcium aluminate cement HAC high alumina cement CH calcium hydroxide C4AF tetracalcium aluminoferrite (ferrite) ggbs ground granulated blastfurnace slag HAC high alumina cement LCC low cement castables LOI loss on ignition OPC ordinary Portland cement pfa pulverised-fuel ash LCC low cement castables w/c water/cement ratio w/s water/solid ratio

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CONTENTS Preface v Organising Committees vi PART ONE INTRODUCTION 1 1 100 years of calcium aluminate cements 3 K. L. Scrivener 2 Quantitative mineralogical, chemical and application investigations of high alumina cements from different sources 7 H. Pllmann, R. Oberste-Padberg, S. Stober, J. Gske and B. Raab 3 Thermodynamic modelling of the system Ca, Al, Si, Fe, O, in the part relevant to high alumina cement 17

F. Sorrentino PART TWO CLINKER 31 4 Compliance of aluminous cements with the European directive regarding chromium 33

B. Touzo 5 High quality sintered calcium aluminate cement produced in a rotary kiln 39

G. Liu, J. Zhou, J. Wang and L. Van Nes 6 From calcium aluminate cement to manganese cement 47

H. Pllmann, R. Oberste-Padtberg and S. Stber 7 Synthesis and crystal chemistry of manganese melilites and related phases 59

S. Stber and H. Pllmann 8 Structure and properties of hydraulic calcium aluminates modified by

phosphorous and zinc 69 S. Li and J. Hu

PART THREE HYDRATION STUDIES 77 9 Investigations of the hydration behaviour of pure cement phases by different

synthesis methods 79 B. Raab, S. Stber and H. Pllmann 10 Hydration behaviour of CAC at various temperatures by isoperibolic heat flow

calorimetry using acetates 93 M. Schmidt and H. Pllmann

11 Microstructure development of calcium aluminate cements accelerated by lithium sulfate 109

C. Gosselin and K. L. Scrivener

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12 Cryo-SEM-FEG investigations on calcium aluminate cements 123 H. Pllmann, R. Wenda, M. Fylak and J. Gske

PART FOUR PROPERTIES 139 13 Early-age properties of calcium aluminate cement concrete with rigid cracking and free shrinkage frames: isothermal testing 141

J. H. Ideker, K. J. Folliard and M. D. A. Thomas 14 Accelerated test for conversion of calcium aluminate cement concrete 159 H. Fryda, E. Charpentier and J.M. Bertino 15 Drying and shrinkage of CAC-based concrete 171 S. Lamberet, H. Fryda, P. Brigandat, F. Saucier and A. Mouchot 16 Hydration kinetics of calcium aluminate cement in presence of Li2CO3 181

F. Goetz-Neunhoeffer 17 Synthesis and crystal chemistry of manganese containing perovskites: phases with brownmillerite structures 197

S. Stber, O. Prokhnenko, S. Schorr, T. Dring and H. Pllmann PART FIVE LONG TERM PERFORMANCE 207 18 Calcium aluminate cement concrete in old marine structures 209

H. Fryda, S. Lamberet and A. Dunster 19 Carbonation and reinforcement corrosion in CAC concrete 221

A. Dunster and G. Sergi 20 Corrosion of rebar in pore solutions simulating calcium aluminate cement 235

L. Mammoliti, B. Bergsma and C. M. Hansson 21 The durability of CAC concrete exposed to seawater and de-icing salts 249

M. D. A. Thomas, H. Yi and R. Dhole 22 De-icer salt scaling resistance of CAC concretes exposed to various de-icer salts 259

M. Jolin and F. Gagnon PART SIX WASTEWATER APPLICATIONS 267 23 Field investigations of high performance calcium aluminate mortar for wastewater applications 269

S. Lamberet, D. Guinot, E. Lempereur, J. Talley and C. Alt 24 Experiences with a full-scale experimental sewer made with CAC and other cementitious binders in Virginia, South Africa 279

M. G. Alexander, A. M. Goyns and C. W. Fourie 25 Applying experimental data to concrete sewer design and rehabilitation 293

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 309

V. A. Geoffroy, M. Bachelet, J-L. Crovisier, G. Aouad and D. Damidot

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27 Development of CAC concrete jacking pipe for sewer application in Singapore 321 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 331

H. Saricimen PART SEVEN SPECIAL APPLICATIONS 343 29 Current calcium aluminate cement applications in well plugging 345

J. Bensted 30 Rapid setting calcium aluminate cement blends for offshore concrete pipeline applications 357

F. A. Orr-Adams 31 Rapid repair of airfield runway in cold weather using CAC mortar 365

H. Justnes 32 Non-efflorescing cementitious compositions based on calcium aluminate technologies 373

L. Amathieu, S. Lamberet, C. Hu and R. Roesky 33 High alumina cement in low-activation mortar and concrete for use in nuclear reactor shield walls 383

T. Mori, T. Higuchi, R. Yoshino, M. Kinno and A. Hasegawa 34 Microstructures and the reaction in autoclaved ordinary Portland cementsilica powder system with alumina cement and CaSO4 395

E. Sakai, T. Saito, A. Azuma, M. Daimon, T. Sanda and K. Yamamoto PART EIGHT REFRACTORY APPLICATIONS 403 35 Comparison of a new temperature independent cement with other 70% Al2O3 cements for low and Ultra low cement refractory castables 405

A. Buhr, D. Gierisch, H-L. Gro, F. Kraaijenbos, G. Wams and J. Dutton 36 High purity calcium aluminate binders for demanding high temperature applications 417

C. Parr, Ch. Whrmeyer, D. Verat and J. P. Letourneux 37 Hydration of calcium aluminates in the presence of yeelenite 429

M. Muntean, A. Ionescu, I. Ropot and O. Muntean PART NINE USE OF FILLERS AND REACTIVE POWDERS 435 38 Mechanical properties and microstructures of calcium aluminate based ultra high strength cement 437

E. Sakai, T. Saito, T. Sugiyama and M. Daimon 39 Durability of concrete made with calcium aluminate cement and ground granulated blastfurnace slag in sulfate and marine environments 443

A. M. Dunster, F. Moulinier, K. C. Quillin and G. J. Osborne

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40 Alkali activation of calcium aluminate cement 455 C. Pastor, A. Fernndez-Jimnez, T. Vzquez and A. Palomo

41 CAC plus metakaolin binders: alkaline hydration 465

A. Palomo, A. Fernndez-Jimnez and T. Vazquez 42 Calcium aluminate cement with supplementary cementitious materials: fly ashes 475

L. Fernndez-Carrasco and E. Vzquez PART TEN BLENDS OF CEMENTS 485 43 Strength development of calcium aluminate cement - Portland cement blends at different temperatures 487

. Krca, I. . Yaman and M. Tokyay 44 Microstructure development of ternary binders based on calcium aluminate cement, calcium sulfate and portland cement 501

S. Lamberet, L. Amathieu and K. L. Scrivener 45 Ternary system: calcium alumina cement portland cement gypsum 511

S. Maier 46 Suitable dispersant for calcium aluminate cement 527

K. Yamada, K. Tsukada, H. Nakanishi, Hanehara 47 Dimensional change of self-levelling materials developed by mixing aluminous cement, Portland cement and anhydrite 533

Y. Hirano, K. Makida, R. Komatsu and K. Ikeda PART ELEVEN BUILDING CHEMISTRY 541 48 The efficiencies of -, - and -casein fractions for plasticising cement-based self levelling grouts 543

C. Winter, J. Plank and R. Sieber 49 Development of self-levelling screed based on calcium aluminate cement 557

J. Ambroise and J. Pera 50 Kinetics of two types of flooring mortar: PC dominated vs CAC dominated 567

J. Kighelman, K. L. Scrivener and R. Zubriggen 51 Mutual influence of additive fractionation and hydration kinetics in self-levelling flooring mortars 573

A. De Gasparo, U. M. Herwegh and R. Zubriggen 52 Characterisation of the microstructure of self-levelling compounds (SLC) using 2-dimensional XRD (GADDS) 581

S. Seifert, J. Neubauer, F. Goetz-Neunhoeffer and H. Motzet Author Index 593 Subject Index 595

Contents