Sulfate Attack on Concrete © 2002 Jan Skalny, Jacques Marchand and Ivan Odler Modern Concrete Technology Series A series of books presenting the state-of-the-art in concrete technology Series Editors Arnon Bentur Sydney Mindess National Building Research Institute Office of the President Technion–Israel Institute of Technology University of British Colombia Technion City 6328 Memorial Road Haifa 32 000 Vancouver, B.C. Israel Canada V6T 1Z2 1. Fibre Reinforced Cementitious Composites A. Bentur and S. Mindess 2. Concrete in the Marine Environment P.K. Mehta 3. Concrete in Hot Environments I. Soroka 4. Durability of Concrete in Cold Environments M. Pigeon and R. Pleau 5. High Performance Concrete P C. Aïtcin 6. Steel Corrosion in Concrete A. Bentur, S. Diamond and N. Berke 7. Optimization Methods for Material Design of Cement-based Composites Edited by A. Brandt 8. Special Inorganic Cements I. Odler 9. Concrete Mixture Proportioning F. de Larrard 10. Sulfate Attack on Concrete J. Skalny, J. Marchand and I. Odler 11. Determination of Pore Structure Parameters K. Aligizaki 12. Fundamentals of Durable Reinforced Concrete M.G. Richardson © 2002 Jan Skalny, Jacques Marchand and Ivan Odler Sulfate Attack on Concrete Jan Skalny, Jacques Marchand and Ivan Odler London and New York © 2002 Jan Skalny, Jacques Marchand and Ivan Odler First published 2002 by Spon Press 11 New Fetter Lane, London EC4P 4EE Simultaneously published in the USA and Canada by Spon Press 29 West 35th Street, New York, NY 10001 Spon Press is an imprint of the Taylor & Francis Group © 2002 Jan Skalny, Jacques Marchand and Ivan Odler All rights reserved. No part of this book may be reprinted or reproduced or utilised in any form or by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying and recording, or in any information storage or retrieval system, without permission in writing from the publishers. The publisher makes no representation, express or implied, with regard to the accuracy of the information contained in this book and cannot accept any legal responsibility or liability for any errors or omissions that may be made. British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging in Publication Data A catalogue record has been requested ISBN 0–419–24550–2 This edition published in the Taylor & Francis e-Library, 2003. ISBN 0-203-30162-5 Master e-book ISBN ISBN 0-203-34224-0 (Adobe eReader Format) (Print Edition) © 2002 Jan Skalny, Jacques Marchand and Ivan Odler Contents Preface Acknowledgments 1Introduction References 2Chemistry and physics of cement paste 2.1Concrete components 2.1.1Hydraulic cements 2.1.2Aggregates 2.1.3 Mineral and chemical admixtures 2.1.4Water 2.2Hydration of Portland clinker-based cements 2.2.1Chemistry of hydration reactions 2.3 Hydrated cement paste, mortar and concrete 2.3.1Microstructural development 2.3.2Development of physical properties References 3Concrete deterioration 3.1Principal causes of concrete deterioration 3.1.1Deterioration caused by dissolution of paste components 3.1.2Deterioration caused by ingress of external chemicals 3.1.3Expansive reactions with aggregate 3.1.4Frost-related deterioration 3.1.5Corrosion of embedded steel 3.1.6Abrasion, erosion and cavitation 3.2Selection of materials 3.2.1Importance of mix design © 2002 Jan Skalny, Jacques Marchand and Ivan Odler 3.3Concrete processing 3.3.1Mixing, curing, placing, finishing, and maintenance 3.4Effect of environmental exposure 3.4.1Effect of chemical environment 3.4.2Effects of temperature and humidity changes 3.5Known prevention techniques References 4Sulfate attack 4.1Forms of sulfate attack 4.1.1Manifestations of sulfate attack 4.2Source of sulfates in sulfate attack 4.2.1Internal sources 4.2.2External sources 4.3 Mechanisms of sulfate-related deterioration 4.3.1Sulfate attack mechanisms – a brief history 4.4Types of expansive reactions 4.4.1Increase of the solid volume 4.4.2Expansion in a topochemical reaction 4.4.3 Oriented crystal growth 4.4.4Expansion caused by crystallization pressure 4.4.5Expansion caused by swelling phenomena 4.4.6Other expansive processes 4.5Ettringite formation and expansion 4.6Other forms of sulfate-related expansion 4.7Interaction of sulfates with the C-S-H phase 4.8Internal sulfate attack 4.8.1Internal sulfate attack at ambient temperature 4.8.2Heat-induced sulfate attack or DEF 4.8.3 Concluding comments on internal sulfate attack 4.9External sulfate attack 4.9.1Na 2 SO 4 and K 2 SO 4 4.9.2CaSO 4 4.9.3 MgSO 4 4.9.4H 2 SO 4 4.9.5(NH 4 ) 2 SO 4 4.9.6Sulfate attack in the presence of SiO 2 and CO 2 4.9.7Sea water 4.9.8Concluding comments on external sulfate attack © 2002 Jan Skalny, Jacques Marchand and Ivan Odler 4.10Sulfate resistant cements – mechanism of action 4.11Physical sulfate attack or salt crystallization 4.12Bacteriogenic corrosion of concrete in waste water networks 4.13 Conditions affecting sulfate attack References 5Consequences of sulfate attack on concrete 5.1Introduction 5.2External appearance and volume stability of concrete attacked by sulfate 5.2.1External appearance and volume stability of concrete subjected to internal sulfate attack 5.2.2External appearance and volume stability of concrete subjected to external sulfate attack 5.3 Consequences of sulfate attack on the microstructure of concrete 5.4Consequences of sulfate attack on the mechanical properties of concrete 5.5Concluding remarks References 6Prevention of sulfate attack 6.1Introduction 6.2Measures to protect concrete against composition-induced internal sulfate attack 6.3 Measures to protect concrete against heat-induced internal sulfate attack 6.4Measures to protect concrete against external sulfate attack 6.5Concluding remarks References 7Modeling of deterioration processes 7.1Introduction 7.2Microstructure-based performance models 7.2.1Empirical models 7.2.2Mechanistic models 7.2.3 Numerical models 7.3 Concluding remarks Note References © 2002 Jan Skalny, Jacques Marchand and Ivan Odler 8Case histories 8.1Deterioration of residential buildings in Southern California 8.2Sulfate attack damage brought about by heat treatment (DEF) 8.3 Concrete railroad sleepers: heat-induced internal sulfate attack (DEF) or ASR? 8.4Deterioration of UK concrete bridge foundations caused by the thaumasite form of sulfate attack (TSA) Acknowledgments Notes References 9Assessment of cement and concrete performance under sulfate attack 9.1Prescriptive standards for assessing sulfate resistance of cements 9.2Prescriptive standards for concrete to be exposed to sulfate attack 9.3 Performance standards References Concluding remarks © 2002 Jan Skalny, Jacques Marchand and Ivan Odler Preface We consider it to be a great honor to be chosen by Professors A. Bentur and S. Mindess to prepare this book for publication by Spon Press and it was not without trepidation that we accepted the task to summarize the available knowledge on the effect of sulfates on concrete. We were hesitant because the mechanistic issues of sulfate attack on concrete are complex and sometimes controversial. The multidimensionality of the sulfate attack issues becomes obvious when one realizes the variability of the environmental conditions under which concrete is used, of the complex chemistry and mineralogy of the con- crete components, and of the less-than-well-defined processing conditions used in making concrete to be used in a variety of structures. In discussing sulfate attack mechanisms, one has to deal, among others, with issues of chemical and mineralogical composition of the aggressive species, properties of amorphous to crystalline reaction products, variability and limited con- trollability of the reaction (curing) conditions, and to consider difficult issues related to best testing methodology, standardization, prediction of service life by modeling, etc. All the above make consolidation of the existing know- ledge a considerable challenge. The book is prepared for an audience consisting of students of materials engineering, construction practitioners, and researchers. As the loss of dur- ability of concrete almost always involves chemical and physico-chemical processes, it may be difficult for some readers to follow the intricate details of sulfate attack mechanisms. To overcome this, we included a few chapters summarizing the basics of cement hydration and concrete deterioration. It is entirely possible that for some, the book contains excessive information; others may consider the given details to be inadequate. There will be voices disagreeing with our interpretation of the “average” literature data. To these we can only say that we did our best to consolidate the available data in an understandable manner and we suggest that, if needed, the readers visit the references given at the end of each chapter. We hope that this book will be considered a good introduction to the scientific and practical intricacies of sulfate attack mechanisms, as well as becoming an impetus to younger researchers to develop a romance with engineering materials. © 2002 Jan Skalny, Jacques Marchand and Ivan Odler Acknowledgments The authors would like to thank the numerous colleagues who helped in realizing this complex project. First of all, we would like to acknowledge the invitation by Professors A. Bentur and S. Mindess, the Editors of this Spon Press series of books on concrete technology, to prepare this manuscript for publication. Although an honor, the consolidation of all the available controversial data was not without difficulties and frus- trations. We are most thankful to Messrs P.W. Brown, S. Diamond, J. Gebauer, V. Johansen, B. Mather, K.L. Scrivener, H.F.W. Taylor, N. Thaulow, M. Thomas and unnamed others for most useful and critical discussions on mechanistic aspects of various forms of sulfate attack. We would like to acknowledge our gratefulness to J.J. Beaudoin, N.J. Crammond, S. Diamond, G. Frohnsdorff and E.M. Gartner for their critical review of parts of the manuscript, and to N.J. Crammond and coworkers for con- tributing the case study on thaumasite. Special in memoriam thanks are due to C.D. Lawrence who made us available his unpublished bibliography of “DEF” literature and J. Jambor who left with us his unpublished report on sulfate attack. We would also like to acknowledge the authors of the high-quality photographic material used throughout the book (obtained from Messrs M. Alexander, S. Badger, C. Fourie, U. Hjorth Jakobsen, S. Sahu, P. Stutzman, N. Thaulow and M. Thomas), as well as photographic and other material obtained from CEMBUREAU (Belgium), G.M. Idorn Consult (Denmark), BRE – Building Research (United Kingdom), R.J. Lee Group (USA), The Erlin Company (USA), Portland Cement Association (USA), and other sources. Our thanks are also due to J. Parent (Laval University, Quebec, Canada) for preparation of the graphic material. Our deep thanks are due to the staff of Spon Press, specifically Marie- Louise Logan and Richard Whitby, for their dedicated work and profession- alism. Finally, important thanks are also due to our spouses – Magdalena, © 2002 Jan Skalny, Jacques Marchand and Ivan Odler [...]...Marie-Helene and Marika – for exercising patience that some of us cannot reciprocate with Jan Skalny (jpskalny@aol.com) Jacques Marchand (jacques.marchand@gci.ulaval.ca) Ivan Odler (ivanodler@aol.com) January 200 1 © 200 2 Jan Skalny, Jacques Marchand and Ivan Odler . 0 419–245 50 2 This edition published in the Taylor & Francis e-Library, 200 3. ISBN 0- 2 0 3-3 01 6 2-5 Master e-book ISBN ISBN 0- 2 0 3-3 422 4 -0 (Adobe eReader Format) (Print Edition) © 200 2 Jan Skalny, Jacques. crystallization 4.12Bacteriogenic corrosion of concrete in waste water networks 4.13 Conditions affecting sulfate attack References 5Consequences of sulfate attack on concrete 5.1Introduction 5.2External. subjected to external sulfate attack 5.3 Consequences of sulfate attack on the microstructure of concrete 5.4Consequences of sulfate attack on the mechanical properties of concrete 5.5Concluding remarks References 6Prevention