Science and Technology of Concrete Admixtures Related titles Advances in Asphalt Materials (ISBN 978-0-08-100269-8) Acoustic Emission and Related Non-destructive Evaluation Techniques in the Fracture Mechanics of Concrete (ISBN 978-1-78242-345-4) Handbook of Alkali-activated Cements, Mortars and Concretes (ISBN 978-1-78242-276-1) Understanding the Rheology of Concrete (ISBN 978-0-85709-028-7) Woodhead Publishing Series in Civil and Structural Engineering: Number 59 Science and Technology of Concrete Admixtures Edited by Pierre-Claude Aïtcin and Robert J Flatt Knowing is not enough: we must apply Willing is not enough: we must –Goethe AMSTERDAM • BOSTON • CAMBRIDGE • HEIDELBERG LONDON • NEW YORK • OXFORD • PARIS • SAN DIEGO SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO Woodhead Publishing is an imprint of Elsevier Woodhead Publishing is an imprint of Elsevier 80 High Street, Sawston, Cambridge, CB22 3HJ, UK 225 Wyman Street, Waltham, MA 02451, USA Langford Lane, Kidlington, OX5 1GB, UK Copyright © 2016 Elsevier Ltd All rights reserved No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein) Notices Knowledge and best practice in this field are constantly changing As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein ISBN: 978-0-08-100693-1 (print) ISBN: 978-0-08-100696-2 (online) British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Library of Congress Control Number: 2015952093 For information on all Woodhead Publishing publications visit our website at http://store.elsevier.com/ Contents About the contributors Woodhead Publishing Series in Civil and Structural Engineering Preface Acknowledgments Introduction Terminology and definitions Glossary Historical background of the development of concrete admixtures Part One Theoretical background on Portland cement and concrete The importance of the water–cement and water–binder ratios P.-C Aïtcin 1.1 Introduction 1.2 The hidden meaning of the w/c 1.3 The water–cement and water–binder ratios in a cement paste made with a blended cement 1.4 How to lower the w/c and w/b ratios 1.5 Conclusion References xiii xv xix xxiii xxv xxxi xxxvii xli 3 11 12 13 Phenomenology of cement hydration P.-C Aïtcin 2.1 Introduction 2.2 Le Chatelier’s experiment 2.3 Powers’ work on hydration 2.4 Curing low w/c ratio concretes 2.5 Conclusion References 15 Portland cement P.-C Aïtcin 3.1 Introduction 3.2 The mineral composition of Portland cement clinker 3.3 The fabrication of clinker 3.4 Chemical composition of Portland cement 27 15 15 16 22 24 24 27 28 31 33 vi Contents 3.5 3.6 3.7 3.8 3.9 3.10 The grinding of Portland cement The hydration of Portland cement Hydrated lime (portlandite) Present acceptance standards for cements Side-effects of hydration reaction Conclusion Appendices References 36 39 43 44 44 45 45 50 Supplementary cementitious materials and blended cements P.-C Aïtcin 4.1 Introduction 4.2 Crystallized and vitreous state 4.3 Blast-furnace slag 4.4 Fly ashes 4.5 Silica fume 4.6 Calcined clays 4.7 Natural pozzolans 4.8 Other supplementary cementitious materials 4.9 Fillers 4.10 Ground glass 4.11 Blended cements 4.12 Conclusion References 53 Water and its role on concrete performance P.-C Aïtcin 5.1 Introduction 5.2 The crucial role of water in concrete 5.3 Influence of water on concrete rheology 5.4 Water and cement hydration 5.5 Water and shrinkage 5.6 Water and alkali/aggregate reaction 5.7 Use of some special waters 5.8 Conclusion References 75 Entrained air in concrete: rheology and freezing resistance P.-C Aïtcin 6.1 Introduction 6.2 Entrapped air and entrained air 6.3 Beneficial effects of entrained air 6.4 Effect of pumping on the air content and spacing factor 6.5 Entraining air in blended cements 6.6 Conclusion References 87 53 54 57 60 62 65 66 67 67 69 70 72 72 75 75 77 78 78 83 83 84 85 87 87 88 93 93 94 94 Contents vii 97 Concrete rheology: a basis for understanding chemical admixtures A Yahia, S Mantellato, R.J Flatt 7.1 Introduction 7.2 Definition of rheology 7.3 Different rheological behaviours 7.4 Micromechanical behaviour of suspensions 7.5 Factors affecting concrete rheology 7.6 Thixotropy of concrete 7.7 Conclusions Terminology and definitions Acknowledgements References Mechanisms of cement hydration D Marchon, R.J Flatt 8.1 Introduction 8.2 Hydration of C3A 8.3 Hydration of alite 8.4 Hydration of ordinary Portland cement 8.5 Conclusions Acknowledgments References Part Two 10 Chemistry and working mechanisms 97 98 101 104 110 116 120 121 122 122 129 129 130 131 138 141 141 141 147 Chemistry of chemical admixtures G Gelardi, S Mantellato, D Marchon, M Palacios, A.B Eberhardt, R.J Flatt 9.1 Introduction 9.2 Water reducers and superplasticizers 9.3 Retarders 9.4 Viscosity-modifying admixtures 9.5 Air-entraining admixtures 9.6 Shrinkage-reducing admixtures 9.7 Conclusions Acknowledgements References 149 Adsorption of chemical admixtures D Marchon, S Mantellato, A.B Eberhardt, R.J Flatt 10.1 Introduction 10.2 Adsorption and fluidity 10.3 Adsorption isotherms 10.4 Molecular structure and adsorption 10.5 Dynamic exchanges between surface and solution 219 149 150 171 175 182 197 207 207 207 219 220 221 226 232 viii Contents 10.6 10.7 10.8 10.9 11 12 13 14 Consumption (ineffective adsorption) Surfactant adsorption at the liquid–vapor interface Experimental issues in measuring adsorption Conclusions Acknowledgments References 234 239 241 248 248 248 Working mechanisms of water reducers and superplasticizers G Gelardi, R.J Flatt 11.1 Introduction 11.2 Dispersion forces 11.3 Electrostatic forces 11.4 DLVO theory 11.5 Steric forces 11.6 Effect of superplasticizers 11.7 Conclusions Acknowledgements References 257 Impact of chemical admixtures on cement hydration D Marchon, R.J Flatt 12.1 Introduction 12.2 Mechanisms of retardation 12.3 Retardation by superplasticizers 12.4 Retardation by sugars 12.5 Conclusions Acknowledgment References 279 Working mechanisms of shrinkage-reducing admixtures A.B Eberhardt, R.J Flatt 13.1 Introduction 13.2 Basic principles of the shrinkage of cementitious systems 13.3 Impact of SRAs on drying shrinkage 13.4 Dosage response of SRA on drying shrinkage 13.5 Conclusions References 305 Corrosion inhibitors for reinforced concrete B Elsener, U Angst 14.1 Introduction 14.2 Corrosion mechanisms of reinforcing steel in concrete 14.3 Corrosion inhibitors for steel in concrete 14.4 Critical evaluation of corrosion inhibitors 321 257 257 258 262 266 268 275 275 275 279 281 287 290 299 299 299 305 306 311 315 318 318 321 322 326 334 Contents ix 14.5 Concluding remarks References Part Three 15 Formulation of commercial products S Mantellato, A.B Eberhardt, R.J Flatt 15.1 Introduction 15.2 Performance targets 15.3 Cost issues 15.4 Conclusions Acknowledgments References Section One 16 17 Admixtures that modify at the same time the properties of the fresh and hardened concrete 341 343 343 343 346 347 347 347 351 Superplasticizers in practice P.-C Nkinamubanzi, S Mantellato, R.J Flatt 16.1 Introduction 16.2 Application perspective on superplasticizers and their use 16.3 Impact of superplasticizers on rheology 16.4 Unexpected or undesired behaviors 16.5 Conclusions Acknowledgments References 353 Air entraining agents R Gagné 17.1 Introduction 17.2 Mechanisms of air entrainment 17.3 Principal characteristics of a bubble network 17.4 Production of a bubble network 17.5 Stability of the network of entrained bubbles 17.6 Conclusion References 379 Section Two 18 The technology of admixtures 335 336 Admixtures that modify essentially the properties of the fresh concrete Retarders P.-C Aïtcin 18.1 Introduction 18.2 Cooling concrete to retard its setting 18.3 The use of retarders 353 354 357 362 371 372 372 379 379 380 381 388 390 390 393 395 395 396 397 ... considerations of the principles governing the formulation of commercial admixtures, we present the technology of four categories of concrete admixtures: • • • • Admixtures Admixtures Admixtures Admixtures... result of a massive research effort that has created a true science of concrete and a true science of admixtures It is the prime objective of this book to present the current state of the art of. .. The future of admixtures Conclusions and outlook on the future of concrete admixtures R.J Flatt 28.1 Chemical admixtures are to concrete, what spices are to cooking 28.2 Of good and bad concrete