Chemical Admixtures for Concrete

1999 Roger Rixom and Noel Mailvaganam

Chemical Admixtures for Concrete

Third edition

Roger Rixom and Noel Mailvaganam

1999 Roger Rixom and Noel Mailvaganam

First edition published 1978 by E. & F.N.Spon Ltd 11 New Fetter Lane, London EC4P 4EE Second edition published 1986 by E & FN Spon, an imprint of Chapman & Hall This edition 1999 by E & FN Spon 11 New Fetter Lane, London EC4P 4EE Simultaneously published in the USA and Canada by Routledge 29 West 35th Street, New York, NY 10001 This edition published in the Taylor & Francis e-Library, 2002. E & FN Spon is an imprint of the Taylor & Francis Group 1999 Roger Rixom and Noel Mailvaganam 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 hearafter 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 Rixom, M.R. Chemical admixtures for concrete/Roger Rixom and Noel Mailvaganam. 3rd ed. p. cm. Includes bibliographical references and index. I. Concrete-Additives. I. Mailvaganam, N.P. (Noel P., 1938- . II. Title. TP884.A3R59 1999 666.893dc21 ISBN 0-419-22520-X (Print Edition) ISBN 0-203-01724-2 Master e-book ISBN ISBN 0-203-13711-6 (Glassbook Format)

9843377 CIP

1999 Roger Rixom and Noel Mailvaganam

To my wife Joan and our children Tony, Di, Anne, Sue and Andrew (Roger Rixom) To my parents Josephine and Arullapa, wife Nalini and sons Dimitri and Stefan (Noel Mailvaganam)

1999 Roger Rixom and Noel Mailvaganam

Contents

Disclaimer Foreword to third edition Acknowledgements 1 Water-reducing agents 1.1 Background and definitions 1.2 The chemistry of water-reducing admixtures 1.2.1 Lignosulfonates 1.2.2 Hydroxycarboxylic acids 1.2.3 Hydroxylated polymers 1.3 The effects of water-reducing admixtures on the water-cement system 1.3.1 Rheological considerations 1.3.2 Initial surface effects 1.3.3 Effects on the products and kinetics of hydration 1.3.4 Interpretation in terms of a mode of action 1.4 The effects of water-reducing admixtures on the properties of concrete 1.5 The effects of water-reducing admixtures on the properties of plastic concrete 1.5.1 Air entrainment 1.5.2 Workability 1.5.3 Workability loss 1.5.4 Water reduction 1.5.5 Setting characteristics of fresh concrete containing water-reducing admixtures 1.5.6 The stability of fresh concrete containing water-reducing admixtures 1.5.7 Mix design considerations 1.6 The effects of water-reducing admixtures on the properties of hardened concrete
1999 Roger Rixom and Noel Mailvaganam

1.6.1 Structural design parameters 1.6.2 Durability aspects 1.6.3 Durability guidelines References 2 Superplasticizers 2.1 Background and definitions 2.2 The chemistry of superplasticizers 2.2.1 Sulfonated naphthalene formaldehyde 2.2.2 Sulfonated melamine formaldehyde 2.2.3 Polyacrylates 2.3 Effects on the water-cement system 2.3.1 Rheological effects 2.3.2 Zeta potential 2.3.3 Adsorption 2.3.4 Effects on the products and kinetics of hydration 2.3.5 Interpretation in terms of a mode of action 2.4 Effects of superplasticizers on the properties of concrete 2.5 The effects of superplasticizers on the properties of plastic concrete 2.5.1 Air entrainment 2.5.2 Workability 2.5.3 Setting time 2.6 The effects of superplasticizers on the properties of hardened concrete 2.6.1 Compressive strength 2.6.2 Shrinkage and creep 2.6.3 Freeze-thaw durability 2.6.4 Sulfate resistance References 3 Air-entraining agents 3.1 Background and definitions 3.1.1 Durability 3.1.2 Cohesion 3.1.3 Density 3.2 The chemistry of air-entraining agents 3.2.1 Neutralized wood resins 3.2.2 Fatty-acid salts 3.2.3 Alkyl-aryl sulfonates 3.2.4 Alkyl sulfates
1999 Roger Rixom and Noel Mailvaganam

3.2.5 Phenol ethoxylates The effects of air-entraining agents on the water-cement system 3.3.1 Rheology 3.3.2 Air content and characteristics 3.3.3 Distribution between solid and aqueous phases 3.3.4 Effects on the hydration chemistry of cement 3.3.5 Interpretation as a mechanism of action 3.4 The effect of air-entraining agents on the properties of plastic concrete 3.4.1 Volume of air entrained 3.4.2 The stability of the entrained air 3.4.3 Workability 3.4.4 Water reduction 3.4.5 Mix stability 3.4.6 Mix design requirements 3.5 The effects of air-entraining agents on the properties of hardened concrete 3.5.1 Structural design parameters 3.5.2 Durability aspects References 3.3 4 Concrete dampproofers 4.1 Background and definitions 4.2 The chemistry of concrete dampproofers 4.2.1 Materials which react with cement hydration products 4.2.2 Materials which coalesce on contact with cement hydration products 4.2.3 Finely divided hydrophobic materials 4.3 The effects of dampproofers on the water-cement system 4.3.1 Bleeding of cement pastes 4.3.2 Hydration of cement pastes 4.3.3 Effects on the capillary system of hardened paste 4.4 The effects of dampproofers on the properties of plastic concrete 4.5 The effects of dampproofers on the properties of hardened concrete 4.5.1 Structural design parameters 4.5.2 Durability aspects References
1999 Roger Rixom and Noel Mailvaganam

5 Accelerators 5.1 Background and definitions 5.2 The chemistry of accelerators 5.2.1 Calcium chloride 5.2.2 Calcium formate 5.2.3 Triethanolamine 5.3 The effects of accelerators on the water-cement system 5.3.1 Rheological effects 5.3.2 Chemical effects 5.3.3 Effects on cement hydration 5.3.4 Mechanism of action 5.4 The effects of accelerators on the properties of plastic concrete 5.4.1 Effect on heat evolution 5.4.2 Effect on setting time 5.5 The effects of accelerators on the properties of hardened concrete 5.5.1 Structural design parameters 5.5.2 Durability aspects References 6 Special purpose admixtures 6.1 Introduction 6.2 Alkali-aggregate expansion-reducing admixtures 6.2.1 Alkali-aggregate reaction 6.2.2 Types of admixtures 6.2.3 Mode of action 6.2.4 Effects on the plastic and hardened properties of mortar and concrete 6.3 Antifreeze admixtures 6.3.1 Chemical composition and mode of action 6.4 Antiwashout admixtures 6.4.1 Categories 6.4.2 Formulating non-dispersible underwater concrete 6.4.3 Effects produced on plastic and hardened concrete 6.4.4 Factors affecting the performance of antiwashout admixtures 6.4.5 Mixture and storage 6.4.6 Applications 6.5 Corrosion-inhibiting admixtures
1999 Roger Rixom and Noel Mailvaganam

6.5.1 Material parameters 6.5.2 Types of corrosion inhibitors 6.5.3 Research on other corrosion inhibitors 6.6 Calcium-sulfoaluminate-based expanding admixtures 6.6.1 Chemical composition 6.6.2 Mode of action 6.6.3 Mix proportioning, mixing and curing 6.6.4 Factors influencing the reaction 6.6.5 Effects on the plastic and hardened properties of mortar and concrete 6.6.6 Applications 6.7 Polymer-based admixtures 6.7.1 Categories 6.7.2 Material parameters influencing performance 6.7.3 Modification of the cementitious matrix 6.7.4 Mix proportioning 6.7.5 Mixing, placing and curing 6.7.6 Properties of latex-modified mortar and concrete 6.7.7 Applications 6.7.8 Standards and specifications 6.8 Admixtures for recycling concrete waste 6.8.1 Chemical composition and mechanism of action 6.8.2 Effects on hardened properties of concrete 6.9 Shotcrete admixtures 6.9.1 Types of admixtures and mode of action 6.9.2 Factors influencing the effects of the admixture 6.9.3 Effects on the plastic and hardened properties of concrete and mortars 6.9.4 Guidelines for use 6.10 Shrinkage-reducing admixtures 6.10.1 Effects on the fresh concrete properties 6.10.2 Effects on the hardened properties of concrete 6.10.3 Factors affecting the performance of shrinkage-reducing admixtures References 7 Applications of admixtures 7.1 Introduction 7.1.1 Reasons for use of admixtures 7.2 Air-entraining admixtures
1999 Roger Rixom and Noel Mailvaganam

7.3

7.4

7.5

7.6

7.7

7.8 7.9 7.10 7.11

7.12

7.2.1 Control measures used to ensure proper air entrainment 7.2.2 Methods of placing 7.2.3 Air-entraining admixture/superplasticizer compatibility 7.2.4 Composite air-entrainingwater-reducing admixtures Normal-setting water-reducing admixtures 7.3.1 Ready-mixed concrete 7.3.2 High-strength/high-performance concrete 7.3.3 High-workability mixes 7.3.4 Pumping 7.3.5 Watertight concrete 7.3.6 Piling Set-retarding and water-reducing admixtures 7.4.1 Retarded concrete for large pours 7.4.2 Slip-forming 7.4.3 Marine structures 7.4.4 Tilt-up construction Accelerating admixtures 7.5.1 Purpose and advantages resulting from the use of accelerators 7.5.2 Non-chloride admixtures 7.5.3 Accelerators for use in blended cement (fly ash or slag) mixtures Superplasticizers (high-range water reducers) 7.6.1 Flowing concrete 7.6.2 High-range water-reduced concrete 7.6.3 High-performance concrete and mortar Viscosity-enhancing admixtures 7.7.1 Grouting applications 7.7.2 Underwater concrete 7.7.3 Formulation of construction products Damp-proofing admixtures Recycling of cementitious wastes Hot-weather concreting Cold-weather concreting 7.11.1 Acceleration of hydration and depression of freezing point of the water mix 7.11.2 Reduction of freezable water 7.11.3 Case studies Economic aspects of admixture use 7.12.1 Economies in mix proportioning

1999 Roger Rixom and Noel Mailvaganam

7.12.2 Economies from improved durability 7.12.3 Economies from improved placing characteristics and construction methods 7.12.4 Precast concrete 7.12.5 Economic benefits of cold-weather admixtures 7.12.6 Economic benefits from the recycling of plastic concrete and wash water 7.13 Guidelines for the use of admixtures 7.13.1 Evaluation and selection 7.13.2 Admixture uniformity 7.13.3 Precautions in the use of admixtures 7.13.4 Mix proportioning using computers 7.13.5 Safety and hygienic aspects in the handling of admixtures 7.13.6 Admixture problemslimitations and incompatibility 7.14 Batching and dispensing of admixtures 7.14.1 Manufacture 7.14.2 Packaging and delivery 7.14.3 Labels 7.14.4 Storage 7.14.5 Dispensing of admixtures 7.14.6 Dispensing equipment 7.14.7 Calibration and maintenance of batching systems 7.14.8 Computer batching References

1999 Roger Rixom and Noel Mailvaganam

Disclaimer

The information and recommendations presented in this book are represented in good faith and believed to correct as of the date of publication. However the publisher, the authors and the organizations to which the authors belong make no representation or warranties, either express or implicit as to the completeness or accuracy thereof. Information is presented upon the condition that the persons receiving the same will make their own determination as to its suitability for their purposes prior to use. In no event will the publisher, the authors and the organizations to which the authors belong be responsible for damages whatsoever resulting from the use or reliance on the information contained in this book.

1999 Roger Rixom and Noel Mailvaganam

Foreword to the third edition

It is now 20 years and 13 years since the first and second editions respectively of Chemical Admixtures for Concrete were published. A first glance at the international admixture business could lead to the impression that not a lot had changed in 20 years; certainly not enough to justify the complete revision of the second edition of the book. While it is true that products based on lignosulfonates, sodium glucoheptonate and corn syrup are still provided to the market in thousands of tonnes every year, there have been several significant changes: 1. A change in the supply situation of Vinsol resin with a commensurate price increase as well as the more widespread use of supplementary materials led almost all admixture companies to reformulate their air-entraining agents using synthetic or alternative natural products such as tall oil or rosins. In a period of about 2 years, a product that had been in dominant use for 40 years was relegated to a lesser role in the industry. A whole new category of water-reducing agents, the mid-range products, have emerged as a major benefit to the concrete industry, allowing easier-toplace high-slump concrete to be produced at minimal cost and with little effect on setting time. In the USA, this is the fastest growing sector of the admixture industry. Whilst the use of superplasticizers has not grown as fast as had been anticipated, and still accounts for less than 10% of concrete produced, there have been technical developments in this area. New chemical types of these products have been developed based on polyacrylates and have begun to be used in formulations. With the advent of high-performance concrete, such developments have been timely. Since the new acrylatebased materials maintain higher slumps for longer periods, and can therefore be added at a central mixing facility, ready-mixed highperfomance concrete is now a reality. Other types of chemical admixtures that were supplied in very small quantities 15 or 20 years ago, such as corrosion inhibitors etc., have become highvolume products and have helped to double the concrete admixture market since the last edition.

2.

3.

4.

1999 Roger Rixom and Noel Mailvaganam

Even the companies supplying the international market have seen changes: Master Builders Technologies has changed ownership to the German company SKW GmbH (a member of the VIAG Group), which has resulted in the largest construction chemicals business in the world with sales approaching $2 billion per year and having a clear commitment to the industry and a strong track record in research. Further consolidation is evident by the acquisition by W.R.Grace & Company of Cormix Construction Chemicals, which itself had absorbed the Gifford Hill and American Admixtures business some years previously. Again, this company is committed to the advancement of the industry through research and development. The vacuum left by the acquisition of smaller companies by the two larger ones is predictably being filled by the spawning of new companies, usually on a strong regional basis, such as GRT in Minnesota and Arrmacrete Construction Chemicals in Florida. These companies are bringing their own changes to the industry in terms of innovation and service. In academia too, workers have advanced our knowledge of how water-reducing agents and superplasticizers function and have made our earlier theories look simplistic and pedantic. Other authors have also been active; when Chemical Admixtures for Concrete was first published, it was almost the only book available on the subject. Now there are several others, and two of them in particular, by Ramachandran and Dodson, belong on the shelf of anyone with a serious interest in chemical admixtures. Against this background therefore, the authors felt that there was still a need for a comprehensive treatise that would fill the needs of all those interested in the subject, whether they be a student, a user, a manufacturer, or a specifier, and that not just a general update, but a deep revision was justified. Specifically, the following changes have been made: 1. A general update of references and developments in all chapters including a major new chapter on superplasticizers, or high-range water-reducing agents. Addition of a new section on miscellaneous admixtures including shotcrete admixtures, corrosion inhibitors, and admixtures for recycling wash water and plastic concrete. Expansion of the chapter on applications, including an additional section on troubleshooting.

2.

3.

The book is a survey of current work and thinking and contains both the latest understanding of the complex process of admixture-cement interactions and the techniques that enable improvements in the performance of concrete. We have attempted to present the subject in a manner that can be readily applied and is therefore structured for the practicing engineer, providing a balance between theory and a hands-on approach of admixture use on the job site.
1999 Roger Rixom and Noel Mailvaganam

Reluctantly, we have dropped the chapter on specifications and standards on the grounds of space for the new expanded areas; also the timing of the new unified European Standards did not meet the deadline for publication. Both authors have been resident and active in the construction chemicals field in North America for some years now and despite having previously been active on three other continents for a combined total of over 60 years, the parochialism does show through and we apologize for this. As always, we welcome suggestions and constructive criticism so that in the unlikely event of a fourth addition, we can do a better job.

1999 Roger Rixom and Noel Mailvaganam

Acknowledgements

The authors of the third edition of Chemical Admixtures for Concrete acknowledge with appreciation the help and cooperation of the following companies and individuals for providing: The Canadian National Research Councils Institute for Research in Construction, Ottawa, Canada Master Builders Technologies, Canada and USA Sternson Ltd, Brantford, Canada Euclid Chemicals Canada and USA Marcotte Instruments, Quebec, Canada Cormix Inc., UK Conchem Research Associates, Orleans, Canada Structural Preservation Systems, Baltimore, USA Fritz Admixtures, Texas, USA Sika Corporation, Canada and Switzerland Halsall Associates, Ottawa, Canada W.R.Grace, Canada and USA Arr-Maz Products Company, Florida, USA Dr D.R.Morgan, Prof. Paulo, Helene (University of Sao Paulo) and Prof. L.Pudencio (University of St. Catarina) of Brazil Prof. N.Banthia (Univ. of British Columbia, Canada) Claude Beddard, Prof. C.Jollicoeur (Univ. of Sherbrooke, Canada) Dr C.Nmai, Dr A. Vaysburd, Prof. N.Swamy (Univ. of Sheffield, UK) Prof. Bassheer (Univ. of Ulster, N.Ireland) Dr V.S.Ramanchandran, Prof. K.Hover (Cornell University, USA) Prof. G.Razaqpur (Carleton University, Ottawa) Mr C.Chun (Project Manager Sehoe Bridge Project, Pago Korea) Mr M.Y. Shim (Dongnam Industries, Seoul, Korea). Special recognition is given to the following individuals who helped at various stages of the preparation of the manuscript: Mrs Nalini Mailvaganam, Dimitri and Rex Mailvaganam, Dr W.Repette, O.Maadani, Mrs L.Dessereault. The information presented in the sections on polymerbased admixtures and cold and hot water concreting has been largely derived from the publications of Prof. Y.Ohama (Univ. of Kyoto, Japan) Prof. I.Soroka (Technion, Israel) and Dr C.Nmai (Master Builders Technologies). Their cooperation in giving approval for the use of a number of figures is gratefully acknowledged.

1999 Roger Rixom and Noel Mailvaganam