Advande in Cement Technology Advande in Cement Technology Advande in Cement Technology Advande in Cement Technology Advande in Cement Technology Advande in Cement Technology Advande in Cement Technology Advande in Cement Technology Advande in Cement Technology
Advances in Cement Technology Other Pergamon Titles of Interest DHIR DHIR GIBSON HARRISON HENDRY HORNE LIVESLEY ROZVANY RYAN SACHS SHARP WARBURTON WHITAKER WORRALL Advances in Concrete Slab Technology Advances in Ready-Mixed Concrete Technology Thin Shells Structural Analysis and Design Elements of Experimental Stress Analysis, SI Edition Plastic Theory of Structures, 2nd Edition Matrix Methods of Structural Analysis, 2nd Edition Optimal Design of Flexural Systems - Beams, Grillages, Slabs, Plates and Shells Properties of Ceramic Raw Materials, 2nd Edition in Si/Metric Units Wind Forces in Engineering, 2nd Edition Concrete in Highway Engineering Dynamical Behaviour of Strutures, 2nd Edition The Design of Piled Foundations, 2nd Edition Ceramic Raw Materials, 2nd Edition Pergamon Related Journals Free Specimen Copy Gladly Sent on Request Cement and Concrete Research Civil Engineering for Design and Practising Engineers International Journal of Engineering Sciences International Journal of Solids and Structures Materials Research Bulletin Progress in Materials Science Underground Space Advances in Cement Technology Critical Reviews and Case Studies on Manufacturing, Quality Control, Optimization and Use Edited by S N GHOSH Cement Research Institute of India, New Delhi, India «EV PERGAMON PRESS OXFORD · NEW YORK · TORONTO · SYDNEY · PARIS · FRANKFURT U.K Pergamon Press Ltd., Headington Hill Hall, Oxford OX3 OBW, England U.S.A Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S.A CANADA Pergamon Press Canada Ltd., Suite 104, 150 Consumers Road, Willowdale, Ontario M2J 1P9, Canada AUSTRALIA Pergamon Press (Aust.) Pty Ltd., P.O Box 544, Potts Point, N.S.W 2011, Australia FRANCE Pergamon Press SARL, 24 rue des Ecoles, 75240 Paris, Cedex 05, France FEDERAL REPUBLIC OF GERMANY Pergamon Press GmbH, 6242 Kronberg-Taunus, Hammerweg 6, Federal Republic of Germany Copyright © 1983 Pergamon Press Ltd All Rights Reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic tape, mechanical photocopying, recording or otherwise, without permission in writing from the publishers First edition 1983 Library of Congress Cataloging in Publication Data Main entry under title: Advances in cement technology Portland cement—Addresses, essays, lectures L Ghosh, S N TP883.A38 1982 6ό6'.94 82-7576 British Library Cataloguing in Publication Data Ghosh, S.N Advances in cement technology Portland cement I Title 666'.94 TP883 ISBN 0-08-028670-4 In order to make this volume available as economically and as rapidly as possible the typescript has been reproduced in its original form This method unfortunately has its typographical limitations but it is hoped that they in no way distract the reader Printed in Great Britain by A Wheaton & Co Ltd., Exeter Foreword I have endeavoured to present in this book critical reviews of important aspects on the science and technology of cement This is evident from its contents which covers areas such as Geology, Raw-materials, Manufacture, Chemistry, Additions, Admixtures, Industrial wastes and some useful analytical methods The compilation is the first of its kind to bring the latest advances in the field in a single volume I hope that it will be useful to persons working in cement and concrete industries and laboratories My sincere thanks are due to the authors of the different chapters for their excellent cooperations I owe also to many others for their help, particularly to Dr J -Bensted, Dr V N Viswanathan, Mr G Ramaseshan and Mr S C Majumder I thank my wife Nilima for her secretarial assistance in the project New Delhi November 1981 S N Ghosh V Contributors Professor UT Kurdowski Dr J Bensted Professor L Ben-Dor Professor B Marchese Dr A K Chatterjee Professor F Massazza Mr ï K Chatterjee Dr J Mukerji Dr G Frigione Dr V S Ramachandran Dr S N Ghosh Dr R Rehsi Dr S P Ghosh Dr S L Sarkar Dr I Jelenic Professor R Sersale Dr H Jennings Dr V N Viswanathan vi Contents List of Abbreviations ix Raw Materials - Geological Characteristics, Nomenclature, Origin, Occurrences and Exploration S P Ghosh Chemico - Physico - Mineralogical Characteristics of Raw Materials of Portland Cement A K Chatterjee 39 Burnability and Clinkerization of Cement Raw Mixes T K Chatterjee 69 Cement Burning Technologies W Kurdowski 115 Mineralizers and Fluxes in Clinkerization S N Ghosh and V N Viswanathan 177 Role of Volatiles in Cement Manufacture A K Chatterjee 203 Refractories in Cement Making J Mukerj i 265 Portland Cement Phases: Polymorphism, Solid Solution, Defect Structure and Hydraulicity S N Ghosh 289 Hydration of Portland Cement J Bensted 307 The Developing Microstructure in Portland Cement H M Jennings 349 Kinetics of Hydration of Cement Phases I Jelenic 397 vii Vlll Content? Microstructure and Strength Development in Cement Paste B Marchese 441 Magnesium Oxide in Portland Cement S S Rensi 467 Gypsum in Cement G Frigione 485 Aspects of the Chemistry of Additions R Sersale 537 Admixtures in Concrete F Massazza 569 Waste and Recycled Materials in Concrete Technology V S Ramachandran 649 Thermal Methods L Ben-Dor 673 EXDA in the Analysis of Cement S L Sarkar 711 Electron and Optical Microscopy in Cement L Ben-Dor 733 Index 793 List of Abbreviations Cement Chemists' Notations A C rs A1 M = MgO s CaO K = Na C * C02 F s Fe S = Si02 S - S0 K *' K20 P = P205 H s: H20 International Symposium/Congress on the Chemistry of Cement has been abbreviated as ISCC or ICCC in the lists of references ix Chemico-Mineralogical Characteristics of Raw Materials 57 Time, m m Fig (c) Variable rates of dissociation for different species of limestone Particle size in ground limestone It has sometimes been observed that coarsely ground raw mixes show two stages of decarbonation [2l,25J in the DTA curve, which has not been confirmed in [26] at least for the coarsely ground medium-grained limestones In the latter study, it was found that there was no consistent trend of increase of decomposition temperature or decrease in the decarbonation rate with decrease in the limestone fineness (Table 11) (d) Activation energy of dissociation The activation energy of a large number of limestones of varying composition and origin have been reported [26] The following findings are significant: (i) For most of the limestones, a two-stage decomposition with different values of E a for the lower and upper stages could be obtained The ultimate activation energy of all limestones lay in the range 30-60 kcal/mole (Table 11) (ii) The finer the grain size and the more impure a limestone, the lower is the activation energy of dissociation (iii) With many exceptions, an apparent relation seems to exist between ^a *"Tmax °* decomposition and Ea-decomposition rate (Fig 7) 58 A K Chatterjee Table 1 Limestone Fineness, microns Decarbonation rate x!0 J g/min -45 -150 -250 -45 -150 -250 -45 -150 -250 -45 -45 -150 -250 -45 -150 -250 -45 -150 -250 -45 -150 -250 5.4 Decarbonation temperature, °C T Temperature range of decarbonation max Activation energy kcal/mole °C E a 8.37 10.1 11.0 870 920 925 375 360 360 42.42 13.03 14.26 13.88 930 940 920 340 295 320 39.91 12 11.05 940 940 935 400 335 290 45.80 1 52 15.0 14.1 910 925 980 290 270 320 49.91 7.95 9.86 1.42 915 960 900 400 390 325 32.91 12.57 13.82 13.97 895 905 935 285 290 305 51 67 13.66 15.60 13.38 920 930 930 270 270 295 59.31 13.75 13.0 6.83 945 925 915 250 250 260 58.56 9.0 -150 -250 Effect of Fineness on Limestone Dissociation [26] (based on DTA) - - - - - - - Silica and Silicate Phases It is known that the rate of diffusion of CaO in S1O9 lattice is 4-5 times higher than that of S1O2 in CaO lattice [21], Therefore, the silica-bearing phases often become the determining factor in the reactivity of raw mixes Silica in active form may appear, depending on the mineral form, at 500-1100 C Other conditions being equal, the grain size and specific surface of silica in free form, and particularly of the least reactive forms like quartz and chalcedony, determine the rate of reaction in a kiln feed According to Makashev [24] the reactivity of different types of silica, free or combined, increases in the order: Chemico-Mineraloaical Characteristics of Raw Materials 59 Quartz < chalcedony < opal < α-cristobalite and α-tridymite < silica from feldspars < silica from mica and amphibole < silica from clay minerals < silica from glassy slags, whereas it has been demonstrated [27] that the silica of volcanic glasses and that of clayey minerals are more reactive than that of blast furnace slags Notwithstanding this difference in observation, it is obvious that silica in amorphous state or as silicates or hydrosilicates is preferable to silica in other forms Activation energy E a kcal/mole 60 50 S: 0S2 930 (3 g 920 ί oS5 0) D 4D S Ỵ / / I / s^t 910 a> • Sa Q E ί s Se- -j, $> 900 h D 0) CL , S7I K / •s8 880 / / /s 30 / / / / i /