Chemistry of Glasses
'The preface ... either serves for the explanation of the purpose of the book, or for justification and as an answer to critics'. Lermontov This book is based mainly on the lectures on the Chemistry of Glasses which I gave at the University of Sheffield t
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Chemistry of Glasses A. PAUL Professor of Materials Science Indian Institute of Technology Kharagpur
London
New York
CHAPMAN AND HALL
First published 1982 by Chapman and Hall Ltd 11 New Fetter Lane, London EC4P 4EE Published in the USA by Chapman and Hall in association with Methuen, Inc. 733 Third Avenue, New York NY 10017 CO 1982 A. Paul Softcover reprint of the hardcover 1st edition 1982
Photo typeset by Macmillan India Ltd., Bangalore
All rights reserved. No part of this book may be reprinted, or reproduced or utilized 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 publisher.
British Library Cataloguing in Publication Data
Paul, A. Chemistry of glasses. I. Glass manufacture 1. Title TP845 666'. 12
Library of Congress Cataloging in Publications Data
PauL A. (Amal) Chemistry of glasses. Includes index. \. Glass. 1. Title. QDl39.G5P38 620.1'44
81-16793 AACR2
ISBN-l3: 978-94-009-5920-0 e-ISBN-13: 978-94-009-5918-7 DOl: 10.1007/978-94-009-5918-7
To my teachers Professor D. Lahiri and Professor R. W. Douglas who introduced me to glass science.
Contents
PREFACE
ix
GLASS FORMATION 1.1 General Aspects 1.2 Glass Formers 1.3 Atomistic Hypotheses of Glass Formation 1.4 Kinetic Approach to Glass Formation
5 9 l3
2 PHASE TRANSFORMATIONS IN GLASS 2.1 Crystallization 2.2 Liquid -Liquid Phase Separation 2.3 Glass-Ceramics
16 17 29 41
3 PHYSICAL PROPERTIES 3.1 Density of Glasses 3.2 Partial Molar Volume of Constituent Oxides in Glasses and Melts 3.3 Refractive Index of Glasses 3.4 Thermal Expansion of Glasses 3.5 Viscosity of Glasses 3.6 Surface Tension of Glasses 3.7 Electrical Properties of Glasses
51 51 56 63 67 76 85 89
4 CHEMICAL DURABILITY OF GLASS 4.1 Mechanism of Reactions of Glasses with Aqueous Solution 4.2 Factors Affecting Chemical Durability Measurements of a Glass 4.3 Effect of Glass Composition 4.4 Effect of pH of the Solution on Chemical Durability of SiO z (quartz) 4.5 Solubility of Silica in Aqueous Solutions 4.6 Glass Electrodes
108 109 113 117
Vll
120 125 139
CONTENTS
5 OXIDATION-REDUCTION EQUILIBRIUM IN GLASS 5.1 General 5.2 Activity Corrections 5.3 Oxidation -Reduction in Glass 5.4 Theory of Redox Reactions in Solutions
148 148 155 157 168
6 ACID-BASE CONCEPTS IN GLASS 6.1 Introduction 6.2 Acid-Base Relationships in Glasses 6.3 Oxygen Ion Activity 6.4 Transition Metal Ions as Acid-Base Indicators in Glass 6.5 Oxidation-Reduction Equilibrium in Glass 6.6 Filled Shell Ions with ns 2 Configuration as an Acid-Base Indi-
174 174 176 178 183 196
cator in Glass
6.7 Vanadyl Ion as an Acid-Base Indicator in Glass 7 COLOURED GLASSES 7.1 Atomic Structure and the Periodic Classification of Transition
198 200 204
Metals 204 7.2 Theories of Chemical Bonding in Transition Metal Complexes 205 7.3 Application of Bonding Theories in Interpreting d-d
228 233 243 Anionic Substitution in Glass 251 Photosensitive Gla
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