Calphad Calculation Of Phase Diagrams: A Comprehensive Guide

PERGAMON MATERIALS SERIES VOLUME 1 CALPHAD (Calculation of Phase Diagrams): A Comprehensive Guide PERGAMON MATERIALS SERIES VOLUME 1 CALPHAD (Calculation of Phase Diagrams): A Comprehensive Guide PERGAMON MATERIALS SERIES Series Editor: Robert W. Cahn FRS Department of Materials Science and Metallurgy, University of Cambridge, UK Vol. 1 CALPHAD (Calculation of Phase Diagrams): A Comprehensive Guide by N. Saunders and A. P. Miodownik A selection of further titles: Non-equilibrium Processing of Materials edited by C. Suryanarayana Phase Transformations in Titanium- and Zirconium-based Alloys by S. Banerjee and P. Mukhopadhyay Wettability at High Temperatures by N. Eustathopoulos, M. G. Nicholas and B. Drevet Ostwald Ripening by S. Marsh Nucleation by A. L. Greer and K. F. Kelton Underneath the Bragg Peaks: Structural Analysis of Complex Materials by T. Egami and S. J. L. Billinge The Coming of Materials Science by R. W. Calm P E R G A M O N M A T E R I A L S SERIES I-I Calculation of Phase Diagrams A Comprehensive Guide by N. Saunders Thermotech Ltd., Guildford, UK and A. P. Miodownik Professor Emeritus, School of Mechanical and Materials Engineering, University of Surrey, Guildford, UK PERGAMON UK Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington, Oxford OX5 IGB USA Elsevier Science Inc., 655 Avenue of the Americas, New York, NY 10010, USA JAPAN Elsevier Science Japan, 9-15 Higashi-Azabu I-~home, Minato-ku, Tokyo 106, Japan Copyright 9 1998 Elsevier Science 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, electostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the publishers. Library of Congress Cataloging in Publication Data Saunders, N. (Nigel) CALPHAD (calculation of phase diagrams) : a comprehensive guide / by N. Saunders and A. P. Miodownik. p. c m . - (Pergamon materials series : v. 1) Includes bibliographical references. ISBN 0-08-042129-6 (alk. paper) 1. Phase diagrams---Data processing. 2. Thermochemistry~Data processing. I. Miodownik, A. P. (A. Peter) II. Title. III. Series. QD503.$265 1998 530.4'74--DC21 98-15693 CIP British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0-08-0421296 Transferred to digital printing 2005 Contents Series preface Preface Foreword xiv XV xvi CHAPTER 1 INTRODUCTION CHAPTER 2 History of CALPHAD 2.1. Introduction 2.2. The Early Years 2.3. The Intermediate Years 2.4. The Last Decade 2.5. The Current Status of CALPHAD References CHAPTER 3 BASIC THERMODYNAMICS 3.1. Introduction 3.2. The First Law of Thermodynamics 3.2.1 The Definition of Enthalpy and Heat Capacity 3.2.2 Enthalpy of Formation 3.2.3 Hess's Law 3.2.4 Kirchhoff's Law 3.3. The Second Law of Thermodynamics 3.3.1 The Gibbs-Helmholtz Equation 3.3.2 Calculation of Entropy and Gibbs Energy Change from Heat Capacities 3.3.3 The Physical Nature of Entropy 3.4. The Third Law of Thermodynamics 3.5. Thermodynamics and Chemical Equilibrium 3.5.1 The Law of Mass Action and the Equilibrium Constant 7 7 14 21 24 26 33. 33 33 34 36 36 37 38 39 39 40 41 41 41 3.5.2 The Van't Hoff Isotherm 3.6. Solution Phase Thermodynamics 3.6.1 Gibbs Energy of Binary Solutions 3.6.1.1 Ideal Mixing 3.6.1.2 Non-ideal Mixing 3.6.2 Partial Gibbs Energy and Activity in Binary Solutions 3.7. Thermodynamics of Phase Equilibria and Some Simple Calculated Phase Diagrams 3.7.1 Topological Features of Phase Diagrams Calculated Using Regular Solution Theory References CHAPTER 4 EXPERIMENTAL DETERMINATION OF THER