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Engineering Materials and Processes

Series Editor

Professsor Brain Derby, Professor of Material Science Manchester Science Centre, Grosvenor Street, Manchester, Ml 7HS, UK

Bruno Predel· Michael Hoch . Monte Pool

Phase Diagrams and Heterogeneous Equilibria

A Practical Introduction

With Technical Cooperation of Felicitas Predel

With 270 Figures

~ Springer

Prof. em. Dr. Dr. h. c. Bruno Predel

Prof. em. Dr. Michael Hoch

Haugstr.26

5300 Hamilton Av., Apt. 1706

D-70563 Stuttgart

Cincinnati, OH 45224-3165

Germany

USA

predel@mf.mpg.de

niklah@fuse.net

Prof. em. Dr. Monte Pool University of Cincinnati

and University of Cincinnati

Dept. of Chemical and Materials Engineering PO Box 21 00 l2 Cincinnati, OH 45221-00l2 USA

Dept. of Chemical and Materials Engineering P.O. Box 210012 Cincinnati, OH 45221-0012

monte.pool@uc.edu

USA

With Technical Cooperation of Felicitas Predel Max-Planck-Institut fUr Metallforschung, Stuttgart

Original German Edition published by SteinkopffVerlag Darmstadt, 1992

Library of Congress Cataloging-in-Publication Data Predel, Bruno. Phase diagrams and heterogeneous equilibria: a practical introduction I Bruno Predel, Michael Hoch, Monte Pool. p. cm. - (Engineering materials and processes) Includes bibliographical references and index.

ISBN 978-3-642-05727-4 DOI 10.1007/978-3-662-09276-7

ISBN 978-3-662-09276-7 (eBook)

1. Phase diagrams. 2. Phase rule and equilibrium. 3. Thermodynamics. 4. Chemistry, Metallurgic. I. Hoch, M.J.R. (Michael J. R.), 1936 - II. Pool, Monte. III. Title. IV. Series. QD503.P72 2003 541' .363-dc22

ISBN 978-3-642-05727-4

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broad- casting, reproduction on microfilms or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from

Springer-Verlag Berlin Heidelberg GmbH.

Violations are liable for prosecution act under German Copyright Law. springeronline.com

© Springer-Verlag Berlin Heidelberg 2004

Originally published by Springer-Verlag Berlin Heidelberg N ew York in 2004

Softcover reprint of the hardcover 1st edition 2004

The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

Typesetting: medionet AG, Berlin, Germany Cover Design: Erich Kirchner, Springer Heidelberg, Germany

Printed on acid-free paper 62/3020/M 543210

Preface

Since J.W. Gibbs in 1878 succeeded comprehensively in establishing the basic principles for an understanding of equilibria in heterogeneous systems, numer- ous books concerning constitution diagrams have been written, some of them providing a formal treatment of phase equilibria down to the small detail. The purpose of the present book is to provide an introduction to the practical ap- plications of phase diagrams. In the first instance it is intended for students of chemistry, metallurgy, mineralogy and materials science, but also for engineers and students of science and engineering disciplines concerned with materials. To facilitate the start of an involvement with heterogeneous equilibria, reactions and dynamic equilibria will be treated first, since these are familiar to chemists and metallurgists. Of course, a description of phase equilibria is not possible without a mini- mum of formalism. The formalistic description, however, will be made lighter by clear explanations of experimental methods used to determine the constitu- tion of a system, by application examples, as well as by discussing realistic cas- es from chemistry, metallurgy, materials science and mineralogy. By this, the ne- cessity of the knowledge of phase diagrams can be shown. On the other hand a practical exercise is possible. The physical and energetic background to phase equilibria will also be treat- ed. In so doing, the principles of thermodynamics of mixtures will be discussed and the correlation between energetics and constitution demonstrated. In this way, the more qualitative framework which often surrounds the teaching of con- stitution will be surmounted and the interested reader will be provided with a tool enabling him to make quantitative predictions also concerning phenom- enological energetics and the structural and physical factors governing an in- dividual system. It will also be possible to make predictions concerning phase equilibria for systems for which experimental results can only be obtained with difficulty. From the standpoint of practical application, the treatment of nucleation of phase transitions, the production and stability of technologically important metastable phases and attempts to understand metallic glasses will also be dis- cussed. There is currently a large-scale technologically motivated research ef-

VI

Preface

fort in this area which is providing a broader and deeper understanding. A short survey of the most important facts will be presented. Finally, a condensed presentation of the thermodynamics and constitution of polymer systems is included. The book "Heterogene Gleichgewichte" though printed in 1982 is still very actual. We tried to make it a thermodynamic treatment for all materials: cover ceramics, organic materials, polymers and aqueous solutions (for geologists). To upgrade the book, we introduced two new solution models, which permit the calculation of enthalpy of mixing and of phase diagrams in ternary, qua- ternary, quinary and larger systems from binary data alone. This is important in practical applications, where after calculations a few experimental measure- ments are sufficient to check the results. We also deal in greater detail with sec- ond order transitions in metals and polymers. For the use of ceramicists, we especially described the phase rule in ternary systems. In the aqueous solutions we show, how solubilities of several salts in water can be calculated, again using only binary data. Last but not least, we show that the same thermodynamic for- mulas used for metals and ceramic materials can be applied to organic materi- als, polymers and aqueous solutions. No other text to our knowledge covers all these areas. For critical review of the text, we are grateful to several experts in the field, especially Prof. Dr. Dr. h.c. mult G. Petzow, Prof. Dr. Dr. h.c. W. Gust, Prof. Dr. F. Sommer, Prof. Dr. W. Funke, Dr. I. Arpshofen and T. Godecke. Mrs. G. Kiim- merling and Dr. I. Arpshofen have prepared drawings.

Stuttgart and Cincinnati, Summer 2003

Bruno Predel Michael Hoch, Monte Pool

Contents

List of Symbols

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XIII

1

Fundamental Facts and

 

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1.1

General.

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1.2

Vaporization Equilibrium

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Phase Equilibria in One-Component Systems ..................

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  • 2.1 General.

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  • 2.2 Transformation Equilibria in the

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  • 2.3 Monotropic Transformations.

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15

3

Phase Equilibria in Two-Component Systems

 

Under Exclusion of the Gas

 

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  • 3.1 Definition ofthe Composition

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  • 3.2 Partial Reactions of the Solid-Liquid Transition.

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  • 3.3 Process of Fusion in a Two-Component System.

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Eutectic System.

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  • 3.5 Eutectic Real Systems .......................................

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  • 3.6 The Gibbs Phase Rule

 

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  • 3.7 Application of the Phase Rule ................................

28

  • 3.8 The Lever Rule

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  • 3.9 Thermal Analysis.

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  • 3.10 Light Microscopic and Electronmicroscopic Research Methods

 

to Determine Phase Diagrams.

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  • 3.11 X-Ray Diffraction

 

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  • 3.12 Other Experimental Methods

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  • 3.13 Eutectic Crystallization

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  • 3.14 Crystallization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Dendritic

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  • 3.15 Simple Phase Equilibria with Complete Solubility

 

in the Solid and Liquid

 

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VIII

Contents

  • 3.16 Phase Equilibria with Complete Solubility in the Solid and Liquid Phases and a Melting Point Minimum or Melting Point Maximum ..................................

 

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  • 3.17 Real Phase Diagrams with Complete Solubility

 

in the Solid and Liquid

 

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  • 3.18 in the Solid Phase

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  • 3.19 Phase Diagram with Peritectic Equilibrium.

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  • 3.20 in the Liquid Phase.

Miscibility Gap

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  • 3.21 Real Phase Diagrams with a Miscibility Gap in the Liquid Phase

 

and an Upper Critical Point Exclusively.

 

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  • 3.22 Superlattice. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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  • 3.23 Systems with a Congruently Melting Compound.

 

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  • 3.24 Phase Diagram with a Non-Congruently Melting

 

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  • 3.25 Phase Diagram with a Compound Forming from Two Melts

 

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  • 3.26 Real Diagrams with Compounds

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  • 3.27 Equilibria. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Transformation

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  • 3.28 The Iron-Carbon Phase Diagram

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4

Phase Equilibria in Three-Component Systems and Four-

 

Component Systems with Exclusion of the Gas

 

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  • 4.1 The Composition Triangle

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  • 4.2 Lever Rule in Ternary Systems

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  • 4.3 Compatibility Triangle ......................................

92

  • 4.4 Four-Phase Equilibria.

 

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  • 4.5 Representation of Ternary Phase Diagrams.

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  • 4.6 A Simple System with a Ternary

 

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  • 4.8 Cuts at Constant Temperature

 

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  • 4.9 Vertical Cuts.

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  • 4.10 Temperature-Composition Cut through a Corner

 

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  • 4.11 Temperature-Composition Cut Parallel to One Side

 

of the Composition Triangle.

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102

  • 4.12 Simple Real Diagrams with a Ternary Eutectic ..................

 

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  • 4.13 Thermal Analysis and Structure of Simple Ternary Eutectic Systems ............................................

105

  • 4.14 Properties of Neighboring Phase Fields.

 

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  • 4.15 Non-Regular Sections.

 

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111

  • 4.16 Critical Point.

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112

  • 4.17 Schreinemakers' Rule.

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113

  • 4.18 Ternary Systems with Unlimited Solubility in the Solid and Liquid State, and without a Melting Point Minimum

 

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114

Contents

IX

  • 4.19 Isothermal Section through a Ternary System

with Unlimited Solution

 

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  • 4.20 Temperature-Composition Section through a Ternary System

 

with Unlimited Solid Solution

 

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  • 4.21 System with a Ternary Eutectic and Limited Solid

 

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  • 4.22 Ternary System with a Congruently Melting Binary Compound

 

and a Pseudobinary

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  • 4.23 Ternary System with a Binary Compound

 

without a Pseudobinary Section

 

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  • 4.24 Isothermal Section and Temperature-Composition Section through a Ternary System with a Binary Compound

 

with no Pseudo binary

 

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  • 4.25 Ternary System with

 

Two Binary Compounds

 

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  • 4.26 Ternary Compounds

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  • 4.27 Real Ternary Systems with Binary and Ternary Compounds

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  • 4.28 Ternary System with Two Eutectic Bounding Binary Systems with Limited Solubility in the Solid and Complete Miscibility

 

in the Third Bounding Binary

 

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  • 4.29 Ternary System with Two Peritectic Bounding Systems

 

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  • 4.30 Transition between an Univariant Peritectic

 

and an Univariant Eutectic Reaction.

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133

  • 4.31 the Liquid Phase.

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  • 4.32 Monotectic Four-Phase

 

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  • 4.33 Real Ternary Diagrams with Limited Solubility

 

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Reaction Schemes.

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138

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  • 4.35 Systems ....................................

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  • 4.36 Simple Equilibria in Four-Component Systems .................

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  • 4.37 Reciprocal Systems.

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146

  • 4.38 Solubility of Reciprocal Salt Pairs in Water

 

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  • 4.39 Comments to the Extent of Higher Order Systems.

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150

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152

5

Phase Equilibria Including a Vapor Phase ......................

155

  • 5.1 Vapor-Liquid Equilibrium in a One-Component System

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  • 5.2 Phase Equilibria between Liquid and Vapor in Binary Systems

 

without a Miscibility

 

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  • 5.3 Gas-Solid Equilibria in a Binary System ........................

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  • 5.4 Phase Equilibria in a Binary System in which Solid, Liquid

 

and Gas can

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  • 5.5 Phase Equilibria with Participation of the Gas Phase

 

with Limited Solubility in the Liquid

 

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  • 5.6 Vapor-Solid Equilibria with Solid Solution

 

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X

Contents

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  • 5.8 Heterogeneous Equilibria at Chemical Transport Reaction

 

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173

6

Thermodynamics.

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  • 6.1 .

General.

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  • 6.2 Basic Thermodynamic Concepts and Definitions.

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  • 6.3 Integral Quantities of Mixing.

 

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  • 6.4 Partial Quantities of Mixing.

 

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  • 6.5 Ideal Solution.

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  • 6.6 Model of the Regular Solution.

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  • 6.7 Real Solutions and Excess

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  • 6.8 Analysis of Experimental Thermodynamic

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  • 6.9 Influence of the Atomic Size Difference.

 

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6.10

The Association Model.

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  • 6.10.1 Basic Formulae of the Association Model

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  • 6.10.2 Application to Liquid Binary and Ternary Alloys

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  • 6.11 The Hoch-Arpshofen ModeL

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  • 6.12 Difference in Heat Capacity between Liquid and Solid Cp(L-S)

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Calculation of Thermodynamic Functions

 

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  • 6.14 The Thermodynamic Activity ...............................

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  • 6.15 General Comments about Experimental Methods to Determine Thermodynamic Mixing Properties

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  • 6.16 The High-Temperature Calorimeter ..........................

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  • 6.17 Partial Vapor Pressure Measurements ........................

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  • 6.18 Activity Determination from the EMF of Galvanic Cells

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  • 6.19 Fusion Equilibrium in a One-Component System

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  • 6.20 Fusion Equilibria in Binary Systems ..........................

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  • 6.21 Equilibrium between a Binary Liquid and the Crystal of one Component in the Ideal System

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  • 6.22 Equilibrium between a Binary Liquid and a Solid Solution

 

in an Ideal System .........................................

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  • 6.23 Fusion Equilibrium in a Regular System ......................

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  • 6.24 Fusion Equilibrium in a Real System

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  • 6.25 Melting Point Minimum ....................................

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  • 6.26 Phase Equilibrium During Demixing

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  • 6.27 Calculation of the Miscibility Gap Based on the Regular

 

Solution Model ............................................

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  • 6.28 Evaluation of Solubility Equilibria

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  • 6.29 Evaluation of a Fusion Equilibrium with Small Liquidus

 

Concentrations ............................................

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  • 6.30 Critical Demixing Temperature in Real Solutions ...............

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  • 6.31 The Spinodal ..............................................

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Contents

XI

  • 6.32 Calculation of a Simple Ordering Reaction in Solid Solutions

 

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  • 6.33 Degree of Order in a Superlattice as a Function of Temperature

 

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  • 6.34 Comments on the Character of Phase Transformations ..........

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  • 6.35 Thermodynamic Properties of Ternary Alloys

 

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  • 6.36 Calculation of Fusion Equilibria in

 

Ternary

 

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References.

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7

Nucleation During Phase Transitions.

 

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