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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 Dept. of Chemical and Materials Engineering PO Box 21 00 l2 Cincinnati, OH 45221-00l2 USA monte.pool@uc.edu

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

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

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

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

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© 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

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

 

1

1.1

General.

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1

1.2

Vaporization Equilibrium

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References.

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7

2

Phase Equilibria in One-Component Systems

 

9

2.1

General.

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2.2

Transformation Equilibria in the Solid State.

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2.3

Monotropic Transformations.

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12

References.

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15

3

Phase Equilibria in Two-Component Systems Under Exclusion of the Gas

 

17

3.1

Definition ofthe Composition

 

17

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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21

3.4

Eutectic System.

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24

3.5

Eutectic Real Systems

 

25

3.6

The Gibbs Phase Rule

 

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26

3.7

Application of the Phase Rule

 

28

3.8

The Lever Rule

 

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29

3.9

Thermal Analysis.

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30

3.10

Light Microscopic and Electronmicroscopic Research Methods

 

to Determine Phase Diagrams.

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34

3.11

X-Ray Diffraction

 

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40

3.12

Other Experimental Methods

 

41

3.13

Eutectic Crystallization

 

41

3.14

Dendritic

 

46

3.15

Simple Phase Equilibria with Complete Solubility in the Solid and Liquid

 

47

VIII

Contents

3.16

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

 

50

3.17

Real Phase Diagrams with Complete Solubility in the Solid and Liquid

 

52

3.18

Miscibility Gap

in the Solid Phase

 

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54

3.19

Phase Diagram with Peritectic Equilibrium.

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56

3.20

Miscibility Gap

in the Liquid Phase.

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58

3.21

Real Phase Diagrams with a Miscibility Gap in the Liquid Phase

 

and an Upper Critical Point Exclusively.

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62

3.22

Phases with a

 

64

3.23

Systems with a Congruently Melting Compound.

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3.24

Phase Diagram with a Non-Congruently Melting

 

71

3.25

Phase Diagram with a Compound Forming from Two Melts

 

73

3.26

Real Diagrams with Compounds

 

74

3.27

Transformation

 

77

3.28

The Iron-Carbon Phase Diagram

 

81

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86

4

Phase Equilibria in Three-Component Systems and Four- Component Systems with Exclusion of the Gas

 

89

4.1

The Composition Triangle

 

89

4.2

Lever Rule in Ternary Systems

 

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91

4.3

Compatibility Triangle

 

92

4.4

Four-Phase Equilibria.

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93

4.5

Representation of Ternary Phase

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94

4.6

A Simple System with a Ternary

 

95

4.7

Phase Fields in a Ternary Eutectic System.

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4.8

Cuts at Constant Temperature

 

98

4.9

Vertical Cuts.

 

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100

4.10

Temperature-Composition Cut through a Corner of the Composition

 

101

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

 

103

4.13

Thermal Analysis and Structure of Simple Ternary Eutectic Systems

 

105

4.14

Properties of Neighboring Phase Fields.

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108

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

 

or Maximum.

 

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114

Contents

IX

4.19

Isothermal Section through a Ternary System with Unlimited Solution

 

115

4.20

Temperature-Composition Section through a Ternary System

 

with Unlimited Solid Solution

 

117

4.21

System with a Ternary Eutectic and Limited Solid

 

118

4.22

Ternary System with a Congruently Melting Binary Compound and a Pseudobinary

 

120

4.23

Ternary System with a Binary Compound without a Pseudobinary Section

 

122

4.24

Isothermal Section and Temperature-Composition Section through a Ternary System with a Binary Compound with no Pseudobinary

 

124

4.25

Ternary System with

 

Two Binary Compounds

 

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125

4.26

Ternary Compounds

with Melting Point Maxima.

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127

4.27

Real Ternary Systems with Binary and Ternary Compounds

 

128

4.28

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

129

4.29

Ternary System with Two Peritectic Bounding Systems and Complete Solubility in the Third Bounding System

 

131

4.30

Transition between an Univariant Peritectic

 

and an Univariant Eutectic Reaction.

 

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133

4.31

Miscibility Gap in

the Liquid Phase.

 

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134

4.32

Monotectic Four-Phase

 

137

4.33

Real Ternary Diagrams with Limited Solubility

 

in the Liquid

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138

4.34

Reaction Schemes.

 

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141

4.35

Four-Component Systems

 

143

4.36

Simple Equilibria in Four-Component Systems

 

145

4.37

Reciprocal Systems.

 

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146

4.38

Solubility of Reciprocal

Salt Pairs in Water

 

148

4.39

Comments to the Extent of Higher Order Systems.

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150

References.

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152

5

Phase Equilibria Including a Vapor Phase

 

155

5.1

Vapor-Liquid Equilibrium in a One-Component System

 

155

5.2

Phase Equilibria between Liquid and Vapor in Binary Systems without a Miscibility

 

156

5.3

Gas-Solid Equilibria in a Binary System

 

160

5.4

Phase Equilibria in a Binary System in which Solid, Liquid and Gas can

 

163

5.5

Phase Equilibria with Participation of the Gas Phase with Limited Solubility in the Liquid

 

167

X

Contents

5.7

Gas-Solid Equilibria in Systems with

 

169

5.8

Heterogeneous Equilibria at Chemical Transport Reaction

 

172

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173

6

Thermodynamics.

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175

6.1

General.

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175

6.2

Basic Thermodynamic Concepts and Definitions.

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176

6.3

Integral Quantities of Mixing.

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178

6.4

Partial Quantities of Mixing.

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181

6.5

The

Ideal Solution.

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183

6.6

The

Model of the Regular Solution.

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183

6.7

Real Solutions and Excess

Functions.

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185

6.8

Analysis of Experimental Thermodynamic

 

188

6.9

Influence of the Atomic Size Difference.

 

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188

6.10

6.10.1

. Basic Formulae of the Association Model

The Association Model.

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