Thermodynamics of Point Defects and Their Relation with Bulk Properties, Volume 14

Preface

1 Introduction

1.1 Scope and Organisation of the Book

1.2 Notations

1.3 Symbols

Part 1 - Thermodynamics

2 Thermodynamic Functions

2.1 Conditions for Equilibrium

2.2 Temperature Dependence of Thermodynamic Functions of Solids

2.3 Pressure Dependence of Thermodynamic Functions of Solids

3 Formation of Vacancies

3.1 Isobaric and Isochoric Perfect Crystals

3.2 Parameters from the Comparison with the Isobaric Perfect Crystal

3.3 Parameters from the Comparison with the Isochoric Perfect Crystal

3.4 Relation Between Isobaric and Isochoric Parameters

3.5 Statistical Approach to Vacancy Parameters

3.6 Types of Experiments Leading to the Determination of Formation Parameters

4 Formation of Other Point Defects

4.1 Schottky Defects

4.2 Frenkel Defects in Ionic Solids of NaCl-Structure

5 Migration

5.1 Introduction

5.2 Rate Theory and the Dynamical Theory of Migration

6 Thermodynamics of the Specific Heat

6.1 Introduction

6.2 Contribution of Vacancies to an Isobaric Perfect Crystal

6.3 Contribution of Vacancies to an Isochoric Perfect Crystal

6.4 Specific Heat of One Vacancy

6.5 Connections Between the Specific Heats of Perfect Crystals

6.6 Specific Heats of Other Defects

6.7 Criteria of Microscopic Calculations from Specific Heats

7 Analysis of Experiments Yielding Defect Parameters

7.1 X-Ray Parameters

7.2 Analysis of Specific Heat Measurements

7.3 Self-Diffusion

7.4 Ionic Conductivity and Reorientation of Dipoles

7.5 Comments on Solubility

Part 2 - Defect Parameters as a Function of Bulk Properties: The cBΩ-Model

8 Connection of Defect Parameters to Bulk Properties

8.1 Introduction

8.2 Parameters by Comparing with the Isobaric Perfect Crystal

8.3 Parameters by Comparing with the Isochoric Perfect Crystal

9 The cBΩ-Model: Defect Entropy and Enthalpy. Self-Diffusion

9.1 Introduction

9.2 fcc Metals

9.3 bcc Metals

9.4 Hexagonal and Tetragonal Metals

9.5 Noble Gas Solids

9.6 Alkali Halides

9.7 Silver Halides

9.8 Summary of the Progress in the Study of Point Defects in Ionic Crystals

10 The cBΩ-Model: Defect Volume and Gibbs Energy

10.1 Introduction

10.2 Metals

10.3 Noble Gas Solids

10.4 Ionic Crystals

10.5 Correlation Between the Defect Volume and the Enthalpy

11 The cBΩ-Moad: Heterodiffusion

11.1 Temperature Dependence of Heterodiffusion

11.2 Correlation Between the Diffusion Coefficients of Atoms Diffusing in a Given Matrix

12 Mixed Alkali and Silver Halides

12.1 Variation of the Mean Atomic (or Molecular) Volume with Composition

12.2 Variation of the Bulk Modulus with Composition

12.3 Composition for Maximum Conductivity and Diffusivity from the cBΩ-Model

12.4 Thermal Expansivity

13 Explanation of Various Empirical Laws

13.1 Connection of the Enthalpy to the Melting Point

13.2 Explanation of the Empirical Laws Connecting Activation Entropy and Enthalpy to the Activation Volume

13.3 Connection of Defect Parameters to the Grüneisen Constant

13.4 Compatibility with the Jost-Model of the Dielectric Continuum

13.5 Correlation of Activation Parameters Resulting from Dielectric Loss or ITC-Experiments

14 Theoretical Basis of the cBΩ-Model

14.1 Introduction

14.2 Preliminary Aspects

14.3 Proof of the cBΩ-Model with a Pressure-Independent c

14.4 On the Temperature Dependence of c

14.5 Survey of the Proof of the cBΩ-Formula

Appendix

A.1 Introduction

A.2 Linear and Curved Simmons-Balluffi Plots

A.3 Stimulated Current Emission in the Earth

A.4 Self-Diffusion

A.5 Discussion on the Values of s/h and v/g

A.6 Recent Developments in the Detection of Preseismic Electric Signals

A.7 Mixed Ionic Crystals

A.8 Calculation of Defect Parameters from First Principles

A.9 Determination of the Concentration of Vacancies from a Constant Volume X-Ray Study at Various Temperatures. Thermal Vacancies in Solid 3He

A.10 Self-Diffusion Probed by Spin-Lattice Relaxation

A.11 Notes Added After the Completion of the Main Text

General Thermodynamics (Notes 1-3)

Microscopic Calculations (Notes 4-7)

Piezostimulated Currents and Related Geophysical Aspects (Notes 8-14)

Diffusion (Notes 15-17)

Dielectric Losses and Thermally Stimulated Currents (Notes 18-22)

Comments on the Compressibility and Expansivity of a Mixed Crystal (Note 23)

References

List of Main Symbols

Author Index

Subject Index

Defects in Solids, Volume 14: Thermodynamics of Point Defects and Their Relation with Bulk Properties focuses on the methodologies, approaches, and reactions involved in the study of point defects in solids. The book first offers information on thermodynamic functions and formation of vacancies. Topics include parameters from the comparison with isochoric perfect crystal; relation between isobaric and isochoric parameters; temperature dependence of thermodynamic functions of solids; and statistical approach to vacancy parameters. The text then ponders on the formation of other point defects, migration, and thermodynamics of specific heat. The publication explains the analysis of experiments yielding defect parameters, including X-ray parameters, analysis of specific heat measurements, and ionic conductivity and reorientation of dipoles. The text also takes a look at mixed alkali and silver halides, explanation of empirical laws, as well as explanation of the empirical laws connecting activation entropy and enthalpy to the activation volume and variation of the bulk modulus with composition. The selection is a dependable reference for scientists and geophysicists interested in the thermodynamics of point defects.