Thermodynamics of Point Defects and Their Relation with Bulk Properties (eBook)

Front Cover 1
Thermodynamics of Point Defects and their Relation with Bulk Properties 4
Copyright Page 5
Table of Contents 8
Preface 6
Chapter 1. Introduction 16
1.1 Scope and organisation of the book 16
1.2 Notations 21
1.3 Symbols 23
Part 1: Thermodynamics 24
Chapter 2. Thermodynamic functions 26
2.1 Conditions for equilibrium 26
2.2 Temperature dependence of thermodynamic functions of solids 28
2.3 Pressure dependence of thermodynamic functions of solids 31
Chapter 3. Formation of vacancies 38
3.1 Isobaric and isochoric perfect crystals 39
3.2 Parameters from the comparison with the isobaric perfect crystal 40
3.3 Parameters from the comparison with the isochoric perfect crystal 52
3.4 Relation between isobaric and isochoric parameters 59
3.5 Statistical approach to vacancy parameters 62
3.6 Types of experiments leading to the determination of formation parameters 67
Chapter 4. Formation of other point defects 78
4.1 Schottky defects 78
4.2 Frenkel defects in ionic solids of NaCl-structure 81
Chapter 5. Migration 86
5.1 Introduction 86
5.2 Rate theory and the dynamical theory of migration 89
Chapter 6. Thermodynamics of the specific heat 100
6.1 Introduction 100
6.2 Contribution of vacancies to an isobaric perfect crystal 103
6.3 Contribution of vacancies to an isochoric perfect crystal 109
6.4 Specific heat of one vacancy 111
6.5 Connections between the specific heats of perfect crystals 117
6.6 Specific heats of other defects 118
6.7 Criteria of microscopic calculations from specific heats 120
Chapter 7. Analysis of experiments yielding defect parameters 122
7.1 X-ray parameters 122
7.2 Analysis of specific heat measurements 127
7.3 Self-diffusion 132
7.4 Ionic conductivity and reorientation of dipoles 143
7.5 Comments on solubility 157
Part 2: Defect parameters as a function of bulk properties: the cB.-model 160
Chapter 8. Connection of defect parameters to bulk properties 162
8.1 Introduction 162
8.2 Parameters by comparing with the isobaric perfect crystal 163
8.3 Parameters by comparing with the isochoric perfect crystal 173
Chapter 9. The cB.-model: Defect entropy and enthalpy. Self-diffusion 178
9.1 Introduction 178
9.2 fee metals 183
9.3 bec metals 210
9.4 Hexagonal and tetragonal metals 241
9.5 Noble gas solids 257
9.6 Alkali halides 261
9.7 Silver halides 275
9.8 Summary of the progress in the study of point defects in ionic crystals 282
Chapter 10. The cB.-modoi: Defect volume and Gibbs energy 284
10.1 Introduction 284
10.2 Metals 290
10.3 Noble gas solids 298
10.4 Ionic crystals 299
10.5 Correlation between the defect volume and the enthalpy 318
Chapter 11. The cBO-moad: Heterodiffusion 322
11.1 Temperature dependence of heterodif fusion 322
11.2 Correlation between the diffusion coefficients of atoms diffusingin a given matrix 324
Chapter 12. Mixed alkali and silver halides 340
12.1 Variation of the mean atomic (or molecular) volume with composition 340
12.2 Variation of the bulk modulus with composition 344
12.3 Composition for maximum conductivity and diffusivity fromthe cB.-model 350
12.4 Thermal expansivity 356
Chapter 13. Explanation of various empirical laws 364
13.1 Connection of the enthalpy to the melting point 364
13.2 Explanation of the empirical laws connecting activation entropy and enthalpy to the activation volume 369
13.3 Connection of defect parameters to the Gruneisen constant 370
13.4 Compatibility with the Jost-model of the dielectric continuum 373
13.5 Correlation of activation parameters resulting from dielectricloss or ITC-experiments 376
Chapter 14. Theoretical basis of the cB.-model 378
14.1 Introduction 378
14.2 Preliminary aspects 380
14.3 Proof of the cB.-model with a pressure-independent c 386
14.4 On the temperature dependence of c 403
14.5 Survey of the proof of the cB.-formula 411
Appendix 418
A.l Introduction 418
A.2 Linear and curved Simmons–Balluffi plots 418
A.3 Stimulated current emission in the earth 418
A.4 Self-diffusion 421
A.5 Discussion on the values of s/h and v/g 422
A.6 Recent developments in the detection of preseismic electricsignals 425
A.7 Mixed ionic crystals 427
A.8 Calculation of defect parameters from first principles 427
A.9 Determination of the concentration of vacancies from aconstant volume X-ray study at various temperatures. Thermal vacancies in solid 3 He 429
A.10 Self-diffusion probed by spin-lattice relaxation 429
A.11 Notes added after the completion of the main text 430
References 440
List of main symbols 462
Author index 462
Subject index 478