Nucleation (eBook)

Front Cover 1
Nucleation: Basic Theory with Applications 4
Copyright Page 5
Contents 6
Preface 10
Symbols and abbreviations 14
Part 1: Thermodynamics of nucleation 22
Chapter 1. First-order phase transitions 24
Chapter 2. Driving force for nucleation 30
Chapter 3. Work for cluster formation 38
3.1 Homogeneous nucleation 41
3.2 Heterogeneous nucleation 51
3.3 General formulae 61
3.4 Absence of one-dimensional nucleation 63
Chapter 4. Nucleus size and nucleation work 66
4.1 General formulae 66
4.2 Homogeneous nucleation 67
4.3 Heterogeneous nucleation 71
4.4 Atomistically small nuclei 76
Chapter 5. Nucleation theorem 79
5.1 Phenomenological proof 80
5.2 Thermodynamic proof 85
5.3 Generalizations 86
5.4 Integral form 88
Chapter 6. Properties of clusters 91
6.1 Inside pressure 91
6.2 Chemical potential 92
6.3 Vapour pressure 94
6.4 Solubility 98
6.5 Melting point 99
6.6 Specific surface energy 100
Chapter 7. Equilibrium cluster size distribution 104
7.1 Equilibrium concentration of clusters 105
7.2 Equilibrium concentration of nuclei 114
Chapter 8. Density-functional approach 118
8.1 General considerations 118
8.2 Gradient approximation 121
8.3 Hard-sphere approximation 123
8.4 Quasi-thermodynamics 125
8.5 Quasi-thermodynamic formulation 128
Part 2: Kinetics of nucleation 134
Chapter 9. Master equation 136
9.1 General formulation 136
9.2 Nucleation stage 145
9.3 Coalescence stage 151
9.4 Ageing stage 153
Chapter 10. Transition frequencies 157
10.1 Monomer attachment frequency 157
10.2 Monomer detachment frequency 178
10.3 Multimer attachment frequency 186
10.4 Multimer detachment frequency 192
10.5 General formulae 193
Chapter 11. Nucleation rate 195
Chapter 12. Equilibrium 199
Chapter 13. Stationary nucleation 205
13.1 Stationary cluster size distribution 205
13.2 Stationary rate of nucleation 213
13.3 Particular cases 225
13.4 Concentration of supernuclei 235
13.5 Comparison with experiment 235
Chapter 14. First application of the nucleation theorem 245
Chapter 15. Non-stationary nucleation 252
15.1 Non-stationary cluster size distribution 253
15.2 Non-stationary rate of nucleation 264
15.3 Time lag of nucleation 270
15.4 Delay time of nucleation 279
15.5 Concentration of supernuclei 288
15.6 Suggestion 291
15.7 Finding the equilibrium concentration of nuclei 291
Chapter 16. Second application of the nucleation theorem 295
Chapter 17. Nucleation at variable supersaturation 300
17.1 Quasi-stationary cluster size distribution 301
17.2 Quasi-stationary rate of nucleation 304
17.3 Condition for quasi-stationarity 306
Part 3: Factors affecting nucleation 312
Chapter 18. Seed size 314
Chapter 19. Line energy 321
Chapter 20. Strain energy 330
Chapter 21. Electric field 336
21.1 General formulae 336
21.2 Nucleation on ions 338
21.3 Nucleation in external electric field 344
Chapter 22. Carrier-gas pressure 351
Chapter 23. Solution pressure 359
Chapter 24. Pre-existing clusters 367
24.1 Non-stationary cluster size distribution 367
24.2 Non-stationary rate of nucleation 374
24.3 Concentration of supernuclei 377
24.4 Delay time of nucleation 383
Chapter 25. Active centres 387
Part 4: Applications 392
Chapter 26. Overall crystallization 394
26.1 General formulae 394
26.2 Polynuclear mechanism 398
26.3 Mononuclear mechanism 404
26.4 Two-stage crystallization 408
Chapter 27. Crystal growth 412
27.1 Continuous growth 412
27.2 Nucleation-mediated growth 417
27.3 Spiral growth 425
Chapter 28. Third application of the nucleation theorem 431
Chapter 29. Induction time 434
Chapter 30. Fourth application of the nucleation theorem 449
Chapter 31. Metastability limit 451
Chapter 32. Maximum number of supernuclei 457
32.1 General formulae 458
32.2 Instantaneous nucleation 461
32.3 Progressive nucleation 461
Chapter 33. Size distribution of supernuclei 467
33.1 General formulae 468
33.2 Particular cases 473
Chapter 34. Growth of thin films 489
Chapter 35. Rupture of amphiphile bilayers 501
Appendices 510
A1 Exact formula for the non-stationary nucleation rate 510
A2 Approximate formula for the non-stationary nucleation rate 512
A3 Initial concentration of supernuclei in previously supersaturated systems 513
References 516
Author index 536
Subject index 546