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Contents
Foreword XI
Preface XIII
1 Introduction 1
2 Basic Equations: Determination of the Coefficients of Emission in Nucleation
Theory 7
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 BasicKineticEquations .......................... 9
2.3 Ratio of the Coefficients of Absorption and Emission of Particles . . . . . 10
2.3.1 TraditionalApproach............................ 11
2.3.2 A New Method of Determination of the Coefficients of Emission . . . . . 16
2.3.3 Applications ................................ 22
2.4 Generalization to Multicomponent Systems . . . . . . . . . . . . . . . . 22
2.4.1 TraditionalApproach............................ 23
2.4.2 NewApproach ............................... 24
2.4.3 Applications ................................ 25
2.5 Generalization to Arbitrary Boundary Conditions . . . . . . . . . . . . . 26
2.6 Initial Conditions for the Cluster-Size Distribution Function . . . . . . . 28
2.7 Description of Cluster Ensemble Evolution along a Given Trajectory . . . 30
2.7.1 Motivation ................................. 30
2.7.2 EffectiveDiffusionCoefficients ...................... 31
2.7.3 Evolution of the Cluster-Size Distribution Functions . . . . . . . . . . . 36
2.8 Conclusions................................. 37
3 Kinetics of Nucleation¨CGrowth Processes: The First Stages 39
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.2 BasicKineticEquations .......................... 41
3.3 Nonsteady-State Effects in the Initial Stage of Nucleation . . . . . . . . . 46
3.3.1 Approximative Solution in the Range1nnc−¦Änc ......... 47
3.3.2 Time Scale of Establishment of Steady-State Cluster-Size Distributions in
the Range1nnc−¦Änc........................ 50
3.3.3 Results for the Rangenc−¦Äncnnc+¦Änc ............. 51
3.3.4 Steady-State Nucleation Rate and Steady-State Cluster-Size Distribution in
the Range1nnc+¦Änc........................ 51
3.4 Flux and Cluster Distributions in the Range of Supercritical Cluster Sizes 54
3.4.1 Results in the Rangencn8nc .................... 55
3.4.2 Results in the Rangen8nc ....................... 57
3.5 TimeIntervalforSteady-StateNucleation................. 65
3.5.1 KineticallyLimitedGrowth ........................ 66
3.5.2 Diffusion-LimitedGrowth ......................... 68
3.5.3 Nonsteady-State Time Lag and the Time Scale of Steady-State Nucleation 68
3.6 Further Basic Characteristics of Nucleation¨CGrowth Processes . . . . . . 69
3.6.1 NumberofClustersFormedbyNucleation ................ 69
3.6.2 AverageSizeoftheClusters ........................ 70
3.6.3 TimeIntervalofIndependentGrowth ................... 71
3.7 Time of Steady-State Nucleation and Induction Time . . . . . . . . . . . 73
3.8 Formation of a New Phase with a Given Stoichiometric Composition . . 76
3.8.1 TheModel ................................. 76
3.8.2 BasicEquations............................... 76
3.8.3 Applications ................................ 81
3.9 SummaryofResults ............................ 86
3.9.1 Results for the Range of Cluster Sizesnnc ............... 86
3.9.2 Results for the Range of Cluster Sizesnnc ............... 87
3.9.3 Integral Characteristics of the Nucleation¨CGrowth Process . . . . . . . . 89
3.10 Conclusions................................. 91
4 Theory of the Late Stages of Nucleation¨CGrowth Processes: Ostwald Ripening 93
4.1 Coarsening ................................. 93
4.1.1 Introduction: Formulation of the Problem . . . . . . . . . . . . . . . . . 93
4.1.2 Asymptotic Behavior of the Critical Cluster Size . . . . . . . . . . . . . 96
4.1.3 Asymptotic Behavior of the Distribution Function . . . . . . . . . . . . . 100
4.1.4 Boundary Effects and Theory of Sintering . . . . . . . . . . . . . . . . . 105
4.1.5 Diffusive Decomposition Involving Different Mass-transfer Mechanisms 109
4.1.6 Effects of Competition of Several Mass-Transfer Mechanisms . . . . . . 113
4.1.7 Asymptotic Stability of Solid Solutions . . . . . . . . . . . . . . . . . . 119
4.2 Rigorous Analysis of the Transformation of an Arbitrary Initial Distribution
FunctionintoaUniversalOne ....................... 125
4.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.2.2 Canonical Form of the Basic System of Equations . . . . . . . . . . . . . 125
4.2.3 Coarsening in the Case of Power-Dependent Initial Cluster Size Distributions..................................... 131
4.2.4 Coarsening in the Case of Exponentially Decaying Initial Cluster-Size Distributions .................................. 135
4.2.5 Generalizations............................... 141
4.3 Theory of Diffusive Decomposition of Multicomponent Solutions . . . . 143
4.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
4.3.2 BasicEquationsandTheirSolution .................... 144
4.3.3 Regions of Phase Coexistence in Composition Space . . . . . . . . . . . 152
4.3.4 Competition of Different Phases in Coarsening . . . . . . . . . . . . . . 156
4.3.5 Formation of Precipitates of Nonstoichiometric Composition . . . . . . . 161
4.3.6 Comparison with Experimental Data . . . . . . . . . . . . . . . . . . . . 163
4.3.7 Conclusions................................. 165
5 Shapes of Cluster-Size Distributions Evolving in Nucleation and Growth
Processes 171
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
5.2 Analysis of Statistical Approaches: ¡°Equilibrium Distribution¡± of Classical
Nucleation Theory, Fisher¡¯s Droplet, and Similar Models . . . . . . . . . 172
5.3 Thermodynamic Approach: On the Possibility of Evolution of MonodisperseCluster-SizeDistributions ...................... 175
5.4 DynamicalApproach............................ 178
5.4.1 Basic Kinetic Equations: General Expression . . . . . . . . . . . . . . . 178
5.4.2 DeterminationoftheCoefficientsofEmission............... 179
5.4.3 Determination of the Coefficients of Aggregation . . . . . . . . . . . . . 181
5.4.4 DescriptionofGrowthProcessesofClusters................ 181
5.4.5 ApplicationtotheDescriptionofNucleation ............... 184
5.4.6 Basic Kinetic Equations for Different Important Growth Mechanisms . . 185
5.5 Numerical Solution of the Kinetic Equations . . . . . . . . . . . . . . . 187
5.5.1 PrecipitationinaPerfectSolution ..................... 187
5.5.2 Effect of Nonlinear Inhibition of Cluster Growth on the Shape of the
Cluster-SizeDistributions ......................... 192
5.5.3 Application of Fisher¡¯s Expression for the Work of Cluster Formation . . 196
5.6 Selected Applications and Conclusions . . . . . . . . . . . . . . . . . . 198
5.7 Discussion ................................. 201
6 Coarsening Under the Influence of Elastic Stresses and in Porous Materials 203
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
6.2 Cluster Growth and Coarsening Under the Influence of Elastic Stresses Due
toCluster¨CMatrixInteractions ....................... 205
6.2.1 Models of Elastic Stress in Cluster Growth and Coarsening . . . . . . . . 205
6.2.2 Theoretical Description of Coarsening at a Nonlinear Increase of the Energy
of Elastic Deformations with Cluster Volume: A First Approach . . . . . 206
6.3 Ostwald Ripening in a System of Nondeformable Pores of Equal SizeR0 208
6.3.1 Mathematical Formulation of the Problem and General Solution . . . . . 208
6.3.2 Approximations and Numerical Results . . . . . . . . . . . . . . . . . . 211
6.4 CoarseninginaSystemofWeakPores................... 216
6.5 Coarsening in a System of Nondeformable Pores with a Given Pore-Size
Distribution................................. 219
6.5.1 AFirstApproximation ........................... 219
6.5.2 General Approach: Description of the Method . . . . . . . . . . . . . . . 221
6.5.3 Results ................................... 223
6.6 Influence of Stochastic Effects on Coarsening in Porous Materials . . . . 224
6.7 Discussion ................................. 225
7 Cluster Formation and Growth in Segregation Processes at Given Input Fluxes
of Monomers and Under the Influence of Radiation 227
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
7.2 Coarsening with Input Fluxes of Raw Material . . . . . . . . . . . . . . 228
7.2.1 PreliminaryEstimates ........................... 228
7.2.2 BasicKineticEquations .......................... 230
7.2.3 Results of the Numerical Solution of the Kinetic Equations . . . . . . . . 232
7.2.4 Discussion ................................. 235
7.3 Void Ripening in the Presence of Bulk Vacancy Sources . . . . . . . . . 237
7.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
7.3.2 BasicEquations............................... 237
7.3.3 DampedSources .............................. 239
7.3.4 UndampedSources............................. 243
7.3.5 Conclusions................................. 247
7.4 Growth and Shrinkage of Precipitates under Irradiation . . . . . . . . . . 247
7.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
7.4.2 Diffusion Mechanism of Radiation-Induced Shrinkage of the Precipitates 248
7.4.3 Effect of the Precipitate Incoherence and the Solute Atom Transition into
the Interstitial Sites and Back in the Lattice Sites . . . . . . . . . . . . . 251
7.4.4 TheCaseofIncoherentPrecipitation.................... 255
7.4.5 Conclusion ................................. 256
8 Formation of a Newly Evolving Phase with a Given Stoichiometric Composition 257
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
8.2 BasicSetofEquations ........................... 259
8.3 The Stage of Nucleation of Clusters of the Newly Evolving Phase . . . . 264
8.4 TheTransientStage............................. 272
8.5 Kinetic Equations and Thermodynamic Relationships Accounting for
Solute¨CSoluteInteractions ......................... 275
8.6 Rate of Change of the Number of Structural Elements of an Aggregate of
theNewPhase ............................... 280
8.7 The Coefficient of Components Mass Transfer . . . . . . . . . . . . . . 282
8.8 Steady-StateNucleationRate........................ 285
8.9 Influence of Interaction of the Solute Components on Coarsening Processes 288
8.10 DiscussionandConclusion......................... 289
9 Nucleation and Growth of Gas-Filled Bubbles in Liquids 291
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
9.2 NucleationinaLow-ViscosityLiquid ................... 292
9.2.1 Reduced Equations Describing the Process of Bubble Nucleation . . . . . 292
9.2.2 Time of Establishment of Steady-State Nucleation . . . . . . . . . . . . 296
9.2.3 Quasistationary Distribution of Subcritical Bubbles . . . . . . . . . . . . 299
9.2.4 Distribution Function of Bubbles in the RangeNc<N< N....... 300
9.2.5 Distribution Function of Bubbles in the RangeN> N.......... 302
9.3 TheIntermediateStage........................... 307
9.4 TheLateStage ............................... 314
9.5 ResultsofNumericalComputations .................... 322
9.6 Conclusions................................. 325
9.A Appendices................................. 326
9.A.1 SomeMathematicalTransformations ................... 326
9.A.2 Estimation of the Conditions when Merging of Colliding Bubbles can be
Neglected.................................. 327
10 Phase Separation in Solid
3
He¨C4
He Mixtures 329
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
10.2 Homogeneous Nucleation in Mixtures: Theory . . . . . . . . . . . . . . 331
10.3 Homogeneous Nucleation in
3
He¨C
4
He Solid Solutions: Experiment and
ComparisonwithTheory.......................... 334
10.3.1 Spin Echoes in Restricted Geometry and Cluster Sizes . . . . . . . . . . 334
10.3.2 ExperimentalDetails............................ 335
10.3.3 ResultsandDiscussion........................... 337
10.3.4 Conclusion ................................. 339
10.4 Kinetics of Phase Transition in Solid Solutions of
4
He in
3
He at Different
DegreesofSupersaturation......................... 339
10.4.1 ExperimentalResults............................ 339
10.4.2 Discussion ................................. 340
10.4.3 Conclusion ................................. 345
10.5 Influence of the Degree of Supercooling on the Kinetics of Phase Separation
in Solid Mixtures of
4
He in
3
He ...................... 346
10.6 Comparison between Experiments and Conclusions . . . . . . . . . . . . 349
11 Nucleation versus Spinodal Decomposition in Confined Binary Solutions 353
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
11.2 Spinodal Decomposition in Adiabatically Isolated Systems . . . . . . . . 355
11.2.1 The Cahn¨CHilliard¨CCook Equation . . . . . . . . . . . . . . . . . . . . 355
11.2.2 Thermodynamic Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . 357
11.2.3 ResultsofNumericalCalculations..................... 359
11.2.4 TheoreticalInterpretation.......................... 362
11.2.5 Discussion ................................. 364
11.3 Generalized Cluster Model Approach to the Description of Phase Separation:TheModelSystem .......................... 365
11.4 PhaseSeparationinInfiniteDomains ................... 368
11.4.1 Thermodynamic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 368
11.4.2 Kinetics versus Thermodynamics in Phase Separation . . . . . . . . . . . 373
11.5 PhaseSeparationinFiniteDomains .................... 376
11.5.1 Thermodynamic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 376
11.5.2 Kinetics................................... 384
11.5.3 Transition from Independent Cluster Growth to Coarsening . . . . . . . . 392
11.6 ResultsandDiscussion........................... 395
References 399
Index 413
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