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A unique text presenting practical information on the topic of nucleation and crystal growth processes from metastable solutions and melts Nucleation and Crystal Growth is a groundbreaking text thatoffers an overview and description of the processes and phenomena associated with metastability of solutions and melts. The author--a noted expert in the field--puts the emphasis on low-temperature solutions that are typically involved in crystallization in a wide range of industries. The text begins with a review of the basic knowledge of solutions and the fundamentals of crystallization processes.…mehr
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A unique text presenting practical information on the topic of nucleation and crystal growth processes from metastable solutions and melts Nucleation and Crystal Growth is a groundbreaking text thatoffers an overview and description of the processes and phenomena associated with metastability of solutions and melts. The author--a noted expert in the field--puts the emphasis on low-temperature solutions that are typically involved in crystallization in a wide range of industries. The text begins with a review of the basic knowledge of solutions and the fundamentals of crystallization processes. The author then explores topics related to the metastable state of solutions and melts from the standpoint of three-dimensional nucleation and crystal growth. Nucleation and Crystal Growth is the first text that contains a unified description and discussion of the many processes and phenomena occurring in the metastable zone of solutions and melts from the consideration of basic concepts of structure of crystallization. This important text: * Outlines an interdisciplinary approach to the topic and offers an essential guide for crystal growth practitioners in materials science, physics, and chemical engineering * Contains a comprehensive content that details the crystallization processes starting from the initial solutions and melts, all the way through nucleation, to the final crystal products * Presents a unique focus and is the first book on understanding, and exploiting, metastability of solutions and melts in crystallization processes Written for specialists and researchers in the fields of materials science, condensed matter physics, and chemical engineering. Nucleation and Crystal Growth is a practical resource filled with hands-on knowledge of nucleation and crystal growth processes from metastable solutions and melts.
Produktdetails
- Produktdetails
- Verlag: Wiley
- Seitenzahl: 512
- Erscheinungstermin: 16. Oktober 2018
- Englisch
- Abmessung: 244mm x 155mm x 28mm
- Gewicht: 885g
- ISBN-13: 9781119461579
- ISBN-10: 111946157X
- Artikelnr.: 50989714
- Verlag: Wiley
- Seitenzahl: 512
- Erscheinungstermin: 16. Oktober 2018
- Englisch
- Abmessung: 244mm x 155mm x 28mm
- Gewicht: 885g
- ISBN-13: 9781119461579
- ISBN-10: 111946157X
- Artikelnr.: 50989714
KESHRA SANGWAL is an Emeritus Professor in the Department of Applied Physics, Lublin University of Technology in Poland. The focus of his research is concentrated in the areas of elementary processes of nucleation, growth and dissolution of crystals, structure and properties of solutions, and the mechanical properties of crystalline and noncrystalline solids.
Preface xiii Acknowledgments xix List of Frequently Used Symbols xxi 1
Structure and Properties of Liquids 1 1.1 Different States of Matter 1 1.2
Models of Liquid Structure 6 1.3 Water and Other Common Solvents 12 1.4
Properties of Solutions 15 1.4.1 The Solvation Process 17 1.4.2 The
Concentration of Solutions 19 1.4.3 Density and Thermal Expansivity of
Solutions 21 1.4.4 Viscosity of Solutions 27 1.5 Saturated Solutions 35 1.6
High-Temperature Solvents and Solutions 43 References 46 2
Three-dimensional Nucleation of Crystals and Solute Solubility 49 2.1
Driving Force for Phase Transition 49 2.2 3D Nucleation of Crystals 54
2.2.1 Nucleation Barrier 55 2.2.2 Nucleation Rate 56 2.2.3 3D Heterogeneous
Nucleation 60 2.3 Ideal and Real Solubility 63 2.3.1 Basic Concepts 63
2.3.2 Examples of Experimental Data 68 2.3.3 Mathematical Representation of
Solute Solubility in Solvent Mixtures 76 2.4 Solute Solubility as a
Function of Solvent-Mixture Composition 78 2.4.1 A Simple Practical
Approach 78 2.4.2 Physical Interpretation of the delta Factor and Solvent
Activity 87 2.4.3 Preferential Solvation of Solute by Solvents 89 2.5
Solid-Solvent Interfacial Energy 92 2.6 Solubility and Supersolubility 96
References 101 3 Kinetics and Mechanism of Crystallization 105 3.1 Crystal
Growth as a Kinetic Process 106 3.2 Types of Crystal-Medium Interfaces 107
3.3 Thermodynamic and Kinetic Roughening of Surfaces 108 3.4 Growth
Kinetics of Rough Faces 111 3.5 Growth Kinetics of Perfect Smooth Faces 112
3.6 Growth Kinetics of Imperfect Smooth Faces 116 3.6.1 Surface Diffusion
and Direct Integration Models 117 3.6.2 Bulk Diffusion Models 119 3.6.3
Growth at Edge Dislocations 120 3.7 Simultaneous Bulk-Diffusion and
Surface-Reaction Controlled Growth 121 3.8 Effect of Impurities on Growth
Kinetics 123 3.9 Overall Crystallization 127 3.9.1 Basic Theoretical
Equations 129 3.9.2 Polynuclear Crystallization 133 3.9.2.1 Instantaneous
Nucleation Mode 134 3.9.2.2 Progressive Nucleation Mode 135 3.9.2.3 Trends
of Overall Crystallization Curves 136 3.9.2.4 Some Comments on the KJMA
Theory 138 3.9.3 Mononuclear Crystallization 139 3.9.4 Effect of Additives
on Overall Crystallization 139 References 140 4 Phase Transformation and
Isothermal Crystallization Kinetics 145 4.1 Nucleation and Transformation
of Metastable Phases 146 4.1.1 Thermodynamics of Crystallization of
Metastable Phases 147 4.1.2 Transformation Kinetics of Metastable Phases
151 4.1.3 Transformation of Metastable Phases According to KJMA Theory 158
4.1.4 Effect of Solvent on Transformation of Metastable Phases 160 4.2 Some
Non-KJMAModels of Isothermal Crystallization Kinetics 170 4.2.1 Approach
Involving Formation of an Amorphous Precursor 170 4.2.2 Model of Mazzanti,
Marangoni, and Idziak 175 4.2.3 Gompertz's Model 178 4.2.4 Model of
Foubert, Dewettinck, Jansen, and Vanrolleghem 179 4.3 Comparison of
Different Models of Isothermal Crystallization Kinetics 181 References 186
5 Nonisothermal Crystallization Kinetics and the Metastable Zone Width 189
5.1 Theoretical Interpretations of MSZW 191 5.1.1 N?vlt's Approach 192
5.1.2 Kubota's Approach 194 5.1.3 Self-Consistent N?vlt-Like Equation of
MSZW 195 5.1.4 Approach Based on the Classical Theory of 3D Nucleation 197
5.1.5 Approach Based on Progressive 3D Nucleation 199 5.1.6 Approach Based
on Instantaneous 3D Nucleation 202 5.2 Experimental Results on MSZW of
Solute.Solvent Systems 202 5.2.1 Dependence of Dimensionless Supercooling
on Cooling Rate 204 5.2.2 Effect of Detection Technique on MSZW 210 5.2.3
Relationships between ß and Z and between Phi and F 212 5.2.4 Relationship
between Dimensionless F1 and Crystallization Temperature 220 5.2.5
Dependence of Parameters Phi and F on Saturation Temperature T9 222 5.2.6
Physical Significance of Esat and Its Relationship with DeltaHs 225 5.2.7
The Nucleation Order m 230 5.3 Isothermal Crystallization 232 5.4 Effect of
Additives on MSZW of Solutions 232 5.4.1 Some General Features 233 5.4.2
Theoretical Considerations 236 5.4.2.1 Approach Based on Classical
Nucleation Theory 236 5.4.2.2 Final Expressions for Analysis of
Experimental Data 238 5.4.3 Some Examples of Effect of Impurities on MSZW
239 5.4.3.1 Boric Acid Aqueous Solutions 239 5.4.3.2 KDP Aqueous Solutions
244 5.4.3.3 POP-Acetone Solutions Containing PPP Additive 246 5.4.4
Dependence of Maximum Supersaturation Ratio on Impurity Concentration 250
5.4.5 Solute-Additive Binding Energies and MSZW of Systems 252 5.5 Effects
of Some Other Factors on MSZW of Solutions 255 5.5.1 Effect of Stirring and
Ultrasound on MSZW 255 5.5.2 Effect of Solution Volume on MSZW 255 5.6
Nonisothermal Crystallization Kinetics in Melts 259 References 260 6
Antisolvent Crystallization and the Metastable Zone Width 267 6.1
Observation Techniques for Antisolvent Crystallization 268 6.2 Light
Intensity Measurements 270 6.2.1 Some Experimental Data 270 6.2.2 Processes
Involved in Antisolvent Crystallization 274 6.3 Temperature Measurements
276 6.3.1 Some Experimental Data 276 6.3.2 Kinetics of Temperature Increase
279 6.3.3 Physical Interpretation of Temperature Changes of ADP Solutions
with Antisolvent Feeding Time at Different Rates 286 6.3.4 Origin of Two
Minima and Maximum in Temperature Change DeltaT During Antisolvent
Crystallization 287 6.3.5 Relationship Between Different Temperature
Changes, Antisolvent Feeding Rate, and Antisolvent Content 288 6.3.6
Comparison of Light-intensity and Temperature Measurements 291 6.4 Effect
of Antisolvent Composition on Nucleation Rate 296 6.5 Different Approaches
of MSZW 298 6.5.1 Modified N?vlt-like Approach 298 6.5.2 Kubota's Approach
299 6.5.3 Another Derivation of N?vlt-like Equation 300 6.5.4 Approach
Based on Classical Theory of 3D Nucleation 302 6.6 Experimental Data of
MSZW in Antisolvent Crystallization 303 6.6.1 Analysis of Experimental
Deltaxmax(RA) Data 304 6.6.2 Effect of Detection Technique on MSZW 312
6.6.3 Effect of Stirring on MSZW 315 6.6.4 Threshold and Limiting
Antisolvent Addition Rates 318 6.7 Combined Antisolvent/Cooling
Crystallization 319 References 321 7 Induction Period for Crystallization
325 7.1 Theoretical Background 327 7.1.1 Theoretical Interpretation of
Induction Period 328 7.1.2 Some Other Relations 331 7.1.3 Basic Equations
333 7.2 Induction Period for Isothermal Crystallization 333 7.2.1
Crystallization from Solutions 333 7.2.2 Crystallization from the Melt 338
7.3 Induction Period in Antisolvent Crystallization 343 7.4 Induction
Period for Nonisothermal Crystallization 345 7.4.1 Crystallization from
Solutions 345 7.4.2 Effect of Impurities on Crystallization from Solutions
349 7.4.3 Crystallization from the Melt 354 References 358 8 Ostwald
Ripening, Crystal Size Distribution, and Polymorph Selection 361 8.1
Supersaturation Decay During Antisolvent Crystallization 362 8.1.1 General
Trends 362 8.1.2 Kinetics of Supersaturation Decay 362 8.1.3 Relationship
between ConstantK and Antisolvent Feeding Rate RA 367 8.2 Solvation and
Desolvation Processes 372 8.2.1 Origin of Minima in DeltaTsw(t) Plots 373
8.2.2 Kinetics of Evolution of Minima in DeltaTsw(t) Plots 374 8.3
Evolution of Desupersaturation Curves 383 8.4 Crystal Morphology 388 8.5
Growth Rate Dispersion 396 8.6 Ostwald Ripening 398 8.7 Crystal Size
Distribution 403 8.8 Control of Phase and Size of Crystallizing Particles
412 References 417 9 Glass Formation and Crystallization Processes 423 9.1
Glass Formation by Cooling of Melts 424 9.2 Temperature Dependence of
Viscosity and the Glass Transition Temperature 426 9.3 Composition
Dependence of Glass Transition Temperature 431 9.4 Relationship between
Glass Transition Temperature and Metastable Zone Width of Solutions 435 9.5
Metastable Zone Width of Melts and Glass Formation 438 9.5.1 Derivation of
Basic Equations 438 9.5.2 Effect of Melt Viscosity and Additives on Z and F
Parameters 441 9.5.3 Calculations of RLlim, Z, F, and TN for Molten
Elements and Electrolytes 444 9.5.4 Relationship between Tg and Tm for
Various Substances 446 9.5.5 Comparison of Cooling Behavior of Melts and
Electrolyte Solutions 449 References 451 Appendix A Volumetric Thermal
Expansion Coefficient of Melts 453 References 455 Appendix B Relationship
between alphaV and Other Physical Properties 457 B.1 Molten Elements 457
B.2 Molten Halite-Type Electrolytes 457 Reference 461 Appendix C
Relationship between Densities dm of Molten Metals and Electrolytes and
Atomic Mass M 463 Reference 464 Index 465
Structure and Properties of Liquids 1 1.1 Different States of Matter 1 1.2
Models of Liquid Structure 6 1.3 Water and Other Common Solvents 12 1.4
Properties of Solutions 15 1.4.1 The Solvation Process 17 1.4.2 The
Concentration of Solutions 19 1.4.3 Density and Thermal Expansivity of
Solutions 21 1.4.4 Viscosity of Solutions 27 1.5 Saturated Solutions 35 1.6
High-Temperature Solvents and Solutions 43 References 46 2
Three-dimensional Nucleation of Crystals and Solute Solubility 49 2.1
Driving Force for Phase Transition 49 2.2 3D Nucleation of Crystals 54
2.2.1 Nucleation Barrier 55 2.2.2 Nucleation Rate 56 2.2.3 3D Heterogeneous
Nucleation 60 2.3 Ideal and Real Solubility 63 2.3.1 Basic Concepts 63
2.3.2 Examples of Experimental Data 68 2.3.3 Mathematical Representation of
Solute Solubility in Solvent Mixtures 76 2.4 Solute Solubility as a
Function of Solvent-Mixture Composition 78 2.4.1 A Simple Practical
Approach 78 2.4.2 Physical Interpretation of the delta Factor and Solvent
Activity 87 2.4.3 Preferential Solvation of Solute by Solvents 89 2.5
Solid-Solvent Interfacial Energy 92 2.6 Solubility and Supersolubility 96
References 101 3 Kinetics and Mechanism of Crystallization 105 3.1 Crystal
Growth as a Kinetic Process 106 3.2 Types of Crystal-Medium Interfaces 107
3.3 Thermodynamic and Kinetic Roughening of Surfaces 108 3.4 Growth
Kinetics of Rough Faces 111 3.5 Growth Kinetics of Perfect Smooth Faces 112
3.6 Growth Kinetics of Imperfect Smooth Faces 116 3.6.1 Surface Diffusion
and Direct Integration Models 117 3.6.2 Bulk Diffusion Models 119 3.6.3
Growth at Edge Dislocations 120 3.7 Simultaneous Bulk-Diffusion and
Surface-Reaction Controlled Growth 121 3.8 Effect of Impurities on Growth
Kinetics 123 3.9 Overall Crystallization 127 3.9.1 Basic Theoretical
Equations 129 3.9.2 Polynuclear Crystallization 133 3.9.2.1 Instantaneous
Nucleation Mode 134 3.9.2.2 Progressive Nucleation Mode 135 3.9.2.3 Trends
of Overall Crystallization Curves 136 3.9.2.4 Some Comments on the KJMA
Theory 138 3.9.3 Mononuclear Crystallization 139 3.9.4 Effect of Additives
on Overall Crystallization 139 References 140 4 Phase Transformation and
Isothermal Crystallization Kinetics 145 4.1 Nucleation and Transformation
of Metastable Phases 146 4.1.1 Thermodynamics of Crystallization of
Metastable Phases 147 4.1.2 Transformation Kinetics of Metastable Phases
151 4.1.3 Transformation of Metastable Phases According to KJMA Theory 158
4.1.4 Effect of Solvent on Transformation of Metastable Phases 160 4.2 Some
Non-KJMAModels of Isothermal Crystallization Kinetics 170 4.2.1 Approach
Involving Formation of an Amorphous Precursor 170 4.2.2 Model of Mazzanti,
Marangoni, and Idziak 175 4.2.3 Gompertz's Model 178 4.2.4 Model of
Foubert, Dewettinck, Jansen, and Vanrolleghem 179 4.3 Comparison of
Different Models of Isothermal Crystallization Kinetics 181 References 186
5 Nonisothermal Crystallization Kinetics and the Metastable Zone Width 189
5.1 Theoretical Interpretations of MSZW 191 5.1.1 N?vlt's Approach 192
5.1.2 Kubota's Approach 194 5.1.3 Self-Consistent N?vlt-Like Equation of
MSZW 195 5.1.4 Approach Based on the Classical Theory of 3D Nucleation 197
5.1.5 Approach Based on Progressive 3D Nucleation 199 5.1.6 Approach Based
on Instantaneous 3D Nucleation 202 5.2 Experimental Results on MSZW of
Solute.Solvent Systems 202 5.2.1 Dependence of Dimensionless Supercooling
on Cooling Rate 204 5.2.2 Effect of Detection Technique on MSZW 210 5.2.3
Relationships between ß and Z and between Phi and F 212 5.2.4 Relationship
between Dimensionless F1 and Crystallization Temperature 220 5.2.5
Dependence of Parameters Phi and F on Saturation Temperature T9 222 5.2.6
Physical Significance of Esat and Its Relationship with DeltaHs 225 5.2.7
The Nucleation Order m 230 5.3 Isothermal Crystallization 232 5.4 Effect of
Additives on MSZW of Solutions 232 5.4.1 Some General Features 233 5.4.2
Theoretical Considerations 236 5.4.2.1 Approach Based on Classical
Nucleation Theory 236 5.4.2.2 Final Expressions for Analysis of
Experimental Data 238 5.4.3 Some Examples of Effect of Impurities on MSZW
239 5.4.3.1 Boric Acid Aqueous Solutions 239 5.4.3.2 KDP Aqueous Solutions
244 5.4.3.3 POP-Acetone Solutions Containing PPP Additive 246 5.4.4
Dependence of Maximum Supersaturation Ratio on Impurity Concentration 250
5.4.5 Solute-Additive Binding Energies and MSZW of Systems 252 5.5 Effects
of Some Other Factors on MSZW of Solutions 255 5.5.1 Effect of Stirring and
Ultrasound on MSZW 255 5.5.2 Effect of Solution Volume on MSZW 255 5.6
Nonisothermal Crystallization Kinetics in Melts 259 References 260 6
Antisolvent Crystallization and the Metastable Zone Width 267 6.1
Observation Techniques for Antisolvent Crystallization 268 6.2 Light
Intensity Measurements 270 6.2.1 Some Experimental Data 270 6.2.2 Processes
Involved in Antisolvent Crystallization 274 6.3 Temperature Measurements
276 6.3.1 Some Experimental Data 276 6.3.2 Kinetics of Temperature Increase
279 6.3.3 Physical Interpretation of Temperature Changes of ADP Solutions
with Antisolvent Feeding Time at Different Rates 286 6.3.4 Origin of Two
Minima and Maximum in Temperature Change DeltaT During Antisolvent
Crystallization 287 6.3.5 Relationship Between Different Temperature
Changes, Antisolvent Feeding Rate, and Antisolvent Content 288 6.3.6
Comparison of Light-intensity and Temperature Measurements 291 6.4 Effect
of Antisolvent Composition on Nucleation Rate 296 6.5 Different Approaches
of MSZW 298 6.5.1 Modified N?vlt-like Approach 298 6.5.2 Kubota's Approach
299 6.5.3 Another Derivation of N?vlt-like Equation 300 6.5.4 Approach
Based on Classical Theory of 3D Nucleation 302 6.6 Experimental Data of
MSZW in Antisolvent Crystallization 303 6.6.1 Analysis of Experimental
Deltaxmax(RA) Data 304 6.6.2 Effect of Detection Technique on MSZW 312
6.6.3 Effect of Stirring on MSZW 315 6.6.4 Threshold and Limiting
Antisolvent Addition Rates 318 6.7 Combined Antisolvent/Cooling
Crystallization 319 References 321 7 Induction Period for Crystallization
325 7.1 Theoretical Background 327 7.1.1 Theoretical Interpretation of
Induction Period 328 7.1.2 Some Other Relations 331 7.1.3 Basic Equations
333 7.2 Induction Period for Isothermal Crystallization 333 7.2.1
Crystallization from Solutions 333 7.2.2 Crystallization from the Melt 338
7.3 Induction Period in Antisolvent Crystallization 343 7.4 Induction
Period for Nonisothermal Crystallization 345 7.4.1 Crystallization from
Solutions 345 7.4.2 Effect of Impurities on Crystallization from Solutions
349 7.4.3 Crystallization from the Melt 354 References 358 8 Ostwald
Ripening, Crystal Size Distribution, and Polymorph Selection 361 8.1
Supersaturation Decay During Antisolvent Crystallization 362 8.1.1 General
Trends 362 8.1.2 Kinetics of Supersaturation Decay 362 8.1.3 Relationship
between ConstantK and Antisolvent Feeding Rate RA 367 8.2 Solvation and
Desolvation Processes 372 8.2.1 Origin of Minima in DeltaTsw(t) Plots 373
8.2.2 Kinetics of Evolution of Minima in DeltaTsw(t) Plots 374 8.3
Evolution of Desupersaturation Curves 383 8.4 Crystal Morphology 388 8.5
Growth Rate Dispersion 396 8.6 Ostwald Ripening 398 8.7 Crystal Size
Distribution 403 8.8 Control of Phase and Size of Crystallizing Particles
412 References 417 9 Glass Formation and Crystallization Processes 423 9.1
Glass Formation by Cooling of Melts 424 9.2 Temperature Dependence of
Viscosity and the Glass Transition Temperature 426 9.3 Composition
Dependence of Glass Transition Temperature 431 9.4 Relationship between
Glass Transition Temperature and Metastable Zone Width of Solutions 435 9.5
Metastable Zone Width of Melts and Glass Formation 438 9.5.1 Derivation of
Basic Equations 438 9.5.2 Effect of Melt Viscosity and Additives on Z and F
Parameters 441 9.5.3 Calculations of RLlim, Z, F, and TN for Molten
Elements and Electrolytes 444 9.5.4 Relationship between Tg and Tm for
Various Substances 446 9.5.5 Comparison of Cooling Behavior of Melts and
Electrolyte Solutions 449 References 451 Appendix A Volumetric Thermal
Expansion Coefficient of Melts 453 References 455 Appendix B Relationship
between alphaV and Other Physical Properties 457 B.1 Molten Elements 457
B.2 Molten Halite-Type Electrolytes 457 Reference 461 Appendix C
Relationship between Densities dm of Molten Metals and Electrolytes and
Atomic Mass M 463 Reference 464 Index 465
Preface xiii Acknowledgments xix List of Frequently Used Symbols xxi 1
Structure and Properties of Liquids 1 1.1 Different States of Matter 1 1.2
Models of Liquid Structure 6 1.3 Water and Other Common Solvents 12 1.4
Properties of Solutions 15 1.4.1 The Solvation Process 17 1.4.2 The
Concentration of Solutions 19 1.4.3 Density and Thermal Expansivity of
Solutions 21 1.4.4 Viscosity of Solutions 27 1.5 Saturated Solutions 35 1.6
High-Temperature Solvents and Solutions 43 References 46 2
Three-dimensional Nucleation of Crystals and Solute Solubility 49 2.1
Driving Force for Phase Transition 49 2.2 3D Nucleation of Crystals 54
2.2.1 Nucleation Barrier 55 2.2.2 Nucleation Rate 56 2.2.3 3D Heterogeneous
Nucleation 60 2.3 Ideal and Real Solubility 63 2.3.1 Basic Concepts 63
2.3.2 Examples of Experimental Data 68 2.3.3 Mathematical Representation of
Solute Solubility in Solvent Mixtures 76 2.4 Solute Solubility as a
Function of Solvent-Mixture Composition 78 2.4.1 A Simple Practical
Approach 78 2.4.2 Physical Interpretation of the delta Factor and Solvent
Activity 87 2.4.3 Preferential Solvation of Solute by Solvents 89 2.5
Solid-Solvent Interfacial Energy 92 2.6 Solubility and Supersolubility 96
References 101 3 Kinetics and Mechanism of Crystallization 105 3.1 Crystal
Growth as a Kinetic Process 106 3.2 Types of Crystal-Medium Interfaces 107
3.3 Thermodynamic and Kinetic Roughening of Surfaces 108 3.4 Growth
Kinetics of Rough Faces 111 3.5 Growth Kinetics of Perfect Smooth Faces 112
3.6 Growth Kinetics of Imperfect Smooth Faces 116 3.6.1 Surface Diffusion
and Direct Integration Models 117 3.6.2 Bulk Diffusion Models 119 3.6.3
Growth at Edge Dislocations 120 3.7 Simultaneous Bulk-Diffusion and
Surface-Reaction Controlled Growth 121 3.8 Effect of Impurities on Growth
Kinetics 123 3.9 Overall Crystallization 127 3.9.1 Basic Theoretical
Equations 129 3.9.2 Polynuclear Crystallization 133 3.9.2.1 Instantaneous
Nucleation Mode 134 3.9.2.2 Progressive Nucleation Mode 135 3.9.2.3 Trends
of Overall Crystallization Curves 136 3.9.2.4 Some Comments on the KJMA
Theory 138 3.9.3 Mononuclear Crystallization 139 3.9.4 Effect of Additives
on Overall Crystallization 139 References 140 4 Phase Transformation and
Isothermal Crystallization Kinetics 145 4.1 Nucleation and Transformation
of Metastable Phases 146 4.1.1 Thermodynamics of Crystallization of
Metastable Phases 147 4.1.2 Transformation Kinetics of Metastable Phases
151 4.1.3 Transformation of Metastable Phases According to KJMA Theory 158
4.1.4 Effect of Solvent on Transformation of Metastable Phases 160 4.2 Some
Non-KJMAModels of Isothermal Crystallization Kinetics 170 4.2.1 Approach
Involving Formation of an Amorphous Precursor 170 4.2.2 Model of Mazzanti,
Marangoni, and Idziak 175 4.2.3 Gompertz's Model 178 4.2.4 Model of
Foubert, Dewettinck, Jansen, and Vanrolleghem 179 4.3 Comparison of
Different Models of Isothermal Crystallization Kinetics 181 References 186
5 Nonisothermal Crystallization Kinetics and the Metastable Zone Width 189
5.1 Theoretical Interpretations of MSZW 191 5.1.1 N?vlt's Approach 192
5.1.2 Kubota's Approach 194 5.1.3 Self-Consistent N?vlt-Like Equation of
MSZW 195 5.1.4 Approach Based on the Classical Theory of 3D Nucleation 197
5.1.5 Approach Based on Progressive 3D Nucleation 199 5.1.6 Approach Based
on Instantaneous 3D Nucleation 202 5.2 Experimental Results on MSZW of
Solute.Solvent Systems 202 5.2.1 Dependence of Dimensionless Supercooling
on Cooling Rate 204 5.2.2 Effect of Detection Technique on MSZW 210 5.2.3
Relationships between ß and Z and between Phi and F 212 5.2.4 Relationship
between Dimensionless F1 and Crystallization Temperature 220 5.2.5
Dependence of Parameters Phi and F on Saturation Temperature T9 222 5.2.6
Physical Significance of Esat and Its Relationship with DeltaHs 225 5.2.7
The Nucleation Order m 230 5.3 Isothermal Crystallization 232 5.4 Effect of
Additives on MSZW of Solutions 232 5.4.1 Some General Features 233 5.4.2
Theoretical Considerations 236 5.4.2.1 Approach Based on Classical
Nucleation Theory 236 5.4.2.2 Final Expressions for Analysis of
Experimental Data 238 5.4.3 Some Examples of Effect of Impurities on MSZW
239 5.4.3.1 Boric Acid Aqueous Solutions 239 5.4.3.2 KDP Aqueous Solutions
244 5.4.3.3 POP-Acetone Solutions Containing PPP Additive 246 5.4.4
Dependence of Maximum Supersaturation Ratio on Impurity Concentration 250
5.4.5 Solute-Additive Binding Energies and MSZW of Systems 252 5.5 Effects
of Some Other Factors on MSZW of Solutions 255 5.5.1 Effect of Stirring and
Ultrasound on MSZW 255 5.5.2 Effect of Solution Volume on MSZW 255 5.6
Nonisothermal Crystallization Kinetics in Melts 259 References 260 6
Antisolvent Crystallization and the Metastable Zone Width 267 6.1
Observation Techniques for Antisolvent Crystallization 268 6.2 Light
Intensity Measurements 270 6.2.1 Some Experimental Data 270 6.2.2 Processes
Involved in Antisolvent Crystallization 274 6.3 Temperature Measurements
276 6.3.1 Some Experimental Data 276 6.3.2 Kinetics of Temperature Increase
279 6.3.3 Physical Interpretation of Temperature Changes of ADP Solutions
with Antisolvent Feeding Time at Different Rates 286 6.3.4 Origin of Two
Minima and Maximum in Temperature Change DeltaT During Antisolvent
Crystallization 287 6.3.5 Relationship Between Different Temperature
Changes, Antisolvent Feeding Rate, and Antisolvent Content 288 6.3.6
Comparison of Light-intensity and Temperature Measurements 291 6.4 Effect
of Antisolvent Composition on Nucleation Rate 296 6.5 Different Approaches
of MSZW 298 6.5.1 Modified N?vlt-like Approach 298 6.5.2 Kubota's Approach
299 6.5.3 Another Derivation of N?vlt-like Equation 300 6.5.4 Approach
Based on Classical Theory of 3D Nucleation 302 6.6 Experimental Data of
MSZW in Antisolvent Crystallization 303 6.6.1 Analysis of Experimental
Deltaxmax(RA) Data 304 6.6.2 Effect of Detection Technique on MSZW 312
6.6.3 Effect of Stirring on MSZW 315 6.6.4 Threshold and Limiting
Antisolvent Addition Rates 318 6.7 Combined Antisolvent/Cooling
Crystallization 319 References 321 7 Induction Period for Crystallization
325 7.1 Theoretical Background 327 7.1.1 Theoretical Interpretation of
Induction Period 328 7.1.2 Some Other Relations 331 7.1.3 Basic Equations
333 7.2 Induction Period for Isothermal Crystallization 333 7.2.1
Crystallization from Solutions 333 7.2.2 Crystallization from the Melt 338
7.3 Induction Period in Antisolvent Crystallization 343 7.4 Induction
Period for Nonisothermal Crystallization 345 7.4.1 Crystallization from
Solutions 345 7.4.2 Effect of Impurities on Crystallization from Solutions
349 7.4.3 Crystallization from the Melt 354 References 358 8 Ostwald
Ripening, Crystal Size Distribution, and Polymorph Selection 361 8.1
Supersaturation Decay During Antisolvent Crystallization 362 8.1.1 General
Trends 362 8.1.2 Kinetics of Supersaturation Decay 362 8.1.3 Relationship
between ConstantK and Antisolvent Feeding Rate RA 367 8.2 Solvation and
Desolvation Processes 372 8.2.1 Origin of Minima in DeltaTsw(t) Plots 373
8.2.2 Kinetics of Evolution of Minima in DeltaTsw(t) Plots 374 8.3
Evolution of Desupersaturation Curves 383 8.4 Crystal Morphology 388 8.5
Growth Rate Dispersion 396 8.6 Ostwald Ripening 398 8.7 Crystal Size
Distribution 403 8.8 Control of Phase and Size of Crystallizing Particles
412 References 417 9 Glass Formation and Crystallization Processes 423 9.1
Glass Formation by Cooling of Melts 424 9.2 Temperature Dependence of
Viscosity and the Glass Transition Temperature 426 9.3 Composition
Dependence of Glass Transition Temperature 431 9.4 Relationship between
Glass Transition Temperature and Metastable Zone Width of Solutions 435 9.5
Metastable Zone Width of Melts and Glass Formation 438 9.5.1 Derivation of
Basic Equations 438 9.5.2 Effect of Melt Viscosity and Additives on Z and F
Parameters 441 9.5.3 Calculations of RLlim, Z, F, and TN for Molten
Elements and Electrolytes 444 9.5.4 Relationship between Tg and Tm for
Various Substances 446 9.5.5 Comparison of Cooling Behavior of Melts and
Electrolyte Solutions 449 References 451 Appendix A Volumetric Thermal
Expansion Coefficient of Melts 453 References 455 Appendix B Relationship
between alphaV and Other Physical Properties 457 B.1 Molten Elements 457
B.2 Molten Halite-Type Electrolytes 457 Reference 461 Appendix C
Relationship between Densities dm of Molten Metals and Electrolytes and
Atomic Mass M 463 Reference 464 Index 465
Structure and Properties of Liquids 1 1.1 Different States of Matter 1 1.2
Models of Liquid Structure 6 1.3 Water and Other Common Solvents 12 1.4
Properties of Solutions 15 1.4.1 The Solvation Process 17 1.4.2 The
Concentration of Solutions 19 1.4.3 Density and Thermal Expansivity of
Solutions 21 1.4.4 Viscosity of Solutions 27 1.5 Saturated Solutions 35 1.6
High-Temperature Solvents and Solutions 43 References 46 2
Three-dimensional Nucleation of Crystals and Solute Solubility 49 2.1
Driving Force for Phase Transition 49 2.2 3D Nucleation of Crystals 54
2.2.1 Nucleation Barrier 55 2.2.2 Nucleation Rate 56 2.2.3 3D Heterogeneous
Nucleation 60 2.3 Ideal and Real Solubility 63 2.3.1 Basic Concepts 63
2.3.2 Examples of Experimental Data 68 2.3.3 Mathematical Representation of
Solute Solubility in Solvent Mixtures 76 2.4 Solute Solubility as a
Function of Solvent-Mixture Composition 78 2.4.1 A Simple Practical
Approach 78 2.4.2 Physical Interpretation of the delta Factor and Solvent
Activity 87 2.4.3 Preferential Solvation of Solute by Solvents 89 2.5
Solid-Solvent Interfacial Energy 92 2.6 Solubility and Supersolubility 96
References 101 3 Kinetics and Mechanism of Crystallization 105 3.1 Crystal
Growth as a Kinetic Process 106 3.2 Types of Crystal-Medium Interfaces 107
3.3 Thermodynamic and Kinetic Roughening of Surfaces 108 3.4 Growth
Kinetics of Rough Faces 111 3.5 Growth Kinetics of Perfect Smooth Faces 112
3.6 Growth Kinetics of Imperfect Smooth Faces 116 3.6.1 Surface Diffusion
and Direct Integration Models 117 3.6.2 Bulk Diffusion Models 119 3.6.3
Growth at Edge Dislocations 120 3.7 Simultaneous Bulk-Diffusion and
Surface-Reaction Controlled Growth 121 3.8 Effect of Impurities on Growth
Kinetics 123 3.9 Overall Crystallization 127 3.9.1 Basic Theoretical
Equations 129 3.9.2 Polynuclear Crystallization 133 3.9.2.1 Instantaneous
Nucleation Mode 134 3.9.2.2 Progressive Nucleation Mode 135 3.9.2.3 Trends
of Overall Crystallization Curves 136 3.9.2.4 Some Comments on the KJMA
Theory 138 3.9.3 Mononuclear Crystallization 139 3.9.4 Effect of Additives
on Overall Crystallization 139 References 140 4 Phase Transformation and
Isothermal Crystallization Kinetics 145 4.1 Nucleation and Transformation
of Metastable Phases 146 4.1.1 Thermodynamics of Crystallization of
Metastable Phases 147 4.1.2 Transformation Kinetics of Metastable Phases
151 4.1.3 Transformation of Metastable Phases According to KJMA Theory 158
4.1.4 Effect of Solvent on Transformation of Metastable Phases 160 4.2 Some
Non-KJMAModels of Isothermal Crystallization Kinetics 170 4.2.1 Approach
Involving Formation of an Amorphous Precursor 170 4.2.2 Model of Mazzanti,
Marangoni, and Idziak 175 4.2.3 Gompertz's Model 178 4.2.4 Model of
Foubert, Dewettinck, Jansen, and Vanrolleghem 179 4.3 Comparison of
Different Models of Isothermal Crystallization Kinetics 181 References 186
5 Nonisothermal Crystallization Kinetics and the Metastable Zone Width 189
5.1 Theoretical Interpretations of MSZW 191 5.1.1 N?vlt's Approach 192
5.1.2 Kubota's Approach 194 5.1.3 Self-Consistent N?vlt-Like Equation of
MSZW 195 5.1.4 Approach Based on the Classical Theory of 3D Nucleation 197
5.1.5 Approach Based on Progressive 3D Nucleation 199 5.1.6 Approach Based
on Instantaneous 3D Nucleation 202 5.2 Experimental Results on MSZW of
Solute.Solvent Systems 202 5.2.1 Dependence of Dimensionless Supercooling
on Cooling Rate 204 5.2.2 Effect of Detection Technique on MSZW 210 5.2.3
Relationships between ß and Z and between Phi and F 212 5.2.4 Relationship
between Dimensionless F1 and Crystallization Temperature 220 5.2.5
Dependence of Parameters Phi and F on Saturation Temperature T9 222 5.2.6
Physical Significance of Esat and Its Relationship with DeltaHs 225 5.2.7
The Nucleation Order m 230 5.3 Isothermal Crystallization 232 5.4 Effect of
Additives on MSZW of Solutions 232 5.4.1 Some General Features 233 5.4.2
Theoretical Considerations 236 5.4.2.1 Approach Based on Classical
Nucleation Theory 236 5.4.2.2 Final Expressions for Analysis of
Experimental Data 238 5.4.3 Some Examples of Effect of Impurities on MSZW
239 5.4.3.1 Boric Acid Aqueous Solutions 239 5.4.3.2 KDP Aqueous Solutions
244 5.4.3.3 POP-Acetone Solutions Containing PPP Additive 246 5.4.4
Dependence of Maximum Supersaturation Ratio on Impurity Concentration 250
5.4.5 Solute-Additive Binding Energies and MSZW of Systems 252 5.5 Effects
of Some Other Factors on MSZW of Solutions 255 5.5.1 Effect of Stirring and
Ultrasound on MSZW 255 5.5.2 Effect of Solution Volume on MSZW 255 5.6
Nonisothermal Crystallization Kinetics in Melts 259 References 260 6
Antisolvent Crystallization and the Metastable Zone Width 267 6.1
Observation Techniques for Antisolvent Crystallization 268 6.2 Light
Intensity Measurements 270 6.2.1 Some Experimental Data 270 6.2.2 Processes
Involved in Antisolvent Crystallization 274 6.3 Temperature Measurements
276 6.3.1 Some Experimental Data 276 6.3.2 Kinetics of Temperature Increase
279 6.3.3 Physical Interpretation of Temperature Changes of ADP Solutions
with Antisolvent Feeding Time at Different Rates 286 6.3.4 Origin of Two
Minima and Maximum in Temperature Change DeltaT During Antisolvent
Crystallization 287 6.3.5 Relationship Between Different Temperature
Changes, Antisolvent Feeding Rate, and Antisolvent Content 288 6.3.6
Comparison of Light-intensity and Temperature Measurements 291 6.4 Effect
of Antisolvent Composition on Nucleation Rate 296 6.5 Different Approaches
of MSZW 298 6.5.1 Modified N?vlt-like Approach 298 6.5.2 Kubota's Approach
299 6.5.3 Another Derivation of N?vlt-like Equation 300 6.5.4 Approach
Based on Classical Theory of 3D Nucleation 302 6.6 Experimental Data of
MSZW in Antisolvent Crystallization 303 6.6.1 Analysis of Experimental
Deltaxmax(RA) Data 304 6.6.2 Effect of Detection Technique on MSZW 312
6.6.3 Effect of Stirring on MSZW 315 6.6.4 Threshold and Limiting
Antisolvent Addition Rates 318 6.7 Combined Antisolvent/Cooling
Crystallization 319 References 321 7 Induction Period for Crystallization
325 7.1 Theoretical Background 327 7.1.1 Theoretical Interpretation of
Induction Period 328 7.1.2 Some Other Relations 331 7.1.3 Basic Equations
333 7.2 Induction Period for Isothermal Crystallization 333 7.2.1
Crystallization from Solutions 333 7.2.2 Crystallization from the Melt 338
7.3 Induction Period in Antisolvent Crystallization 343 7.4 Induction
Period for Nonisothermal Crystallization 345 7.4.1 Crystallization from
Solutions 345 7.4.2 Effect of Impurities on Crystallization from Solutions
349 7.4.3 Crystallization from the Melt 354 References 358 8 Ostwald
Ripening, Crystal Size Distribution, and Polymorph Selection 361 8.1
Supersaturation Decay During Antisolvent Crystallization 362 8.1.1 General
Trends 362 8.1.2 Kinetics of Supersaturation Decay 362 8.1.3 Relationship
between ConstantK and Antisolvent Feeding Rate RA 367 8.2 Solvation and
Desolvation Processes 372 8.2.1 Origin of Minima in DeltaTsw(t) Plots 373
8.2.2 Kinetics of Evolution of Minima in DeltaTsw(t) Plots 374 8.3
Evolution of Desupersaturation Curves 383 8.4 Crystal Morphology 388 8.5
Growth Rate Dispersion 396 8.6 Ostwald Ripening 398 8.7 Crystal Size
Distribution 403 8.8 Control of Phase and Size of Crystallizing Particles
412 References 417 9 Glass Formation and Crystallization Processes 423 9.1
Glass Formation by Cooling of Melts 424 9.2 Temperature Dependence of
Viscosity and the Glass Transition Temperature 426 9.3 Composition
Dependence of Glass Transition Temperature 431 9.4 Relationship between
Glass Transition Temperature and Metastable Zone Width of Solutions 435 9.5
Metastable Zone Width of Melts and Glass Formation 438 9.5.1 Derivation of
Basic Equations 438 9.5.2 Effect of Melt Viscosity and Additives on Z and F
Parameters 441 9.5.3 Calculations of RLlim, Z, F, and TN for Molten
Elements and Electrolytes 444 9.5.4 Relationship between Tg and Tm for
Various Substances 446 9.5.5 Comparison of Cooling Behavior of Melts and
Electrolyte Solutions 449 References 451 Appendix A Volumetric Thermal
Expansion Coefficient of Melts 453 References 455 Appendix B Relationship
between alphaV and Other Physical Properties 457 B.1 Molten Elements 457
B.2 Molten Halite-Type Electrolytes 457 Reference 461 Appendix C
Relationship between Densities dm of Molten Metals and Electrolytes and
Atomic Mass M 463 Reference 464 Index 465