Nucleation and Crystal Growth : Metastability of Solutions and Melts.

Intro -- Title Page -- Copyright Page -- Contents -- Preface -- Acknowledgments -- List of Frequently Used Symbols -- Chapter 1 Structure and Properties of Liquids -- 1.1 Different States of Matter -- 1.2 Models of Liquid Structure -- 1.3 Water and Other Common Solvents -- 1.4 Properties of Solutions -- 1.4.1 The Solvation Process -- 1.4.2 The Concentration of Solutions -- 1.4.3 Density and Thermal Expansivity of Solutions -- 1.4.4 Viscosity of Solutions -- 1.5 Saturated Solutions -- 1.6 High-Temperature Solvents and Solutions -- References -- Chapter 2 Three-dimensional Nucleation of Crystals and Solute Solubility -- 2.1 Driving Force for Phase Transition -- 2.2 3D Nucleation of Crystals -- 2.2.1 Nucleation Barrier -- 2.2.2 Nucleation Rate -- 2.2.3 3D Heterogeneous Nucleation -- 2.3 Ideal and Real Solubility -- 2.3.1 Basic Concepts -- 2.3.2 Examples of Experimental Data -- 2.3.3 Mathematical Representation of Solute Solubility in Solvent Mixtures -- 2.4 Solute Solubility as a Function of Solvent-Mixture Composition -- 2.4.1 A Simple Practical Approach -- 2.4.2 Physical Interpretation of the δ Factor and Solvent Activity -- 2.4.3 Preferential Solvation of Solute by Solvents -- 2.5 Solid-Solvent Interfacial Energy -- 2.6 Solubility and Supersolubility -- References -- Chapter 3 Kinetics and Mechanism of Crystallization -- 3.1 Crystal Growth as a Kinetic Process -- 3.2 Types of Crystal-Medium Interfaces -- 3.3 Thermodynamic and Kinetic Roughening of Surfaces -- 3.4 Growth Kinetics of Rough Faces -- 3.5 Growth Kinetics of Perfect Smooth Faces -- 3.6 Growth Kinetics of Imperfect Smooth Faces -- 3.6.1 Surface Diffusion and Direct Integration Models -- 3.6.2 Bulk Diffusion Models -- 3.6.3 Growth at Edge Dislocations -- 3.7 Simultaneous Bulk-Diffusion and Surface-Reaction Controlled Growth -- 3.8 Effect of Impurities on Growth Kinetics.

3.9 Overall Crystallization -- 3.9.1 Basic Theoretical Equations -- 3.9.2 Polynuclear Crystallization -- 3.9.2.1 Instantaneous Nucleation Mode -- 3.9.2.2 Progressive Nucleation Mode -- 3.9.2.3 Trends of Overall Crystallization Curves -- 3.9.2.4 Some Comments on the KJMA Theory -- 3.9.3 Mononuclear Crystallization -- 3.9.4 Effect of Additives on Overall Crystallization -- References -- Chapter 4 Phase Transformation and Isothermal Crystallization Kinetics -- 4.1 Nucleation and Transformation of Metastable Phases -- 4.1.1 Thermodynamics of Crystallization of Metastable Phases -- 4.1.2 Transformation Kinetics of Metastable Phases -- 4.1.3 Transformation of Metastable Phases According to KJMA Theory -- 4.1.4 Effect of Solvent on Transformation of Metastable Phases -- 4.2 Some Non-KJMA Models of Isothermal Crystallization Kinetics -- 4.2.1 Approach Involving Formation of an Amorphous Precursor -- 4.2.2 Model of Mazzanti, Marangoni, and Idziak -- 4.2.3 Gompertz´s Model -- 4.2.4 Model of Foubert, Dewettinck, Jansen, and Vanrolleghem -- 4.3 Comparison of Different Models of Isothermal Crystallization Kinetics -- References -- Chapter 5 Nonisothermal Crystallization Kinetics and the Metastable Zone Width -- 5.1 Theoretical Interpretations of MSZW -- 5.1.1 Nývlt's Approach -- 5.1.2 Kubota's Approach -- 5.1.3 Self-Consistent Nývlt-Like Equation of MSZW -- 5.1.4 Approach Based on the Classical Theory of 3D Nucleation -- 5.1.5 Approach Based on Progressive 3D Nucleation -- 5.1.6 Approach Based on Instantaneous 3D Nucleation -- 5.2 Experimental Results on MSZW of Solute−Solvent Systems -- 5.2.1 Dependence of Dimensionless Supercooling on Cooling Rate -- 5.2.2 Effect of Detection Technique on MSZW -- 5.2.3 Relationships between β and Z and between Φ and F -- 5.2.4 Relationship between Dimensionless F1 and Crystallization Temperature.

5.2.5 Dependence of Parameters Φ and F on Saturation Temperature T0 -- 5.2.6 Physical Significance of Esat and Its Relationship with ΔHs -- 5.2.7 The Nucleation Order m -- 5.3 Isothermal Crystallization -- 5.4 Effect of Additives on MSZW of Solutions -- 5.4.1 Some General Features -- 5.4.2 Theoretical Considerations -- 5.4.2.1 Approach Based on Classical Nucleation Theory -- 5.4.2.2 Final Expressions for Analysis of Experimental Data -- 5.4.3 Some Examples of Effect of Impurities on MSZW -- 5.4.3.1 Boric Acid Aqueous Solutions -- 5.4.3.2 KDP Aqueous Solutions -- 5.4.3.3 POP-Acetone Solutions Containing PPP Additive -- 5.4.4 Dependence of Maximum Supersaturation Ratio on Impurity Concentration -- 5.4.5 Solute-Additive Binding Energies and MSZW of Systems -- 5.5 Effects of Some Other Factors on MSZW of Solutions -- 5.5.1 Effect of Stirring and Ultrasound on MSZW -- 5.5.2 Effect of Solution Volume on MSZW -- 5.6 Nonisothermal Crystallization Kinetics in Melts -- References -- Chapter 6 Antisolvent Crystallization and the Metastable Zone Width -- 6.1 Observation Techniques for Antisolvent Crystallization -- 6.2 Light Intensity Measurements -- 6.2.1 Some Experimental Data -- 6.2.2 Processes Involved in Antisolvent Crystallization -- 6.3 Temperature Measurements -- 6.3.1 Some Experimental Data -- 6.3.2 Kinetics of Temperature Increase -- 6.3.3 Physical Interpretation of Temperature Changes of ADP Solutions with Antisolvent Feeding Time at Different Rates -- 6.3.4 Origin of Two Minima and Maximum in Temperature Change ΔT During Antisolvent Crystallization -- 6.3.5 Relationship Between Different Temperature Changes, Antisolvent Feeding Rate, and Antisolvent Content -- 6.3.6 Comparison of Light-intensity and Temperature Measurements -- 6.4 Effect of Antisolvent Composition on Nucleation Rate -- 6.5 Different Approaches of MSZW.

6.5.1 Modified Nvlt-like Approach -- 6.5.2 Kubota´s Approach -- 6.5.3 Another Derivation of Nvlt-like Equation -- 6.5.4 Approach Based on Classical Theory of 3D Nucleation -- 6.6 Experimental Data of MSZW in Antisolvent Crystallization -- 6.6.1 Analysis of Experimental Δxmax(RA) Data -- 6.6.2 Effect of Detection Technique on MSZW -- 6.6.3 Effect of Stirring on MSZW -- 6.6.4 Threshold and Limiting Antisolvent Addition Rates -- 6.7 Combined Antisolvent/Cooling Crystallization -- References -- Chapter 7 Induction Period for Crystallization -- 7.1 Theoretical Background -- 7.1.1 Theoretical Interpretation of Induction Period -- 7.1.2 Some Other Relations -- 7.1.3 Basic Equations -- 7.2 Induction Period for Isothermal Crystallization -- 7.2.1 Crystallization from Solutions -- 7.2.2 Crystallization from the Melt -- 7.3 Induction Period in Antisolvent Crystallization -- 7.4 Induction Period for Nonisothermal Crystallization -- 7.4.1 Crystallization from Solutions -- 7.4.2 Effect of Impurities on Crystallization from Solutions -- 7.4.3 Crystallization from the Melt -- References -- Chapter 8 Ostwald Ripening, Crystal Size Distribution, and Polymorph Selection -- 8.1 Supersaturation Decay During Antisolvent Crystallization -- 8.1.1 General Trends -- 8.1.2 Kinetics of Supersaturation Decay -- 8.1.3 Relationship between Constant K and Antisolvent Feeding Rate RA -- 8.2 Solvation and Desolvation Processes -- 8.2.1 Origin of Minima in ΔTsw(t) Plots -- 8.2.2 Kinetics of Evolution of Minima in ΔTsw(t) Plots -- 8.3 Evolution of Desupersaturation Curves -- 8.4 Crystal Morphology -- 8.5 Growth Rate Dispersion -- 8.6 Ostwald Ripening -- 8.7 Crystal Size Distribution -- 8.8 Control of Phase and Size of Crystallizing Particles -- References -- Chapter 9 Glass Formation and Crystallization Processes -- 9.1 Glass Formation by Cooling of Melts.

9.2 Temperature Dependence of Viscosity and the Glass Transition Temperature -- 9.3 Composition Dependence of Glass Transition Temperature -- 9.4 Relationship between Glass Transition Temperature and Metastable Zone Width of Solutions -- 9.5 Metastable Zone Width of Melts and Glass Formation -- 9.5.1 Derivation of Basic Equations -- 9.5.2 Effect of Melt Viscosity and Additives on Z and F Parameters -- 9.5.3 Calculations of RLlim, Z, F, and TN for Molten Elements and Electrolytes -- 9.5.4 Relationship between Tg and Tm for Various Substances -- 9.5.5 Comparison of Cooling Behavior of Melts and Electrolyte Solutions -- References -- Appendix A Volumetric Thermal Expansion Coefficient of Melts -- References -- Appendix B Relationship between αV and Other Physical Properties -- B.1 Molten Elements -- B.2 Molten Halite-Type Electrolytes -- Reference -- Appendix C Relationship between Densities dm of Molten Metals and Electrolytes and Atomic Mass M -- Reference -- Index -- EULA.

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