Cover image for Additives and crystallization processes : from fundamentals to applications
Title:
Additives and crystallization processes : from fundamentals to applications
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Publication Information:
Chichester, England : Wiley, 2007
ISBN:
9780470061534

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30000010164189 QD921 S26 2007 Open Access Book Book
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30000003491424 QD921 S26 2007 Open Access Book Book
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Summary

Summary

Crystal growth technology involves processes for the production of crystals essential for microelectronics, communication technologies, lasers and energy producing and energy saving technology. A deliberately added impurity is called an additive and in different industries these affect the process of crystal growth. Thus, understanding of interactions between additives and the crystallizing phases is important in different processes found in the lab, nature and in various industries.

This book presents a generalized description of the mechanisms of action of additives during nucleation, growth and aggregation of crystals during crystallization and has received endorsement from the President of the International Organization for Crystal Growth. It is the first text devoted to the role of additives in different crystallization processes encountered in the lab, nature and in industries as diverse as pharmaceuticals, food and biofuels.

A unique highlight of the book are chapters on the effect of additives on crystal growth processes, since the phenomena discussed is an issue of debate between researchers


Author Notes

Professor Keshra Sangwal is Senior Professor of Physics (since 1997) and Head of the Department of Applied Physics and Lublin University of Technology, Poland. He is author or co-author of over 160 publications in the field of elementary processes of growth and dissolution, real structure of crystals, structure and properties of electrolyte solutions, and mechanical properties of crystalline solids, including three books (see Author's Previous Works).

He has served as Guest Editor of several issues of Crystal Research and Technology and is a member of the advisory boards of 'Crystal Research and Technology' (Wiley-VCH),' Journal of Optoelectronics and Advanced Materials', and the 'Indian Journal of Engineering and Materials Science'. He is a member of the Polish Physical Society, Polish Society of Crystal Growth and the Crystallography Committee of the Polish Academy of Sciences. He is a co-founder of the Polish Society of Crystal Growth and served as its President from 1998 - 2001. He has worked as a visiting scientists in the Instituto de Ciencia de Materiales de Barcelona, a UNDP specialist in Anna University (India), and a visiting professor at the University of Barcelona, and Hiroshima University.


Table of Contents

Prefacep. xiii
1 Complexes in Solutionsp. 1
1.1 Structure of Common Solventsp. 2
1.2 Structure of Pure Aqueous Electrolyte Solutionsp. 4
1.2.1 Solvation of Electrolyte Ions in Solutionsp. 4
1.2.2 Concentrated and Saturated Electrolyte Solutionsp. 6
1.2.3 Formation of Aquo and Partially Aquo Complexesp. 8
1.3 Structure of Aqueous Electrolyte Solutions Containing Additivesp. 10
1.4 Polyelectrolytes and Surfactants in Solutionsp. 16
1.5 Polydentate Ligands and Molecular Additivesp. 18
1.6 Crystal-Additive interactionsp. 19
Referencesp. 19
2 Three-Dimensional Nucleation and Metastable Zone Widthp. 21
2.1 Driving Force for Phase Transitionp. 22
2.2 Three-Dimensional Nucleation of Crystalsp. 25
2.2.1 Three-Dimensional Nucleation Ratep. 25
2.2.2 Three-Dimensional Heterogeneous Nucleationp. 30
2.3 Metastable Zone Widthp. 35
2.4 Nucleation and Transformation of Metastable Phasesp. 38
2.4.1 Crystallization of Metastable Phasesp. 38
2.4.2 Overall Crystallizationp. 41
2.5 Induction Period for Crystallizationp. 47
2.6 Effects of Additivesp. 52
2.6.1 Solubilityp. 52
2.6.2 Three-Dimensional Nucleation Ratep. 56
2.6.3 Metastable Zone Widthp. 56
Referencesp. 62
3 Kinetics and Mechanism of Crystal Growth: An Overviewp. 65
3.1 Crystal Growth as a Kinetic Processp. 66
3.2 Types of Crystal-Medium Interfacesp. 67
3.3 Roughening of Steps and Surfacesp. 69
3.3.1 Thermodynamic Roughening and the Surface Entropy Factorp. 70
3.3.2 Kinetic Rougheningp. 72
3.4 Growth Kinetics of Rough Facesp. 73
3.5 Growth Kinetics of Perfect Smooth Facesp. 75
3.6 Growth Kinetics of Imperfect Smooth Facesp. 78
3.6.1 Surface Diffusion and Direct Integration Modelsp. 78
3.6.2 Bulk Diffusion Modelsp. 80
3.6.3 Growth by a Group of Cooperating Screw Dislocationsp. 82
3.6.4 Preferential Growth at Edge Dislocationsp. 84
3.7 Effect of Foreign Substances on Growth Kineticsp. 85
3.7.1 Some General Considerationsp. 87
3.7.2 Growth Kinetics by Heterogeneous Two-Dimensional Nucleationp. 90
3.8 Real Crystal Growth Mechanismsp. 96
3.8.1 Structure of Interfacial Layerp. 96
3.8.2 Sources of Growth Stepsp. 100
3.9 Techniques for Studying Growth Kineticsp. 104
Referencesp. 105
4 Effect of Impurities on Crystal Growth Kineticsp. 109
4.1 Mobile and Immobile Impuritiesp. 109
4.2 Surface Coverage and Adsorption Isothermsp. 112
4.2.1 Adsorption Isothermsp. 113
4.2.2 Changes in Surface Free Energy by Adsorption of Impuritiesp. 115
4.3 Kinetic Models of Impurity Adsorptionp. 115
4.3.1 Earlier Modelsp. 115
4.3.2 Velocity of Carved Stepsp. 116
4.3.3 Impurity Adsorption at Kinks in Steps: Kubota-Mullin Modelp. 118
4.3.4 Impurity Adsorption at Surface Terrace: Cabrera-Vermilyea Modelp. 119
4.3.5 Effectiveness Factor for Impurity Adsorptionp. 121
4.3.6 Adsorption of Two Competing Impuritiesp. 124
4.4 Confrontation of Impurity Adsorption Mechanisms with Experimental Datap. 127
4.5 Time-Dependent Impurity Adsorptionp. 132
4.6 Growth Kinetics in the Presence of Impuritiesp. 136
4.6.1 Basic Kinetic Equationsp. 136
4.6.2 Time Dependence of Face Displacementp. 141
4.6.3 Dependence of Kinetic Coefficient for Step Motion on Impurity Concentrationp. 142
4.7 Tapering of KDP-Type Crystalsp. 143
4.8 Growth-Promoting Effects of Impuritiesp. 146
4.8.1 Decrease in Step Free Energy and Roughening of Stepsp. 147
4.8.2 Formation of Surface Macroclustersp. 152
4.9 Impurity Adsorption on Rough Facesp. 157
4.10 Formation of Two-Dimensional Adsorption Layerp. 158
4.11 Interactions Between Additives and Crystal Interfacep. 160
4.11.1 Nature of Impurity-Crystal Interactionsp. 160
4.11.2 Chemical Aspects of Impurity-Crystal Interactionsp. 166
4.12 Tailor-Made Additivesp. 172
Referencesp. 174
5 Dead Supersaturation Zone and Threshold Supersaturations for Growthp. 177
5.1 Origin of Threshold Supersaturations for Growthp. 179
5.1.1 Basic Kinetic Equationsp. 179
5.1.2 Three Different Distances Between Impurity Particlesp. 182
5.2 Determination of Threshold Supersaturations from v([sigma]) and R([sigma]) Datap. 184
5.2.1 Relationship Between the Model Involving Cooperating Spirals and the Power-Law Approachp. 185
5.2.2 Relationship Between the Power-Law Approach and an Empirical Expression with Corrected Supersaturationp. 185
5.2.3 Determination of [sigma]p. 186
5.3 Dependence of Threshold Supersaturations on Impurity Concentration: Basic Theoretical Equations and Linear Approximationsp. 187
5.4 Confrontation of Theoretical Equations with Experimental Datap. 190
5.4.1 Impurity Adsorption at Kinks and Surface Terracep. 190
5.4.2 Threshold Supersaturations and Impurity Adsorption Isothermsp. 193
5.5 Impurity Adsorption and Solution Supersaturationp. 197
5.6 Dependence of Ratios [sigma subscript d]/[sigma] and [sigma]/[sigma] on c[subscript i]p. 198
Referencesp. 202
6 Mineralization in Natural and Artificial Systemsp. 205
6.1 Biomineralization as a Processp. 205
6.1.1 Structure and Composition of Biomineralsp. 205
6.1.2 Humans and Animalsp. 206
6.1.3 Plantsp. 209
6.1.4 Mollusk Shells and Avian Eggshellsp. 211
6.2 Pathological Mineralizationp. 216
6.3 Effect of Biologically Active Additives on Crystallization Processesp. 222
6.3.1 Overall Precipitation Kineticsp. 222
6.3.2 Overall Growth Kineticsp. 230
6.3.3 Phases and Polymorphs of Crystallizing Calcium Saltsp. 242
6.3.4 Transformation of Metastable Phasesp. 247
6.4 Scale Formation and Salt Weatheringp. 258
Referencesp. 262
7 Morphology and Size Distribution of Crystalsp. 265
7.1 Growth Morphology of Crystalsp. 266
7.1.1 General Conceptsp. 266
7.1.2 Effect of Additives on Surface Morphologyp. 273
7.1.3 Effect of Solvent on Crystal Morphologyp. 275
7.1.4 Growth Morphodromsp. 276
7.2 Ostwald Ripening and Crystal Size Dispersionp. 282
7.3 Crystal Size Distributionp. 284
7.3.1 Population Balance Approachp. 285
7.3.2 Balanced Nucleation-Growth Approachp. 289
7.3.3 Approach Based on Law of Proportionate Effectp. 291
7.3.4 Effect of Additives on Crystal Size Distributionp. 295
7.4 Control of Shape and Size of Particlesp. 298
7.4.1 Growth-Directed Synthesisp. 298
7.4.2 Template-Directed Synthesisp. 307
7.5 Biological Tissue Engineeringp. 311
Referencesp. 314
8 Additives and Crystallization Processes in Industriesp. 319
8.1 Pharmaceutical Industryp. 320
8.1.1 Nucleation, Growth and Morphology of Drug Crystalsp. 321
8.1.2 Preparation and Size Distribution of Drug Particlesp. 324
8.2 Petroleum Industryp. 330
8.2.1 Some Basic Conceptsp. 331
8.2.2 Crystallization Behavior of Linear Long-Chain n-Alkanesp. 332
8.2.3 Biodiesels and their Crystallization Behaviorp. 338
8.3 Food Industryp. 348
8.3.1 Some Basic Conceptsp. 351
8.3.2 Crystallization of Food Fats in the Bulkp. 356
8.3.3 Crystallization of Polymorphsp. 361
8.3.4 Crystallization of Fats and Oils in Emulsion Dropletsp. 366
8.3.5 Number of Nucleation Centers and Overall Crystallization in Emulsion Systemsp. 372
Referencesp. 377
9 Incorporation of Impurities in Crystalsp. 381
9.1 Types of Impurity Incorporation and the Segregation Coefficientp. 382
9.2 Equilibrium Segregation Coefficientp. 386
9.2.1 Binary Mixture Approachp. 386
9.2.2 Thermodynamic Approachp. 388
9.2.3 Theoretical Predictions and their Comparison with Experimental Data on Segregation Coefficientp. 389
9.3 Effective Segregation Coefficientp. 396
9.3.1 Volume Diffusion Modelp. 396
9.3.2 Diffusional Relaxation Approachp. 397
9.3.3 Statistical Selection Approachp. 401
9.3.4 Surface Adsorption Approachp. 402
9.4 Relationship Between Effective Segregation Coefficient and Face Growth Ratep. 410
9.5 Threshold Supersaturation for Trapping of Impurities During Growthp. 413
9.6 Effective Segregation Coefficient and Internal Stresses Caused by Impuritiesp. 416
Referencesp. 418
List of Symbolsp. 421
Subject Indexp. 427
Author Indexp. 437