Additives and Crystallization Processes: From Fundamentals to Applications / Edition 1

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Additives and Crystallization Processes: From Fundamentals to Applications presents a generalized description of the mechanisms of the action of additives during nucleation, growth and aggregation of crystals during various types of crystallization. Many of the topics discussed here fall in the domains of specialized fields such as industrial crystallization, crystal growth technology, and biomineralization, and are included to expose the reader to the importance of additives in crystallization processes, from a physicist's perspective, in diverse fields of basic research and applied activities such as chemical engineering, industrial crystallization, materials science, and technology of growth of crystals.

The contents of the book can be divided into four parts. The first part is introductory where basic concepts about the nature of complexes in dilute and concentrated solutions; three-dimensional nucleation and metastable zone width; and crystal growth processes are outlined. The second part consists of two chapters, and is addressed to the effect of additives on crystal growth kinetics and the observation of threshold supersaturations for growth. The third part presents an overview of processes of mineralization in natural and artificial systems and morphology and size distribution of crystals, with emphasis on the role of additives in these processes. The last part addresses applied aspects of additives in pharmaceutical, food and petroleum Industries, and processes of segregation during crystallization.

This work is primarily aimed at specialists, as well as graduate students, of industrial crystallization, chemical engineering, materials science and condensed matterphysics, who are interested in looking for a comprehensive review of the fundamentals of the processes of nucleation and growth of crystals from pure systems in general and from systems containing a variety of additives in particular both in basic and applied research. In addition, it will also serve as a ready source of reference for materials scientists interested in using the basic principles of additive material interactions to design and prepare novel composite materials.

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Product Details

  • ISBN-13: 9780470061534
  • Publisher: Wiley
  • Publication date: 11/16/2007
  • Edition number: 1
  • Pages: 468
  • Product dimensions: 6.93 (w) x 9.94 (h) x 1.32 (d)

Table of Contents

Preface     xiii
Complexes in Solutions     1
Structure of Common Solvents     2
Structure of Pure Aqueous Electrolyte Solutions     4
Solvation of Electrolyte Ions in Solutions     4
Concentrated and Saturated Electrolyte Solutions     6
Formation of Aquo and Partially Aquo Complexes     8
Structure of Aqueous Electrolyte Solutions Containing Additives     10
Polyelectrolytes and Surfactants in Solutions     16
Polydentate Ligands and Molecular Additives     18
Crystal-Additive interactions     19
References     19
Three-Dimensional Nucleation and Metastable Zone Width     21
Driving Force for Phase Transition     22
Three-Dimensional Nucleation of Crystals     25
Three-Dimensional Nucleation Rate     25
Three-Dimensional Heterogeneous Nucleation     30
Metastable Zone Width     35
Nucleation and Transformation of Metastable Phases     38
Crystallization of Metastable Phases     38
Overall Crystallization     41
Induction Period for Crystallization     47
Effects of Additives     52
Solubility     52
Three-DimensionalNucleation Rate     56
Metastable Zone Width     56
References     62
Kinetics and Mechanism of Crystal Growth: An Overview     65
Crystal Growth as a Kinetic Process     66
Types of Crystal-Medium Interfaces     67
Roughening of Steps and Surfaces     69
Thermodynamic Roughening and the Surface Entropy Factor     70
Kinetic Roughening     72
Growth Kinetics of Rough Faces     73
Growth Kinetics of Perfect Smooth Faces     75
Growth Kinetics of Imperfect Smooth Faces     78
Surface Diffusion and Direct Integration Models     78
Bulk Diffusion Models     80
Growth by a Group of Cooperating Screw Dislocations     82
Preferential Growth at Edge Dislocations     84
Effect of Foreign Substances on Growth Kinetics     85
Some General Considerations     87
Growth Kinetics by Heterogeneous Two-Dimensional Nucleation     90
Real Crystal Growth Mechanisms     96
Structure of Interfacial Layer     96
Sources of Growth Steps     100
Techniques for Studying Growth Kinetics     104
References     105
Effect of Impurities on Crystal Growth Kinetics      109
Mobile and Immobile Impurities     109
Surface Coverage and Adsorption Isotherms     112
Adsorption Isotherms     113
Changes in Surface Free Energy by Adsorption of Impurities     115
Kinetic Models of Impurity Adsorption     115
Earlier Models     115
Velocity of Carved Steps     116
Impurity Adsorption at Kinks in Steps: Kubota-Mullin Model     118
Impurity Adsorption at Surface Terrace: Cabrera-Vermilyea Model     119
Effectiveness Factor for Impurity Adsorption     121
Adsorption of Two Competing Impurities     124
Confrontation of Impurity Adsorption Mechanisms with Experimental Data     127
Time-Dependent Impurity Adsorption     132
Growth Kinetics in the Presence of Impurities     136
Basic Kinetic Equations     136
Time Dependence of Face Displacement     141
Dependence of Kinetic Coefficient for Step Motion on Impurity Concentration     142
Tapering of KDP-Type Crystals     143
Growth-Promoting Effects of Impurities     146
Decrease in Step Free Energy and Roughening of Steps     147
Formation of Surface Macroclusters     152
Impurity Adsorption on Rough Faces      157
Formation of Two-Dimensional Adsorption Layer     158
Interactions Between Additives and Crystal Interface     160
Nature of Impurity-Crystal Interactions     160
Chemical Aspects of Impurity-Crystal Interactions     166
Tailor-Made Additives     172
References     174
Dead Supersaturation Zone and Threshold Supersaturations for Growth     177
Origin of Threshold Supersaturations for Growth     179
Basic Kinetic Equations     179
Three Different Distances Between Impurity Particles     182
Determination of Threshold Supersaturations from v([sigma]) and R([sigma]) Data     184
Relationship Between the Model Involving Cooperating Spirals and the Power-Law Approach     185
Relationship Between the Power-Law Approach and an Empirical Expression with Corrected Supersaturation     185
Determination of [sigma]     186
Dependence of Threshold Supersaturations on Impurity Concentration: Basic Theoretical Equations and Linear Approximations     187
Confrontation of Theoretical Equations with Experimental Data     190
Impurity Adsorption at Kinks and Surface Terrace     190
Threshold Supersaturations and Impurity Adsorption Isotherms     193
Impurity Adsorption and Solution Supersaturation      197
Dependence of Ratios [sigma subscript d]/[sigma] and [sigma]/[sigma] on c[subscript i]     198
References     202
Mineralization in Natural and Artificial Systems     205
Biomineralization as a Process     205
Structure and Composition of Biominerals     205
Humans and Animals     206
Plants     209
Mollusk Shells and Avian Eggshells     211
Pathological Mineralization     216
Effect of Biologically Active Additives on Crystallization Processes     222
Overall Precipitation Kinetics     222
Overall Growth Kinetics     230
Phases and Polymorphs of Crystallizing Calcium Salts     242
Transformation of Metastable Phases     247
Scale Formation and Salt Weathering     258
References     262
Morphology and Size Distribution of Crystals     265
Growth Morphology of Crystals     266
General Concepts     266
Effect of Additives on Surface Morphology     273
Effect of Solvent on Crystal Morphology     275
Growth Morphodroms     276
Ostwald Ripening and Crystal Size Dispersion     282
Crystal Size Distribution      284
Population Balance Approach     285
Balanced Nucleation-Growth Approach     289
Approach Based on Law of Proportionate Effect     291
Effect of Additives on Crystal Size Distribution     295
Control of Shape and Size of Particles     298
Growth-Directed Synthesis     298
Template-Directed Synthesis     307
Biological Tissue Engineering     311
References     314
Additives and Crystallization Processes in Industries     319
Pharmaceutical Industry     320
Nucleation, Growth and Morphology of Drug Crystals     321
Preparation and Size Distribution of Drug Particles     324
Petroleum Industry     330
Some Basic Concepts     331
Crystallization Behavior of Linear Long-Chain n-Alkanes     332
Biodiesels and their Crystallization Behavior     338
Food Industry     348
Some Basic Concepts     351
Crystallization of Food Fats in the Bulk     356
Crystallization of Polymorphs     361
Crystallization of Fats and Oils in Emulsion Droplets     366
Number of Nucleation Centers and Overall Crystallization in Emulsion Systems     372
References      377
Incorporation of Impurities in Crystals     381
Types of Impurity Incorporation and the Segregation Coefficient     382
Equilibrium Segregation Coefficient     386
Binary Mixture Approach     386
Thermodynamic Approach     388
Theoretical Predictions and their Comparison with Experimental Data on Segregation Coefficient     389
Effective Segregation Coefficient     396
Volume Diffusion Model     396
Diffusional Relaxation Approach     397
Statistical Selection Approach     401
Surface Adsorption Approach     402
Relationship Between Effective Segregation Coefficient and Face Growth Rate     410
Threshold Supersaturation for Trapping of Impurities During Growth     413
Effective Segregation Coefficient and Internal Stresses Caused by Impurities     416
References     418
List of Symbols     421
Subject Index     427
Author Index     437
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