Additives and Crystallization Processes: From Fundamentals to Applications

Table of Contents:
Preface xiii 1 Complexes in Solutions 1 1.1 Structure of Common Solvents 2 1.2 Structure of Pure Aqueous Electrolyte Solutions 4 1.2.1 Solvation of Electrolyte Ions in Solutions 4 1.2.2 Concentrated and Saturated Electrolyte Solutions 6 1.2.3 Formation of Aquo and Partially Aquo Complexes 8 1.3 Structure of Aqueous Electrolyte Solutions Containing Additives 10 1.4 Polyelectrolytes and Surfactants in Solutions 16 1.5 Polydentate Ligands and Molecular Additives 18 1.6 Crystal–Additive Interactions 19 References 19 2 Three-Dimensional Nucleation and Metastable Zone Width 21 2.1 Driving Force for Phase Transition 22 2.2 Three-Dimensional Nucleation of Crystals 25 2.2.1 Three-Dimensional Nucleation Rate 25 2.2.2 Three-Dimensional Heterogeneous Nucleation 30 2.3 Metastable Zone Width 35 2.4 Nucleation and Transformation of Metastable Phases 38 2.4.1 Crystallization of Metastable Phases 38 2.4.2 Overall Crystallization 41 2.5 Induction Period for Crystallization 47 2.6 Effects of Additives 52 2.6.1 Solubility 52 2.6.2 Three-Dimensional Nucleation Rate 56 2.6.3 Metastable Zone Width 56 References 62 3 Kinetics and Mechanism of Crystal Growth: An Overview 65 3.1 Crystal Growth as a Kinetic Process 66 3.2 Types of Crystal–Medium Interfaces 67 3.3 Roughening of Steps and Surfaces 69 3.3.1 Thermodynamic Roughening and the Surface Entropy Factor 70 3.3.2 Kinetic Roughening 72 3.4 Growth Kinetics of Rough Faces 73 3.5 Growth Kinetics of Perfect Smooth Faces 75 3.6 Growth Kinetics of Imperfect Smooth Faces 78 3.6.1 Surface Diffusion and Direct Integration Models 78 3.6.2 Bulk Diffusion Models 80 3.6.3 Growth by a Group of Cooperating Screw Dislocations 82 3.6.4 Preferential Growth at Edge Dislocations 84 3.7 Effect of Foreign Substances on Growth Kinetics 85 3.7.1 Some General Considerations 87 3.7.2 Growth Kinetics by Heterogeneous Two-Dimensional Nucleation 90 3.8 Real Crystal Growth Mechanisms 96 3.8.1 Structure of Interfacial Layer 96 3.8.2 Sources of Growth Steps 100 3.9 Techniques for Studying Growth Kinetics 104 References 105 4 Effect of Impurities on Crystal Growth Kinetics 109 4.1 Mobile and Immobile Impurities 109 4.2 Surface Coverage and Adsorption Isotherms 112 4.2.1 Adsorption Isotherms 113 4.2.2 Changes in Surface Free Energy by Adsorption of Impurities 115 4.3 Kinetic Models of Impurity Adsorption 115 4.3.1 Earlier Models 115 4.3.2 Velocity of Curved Steps 116 4.3.3 Impurity Adsorption at Kinks in Steps: Kubota–Mullin Model 118 4.3.4 Impurity Adsorption at Surface Terrace: Cabrera–Vermilyea Model 119 4.3.5 Effectiveness Factor for Impurity Adsorption 121 4.3.6 Adsorption of Two Competing Impurities 124 4.4 Confrontation of Impurity Adsorption Mechanisms with Experimental Data 127 4.5 Time-Dependent Impurity Adsorption 132 4.6 Growth Kinetics in the Presence of Impurities 136 4.6.1 Basic Kinetic Equations 136 4.6.2 Time Dependence of Face Displacement 141 4.6.3 Dependence of Kinetic Coefficient for Step Motion on Impurity Concentration 142 4.7 Tapering of KDP-Type Crystals 143 4.8 Growth-Promoting Effects of Impurities 146 4.8.1 Decrease in Step Free Energy and Roughening of Steps 147 4.8.2 Formation of Surface Macroclusters 152 4.9 Impurity Adsorption on Rough Faces 157 4.10 Formation of Two-Dimensional Adsorption Layer 158 4.11 Interactions Between Additives and Crystal Interface 160 4.11.1 Nature of Impurity–Crystal Interactions 160 4.11.2 Chemical Aspects of Impurity–Crystal Interactions 166 4.12 Tailor-Made Additives 172 References 174 5 Dead Supersaturation Zone and Threshold Supersaturations for Growth 177 5.1 Origin of Threshold Supersaturations for Growth 179 5.1.1 Basic Kinetic Equations 179 5.1.2 Three Different Distances Between Impurity Particles 182 5.2 Determination of Threshold Supersaturations from v (σ) and R (σ) Data 184 5.2.1 Relationship Between the Model Involving Cooperating Spirals and the Power-Law Approach 185 5.2.2 Relationship Between the Power-Law Approach and an Empirical Expression with Corrected Supersaturation 185 5.2.3 Determination of σ∗ 186 5.3 Dependence of Threshold Supersaturations on Impurity Concentration: Basic Theoretical Equations and Linear Approximations 187 5.4 Confrontation of Theoretical Equations with Experimental Data 190 5.4.1 Impurity Adsorption at Kinks and Surface Terrace 190 5.4.2 Threshold Supersaturations and Impurity Adsorption Isotherms 193 5.5 Impurity Adsorption and Solution Supersaturation 197 5.6 Dependence of Ratios σd/σ∗ and σ∗/σ∗∗ on ci 198 References 202 6 Mineralization in Natural and Artificial Systems 205 6.1 Biomineralization as a Process 205 6.1.1 Structure and Composition of Biominerals 205 6.1.2 Humans and Animals 206 6.1.3 Plants 209 6.1.4 Mollusk Shells and Avian Eggshells 211 6.2 Pathological Mineralization 216 6.3 Effect of Biologically Active Additives on Crystallization Processes 222 6.3.1 Overall Precipitation Kinetics 222 6.3.2 Overall Growth Kinetics 230 6.3.3 Phases and Polymorphs of Crystallizing Calcium Salts 242 6.3.4 Transformation of Metastable Phases 247 6.4 Scale Formation and Salt Weathering 258 References 262 7 Morphology and Size Distribution of Crystals 265 7.1 Growth Morphology of Crystals 266 7.1.1 General Concepts 266 7.1.2 Effect of Additives on Surface Morphology 273 7.1.3 Effect of Solvent on Crystal Morphology 275 7.1.4 Growth Morphodroms 276 7.2 Ostwald Ripening and Crystal Size Dispersion 282 7.3 Crystal Size Distribution 284 7.3.1 Population Balance Approach 285 7.3.2 Balanced Nucleation-Growth Approach 289 7.3.3 Approach Based on Law of Proportionate Effect 291 7.3.4 Effect of Additives on Crystal Size Distribution 295 7.4 Control of Shape and Size of Particles 298 7.4.1 Growth-Directed Synthesis 298 7.4.2 Template-Directed Synthesis 307 7.5 Biological Tissue Engineering 311 References 314 8 Additives and Crystallization Processes in Industries 319 8.1 Pharmaceutical Industry 320 8.1.1 Nucleation, Growth and Morphology of Drug Crystals 321 8.1.2 Preparation and Size Distribution of Drug Particles 324 8.2 Petroleum Industry 330 8.2.1 Some Basic Concepts 331 8.2.2 Crystallization Behavior of Linear Long-Chain n-Alkanes 332 8.2.3 Biodiesels and their Crystallization Behavior 338 8.3 Food Industry 348 8.3.1 Some Basic Concepts 351 8.3.2 Crystallization of Food Fats in the Bulk 356 8.3.3 Crystallization of Polymorphs 361 8.3.4 Crystallization of Fats and Oils in Emulsion Droplets 366 8.3.5 Number of Nucleation Centers and Overall Crystallization in Emulsion Systems 372 References 377 9 Incorporation of Impurities in Crystals 381 9.1 Types of Impurity Incorporation and the Segregation Coefficient 382 9.2 Equilibrium Segregation Coefficient 386 9.2.1 Binary Mixture Approach 386 9.2.2 Thermodynamic Approach 388 9.2.3 Theoretical Predictions and their Comparison with Experimental Data on Segregation Coefficient 389 9.3 Effective Segregation Coefficient 396 9.3.1 Volume Diffusion Model 396 9.3.2 Diffusional Relaxation Approach 397 9.3.3 Statistical Selection Approach 401 9.3.4 Surface Adsorption Approach 402 9.4 Relationship Between Effective Segregation Coefficient and Face Growth Rate 410 9.5 Threshold Supersaturation for Trapping of Impurities During Growth 413 9.6 Effective Segregation Coefficient and Internal Stresses Caused by Impurities 416 References 418 List of Symbols 421 Subject Index 427 Author Index 437

About the Author :
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.

Review :
"A welcome contribution to the literature on crystal growth. Its contents can clearly serve a wide ranging audience including graduate students, postdoctoral investigators and teachers." (Progress in Crystal Growth and Characterization of Materials, September 2008) "This book is stimulating for both beginners and experts engaged in crystallization from solution … .[A] very readable and an up-to-date research handbook." (Crystal Research and Technology, September 2008)