Preface ix
1 Mesocrystals and Nonclassical Crystallization 1
1.1 Introduction 1
References 6
2 Physico-Chemical Principles of Crystallization 7
2.1 Classical Crystallization 7
2.2 Definition of a Crystal and Crystal Growth 9
2.3 Nucleation Theories 15
2.3.1 Classical Nucleation Theory 15
2.3.2 Experimental Tests of Nucleation Theories 19
2.4 Some Points towards a More Realistic View of Supersaturation and Crystallization 19
2.4.1 Concentration Fluctuations and 'Spinodal Crystallization' 19
2.4.2 Reduction of Supersaturation by the Formation of Clusters and Amorphous Intermediates 21
2.5 Thermodynamic and Kinetic Crystallization Pathways 22
2.6 Polymorph Control 25
2.7 Crystal Morphology and the Role of Additives and Selective Adsorption 28
2.7.1 Crystal Morphology 30
2.7.2 What Determines Adsorption of an Additive? 36
2.8 Properties of Single Crystals and Polycrystals 39
2.8.1 Electrical Polarization 39
2.8.2 Light Refraction and Birefringence 43
2.8.3 Mechanical Properties 44
References 47
3 Examples of Crystals Challenging the Classical Textbook Mechanism 51
3.1 Some Biomineral Examples 51
3.1.1 Elongated Magnetite Nanocrystals in Magnetotactic Bacteria 52
3.1.2 Calcite with Complex Form and Single Crystal Behavior in Foraminifera 53
3.1.3 Calcite with Complex Form and Single Crystal Behavior in Sea Urchin Spines 56
3.1.4 Calcite Single Crystals with Complex Form in Coccoliths 57
3.1.5 Morphological Complexity Develops with Time 58
3.2 From Biology to Biomimetics: In Vitro Mineralization Examples 59
3.3 Biomorphs 68
3.4 Other Synthetic Examples 69
References 71
4 Nonclassical Crystallization 73
4.1 Amorphous Precursors 75
4.2 Liquid Precursors 78
4.3 Oriented Attachment 83
4.4 Mesocrystals 96
References 98
5 Self-Assembly and Self-Organization 103
References 106
6 Colloidal Crystals with Spherical Units: Opals and Colloidal Nanocrystals 107
References 111
7 Mesocrystal Systems 113
7.1 Mesocrystals and Their Properties 113
7.2 Early Reports on Mesocrystals 114
7.3 One-Dimensional Mesocrystals 117
7.4 Two-Dimensional Mesocrystals 118
7.5 Mesocrystals in Biomineralization 122
7.6 Mesocrystals in Gels 129
7.7 Mesocrystals Formed without Additives 135
7.8 Mesocrystals Formed with Simple Ion Additives 138
7.9 Mesocrystals Formed with Polymer Additives 142
7.10 Mesocrystals in Nonaqueous Systems 152
7.11 Mesocrystals Formed via Solid-State Reactions 157
7.11.1 Solid Matrices for Mesocrystal Formation 157
7.11.2 Topotactic Reactions 159
7.12 Liquid Crystals, Tactoids, Somatoids, and Schiller Layers 163
References 173
8 Mechanisms of Mesocrystal Formation 179
8.1 Principal Mechanisms Leading to Mesocrystals 179
8.2 Conditions for Mesocrystal Formation 186
8.3 Alignment by Colloidal Forces, Capillarity and Other Short-Ranged Physical Fields 190
8.3.1 Alignment by Capillary Forces 190
8.3.2 Alignment by Hydrophobic Forces and Interface Energies 192
8.3.3 Alignment by Minimization of the Interfacial Energy 192
8.3.4 Alignment by Additive Coding of Nanoparticles 194
8.3.5 Alignment by a Mechanical Stress Field 196
8.4 The Role of Magnetic Fields 198
8.5 The Role of Dipole and Polarization Forces 204
8.5.1 Polarization Forces 204
8.6 The Role of External Electric Fields 219
8.7 Self-Similar Assembly and Shape Constraints 222
8.8 Shaping of Mesocrystals 226
8.9 Mesocrystals as Intermediates in Single Crystal Formation 228
References 233
9 Analysis of Mesocrystals 237
9.1 Nucleation and Growth of Primary Nanoparticles 238
9.2 Rapid Aggregation and Formation of Randomly Oriented Aggregates 239
9.3 Mesocrystal Formation 239
9.4 Fusion of the Mesocrystal to a Single Crystal/Ripening and Ion-Mediated Recrystallization Towards an Outer Single Crystalline Shell 240
9.5 Analytical Techniques for Mesocrystals 241
References 244
10 Tuning of Properties 247
References 249
11 A Unifying Crystallization Mechanism 251
References 255
12 Analogy between Oriented Attachment or Hierarchically Structured Crystals and Polymers 257
12.1 Analogy between Oriented Attachment and Polymerization 259
12.2 Structural Levels in Hierarchically Structured Crystals and
Biopolymers 263
References 264
13 Summary and Outlook 265
13.1 Summary 265
13.2 Outlook 267
References 270
Index 271
