Mesocrystals and Nonclassical Crystallization

Mesocrystals and Nonclassical Crystallization......Page 1
Contents......Page 7
Preface......Page 11
1.1 Introduction......Page 15
References......Page 20
2.1 Classical Crystallization......Page 21
2.2 Definition of a Crystal and Crystal Growth......Page 23
2.3.1 Classical Nucleation Theory......Page 29
2.4.1 Concentration Fluctuations and Spinodal Crystallization......Page 33
2.4.2 Reduction of Supersaturation by the Formation of Clusters and Amorphous Intermediates......Page 35
2.5 Thermodynamic and Kinetic Crystallization Pathways......Page 36
2.6 Polymorph Control......Page 39
2.7 Crystal Morphology and the Role of Additives and Selective Adsorption......Page 42
2.7.1 Crystal Morphology......Page 44
2.7.2 What Determines Adsorption of an Additive?......Page 50
2.8.1 Electrical Polarization......Page 53
2.8.2 Light Refraction and Birefringence......Page 57
2.8.3 Mechanical Properties......Page 58
References......Page 61
3.1 Some Biomineral Examples......Page 65
3.1.1 Elongated Magnetite Nanocrystals in Magnetotactic Bacteria......Page 66
3.1.2 Calcite with Complex Form and Single Crystal Behavior in Foraminifera......Page 67
3.1.3 Calcite with Complex Form and Single Crystal Behavior in Sea Urchin Spines......Page 70
3.1.4 Calcite Single Crystals with Complex Form in Coccoliths......Page 71
3.1.5 Morphological Complexity Develops with Time......Page 72
3.2 From Biology to Biomimetics:In VitroMineralization Examples......Page 73
3.3 Biomorphs......Page 82
3.4 Other Synthetic Examples......Page 83
References......Page 85
4 Nonclassical Crystallization......Page 87
4.1 Amorphous Precursors......Page 89
4.2 Liquid Precursors......Page 92
4.3 Oriented Attachment......Page 97
4.4 Mesocrystals......Page 110
References......Page 112
5 Self-Assembly and Self-Organization......Page 117
References......Page 120
6 Colloidal Crystals with Spherical Units: Opals and Colloidal Nanocrystals......Page 121
References......Page 125
7.1 Mesocrystals and Their Properties......Page 127
7.2 Early Reports on Mesocrystals......Page 128
7.3 One-Dimensional Mesocrystals......Page 131
7.4 Two-Dimensional Mesocrystals......Page 132
7.5 Mesocrystals in Biomineralization......Page 136
7.6 Mesocrystals in Gels......Page 143
7.7 Mesocrystals Formed without Additives......Page 149
7.8 Mesocrystals Formed with Simple Ion Additives......Page 152
7.9 Mesocrystals Formed with Polymer Additives......Page 156
7.10 Mesocrystals in Nonaqueous Systems......Page 166
7.11.1 Solid Matrices for Mesocrystal Formation......Page 171
7.11.2 Topotactic Reactions......Page 173
7.12 Liquid Crystals, Tactoids, Somatoids, and Schiller Layers......Page 177
References......Page 187
8.1 Principal Mechanisms Leading to Mesocrystals......Page 193
8.2 Conditions for Mesocrystal Formation......Page 200
8.3.1 Alignment by Capillary Forces......Page 204
8.3.3 Alignment by Minimization of the Interfacial Energy......Page 206
8.3.4 Alignment by Additive Coding of Nanoparticles......Page 208
8.3.5 Alignment by a Mechanical Stress Field......Page 210
8.4 The Role of Magnetic Fields......Page 212
8.5.1 Polarization Forces......Page 218
8.6 The Role of External Electric Fields......Page 233
8.7 Self-Similar Assembly and Shape Constraints......Page 236
8.8 Shaping of Mesocrystals......Page 240
8.9 Mesocrystals as Intermediates in Single Crystal Formation......Page 242
References......Page 247
9 Analysis of Mesocrystals......Page 251
9.1 Nucleation and Growth of Primary Nanoparticles......Page 252
9.3 Mesocrystal Formation......Page 253
9.4 Fusion of the Mesocrystal to a Single Crystal/Ripening and Ion-Mediated Recrystallization Towards an Outer Single Crystalline Shell......Page 254
9.5 Analytical Techniques for Mesocrystals......Page 255
References......Page 258
10 Tuning of Properties......Page 261
References......Page 263
11 A Unifying Crystallization Mechanism......Page 265
References......Page 269
12 Analogy between Oriented Attachment or Hierarchically Structured Crystals and Polymers......Page 271
12.1 Analogy between Oriented Attachment and Polymerization......Page 273
12.2 Structural Levels in Hierarchically Structured Crystals and Biopolymers......Page 277
References......Page 278
13.1 Summary......Page 279
13.2 Outlook......Page 281
References......Page 284
Index......Page 285