Mesocrystals and Nonclassical Crystallization

Helmut Cöelfen and Markus Antonietti are the authors of Mesocrystals and Nonclassical Crystallization, published by Wiley.

• Preface ix1 Mesocrystals and Nonclassical Crystallization 11.1 Introduction 1References 62 Physico-Chemical Principles of Crystallization 72.1 Classical Crystallization 72.2 Definition of a Crystal and Crystal Growth 92.3 Nucleation Theories 152.3.1 Classical Nucleation Theory 152.3.2 Experimental Tests of Nucleation Theories 192.4 Some Points towards a More Realistic View of Supersaturation and Crystallization 192.4.1 Concentration Fluctuations and ‘Spinodal Crystallization’ 192.4.2 Reduction of Supersaturation by the Formation of Clusters and Amorphous Intermediates 212.5 Thermodynamic and Kinetic Crystallization Pathways 222.6 Polymorph Control 252.7 Crystal Morphology and the Role of Additives and Selective Adsorption 282.7.1 Crystal Morphology 302.7.2 What Determines Adsorption of an Additive? 362.8 Properties of Single Crystals and Polycrystals 392.8.1 Electrical Polarization 392.8.2 Light Refraction and Birefringence 432.8.3 Mechanical Properties 44References 473 Examples of Crystals Challenging the Classical Textbook Mechanism 513.1 Some Biomineral Examples 513.1.1 Elongated Magnetite Nanocrystals in Magnetotactic Bacteria 523.1.2 Calcite with Complex Form and Single Crystal Behavior in Foraminifera 533.1.3 Calcite with Complex Form and Single Crystal Behavior in Sea Urchin Spines 563.1.4 Calcite Single Crystals with Complex Form in Coccoliths 573.1.5 Morphological Complexity Develops with Time 583.2 From Biology to Biomimetics: In Vitro Mineralization Examples 593.3 Biomorphs 683.4 Other Synthetic Examples 69References 714 Nonclassical Crystallization 734.1 Amorphous Precursors 754.2 Liquid Precursors 784.3 Oriented Attachment 834.4 Mesocrystals 96References 985 Self-Assembly and Self-Organization 103References 1066 Colloidal Crystals with Spherical Units: Opals and Colloidal Nanocrystals 107References 1117 Mesocrystal Systems 1137.1 Mesocrystals and Their Properties 1137.2 Early Reports on Mesocrystals 1147.3 One-Dimensional Mesocrystals 1177.4 Two-Dimensional Mesocrystals 1187.5 Mesocrystals in Biomineralization 1227.6 Mesocrystals in Gels 1297.7 Mesocrystals Formed without Additives 1357.8 Mesocrystals Formed with Simple Ion Additives 1387.9 Mesocrystals Formed with Polymer Additives 1427.10 Mesocrystals in Nonaqueous Systems 1527.11 Mesocrystals Formed via Solid-State Reactions 1577.11.1 Solid Matrices for Mesocrystal Formation 1577.11.2 Topotactic Reactions 1597.12 Liquid Crystals, Tactoids, Somatoids, and Schiller Layers 163References 1738 Mechanisms of Mesocrystal Formation 1798.1 Principal Mechanisms Leading to Mesocrystals 1798.2 Conditions for Mesocrystal Formation 1868.3 Alignment by Colloidal Forces, Capillarity and Other Short-Ranged Physical Fields 1908.3.1 Alignment by Capillary Forces 1908.3.2 Alignment by Hydrophobic Forces and Interface Energies 1928.3.3 Alignment by Minimization of the Interfacial Energy 1928.3.4 Alignment by Additive Coding of Nanoparticles 1948.3.5 Alignment by a Mechanical Stress Field 1968.4 The Role of Magnetic Fields 1988.5 The Role of Dipole and Polarization Forces 2048.5.1 Polarization Forces 2048.6 The Role of External Electric Fields 2198.7 Self-Similar Assembly and Shape Constraints 2228.8 Shaping of Mesocrystals 2268.9 Mesocrystals as Intermediates in Single Crystal Formation 228References 2339 Analysis of Mesocrystals 2379.1 Nucleation and Growth of Primary Nanoparticles 2389.2 Rapid Aggregation and Formation of Randomly Oriented Aggregates 2399.3 Mesocrystal Formation 2399.4 Fusion of the Mesocrystal to a Single Crystal/Ripening and Ion-Mediated Recrystallization  Towards an Outer Single Crystalline Shell 2409.5 Analytical Techniques for Mesocrystals 241References 24410 Tuning of Properties 247References 24911 A Unifying Crystallization Mechanism 251References 25512 Analogy between Oriented Attachment or Hierarchically Structured Crystals and Polymers 25712.1 Analogy between Oriented Attachment and Polymerization 25912.2 Structural Levels in Hierarchically Structured Crystals andBiopolymers 263References 26413 Summary and Outlook 26513.1 Summary 26513.2 Outlook 267References 270Index 271