Mesocrystals and nonclassical crystallization

Through both explanation and discussion, this title presents a complete review into mesocrystals, and accurately describes this relatively new study of established materials. This book also provides an introduction to other areas of crystallisation including self-assembly, classical crystallisation and colloidal crystals.

Key features:

Description of crystals as well as their formation processes and ways to modify them. Examines new ways towards the design of new materials and aids comprehension of the building principles of biominerals. Helps to explain many unusual observations made in the study of crystallisation.

Written by the professionals in this subject 'Mesocrystals: New Self-Assembled Structures' outlines the future potential of this topic within a variety of disciplines including engineering science, physics and chemistry, making it a versatile and valuable text.

Author Notes

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

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

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Table of Contents