CRYSTALLIZATION AND MATERIAL SCIENCE OF MODERN ARTIFICIAL AND NATURAL CRYSTALS Edited by Elena Borisenko and Nikolai Kolesnikov Crystallization and Materials Science of Modern Artificial and Natural Crystals Edited by Elena Borisenko and Nikolai Kolesnikov Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2011 InTech All chapters are Open Access distributed under the Creative Commons Attribution 3.0 license, which allows users to download, copy and build upon published articles even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. After this work has been published by InTech, authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. As for readers, this license allows users to download, copy and build upon published chapters even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. Notice Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published chapters. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book. Publishing Process Manager Sasa Leporic Technical Editor Teodora Smiljanic Cover Designer InTech Design Team First published January, 2012 Printed in Croatia A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Crystallization and Materials Science of Modern Artificial and Natural Crystals, Edited by Elena Borisenko and Nikolai Kolesnikov p. cm. ISBN 978-953-307-608-9 free online editions of InTech Books and Journals can be found at www.intechopen.com Contents Preface IX Part 1 Structure and Properties of Advanced Inorganic Materials 1 Chapter 1 Crystallographic Observation and Delamination Damage Analyses for Thermal Barrier Coatings Under Thermal Exposure 3 Kazunari Fujiyama 17 Chapter 2 Nucleation and Crystal Growth in Phase Separated Glasses in the Lithium Silicate System 23 G. A. Sycheva Chapter 3 Elaboration of a Specific Class of Metamaterial: Glass in Single Crystal 49 Bertrand Poumellec, Matthieu Lancry, Santhi Ani-Joseph, Guy Dhalenne and Romuald Saint Martin Part 2 Inorganic/Organic Materials for High Technology 77 Chapter 4 Effect of Amino Acid Additives on Crystal Growth Parameters and Properties of Ammonium Dihydrogen Phosphate Crystals 79 P.V. Dhanaraj and N.P. Rajesh Chapter 5 Topochemical Conversion of Inorganic–Organic Hybrid Compounds into Low-Dimensional Inorganic Nanostructures with Smart Control in Crystal-Sizes and Shapes 99 Deliang Chen Chapter 6 Synthesis of Cobalt-Zinc Phosphates Templated by Polyamines 139 Yue Ding, Niu Li, Daiping Li, Ailing Lu, Naijia Guan and Shouhe Xiang VI Contents Part 3 Biomineralization 155 Chapter 7 Unusual Crystal Formation in Organisms - Exceptions that Confirm Biomineralization Rules 157 Davorin Medaković and Stanko Popović Chapter 8 Biomimetic and Bioinspired Crystallization with Macromolecular Additives 185 Il Won Kim Part 4 Crystal Growth for Health Protection 201 Chapter 9 Freezing Properties of Disaccharide Solutions: Inhibition of Hexagonal Ice Crystal Growth and Formation of Cubic Ice 203 Tsutomu Uchida, Satoshi Takeya, Masafumi Nagayama and Kazutoshi Gohara Chapter 10 Crystal Growth of Pharmaceuticals from Melt 225 J.S. Redinha and A.J. Lopes Jesus Chapter 11 Alternative Protein Crystallization Technique: Cross-Influence Procedure (CIP) 249 Ivana Nemčovičová and Ivana Kutá Smatanová Part 5 Molecular Crystals 277 Chapter 12 Optical Properties of Molecular Crystals: The Effect of Molecular Packing and Polymorphism 279 Silvia Tavazzi, Leonardo Silvestri and Peter Spearman Chapter 13 Parity Violation in Unstirred Crystallization from Achiral Solutions 305 Marian Szurgot Preface Crystal growth is a fundamental phenomenon, which provides the basis for a wide variety of naturally occurring processes, and an astonishing range of diverse human activities. This book includes a representative collection of contemporary studies on crystal growth across various aspects, including; problems concerning crystal growth in high technology, medicine, pharmacy, and mineralization of marine organisms; modern techniques developed for crystal growth of inorganic and organic crystals from melt, solutions, via chemical synthesis, and atmospheric plasma spraying; phase transitions in solid and liquid states; a particular problem of vitrification and formation of glass-crystalline composites in complex systems of oxides; interaction between organic and inorganic materials leading to formation of the advanced class of inorganic/organic composites; macromolecular crystallization, biomineralization, and biomimetic crystallization; modern investigative techniques, such as x-ray diffraction (XRD), scanning electron microscopy (SEM), electron back scattering diffraction (EBSD), energy dispersive x-ray spectroscopy (EDS), x-ray electron probe microanalysis (EPMA), IR spectroscopy (IRS), Raman light spectroscopy (RS), photoluminescence (PL), optical microscopy, thermogravimetric (TG) and differential thermal analysis (DTA), used to study phase transitions, crystal structure, morphology, microstructure and properties of the grown materials. The first chapter Structure and Properties of Advanced Inorganic Materials contains the studies of thermal barrier ceramic coatings, in particular; yttrium-partially stabilized zirconium (PSZ) produced by atmospheric plasma spraying; the role of oxide formation in crack nucleation and growth in PSZ; optical microscopy, SEM, EBSD, used to study morphology of grain structure, distribution of crystal orientations (crystallographic texture) and crystal symmetry of the coatings. EDS was applied to find a correlation between formation of Cr and Al oxides, and crack propagation in the coating layers. The second chapter considers the nucleation and crystal growth in phase separated lithium silicate glasses, and studies the dependences of crystal growth rate in the lithium silicate systems on SiO 2 content, and heating temperature It has been found that, - comtrary to the perception -phase separation does not facilitate the conditions for the formation and growth of crystals.On the contrary, in some cases even retards the crystal growth process. As a result of the studies, optimum compositions and X Preface annealing regimes are recommended for formation of the lithium silicate glass-ceramic materials for practical applications. Third chapter deals with Cu-SiO2-GeO2 metamaterials consisting of glass and crystalline phase, grown by the floating zone technique in the pseudo-ternary system; Eutectic crystallization, phase composition, microstructure, and optical properties of the grown materials are studied, and self-organization of a structure is examined, depending on growth parameters and chemical composition, to find optimal fiber sizes and filling factor. Crystal state of the materials is studied by x-ray diffraction, EBSD and Fourier transformation techniques. These results in combination with EPMA data and analysis of diffusion of the components are used to revise the pseudo- ternary diagram. A phase boundary of vitrification for a silica glass containing Cu is demonstrated in graphic form. Shape and crystallography of the etched crystalline matrix and glass fibers are studied, and increase in a difference of refraction indexes in the self-organized structure and optical band gap opening caused by fiber etching are analyzed. Within the second section of the book Inorganic/Organic Materials for High Technology, the effect of amino acid additives on crystal growth of ammonium dihydrogen phosphate (ADP) is studied; a metastable zone width of pure and doped ADP is measured; a dependence of induction period of nucleation on supersaturation is investigated; the effect of amino acid additives on crystal growth conditions, including crystal growth rate is discussed. Powder x-ray diffraction (XRD) experiments confirm that pure and doped crystals are single phased. High resolution XRD (HRXRD) proves high perfection of the doped crystals. Some optical, electric and piezoelectric properties of the pure and doped ADP are studied. These materials are regarded as promising for application in non-linear optic, and they are used as piezoelectric crystals. The following chapter is a study of topochemical conversion from inorganic-organic hybrid precursors to inorganic nanoplates and nanofilms. Oriented films were produced from WO 3·H2O and WO3 tungsten oxide nanoplates through dropping– evaporation process. Topochemical conversion of tungstate-based inorganic-organic hybrid belts to W2N nanoplates is considered. Average particle size calculated from XRD patterns is 3.2 nm. TEM images indicate that the nanoplates are composed of nanocrystals. Application fields of the nanoplates are shown; WO3 nanoplates are used as a photocatalyst. An amount of O 2 generated when using WO3 nanoplates for visible- light-induced water splitting is greater than that of commercial WO 3 powders by an order of magnitude. The enhanced photocatalytic properties should be attributed to the developed specific surface area and high crystal perfection of the synthesized WO3 crystal nanoplates. WO 3 (α-MoO3) gas sensors were fabricated and tested. The third chapter of this section describes open-framework structures of metal phosphates synthesized under hydrothermal or solvothermal conditions in the presence of linear polyamines used as the structure-directing agents (SDA). [...]... Fig 8 Matching of SEM observations and IPF map of as-sprayed sample Crystallographic Observation and Delamination Damage Analyses for Thermal Barrier Coatings Under Thermal Exposure (a) Location of observation (b) Bottom portion Fig 9 Matching of IPF maps and SEM image for the sample exposed at 900ºC for 500h 11 12 Crystallization and Materials Science of Modern Artificial and Natural Crystals (c) Middle... statistics of distributions of enantiomeric excess of laevorotatory (L) and dextrorotatory (D) NaBrO3 crystals grown from aqueous solution A character of the distribution depending on growth conditions is studied and a conclusion is drawn on the effect of temperature, supersaturation, crystal growth rate, a type of crystallizer, handedness of seeds on a relative percentage of L and D -crystals, and racemates... effect of crystallographic characteristics on micro cracking in TBCs by upgrading EBSD analysis techniques for more precise crystalline system’s identification and damage evaluation 22 Crystallization and Materials Science of Modern Artificial and Natural Crystals 6 References [1] Okazaki, M., The Potential for the Improvement of High Performance Thermal Barrier Coatings (Review), Material Science. .. difficulties in preparing the observation surface of TBCs and in identifying the exact crystal systems We demonstrate the current status for visualizing the splat morphologies in top coat by EBSD and depict some problems in applying the technique EDS(Energy Dispersive Spectroscopy) 4 Crystallization and Materials Science of Modern Artificial and Natural Crystals analyses and indentation tests are also used as... decreasing trend was not monotonic The area fraction of pores showed similar levels exposed at 900°C for 500h and at 1000°C for 75h 6 Crystallization and Materials Science of Modern Artificial and Natural Crystals A Top coat Bond coat Substrate A (A-A : Observed portion) 500μm (a)As sprayed 500μm (b)900ºC 100h 500μm (c)900ºC 300h Crystallographic Observation and Delamination Damage Analyses for Thermal Barrier... Optical microscope observation of the cross section at 900 ºC exposure tests 500μm Fig 4 Optical microscope observation of the cross section at 1000 ºC-50h exposure test 100 Exposure hours at 900˚C 500 1000 50 Exposure hours at 1000˚C 75 100 As sprayed Fig 5 Optical microscope observation of top coat 8 Crystallization and Materials Science of Modern Artificial and Natural Crystals 100 Exposure hours... shows the local zoomed up IPF maps with SEM image of green circle region in Fig.12 before and after indentation test This map clearly indicated the transgranular cracking path from the indentation corner and coalesced with the pre-existing crack across relatively large particles 10 Crystallization and Materials Science of Modern Artificial and Natural Crystals 10μm 100μm (a)Observed portion(SEM image)... well-illustrated scientific description of modern alternative techniques used in macromolecular crystallization of proteins It considers general principles of macromolecular crystallization and finds correlations between the nucleation and growth kinetics, and the phase diagram Crystallization of a protein in presence of a precipitant is considered on a basis of twodimensional solubility diagram There... Alternative crystallization techniques involve additives, which affect crystallization Additive screening, use of cofactors, ligands and heavy-atom ligands are considered Salting out is described as the precipitation process in which solute– solute interactions play an important role The effect of pH of additives on crystallization kinetics of proteins is considered The final section of this book, Molecular Crystals, ... features of molecular crystalline structure However, in this section the focus is on physical properties, which are of interest for technical applications General problem of statistics of the spontaneous breakage of chiral symmetry in crystallization processes and distribution of left (L) and right-handed (D) forms in molecules or crystals are studied Preface In the first chapter optical properties of prototypical . CRYSTALLIZATION AND MATERIAL SCIENCE OF MODERN ARTIFICIAL AND NATURAL CRYSTALS Edited by Elena Borisenko and Nikolai Kolesnikov Crystallization and Materials Science . Spectroscopy) Crystallization and Materials Science of Modern Artificial and Natural Crystals 4 analyses and indentation tests are also used as the tools for investigating the sintering of top coatings. of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Crystallization and Materials Science of Modern Artificial and Natural Crystals,