CRYSTALLIZATION – SCIENCE AND TECHNOLOGY Edited by Marcello Rubens Barsi Andreeta Crystallization – Science and Technology Edited by Marcello Rubens Barsi Andreeta Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2012 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 Vana Persen Technical Editor Damir Jovic Cover Designer InTech Design Team First published September, 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@intechopen.com Crystallization – Science and Technology, Edited by Marcello Rubens Barsi Andreeta p. cm. ISBN 978-953-51-0757-6 Contents Preface IX Section 1 Fundamentals and Theoretical Aspects 1 Chapter 1 Crystallization in Glass Forming Substances: The Chemical Bond Approach 3 Elena A. Chechetkina Chapter 2 Crystallization Kinetics of Chalcogenide Glasses 29 Abhay Kumar Singh Chapter 3 Numerical Models of Crystallization and Its Direction for Metal and Ceramic Materials in Technical Application 65 Frantisek Kavicka, Karel Stransky, Jana Dobrovska, Bohumil Sekanina, Josef Stetina and Jaromir Heger Chapter 4 A Mathematical Model for Single Crystal Cylindrical Tube Growth by the Edge-Defined Film-Fed Growth (EFG) Technique 91 Loredana Tanasie and Stefan Balint Chapter 5 Crystallization in Microemulsions: A Generic Route to Thermodynamic Control and the Estimation of Critical Nucleus Size 121 Sharon Cooper, Oliver Cook and Natasha Loines Chapter 6 Chemical, Physicochemical and Crystal – Chemical Aspects of Crystallization from Aqueous Solutions as a Method of Purification 149 Marek Smolik Chapter 7 Recrystallization of Active Pharmaceutical Ingredients 183 Nicole Stieger and Wilna Liebenberg VI Contents Section 2 Applications, Techniques and Mineral Formation 205 Chapter 8 Preparation of Selected Ceramic Compounds by Controlled Crystallization Under Hydrothermal Conditions 207 Juan Carlos Rendón-Angeles, Zully Matamoros-Veloza and Kazumichi Yanagisawa Chapter 9 Fe-Based Nanocomposite Formed by Thermal Treatment of Rapid-Quenched Fe 81 B 13 Si 4 C 2 Alloy 243 Dragica M. Minić, Vladimir A. Blagojević and Dušan M. Minić Chapter 10 Crystallization of Iron-Containing Oxide-Sulphide Melts 271 Evgeniy Selivanov and Roza Gulyaeva Chapter 11 Real-Time Analysis to Evaluate Crystallization Processes 303 João F.Cajaiba da Silva, Andréia P. M. da Silva and Rodrigo C. de Sena Chapter 12 Phenacetin Crystallization: Cooling Regimes and Crystal Morphology 329 Humphrey A. Moynihan and Dawn M. Kelly Chapter 13 Macromolecular Crystallization Controlled by Colloidal Interactions: The Case of Urate Oxidase 349 Françoise Bonneté Chapter 14 Crystallization by Antisolvent Addition and Cooling 379 Marco Giulietti and André Bernardo Chapter 15 Thin Film Growth Through Sputtering Technique and Its Applications 397 Edgar Alfonso, Jairo Olaya and Gloria Cubillos Chapter 16 Crystallization of Ge:Sb:Te Thin Films for Phase Change Memory Application 433 J. J. Gervacio Arciniega, E. Prokhorov, F. J. Espinoza Beltran and G. Trapaga Chapter 17 Metal Induced Crystallization 461 Ahamad Mohiddon Mahamad and Ghanashyam Krishna Mamidipudi Chapter 18 ArF Excimer Laser Annealing of Polycrystalline Silicon Thin Film 481 Noriah Bidin and Siti Noraiza Ab Razak Contents VII Chapter 19 Oriented Lateral Growth and Defects in Polycrystalline- Silicon Thin Films on Glass Substrates 507 Kuninori Kitahara and Akito Hara Chapter 20 Crystallization, Fractionation and Solidification of Co-Magmatic Alkaline Series Sequentially Emplaced in the Carbonatite Complex of Tiruppattur, Tamil Nadu, India 535 R. Ramasamy Preface Crystallization is one of the first items of technological knowledge acquired by mankind. In fact, the use of crystallization processes can be considered as ancient as writing. One example of this is a Chinese document dating back to 2700 BC, which describes the process of artificial evaporation for the production of salt [1]. Crystallization is also one of the most interdisciplinary topics of research, ranging from inorganic to organic compounds, and crystals can be produced from melts, liquid solutions, vapors or even in the solid state. The nature of the crystallization process has been described by researchers with diverse scientific backgrounds, each one presenting a different facet of the theme, be it from the standpoint of Chemistry, Physics, Biology, Geology or Engineering. Despite its inherently high complexity, the crystallization process is part of our everyday lives: from ice-making in our homes or falling snow to the most state-of-the-art chemical and electronic industry. This book offers the reader an overview of the science and technology involved in different crystallization processes, compiled by researchers with different scientific backgrounds. In the first part of the book, entitled Fundamentals and Theoretical Aspects, the reader is introduced to various different perspectives of the crystallization process. The first two chapters review the crystallization processes of glasses. The first chapter describes crystallization using the chemical bond approach. This new approach, as presented by Chechetkina, is based on the hypothesis of initial reorientation, which is considered a specific pre-nucleation stage, and on the bond wave model, considered a carrier for collective processes in glass formers. Chapter two describes the crystallization of chalcogenide glasses, with Singh discussing the fundamentals of nucleation, growth and crystallization processes in amorphous glassy materials based on the classical ideas of crystallization. The next two chapters deal with aspects of the crystallization process using mathematical models. In chapter three, which contains a numerical model of the crystallization of steel, ductile cast iron and ceramic corundo-baddeleyite material, Kavicka and collaborators describe the optimization of the production and properties of these materials after casting. Chapter four consists of a theoretical modeling of the growth process of a single crystal in the shape of a cylindrical tube, obtained by the edge-defined film-fed growth (EFG) technique. Tanasie and Balint use this model to demonstrate that it can be employed in determining the pulling rate, and X Preface the thermal and capillary conditions of an actual experiment. In chapter five, Cooper and collaborators present a thermodynamic discussion about crystallization in microemulsions. The authors show that the critical nucleus can be estimated with good accuracy under conditions of thermodynamic control and that the stable form of a material can be identified and readily produced under ambient conditions. The authors of the last two chapters describe the recrystallization process. Smolik focuses his analysis on the chemical, physicochemical and crystal-chemical aspects of the recrystallization process, discussing its effects on the cocrystallization coefficient, D 2/1. Stinger and Liebenberg, in turn, review the aspects of recrystallization of active pharmaceutical ingredients (API). They draw attention to the possibility of the process creating undesirable polymorphic modifications, and the reason why some of these forms have gone undetected for decades. The second part of the book, Applications, Techniques and Mineral Formation, is dedicated to the practical application of crystallization processes and concepts. This section begins with Chapter 8, which describes the crystallization process under hydrothermal conditions. Rendón-Angeles and collaborators have contributed not only with an interesting review of the hydrothermal method, but have also presented results of synthesis of different perovskite oxides and mineral replacement reactions as a new approach to prepare inorganic materials. Chapters 9 and 10 describe crystallization in Fe-based compounds. Minić and collaborators use a technique to rapid-quench an iron-based compound, producing an amorphous alloy. They demonstrate that under the correct heat treatment, these alloys can be used as precursors in the preparation of nanocomposite materials composed of nanocrystals in the amorphous matrix. In chapter 10, Selivanov and Gulyaeva report on a study of the composition of metallurgical slag and the influence of iron on the different metals it contains. They show that iron oxidation and the ratio of calcium oxide to silicon oxide play a major role in determining the types of non-ferrous metals in crystallized slag. The next four chapters introduce techniques and discussions about aspects of organic and large molecule crystallization. In chapter 11, Silva and co-authors describe a technique to monitor the formation of adipic acid crystals in real time, which can be applied industrially in place of off-line measurements. They demonstrate that the off- line measurements used in industry to determine the onset of crystallization present a much higher error than the real-time analysis they have developed. In chapter 12, Moynihan and Kelly present a study of the crystallization of phenacetin. They discuss the influence of two different cooling procedures on the control of crystal size distribution. In the next work, in chapter 13, Françoise presents a review of macromolecular crystallization. He exemplifies this process by using urate oxidase, and shows that pH, salt and polymers play a crucial role when crystallization is controlled by colloidal interactions. In chapter 14, Giulietti and Bernardo describe their [...]... Se-As and Se-Ge series, the additions belong to other groups of Periodic Table (IV for Ge and V for As), so one can expect another property-composition behaviour Accordingly, 16 Crystallization – Science and Technology the V(N) and r(N) dependencies change in the same way in Se-As glasses (maximum on the both), in contrast with the behaviour in Se-Te and Se-S glasses, which display a maximum on V(N) and. .. in the r(N) graphs in Fig.5 for the as-prepared glasses and the G(N) graphs in Fig.8 for the aged glasses, and not only in the extrema location, 18 Crystallization – Science and Technology which coincides for every Se-X series, but also in the dependence shape which is qualitatively the same for the Se-Te, Se-As and Se-Cl series For the Se-S and Se-Ge series, the shapes are somewhat different One should... silica and enriched in volatile constituents such as H2O and CO2 With the low viscousness and high temperature of shonkinite magma, clinopyroxenes are crystallized with enrichment of Ca, Mg, Fe, Ti and Al and depletion of Si, Al, Na and K in low pressure zones towards the top of the magmatic column On the other hand, from the top of the magmatic column, sinking clinopyroxenes release Ca, Mg, Fe, Ti and. .. was introduced by Muscher in 1969 [42], has a long and controversial history, beginning from the 1920s up until the present (see [43] for an introduction) Currently, a large number of hypervalent molecules is known, and various methods of their theoretical description exist For a long time, one of the most popular was 10 Crystallization – Science and Technology the Pimentel’s model [44] of the electron-rich... Grove, and J.A Palermo, The early history of crystallization Journal of Chemical Education, 1956 33(8): p 373 Section 1 Fundamentals and Theoretical Aspects 1 Crystallization in Glass Forming Substances: The Chemical Bond Approach Elena A Chechetkina Institute of General and Inorganic Chemistry of Russian Academy of Sciences, Moscow, Russia 1 Introduction Glassy materials are strongly connected with crystallization. .. crystal nucleation and growth is possible [21] IReO means that neither nucleation nor crystal growth can proceed in a non-oriented - i.e., a truly “amorphous” - medium Since IReO is a simple activation process with the ΔG# barrier, the reoriented fraction increases exponentially with time, as the dotted line in Fig.2 shows 8 Crystallization – Science and Technology Fig 2 Isothermal crystallization after... non-linearity, spontaneous ordering and the memory effect discussed above are signs of a self-organizing system, a system that possesses various scenarios for evolution, depending upon the system’s nature and the information provided by external medium [66] When glass is considered as a self-organizing system with bond waves as the basis for self- 22 Crystallization – Science and Technology organization, one... populated with HVB), to the non-crystalline long-range order generated by bond waves Insofar as bond waves change their parameters and direction during melt cooling, being frozen in solid glass, the non-crystalline long-range order depends not only 4 Crystallization – Science and Technology on the substance under consideration but also on the sample prehistory This is a principal distinction from the ordinary... temperature As such, the problem of crystallization in glass can be considered as a competition between two types of order, and hypervalent bonds and their self-organization in the form of a bond wave play a central role in this process In Section 3 and Section 4, original crystallization experiments based on the above approach are described In Section 3, we consider crystallization in solid Se-X glasses,... discusses the crystallization, fractionation and solidification of a co-magmatic alkaline series emplaced sequentially in the carbonatite complex He shows that, as the first crystallization occurs, the composition of the parent magma evolves to become poor in alumina and silica, and acts as a primary magma in a closed magmatic chamber under a volatile enriched condition Later on, during the early crystallizations . CRYSTALLIZATION – SCIENCE AND TECHNOLOGY Edited by Marcello Rubens Barsi Andreeta Crystallization – Science and Technology Edited by Marcello Rubens Barsi Andreeta. Crystallization – Science and Technology, Edited by Marcello Rubens Barsi Andreeta p. cm. ISBN 978-953-51-0757-6 Contents Preface IX Section 1 Fundamentals and Theoretical. change their parameters and direction during melt cooling, being frozen in solid glass, the non-crystalline long-range order depends not only Crystallization – Science and Technology 4 on