**Meet the editor**

Marcello Rubens Barsi Andreeta earned his BSc degree in Physics in 1994, his MSc degree in Applied Physics in 1996 and his PhD in Materials Science and Engineering in 2001 from the Physics Institute of São Carlos (IFSC), University of São Paulo (USP), Brazil. His major field of research is crystal growth from melts, particularly of oxide compounds. His research interests include solid

state lasers, X-ray diffraction, Raman spectroscopy and AFM microscopy. Currently, he is developing new crystalline compounds for optical and electric devices using the Laser-Heated Pedestal Growth technique at the Crystal Growth and Ceramic Materials Laboratory (IFSC-USP) in São Carlos, SP, Brazil.

Contents

**Preface IX** 

Elena A. Chechetkina

Abhay Kumar Singh

**Section 1 Fundamentals and Theoretical Aspects 1** 

Chapter 1 **Crystallization in Glass Forming Substances: The Chemical Bond Approach 3** 

Chapter 3 **Numerical Models of Crystallization and Its** 

**Technical Application 65**  Frantisek Kavicka, Karel Stransky, Jana Dobrovska, Bohumil Sekanina, Josef Stetina and Jaromir Heger

**Growth (EFG) Technique 91**  Loredana Tanasie and Stefan Balint

Chapter 5 **Crystallization in Microemulsions:** 

and Natasha Loines

Marek Smolik

Sharon Cooper, Oliver Cook

Chapter 2 **Crystallization Kinetics of Chalcogenide Glasses 29** 

**Direction for Metal and Ceramic Materials in** 

Chapter 4 **A Mathematical Model for Single Crystal Cylindrical Tube Growth by the Edge-Defined Film-Fed** 

> **A Generic Route to Thermodynamic Control and the Estimation of Critical Nucleus Size 121**

Chapter 7 **Recrystallization of Active Pharmaceutical Ingredients 183** 

Chapter 6 **Chemical, Physicochemical and Crystal – Chemical Aspects of Crystallization from Aqueous Solutions as a Method of Purification 149** 

Nicole Stieger and Wilna Liebenberg

## Contents

## **Preface XIII**


X Contents


Contents VII

Chapter 19 **Oriented Lateral Growth and Defects in Polycrystalline-Silicon Thin Films on Glass Substrates 507** 

> **Solidification of Co-Magmatic Alkaline Series Sequentially Emplaced in the Carbonatite Complex**

**of Tiruppattur, Tamil Nadu, India 535** 

Kuninori Kitahara and Akito Hara

Chapter 20 **Crystallization, Fractionation and** 

R. Ramasamy

Noriah Bidin and Siti Noraiza Ab Razak

Chapter 19 **Oriented Lateral Growth and Defects in Polycrystalline-Silicon Thin Films on Glass Substrates 507**  Kuninori Kitahara and Akito Hara

VI Contents

**Section 2 Applications, Techniques and Mineral Formation 205** 

**Compounds by Controlled Crystallization Under** 

Juan Carlos Rendón-Angeles, Zully Matamoros-Veloza

Chapter 10 **Crystallization of Iron-Containing Oxide-Sulphide Melts 271** 

João F.Cajaiba da Silva, Andréia P. M. da Silva

**Treatment of Rapid-Quenched Fe81B13Si4C2 Alloy 243**

Chapter 8 **Preparation of Selected Ceramic**

and Dušan M. Minić

Chapter 11 **Real-Time Analysis to Evaluate** 

Françoise Bonneté

and Rodrigo C. de Sena

**Crystal Morphology 329** 

Chapter 13 **Macromolecular Crystallization Controlled**

Marco Giulietti and André Bernardo

**and Its Applications 397** 

Chapter 16 **Crystallization of Ge:Sb:Te Thin Films for** 

Chapter 18 **ArF Excimer Laser Annealing of Polycrystalline** 

Noriah Bidin and Siti Noraiza Ab Razak

Chapter 17 **Metal Induced Crystallization 461**  Ahamad Mohiddon Mahamad and Ghanashyam Krishna Mamidipudi

**Silicon Thin Film 481** 

Chapter 15 **Thin Film Growth Through Sputtering Technique** 

Edgar Alfonso, Jairo Olaya and Gloria Cubillos

**Phase Change Memory Application 433**  J. J. Gervacio Arciniega, E. Prokhorov, F. J. Espinoza Beltran and G. Trapaga

and Kazumichi Yanagisawa

**Hydrothermal Conditions 207** 

Chapter 9 **Fe-Based Nanocomposite Formed by Thermal** 

Evgeniy Selivanov and Roza Gulyaeva

Chapter 12 **Phenacetin Crystallization: Cooling Regimes and** 

Humphrey A. Moynihan and Dawn M. Kelly

Chapter 14 **Crystallization by Antisolvent Addition and Cooling 379** 

**by Colloidal Interactions: The Case of Urate Oxidase 349** 

**Crystallization Processes 303** 

Dragica M. Minić, Vladimir A. Blagojević

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

backgrounds.

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

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

## 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

#### XIV 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, D2/1. 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.

Preface XI

work on the sugar crystallization process using an antisolvent approach. They demonstrate that the addition of alcohol or ketone, combined with the use of a suitable cooling system, can improve sugar crystallization. The authors show that this decreases the system's viscosity and also causes the organic antisolvent and the solute to compete for water, thereby segregating the solute from the solution and promoting

Thin films are the theme of the next five chapters. We begin with a review of the sputtering technique for thin film deposition. In chapter 15, Alfonso and co-workers discuss the physicochemical parameters involved in the formation of well crystallized thin films, using the sputtering technique. Arciniega and co-authors, in chapter 16, discuss the crystallization of Ge:Sb:Te thin films and the viability of their use as phase change memory devices. In chapter 17, Mohamad and Mamidipudi review the work on metal-induced crystallization in silicon thin films. The authors describe the possible mechanisms involved in this process and discuss Sn and Cr-induced crystallization of silicon thin films. The use of an Excimer laser in the copper-induced crystallization of silicon thin films is discussed by Bidin and Razak in chapter 18. The authors used an Excimer laser to promote surface annealing of the film, creating the condition necessary for the silicon thin film to recrystallize. They also demonstrate that this procedure allows for the production of large grain silicon thin films for potential use in ultra-large-scale integrated circuit devices. In chapter 19, the authors also discuss the use of an Excimer laser in silicon thin film crystallization. Kitahara and Hara investigate the lateral growth orientation of silicon thin films on glass substrates, and report that relatively small defect densities are observed in the case of pure Si films.

This book concludes with a discussion about the formation of minerals through a natural crystallization process. Ramasamy describes the carbonatite complex of Tiruppattur, Tamil Nadu, India. The author 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 of calcium-rich clinopyroxenes, the residual magma becomes impoverished in 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 Al and accumulate Na and Al, with

Finally, I would like to thank the authors for their hard work and patience. Not only did they work on the formatting and language review of their chapters, but also did a

crystallization.

crystallization of subsolidus aegirine.

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 offline 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 work on the sugar crystallization process using an antisolvent approach. They demonstrate that the addition of alcohol or ketone, combined with the use of a suitable cooling system, can improve sugar crystallization. The authors show that this decreases the system's viscosity and also causes the organic antisolvent and the solute to compete for water, thereby segregating the solute from the solution and promoting crystallization.

X Preface

forms have gone undetected for decades.

a new approach to prepare inorganic materials.

in crystallized slag.

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, D2/1. 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

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

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

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 offline 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 Thin films are the theme of the next five chapters. We begin with a review of the sputtering technique for thin film deposition. In chapter 15, Alfonso and co-workers discuss the physicochemical parameters involved in the formation of well crystallized thin films, using the sputtering technique. Arciniega and co-authors, in chapter 16, discuss the crystallization of Ge:Sb:Te thin films and the viability of their use as phase change memory devices. In chapter 17, Mohamad and Mamidipudi review the work on metal-induced crystallization in silicon thin films. The authors describe the possible mechanisms involved in this process and discuss Sn and Cr-induced crystallization of silicon thin films. The use of an Excimer laser in the copper-induced crystallization of silicon thin films is discussed by Bidin and Razak in chapter 18. The authors used an Excimer laser to promote surface annealing of the film, creating the condition necessary for the silicon thin film to recrystallize. They also demonstrate that this procedure allows for the production of large grain silicon thin films for potential use in ultra-large-scale integrated circuit devices. In chapter 19, the authors also discuss the use of an Excimer laser in silicon thin film crystallization. Kitahara and Hara investigate the lateral growth orientation of silicon thin films on glass substrates, and report that relatively small defect densities are observed in the case of pure Si films.

This book concludes with a discussion about the formation of minerals through a natural crystallization process. Ramasamy describes the carbonatite complex of Tiruppattur, Tamil Nadu, India. The author 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 of calcium-rich clinopyroxenes, the residual magma becomes impoverished in 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 Al and accumulate Na and Al, with crystallization of subsolidus aegirine.

Finally, I would like to thank the authors for their hard work and patience. Not only did they work on the formatting and language review of their chapters, but also did a

#### XVI Preface

fantastic job in following the proposed editorial guidelines. Their dedication has enabled us to produce a book with new insights, containing crucial and very useful information for researchers working in this field, while simultaneously creating a comprehensive text about crystallization processes that may serve as a starting point for readers with different backgrounds.

#### **Dr. Marcello Rubens Barsi Andreeta**

Crystal Growth and Ceramic Materials Group, Department of Physics and Material Science, Physics Institute of São Carlos, University of São Paulo, São Carlos, SP, Brazil

#### Reference

Schoen, H.M., C.S. Grove, and J.A. Palermo, *The early history of crystallization.* Journal of Chemical Education, 1956. 33(8): p. 373.
