Glass Nanocomposites: Synthesis, Properties and Applications
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Glass Nanocomposites: Synthesis, Properties and Applications provides the latest information on a rapidly growing field of specialized materials, bringing light to new research findings that include a growing number of technologies and applications. With this growth, a new need for deep understanding of the synthesis methods, composite structure, processing and application of glass nanocomposites has emerged.
In the book, world renowned experts in the field, Professors Karmakar, Rademann, and Stepanov, fill the knowledge gap, building a bridge between the areas of nanoscience, photonics, and glass technology. The book covers the fundamentals, synthesis, processing, material properties, structure property correlation, interpretation thereof, characterization, and a wide range of applications of glass nanocomposites in many different devices and branches of technology.
Recent developments and future directions of all types of glass nanocomposites, such as metal-glasses (e.g., metal nanowire composites, nanoglass-mesoporous silica composites), semiconductor-glass and ceramic-glass nanocomposites, as well as oxide and non-oxide glasses, are also covered in great depth. Each chapter is logically structured in order to increase coherence, with each including question sets as exercises for a deeper understanding of the text.
- Provides comprehensive and up-to-date knowledge and literature review for both the oxide and non-oxide glass nanocomposites (i.e., practically all types of glass nanocomposites)
- Reviews a wide range of synthesis types, properties, characterization, and applications of diverse types of glass nanocomposites
- Presents future directions of glass nanocomposites for researchers and engineers, as well as question sets for use in university courses
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Glass Nanocomposites - Basudeb Karmakar
Glass Nanocomposites
Synthesis, Properties and Applications
First Edition
Basudeb Karmakar
Klaus Rademann
Andrey L. Stepanov
Table of Contents
Cover image
Title page
Copyright
Foreword
Preface
Acknowledgments
Contributors
Short Biography of Editors
Editor-in-Chief
Editor
Editor
I: Introduction
Chapter 1: Fundamentals of Glass and Glass Nanocomposites
Abstract
Acknowledgments
1.1 Introduction
1.2 Fundamentals of Glass
1.3 Fundamentals of Glass Nanocomposites
1.4 Conclusions and Future Outlook
Exercises
II: Oxide Glass Nanocomposites
Chapter 2: Glass-Based Nanocomposites
Abstract
Acknowledgments
2.1 Introduction
2.2 Glasses with Metal Nanoparticles
2.3 Glass Ceramics with Metal Nanoparticles
2.4 Glasses with Metal Core Metal Oxide Shell Nanostructures and Their Optical Properties
2.5 Glass Metal Nanowire Composites and Their Electrical Properties
2.6 Nanocomposites Synthesized by Electrodeposition
2.7 Glass Silver Nanowire Composites and Their Dielectric Properties
2.8 Multiferroic Behavior of Glass Nanocomposites with a Core Shell Nanostructure
2.9 Semiconductor-Nanoglass Composites
2.10 Nanoglass-Mesoporous Silica Composites
2.11 Applications
2.12 Future Outlook
Exercises
Chapter 3: Crystallization and Growth Mechanisms of Nanostructures in Silicate Glass: From Complete Characterization Toward Applications
Abstract
3.1 Introduction
3.2 Synthesis
3.3 Characterization
3.4 Crystallization and Growth Mechanisms
3.5 Energy Related Applications
3.6 Conclusions and Summary
3.7 Future Outlook
Exercises
Chapter 4: Laser Annealing of Metal Nanoparticles Synthesized in Glasses by Ion Implantation
Abstract
Acknowledgments
4.1 Introduction
4.2 Ion Synthesis of MNPs in Glasses
4.3 Interaction of Excimer Laser Pulses with SLSG Containing Silver Nanoparticles
4.4 Interaction of Multipulses with SLSG Containing Silver Nanoparticles
4.5 Applications
4.6 Summary
Chapter 5: Enhanced Photoluminescence and Planar Waveguide of Rare-Earth Doped Germanium Oxide Glasses with Metallic Nanoparticles
Abstract
Acknowledgments
5.1 Introduction
5.2 Experimental Details
5.3 Results and Discussion
5.4 Summary
Chapter 6: Sol-Gel Synthesis of Metal Nanoparticle Incorporated Oxide Films on Glass
Abstract
6.1 Introduction
6.2 Properties of Metals in Nanoscale
6.3 Synthesis of Supported Metal Nanoparticle Films by In Situ and Ex Situ Methods
6.4 Characterization Techniques
6.5 Applications of Metal Nanoparticle Incorporated Metal Oxide Thin Films
6.6 Conclusions
6.7 Future outlook
Chapter 7: Nonlinear Optical Properties of Metal Nanoparticles in Silicate Glass
Abstract
Acknowledgments
7.1 Introduction
7.2 Nonlinear Absorption and Optical Limiting of Copper Nanoparticles
7.3 Nonlinear Refraction of Cu and Ag Nanoparticles
7.4 Applications
7.5 Summary
Chapter 8: Electrical Transport Properties of Ion-Conducting Glass Nanocomposites
Abstract
Acknowledgments
8.1 Introduction
8.2 Ion-Conducting Glass Nanocomposites
8.3 Theory of Ion Conduction and Relaxation in Glasses and Glass Nanocomposites
8.4 Preparation of Ion-Conducting Glass Nanocomposites
8.5 Characterization Techniques
8.6 Properties
8.7 Applications
8.8 Conclusions
8.9 Future Outlook
Exercises
Chapter 9: Plasmonic Antimony and Bismuth Oxide Glass Nanocomposites: Synthesis and Enhanced Photoluminescence
Abstract
Acknowledgments
9.1 Introduction
9.2 Theoretical Basis of Glass-Metal-NCs and Mechanism of Plasmon-Enhanced Photoluminescence in Glass-Metal-Lanthanide(III) Hybrid NCs
9.3 Objectives
9.4 Experimental
9.5 Results and Discussion
9.6 Conclusions
Chapter 10: Silver Glass Nanocomposites: Preparation, Properties, and Applications
Abstract
Acknowledgments
10.1 Introduction
10.2 Preparation and Properties of Silver Glass NCs
10.3 Applications
10.4 Summary and Future Outlook
Chapter 11: Functionality of Reversible Glass Nanocomposites and Their Applications
Abstract
Acknowledgments
11.1 Introduction
11.2 Reversible Photochromic Glass Nanocomposites
11.3 Reversible Radiophotoluminescent Glass Nanocomposites
11.4 Summary and Future Outlook
Chapter 12: Semiconductor Glass Nanocomposites: Preparation, Properties, and Applications
Abstract
Acknowledgments
12.1 Introduction
12.2 Semiconductors
12.3 Related Theory
12.4 Preparation
12.5 Properties
12.6 Applications
12.7 Conclusions
12.8 Future Outlook
Chapter 13: Advanced Glass-Ceramic Nanocomposites for Structural, Photonic, and Optoelectronic Applications
Abstract
Acknowledgments
13.1 Introduction
13.2 Synthesis and Characterization of GC Nanocomposites
13.3 GC Nanocomposites for Structural Applications
13.4 GC Nanocomposites for Photonic Applications
13.5 Ferroelectric GC Nanocomposites for Optoelectronic Applications
13.6 Conclusions
13.7 Future Outlook
III: Nonoxide Glass Nanocomposites
Chapter 14: Effects of Gamma-Irradiation and Ion Implantation in Chalcogenide Glasses
Abstract
Acknowledgments
14.1 Introduction
14.2 Experimental
14.3 Effects of Gamma-Irradiation in ChGs
14.4 Effects of Ion Implantation in ChGs
Chapter 15: Nanoglass and Nanostructured Chalcogenide Glasses
Abstract
Acknowledgments
15.1 Introduction
15.2 Nanoglass
15.3 Nanometal and Nanocrystallinity in ChGs
15.4 Summary and Future Outlook
Index
Copyright
William Andrew is an imprint of Elsevier
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This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.
Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
For information on all William Andrew publications visit our website at http://store.elsevier.com/
ISBN: 978-0-323-39309-6
Foreword
It is my pleasure and honor to contribute the foreword for this book entitled, Glass Nanocomposites: Synthesis, Properties and Applications edited by Basudeb Karmakar, Klaus Rademann, and Andrey L. Stepanov. Due to rapid growth of the area of glassy materials as well as glassy nanocomposites, this book will be a useful mine of state-of-the-art information for those who are pursuing work, research, and education in this domain. A wide range of synthesis techniques, properties, and applications of these nanocomposites is already recognized and further progress is being explored at a remarkable rate.
The book covers different types of synthesis, properties, and applications of various kinds of glass nanocomposites. The editors have succeeded in assembling some of the leading expert groups of authors in this field to cover different topics in this area, which would otherwise have been very difficult to cover just by one or two people. In fact, the authors have succeeded in covering a wide spectrum of glasses starting from oxide, nonoxide to metallic nanostructured glasses. Diverse synthesis techniques such as melt-quenching, sol-gel, laser annealing, inert gas condensation, magnetron sputtering, etc., have been described. Various properties, for example, physical, thermal, optical, nonlinear, optoelectronic, spectroscopic, microscopic, electrical, magnetic, etc., have been considered.
In the beginning, a broadly based, scholarly introduction has been provided on the fundamentals of glass and glass nanocomposites. Subsequently, glass-based nanocomposites, crystallization, and growth mechanisms of nanostructures in silicate glass, laser annealing of ion implanted metal glass nanocomposites, enhanced photoluminescence in different plasmonic metal glass nanocomposites, sol-gel synthesis of metal nanoparticle incorporated oxide films, nonlinear optical properties of metal nanoparticles in glass, reversible, and nonreversible silver glass nanocomposites, semiconductor glass nanocomposites, glass-ceramic nanocomposites, effects of gamma-irradiation and ion implantation in chalcogenide glasses, and finally, nanoglass and nanostructured chalcogenide glasses were described with special emphasis on their synthesis, various properties, and applications.
Obviously, there is a constant demand for developing novel glass nanocomposites with improved properties and functionalities for their future technological utilization. This motivation has resulted in a rapid growth of glass nanocomposites in the last several years primarily due to the availability of new strategies for synthesis, tools for characterization, and endeavors for applications. The editors and authors have tried to build this book as a knowledge bank on glass nanocomposites embodying the majority of those developments. As a consequence of the rapidly growing diversity of the field of glass nanocomposites, further progress in this area is likely to depend critically on the availability of overviews in which the wide spectrum of the growing number of new results is presented in a critical way. In fact, the crucial tasks of these overviews has to be threefold: to summarize the existing knowledge, to focus critically on the new insights gained by the recently published papers, and to create the basis on which the next generation of researchers can safely stand when they try to look beyond the presently existing limits. Hence, this book most likely will not only be an outstanding source of information for materials scientists working on glassy materials, but also for many interdisciplinary scientists specifically from chemistry, physics, ceramics, metallurgy, and various disciplines of engineering.
Prof. Dr. Herbert Gleiter, Institut für Nanotechnologie, KIT, Eggenstein, Germany, Herbert Gleiter Institute of Nanoscience, Nanjing University of Science and Technology, Nanjing, Jiangsu, P. R. China
Preface
In 1959, Richard Phillips Feynman (Nobel Laureate, Physics, 1965), the American theoretical physicist in his now-famous visionary talk on There's Plenty of Room at the Bottom explored the immense possibilities afforded by miniaturization and consequently established the foundation for the future wonders of nanoscience and nanotechnology. What was supposed to be impossible then, now is the real world—the nano world. At present, after more than half a century later, nobody would doubt considering the twenty-first century as the Nano Era.
Nanoscience and nanotechnology are based on the smallest unit of matter to engineer new materials and devices through monitoring atom-by-atom and molecule-by-molecule, targeting at achieving superior or unprecedented properties and performance, utilizing the atomic- or molecular-scale architectures.
In a composite material, there are at least two types of materials, one is the host and the other is the guest. In the nanocomposites, the guest has the dimension of the range 1-100 nm. Glass is an excellent host material owing to its several inherent superior properties compared to those of other similar encapsulating hosts. This fact has attracted the researchers exploring many types of glass nanocomposites depending on the varieties, sizes, and shapes of the nano guests as well as processing parameters. As a result, there are a wide range of reports in the published domain of the literature on glass nanocomposites. But there is no suitable book reviewing all these developments and recent literature. This book intends to fill this gap. This is as a consequence of the fact; a rapid development in a particular field requires a book which covers the forefront research in a widespread range including material synthesis, property evaluation, and applications.
This book contains 15 chapters which are divided into three parts. Part I is the introduction and it describes the fundamentals of glass and glass nanocomposites (Chapter 1). Part II covers oxide glass based different nanocomposites. These are glass-based nanocomposites (Chapter 2), crystallization, and growth mechanisms of nanostructures in silicate glass: from complete characterization towards applications (Chapter 3), laser annealing of metal nanoparticles synthesized in glasses by ion implantation (Chapter 4), enhanced photoluminescence and planar waveguide of rare-earth doped germanium oxide glasses with metallic nanoparticles (Chapter 5), sol-gel synthesis of metal nanoparticle incorporated oxide films on glass (Chapter 6), nonlinear optical properties of metal nanoparticles in silicate glass (Chapter 7), electrical transport properties of ion-conducting glass nanocomposites (Chapter 8), plasmonic antimony and bismuth oxide glass nanocomposites: synthesis and enhanced photoluminescence (Chapter 9), silver glass nanocomposites: preparation, properties, and applications (Chapter 10), functionality of reversible glass nanocomposites and their applications (Chapter 11), semiconductor glass nanocomposites: preparation, properties, and applications (Chapter 12), and advanced glass-ceramic nanocomposites for structural, photonic and optoelectronic applications (Chapter 13). Part III discusses nonoxide glass based different nanocomposites, which are effects of gamma-irradiation and ion implantation in chalcogenide glasses (Chapter 14), and nanoglass and nanostructured chalcogenide glasses (Chapter 15). The book covers all the types of glasses starting from oxide, nonoxide to metallic nanoglasses; diverse synthesis techniques (e.g., melt-quenching, sol-gel, laser annealing, inert gas condensation, magnetron sputtering, etc.); various properties (e.g., physical, thermal, optical, nonlinear, photonic, optoelectronic, spectroscopic, microscopic, electrical, magnetic, etc.); and numerous applications.
This is a timely book. The chapters have been written by an excellent group of expert authors based on their knowledge and work experience accumulated through research and teaching in the area of glass nanocomposites. We have tried to create this book as a treasure of up-to-date understanding and information on various types of glass nanocomposites.
In spite of our best effort to make this book perfect, there may be some mistakes. If you find anything that needs to be corrected, please feel free to e-mail us at basudebk@cgcri.res.in or basudebk@hotmail.com.
This book is envisioned for the post graduate students, researchers, educators, scientists, professionals, practitioners in industry, and R & D managers and planners, not only of the glass and materials science and engineering, but also for many interdisciplinary areas like chemistry, physics, ceramics, metallurgy, electronics, optoelectronics, photonics, and electrical engineering.
We believe that this book will be very helpful to the readers to broaden their knowledge and insight into the different subjects of this interdisciplinary area. We also hope that this book will certainly enhance the rapid progress of science and technology of glass nanocomposites.
We wish you a very pleasant journey on your way to discovering the fascinating world of glass nanocomposites.
Basudeb Karmakar, CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
Klaus Rademann, Institut für Chemie, Humboldt-Universität zu Berlin, Berlin, Germany
Andrey L. Stepanov, Russian Academy of Sciences, Kazan, Russian Federation, Kazan Federal University, Kazan, Russian Federation, Kazan National Research Technological University, Kazan, Russian Federation, May 2015
Acknowledgments
Basudeb Karmakar
Klaus Rademann
Andrey L. Stepanov
This book emerged as a result of the experience accumulated by all of us during many years of research and teaching in the area of glass science and technology. Many people have contributed to this book directly or indirectly. We greatly appreciate their encouragement and support that they extended during the writing of this book.
We would like to thank the authors whose research results and ideas are presented here. We are indebted to them. We would also like to thank the individuals, trustees, and publishers who have permitted the reproduction of their photographs and figures.
We express our profound and sincere gratitude and appreciation to all of the chapter authors who made this book possible, for their hard work and contributions.
We are very grateful to Prof. Dr. Herbert Gleiter for his contribution of the foreword of this book and providing some valuable latest information on the nanoglass.
We thank the referees for their critical reading, suggestions, and constructive criticism.
We also wish to express our great appreciation to our publisher, Elsevier Inc., for their trust and encouragement. Our special thanks are due to Jeff Freeland, Editorial Project Manager, Elsevier Inc., for constant help and communication in the progress of this book and success of this project. Finally, we would like to thank the many unnamed editorial and production members of Elsevier Inc. for their expert work.
Last, but certainly not least; we are deeply indebted to our families. Without their sacrifice, support, and inspiration, this book is impossible.
Contributors
S. Bhattacharya Siliguri Institute of Technology, Darjeeling, West Bengal, India
D. Chakravorty Indian Association for the Cultivation of Science, Kolkata, India
S. Chatterjee Indian Association for the Cultivation of Science, Kolkata, India
C.B. de Araújo Universidade Federal de Pernambuco, Recife, PE, Brazil
G. De CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
C. Dey CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
M. Garai CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
A. Hoell Helmholtz Zentrum Berlin für Materialien und Energie, Berlin, Germany
B. Karmakar CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
L.R.P. Kassab Faculdade de Tecnologia de São Paulo, FATEC-SP, CEETEPS, São Paulo, SP, Brazil
T.S. Kavetskyy Drohobych Ivan Franko State Pedagogical University, Drohobych, Ukraine, and The John Paul II Catholic University of Lublin, Lublin, Poland
A. Mitra CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
A.R. Molla CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
K. Rademann Humboldt-Universität zu Berlin, Berlin, Germany
V.S. Raghuwanshi Humboldt-Universität zu Berlin, Berlin, Germany and Monash University, Melbourne, Victoria, Australia
S.K. Saha Indian Association for the Cultivation of Science, Kolkata, India
N. Sasmal CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
N. Shasmal CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
S.P. Singh Federal University of Sao Carlos, Sao Carlos, São Paulo, Brazil
T. Som Humboldt-Universität zu Berlin, Berlin, Germany
A.L. Stepanov
Russian Academy of Sciences
Kazan Federal University, and Kazan National Research Technological University, Kazan, Russian Federation
A. Tarafder CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
Short Biography of Editors
Editor-in-Chief
Basudeb Karmakar is now the Senior Principal Scientist and Head, Glass Science & Technology Section, CSIR-Central Glass & Ceramic Research Institute, Kolkata, India. He is also the Professor of the Academy of Scientific and Innovative Research (AcSIR) and Fellow of the Indian Institute of Ceramics (FIICeram). He received his post-graduate degree in Inorganic Chemistry from the Calcutta University, Kolkata and earned his Ph.D. in Materials Science from the Jadavpur University, Kolkata. He has over 34 years of research and teaching experience. His major research areas are on the preparation, characterization, and property evaluation of different types of glasses (viz., silica, silicate, borate, borosilicate, phosphate, fluorophosphate, antimony oxide, bismuth oxide, etc.), glass-ceramics, ceramic oxide powders, gels, etc., synthesized employing either by the melt-quenching or sol-gel techniques. His notable R&D contributions are in the area of metal-glass nanocomposites, semiconductor-glass nanocomposites, rare-earth doped glass and glass-ceramic nanocomposites, photoluminescent glasses, radiophotoluminescent (RPL) glass, lead-free environmentally friendly glass powders and pastes for plasma display panel (PDP), thermally cyclable glass sealant for solid oxide fuel cell (SOFC), high density radiation shielding window glass, Nd-doped phosphate laser glass, ultra-low expansion transparent glass-ceramics, machinable glass-ceramics, chalcogenide glasses, high-purity silica glass, etc. He guided nearly 30 graduate and post-graduate students to accomplish their project or thesis work on glass, glass nanocomposites, and glass-ceramic nanocomposites. Under his supervision, four students received the Ph.D. degree and currently four more students are working for their Ph.D. dissertation on glass, glass nanocomposites, or glass-ceramic nanocomposites. He is the recipient of 12 different prestigious awards. He is a DAAD (Germany) fellow and visited Germany, Russia, and Czech Republic in connection with research. He is the peer-reviewer of about 35 international journals and life member of seven different professional institutions. He has published more than 110 research papers in international peer-reviewed journals (Total citations: 1297; h-index: 21), 90 contributions in International and National Conferences/Symposia and invited presentations, three book chapters and 11 patents. He was involved and completed more than 25 R&D projects on glass and glass-ceramics. His current research interests include the areas such as efficiency enhancement of silicon solar cell using plasmonic metal-glass hybrid nanocomposites, semiconductor-glass hybrid nanocomposites, different functional glasses and glass-ceramic nanocomposites, photoluminescent glasses, chalcogenide glasses, thermally cyclable glass sealant for solid oxide fuel cell, etc.
Editor
Since 1993, Klaus Rademann has been Full Professor in the area of physical and theoretical chemistry in the Institute of Chemistry. He belongs to the Faculty of Natural Sciences located in Adlershof, Berlin, Germany. The faculty is part of the world famous Humboldt-Universität zu Berlin. In 2015, he became Dean of Studies and Teaching for 6000 science students in Adlershof. He recently invented a new method for Advanced Chemistry Teaching (ACT) for Bachelor’s and Master’s students. His research is generally interdisciplinary and systematically based on co-operations with nonuniversity institutions: Helmholtz-Zentrum Berlin für Materialien und Energie (HZB) and BESSY II, the Federal Institute for Materials Research and Testing (BAM), and the Fritz-Haber-Institute. Here he participates in the International Max Planck Research School (IMPRS), which covers a wide range of experimental and theoretical approaches to the study of the properties of complex materials. He appreciates working with students from all over the world.
Rademann worked in industry at BASF-The Chemical Company (1967–1974), studied radio chemistry, physical chemistry, physics and mathematics at FU Berlin (1974–1981) towards a diploma degree in chemistry (1981). He received a doctoral degree in Physical Chemistry (Dr. rer. nat. 1983) in Berlin, being supervised by Prof. Baumgärtel. He did post-doctoral research work (1983–1985) in Tel-Aviv with Prof. Even and Prof. Jortner in the field of energy transfer on a picosecond timescale in the gas phase and on VYCOR® glasses, which exhibit fractal structures. Rademann’s work on metal-to-insulator transitions of divalent clusters (Hg, Cd, Zn) as a function of size was completed in Prof. Hensel’s group at Philipps-University in Marburg/Lahn between 1985 and 1989. He researched as Privatdozent for Physical Chemistry at Philipps-Universität in Marburg/Lahn (1990–1993).
Research in the group of Rademann at the Humboldt-Universität in the Physical Chemistry Department is strongly focused on functionalized nanoparticles of copper, silver, gold, and palladium at surfaces (a) and in solutions for catalytic applications of colloidal nanoparticles (b). A third focus (c) is on the preparation of noble metals and oxides in glassy matrices (SIMO glasses) for the exploration of energy transfer processes. Luminescent glassy materials are produced for optical up- and down conversion processes as well as for warm white light emissions. Particularly interesting is the change of properties of metal nanoparticles exactly at the borderline between chemical bonding (localized electrons) and delocalized electrons (plasmonics) with relevance to energy conversion mechanisms.
Editor
Andrey L. Stepanov was born in Kazan, Russia (USSR), in 1963. He received the Physical-mathematical degree, the Ph.D. and Dr. Sci. degrees from the Kazan Federal University, Kazan, Russia, in 1985, 1991, and 2009, respectively. The title of his Dr. Sci. degree is Synthesis and optical properties of metamaterials with metal nanoparticles.
Since 1992, Stepanov has been with the Department of Radiation Physics of Kazan Physical-Technical Institute, Russian Academy of Sciences. In 1997–1999, he was a Research Fellow at the Sussex University, Brighton, UK (group of Prof. P. D. Townsend) with the support from the Royal Society/NATO Fellowships. From 1999 to 2003, Stepanov was a Research Fellow of the RWTH Aachen University (Rheinisch-Westfälische Technische Hochschule Aachen) in Germany (group of Prof. U. Kreibig) with support from the Alexander von Humboldt Foundation and DFG. During 2003–2004 he was granted by Lise Meitner Fellowship from Austrian Scientific Society to stay in Karl-Franzens-University in Graz, Austria (group of Prof. J. R. Krenn and Prof. F. R. Aussenegg). In 2004, 2006, 2010, and 2011. Stepanov was a Visiting Research Fellow in Laser Zentrum Hannover in Germany with support from the DAAD, DFG and the Alexander von Humboldt Foundations (group of Prof. B. Chichkov). From 2009 he was in Kazan Federal University, Russia. From 2010 to 2012 he got a professorship in the Kazan National Research Technological University, Russia. In 2013, he was granted by the National Scholarship of the Slovak Republic from Slovak Academic Information Agency to do his study in Institute of Physics of Slovak Academy of Sciences. Main research subjects of his interest are nanooptics, nanoplasmonics, nanophotonics, metal nanoparticles, nonlinear optics, laser annealing, and ion implantation. He has more than 200 publications in periodic journals, 10 patents, more than 18 invited book chapters and three monographs. According of the ISI Web of Knowledge database, Stepanov has more than 2500 citations in scientific publications and his Hirsch index is 27.
I
Introduction
Chapter 1
Fundamentals of Glass and Glass Nanocomposites
B. Karmakar CSIR-Central Glass and Ceramic Research Institute, Kolkata, India
Abstract
This chapter begins with a brief introduction of this book. Then it describes several important aspects of the fundamentals of glass and glass nanocomposites (GNCs). In the fundamentals of glass section, it covers topics such as glass transformation, fictive temperature of glass, definition of glass, structural theories of glass formation, kinetic theory of glass formation, synthesis of glasses (e.g., melt-quenching technique and sol-gel processing) and glass-ceramics, structure of glasses, and vibrational, namely infrared (IR) and Raman spectroscopies of glasses. IR and Raman spectra of various glasses are discussed elaborately and their band assignments are listed with current literature for benefit of the investigators. In the section of fundamentals of GNCs, the basic concepts of composite, nanocomposite (NC), and GNC have been presented. In addition, different types of GNCs such as metal-GNC, semiconductor-GNC, glass-ceramic NC, and nanoglass have been described with the state-of-the-art literature.
Keywords
Glass
Definition
Structural theory
Kinetic theory
Infrared spectra
Raman spectra
Synthesis
Glass-ceramics
Glass nanocomposite
Metal-glass nanocomposite
Semiconductor-glass nanocomposite
Glass-ceramic nanocomposite
Nanoglass
Outline
1.1 Introduction 4
1.2 Fundamentals of Glass 4
1.2.1 Introduction 4
1.2.2 Glass Transformation and Fictive Temperature 6
1.2.3 Definition of Glass 7
1.2.4 Structural Theories of Glass Formation 11
1.2.4.1 Zachariasen’s Random Network Theory 11
1.2.4.2 Dietzel’s Field Strength Theory 12
1.2.4.3 Sun’s Single Bond Strength Theory 12
1.2.5 Kinetic Theory of Glass Formation 13
1.2.6 Synthesis of Glasses 16
1.2.6.1 Melt-Quenching Technique 16
1.2.6.2 Sol-Gel Processing 17
1.2.7 Synthesis of Glass-Ceramics 19
1.2.8 Structure of Glasses 21
1.2.9 Vibrational Spectroscopy of Glasses 22
1.2.9.1 Infrared Spectroscopy 23
1.2.9.2 Raman Spectroscopy 29
1.3 Fundamentals of Glass Nanocomposites 34
1.3.1 Composite 34
1.3.2 Nanocomposite 36
1.3.3 Glass Nanocomposite 36
1.3.3.1 Metal-Glass Nanocomposite 38
1.3.3.2 Semiconductor-Glass Nanocomposite 41
1.3.3.3 Glass-Ceramic nanocomposite 42
1.3.3.4 Miscellaneous Glass-Ceramic Nanocomposite 44
1.3.3.5 Nanoglass 45
1.4 Conclusions and Future Outlook 45
Exercises 46
Acknowledgments 46
References 46
Acknowledgments
The author thanks Mr. Kamal Dasgupta, Acting Director and Dr. R. Sen, Head, Glass Division of CSIR-CGCRI for their support to carry out this work. He also acknowledges Council of Scientific and Industrial Research (CSIR), New Delhi, India for the financial support under the CSIR-TAPSUN Project NWP0055.
1.1 Introduction
Now we are moving through the emerging period of nanoscience and nanotechnology which has started growing fast since 1983. Nanoscience is learning the phenomena of particle size range of 1-100 nm and nanotechnology is the ability to create the articles containing novel materials of this size range with specific functional properties. Glass is an excellent host material. It is superior to other materials owing to several unique properties, such as high optical transparency, compositional flexibility, structural rigidity, and finally, property tailoring suitability. All these properties of glasses offer the opportunity to produce nanoparticles of various crystals, metals, semiconductors, oxides, etc., in the glass matrices to obtain different types of glass nanocomposites (GNCs) with novel and unprecedented properties. In fact, the subject of GNCs is an interdisciplinary area of chemistry, physics, materials science, and engineering. Nevertheless, the technology of GNCs is not new. It was started during the Roman Era (753 BC to 476 AD). The most famous example is the Lycurgus Cup that was produced around 400 AD, incorporating a small amount of nanosized (50-70 nm) gold (40 ppm Au) and silver (330 ppm Ag) in a silicate glass matrix. It is observed that there are a wide variety of reports in the published literature on GNCs. But there is no suitable book reviewing all these developments and recent literature. This book intends to fill that gap. Before discussing different kinds of GNCs which is the mandate of this book, the fundamentals of glass and GNCs are given in this chapter for the readers’ benefit.
1.2 Fundamentals of Glass
1.2.1 Introduction
Glass is an ancient product of human civilization. The oldest manmade opaque glass was found in Egyptian potteries which are dated back to 8000 BC. Humans are attracted to glass due to its unique properties, such as optical transparency, structural rigidity, compositional flexibility, property tailoring suitability, and durability. All these properties make glass befitting both for traditional as well as advanced technological uses. Windows, containers, lighting, lenses, and hand-crafted art objects are the some of the examples of traditional uses. Laser glass, optical communication fibers, bioglass, armor glass, solar glass, etc. are some of the examples of advanced technological uses. Some examples of the many purposes and their corresponding products showing various uses of glass are depicted in Figure 1.1.
Figure 1.1 Different purposes of use of glass (middle column) and their corresponding products (right column).
It is necessary to know the hierarchical relationships of different types of glasses to understand the GNCs. This is depicted in Figure 1.2. From this figure, it is evident that glass may be mainly divided into two classes: inorganic and organic glasses, depending on their chemical composition. Inorganic glasses are of two types: natural (obsidian or pechsteins) and synthetic (manmade or artificial) glasses, depending on their origin. Natural glasses were found in volcanic rocks whereas humans produced the synthetic glasses by melting the raw materials and applying their manufacturing skill. Again, the synthetic glasses can broadly be divided into the categories: common and specialty glasses. The glasses that we find around us and that are used for general purposes in our daily life (e.g., windows, tumblers, bottles, lamps, spectacles, mirrors, etc.) are collectively known as common glass. The specialty glasses (e.g., laser glass, radiation shielding glass, dosimeter, optical fiber, ultra-low expansion transparent glass-ceramics, bioglass, micronutrient glass, etc.) are those which possess specific functional properties and are used to meet some specific demands of advanced and sophisticated technologies. Thus, the specialty glasses may also be called the functional glasses considering their functional activities. The GNCs are, therefore, a separate group of specialty or functional glasses where the nanosized (1-100 nm) reinforcements or dispersants remain embedded in the different glass matrices. Based on the chemical composition of the glass matrix, the GNCs may be either inorganic or organic GNCs. This is described later in detail in Section 1.3.
Figure 1.2 Hierarchical relationships of different types of glasses and glass nanocomposites.
1.2.2 Glass Transformation and Fictive Temperature
The glass transformation behavior is conventionally described by the diagram based on either the volume or enthalpy changes as a function of temperature, owing to both the volume and enthalpy of a glass-forming system performing in a similar manner. This is illustrated in Figure 1.3. If the liquid is allowed to cool, the atomic structure of the molten mass will gradually change with temperature and will exhibit a correlation between the structure and temperature. Very slow cooling to any temperature below the melting temperature (Tm) of the liquid would customarily transform into the crystalline state. This transformation from liquid to crystal would occur with a sudden decrease in volume or enthalpy. Under this condition the volume or enthalpy reaches a value very close to that of the crystal. Further cooling results in a very small decrease in volume or enthalpy and attains the exact values of the crystal.
Figure 1.3 Volume and enthalpy changes as a function of temperature associated with cooling and heating of a glass-forming system showing glass transformation range, glass transformation, and fictive temperature.
If the liquid is cooled avoiding crystallization, a supercooled liquid state is attained. As the temperature is decreased, the structure of the liquid continues to rearrange without sudden decrease in volume or enthalpy as a result of the occurrence of discontinuous structural rearrangements. However, the viscosity of the liquid increases upon further cooling. This increase in viscosity gradually becomes so high that the atoms of the liquid cannot completely reorganize themselves to the equilibrium liquid structure due to shortage of experimental time, that is, the cooling time. It would attain the equilibrium liquid structure if enough time is given. As a result, the volume or enthalpy initiates to depart from the equilibrium line progressively reducing the slope, until it attains the heat capacity of the frozen liquid. Under this situation, the viscosity of the liquid becomes exorbitantly very high and is no longer dependent of temperature. The temperature range lying between the limits of the volume or enthalpy of the equilibrium liquid and frozen liquid (solid) is called glass transformation range and the frozen liquid (solid) is the glass.
It is seen from Figure 1.3 that the fast and slow cooling rates permit the volume or enthalpy to follow the equilibrium curves to higher and lower temperatures, respectively. Similarly, the glass transformation regions will also shift toward the higher and lower temperatures respectively. This is due to the fact that the glass obtained with a faster cooling rate will have the higher enthalpy than that of the glass obtained with the slower cooling rate. If the glass and the supercooled liquid lines are extrapolated, they intersect at a temperature which is defined as fictive temperature (Tf). For fast and slow cooling rates, we get two different fictive temperatures and they are symbolized as Tfslow and Tffast, respectively. The fictive temperature is, therefore, dependent on the thermal history of the glass and not a fixed temperature. It makes available a useful parameter for discussion of the effect of changes in cooling rate on glass structure and properties. Therefore, it is necessary to define a more accurate term. It is appropriate to use just a single temperature as an indication of the onset of the glass transformation range during heating of a glass. This temperature is termed as the glass transformation temperature or glass transition temperature (Tg). It can be seen from the Figure 1.3 that the Tg usually lies between the Tfslow and Tffast. It can be determined from the changes in either thermal analysis (e.g., differential scanning calorimeter (DSC) or differential thermal analyzer (DTA)) or thermal expansion (dilatometric) curves.
1.2.3 Definition of Glass
It is well known that the nature of glass is complex but its preparation is relatively simple. The concept of glass has changed gradually with time with the progress of science and technology. This has happened mainly due to the discovery of sophisticated glass characterization instruments and broadening the understanding of the nature of glass. As a result, we find different types of definitions of glass in the literature proposed by different authors at different times. These definitions have been recorded in Table 1.1 with respect to the year of publication and author. The facts described in the table provide us with a clear picture of altering of the definition of glass with time and from one author to another.
Table 1.1
Diverse Definitions of Glass
At the beginning, it is found that the traditional definition of glass is Glasses are supercooled liquids or supercooled as solids. This definition is found in the present-day publications [1] as well as in older publications [2]. It is very difficult to identify its correct author and the year of publication. In 1930, Simon [3] defined glass from the point of view of a physical chemist as In the physicochemical sense, glass is a frozen-in undercooled liquid. But one thing is clear from these definitions that in the early stages glass was prepared only by cooling (quenching) the molten glass (the liquid) of higher temperature down to its solidus temperature. Other processes of glass preparation were perhaps unknown at that time.
Zachariasen [2] defined glass based on the energy content of the glass network as A glass has an extended three-dimensional network and its energy content is comparable to that of the corresponding crystal but without periodicity and symmetry. He defined glass in this manner because of the fact that the atoms in glass are linked together by forces essentially the same as in crystals. Tammann [4] demarcated glass as In the glassy state, there are solids, un-crystallized materials.
According to Morey [5] A glass is an inorganic substance in a condition which is continuous with, and analogous to, the liquid state of that substance, but which, as the result of having been cooled from the fused condition, has attained so high a degree of viscosity as to be, for all practical purposes, rigid and … cooled to a rigid condition without crystallizing. In 1945, Committee C-14, ASTM (American Society for Testing Materials) [6,7] approved the standard definition of glass which is Glass is an inorganic product of fusion which has cooled to a rigid condition without crystallizing. At that time, the purpose of formulating a definition was to specify a glass product that was then accepted by the technologists, engineers, manufacturers, and users of glass without misunderstanding. But in the light of the present-day knowledge of glass, this definition seems to not be appropriate. The major disagreements are found with the words inorganic
and fusion.
Besides the inorganic materials, there are many organic (e.g., compounds, polymers, plastics, liquids, etc.) and metallic materials which are known to form glass or conceivably to transform into the glassy state. There are other techniques of glass preparation, such as sol-gel process, solid-state amorphization, and chemical vapor deposition, which do not require fusion of the glass component(s). Thus, fusion is not the only technique to prepare glass. Yes, one can argue that the word fusion
is not only used to mean melt or liquefy, but also to mean synthesis, union, combination, mixture, blending, etc.
The following two definitions are based on viscosity which is a liquid-state property. According to Jones [8] A glass … is a material, formed by cooling from the normal liquid state, which has no discontinuous change … at any temperature, but has become more or less rigid through a progressive increase in its viscosity. Winter [9] defined glass as Glass is a solid body below the temperature, Tv, for which the viscosity, η, equals 10¹⁵ poises (1 poise = 1 dPa.s). It may be mentioned here that the viscosity of aluminum at room temperature is approximately equal to 10¹⁵ poises.
On the other hand, in 1960, Mackenzie [10] for the first time considered both the inorganic and organic materials in defining glass as Any isotropic material, whether it is inorganic or organic, in which three-dimensional atomic periodicity is absent and the viscosity of which is greater than about 10¹⁴ poise, may be described as a glass. (By the three-dimensional atomic periodicity, we imply a long-range order, dependent on the material in question, of greater than, say, 20 angstrom units).
In 1968, Materials Advisory Board, United State National Research Council (US-NRC) [11] accepted the following definition as a standard for glass. Glass is an X-ray amorphous solid which exhibits the glass transition, the latter being defined as that phenomenon in which a solid amorphous phase exhibits with changing temperature a more or less sudden change in the derivative thermodynamic properties, such as heat capacity and expansion coefficient, from crystal-like to liquid-like values.
Doremus [12] defined glass as Glass is an amorphous solid. A material is amorphous when it has no long-range order, that is, when there is no regularity in the arrangement of its molecular constituents on a scale larger than a few times the size of these groups. Cooper and Gupta [13] have described an operational definition of glass constructed on structural relaxation time which is Glass is an isotropic material with long structural relaxation time (τ) such as 10³ s.
Elliott [14] defined glass as A glass is an amorphous solid which exhibits a glass transition. Zarzycki [15] described as A glass is a non-crystalline solid exhibiting the phenomenon of glass transition. Varshneya [16] described it as Glass is a noncrystalline or simple amorphous solid with a liquid-like structure. Gupta [17] defined it as A non-crystalline solid is a ‘glass’ if its short range order (SRO) equals to that of its melt. In 1997, Shelby [18] defined it as A glass is an amorphous solid completely lacking in long range, periodic atomic structure, and exhibiting a region of glass transformation behavior. Any material, inorganic, organic, or metallic, formed by any technique, which exhibits glass transformation behavior is a glass. It is observed that during the period of 1968-1997, some preferred the term amorphous solid
whereas the others preferred to use the term noncrystalline solid
to define glass. Fortunately, Gupta [17] thermodynamically distinguished the three terms: noncrystalline solid, amorphous solid, and glass. A noncrystalline solid has the disordered three-dimensional network with short-range order (SRO) without periodicity. In the thermodynamic viewpoint, a noncrystalline solid may or may not exhibit the glass transition temperature (Tg). The noncrystalline solids which exhibit the glass transition temperature (Tg) are glasses, on the other hand, which do not exhibit the glass transition temperature (Tg) are amorphous solids. Therefore, all amorphous solids are noncrystalline solids, but not the glass.
In 2009, Wright [19] defined glass as Glass is an inorganic material that has been quenched from the liquid to a rigid state without crystallizing. This definition is not correct because only the inorganic materials, excluding organic and metallic materials, were considered as glass. In a consequence of Wright’s paper, Varshneya and Mauro [20] in 2010 defined glass as Glass is a solid having a non-crystalline structure, which continuously converts to a liquid upon heating. By the final part of the definition, continuously converts to a liquid upon heating, these authors excluded the amorphous solids, which do not exhibit the glass transition temperature (Tg).
Considering the statements of the altered definitions of glass formulated by different authors at different time, it is seen that two authors, Gupta [13,17] and Varshneya [16,20] have changed their definitions with time [13,16,17,20] based on the progress of understanding.
To cut a long story short, in our opinion, for straightforwardness, it is better to define glass as Glass is a noncrystalline solid which exhibits the glass transformation range in the volume (or enthalpy)—temperature relationship (see Figure 1.3).
1.2.4 Structural Theories of Glass Formation
There are several structural theories of glass formation, for example, Goldschmidt’s cation-anion radius ratio rule, Zachariasen’s random network theory, Dietzel’s field strength theory, Sun’s single bond