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Handbook of Advanced Ceramics

Materials, Applications, Processing, and Properties

Second Edition

Shigeyuki Somiya

Editor-in-Chief

Professor Emeritus of Tokyo Institute of Technology, Japan

Table of Contents

Cover image

Title page

Copyright

Dedications

Preface to the First Edition

Preface to the Second Edition

Acknowledgments to the First Edition

Acknowledgments to the Second Edition

List of Editors

List of Contributors

Fine Ceramics

Part 1: Methods for Characterization of Advanced Ceramics

1.1: Electron Microscopy

Chapter 1.1.1. The Latest Analytical Electron Microscope and its Application to Ceramics

1 Introduction

2 General Overview of Analytical Electron Microscope

3 Transmission Electron Microscopy

4 Scanning Transmission Electron Microscopy

5 Analysis Method

6 Application of Analytical Electron Microscopy to Ceramics

7 Conclusion

References

Part 2: Advanced Carbons

Chapter 2.1. Advanced Carbon Materials

1 Carbon Materials

2 Chemical Bonding and Carbon Families

3 Structure

4 Carbonization and Graphitization

5 Various Carbon Materials

6 Importance of Textures in Carbon Materials

References

Chapter 2.2. Novel Carbon-Based Nanomaterials: Graphene and Graphitic Nanoribbons

1 Introduction

2 Theoretical Studies on Physical–Chemical Properties of Graphene Nanoribbons

3 Defects in Graphene and Graphene Nanoribbons

4 Synthesis Methods of Graphene and Graphitic Nanoribbons

5 Role of Chemical Doping in Graphene Nanoribbons

6 Experimental Detection of Edge-States in Graphene Nanoribbons

7 Graphene Applications

8 Future Work

Acknowledgments

References

Chapter 2.3. Nanodiamond—An Emerging Nano-carbon Material

1 Diamond as ceramics

2 Discovery of Nano Single-Crystalline Diamond

3 Characteristic Properties and Behaviors of NSCD

4 Potential Applications of NSCD

5 Summary and Perspectives

Acknowledgments

References

Chapter 2.4. Catalytic Carbons – Cathode Catalytic Carbons

1 Introduction

2 Carbon Alloys

References

Chapter 2.5. Nuclear Graphite

1 Introduction

2 Outline of HTGRS

3 R&DS for VHTR Developments

4 Concluding Remarks

References

Chapter 2.6. Carbon Materials for Si Semiconductor Manufacturing

1 Introduction

2 Silicon Semiconductor Manufacturing Processes

3 Manufacturing Processes for Polycrystalline Silicon

4 Manufacturing Process for Monocrystalline Silicon

5 Processes of Machining a Silicon Single-Crystal Ingot

6 Manufacturing Process of Epitaxial Wafers

7 CVD Membrane Forming Process

8 Dry-Etching Process

9 Ion Implantation Process

10 Thermal Diffusion Process

Chapter 2.7. Isotropic Graphite for Electric Discharge Machining

1 What is Electric Discharge Machining?

2 What is a Mold?

3 Choice Between Electric Discharge Machining and Cutting to Best Suit the Purpose

4 Principle of Electric Discharge Machining

5 Kinds of Electrode used in Electric Discharge Machining

6 Kinds of Graphite Electrode Material for Electrical Discharge Machining

7 High-performance Graphite

8 Concluding Remarks

Chapter 2.8. Carbon Fibers

1 Background

2 PAN-based Carbon Fibers

3 Pitch-based Carbon Fibers

4 Rayon and Bio-based Precursors

Acknowledgments

References

Chapter 2.9. Activated Carbon Fibers

1 Introduction

2 Preparation of ACFS

3 Activated Carbon Nanofibers (ACNFs) and Activated Multiwalled Carbon Nanotubes (AMWCNTS)

4 Some Examples on ACF Applications

5 Conclusions

Acknowledgments

References

Chapter 2.10. Carbon–Carbon Composites

1 Fibrous Preforms

2 Processing of C/CS

3 Properties of C/CS

4 Oxidation Protection of C/CS

5 Applications of C/CS

References

Chapter 2.11. Carbon Materials used for Polymer Electrolyte Fuel Cells

1 Introduction

2 Operating Principles and Characteristics of PEFCs

3 Separators

4 Current Collectors

5 Electrocatalyst

6 Proton Conductor

7 Conclusion

References

Chapter 2.12. Carbons for Supercapacitors

1 Electric Double-Layer Capacitors

2 General Aspects of Carbons for EDLCs

3 Template Method for Pore Structure Control of Electrode Carbons

4 Nitrogen-Enriched Carbons

5 Exfoliated Carbon Fibers

6 Carbon-Coated Transition-Metal Carbides

7 Carbon Xerogels with Conductive Polymer Nano-Coating

8 Summary

References

Part 3: Advanced Non-Oxide Ceramics

Chapter 3.1. Silicon Carbide and Other Carbides: From Stars to the Advanced Ceramics

1 Introduction

2 Carbides in Nature

3 Transition Metal Carbides

4 Covalent Carbides

5 Synthesis

6 Extreme Environment Application

7 Importance of Natural and Synthetic Carbides

References

Chapter 3.2. Review and Overview of Silicon Nitride and SiAlON, Including their Applications

Introduction

Sub Chapter 1 High Thermal Conductivity Silicon Nitride Ceramics

Sub Chapter 2 Development of Silicon Nitride for High-Temperature Use

Sub Chapter 3 Low-Friction Si3N4 Ceramics with Carbon Fiber

Sub Chapter 4 Frictional Properties and Microstructure of Si3N4 Containing Mo and Fe Compounds Prepared by Hot Pressing [1,2]

Sub Chapter 5 Low-cost Fabrication of Silicon Nitride Ceramics

Sub Chapter 6 High-Strength and High-Toughness Silicon Nitride Ceramics

Sub Chapter 7 Development of Fine-Grained Silicon Nitride Ceramics with a Small Amount of Sintering Additive

Sub Chapter 8 Development of Advanced α-SiAlON Ceramics

Sub Chapter 9 Applications

9.1 Automotive Applications

9.2 Industrial Applications

Chapter 3.3. Recent Progress in Zr(Hf)B2 Based Ultrahigh Temperature Ceramics

1 Introduction

2 Processing of Zr(Hf)B2-Based UHTCs and their Composites

3 Oxidation Behavior of Zr(Hf)B2 Ceramics and Composites

4 Mechanical Properties

5 Deformation Behavior of UHTCs

6 Summary

Acknowledgment

References

Chapter 3.4. Ceramic Bearings and Seals

1 Introduction

2 Ceramic Bearings

3 Ceramic Sliding Bearings and Mechanical Seals

4 Corrosion of Ceramic Sealing and Bearing Materials

References

Part 4: Advanced Ceramics Related to Energy Generation and Storage

Chapter 4.1. Hydrogen-Production Technologies Using Amorphous Silica Membranes

1 Introduction

2 Pore-Size Control of Silica Membranes Prepared by Chemical Vapor Deposition

3 Membrane Performance Under Hydrothermal Conditions

4 Prediction of the Performance of Membrane Reactors

5 Dehydrogenating Organic Hydrides

6 Decomposing Hydrogen Sulfide

7 Methane Steam Reforming

8 Summary

References

Chapter 4.2. All-Solid-State Li Battery for Future Energy Technology

1 Introduction

2 Honeycomb-Type 3D Battery

3 All-Solid-State Battery With 3DOM Structure

4 Summary

References

Chapter 4.3. Advanced Ceramics for Nuclear Applications

1 Introduction

2 Basics of Neutron Irradiation Effects with Matter

3 Radiation Damage of Advanced Ceramics

4 Advanced Ceramics for Fission Reactors and Fuel Cycle

5 Advanced Ceramics for Fusion Reactors

6 Conclusion

References

Part 5: Advanced Optical Ceramics

Chapter 5.1. Glass-Ceramics

1 Introduction

2 Glass-Ceramics With Minimal Thermal Expansion

3 Glass-Ceramics With Special Optical Properties

4 Machinable Glass-Ceramics

5 High-strength and High-toughness Glass-ceramics

6 Biomaterials

7 Products With Special Electrical and Magnetic Properties

8 Applications in Energy Technology

References

Chapter 5.2. New Glasses for Photonics

1 Introduction

2 Nonlinear Optical Glass

3 Magneto-optical Glass

4 Other Important Glasses for Photonics

5 Summary

References

Chapter 5.3. Optical Resonators and Amplifiers: Fiber, Waveguide, and Spherical Lasers

1 Introduction

2 Fiber Lasers and Fiber Amplifiers

3 Spherical Cavity Glass Lasers

4 Concluding Remarks

References

Part 6: Advanced Electroceramics

Chapter 6.1. Multi-layered Ceramic Capacitors

1 High-Capacitance MLCCs With Nickel Internal Electrodes

2 Nonlinear Dielectricity of MLCCs

3 Capacitance Aging in MLCCs

4 Size Effect of BaTiO3 Ceramics

5 Reliability of MLCCS – Lifetime in HALT

6 Computer Simulation and Further Prospective of MLCC Technology

References

Chapter 6.2. Lead-Free Piezoelectric Ceramics

1 Introduction

2 Perovskite-structured Piezoelectric Ceramics

3 Summary

References

Chapter 6.3. Heat Capacity Study of Functional Ceramics

1 Introduction

2 Thermodynamic Properties of Formation and Growth of Ferroelectric Nanoregion in Relaxors

3 Thermodynamic Studies of Giant Particle-Size Effect on the Phase Transition in Dielectric Crystals

4 Conclusion

References

Chapter 6.4. New Frontiers Opened Up Through Function Cultivation in Transparent Oxides

1 Introduction

2 Research Concept and Strategy

3 Light metal TCO: 12CaO·7Al2O3 with Built-in Nano-Porous Structure

4 Transparent Amorphous Oxide Semiconductors

5 Iron-Pnictide Superconductors

6 Future Challenge: Ubiquitous Element Strategy

Acknowledgments

References

Chapter 6.5. Rapid Prototyping of Ceramics

1 Introduction

2 Process Chain in Ceramic Solid Freeform Fabrication

3 3D Additive Manufacturing Techniques

4 Data File Formats

5 Applications of RP Techniques

References

Part 7: Advanced Bio- and Medical Ceramics

Chapter 7.1. Biomorphous Ceramics from Lignocellulosic Preforms

1 Introduction

2 Lignocellulosic Cellular Preforms

3 Processing

4 Microstructure and Mechanical Properties

5 Applications

6 Conclusions

References

Chapter 7.2. Application of a Quartz Crystal Microbalance with Dissipation for In Situ Monitoring of Interfacial Phenomena between Bioceramics and Cells

1 Introduction

2 Interface Between Bioceramics and Cells

3 In Situ Monitoring of Interfacial Phenomena

4 Summary

References

Chapter 7.3. Anticancer Diagnoses and Treatments Using Ferrite Nanoparticles and Bulk

1 Introduction

2 High-Performance MRI Contrast Agent

3 Mediators for Self-controlled Induction Heating

4 Sentinel Lymph Node Mapping for Monitoring Cancer Metastasis

References

Part 8: Advanced Combustion Engine Parts

Chapter 8.1. Diesel Particulate Filters

1 Introduction

2 Diesel Particulate Matter (DPM)

3 Limits

4 Working Principle of DPFS

5 Design and Properties of DPFS

6 Ceramic DPFS

7 Market Situation

8 Outlook

References

Part 9: Advanced Ceramics Related to Mechanical Properties and Fracture Mechanics

Chapter 9.1. Mechanical Properties of Ceramics

1 Important Properties

2 Elastic Properties

3 Plasticity, Compressive Strength, Yield Strength, and Hardness

4 Thermal Strains and Thermal Stresses

5 Thermal Diffusion

6 Toughness

7 Strength

8 Strength Degradation with Time

9 Final Remarks

References

Chapter 9.2. Testing and Evaluation of Mechanical Properties

1 Introduction

2 Fracture Strength

3 Fatigue and Slow Crack Growth

4 Creep and Creep Rupture

References

Chapter 9.3. Microstructural Control and Mechanical Properties

1 Introduction

2 Grain Morphology Control

3 Fibrous Grain Alignment

4 Grain Boundary Phase Control

5 Porous Structure Control

References

Chapter 9.4. Determination of the Mechanical Reliability of Brittle Materials

1 Introduction

2 Lifetime Prediction Expressions

3 Measurement Procedures

4 Uncertainty Calculations

5 Summary

Acknowledgments

References

Chapter 9.5. Fracture Mechanics

1 Introduction

2 Linear-elastic Fracture Mechanics

3 Methods for the Determination of Fracture Toughness KIc

4 Mode-II and Mixed-Mode Fracture Toughness

5 Fracture of Piezoelectric Ceramics

6 R-Curve Behavior

7 Subcritical Crack Growth

8 The Loading Parameter C∗

References

Chapter 9.6. Fracture Mechanics Measurements

Glossary

1 Introduction

2 Fracture Mechanics Background

3 Fracture Mechanics Specimens

4 Double Torsion Test

5 Tests Based on Flexural Loading

6 Indentation Methods

7 Double Cleavage Drilled Compression

8 Interpretation and Use of Fracture Mechanics Data

9 Summary

Acknowledgments

References

Chapter 9.7. Layered Ceramics

1 Introduction

2 Residual Stresses in Layered Ceramics

3 Mechanical Behavior

4 Design Guidelines to Optimize Strength and Toughness

5 Outlook

References

Chapter 9.8. Environmentally Enhanced Fracture of Glasses and Ceramics

1 Introduction

2 Early Studies

3 Direct Crack Growth Studies

4 Mathematical Modeling

5 Polycrystalline Materials

6 Summary

7 What is yet Unknown

Acknowledgments

References

Chapter 9.9. Development of Superplastic Ceramics

1 Introduction

2 Mechanical Properties and Mechanism of Superplasticity

3 Superplastic Ceramics

4 Application of Superplasticity

References

Part 10: Advanced Ceramic Coating: Science and Technology

Chapter 10.1. Joining Ceramics and Metals

1 Introduction

2 Interface Chemistries

3 Physical Contact at Interface

4 Surface Roughness and Damage of Bond Face of Ceramics

5 Thermal Stress

6 Joining Process

7 Summary

References

Chapter 10.2. Heat-Resistant Coating Technology for Gas Turbines

1 Introduction

2 Development of Heat-Resistant Superalloys for Gas Turbines

3 Development of Heat-Resistant Coatings for Gas Turbines

4 Development of Thermal Barrier Coatings

5 Damage Modes Observed in Thermal Barrier Coatings

6 Heat-Resistant Evaluation Technology

7 Conclusions

References

Chapter 10.3. Application of High-Temperature Corrosion-Resistant Ceramics and Coatings under Aggressive Corrosion Environment in Waste-To-Energy Boilers

1 Introduction

2 Corrosion Environments of Waste-To-Energy Boilers

3 Application of Advanced Refractory Materials

4 Advances in High-Temperature Corrosion-resistant Materials and Coatings

5 Field Experiences of Cermet and Ceramic Coatings for Superheaters

6 Deterioration Mechanisms of Coatings

7 Summary

References

Chapter 10.4. A New Thick Film Coating Technology-Laser Chemical Vapor Deposition

1 Introduction

2 CVD for High-Speed Deposition

3 YSZ Thermal Barrier Coating

4 α-Al2O3 Coating for Cutting Tools

5 HAp Coating for Dental Implants

6 Summary

References

Chapter 10.5. Aerosol Deposition Method for Room-Temperature Ceramic Coating and Its Applications

1 Introduction

2 Aerosol Deposition Method

3 Room-Temperature Impact Consolidation (RTIC)

4 Deposition Properties and Layer Patterning

5 Electrical Properties and Recovering Properties by Heat Treatment

6 Antiplasma Corrosion Components Using AD-yttrium Oxide Layer [18]

7 Application to MEMS Devices

8 Potential of Energy Application

9 Future Prospects for Using AD Methods in Material Integration Technology

References

Part 11: Processing, and Related Materials, and Their Applications and Properties

11.1: Advanced Powder

Chapter 11.1.1. Ceramic Powders for Advanced Ceramics: What are Ideal Ceramic Powders for Advanced Ceramics?

1 Introduction

2 Characteristics of Powders [8,11,12,15]

3 Methods to Produce Fine Ceramic Powders [1,5,11,12,15,19–23][1,5,11,12,15,19–23]

4 Hydrothermal Syntheses and Characteristics of Hydrothermal Powders [4,5,11,25,36–45][4,5,11,25,36–45]

5 Summary

Acknowledgments

References

Chapter 11.1.2. Sol–Gel Process and Applications

1 Introduction

2 Chemical Reactions in Sol–Gel Solutions

3 Formation of Shapes and Microstructures

4 Applications

5 Recent Topics on Sol–Gel Method

6 Concluding Remarks

References

Chapter 11.1.3. Colloidal Processing Fundamentals

1 Introduction of Powder Processing

2 Colloidal Processing Concepts and Theories

3 Rheological Properties of Ceramic Slurries

4 Processing Additives

5 Forming Techniques

6 Summary and Outlook

References

Chapter 11.1.4. Solvothermal Synthesis of Metal Oxides

1 Introduction

2 Safety Consideration

3 Solvothermal Synthesis of Metal Oxides – Case Studies

4 Concluding Remarks

References

Chapter 11.1.5. Supercritical Hydrothermal Synthesis

1 Introduction

2 Basic Principles of Supercritical Hydrothermal Synthesis

3 Apparatus

4 NP Synthesis by Supercritical Hydrothermal Synthesis

5 Supercritical Hydrothermal Synthesis of Organic–Inorganic Hybrid Nanoparticles

6 Self-assembly of Hybrid Organic–Inorganic Nanoparticles

7 Hybrid Nanomaterials

8 Summary

References

Chapter 11.1.6. Controlled Thermal Plasma Processing of Ceramic Nanopowders

1 Introduction

2 Controlled RF Thermal Plasma Processing of TiO2-based Ultrafine Particles

3 Summary

References

Chapter 11.1.7. Development of Easy-Handling Ceramic Nanoparticles: Present and Future

1 Introduction

2 Experimental

3 Core–Shell-Type Ceria/Polymer Nanoparticles

4 Control of Particle Size

5 Change of Row Materials

6 Formation Mechanism

7 Application of Nanoparticle

8 Core–Shell-Type Other Oxide

9 Future

10 Summary

References

Chapter 11.1.8. Sonoprocess of Ceramic Materials

1 Introduction

2 Apparatus for Sonoprocess –How to Create Sonochemical Field

3 Sonochemical Effects on Ceramic Process in Practice

Acknowledgments

References

Chapter 11.1.9. Organic–Inorganic Hybrid Materials Prepared Through Supramolecular Assembly

1 Introduction

2 Cerasome as a Liposomal Organic–Inorganic Nanohybrid Hollow Spheres

3 Nanohybrid Coatings via Layer-by-Layer Assembly of Water-Soluble Precursor

4 Organic–Inorganic Hybrid Hollow Capsules Prepared by Colloid Templating

5 Summary

Acknowledgments

References

Chapter 11.1.10. Precursor-Derived Ceramics

1 Introduction

2 Precursor Synthesis

3 Polymer-to-Ceramic Transformation

4 High Temperature Properties

5 Applications

6 Conclusions

References

Chapter 11.1.11. Combinatorial Nanoscience and Technology for Solid-State Materials

1 The Why and How of Combinatorial Technology in Materials Research

2 Instrumentation of Combinatorial Technology

3 Combinatorial Methods Applied to Ceramics Research

4 Discoveries Made by Combinatorial Technology

5 High-Tech Venture: Combinatorial Material Business

6 Conclusion

Acknowledgments

References

11.2: Advanced Non-Powder

Chapter 11.2.1. Stereo Fabric Modeling Technology in Manufacturing Ceramics

References

Chapter 11.2.2. Porous Ceramic Materials

1 Introduction

2 Partial Sintering

3 Sacrificial Fugitives

4 Replica Templates

5 Direct Foaming

6 Gas Permeability

7 Summary

References

Chapter 11.2.3. Spark Plasma Sintering (SPS) Method, Systems, and Applications

1 Introduction

2 Historical Background

3 Suitable Materials For SPS Process

4 Principles of the SPS Process

5 Examples of SPS Process Applications

6 Summary and Outlook

References

Chapter 11.2.4. Functionally Graded Materials

1 Fundamentals of FGMS

2 Natural Materials with Graded Structures

3 Fabrication Processes

4 Typical Applications of FGMS

5 Future of FGMS

References

Chapter 11.2.5. Nature Technology for the Creation of Innovative Life

1 LifeStyles and Technologies Based on Environmental Issues [1]

2 A System to Create Nature Technology [1]

3 Some Present Examples [1]

4 Creation of the Functional Materials by Hydrothermal Reaction which Support the Earth Circulation

References

Chapter 11.2.6. Recent Advances in HIP Technology and Atmosphere Control in HIP Treatment

1 Introduction

2 HIP Technology

3 Conclusions and Future Perspectives

References

Index

Copyright

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Second edition 2013

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Library of Congress Cataloging-in-Publication Data

Handbook of advanced ceramics: materials, applications, processing, and properties / edited by Shigeyuki Somiya and Masayuki Kaneno.

  pages cm

 Includes bibliographical references and index.

 ISBN 978-0-12-385469-8 (alk. paper)

 1. Ceramics. I. Somiya, Shigeyuki, editor of compilation. II. Kaneno, Masayuki, editor of compilation.

 TP807.H34 2013

 666—dc23

              2012039863

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

ISBN: 978-0-12-385469-8

For information on all Elsevier publications visit our web site at store.elsevier.com

Printed and bound in the United States of America

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Dedications

To Mentors

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Prof. Fritz Aldinger

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Editor-in-Chief Shigeyuki Somiya

Preface to the First Edition

In 1989 Shigeyuki Somiya, the Editor-in-Chief of this book, published Advanced Technical Ceramics (Academic Press, Inc.; original publication in Japanese, 1984). Well over a decade has passed without the appearance of an authoritative new title on the ever-changing subject of Advanced Ceramics. The purpose of this book is to provide an up-to-date account of the present status of Advanced Ceramics, from fundamental science and processing to application.

The Handbook of Advanced Ceramics has an internationally renowned group of contributing editors. They are well known throughout the world in their fields of study. These editors discussed the contents and chose the authors of each of the book’s chapters very carefully. The chapters consist of review and overview papers written by experts in the field.

Up until about 50 years ago, ‘ceramics’ were considered to be porcelains, bottle glass, sheet glass, refractory bricks, enamels, cements, lime, gypsum and abrasives. In recent years the field of ceramics has broadened and expanded. Ceramics are now used in new fields of research as well as in the old fields. This handbook describes these developments and the new processes and applications.

The handbook will enable the reader to understand the present status of Ceramics and will also act as an introduction, which may encourage further study, as well as an estimation of the role advanced ceramics may have in the future.

The handbook is a two-volume set. Part I deals with Materials Science and Part II with Processing and Applications.

Part I serves as an introduction to the basic science, raw materials, forming, drying, sintering, innovative processing, single crystal growth, machining, joining, coating, fracture mechanics, testing, evaluation, etc. Part I is intended to provide the reader with a good understanding of the new techniques in advanced ceramics, such as thin films, colloidal processing, active and passive filler, pyrolyses process and precursor derived ceramics, as well as providing a template for the deposition of ceramics from aqueous solutions.

Part II deals with more recent processes and applications and functional and engineering ceramics. The engineering ceramics covered in this book were developed within the last decade. The functional ceramics covered include electro-ceramics, optoelectro-ceramics, superconductive ceramics, etc. as well as the more recent development of piezoelectric ceramics and dielectric ceramics.

The use of ‘Engineering’ Ceramics, introduces entirely new fields to be considered. These include mechanical properties, decorative ceramics, environmental uses, energy applications, bioceramics, composites, functionally graded materials, intelligent ceramics and so on.

The term Advanced Ceramics is opposite in meaning to ‘Traditional’ or ‘Classical’ Ceramics. In the past, Advanced Ceramics were often confused with New or Newer Ceramics, Modern Ceramics, Special Ceramics and so on. Furthermore, Fine Ceramics, at least in the USA and Europe, is synonymous with Fine Grain Ceramic Products and/or Fine Grain Porcelain; Fine Ceramics in Japan is similar to what we understand as Advanced Ceramics. So for this edition, the term Advanced Ceramics was chosen as the most suitable title for a book providing an in-depth survey of the current state of Ceramics Science and its applications.

It is the editors’ wish that this book will provide the reader with a detailed understanding of the many applications of Advanced Ceramics in both today’s world and in that of the future.

The editors wish to thank all those who participated in the preparation of this book such as authors, publishers and copyright owners in Europe, USA, Asia and the rest of the world.

Fritz Aldinger

Nils Claussen

Masayuki Kaneno

Kunihito Koumoto

Shigeyuki Somiya

Editor-in-Chief

Richard M. Spriggs

Kenji Uchino

Preface to the Second Edition

The first edition of the Handbook of Advanced Ceramics from Elsevier was published in 2003 and almost 10 years has passed. Science and technology in the field of ceramics, however, have developed day by day. This is one of reasons why the second edition of the Handbook of Advanced Ceramics has been published.

First ceramic products would be low-firing earthenware appeared some 15,000 years ago. This is a starting point subsequent to developments of ceramics. Until about 200 years ago, the word ceramics meant pottery, and ceramic products were limited to tableware, roofing tiles, bricks, and clay pipes. These ceramics or ceramic products are called traditional ceramics or classic ceramics.

In the nineteenth century, products of the iron and steel industry required new refractory bricks containing silica, alumina, chrome-magnesia, and magnesia, which were different from traditional fireclay bricks. Since then ceramics also have made essential contributions in many fields of the society.

There are a few words to express ceramics against classic ceramics or traditional ceramics: advanced ceramics, new ceramics, modern ceramics, special ceramics, and technical ceramics. New and modern ceramics mean ceramics against classic or traditional ceramics. Moreover, special ceramics also has a similar meaning as new and modern ceramics, and it originated from special refractories or special porcelains. As for technical ceramics, it includes all industrial ceramics except products related to traditional ceramics, such as pottery, porcelain, and tableware. The meaning of advanced ceramics is similar to the meaning of technical ceramics. However, advanced ceramics particularly emphasizes advanced features in ceramics. Therefore, advanced ceramics is used in this handbook to express current ceramics.

By the way, fine ceramics used in the Japanese language means high-value-added inorganic materials produced from high-purity synthetic powders, and microstructure and properties of the materials are highly controlled (Reference: Somiya S. Ceramics: definitions. In: Somiya S, editor. Advanced technical ceramics. Tokyo, Japan: Academic Press Japan; (1989). pp. 3–9). Fine ceramics in English would mean fine grain ceramics, but fine ceramics in Japanese is similar to advanced ceramics. Fine ceramics as in The Japan Fine Ceramics Association may mean advanced ceramics.

Applications of advanced ceramics are based on and resistant to various properties, such as biological, chemical, electrical, mechanical, optical, physical, structural, and thermal properties. In addition, there are various applications: For example, biocompatible parts, catalysts, sensors, electrical conductors, electrical insulators, semiconductors, superconductors, positive and negative temperature coefficient resistors, magnetic parts, dielectrics, ferroelectrics, piezoelectrics, pyroelectrics, abrasives, carbon fibers, hard parts, lubricants, high-temperature structural parts, automobile engine parts, cutting tools, optical fibers, laser oscillators, optically transparent parts, thermal conductors, thermal insulators, heaters, low-thermal expansion coefficient products, and jewelry.

Materials used for advanced ceramics are borides (e.g. boron nitride (BN)), carbides (e.g. silicon carbide (SiC)), carbons (e.g. diamond (C)), hydroxides (e.g. hydroxyapatite (Ca5(PO4)3(OH))), nitrides (e.g. boron nitride (BN), SiALON (Si3N4–Al2O3), and silicon nitride (Si3N4)), oxides (e.g. alumina (Al2O3), barium titanate (BaTiO3), mullite (3Al2O3–2SiO2), silicon oxide (SiO2), titanium oxide (TiO2), zirconia (ZrO2)), and so on (References to applications and materials of advanced ceramics: (1) Banno, H. (1984). New Ceramics. Tokyo, Japan: Pawaa-Sha (in Japanese); (2) The Japan Fine Ceramics Association (Ed). (1989). FC Annual Report for Overseas Readers: Fine Ceramics for Future Creation, p. 2; (3) Miyajima, S. (1994). New Ceramics. Tokyo, Japan: Chijin Shokan (in Japanese).)

In recent years, fields of ceramics have become broad. This handbook describes developments, processes, properties, characterization, and applications in fields of advanced ceramics: For instance, powder preparation, coating, mechanical properties, fracture mechanics, and measurement methods. In addition, it covers ceramics materials, such as carbides, carbons, and oxides.

Authors are experts in their fields and well-known scholars and engineers. The purpose of this handbook is same as the first edition of the handbook and to provide an up-to-date account of the present status of several fields of advanced ceramics from fundamental science and technology, to processing, to applications.

This handbook will enable readers, graduate students, professors, and engineers to introduce and understand the status of advanced ceramics.

Shigeyuki Somiya

(on behalf of editors)

Editor-in-Chief

Acknowledgments to the First Edition

First and foremost, I would like to thank all the co-editors, Fritz Aldinger, Nils Claussen, Richard M. Spriggs, Kenji Uchino, Kunihito Koumoto and Masayuki Kaneno for their valuable suggestions with regard to the chapters, authors, and their editorial assistance. Without their help, this book would not have been possible. Especially, Fritz Aldinger, Nils Claussen, and Richard M. Spriggs gave me good advice for this book. Mr Kaneno offered secretarial assistance.

Second, I wish to thank all the publishers who gave permissions to authors to reproduce and use the materials from their original published papers.

Third, many authors wrote their chapters within a short time in spite of their tight schedule. I would like to express my gratitude to all these authors.

I would also like to extend my appreciation to Ms Amanda Weaver and her group at Elsevier, Oxford for their contribution to the publishing works.

Finally, I was able to study abroad in the USA under the Fulbright Exchange Program and in Germany under the scholarship program by Max Planck Institut far Metallforschung, Pulvermetallgisches Laboratorium. Without these experiences, I would not have made it as Editor-in-Chief of this book. I thank all my professors and friends around the world who have made this possible.

Shigeyuki Somiya

Editor-in-Chief

Acknowledgments to the Second Edition

First, I would like to thank

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Dr. Paul F. Becher, Prof. Arthur H. Heuer, and Prof. Günter Petzow because they recommended coeditors of this book. Without their efforts, it was difficult to find excellent members.

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Second, I would like to thank all the coeditors:

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Prof. Robert Danzer, Dr. Steve Freiman, Prof. Peter Greil,

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Dr. Mathias Herrmann, Mr. Masayuki Kaneno, Prof. Katsutoshi Komeya,

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Dr. Tatsuki Ohji, and Prof. Eiichi Yasuda.

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Coeditors made their valuable suggestions and advice with regards to editorial work, such as the organization of chapters and sessions, and the recommendation of authors. Without them, this book would have not been created. For example, Editor Masayuki Kaneno offered excellent secretarial assistance.

Third, I would like to express my appreciation to all authors for this book and people who recommended authors.

Fourth, I would like to extend my appreciation to

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Louisa Hutchins, Poulouse Joseph, Steve Merken,

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Graham Nisbet, and people at Elsevier for their contribution to the publication of this book.

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Fifth, I would like to thank all organizations and publishers who have given permissions to authors to reproduce and use materials from original papers.

Sixth, I appreciate my father-in-law Uichi Hashimoto and my father Takayuki Somiya. They kept encouraging my study. Without them, it was difficult to find mentors and friends, especially friends in the world.

I studied at the Department of Geochemistry, The Pennsylvania State University in the U.S.A. under the Fulbright Exchange Student Program, and at the Pulvermetallurgisches Laboratorium in the Max Planck Institute for Metals Research (at present the Max Planck Institute for Intelligent Systems) in the F. R. G. (West Germany; at present Germany) under the scholarship program supported by the Pulvermetallurgisches Laboratorium. Without these experiences, I would not have accomplished this publication as editor in chief.

Last, I would like to thank mentors, colleagues, students, friends, and my family who have made this publication possible.

Shigeyuki Somiya

Editor-in-Chief

List of Editors

Robert Danzer, Professor of University of Leoben (Institute for Structural and Functional Ceramics), Austria

Stephen W. Freiman, Freiman Consulting, United States, Former Position: Division Head, United States National Institute of Standards and Technology, United States

Peter Greil, Professor of University of Erlangen-Nuernberg (Department of Materials Science and Engineering, (Glass and Ceramics)), Germany

Mathias Herrmann, Division Head, Sintering and Characterization, Fraunhofer IKTS (Fraunhofer Institute for Ceramic Technologies and Systems), Germany

Masayuki Kaneno, Former Position: Manager, Nagoya Industrial Science Research Institute, Japan

Katsutoshi Komeya, Professor Emeritus of Yokohama National University, Japan

Tatsuki Ohji, Prime Senior Research Scientist, AIST Chubu, National Institute of Advanced Industrial Science and Technology, Japan

Shigeyuki Somiya, (Editor-in-Chief, the First and the Second Edition) Professor Emeritus of Tokyo Institute of Technology, Japan and Teikyo University of Science and Technology, Japan

Eichi Yasuda, Professor Emeritus of Tokyo Institute of Technology, Japan

List of Contributors

Masanori Abe, Professor Emeritus of Tokyo Institute of Technology, Japan

(Ch. 7.3)

Joerg Adler, Fraunhofer-Institut fuer Keramische Technologien und Systeme (Fraunhofer IKTS; Fraunhofer Institute for Ceramic Technologies and Systems), Winterbergstrasse 28, 01277 Dresden, Germany

(Ch. 8.1)

Tadafumi Adschiri, World Premier International Research Center-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan

(Ch. 11.1.5)

Kazuki Akamatsu, Department of Environmental and Energy Chemistry, Faculty of Engineering, Kogakuin University, 2665-1 Nakano-machi, Hachioji-shi, Tokyo 192-0015, Japan.

(Ch. 4.1)

Jun Akedo, National Institute of Advanced Industrial Science & Technology (AIST)

(Ch. 10.5)

Fritz Aldinger, Max-Planck-Institut für Metallforschung, Heisenbergstrasse 3, Stuttgart, Germany

(Ch. 11.1.10)

R. Alway-Cooper, Center for Advanced Engineering Fibers and Films, and Department of Chemical and Biomolecular Engineering, Clemson University, Clemson, SC

(Ch. 2.8)

Nobuaki Aoki, World Premier International Research Center-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan

(Ch. 11.1.5)

Toshihiko Arita, Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan

(Ch. 11.1.5)

A. Badev, SPCTS UMR 7315 – CNRS European Ceramic Center (CEC), 12, Rue Atlantis, Limoges, France

(Ch. 6.5)

G.H. Beall, Corning Inc. SP-FR-05-1, Corning, New York 14831, United States

(Ch. 5.1)

Raul Bermejo, Institut für Struktur- und Funktionskeramik, Montanuniversität Leoben, Franz Josef Strasse 18, 8700 Leoben, Austria

(Ch. 9.7)

Diego Cazorla-Amorós, Dpto. de Química Inorgánica e Instituto de Materiales, Universidad de Alicante, Alicante, Spain

(Ch. 2.9)

T. Chartier, SPCTS UMR 7315 – CNRS European Ceramic Center (CEC), 12, Rue Atlantis, Limoges, France

(Ch. 6.5)

Toyohiro Chikyo, Comet Inc., Tsukuba, Japan; National Institute for Materials Science, Tsukuba, Japan

(Ch. 11.1.11)

R. Danzer, University of Leoben, Institut für Struktur- und Funktionskeramik, Leoben, Austria; Materials Center Leoben, Leoben, Austria

(Ch. 9.1)

Marco Deluca, Institut für Struktur- und Funktionskeramik, Montanuniversität Leoben, Franz Josef Strasse 18, 8700 Leoben, Austria, Materials Center Leoben Forschung GmbH, Roseggerstrasse 12, 8700 Leoben, Austria

(Ch. 9.7)

M.S. Dresselhaus, Department of Physics and Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307, USA

(Ch. 2.2)

M. Endo, Faculty of Engineering, Shinshu University, Wakasato 4-17-1, Nagano 380-8553, Japan

(Ch. 2.2)

Naoya Enomoto, Department of Applied Chemistry, Faculty of Engineering, Kyushu University, Fukuoka 819-0395, Japan

(Ch. 11.1.8)

T. Fett, Institut fuer Angewandte Materialien-Keramik im Maschinenbau (IAM-KM) (Institute for Ceramics in Mechanical Engineering), KIT (Karlsruher Institut fuer Technologie; Karlsruhe Institute of Technology), Haid- und Neu-Strasse 7, 76131 Karlsruhe, Germany

(Ch. 9.5)

Tobias Fey, Department of Materials Science and Engineering – Glass and Ceramics, University of Erlangen-Nuernberg, Erlangen, Germany

(Ch. 7.1)

Jeffrey T. Fong, Applied and Computational Mathematics Division, National Institute of Standards and Technology, Gaithersburg, MD, USA

(Ch. 9.4)

Stephen W. Freiman, Freiman Consulting, Potomac, MD, USA

(Chs. 9.4, 9.6, 9.8)

Takao Fujikawa, Metal Technology Co., Ltd., 27th floor Harmony-Tower, 1-32-2 Honcho, Nakano-ku, Tokyo, Japan 164-8721

(Ch. 11.2.6)

Koji Fujita, Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan

(Ch. 5.2)

Ryuzo Furukawa, Graduate School of Environmental Studies, Tohoku University, Japan

(Ch. 11.2.5)

Dipankar Ghosh, Materials Science and Engineering, University of Florida, Gainesville, FL 32607, USA

(Ch. 3.3)

Takashi Goto, Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Japan

(Ch. 10.4)

E. Gracia-Espino, Department of Chemistry, and Department of Physics, Umeå University, SE-901 87 Umeå, Sweden

(Ch. 2.2)

Peter Greil, Department of Materials Science and Engineering – Glass and Ceramics, University of Erlangen-Nuernberg, Erlangen, Germany

(Ch. 7.1)

Hiroshi Handa, Tokyo Institute of Technology

(Ch. 7.3)

Yoshiyasu Harada, JEOL Ltd.

(Ch. 1.1.1)

Mamoru Hatakeyama, Tokyo Institute of Technology

(Ch. 7.3)

T. Hayashi, Faculty of Engineering, Shinshu University, Wakasato 4-17-1, Nagano 380-8553, Japan

(Ch. 2.2)

Mathias Herrmann, Fraunhofer Institute for Ceramic Technologies and Systems, Dresden, Germany

(Ch. 3.4)

Kiyoshi Hirao, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Shimo-Shidami, Moriyama-ku, Nagoya 463-8560, Japan

(Ch. 3.2)

Daisuke Hojo, World Premier International Research Center-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan

(Ch. 11.1.5)

W. Höland, Research and Development, Ivoclar Vivadent AG, Bendererstrasse 2, 9494 Schaan, Liechtenstein

(Ch. 5.1)

Takuya Hoshina, Graduate School of Science and Engineering, Tokyo Institute of Technology

(Ch. 6.1)

Hideo Hosono, Frontier Collaborative Research Center & Materials and Structures Laboratory, Tokyo Institute of Technology, Mail Box R3-1, 4259 Nagatsuta, Midori- ku, Yokohama 226-8503, Japan

(Ch. 6.4)

Mikinori Hotta, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Shimo-Shidami, Moriyama-ku, Nagoya 463-8560, Japan

(Ch. 3.2)

Hideki Hyuga, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Shimo-Shidami, Moriyama-ku, Nagoya 463-8560, Japan

(Ch. 3.2)

Toshiyuki Ikoma, Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8550, Japan

(Ch. 7.2)

Yuichi Ikuhara, Institute of Engineering Innovation, The University of Tokyo, Japan

(Ch. 1.1.1)

Michio Inagaki, Professor Emeritus of Hokkaido University

(Ch. 2.1)

Masashi Inoue, Professor Emeritus of Kyoto University, Japan

(Ch. 11.1.4)

Emanuel Ionescu, Technische Universität Darmstadt, Institut für Materialwissenschaft, Petersenstrasse 23, Darmstadt, Germany

(Ch. 11.1.10)

Emile H. Ishida, Graduate School of Environmental Studies, Tohoku University, Japan

(Ch. 11.2.5)

Hiroaki Itami, Toyo Tanso Co., Ltd. Product Planning Dept.

(Ch. 2.7)

Toshio Itoh, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya 463-8560 Japan

(Ch. 11.1.7)

Noriya Izu, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya 463-8560 Japan

(Ch. 11.1.7)

Y-P. Jeon, Center for Advanced Engineering Fibers and Films, and Department of Chemical and Biomolecular Engineering, Clemson University, Clemson, SC

(Ch. 2.8)

Se-Young Jeong, Department of Cogno-Mechatronics Engineering, Pusan National University, Miryang, Korea

(Ch. 11.1.11)

K. Kanamura, Tokyo Metropolitan University

(Ch. 4.2)

Kiyofumi Katagiri, Department of Applied Chemistry, Nagoya University; Department of Applied Chemistry, Hiroshima University

(Ch. 11.1.9)

Yuuzou Kawahara, The former Mitsubishi Heavy Industries, Co., Ltd., Yokohama R&D Center, Dai-Ichi High Frequency Co., Ltd., 1-45, Mizue-chyo, Kawasaki-ku, Kawasaki City, 210-0866 Japan

(Ch. 10.3)

Hitoshi Kawaji, Materials and Structures Laboratory, Tokyo Institute of Technology

(Ch. 6.3)

Y.A. Kim, Faculty of Engineering, Shinshu University, Wakasato 4-17-1, Nagano 380-8553, Japan

(Ch. 2.2)

Hideki Kita, Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, Aichi 464-8603, Japan, Former Affiliate: National Institute of Advanced Industrial Science and Technology, 2266-98 Anagahora, Shimo-Shidami, Moriyama, Nagoya, Aichi 463-8550, Japan

(Chs. 3.2, 11.2.1)

Hideomi Koinuma, Graduate School of Frontier Sciences, University of Tokyo, Kashiwa, Chiba, Japan; Department of Cogno-Mechatronics Engineering, Pusan National University, Miryang, Korea; Comet Inc., Tsukuba, Japan

(Ch. 11.1.11)

Sridhar Komarneni, Materials Research Institute, Materials Research Laboratory building, The Pennsylvania State University, University Park, Pennsylvania, USA.

(Ch. 11.1.11)

Naoki Kondo, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Shimo-Shidami, Moriyama-ku, Nagoya 463-8560, Japan

(Ch. 3.2)

M. Kotobuki, Tokyo Metropolitan University

(Ch. 4.2)

Kunihito Koumoto, Department of Applied Chemistry, Nagoya University

(Ch. 11.1.9)

Ji-Guang Li, National Institute for Materials Science, Tsukuba, Ibaraki, Japan

(Ch. 11.1.6)

Angel Linares-Solano, Dpto. de Química Inorgánica e Instituto de Materiales, Universidad de Alicante, Alicante, Spain

(Ch. 2.9)

Mikk Lippmaa, Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba, Japan

(Ch. 11.1.11)

F. López-Urías, Advanced Materials Department, IPICYT, Camino a la Presa San José 2055, Col. Lomas 4a sección, 78216, San Luis Potosí, SLP, México

(Ch. 2.2)

T. Lube, University of Leoben, Institut für Struktur- und Funktionskeramik, Leoben, Austria

(Ch. 9.1)

Hirotaka Maeda, Center for Fostering Young and Innovative Researchers, Nagoya Institute of Technology, Japan

(Ch. 11.2.5)

Yasuo Manabe, Machinery Division, Kobe Steel, Ltd., 2- 3-1, Shinhama, Arai-cho, Takasago City, Japan 676-8670

(Ch. 11.2.6)

Lalit M. Manocha, Department of Materials Science and Centre for Advanced Studies in Carbon and Nanomaterials, Sardar Patel University, Vallabh Vidyanagar, Gujarat-388120, India

(Ch. 2.10)

Branko Matović, Vinca Institute of Nuclear Sciences, University of Belgrade, 11001 Belgrade, Serbia

(Chs. 3.1, 4.3)

Ichiro Matsubara, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya 463-8560 Japan

(Ch. 11.1.7)

Yuji Matsumoto, Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama, Japan

(Ch. 11.1.11)

David McKinney, MM Virtuoso, Gainesville, FL

(Ch. 11.1.3)

Kimitaka Minami, New Industry Creation Hatchery Center, Tohoku University, 6-6-10 Aoba, Aramaki, Aoba-ku, Sendai, Miyagi 780-8577, Japan

(Ch. 11.1.5)

M. Morales, Center for Advanced Engineering Fibers and Films, and Department of Chemical and Biomolecular Engineering, Clemson University, Clemson, SC

(Ch. 2.8)

R. Morrell, National Physical Laboratory, Materials Division, Teddington, TW11 0LW, UK

(Ch. 9.1)

H. Munakata, Tokyo Metropolitan University

(Ch. 4.2)

D. Munz, Professor Emeritus of Karlsruhe Institute of Technology (Karlsruher Institut fuer Technologie), Germany

(Ch. 9.5)

Shunsuke Murai, Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan

(Ch. 5.2)

H. Muramatsu, Faculty of Engineering, Shinshu University, Wakasato 4-17-1, Nagano 380-8553, Japan

(Ch. 2.2)

Takashi Nakagawa, Osaka University

(Ch. 7.3)

Shin-ichi Nakao, Department of Environmental and Energy Chemistry, Faculty of Engineering, Kogakuin University, 2665-1 Nakano-machi, Hachioji-shi, Tokyo 192-0015, Japan

(Ch. 4.1)

A.A. Ogale, Center for Advanced Engineering Fibers and Films, and Department of Chemical and Biomolecular Engineering, Clemson University, Clemson, SC

(Ch. 2.8)

Tatsuki Ohji, National Institute of Advanced Industrial Science and Technology (AIST) Nagoya 463-8560, Japan

(Chs. 9.2, 9.3, 11.2.2)

Osamu Okada, Toyo Tanso Co., Ltd. Product Planning Dept.

(Ch. 2.6)

Eiji Osawa, NanoCarbon Research Institute, Ltd, AREC (Asama Research Extension Center), Faculty of Textile Science and Technology, Shinshu University, Ueda, Nagano, Japan

(Ch. 2.3)

Jun-ichi Ozaki, Graduate School of Engineering, Gunma University, 1-5-1, Tenjin-cho, Kiryu, Gunma 376-8515, JAPAN

(Ch. 2.4)

Uwe Petasch, Fraunhofer-Institut fuer Keramische Technologien und Systeme (Fraunhofer IKTS; Fraunhofer Institute for Ceramic Technologies and Systems), Winterbergstrasse 28, 01277 Dresden, Germany

(Ch. 8.1)

Ralf Riedel, Technische Universität Darmstadt, Institut für Materialwissenschaft, Petersenstrasse 23, Darmstadt, Germany

(Ch. 11.1.10)

Rustum Roy, Materials Research Institute, Materials Research Laboratory building, The Pennsylvania State University, United States; Passed away on August 26, 2010

(Ch. 11.1.1)

Sumio Sakka, Professor Emeritus of Kyoto University, (Home Address) Kuzuha-Asahi 2-7-30, Hirakata City, Osaka-Fu, Japan

(Ch. 11.1.2)

Yoshio Sakka, National Institute for Materials Science, Tsukuba, Ibaraki, Japan

(Ch. 11.1.6)

Cross Jeffrey Scott, Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8550, Japan

(Ch. 7.2)

Taiju Shibata, Japan Atomic Energy Agency, 4002 Narita, Oarai-machi, Higashi-ibaraki-gun, Ibaraki, Japan

(Ch. 2.5)

Shuichi Shibata, Department of Chemistry and Materials Science, Tokyo Institute of Technology, Address: 2-12-1 Ookayama, Meguro-ku, Tokyo, 152-8550 Japan

(Ch. 5.3)

Woosuck Shin, National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya 463-8560 Japan

(Ch. 11.1.7)

Yoshikazu Shinohara, National Institute for Materials Science, Tsukuba, Ibaraki, Japan

(Ch. 11.2.4)

Hiroshi Shioyama, National Institute of Advanced Industrial Science and Technology, Ikeda, Osaka, Japan

(Ch. 2.11)

Wolfgang Sigmund, Department of Materials Science and Engineering, University of Florida, Gainesville, FL 32611-6400, USA; WCU Department of Energy Engineering, Hanyang University, Seoul, South Korea

(Ch. 11.1.3)

Shigeyuki Somiya, Professor Emeritus of Tokyo Institute of Technology, Japan

(Ch. 11.1.1)

Yasushi Soneda, Energy Storage Materials Group, Energy Technology Research Institute, Tsukuba West Office, National Institute of Advanced Industrial Science and Technology, Onogawa, Tsukuba, Ibaraki, Japan

(Ch. 2.12)

Ghatu Subhash, Mechanical and Aerospace Engineering, University of Florida, Gainesville, FL 32607, USA

(Ch. 3.3)

Katsuaki Suganuma, Institute for Scientific and Industrial Research, Osaka University Mihogaoka 8-1, Ibaraki, Osaka 567, Japan

(Ch. 10.1)

P. Supancic, University of Leoben, Institut für Struktur- und Funktionskeramik, Leoben, Austria; Materials Center Leoben, Leoben, Austria

(Ch. 9.1)

Yuko Suto, Graduate School of Environmental Studies, Tohoku University, Japan

(Ch. 11.2.5)

Setsu Suzuki, Comet Inc., Tsukuba, Japan

(Ch. 11.1.11)

Motohiro Tagaya, Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8550, Japan

(Ch. 7.2)

Ryota Takahashi, Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba, Japan

(Ch. 11.1.11)

Seiichi Takami, Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan

(Ch. 11.1.5)

Tadashi Takenaka, Faculty of Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan

(Ch. 6.2)

Katsuhisa Tanaka, Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan

(Ch. 5.2)

Junzo Tanaka, Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8550, Japan

(Ch. 7.2)

H. Terrones, Visiting scientist, Oak Ridge National Laboratory, One Bethel Valley Road, Oak Ridge, TN 37831-6367, USA

(Ch. 2.2)

M. Terrones, Department of Physics, Department of Materials Science and Engineering and Materials Research Institute, The Pennsylvania State University, 104 Davey Lab., University Park, PA 16802-6300, USA & Research Center for Exotic Nanocarbons (JST), Shinshu University, Wakasato 4-17-1, Nagano 380-8553, Japan

(Ch. 2.2)

Takanari Togashi, World Premier International Research Center-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan; Department of Material and Biological Chemistry, Faculty of Science, Yamagata University 1-4-12 Kojirakawa-machi, Yamagata 990-8560, Japan

(Ch. 11.1.5)

Masao Tokita, NJS Co., Ltd. 301 Office Shinyokohama, 2-14-8, Shinyokohama, Kouhoku-ku, Yokohama, Kanagawa, 222-0033, Japan

(Ch. 11.2.3)

Takaaki Tsurumi, Graduate School of Science and Engineering, Tokyo Institute of Technology

(Ch. 6.1)

Tomoaki Ueda, Tokyo Institute of Technology

(Ch. 7.3)

Fumihiro Wakai, Secure Materials Center, Materials and Structures Laboratory, Tokyo Institute of Technology, R3-23 4259 Nagatsuta, Midori, Yokohama, Japan

(Ch. 9.9)

Markus Weinmann, H.C. Starck GmbH, Im Schleeke 78-91, Goslar, Germany

(Ch. 11.1.10)

Toyohiko Yano, Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro, Tokyo 152-8550, Japan

(Chs. 3.1, 4.3)

ITO Yoshiyasu, Thermal Spraying R&D Center, TOCALO Co., Ltd., 14-3, Minamifutami, Futami-cho, Akashi, Hyogo, 674-0093, Japan

(10.2)

Cordt Zollfrank, Department of Materials Science and Engineering – Glass and Ceramics, University of Erlangen-Nuernberg, Erlangen, Germany

(Ch. 7.1)

Fine Ceramics

The picture Fine ceramic tree shows relationships between advanced ceramic materials and properties. The Japan Fine Ceramics Association provided it. In Japan, the expression Fine Ceramics is similar to advanced ceramics and used rather than advanced ceramics. The Japan Fine Ceramics Association is acknowledged.

Part 1

Methods for Characterization of Advanced Ceramics

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1.1 Electron Microscopy

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1.1

Electron Microscopy

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Chapter 1.1.1 The Latest Analytical Electron Microscope and its Application to Ceramics

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Chapter 1.1.1

The Latest Analytical Electron Microscope and its Application to Ceramics

Yoshiyasu Harada∗ and Yuichi Ikuhara†, ∗JEOL Ltd., †Institute of Engineering Innovation, The University of Tokyo, Japan

Chapter Outline

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1. Introduction

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2. General Overview of Analytical Electron Microscope

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3. Transmission Electron Microscopy

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4. Scanning Transmission Electron Microscopy

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5. Analysis Method

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6. Application of Analytical Electron Microscopy to Ceramics

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7. Conclusion

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References

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1 Introduction

The transmission electron microscope (TEM) has been utilized for observation of fine structures and analysis of a crystalline structure of material, since its invention in 1932 [1]. After that, in the 1970s, the functions of scanning transmission electron microscope (STEM), energy dispersive spectroscopy (EDS), electron energy loss spectroscopy (EELS), etc. were built in TEM, and its application fields have been drastically expanded to include compositional analysis and analysis of an electronic structure as well as image observation by TEM/STEM up to the present date. As such, the TEM/STEM, which can make both the image observation and the analysis, is called an analytical electron microscope (AEM) [2,3].

Then, the electron gun and objective lens, which are important elemental technologies of the electron microscope, have been greatly improved, and the performance of AEM has improved drastically. That is, as for the electron gun, in the 1990s, instead of the conventional thermionic emission electron gun (TEG), field emission electron gun (FEG) of high brightness has been put into practical use, and the current of the nano-probe focused on a specimen has been greatly increased. In addition, as for the objective lens, by commercialization of TEM equipped with a condenser objective lens (C/O lens) in the 1980s, observation of TEM image and STEM image became possible by using the identical objective lens excitation, and then research of material science field has been developed. Moreover, in the 2000s, the corrector of spherical aberration, which used to restrict the resolution of TEM/STEM, has been put into practical use; therefore, the image observation and the analysis of atomic levels have become possible, and AEM has been utilized as a useful evaluation instrument in the most advanced area of material development in the material science fields such as metal, semiconductor, and ceramics, etc.

In this article, we will describe the general overview of the most advanced AEM first, and will especially explain the electron gun and objective lens as well as the spherical aberration corrector, which relates to the AEM performance. Next, we will describe the image formation in TEM and STEM and analysis method (EDS and EELS), which are indispensable for applying AEM to material science field. Finally, we will introduce how AEM is utilized in research of ceramics material concretely based on several application examples.

2 General Overview of Analytical Electron Microscope

2.1 Various Information Obtained by Interaction between Electron Beam and Specimen

When electron beams are irradiated to a specimen, as shown in Figure 1, as a result of an interaction between the electron beam and specimen, information such as the secondary electron, Auger electron, backscattered electron, absorbed electron, characteristic X-ray, cathode luminescence, etc. can be obtained. In addition, in case the specimen is a thin film, by interaction between the electron beam and the specimen, information of the transmitted electron, which suffered elastic scattering and inelastic scattering, can be obtained. By utilizing this information, AEM can obtain a great deal of knowledge about a specimen.

FIGURE 1 Various information obtained by interaction between primary electrons and specimen.

In this chapter, we cover major image-forming methods by TEM and STEM which obtain magnified images of a specimen by using transmitted electrons; in addition, we describe the compositional analysis and chemical state analysis of a specimen using EDS and EELS.

2.2 Composition of Analytical Electron Microscope

Figure 2 shows the appearance of the most advanced AEM (JEM-ARM200F) with spherical aberration corrector (Cs-corrector), which enables the observation of both TEM image and STEM image [4]. Electron beams are emitted from the electron gun at the top, and the emitted electron beams are accelerated and magnified (in the case of TEM) or demagnified (in the case of STEM) by the illumination lens system, and then irradiated to the specimen. In the case of TEM, electrons passing through a specimen are formed into an image by image-forming lens system, and the image are observed on a fluorescent screen in an image observation chamber. In addition, they can be observed through a CCD camera in an image observation chamber or, at the lower part of it, on a liquid crystal monitor.

FIGURE 2 Appearance of an analytical electron microscope (JEM-ARM200F). For color version of this figure, the reader is referred to the online version of this book.

In the case of STEM, by scanning a demagnified electron probe, a synchronized signal is detected by various detectors attached at the lower part of the image observation chamber, and the image can be observed on a liquid crystal monitor. Also, as analysis function, EDS detector is attached in the specimen chamber, and EELS detector is attached at the lower part of the camera chamber; thus, compositional analysis can be possible.

Among many elements composing of AEM, the factors to determine the performance are the electron gun and objective lens (OL) including aberration correction technology. With the instrument shown in Figure 2, FEG is provided as an electron gun; however, there are instruments which have TEG where tungsten (W) hairpin filament and lanthanum hexaboride (LaB6), etc. are used as an electron source. We describe the characteristics comparison of these electron guns in 2.3. In addition, as for the OL and aberration correction technology, we describe in 2.4 and 2.5 respectively.

2.3 Performance Comparison of Various Electron Guns

Table 1 shows the features of various electron guns. Since the invention of the electron microscope, TEG with W hairpin filament has been utilized as a standard electron gun until the 1970s, but in the 1980s, the use of TEG with LaB6 [5] of high brightness became popular. Later on, in the 1990s, FEG of higher brightness was put into practical use, and began being used as the electron gun of AEM. There are principally two types of FEGs. One is the cold-type FEG(C-FEG) which uses W(310) as electron source which is kept at room temperature [6]. The other is the thermal-type FEG (T-FEG) with heated ZrO/W(100) [7] as an electron source. The feature of C-FEG is that the energy spread of an emission current is small, while the features of T-FEG are that large emission currents can be taken, the current stability is high, and that the ease of operation is also good. With the most advanced AEM, though it has both advantages and disadvantages, either type of FEG has been used as a standard. Recently, Schottky-type electron gun whose feature is about same as the T-FEG is commonly used in place of T-FEG.

TABLE 1

Comparison of Characteristics of Various Electron Guns

2.4 Objective Lens

The resolution (d) of the TEM is expressed as d = 0.65Cs¹/⁴·λ³/⁴. Here, Cs is the spherical aberration coefficient and λ is the wavelength of electron. Since the invention of the electron microscope, in order to improve the resolution, efforts have been made whether making spherical aberration coefficient of OL smaller or raising the accelerating voltage, that is, making λ shorter. At present, the standard accelerating voltage of AEM is 200–300 kV, that is, λ is 0.00251–0.00197 nm.

On the other hand, the efforts to reduce Cs of the OL have been done by many researchers since the invention of TEM. There are principally two trends. In other words, the shape of the OL pole pieces differs greatly, whether inserting a specimen from the top through the upper bore of the pole piece (top entry method) or inserting a specimen from the side through the gap (side entry method) to enter a specimen in the gap between pole pieces . To correspond to the top entry method, it is necessary to select asymmetric pole pieces where the bore diameter of the upper pole (b1) is larger than that of the lower pole (b2). Also, to correspond to the side entry method, it is necessary to select symmetric pole pieces of b1 = b2, and to make the gap length(s) of the pole pieces relatively greater. As for the asymmetric pole pieces, since the top entry specimen stage is more stable in terms of antivibration properties, it has been improved along the trend that pursues the resolution of the TEM image. However, in order to use it in the case of AEM, it is necessary to change the excitation of the OL in order to switch from TEM image to STEM image, which is difficult in terms of ease of operation, so that its use in standard AEM was stopped in the mid-1980s. On the other hand, as for the symmetric pole pieces, in consideration that the improvement of antivibration properties of the side entry specimen stage has advanced, as the TEM image and STEM image can be observed by using an identical excitation of the OL, it is excellent in terms of ease of operation; therefore, it developed rapidly in the 1980s, and it has been used as a standard OL of AEM up to the present date. is the excitation parameter (NI: ampere turn, Vr: relativistic accelerating voltage). In the case of an asymmetric lens [8], it is necessary to make b1 great, therefore, b1 = 5 mm. In addition, in the case of a symmetric lens which is used as C/O lens [9], it is necessary to make s relatively large, therefore, s = 2.5 mm. If we assume that Cs of approximately 0.5 mm can be realized at the accelerating voltage in the range of 100–300 kV with either OL, the resolution at that time will be 0.26 nm, 0.19 nm, and 0.16 nm, respectively, at 100 kV, 200 kV, and 300 kV. When the Cs-corrector is not used, these resolutions are the best at each accelerating voltage.

TABLE 2

Comparison of Optical Properties of Symmetrical and Asymmetrical Objective Lenses

2.5 Spherical Aberration Corrector

In the mid-1990s, Cs-corrector was put into practical use, and, in the 2000s, AEM with Cs-corrector of TEM/STEM has rapidly become widely used, until today.

Right after the electron microscope was invented, a study on the aberration of the electron lens was executed actively. Scherzer demonstrated that Cs and chromatic aberration coefficient (Cc) of rotational symmetric electron lens cannot take a negative value [10], and proposed a method to correct these aberrations by using a rotational asymmetric electron lens which can take a negative value of these aberration coefficients [11].

Later on, many researchers have done theoretical and experimental studies of aberration correction by using rotational asymmetric electron lens such as the quadrupole lens, octupole lens, hexapole lens, and dodecapole lens; however, these were hardly put into practical use. The reasons are that (1) the simulation of rotational asymmetric electron lens has never been accurately done, (2) the technology to process the rotational asymmetric electron lens with accuracy was not available, (3) the electric stability of rotational asymmetric electron lens has never been improved, and (4) the electric stability of the electron microscope basic unit has not been sufficient. However, in 1995, about 50 years after the proposal by Scherzer, the above-described problems were resolved by Rose and Haider who are the successors of Scherzer’s research laboratory, and Cs-corrector using a 2-stage hexapole lens was put into practical use [12,13]. Lens structure of the corrector, which can correct spherical aberration of the third order, is shown in Figure 3.

FIGURE 3 TEM (a) and STEM (b) Cs-correctors with two hexapole elements.

Figure 3(a) is the case of TEM which forms a magnified image of the specimen, and Cs-corrector is placed at the lower side of the OL. Figure 3(b) shows the case of STEM which forms the nano-probe on the specimen, and the Cs-corrector is placed at the upper side of OL. With this Cs-corrector, along with the large three-fold astigmatism, negative spherical aberration appearing in terms of higher order from the three-fold astigmatism is utilized for the spherical aberration correction of the OL with the 1st-stage and 2nd-stage hexapole lens. The three-fold astigmatism arising from the hexapole lens of the 1st stage and the other of 2nd stage is set in reverse directions; therefore, it became the optical system that makes three-fold astigmatism zero as a whole.

With the electron microscope which has the Cs-corrector, if the accelerating voltage is 300 kV, the resolution of 0.05 nm is obtained in TEM/STEM, and the minimum probe diameter on the specimen is approximately 0.1 nm[14]. In addition, in case the accelerating voltage is 200 kV, the resolution is 0.1 nm in TEM/STEM, and approximately 0.1 nm as the minimum probe diameter on the specimen is obtained [4].

3 Transmission Electron Microscopy

3.1 Electron Microscope Image and Electron Diffraction Pattern

In the case of an observation of a magnified image and observation of an electron diffraction pattern, which are the basic observation methods of TEM, the ray diagram of the image-forming lens system is shown in Figure 4. Observation of a wide range of magnified images is possible from low magnification of 50 times to high magnification of 1,000,000 times.

FIGURE 4 Ray path of image-forming lens system to observe image (a) and (b) and diffraction (c).

Figure 4(a) shows a ray diagram to obtain low magnification of 50–1000 times, and in order to observe an image of a wide field of view with small aberration, excitation of OL is cut, objective mini (OM) lens is used instead of the OL, and the image is magnified by the intermediate lens (IL) and projector lens (PL), and can be observed on the fluorescent screen. Figure 4(b) is the ray diagram to obtain a magnified image at high magnification of 1000–1000,000 times, and the image magnified by the OL is magnified by several intermediate lens (IL1–IL3) and PL further, and observed on the fluorescent screen. The insertion of OL aperture on the back focal plane of the OL is possible, and by selecting the size of the OL aperture, observation of magnified image, which has various contrasts, is possible. Figure 4(c) is the ray diagram to obtain an electron diffraction pattern. The electron diffraction pattern formed at the back focal plane of the OL, is magnified by IL and PL, and observed on the fluorescent screen. By selecting the size of the selected-area (SA) aperture placed on the object plane of the IL1, selection of an area on the specimen, which corresponds to the electron diffraction pattern, is possible.

Electron microscope image and electron diffraction pattern can be switched on at the flip of a switch and observed. In case the specimen is crystal, a spot-shaped electron diffraction pattern is obtained by Bragg reflection on the crystal plane which is parallel to the incident electron beam, and by selecting only the transmitted spot without being diffracted by the OL aperture, a bright field image can be observed, and by selecting the diffraction spot only, a dark field image can be observed. With a bright field image and dark field image, the bright and dark contrasts are observed, and these contrasts differ depending on the specimen thickness and the local distortion accompanied by the curvature of the crystal plane, dislocation, stacking fault, etc. As for the reason why these contrasts are formed, explanation by the electron diffraction theory [15], which consists of the kinematical theory and dynamical theory, is possible, but we do not cover it here.

3.2 High-Resolution Electron Microscopy

There are principally two methods of high-resolution electron microscopy (HREM) to study crystal material [16]. One is the observation of crystal lattice images. When the electron beam is illuminated in parallel to crystal zone