9781402025686

Binary Rare Earth Oxides is the first book in the field of rare earth oxides that provides coverage from the basic science through to recent advances. This book introduces the unique characteristics of the binary rare earth oxides with their chemistry, physics and applications. It provides a comprehensive review of all the characteristics of rare earth oxides, essential for scientists and engineers involved with rare earths, oxides, inorganic materials, ceramics, and structures. The binary rare earth oxides bring us a variety of interesting characteristics. Understanding their fundamental mechanisms builds a bridge between solid-state chemistry and materials science.The book begins with a brief introduction to binary rare earth oxides, their physical and chemical stabilities, polymorphism, crystal structures and phase transformation and the association with current applications. The book goes on to present the band structure of the oxides using several quantum chemical calculations, which belong to a newly developed area in the binary rare earth oxides. Central to this chapter are the characterizations of electrical, magnetic and optical properties, as well as details of single crystal growth and particle preparation methods that have progressed in recent years. Later chapters concentrate on thermo-chemical properties and trace determination techniques. The final chapter contains a variety of useful applications in various fields such as phosphors, glass abrasives, automotive catalysts, fuel cells, solid electrolytes, sunscreens, iron steels, and biological materials.This book is an invaluable resource for materials scientists and solid-state physicists and chemists with an interest in rare earth oxides, as well as advanced students and graduates who require an approach to familiarize them with this field. This book provides guidance through a comprehensive review of all the characteristics of binary rare earth oxides.

1. Introduction

Gin-ya Adachi and Zhenchuan Kang

(8)

1.1. Why Are Rare Earth Oxides So Important?

1.2. A Variety of Rare Earth Oxides

1.3. Simplicity and Complexity of Rare Earth Oxides

2. Chemical Reactivity of Binary Rare Earth Oxides

Serafin Bernal, Ginesa Blanco, José Manuel Gatica, José Antonio Pérez Omil, José Maria Pintado, and Hilario Vidal

(48)

2.1. Introduction

2.2. Chemical Reactivity of the Rare Earth Sesquioxides

2.2.1. Preliminary Considerations about the Ln2O3-H2O-CO2 System

2.2.2. The Chemistry of the Ln2O3-CO2-H2O Systems

2.2.3. Other Studies on the Chemical Reactivity of the Rare Earth Sesquioxides

2.3. Chemical Reactivity of the Higher Rare Earth Oxides

2.3.1. Redox Chemistry of the Higher Rare Earth Oxides

2.3.2. Temperature Programmed Oxygen Evolution Studies

2.3.3. Temperature Programmed Reduction Studies

2.3.4. Reduction by CO of the Higher Rare Earth Oxides

2.3.5. Re-oxidation of Pre-reduced Higher Rare Earth Oxides

2.3.6. Modification of the Redox Behavior of the Higher Rare Earth Oxides

2.3.7. Other Studies on the Reactivity of the Higher Rare Earth Oxides

3. Structural Features of Rare Earth Oxides

Eberhard Schweda and Zhenchuan Kang

(38)

3.1. Introduction

3.2. The Dioxides

3.2.1. The Fluorite Structure

3.2.2. The Structure of Intermediate Ce-, Pr-, and Tb-Oxides

3.2.3. The Structure of Intermediate Rare Earth Oxides

3.2.4. Interpretation and Simulation of defect Separations in the Rare Earth Oxides

3.2.5. Phase Transformation

3.3. The Sesquioxides

3.3.1. Structure of Sesquioxides

3.3.2. Polymorphism

3.4. The Lower Oxides (Monoxides LnO and Eu3O4)

3.5. High Resolution Electron Microscopy (HREM)

3.5.1. Electron Daction Data of the Oxygen Deficient Fluorite-related Homologous Series of the Binary, Rare Earth Oxides

3.5.2. Composition Domain and Hysteresis Loop

3.5.3. Surface Structure of the Rare Earth Higher Oxides

3.5.4. Defect and Chemical Reactivity of the Rare Earth Higher Oxides

3.5.5. Phase Transition from Tb48O88 (β(3)) to Tb24O44 (β(2))

4. Chemical Bonds and Calculation Approach to Rare Earth Oxides

Yukio Makino and Satoshi Uchida

(16)

4.1. Introduction

4.2. Electronic Structure of Sesquioxides

4.3. Electronic Structure of Fluorite Oxides

5. Physical and Chemical Properties of Rare Earth Oxides

Nobuhito Imanaka

111

(24)

5.1. Electrical Properties

5.2. Magnetic Properties

5.3. Spectroscopic Properties

5.4. Atomic Transport Properties

6. Particles and Single Crystals of Rare Earth Oxides

Nobuhito Imanaka and Toshiyuki Masui

135

(28)

6.1. Particles

6.1.1. Breakdown and Buildup Method

6.1.2. Gas Condensation

6.1.3. Chemical Vapor Deposition

6.1.4. Precipitation Method

6.1.5. Hydrothermal and Solvothermal Methods

6.1.6. Sol-gel Method

6.1.7. Emulsion and Microemulsion Method

6.1.8. Ultrasound and Microwave Irradiation Method

6.1.9. Spray Pyrolysis

6.1.10. Electrochemical Method

6.1.11. Mechanochemical Method

6.1.12. Flux Method and Alkalide Reduction Method

6.2. Single Crystals

6.2.1. Conventional Crystal Growth from Melt

6.2.2. Hydrothermal Crystallization Growth

6.2.3. Recent Advance in Single Crystal Growth of Rare Earth Oxides

7. Thermochemistry of Rare Earth Oxides

Lester R. Morss and Rudy J.M. Konings

163

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7.1. Introduction and Scope

7.2. Historical

7.3. Thermochemical Techniques

7.3.1. Combustion Calorimetry

7.3.2. Solution Calorimetry

7.3.3. Low-temperature Adiabatic Calorimetry

7.3.4. High-temperature Drop Calorimetry

7.3.5. Mass Spectrometry

7.4. Solid Rare Earth Sesquioxides

7.4.1. Enthalpies of Formation

7.4.2. Standard Entropies and Heat Capacities

7.5. Other Solid Binary Rare Earth Oxides

7.5.1. Solid Rare Earth Monoxides

7.5.2. Solid Rare Earth Dioxides

7.5.3. Nonstoichiometric Solid Rare Earth Oxides

7.6. Gaseous Rare Earth Oxides

7.7. Conclusions

8. Trace and Ultratrace Determination of Lanthanides in Material and Environmental Samples

T. Prasada Rao

189

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8.1. Introduction

8.2. Analytical Techniques

8.2.1. Molecular Absorption Spectrometry (MAS)

8.2.2. Higher Order Derivative MAS (HDMAS)

8.2.3. Molecular Fluorescence Spectrometry (MFS)

8.2.4. Atomic Absorption Spectrometry (AAS)

8.2.5. X- ray Fluorescence (XRF)

8.2.6. Luminescence Spectrometry (LS)

8.2.7. Neutron Activation Analysis (NAA)

8.2.8. Atomic Emission Spectrometry (AES)

8.2.9. Mass Spectrometric Techniques (MS)

8.2.10. Ion Chromatography (IC)

8.2.11. Coupled Techniques

8.3. Conclusions

9. Applications

Jean-Pierre Cuif, Emmanuel Rohart, Pierre Macaudiere, Celine Bauregard, Eisaku Suda, Bernard Pacaud, Nobuhito Imanaka, Toshiyuki Masui, and Shinji Tamura,

215

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9.1. Phosphors

9.1.1. A Wide Range of Applications, Thanks to a Grea Variety of Emissions

9.1.2. New Demands and Recent Developments in Applications: A Step Forward for Phosphors

9.2. Catalysts

9.2.1. Three Way Catalysis (TWC) and NOx, Trap Catalyst

9.2.2. A New Catalytic Solution for Diesel Engine Exhausts Cleaning

9.3. Glass Industry

9.3.1. Glass Composition

9.3.2. Glass Polishing

9.4. Fuel Cells

9.4.1. Introduction to Fuel Cells

9.4.2. Principle of SOFCs

9.4.3. Use and Role of Rare Earths in SOFCs Materials

9.4.4. Requirements and New Solutions of Materials for SOFCs

9.5. Solid Electrolytes

9.5.1. Yttria Stabilized Zirconia

9.5.2. Solid Electrolytes Based on Ceria

9.6. Sunscreen Cosmetics

9.6.1. CeO2 for Sunscreens

9.6.2. Modification of CeO2

9.6.3. New Materials for Sunscreens

9.7. Additive for Iron and Steel Industry

9.7.1. Deoxigenation

9.7.2. Surface Modification

9.8. Biological Application

9.8.1. Radiotherapy for Cancer

9.8.2. Basic Studies on Markers for Brain Tumor and Digestibility Estimation

10. Concluding Remarks

Gin-ya Adachi, Nobuhito Imanaka, and Zhenchuan Kang

257

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Binary Rare Earth Oxides

1402025688

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