Nonstoichiometric Oxides

1st Edition - November 12, 2012
Editor: O.T. Soerensen
Language: English
Paperback ISBN:
9 7 8 - 0 - 1 2 - 4 3 1 1 8 2 - 4
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 1 4 9 8 0 - 8

Nonstoichiometric Oxides discusses the thermodynamic and structural studies of nonstoichiometric oxides. This eight-chapter text also covers the defect-defect interactions in these… Read more

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Nonstoichiometric Oxides discusses the thermodynamic and structural studies of nonstoichiometric oxides. This eight-chapter text also covers the defect-defect interactions in these compounds. The introductory chapters describe the thermodynamic properties of nonstoichiometric oxides in terms of defect complexes using the classical thermodynamic principles and from a statistical thermodynamics point of view. These chapters also include statistical thermodynamic models that indicate the ordered nonstoichiometric phase range in these oxides. The subsequent chapters examine the transport properties, such as diffusion and electrical conductivity. Diffusion theories and experimental diffusion coefficients for several systems, as well as the electrical properties of the highly defective ionic and mixed oxide conductor, are specifically tackled in these chapters. The concluding chapters present the pertinent results obtained in nonstoichiometric oxide structural studies using high-resolution electron microscopy and X-ray and neutron diffraction. Inorganic chemists and inorganic chemistry teachers and students will greatly appreciate this book.

List of Contributors

Preface

1 Thermodynamics and Defect Structure of Nonstoichiometric Oxides

I. Introduction

II. General Thermodynamic Considerations of the Phase Relationships in Nonstoichiometric Oxides

III. Classification of Nonstoichiometric Oxides

IV. Thermodynamics and Defect Structure of Oxygen-Deficient Oxides

V. Thermodynamics and Defect Structure of Metal-Deficient Oxides

VI. Thermodynamics and Defect Structure of Metallic Transition Metal Monoxides

VII. Thermodynamics and Defect Structure of Excess-Oxygen Oxides

VIII. Thermodynamics and Defect Structure of Oxides Existing as both Oxygen-Excess and Oxygen-Deficient Compounds

IX. Recommendations for Future Work on Nonstoichiometric Oxides

References

2 Defect Clustering in Nonstoichiometric Oxides

I. Introduction

II. Nonstoichiometry and Disorder

III. Determination and Characterization of the Defect Structure of Grossly Defective Phases

IV. Point Defect Aggregates

V. Extended Defect Structures

VI. Summary and Conclusions

References

3 A New Method of Statistical Thermodynamics and Its Application to Oxides of the Lanthanide and Actinide Series

I. Statistical Thermodynamic Concepts for Grossly Nonstoichiometric Compounds

II. Basic Concepts and Formalism of Spacing Statistics

III. Applications of Spacing Statistics

IV. Conclusions and Recommendations for Future Work

References

4 Diffusion in Nonstoichiometric Oxides

I. Introduction

II. Crystal Structures Considered

III. Point Defects and Clustering

IV. Tracer Diffusion and Related Processes

V. Diffusion in the Fluorite Structure: UO2, (U, Pu) O2, CeO2, ZrO2, ThO2

VI. Diffusion in the Rutile Structure: TiO2

VII. Diffusion in the Rock-Salt Structure: FeO, CoO, NiO

VIII. Results for More Complex Nonstoichiometric Oxides

IX. Concluding Remarks

References

5 Mass Transport in Anion-Deficient Fluorite Oxides

I. Introduction

II. Cation Mobility in Anion-Deficient Fluorite Oxides

III. Anion Mobility in Anion-Deficient Oxides

IV. The Effects of Microstructure

V. Defect Chemistry and Conductivity

VI. Fluorite Oxides

VII. Other Oxygen Ion Conductors

VIII. General Conclusions

References

6 Mixed Conduction in Nonstoichiometric Oxides

I. Introduction

II. Electrical Conduction in Oxides

III. Defect Equilibria

IV. Thermodynamic and Kinetic Processes

V. Mixed Conduction in Oxides—A Survey

References

7 Structure, Defects, and Nonstoichiometry in Oxides: An Electron Microscopic View

I. Introduction

II. The Techniques of High-Resolution Electron Microscopy

III. The Application of Microscopy to the Study of Nonstoichiometry in Oxides

IV. Application of HRTEM to Chemical Dynamics

V. Concluding Remarks

References

8 Structural Studies on Nonstoichiometric Oxides Using X-Ray and Neutron Diffraction

I. Introduction

II. Comparative Roles of Diffraction Methods and Electron Microscopy

III. X Rays or Neutrons?

IV. Nonstoichiometric Binary Oxides

V. Crystallographic Shear Structures

VI. Block Structures

VII. Infinitely Adaptive Structures

VIII. Conclusion

References

Index