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