9780195110142

The Defect Chemistry of Metal Oxides

by
  • ISBN13:

    9780195110142

  • ISBN10:

    0195110145

  • Edition: 1st
  • Format: Hardcover
  • Copyright: 2000-06-15
  • Publisher: Oxford University Press

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Summary

The Defect Chemistry of Metal Oxides is a unique introduction to the equilibrium chemistry of solid inorganic compounds with a focus on metal oxides. Accessible to students with little or no background in defect chemistry, it explains how to apply basic principles and interpret the related behavior of materials. Topics discussed include lattice and electronic defects, doping effects, nonstoichiometry, and mass and charge transport. The text distinctly emphasizes the correlation between the general chemical properties of the constituent elements and the defect chemistry and transport properties of their compounds. It covers the types of defects formed, the effects of dopants, the amount and direction of nonstoichiometry, the depths of acceptor and donor levels, and more. Concluding chapters present up-to-date and detailed analyses of three systems: titanium dioxide, cobalt oxide and nickel oxide, and barium titanate. The Defect Chemistry of Metal Oxides is the only book of its kind that incorporates sample problems for students to solve. Suitable for a variety of courses in materials science and engineering, chemistry, and geochemistry, it also serves as a valuable reference for researchers and instructors.

Table of Contents

Preface ix
Introduction
1(3)
Reference
3(1)
A Few Useful Crystal Structures
4(17)
Introduction
4(2)
Close-Packed Structures
6(7)
Structures for Eight-Coordinate Cations
13(3)
Structures for Ternary Compounds
16(4)
Conclusion
20(1)
References
20(1)
Problems
20(1)
Lattice Defects and the Law of Mass Action
21(13)
Introduction
21(1)
Lattice Defects as Part of the Equilibrium State
22(4)
The Law of Mass Action
26(2)
Another View of Mass Action
28(2)
Lattice Disorder in Elemental Solids
30(2)
Summary
32(1)
References
33(1)
Intrinsic Ionic Disorder
34(23)
Lattice Defects and Reference States
34(2)
Conservation Rules
36(1)
Defect Notation
37(1)
Major Types of Intrinsic Ionic Disorder
38(10)
General Comments on Intrinsic Ionic Disorder
48(7)
References
55(1)
Problems
55(2)
Extrinsic Ionic Disorder
57(18)
Introduction
57(1)
The AgCl--CdCl2 System
58(4)
The CaF2--CaO System
62(1)
The TiO2--Nb2O5 System
63(1)
Summary of Important Points
64(1)
Schematic Representation of Defect Concentrations
65(7)
Summary of Extrinsic Ionic Disorder
72(1)
References
73(1)
Problems
73(2)
Defect Complexes and Associates
75(16)
Introduction
75(1)
Complexes Containing an Impurity Center and an Ionic Defect
76(6)
Intrinsic Ionic Defect Associates
82(3)
The Effect of Impurities on the Concentrations of Defect Complexes and Associates
85(4)
References
89(2)
Ionic Transport
91(27)
Introduction
91(1)
Basic Concepts of Diffusion
91(4)
Ionic Conduction in Crystalline Solids
95(5)
Intrinsic and Extrinsic Ionic Conduction
100(12)
Fast Ion Conductors
112(5)
References
117(1)
Intrinsic Electronic Disorder
118(20)
Introduction
118(1)
The Development of Energy Bands
118(3)
The Mass-Action Approach
121(2)
The Fermi Function
123(3)
Holes, Waves, and Effective Masses
126(3)
Electronic Conductivity
129(3)
Hopping Mechanisms
132(1)
The Band Structure of Compounds
133(1)
Chemistry and the Band Gap
134(3)
Summary
137(1)
References
137(1)
Extrinsic Electronic Disorder
138(24)
Introduction
138(1)
Interactions with the Gaseous Ambient
138(3)
The Choice of Compensating Defect
141(4)
The Chemical Consequences of Electronic Compensation
145(1)
The Interactions of Impurity Centers with Electrons and Holes
146(10)
The Situation for Compounds
156(5)
Summary
161(1)
References
161(1)
Intrinsic Nonstoichiometry
162(35)
Introduction
162(1)
Nonstoichiometry in Pure Crystalline Compounds
163(4)
Nonstoichiometry and Equilibrium Defect Concentrations
167(1)
The Hypothetical Compound MX with Schottky Disorder
167(7)
Summary of the Kroger--Vink Diagram for MX
174(10)
Conclusion of the Discussion of MX
184(1)
A More Complex Kroger--Vink Diagram
185(8)
Summary of the Kroger--Vink Diagrams for Intrinsic Nonstoichiometry
193(1)
Enthalpy Relationships
193(1)
Conclusion
194(1)
Reference
194(1)
Problems
194(3)
Extrinsic Nonstoichimetry
197(20)
Introduction
197(1)
A Simple Example: Donor-Doped MX
198(7)
Enthalpy Relationships
205(2)
A More Complex Example: Acceptor-Doped M2O3
207(3)
General Considerations
210(4)
Nonstoichiometric Reactions in the Impurity-Controlled Region
214(1)
Problems
215(2)
Titanium Dioxide
217(22)
Introduction
217(3)
The Amount of Nonstoichiometry
220(2)
The Equilibrium Electrical Conductivity of Undoped TiO2
222(6)
The Seebeck Coefficient of Undoped TiO2
228(1)
Ionic Conduction in TiO2
228(2)
The Effect of Dopants on TiO2
230(5)
General Comments on the Defect Chemistry of TiO2
235(2)
References
237(1)
Problems
238(1)
Cobalt Oxide and Nickel Oxide
239(14)
Introduction
239(1)
Cobaltous Oxide, CoO
240(7)
Nickelous Oxide, NiO
247(5)
Summary
252(1)
References
252(1)
Barium Titanate
253(30)
Introduction
253(2)
General Expectations
255(1)
The Equilibrium Conductivity of Undoped BaTiO3
256(6)
Insulting Properties of BaTiO3
262(6)
Acceptor-Doped BaTiO3
268(3)
Ionic Conduction in BaTiO3
271(4)
Donor-Doped BaTiO3
275(3)
Trivalent Dopants in BaTiO3
278(3)
Summary
281(1)
References
281(2)
Order Versus Disorder
283(8)
Block Structures
287(1)
Summary
288(1)
References
289(2)
Index 291

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