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Defect Thermodynamics-Historical

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Book cover Defects and Transport in Oxides

Part of the book series: Battelle Institute Materials Science Colloquia ((BIMSC))

Abstract

Ionic conduction in crystals was initially attributed to dissociation. In 1926 Frenkel introduced the concept of atomic disorder. Schottky and Wagner (1931-1935) introduced further types of disorder and nonstoichiometry. Quasi-chemical-defect reactions and the corresponding mass-action relations were introduced in 1933. Medium- and short-range interaction between defects is accounted for by Debye-Hückel theory (Dünwald and Wagner, 1933) and pairing (Schottky, 1939). Regulation of defect concentrations by doping with aliovalent foreign atoms began with the work on AgBr + CdBr2 by Koch and Wagner (1937), followed by semiconductor work after 1942. Application of the Schottky-Wagner approach to all possible defects, combined with a graphical method of representation using log-log or log-l/T plots and approximation of the neutrality condition (Brouwer, 1954), has become known as defect chemistry (Kröger and Vink, 1954, 1958). The method was extended to ternary compounds (Schmalzried and Wagner, 1962). Near surfaces (Frenkel, 1964), grain boundaries, solid-liquid interfaces (Grimley and Mott, 1947), and dislocations (eshelby et al., 1958), local neutrality is not maintained; we have planar or linear charges of one type balanced by a space charge in the crystal nearby. This makes it possible to determine the chemical potential of individual defects. Magneli (1950) observed extended defects in ßWO3 giving rise to shear structures (Wedsley, 1955).

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  1. Department of Materials Science, University of Southern California, Los Angeles, California, USA

    F. A. Kröger

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  1. Materials Science Department, Battelle Memorial Institute, Columbus Laboratories, USA

    Martin S. Seltzer  & Robert I. Jaffee  & 

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Kröger, F.A. (1974). Defect Thermodynamics-Historical. In: Seltzer, M.S., Jaffee, R.I. (eds) Defects and Transport in Oxides. Battelle Institute Materials Science Colloquia. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-8723-1_1

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