Theory of Ionic Conduction in Solids Based on the Homogeneous Generation of Defect Pairs and Its Application to Anodic Oxidation

Abstract

The theory for ionic conduction in solids based upon the homogeneous, field-assisted generation of defect pairs is developed in a general, three dimensional form, and its range of applicability is examined. At high field strengths the equations reduce to those of the so-called high field Frenkel defect theory, proposed originally by Bean, Fisher, and Vermilyea. At low field strengths, the steady-state expression reduces to the well-known conduction equation derived originally by Mott for ionic conduction in the alkali halides. At intermediate field strengths, more complicated relationships obtain. The homogeneous generation of defect pairs, whether field or current assisted, is shown to be inapplicable as a mechanism for the high field anodic oxidation of the valve metals, since either type of theory predicts unacceptable behavior for the mean free path of the mobile defects. Any such conduction mechanism can be acceptable only for the case of thick films (» 104 Å).