Abstract
In alloys, the directions of successive vacancy jumps are correlated to one another. This tends to reduce the net vacancy flux in a Kirkendall shift experiment. The magnitude of the vacancy flux, including correlation effects, is calculated assuming that vacancies are not bound to any particular atoms and that fluctuations in average local composition can be ignored. New equations for the intrinsic diffusion coefficients, Kirkendall shift, and interdiffusion coefficient in binary alloys are obtained. The Kirkendall shift and interdiffusion coefficient given by these equations are larger than those predicted by Darken but smaller than those obtained when vacancy correlations are neglected. The appearance of cross terms and additional diagonal terms in the general thermodynamic equations is discussed.
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