The density and diffusivity in must refer to the same carrier species and correlation convention. Oxygen vacancy diffusivity belongs with vacancy density; tracer diffusion of oxygen atoms is not automatically the vacancy diffusivity. A transport inversion may determine an effective density without uniquely determining a chemical defect concentration.
Past exam of the materials science course of the University of Cambridge 2016 Paper 1 2 d Solution Created 2026-10-20 Updated 2026-10-20
The numerical vacancy fraction depends on what the supplied diffusivity describes. In the usual effective mobile-vacancy calculation, the carriers per cell are oxygen vacancies, each of effective charge . There are eight oxygen sites, so that convention givesThere is a real qualification: the printed description calls the measured particles oxygen carrier ions. If is their tracer diffusivity and every occupied oxygen site is counted as an uncorrelated carrier, the inversion instead gives , formally . Such an enormous oxygen deficiency is inconsistent with the ordinary lightly doped fluorite picture; it is not a credible deduction of vacancies in stabilized zirconia.
More generally the conductivity involves a collective diffusion coefficient, whereas tracer diffusion includes jump correlations. With the explicitly defined convention ,Without a carrier definition and the relevant correlation information, the literal tracer data do not uniquely establish the vacancy fraction. The consistent vacancy-carrier interpretation gives the boxed estimate. Interpreting the same measured as an oxygen-ion tracer diffusivity requires the collective/tracer conversion above; ordinary Nernst-Einstein relation arithmetic cannot identify these two carrier populations. This states the model assumption needed for the numerical result without treating the physically implausible uncorrelated oxygen-ion inversion as an established material composition.