Past exam of the materials science course of the University of Cambridge / 2016 / Paper 1 / 2 / d

The numerical vacancy fraction depends on what the supplied diffusivity describes. In the usual effective mobile-vacancy calculation, the $0.9236$ carriers per cell are oxygen vacancies, each of effective charge $+2e$. There are eight oxygen sites, so that convention givesThere is a real qualification: the printed description calls the measured particles oxygen carrier ions. If $D$ is their tracer diffusivity and every occupied oxygen site is counted as an uncorrelated carrier, the inversion instead gives $N_O=0.9236$, formally $f_v=1-N_O/8=0.8845$. Such an enormous oxygen deficiency is inconsistent with the ordinary lightly doped fluorite picture; it is not a credible deduction of $88.5\%$ vacancies in stabilized zirconia.

More generally the conductivity involves a collective diffusion coefficient, whereas tracer diffusion includes jump correlations. With the explicitly defined convention $H_R=D_{\mathrm{tr}}/D_{\sigma }$,Without a carrier definition and the relevant correlation information, the literal tracer data do not uniquely establish the vacancy fraction. Thus $11.5\%$ is a conditional effective-vacancy answer, rather than a convention-free inference. TODO: establish the intended carrier/diffusivity convention if an authoritative clarification becomes available.