A formalism to describe demixing of mixed oxides of large and small grain size in an electric field

In this paper. we address the theory of electric field demixing of the cations in semi-conducting and initially homogeneous mixed ceramic oxides. We include the off-diagonal phenomenological transport coefficients by assuming a random distribution of cations and making use of an exact sum-rule expression. The steady state atomic composition profiles are shown to be quite different when different assumptions are made about vacancy equilibration. We show that in the case of large grained material (where vacancies in the interior do not equilibrate easily to the external oxygen partial pressure), a maximum develops in the steady state vacancy composition profiles. This behaviour is verified by independent Monte Carlo simulations.