A model for time-dependent grain boundary diffusion of ions and electrons through a film or scale, with an application to alumina

Abstract

A model for ionic and electronic grain boundary transport through thin films, scales or membranes with columnar grain structure is introduced. The grain structure is idealized as a lattice of identical hexagonal cells -a honeycomb pattern. Reactions with the environment constitute the boundary conditions and drive the transport between the surfaces. Timedependent simulations solving the Poisson equation self-consistently with the Nernst-Planck flux equations for the mobile species are performed. In the resulting Poisson-Nernst-Planck system of equations, the electrostatic potential is obtained from the Poisson equation in its integral form by summation. The model is used to interpret alumina membrane oxygen permeation experiments, in which different oxygen gas pressures are applied at opposite membrane surfaces and the resulting flux of oxygen molecules through the membrane is measured. Simulation results involving four mobile species, charged aluminum and oxygen vacancies, electrons, and holes, provide a complete description of the measurements and insight into the microscopic processes underpinning the oxygen permeation of the membrane. Most notably, the hypothesized transition between p-type and n-type ionic conductivity of the alumina grain boundaries as a function of the applied oxygen gas pressure is observed in the simulations. The range of validity of a simple analytic model for the oxygen permeation rate, similar to the Wagner theory of metal oxidation, is quantified by comparison to the numeric simulations. The three-dimensional model we develop here is readily adaptable to problems such as transport in a solid state electrode, or corrosion scale growth.

Multiscale modeling of interface-mediated mechanical, thermal, and mass transport in heterogeneous materials: Perspectives and applications

“…In sequential approaches, the pertinent information is extracted from atomistically resolved simulations, e.g., molecular dynamics (MD) or density functional theory (DFT) calculations. This information is then used to inform higher length-scale models, such as dislocation dynamics (DD) [65][66][67][68][69][70][71], Boltzmann transport equation (BTE) [72][73][74], Poisson's equation of diffusion [75][76][77] (Fig. 2a-c), and among many others.…”