Bulk Diffusion of Cl through O Vacancies in α-Cr2O3: A Density Functional Theory Study

Abstract

Many metals form passive oxides which are broken or weakened by anionic-induced degradation leading to material failure and anionic diffusion is an important step of this degradation process. The diffusion of anionic species through oxides involves a combination of diffusion along grain boundaries, cracks, and channels, as well as bulk diffusion via point defects which is the focus of this study. Using density functional theory, we study bulk diffusion of Cl through O vacancies in α-Cr2O3 as a model system for passive metal oxides. Little is known about Cl diffusion and bonding characteristics, so we benchmark our work through comparison to numerous studies on O diffusion in α-Cr2O3 to analyze similarities and differences between the O and Cl diffusion in the passivation and degradation process of α-Cr2O3 respectively. Unlike O diffusion, the lowest diffusion barrier for Cl is cross-plane diffusion between two (0001) planes through a vacant cation site but the much shorter in-plane diffusion path within the same coordination polyhedron has 35% higher barrier. This work provides the basis for considering the contributions of Cl bulk-diffusion in the overall diffusion kinetics of Cl through α-Cr2O3.