Energy ordering of grain boundaries in Cr2O3: Insights from theory

TL;DR

This study uses theoretical calculations to determine the energy hierarchy of various grain boundaries in Cr2O3, revealing which interfaces are most stable and potentially influential in corrosion processes.

Contribution

It provides the first theoretical comparison of different grain boundary types in Cr2O3, identifying the most energetically favorable interfaces.

Findings

Prismatic screw GB with Cr-O interface is most stable.

Rhombohedral GB with screw symmetry and Cr vacancy is second.

More in-plane Cr atoms at the interface increase stability.

Abstract

The grain boundaries, GBs, of corundum Cr2O3 are known to play an important role in the diffusion of ions within the oxide, which is an important phenomenon for the corrosion of the stainless steels. The extent of the growth of oxide layers in stainless steel depends upon which interfaces are preferred within Cr2O3. Therefore, we have constructed four different grain boundary planes (rhombohedral, basal, prismatic and pyramidal) and their various associated interface symmetries known in literature for corundum Al2O3. Their structural, electronic, and energetic properties are investigated theoretically with periodic calculations using the DFT+U approach. We find that the prismatic screw GB with a Cr-O plane interface is the energetically preferred GB with the rhombohedral GB with screw symmetry and Cr vacancy termination being the second energetically preferred GB. The increase of the number of in-plane Cr atoms at the interface of prismatic GB enhances the stability which is also evident in the electronic density of states.