Dft Study on Mo-Stabilized Passive Films: Hydroxylation Effects on Chromium and Iron Oxide Surfaces

Abstract

Hydrous Cr2O3 and Fe2O3 surfaces without and with substitutional molybdenum were simulated by DFT modelling to investigate at the atomic scale the role of Mo in improving the corrosion resistance of passive films on stainless steels. The surface structures most energetically favoured were determined in the conditions of interest. For highly hydroxylated surfaces, the preferential location of substitutional Mo is just under the hydroxyl groups, in agreement with the experimental observations. The substitution by Mo is exothermic and Mo preferentially substitutes in Fe- than in Cr-rich zone of the inner barrier layer of passive films.

Keywords: stainless steel, Cr2O3, Fe2O3, DFT, Mo effects, hydrous surfaces