Three-dimensional modelling of selective dissolution and passivation of iron–chromium alloys

Abstract

A three-dimensional model has been developed for modelling the selective dissolution and passivation of alloys. The model has been used to simulate the passivation of iron–chromium alloys. The real structure of the alloy is taken into account (bcc in the present case), as well as the structure of the initial surface. The passivation is modelled in considering the formation of “oxide” nuclei, resulting from the presence of local chromium-rich clusters. During the dynamic evolution of the model, based on the Monte Carlo method, surface diffusion and dissolution of atoms occur according to probabilities dependent on the nature of the atom (Cr or Fe) and on its chemical environment. The conditions of simulation can be changed through a set of parameters defining the rules for surface diffusion, selective dissolution and number of Cr atoms in the Cr clusters required to initiate locally the passivation. The effects of these parameters on the simulation have been tested for an alloy containing 22 at.% Cr and compared with experimental data. The results show that the diffusion of Fe has little influence on the course of passivation while the diffusion of Cr has a marked effect. When the number of surface chromium atoms required to form a nucleus of passive film increases, the passivation becomes less rapid, with a marked effect on the composition of the passivated layer. The extent of the chromium enrichment in the passivated surface obtained in the model for the initial stages of passivation is not as high as the one measured experimentally in the stationary state of passivity. Other simulations have then been performed with various chromium contents in the alloy. The results show the existence of a transition, which is not sharp but progressive, between alloys that cannot be passivated to alloys that are passivated.