Influence of substitutional atoms on the diffusion of oxygen in dilute iron alloys

A multiscale approach including density functional theory (DFT) and atomistic kinetic Monte Carlo (AKMC) simulations is applied to investigate the diffusion of interstitial oxygen atoms in bcc Fe under the influence of substitutional foreign atoms (Al, Si, P, S, Ti, Cr, Mn, Ni, Y, Mo, and W). The substitutional atoms can be assumed to be immobile since their diffusion coefficient is much smaller than that of oxygen. First, jumps of oxygen in pure bcc Fe between first-, second-, and third-neighbor octahedral interstitial sites are investigated. It is found that the first-neighbor jump is most relevant, with the tetrahedral site as the saddle point. The second-neighbor jump consists of two consecutive first-neighbor jumps. The barrier for a direct third-neighbor jump is too high to be significant for the diffusion process. In the presence of substitutional atoms the most important migration paths are first-neighbor jumps between modified octahedral sites with modified tetrahedral sites as saddle points. Calculations show that Si, P, Ni, Mo, and W cause some modifications of the migration barriers of oxygen and their interaction with O is mainly repulsive. Al, Cr, and Mn have a significant influence on the barriers and they exhibit strong attractive interactions with O. The most important modification of the barriers is found for S, Ti, and Y where deep attractive states exist. Based on the migration energies obtained by DFT, AKMC simulations on a rigid lattice are employed to determine the diffusion coefficient of oxygen in a dilute iron alloy containing the different substitutional atoms. It is found that Si, P, Ni, Mo, and W have almost no influence on the diffusivity of O. The presence of Al, Cr, Mn, S, Ti, and Y causes a significant reduction of the mobility of oxygen. In these cases the temperature dependence of the oxygen diffusion coefficient shows considerable deviations from an Arrhenius law. These phenomena are discussed in detail by considering the occupation time for the different states. The present findings on the strong dependence on the kind of substitutional atoms change the picture of oxygen diffusion in dilute iron alloys substantially.