Molecular dynamics simulation study of nanoscale passive oxide growth on Ni-Al alloy surfaces at low temperatures

Oxidation kinetics of Ni-Al (100) alloy surface is investigated at low temperatures (300-600 K) and at different gas pressures using molecular dynamics (MD) simulations with dynamic charge transfer between atoms. Monte Carlo simulations employing the bond order simulation model are used to generate the surface segregated minimum energy initial alloy configurations for use in the MD simulations. In the simulated temperature-pressure-composition regime for Ni-Al alloys, we find that the oxide growth curves follow a logarithmic law beyond an initial transient regime. The oxidation rates for Ni-Al alloys were found to decrease with increasing Ni composition. Structure and dynamical correlations in the metal/oxide/gas environments are used to gain insights into the evolution and morphology of the growing oxide film. Oxidation of Ni-Al alloys is characterized by the absence of Ni-O bond formation. Oxide films formed on the various simulated metal surfaces are amorphous in nature and have a limiting thickness ranging from similar to 1.7 nm for pure At to 1. 1 nm for 15% Ni-Al surfaces. Oxide scale analysis indicates significant charge transfer as well as variation in the morphology and structure of the oxide film formed on pure At and 5% Ni-Al alloy. For oxide scales thicker than I urn, the oxide structure in case of pure At exhibits a mixed tetrahedral (AIO(4) similar to 37%) and octahedral (AIO(6) similar to 19%) environment, whereas the oxide scale on Ni-Al alloy surface is almost entirely composed of tetrahedral environment (AIO(4) similar to 60%) with very little AIO(6) (< 1%). The oxide growth kinetic curves are fitted to Arrhenius-type plots to get an estimate of the activation energy barriers for metal oxidation. The activation energy barrier for oxidation on pure At was found to be 0.3 eV lower than that on 5% Ni-Al surface. Atomistic observations as well as calculated dynamical correlation functions indicate a layer by layer growth on pure Al, whereas a transition from an initial island growth mode (< 75 ps) to a layer by layer mode (> 100 ps) occurs in case of 5% Ni-Al alloy. The oxide growth on both pure At and Ni-Al alloy surfaces occurs by inward anion and outward cation diffusions. The cation diffusion in both the cases is similar, whereas the anion diffusion in case of 5% Ni-Al is 25% lower than pure At, thereby resulting in reduced self-limiting thickness of oxide scale on the alloy surface. The simulation findings agree well with previously reported experimental observations of oxidation on Ni-Al alloy surface.