Quantum chemical molecular dynamics study of stress corrosion cracking behavior for fcc Fe and Fe–Cr surfaces

Abstract Quantum chemical molecular dynamics simulation was applied to study the oxidation of bare Fe (1 1 1) and Fe–Cr (1 1 1) surfaces with strain in high temperature water. Simulation results implied the surface morphologies differ from Fe to Fe–Cr because of strong bond between oxygen and chromium atoms. Oxygen atoms were trapped around chromium atoms at Fe–Cr surface, whereas oxygen penetrated into the lattice of Fe bare surface. As a result, the oxygen diffusivity into the Fe–Cr crystal surface reduced. It indicated that the preferential oxidation of chromium would take place on Fe–Cr clean surface at the beginning of the oxidation process. Diffusion of hydrogen and oxygen significantly increased when strain applied to the defective surface. Hydrogen atoms being in the lattice of metal possessed the highly negative charge which indicated the surface oxidized by this negative charge H. Negative charged oxygen atoms make bond with the metallic atom which breakage ultimate metal–metal bond. These bond breakages indicated the formation of oxide layer on the surface and play a key role in subsequent localized corrosion nucleation like stress corrosion cracking.