Theoretical study of fluorine-induced surface segregation of Cr in non-passivated Ni-based alloys

The effects of fluorine adsorption on the surface segregation behaviors of chromium in nickel-based alloys are systematically investigated by selecting three typical low-index Cr-doped Ni (111), (100), and (110) surfaces based on the first-principles calculations. The Cr doped in the nickel substrate is identified to possess a local trapping effect for fluorine in the full space and contributes to the more exothermic adsorption of fluorine. In turn, the chemisorption of fluorine on the Cr-doped Ni surfaces can dramatically incur the preferential top-surface segregation for Cr from nickel bulk. The increased adsorption energy of fluorine on Cr-doped Ni surfaces compensates for the larger surface energy of Cr relative to Ni. The strong F-Cr bonding from the deeper hybrid state of F 2p-Cr 3d helps to release strain energy caused by atomic size mismatch. At higher fluorine coverage, the driving force for Cr to segregate at nickel surfaces is significantly increased, as the fluorine starts to agglomerate in th...