Abstract
The mechanisms of initial oxide growth on the equiatomic CoCrFeMnNi high entropy alloy were studied in situ by X-ray photoelectron spectroscopy on clean, oxide-free surfaces exposed stepwise to low-pressure gaseous oxygen. Cr(III), Mn(III), Fe(III), Co(II) but no Ni(II) oxides were formed at 100 °C, and Mn(II) at 200 °C. Data quantification revealed a transition mechanism from selective initial oxidation to 3D kinetically-controlled growth, leading to stratification of the oxide film. Formation of the Co-rich outer layer above the Cr-rich inner layer first formed implies predominant cationic outward oxide growth supported by the overall stoichiometry of the film.
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