Effects of sulfur upon Fe and Cr oxide thermal stability in 304 stainless steel

X-ray photoelectron spectroscopy measurements show that exposure of an Fe–Cr–Ni alloy to H₂S and O₂ under ultrahigh vacuum (UHV) conditions leads to the thermal instability of the Fe oxide without affecting the Cr oxide. An atomically clean metal surface, predominantly Fe in composition and free of internal sulfur, was exposed to H₂S under controlled conditions in order to form a sulfided monolayer. Adsorbed S inhibited surface oxidation at temperatures between 325 K and 825 K. The presence of adsorbed S did not, however, inhibit the surface segregation of Cr for temperatures >600 K, compared to a S-free sample. Upon annealing of a sulfided sample to 900 K in UHV, the Fe oxide largely disappears, while no change is observed in the Cr oxide. The S-free sample shows no significant change in either the Fe or Cr oxides upon annealing. The results presented in this paper show that sulfidation of an alloy surface prior to oxidation and surface segregation can adversely affect the thermal stability of the Fe oxide without affecting the Cr oxide overlayer resulting from surface segregation and preferential oxidation.