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Characteristics of the oxide films formed on 304 stainless steel exposed to 290 degrees C oxygenated water in a nickel-lined autoclave were examined. The oxides evolve from dominating irregularly shaped hematite to faceted spinels with increasing immersion time. The surface layer of oxide film is first Cr-enriched and then Ni-enriched as immersion time increases. The oxides nucleate by solid-state reactions with selective dissolution of Fe and Ni, and then grow up through precipitation of cations from solution. Nickel ions dissolved from the nickel lining could promote the stability of NiFe(2)O(4) spinel and influence the oxidation behaviour of 304 stainless steel significantly. (C) 2010 Elsevier Ltd. All rights reserved.