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[en] Highlights: • Synchrotron based methods provide a powerful approach to understand the oxidation of Alloy 33. • Superheated steam environment was used to assess Alloy 33 as an accident tolerant cladding. • Continuous oxide scale consisted of two layers, chromium oxide and spinel phase (FeCr2O4) oxides. • Concentration of the spinel phase decreased from the oxide surface to the alloy-oxide interface. • Increase in temperature from 800 °C to 1000 °C led to increase in surface oxidation. - Abstract: Alloys of iron-chromium-nickel are being explored as alternative cladding materials to improve safety margins under severe accident conditions. Our research focuses on non-destructively investigating the oxidation behavior of the FeCrNi alloy “Alloy 33” using synchrotron-based methods. The evolution and structure of oxide layer formed in steam environments were characterized using X-ray diffraction, hard X-ray photoelectron spectroscopy, X-ray fluorescence methods and scanning electron microscopy. Our results demonstrate that a compact and continuous oxide scale was formed consisting of two layers, chromium oxide and spinel phase (FeCr2O4) oxides, wherein the concentration of the FeCr2O4 phase decreased from the surface to the bulk-oxide interface.