[en] The effects of the as-cast microstructure on the oxidation characteristics of two Ni-Al-Cr alloys with either gamma or gamma' primary solidification were investigated with an in-situ, time-resolved X-ray diffraction (TRXRD) technique using synchrotron radiation. The measurements, carried out during rapid heating and cooling, showed that a segregated microstructure in these cast alloys leads to the preferential formation of zirconium oxide before the formation of aluminum oxides is detected. The oxidation leads to a change in the phase stability and to the modification of surface microstructures. Computational thermodynamic models were used to explain the preferential formation of oxides in the as-cast microstructure