Transient oxidation in Fe-Cr-Ni alloys: A Raman-scattering study

Using Raman scattering we have investigated the oxidation, in air, of the Fe-Cr-Ni stainless steels Fe-25Cr-20Ni, Fe-25Cr-20Ni-3Zr, and Fe-24Cr-3Zr (wt.%) as a function of temperature in the range 300 to 1000°C. The Raman technique is very sensitive to, and provides a clear identification of, the oxides Fe₂O₃ and Cr₂O₃. However, the technique is insensitive to NiO, FeO, and does not give a clear identification of spinels. The Fe–Cr–Ni alloys form chromia scales at temperatures greater than 800°C. At lower oxidation temperatures, transient phases are observed. With a 1-h heat treatment at 300°C, we observe the formation of an unidentified scale; we speculate that it is either amorphous or consists of disordered spinel(s). Near 400°C we begin to observe hematite (Fe₂O₃). The intensity of the Fe₂O₃ signal increases with temperature to 600°C and then decreases, being largely replaced by the signal from Cr₂O₃. The thickness of the Cr₂O₃ scale increases with temperature up to 1000°C above which spallation becomes apparent. Spinel phases also apparently persist in the scale to 1000°C.