The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal

Abstract

The oxidation behavior at 900°C of pure Cr and Cr implanted with 2×1016 Y ions/cm2 was studied. The kinetics of oxidation were measured thermogravimetrically and manometrically. The mechanisms of oxide growth were studied using18O-tracer oxidation experiments, and the composition and microstructure of the oxide scales were characterized by TEM and STEM. Segregation of Y cations at Cr2O3 grain boundaries was found to be the critical factor governing changes in the oxidation behavior of Cr upon the addition of Y. In the absence of Y, pure Cr oxidized by the outward diffusion of cations via grain boundaries in the Cr2O3 scale. When Y was present at high concentration in the scale, as when Cr implanted with 2×1010 Y ions/cm2 was oxidized, anion diffusion predominated. It is concluded that strain-induced segregation of Y at grain boundaries in the oxide reduced the cation flux along the grain boundaries. The rate of oxidation was reduced because the grain-boundary diffusivity of cations became lower than the grain-boundary diffusivity of the anions, which then controlled the rate of oxidation. Changes in the relative rates of Cr3+ and O2− transport, as well as a solute-drag effect exerted by Y on the oxide grain boundaries, resulted in changes in the microstructure of the oxide.