In situ oxidation of zirconium binary alloys by environmental SEM and analysis by AFM, FIB, and TEM

Abstract

Binary Zr-alloys containing 1%Fe and 1% Ni (large precipitates) and 1% Cr and 0.6% Nb (small precipitates), as well as a pure Zr sample were exposed in situ at 130 Pa water vapour pressure at 415 °C in an environmental SEM. The surface topography and composition of each sample was characterised before in situ experiments, during and after oxidation. After oxidation the surface was characterised by SEM and EDS, AFM and TEM combined with EDS. Focused ion beam was used to prepare cross sections of the metal–oxide interface and for the preparation of TEM thin foils. The oxidation behaviour of precipitates for these alloying elements can be characterised into two large families, those which show a rapid oxidation and those which induce a delayed oxidation in comparison with the Zr-matrix. At 415 °C after 1 h of oxidation for Zr1%Fe and Zr1%Ni, the formation of protrusions could be detected at the surface, being related to underlying SPP in the oxide. On Zr1%Cr and Zr0.6%Nb unoxidised SPPs were observed in the oxide, close to the metal–oxide interface. These SPPs were, however, oxidised close to the outer surface of the oxide. The surface roughness was increased for all materials after in situ oxidation, however, only for Zr1%Fe and Zr1%Ni protrusions appeared on the surface during oxidation. It was subsequently demonstrated that these latter correspond to the position of SPPs. For Zr1%Fe the surface roughness increased more than in the other materials and on these protrusions small iron oxide crystals have been observed at the surface. These observations confirm that Fe has a different behaviour compared to the other SPP forming elements, and it diffuses out to the free surface of the material. These alloying elements being the constituents of the commercial alloys (Fe and Cr for Zircaloy-4; Fe, Cr and Ni for Zircaloy-2 and Nb for all Nb-containing alloys), this study allows to separate their individual influence and can allow a subsequent comparison to the behaviour of those more complex alloys.