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Raman investigation of pre- and post-breakaway oxide scales formed on Zircaloy-4 and M5ARG in air at high temperature
Ist Teil von
Journal of nuclear materials, 2012-02, Vol.421 (1-3), p.160-171
Erscheinungsjahr
2012
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
For nuclear facility safety analysis purposes, the Zircaloy-4 and M5ARG air oxidation scales produced in the 800a1000 degree C temperature range have been investigated with micro-Raman spectroscopy. The oxides were characterized to determine the microstructures associated with protective and non-protective behaviors. Systematic scans, from the oxide/metal interface to the scale surface, were performed to study the variations in crystal structure and composition as a function of position in the oxide. The results presented here tend to indicate that the crystallographic phases that are present in the scales are strongly dependent on alloy composition. In particular, looking at scales grown at 800 degree C, the crystallographic phases observed for the M5ARG alloy, t-ZrO2 and m-ZrO2, are similar in many respects to those already identified in scales grown in pure oxygen or steam. This is not the case for Zircaloy-4, since we clearly observed additional Raman signatures which most probably track the presence of nitrogen in the layers well before the occurrence of the kinetic transition. Indeed, the Raman measurements first show the presence of cubic zirconia in the layers, and strongly suggest the presence of zirconium nitride and oxynitride. Increasing the oxidation temperature, zirconium nitride is clearly detected in the scales well before the occurrence of the kinetic transition. Thus, any mechanism proposed to explain this oxidation behavior must consider the fact that both nitrogen and oxygen participate in the scaling reaction.