In PWRs, the Zr-1Nb-O alloy shows a marked enhancement in corrosion resistance in comparison with Zircaloy-4. The aim of this work is to analyze the reasons for these different behaviors and to determine the respective nature of the oxide growth controlling mechanisms under irradiation. Samples taken from Zircaloy-4 irradiated 1, 2, and 4 cycles and Zr-1Nb-O irradiated 1 and 3 cycles have been systematically characterized by optical microscopy, SEM coupled with image analysis, hydride distribution, and XRD. Specific TEM characterizations have been performed on the Zr-1Nb-O samples. A XPS analysis of a nonirradiated sample is also reported. It has been shown that under irradiation the slow oxidation kinetics of the Zr-1Nb-O alloy is associated with very regular metal-oxide interface and oxide layer. On the contrary, the accelerated oxidation kinetics of Zircaloy-4 is associated with highly perturbed metal-oxide interface and oxide layer. On both irradiated alloys, cracks are observed to initiate preferentially above the delayed parts of the oxidation front. Hydrogen intake during water oxidation in PWR environment is found to be much lower on the Zr-1Nb-O alloy than on Zircaloy-4. More β-ZrO₂ is found on the oxide layer formed on Zircaloy-4 than on Zr-1Nb-O after oxidation in PWR. Classical irradiation-induced microstructural evolution is observed in the Zr-1Nb-O metallic alloy after 3 cycles, i.e., a fine β-Nb precipitation. β-Nb precipitates are observed to undergo a delayed oxidation associated with a crystalline to amorphous transformation. After water oxidation in autoclave, a pronounced Nb segregation is detected on the oxide surface of a Zr-1Nb-O sample.

These results suggest that the oxidation kinetics of Zircaloy-4 is controlled essentially by oxygen diffusion through the inner barrier layer, which is significantly accelerated under irradiation. The oxidation kinetics of Zr-1Nb-O is controlled by both oxygen diffusion through the inner barrier and by water reduction at the oxide-environment interface; these two mechanisms are less affected by irradiation on this alloy.