Oxidation of UO 2 fuel pellets in air at 503 and 543 K studied using X-ray photoelectron spectroscopy and X-ray diffraction

Abstract

An understanding of the low temperature oxidation behaviour of UO 2 pellets in air is important in the unlikely event of gas ingress to a fuel can during handling or storage. The main parameter of concern is the production time of U 3O 8 particulate as a function of temperature. Factors which affect the UO 2 → U 3 O 8 transformation have been investigated by sequentially oxidising UO 2 fuel pellets in air at 503 and 543 K and monitoring the growth of U 3 O and U 3O 7 using X-ray photoelectron spectroscopy, X-ray diffraction and scanning electron microscopy. Initially oxidation proceeded at a linear rate by the inward diffusion of oxygen to form a complete layer of substoichiometric U 3O 7. This phase was tetragonal with a c a ratio of 1.015, significantly less than the value of 1.03 measured on UO 2 powder when oxidised under identical conditions. This difference and the preferred orientation exhibited by surface grains were caused by growth stresses induced in the pellet surface. Both intergranular and transgranular cracking occurred and became nucleation sites for the growth of U 3O 8. The linear oxidation period associated with U 3O 7 growth was much shorter at 543 than at 503 K and U 3O 8 nucleated earlier. Spallation and the production of particulate were only observed during the formation of U 3O 8 when a 30% increase in volume arose from the U 3 O 7 → U 3 O 8 phase change.