Oxidation of spent fuel in air at 175 degree to 195 degree C

Oxidation tests in dry air were conducted on four LWR spent fuels at 175{degrees} and 195{degrees}C to determine the effect of the fuel characteristics on the oxidation state likely to exist at the time leaching occurs in a potential repository. Weight changes were measured and samples were examined by XRD, ceramography, TEM, and TGA. Despite local variations in the grain boundary susceptibility to oxidation, all four fuels progressed toward an apparent endpoint at an oxygen-to-metal (O/M) ratio of 2.4. The sole oxidation product was U{sub 4}O{sub 9+x,} a cubic phase structurally related to UO{sub 2} but with a slightly smaller lattice constant. The growth of the U{sub 4}O{sub 9+x} from the grain boundaries into the UO{sub 2} grains followed parabolic kinetics and had an activation energy of 26.6 kcal/mol. Based on the kinetics, the time required at 95{degrees}C to completely oxidize LWR spent fuel to U{sub 4}O{sub 9+x} would be at least 2000 yr. The next oxidation product to form after the U{sub 4}O{sub 9+x} phase may be U{sub 3}O{sub 8,} but no U{sub 3}O{sub 8} or other dilatational oxidation product has been detected in these accelerated tests conducted up to 25,000 h