Submicrometer spectromicroscopy of UO2 aged under high humidity conditions

Abstract

The oxidation of uranium dioxide is a complicated process, depending on factors including humidity, temperature, and microstructure. To further determine the characteristics of this process, UO2 particles were allowed to age and agglomerate under 98% relative humidity at room temperature for 378 days. A focused ion beam (FIB) section of this agglomeration was then measured at the O K-edge, U N5-edge, and C K-edge using the scanning transmission x-ray microscope (STXM) at the Advanced Light Source. O K-edge and U N5-edge x-ray absorption measurements allowed for the elemental and chemical species mapping of the agglomerates and indicated the formation of schoepite at the submicrometer scale in specific locations. Non-negative matrix factorization was employed to elucidate the main components at the O K-edge, which were uranyl (schoepite) formed primarily at the interface of the sample with controlled atmosphere, a UO2-like bulk component present in the majority of the sample, and an oxygen species present at the surface of the FIB section, which is likely adsorbed water. STXM spectromicroscopy measurements at the U N5-edge measurements also confirmed the location of oxidized uranium. This analysis is a valuable insight into the formation of schoepite on UO2 and shows the sensitivity to and utility of STXM spectromicroscopy for uranium speciation.