An Atomic-Scale Understanding of UO Surface Evolution during Anoxic Dissolution.

Our present understanding of surface dissolution of nuclear fuels such as uranium dioxide (UO) is limited by the use of nonlocal characterization techniques. Here we discuss the use of state-of-the-art scanning transmission electron microscopy (STEM) to reveal atomic-scale changes occurring to a UO thin film subjected to anoxic dissolution in deionized water. No amorphization of the UO film surface during dissolution is observed, and dissolution occurs preferentially at surface reactive sites that present as surface pits which increase in size as the dissolution proceeds. Using a combination of STEM imaging modes, energy-dispersive X-ray spectroscopy (STEM-EDS), and electron energy loss spectroscopy (STEM-EELS), we investigate structural defects and oxygen passivation of the surface that originates from the filling of the octahedral interstitial site in the center of the unit cells and its associated lattice contraction. Taken together, our results reveal complex pathways for both the dissolution and infiltration of solutions into UO surfaces.