Time-dependent surface modification of uranium oxides exposed to water plasma

Abstract

Thin UO₂ films exposed to water plasma under UHV conditions have been shown to be interesting models for radiation induced oxidative dissolution of spent nuclear fuel. This is partly attributed to the fact that several of the reactive oxidizing and reducing species in a water plasma are also identified as products of radiolysis of water. Exposure of UO₂ films to water plasma has previously been shown to lead to oxidation from U(IV) to U(V) and (VI). In this work we have studied the dynamics of water plasma induced redox changes in UO₂ films by monitoring UO₂ films using X-Ray photoelectron Photoemission (XPS) and Ultra-Violet Photoemission (UPS) spectroscopy as a function of exposure time. The surface composition in terms of oxidation states obtained from U4f7/2 peak deconvolution could be retraced along the exposure time, and compared to the valence band. The spectral analysis showed that U(IV) is initially oxidized to U(V) which is subsequently oxidized to U(VI). For extended exposure times it was shown that U(VI) is slowly reduced back to U(V). UPS data show that, unlike the U(V) formed on the surface upon oxidation of U(IV), the U(V) formed upon reduction of U(VI) is localized in the bulk of the film. It also displays a different reactivity than the initially formed U(V). The experiments can be reproduced using a simple kinetic model describing the redox processes involved.