Instability of U3Si2 in pressurized water media at elevated temperatures.

Following the Fukushima Daiichi accident, significant efforts from industry and the scientific community have been directed towards the development of alternative nuclear reactor fuels with enhanced accident tolerance. Among the proposed materials for such fuels is a uranium silicide compound (U3Si2), which has been selected for its enhanced thermal conductivity and high density of uranium compared to the reference commercial light water reactor (LWR) nuclear fuel, uranium oxide (UO2). To be a viable candidate LWR fuel, however, U3Si2 must also demonstrate that, in the event of this fuel coming in contact with aqueous media, it will not degrade rapidly. In this contribution, we report the results of experiments investigating the stability of U3Si2 in pressurized water at elevated temperatures and identify the mechanisms that control the interaction of U3Si2 under these conditions. Our data indicate that the stability of this material is primarily controlled by the formation of a layer of USiO4 (the mineral, coffinite) at the surface of U3Si2. The results also show that these layers are destabilized at T > 300 °C, leading to the complete decomposition of U3Si2 and its pulverization due to its full oxidation to UO2.

Challenging the thorium-immobility paradigm.

Thorium is the most abundant actinide in the Earth's crust and has universally been considered one of the most immobile elements in natural aqueous systems. This view, however, is based almost exclusively on solubility data obtained at low temperature and their theoretical extrapolation to elevated temperature. The occurrence of hydrothermal deposits with high concentrations of Th challenges the Th immobility paradigm and strongly suggests that Th may be mobilized by some aqueous fluids. Here, we demonstrate experimentally that Th, indeed, is highly mobile at temperatures between 175 and 250 °C in sulfate-bearing aqueous fluids due to the formation of the highly stable Th(SO4)2 aqueous complex. The results of this study indicate that current models grossly underestimate the mobility of Th in hydrothermal fluids, and thus the behavior of Th in ore-forming systems and the nuclear fuel cycle needs to be re-evaluated.