Stability of Alternative Nuclear Fuel Materials in Aqueous Systems
Time: Tue 2022-12-20 10.00
Location: Kollegiesalen, Brinellvägen 8, Stockholm
Subject area: Chemistry
Doctoral student: Sawsan El Jamal , Tillämpad fysikalisk kemi, Nuclear Chemistry Group
Opponent: Professor Claire Corkhill, University of Sheffield, Department of Materials Science and Engineering
Supervisor: Professor Mats Jonsson, Tillämpad fysikalisk kemi; Professor Mats Johnsson, Stockholm University, Department of Materials and Environmental Chemistry
Nuclear power produces a large portion of the electricity worldwide. It has been the largest low-carbon energy source for more than 30 years and has played an essential role in the security of energy supplies for many countries. However, despite its advantages, its future is unknown mainly because of accidents that can happen under reactor operation and the high radioactivity of the fuel after use. Therefore, Generation IV nuclear power has been introduced as it promises a sustainable and economical way of producing energy and reduces some of the risks observed in current reactors. UC and UN have advantageous properties compared to conventional UO2-based fuel which makes them promising fuel candidates for Generation IV nuclear reactors. Even though the fuel for Generation IV reactors is planned to be reprocessed, unexpected political decisions may change these plans, and the used fuel could end up in a geological repository. Therefore, the behavior of these new fuel materials must be understood in accident scenarios in reactors as well as under deep geological repository conditions. The radioactivity of the used fuel will induce radiolysis of water that comes in contact with it. This will lead to oxidative dissolution of the fuel and this is one of the potential routes for radionuclide release in the environment.
In the first part of this thesis, UC and UN have been investigated in aqueous solutions under anoxic conditions, and under the influence of external γ-radiation and H2O2, the latter mimicking the impact of α-radiolysis. The hydrolysis of these materials in aqueous systems resulted in matrix dissolution which is not observed for UO2. The oxidative dissolution induced by H2O2 is more prominent than hydrolysis in water with or without added HCO3- where higher concentrations of dissolved uranium can be detected. In addition, the differences in reactivity are discussed for these materials and H2O2 is most reactive towards UN followed by UC and finally UO2, yet the dissolution yield is the lowest for UN. The change in UC and UN behavior with consecutive exposure to H2O2 was attributed to a change in surface reactivity where catalytic decomposition of H2O2 becomes possible. As it was observed for H2O2 additions, radiation induced oxidative dissolution also dominates over hydrolysis. Unexpectedly high concentrations of H2O2 were observed in the irradiated systems. This was found to be due to formation of nano-particulate studtite that could not be separated from the solutions samples by filtration. Hence, it turned out to be impossible to determine the free U(VI) and H2O2 concentrations in these systems.
Finally, the stability of pure and ZrN containing UN pellet fragments was investigated in aqueous system under external γ-radiation or H2O2 exposure. The behavior of these pellet fragments was similar to the UN powder where the dissolution of uranium was enhanced under oxidizing conditions if compared with anoxic conditions (hydrolysis). Consecutive exposures of UN pellet fragments to H2O2 showed a change in surface reactivity. This change is attributed to the formation of an oxide layer on the surface of UN, as UO2 is less reactive towards H2O2 and UO2 pellets display lower dissolution yields than UN pellets. In addition, the impact of ZrN as a stabilizing additive to UN pellets was studied. The addition of ZrN to UN is expected to stabilize the UN matrix and thus render a more accident tolerant fuel. Interestingly, it was shown that under oxidizing conditions, ZrN did not have a significant impact on the stability of UN pellets in aqueous systems