ATOMIC SCALE SIMULATION OF ACCIDENT TOLERANT FUEL MATERIALS FOR FUTURE NUCLEAR REACTORS

The 2011 accident at the Fukushima-Daiichi power station following the earthquake and tsunami in Japan put renewed emphasis on increasing the accident tolerance of nuclear fuels. Although the main concern in this incident was the loss of coolant and the Zr cladding reacting with water to form hydrogen, the fuel element is an integral part of any accident tolerant fuel (ATF) concept. Therefore, to license a new commercial nuclear fuel, the prediction of fuel behavior during operation becomes a necessity. This requires knowledge of its properties as a function of temperature, pressure, initial fuel microstructure and irradiation history, or more precisely the changes in microstructure due to irradiation and/or oxidation. Amongst other nuclear fuels, uranium diboride (UB2) and uranium silicide (U3Si2) are considered as potential fuels for the next generation of nuclear reactors due to their high uranium density and high thermal conductivity compared to uranium dioxide (UO2). However, the thermophysical properties and behavior of these fuels under extreme conditions are not well known, neither are they readily available in the literature. Therefore, in this thesis, density functional theory (DFT) and classical molecular dynamic (MD) simulations were used to investigate the thermophysical properties, radiation tolerance and oxidation behavior of UB2 and U3Si2 as potential fuels or burnable absorbers for the next generation of nuclear reactors. UB2 was studied in order to understand its thermophysical properties as a function of temperature. The phonon-assisted thermal conductivity (kph) exhibits large directional anisotropy with larger thermal conductivity parallel to the crystal direction. This has implications for the even dissipation of heat. The increase in thermal conductivity with temperature is justified by the electronic contribution to the thermal transport, especially at high temperatures. This shows that UB2 is a potential ATF candidate. In terms of radiation tolerance, Zr is more soluble in UB2 than Xe, while uranium vacancy is the most stable solution site. Furthermore, as the concentration of Zr fission product (FP) increases, there is a contraction in the volume of UB2, while an increase in Xe results in swelling of the fuel matrix. In terms of diffusion, the presence of an FP in the neighboring U site increases the migration of U in UB2, making U migrate more readily than B as observed in the ideal system. The thermophysical properties of U3Si2 as a possible ATF were studied and discussed considering the neutronic penalty of using a SiC cladding in a reactor. The calculated molar heat capacity and experimental data are in reasonable agreement. Due to the anisotropy in lattice expansion, a directional dependence in the linear thermal expansion coefficient was noticed, which has also been experimentally observed. The thermal conductivity of U3Si2 increases with temperature due to the electronic contribution while the phonon contribution decreases with increasing temperature. A comparison of the thermal conductivity in two different crystallographic directions sheds light on the spatial anisotropy in U3Si2 fuel material. The inherent anisotropic thermophysical properties can be used to parametrize phase field models by incorporating anisotropic thermal conductivity and thermal expansion. This allows for a more accurate description of microstructural changes under variable temperature and irradiation conditions. Due to the metallic nature of U3Si2, the oxidation mechanism is of special interest and has to be investigated. Oxidation in O2 and H2O was investigated using experimental and theoretical methods. The presence of oxide signatures was established from X-ray diffraction (XRD) and Raman spectroscopy after oxidation of the solid U3Si2 sample in oxygen. Surface oxidation of U3Si2 can be linked to the significant charge transfer from surface uranium ions to water and/or oxygen molecules. Detailed charge transfer and bond length analysis revealed the preferential formation of mixed oxides of U-O and Si-O on the U3Si2 (001) surface as well as UO2 alone on the U3Si2 (110) and (111) surfaces. Formation of elongated O−O bonds (peroxo) confirmed the dissociation of molecular oxygen before U3Si2 oxidation. Experimental analysis by Raman spectroscopy and XRD of the oxidized U3Si2 samples has revealed the formation of higher uranium oxides such as UO3 and U3O8. Overall, this work serves as a step towards understanding the complex anisotropic behavior of the thermophysical properties of metallic UB2 and U3Si2 considered as potential accident tolerant nuclear fuel. The calculated anisotropy of thermophysical properties can be used to parametrize phase field model and to incorporate in it anisotropic thermal conductivity and thermal expansion