Experimental and computational assessment of U Si N ternary phases
Uranium nitride-silicide composites are being considered as a high-density and high thermal conductivity fuel option for light water reactors. During development, chemical interactions were observed near the silicide melting point which resulted in formation of an unknown U-Si-N ternary phase. Here in the present work, U-Si-N composite samples were produced by arc-melting U 3 Si 2 under an argon-nitrogen atmosphere to form the ternary phase. The resulting samples were characterized by SEM/EDS-EPMA and XRD, and demonstrated an equilibrium between U 3 Si 2 , UN, USi and a U-Si-N phase with a distinct crystallographic structure. Rietveld refinement of the ternary structure was performed, considering the ternary structures existent in the analogue U-Si-C system, and a good fit was obtained for the hexagonal U 20 Si 16 N 3 phase. DFT + U calculations were performed in parallel to evaluate the thermodynamic and dynamic stability of the ternaries U 20 Si 16 N 3 and U 3 Si 2 N 2 . The calculated enthalpy of formation and phonon dispersion support the existence of stable U 20 Si 16 N 3 and U 3 Si 2 N 2 , although some soft modes in the U 20 Si 16 N 3 phase phonons are observed. The results presented here thus demonstrate the occurrence of at least one ternary phase in the U-Si-N system.