Structural investigation of thorium in molten lithium-calcium fluoride mixtures for salt treatment process in molten salt reactor

X-ray absorption fine structure (XAFS) measurements on thorium fluoride in molten lithium-calcium fluoride mixtures and molecular dynamics (MD) simulation of zirconium and yttrium fluoride in molten lithium-calcium fluoride mixtures have been carried out. In the molten state, coordination number of thorium (N_i) and inter ionic distances between thorium and fluorine in the first neighbor (r_i) are nearly constant in all mixtures. However the fluctuation factors (Debye-Waller factor (σ²) and C₃ cumulant) increase until xCaF₂ = 0.17 and decrease by addition of excess CaF₂. It means that the local structure around Th⁴⁺ is disordered until xCaF₂ = 0.17 and stabilized over xCaF₂ = 0.17. The variation of fluctuation factors is related to the number density of F⁻ in ThF₄ mixtures and the stability of local structure around Th⁴⁺ increases with decreasing the number density of F⁻ in ThF₄ mixtures. This tendency is common to those in the ZrF₄ and YF₃ mixtures. However, in the case of YF₃ mixtures, the local structure around Y³⁺ becomes disordered until xCaF₂ = 0.40 and it becomes stabilized by addition of excess CaF₂. The difference between ThF₄ mixtures and YF₃ mixtures is related to the difference of Coulumbic interaction between Th⁴⁺-F⁻ and Y³⁺-F⁻. Therefore, the variation of local structure around cation is related to not only number density of F⁻ in molten salts but also the Coulumbic interaction between cation and anion.