A thermodynamic model for the Na-O system was developed for the first time using the CALPHAD method after review of the structural, thermodynamic, and phase diagram data available on this system. Differential Scanning Calorimetry measurements were moreover performed to assess the phase equilibria and liquidus temperature in the Na2O-Na2O2 composition range. A CALPHAD model for the Na-U-O system was furthermore developed on the basis of both reviewed experimental data, and thermodynamic functions of the sodium uranates derived by combining ab initio calculations and a quasi-harmonic statistical model. The phase equilibria in this ternary system are particularly relevant for the safety assessment of the nuclear fuel-sodium coolant interaction in Sodium-cooled Fast reactors (SFRs). The model predicts the stability of the ternary phase field UO2-Na3UO4-Na4UO5, which is consistent with the most recent literature data. Further optimization was moreover performed to fit the sodium partial pressures measured experimentally in the NaUO3-Na2U2O7-UO2 and NaUO3-Na2UO4-Na2U2O7 phase fields, yielding an overall consistent description. Finally, the oxygen content required to form pentavalent Na3UO4 and hexavalent Na4UO5 in liquid sodium at 900 K were calculated to be 0.7 and 1.5 wppm, respectively, which are levels typically encountered in SFRs.@en

A thorough understanding of the corrosion chemistry between molten salt fuel and structural materials (e.g., steel) is key for the advancement of Molten Salt Reactor technology. In this work, we consider more specifically the case of a chloride fuel salt mixture and the thermochemistry of a salt mixture such as (NaCl-MgCl2-PuCl3) in interaction with (Fe, Cr, Ni). The present work aims at the development of a thermodynamic model of the key subsystems NaCl-CrCl2, NaCl-CrCl3, and FeCl2-CrCl2 to predict corrosion products that may form between molten salt and structural materials. The Modified Quasichemical Model in the quadruplet approximation is used to describe the Gibbs energy of the liquid phase. A critical review of the existing phase diagram and thermodynamic data on theses systems is first presented. To alleviate the lack of data, ab initio calculations coupled with a quasi-harmonic approach are performed to estimate the thermodynamic properties for the intermediate solid compounds Na2CrCl4 and Na3CrCl6, which exist in the NaCl-CrCl2 and NaCl-CrCl3 systems, respectively. These atomistic simulation data together with selected experimental data are then used as input for the thermodynamic assessment of the three subsystems.@en