Thermodynamic Assessment of the NaF-KF-UF4 System

In the Molten Salt Reactor (MSR) concept, metal fluorides are key components of possible fuel and coolant salts. The fast reactor option opens the possibility for alternatives to the Li based matrix salts, avoiding the costly 7Li enrichment and the tritium production from residual 6Li. Such alternatives can be based on NaF and KF as matrix components. In this study, two pseudo-binary phase diagrams of NaF-UF4 and KF-UF4, and the NaF-KF-UF4 pseudo-ternary system were experimentally investigated using Differential Scanning Calorimetry (DSC). The obtained data were used to perform a full thermodynamic assessment of the NaF-KF-UF4 system. The calculated pseudo-ternary eutectic was found at 807 K and a 68.9-7.6-23.5 mol% NaF-KF-UF4 composition. The comprehensive experimental and modelling data obtained in this work provide further extension of the JRCMSD thermodynamic database describing thermodynamic properties of key fuel and coolant salts for the MSR technology.

Theoretical Study on the Lewis Acidity of the Pristine AlF3 and Cl-Doped α-AlF3 Surfaces

In the past two decades, metal fluorides have gained importance in the field of heterogenous catalysis of bond activation reaction, e.g., hydrofluorination. One of the most investigated metal fluorides is AlF3. Together with its chlorine-doped analogon aluminiumchlorofluoride (AlClxF3−x, x = 0.05–0.3; abbreviated ACF), it has attracted much attention due to its application in catalysis. Various surface models for α-AlF3 and their chlorinated analogues (as representatives of amorphous ACF) are investigated with respect to their Lewis acidity of the active centres. First-principle density functional theory (DFT) methods with dispersion correction are used to determine the adsorption structure and energy of the probe molecules CO and NH3. The corresponding vibrational frequency shift agrees well with the measured values. With this insight we predict the local structure of the active sites and can clarify the importance of secondary interactions to the local anionic surrounding of the catalytic site.