The thermodynamic and thermo-physical properties of the molten salt system [Formula presented] have been investigated using an experimental and modelling approach. This molten salt system includes a single intermediate compound [Formula presented], whose structure has been investigated using X-ray and neutron diffraction. Furthermore, this system exhibits solubility of [Formula presented] in [Formula presented] at high temperatures up to a concentration of around 25% [Formula presented] at 1060 K. Additionally, our measurements show solubility of [Formula presented] in [Formula presented] up to about 5% [Formula presented] at 973 K. The investigation of these solid solutions has been performed using quenching experiments and subsequent post-characterisation by X-ray diffraction (XRD). Phase diagram equilibria have also been investigated using differential scanning calorimetry (DSC). Using the aforementioned information on phase transitions, intermediate compound formation, and mutual solid solubility, a thermodynamic assessment of the system has been performed using the CALPHAD method. The model for the Gibbs energy of the liquid solution is the quasi-chemical formalism in the quadruplet approximation, while the model for the Gibbs energy of the solid solutions is a two-sublattice polynomial model.

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The quaternary compound Cs₂Pb(MoO₄)₂ was synthesized and its structure was characterized using X-ray and neutron diffraction from 298 to 773 K, while thermal expansion was studied from 298 to 723 K. The crystal structure of the high-temperature phase β-Cs₂Pb(MoO₄)₂ was elucidated, and it was found to crystallize in the space group R3̅m (No. 166), i.e., with a palmierite structure. In addition, the oxidation state of Mo in the low-temperature phase α-Cs₂Pb(MoO₄)₂ was studied using X-ray absorption near-edge structure spectroscopy. Phase diagram equilibrium measurements in the Cs₂MoO₄-PbMoO₄ system were performed, revisiting a previously reported phase diagram. The equilibrium phase diagram proposed here includes a different composition of the intermediate compound in this system. The obtained data can serve as relevant information for thermodynamic modeling in view of the safety assessment of next-generation lead-cooled fast reactors.

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The ternary cesium molybdates Cs₂Mo₂O₇, Cs₂Mo₃O₁₀, Cs₂Mo₅O₁₆ and Cs₂Mo₇O₂₂ have been synthesized in this work using a solid state route and their structures have been characterized using X-ray diffraction. The enthalpies of formation of Cs₂Mo₂O₇ and Cs₂Mo₃O₁₀ have been measured using solution calorimetry, yielding Δ_fH_m^o(Cs₂Mo₂O₇, cr, 298.15 K) = −(2301.6 ± 4.7) kJ · mol⁻¹ and Δ_fH_m^o(Cs₂Mo₃O₁₀, cr, 298.15 K) = −(3075.6 ± 6.5) kJ · mol⁻¹, respectively. In addition, the transition temperatures and transition enthalpies of Cs₂Mo₂O₇, Cs₂Mo₃O₁₀, Cs₂Mo₅O₁₆ and Cs₂Mo₇O₂₂ have been determined using differential scanning calorimetry. Finally, phase diagram equilibria measurements in the Cs₂MoO₄-MoO₃ pseudo-binary section have been performed, that have yielded generally slightly lower transition temperatures than reported in previous studies. Those data can serve as valuable input for thermodynamic modelling purposes of the fission products chemistry in Light Water Reactors and next generation Sodium-cooled Fast Reactors and Lead-cooled Fast Reactors.

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© 2021 The Authors LiF-UF4 is a key binary system for molten fluoride reactor technology, which has not been scrutinized as thoroughly as the closely related LiF-ThF4 system. The phase diagram equilibria in the system LiF-UF4 are explored in this work with X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The short-range ordering in the molten salt solution is moreover surveyed with Extended X-ray Absorption Fine Structure spectroscopy (EXAFS) and interpreted using a combination of standard fitting of the EXAFS data and Molecular Dynamics (MD) simulations with a Polarizable Ion Model (PIM) potential. The density, excess molar volume, thermal expansion, heat capacity, and enthalpy of mixing are extracted from the MD simulations across a range of temperatures and compositions; the behavior is non-ideal, with reasonably good agreement with the experimental data. Also calculated is the distribution of heteropolyanions in the liquid solution, and modelled using the quasi-chemical formalism in the quadruplet approximation taking into account the existence of the single-shell complexes [UF7]3−, [UF8]4−, and the dimeric species [U2F14]6−. Subjecting the optimization of the excess Gibbs energy parameters of the liquid solution to the constraints of the phase diagram data and local structure of the melt as derived from the EXAFS and coupled MD simulations, a CALPHAD-type assessment is proposed, linking structural and thermodynamic properties, with a rigorous physical description of the melt.@en

The short-range structures of LiF-ThF4, NaF-AnF4, KF-AnF4, and Cs-AnF4 (An = Th, U), were probed using in situ high temperature Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Signally, the EXAFS spectra of pure molten ThF4 and UF4 were measured for the first time. The data were interpreted with the aid of Molecular Dynamics (MD) and standard fitting of the EXAFS equation. As in related studies, a speciation distribution dominated by [AnFx]4-x (x = 7, 8, 9) coordination complexes was observed. The average coordination number was found to decrease with the increasing size of the alkali cation, and increase with AnF4 content. An average coordination number close to 6, which had not been detected before in melts of alkali actinide fluorides, was seen when CsF was used as solvent. This journal is

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The development at the Delft University of Technology (TU Delft, The Netherlands) of an experimental set-up dedicated to high-temperature in situ EXAFS measurements of radioactive, air-sensitive and corrosive fluoride salts is reported. A detailed description of the sample containment cell, of the furnace design, and of the measurement geometry allowing simultaneous transmission and fluorescence measurements is given herein. The performance of the equipment is tested with the room-temperature measurement of thorium tetrafluoride, and the Th—F and Th—Th bond distances obtained by fitting of the EXAFS data are compared with the ones extracted from a refinement of neutron diffraction data collected at the PEARL beamline at TU Delft. The adequacy of the sample confinement is checked with a mapping of the thorium concentration profile of molten salt material. Finally, a few selected salt mixtures (LiF:ThF₄) = (0.9:0.1), (0.75:0.25), (0.5:0.5) and (NaF:ThF₄) = (0.67:0.33), (0.5:0.5) are measured in the molten state. Qualitative trends along the series are discussed, and the experimental data for the (LiF:ThF₄) = (0.5:0.5) composition are compared with the EXAFS spectrum generated from molecular dynamics simulations.

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A series of Ba2-xEuxMgSi2O7 phosphors was prepared by a solid-state reaction method at high temperature. The theoretical density of the optimal Ba1.93Eu0.07MgSi2O7 material was calculated from the Rietveld refinement result. Eu L3-edge X-ray absorption near edge structure (XANES) spectrum was measured to confirm the valence of Eu ions in Ba2MgSi2O7. The X-ray excited radioluminescence and the thermoluminescence after β-ray irradiation were investigated based on the VUV-vis photoluminescence. The light yield of the optimal Ba1.93Eu0.07MgSi2O7 sample under X-ray excitation was estimated to be ~29,000±6000 photons/M eV. So the temperature-dependent luminescence properties of this sample under X-ray and 344 nm excitation were further studied, and the charge traps in the scintillation process were discussed through thermoluminescence spectra. The high scintillation intensity together with an appropriate intrinsic decay time and its non-hygroscopicity endow the further optimized phosphor Ba1.93Eu0.07MgSi2O7 a promising scintillation material for X-ray detection.@en