Uranium is arguably the most essential element in the actinide series, serving as a crucial component of nuclear fuels. While U is recognized for engaging the 5f orbitals in chemical bonds under normal conditions, little is known about its coordination chemistry and the nature of bonding interactions at extreme conditions of high temperature. Here we report experimental and computational evidence for the shrinkage of the average U-ligand distance in UCl3 upon the solid-to-molten phase transition, leading to the formation of a significant fraction of short, transient U-Cl bonds with the enhanced involvement of U 5f valence orbitals. These findings reveal that extreme temperatures create an unusual heterogeneous bonding environment around U(III) with distinct inner- and outer-coordination subshells.

The densities of eutectic (LiF)2-BeF2 and mixtures of this salt (FLiBe) with LaF3 were measured by dilatometry and by neutron attenuation from 673 K to 1,073 K. Because LaF3 has a limited solubility in FLiBe, it was necessary to determine the amount of LaF3 in solution before the density could be determined. The FLiBe density determination was favorably benchmarked against the literature data. A simple comparison was not available for the LaF3-FLiBe mixtures, so extrapolation of published data was necessary based on analysis using the Molten Salt Thermal Properties Database-Thermochemistry, or MSTDB-TC, developed by the US Department of Energy. Solubilities for LaF3 in FLiBe ranged from 1 to 4 mol % over 673 to 1,073 K. The salt system was heated and cooled over 24 h to evaluate potential changes in composition and hysteresis during the measurement. Changes in the meniscus were observed, and these were included in the correction for density determinations. Salt surface tension may have led to supersaturation of LaF3 in the salt because the solubility curve was nonlinear with respect to the inverse temperature, as would be expected for an ideal system. Surface tension measurements are currently underway to test this hypothesis.

High-entropy rare-earth (RE) sesquioxides (RE2O3) containing five cations in equimolar amounts have been investigated for a variety of applications, but little is known about their polymorphic behavior and coefficient of thermal expansion. Here, we evaluate the effect of the average ionic radius (AIR) on the polymorphism of high-entropy RE2O3. Powder samples of compositions 1 (Lu,Y,Ho,Nd,La)2O3 (AIR = 0.938 angstrom) and 2 (Gd,Eu,Sm,Nd,La)2O3 (AIR = 0.982 angstrom) were synthesized via a wet chemical method, and bead samples were prepared for aerody-namic levitation by melting the powders in a copper hearth. Structural transitions were monitored upon cooling from the melt to 1000 degrees C via in situ X-ray diffraction on aerodynamically levitated samples. The phase evolution was liquid, hexagonal H-type, and monoclinic B-type for composition 1 and liquid, cubic X-type, H-type, and B-type for composition 2. Based on their AIR, the general polymorphic transformations of the high-entropy RE2O3 follow the trend of single-RE RE2O3, but the transition temperatures differ from those of single-RE RE2O3. The coefficient of thermal expansion values of the B-type phase of compositions 1 and 2 are similar to those of Gd2O3 and previously published high-entropy RE2O3.

With an increased interest in the use of molten salts for energy generation, obtaining thermophysical properties of salt mixtures becomes critical for the understanding of salt performance and behavior. Density is one of the significant thermophysical properties of salt systems. This work presents the density measurement of molten chloride salt mixtures using neutron imaging. This work was performed at the Oak Ridge National Laboratory High-Flux Isotope Reactor. Resulting densities as a function of temperature for different molten chloride salts from this work were compared with calculated values using Redlich-Kister modeling. Agreement between the calculated and measured values was within 1-10%, with the exception of the ternary UCl3-NaCl- KCl salt that showed a 32% discrepancy between several literature reports; however, the results did align well with another neutron radiography article. Analysis of the radiographs suggests that microbubbles in the ternary mixture might have biased the density measurements.

Molten salts have favorable material properties for use in high-temperature energy systems, including thermal energy storage systems, concentrating solar power plants, nuclear reactors, and various industrial manufacturing processes. Knowledge of chemical and thermophysical property data is essential for the design and optimization of these systems, yet data are often limited or uncertain for many candidate salts due to the difficulty of thermophysical property measurements at relevant temperatures (e.g., 500-900 degrees C). Here, the density of molten LiF-NaF-KF eutectic is reassessed through review of previous experimental data, new density measurements from 470 to 800 degrees C, and semiempirical modeling. The density was measured using the displacement technique. Compositional and temperature-dependent density estimates were calculated with a multidimensional Redlich-Kister model. The results of the new experimental measurements agree within 2% of the modeled density of molten eutectic LiF-NaF-KF. The Redlich-Kister model's prediction shows a near-ideal density behavior for the LiF-NaF-KF system and is promising for the estimation of off-eutectic LiF-NaK-KF densities. Finally, through review of the existing literature and comparison to new measurements, recommendations are made for the density of LiF-NaF-KF.

The challenge of growing rare-earth (RE) sesquioxide crystals can be overcome by tailoring their structural stability and melting point via composition engineering. This work contributes to the advancement of the field of crystal growth of high-entropy oxides. A compound with only small REs (Lu,Y,Ho,Yb,Er) 2 O 3 maintains a cubic C-type structure upon cooling from the melt, as observed via in-situ high-temperature neutron diffraction on aerodynamically levitated samples. On the other hand, a compound with a mixture of small and large REs (Lu,Y,Ho,Nd,La) 2 O 3 crystallizes as a mixture of a primary C-type phase with an unstable secondary phase. Crystals of compositions (Lu,Y,Ho,Nd,La) 2 O 3 and (Lu,Y,Gd,Nd,La) 2 O 3 were grown by the micro-pulling-down (mPD) method with a single monoclinic B-type phase, while a powder of (Lu,Y,Ho,Yb,Er) 2 O 3 did not melt at the maximum operating temperature of an iridium-rhenium crucible. The minimization of the melting point of the two grown crystals is attributed to the mismatch in cation sizes. The electron probe microanalysis reveals that the general element segregation behavior in the crystals depends on the composition.

The development of next-generation molten salt reactors relies on accurate knowledge of the thermophysical properties of the candidate coolant and fueled molten salts. These thermophysical properties include density, viscosity, thermal conductivity, and heat capacity. Because of difficulties in measuring thermophysical properties of molten salts, there are many gaps in the current state of thermophysical property knowledge of these salts, particularly those that contain actinides or beryllium. Therefore, leveraging modeling techniques to estimate unknown molten salt thermophysical properties and guide future experimental measurements has high value for the nuclear industry. In this study, the densities of molten fluoride pseudo-ternary salt systems, which are of interest to the nuclear industry, were estimated using Redlich-Kister expansion and Muggianu interpolation techniques. The pseudo-ternary systems considered for estimation in this study were NaF-LiF-ZrF4, LiF-BeF2-ZrF4, LiF-BeF2-ThF4, NaF-LiF-BeF2, NaF-KF-BeF2, NaF-ZrF4-UF4, and NaF-BeF2-UF4. This Redlich-Kister estimation approach accounts for nonideal mixing behavior based on pseudo-binary subsystem interaction parameters determined from experimentally measured pseudo-binary system density data sets. The Redlich-Kister estimation was compared with the method of additive molar volumes, which assumes ideal mixing. The Redlich-Kister approach was also used to determine previously unknown binary and ternary interaction parameters based on experimentally measured density data sets for select pseudo-ternary salt systems. The results of this study show improvement in density estimation using the Redlich-Kister approach for all systems considered compared with estimation by additive molar volumes. Furthermore, this analysis allowed for the estimation of nonideal density behavior in experimentally unstudied ZrF4-UF4 and BeF2-UF4, as well as the quantification of ternary interaction in NaF-LiF-ZrF4, NaF-BeF2-UF4, and NaF-ZrF4-UF4. Published by Elsevier Ltd.

We demonstrate effects of Cs ions on the melting transition and molecular structure of molten FLiNaK (a eutectic mixture of LiF-NaF-KF). FLiNaK is a commonly studied multi-component model system, which represents the physical and chemical behavior of fluoride salts for nuclear energy applications. Dissolution of nuclear fuels leads to the formation of fission products directly in the molten salt. Cs is one of the most important fission products, due to its relative abundance, long half life, and potential environmental and health effects. Here, we determine the molecular structure and phase equilibria of dissolved Cs in FLiNaK by a combination of X-ray diffraction, X-ray total scattering, ab initio molecular dynamics calculations, and computational thermodynamics. Although Cs ions have a relatively large size, we did not find significant evidence that they disrupt the existing molecular structure of the liquid. We found good agreement between our simulated and measured structure factors, and calculated that the coordination number of Cs is close to 10. X-ray diffraction in combination with computational thermodynamics demonstrates that upon freezing Cs ions are captured into a CsLiF2 compound, with a lower melting temperature than the FLiNaK mixture and much higher than that predicted for CsLiF2 by computational thermodynamics. We also demonstrated a novel sample environment that we developed to X-ray measurements of molten fluoride or fuel salts.

Densities of molten KCl-NaCl-UCl3 and KCl-NaCl-YCl3 ternary systems have been estimated using a multidimensional Redlich-Kister model. Temperature and composition dependent Redlich-Kister functions have been used to generate binary interaction parameters in the outlined ternary salt systems. These binary interactions have been used in the extrapolation to ternary system densities. The results of the density extrapolations by Muggianu interpolation scheme provide agreement within 2-3% for the NaCl-KCl-YCl3 liquids and 11% in NaCl-KCl-UCl3 liquids compared to the available experimental data. Modeling NaCl-KCl-UCl3 molten phase density with a ternary interaction parameter improved the agreement within 4%. Thermophysical modeling used in this study has shown promising results for use in other material properties, such as viscosity, thermal conductivity, and heat capacity of the molten salts. Furthermore, the outlined modeling method applied in these specific molten salt ternaries can be used for quaternary or higher multicomponent molten salt systems. (C) 2021 Elsevier Ltd. All rights reserved.

without an off-gas system, maintenance, off-normal events, and severe reactor accidents. This document highlights those mechanistic behaviors for which models are needed. Simulations of reactor behavior require these models to be developed for molten salt reactors (MSRs), especially if not part of the suite used in describing LWR behavior. The document concludes with recommendations how to develop these models based on what is already known about reactor safety and fission product behavior.

This report describes the thermodynamic assessments for the ZrF4-BeF2, AlCl3-NaCl, AlCl3-KCl and the PuCl3-CsCl pseudo-binary subsystems. Calculation results are compared to the inputs used to optimize the adjustable model parameters. The data came from experimental studies reported in the open literature, from the MSR research community, and/or computational results generated within the NEAMS program and from collaborators. The models from the thermodynamic assessment of these salt systems are integrated into the MSTDB-TC (Molten Salt Thermal Properties Database-Thermochemical). A brief description of the companion MSTDB-TP (Molten Salt Thermal Properties Database-Thermophysical) is given along with an overview of the approach for predicting both thermodynamic and thermophysical property behavior of multicomponent systems.

and has introduced an advanced reactor strategic plan which will address policy issues that need to be addressed to accommodate advanced reactor concepts within the existing regulatory framework. Examples of some of these policy issues are the use of functional containment, the use of mechanistic source terms, and more reliance on performance-based and risk-informed regulatory processes, such as the Licensing Modernization Project, which emphasizes the use of risk-informed processes to select licensing basis events, safety categorization of SSC, and well-defined defense-in-depth systems. Applying performance-based, risk-informed regulatory processes is, consequently, vital to substantially decreasing the cost, time, and uncertainty of commercial MSR reactor licensing while providing for the health and safety of the public and protecting the environment. This document is intended to provide a roadmap for the MSR licensing and safety activities necessary to provide a success path to commercialization.

An initial interface for thermophysical data was generalized for broader incorporation into modeling and simulation codes used for molten salt reactor analysis. A quality assurance review of the thermophysical properties data was conducted; errors were fixed, and improvements were made with consistency and accuracy to references. The Saline code application programming interface was created to facilitate access and integration of thermophysical properties. This report describes the thermophysical data, the quality assurance improvements, and the Saline interface.

The melting behavior of spinel in the Fe-Al-O system at high temperatures (1500-1800 degrees C) was studied by a combination of experimental and computational investigations. Differential thermal analysis (DTA) at ultra-high temperatures coupled with cooling traces on CO2 laser-heated levitated samples provided melting temperatures and the heats of fusion of (Fe,Al)(3)O-4 spinel phases. The experimental results are in fair agreement with the predictions using a published CALPHAD description and areas for modeling improvement are identified. New insights into the melting of defect spinel are provided.

An aerodynamic conical nozzle levitator (CNL) has been used to measure the melting temperatures of refractory ceramics. The well-established method of cooling traces has been adapted to allow measurements for air-sensitive samples using a controlled atmosphere, where the oxygen partial pressure can be adjusted and monitored in real time. In this study, we explain the details of a system that we developed for use at the Spallation Neutron Source (Oak Ridge National Laboratory). Measurements of the melting behavior of (Fe,Cr,Al)(3)O-4 spinels were made between log (P-O2 (atm)) of -0.7 and -5. The melting temperature of hercynite is found to be oxygen potential dependent, ranging between 1692 and 1767 degrees C at log (P-O2) values from -4.42 to -0.70.

The modeling of a loss-of-coolant-accident scenario involving nuclear fuels with FeCrAl cladding materials in consideration to replace a Zircaloy requires knowledge of the thermodynamics of oxidized structures. At temperatures higher than 1500 °C, oxidation of FeCrAl alloys forms (Fe,Cr,Al)3O4 spinels. In situ high-energy X-ray diffraction in a conical nozzle levitator installed at beamline 6-ID-D of the APS was used to study the structural evolution of the oxides as a function of the temperature. Single-phase (spinel) and multiphase (spinel-corundum-FeAlO3) regions are mapped as a function of the temperature for three different compositions of FeCrAl oxidation products. The thermal expansion coefficients and cation distribution in the spinel structure have been refined. The temperature at which complete melting of the fuel cladding is expected has been determined by the liquidus temperatures of the oxidized products to be between 1657 and 1834 °C in a 20% O2/Ar atmosphere using the cooling trace method. The liquidus temperature increases with increasing Al and Cr content in the spinel phase.

The BaO-Sm2O3 system is of interest for the optimization of synthesis of electroceramics. The only systematic experimental study of phase equilibria in the system was performed more than 40 years ago. The reported experimental values of the enthalpy of formation of BaSm2O4 are in conflict, and the reported compound Ba3Sm4O9 has never been confirmed. In this work we synthesized BaSm2O4 by solid-state reaction and determined its heat capacity, enthalpy of formation, and phase transitions by differential scanning calorimetry, high-temperature oxide melt solution calorimetry and ultra-high-temperature differential thermal analysis, respectively. We confirmed the existence of Ba3Sm4O9 and its apparent stability from 1873 to 2273 K by X-ray diffraction on quenched laser-melted samples but were not able to obtain single-phase material for calorimetric measurements. The CALPHAD method was used to assess phase equilibria in the BaO-Sm2O3 system, using both available literature data and our new measurements. A self-consistent thermodynamic database and the calculated phase diagram of the BaO-Sm2O3 system are provided. This work can be used to model and thus to understand the relationships among composition, temperature, and microstructure for multicomponent systems with BaO and Sm2O3.