Transient Covalency in Molten Uranium(III) Chloride
Not Available
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Engineering topics
Agca, Can
Publications and source records attributed to Agca, Can.
Density Measurements of Molten LiF–BeF 2 and LiF–BeF 2 –LaF 3 Salt Mixtures by Neutron Radiography
The densities of eutectic (LiF) 2 –BeF 2 and mixtures of this salt (FLiBe) with LaF 3 were measured by dilatometry and by neutron attenuation from 673 K to 1,073 K. Because LaF 3 has a limited solubility in FLiBe, it was necessary to determine the amount of LaF 3 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 LaF 3 –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 LaF 3 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 LaF 3 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.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
In Situ High-Temperature Structural Analysis of High-Entropy Rare-Earth Sesquioxides
High-entropy rare-earth (RE) sesquioxides (RE 2 O 3 ) 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, in this work, we evaluate the effect of the average ionic radius (AIR) on the polymorphism of high-entropy RE 2 O 3 . Powder samples of compositions 1 (Lu,Y,Ho,Nd,La) 2 O 3 (AIR = 0.938 Å) and 2 (Gd,Eu,Sm,Nd,La) 2 O 3 (AIR = 0.982 Å) were synthesized via a wet chemical method, and bead samples were prepared for aerodynamic levitation by melting the powders in a copper hearth. Structural transitions were monitored upon cooling from the melt to 1000 °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 RE 2 O 3 follow the trend of single-RE RE 2 O 3 , but the transition temperatures differ from those of single-RE RE 2 O 3 . The coefficient of thermal expansion values of the B-type phase of compositions 1 and 2 are similar to those of Gd 2 O 3 and previously published high-entropy RE 2 O 3 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Density Measurements of Various Molten Sodium, Magnesium, Potassium, and Uranium Chloride Salt Compositions Using Neutron Imaging
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. Here, 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 UCl 3 –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.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tuning the melting point and phase stability of rare-earth oxides to facilitate their crystal growth from the melt
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.
36 MATERIALS SCIENCE↗
Application of the Redlich-Kister expansion for estimating the density of molten fluoride psuedo-ternary salt systems of nuclear industry interest
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. Here, 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-ZrF 4 , LiF-BeF 2 -ZrF 4 , LiF-BeF 2 -ThF 4 , NaF-LiF-BeF 2 , NaF-KF-BeF 2 , NaF-ZrF 4 -UF 4 , and NaF-BeF 2 -UF 4 . 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. Additionally, the Redlich-Kister approach was 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 ZrF 4 -UF 4 and BeF 2 -UF 4 , as well as the quantification of ternary interaction in NaF-LiF-ZrF 4 , NaF-BeF 2 -UF 4 , and NaF-ZrF 4 -UF 4 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Molecular Structure and Phase Equilibria of Molten Fluoride Salt with and without Dissolved Cesium: FLiNaK–CsF (5 mol %)
Not Available
36 MATERIALS SCIENCE↗
Assessment of Molten Eutectic LiF-NaF-KF Density through Experimental Determination and Semiempirical Modeling
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 °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 °C, and semiempirical modeling. Additionally, 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.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Empirical estimation of densities in NaCl-KCl-UCl 3 and NaCl-KCl-YCl 3 molten salts using Redlich-Kister expansion
Densities of molten KCl-NaCl-UCl 3 and KCl-NaCl-YCl 3 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-YCl 3 liquids and 11% in NaCl-KCl-UCl 3 liquids compared to the available experimental data. Modeling NaCl-KCl-UCl 3 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. Lastly, the outlined modeling method applied in these specific molten salt ternaries can be used for quaternary or higher multicomponent molten salt systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Saline: An API for Thermophysical Properties
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.
21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
Thermal Property Characterization of Molten Salt Reactor–Relevant Salts
The thermochemical and thermophysical properties of molten salt systems are necessary input for the design, licensing, and deployment of molten salt reactor concepts. The thermochemical and thermophysical property measurement capabilities being used and developed at Oak Ridge National Laboratory (ORNL) include liquid density, volumetric thermal expansion, viscosity, vapor pressure, phase behavior, and heat capacity and thermal conductivity measurement capabilities. Properties of eutectic LiF-NaF-KF (FLiNaK) and NaCl-KCl are being measured to validate the measurement techniques to be used to provide data to reactor developers and to better quantify the uncertainty of measurements. This report summarizes the status of thermal conductivity, viscosity, specific heat capacity, and density. A method for property estimation using Redlich Kister expansion is also described. This technique will be used to help validate measured properties and to guide future experiments by targeting mixtures or components for which data are uncertain or lacking.
21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
FY21 Status Report on the Molten Salt Thermal Properties Database (MSTDB) Development
This report describes the thermodynamic assessments for the ZrF 4 -BeF 2 , AlCl 3 -NaCl, AlCl3-KCl and the PuCl 3 -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.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Roadmap for thermal property measurements of Molten Salt Reactor systems
Thermal properties of molten salts, both with and without fissile and fertile material, are fundamental to modeling and simulation that supports design, construction, operation, and accident progression evaluation of molten salt reactors. This roadmap provides guidance to the research community on the types and amounts of required data for base, or carrier, salt systems, recommends simulated burnup fuel salt compositions to evaluate, and provides a technical foundation for a focused salt property evaluation matrix. The property values generated from both computation and experimental methods are used to develop models that constitute the Molten Salt Thermal Properties Database (MSTDB). While the building blocks of MSTDB are fundamental in nature, its data facilitates constructing engineering models that allow stakeholders to investigate the behavior of specific compositions of interest and supports broader modeling and simulation of MSRs through coupling to multi-physics, multi-scale mass accountancy tools.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗