Thermophysical Properties Of Molten Salts Research Articles

Thermophysical properties of Molten FLiNaK: A moment tensor potential approach

Fluoride salts demonstrate significant potential for applications in next-generation nuclear reactors, necessitating a comprehensive understanding of their thermophysical properties for technological advancements. Experimental measurement of these properties poses challenges, due to factors such as high temperatures, impurity control, and corrosion. Consequently, precise computational modeling methods become essential for predicting the thermophysical properties of molten salts. In this work, we performed molecular dynamics (MD) simulations of several thermophysical properties of the eutectic salt mixture LiF-NaF-KF (FLiNaK) melt, including density, self-diffusion coefficients, viscosity, and thermal conductivity. We demonstrated the successful application of moment tensor potentials (MTP) as an accurate model for interatomic interactions in FLiNaK. Our results on thermophysical properties calculations exhibit strong agreement with experimental data. An important aspect of our methodology is the incorporation of an active learning scheme, which enables the generation of a robust and accurate potential, while maintaining a moderate-sized training dataset.

Enhanced heat transfer and thermal storage performance of molten K2CO3 by ZnO nanoparticles: A molecular dynamics study

Molten salt serves as a popular medium for thermal storage and transfer in concentrated solar power (CSP) systems. The existing experimental studies have found the capacity of enhancing the heat storage property of the molten carbonate by doping ZnO nanoparticles. However, it has been rarely reported to conduct simulations of ZnO/molten carbonate nanofluids, and the underlying mechanism of how ZnO nanoparticles enhance the heat transfer and storage capacity has less been explored. In this study, molecular dynamics (MD) simulation has been used to investigate the heat transfer and storage properties of a molten K2CO3 nanofluid containing ZnO nanoparticles. It was found that as the nanoparticle mass ratio in molten salt based nanofluids rises, their specific heat capacity initially increases but subsequently diminishes. The specific heat capacity peaks when the ZnO mass ratio is at 1 wt%, resulting in an increase of 17.83 % compared with the base salt. The thermal conductivity in nanofluids based on molten salt increases with the increasing of ZnO mass ratio. Multi-perspective analysis of the mechanism how ZnO nanoparticles enhance the thermal energy storage performance of molten salt, including the microstructural analysis, number density, vibrational density of state, and heat flow decomposition, is conducted. In addition, results of the number density illustrates that a compressed layer of K+ is formed surrounding the ZnO nanoparticles, and the change in the potential energy leads to an increasing heat capacity. Analysis of the heat flow decomposition suggests that the enhanced nonbonded interaction is the main reason for the improvement of thermal conductive performance in the nanofluids based on molten salt. The findings in the present study provide a new perspective of how ZnO nanoparticles enhance the thermophysical properties of molten salts.

Predicting thermophysical properties of molten salts in the MgCl2-NaCl-KCl-LiCl system with a shell-model potential

Ternary eutectic salts composed of MgCl2, NaCl, and KCl, referred to as MNK salts, have recently emerged as promising candidates as high-temperature heat transfer fluids and thermal energy storage media. In this study, we performed classical molecular dynamics (MD) simulations to predict the densities, specific heat capacities, viscosities, and ionic self-diffusivities for MNK salts over a wide temperature range. The impact of LiCl additive on their thermophysical properties was also investigated. To capture the electronic polarization of Cl anions by neighboring cations, we developed a novel shell-model potential using the force-matching method and a dataset of ab initio calculated interatomic forces. Our extensive MD simulations predict structure and properties for pure salts and binary/ternary salt mixtures in the MgCl2-NaCl-KCl-LiCl system in overall good agreement with available experimental and theoretical data, which corroborates the accuracy and reliability of our developed potential.

Effect of Al2O3 nanoparticle dispersion on the thermal properties of a eutectic salt for solar power applications: Experimental and molecular simulation studies

Thermophysical properties of molten salts aid in determining the storage efficiency of thermal energy storage (TES) systems in concentrating solar power plants. In this research, a novel ternary molten salt (4NaCl–37KCl–59LiNO3, mol%) was utilized as the phase change material (PCM), while Al2O3 nanoparticles (NPs) were employed as a thermal conductivity enhancer. Experimental measurements and molecular dynamics simulations were conducted to confirm that the introduction of Al2O3 NPs as dopants enhanced the specific heat, thermal conductivity, and energy storage density of the eutectic salt. Specifically, at an Al2O3 NP content of 0.5 wt%, the composite PCM exhibited a 44.23 % increase in liquid-state specific heat and a 40.82 % increase in liquid-state thermal conductivity, along with a 15.73 % increase in storage density. This study demonstrates that the enhanced thermal properties of eutectic salts by adding Al2O3 NPs are primarily attributed to the emergence of nanostructures and alterations in atomic potential energy, as evidenced by both experimental and simulated microstructural analyses. These findings offer valuable insight into the selection of thermal storage materials and additives, as well as their implementation in medium-temperature TES systems, with the objective of optimizing the efficient utilization of solar energy.

Uncertainty analysis of heat transfer of TMSR-SF0 simulator

The TMSR-SF0 simulator is an integral effect thermal-hydraulic experimental system for the development of thorium molten salt reactor (TMSR) program in China. The simulator has two heat transport loops with liquid FLiNaK. In literature, the 95% level confidence uncertainties of the thermophysical properties of FLiNaK are recommended, and the uncertainties of density, heat capacity, thermal conductivity and viscosity are ±2%, ±10, ±10% and ±10% respectively. In order to investigate the effects of thermophysical properties uncertainties on the molten salt heat transport system, the uncertainty and sensitivity analysis of the heat transfer characteristics of the simulator system are carried out on a RELAP5 model. The uncertainties of thermophysical properties are incorporated in simulation model and the Monte Carlo sampling method is used to propagate the input uncertainties through the model. The simulation results indicate that the uncertainty propagated to core outlet temperature is about ±10°C with a confidence level of 95% in a steady-state operation condition. The result should be noted in the design, operation and code validation of molten salt reactor. In addition, more experimental data is necessary for quantifying the uncertainty of thermophysical properties of molten salts.

Ab-Initio molecular dynamics simulations of binary NaCl-ThCl4 and ternary NaCl-ThCl4-UCl3 molten salts

Molten salt reactor (MSR) with Thorium (Th) fuel cycle has attracted growing attention due to its merits such as safety, low radioactive waste production, and non-proliferation. The design and safe operation of MSR rely on a thorough understanding of the thermophysical properties of molten salts over a wide range of composition and temperature. However, experimental data of Th-based molten salts are limited due to the inherent challenges of dealing with corrosive molten salts and the radioactive nature of actinides. In this work, thermophysical properties including density, heat capacity, thermal expansion coefficient, and mixing energy of binary NaCl-ThCl4 and ternary NaCl-ThCl4-UCl3 molten salts are explored using ab-initio molecular dynamic simulations (AIMD) with the dDsC dispersion correction. The calculated mixing energy of binary NaCl-ThCl4 exhibits a minimum close to the eutectic composition. The heat capacity of the mixtures is linearly dependent on the mole fraction of each component. 7-fold and 6-fold coordinated Th complexes are dominant in the mixtures. 8-fold coordinated Th complex increases with ThCl4 fraction due to the formation of network structures. The average coordination number of Th exhibits a minimum near the eutectic composition. The minimum mixing energy for the ternary mixtures is observed in systems with a composition close to [NaCl]0.5[ThCl4]0.25[UCl3]0.25. The density positively deviates from the ideal solution in mixtures near this composition. These results are important to fill the data and knowledge gap of ThCl4 molten salts.

Investigation of the thermal conductivity of molten LiF-NaF-KF with experiments, theory, and equilibrium molecular dynamics

• Thermal conductivity of molten eutectic LiF-NaF-KF is measured from 834 to 1195 K with the variable gap technique. • Thermal conductivity of LiF-NaF-KF is predicted with a kinetic theory derived model and equilibrium molecular dynamics. • Temperature dependence of the thermal conductivity of LiF-NaF-KF is discussed from an experimental and theoretical viewpoint. • Inconsistencies between experimental data on thermal conductivity of molten LiF-NaF-KF reported in literature are discussed. • Mapping of the thermal conductivity of LiF-NaF-KF is proposed in the entire range of temperature from 750 K to 1300 K. Molten salts are being proposed for numerous advanced energy applications, including advanced nuclear reactors, concentrating solar power plants, thermal energy storage, and fusion reactors. Accurate knowledge of the thermophysical properties of molten salts directly impact the performance of these energy systems and are essential for design and safety analyses. Thermal conductivity data for fluoride molten salt and mixtures are especially lacking. In this work, experimental measurements of thermal conductivity using the steady-state variable gap technique were performed on eutectic LiF-NaF-KF from 834 to 1195 K. The experiment accounts for radiative, convective, and conductive heat losses. In addition, theoretical and molecular dynamics models are used, from 750 K up to 1300 K, to estimate the thermal conductivity for comparison with the experimental results. The results of experiments show a weak negative deviation of thermal conductivity with temperature, unlike previous experimental results in the literature. The measured thermal conductivity magnitudes agree with the theoretical and molecular dynamics predictions, aside from the data above 1100 K, where heat losses and radiative errors are the most significant, having a 16% maximum deviation from theory. These experimental results provide new thermal conductivity data for the LiF-NaF-KF system and further validation of the predictive models. The theoretical model was used to map the composition and temperature dependent thermal conductivity of LiF-NaF-KF and the mapping’s deviation from a linear additivity estimation of thermal conductivity. This mapping showed the highest deviations from linearity for KF-LiF rich mixtures and increasing deviation with temperature. Notably, the deviation from linearity near the LiF-NaF-KF eutectic composition was around 25%.

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. 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.

Effect of silica nanoparticle size on the stability and thermophysical properties of molten salts based nanofluids for thermal energy storage applications at concentrated solar power plants

Molten salts-based nanofluids are attractive candidates for thermal energy storage applications due to their enhanced thermophysical properties. However, their stability remains an open issue. In the present work, the size effect of SiO2 nanoparticles on the stability and thermophysical properties of molten binary nitrate salt was studied. For that purpose, the effect of SiO2 based nanofluids was systematically studied by using in-situ high-temperature observations and zeta potential experiments. From the analysis, the nanofluids having nanoparticles larger than 450 nm demonstrate superior stability compared to the ones with nanoparticles of 27 nm. Moreover, in contrast to the case of 27 nm particles increase of viscosity was shown to be negligible for particles larger than 450 nm. The absence of specific heat capacity (Cp) or thermal conductivity enhancement for the cases of larger nanoparticles suggests that the development of molten salts-based nanofluids is bounded by the compromise between the stability and improvement of thermophysical properties, depending on the particle size. These results open a pathway for the development of stable molten salt-based nanofluids with enhanced thermophysical properties where the size of the nanoparticles must be optimized.

A new approach for coupled modelling of the structural and thermo-physical properties of molten salts. Case of a polymeric liquid LiF-BeF2

The (Li,Be)Fx fluoride salt is an ionic liquid with complex non-ideal thermodynamic behaviour due to the formation of short-range order. In this work, we explore the relationship between local structure, thermo-physical and thermodynamic properties in this system using a multidisciplinary approach that couples molecular dynamics simulations using the Polarizable Ion Model (PIM) and thermodynamic modelling assessment using the CALPHAD method. The density, thermal expansion, viscosity, thermal conductivity, molar and mixing enthalpies and heat capacity of the (Li,Be)Fx melt are extracted from the polarizable ionic interaction potentials and investigated across a wide range of compositions and temperatures. The agreement with the available experimental data is generally very good. The local structure is also examined in detail, in particular the transition between a molecular liquid with Li+, BeF42− and F− predominant species at low BeF2 content, and a polymeric liquid at high BeF2 content, with the formation of polymers (Be2F73−, Be3F104−, Be4F135−, etc.), and finally of a three-dimensional network of corner-sharing tetrahedrally coordinated Be2+ cations for pure BeF2. Based on the available experimental information and the output of the MD simulations, we moreover develop for the first time a coupled structural-thermodynamic model for the LiF-BeF2 system based on the quasi-chemical formalism in the quadruplet approximation, that provides a physical description of the melt and reproduces (in addition to the thermodynamic data) the chemical speciation of beryllium polymeric species predicted from the simulations.

Compatibility of container materials for Concentrated Solar Power with a solar salt and alumina based nanofluid: A study under dynamic conditions

Thermal energy storage (TES) is an efficient solution for improving the dispatchability of Concentrated Solar Power (CSP) plants. A system, consisting of two tanks with Solar Salt (NaNO3 60% wt. and KNO3 40% wt.) is commonly used. However, the investment cost of this technology is very high, due to the huge amount of salts required (thousands of tons). A pronounced interest is evident for improving the thermophysical properties of molten salts by adding small amounts of nanoparticles in order to reduce the mass of molten salts at CSP. At the moment, the effect of nanoparticle addition on corrosion of container materials is poorly explored. In particular, there are no works regarding the dynamic effect of nanoparticles on the corrosivity of molten salts. In this work we present first ever dynamic corrosion tests for Solar salt doped with alumina nanoparticles (1% wt.). Carbon Steel A516 and SS347, used in double-tank system, were tested. Corrosion rates were 94.8 μm yr−1 and negligible respectively (1000 h, 385 °C). Detailed examination of construction materials revealed incorporation of nanoparticles into the corrosion layer and considerably lower corrosion rate as compared to the previously reported work on the nanoparticles-free Solar salt.

Precise Viscosity Analysis of Alkali Metal Molten Salts at High Temperature

Recently, solar thermal energy has been attracted considerable attention as a renewable energy alternative to fossil fuels. The operation and efficiency of solar thermal energy plants employing thermal energy storage techniques have been proved at both experimental and commercial scales.1 In solar thermal energy plants, alkali metal molten salts have recently attracted as thermal storage media and heat transfer fluids, because these salts have a low melting point, high heat capacity, and moderate energy density.2 In addition, alkali metal molten salts are less expensive and more environmentally friendly than currently available high-temperature oils. However, many investigations are scarce focusing on thermophysical properties of molten salts at high temperature. In particular, the viscosity of alkali metal molten salts is few reported and the reported viscosities are shown larger difference by analysis method or other one. In this study, therefore, we are measured the viscosity of alkali metal molten salts at high temperature above 500 °C by rotation method using high temperature rheometer system (MCR 502, Anton Paar) and reliability of obtained viscosity values is evaluated.3 This work was supported by Council for Science, Technology and Innovation (CSTI), Cross-ministerial Strategic Innovation Promotion Program (SIP), "energy carrier" (Funding agency: JST). References Q. Peng, X. Yang, J. Ding, X. Wei, and J. Yang, Appl. Energy, 112 (2013) 682.S.M. Flueckiger and S.V. Garimella, Sol. Energy, 86 (2012) 1631.S.W. Kim, K. Uematsu, K. Toda, and M. Sato, J. Ceram. Soc. Jpn., (2015) in press.

Measurement of thermophysical properties of molten salts: Mixtures of alkaline carbonate salts

The purpose of this study is to develop measuring methods for the thermal diffusivity, the specific heat capacity, and the density of molten salts, as well as to measure these properties of mixtures of alkaline carbonate salts. The thermal diffusivity is measured by the stepwise heating method. The sample salt is poured into a thin container, and as a result, a three-layered cell is formed. The thermal diffusivity is obtained from the ratio of temperature rises at different times measured at the rear surface of the cell when the front surface is heated by the stepwise energy from an iodine lamp. The specific heat capacity is measured using an adiabatic scanning calorimeter. The density is measured by Archimedes' principle. Thermal conductivity is determined from the above properties. Measured samples are Li2CO3-K2CO3 (42.7–57.3, 50.0-50.0, and 62.0-38.0 mol%).

Thermophysical properties of molten salts: Hypersonic velocities of molten alkali nitrates and their mixtures

By means of Brillouin scattering spectroscopy, hypersonic velocities in NaNO3-KNO3 binary melts have been measured at temperatures from the liquidus temperatures of the melts to 200 K above them over the entire range of compositions. The light beam scattered by the melt is analyzed with a pressure-scanned Fabry-Perot spectrometer. The hypersonic velocities obtained are about the same as the ultrasonic velocities reported at compositions rich in NaNO3, but are markedly larger than those at compositions rich in KNO3, indicating the occurrence of structural relaxation. Thermodynamic values such as adiabatic and isothermal compressibilities, constant-volume heat capacity, and internal pressure calculated from the sound velocity obtained show that the melt can be treated as a typical ionic liquid, though it contains a certain amount of associated species.