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DOE OSTI2021

Operational Limits of Redox Metal Oxides Performing Thermochemical Water Splitting

Solar thermochemical hydrogen production is an attractive technology that stores intermittent solar energy in the form of chemical bonds. Efficient operation requires the identification of a redox-active metal oxide (MO x ) material that can achieve high conversion of water to hydrogen at minimal energy input. Water splitting occurs by consecutive reduction and reoxidation reactions of MO x . MO x is reduced to MO x-δ and, in the second step, is reoxidized by water recovering the initial MO x and generate H 2 . The material must reduce at temperatures achievable in concentrated solar receiver/reactors, while maintaining a thermodynamic driving force to split water. At equilibrium, extent of reduction depends on temperature and oxygen partial pressure, and in this analysis, a set of thermodynamic properties, namely, enthalpy and entropy of oxygen vacancy formation, is sufficient to represent MO x . Herein, a method to easily classify materials based on these thermodynamic properties under any condition of oxygen partial pressure and temperature is presented. This method is based on fundamental thermodynamic principles and is applicable for any redox material with known thermodynamic properties. Despite the simplicity of the method, it is believed that this analysis will support future research in targeting thermodynamic properties of redox-active metal oxides.

water splitting↗

DOE OSTI2023

Molecular dynamics simulation studies of 1,3-dimethyl imidazolium nitrate ionic liquid with water

The fundamental understanding of intermolecular interactions of ionic liquids (ILs) with water is essential in predicting IL–water thermodynamic properties. In this study, intermolecular or noncovalent interactions were studied for 1,3-dimethyl imidazolium [DMIM]+ cation and nitrate [NO 3 ] – anion with water, employing quantum mechanics and molecular dynamics simulations. Molecular dynamics simulations were performed using a revised multipolar polarizable force field. The effect of water on ionic liquids was evaluated in terms of thermodynamic and dynamic properties. Thermodynamic properties included liquid densities ρ, excess molar volumes ΔV E , and liquid structures g(r)⁠. Dynamic properties included self-diffusion coefficients D of mixture constituents as a function of water concentration. The density of ionic liquid–water mixtures monotonically decrease with increasing concentration of water. A negative excess volume was obtained for low and high water concentrations, demonstrating strong intermolecular interactions of water with ionic liquid components. Liquid structures of ionic liquid–water mixtures revealed a tendency for anions to interact with cations at shorter intermolecular distances when the water concentration is increased. Diffusion rates were found to increase for all mixture components with increase in the fraction of water. A significant change in the diffusion rate was found at ~0.3 weight fraction of water. However, the water self-diffusion coefficient was dominant at all concentrations. Furthermore, the ratio of water/anion and anion/cation self-diffusion coefficients was found to decrease linearly with increasing concentration of water molecules.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Machine learning molecular dynamics simulations toward exploration of high-temperature properties of nuclear fuel materials: case study of thorium dioxide

Predicting materials properties of nuclear fuel compounds is a challenging task in materials science. Their thermodynamical behaviors around and above the operational temperature are essential for the design of nuclear reactors. However, they are not easy to measure, because the target temperature range is too high to perform various standard experiments safely and accurately. Moreover, theoretical methods such as first-principles calculations also suffer from the computational limitations in calculating thermodynamical properties due to their high calculation-costs and complicated electronic structures stemming from f-orbital occupations of valence electrons in actinide elements. Here, we demonstrate, for the first time, machine-learning molecular-dynamics to theoretically explore high-temperature thermodynamical properties of a nuclear fuel material, thorium dioxide. The target compound satisfies first-principles calculation accuracy because f-electron occupation coincidentally diminishes and the scheme meets sampling sufficiency because it works at the computational cost of classical molecular-dynamics levels. We prepare a set of training data using first-principles molecular dynamics with small number of atoms, which cannot directly evaluate thermodynamical properties but captures essential atomistic dynamics at the high temperature range. Then, we construct a machine-learning molecular-dynamics potential and carry out large-scale molecular-dynamics calculations. Consequently, we successfully access two kinds of thermodynamic phase transitions, namely the melting and the anomalous λ transition induced by large diffusions of oxygen atoms. Furthermore, we quantitatively reproduce various experimental data in the best agreement manner by selecting a density functional scheme known as SCAN. Our results suggest that the present scale-up simulation-scheme using machine-learning techniques opens up a new pathway on theoretical studies of not only nuclear fuel compounds, but also a variety of similar materials that contain both heavy and light elements, like thorium dioxide.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2026

The solubility of NdPO 4 and DyPO 4 and stability of Nd and Dy chloride and hydroxyl complexes as a function of pH and salinity to 450 °C

The mobility of rare earth elements (REE) in geological systems is often controlled by the stability of monazite and xenotime, which are important hosts for the light and heavy REE. These REE phosphates constitute important resources and provide information on ore formation conditions and timing due to their uses as geothermometers and geochronometers. While the thermodynamic properties for these minerals are well-established up to high temperature and pressure, the properties for the aqueous REE complexes are not well constrained with limited information up to 300 °C. In this study, the solubility of synthetic NdPO 4 and DyPO 4 endmembers were measured in hydrothermal sub- to supercritical NaCl-bearing aqueous solutions from 350 at saturated water vapor pressure to 450 °C at 700 bar. The speciation of Nd and Dy was determined in acidic to alkaline solutions (pH 25 °C values from 2 to 10), and indicates that the hydroxyl species REE(OH) 2 + and REE(OH) 3 0 predominate at low salinity (0.01 mol/kg NaCl) with some contribution of REE chloride species REECl 2+ and REECl 2 + in acidic fluids. The REE phosphate solubility measured in these experiments is up to two orders of magnitude higher than predicted using existing thermodynamic properties from literature for aqueous species extrapolated from lower temperature data to supercritical conditions. To address this discrepancy, the thermodynamic properties of the REE aqueous species were optimized using GEMSFITS to derive the formation constants for the REE chloride (β Cl ) and hydroxyl (β OH ) complexes in the studied temperature range. This study highlights the importance of the hydroxyl species REE(OH) 2 + and REE(OH) 3 0 over a wide range of pH and temperature. As a result, the revised thermodynamic properties for Dy and Nd chloride and hydroxyl species more accurately predict the solubility of NdPO 4 and DyPO 4 and provide insight into the speciation and mobility of the light and heavy REE in hydrothermal supercritical fluids in the crust.

58 GEOSCIENCES↗

DOE OSTI2022

Evaluation of thermodynamic closure models for partially reacted two-phase mixture of condensed phase explosives

One of the key fundamental issues that is crucial in the continuum modeling of reactive flow phenomena is the thermodynamically consistent description of reaction mixture properties. To define the mixture properties, thermodynamic closure rules that relate the properties of the individual reaction components to the mixture properties are required. In the context of reactive two-phase modeling approaches, various strategies to define the thermodynamic closures have been adopted such as pressure temperature (PT) equilibrium between the individual reaction components, pressure (specific) volume (PV) equilibrium, etc. The choice of closure rules determines the relative distribution of specific volume and energy across the reaction components that comprise the mixture. Therefore, depending on the choice of the closure, the mixture thermodynamic behavior can vary. The present work examines the effect of different closure approaches on the thermodynamic properties of the reaction mixture. The analysis is performed for a condensed phase HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) based plastic bonded explosive (PBX) 9501 explosive using four different thermodynamic closures, viz., PT equilibrium, PV equilibrium, volume temperature (VT) equilibrium, and pressure (P) equilibrium with reactants on an isentrope. Furthermore, the relative variations in the thermodynamic properties of the mixture are analyzed and compared under both compression and expansion loading regimes. It is shown that out of the four closure models, only PT equilibrium and P equilibrium closures lead to a thermodynamically accurate description of the mixture under both compression and expansion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Profiles of Radiative Fluxes at ENA

Profiles of radiative fluxes observed at the Atmospheric Radiation Measurement (ARM)’s Eastern North Atlantic (ENA) observatory along with the ancillary measurements are reported. The below-cloud drizzle properties were derived by combining the data from the ceilometer and Ka-band ARM Zenith Radar (KAZR) following the technique explained by Ghate et al. (2021 JAMC). The cloud and drizzle water path values were derived from the brightness temperatures reported by the microwave radiometer following the technique of Cadeddu et al. (2020 AMT). The cloud water path was then scaled to the KAZR-reported radar reflectivity to calculate profiles of liquid water content (LWC). Following the analysis from Ghate et al. (2023 JGR), cloud droplet effective radius was calculated using the number concentration value of 100 cm-3. The cloud properties, along with the thermodynamic properties, served as an input to the Rapid Radiative Transfer Model (RRTM) to yield profiles of radiative fluxes at a 1-minute temporal and 50-m vertical resolution. The fluxes were then averaged to hourly temporal resolution for analysis. In Mitra et al. (2025 JClim), the calculated profiles were compared against those derived from the satellite measurements (SYN1deg). Flux profiles from the SYN1deg and the thermodynamic and cloud properties used for deriving them are also reported here. Both all-sky and clear-sky radiative flux profiles were calculated. Due to the large data volume, the surface and top-of-atmosphere (TOA) radiative fluxes for the six-year period, and the hourly profiles of the radiative fluxes for January 2018, are submitted here. Full profiles of radiative fluxes calculated from the thermodynamic and cloud properties measured at the ENA site at 1-minute temporal and 50-m vertical resolution for a six-year period are available from the authors. Six files here correspond to the following data: 1_ENARAD_CERES_with_cld_amount_timeseries.nc: Time-series of hourly values of RRTM-simulated values of upwelling and downwelling fluxes at the surface and TOA, observed boundary-layer cloud fractions, and upwelling and downwelling fluxes from the SYN1deg from July 2015 to January 2022. 2_CERES_2018_at_CERES_levels.nc: SYN1deg radiative fluxes at six levels for the year 2018. 3_ENARad_2018_at_CERES_levels.nc: RRTM calculated fluxes at the SYN1deg vertical levels for the year 2018. 4_ENARad_rrtminputs_hourly_201801.nc: Thermodynamic and cloud properties used as an input to the RRTM for January 2018. 5_CERES_inputs_hourly_201801.nc: Thermodynamic and cloud properties utilized by SYN1deg algorithm for January 2018. 6_ENARAD_hourly_201801.nc: Full profiles of hourly averaged radiative fluxes from the RRTM simulations for January 2018.

Atmosphere↗

DOE OSTI2026

The solubility and speciation of REE phosphate endmembers (CePO 4 and YPO 4 ) in Cl-rich aqueous fluids from 350 to 450 °C and implications for natural systems

The rare earth elements (REE) are important metals used increasingly in advanced technologies. Within the crust, the elements Ce and Y are commonly more abundant compared to other lanthanides and comprise important end-member constituents of REE-bearing minerals. Specifically, Ce is part of the light (L) REE which have larger ionic radii than the heavy (H) REE, which are grouped together with Y. These differences in ionic radius can lead to important physico-chemical trends within the lanthanide group. Despite a recent increase in experimental and thermodynamic data for the REE at high temperature and pressure, there is still a significant lack of these data at supercritical conditions. In this study we conducted batch-type experiments to measure the solubility of REE phosphates (CePO 4 and YPO 4 ) at varying starting pH (1.5–10), and salinity (0.01–1.4 mol/kg NaCl) at 350 and P sat , and from 400 to 450 °C at 700 bar. Results show that the solubility of Ce (33–0.14 ppb) is generally higher than Y (13–0.13 ppb) and that Ce complexes more strongly with both chloride and hydroxyl ligands compared to Y. The solubilities of both REE phosphates are highly pH-dependent and, to a lesser extent, depend on salinity at the studied conditions. The solubility data from this study were implemented into the GEMSFITS program to optimize the thermodynamic properties of Ce and Y hydroxyl and chloride species. The updated standard partial molal Gibbs energies of formation (Δ f G 0 T,P ) are used within the experimental temperature and pressure range to accurately predict the CePO 4 and YPO 4 solubility and Ce and Y speciation behavior. Based on the updated thermodynamic properties we also provide formation constants (log β n Cl,OH ) for Ce and Y hydroxyl and chloride species. Updated thermodynamic properties are applied to model REE-apatite dissolution and REE mobility based on the Pea Ridge iron oxide apatite deposit in Missouri, USA. The apatite dissolution model replicates natural observations including the replacement of monazite and xenotime after apatite and is an example of the utility of the new thermodynamic constants applied to supercritical crustal fluids. Furthermore, the findings of this study advance the predictive capabilities of geochemical models, our understanding of the behavior of individual REE, and permit modeling the overarching fractionation trends between LREE and HREE in supercritical crustal fluids.

58 GEOSCIENCES↗

DOE OSTI2023

Thermodynamic description of molten salt systems: KCl-LiCl-NaCl and KCl-LiCl-NdCl 3

The mixture of KCl and LiCl has been used as electrolyte in the electrorefining process to recover uranium from used nuclear fuels due to the low melting point. However, lanthanides and sodium in the reactor waste continuously dissolve into it and thus alter its thermodynamic properties. To understand the thermodynamic behavior evolution of the electrolyte with the accumulation of impurities, thermodynamic modeling for KCl-LiCl-NaCl and KCl-LiCl-NdCl 3 and four constituent binary systems in the entire composition space was performed using the CALPHAD (CALculation of PHAse Diagrams) approach. The ionic liquid was described by the two-sublattice model, where neutral species were introduced to consider short-range ordering (SRO) within the melt, whereas the solid solution was modeled based on the Compound Energy Formalism. Literature data on phase equilibria and thermochemical properties were critically evaluated and used during the optimization of thermodynamic parameters for KCl-LiCl-NaCl and KCl-LiCl-NdCl 3 and their subsystems. The calculated phase diagrams and mixing enthalpies are in good agreement with the experimental data. The thermodynamic modeling for the KCl-LiCl-NdCl 3 system was carried out for the first time. To fill the gap in experimental measurement, enthalpy of mixing for the KCl-LiCl-NdCl 3 melt was estimated using the surrounded-ion model. These data then served as critical inputs for thermodynamic optimization. Furthermore, the present study can provide insights into thermodynamic property evolution of the electrolyte and solubility limit of various impurities during the electrorefining process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2026

The solubility of ErPO 4 and Er speciation in hydrothermal fluids at varying pH and salinity between 350 and 450 °C

The rare earth elements (REE) are important for the green-energy transition and can be incorporated into the REE phosphates, such as xenotime-(Y), which also hosts heavy REE (Tb– Lu). Xenotime-(Y) is a common accessory mineral in metamorphic rocks and a range of mineral deposits where it controls the mobility of heavy REE, however, the impact of high temperature aqueous fluids on the behavior of heavy REE is largely unknown. Thermodynamic modeling can be utilized as a tool to predict the mobility of REE in hydrothermal aqueous fluids, but must be supported by accurate experimental data. Here, we measured the solubility of endmember synthetic xenotime-structured ErPO4 in NaCl-HCl-NaOH-bearing aqueous solutions at 350 °C and water vapor saturation pressure, at 400 and at 450 °C and 500 bar using batch-type Inconel reactors. Erbium speciation was investigated as a function of pH from 2.8 to 8, where Er chloride species are predominant at acidic conditions (pH <3) and Er hydroxyl complexes are predominant at near- neutral to alkaline conditions (pH >3). At pH 7–9, the measured ErPO 4 solubility (-9.8 to -7.5 log m Er ) is up to 2.5 orders of magnitude lower than thermodynamic predictions (-9.4 to -6.7 log m Er ) using existing thermodynamic databases. At pH 2–3, the predicted ErPO 4 solubility is ~0.5 orders of magnitude higher at 350 °C and ~1 order of magnitude lower at 450 °C compared to experimentally measured Er concentrations. The thermodynamic properties of aqueous Er species were therefore revised in this study. The partial molal Gibbs energy of formation (Δ f G 0 T,P ) for aqueous Er hydroxyl and chloride species are optimized using GEMSFITS and the logarithmic formation constants (logβ n ( Cl,OH) ) were derived at each experimental temperature and pressure. The updated thermodynamic properties for Er hydroxyl species (Er(OH) +2 , Er(OH) 2 + , and Er(OH) 3 0 ) show that their stability shifts to more acidic conditions at and below 400 °C. The Er chloride species (ErCl +2 and ErCl 2 + ) show increased stability compared to Er hydroxyl species at temperatures of 450 °C and 0.01 mol/kg NaCl. The updated thermodynamic properties are implemented into the GEM-Selektor modeling package to investigate the mobility of Er in saline hydrothermal fluids in equilibrium with alkaline rocks. Importantly, the updated properties for Er hydroxyl species result in low Er solubility at rock equilibrated pH conditions due to an expanded hydroxyl predominance zone, but lower aqueous complex stability overall, whereas previous models suggest greater stability for aqueous Er species. Furthermore, ErPO 4 solubility increases with decreasing temperature due to the deprotonation of HCl, which increases the acidity of hydrothermal fluids and the availability of Cl - to complex with the REE. These simulations highlight how fluid-rock reaction and temperature affect the mobility of REE in hydrothermal ore-forming systems.

58 GEOSCIENCES↗

DOE OSTI2020

Experimental determination of the solubility constant of kurnakovite, MgB3O3(OH)5·5H2O

In this study, I present experimental results on the equilibrium between boracite [Mg 3 B 7 O 13 C1(cr)] and kurnakovite [chemical formula, Mg 2 B 6 O 11 ·15H 2 O(cr); structural formula, MgB 3 O 3 (OH) 5 ·5H 2 O(cr)] at 22.5 ± 0.5 °C from a long-term experiment up to 1629 days, approaching equilibrium from the direction of supersaturation, Mg 3 B 7 O 13 C1(cr) + H + + 2B(OH)$^-_4$ + 18H 2 O(1) ⇌ 3MgB 3 O 3 (OH) 5 ·5H 2 O(cr) + C1 - . Based on solubility measurements, the 10-based logarithm of the equilibrium constant for the above reaction at 25 °C is determined to be 12.83 ± 0.08 (2σ). Based on the equilibrium constant for dissolution of boracite, Mg 3 B 7 O 13 C1(cr) + 15H 2 O(1) = 3Mg 2+ + 7B(OH)$^-_4$ + C1 - + 2H + at 25 °C measured previously (Xiong et al. 2018) and that for the reaction between boracite and kurnakovite determined here, the equilibrium constant for dissolution of kurnakovite, MgB 3 O 3 (OH) 5 ·5H 2 O(cr) = Mg 2+ + 3B(OH)$^-_4$ + H + + H 2 O(1) is derived as -14.11 ± 0.40 (2σ). Using the equilibrium constant for dissolution of kurnakovite obtained in this study and the experimental enthalpy of formation for kurnakovite from the literature, a set of thermodynamic properties for kurnakovite at 25 °C and 1 bar is recommended as follows: Δ H $^0_f$ = -4813.24 ± 4.92 kJ/mol, Δ G$^0_f$ = -4232.0 ± 2.3 kJ/mol, and S 0 = 414.3 ± 0.9 J/(mol·K). Among them, the Gibbs energy of formation is based on the equilibrium constant for kurnakovite determined in this study; the enthalpy of formation is from the literature (Li et al. 1997), and the standard entropy is calculated internally with the Gibbs-Helmholtz equation in this work. The thermodynamic properties of kurnakovite estimated using the group contribution method for borate minerals based on the sums of contributions from the cations, borate polyanions, and structural water to the thermodynamic properties from the literature (Li et al. 2000) are consistent, within their uncertainties, with the values listed above. Since kurnakovite usually forms in salt lakes rich in sulfate, studying the interactions of borate with sulfate is important to modeling kurnakovite in salt lakes. Finally, for this purpose, I have re-calibrated our previous model (Xiong et al. 2013) describing the interactions of borate with sulfate based on the new solubility data for borax in Na 2 SO 4 solutions presented here.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Hydrothermal solubility of Dy hydroxide as a function of pH and stability of Dy hydroxyl aqueous complexes from 25 to 250 °C

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.

58 GEOSCIENCES↗

DOE OSTI2021

Transformative Materials for High-Efficiency Thermochemical Production of Solar Fuels (Final Report)

Metal oxide-based two-step solar thermochemical (STC) H 2 O and CO 2 -splitting cycles are a promising route to convert solar thermal energy into fuels. The metal oxide materials are reduced at high temperatures (Step 1), and then at low (but still elevated) temperatures, the reduced oxide is used to split H 2 O or CO 2 (Step 2). However, current applications of these cycles are limited by the efficiency of the metal oxide materials. A lower temperature for reduction is desirable, but that brings a concomitant reduction in the driving force for gas splitting. So, designing novel, high-efficiency materials is challenging. Here, we devised and performed a joint computational-experimental project, combined with materials design strategies and high-throughput approaches with the goal to quickly discover and demonstrate novel thermochemical materials with superior properties. Our approach involves an active feedback loop between experimental and computational research. We have use our previously developed materials design map, to efficiently screen results from high-throughput first- principles computation to predict new compositions and subsequently to experimentally study the properties of novel, predicted materials. Experimental measurements of the thermodynamic properties of selected materials serve as a critical benchmark, not only in evaluating the STCH properties of synthesized compounds, but also serving as a validation dataset for computational approaches. We experimentally explored a set of predicted ABO3 perovskites and focus on obtaining high quality thermodynamic properties for validation of computational prediction of enthalpy and entropy of reduction. These thermodynamic quantities play a major role in designing materials with reduced temperatures of reduction but sufficient gas-splitting rates. Finding good validation between experimental and computational data for enthalpies of reduction, we turn to promising ABO3 materials modified by A and B site substitutions, opening an enormous combinatorial space of materials. We use our high-throughput approach to “tune in” the desired solar thermochemical (STC) properties for STC. This vast composition space can only be reasonably explored using the high-throughput approaches, both computational and experimental, of this proposal. Several promising novel oxide materials have been predicted, synthesized, and verified using our materials design approach.

08 HYDROGEN↗

DOE OSTI2023

Numerical and Experimental Study of an Aircraft Igniter Plasma Jet Discharge

The spark discharge of an aircraft plasma jet igniter is studied using high-fidelity numerical simulations and X-ray radiography measurements. The target problem here features the thermal expansion of hot gas introduced by the electric spark within a confined igniter cavity, which eventually evolves into a pulsed jet of a high-temperature kernel. A comprehensive set of models adapted from existing strategies for internal combustion engine spark plug discharge is extended to the target problem, including the modeling of energy deposition, plasma reactions, thermodynamic properties, and heat losses. A series of validation and parameter studies are performed and presented. The kernel size is found to be sensitive to heat losses arising from radiation and hot gas remained within the discharge cavity, rather than heat conduction to the wall in the discharge cavity. Depending on the enforced shape of the post-breakdown electric arc, the spark kernel can be off-centered, tilted, and considerably asymmetric. These features have been previously not considered when studying such igniter configurations and may have a first-order impact on the ignition process. Provided a proper setup of the heat loss models and electric arc shape, the numerical results are quantitatively comparable to the experimental results in terms of the kernel size, shape, and velocity throughout different stages after the spark discharge.

Tang, Yihao↗

DOE OSTI2021

Bayesian automated weighting of aggregated DFT, MD, and experimental data for candidate thermodynamic models of aluminum with uncertainty quantification

Atomic-scale modeling methods such as density functional theory (DFT) and molecular dynamics (MD) can predict the thermodynamic properties of materials at a lower cost than experimental measurements. However, their regular usage in thermodynamic model construction is hampered by the lack of quantitative agreement with experimental measurements and the lack of uncertainty estimates on the data. To make regular usage of this atomistic simulation data, it is important to assess whether the atomistic simulation datasets, by themselves or in combination with experimental measurements, result in the same physics-informed models best supported by experimental measurements alone. Here, models of aluminum thermodynamic properties are discussed using three data sources: atomistic calculations (DFT and MD), experiments, and a combination of atomistic calculations and experiments. The study shows that, after ensuring self-consistency in predicting key invariant points, both experimental measurements and atomistic calculations can significantly contribute to an optimal model.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Thermal Property Modeling and Assessment of the Physical Properties of FLiNaK

Here, the thermodynamic properties of the LiF–NaF–KF system and its subsystems were re-evaluated using the CALPHAD method, focusing on the deviations from ideality in the heat capacity [C p (T)] of mixtures, temperature-dependence of mixing enthalpies (Δ mix H), vapor pressures of mixtures, and enthalpies of fusion (ΔH fus ) using reported values and measurements. The results of this work confirmed a pseudoternary eutectic at 732.9 K and 46.5LiF–11.5NaF–42KF mol % (FLiNaK) with determined Cp(T) = 69.822 + 0.000679T + 2,137,152T –2 J mol –1 K –1 (732.9 < T < 1200 K) and ΔH fus = 18,051 J mol –1 in good agreement to the experimental values. The resulting accurate thermodynamic representation can be used to find relevant excess thermochemical properties in the whole pseudoternary space and provide insights into their composition and temperature dependence. A detailed evaluation of select thermophysical properties was also conducted to determine recommended density, thermal diffusivity, thermal conductivity, vapor pressures, and boiling point with calculated uncertainties over the temperature range of interest for FLiNaK–salt energy applications.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2024

Linear Correlations of Gibbs Free Energy of REE Phosphates (Monazite, Xenotime, and Rhabdophane) and Internally Consistent Binary Mixing Properties

Rare Earth Elements (REE) phosphates (monazite, xenotime, and rhabdophane) are critical REE-bearing minerals typically formed in hydrothermal and magmatic ore deposits. The thermodynamic properties of those REE minerals are crucial to understanding the solubility, speciation, and transport of REE complexes. However, the standard-state Gibbs free energy of formation (∆G°f) values reported for these minerals in the literature vary by up to 25 kJ mol−1. Here, we present linear free energy relationships that allow the evaluation and estimation of the ∆G°f values at 25 °C and 1 bar for the three minerals from the ionic radius (rREE3+) and the non-solvation Gibbs free energy contribution to the REE3+ aqua ion (∆G°n, REE3+): ∆G°f,monazite − 399.71 rREE3+ = 1.0059 ∆G°n,REE3+ − 2522.51; ∆G°f,xenotime − 344.08 rREE3+ = 0.9909 ∆G°n,REE3+ − 2451.53; and ∆G°f,rhabdophane − 416.17 rREE3+ = 1.0067 ∆G°n, REE3+ − 2688.86. Moreover, based on the new dataset derived for REE end-members, we re-fitted the binary Margules parameter (W) from previous theoretical calculations into linear correlations: W + 0.00204 ∆G°’n,monazite = 39.3549 ∆V + 0.0641; W + 0.00255 ∆G°’n,xenotime = 25.4885 ∆V − 0.0062. The internally consistent thermodynamic properties of these REE phosphates are incorporated into the computer program Supcrtbl, which is available online at Zhu’s research website.

Pan, Ruiguang (ORCID:0000000324896545)↗

DOE OSTI2023

Dependence of predicted bulk properties of hexagonal hydroxyapatite on exchange-correlation functional

Hydroxyapatite (HA) is the main component of human bones and teeth. HA has also been widely applied in various technological fields due to its unique properties. Reliable computational simulations for this critical material often require input parameters obtained from the first-principles density functional theory (DFT) calculations with appropriate exchange–correlation functionals. Previous DFT calculations are insufficient to verify the reliabilities of various functionals, particularly as they fail to assess predictions for multiple properties of the material. In this paper, we first select 18 different functionals to calculate geometric, elastic, electronic, and thermodynamic properties of hexagonal HA bulk crystal. We find that the results from optB86b-vdW and optB88-vdW functionals with dispersion corrections have the overall best agreement with available experimental data. Then, we choose optB88-vdW functional, as well as PBE functional without dispersion corrections as a comparison, to perform extensive first-principles DFT phonon calculations under the quasiharmonic approximation. Various thermodynamic properties (including phonon contributions to internal energy, entropy, and Helmholtz free energy) and thermal parameters (including thermal expansions of volume, thermal expansion coefficients, heat capacities, isothermal bulk moduli, etc.) versus temperature are consequently obtained. By comparing these quantities, we report that the results from optB88-vdW functional have significantly better agreement with available experimental data than those from PBE functional although the latter has been widely used in previous DFT calculations for HA-based material systems.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Calorimetric study of skutterudite (CoAs2.92) and heazlewoodite (Ni3S2)

Abstract Nickel and cobalt arsenides, sulfarsenides, and sulfides occur in many hydrothermal ore deposits, but their thermodynamic properties are not well known, in some cases not known at all. In this work, we determined a full set of thermodynamic properties for heazlewoodite and skutterudite. Both phases were synthesized in evacuated silica tubes at elevated temperatures, and electron microprobe analyses gave their compositions as Ni3S2 and CoAs2.92, respectively. Enthalpies of formation were measured by high-temperature oxide-melt solution calorimetry. The reference phases were pure elements, thus eliminating any systematic errors related to such phases. The enthalpies of formation at T = 298.15 K and P = 105 Pa are –216.0 ± 8.4(2σ) and –88.2 ± 6.1 kJ·mol−1 for Ni3S2 and CoAs2.92, respectively. Entropies were calculated from low-temperature heat capacity (CP) data from relaxation (PPMS) calorimetry and are 133.8 ± 1.6 and 106.4 ± 1.3 J·mol–1·K–1, respectively. The calculated Gibbs free energies of formation are –210.0 ± 8.4 and –79.9 ± 6.2 kJ·mol−1 for Ni3S2 and CoAs2.92, respectively. The PPMS CP data, together with a set of differential scanning calorimetry measurements, were used to derive CP polynomials up to 700 K with the Kieffer model based on previously published frequencies of acoustic and optic modes. Equilibrium constants for selected reactions with an aqueous phase were calculated up to 700 K. Geochemical modeling in these systems, however, should await until more reliable data for other phases from the system Co-Ni-As-S are available.

Geochemistry & Geophysics↗