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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Thermodynamic properties of Gd-Bi alloys determined by emf measurements in LiCl-KCl-GdCl 3 electrolyte

Thermodynamic properties of binary Gd-Bi alloys (mole fraction, x Gd = 0.02–0.35) were determined using electromotive force (emf) measurements in molten LiCl-KCl-GdCl 3 electrolyte in complement with structural, microstructural, and thermal characterization. X-ray diffractometry (XRD) and scanning electron microscopy (SEM) identified the phase constituents of Gd-Bi alloys (x Gd = 0.02–0.35) as Bi matrix and GdBi compound. According to differential scanning calorimetry (DSC) measurements up to 1250 K, a eutectic transition [L = Bi + GdBi] was observed at 543 K but the reported peritectic transition [L + GdBi = GdBi 2 ] was not detected, suggesting the absence of the GdBi 2 compound. Based on structural, microstructural, and thermal characterization of Gd-Bi alloys (x Gd = 0.02–0.35), the GdBi 2 compound was not detected, and its thermodynamic stability is questionable. The emf of Gd-Bi alloy (x Gd = 0.16) at 700–1048 K relative to Gd(s) was measured by electrodepositing pure Gd metal at 25 K increments. Further, the emf values of Gd-Bi alloys were determined via coulometric titration of Gd into liquid Bi using a two-phase [L + GdBi] alloy as a reference electrode at 773–973 K. The solubility of Gd in liquid Bi was also estimated to be 0.50 mol% (773 K), 0.99 mol% (873 K), and 2.21 mol% (973 K) and the excess partial molar Gibbs energy (Δ$\mathrm{\bar{G}^{ex}_{Gd}}$) of liquid Gd-Bi alloys was as low as 65 kJ mol –1 , indicating strong chemical interactions between Gd and Bi.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The universal thermodynamic properties of extremely compact objects

An extremely compact object (ECO) is defined as a quantum object without horizon, whose radius is just a small distance s outside its Schwarzschild radius. We show that any ECO of mass M in d + 1 dimensions with s << (M/m p ) 2/(d-2)(d+1) lp must have (at leading order) the same thermodynamic properties—temperature, entropy and radiation rates—as the corresponding semiclassical black hole of mass M. An essential aspect of the argument involves showing that the Tolman–Oppenheimer–Volkoff equation has no consistent solution in the region just outside the ECO surface, unless this region is filled with radiation at the (appropriately blueshifted) Hawking temperature. In string theory it has been found that black hole microstates are fuzzballs—objects with no horizon—which are expected to have a radius that is only a little larger than the horizon radius. Thus the arguments of this paper provide a nice closure to the fuzzball paradigm: the absence of a horizon removes the information paradox, and the thermodynamic properties of the semiclassical hole are nonetheless recovered to an excellent approximation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Thermodynamic properties and superconductivity of natural carrollite (CuCo 2 S 4 )

The thermodynamic properties of natural carrollite with a formula Cu 0.92 Co 2.07 S 4 are studied using low temperature heat capacity and high temperature oxidative solution calorimetry. The standard thermodynamic functions at 298.15 K are: C p,m °, S m °, H m °, and Φ m ° are 158.48 J∙K −1 ∙mol −1 , 176.33 J∙K −1 ∙mol −1 , 28.40 kJ∙mol −1 , and 81.07 kJ∙mol −1 with an estimated error of 1%. The enthalpies (Δ f H), entropies (Δ f S), and Gibbs energies of formation (Δ f G) from elements at 298.15 K are: −344.46 ± 12.87 kJ∙mol −1 , −45.22 ± 1.81 J∙K −1 ∙mol −1 , and −331.14 ± 1.89 J∙K −1 ∙mol −1 . The stability of carrollite relative to the elements is demonstrated with a negative Gibbs energy (ΔG r °) of formation for several temperatures between 0 and 300 K. Furthermore, a superconductivity transition, which has been observed previously for synthetic carrollite, is confirmed by both the low temperature heat capacity and magnetization measurements.

Chemistry↗
DOE OSTI2025

Computing chemical potentials with machine-learning-accelerated simulations to accurately predict thermodynamic properties of molten salts

The successful design and deployment of next-generation nuclear technologies heavily rely on thermodynamic data for relevant molten salt systems. However, the lack of accurate force fields and efficient methods has limited the quality of thermodynamic predictions from atomistic simulations. Here we propose an efficient free energy framework for computing chemical potentials, which is the central free energy quantity behind many thermodynamic properties. We accelerate our simulations without sacrificing accuracy by using machine learning interatomic potentials trained on density functional theory (DFT) data. Using lithium chloride as our model system, we compute chemical potentials with DFT-accuracy for solid and liquid phases by transmuting ions into noninteracting particles. Notably, in the liquid phase, we demonstrate consistency whether we transmute one ion pair or the entire system into ideal gas particles. By locating the temperature where the chemical potential of solid and liquid phases cross, we predict a melting point of 880 ± 18 K for lithium chloride, which is remarkably close to the experimental value of 883 K. With this successful demonstration, we lay the foundation for high-throughput thermodynamic predictions of many properties that can be derived from the chemical potentials of the minority and majority components in molten salts.

Gibson, Luke D. [Oak Ridge National Laboratory (OR↗
DOE OSTI2020

Thermodynamic properties of metaschoepite predicted from density functional perturbation theory

Density functional perturbation theory (DFPT) calculations of the thermodynamic properties of metaschoepite, (UO 2 ) 8 0 2 (OH) 12 •10H 2 0, are reported. Using a recently revised crystal structure of metaschoepite, the predicted molar entropy and isobaric heat capacity are overall significantly smaller than previous calculations using an earlier orthorhombic crystal structure model. The present DFPT calculations also show large differences between the thermo-dynamic functions of metaschoepite and schoepite, which might reflect the change in phonon properties upon removal of two H 2 0 molecules per formula unit and alteration of the H-bonded interlayer water network from schoepite to metaschoepite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Equation of State for the Thermodynamic Properties of Trans-1,2-dichloroethene [R-1130(E)]

We present an empirical equation of state in terms of the Helmholtz energy for trans-1,2-dichloroethene [R-1130(E)]. The range of validity is from the triple-point temperature, 223.31 K to 525 K with pressures up to 30 MPa. It may be used to calculate all thermodynamic properties in the fluid phase, including liquid, gas, and supercritical regions. Comparisons are given with existing literature data and estimated uncertainties are provided. In addition, checks were made for correct extrapolation behavior so that the equation behaves in a physically realistic manner when used outside of its range of validity, enabling its use in mixture models. The estimated uncertainties (at a k = 2 or 95 % level of confidence) are based on comparisons with critically assessed data and are 0.25 % for vapor pressure for temperatures in the range 300 K < T < 454 K, rising to 1.5 % as the temperature decreases from 300 K to 265 K. For density in the liquid phase the estimated uncertainty is 0.14 % for temperatures 270 K < T < 410 K and for pressures up to 30 MPa. For the vapor phase the estimated uncertainty in density is 3 %. The uncertainty for liquid-phase heat capacity is 1 % at atmospheric pressure over the temperature range 268 K < T < 309 K, and the uncertainty for the speed of sound in the liquid phase is 0.25 % for temperatures 230 K < T < 420 K and for pressures up to 30 MPa. The uncertainties are larger outside of these specified ranges and in the critical region.

1,2-Dichloroethene↗
DOE OSTI2021

Thermodynamic properties of the Nd-Bi system via emf measurements, $\mathrm{DFT}$ calculations, machine learning, and $\mathrm{CALPHAD}$ modeling

Thermodynamic properties of the Nd-Bi system were investigated using a combination of experimental measurements, first-principles calculations based on density functional theory (DFT), data mining and machine learning (DM + ML) predictions, and calculation of phase diagrams (CALPHAD) modeling. The electromotive force (emf) of Nd-Bi alloys in molten LiCl-KCl-NdCl 3 at 773–973 K was measured via coulometric titration of Nd into Bi for the determination of thermochemical properties such as activity coefficients and solubilities of Nd in Bi. A new peritectic reaction of [liquid + NdBi 2 = Nd 3 Bi 7 ] at 774 K was confirmed using differential scanning calorimetry, structural (X-ray diffraction), and microstructural (scanning electron microscopy) analyses. The unknown crystal structure of NdBi2 was suggested to be a mixture of the anti-La 2 Sb configuration and the La 2 Te-type configuration based on ML predictions for over 26,000 data-mined AB 2 -type configurations together with DFT-based verifications. Using the newly acquired experimental data and DFT-based calculations, the thermodynamic description of the Nd-Bi system was remodeled, and a more complete Nd-Bi phase diagram was calculated, including the Nd 3 Bi 7 compound, invariant transition reactions, and liquidus temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A noncollinear density functional theory ansatz for the phononic and thermodynamic properties of α -Pu

Plutonium's phase diagram is host to complex structures and interactions that make the description of its ground state properties elusive. Using all-electron density functional theory calculations, we study the thermodynamic properties of α-Pu. To do this, we build on recent work in the literature by introducing a novel noncollinear magnetic ansatz for α-Pu's ground state. We show that the noncollinear ansatz improves the description of the experimental phonon density of states, heat capacity, and thermal expansion over previous results obtained with a collinear ansatz. Here, despite lacking a bond-equivalent picture of the bonding, these new results for α-Pu, along with recent results on δ-Pu, demonstrate the efficacy of noncollinear ansatzes for the description of plutonium.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular simulation of the structural and thermodynamic properties of n-alkane/brine interfacial systems with nonionic surfactants

All-atom molecular dynamics (MD) simulations are used to study the structural and thermodynamic properties of water + n-heptane interfacial systems in the presence of salinity (NaCl, NaI, KCl, and KI) and two different nonionic surfactants. Excellent qualitative and quantitative agreement with interfacial tension experimental data is obtained, but this requires applying a charge scaling factor to the ionic species, suggesting the likely role of polarizability effects. Tensoactive behavior is observed for the NaI and KI systems, coinciding with layering of the iodide species near the interface. Further, there are significant interaction differences between the surfactants and the different ionic species, but the structural and thermodynamic behavior of the surfactant molecules is relatively unaffected by the specific salt species. Our analysis suggest that the surfactant-surfactant interactions play a critical role in determining the interfacial behavior, with a much smaller impact associated with the composition of the brine phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Consistent thermodynamic properties for alicyclic components of jet fuels: Experimental data, estimation methods, and homologous series trends

Alkylcycloalkanes represent a significant fraction of jet fuel components. An evaluation of their thermodynamic properties, enthalpies of formation in liquid and gas phases and enthalpies of vaporization, was conducted. A combination of available experimental data, up-to-date group-contribution methods, high-level quantum-chemical calculations, and homologous series trends was used to identify outliers and to recommend the most reliable values. The group-contribution approach was found to work well for the enthalpies of vaporization. Its performance for the enthalpies of formation in the liquid and gas phases was found to be substantially less effective, especially considering notable differences in this property among stereoisomers. Computationally affordable high-level ab initio results and homologous series trend analysis appeared more reliable. In conclusion, the recommended property values for 212 individual compounds and their isomeric mixtures were provided.

09 BIOMASS FUELS↗
DOE OSTI2022

Anharmonic thermodynamic properties and phase boundary across the postperovskite transition in MgSi O 3

To address the effects of lattice anharmonicity across the perovskite to postperovskite transition in MgSiO 3 , we conduct calculations using the phonon quasiparticle (PHQ) approach. The PHQ is based on abinitio molecular dynamics and, in principle, captures full anharmonicity. Free energies in the thermodynamic limit (N → ∞) are computed using temperature-dependent quasiparticle dispersions within the phonon gas model. Systematic results on anharmonic thermodynamic properties and phase boundary are reported. Both the local density approximation and the generalized gradient approximation calculations are performed to provide confident constraints on these properties. Anharmonic effects are demonstrated by comparing results with those obtained using the quasiharmonic approximation (QHA). The inadequacy of the QHA is indicated by its overestimation of thermal expansivity and thermodynamic Grüneisen parameter and its converged isochoric heat capacity in the high-temperature limit. The PHQ phase boundary has a Clapeyron slope (dP/dT) that increases with temperature. This result contrasts with the nearly zero curvature of the QHA phase boundary. Anharmonicity bends the phase boundary to lower temperatures at high pressures. Implications for the double-crossing of the phase boundary by the mantle geotherm are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Magnetic field dependent thermodynamic properties of square and quadrupolar artificial spin ice

Applied magnetic fields are an important tuning parameter for artificial spin ice (ASI) systems, as they can drive phase transitions between different magnetic ground states or tune through regimes with high populations of emergent magnetic excitations (e.g., monopole-like quasiparticles). Here, using simulations supported by experiments, we investigate the thermodynamic properties and magnetic phases of square and quadrupolar ASI as a function of applied in-plane magnetic fields. Monte Carlo simulations are used to generate field-dependent maps of the magnetization, the magnetic specific heat, the thermodynamic magnetization fluctuations, and the magnetic order parameters, all under equilibrium conditions. These maps reveal the diversity of magnetic orderings and the phase transitions that occur in different regions of the phase diagrams of these ASIs, and are experimentally supported by magnetooptical measurements of the equilibrium “magnetization noise” in thermally active ASIs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Electronic structural and lattice thermodynamic properties of MAlO2 and M5AlO4 (M = Li, Na, K) sorbents for CO2 capture applications

Abstract The electronic properties and thermal stabilities of MAlO 2 and M 5 AlO 4 (M = Li, Na, K) are investigated by density functional theory and lattice phonon dynamics. Based on the calculated electronic and lattice thermodynamic properties, their abilities to capture CO 2 as solid sorbents are analyzed. The calculated electronic structural properties of MAlO 2 and M 5 AlO 4 indicate that all these alkali aluminates are semiconductors with a bandgap range of 2.4 ~ 6.4 eV. The 1st valence bands of these alkali aluminates are located 0 ~ − 6 eV under Fermi levels and are mainly contributed by p orbitals of O, s and p orbitals of Al and M. The phonon vibrational frequencies of M 5 AlO 4 spread at a lower frequency range compared to their MAlO 2 phases. With increasing temperature, the calculated phonon free energies of M 5 AlO 4 decrease faster than their corresponding MAlO 2 while their entropies have opposite trends. The reaction 2MAlO 2 + CO 2 = M 2 CO 3 + Al 2 O 3 has higher reaction heat and Gibbs free energy change than those of corresponding reaction 2 / 5 M 5 AlO 4 + CO 2 = M 2 CO 3 + 1 / 5 Al 2 O 3 , which shows the former reaction possesses lower turnover temperature. Among the alkali aluminates studied, the β-NaAlO 2 , lt-KAlO 2 , and γ-LiAlO 2 are better candidates that could be applied for CO 2 capture technologies. Graphical Abstract

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effect of Multiple Oxygen Vacancies on the Optical and Thermodynamic Properties of La 0.75 Sr 0.25 Co 0.25 Fe 0.75 O 3-δ Perovskite

We report the oxygen vacancy concentration of perovskite changes with the work condition in applications such as oxygen carriers and oxygen sensors. To explore the effect of multiple oxygen vacancies on the optical and thermodynamic properties, we perform first-principles calculations to investigate the formation of multiple oxygen vacancies in the paramagnetic La 0.75 Sr 0.25 Co 0.25 Fe 0.75 O 3-δ . Our results show that the higher VO concentration in La 0.75 Sr 0.25 Co 0.25 Fe 0.75 O 3-δ occurs at the conditions of higher temperatures and lower oxygen partial pressures. The electrons liberated upon oxygen vacancy formation are partially localized on the nearby Fe/Co sites and partially delocalized through the lattice, with the result that the unoccupied Fe/Co states near the Fermi level decrease and the Fermi level shows an upward shift. From the results of optical absorption, the peaks from 250 to 600 nm are weakened and blue-shifted with increase of oxygen vacancy concentration, due to the decrease of empty Fe states and an upward shift of the Fermi level. The obvious change of optical absorption with oxygen vacancy concentration indicates that La 0.75 Sr 0.25 Co 0.25 Fe 0.75 O 3-δ could be a good candidate for optical oxygen sensors in the visible spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Equilibrium Thermodynamic Properties of Aqueous Solutions of Ionic Liquid 1-Ethyl-3-Methylimidazolium Methanesulfonate [EMIM][MeSO3]

Abstract The ionic liquid 1-ethyl-3-methylimidazolium methanesulfonate ([EMIM][MeSO 3 ]) has been considered as a promising alternative desiccant to triethylene glycol and lithium bromide commonly used in the industry. In this paper, the water activity coefficient of this binary system was measured from 303 K to 363 K with water concentration from 18% to 92%. The interaction energies between the ionic liquid molecules ( $${g}_{22}$$ g 22 ) and between the ionic liquid and water molecules ( $${g}_{12}$$ g 12 ) for the [EMIM][MeSO 3 ]/water binary system were determined from the water activity coefficient data using the Non-Random Two-Liquid (NRTL) model. The magnitude of the interaction energy between the [EMIM][MeSO 3 ] and water molecules ( $${g}_{12}$$ g 12 ) was found to be in the range of 45~49 kJ/mol, which was about 20% larger than that between the water molecules ( $${g}_{11}$$ g 11 ) in the [EMIM][MeSO 3 ]/water system. The large ( $${g}_{12}$$ g 12 ) can explain many observed macroscopic thermodynamic properties such as strong hygroscopicity in the ionic liquid [EMIM][MeSO 3 ]. These interaction energies were used to determine the heat of desorption of the [EMIM][MeSO 3 ]/water system, and the obtained heat of desorption was in good agreement with that calculated from the conventional Clausius-Clapeyron Equation.

42 ENGINEERING↗
DOE OSTI2020

A data-driven model for thermodynamic properties of a steam generator under cycling operation

The varying electricity demand from coal power plants due to the intermittent nature of renewable sources leads to load-follow and on/off operations referred to as cycling. Cycling causes transients of properties such as pressure and temperature within various components of the steam generation system.These transients cause increased damage because of fatigue and creep-fatigue interactions shortening the life of components. An algorithm is developed to identify cycling operations from the gross power data. The data-driven model based on artificial neural networks (ANN) is developed using 10 years data from Coal Creek Station power plant located in North Dakota, USA to estimate properties of the steam generator components during cycling operations. Furthermore, the uniqueness of this model is the ability to predict component properties for the cycling as well as base-load operations and is reported for the first time. The ANN model estimates the component properties, for a given gross power profile and initial conditions, as they vary during cycling operations. As a representative example, the ANN estimates are presented for the superheater outlet pressure, reheater inlet temperature, and flue gas temperature at the air heater inlet. The changes in these variables as a function of the gross power over the time duration are compared with measurements to assess the predictive capability of the model. Mean square errors of 4.49E-04 for superheater outlet pressure, 1.62E-03 for reheater inlet temperature, and 4.14E-04 for flue gas temperature at the air heater inlet were observed.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

First-principles investigation of elastic, vibrational, and thermodynamic properties of kagome metals CsM 3 Te 5 (M = Ti, Zr, Hf)

Kagome metals are a unique class of quantum materials characterized by their distinct atomic lattice arrangement, featuring interlocking triangles and expansive hexagonal voids. These lattice structures impart exotic properties, including superconductivity, interaction-driven topological many-body phenomena, and magnetism, among others. The kagome metal CsM 3 ⁢Te 5 (where M = Ti, Zr, or Hf) exhibits both superconductivity and nontrivial topological electronic properties, offering a promising platform for exploring topological superconductivity. This study employs first-principles density functional theory calculations to systematically analyze the elastic, mechanical, vibrational, thermodynamic, and electronic properties of CsM 3 ⁢Te 5 (M = Ti, Zr, Hf). Our calculations reveal that the studied compounds—CsTi 3 ⁢Te 5 , CsZr 3 ⁢Te 5 , and CsHf 3 ⁢Te 5 —are ductile metals with elastic properties akin to the hexagonal Bi and Sb, with average elastic constants, including a bulk modulus of 27 GPa, a shear modulus of 11 GPa, and Young's modulus of 29 GPa. We observe peculiar dispersionless, flat, phonon branches in the vibrational spectra of these metals. Additionally, we thoroughly analyze the symmetries of the zone-center phonon eigenvectors and predict vibrational fingerprints of the Raman- and infrared-active phonon modes. The analysis of thermodynamic properties reveals the Einstein temperature for CsTi 3 ⁢Te 5 , CsZr 3 ⁢Te 5 , and CsHf 3 ⁢Te 5 to be 66, 54, and 53 K, respectively. Our orbital-decomposed electronic structure calculations reveal significant in-plane steric interactions and multiple Dirac band crossings near the Fermi level. We further investigate the role of spin-orbit coupling effect on the studied properties. Furthermore, this theoretical investigation sheds light on the intriguing quantum behavior of kagome metals.

36 MATERIALS SCIENCE↗