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Results for “Thermodynamic Modeling”

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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Thermodynamic Modeling of Point Defects in Triple Conducting Perovskite Ba 0.95 La 0.05 FeO 3- $_δ$ with Incorporation of the Hydride Defect Formation Reaction for Solid Oxide Cells

Distinct from the proton defect, the hydride defect species may be present in certain perovskite materials in reducing environments such as in fuel electrodes of solid oxide cells (SOCs) or on the reducing side of ceramic membranes. A generalized defect thermodynamic model was developed for the triple-conducting perovskites (La,Ba)Fe 1-x M x O 3-δ (M = Y and Zr) to allow inclusion of the hydride defect formation reaction in addition to the other three main defect reactions, namely, the oxygen vacancy formation, hydration, and charge disproportionation reactions. This comprehensive defect model also allows the incorporation of polynomial functional forms of oxygen nonstoichiometry δ to describe the defect reaction energies and entropies and to enable refinements of the defect reaction equilibrium constants in the defect thermodynamic analysis. As a first step, the developed model is applied to the Ba 0.95 La 0.05 FeO 3-δ material as an illustrative system to obtain its Brouwer diagrams with both the proton and hydride defects in relevant SOC conditions, particularly for more reducing environments. In conclusion, the results provide direct guidance on the influence of electronic and ionic defect concentrations upon thermodynamic properties and ultimately on the performance of Ba 0.95 La 0.05 FeO 3-δ and potentially other (La,Ba)Fe 1-x M x O 3-δ perovskite materials involved in SOC applications.

25 ENERGY STORAGE↗
DOE OSTI2023

Thermodynamic modeling of the Nb-Ni system with uncertainty quantification using PyCalphad and ESPEI

Here, the Nb–Ni system is remodeled with uncertainty quantification (UQ) using software tools of PyCalphad and ESPEI (the Extensible, Self-optimizing Phase Equilibria Infrastructure) with the presently implemented capability of modeling site fraction based on Wyckoff positions. The five- and three-sublattice models are used to model the topologically close pack (TCP) μ-Nb 7 Ni 6 and δ-NbNi 3 phases according to their Wyckoff positions. The inputs for CALPHAD-based thermodynamic modeling include the thermochemical data as a function of temperature predicted by first-principles and phonon calculations based on density functional theory (DFT), ab initio molecular dynamics (AIMD) simulations, together with phase equilibrium and site fraction data in the literature. In addition to phase diagram and thermodynamic properties, the CALPHAD-based predictions of site fractions of Nb in μ-Nb 7 Ni 6 agree well with experimental data. Furthermore, the UQ estimation using the Markov Chain Monte Carlo (MCMC) method as implemented in ESPEI is applied to study the uncertainty of site fraction in μ-Nb 7 Ni 6 and enthalpy of mixing (ΔH mix ) in liquid.

36 MATERIALS SCIENCE↗
NASA NTRS1991

Improved thermodynamic modelling of the no-vent fill process and correlation with experimental data

The United States plans to establish a permanent manned presence in space and to explore the Solar System have created the need to efficiently handle large quantities of subcritical cryogenic fluids, particularly propellants such as liquid hydrogen and liquid oxygen, in low- to zero-gravity environments. One of the key technologies to be developed for fluid handling is the ability to transfer the cryogens between storage and spacecraft tanks. The no-vent fill method has been identified as one way to perform this transfer. In order to understand how to apply this method, a model of the no-vent fill process is being developed and correlated with experimental data. The verified models then can be used to design and analyze configurations for tankage and subcritical fluid depots. This paper discusses the development of an improved macroscopic thermodynamic model of the no-vent fill process and correlates the analytical results from the computer program implementation of the model with experimental results for two different test tanks at NASA Lewis Research Center.

Taylor, W. J.↗
DOE OSTI2023

Thermodynamic modeling of double azeotropy systems

Azeotropes are boiling liquid mixtures which have identical vapor and liquid compositions. Known as polyazeotropy, azeotropic mixtures may exhibit more than one azeotrope at a given temperature or pressure. While the thermodynamic condition for azeotrope formation in vapor-liquid equilibrium is well established, thermodynamic modeling of mixtures exhibiting polyazeotropy remains challenging and prior modeling studies often failed to satisfactorily correlate the polyazeotropic behavior of associating systems. Based on the association NRTL model, this study presents successful correlation and analysis of double azeotrope formation for three diverse systems: strongly associating methanol + diethylamine binary, weakly associating ammonia + pentafluoroethane binary, and non-associating benzene + hexafluorobenzene binary systems. Furthermore, these systems exhibit polyazeotropic behavior as the temperature increases and approaches their Bancroft points.

42 ENGINEERING↗
NASA NTRSDate not supplied

A Case Study of AI-assisted Creation of a Thermodynamics Model of Precipitation Formation During Rapid Depressurization of a Vented Container

Precipitation may form in humid containers undergoing rapid depressurization. This precipitation may be liquid, i.e. fog, if the dewpoint is crossed above the freezing point of water, or direct snow crystallization if the dewpoint is crossed below the freezing point. Accurate modeling of this effect is potentially important for rapidly ascending vented containers in aircraft, spacecraft, and launch vehicles, as well as rapidly depressurizing vacuum chambers. A transient thermodynamics model of precipitation formation during the rapid depressurization of a container was developed in python. The model is written for a generic container and includes an optional water pool and water vapor source. Details of the model and results from several example cases spanning the full capabilities of the model, including a validation case, will be presented. Although the model is not novel, in contrast to prior works, this one was treated as a case study of the assistance of AI Large Language Models (LLMs) to create physical models. Impressions, performance, time, and cost of using AI for this task will be discussed.

precipitation↗
DOE OSTI2023

Thermodynamic modeling of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems

Molten salt electrolysis can recover the actinides from spent nuclear fuels, and it involves a eutectic LiCl-KCl in molten form as an electrolyte. During reprocessing, the concentration of fission products such as La, Nd, Pr, etc., increases and affects the recovery efficiency of the electrolyte. In this work, thermodynamic modeling of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems was carried out using the CALPHAD (Calculation of Phase Diagrams) approach for the first time. The thermodynamic functions for the pure salts were taken from the SGTE (Scientific Group Thermodata Europe) Substances (SSUB) database. The experimental thermochemical and phase equilibria data available in the literature were used as input for the assessment of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems. The model parameters for the KCl-LiCl system were adjusted to include the new Gibbs energy descriptions for the pure salts. In addition, the sublattice model for the liquid phase in the LiCl-PrCl 3 system was modified and reassessed to ensure the model compatibility for higher-order extrapolation. There is a good agreement between the experimental and calculated thermochemical and phase diagram data for all the optimized constituent binaries and the ternary system. Furthermore, this work will be beneficial for determining the solubility limit of PrCl 3 in molten LiCl-KCl electrolytes and their thermodynamic properties for improving the efficiency of the pyrochemical process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS2024

Thermodynamic Modeling of Calcium and Magnesium Partitioning Between Sulfide and Silicate and Implications for Mercury’s Differentiation

Mercury is the least oxidized terrestrial planet of the solar system and is enriched in sulfur, which may be saturated in its mantle, possibly forming Ca- and Mg-rich sulfides. Using literature experimental data, we developed a thermodynamic model for calcium and magnesium partitioning between sulfide and silicate melts to enhance our understanding of the chemical equilibria involved in Mercury’s mantle-crust differentiation. Our models show that temperature and carbon abundance in sulfide have a positive effect on Ca partitioning into sulfides, while pressure decreases it. In addition, carbon abundance and sulfur concentration in the silicate melt are the primary controls on Mg partitioning, both favoring Mg partitioning into sulfides. Our results will be used to better understand the abundance as well as presence of calcium and magnesium sulfides within Mercury’s mantle and crust.

Taylor McCombs↗
DOE OSTI2024

Comment on “Thermodynamic Models for the (HClO 4 + NaClO 4 ){aq} and (HBr + NaBr){aq} Systems at 298.15 K and 0.1 MPa” Authored by Oakes, C. S., Ward, A. L., Chugunov, N. Journal of Chemical & Engineering Data , 68 , 2554–2562

Oakes et al. (2023) published a review article in this journal. In that paper, Oakes et al. (2023) developed thermodynamic models to describe electrolyte solutions for HClO 4 –NaClO 4 –H 2 O and HBr–NaBr–H 2 O systems, based on literature data. In their paper, previously published work from researchers in the field was criticized; some of it is ours. Here, in this brief Comment, we first comment on their models, and then we briefly provide a technical response to that criticism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Calcium and Magnesium Distribution Between Sulfide and Silicate Melts: Thermodynamic Modeling and Insights into Mercury's Mantle-Crust Differentiation

Mercury stands out as the terrestrial planet with the lowest degree of oxidation among all planets of our solar system. It is characterized by a high abundance of sulfur, which is expected to replace oxygen in silicate melts. This sulfur enrichment could lead to sulfide saturation in its mantle, potentially resulting in the formation of sulfides rich in calcium and magnesium. Utilizing experimental data from the literature, we constructed a thermodynamic model to explore the partitioning of calcium and magnesium between sulfide and silicate melts. This model aims to improve our comprehension of the chemical equilibria driving the process of mantle-crust differentiation on Mercury. Our models indicate that increased temperature, decreased pressure, and low concentrations of iron, oxygen, and carbon within the sulfide phase, along with low sulfur concentrations in the silicate phase, favor calcium’s partitioning into the sulfide. Additionally, magnesium partitioning into the sulfide melt is favored with decreased pressure, decreased temperature, low concentrations of iron and calcium within the sulfide, and low concentrations of sulfur within the silicate. Our results suggest that up 9.4% and 5.6% Ca and Mg, respectively, can be present in sulfides equilibrated with sulfide-saturated silicate melts during mantle-crust differentiation. Further investigation will focus on the distribution of sulfide phases within the mantle and crust to better constrain Mercury’s internal structure.

Taylor McCombs↗
DOE OSTI2024

High-Pressure Melting Experiments of Fe 3 C and a Thermodynamic Model of Fe-C Liquids for the Earth's Core

Melting experiments of Fe 3 C were conducted to 85 GPa in laser-heated diamond anvil cells with in situ X-ray diffraction and post-experiment textural observation. From the determined pressure-temperature conditions of the melting curve for Fe 3 C, together with literature data on the melting point of diamond and eutectic point of the system Fe-Fe 3 C/Fe 7 C 3 under high pressures, we established a self-consistent thermodynamic model for high-pressure melting of the system Fe-C including the mixing parameters for liquids. The results show that mixing of Fe and C liquids is negatively nonideal from 1 bar to the pressure at the center of the Earth. The departure from ideal mixing becomes progressively larger with increasing pressure, which leads to greatly stabilized liquids under core pressures. The modeled carbon content in eutectic melts under core pressures is 3.3–4.4 wt%. From the Gibbs free energy, we derived an internally consistent parameters for Fe-C outer cores which included the crystallizing points at their bottoms, isentropic thermal profiles, and densities and longitudinal seismic wave speeds (Vp). While the addition of carbon in excess of the eutectic melt composition effectively reduces the density of iron liquid, the Vp of iron liquid is not greatly changed. Therefore, the low density and high Vp of PREM relative to pure iron cannot be reconciled by an Fe-C liquid. Therefore, the Earth's core cannot be approximated by the system Fe-C and should include another light element.

58 GEOSCIENCES↗
NASA NTRSDate not supplied

Thermodynamic Modeling of the Vapor in Equilibrium With Apollo 17 Basalts.

Lunar mare basalts sampled during the Apollo 17 mission provide insight to the chemical evolution of mare basalt magmas and their associated vapor as these samples erupted and cooled rapidly at the lunar surface. We focus on minerals present on vesicle and vug surfaces in Apollo 17 basalts, such as 71036, which was opened as part of the Apollo Next Generation Sample Analysis (ANGSA) program. The mineral assemblage observed includes native Fe, SiO2, and a Mg-P mineral, possibly merrillite [1, 2]. The pet-rographic context of these phases suggests that they may have been deposited directly from the vapor phase after eruption. Here we use thermodynamic modeling to assess the plausibility of the vapor-phase deposition hypothesis.

D. L. Thompson↗
DOE OSTI2023

A Thermodynamic Model for Nd(III)–Sulfate Interaction at High Ionic Strengths and Elevated Temperatures: Applications to Rare Earth Element Extraction

Neodymium (Nd), a rare earth element (REE), is critical to numerous industries. Neodymium can be extracted from ore concentrates, waste materials, or recycled materials such as recycled Nd-Fe-B permanent magnets. In a standard process, concentrated sulfuric acid (H 2 SO 4 ) is used as an extraction/leaching agent. Therefore, knowledge of Nd(III)–sulfate interaction at high ionic strengths is important for optimization of the extraction process. In addition, sulfate is also a major species in natural surface waters and present in nuclear waste streams. Nd(III) has been used a chemical analog to trivalent actinides in nuclear waste research and development. Consequently, knowledge of Nd(III)-sulfate interactions is also impactful to the field of nuclear waste management. Here, in this study, we have developed a thermodynamic model that can describe the interaction of Nd(III) with sulfate to ionic strengths up to ~ 16.5 mol·kg –1 and to temperatures up to 100 °C. The model adopts the Pitzer formulation to describe activity coefficients of aqueous species. This model can be used to design and optimize a chemical process for REE recovery from ore concentrates, recycled materials, and acid mine drainage (AMD) and to understand the mobility of REEs and actinides in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Aqueous Alteration and Hydrogen Generation on Parent Bodies of Unequilibrated Ordinary Chondrites: Thermodynamic Modeling for the Semarkona Composition

Ordinary chondrites are the most abundant class of meteorites that could represent rocky parts of solar system bodies. However, even the most primitive unequilibrated ordinary chondrites (UOC) reveal signs of mild alteration that affected the matrix and peripheral zones of chondrules. Major chemical changes include oxidation of kamacite, alteration of glass, removal of alkalis, Al, and Si from chondrules, and formation of phases enriched in halogens, alkalis, and hydrogen. Secondary mineralogical changes include formation of magnetite, ferrous olivine, fayalite, pentlandite, awaruite, smectites, phosphates, carbonates, and carbides. Aqueous alteration is consistent with the oxygen isotope data for magnetite. The presence of secondary magnetite, Ni-rich metal alloys, and ferrous silicates in UOC implies that H2O was the oxidizing agent. However, oxidation by H2O means that H2 is produced in each oxidative pathway. In turn, production of H2, and its redistribution and possible escape should have affected total pressure, as well as the oxidation state of gas, aqueous and mineral phases in the parent body. Here we use equilibrium thermodynamic modeling to explore water-rock reactions in UOC. The chemical composition of gas, aqueous, and mineral phases is considered.

Zolotov, M. Y.↗
DOE OSTI2022

High-Temperature Thermodynamics Modeling of Graphite

We present high-temperature thermodynamic properties for graphite from first-principles anharmonic theory. The ab initio electronic structure is obtained from density-functional theory coupled to a lattice dynamics method that is used to model anharmonic lattice vibrations. This combined approach produces free energies and specific heats for graphite that compare well with available experiments and results from models that empirically represent experimental data, such as CALPHAD. We show that anharmonic theory for the phonons is essential for accurate thermodynamic quantities above about 1000 K.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Experimental investigation and thermodynamic modeling of the binary Pt–Sn system

Here, the thermodynamics of the Pt–Sn system is revisited with attention to phase equilibria involving PtSn 4 , a topological quantum material with interesting physical properties. The phase relationship in the Sn-rich region of the Pt–Sn binary system was investigated by a combination of differential scanning calorimetry and equilibration experiments. Based on the present experiments and a critical evaluation of the available thermodynamic and phase diagram data reported in the literature, thermodynamic assessments of the entire Pt–Sn system were performed using the CALPHAD approach. Two sets of thermodynamic parameters were optimized, where the liquid phase was described using the Bragg-Williams random mixing model and the associate solution model, respectively. The modeling results are compared with the reliable experimental data and are shown to provide good representations of the phase equilibria and thermodynamic properties in this system.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Thermodynamic modeling of the Pd–Zn system with uncertainty quantification and its implication to tailor catalysts

Pd–Zn intermetallic catalysts show encouraging combinations of activity and selectivity on well-defined active site ensembles. Thermodynamic description of the Pd–Zn system, delineating phase boundaries and enumerating site occupancies within intermediate alloy phases, is essential to determining the ensembles of Pd–Zn atoms as a function of composition and temperature. Combining the present extensive first-principles calculations based on density functional theory (DFT) and available experimental data, the Pd–Zn system was remodeled using the CALculation of PHAse Diagrams (CALPHAD) approach. High throughput modeling tools with uncertainty quantification, i.e., ESPEI and PyCalphad, were incorporated in the phase analysis. Here, the site occupancies across the γ phase composition region were given special attention. A four-sublattice model was used for the γ phase owing to its four Wyckoff positions, i.e., the outer tetrahedral (OT) site 8c, the inner tetrahedral (IT) site 8c, the octahedral (OH) site 12e, and the cuboctahedral (CO) site 24g. The site fractions of Pd and Zn calculated from the present thermodynamic model show the occupancy preference of Pd in the OT and OH sublattices in agreement with experimental observations. The force constants obtained from DFT-based phonon calculations further supports the tendency of Pd occupying the OH sublattice compared with the IT and CO sublattice. The catalytic ensembles changing from Pd monomers (Pd 1 ) to trimers (Pd 3 ) on the surface of γ phase are attributed to the increase of Pd occupancy in the OH sublattice.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Critical evaluation and thermodynamic modeling of the Pd–Sn system

The single crystalline material PdSn 4 , a homologue of the Dirac nodal arc semimetal PtSn 4 , is a promising candidate to search for new topological states with fascinating quantum physical properties. In the present work, the thermochemistry and phase diagram information of the Pd–Sn system published in the literature was collected and critically reviewed, two thermodynamic reassessments of the Pd–Sn system were carried out in the frame of the CALPHAD approach to optimize the Gibbs free energy of each phase presented in the system. The liquid phase was described using respectively the Bragg-Williams random mixing model and the associate solution model. All the reliable thermodynamic property and phase equilibria data can be generally described using the presently obtained thermodynamic descriptions of the Pd–Sn system. Issues related to the further improvement of the thermodynamic descriptions of the Pd–Sn system are discussed.

36 MATERIALS SCIENCE↗