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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Beyond Thermodynamics: Assessing the Dynamical Softness of Hydrated Ions from First Principles

Ion (de)hydration is a key rate-determining step in interfacial processes from corrosion to electrochemical energy storage. However, predicting the kinetics of ion (de)hydration remains challenging, prompting the use of static proxies such as hydration energy and valence. While useful for assessing thermodynamic preferences, such descriptors cannot fully capture the dynamical softness of the hydration shell that dictates kinetics. Accordingly, we use first-principles molecular dynamics to analyze hydration shell softness for a diverse set of metal cations. Additionally, three dynamic metrics are introduced to intuitively describe the bond rigidity, shape deformability, and exchange fluidity of the solvation shell. Together, these metrics capture the relevant physics in the static descriptors, while offering a far more complete and efficient representation for the overall propensity for (de)hydration. Application to the hydrated ion set demonstrates a weak connection between dynamical softness and hydration energy, confirming that dynamical descriptors of hydration are key for correctly describing ion transfer processes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Thermodynamic assessment of nonstoichiometric oxides for solar thermochemical fuel production

Two-step solar thermochemical cycling (STC) based on nonstoichiometric oxides is an ideal means of solar fuel (e.g., H 2 , CO) production. Screening of nonstoichiometric oxides with excellent thermodynamic performance is key to achieving high solar-to-fuel efficiency. However, application-driven materials assessment intended for reactor-level solar fuel production performance requires mimicking realistic operating conditions of on-sun tests in a laboratory setting, which makes oxides assessment and screening an onerous task to accomplish experimentally. In this work, a rapid assessment and screening model of nonstoichiometric oxides for two-step solar thermochemical cycling assuming fixed-bed flow pattern and quasi-equilibration of the solid with the flowing gas phase is developed, with solar-to-fuel efficiency being the target function of optimization. The model accounts for the thermodynamic parameters of oxide materials and typical operating conditions of experimental thermochemical cycling. This study employed the model to explore and compare two groups of typical nonstoichiometric oxides (CeO 2 - and (LaSr)MnO 3 -based) for their maximum efficiency under their uniquely optimized cycling conditions. The results show that CeO 2 can reach a maximum efficiency of 12.9% at reduction temperature of 1500 °C, which is superior to other candidate materials, including 20 mol% Zr-doped CeO 2 (10.1%), La 0.6 Sr 0.4 MnO 3 (2.5%) and La 0.8 Sr 0.2 MnO 3 (3.3%). Even when the reduction temperature is lowered to 1350 °C, ceria yields the highest efficiency amongst the candidate STC materials considered. The optimal cycling strategy depends on the inherent thermodynamic properties of the oxides. This approach serves as a framework for assessing the maximum efficiency and optimal conditions of candidate thermochemical materials within a range of constraints rather than comparing materials under arbitrary cycling conditions, which may inherently favor one material over another. For oxidation temperatures below 800–1000 °C, the model could be further improved by considering reaction kinetics.

14 SOLAR ENERGY↗
DOE OSTI2025

First-Principles Thermodynamic Assessments of Sr-Containing Secondary Phase Formation in La1-xSrxMnO3±δ Perovskites for Solid Oxide Cell Applications

Sr-secondary phase formation is a potentially significant degradation mode threatening solid-oxide cell (SOC) commercial viability. A first-principles thermodynamic study was performed for rhombohedral perovskite (La1-xSrx) MnO3±δ (LSM) to assess its stability against Sr secondary phase formation in SOC applications. In this work, the Sr secondary phase formation reaction free energies were determined by combining ab initio lattice dynamics calculations for the solid phases and an ab initio thermodynamics approach for the gas phases. Furthermore, this approach goes beyond previous thermodynamic modeling studies by integrating first-principles based point-defect equilibria into the analyses. The modeling results indicate an increased tendency to form SrO oxide from LSM upon decreasing the oxygen partial pressure. Additionally, enhancing factors to form the Sr-related secondary phase from the associated SrO activity in LSM are further quantified by considering the equilibrium of SrO reacting with contaminant gas species as a function of temperature and gas pressure.

Defect and phase stability↗
DOE OSTI2026

First-principles thermodynamic assessment of Sr-containing secondary phase formation in strontium-substituted lanthanum manganites for solid oxide cell applications

Sr-secondary phase formation is a potentially significant degradation mode with direct impact upon solid-oxide cell (SOC) commercial viability. A first-principles based thermodynamic study was performed for La 1−x Sr x MnO 3±δ (LSM) perovskites to assess their stability against formation of different Sr-secondary phases, including SrO, SrCrO 4 , SrSO 4 , SrCO 3 , and Sr(OH) 2 , for SOC applications. The Sr-secondary phase formation reaction free energies were determined via a thermodynamic model by combining ab initio lattice dynamics calculations for the solid phases and ab initio thermodynamic data for the gas phases. The current approach expands the previously reported thermodynamic modeling studies by integrating first-principles based point defect equilibria into the thermodynamic analysis. The modeling results obtained using this new approach indicate an increased tendency to form the SrO oxide upon decreasing the oxygen partial pressure. Additionally, the enhancing factors to form the Sr-related secondary phase from the associated SrO activity in LSM are further quantified by considering the equilibrium of SrO reacting with the contaminant gas species as a function of temperature and pressure.

defect thermodynamics modeling↗
DOE OSTI2026

Uncertainty-Driven Rapid Thermodynamic Assessment of Nb-Ta-Zr System and Effects of C impurities (L25GF9298S): Annual Progress Report

An integrated computational materials engineering (ICME) method is in development for rapid thermodynamic experimental investigation and high-fidelity computational modeling of refractory multi-principal element alloys (RMPEAs). These ultra-high-temperature (UHT) alloys are of interest for structural applications in extreme environments, but deficiency of reliable data, especially melting temperatures, impedes the prediction of alloys with favorable properties. The method leverages UHT capabilities and computational expertise of LLNL’s Materials Science Division and the McCormack Lab’s UHT conical nozzle levitation (CNL) system to iteratively map the Nb-Ta-Zr phase space, with focus on the liquidus surface, through targeted experiments selected by quantifying uncertainty in the thermodynamic model fitting parameters. This method will reduce the time to map uncharted RMPEA phase space and thereby accelerate discovery and development of advanced materials for applications in extreme environments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Thermodynamic assessment of the quaternary WTaCrV refractory high entropy alloy as a means to guide experimental approaches

The deployment of fusion energy poses challenges for materials in plasma facing components to withstand high temperatures and thermal gradients, particle implantation and neutron damage. The current material of choice is tungsten, although property degradation limits its consideration in future fusion reactors. Hence, materials with better resistance to harsh environments need to be developed for fusion energy to become a reality. High entropy alloys are being explored as potential candidates with some compositions showing good radiation resistance to defect cluster formation. One of these materials is the WTaCrV system, although only one composition has been tested under ion irradiation. In this work, we study the thermodynamic properties of the entire quaternary alloy composition range. Coupling first principles calculations, cluster expansion approaches, and Monte Carlo methods, we access the free energy functionals, short-range ordering as a function of temperature, and atomic configurations that can be compared to experimental observations. We use this data to inform experiments into compositions with higher propensity to form solid solutions, instead of phase separating. With this formalism we have developed thermodynamic database (TDB) files that can be used to plot quaternary phase diagrams.

Cluster Expansion↗
DOE OSTI2022

Thermodynamic assessment of lithium halide reciprocal salt systems for energy applications

Lithium halides are of interest because of their unique applications as fuel or coolants in molten salt reactors (MSRs) and electrolytes in thermally activated batteries. Because iodine is an important fission product for MSRs, the Molten Salt Thermal Properties Database-Thermochemical (MSTDB-TC) is being expanded to include relevant iodide reciprocal salt systems. In this work, we assess the thermochemical properties of lithium halide pseudobinary systems based on reported experimental phase diagrams, eutectic temperatures, and enthalpies of mixing. Within the framework of the modified quasi-chemical model in the quadruplet approximation (MQMQA), extrapolations to the related pseudoternary and pseudoquaternary systems have been performed. The pseudoquaternary representations of phase equilibria, enthalpy, entropy, and heat capacity are represented in the resultant models. Of interest for generating source terms for accident analysis is the ability to compute the vapor pressures of the dominant iodide species for the systems at any composition. Here, an example of such calculations is provided for the LiF-LiI system at x LiI = 0.01 and x LiI = 0.70, in this case indicating that the LiI vapor species are predominant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Thermodynamic Assessment of the Y2o3-yb2o3-zro2 System

Yttria-zirconia (Y2O3-ZrO2) is the most widely used of the rare earth oxide-zirconia systems. There are numerous experimental studies of the phase boundaries in this system. In this paper, we assess these data and derive parameters for the solution models in this system. There is current interest in other rare earth oxide-zirconia systems as well as systems with several rare earth oxides and zirconia, which may offer improved properties over the Y2O3-ZrO2 system. For this reason, we also assess the ytterbia-zirconia (Yb2O3-ZrO2) and Y2O3-Yb2O3-ZrO2 system.

Jacobson, Nathan S.↗
DOE OSTI2021

Ab initio Molecular Dynamics Assessment of Thermodynamic and Transport Properties in (K,Li)Cl and (K, Na)Cl Molten Salt Mixtures

Molten salt mixtures are integral part of highly important technological applications such as nuclear reactors. However, due to inherent difficulties associated with experiment at high temperatures and the intrinsic complexity of liquid-phase multi-component systems, understanding their properties at a molecular level remains a challenge. Here, we report on an ab initio molecular dynamics investigation on structural, electronic, transport, and thermal properties of two common molten salt mixtures, (K, Li)Cl and (K,Na)Cl, at five different compositions and three temperatures. Most of the properties were found to depend on both composition and temperature. While properties, like atomic charges, show additive behaviors, other properties, such as electrical conductivity, show considerable deviations from additivity. We shall show that the mixing of the molten salt mixtures is mainly driven by entropy, and that the KCl and LiCl mix better than KCl and NaCl. Our computational results are in general consistent with available experimental data. Comparison with available theoretical data is also provided.

Nguyen, Manh Thuong↗
DOE OSTI2021

FY21 Status Report on the Molten Salt Thermal Properties Database (MSTDB) Development

This report describes the thermodynamic assessments for the ZrF 4 -BeF 2 , AlCl 3 -NaCl, AlCl3-KCl and the PuCl 3 -CsCl pseudo-binary subsystems. Calculation results are compared to the inputs used to optimize the adjustable model parameters. The data came from experimental studies reported in the open literature, from the MSR research community, and/or computational results generated within the NEAMS program and from collaborators. The models from the thermodynamic assessment of these salt systems are integrated into the MSTDB-TC (Molten Salt Thermal Properties Database-Thermochemical). A brief description of the companion MSTDB-TP (Molten Salt Thermal Properties Database-Thermophysical) is given along with an overview of the approach for predicting both thermodynamic and thermophysical property behavior of multicomponent systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Assessment of thermodynamic stability of sapphire in eutectic molten chloride environment

The continued development of molten salt reactors requires highly efficient and stable instruments that can efficiently track monitor conditions of the molten salt during long-term application operation in both the fuel and coolant/heat transfer fluid loops. Sapphire (Al 2 O 3 ) fibers have shown tremendous potential by enabling radiation resistance and a broader operational range of temperature . Thermodynamic modeling using the ThermoCalc and the SGTE Molten Salts (SALT1) and Pure Substances (Pure5) database is done performed to understand the compatibility of Al 2 O 3 fibers with NaCl-MgCl 2 eutectic molten salt in the temperature range of 600 to 1000°C. The thermodynamic calculations show that sapphire fibers are not expected to be compatible with long term exposure to molten chloride salts within this temperature range. Furthermore, various pure metallic elements were evaluated as potential cladding materials for part of the Al 2 O 3 fibers. Based on the thermodynamic analysis, molybdenum (Mo) and nickel (Ni) could be effective cladding materials to enhance the stability of Al 2 O 3 in NaCl and MgCl 2 chloride salt molten bath in the desired temperature range. The presence of a metallic cladding leads to the suppression of aluminum dissolution from Al 2 O 3 , thus improving its stability in chloride salts. Additionally, it is also shown that Al 2 O 3 remains stable up to 2300 K in the presence of pre-existing Al 2 MgO 4 and Al 2 NiO 4 in the eutectic molten chloride bath environment.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗