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Results for “thermodynamic equilibrium”

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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Plasma decay in hydrocarbons and hydrocarbon- and H 2 O-containing mixtures excited by high-voltage nanosecond discharge at elevated gas temperatures

Plasma decay after a high-voltage nanosecond discharge was experimentally and numerically studied in pure hydrocarbons (C 2 H 6 and C 3 H 8 ), and H 2 O:N 2 and C 3 H 8 :O 2 mixtures for pressures in the range 2–4 Torr and gas temperatures from 300 to 600 K. In a stoichiometric C 3 H 8 :O 2 mixture, plasma decay was also studied in a repetitively pulsed discharge for varing numbers of discharge pulses (varying degrees of fuel oxidation). The rate of plasma decay was determined from the temporal evolution of electron density measured using the microwave interferometer. It was observed that gas heating to 600 K leads to a decrease in the rate of plasma decay in all cases. The effect of heating on plasma decay was most profound in the H 2 O:N 2 mixture (after a single discharge pulse) and in the C 3 H 8 :O 2 mixture for high degrees of fuel oxidation. A kinetic scheme was developed to numerically simulate the plasma decay in hydrocarbons and combustible mixtures. Numerical analysis showed that, under the conditions studied, plasma decay was controlled by dissociative electron recombination with simple molecular and cluster ions. Gas heating led to a decrease in the rate of the electron-ion recombination and the rate of conversion of molecular ions to cluster ions. As a result, the gas temperature increase caused a decrease in the fraction of cluster ions for which the recombination coefficients are an order of magnitude higher than the recombination coefficients for molecular ions. The influence of gas heating on the decrease of the amount of cluster ions was more important when the ion composition was dominated by hydrated H 3 O + (H 2 O) k ions. The rates of the formation of these ions are extremely sensitive to any variations in gas temperature. A result, in agreement with our observations, gas heating led to an anomalous decrease in the rates of plasma decay in the H 2 O:N 2 mixture, as well as in the C 3 H 8 :O 2 mixture when H 2 O molecules were produced due to fuel oxidation.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

Computational Prediction of Water Sorption in Facilitated Transport Membranes

Polymeric facilitated transport membranes (FTMs) have emerged as an innovative class of promising carbon capture technology. Studies have shown that the transport properties of an FTM are significantly influenced by its water uptake. In order to better quantify FTM performance, we herein explore the potential of computational techniques to predict the equilibrium water uptake values of FTMs. Two prediction approaches were examined. First, the water sorption was explicitly simulated by iteratively conducting grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Second, the water sorption was predicted based on the chemical potential of the adsorbed water, which was calculated using the Widom insertion or continuous fractional component Monte Carlo (CFCMC) method. The chemical potential-based approach with CFCMC demonstrated good prediction of the equilibrium water uptake values of FTMs with poly(N-vinylformamide-co-vinylamine) as fixed-site carrier and 2-(1-piperazinyl)ethylamine sarcosinate as mobile carrier. The predicted water uptake values increased with increasing mobile carrier content and were in good agreement with the experimental values. Furthermore, the higher water uptake promoted the diffusion of CO 2 , N 2 , and mobile carrier as well as slightly stifled the sorption of N 2 . Such an approach significantly contributes to a more comprehensive theoretical evaluation of FTMs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Navigating phase diagram complexity to guide robotic inorganic materials synthesis

Abstract Efficient synthesis recipes are needed to streamline the manufacturing of complex materials and to accelerate the realization of theoretically predicted materials. Often, the solid-state synthesis of multicomponent oxides is impeded by undesired by-product phases, which can kinetically trap reactions in an incomplete non-equilibrium state. Here we report a thermodynamic strategy to navigate high-dimensional phase diagrams in search of precursors that circumvent low-energy, competing by-products, while maximizing the reaction energy to drive fast phase transformation kinetics. Using a robotic inorganic materials synthesis laboratory, we perform a large-scale experimental validation of our precursor selection principles. For a set of 35 target quaternary oxides, with chemistries representative of intercalation battery cathodes and solid-state electrolytes, our robot performs 224 reactions spanning 27 elements with 28 unique precursors, operated by 1 human experimentalist. Our predicted precursors frequently yield target materials with higher phase purity than traditional precursors. Robotic laboratories offer an exciting platform for data-driven experimental synthesis science, from which we can develop fundamental insights to guide both human and robotic chemists.

Chen, Jiadong (ORCID:0009000476038838)↗
DOE OSTI2023

Guest-dependent bond flexibility in UiO-66, a “stable” MOF

We report “flexibility constants”—a conceptual analog to metal–ligand stability constants—of UiO-66, the prototypical “stable” MOF, across a wide temperature range in both vacuum and in the presence of typical guest solvents. With these data, we extract key thermodynamic parameters governing the reversible bond equilibrium and demonstrate that guest molecules strongly favor the reversible dissociation of MOF metal–linker bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Coalescence and splashing threshold for head-on collisions of liquid metal nanodroplets

Head-on collisions of liquid metal nanodroplets in a vacuum are investigated through molecular dynamics simulations in order to determine the transition threshold between the coalescing and splashing regimes for six different materials (aluminum, calcium, cerium, gold, platinum, and tin). Droplets of various sizes and initial speeds are simulated, and it is found that the Reynolds and Ohnesorge numbers are able to predict the transition between the coalescing and splashing regimes. An energy balance for coalescing droplets shows that the initial energy is mainly converted to thermal energy increasing the temperature of the combined droplets by several hundred to several thousand kelvin depending on the material, and this result is confirmed in the simulations. Furthermore, when splashing occurs, the number of smaller droplets formed and the spreading rate are found to be dependent on the initial size and initial speed of the original droplets.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Asymptotic reversibility of thermal operations for interacting quantum spin systems via generalized quantum Stein’s lemma

Abstract For quantum spin systems in any spatial dimension with a local, translation-invariant Hamiltonian, we prove that asymptotic state convertibility from a quantum state to another one by a thermodynamically feasible class of quantum dynamics, called thermal operations, is completely characterized by the Kullback–Leibler (KL) divergence rate, if the state is translation-invariant and spatially ergodic. Our proof consists of two parts and is phrased in terms of a branch of the quantum information theory called the resource theory. First, we prove that any states, for which the min and max Rényi divergences collapse approximately to a single value, can be approximately reversibly converted into one another by thermal operations with the aid of a small source of quantum coherence. Second, we prove that these divergences collapse asymptotically to the KL divergence rate for any translation-invariant ergodic state. We show this via a generalization of the quantum Stein’s lemma for quantum hypothesis testing beyond independent and identically distributed situations. Our result implies that the KL divergence rate serves as a thermodynamic potential that provides a complete characterization of thermodynamic convertibility of ergodic states of quantum many-body systems in the thermodynamic limit, including out-of-equilibrium and fully quantum situations.

Physics↗
DOE OSTI2020

A Numerical Study on the Impact of Cathode Catalyst Layer Loading on the Open Circuit Voltage

The open-circuit voltage (OCV) is the measured potential when no current is drawn from a cell. Additionally, theoretically this potential is given by the equilibrium potential, which is determined from thermodynamics based on the operating conditions. In practice, the actual potential at zero current is measured to be approximately 300 mV lower than the theoretical value.

42 ENGINEERING↗
DOE OSTI2021

Modeling Phase Equilibrium of Common Sugars Glucose, Fructose, and Sucrose in Mixed Solvents

The industrial processing of sugars and sugar-containing mixtures is gaining widespread use as a form of renewable manufacturing from biomass. To aid in process modeling for design and optimization, a commonly available thermodynamic model is needed that describes the phase equilibrium of these compounds. This work compiles and compares models for solid–liquid and vapor–liquid phase equilibrium from the available data for the representative sugars glucose, fructose, and sucrose in the representative solvents water, methanol, and ethanol, including data for multisugar, multisolvent systems. Additionally, the nonrandom two-liquid (NRTL) model was chosen for these systems because of its widespread use in industry and the availability of parameters for many solvents and cosolutes. The association-NRTL (aNRTL) model was investigated as an improvement for modeling sugars, which may experience a high degree of association because of their many hydroxy groups. Both models accurately capture the data and are able to predict the behavior of multisugar systems with only solute–solvent interaction parameters. The aNRTL model shows an improvement over the baseline NRTL model that is most significant for sucrose, the component with the highest association strength, and least significant for fructose, which has the lowest association strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Materials Genomics Search for Possible Helium‐Absorbing Nano‐Phases in Fusion Structural Materials

Abstract Civilian fusion demands structural materials that can withstand the harsh environments imposed inside fusion plasma reactors. The structural materials often transmute under 14.1 MeV fast neutrons, producing helium (He), which embrittles the grain boundary (GB) network. Here, it is shown that neutron‐friendly and mechanically strong nano‐phases with atomic‐scale free volume can have low He‐embedding energy and >10 at.% He‐absorbing capacity, and can be especially advantageous for soaking up He on top of resisting radiation damage and creep, provided they have thermodynamic compatibility with the matrix phase, satisfactory equilibrium wetting angle, as well as a high enough melting point. The preliminary experimental demonstration proves that is a good ab initio predictor of He shielding potency in nano‐heterophase materials, and thus, is used as a key feature for computational screening. In this context, a list of viable compounds expected to be good He‐absorbing nano‐phases is presented, taking into account , the neutron absorption and activation cross‐sections, the elastic moduli, melting temperature, the thermodynamic compatibility, and the equilbrium wetting angle of the nano‐phases with the Fe matrix as an example.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Inducing thermodynamically blocked atomic ordering via strongly driven nonequilibrium kinetics

Ultrafast light-matter interactions enable inducing exotic material phases by promoting access to kinetic processes blocked in equilibrium. Despite potential opportunities, actively using nonequilibrium kinetics for material discovery is limited by the poor understanding on intermediate states of driven systems. Here, using single-pulse time-resolved imaging with x-ray free-electron lasers, we found intermediate states of photoexcited bismuth nanoparticles that showed kinetically reversed surface ordering during ultrafast melting. This entropy-lowering reaction was further investigated by molecular dynamics simulations to reveal that observed kinetics were thermodynamically buried in equilibrium, which emphasized the critical role of electron-mediated ultrafast free-energy modification in inducing exotic material phases. This study demonstrated that ultrafast photoexcitations of electrons provide an efficient strategy to induce hidden material phases by overcoming thermodynamic barriers via nonequilibrium reaction pathways.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Probing the thermodynamics and kinetics of ethylene carbonate reduction at the electrode–electrolyte interface with molecular simulations

Understanding the formation of the solid-electrolyte interphase (SEI) in lithium-ion batteries (LIBs) is an ongoing area of research due to its high degree of complexity and the difficulties encountered by experimental studies. Herein, we investigate the initial stage of SEI growth, the reduction reaction of ethylene carbonate (EC), from both a thermodynamic and kinetic approach with theory and molecular simulation. We employed both the potential distribution theorem (PDT) and the SMD implicit solvent model to EC solvation for the estimation of reduction potentials of Li$^+$, EC, and Li$^+$-solvating EC (s-EC), as well as reduction rate constants of EC and s-EC. We find that solvation effects greatly influence these quantities of interest, particularly the Li$^+$/Li reference electrode potential in EC solvent. Further, we also compute the inner- and outer-sphere reorganization energies for both EC and s-EC at the interface of liquid EC and a hydroxyl-terminated graphite surface, where total reorganization energies are predicted to be 76.6 and 88.9 kcal/mol, respectively. With the computed reorganization energies, we estimate reduction rate constants across a range of overpotentials and show that EC has a larger electron transfer rate constant than s-EC at equilibrium, despite s-EC being more thermodynamically favorable. Furthermore, this manuscript demonstrates how ion solvation effects largely govern the prediction of reduction potentials and electron transfer rate constants at the electrode-electrolyte interface.

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

Underpotential lithium plating on graphite anodes caused by temperature heterogeneity

Rechargeability and operational safety of commercial lithium (Li)-ion batteries demand further improvement. Plating of metallic Li on graphite anodes is a critical reason for Li-ion battery capacity decay and short circuit. It is generally believed that Li plating is caused by the slow kinetics of graphite intercalation, but in this paper, we demonstrate that thermodynamics also serves a crucial role. We show that a nonuniform temperature distribution within the battery can make local plating of Li above 0 V vs. Li 0 /Li + (room temperature) thermodynamically favorable. This phenomenon is caused by temperature-dependent shifts of the equilibrium potential of Li 0 /Li + . Supported by simulation results, we confirm the likelihood of this failure mechanism during commercial Li-ion battery operation, including both slow and fast charging conditions. This work furthers the understanding of nonuniform Li plating and will inspire future studies to prolong the cycling lifetime of Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Phase Stability Through Machine Learning

Understanding the phase stability of a chemical system constitutes the foundation of materials science. Knowledge of the equilibrium state of a system under arbitrary thermodynamic conditions provides valuable information about the types of phases that are likely to be synthesized and how to get there. Accessing the phase diagram in a materials system provides one with the information necessary to design materials and microstructures with optimal properties. While the materials science community has long been focused on exploiting this knowledge to navigate the materials space, recent advances in machine learning (ML) and artificial intelligence (AI) have provided the community with novel ways of interrogating the materials thermodynamics space. Furthermore, this work presents some of the most recent advances in ML/AI applied to phase stability and thermodynamics of materials. Prof. John Morral always had a passion for understanding and teaching the fundamental characteristics of phase diagrams. This review is written to honor his memory.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Temperature and density dependent pair potential for deuterium under shock

Large-scale classical molecular dynamics (CMD) simulations naturally include the microscopic physics necessary for atomistic modeling of shock release at the ablator-fuel interface in an inertial confinement fusion (ICF) capsule. Here, the multi-megabar shocks utilized in ICF experiments can drive the deuterium fuel from ambient to electron volt temperatures (T) and multi-fold compression. Modeling interatomic interactions over such an extreme range of conditions is challenging for empirical bond order potentials. We generate a pair potential for deuterium with explicit temperature and mass density dependence from ab initio density functional theory molecular dynamics using the iterative Boltzmann inversion method. This potential accurately reproduces the radial distribution functions and pressures from DFT in CMD equilibrium simulations across a wide range of thermodynamic conditions, yet fails to return the expected Hugoniot relations when used in direct CMD shock simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Decarburization and Carburization Behavior of Grade 91 Steel in Sodium Environments

Two heats of G91 steel have been investigated in sodium at 550-650°C to understand its corrosion behaviour, microstructural evolution, and tensile properties. Sodium exposure tests of subsized tensile and coupon specimens of G91 base metal and weldment were conducted in Argonne’s forced convection sodium materials testing loops. Maximum exposure times of ~39,000 h at 550°C, ~37,000 h at 600°C, and ~20,000 h at 650°C have been achieved, respectively. Thermal aging experiments of G91 steel were conducted in parallel, and the data of the sodium-exposed specimens were compared with the thermal aging data of the same heat to isolate the thermal aging effect from the effect of sodium exposure. It was found that the tensile strength of G91 steel can be reduced by more than 50% after sodium exposures at 650°C. The effect of a sodium environment on tensile properties is largely dependent on the carburization/decarburization behavior of G91 steel exposed to sodium. The carbon concentrations in sodium in Argonne’s SMT-1 and SMT-2 loops were determined by the equilibration method. The carbon activity in sodium was established by equilibrating high-purity nickel in sodium, analyzing the material for carbon, and using the reported data on the carbon solubility for this material. The carbon activity results were combined with the carbon solubility data in sodium to establish the carbon concentration in sodium. The carbon concentrations in the SMT-1 and SMT-2 loop were estimated to be 1.23 and 0.25 ppm, respectively. With this initial success, we will continue to monitor the carbon contents in the two loops to correlate the microstructural and mechanical property changes with the sodium purity. Future experiments will also consider sodium exposure tests in controlled carbon activities. Online monitoring and control of carbon contents in sodium in nuclear reactors would also be of interest. Thermodynamic analysis was conducted to understand the carburization-decarburization behavior of G91 steel exposed to sodium in the SMT-1 and SMT-2 loops. The equilibrium carbon activity in the alloy was evaluated by the thermodynamics of M 23 C 6 carbides. The calculated carburization-decarburization boundary showed that G91 would undergo decarburization at 650°C in the SMT-1 loop and carburization at 600°C in the SMT-2 loop, which is consistent with our findings from the sodium exposure tests. Future work will include thermodynamic analysis of the carbon concentration – activity relationship including the effect of carbide-forming elements, vanadium and niobium in G91 steel. Kinetics of carbon diffusion and the effect on microstructure and mechanical performance under various service conditions will also be investigated. The ultimate goal is to understand the mechanisms and the kinetics of carbon transfer in the sodium-steel system and to provide a basis for predicting the effect of long-term decarburization-carburization process on the integrity of reactor components.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

eQuilibrator 3.0: a database solution for thermodynamic constant estimation

Abstract eQuilibrator (equilibrator.weizmann.ac.il) is a database of biochemical equilibrium constants and Gibbs free energies, originally designed as a web-based interface. While the website now counts around 1,000 distinct monthly users, its design could not accommodate larger compound databases and it lacked a scalable Application Programming Interface (API) for integration into other tools developed by the systems biology community. Here, we report on the recent updates to the database as well as the addition of a new Python-based interface to eQuilibrator that adds many new features such as a 100-fold larger compound database, the ability to add novel compounds, improvements in speed and memory use, and correction for Mg2+ ion concentrations. Moreover, the new interface can compute the covariance matrix of the uncertainty between estimates, for which we show the advantages and describe the application in metabolic modelling. We foresee that these improvements will make thermodynamic modelling more accessible and facilitate the integration of eQuilibrator into other software platforms.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Thermodynamic re-modeling of the Yb-Sb system aided by first-principles calculations

Here, the thermodynamic description of the Yb-Sb binary system is developed by means of the CALculations of PHAse Diagrams (CALPHAD) method by combining experimental data in the literature and predictions from first-principles calculations based on density functional theory (DFT) in the literature and the present work. Two pseudopotentials of Yb are compared in the present DFT-based calculations with 14 and 13 f-electrons frozen in the core, i.e., 5p 6 6s 2 and 5p 6 6s 2 5 d 1 electrons as valence electrons, termed Yb_2 and Yb_3, respectively. It is shown that the phonon spectrum of the YbSb phase calculated using the Yb_3 pseudopotential does not have imaginary phonon modes and is subsequently used to predict its temperature dependent thermodynamic properties by the DFT-based quasiharmonic phonon calculations. The present thermodynamic database includes the Yb 16 Sb 11 phase in addition to five intermetallic phases that were considered in previous modeling studies, i.e., YbSb 2 , YbSb, Yb 11 Sb 10 , Yb 4 Sb 3 , and Yb 5 Sb 3 . The high temperature orthorhombic structure of the Yb 5 Sb 3 phase is not considered in the present work as it was stabilized by hydrogen. The associate solution model is used to describe the short-range ordering behavior in the liquid phase. The calculations from the present thermodynamic model show good agreement with thermochemical and phase equilibrium data from both the present work and the literature.

36 MATERIALS SCIENCE↗