Search NASA⌕ Search

SEARCH · Search NASA

Results for “thermodynamic analyses”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Molten-salt-mediated carbon dioxide capture and superequilibrium utilization with ethane oxidative dehydrogenation

Existing CO 2 -mediated oxidative dehydrogenation (CO 2 -ODH) of ethane has yet to demonstrate >60% single-pass CO yield due to the intrinsic equilibrium limitations. We report a unique approach with mixed molten carbonates as a reaction medium for CO 2 -ODH, which strategically partitions the CO 2 -ODH reactions into gas and molten-salt phases and facilitates integrated CO 2 capture from power plant flue gases. An 89% CO yield was achieved at 770°C, doubling the equilibrium limitation of conventional CO 2 -ODH. The high CO yield in turn enhances ethylene formation. Further characterizations confirmed that molten-salt mediated ODH (MM-ODH) proceeds through a gas-phase cracking and molten-salt mediated reverse water-gas-shift reaction pathway. Based on this understanding, thermodynamic analysis and ab initio molecular dynamics simulations were conducted to develop general principles to optimize the molten-salt reaction medium. Process analyses confirm that MM-ODH has the potential to be significantly more efficient for CO 2 capture and utilization than conventional CO 2 -ODH.

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

Time-Lapse Integration at FWU: Fluids, Rock Physics, Numerical Model Integration, and Field Data Comparison

We present the current status of time-lapse seismic integration at the Farnsworth (FWU) CO2 WAG (water-alternating-gas) EOR (Enhanced Oil Recovery) project at Ochiltree County, northwest Texas. As a potential carbon sequestration mechanism, CO2 WAG projects will be subject to some degree of monitoring and verification, either as a regulatory requirement or to qualify for economic incentives. In order to evaluate the viability of time-lapse seismic as a monitoring method the Southwest Partnership (SWP) has conducted time-lapse seismic monitoring at FWU using the 3D Vertical Seismic Profiling (VSP) method. The efficacy of seismic time-lapse depends on a number of key factors, which vary widely from one application to another. Most important among these are the thermophysical properties of the original fluid in place and the displacing fluid, followed by the petrophysical properties of the rock matrix, which together determine the effective elastic properties of the rock fluid system. We present systematic analysis of fluid thermodynamics and resulting thermophysical properties, petrophysics and rock frame elastic properties, and elastic property modeling through fluid substitution using data collected at FWU. These analyses will be framed in realistic scenarios presented by the FWU CO2 WAG development. The resulting fluid/rock physics models will be applied to output from the calibrated FWU compositional reservoir simulation model to forward model the time-lapse seismic response. Modeled results are compared with field time-lapse seismic measurements and strategies for numerical model feedback/update are discussed. While mechanical effects are neglected in the work presented here, complementary parallel studies are underway in which laboratory measurements are introduced to introduce stress dependence of matrix elastic moduli.

4D↗
DOE OSTI2026

Process-driven roadmap for depositing super duplex stainless steel via wire Arc additive manufacturing

Here, this study systematically investigates the effects of shielding gas, bead spacing, weld mode, and travel speed on the phase balance, porosity, and hardness of wire arc additively manufactured (WAAM) super duplex stainless steel (ER2594). Robotic WAAM was employed to fabricate multilayer walls under systematically varied process conditions, followed by phase transformation simulations, X-ray computed tomography (XCT), electron backscatter diffraction (EBSD), and microhardness evaluation. Thermodynamic simulations predicted rapid cooling of AM process can suppress the potential formation of deleterious precipitates which was later validated via cross-sectional microstructure analyses of printed samples. XCT revealed porosity levels below 0.2% for all deposits, with reduced travel speed significantly lowering defect volume. Microstructural analyses revealed the evolution of various austenite precipitates, including grain boundary austenite (GBA), Widmanstätten austenite (WA), and intergranular austenite (IGA), sequentially upon cooling of the ferrite phase. Among all process parameters, weld transfer mode exhibited the strongest influence on phase balance; pulsed mode promoted higher ferrite retention (~ 36%) compared to RapidX mode. No consistent relationship between stabilized phase fraction and captured microhardness was observed. This work provides critical insights for optimizing WAAM parameters to control phase balance and mechanical performance, which is essential for producing high-integrity super duplex stainless-steel components for nuclear and marine applications.

Grain orientation↗
DOE OSTI2023

Towards Pareto optimal high entropy hydrides via data-driven materials discovery

The ability to rapidly screen material performance in the vast space of high entropy alloys is of critical importance to efficiently identify optimal hydride candidates for various use cases. Given the prohibitive complexity of first principles simulations and large-scale sampling required to rigorously predict hydrogen equilibrium in these systems, we turn to compositional machine learning models as the most feasible approach to screen on the order of tens of thousands of candidate equimolar high entropy alloys (HEAs). Critically, we show that machine learning models can predict hydride thermodynamics and capacities with reasonable accuracy (e.g. a mean absolute error in desorption enthalpy prediction of ~5 kJ mol H 2 –1 ) and that explainability analyses capture the competing trade-offs that arise from feature interdependence. We can therefore elucidate the multi-dimensional Pareto optimal set of materials, i.e., where two or more competing objective properties can't be simultaneously improved by another material. This provides rapid and efficient down-selection of the highest priority candidates for more time-consuming density functional theory investigations and experimental validation. Various targets were selected from the predicted Pareto front (with saturation capacities approaching two hydrogen per metal and desorption enthalpy less than 60 kJ mol H 2 –1 ) and were experimentally synthesized, characterized, and tested amongst an international collaboration group to validate the proposed novel hydrides. Finally, additional top-predicted candidates are suggested to the community for future synthesis efforts, and we conclude with an outlook on improving the current approach for the next generation of computational HEA hydride discovery efforts.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Evidence of hexagonal germanium grains on annealed monolayer MoS 2

Growing three-dimensional (3D) materials on two-dimensional (2D) van der Waals surface has shown its effectiveness in overcoming materials incompatibility for stacking transferrable membranes toward advanced device manufacturing. Herein, we demonstrate that the nucleation of hexagonal germanium (Ge) grains within a continuous crystalline film, which has been unfeasible through traditional epitaxy techniques, is realized by chemical vapor deposition on top of n-type monolayer molybdenum disulfide (MoS 2 ) substrates. Suggested by quantum molecular dynamics calculation, the hexagonal Ge nucleation is thermodynamically preferable to cubic Ge when growing on monolayer MoS 2 with sulfur vacancies. The strained hexagonal Ge grains have been confirmed by transmission electron microscopy analyses from both real space and reciprocal space. Scanning probe microscopy shows that the hexagonal Ge film possesses higher reflectivity in infrared spectral range, implying a higher carrier concentration resulted from the narrower band gap, as compared to cubic Ge.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A dynamic microbial sulfur cycle in a serpentinizing continental ophiolite

Summary Serpentinization is the hydration and oxidation of ultramafic rock, which occurs as oceanic lithosphere is emplaced onto continental margins (ophiolites), and along the seafloor as faulting exposes this mantle‐derived material to circulating hydrothermal fluids. This process leads to distinctive fluid chemistries as molecular hydrogen (H 2 ) and hydroxyl ions (OH − ) are produced and reduced carbon compounds are mobilized. Serpentinizing ophiolites also serve as a vector to transport sulfur compounds from the seafloor onto the continents. We investigated hyperalkaline, sulfur‐rich, brackish groundwater in a serpentinizing continental ophiolite to elucidate the role of sulfur compounds in fuelling in situ microbial activities. Here we illustrate that key sulfur‐cycling taxa, including Dethiobacter , Desulfitispora and ‘ Desulforudis ’, persist throughout this extreme environment. Biologically catalysed redox reactions involving sulfate, sulfide and intermediate sulfur compounds are thermodynamically favourable in the groundwater, which indicates they may be vital to sustaining life in these characteristically oxidant‐ and energy‐limited systems. Furthermore, metagenomic and metatranscriptomic analyses reveal a complex network involving sulfate reduction, sulfide oxidation and thiosulfate reactions. Our findings highlight the importance of the complete inorganic sulfur cycle in serpentinizing fluids and suggest sulfur biogeochemistry provides a key link between terrestrial serpentinizing ecosystems and their submarine heritage.

Sabuda, Mary C.↗
DOE OSTI2023

Chromium Poisoning Mitigation Strategy in Strontium-Doped Lanthanum Manganite-Based Air Electrodes in Solid Oxide Fuel Cells

Abstract Chromium poisoning of the air electrode remains an obstacle to the long-term performance of solid oxide fuel cells (SOFCs). In Sr-doped LaMnO3 (LSM) air electrodes, the poisoning process results in two types of deposits, chromium oxide (Cr2O3), and Mn, Cr spinel (MnCr2O4). The former forms electrochemically and the latter forms via a chemical reaction. By applying a small anodic reverse bias, Cr2O3 deposits can be removed because their formation is electrochemical in nature. However, MnCr2O4 deposits remain because their formation is chemical, rather than electrochemical, in nature. In situ chemical decomposition of the Mn, Cr spinel was investigated as an alternate removal method as thermodynamics supports its decomposition into constituent oxides below ∼540 °C in pure oxygen. The spinel decomposition process was characterized using thermogravimetric and X-ray diffraction analyses. The experimentally determined rate of spinel decomposition was undetectable (very slow) with isolated MnCr2O4 powders. The addition of 10 mol% gadolinia doped ceria (GDC) and silver powders significantly increased the rate of decomposition. However, the rate is limited by the diffusion of oxygen through the decomposed oxide layer. Although one strategy may be the addition of GDC and silver to the LSM air electrode to enhance spinel decomposition, the more effective mitigation strategy would be to prevent the formation of MnCr2O4 spinel in the first place through the removal of the reactants: Cr2O3 via electrochemical cleaning and mobile Mn ions in the zirconia electrolyte by incorporating a diffusion barrier layer such as GDC between the air electrode and electrolyte.

Electrochemistry↗
DOE OSTI2025

Constraints on cosmology and baryonic feedback with joint analysis of Dark Energy Survey Year 3 lensing data and ACT DR6 thermal Sunyaev-Zel'dovich effect observations

We present a joint analysis of weak gravitational lensing (shear) data obtained from the first three years of observations by the Dark Energy Survey and thermal Sunyaev-Zel'dovich (tSZ) effect measurements from a combination of Atacama Cosmology Telescope (ACT) and Planck data. A combined analysis of shear (which traces the projected mass) with the tSZ effect (which traces the projected gas pressure) can jointly probe both the distribution of matter and the thermodynamic state of the gas, accounting for the correlated effects of baryonic feedback on both observables. We detect the shear$~\times~$tSZ cross-correlation at a 21$\sigma$ significance, the highest to date, after minimizing the bias from cosmic infrared background leakage in the tSZ map. By jointly modeling the small-scale shear auto-correlation and the shear$~\times~$tSZ cross-correlation, we obtain $S_8 = 0.811^{+0.015}_{-0.012}$ and $\Omega_{\rm m} = 0.263^{+0.023}_{-0.030}$, results consistent with primary CMB analyses from Planck and P-ACT. We find evidence for reduced thermal gas pressure in dark matter halos with masses $M < 10^{14} \, M_{\odot}/h$, supporting predictions of enhanced feedback from active galactic nuclei on gas thermodynamics. A comparison of the inferred matter power suppression reveals a $2-4\sigma$ tension with hydrodynamical simulations that implement mild baryonic feedback, as our constraints prefer a stronger suppression. Finally, we investigate biases from cosmic infrared background leakage in the tSZ-shear cross-correlation measurements, employing mitigation techniques to ensure a robust inference. Our code is publicly available on GitHub.

Pandey, S. [Johns Hopkins U.; Columbia U.] (ORCID:↗
DOE OSTI2021

Interfacial Effects on Transport Coefficient Measurements in Li-ion Battery Electrolytes

Development of Li + -containing electrolytes with improved transport properties requires reliable, reproducible, and ideally low volume techniques to rigorously understand ion-transport with varying composition. Precisely measuring the complete set of transport coefficients in liquid electrolytes under battery-relevant operating conditions is difficult and the reliability of these methods are sparsely described in electrolyte transport literature. In this work, we apply a potentiostatic polarization-based transport characterization approach typically used for polymer electrolytes to liquid electrolyte systems in an attempt to fully measure all transport coefficients (conductivity, total salt diffusion coefficient, thermodynamic factor and transference number) for the model system of LiPF 6 in an ethylene carbonate—ethyl methyl carbonate (EC:EMC) mixture. Using systematic timescale and statistical analyses, we find that transport coefficients measured using potentiostatic polarization of Li-Li symmetric cells exhibit strong correlation to Li electrode interfacial resistance, indicating that such methods are probing both bulk and interfacial phenomena. This reveals a major roadblock in characterizing electrolyte systems where the interfacial resistance is significantly larger than ohmic electrolyte resistance. As a result, we find that methods that rely on potentiostatic Li metal stripping/plating do not readily result in reliable liquid electrolyte transport coefficients, unlike similar methods for solid polymer electrolytes, where interfacial resistances are typically smaller than electrolyte resistances at the elevated temperatures typically of interest for such electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2020

Design and Operability of a Pressurized Oxy Combustion System

Fossil fuel powers more than two-thirds of the world’s electricity, a significant share of which is derived from coal power plants. Despite coal being an abundant and energy-rich fuel, the major halt to its progress is greenhouse gas emissions. Pressurized oxy-combustion cycles can achieve theoretically high thermal efficiencies along with a 90% carbon capture rate. Additionally, the high energy density allows smaller turbomachinery and save capital cost. Thus, the primary objective of this dissertation is to present the design and operability of a pressurized oxy-combustor system. The initial part of the dissertation investigates different thermodynamic cycles and presents a model that can be adapted for existing power plants. The thermodynamic model will be used in the later part to design the proposed combustor. The two cycles analyzed are ENEL and TIPS. This study focuses on qualitative analyses of the cycles using a commercially available software called Aspen Plus®. A detailed benchmark study has been performed to validate the modeling process. ENEL and TIPS cycles are designed in the software, adopting the same principles. Recirculation ratio and pressures are varied to find the efficiency range of the cycles. Power calculations are done to find overall and net efficiency for a fixed recirculation ratio. The efficiencies of the cycles are compared to select an optimum cycle. A recirculation ratio of 50% is selected for implementation. The comparison shows that ENEL is marginally efficient over TIPS, at the cost of a pressure difference of about 70bars. Technology Readiness Level analysis is performed to present the availability of the specialized equipment for the cycles. From the TRL analysis, it is seen that the cost and availability of high viii pressure equipment surmount the edge of TIPS over ENEL. Thus, ENEL is chosen as the better cycle for investigating a scaled experiment considering efficiency and viability. The later part of the dissertation focuses on developing the combustor's design for a pressurized oxy-combustion cycle. The proposed combustor is a powerhead-mounted design aimed to produce 1MW of thermal outputThe different aspects of the design of a down-fired pressurized swirl combustor are presented in this dissertation.

Chowdhury, Mehrin↗
DOE OSTI2023

Thermal Extraction and Delivery from Advanced Reactor Systems

This document presents preliminary thermodynamic analysis of thermal extraction and delivery from advanced nuclear reactors. Light-water, high temperature gas, sodium fast, and molten salt reactors are templated and analyzed for thermal extraction from nominal steam production conditions. Uncontrolled, controlled, and partial admission steam extraction methods are described and analyzed to show the differences in system impact from the various methods. Thermal delivery modeling results show comparisons that have become possible through the computational capabilities of the thermal delivery model. Due to the significant degrees of freedom of the problem, specific cases are used to compare the thermodynamic costs of heat transport using various heat transfer fluids. All this work is done using Modelica models, allowing for the future application of models in dynamic analyses beyond the steady-state calculations presented in this report. Appendices describe additional capabilities and methods that can help users analyze complex problems using HYBRID models developed in Modelica.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

Relating phase transitions to pore size distributions and mechanical mortar properties in CSA-OPC-C$ based systems – The potential impact of delayed straetlingite formation

The scope of this research is to investigate the performance evolution of five ternary CSA-OPC-Cs systems. Time resolved thermodynamic modeling was employed to gain insight into changes in the volume fractions of the hydrating pastes and link these changes to trends in the pore size distributions of the mortars. Pore solution analyses were performed to investigate which hydrates have the potential to exert high crystallization pressures. In three out of five blends the resulting tensile stress exceeded the tensile strength of the materials, resulting in the occurrence of coarse pores, which could be linked to the measured compressive strengths. Two damaging crystallization processes were identified in the investigated blends. One is the continuous precipitation of ettringite at high supersaturation in a system with high anhydrite addition. The other is the delayed crystallization of straetlingite at high supersaturation and crystallization pressure in the confined environment of mature pastes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structural motifs and bonding in two families of boron structures predicted at megabar pressures

The complex crystal chemistry of elemental boron has led to numerous proposed structures with distinctive motifs as well as contradictory findings. Herein, evolutionary structure searches performed at 100 GPa have uncovered a series of metastable phases of boron, and bonding analyses were carried out to elucidate their electronic structure. These polymorphs, dynamically stable at 100 GPa, were grouped into two families. Here, the first was derived from the thermodynamic minimum at these conditions, α-Ga, whereas channels comprised the second. Two additional intergrowth structures were uncovered, and it was shown they could be constructed by stacking layers of α-Ga-like and channel-like allotropes on top of each other. A detailed bonding analysis revealed networks of four-center σ-bonding functions linked by two-center B-B bonds in the α-Ga based structures, and networks that were largely composed of three-center σ-bonding functions in the channel-based structures. Seven of these high-pressure phases were found to be metastable at atmospheric conditions, and their Vickers hardnesses were estimated to ≈ 36 GPa.

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

Askival: An altered feldspathic cumulate sample in Gale crater

Askival is a light-toned, coarsely crystalline float rock, which was identified near the base of Vera Rubin Ridge in Gale crater. We have studied Askival, principally with the ChemCam instrument but also using APXS compositional data and MAHLI images. Askival and an earlier identified sample, Bindi, represent two rare examples of feldspathic cumulate float rocks in Gale crater with >65% relict plagioclase. Bindi appears unaltered whereas Askival shows textural and compositional signatures of silicification, along with alkali remobilization and hydration. Askival likely experienced multiple stages of alteration, occurring first through acidic hydrolysis of metal cations, followed by deposition of silica and possible phyllosilicates at low T and neutral-alkaline pH. Through laser-induced breakdown spectroscopy compositional analyses and normative calculations, we suggest that an assemblage of Fe-Mg silicates including amphibole and pyroxene, Fe phases, and possibly Mg-rich phyllosilicate are present. Thermodynamic modeling of the more pristine Bindi composition predicts that amphibole and feldspar are stable within an upper crustal setting. This is consistent with the presence of amphibole in the parent igneous rocks of Askival and suggests that the paucity of amphiboles in other known Martian samples reflects the lack of representative samples of the Martian crust rather than their absence on Mars.

58 GEOSCIENCES↗
DOE OSTI2023

Asymmetries in cloud microphysical properties ascribed to sea ice leads via water vapour transport in the central Arctic

To investigate the influence of sea ice openings like leads on wintertime Arctic clouds, the air mass transport is exploited as a heat and humidity feeding mechanism which can modify Arctic cloud properties. Cloud microphysical properties in the central Arctic are analysed as a function of sea ice conditions during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition in 2019–2020. The Cloudnet classification algorithm is used to characterize the clouds based on remote sensing observations and the atmospheric thermodynamic state from the observatory on board the research vessel (RV) Polarstern. To link the sea ice conditions around the observational site with the cloud observations, the water vapour transport (WVT) being conveyed towards RV Polarstern has been utilized as a mechanism to associate upwind sea ice conditions with the measured cloud properties. This novel methodology is used to classify the observed clouds as coupled or decoupled to the WVT based on the location of the maximum vertical gradient of WVT height relative to the cloud-driven mixing layer. Only a conical sub-sector of sea ice concentration (SIC) and the lead fraction (LF) centred on the RV Polarstern location and extending up to 50 km in radius and with an azimuth angle governed by the time-dependent wind direction measured at the maximum WVT is related to the observed clouds. We found significant asymmetries for cases when the clouds are coupled or decoupled to the WVT and selected by LF regimes. Liquid water path of low-level clouds is found to increase as a function of LF, while the ice water path does so only for deep precipitating systems. Clouds coupled to WVT are found to generally have a lower cloud base and larger thickness than decoupled clouds. Thermodynamically, for coupled cases the cloud-top temperature is warmer and accompanied by a temperature inversion at the cloud top, whereas the decoupled cases are found to be closely compliant with the moist adiabatic temperature lapse rate. The ice water fraction within the cloud layer has been found to present a noticeable asymmetry when comparing coupled versus decoupled cases. This novel approach of coupling sea ice to cloud properties via the WVT mechanism unfolds a new tool to study Arctic surface–atmosphere processes. With this formulation, long-term observations can be analysed to enforce the statistical significance of the asymmetries. Furthermore, our results serve as an opportunity to better understand the dynamic linkage between clouds and sea ice and to evaluate its representation in numerical climate models for the Arctic system.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Modification at the C2'-O-Position with 2-Methylbenzothiophene Induces Unique Structural Changes and Thermal Transitions on Duplexes of RNA and DNA

Oligonucleotides can be chemically modified for a variety of applications that include their use as biomaterials, in therapeutics, or as tools to understand biochemical processes, among others. This work focuses on the functionalization of oligonucleotides of RNA and DNA (12- or 14-nucleotides long) with methylbenzothiophene (BT), at the C2'-O-position, which led to unique structural features. Circular dichroism (CD) analyses showed that positioning the BT units on one strand led to significant thermal destabilization, while duplexes where each strand contained 4-BT rings formed a distinct arrangement with cooperativity/interactions among the modifications (evidenced from the appearance of a band with positive ellipticity at 235 nm). Interestingly, the structural arrays displayed increased duplex stabilization (>10 °C higher than the canonical analogue) as a function of [Na + ] with an unexpected structural rearrangement at temperatures above 50 °C. Density functional theory–polarizable continuum model (DFT-PCM) calculations were carried out, and the analyses were in agreement with induced structural changes as a function of salt content. A model was proposed where the hydrophobic surface allows for an internal nucleobase rearrangement into a more thermodynamically stable structure, before undergoing full denaturation, with increased heat. While this behavior is not common, B- to Z-form duplex transitions can occur and are dependent on parameters that were probed in this work, i.e., temperature, nature of modification, or ionic content. To take advantage of this phenomenon, we probed the ability of the modified duplexes to be recognized by Zα (an RNA binding protein that targets Z-form RNA) via electrophoretic analysis and CD. Interestingly, the protein did not bind to canonical duplexes of DNA or RNA; however, it recognized the modified duplexes, in a [monovalent/divalent salt] dependent manner. Overall, the findings describe methodology to attain unique structural motifs of modified duplexes of DNA or RNA, and control their behavior as a function of salt concentration. While their affinity to RNA binding proteins, and the corresponding mechanism of action, requires further exploration, the tunable properties can be of potential use to study this, and other, types of modifications. The novel arrays that formed, under the conditions described herein, provide a useful way to explore the structure and behavior of modified oligonucleotides, in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗