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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity

In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of $Na$ $^+_2$ in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of $Na$ $^+_2$ in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For $Na$ $^+_2$ in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. Here, the results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.

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

Microstructural changes and mass transport in cement-based materials: A modeling approach

Highlights: • Concept to relate microstructural changes, mass transport, and chemical reactions in cement-based materials is presented. • Multi-physics modeling approach utilizing an extended version of the PNP equation and the geochemical code IPHREEQC. • Case studies indicate significant changes in mass transport properties due to alterations in the microstructure. • Microstructural changes depend on exposure and interactions between chemical reactions, pore structure, and mass transport. A generic modeling framework is presented to relate microstructural changes, i.e. changes in the pore volume distribution and phase assemblage, and mass transport in cement-based materials. The modeling framework accounts for mass transport and chemical equilibrium between ions in the pore solution and solid hydrates by means of an extended version of the Poisson-Nernst-Planck equation, in which the chemical equilibrium is solved by the external geochemical code IPHREEQC. Results of numerical studies concerning carbonation and leaching of a cement-based material indicate significant changes in mass transport properties due to chemical reactions leading to alterations in the microstructure. The resulting highly non-linear (both spatial and temporal) microstructural changes are thereby depending on the exposure and indicate that interactions between chemical reactions, pore structure changes, and mass transport have to be accounted for as a whole.

36 MATERIALS SCIENCE↗
NASA NTRS1981

Significance of turbulence and transition location on radiative heating with ablation injection

This paper presents forebody flowfield solutions for Jupiter entry conditions where the ablation injection rate is coupled with the surface heating rate. The calculations are made with a time-dependent viscous-shock-layer analysis where the flow is assumed to be in chemical equilibrium. Both laminar and turbulent solutions are presented to describe the impact of turbulence on surface mass loss rates for flow conditions where the heating is due primarily to radiation. Results are also presented where the transition location to turbulent flow is arbitrarily varied. Results show that the radiative heating rate values based on several downstream transition locations adjust quickly to the corresponding values based on transition near the stagnation point.

Moss, J. N.↗
DOE OSTI2025

Exploring Catalyst Compositions for Microwave-Assisted Methane Dehydroaromatization

The flaring of natural gas in U.S. shale regions remains a challenge for producers. One alternative to flaring is converting the wasted gas into valuable chemicals. Microwave-based processes offer a promising solution, potentially enabling the development of compact, modular systems for on-site production of chemicals, such as aromatics, from natural gas. This is due to the advantages of microwave heating, including efficient heating of compact volumes, accelerated reaction rates, and electrification of heating. However, developing effective catalysts for microwave-based processes is challenging, as conventional materials often require modification to be effectively heated by microwaves. This study provides an overview of a catalyst development project focused on a molybdenum-supported zeolite catalyst, optimized for the direct conversion of methane into aromatics under microwave irradiation. It details the synthesis, characterization, and the effects of promoters, as well as computational efforts undertaken to understand and enhance the catalyst's performance.

flare gas↗
DOE OSTI2026

Peak2Patch: High-Fidelity Functional Group Identification through Attention-Based Fusion of Infrared and Mass Spectra

Identifying molecular structure based on spectroscopic readings is a key task in a variety of chemical and biological applications. Common spectroscopy techniques, such as Infrared (IR) Spectroscopy and Mass Spectrometry (MS), provide detailed information on the structure of molecular compounds but nonetheless require expert-level knowledge to decode. Machine learning has emerged as a potential solution for automating structure prediction from chemical spectra; however, current approaches generally focus on single sensor modalities, neglecting to leverage the complementary information contained within differing spectra. In this paper, we introduce Peak2Patch, a novel approach to fusion-enhanced prediction of functional groups from IR and mass spectra. First, we perform a detailed comparison of backbone networks for encoding both sparse mass spectra and dense IR spectra and demonstrate the superior performance of transformer neural networks over current state-of-the-art convolutional neural networks. Second, we evaluate three broad categories of fusion: early (raw feature), middle (deep feature), and late (decision) fusion, demonstrating the potential of a deep feature fusion-based approach. Lastly, we present Peak2Patch, our attention-based fusion scheme, which leverages cross-attention to mix features between encoded tokens of the two modalities. We validate our approach on a publicly available multimodal spectroscopic data set of 790k simulated molecules, demonstrating a large improvement in functional group prediction over both the previous state-of-the-art and our own strong single-modal baselines.

Jacobson, Philip [Sandia National Laboratories (SN↗
DOE OSTI2025

Data-Driven Kinetic Reaction Networks for Separation Chemistry

Understanding complex, multistep chemical reactions at the molecular level is a major challenge whose solution would greatly benefit the design and optimization of numerous chemical processes. The separation of rare-earth (4f) and actinide (5f) elements is an example where improving our chemical understanding is important for designing and optimizing new chemistries, even with a limited number of observations. Here, in this work, we leverage data-driven artificial intelligence and machine-learning approaches to develop kinetic reaction networks that describe the liquid–liquid extraction mechanism of uranium using N,N-di-2-ethylhexyl-isobutyramide (DEHiBA). Specifically, we compare and contrast the properties of two classes of models: (1) purely data-driven models that are regularized using chemistry-agnostic, L1 regression and (2) chemistry-informed models that are regularized using relative reaction energies provided by quantum mechanical calculations. We observe that purely data-driven models are unbiased, simple, and accurate in their predictions of experimental measurements when provided with sufficient data but are difficult to fully constrain and interpret. In contrast, chemistry-informed models exhibit significantly improved chemical interpretability and consistency, providing a detailed description of the separation process while achieving high accuracy through ensemble averaging. Overall, the dominant species predicted to be extracted into the organic phase is UO 2 (NO 3 ) 2 (DEHiBA) 2 , agreeing with experimental slope analysis, thermodynamic modeling, EXAFS, and crystal structures. This work demonstrates that leveraging the fundamental structure of the problem can lead to efficient learning schemes that provide both accurate predictions and chemical insights at a low computational cost.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Fiber Attachment Module Experiment (FAME): Using a Multiplexed Miniature Hollow Fiber Membrane Bioreactor Solution for Rapid Process Testing

Bioreactor research is mostly limited to continuous stirred-tank reactors (CSTRs) which are not an option for microgravity (g) applications due to the lack of a gravity gradient to drive aeration as described by the Archimedes principle. Bioreactors and filtration systems for treating wastewater in g could avoid the need for harsh pretreatment chemicals and improve overall water recovery. Solution: Membrane Aerated Bioreactors (MABRs) for g applications, including possible use for wastewater treatment systems for the International Space Station (ISS).

Module Experiment↗
NASA NTRS1981

An evaluation of computer codes for simulating the Galileo Probe aerothermal entry environment

The approaches of three computer flow field codes (HYVIS, COLTS, and RASLE), used to determine the Galileo Probe aerothermal environment and its effect on the design of the thermal protection system, are analyzed in order to resolve differences in their predicted results. All three codes account for the hypersonic, massively blown, radiation shock layers, characteristic of Jupiter entry. Significant differences, however, are evident in their solution procedures: the governing conservation equations, the numerical differencing methods, the governing physics (chemical, radiation, diffusion, and turbulence models), and the basic physical data (thermodynamic, transport, chemical, and spectral properties for atomic and molecular species). Solutions are compared for two near peak heating entry conditions for a Galileo Probe baseline configuration, having an initial mass of 242 kg and simulating entry into the Orton nominal atmosphere. The modern numerical methodology of COLTS and RASLE appear to provide an improved capability for coupled flow-field solutions.

Menees, G. P.↗
NASA NTRS2003

Computational Aeroheating Predictions for Mars Lander Configurations

The proposed Mars Science Laboratory (MSL) mission is intended to deliver a large rover to the Martian surface within 10 km of the target site. This paper presents computational fluid dynamics (CFD) predictions of forebody heating rates for two MSL entry configurations with fixed aerodynamic trim tabs. Results are compared to heating on a 70-deg sphere-cone reference geometry. All three heatshield geometries are designed to trim hypersonically at a 16 deg angle of attack in order to generate the lift-to-drag ratio (L/D) required for precision landing. Comparisons between CFD and tunnel data are generally in good agreement for each configuration, but the computations predict more flow separation and higher heating on a trim tab inclined 10 deg relative to the surface. CFD solutions at flight conditions were obtained using an 8-species Mars gas in chemical and thermal nonequilibrium. Laminar and Baldwin-Lomax solutions were used to estimate the effects of the trim tabs and turbulence on heating. A tab extending smoothly from the heatshield flank is not predicted to increase laminar or turbulent heating rates above the reference levels. Laminar heating on a tab deflected 10 deg from the conical heatshield is influenced by flow separation and is up to 35% above the baseline heating rate. The turbulent solution on the inclined tab configuration predicts attached flow and a 43% heating increase above the reference level.

Edquist, Karl T.↗
NASA NTRS1971

Thermodynamics of rock forming crystalline solutions

Analysis of phase diagrams and cation distributions within crystalline solutions as means of obtaining thermodynamic data on rock forming crystalline solutions is discussed along with some aspects of partitioning of elements in coexisting phases. Crystalline solutions, components in a silicate mineral, and chemical potentials of these components were defined. Examples were given for calculating thermodynamic mixing functions in the CaW04-SrW04, olivine-chloride solution, and orthopyroxene systems.

Saxena, S. K.↗
DOE OSTI2023

Selective permeation up a chemical potential gradient to enable an unusual solvent purification modality

The need for energy-efficient recovery of organic solutes from aqueous streams is becoming more urgent as chemical manufacturing transitions toward nonconventional and bio-based feedstocks and processes. In addition to this, many aqueous waste streams contain recalcitrant organic contaminants, such as pharmaceuticals, industrial solvents, and personal care products, that must be removed prior to reuse. We observe that rigid carbon membrane materials can remove and concentrate organic contaminants via an unusual liquid-phase membrane permeation modality. Surprisingly, detailed thermodynamic calculations on the chemical potential of the organic contaminant reveal that the organic species has a higher chemical potential on the permeate side of the membrane than on the feed side of the membrane. This unusual observation challenges conventional membrane transport theory that posits that all permeating species move from high chemical potential states to lower chemical potential states. Based on experimental measurements, we hypothesize that the organic is concentrated in the membrane relative to water via favorable binding interactions between the organic and the carbon membrane. The concentrated organic is then swept through the membrane via the bulk flow of water in a modality known as “sorp-vection.” We highlight via simplified nonequilibrium thermodynamic models that this “uphill” chemical potential permeation of the organic does not result in second-law violations and can be deduced via measurements of the organic and water sorption and diffusion rates into the carbon membrane. Moreover, this work identifies the need to consider such nonidealities when incorporating unique, rigid materials for the separations of aqueous waste streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Analysis of bipolar membranes for electrochemical CO 2 capture from air and oceanwater

Carbon dioxide (CO 2 ) must be removed from the atmosphere to mitigate the negative effects of climate change. However, the most scalable methods for removing CO 2 from the air require heat from fossil-fuel combustion to produce pure CO 2 and continuously regenerate the sorbent. Bipolar-membrane electrodialysis (BPM-ED) is a promising technology that uses renewable electricity to dissociate water into acid and base to regenerate bicarbonate-based CO 2 capture solutions, such as those used in chemical loops of direct-air-capture (DAC) processes, and in direct-ocean capture (DOC) to promote atmospheric CO 2 drawdown via decarbonization of the shallow ocean. In this study, we develop an experimentally validated 1D model for the electrochemical regeneration of CO 2 from bicarbonate-based carbon capture solutions and seawater using BPM-ED. For DAC, our experimental and computational results demonstrate that pH swings induced by BPM water dissociation drive the formation of CO 2 at the cation-exchange layer|catholyte interface with energy-intensities of less than 150 kJ mol -1 . However, high rates of bubble formation increase energy intensity at current densities >100 mA cm -2 . Correspondingly, accelerating water dissociation catalysis and enacting bubble removal could enable CO 2 recovery at energy intensities <100 kJ mol -1 and current densities >100 mA cm -2 . For DOC, mass transport limitations associated with low carbon concentrations in oceanwater suggest that DOC is best suited for clean production of acid and base usable in downstream processes. Further, these results provide design principles for industrial-scale CO 2 recovery using BPM-ED.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1989

Nonaqueous chemical depth profiling of YBa2Cu3O(7-x)

A nonaqueous solution of Br in absolute ethanol (EtOH) has recently been reported to be effective at removing nonsuperconducting surface species from YBa2Cu3O(7-x) films, leaving the surface close to the ideal stoichiometry. This same etchant is shown here to be an effective bulk etchant in chemical depth profiling through 1-micron-thick films. The Cu remains in the 2 + oxidation state and the stoichiometry, as determined by X-ray photoelectron spectroscopy, is close to ideal and nearly constant throughout the profile, indicating the absence of any large preferential etching effects. The reaction of YBa2Cu3O(7-x) films with HF/EtOH, HCl/EtOH, and I/EtOH solutions is also reported.

Vasquez, R. P.↗
NASA NTRS2013

Automated, Ultra-Sterile Solid Sample Handling and Analysis on a Chip

There are no existing ultra-sterile lab-on-a-chip systems that can accept solid samples and perform complete chemical analyses without human intervention. The proposed solution is to demonstrate completely automated lab-on-a-chip manipulation of powdered solid samples, followed by on-chip liquid extraction and chemical analysis. This technology utilizes a newly invented glass micro-device for solid manipulation, which mates with existing lab-on-a-chip instrumentation. Devices are fabricated in a Class 10 cleanroom at the JPL MicroDevices Lab, and are plasma-cleaned before and after assembly. Solid samples enter the device through a drilled hole in the top. Existing micro-pumping technology is used to transfer milligrams of powdered sample into an extraction chamber where it is mixed with liquids to extract organic material. Subsequent chemical analysis is performed using portable microchip capillary electrophoresis systems (CE). These instruments have been used for ultra-highly sensitive (parts-per-trillion, pptr) analysis of organic compounds including amines, amino acids, aldehydes, ketones, carboxylic acids, and thiols. Fully autonomous amino acid analyses in liquids were demonstrated; however, to date there have been no reports of completely automated analysis of solid samples on chip. This approach utilizes an existing portable instrument that houses optics, high-voltage power supplies, and solenoids for fully autonomous microfluidic sample processing and CE analysis with laser-induced fluorescence (LIF) detection. Furthermore, the entire system can be sterilized and placed in a cleanroom environment for analyzing samples returned from extraterrestrial targets, if desired. This is an entirely new capability never demonstrated before. The ability to manipulate solid samples, coupled with lab-on-a-chip analysis technology, will enable ultraclean and ultrasensitive end-to-end analysis of samples that is orders of magnitude more sensitive than the ppb goal given in the Science Instruments.

Mora, Maria F.↗
DOE OSTI2022

Tuning Organic Electrochemical Transistor Threshold Voltage using Chemically Doped Polymer Gates

Organic electrochemical transistors (OECTs) have shown promise as transducers and amplifiers of minute electronic potentials due to their large transconductances. Tuning the OECT threshold voltage is important to achieve low-powered devices with amplification properties within the desired operational voltage range. However, traditional design approaches have struggled to decouple channel and materials properties from threshold voltage, thereby compromising on several other OECT performance metrics, such as electrochemical stability, transconductance, and dynamic range. In this work, simple solution-processing methods are utilized to chemically dope polymer gate electrodes, thereby controlling their work function, which in turn tunes the operation voltage range of the OECTs without perturbing their channel properties. Chemical doping of initially air-sensitive polymer electrodes further improves their electrochemical stability in ambient conditions. Thus, OECTs that are simultaneously low-powered and electrochemically resistant to oxidative side reactions under ambient conditions are demonstrated. Furthermore, this approach shows that threshold voltage, which is once interwoven with other OECT properties, can in fact be an independent design parameter, expanding the design space of OECTs.

chemical doping↗
NASA NTRS1973

Research study on materials processing in space, experiment M512

Gallium arsenide, a commercially valuable semiconductor, has been prepared from the melt (M.P. 1237C), by vapor growth, and by growth from metallic solutions. It has been established that growth from metallic solution can produce material with high, and perhaps with the highest possible, chemical homogeneity and crystalline perfection. Growth of GaAs from metallic solution can be performed at relatively low temperatures (about 600C) and is relatively insensitive to temperature fluctuations. However, this type of crystal growth is subject to the decided disadvantage that density induced convection currents may produce variations in rates of growth at a growing surface. This problem would be minimized under reduced gravity conditions.

Rubenstein, M.↗