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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Optically detected NMR in a diamond-anvil cell for geochemistry

Developments in quantum-information processing are being adapted to perform nuclear-magnetic resonance (NMR) measurements on solutions in very small volumes. Here we describe efforts to adapt the technology to a diamond-anvil cell (DAC), with the goal of conducting solution NMR measurements at elevated pressures and temperatures. At the center of the method is the use of diamonds that have a particular type of defect that pairs a nitrogen atom substitution for near-surface carbon with a vacancy. These NV sites have unpaired electrons that can be excited while conserving electron spins and the amount of light released upon decay of the excited state depends upon the orientation of the electron spin. Under certain conditions the NV centers can probe AC magnetic fields from nearby nuclei with exquisite sensitivity.

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

Reactions of Propyl Radicals: A Shock Tube - VUV Photoionization Mass Spectrometry Study

The pyrolytic reactions of n-propyl and i-propyl radicals and their precursors have been investigated at elevated temperatures and pressures (600 – 900 K and 5 – 8 bar). The studies were performed in a miniature high repetition rate shock tube with synchrotron vacuum ultraviolet photoionization mass spectrometry yielding comprehensive datasets of temporal and photoionization energy dependencies of reagents and products. The propyl radicals were generated by pyrolysis of alkyl nitrites. In addition to the main decomposition path, NO elimination, the mass spectra allowed an alternative minor path via HNO elimination to be identified and quantified. For the n-propyl precursor the HNO elimination route accounted for 9% of the alkyl nitrite while for the i-propyl precursor it was 2.5%. These values are in good agreement with a recent study on i-butyl radicals in the same apparatus at similar conditions. The ratio of disproportionation/recombination was obtained for n- propyl from the relative concentrations of n-hexane and propene and for i-propyl from 2,3-dimethyl butane and propene. For n-propyl the ratio is 0.3 and 1.2 for i-propyl, both are independent of temperature and pressure over the experimental range. The disproportionation/recombination ratios are about a factor of 2 higher than prior evaluations that are based mainly on room temperature data. The experimental results are some of the first from the apparatus used and comments are made about the technique, challenges encountered, and suggestions for future developments.

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

Impact of organic solutes on capillary phenomena in water-CO2-quartz systems

Hypothesis: The migration of supercritical CO2 (scCO2) injected into underground reservoirs as part of carbon capture and storage is influenced by organic contamination affecting mineral wettability. Molecular dynamics (MD) simulations of relevant systems that incorporate representative organic solutes allow detailed investigation of changes in fundamental interfacial and capillary properties. Experiments: We use MD simulations to explore the effects of four organic solutes (quinoline, decanoic acid, coronene, sorgoleone) on the wettability of quartz by water in the presence of scCO2. We examine the impacts of polar, alkyl, and aromatic moieties as well as fluid flow velocity at elevated temperatures and pressures. Findings: Organic molecules accumulate at the water-CO2 interface, where they distribute according to their size and functional groups. Certain organics penetrate the adsorbed water film at the quartz-CO2 interface, revealing two modes of hydrogen bonding between polar organic functional group, water, and quartz surface –OH groups. Interfacial energies and contact angles are minimally impacted by organic adsorption at the water-CO2 interface, possibly due to simultaneous CO2 desorption. Non- equilibrium MD simulations reveal that flow-induced redistribution of organic compounds modulates the radii of curvature of the advancing and receding water-CO2 interfaces. Our results indicate that organic adsorption on water surfaces is likely ubiquitous during multi-phase flow in soils and sedimen- tary rocks, with implications for the mobilization and transport of organic compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Study of CO 2 Adsorption Properties on the SrTiO 3 (001) Surface with Ambient Pressure XPS

The adsorption properties of CO 2 on the SrTiO 3 (001) surface were investigated using ambient pressure X-ray photoelectron spectroscopy under elevated pressure and temperature conditions. On the Nb-doped TiO 2 -enriched (1 × 1) SrTiO 3 surface, CO 2 adsorption, i.e., the formation of CO 3 surface species, occurs first at the oxygen lattice site under 10 –6 mbar CO 2 at room temperature. The interaction of CO 2 molecules with oxygen vacancies begins when the CO 2 pressure increases to 0.25 mbar. The adsorbed CO 3 species on the Nb-doped SrTiO 3 surface increases continuously as the pressure increases but starts to leave the surface as the surface temperature increases, which occurs at approximately 373 K on the defect-free surface. On the undoped TiO 2 -enriched (1 × 1) SrTiO 3 surface, CO 2 adsorption also occurs first at the lattice oxygen sites. Both the doped and undoped SrTiO 3 surfaces exhibit an enhancement of the CO 3 species with the presence of oxygen vacancies, thus indicating the important role of oxygen vacancies in CO 2 dissociation. When OH species are removed from the undoped SrTiO 3 surface, the CO 3 species begin to form under 10 –6 mbar at 573 K, thus indicating the critical role of OH in preventing CO 2 adsorption. The observed CO 2 adsorption properties of the various SrTiO 3 surfaces provide valuable information for designing SrTiO 3 -based CO 2 catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Formic Acid: A Hydrogen-Bonding Cocatalyst for Formate Decomposition

Hydrogen bonding accelerates many catalytic reactions by orienting intermediates, stabilizing transition states, and even opening reaction pathways. However, most mechanistic studies regarding the decomposition of formic acid (FA), a promising hydrogen storage material, neglect hydrogen-bonding interactions even though FA is a strong hydrogen-bond donor and acceptor. Here, we probe the formation of bimolecular hydrogen-bonded complexes between FA and formate (FA–HCOO complexes) adsorbed on metal surfaces and how these complexes affect HCOO* decomposition. Using first-principles density functional theory (DFT) calculations on 12 close-packed (111)/(0001) and 8 open (100) surfaces of 12 transition metals—Ag, Au, Co, Cu, Ir, Ni, Os, Re, Pd, Pt, Rh, and Ru, we—show that FA–HCOO complexes are generally thermodynamically stable, even at elevated temperatures and pressures. We then illustrate that these complexes produce infrared spectroscopic signatures consistent with as yet unassigned experimental peaks. We last demonstrate that by stabilizing the dangling bond of monodentate HCOO*, these complexes significantly lower the barriers for rotation of HCOO* from a bidentate to a monodentate configuration, the rate-limiting step for HCOO* decomposition on many surfaces. FA thus acts as a cocatalyst for HCOO* decomposition. Our results may guide the community toward improved catalysts for reactions involving HCOO* such as FA decomposition, methanol steam reforming, and the water gas shift reaction. More broadly, our work highlights the ability of hydrogen bonding to modify the adsorbed structures of intermediates and lower the barriers for their reaction on heterogeneous catalysts. Lastly, this phenomenon can be relevant for other reactions involving ammonia, alcohols, and carboxylic acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Decadal-Scale Hydrothermal Alteration of Basalt: Implications for Long-Term Reactivity in Subsurface Technologies

Global demands to secure critical mineral supply chains and managing water resources require innovative resource management strategies. Subsurface basalt reservoirs offer a dual-purpose application, where CO2 enhanced critical metal recovery can be coupled with water remediation strategies for the extraction of economically important and environmentally relevant elements. This study utilizes static batch experiments conducted on Columbia River Basalt Group samples to evaluate long-term fluid–rock interactions relevant to coupled subsurface applications. Samples were reacted under elevated temperature and pressure conditions, for 296 and 4,061 days, providing a unique dataset to assess geochemical evolution, element partitioning, and aqueous chemistry over decadal timescales. The alteration was dominated by silicate, aluminosilicate, and oxide phases. Progressive hydrothermal alteration increased the cation exchange capacity through the formation of secondary minerals (e.g. clays and zeolites), influencing solute retention, ion exchange behavior, and aqueous chemistry. Grain-scale and bulk analyses revealed selective cation release and retention patterns, establishing a mechanistic baseline for predicting element mobility. These geochemical constraints inform the prospective use of CO2-enhanced metal recovery for critical resources (e.g. Co, Ni, Mn, Mg, Ti, Fe) and associated water-quality impacts, providing a foundation for the design and management of engineered fluid–rock systems in basalt reservoirs.

Gibson, Marie N.↗
DOE OSTI2025

Engineered enzymatic cascade converts diols to amino alcohols

Aliphatic amino alcohols such as 6-amino-1-hexanol are potential platform chemicals for a variety of advanced materials, but applications are currently limited by reagent costs. Aliphatic amino alcohols can currently be synthesized from biomass-derived diols at elevated temperatures and pressures using Ru-based catalysts that produce a mixture of amino-alcohol, diamine, and cyclic amine products. Replacing chemical amination with an enzymatic cascade would reduce resource needs and enable reactions under milder conditions. In this work, we characterized a two-enzyme cascade that selectively converts C4–C7 diols to the corresponding amino alcohols under aqueous conditions at room temperature and pressure. By engineering the rate-limiting enzyme and optimizing reaction conditions, we increased amino alcohol production nearly 30-fold, achieving a selectivity of 99%. The same enzyme cascade could also be used to convert amino alcohols into cyclic amines through reduction of the corresponding cyclic imine. This engineered cascade provides a green opportunity to sustainably synthesize asymmetric bifunctional platform chemicals.

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

Atomic-Scale Dynamic Interaction of H 2 O Molecules with Cu Surface

Atomic-scale interaction of water vapor with metal surfaces beyond surface adsorption under technologically relevant conditions remains mostly unexplored. Using aberration-corrected environmental transmission electron microscopy, we reveal the dynamic surface activation of Cu by H 2 O at elevated temperature and pressure. In this study, we find a structural transition from flat to corrugated surface for the Cu(011) under low water-vapor pressure. Increasing the water-vapor pressure leads to the surface reaction of Cu with dissociated H 2 O, resulting in the formation of a metastable “bilayer” Cu-O-H phase. Corroborated by density functional theory and ab initio molecular dynamics calculations, the cooperative O and OH interaction with Cu is responsible for the formation and subsurface propagation of this phase.

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

Modeling of Supercritical CO2 Shell-and-Tube Heat Exchangers Under Extreme Conditions: Part II: Heat Exchanger Model

Abstract Heat exchangers play a critical role in supercritical CO2 Brayton cycles by providing necessary waste heat recovery. Supercritical CO2 thermal cycles potentially achieve higher energy density and thermal efficiency operating at elevated temperatures and pressures. Accurate and computationally efficient estimation of heat exchanger performance metrics at these conditions is important for the design and optimization of sCO2 systems and thermal cycles. In this paper (Part II), a computationally efficient and accurate numerical model is developed to predict the performance of shell-and-tube heat exchangers (STHXs). Highly accurate correlations reported in Part I of this study are utilized to improve the accuracy of performance predictions, and the concept of volume averaging is used to abstract the geometry and reduce computation time. The numerical model is validated by comparison with computational fluid dynamics (CFD) simulations and provides high accuracy and significantly lower computation time compared to existing numerical models. A preliminary optimization study is conducted and the advantage of using supercritical CO2 as a working fluid for energy systems is demonstrated.

Engineering↗
DOE OSTI2023

Thermopile Energy Harvesting for Subsurface Wellbore Sensors (Final Report)

Robust in situ power harvesting underlies all efforts to enable downhole autonomous sensors for real-time and long-term monitoring of CO 2 plume movement and permeance, wellbore health, and induced seismicity. This project evaluated the potential use of downhole thermopile arrays, known as thermoelectric generators (TEGs), as power sources to charge sensors for in situ real-time, long-term data capture and transmission. Real-time downhole monitoring will enable “Big Data” techniques and machine learning, using massive amounts of continuous data from embedded sensors, to quantify short- and long-term stability and safety of enhanced oil recovery and/or commercial-scale geologic CO 2 storage. This project evaluated possible placement of the TEGs at two different wellbore locations: on the outside of the casing; or on the production tubing. TEGs convert heat flux to electrical power, and in the borehole environment, would convert heat flux into or out of the borehole into power for downhole sensors. Such heat flux would be driven by pumping of cold or hot fluids into the borehole—for instance, injecting supercritical CO 2 —creating a thermal pulse that could power the downhole sensors. Hence, wireless power generation could be accomplished with in situ TEG energy harvesting. This final report summarizes the project’s efforts that accomplished the creation of a fully operational thermopile field unit, including selection of materials, laboratory benchtop experiments and thermal-hydrologic modeling for design and optimization of the field-scale power generation test unit. Finally, the report describes the field unit that has been built and presents results of performance and survivability testing. The performance and survivability testing evaluated the following: 1) downhole power generation in response to a thermal gradient produced by pumping a heated fluid down a borehole and through the field unit; and 2) component survivability and operation at elevated temperature and pressure conditions representative of field conditions. The performance and survivability testing show that TEG arrays are viable for generating ample energy to power downhole sensors, although it is important to note that developing or connecting to sensors was beyond the scope of this project. This project’s accomplishments thus traversed from a low Technical Readiness Level (TRL) on fundamental concepts of the application and modeling to TRL-5 via testing of the fully integrated field unit for power generation in relevant environments. A fully issued United States Patent covers the wellbore power harvesting technology and applications developed by this project.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Nitrogen Vacancy Center in Diamond for the Stress and Field Sensing Applications

The nitrogen-vacancy (NV) center in a nanodiamond (ND) crystal is a promising material for quantum information processing, sensing, and computing applications. It is one of the best candidate materials for quantum sensing and metrology expected to work at elevated temperatures and pressures conditions. We computationally show the effect of strain on the defect band edges and band gaps in the NV center diamond. A low energy Hamiltonian is developed for the ±1 spin manifold at the ground state. We show the quantum sensing device is a few orders of magnitude superior in sensing than the traditional optical sensing devices. We also discuss experimental results from the optically detected magnetic resonance (ODMR) and the spin relaxometry for the field sensing applications. The presentation concludes by providing a model for free spins detection of the rare earth ions.

field sensing applications↗
NASA NTRS1979

Oxygen and nitrogen raman spectra

Engineering design computer program that calculates rotational Raman spectrum of either nitrogen or oxygen can be used to increase performance of gas-turbine engines by predicting extent of pressure broadening associated with temperature measurements at elevated pressure.

Fralick, G. C.↗
NASA NTRS1986

Ignition of metals and alloys by high-velocity particles

The ignition of metals and alloys by impacting high-velocity particles in gaseous oxygen was investigated. A convergent/divergent nozzle was used to accelerate the flowing oxygen, which in turn accelerated the particles to velocities greater than 305 m/s (1000 ft/s). The test sample (target) was placed at the end of the chamber in the flow path. Aluminum 6061, type 316 stainless steel, type 304 stainless steel, and Inconel 718 were ignited with 1600-micron aluminum 2017 particles at elevated temperatures and pressures whereas Monel 400 could not be ignited. The ignition susceptibility of metals and alloys appeared to increase as the inlet pressure, sample temperature, and particle size were increased. Type 304 stainless steel particles required more extreme conditions for ignition of materials than similar sized aluminum particles. The results indicated that ignition and subsequent burning of the particles were required for ignition of the target materials with the possible exception of aluminum 6061.

Benz, F. J.↗
NASA NTRS1995

Langley Research Center - Soluble Imide (LaRC-SI)

This report is about experimenting and developing uses for the new thermal plastic developed by Dr. Robert Bryant called the 'Langley Research Center - Soluble Imide' (LaRC-SI). The three developments are: the use of the LaRC-SI as a dielectric for thin film sensors, as an adhesive to place diamonds on surfaces to increase thermal conductivity, and as an intermediate layer to allow the placement of metal on aluminum nitride. The LaRC-SI was developed by Dr. Robert G. Bryant, a chemical engineer at NASA Langley Research Center. The unique properties of this material is that it is an amorphous thermoplastic. This means that it can be reformed at elevated temperature and pressures. It can be applied in the form of a spray, spin, dip coating, paint, or spread with a doctors blade. The LaRC-SI has excellent adhesive and dielectric properties. It can also be recycled. Potential applications for this material are resin for mechanical parts such as gears, bearings and valves, advanced composites like carbon fiber, high strength adhesives, thin film circuits, and as a dielectric film for placing electrical components on conductive materials.

Stang, David↗
NASA NTRS2012

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Socki, Richard A.↗
NASA NTRS2012

Processing and Damage Tolerance of Continuous Carbon Fiber Composites Containing Puncture Self-Healing Thermoplastic Matrix

Research at NASA Langley Research Center (NASA LaRC) has identified several commercially available thermoplastic polymers that self-heal after ballistic impact and through-penetration. One of these resins, polybutadiene graft copolymer (PB(sub g)), was processed with unsized IM7 carbon fibers to fabricate reinforced composite material for further evaluation. Temperature dependent characteristics, such as the degradation point, glass transition (T(sub g)), and viscosity of the PBg polymer were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic parallel plate rheology. The PBg resin was processed into approximately equal to 22.0 cm wide unidirectional prepreg tape in the NASA LaRC Advanced Composites Processing Research Laboratory. Data from polymer thermal characterization guided the determination of a processing cycle used to fabricate quasi-isotropic 32-ply laminate panels in various dimensions up to 30.5cm x 30.5cm in a vacuum press. The consolidation quality of these panels was analyzed by optical microscopy and acid digestion. The process cycle was further optimized based on these results and quasi-isotropic, [45/0/-45/90]4S, 15.24cm x 15.24cm laminate panels were fabricated for mechanical property characterization. The compression strength after impact (CAI) of the IM7/pBG composites was measured both before and after an elevated temperature and pressure healing cycle. The results of the processing development effort of this composite material as well as the results of the mechanical property characterization are presented in this paper.

Grimsley, Brian W.↗