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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Syntheses and characterization of isotopically labeled 1,3,5-triamino-2,4,6-trinitrobenzene (TATB)

Synthesis and characterization of chemical analogues of TATB, where specific atoms in the structure have been isotopically substituted, are reported. 15 N, 2 H, and 18 O have replaced the naturally occurring isotope distributions in the amino and/or the nitro attendant sites and 13 C has replaced the carbon in the ring structure. A modified wet-amination method was used to produce the analogues, and the isotopic replacements were performed by selective choice of labeled precursors. Four 15 N-labeled compounds (N replaced in the amino and nitro positions), two deuterium-labeled compounds (hydrogens replaced on the amino groups), and one 13 C-labeled compound (C in the ring substituted) were synthesized of high isotopic and chemical purity. One partially labeled 18 O-labeled compound (O in the nitro position) was a result of incomplete labeling due to exchange reactions during synthesis. The compounds were characterized by various spectroscopic methods – mass spectrometry (MS), solid-state nuclear magnetic resonance (SS-NMR), infrared (FTIR), powder x-ray diffraction (PXRD), and differential scanning calorimetry (DSC), depending upon the substitution. In conclusion, these compounds have been critical to the efforts in understanding the decomposition pathways of TATB when exposed to abnormal thermal environments.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Alkaline-Earth Chalcogenide Nanocrystals: Solution-Phase Synthesis, Surface Chemistry, and Stability

Increasing demand for effective energy conversion materials and devices has renewed interest in semiconductors comprised of earth-abundant and biocompatible elements. Alkaline-earth sulfides doped with rare earth ions are versatile optical materials. However, relatively little is known about controlling the dimensionality, surface chemistry, and inherent optical properties of the undoped versions of alkaline-earth monoand polychalcogenides. Here, we describe the colloidal synthesis of alkaline-earth chalcogenide nanocrystals through the reaction of metal carboxylates with carbon disulfide or selenourea. Systematic exploration of the synthetic phase space allows us to tune particle sizes over a wide range using a mixture of commercially available carboxylate precursors. Solid-state NMR spectroscopy confirms the phase purity of the selenide compositions. Surface characterization reveals that bridging carboxylates and amines preferentially terminate the surface of the nanocrystals. While these materials are colloidally stable in the mother solution, the selenides are susceptible to oxidation over time, eventually degrading to selenium metal through polyselenide intermediates. As part of these investigations, we have developed the colloidal syntheses of barium di- and triselenides, two among few reported nanocrystalline alkaline-earth polychalcogenides. Electronic structure calculations reveal that both materials are indirect band gap semiconductors. The colloidal chemistry presented here may enable the synthesis of more complex, multinary chalcogenide materials containing alkaline-earth elements.

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

Integrated Ion-Exchange Membrane Resin Wafer Assemblies for Aromatic Organic Acid Separations Using Electrodeionization

Aromatic acids, such as p-coumaric acid, are valuable chemical intermediates that are used in the specialty chemical industries because they are precursors to phenylpropanoid compounds. The separation of p-coumaric acid from fermentation broths is a critical step in the biochemical production process and more broadly the circular carbon economy. Electrodeionization (EDI) has been applied toward separations of low-carbon chain acids, but purifying p-coumaric acid has been challenging due to fouling and irreversible binding with ion-exchange membranes and resins. Here, we report a new membrane wafer assembly (MWA) consisting of laminated ion exchange membranes to porous ionomer-binder resin wafers for EDI. The MWAs in an EDI stack showed a 7-fold increase in p-coumaric acid capture while also using 70% less specific energy consumption when benchmarked against state-of-the-art resin wafer EDI modules. The more efficient p-coumaric acid recovery was ascribed to (i) the 38% reduction in interfacial transport resistance between the membrane and resin wafer and (ii) using imidazolium anion exchange membranes and ionomer binders in the MWA. MD simulations revealed enhanced transport rates for p-coumarate in imidazolium ionomers through π–π interactions. As a result, adopting the new MWA significantly reduced the amount of ion-exchange membranes in EDI and may lead to drastic capital cost savings.

42 ENGINEERING↗
DOE OSTI2020

Nano-layer deposition of metal oxides via a condensed water film

Abstract Nanocoatings on solids can be achieved by various processes, including sol-gel and atomic layer deposition. However, challenges remain for achieving uniform nanocoatings on nanoscale substrates at a large scale. Here, we report a versatile and fundamentally different technique, termed condensed layer deposition, for depositing conformal metal oxide nanocoatings on nanoparticles and nanofibers. This approach involves water in liquid hydrocarbons condensing as a nanoscale water film on the substrate surface, enabled by interfacial tension between polar water and nonpolar liquid hydrocarbons. Chemical precursors are then added, which react with the condensed water film to form a metal oxide nanocoating. We demonstrate this for titania, alumina, and niobia on substrates including carbon nanotubes, iron oxide particles and carbon black. Condensed layer deposition can achieve oxide nanocoatings on a variety of substrates with tunable thickness, in one pass, at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A nitrogenase-like enzyme system catalyzes methionine, ethylene, and methane biogenesis

Bacterial production of hydrocarbon gases like ethylene and methane affects soil ecosystems and the climate. This study reveals that methane and ethylene from land and freshwater bacteria are directly produced by a previously unknown methionine biosynthesis pathway. This pathway employs a nitrogenase-like reductase that is distinct from known nitrogenases and nitrogenase-like reductases. The nitrogenase-like methylthio-alkane reductase specifically functions in carbon-sulfur bond breakage to reduce ubiquitous and significant volatile organic sulfur compounds such as dimethyl sulfide and (2-methylthio)ethanol. The liberated methanethiol serves as the immediate precursor to methionine. Whereas ethylene or methane is released into the environment. This pathway provides a biological route to the synthesis of ethylene in the absence of oxygen. Finally, anaerobic ethylene production by this pathway apparently explains the long-standing observation of ethylene accumulation in oxygen-depleted soils Methane production reveals an additional bacterial pathway that is distinct from archaeal methanogenesis.

10 SYNTHETIC FUELS↗
NASA NTRS2001

Secondary metabolism in simulated microgravity

We have studied microbial secondary metabolism in a simulated microgravity (SMG) environment provided by NASA rotating-wall bioreactors (RWBs). These reactors were designed to simulate some aspects of actual microgravity that occur in space. Growth and product formation were observed in SMG in all cases studied, i.e., Bacillus brevis produced gramicidin S (GS), Streptomyces clavuligerus made beta-lactam antibiotics, Streptomyces hygroscopicus produced rapamycin, and Escherichia coli produced microcin B17 (MccB17). Of these processes, only GS production was unaffected by SMG; production of the other three products was inhibited. This was determined by comparison with performance in an RWB positioned in a different mode to provide a normal gravity (NG) environment. Carbon source repression by glycerol of the GS process, as observed in shaken flasks, was not observed in the RWBs, whether operated in the SMG or NG mode. The same phenomenon occurred in the case of MccB17 production, with respect to glucose repression. Thus, the negative effects of carbon source on GS and beta-lactam formation are presumably dependent on shear, turbulence, and/or vessel geometry, but not on gravity. Stimulatory effects of phosphate and the precursor L-lysine on beta-lactam antibiotic production, as observed in flasks, also occurred in SMG. An almost complete shift in the localization of produced MccB17 from cells to extracellular medium was observed when E. coli was grown in the RWB under SMG or NG. If a plastic bead was placed in the RWB, accumulation became cellular, as it is in shaken flasks, indicating that sheer stress favors a cellular location. In the case of rapamycin, the same type of shift was observed, but it was less dramatic, i.e., growth in the RWB under SMG shifted the distribution of produced rapamycin from 2/3 cellular:1/3 extracellular to 1/3 cellular:2/3 extracellular. Stress has been shown to induce or promote secondary metabolism in a number of other microbial systems. RWBs provide a low stress SMG environment, which, however, supports only poor production of MccB17, as compared to production in shaken flasks. We wondered whether the poor production in RWBs under SMG is due to the low level of stress, and whether increasing stress in the RWBs would raise the amount of MccB17 formed. We found that increasing shear stress by adding a single Teflon bead to the RWB improved MccB17 production. Although shear stress seems to have a marked positive effect on MccB17 production in SMG, addition of various concentrations of ethanol to RWBs (or to shaken flasks) failed to increase MccB17 production. Ethanol stress merely decreased production and, at higher concentrations, inhibited growth. Interestingly, cells growing in the RWB were much more resistant to the growth- and production-inhibitory effects of ethanol than cells growing in shaken flasks. With respect to S. hygroscopicus, addition of Teflon beads to the RWB reversed the inhibition of growth, but rapamycin production was still markedly inhibited, and the distribution did not revert back to a preferential cellular site.

NASA Discipline Cell Biology↗
DOE OSTI2023

Lithium metal negative electrode and method of manufacturing the same

A negative electrode for an electrochemical cell of a secondary lithium metal battery is manufactured by a method in which a precursor solution is applied to a major surface of a lithium metal substrate to form a precursor coating thereon. The precursor solution includes an organophosphate, a nonpolar organic solvent, and a lithium-containing inorganic ionic compound dissolved therein. At least a portion of the nonpolar organic solvent is removed from the precursor coating to form a protective interfacial layer on the major surface of the lithium metal substrate. The protective interfacial layer exhibits a composite structure including a carbon-based matrix component and a lithium-containing dispersed component. The lithium-containing dispersed component is embedded in the carbon-based matrix component and includes a plurality of lithium-containing inorganic ionic compounds, e.g., lithium phosphate (Li3PO4) and lithium nitrate (LiNO3).

Xiao, Xingcheng↗
DOE OSTI2025

Divergent Responses of Carbon Nitride Dot‐Based Amorphous Species and Small Molecule Hybrids to Trace Level Analytes

Bottom-up synthesis of carbon nitride dots (CNDs) offers a versatile platform for the creation of diverse nanomaterials with tunable properties. Here, we report a facile hydrothermal approach using citric acid (CA) and urea (U) as precursors to synthesize CNDs with varying degrees of condensation and crystallinity. By carefully controlling reaction conditions and post-synthetic treatments, we obtained two distinct fractions: a polycrystalline fraction composed of small-molecule hybrids and an amorphous fraction containing CNDs. We then sought to understand how the dominant species in these fractions impact sensing abilities using trace-level explosive exemplars. In conclusion, the results have important implications for sensing and related applications where understanding the complex interplay between synthetic conditions and post-synthetic processing play vital roles in determining the final properties of CND materials.

carbon nitride dots↗
NASA NTRS2012

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for ~-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

Elsila, Jamie E.↗
NASA NTRSDate not supplied

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permanent presence on the moon and in preparation for future Mars exploration, it is imperative that all resources are utilized to their fullest potential.[1] In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen(LO2) for not only breathable air, but also for rocket propellant. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith.[2],[3] Although there are numerous minerals within regolith and various processes to extract O2,this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2(or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide(CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28.

Mass Spectrometry↗
DOE OSTI2022

Coal-derived graphene foam and micron-sized silicon composite anodes for lithium-ion batteries

Silicon-based materials demonstrate significant potential as lithium-ion batteries (LIBs) anode, but their expansion and degradation present engineering design challenges for commercial application. In this study, a porous three-dimensional (3D) graphene and micron-sized silicon composite anode (Si@G foam) was synthesized using humic acid (HA) derived from coal as a graphene precursor. In-situ formation of graphene structure through reducing HA was confirmed by Raman spectra. The reduced HA (rHA) shows similar electrical conductivity compared to the commercial conductive carbon. SEM images depict a 3D skeleton of coal-derived graphene, with silicon particles distributed on the 3D graphene foam's internal surface. The Si@G composite-anode displays a good reversible capacity of ~656 mAh/g at a current density of 50 mA/g, as well as a high-rate capability of ~433 mAh/g at a current density of 800 mA/g, and outstanding cycling stability –89.8% capacity retention after 300 cycles, which is significantly higher than that of other foam structures. During lithiation and de-lithiation, the graphene foam serves as a matrix of electrical conductors and a volume expansion support for silicon. This 3D graphene network will be beneficial for developing advanced silicon-based anodes for high-performance LIBs.

25 ENERGY STORAGE↗
NASA NTRS1996

Nitrogen metabolism in Lignifying Pinus taeda cell cultures

The primary metabolic fate of phyenylalanine, following its deamination in plants, is conscription of its carbon skeleton for lignin, suberin, flavonoid, and related metabolite formation. Since this accounts for approximately 30-40% of all organic carbon, an effective means of recycling the liberated ammonium ion must be operative. In order to establish how this occurs, the uptake and metabolism of various 15N-labeled precursors (15N-Phe, 15NH4Cl, 15N-Gln, and 15N-Glu) in lignifying Pinus taeda cell cultures was investigated, using a combination of high performance liquid chromatography, 15N NMR, and gas chromatograph-mass spectrometry analyses. It was found that the ammonium ion released during active phenylpropanoid metabolism was not made available for general amino acid/protein synthesis. Rather it was rapidly recycled back to regenerate phenylalanine, thereby providing an effective means of maintaining active phenylpropanoid metabolism with no additional nitrogen requirement. These results strongly suggest that, in lignifying cells, ammonium ion reassimilation is tightly compartmentalized.

NASA Discipline Number 40-50↗
NASA NTRS2007

Future Climate Impacts of Direct Radiative Forcing Anthropogenic Aerosols, Tropospheric Ozone, and Long-lived Greenhouse Gases

Long-lived greenhouse gases (GHGs) are the most important driver of climate change over the next century. Aerosols and tropospheric ozone (O3) are expected to induce significant perturbations to the GHG-forced climate. To distinguish the equilibrium climate responses to changes in direct radiative forcing of anthropogenic aerosols, tropospheric ozone, and GHG between present day and year 2100, four 80-year equilibrium climates are simulated using a unified tropospheric chemistry-aerosol model within the Goddard Institute for Space Studies (GISS) general circulation model (GCM) 110. Concentrations of sulfate, nitrate, primary organic (POA) carbon, secondary organic (SOA) carbon, black carbon (BC) aerosols, and tropospheric ozone for present day and year 2100 are obtained a priori by coupled chemistry-aerosol GCM simulations, with emissions of aerosols, ozone, and precursors based on the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenario (SRES) A2. Changing anthropogenic aerosols, tropospheric ozone, and GHG from present day to year 2100 is predicted to perturb the global annual mean radiative forcing by +0.18 (considering aerosol direct effects only), +0.65, and +6.54 W m(sup -2) at the tropopause, and to induce an equilibrium global annual mean surface temperature change of +0.14, +0.32, and +5.31 K, respectively, with the largest temperature response occurring at northern high latitudes. Anthropogenic aerosols, through their direct effect, are predicted to alter the Hadley circulation owing to an increasing interhemispheric temperature gradient, leading to changes in tropical precipitation. When changes in both aerosols and tropospheric ozone are considered, the predicted patterns of change in global circulation and the hydrological cycle are similar to those induced by aerosols alone. GHG-induced climate changes, such as amplified warming over high latitudes, weakened Hadley circulation, and increasing precipitation over the Tropics and high latitudes, are consistent with predictions of a number of previous GCM studies. Finally, direct radiative forcing of anthropogenic aerosols is predicted to induce strong regional cooling over East and South Asia. Wintertime rainfall over southeastern China and the Indian subcontinent is predicted to decrease because of the increased atmospheric stability and decreased surface evaporation, while the geographic distribution of precipitation is also predicted to be altered as a result of aerosol-induced changes in wind flow.

Chen, Wei-Ting↗
NASA NTRS2005

Development of Carbon-Nanotube/Polymer Composites

A report presents a short discussion of one company's effort to develop composites of carbon nanotubes in epoxy and other polymer matrices. The focus of the discussion is on the desirability of chemically modifying carbon nanotubes to overcome their inherent chemical nonreactivity and thereby enable the formation of strong chemical bonds between nanotubes and epoxies (or other polymeric matrix materials or their monomeric precursors). The chemical modification is effected in a process in which discrete functional groups are covalently attached to the nanotube surfaces. The functionalization process was proposed by the company and demonstrated in practice for the first time during this development effort. The covalently attached functional groups are capable of reacting with the epoxy or other matrix resin to form covalent bonds. Furthermore, the company uses this process to chemically modify the nanotube surfaces, affording tunable adhesion to polymers and solubility in select solvents. Flat-sheet composites containing functionalized nanotubes demonstrate significantly improved mechanical, thermal, and electrical properties.

Reynolds, Thomas A.↗
DOE OSTI2021

Heterogeneous Growth of UiO-66-NH 2 on Oxidized Single-Walled Carbon Nanotubes to Form “Beads-on-a-String” Composites

In this work we demonstrate a facile synthesis of UiO-66-NH 2 metal-organic framework (MOF)/oxidized single-walled carbon nanotubes (ox-SWCNTs) composite at room temperature. Acetic acid (HAc) was used as a modulator to manipulate the morphology of the MOF in these composites. With zirconium oxide-cluster (Zr) to 2-aminoteraphthalate linker (ATA) 1:1.42 ratio and acetic acid modulator, we achieved predominately heterogeneous MOF growth on the sidewalls of CNTs. Understanding the growth mechanism of these composites was facilitated by conducting DFT calculations to investigate the interactions between ox-SWCNTs and the MOF precursors. The synthesized composites combine both micro-porosity of the MOF and electrical conductivity of the SWCNTs. Gas sensing tests demonstrated higher response for UiO-66-NH 2 /ox-SWCNT hybrid toward dry air saturated with dimethyl methylphosphonate (DMMP) vapor compared to oxidized single-walled carbon nanotubes (ox-SWCNTs) alone.

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

Unveiling the Influence of Carbon Impurity on Recovered NCM622 Cathode Material

With the proliferation of market demand for lithium-ion batteries (LIBs) over the past decades, battery recycling has aroused extensive attention due to the environmental, supply, and economic issues caused by waste batteries. Here, the hydrometallurgical recycling method has been widely adopted to recover cathode materials as a result of its wide applicability and high productivity. However, it is hard to completely eliminate impurities such as copper, aluminum, and carbon, which could bring significant impacts on recovered materials. Here, the influence of the carbon impurity on recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode material is systematically investigated. It shows that the carbon impurity promotes nucleation during coprecipitation and forms holes in the cathode secondary particles after sintering which could enhance cyclability of the NCM622 cathode. The cathode with 0.2 atom % of carbon impurity displays the highest capacity of 159.9 mAh/g with a striking capacity retention rate of 97.9% after 100 cycles at 0.33C, but performs worse at high rates. Nonetheless, excess carbon (5 atom %) results in severe cation disorder and lattice distortion which significantly deteriorates the electrochemical properties of the NCM622 cathode. Therefore, it is important to strictly control carbon impurity during the recycling process for spent LIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Metal nitride materials for solar-thermal ammonia production [Slides]

Solar Thermal Ammonia Production has the potential to synthesize ammonia in a green, renewable process that can greatly reduce the carbon footprint left by the conventional Haber-Bosch reaction. Co 3 Mo 3 N has been identified as a potential candidate for ammonia production. It is synthesized via oxide precursor synthesis followed by nitridation under 10% H 2 /N 2 . The synthesis method can be extended to other candidate nitrides. The Co 3 Mo 3 N → Co 6 Mo 6 N reduction is demonstrated on TGA with rapid kinetics. The formation of NH 3 is qualitatively observed, but not quantitatively determined. The material retains crystal structure, but no secondary phases are observed in XRD. Partial re-nitridation back to CMN331 of ~35% of max nitridation is observed. Reaction parameters in TGA differ from experimental conditions in the literature. Experiments at Georgia Tech better mimic re-nitridation conditions with more sensitive, quantitative analytical techniques (GC-MS). The ASU NH 3 synthesis/re-nitridation reactor is under development and will permit experiments (reduction/re-nitridation) under precisely controlled T, pH 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Process for coating an object with silicon carbide

A process for coating a carbon or graphite object with silicon carbide by contacting it with silicon liquid and vapor over various lengths of contact time. In the process, a stream of silicon-containing precursor material in gaseous phase below the decomposition temperature of said gas and a co-reactant, carrier or diluent gas such as hydrogen is passed through a hole within a high emissivity, thin, insulating septum into a reaction chamber above the melting point of silicon. The thin septum has one face below the decomposition temperature of the gas and an opposite face exposed to the reaction chamber. The precursor gas is decomposed directly to silicon in the reaction chamber. A stream of any decomposition gas and any unreacted precursor gas from said reaction chamber is removed. The object within the reaction chamber is then contacted with silicon, and recovered after it has been coated with silicon carbide.

Levin, Harry↗