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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Design and Characterization of Hybrid Multilayer Structures: Layer-by-Layer Growth of Polymer and Graphene Oxide Assemblies and Their Utility in Fuel Cell Applications

We report the layer-by-layer growth of poly- (ethylenimine) (PEI) that has been modified with sulfamate functionalities (S-PEI) using Zr 4+ -complexation interlayer linking chemistry. We have also deposited adlayers of graphene oxide (GO) that have been modified to possess sulfate functionalities (SGO), onto the S-PEI layers. The multilayer assemblies are formed with sulfamate/sulfate and sulfate/sulfate (S-PEI + S-GO) interlayer linking chemistry. In all cases the adlayer thickness is consistent with predictions based on van der Waals volume and/or molecular mechanics calculations. X-ray photoelectron spectroscopy (XPS) is used to characterize the Zr/S stoichiometry in the multilayer assembly. The utility of these hybrid multilayer structures is demonstrated in a Proton Exchange Membrane (PEM) fuel cell, where they are shown to reduce H 2 gas crossover by 15% with only a 12 nm thick layer.

fuel cell↗
DOE OSTI2025

Reversible CO 2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex

Abstract The authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir 3 H 6 ( μ 3 ‐H)(PN) 3 ] 2+ ( 2‐H , PN = (2‐pyridyl)CH 2 PBu t 2 ). Despite its unusual stability to unsaturated organics, electrophiles, and even CF 3 SO 3 D, they find that complex 2‐H catalyzes hydrogenation of CO 2 to formate (TON Ir = 9600) and reverse formic acid dehydrogenation (TON Ir = 54 400). The hydrogenation operates via a reactive intermediate [Ir 3 H 4 ( μ ‐H) 4 (PN) 3 ] + ( 5 ). Neutron crystallography and DFT‐supported neutron vibrational spectroscopy of 2‐H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir 3 H 7 core. Stoichiometric oxidation of 2‐H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra‐ and pentanuclear clusters [Ir 3 H 6 ( μ 3 ‐AuPPh 3 )(PN) 3 ] 2+ ( 2‐Au ) and [Ag{Ir 2 H 4 ( μ ‐OAc)(PN) 2 } 2 ] 3+ ( 6 ) are generated using AuPPh 3 + and AgOAc, respectively. Further oxidation to class [Ir 2 H 3 ( μ ‐X) 2 (PN) 2 ] + is possible with AgOAc, Hg(OAc) 2 , or I 2 . Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir 2 Cl 4 ( μ ‐Cl) 2 (PN) 2 ] ( 11 ).

Cherepakhin, Valeriy [Loker Hydrocarbon Research I↗
DOE OSTI2025

Reversible CO 2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex

Here, the authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir 3 H 6 (μ 3 -H)(PN) 3 ] 2+ (2-H, PN = (2-pyridyl)CH 2 PBu t 2 ). Despite its unusual stability to unsaturated organics, electrophiles, and even CF 3 SO 3 D, they find that complex 2-H catalyzes hydrogenation of CO 2 to formate (TON Ir = 9600) and reverse formic acid dehydrogenation (TON Ir = 54 400). The hydrogenation operates via a reactive intermediate [Ir 3 H 4 (μ-H) 4 (PN) 3 ] + (5). Neutron crystallography and DFT-supported neutron vibrational spectroscopy of 2-H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir 3 H 7 core. Stoichiometric oxidation of 2-H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra- and pentanuclear clusters [Ir 3 H 6 (μ 3 -AuPPh 3 )(PN) 3 ] 2+ (2-Au) and [Ag{Ir 2 H 4 (μ-OAc)(PN) 2 } 2 ] 3+ (6) are generated using AuPPh 3 + and AgOAc, respectively. Further oxidation to class [Ir 2 H 3 (μ-X) 2 (PN) 2 ] + is possible with AgOAc, Hg(OAc) 2 , or I 2 . Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir 2 Cl 4 (μ-Cl) 2 (PN) 2 ] (11).

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

Oxidation of biogenic U(IV) mediated by iron-bearing clay minerals, iron-reducing bacteria, and organic ligands

Bioreduction of hexavalent uranium (U(VI)) to tetravalent uranium (U(IV)) by dissimilatory metal-reducing bacteria (DMRB) is considered an effective strategy for uranium immobilization in contaminated environments. However, U(IV) can be reoxidized to U(VI) under fluctuating redox conditions and remobilized. This work investigates the oxidation behavior of biogenic U(IV) in the presence of bioreduced iron-bearing clay minerals (rNAu-2), iron-reducing bacteria (Shewanella putrefaciens CN32), and organic ligands (ethylenediaminetetraacetic acid (EDTA) and citrate). Results demonstrate that the presence of CN32 significantly inhibits U(IV) oxidation. rNAu-2 exerted a context-dependent influence on U(IV) oxidation: its effect was masked by bicarbonate-promoted U(VI) mobilization in the absence of active CN32, but became detectable when CN32-mediated microbial protection slowed U(IV) oxidation. EDTA and citrate markedly accelerate U(IV) oxidation via formation of soluble U(IV)-ligand complexes, changing U(IV) redox potentials, and by promoting clay mineral dissolution that enhances Fe(II)/Fe(III) redox cycling. Collectively, our findings constrain the roles that clay minerals, iron-reducing bacteria, and organic ligands play in governing U(IV) stability, emphasizing the need to account for these factors in developing robust bioremediation strategies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1971

Mechanism of the oxidation of titanium disilicide.

Study of the oxidation of TiSi2 at temperatures of 300 to 1300 C. Wafers prepared using the techniques of powder metallurgy had densities of 95 to 98% of the theoretical value. On oxidation at temperatures up to 600 C, the polished wafers formed a protective, titania-silica glass. The rate data indicate a complex surface and diffusion-limited mechanism. Above 600 deg C, the oxide consisted of an amorphous SiO2 film with crystalline islands of TiO2 (rutile). From 1000 to 1300 C, parabolic kinetics with an activation energy of 21.3 kcal/mole were observed. These data are consistent with a model in which the rate-determining step is the diffusion of oxygen through the silica film with the simultaneous diffusion of titanium from the substrate to the islands of rutile growing on top of the amorphous silica.

Schwettmann, F. N.↗
NASA NTRS1984

Literature survey on oxidations and fatigue lives at elevated temperatures

Nickel-base superalloys are the most complex and the most widely used for high temperature applications such as aircraft engine components. The desirable properties of nickel-base superalloys at high temperatures are tensile strength, thermomechanical fatigue resistance, low thermal expansion, as well as oxidation resistance. At elevated temperature, fatigue cracks are often initiated by grain boundary oxidation, and fatigue cracks often propagate along grain boundaries, where the oxidation rate is higher. Oxidation takes place at the interface between metal and gas. Properties of the metal substrate, the gaseous environment, as well as the oxides formed all interact to make the oxidation behavior of nickel-base superalloys extremely complicated. The important topics include general oxidation, selective oxidation, internal oxidation, grain boundary oxidation, multilayer oxide structure, accelerated oxidation under stress, stress-generation during oxidation, composition and substrate microstructural changes due to prolonged oxidation, fatigue crack initiation at oxidized grain boundaries and the oxidation accelerated fatigue crack propagation along grain boundaries.

Liu, H. W.↗
NASA NTRS1978

Pyrolysis and oxidation of aromatic compounds

A study of the questions associated with the use of alternate fuels demands knowledge of the chemical mechanism of pyrolysis and oxidation of aromatic compounds. Both pyrolysis and oxidation are important, because fuel-rich conditions may mean that pyrolysis is competitive with oxidation. Soot formation is certainly a pyrolysis problem. The complexity of system characteristics makes a detailed study of thermodynamical and kinetic conditions difficult. The matter can be simplified somewhat by generalizing the chemistry by classes of molecules. The criteria for such a generalization of the chemistry are discussed along with an evaluation of the rate constants and their temperature and pressure dependences. Attention is given to the pyrolysis of hydrocarbons, the oxidation of hydrocarbons, the oxidation reactions of alkanes, aspects of codification and extrapolation, group additivity, structural consideration, kinetics, and the pyrolysis of aromatic compounds.

Golden, D. M.↗
NASA NTRS1971

Oxidation/vaporization of silicide coated columbium base alloys

Mass spectrometric and target collection experiments were made at 1600 K to elucidate the mode of oxidative vaporization of two columbium alloys, fused-slurry-coated with a complex silicide former (Si-20Cr-Fe). At oxygen pressures up to 0.0005 torr the major vapor component detected by mass spectrometry for oxidized samples was gaseous silicon monoxide. Analysis of condensates collected at oxygen pressures of 0.1, 1.0 and 10 torr revealed that chromium-, silicon-, iron- and tungsten- containing species were the major products of vaporization. Equilibrium thermochemical diagrams were constructed for the metal-oxygen system corresponding to each constituent metal in both the coating and base alloy. The major vaporizing species are expected to be the gaseous oxides of chromium, silicon, iron and tungsten. Plots of vapor phase composition and maximum vaporization rate versus oxygen pressure were calculated for each coating constituent. The major contribution to weight loss by vaporization at oxygen pressures above 1 torr was shown to be the chromium-containing species.

Kohl, F. J.↗
DOE OSTI2024

Contrasting Effects of Catecholate and Hydroxamate Siderophores on Molybdenite Dissolution

Molybdenum (Mo) is essential for many enzymes but is often sequestered within minerals, rendering it not readily bioavailable. Metallophores, metabolites secreted by microorganisms and plants, promote mineral dissolution to increase metal bioavailability. However, interactions between metallophores and Mo-bearing minerals remain unclear. Here, in this study, catecholate protochelin and hydroxamate desferrioxamine B (DFOB) were utilized to examine their effects on dissolution of the common Mo-bearing mineral, molybdenite (MoS 2 ), under both oxic and anoxic conditions. Protochelin promoted molybdenite dissolution under oxic conditions with the formation of MoO 3 on the surface and Mo-siderophore complexes in solution. This was attributed to air-oxidation of both molybdenite and protochelin, as evidenced by lack of dissolution under anoxic conditions but enhanced dissolution by either pre-oxidized protochelin or pre-oxidized molybdenite. Liquid chromatography-mass spectroscopy (LC-MS), X-ray photoelectron spectroscopy (XPS), and Time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses revealed degradation of protochelin and adsorptions of its byproducts on molybdenite surface to promote dissolution. Conversely, DFOB inhibited molybdenite dissolution under both oxic and anoxic conditions, likely attributed to surface adsorption of DFOB and its weak complexation with Mo(VI) at the circumneutral pH. This work highlights the need to consider the balance between promoting and inhibitory effects of different metallophores on Mo-mineral dissolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cation-π Bonding in Actinides: UO x + (Benzene) ( x = 0, 1, 2) Complexes Studied with Threshold Photodissociation Spectroscopy and Theory

Cation-π complexes of the form UO x + (benzene) (x = 0, 1, 2) are produced by laser vaporization and cooled in a supersonic molecular beam. These ions are mass selected and studied with UV–visible laser photodissociation spectroscopy. Each of these complexes photodissociates by elimination of the benzene ligand. Above an energetic threshold, the absorption and photodissociation are continuous, indicating a high density of strongly coupled electronic states. The thresholds for the dissociation of each of these three complexes are measured and assigned as their respective bond dissociation energies. The bond energies determined [U + –(benzene): 42.5 ± 0.3 kcal/mol; UO + –(benzene): 41.0 ± 0.3 kcal/mol; UO 2 + –(benzene): 39.7 ± 0.3 kcal/mol] are comparable to those of transition metal ion-benzene complexes. Computational studies at the DFT/B3LYP level complement the experiments, predicting dissociation energies in reasonably good agreement with the experiments. Experiments and theory agree that the U+(benzene) complex is more strongly bound than its corresponding oxide ions. This new thermochemistry on actinide cation-π bonding should stimulate higher-level computational studies on these systems.

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

Revealing the atomic and electronic mechanism of human manganese superoxide dismutase product inhibition

Human manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting superoxide (O 2 •– ) to molecular oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) with proton-coupled electron transfers (PCETs). Human MnSOD has evolved to be highly product inhibited to limit the formation of H 2 O 2 , a freely diffusible oxidant and signaling molecule. The product-inhibited complex is thought to be composed of a peroxide (O 2 2– ) or hydroperoxide (HO 2 – ) species bound to Mn ion and formed from an unknown PCET mechanism. PCET mechanisms of proteins are typically not known due to difficulties in detecting the protonation states of specific residues that coincide with the electronic state of the redox center. To shed light on the mechanism, we combine neutron diffraction and X-ray absorption spectroscopy of the product-bound, trivalent, and divalent states of the enzyme to reveal the positions of all the atoms, including hydrogen, and the electronic configuration of the metal ion. The data identifies the product-inhibited complex, and a PCET mechanism of inhibition is constructed.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Iron transformation mediates phosphate retention across a permafrost thaw gradient

Phosphorus limits primary productivity in many (Sub-)Arctic ecosystems and may constrain biological carbon sequestration. Iron (III) oxides strongly bind phosphate in soils but can dissolve under flooded, reducing conditions induced by permafrost thaw and ground collapse. The ability for iron to regulate phosphate storage and solubility in thawing permafrost landscapes remains unclear. Here, iron-rich sediments containing iron oxides and organic-bound iron were incubated with or without added phosphate in soils along a permafrost thaw gradient to evaluate how iron-phosphate associations respond to thaw-induced redox shifts. Iron oxides partially dissolved and released sorbed phosphate when incubated in soils underlain by degraded permafrost. Iron complexed by organic matter remained stable but provided no phosphate binding capacity. Phosphate addition enhanced iron oxide dissolution and phosphorus concentrations in associated microbial biomass. Our study demonstrates that the capacity for iron oxides to immobilize and retain phosphate in permafrost peatlands decreases with permafrost thaw.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1975

Preliminary study of oxide-dispersion-strengthened B-1900 prepared by mechanical alloys

An experimental oxide dispersion strengthened (ODS) alloy based on the B-1900 composition was produced by the mechanical alloying process. Without optimization of the processing for the alloy or the alloy for the processing, recrystallization of the extruded product to large elongated grains was achieved. Materials having grain length-width ratios of 3 and 5.5 were tested in tension and stress-rupture. The ODS B-1900 exhibited tensile strength similar to that of cast B-1900. Its stress-rupture life was lower than that of cast B-1900 at 760 C. At 1095 C the ODS B-1900 with the higher grain length-width ratio (5.5) had stress-rupture life superior to that of cast B-1900. It was concluded that, with optimization, oxide dispersion strengthening of B-1900 and other complex cast nickel-base alloys has potential for improving high temperature properties over those of the cast alloy counterparts.

Glasgow, T. K.↗
NASA NTRS1999

Experimental and Numerical Study of Ammonium Perchlorate Counterflow Diffusion Flames

Many solid rocket propellants are based on a composite mixture of ammonium perchlorate (AP) oxidizer and polymeric binder fuels. In these propellants, complex three-dimensional diffusion flame structures between the AP and binder decomposition products, dependent upon the length scales of the heterogeneous mixture, drive the combustion via heat transfer back to the surface. Changing the AP crystal size changes the burn rate of such propellants. Large AP crystals are governed by the cooler AP self-deflagration flame and burn slowly, while small AP crystals are governed more by the hot diffusion flame with the binder and burn faster. This allows control of composite propellant ballistic properties via particle size variation. Previous measurements on these diffusion flames in the planar two-dimensional sandwich configuration yielded insight into controlling flame structure, but there are several drawbacks that make comparison with modeling difficult. First, the flames are two-dimensional and this makes modeling much more complex computationally than with one-dimensional problems, such as RDX self- and laser-supported deflagration. In addition, little is known about the nature, concentration, and evolution rates of the gaseous chemical species produced by the various binders as they decompose. This makes comparison with models quite difficult. Alternatively, counterflow flames provide an excellent geometric configuration within which AP/binder diffusion flames can be studied both experimentally and computationally.

Smooke, M. D.↗
NASA NTRS2012

Astrobiological Journeys to and from the South Polar Sea of Enceladus - Bidirectional Interactions with the Saturn Magnetosphere

The spectacularly cryovolcanic moon Enceladus is a major source of plasma for the Saturn magnetosphere via ionization of the ejected molecular species and ice grains. Field-aligned plasma flows from the Enceladus environment visibly impact the moon's magnetic footpoint in Saturn's polar auroral region, while water group and other ions from the moon emissions diffuse radially throughout the magnetosphere and may be the dominant source of oxygen for Titan's oxygen-poor upper atmosphere. But the moon-magnetosphere interaction is bidirectional in the sense that the moon surface is globally exposed to constant irradiation by the returning magnetospheric ions and by energetic electrons from the field-aligned and radially diffusing populations. The returning ion source operates both on global scales of the magnetosphere and locally for highly reactive species produced in the ejecta plume. All of these sources likely combine to produce a highly oxidized global surface layer. Since plasma electrons and ions are cooled by interaction with neutral gas and E-ring ice grains from Enceladus, the moon emissions have a governing effect on the seed populations of energetic particles that irradiate the surface. The proposed subsurface polar sea and transient crustal overturn in the south polar region could bring the polar surface oxidants into contact with hydrocarbons and ammonia to make oxidation product gases contributing to the cryovolcanic jets, a process first proposed by Cooper et al. (Plan. Sp. Sci., 2009). As has been previously suggested for Europa, the 'oxidants could contribute to enhanced astrobiological potential of Enceladus, perhaps even higher than for Europa where organic hydrocarbons have not yet been directly detected. Unlike Europa, Enceladus shows no sign of an oxygen-dominated exosphere that could otherwise be indicative of extreme surface and interior oxidation inhibiting the detectable survival and evolution of complex organics.

Cooper, John F.↗
NASA NTRS2016

Development Status and Performance Comparisons of Environmental Barrier Coating Systems for SiCSiC Ceramic Matrix Composites

Environmental barrier coatings (EBC) and SiCSiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft turbine engine systems, because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. This paper presents current NASA EBC-CMC development emphases including: the coating composition and processing improvements, laser high heat flux-thermal gradient thermo-mechanical fatigue - environmental testing methodology development, and property evaluations for next generation EBC-CMC systems. EBCs processed with various deposition techniques including Plasma Spray, Electron Beam - Physical Vapor Deposition, and Plasma Spray Physical Vapor Deposition (PS-PVD) will be particularly discussed. The testing results and demonstrations of advanced EBCs-CMCs in complex simulated engine thermal gradient cyclic fatigue, oxidizing-steam and CMAS environments will help provide insights into the coating development strategies to meet long-term engine component durability goals.

Processing and Properties↗
NASA NTRS2016

Why Do Models Overestimate Surface Ozone in the Southeast United States?

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NO(x) triple bond NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC(exp 4)RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25 deg x 0.3125 deg horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NO(x) from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC(exp 4)RS observations of NO(x) and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NO(x) emissions from mobile and industrial sources must be reduced by 30-60%, dependent on the assumption of the contribution by soil NO(x) emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NO(x) emissions. We find that only half of isoprene oxidation proceeds by the high-NO(x) pathway to produce ozone; this fraction is only moderately sensitive to changes in NO(x) emissions because isoprene and NO(x) emissions are spatially segregated. GEOS-Chem with reduced NO(x) emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NO(x) oxidation products. However, the model is still biased high by 6 plus or minus 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

Oxidation↗
NASA NTRS2023

Soluble Organic Matter Molecular Atlas of Ryugu Reveals Cold Hydrothermalism on C-Type Asteroid Parent Body

The sample from the near-Earth carbonaceous asteroid (162173) Ryugu is analyzed in the context of carbonaceous meteorites soluble organic matter. The analysis of soluble molecules of samples collected by the Hayabusa2 spacecraft shines light on an extremely high molecular diversity on the C-type asteroid. Sequential solvent extracts of increasing polarity of Ryugu samples are analyzed using mass spectrometry with complementary ionization methods and structural information confirmed by nuclear magnetic resonance spectroscopy. Here we show a continuum in the molecular size and polarity, and no organomagnesium molecules are detected, reflecting a low temperature and water-rich environment on the parent body approving earlier mineralogical and chemical data. High abundance of sulfidic and nitrogen rich compounds as well as high abundance of ammonium ions confirm the water processing. Polycyclic aromatic hydrocarbons are also detected in a structural continuum of carbon saturations and oxidations, implying multiple origins of the observed organic complexity, thus involving generic processes such as earlier carbonization and serpentinization with successive low temperature aqueous alteration.

Asteroids, comets and Kuiper belt↗