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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Improved photosynthetic capacity and photosystem I oxidation via heterologous metabolism engineering in cyanobacteria

Significance Cyanobacteria have been increasingly explored as a biotechnological platform, although their economic feasibility relies in part on the capacity to maximize their photosynthetic, solar-to-biomass energy conversion efficiency. Here we show that cyanobacterial photosynthetic capacity can be increased by diverting cellular resources toward heterologous, energy-storing metabolic pathways and by reducing electron flow to photoprotective, but energy-dissipating, oxygen reduction reactions. We further show that these heterologous sinks can partially contribute to photosystem I (PSI) oxidation, suggesting an engineering strategy to improve both energy storage capacity and robustness by selective diversion of excess photosynthetic capacity to productive processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1988

Detailed mechanism of toluene oxidation and comparison with benzene

A detailed mechanism for the oxidation of toluene in both argon and nitrogen dilutents is presented. The mechanism was used to compute experimentally ignition delay times for shock-heated toluene-oxygen-argon mixtures with resonably good success over a wide range of initial temperatures and pressures. Attempts to compute experimentally measured concentration profiles for toluene oxidation in a turbulent reactor were partially successful. An extensive sensitivity analysis was performed to determine the reactions which control the ignition process and the rates of formation and destruction of various species. The most important step was found to be the reaction of toluene with molecular oxygen, followed by the reactions of hydroperoxyl and atomic oxygen with benzyl radicals. These findings contrast with the benzene oxidation, where the benzene-molecular oxygen reaction is quite unimportant and the reaction of phenyl with molecular oxygen dominates. In the toluene mechanism the corresponding reaction of benzyl radicals with oxygen is unimportant. Two reactions which are important in the oxidation of benzene also influence the oxidation of toluene for several conditions. These are the oxidations of phenyl and cyclopentadienyl radicals by molecular oxygen. The mechanism presented successfully computes the decrease of toluene concentration with time in the nitrogen diluted turbulent reactor. This fact, in addition to the good prediction of ignition delay times, shows that this mechanism can be used for modeling the ignition and combustion process in practical, well-mixed combustion systems.

Bittker, David A.↗
NASA NTRS1991

The SiH vibrational stretch as an indicator of the chemical state of interstellar grains

The infrared spectra of amorphous silicate grains and films formed in a variety of laboratory experiments have been measured. It is found that the frequency of the SiH fundamental stretch is extremely sensitive to the chemical environment of the grain in which the silicon is bound and varies from 2270/cm in oxidized grains to 2110/cm in a reducing environment. It is proposed that features previously observed in W33A could be due to -SiH groups in amorphous silica, partially reduced silica, silicon nitride or slightly oxidized silicon carbide. It is predicted that observations at 2270/cm will reveal a feature due to -SiH groups in highly oxidized interstelar and circumstellar grains. Such a feature might also appear in the spectra of comets.

Moore, Marla H.↗
DOE OSTI2019

Plutonium Particles in Samples Extracted from Hanford Tank Waste TX-118 and SY-102 (Interim Report)

This is an interim report on the characterization of plutonium particles from Hanford wastes. Plutonium-bearing particles were located in Hanford Waste Tank solids, SY-102 and TX-118. The particles in SY-102 were small, typically < 5 to 10 µm in length, and were crystalline plutonium oxide with an association of other elements at minor levels, including bismuth, phosphate, and iron based on Sanning Electron Microscopy (SEM) observations. Plutonium particles from SY-102 were extracted from the surface mount using the SEM-Focused Ion Beam (FIB) and prepared for Scanning Transmission Electron Microscopy (STEM). This was the first time that this type of analysis of Hanford tank waste solids has been attempted. The STEM analysis indicated a complex co-precipitation of plutonium oxide with bismuth and phosphate. Diffraction and imaging only partially matched with a PuO 2 phase. Pockets of phosphate and bismuth reside within the plutonium oxide suggesting that these phases formed at the same time. The SEM analysis indicated that the plutonium particles from TX-118 were a mixed bismuth-phosphate phase and plutonium oxide. These particles will be examined with SEM-FIB at a later time and then will undergo more detailed examination in the STEM.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Vanadium oxide for infrared coatings and methods thereof

The present invention relates to vanadium oxide and methods of controlling reaction processes for making such materials (e.g., powders). In particular embodiments, the method includes control of oxygen partial pressure in order to kinetically control the oxidation species of the crystalline vanadium oxide material. Other methods, uses, systems, protocols, and coatings are also described.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Coulombically-stabilized oxygen hole polarons enable fully reversible oxygen redox

Stabilizing high-valent redox couples and exotic electronic states necessitates an understanding of the stabilization mechanism. In oxides, whether they are being considered for energy storage or computing, highly oxidized oxide-anion species rehybridize to form short covalent bonds and are related to significant local structural distortions. In intercalation oxide electrodes for batteries, while such reorganization partially stabilizes oxygen redox, it also gives rise to substantial hysteresis. In this work, we investigate oxygen redox in layered Na 2-x Mn 3 O 7 , a positive electrode material with ordered Mn vacancies. We prove that coulombic interactions between oxidized oxide-anions and the interlayer Na vacancies can disfavor rehybridization and stabilize hole polarons on oxygen (O-) at 4.2 V vs. Na/Na + . These coulombic interactions provide thermodynamic energy saving as large as O–O covalent bonding and enable ~40 mV voltage hysteresis over multiple electrochemical cycles with negligible voltage fade. As such, our results establish a complete picture of redox energetics by highlighting the role of coulombic interactions across several atomic distances and suggest avenues to stabilize highly oxidized oxygen for applications in energy storage and beyond.

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

Influence of Cation Size on the Local Atomic Structure and Electronic Properties of Ta Perovskite Oxynitrides

Partial anion substitution in transition metal oxides provides rich opportunities to control and tune physical and chemical properties, for example, combining the merits of oxides and nitrides. In addition, the possibility of resulting anion sublattice order provides a means to target polar and chiral structures based on a wide array of accessible structural archetypes by design. Here, in this work, we investigate the local structures of a family of perovskite tantalum oxynitrides—ATaO 2 N (A = Ba, Sr, and Ca)—using a combination of experimental and theoretical approaches including neutron total scattering, density functional theory (DFT), and ab initio molecular dynamics (AIMD) simulations. We present the first experimental study of chemical short-range order (CSRO) in CaTaO 2 N, confirming local cis N ordering of the anion sub-lattice. Our systematic exploration of a local structure across the A cation size series (from the larger Ba to the smaller Ca) reveals a perovskite motif increasingly distorted with respect to long-range average structures. DFT and AIMD simulations support the observed trends. Overall, structures with cis ordering of the nitrogen anions in each TaO 4 N 2 octahedron are favored over those with trans ordering. With diminishing A cation size, local cis ordering and Ta off-centering play decreasing roles in overall lattice stability, overshadowed by the stabilizing effects of octahedral tilting. The influence of these factors on local dipole formation and frustrated dipole ordering are discussed.

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

Direct Observation of Morphological and Chemical Changes during the Oxidation of Model Inorganic Ligand-Capped Particles

Functionalization and volatilization are competing reactions during the oxidation of carbonaceous materials and are important processes in many different areas of science and technology. Here, we present a combined ambient pressure X-ray photoelectron spectroscopy (APXPS) and grazing incidence X-ray scattering (GIXS) investigation of the oxidation of oleic acid ligands surrounding NaYF 4 nanoparticles (NPs) deposited onto SiO x /Si substrates. While APXPS monitors the evolution of the oxidation products, GIXS provides insight into the morphology of the ligands and particles before and after the oxidation. Our investigation shows that the oxidation of the oleic acid ligands proceeds at O 2 partial pressures of below 1 mbar in the presence of X-rays, with the oxidation eventually reaching a steady state in which mainly CH x and –COOH functional groups are observed. The scattering data reveal that the oxidation and volatilization reaction proceeds preferentially on the side of the particle facing the gas phase, leading to the formation of a chemically and morphologically asymmetric ligand layer. This comprehensive picture of the oxidation process could be obtained only by combining the X-ray scattering and APXPS data. The investigation presented here lays the foundation for further studies of the stability of NP layers in the presence of reactive trace gases and ionizing radiation and for other nanoscale systems where chemical and morphological changes happen simultaneously and cannot be understood in isolation.

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

Direct evidence of low work function on SrVO 3 cathode using thermionic electron emission microscopy and high-field ultraviolet photoemission spectroscopy

Perovskite SrVO 3 has recently been proposed as a novel electron emission cathode material. Density functional theory (DFT) calculations suggest multiple low work function surfaces, and recent experimental efforts have consistently demonstrated effective work functions of ~2.7 eV for polycrystalline samples, both results suggesting, but not directly confirming, that some fraction of even lower work function surface is present. In this work, thermionic electron emission microscopy (ThEEM) and high-field ultraviolet photoemission spectroscopy (UPS) are used to study the local work function distribution and measure the work function of a partially oriented- (110)-SrVO 3 perovskite oxide cathode surface. Our results show direct evidence of low work function patches of about 2.0 eV on the cathode surface, with a corresponding onset of observable thermionic emission at 750 °C. We hypothesize that, in our ThEEM and UPS experiments, the high applied electric field suppresses the patch field effect, enabling the direct measurement of local work functions. This measured work function of 2.0 eV is comparable to the previous DFT-calculated work function values of the SrVO-terminated (110) SrVO 3 surface (2.3 eV) and SrO-terminated (100) surface (1.9 eV). The measured 2.0 eV value is also much lower than the work function for the (001) LaB 6 single crystal cathode (~2.7 eV) and comparable to the effective work function of B-type dispenser cathodes (~2.1 eV). If SrVO 3 thermionic emitters can be engineered to access domains of this low 2.0 eV work function, they have the potential to significantly improve thermionic emitter-based technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Resource availability governs polyhydroxyalkanoate (PHA) accumulation and diversity of methanotrophic enrichments from wetlands

Aquatic environments account for half of global CH 4 emissions, with freshwater wetlands being the most significant contributors. These CH 4 fluxes can be partially offset by aerobic CH 4 oxidation driven by methanotrophs. Additionally, some methanotrophs can convert CH 4 into polyhydroxyalkanoate (PHA), an energy storage molecule as well as a promising bioplastic polymer. In this study, we investigate how PHA-accumulating methanotrophic communities enriched from wetlands were shaped by varying resource availability (i.e., C and N concentrations) at a fixed C/N ratio. Cell yields, PHA accumulation, and community composition were evaluated in high (20% CH 4 and 10 mM NH 4 + ) and low resource (0.2% CH 4 and 0.1 mM NH 4 + ) conditions simulating engineered and environmental settings, respectively. High resource availability decreased C-based cell yields, while N-based cell yields remained stable, suggesting nutrient exchange patterns differed between methanotrophic communities at different resource concentrations. PHA accumulation was only observed in high resource enrichments, producing approximately 12.6% ± 2.4% (m/m) PHA, while PHA in low resource enrichments remained below detection. High resource enrichments were dominated by Methylocystis methanotrophs, while low resource enrichments remained significantly more diverse and contained only a minor population of methanotrophs. This study demonstrates that resource concentration shapes PHA-accumulating methanotrophic communities. Together, this provides useful information to leverage such communities in engineering settings as well as to begin understanding their role in the environment.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1979

Furnace brazing under partial vacuum

Brazing furnace utilizing partial-vacuum technique reduces tooling requirements and produces better bond. Benefit in that partial vacuum helps to dissociate metal oxides that inhibit metal flow and eliminates heavy tooling required to hold parts together during brazing.

Mckown, R. D.↗
NASA NTRS1991

Two-dimensional imaging of molecular hydrogen in H2-air diffusion flames using two-photon laser-induced fluorescence

The use of a tunable ArF laser at 193.26 nm to record simultaneous single-laser-shot, planar images of molecular hydrogen and hot oxygen in a turbulent H2-air diffusion flame. Excitation spectra of fuel and oxidant-rich flame zones confirm a partial overlap of the two-photon H2 and single-photon O2 Schumann-Runge absorption bands. UV Rayleigh scattering images of flame structure and estimated detection limits for the H2 two-photon imaging are also presented.

Lempert, W.↗
NASA NTRS1992

Glass-Derived Superconductive Ceramic

Critical superconducting-transition temperature of 107.2 K observed in specimen made by annealing glass of composition Bi1.5Pb0.5Sr2Ca2Cu3Ox for 243 h at 840 degrees C. PbO found to lower melting temperature and viscosity of glass, possibly by acting as fluxing agent. Suggested partial substitution of lead into bismuth oxide planes of crystalline phase having Tc of 110 K stabilizes this phase and facilitates formation of it.

Bansal, Narottam P.↗
NASA NTRS1991

Lunar oxygen production by pyrolysis of regolith

Oxygen represents one of the most desirable products of lunar mining and manufacturing. Among the many processes which have been proposed for oxygen production, pyrolysis stands out as one which is uncomplicated and easy to bootstrap. Pyrolysis or vapor-phase reduction involves heating regolith to temperatures sufficient to allow partial decomposition and vaporization. Some metal oxides give up oxygen upon heating, either in the gas phase to form reduced gaseous species or in the condensed phase to form a metallic phase. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2200 K, giving total gas pressures of 0.001 to 0.1 torr. Bulk regolith can be used as a feedstock without beneficiation with concentrated solar radiation supplying most of energy needed. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts.

Senior, Constance L.↗
NASA NTRS1995

Changes in chemical and optical properties of thin film metal mirrors on LDEF

Thin films of the metals Cu, Ni, Pt, Au, Sn, Mo, and W deposited on fused silica flats were exposed at ambient temperature on the leading and trailing faces of the LDEF. Reflectances of these films were measured from 250 to 2500 nm and compared with controls. The exposed films were subjected to the LDEF external environment including atomic oxygen, molecular contamination, and solar ultraviolet. Major changes in optical and infrared reflectance were seen for Cu, Mo, Ni, and W films on the leading face of LDEF and are attributed to partial conversion of metal to metal oxide. Smaller changes in optical properties are seen on all films and are probably caused by thin contaminant films deposited on top of the metal. The optical measurements are correlated with film thickness measurements, x-ray photoelectron spectroscopy, optical calculations, and, in the case of Cu, with x-ray diffraction measurements. In a few cases, comparisons with results from a similar UAH experiment on STS-8 have been drawn.

Peters, Palmer N.↗
NASA NTRS1999

Kinetics and Structure of Superagglomerates Produced by Silane and Acetylene

The evolution of smoke in a laminar diffusion flame involves several steps. The first step is particle inception/nucleation in the high-temperature fuel-rich region of the flame followed by surface growth and coagulation/coalescence of the small particles. As the primary spheres grow in size and lose hydrogen, the colliding particles no longer coalesce but retain their identity as a cluster of primary spheres, termed an agglomerate. Finally, in the upper portion of the flame, the particles enter an oxidizing environment which may lead to partial or complete burnout of the agglomerates. Currently there is no quantitative model for describing the growth of smoke agglomerates up to superagglomerates with an overall dimension of 10 microns and greater. Such particles are produced during the burning of acetylene and fuels containing benzene rings such as toluene and polystyrene. In the case of polystyrene, smoke agglomerates in excess of 1 mm have been observed "raining" out from large fires. Evidence of the formation of superagglomerates in a laminar acetylene/air diffusion flame has been recently reported. Acetylene was chosen as the fuel since the particulate loading in acetylene/air diffusion flames is very high. Photographs were obtained by Sorensen using a microsecond xenon lamp of the "stream" of soot just above the flame. For low flow rates of acetylene, only submicrometer soot clusters are produced and they give rise to the homogeneous appearance of the soot stream. When the flow rate is increased to 1.7 cu cm/s, soot clusters up to 10 microns are formed and they are responsible for the graininess and at a flow rate of 3.4 cu cm/s, a web of interconnected clusters as large as the width of the flame is seen. This interconnecting web of superagglomerates is described as a gel state by Sorensen et al (1998). This is the first observation of a gel for a gas phase system. It was observed that this gel state immediately breaks up into agglomerates due to buoyancy induced turbulence and gravitational sedimentation.

Mulholland, G. W.↗