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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Electrochemical Characterization of Dissolved Oxides in Molten FLiNaK

Molten fluoride salts have long been the subject of investigation given their application in a variety of industrial processes. Oxides are a common exogeneous impurity within these systems, and can lead to many operational and regulatory concerns. In recent studies, the electro-oxidation of dissolved metallic oxides has been attributed to a single step oxygen evolution reaction despite voltametric evidence suggesting otherwise. Here, we first use square wave voltammetry to confirm that the oxidation of dissolved oxides in fluorides proceeds via a two-electron transfer reaction and then demonstrate that the presence of a peroxide-mediated redox reaction better explains the electrochemical data. Numerical simulations were then used to support the determination of improved diffusion coefficients to enable electroanalytical measurements of the oxide concentration across at a variety of temperatures. A linear Arrhenius relationship was observed when the experimental data was corrected for ohmic resistance effects. Concentration measurements using the corrected square wave voltammetry data demonstrated high accuracy across a large range of concentrations, while the uncorrected data showed plateauing and high errors. In total, this work serves to rectify previously misconstrued electrochemical data of oxides in molten salts and demonstrate how accurate, in situ concentration measurements can be achieved in real-world systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1999

Oxidation of the skeletal muscle Ca2+ release channel alters calmodulin binding

This study presents evidence for a close relationship between the oxidation state of the skeletal muscle Ca2+ release channel (RyR1) and its ability to bind calmodulin (CaM). CaM enhances the activity of RyR1 in low Ca2+ and inhibits its activity in high Ca2+. Oxidation, which activates the channel, blocks the binding of 125I-labeled CaM at both micromolar and nanomolar Ca2+ concentrations. Conversely, bound CaM slows oxidation-induced cross-linking between subunits of the RyR1 tetramer. Alkylation of hyperreactive sulfhydryls (<3% of the total sulfhydryls) on RyR1 with N-ethylmaleimide completely blocks oxidant-induced intersubunit cross-linking and inhibits Ca2+-free 125I-CaM but not Ca2+/125I-CaM binding. These studies suggest that 1) the sites on RyR1 for binding apocalmodulin have features distinct from those of the Ca2+/CaM site, 2) oxidation may alter the activity of RyR1 in part by altering its interaction with CaM, and 3) CaM may protect RyR1 from oxidative modifications during periods of oxidative stress.

NASA Discipline Musculoskeletal↗
NASA NTRS1993

Substrate oxidation capacity in rodent skeletal muscle: effects of exposure to zero gravity

A study was conducted, as part of the integrated National Aeronautics and Space Administration Space Life Sciences 1 mission flown in June of 1991, to ascertain the effects of 9 days of exposure to zero gravity on the capacity of rodent skeletal muscle fiber types to oxidize either [14C]pyruvate or [14C]palmitate under state 3 metabolic conditions, i.e., nonlimiting amounts of substrate and cofactors. In addition, activity levels of marker enzymes of the tricarboxylic acid cycle, malate shuttle, and beta-oxidation were measured. Results showed that significant differences in muscle weight occurred in both the predominantly slow vastus intermedius and predominantly fast vastus lateralis of flight vs. control groups (P < 0.05). Total protein content of the muscle samples was similar between groups. Both pyruvate oxidation capacity and the marker oxidative enzymes were not altered in the flight relative to control animals. However, the capacity to oxidize long-chain fatty acids was significantly reduced by 37% in both the high- and low-oxidative regions of the vastus muscle (P < 0.05). Although these findings of a selective reduction in fatty acid oxidation capacity in response to spaceflight are surprising, they are consistent with previous findings showing 1) an increased capacity to take up glucose and upregulate glucose transporter proteins and 2) a marked accumulation of triglycerides in the skeletal muscles of rats subjected to states of unloading. Thus, skeletal muscle of animals exposed to non-weight-bearing environments undergo subcellular transformations that may preferentially bias energy utilization to carbohydrates.

NASA Discipline Musculoskeletal↗
NASA NTRS1992

Adaptability of the oxidative capacity of motoneurons

Previous studies have demonstrated that a chronic change in neuronal activation can produce a change in soma oxidative capacity, suggesting that: (i) these 2 variables are directly related in neurons and (ii) ion pumping is an important energy requiring activity of a neuron. Most of these studies, however, have focused on reduced activation levels of sensory systems. In the present study the effect of a chronic increase or decrease in motoneuronal activity on motoneuron oxidative capacity and soma size was studied. In addition, the effect of chronic axotomy was studied as an indicator of whether cytoplasmic volume may also be related to the oxidative capacity of motoneurons. A quantitative histochemical assay for succinate dehydrogenase activity was used as a measure of motoneuron oxidative capacity in experimental models in which chronic electromyography has been used to verify neuronal activity levels. Spinal transection reduced, and spinal isolation virtually eliminated lumbar motoneuron electrical activity. Functional overload of the plantaris by removal of its major synergists was used to chronically increase neural activity of the plantaris motor pool. No change in oxidative capacity or soma size resulted from either a chronic increase or decrease in neuronal activity level. These data indicate that the chronic modulation of ionic transport and neurotransmitter turnover associated with action potentials do not induce compensatory metabolic responses in the metabolic capacity of the soma of lumbar motoneurons. Soma oxidative capacity was reduced in the axotomized motoneurons, suggesting that a combination of axoplasmic transport, intracellular biosynthesis and perhaps neurotransmitter turnover represent the major energy demands on a motoneuron. While soma oxidative capacity may be closely related to neural activity in some neural systems, e.g. visual and auditory, lumbar motoneurons appear to be much less sensitive to modulations in chronic activity levels.

NASA Discipline Musculoskeletal↗
NASA NTRS2017

The Effects of CDKN1a/p21 on Oxidative Stress and Mitochondrial Function During Long Duration Spaceflight

Spaceflight factors, such as microgravity and space radiation, are known to put astronauts at risk for negative effects to their tissue regeneration and degenerative conditions. On our previous spaceflight research, we found that long duration spaceflight produced increased oxidative stress and activation of the inflammatory response as a major contributor to physiological changes, including alterations to the cardiovascular and musculoskeletal systems, metabolism, and the liver. Proliferation, apoptosis, and ion-channel remodeling of vascular smooth muscle cells, as well as endothelial inflammation, and nitric oxide synthase-nitric oxide system regulation have been shown by spaceflight and simulated spaceflight projects. CDKN1ap21 is a regulatory gene for tissue regeneration and also plays an important role in upregulating oxidative stress caused by radiation. In further research, we have also determined CDKN1ap21 to be overexpressed during spaceflight. When knocked out in mice, however, it protects against unloading-induced changes to the morphology and physiology of carotid arteries. In this proposal, we seek to test a potential dietary countermeasure to down-regulate CDKN1ap21 in the mice and protect against oxidative stress in the rodents. Specifically, we will expose both Wildtype and CDKN1ap21-null mice to hydrogen peroxide to induce oxidative stress and observe the molecular mechanisms in which a dietary supplement protects vascular smooth muscle cells against the consequences of the apoptotic environment within Wildtype mice versus the, hypothetically, sound physiology of CDKN1ap21-null mice. The successful completion of this experiment will conclusively determine accuracy of a dietary supplement as a CDKN1ap21 suppressor. This will provide a new perspective on the problem of increased oxidative stress developing into cardiovascular disease as a result of long-term space flight. This research will address the Human Research Plan Roadmaps Risk of Cardiac Rhythm Problems including CV-8, the Risk of Cardiovascular Disease and Other Degenerative Tissue Effects from Radiation Exposure including Degen-6 and Degen-7, and the Risk of Adverse Health Event from Radiation Exposure including IM-8. Additionally, this research will address Space Biology Research Plans questions SBP CMB-1, SBP CMB-3, and SB AN-2.

Oxidative Stress↗
NASA NTRS2023

AMORE-Isoprene v1.0: A New Reduced Mechanism for Gas-Phase Isoprene Oxidation

Gas-phase oxidation of isoprene by ozone (O 3 ) and the hydroxyl (OH) and nitrate (NO 3 ) radicals significantly impacts tropospheric oxidant levels and secondary organic aerosol formation. The most comprehensive and up-to-date chemical mechanism for isoprene oxidation consists of several hundred species and over 800 reactions. Therefore, the computational expense of including the entire mechanism in large-scale atmospheric chemical transport models is usually prohibitive, and most models employ reduced isoprene mechanisms ranging in size from ∼ 10 to ∼ 200 species. We have developed a new reduced isoprene oxidation mechanism using a directed-graph path-based automated model reduction approach, with minimal manual adjustment of the output mechanism. The approach takes as inputs a full isoprene oxidation mechanism, the environmental parameter space, and a list of priority species which are protected from elimination during the reduction process. Our reduced mechanism, AMORE-Isoprene (where AMORE stands for Automated Model Reduction), consists of 12 species which are unique to the isoprene mechanism as well as 22 reactions. We demonstrate its performance in a box model in comparison with experimental data from the literature and other current isoprene oxidation mechanisms. AMORE-Isoprene's performance with respect to predicting the time evolution of isoprene oxidation products, including isoprene epoxydiols (IEPOX) and formaldehyde, is favorable compared with other similarly sized mechanisms. When AMORE-Isoprene is included in the Community Regional Atmospheric Chemistry Multiphase Mechanism 1.0 (CRACMM1AMORE) in the Community Multiscale Air Quality Model (CMAQ, v5.3.3), O 3 and formaldehyde agreement with Environmental Protection Agency (EPA) Air Quality System observations is improved. O 3 bias is reduced by 3.4 ppb under daytime conditions for O 3 concentrations over 50 ppb. Formaldehyde bias is reduced by 0.26 ppb on average for all formaldehyde measurements compared with the base CRACMM1. There was no significant change in computation time between CRACMM1AMORE and the base CRACMM. AMORE-Isoprene shows a 35 % improvement in agreement between simulated IEPOX concentrations and chamber data over the base CRACMM1 mechanism when compared in the Framework for 0-D Atmospheric Modeling (F0AM) box model framework. This work demonstrates a new highly reduced isoprene mechanism and shows the potential value of automated model reduction for complex reaction systems.

Automated Model Reduction↗
NASA NTRS2024

Isolation, Characterization and Genetic Manipulation of Cold-Tolerant, Manganese-Oxidizing Pseudomonas sp. Strains

Manganese-oxidizing bacteria (MnOB) produce Mn oxide minerals that can be used by humans for bioremediation but the purpose for the bacterium is less clear. This study describes the isolation and characterization of cold-tolerant MnOB strains isolated from a compost pile in Morris, Minnesota, USA: Pseudomonas sp. MS-1 and DSV-1. The strains were preliminarily identified as members of species Pseudomonas psychrophila by 16S rRNA analysis and a multi-locus phylogenetic study using a database of 88 genomes from the Pseudomonas genus. However, the average nucleotide identity (ANI) between these strains and the P. psychrophila sp. CF149 type strain was less than 93%. Thus, the two strains are members of a novel species that diverged from P. psychrophila . DSV-1 and MS-1 are cold tolerant; both grow at 4C but grow faster at 24C. Unlike the mesophilic MnOB P. putida GB-1, both strains are capable of robustly oxidizing Mn at low temperatures. Both DSV-1 and MS-1 genomes contain homologs of several Mn oxidation genes found in P. putida GB-1 ( mnxG, mcoA, mnxS1, mnxS2 and mnxR ). Random mutagenesis by transposon insertion was successfully performed in both strains and identified genes involved in Mn oxidation that were similar to those found in P. putida GB-1. Our results show that MnOB can be isolated from compost, supporting a role for Mn oxidation in plant waste degradation. The novel isolates Pseudomonas spp. DSV-1 and MS-1 both can oxidize Mn at low temperature and likely employ similar mechanisms and regulation as P. putida GB-1.

manganese oxidation↗
DOE OSTI2026

First-Principles Evaluation of Proton Hopping in Tetrahedral Oxide Motifs

Proton-conducting oxides (PCOs) are important materials used as ionic conductors for energy conversion technologies. Existing research efforts on PCO optimization and discovery generally focus on complex perovskite-based oxides that require doping and alloying to engineer oxygen deficiency and high proton conductivity. However, the variety of chemical compositions and coordination environments in oxides poses challenges for efficient materials design. In this computational study, we construct a database of simplified motifs to elucidate the relationship between fundamental materials chemistry and proton kinetics. Specifically, we focus on the zincblende crystal structure as a proxy for tetrahedral metal–oxide (M–O) coordination environments. We systematically quantified the effects of cation type, oxidation states, and M–O bond lengths on the proton hopping barrier, and found that strong M–O bonds and metal cations with large and variable oxidation states (e.g., Mo 6+ , V 5+ ) lead to smaller proton hopping barriers. By mapping the candidate cations and their preferred bond geometries onto materials databases such as the Inorganic Crystal Structure Database (ICSD) and Materials Project, we identified real materials containing the corresponding metal–oxide units. In general, we observed good agreement between the calculated proton hopping barriers obtained in real crystal structures and those predicted by our motif database. We also discuss the limitations of our model and possible future extensions to improve its predictive capabilities. Overall, our model provides a first step for the rational design and quick screening of energy-efficient PCOs.

organic↗
DOE OSTI2026

Manganese Oxidation during Vegetation Burning

Redox recycling of manganese (Mn) plays a key role in organic matter decomposition and nutrient cycling in terrestrial vegetated ecosystems, and it is expected to be changed by fires. This study revealed how Mn is oxidized during vegetation burning, by characterizing the chemical speciation of Mn in fire ash from wildland fires and laboratory burning and evaluating the factors governing its average oxidation state (AOS) and speciation. Manganese in wildland fire ash from different ecosystems showed variable AOS that ranges from 2.5 to 3.3. Laboratory burning experiments showed that Mn oxidation was primarily controlled by fire thermal intensity (temperature × duration) and burning completeness. As heating time increased from 5 min to 5 h at 550 and 700 °C, Mn AOS in the lab-burned vegetation ash increased from 2.7 to 4.0 and the oxidation rate was faster at higher temperature. Diverse Mn species can present in wildland fire ash and differ structurally from biogenic Mn oxides. The oxidized Mn species enable fire ash to mediate oxidative degradation of catechol, demonstrating its potential in mediating organic matter decomposition. This study revealed a new paradigm of Mn redox recycling, as compared to the microbe-mediated Mn redox cycling in the absence of fires.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Comparative proteomics of a versatile, marine, iron-oxidizing chemolithoautotroph

This study conducted a comparative proteomic analysis to identify potential genetic markers for the biological function of chemolithoautotrophic iron oxidation in the marine bacterium Ghiorsea bivora. To date, this is the only characterized species in the class Zetaproteobacteria that is not an obligate iron-oxidizer, providing a unique opportunity to investigate differential protein expression to identify key genes involved in iron-oxidation at circumneutral pH. Over 1000 proteins were identified under both iron- and hydrogen-oxidizing conditions, with differentially expressed proteins found in both treatments. Notably, a gene cluster upregulated during iron oxidation was identified. This cluster contains genes encoding for cytochromes that share sequence similarity with the known iron-oxidase, Cyc2. Interestingly, these cytochromes, conserved in both Bacteria and Archaea, do not exhibit the typical β-barrel structure of Cyc2. This cluster potentially encodes a biological nanowire-like transmembrane complex containing multiple redox proteins spanning the inner membrane, periplasm, outer membrane, and extracellular space. The upregulation of key genes associated with this complex during iron-oxidizing conditions was confirmed by quantitative reverse transcription-PCR. These findings were further supported by electromicrobiological methods, which demonstrated negative current production by G. bivora in a three-electrode system poised at a cathodic potential. This research provides significant insights into the biological function of chemolithoautotrophic iron oxidation.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1975

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Huang, C. J.↗
NASA NTRS1977

Technology of GaAs metal-oxide-semiconductor solar cells

The growth of an oxide interfacial layer was recently found to increase the open-circuit voltage (OCV) and efficiency by up to 60 per cent in GaAs metal-semiconductor solar cells. Details of oxidation techniques to provide the necessary oxide thickness and chemical structure and using ozone, water-vapor-saturated oxygen, or oxygen gas discharges are described, as well as apparent crystallographic orientation effects. Preliminary results of the oxide chemistry obtained from X-ray, photoelectron spectroscopy are given. Ratios of arsenic oxide to gallium oxide of unity or less seem to be preferable. Samples with the highest OVC predominantly have As(+3) in the arsenic oxide rather than As(+5). A major difficulty at this time is a reduction in OCV by 100-200 mV when the antireflection coating is vacuum deposited.

Stirn, R. J.↗
NASA NTRS1980

Effect of W and WC on the oxidation resistance of yttria-doped silicon nitride

The effect of W and WC contamination on the oxidation and cracking in air of sintered Si3N4 - 8 w/o Y2O3 ceramics at 500, 750, and 1350 C is examined. A mixture of Si3N4 - 8Y2O3, milled with alumina balls, was divided into four portions. Three portions were doped with 2 w/o WC W, and 4 w/o W respectively, in order to simulate contamination during milling. The fourth portion was undoped and used on a control. The addition of W or WC did not affect the phase relationships in the system, as all bars with or without additions contained melilite as the major Si-Y-O-N phase after sintering. At 750 C, instability (rapid oxidation and cracking) of W-doped bars appears to have occurred as a result of oxidation of the tungsten containing melilite phase. No intermediate temperature instability was observed in bars containing 2 w/o WC or in bars with no additive. Specimens exposed at 1350 C had good oxidation resistance due to the formation of a protective siliceous oxide layer. A specimen containing 4 w/o W which was preoxidized at 1350 C had improved oxidation resistance at 750 C. The tendency towards oxidation and cracking of Si3N4 - 8 Y2O3 at 750 C is concluded to be related to tungsten content of the sintered bars.

Schuon, S.↗
NASA NTRS1980

Chemical depth profiles of the GaAs/native oxide interface

The final-state oxidation products and their distribution in thin native oxides (30-40 A) on GaAs have been studied using X-ray photoelectron spectroscopy in conjunction with chemical depth profiling. Extended room-temperature-oxidation conditions have been chosen to allow the native oxide to attain its equilibrium composition and structure. The work emphasizes the use of chemical depth-profiling methods which make it possible to examine the variation in chemical reactivity of the oxide structure. A minimum of two distinct regions of Ga2O3 with differing chemical reactivity is observed. Chemical shift data indicate the presence of As2O3 in the oxide together with an elemental As overlayer at the interface. A change in relative charge transfer between oxygen and both arsenic and gallium-oxide species is observed in the region of the interface.

Grunthaner, P. J.↗
NASA NTRS1982

The transport of nitric oxide in the upper atmosphere by planetary waves and the zonal mean circulation

A time-dependent numerical model was developed and used to study the interaction between planetary waves, the zonal mean circulation, and the trace constituent nitric oxide in the region between 55 km and 120 km. The factors which contribute to the structure of the nitric oxide distribution were examined, and the sensitivity of the distribution to changes in planetary wave amplitude was investigated. Wave-induced changes in the mean nitric oxide concentration were examined as a possible mechanism for the observed winter anomaly. Results indicate that vertically-propagating planetary waves induce a wave-like structure in the nitric oxide distribution and that at certain levels, transports of nitric oxide by planetary waves could significantly affect the mean nitric oxide distribution. The magnitude and direction of these transports at a given level was found to depend not only on the amplitude of the planetary wave, but also on the loss rate of nitric oxide at that level.

Jones, G. A.↗
NASA NTRS1982

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

Ishigaki, H.↗
NASA NTRS1983

Oxidation and formation of deposit precursors in hydrocarbon fuels

The oxidation of two jet turbine fuels and some pure hydrocarbons was studied at 130 C with and without the presence of small amounts of N-methyl pyrrole (NMP) or indene. Tendency to form solid-deposit precursors was studied by measuring soluble gum formation as well as dimer and trimer formation using field ionization mass spectrometry. Pure n-dodecane oxidized fastest and gave the smallest amount of procursors. An unstable fuel oil oxidized much slower but formed large amounts of precursors. Stable Jet A fuel oxidized slowest and gave little precursors. Indene either retarded or accelerated the oxidation of n-dodecane, depending on its concentration, but always caused more gum formation. The NMP greatly retarded n-dodecane oxidation but accelerated Jet A oxidation and greatly increased the latter's gum formation. In general, the additive reacted faster and formed most of the gum. Results are interpreted in terms of classical cooxidation theory. The effect of oxygen pressure on gum formation is also reported.

Mayo, F. R.↗
NASA NTRS1983

The oxidation behavior of a model molybdenum/tungsten-containing alloy in air alone and in air with trace levels of NaCl(g)

Thermogravimetric, metallographic, and X-ray studies of a model alloy, Ni-(17 a/o)Al-(10 a/o)Mo+W, oxidized in dry air at 600-1200 C and in air with 10 ppm NaCl gas at 900 C, are reported. The alloy was melted under Ar and pretreated in flowing H2 for 24 h at 1300 C. Polished 1.3 x 1.3 x 0.2-cm specimens were washed and degreased prior to oxidation in a quartz tube within a furnace for up to 120 hr. The oxidation activation energy of the alloy is determined to be about 30 kcal/mole. The specimens oxidized at 900 C and hotter exhibited oxidized and nitrided phases covered by complex NiMoO4, NiWO4, and NiAl2O4 scales and a porous, nonprotective outer layer of NiO. The oxidation behavior is found to be determined by the formation and growth of the scale, especially the (Mo,W)O2 component. Al2O3 scale layers were not formed, and further runs with pure O2 or Ar-(20 percent)O2 ruled out an explanation of this phenomenon based on aluminum nitride formation. The oxidation was accelerated by the addition of NaCl gas, a finding attributed to the reaction of NaCl with external locally protective Al2O3 scales and with the internal(Mo, W)O2 layers.

Smeggil, J. G.↗