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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

An experimental estimate of the O/+/-O resonant charge transfer cross section, collision frequency, and energy transfer rate

The resonant-charge-transfer cross section dominates the interaction between neutral and ionized atomic oxygen at temperatures greater than several hundred degrees Kelvin. This cross section is of direct importance to F-region studies of ion diffusion, ion thermal balance, and neutral atmospheric winds and pressure gradients, since it determines collision frequencies and energy and momentum transfer rates. However, the uncertainty in this cross section is roughly 25-40%. Incoherent-scatter measurements allow determination of the product of the atomic oxygen concentration multiplied by the cross section. If present-day atmospheric models are accepted as statistically representative of F-region atomic oxygen concentrations experimental (aeronomical) data presented indicate that the resonant-charge-transfer cross section is about 1.3 times greater than the value presently in general use, though in excellent agreement with the only other available (laboratory) experimental value. This revised cross section has obvious implications for thermospheric studies.

Carlson, H. C.↗
NASA NTRS1994

Loss of solar He and Ne from IDPS in subducting sediment: Diffusion and the effect of phase changes

The results of the diffusion experiment for solar He and Ne in IDP's in a magnetic separate from Pacific Ocean sediment suggest that solar He and Ne would be easily released from IDP grains and hence lost from subducting slabs at shallow depths. However, since the diffusion experiments was conducted under high vacuum, there may be a possibility that magnetite grains, which are supposedly the main constituent of the magnetic fraction, might be partly reduced to form a metal phase due to low oxygen fugacity in the experimental condition. If this is the case, such a phase change might affect the gas release and hence the results of the diffusion coefficients. In order to examine whether or not such a phase change really occurred in the condition of the diffusion experiment, I conducted a heating experiment for a magnetic separate from Pacific Ocean sediment. In the same condition as in the diffusion experiment, and the run products were examined with an x ray diffraction method. Three samples were prepared: they were wrapped with platinum foil, put in a vacuum line, and heated in a molybdenum crucible for two hours at 500 C, 800 C,and 950 C, respectively. After cooling the furnace, the samples were taken out from the crucible and analyzed with an x ray diffraction method.

Hiyagon, H.↗
DOE OSTI2026

Tetrahedral Zn 2+ doping LiNi 0.6 Mn 0.2 Co 0.2 O 2 improves discharge capacity retention by altering surface Ni valence during cycling and preventing oxygen evolution

5 mol-% Zn 2+ was added to the co-precipitation synthesis of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) to understand Zn's effect on the structural and electronic properties of NMC622. Zn is determined to successfully dope into the NMC crystal lattice as there is an increase in d-spacing along the [003], [104], and [110] directions and an increase in molar volume (100.75 cm 3 mol -1 for NMC622 and 101.00 cm 3 mol -1 for Zn-NMC). Through XPS, Zn is determined to dope on the tetrahedral 6c Wyckoff site in the NMC structure and TEM-EDS reveals that despite a slight ZnO impurity phase, 1.4 mol-% Zn successfully dopes into the crystal structure. Furthermore, cyclic voltammetry shows a suppressed anodic wave associated with oxygen evolution and EIS demonstrates that Zn-doped NMC decreases charge transfer resistance and increases Li diffusion by an order of magnitude. After the formation cycles, NMC has a higher 1 C accessible capacity, 141 mAh/g, over Zn-NMC (132 mAh/g), but after long term cycling Zn-NMC has a higher accessible capacity (117 mAh/g compared to 96 mAh/g for NMC) and increases discharge capacity retention by 18% leading to longer cycle life.

Electrochemistry↗
DOE OSTI2020

In Situ Identification of Reaction Intermediates and Mechanistic Understandings of Methane Oxidation over Hematite: A Combined Experimental and Theoretical Study

Effective methane utilization for either clean power generation or value-added chemical production has been a subject of growing attention worldwide for decades, yet challenges persist mostly in relation to methane activation under mild conditions. Here, we report hematite, an earth-abundant material, to be highly effective and thermally stable to catalyze methane combustion at low temperatures (<500 °C) with a low light-off temperature of 230 °C and 100% selectivity to CO 2 . The reported performance is impressive and comparable to those of precious-metal-based catalysts, with a low apparent activation energy of 17.60 kcal·mol –1 . Our theoretical analysis shows that the excellent performance stems from a tetra-iron center with an antiferromagnetically coupled iron dimer on the hematite (110) surface, analogous to that of the methanotroph enzyme methane monooxygenase that activates methane at ambient conditions in nature. Isotopic oxygen tracer experiments support a Mars van Krevelen redox mechanism where CH 4 is activated by reaction with a hematite surface oxygen first, followed by a catalytic cycle through a molecular-dioxygen-assisted pathway. Surface studies with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations reveal the evolution of reaction intermediates from a methoxy CH 3 –O–Fe, to a bridging bidentate formate b-HCOO–Fe, to a monodentate formate m-HCOO–Fe, before CO 2 is eventually formed via a combination of thermal hydrogen-atom transfer (HAT) and proton-coupled electron transfer (PCET) processes. Finally, the elucidation of the reaction mechanism and the intermediate evolutionary profile may allow future development of catalytic syntheses of oxygenated products from CH 4 in gas-phase heterogeneous catalysis.

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

Modelling and analysis of salt-convection effect on oxide reduction process for uranium oxides using smoothed particle hydrodynamics

Oxygen ion transport via molten salt continuum is a key kinetic feature of electrochemical reduction process for uranium oxides in molten salt. During the electrolysis, the evolution of oxygen ion concentration field in molten salt continuum appears from porous metallic layer to open bulk salt. Despite the important role affecting process throughput, its effect coupled with controlled salt movement was not adequately investigated. To capture the reactive oxygen ion transport phenomena, a multidimensional reduction model based on smoothed particle hydrodynamics (SPH) was combined with the advection-diffusion model. A pelletized oxide fuel bed capturing interconnected salt continuum is considered as a reactant material geometry, which allows forced convective delivery of molten salt through the reactant materials with a relatively low pressure head. Here, in this study, reduction time of a pelletized-fuel bed was quantified with respect to key design parameters of the reactant material configuration. The simulation results demonstrated the advantage of salt convection which effectively removes oxygen ion products from the reactant materials and consequently accelerates the reduction process. Moreover, the reduction-time correlation of a single pelletized fuel was developed as a function of relevant dimensionless parameters and was extended to the application for a pelletized-fuel bed. Finally, several insights and implications in the use of a pelletized oxide fuel were presented. The developed SPH-based framework enabled multi-physics analysis of governing dynamics in appreciating and screening candidate reactant material configurations in a cost-effective manner.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1981

Computations of ion diffusion coefficients from the Boltzmann-Fokker-Planck equation

The Boltzmann-Fokker-Planck equation is solved with the Chapman-Enskog method of analysis for the velocity distribution functions of helium, carbon, nitrogen, and oxygen. The analysis is a perturbation scheme based on the assumption of a collision-dominated gas, and the calculations are carried out to first order. The elements considered are treated as trace constituents in an electron-proton gas. From the resulting distribution functions, diffusion coefficients are computed which are found to be 20-30% less than those obtained by Chapman and Burgers. In addition, it is shown that the return current of cold electrons needed to maintain quasi-neutrality in a plasma with a temperature gradient contributes a term in the thermal diffusion coefficient omitted erroneously in previous works. This added term resolves the longstanding controversy over the discrepancy between the coefficients of Chapman and Burgers, which are seen to be completely equivalent in the light of this analysis. The viscosity coefficient for an electron-proton gas is also computed and found to be 7% less than that obtained by Braginskii.

Roussel-Dupre, R.↗
DOE OSTI2025

Controllable oxygen vacancy defect engineering of BiVO 4 porous structures for room temperature NH 3 detection

Controlling structural features of sensing material while judiciously introducing vacancy defect states for revamping the electronic properties of the sample to obtain its superior gas sensing performance, is quite rare. Herein, we report for the first time, the room temperature (RT) ammonia (NH 3 ) detection of peanut-like porous bismuth vanadate (BiVO 4 ) with a stable monoclinic phase. The developed BiVO 4 possess abundant oxygen vacancies and porosity by virtue of calcinations (400–800 ℃). BiVO 4 calcined at 400 ℃ exhibits high selectivity towards NH 3 with a maximum response of 1421 @ 270 ppm at RT, which is 2.5 fold enhanced compared to without calcined BiVO 4 (response of 547 @ 270 ppm NH 3 ). The oxygen defective BiVO 4 appeared highly durable and stable even under high humid conditions (∼60 %). Besides, the porosity of BiVO 4 not only enhances the specific surface area (19.8 m 2 /g) but also results in fast diffusion of NH 3 molecules, leading to a reduction in the decay time (34 s for 90 ppm NH 3 ). The density functional theory (DFT) uncovers that the oxygen vacancy formation in BiVO 4 augments the NH 3 sensing capabilities by enhancing the adsorption energy of NH 3 . This work provides insight into the sensing mechanism of increased response caused by defect engineering and porosity, which will be favourable for fabricating high-performance NH 3 sensors at RT.

DFT analysis↗
DOE OSTI2020

Molecular Origins of the Barriers to Proton Transport in Acidic Aqueous Solutions

The self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method is used to analyze the structure, thermodynamics, and dynamics of hydrochloric acid solutions. The reorientation timescales of irreversible proton transport are elucidated by simulating 0.43 M, 0.85 M, 1.68 M, and 3.26 M HCl solutions at 270 K, 285 K, 300 K, 315 K, and 330 K. The results indicate increased counter-ion pairing with increasing concentration, which manifests itself via a reduced hydronium oxygen–chloride (O*-Cl) structuring in the radial distribution functions. Increasing ionic concentration also reduces the diffusion of the hydrated excess protons, principally by reducing the contribution of the Grotthuss proton hopping (shuttling) mechanism to the overall diffusion process. In agreement with prior experimental findings, a decrease in the activation energy of reorientation timescales was also observed, which is explicitly explained using activated rate theory and an energy-entropy decomposition of the state-averaged radial distribution functions. Furthermore, these results provide atomistic verification of suggestions from recent two-dimensional infrared spectroscopy experiments that chloride anions (as opposed to hydrated excess protons) create entropic barriers to proton transport.

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

Synthesis of monodisperse high entropy alloy nanocatalysts from core@shell nanoparticles

We report that high-entropy alloy (HEA) nanoparticles (NPs) hold great promise in electrocatalysis because of their nearly unlimited compositions, tailorable active sites, and high durability. However, the synthesis of these compositionally complex structures as monodisperse NPs remains a challenge by colloidal routes because the different rates of metal precursor reduction lead to phase separation. Here, we report the conversion of core@shell NPs into HEA NPs through annealing, with conservation of sample monodispersity. This potentially general route for high-quality HEA NPs was demonstrated by preparing PdCu@PtNiCo NPs via seed-mediated co-reduction, wherein Pt, Ni, and Co were co-deposited on PdCu seeds in solution. These multimetallic NPs were then converted to single-crystalline and single-phase PdCuPtNiCo NPs through annealing. On account of their small particle size, highly dispersed Pt/Pd content, and low elemental diffusivity, these HEA NPs were found to be a highly efficient and durable catalyst for the oxygen reduction reaction. They were also highly selective for the four-electron transfer pathway. We expect that this new synthetic strategy will facilitate the synthesis of new HEA NPs for catalysis and other applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

CO oxidation over a ligand coordinated single site Rh catalyst: identification of the active complex

Single atom catalysis has evolved as a promising strategy to enhance atom utilization efficiency, lower reaction temperatures, and control reaction pathways in heterogeneous catalytic reactions. An important challenge using supported single atom catalysts is the stability of metal single atoms during reactions. Here, we present an approach to stabilize single rhodium atoms on a titania support via a metal–ligand coordination strategy. We explore the reaction activity and mechanism of CO oxidation, as well as the stability under oxidative reaction conditions. Kinetic studies suggest that, with an excess of oxygen in the feed gas, oxygen activation is more facile on defective titania surfaces than on pristine titania surfaces. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis shows that on the pristine titania surface, the 1,10-phenanthroline-5,6-dione (PDO) coordinated Rh catalyst (Rh–PDO/TiO 2 ) catalyzes CO oxidation via the formation of carbonate-like species, which is similar to what occurs on Rh nanoparticle catalysts. However, on the defective titania surface, no carbonate species form for Rh–PDO/def-TiO 2 . The supported Rh–ligand catalysts are also shown to be very stable in such a reaction environment at elevated temperatures, potentially allowing for wide applications.

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

Data from: Understanding the biogeochemical and spatial drivers of methane and carbon dioxide fluxes in a large temperate reservoir

This dataset contains spatially resolved measurements of CO₂ and CH₄ fluxes and associated environmental variables collected across 200 sites in Douglas Reservoir (Tennessee, USA) between July 29-August 2, 2024. Measurements include diffusive fluxes of CO₂ and CH₄, CH₄ ebullition, and biogeochemical and spatial variables such as dissolved oxygen, temperature, conductivity, chlorophyll-a, pH, water depth, and distance from the dam. Sampling was conducted using a spatially balanced design to capture longitudinal and depth-related gradients throughout the reservoir. The dataset is structured to support analyses of spatial variability, flux pathway comparisons, and modeling approaches (e.g., spatial statistics and machine learning) aimed at understanding controls on reservoir CO₂ and CH₄ fluxes and improving upscaling to whole-reservoir and regional estimates.

Neeper, Jamie [ORNL] (ORCID:0009000842342101)↗
NASA NTRS1979

Investigation of the feasibility of CARS measurements in scramjet combustion

Results are presented of analytical and experimental investigations to determine the feasibility of using coherent anti-Stokes Raman spectroscopy (CARS) to measure temperature and species concentrations in supersonic combustion experiments. Experimental CARS spectra of O2 and H2 in a laboratory flat H2 - air diffusion flame are presented. Temperatures deduced from both species generally agree with radiation corrected thermocouple measurements. Oxygen concentrations were determined from the shape of the experimental spectra. Measured H2 CARS signal magnitudes are in good agreement with analytical predictions based on H2 concentration profiles determined from spontaneous Raman scattering. Based on these results, CARS diagnostics appear to be feasible if problems associated with the supersonic flow are not too severe.

Shirley, J. A.↗
NASA NTRS1987

Theoretical study of the dipole moment function of OH(X 2Pi)

A complete theoretical electric dipole moment function mu(r) is computed for OH(X 2Pi) at the full configuration-interaction (FCI) level for DZP + diffuse Gaussian basis set. The energy and dipole moment are also determined with 2d functions on oxygen at seven r values. The following methods are compared to the FCI for both the oxygen 1d and 2d basis sets: single-reference singles-plus-doubles configuration interaction (SDCI), SDCI with Davidson's correction, the coupled pair functional approach (CPF) and a modified form of CPF, CASSCF, and CASSCF-MRSDCI, and the external contracted CI(CCI) method. The dipole moments are evaluated both as an expectation value and by finite-field methods. The results support the superiority of evaluating the dipole moment as an energy derivative rather than as an expectation value.

Langhoff, Stephen R.↗
NASA NTRS1996

CFD Analysis of the 24-inch JIRAD Hybrid Rocket Motor

A series of multispecies, multiphase computational fluid dynamics (CFD) analyses of the 24-inch diameter joint government industry industrial research and development (JIRAD) hybrid rocket motor is described. The 24-inch JIRAD hybrid motor operates by injection of liquid oxygen (LOX) into a vaporization plenum chamber upstream of ports in the hydroxyl-terminated polybutadiene (HTPB) solid fuel. The injector spray pattern had a strong influence on combustion stability of the JIRAD motor so a CFD study was initiated to define the injector end flow field under different oxidizer spray patterns and operating conditions. By using CFD to gain a clear picture of the flow field and temperature distribution within the JIRAD motor, it is hoped that the fundamental mechanisms of hybrid combustion instability may be identified and then suppressed by simple alterations to the oxidizer injection parameters such as injection angle and velocity. The simulations in this study were carried out using the General Algorithm for Analysis of Combustion SYstems (GALACSY) multiphase combustion codes. GALACSY consists of a comprehensive set of droplet dynamic submodels (atomization, evaporation, etc.) and a computationally efficient hydrocarbon chemistry package built around a robust Navier-Stokes solver optimized for low Mach number flows. Lagrangian tracking of dispersed particles describes a closely coupled spray phase. The CFD cases described in this paper represent various levels of simplification of the problem. They include: (A) gaseous oxygen with combusting fuel vapor blowing off the walls at various oxidizer injection angles and velocities, (B) gaseous oxygen with combusting fuel vapor blowing off the walls, and (C) liquid oxygen with combusting fuel vapor blowing off the walls. The study used an axisymmetric model and the results indicate that the injector design significantly effects the flow field in the injector end of the motor. Markedly different recirculation patterns are observed in the vaporization chamber as the oxygen velocity and/or spray pattern is varied. The ability of these recirculation patterns to stabilize the diffusion flame above the surface of the solid fuel gives a plausible explanation for the experimentally determined combustion stability characteristics of the JIRAD motor, and suggests how combustion stability can be assured by modifications to the injector design.

Liang, Pak-Yan↗
NASA NTRS2000

Transitional Gas Jet Diffusion Flames in Microgravity

Drop tower experiments were performed to identify buoyancy effects in transitional hydrogen gas jet diffusion flames. Quantitative rainbow schlieren deflectometry was utilized to optically visualize the flame and to measure oxygen concentration in the laminar portion of the flame. Test conditions consisted of atmospheric pressure flames burning in quiescent air. Fuel from a 0.3mm inside diameter tube injector was issued at jet exit Reynolds numbers (Re) of 1300 to 1700. Helium mole percentage in the fuel was varied from 0 to 40%. Significant effects of buoyancy were observed in near field of the flame even-though the fuel jets were momentum-dominated. Results show an increase of breakpoint length in microgravity. Data suggest that transitional flames in earth-gravity at Re<1300 might become laminar in microgravity.

Agrawal, Ajay K.↗
NASA NTRS1984

LEO atomic oxygen effects on spacecraft materials: STS-5 results

Effects of low Earth orbit (LEO) atomic oxygen were measured on a variety of spacecraft materials which obtained exposure on STS-5. Material degradation dependency on temperature was found in one material. Of the five paints flown, only S13GLO was unaffected. Generally, the glossy paints became Lambertian and the diffuse coatings improved. Scanning electron microscope examinations indicated removal of urethane and epoxy paint binder materials. Reaction products were evident on the surfaces of Z302 paint and Mylar. Thin films showed thickness losses ranging from negligible loss in Teflon to considerable loss in Mylar and Kapton. Glossy films such as black Kapton and white Tedlar became diffused. Kevlar 29 rope lost tensile strength and silver solar cell interconnect material oxidized. Oxidation on the backside of an elevated specimen indicated that reflections of oxygen atoms were occurring and that reflecting surfaces, probably Kapton, were not fully accommodating the incident atoms.

Whitaker, A. F.↗
DOE OSTI2025

Property Measurements of LiF-NaF-KF Molten Salts Doped with Corrosion Products and Oxygen

Measurements of thermophysical properties of molten salts are needed for modeling and simulation activities that support the development of molten salt reactor (MSR) technologies. Properties of interest including transition temperatures, phase behavior, heat capacity, density, volumetric thermal expansion, surface tension, viscosity, thermal diffusivity, thermal conductivity, and vapor pressure are being performed at Argonne. Results of these property measurements are suitable for use in evaluating reactor performance during startup and the early operating life of the reactor. Ingressions of oxygen and moisture into the fuel salt are expected to occur at different times during the operating life of the reactor due to system leaks, maintenance, and refueling activities. The presence of these environmental contaminants induces corrosion of structural materials. The introduction of corrosion-derived species, oxygen and moisture is expected to affect the physical and chemical properties of the salt and operation of the reactor. Previous work performed at Argonne evaluated the effects of fission product dopants on the thermal properties of eutectic LiF-NaF-KF (FLiNaK). Properties of FLiNaK are commonly used to represent those of fluoride-bearing fuel salts. Metallic corrosion products such as chromium and nickel ions together with dissolved oxygen are expected to affect system redox differently than the accumulation of fission products. Work summarized in this report was performed to measure the effects of corrosion products and dissolved oxygen on the phase transitions, and specific heat capacity of FLiNaK. Thermophysical property measurements were made using four salts that were prepared by doping aliquots of a eutectic mixture of FLiNaK with surrogate corrosion products. Controlled additions of CrF 3 and NiF 2 were used as surrogates for corrosion product contamination anticipated during extended reactor operations in which fuel salt is in contact with steel reactor components. Controlled additions of UF 4 from two sources containing known amounts of UO 2 at different concentrations were used to represent oxygen contamination. The phase transitions and specific heat capacities of the four salts were measured by using differential scanning calorimetry. Measurements were made at temperatures spanning the range of 500−900 °C, which is the expected operating range of MSRs. Measured property values were compared to values measured previously with eutectic FLiNaK without dopants. Differences between property values measured for the doped and non-doped salts were compared with the uncertainties of the measurements to determine the significance of the effect of corrosion products and oxygen on salt properties.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
NASA NTRS2002

Fast Three-Dimensional Method of Modeling Atomic Oxygen Undercutting of Protected Polymers

A method is presented to model atomic oxygen erosion of protected polymers in low Earth orbit (LEO). Undercutting of protected polymers by atomic oxygen occurs in LEO due to the presence of scratch, crack or pin-window defects in the protective coatings. As a means of providing a better understanding of undercutting processes, a fast method of modeling atomic-oxygen undercutting of protected polymers has been developed. Current simulation methods often rely on computationally expensive ray-tracing procedures to track the surface-to-surface movement of individual "atoms." The method introduced in this paper replaces slow individual particle approaches by substituting a model that utilizes both a geometric configuration-factor technique, which governs the diffuse transport of atoms between surfaces, and an efficient telescoping series algorithm, which rapidly integrates the cumulative effects stemming from the numerous atomic oxygen events occurring at the surfaces of an undercut cavity. This new method facilitates the systematic study of three-dimensional undercutting by allowing rapid simulations to be made over a wide range of erosion parameters.

Snyder, Aaron↗