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At least 991 records · Page 55

Modeling the Europa plasma torus

The existence of a torus of plasma generated by sputtering from Jupiter's satellite Europa has long been suspected but never yet convincingly demonstrated. Temperature profiles from Voyager plasma observations indicate the presence of hot, possibly freshly picked-up ions in the general vicinity of the orbit of Europa, which may be interpreted as evidence for a local plasma torus. Studies of ion partitioning in the outer regions of the Io torus reveal that the oxygen to sulfur mixing ratio varies with radial distance; this may indicates that oxygen-rich matter is injected from a non-Io source, most probably Europa. We have constructed a quantitative model of a plasma torus near the orbit of Europa which takes into account plasma input from the Io torus, sputtering from the surface of Europa, a great number of ionization and charge exchange processes, and plasma loss by diffusive transport. When the transport time is chosen so that the model's total number density in consistent with the observed total plasma density, the contribution from Europa is found to be significant although not dominant. The model predicts in detail the ion composition, charge states, and the relative fractions of hot Europa-generated and (presumed) cold Io-generated ions. The results are generally consistent with observations from Voyager and can in principle (subject to limitations of data coverage) be confirmed in more detail by Ulysses.

Schreier, Ron↗

Spot Radiative Ignition and Subsequent Three Dimensional Flame Spread Over Thin Cellulose Fuels

Spontaneous radiative ignition and transition to flame spread over thin cellulose fuel samples was studied aboard the USMP-3 STS-75 Space Shuttle mission, and in three test series in the 10 second Japan Microgravity Center (JAMIC). A focused beam from a tungsten/halogen lamp was used to ignite the center of the fuel sample while an external air flow was varied from 0 to 10 cm/s. Non-piloted radiative ignition of the paper was found to occur more easily in microgravity than in normal gravity. Ignition of the sample was achieved under all conditions studied (shuttle cabin air, 21%-50% O2 in JAMIC), with transition to flame spread occurring for all but the lowest oxygen and flow conditions. While radiative ignition in a quiescent atmosphere was achieved, the flame quickly extinguished in air. The ignition delay time was proportional to the gas-phase mixing time, which is estimated using the inverse flow rate. The ignition delay was a much stronger function of flow at lower oxygen concentrations. After ignition, the flame initially spread only upstream, in a fan-shaped pattern. The fan angle increased with increasing external flow and oxygen concentration from zero angle (tunneling flame spread) at the limiting 0.5 cm/s external air flow, to 90 degrees (semicircular flame spread) for external flows at and above 5 cm/s, and higher oxygen concentrations. The fan angle was shown to be directly related to the limiting air flow velocity. Despite the convective heating from the upstream flame, the downstream flame was inhibited due to the 'oxygen shadow' of the upstream flame for the air flow conditions studied. Downstream flame spread rates in air, measured after upstream flame spread was complete and extinguished, were slower than upstream flame spread rates at the same flow. The quench regime for the transition to flame spread was skewed toward the downstream, due to the augmenting role of diffusion for opposed flow flame spread, versus the canceling effect of diffusion at very low cocurrent flows.

Olson, Sandra L.↗

Metasomatic Control of Water in Garnet and Pyroxene from Kaapvaal Craton Mantle Xenoliths

Fourier transform infrared spectrometry (FTIR) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) were used to determine water, rare earth (REE), lithophile (LILE), and high field strength (HFSE) element contents in garnet and pyroxene from mantle xenoliths, Kaapvaal craton, southern Africa. Water enters these nominally anhydrous minerals as protons bonded to structural oxygen in lattice defects. Pyroxene water contents (150-400 ppm in clinopyroxene; 40-250 ppm in orthopyroxene) correlate with their Al, Fe, Ca and Na and are homogeneous within a mineral grains and a xenolith. Garnets from Jagersfontein are chemically zoned for Cr, Ca, Ti and water contents. Garnets contain 0 to 20 ppm H2 Despite the fast diffusion rate of H in mantle m inerals, the observations above indicate that the water contents of mantle xenolith minerals were not disturbed during kimberlite entrainment and that the measured water data represent mantle values. Trace elements in all minerals show various degrees of light REE and LILE enrichments indicative of minimal to strong metasomatism. Water contents of peridotite minerals from the Kaapvaal lithosphere are not related to the degree of depletion of the peridotites. Instead, metasomatism exerts a clear control on the amount of water of mantle minerals. Xenoliths from each location record specific types of metasomatism with different outcomes for the water contents of mantle minerals. At pressures . 5.5 GPa, highly alkaline melts metasomatized Liqhobong and Kimberley peridotites, and increased the water contents of their olivine, pyroxenes and garnet. At higher pressures, the circulation of ultramafic melts reacting with peridotite resulted in co-variation of Ca, Ti and water at the edge of garnets at Jagersfontein, overall decreasing their water content, and lowered the water content of olivines at Finsch Mine. The calculated water content of these melts varies depending on whether the water content of the peridotite (2 wt% HO. 2O) or individual m inerals (<0.5-13 wt% H2O) are used, and also depend on the mineral-melt water partition coefficients. These metasomatic events are thought to have occurred during the Archean and Proterozoic, meaning that the water contents measured here have been preserved since that time and can be used to investigate viscocity and longevity of cratonic mantle roots.

Peslier, Anne H.↗

Minimizing particle aggregation in Sm 2 Fe 17 N 3 powders: A CaO-assisted reduction-diffusion approach

We report a novel synthesis of Sm 2 Fe 17 N 3 powders using a CaO-assisted reduction-diffusion (RD) approach. CaO plays a crucial role during mechanochemical processing – acting both as a dispersant and a surface coating agent, which helps to prevent agglomeration due to sintering of Sm 2 Fe 17 particles during the RD step. Together with the added dispersant, the CaO by-product formed during RD can be easily removed in the washing step resulting in fewer aggregated Sm 2 Fe 17 N 3 particles and lower oxygen contamination in the final product. The impact of varying CaO amounts was examined, and synthesis conditions were optimized to achieve phase-pure Sm 2 Fe 17 N 3 powders with less aggregation of magnetic particles. The powders synthesized with addition of 1 wt% CaO as dispersant exhibited the highest hard-magnetic properties: a coercivity (H c ) of 10.7 kOe and a maximum energy product ((BH) max ) of 17.3 MGOe. By densifying the Sm 2 Fe 17 N 3 powders using high-pressure spark plasma sintering, a bulk magnet with a (BH) max of 21.1 MGOe with 88 % of theoretical density was produced. In conclusion, reducing aggregation of the Sm 2 Fe 17 N 3 increases coercivity and remanence of these magnets.

36 MATERIALS SCIENCE↗

A measurement of the interplanetary radial gradient of low-energy oxygen nuclei from 1-10 AU and implications of this measurement

Cosmic-ray telescopes on the Pioneer 10 and 11 spacecraft has been used to measure the interplanetary radial gradients of oxygen nuclei between 7.1 and 26.6 MeV/nuc between 1 and 10 AU, in 1972-1976. Between 1 and 5 AU the average gradient for 10.6-26.6-MeV/nuc particles is 25 + or - 5%/AU, while between 5 and 10 AU this gradient is 12 + or - 4%/AU. Conventional cosmic-ray transport theory can be used to determine an average diffusion mean free path from these data. The value of lambda sub r for both energy ranges is deduced to be 0.19 + or - 0.04 AU between 1 and 5 AU and 0.40 + or - 0.13 AU between 5 and 10 AU.

Webber, W. R.↗

Stuffed MO layer as a diffusion barrier in metallizations for high temperature electronics

Auger electron spectroscopy was employed to characterize the diffusion barrier properties of molybdenum in the CrSi2/Mo/Au metallization system. The barrier action of Mo was demonstrated to persist even after 2000 hours annealing time at 300 C in a nitrogen ambient. At 340 C annealing temperature, however, rapid interdiffusion was observed to have occurred between the various metal layers after only 261 hours. The presence of controlled amounts of oxygen in the Mo layer is believed to be responsible for suppressing the short circuit interdiffusion between the thin film layers. Above 340 C, its is believed that the increase in the oxygen mobility led to deterioration of its stuffing action, resulting in the rapid interdiffusion of the thin film layers along grain boundaries.

Boah, J. K.↗

Non-Innocent Role of the Ceria Support in Pd-Catalyzed Halophenol Hydrodehalogenation

The hydrodehalogenation (HDH) of halophenols is efficiently catalyzed by palladium supported on high-surface ceria (Pd/CeO2) under mild conditions (35 °C, 1 atm H2). A combination of NMR, diffuse reflectance infrared Fourier transform spectroscopy, Raman spectroscopy, and XPS studies and HDH kinetics of substituted halobenzenes suggests that the reaction proceeds mainly via a sequence of dissociative adsorption of phenolic hydroxyl onto the support, oxidative addition of the C–halogen bond to Pd, and reductive elimination to give phenol and hydrogen halide. The dissociative adsorption of the -OH group onto oxygen vacancies of the ceria support results in an electron-rich intermediate that facilitates the turnover-limiting reductive elimination step. In contrast, the direct pathway catalyzed by Pd without dissociative adsorption of the reactants on the support takes place at a slower rate. The mechanistic insights gained in this study were used to modify the reaction conditions for enabling HDH of recalcitrant halides such as fluorides and iodides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MESA Isochrones and Stellar Tracks (MIST). III. The White Dwarf Cooling Sequence

We present a substantial update to the MESA Isochrones and Stellar Tracks (MIST) library, extending the MIST model grids and isochrones down the white dwarf (WD) cooling sequence with realistic physics for WD cooling timescales. This work provides a large grid of MESA models for carbon–oxygen core WDs with hydrogen atmospheres (spectral type DA/DC), descended from full prior stellar evolution calculations. The model tracks, isochrones, and WD cooling timescale contours are available on the MIST project website and at doi:10.5281/zenodo.15242047. Our WD models provide a very large, publicly available grid with detailed physics for WD cooling timescales: realistic interior and envelope compositions, with element diffusion and heavy-element sedimentation, nuclear burning at the base of the WD hydrogen envelope, core crystallization, and C/O phase separation. As a large grid of open-source stellar evolution models, these WD models provide both out-of-the-box model tracks for comparison with observations and a framework for building further WD models to investigate variations in WD physics.

Astronomy and AstroPhysics↗

Hybrid air revitalization system for a closed ecosystem

An air-revitalization concept is presented with experimental results to assess the practicality and applicability of the proposed system to extended-duration manned missions. The Hybrid Air Revitalization System (HARS) uses plants in a habitat to remove metabolic CO2 and moisture and produce oxygen and food. CO2 and O2 partial pressures, temperature, and humidity are regulated by means of electrochemical CO2 and O2 chemical separators and a moisture condenser separator. A cell-test facility is described in which the electrochemical CO2 removal processes are investigated with and without using H2. Performance is optimized by using 25-30 percent Teflon in the gas-diffusion-type electrode, employing a thin electrolyte matrix, operating at higher temperatures and lower dew points. The HARS concept is found to be a feasible approach to the electrochemical separation of CO2 and O2.

Lee, M. G.↗

Solar Airplanes and Regenerative Fuel Cells

A solar electric aircraft with the potential to "fly forever" has captured NASA's interest, and the concept for such an aircraft was pursued under Aeronautics Environmental Research Aircraft and Sensor Technology (ERAST) project. Feasibility of this aircraft happens to depend on the successful development of solar power technologies critical to NASA's Exploration Initiatives; hence, there was widespread interest throughout NASA to bring these technologies to a flight demonstration. The most critical is an energy storage system to sustain mission power during night periods. For the solar airplane, whose flight capability is already limited by the diffuse nature of solar flux and subject to latitude and time of year constraints, the feasibility of long endurance flight depends on a storage density figure of merit better than 400-600 watt-hr per kilogram. This figure of merit is beyond the capability of present day storage technologies (other than nuclear) but may be achievable in the hydrogen-oxygen regenerative fuel cell (RFC). This potential has led NASA to undertake the practical development of a hydrogen-oxygen regenerative fuel cell, initially as solar energy storage for a high altitude UAV science platform but eventually to serve as the primary power source for NASAs lunar base and other planet surface installations. Potentially the highest storage capacity and lowest weight of any non-nuclear device, a flight-weight RFC aboard a solar-electric aircraft that is flown continuously through several successive day-night cycles will provide the most convincing demonstration that this technology's widespread potential has been realized. In 1998 NASA began development of a closed cycle hydrogen oxygen PEM RFC under the Aeronautics Environmental Research Aircraft and Sensor Technology (ERAST) project and continued its development, originally for a solar electric airplane flight, through FY2005 under the Low Emissions Alternative Power (LEAP) project. Construction of the closed loop system began in 2002 at the NASA Glenn Research Center in Cleveland, Ohio. System checkout was completed, and testing began, in July of 2003. The initial test sequences were done with only a fuel cell or electrolyzer in the test rig. Those tests were used to verify the test apparatus, procedures, and software. The first complete cycles of the fully closed loop, regenerative fuel cell system were successfully completed in the following September. Following some hardware upgrades to increase reactant recirculation flow, the test rig was operated at full power in December 2003 and again in January 2004. In March 2004 a newer generation of fuel cell and electrolyzer stacks was substituted for the original hardware and these stacks were successfully tested at full power under cyclic operation in June of 2004.

Bents, David J.↗

The impact of chemistry on anion migration in bixbyite-structured lanthanide oxides

This manuscript describes atomistic calculations of oxygen vacancy and interstitial migration in bixbyite structured lanthanide oxides. We examine two types of compounds, one in which only one type of lanthanide cation is present and a second class in which two lanthanides are present in a 3:1 ratio as dictated by the symmetry of the bixbyite crystal structure. Using temperature accelerated dynamics and the nudged elastic band method, we quantify the role of chemistry on the energy barriers for the most important pathways for both vacancy and interstitial migration. We then analyze the impact of these variations on the overall diffusivity of each defect, quantifying the contribution of each pathway using the theory of kinosons. We find that vacancy mobility can vary by as much as three orders of magnitude through changes in chemistry at 500 K. Changes in interstitial mobility are more modest but can still vary by an order of magnitude. This points to the ability to tune the mass transport characteristics of these compounds through appropriate choices in chemistry. We have also included supplementary information containing the atomic structures of the relevant pathways.

36 MATERIALS SCIENCE↗

Production of oxygen from lunar ilmenite

The kinetics and the mechanism of reduction of synthetic ilmenite by hydrogen in the temperature range of 807 to 1014 C were investigated. At temperatures below 876 C, the temporal profiles of conversion have a sigmoidal shape and indicate the presence of three different stages (induction, acceleration, and deceleration) during the reduction reaction. The apparent activation energy for the reaction is 22.3 kcal/mole, whereas the intrinsic activation energy is 16.9 kcal/mole. Scanning electron microscopy and energy dispersive x-ray analyses show that the diffusion of Fe product away from the reaction front and through the TiO2 phase, followed by the nucleation and growth of a separate Fe phase is an important step affecting the process kinetics. X-ray diffraction and wavelength dispersive x-ray results indicate that the TiO2 can be reduced to lower oxides of titanium at temperatures higher than 876 C.

Shadman, F.↗

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↗

Radionuclide Waste Disposal: Development of Multi-scale Experimental and Modeling Capabilities (Final Report)

The DOE EPSCoR Implementation project “Radioactive waste management: Development of multi-scale experimental and modeling capabilities” helped to develop a team of scientists and engineers from Clemson University, South Carolina State University, and the University of South Carolina to address the disposition of nuclear wastes and study the transport of radioisotopes from a waste repository in the near and far field. The project involved 20 faculty from the three institutions as well as 13 postdoctoral fellows, 32 graduate students, and 32 undergraduate students and was active from 2014-2019. Additionally, we forged new collaborations with nine researchers from DOE laboratories SRNL, LLNL, and ANL as well as the University of Manchester and the China Academy of Engineering Physics. The overarching goal of the project was to understand the conditions under which important classes of co-reactants, ranging from counter ions in crystal lattices to dissolved oxygen in pores, control the chemistry and transport characteristics of radionuclides in engineered waste forms and natural soils. Our approach was to characterize the time and length scales over which non-equilibrium states are maintained by rate-limiting, or rate-enhancing, reactions between radionuclides and co-reactants due to interactions between physical mass-transfer processes (i.e., advection, diffusion) and (biogeo) chemical reactions. We have focused our project on three specific classes of reactions relevant to radionuclide transport at DOE legacy sites: ion exchange/substitution, ligand complexation, and redox-mediated reactions. Understanding radionuclide migration requires detailed knowledge of how changes to a system – whether engineered or natural – drive the behavior of co-reactants, which in turn provide the geochemical context controlling radionuclide transport. Student engagement and training were a primary focus of the project in order to create a pipeline of researchers who could work in the area of nuclear waste disposition to support the state and the nation. Over the duration of the project we worked with 32 undergraduate, graduated 18 M.S. students and 14 Ph.D. students, and advised 13 postdoctoral fellows. The Ph.D students and postdocs have primarily taken positions at DOE laboratories, academia, and industry. Through our collaborative team, numerous follow on projects have been started with over $5M in sponsored research. Additionally, thus far the team has published 53 peer reviewed papers and given over 75 technical presentations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Detached auroral arcs in the trough region

In a previous paper, Moshupi et al. (1977) have reported on the occurrence of rare auroral 'patches' equatorward of the normally well-defined boundary of diffuse aurora. Some less spectacular but more common arclike features were observed in the same 'trough' region (between the plasmapause and the auroral oval) during the period 1972-1975. These 'detached' arcs show some similarities to stable auroral red arcs in terms of their location and occurrence, but are completely different spectroscopically in that the stable auroral red arcs produce almost pure atomic oxygen red line emissions, whereas the detached arcs are deficient in red line emission - a feature implying totally different production mechanisms. The characteristics of the detached lines are described, including their unusual local time/longitude dependence.

Anger, C. D.↗

Annealing and anomalous high-energy electron irradiation effects in low-cost silicon N+P solar cells

Silicon solar cells of N(+)P type were subjected to 1 MeV electron irradiation (up to 10 to the 16th electrons/sq cm) and then annealed at 450 C for 20 min or annealed with no electron irradiation. Electron irradiation resulted in a degradation of longer wavelength cell response, but produced a marked enhancement of response at shorter wavelengths with a peak change of 40% at 0.44 microns. Subsequent thermal anneal at 450 C reduced the long-wavelength degradation, but enhancement at shorter wavelengths persisted. Excitation at the shorter wavelengths was in the N(+)-diffused layer and in the junction region of the cell. Anneal of unirradiated cells produced shorter-wavelength enhancement with a similar peaking at 0.44 microns, but with a relative change of only 20%. More enhancement was produced in the longer wavelength region (up to 0.8 microns). These effects in the different cell regions are explained by a decrease in the interstitial oxygen-impurity complexes (deep recombination levels) and the formation of substantial oxygen-silicon vacancy centers (donors).

Garlick, G. F. J.↗

Origin of opaque assemblages in C3V meteorites - Implications for nebular and planetary processes

The results of analyses of meteoritic opaque assemblages (OAs) are presented and used in conjunction with literature data on phase equilibria and diffusion to further develop the hypothesis of Blum et al. (1989) for the origin of OAs in Ca,Al-rich inclusions (CAIs). Based on the results of the analyses, it is suggested that OAs formed after the crystallization of host CAIs by exsolution, sulfidation, and oxidation of precursor alloys at low temperatures (about 770 K) and higher than solar gas sulfur and oxygen fugacities. This model contrasts with previous models that call upon the formation of CAI OAs by aggregation of previously formed phases in the solar nebula prior to the crystallization of CAIs.

Blum, Joel D.↗

Theory and observations of electromagnetic ion cyclotron waves in Saturn's inner magnetosphere

High-resolution Voyager 1 magnetic field observations of Saturn's inner magnetosphere are examined for the presence of ULF waves. Quasi-circular left-hand polarized transverse oscillations are found in the near-equatorial region of 5-7 Rs with a wave period about 10 s and peak amplitude of about 2 nT. The wave is identified as the electromagnetic oxygen cyclotron mode occurring at a frequency just below the O(+) ion cyclotron frequency. A theoretical model of wave excitation based on gyroresonant coupling through a temperature anisotropy of O(+) pickup ions is developed which accounts for the principal features of the wave spectrum. It is hypothesized that wave-particle interactions provide a level of scattering commensurate with the weak pitch angle diffusion regime but nonetheless one that regulates and maintains a constant thermal anisotropy of ions along the magnetic field. Arguments are also presented that O(+) was the dominant thermal ion of the Dione-Tethys plasma torus at the time of the Pioneer 11 encounter the year previous to the Voyager 1 measurements.

Barbosa, D. D.↗