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At least 55 records · Page 3

An electrochemical study of Ni/2+/, Co/2+/, and Zn/2+/ ions in melts of composition CaMgSi2O6

Results are reported for a study of the behavior of Ni(2+), Co(2+), and Zn(2+) in molten diopside, determined by cyclic voltametry, as a first step in adapting electrochemical methods for use in experimental geochemistry. The techniques used are described, the theory is briefly discussed, and it is demonstrated that Ni(2+), Co(2+), and Zn(2+) can be reduced, then reoxidized in an uncomplicated case of reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain undissolved in the melt. The kinetics of the reduction process, the effects of concentration, the standard reduction potentials, and the diffusion coefficients are discussed in detail. The observations are consistent with the mechanism of Ni(2+) diffusion by transport from site to site. As the proportion of SiO2 in the melt increases, a higher activation energy is required for Ni(2+) to move, and the rate of diffusion is lowered.

Semkow, K. W.↗

The ilmenite/titano-magnetite assemblage - Kinetics of re-equilibration

The petrogenesis of igneous and metamorphic rocks is a function of several parameters. Of these, temperature and pressure are of particular importance. Information concerning these two parameters is obtained through the use of mineral indicators. One such commonly used geothermometer/oxybarometer is that involving ilmenite/titano-magnetite. Anomalously low temperatures have been reported in cases in which the geothermometer/oxybarometer was employed. The studies suggest that low temperatures result from slow cooling rates which allows the Fe-Ti oxides to re-equilibrate. The current investigation is mainly concerned with the kinetics of the reduction of ilmenite-hematite solid solution, since this is the slower and, consequently, rate-controlling step in the re-equilibration process. The reaction rates determined for the reduction of ilmenites in the investigation are geologically rapid and must be considered when applying the considered geothermometer/oxybarometer.

Hammond, P. A.↗

A High Performance H2-Cl2 Fuel Cell for Space Power Applications

NASA has numerous airborne/spaceborne applications for which high power and energy density power sources are needed. The proton exchange membrane fuel cell (PEMFC) is an attractive candidate for such a power source. PEMFC's offer many advantages for airborne/spaceborne applications. They have high power and energy densities, convert fuel to electrical power with high efficiency at both part and full load, and can rapidly startup and shutdown. In addition, PEMFC's are lightweight and operate silently. A significant impediment to the attainment of very high power and energy densities by PEMFC's is their current exclusive reliance on oxygen as the oxidant. Conventional PEMFC's oxidize hydrogen at the anode and reduce oxygen at the cathode. The electrode kinetics of oxygen reduction are known to be highly irreversible, incurring large overpotential losses. In addition, the modest open circuit potential of 1.2V for the H2-O2 fuel cell is unattainable due to mixed potential effects at the oxygen electrode. Because of the high overpotential losses, cells using H2 and O2 are capable of achieving high current densities only at very low cell voltages, greatly curtailing their power output. Based on experimental work on chlorine reduction in a gas diffusion electrode, we believe significant increases in both the energy and power densities of PEMFC systems can be achieved by employing chlorine as an alternative oxidant.

Anderson, Everett B.↗

Development of Aluminum/Air Battery as High-Capacity Primary Battery Energy Source for SUSAN Electrofan Project

High-capacity, high-performance, and safe battery technologies are demanded by the Subsonic Single Aft eNgine (SUSAN) Electrofan concept design project under National Aeronautics and Space Administration (NASA) electrified aircraft development program. These battery technologies, including both secondary (i.e., rechargeable) batteries for hybrid/electric propulsion and primary batteries (i.e. non-rechargeable or single-use) for backup/emergency use in case of turbine engine failure, are important and vital components in SUSAN concept design. This paper is focused on aluminum (Al)-air battery, which is considered to be the most promising candidate to meet the energy goal of primary batteries for SUSAN project. However, there are challenges for Al-air batteries, including aluminum self-corrosion with hydrogen (H2) gassing and sluggish kinetics of oxygen reduction reaction (ORR) in air-cathode. In this paper, the preliminary results on investigation of electrolytes and additives on controlling aluminum self-corrosion/H2 gassing suppression and the study of air-cathode design for ORR improvement are presented and discussed.

James Wu↗

Progress of Aluminum/Air Battery Development for SUSAN Electrofan Project

Safe and high-performance battery technologies are demanded by the Subsonic Single Aft eNgine (SUSAN) Electrofan concept design project under National Aeronautics and Space Administration (NASA) electrified aircraft development program. Aluminum (Al)-air battery with very high theoretical specific energy density, is considered as promising battery chemistry which has the potential to meet the targeted specific energy goal of primary battery energy technology for the SUSAN project. In addition to having the exceptional electrochemical properties, aluminum is light weight, rich abundance, low cost, environmentally friendly, and has a good electrical conductivity and recyclability, which is among the key characteristics of SUSAN project on battery energy needs. A non-flammable aqueous electrolyte is used to prevent the fire and thermal runaway hazard for the safety of this battery chemistry. However, there are challenges for Al-air battery in practical application, mainly due to self-corrosion of Al and slow kinetics of oxygen reduction in air-cathode to impact the high-rate performance. Progress on addressing these challenges was made and some of the results were reported in our previous paper. In this paper, the focus is on the investigation of various factors, including electrolyte concentrations, temperature, and air-cathode loadings on ionic transport properties and discharge performance at different current densities. The results are discussed, and the progress is reported.

James J Wu↗

Reaction engineering for materials processing in space: Reduction of ilmenite by hydrogen and carbon monoxide

Oxygen is a consumable material which needs to be produced continuously in most space missions. Its use for propulsion as well as life support makes oxygen one of the largest volume chemicals to be produced in space. Production of oxygen from lunar materials is of particular interest and is very attractive possibility. The kinetics and mechanism of reduction of ilmenite by carbon monoxide and hydrogen at 800 to 1100 C were investigated. The temporal profiles of conversion for carbon monoxide have a sigmoidal shape and indicate the presence of three different stages (induction, acceleration, and deceleration) during the reduction reaction. The apparent activation energy decreases from 18 kcal/mole at 10 percent conversion to 10 kcal/mole at 50 percent conversion. The reaction is first order with respect to carbon monoxide under the experimental conditions studied. Both SEM and EDX analysis 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 are important steps affecting the process kinetics. The results from hydrogen reduction show that the mechanism of ilmenite reduction by hydrogen is similar to that by carbon monoxide. However, the titanium dioxide can be further reduced by hydrogen at 800 to 1000 C. The detailed comparison and theoretical modeling of both reduction processes is presented.

Zhao, Y.↗

The reduction of chlorine on carbon in AlCl3-KCl-NaCl melts

Using a rotating vitreous carbon disk electrode, the kinetic parameters for chlorine reduction in an AlCl3-KCl-NaCl (57.5-12.5-30 mol percent) melt were determined. It was found that the reduction of chlorine occurs according to two paths, with the first step probably being rate-determining.

Holleck, G. L.↗

Reduction of iron-bearing lunar minerals for the production of oxygen

The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.

Massieon, Charles↗

Noise, Turbulence, and Thrust of Subsonic Free Jets from Lobed Nozzles

A study of noise benefit, vis-a-vis thrust penalty, and its correlation to turbulence intensities was conducted for free jets issuing from lobed nozzles. Four convergent nozzles with constant exit area were used in the experiments. Three of these were of rectangular lobed configuration having six, ten and fourteen lobes; the fourth was a circular nozzle. Increasing the number of lobes resulted in a progressive reduction in the turbulence intensities as well as in the overall radiated noise. The noise reduction was pronounced at the low frequency end of the spectrum. However, there was an increase in the high frequency noise that rendered the overall benefit less attractive when compared on a scaled-up A-weighted basis. A reduction in noise was accompanied by a commensurate reduction in the turbulent kinetic energy in the flow field. As expected, increasing the number of lobes involved progressive reduction in the thrust coefficient. Among the cases studied, the six-lobed nozzle had the optimum reduction in turbulence and noise with the least thrust penalty.

Zaman, K. B. M. Q.↗

A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by using tabular information from the LLNL skeletal mechanism in conjunction with CHEMKIN II utilized as surrogate ideal functions replacing the necessary functional forms. The test reveals that the similarity concept is indeed justified and that the combustion temperature is well predicted, but that the ignition time is over-predicted, a fact traced to neglecting a detailed description of the processes leading to the heavies chemical decomposition. To palliate this deficiency, functional modeling is incorporated into this conceptual reduction in addition to the modeling the evolution of the global constituent molar density, the enthalpy evolution of the heavies, the contribution to the reaction rate of the unsteady lights from other light species and from the heavies, the molar density evolution of oxygen and water, and the mole fractions of the quasisteady light species. The model is compact in that there are only nine species-related progress variables. Results are presented showing the performance of the model for predicting the temperature and species evolution. The model reproduces the ignition time over a wide range of equivalence ratios, initial pressure, and initial temperature.

Harstad, Kenneth G.↗

Electrochemical studies on niobium triselenide cathode material for lithium rechargeable cells

The electrochemical behavior of NbSe3 in the battery electrolyte 1.5M LiAsF6/2Me-THF is reported. A detailed study has been carried out using various ac and dc electrochemical techniques to establish the mechanism of intercalation of three equivalents of Li with NbSe3 as well as the rate governing processes in the reduction of NbSe3. An equivalent circuit has been formulated to represent the NbSe3-solution interface. The kinetic parameters for the reduction of NbSe3 were evaluated from the ac and dc measurements. The structural change in NbSe3 on lithiation during initial discharge which results in higher cell voltages and different electrochemical response as compared to virgin NbSe3 was identified to be a loss of crystallographic order.

Ratnakumar, B. V.↗

Monitoring the Photosynthetic Apparatus During Space Flight: Interspecific Variation in Chlorophyll Fluorescence Signatures Induced by Different Root Zone Stresses

Chlorophyll fluorescence has been used extensively as a tool to indicate stress to the photosynthetic apparatus in green plants. A rise in fluorescence has been attributed to the blockage of photosystem II photochemistry, and patterns of fluorescence decay (quenching) from dark adapted leaves can be related to specific photochemical and non-photochemical deexcitation pathways of light trapped by the photosynthetic apparatus and thus result in characteristically different fluorescence signatures. Four distantly related plant species, Hypocharis radicata (Asteraceae), Brassica rapa (Brassicaceae), Spinacea oleracea (Chenopodiaceae) and Triticum aestivum (Poaceae), were grown hydroponically for three weeks before the initiation of three different root zone stresses (10 mM Cu, 100 mM NaCl and nitrogen deficient nutrition). After 10 days, characteristic fluorescence signatures for each stress could be noted although the degree varied between species. Fast kinetics analysis showed a reduction in plastoquinone pool size for copper and nitrogen stress for all species but a more species specific result with NaCl stress. Photochemical quenching kinetics varied between species and stress treatments from no quenching in S. oleracea in copper treatments to increased photochemical quenching in NaCl treatments. Non-photochemical quenching kinetics demonstrated a distinct pattern between stresses for all species. Copper treatments characteristically exhibited a shallow, flat non-photochemical quenching profile suggesting a general blockage of electron transport whereas NaCl treatments exhibited a slow rising profile that suggested damage to thylakoid acidification kinetics and nitrogen deficiency exhibited a fast rising and declining profile that suggested an altered state 1-state 2 transition regulated by the phosphorylation of LHCII. These results demonstrate characteristic fluorescence signatures for specific plant stresses that may be applied to different, unrelated plant species. In addition, the potential use of chlorophyll fluorescence for both basic research and diagnostic physiology in space biology is presented.

Bubenheim, David L.↗

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

The lead ruthenate pyrochlore Pb2Ru2O6.5, in both high- and low-area forms, has been characterized using thermogravimetric analysis, X-ray photoelectron spectroscopy, X-ray diffraction, cyclic voltammetry, and O2 reduction and generation kinetic-mechanistic studies. Mechanisms are proposed. Compounds in which part of the Ru is substituted with Ir have also been prepared. They exhibit somewhat better performance for O2 reduction in porous, gas-fed electrodes than the unsubstituted compound. The anodic corrosion resistance of pyrochlore-based porous electrodes was improved by using two different anionically conducting polymer overlayers, which slow down the diffusion of ruthenate and plumbate out of the electrode. The O2 generation performance was improved with both types of electrodes. With a hydrogel overlayer, the O2 reduction performance was also improved.

Prakash, Jai↗

Reynolds-Stress and Triple-Product Models Applied to a Flow with Rotation and Curvature

Turbulence models, with increasing complexity, up to triple product terms, are applied to the flow in a rotating pipe. The rotating pipe is a challenging case for turbulence models as it contains significant rotational and curvature effects. The flow field starts with the classic fully developed pipe flow, with a stationary pipe wall. This well defined condition is then subjected to a section of pipe with a rotating wall. The rotating wall introduces a second velocity scale, and creates Reynolds shear stresses in the radial-circumferential and circumferential-axial planes. Furthermore, the wall rotation introduces a flow stabilization, and actually reduces the turbulent kinetic energy as the flow moves along the rotating wall section. It is shown in the present work that the Reynolds stress models are capable of predicting significant reduction in the turbulent kinetic energy, but triple product improves the predictions of the centerline turbulent kinetic energy, which is governed by convection, dissipation and transport terms, as the production terms vanish on the pipe axis.

Turbulence models↗

Reynolds-Stress and Triple-Product Models Applied to a Flow with Rotation and Curvature

Turbulence models, with increasing complexity, up to triple product terms, are applied to the flow in a rotating pipe. The rotating pipe is a challenging case for turbulence models as it contains significant rotational and curvature effects. The flowfield starts with the classic fully developed pipe flow, with a stationary pipe wall. This well defined condition is then subjected to a section of pipe with a rotating wall. The rotating wall introduces a second velocity scale, and creates Reynolds-shear stresses in the radial-circumferential and circumferential-axial planes. Furthermore, the wall rotation introduces a ow stabilization, and actually reduces the turbulent kinetic energy as the flow moves along the rotating wall section. It is shown in the present work that the Reynolds stress models are capable of predicting significant reduction in the turbulent kinetic energy, but triple product improves the predictions of the centerline turbulent kinetic energy, which is governed by convection, dissipation and transport terms, as the production terms vanish on the pipe axis.

Olsen, Michael E.↗

CH4 production via CO2 reduction in a temperate bog - A source of (C-13)-depleted CH4

The paper reports measurements, taken over two annual cycles, of the flux and delta(C-13) of CH4 released from an acidic peat bog located in the foothills of the Cascade Range in Washington state, U.S. Measurements of the rate of aceticlastic methanogenesis and CO2 reduction in peat soil, using (C-14)-labeled acetate and sodium bicarbonate, show that acetate was not an important CH4 precursor and that CO2 reduction could account for all of the CH4 production. The in situ kinetic isotope effect for CO2 reduction, calculated using the delta-(C-13) of soil water CO2 and CH4 flux, was 0.932 +/- 0.007.

Lansdown, J. M.↗

Flow Field and Acoustic Predictions for Three-Stream Jets

Computational fluid dynamics was used to analyze a three-stream nozzle parametric design space. The study varied bypass-to-core area ratio, tertiary-to-core area ratio and jet operating conditions. The flowfield solutions from the Reynolds-Averaged Navier-Stokes (RANS) code Overflow 2.2e were used to pre-screen experimental models for a future test in the Aero-Acoustic Propulsion Laboratory (AAPL) at the NASA Glenn Research Center (GRC). Flowfield solutions were considered in conjunction with the jet-noise-prediction code JeNo to screen the design concepts. A two-stream versus three-stream computation based on equal mass flow rates showed a reduction in peak turbulent kinetic energy (TKE) for the three-stream jet relative to that for the two-stream jet which resulted in reduced acoustic emission. Additional three-stream solutions were analyzed for salient flowfield features expected to impact farfield noise. As tertiary power settings were increased there was a corresponding near nozzle increase in shear rate that resulted in an increase in high frequency noise and a reduction in peak TKE. As tertiary-to-core area ratio was increased the tertiary potential core elongated and the peak TKE was reduced. The most noticeable change occurred as secondary-to-core area ratio was increased thickening the secondary potential core, elongating the primary potential core and reducing peak TKE. As forward flight Mach number was increased the jet plume region decreased and reduced peak TKE.

RANS CFD↗

Effects of processing and dopant on radiation damage removal in silicon solar cells

Gallium and boron doped silicon solar cells, processed by ion-implantation followed by either laser or furnace anneal were irradiated by 1 MeV electrons and their post-irradiation recovery by thermal annealing determined. During the post-irradiation anneal, gallium-doped cells prepared by both processes recovered more rapidly and exhibited none of the severe reverse annealing observed for similarly processed 2 ohm-cm boron doped cells. Ion-implanted furnace annealed 0.1 ohm-cm boron doped cells exhibited the lowest post-irradiation annealing temperatures (200 C) after irradiation to 5 x 10 to the 13th e(-)/sq cm. The drastically lowered recovery temperature is attributed to the reduced oxygen and carbon content of the 0.1 ohm-cm cells. Analysis based on defect properties and annealing kinetics indicates that further reduction in annealing temperature should be attainable with further reduction in the silicon's carbon and/or divacancy content after irradiation.

Weinberg, I.↗