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51 records · Page 3

Directional Solidification of Nodular Cast Iron

Cerium enhances formation of graphite nodules. Preliminary experiments in directional solidification of cast iron shows quantitative correlation of graphite microstructure with growth rate and thermal gradient, with sufficient spheroidizing element to form spheroidal graphite under proper thermal conditions. Experimental approach enables use of directional solidification to study solidification of spheriodal-graphite cast iron in low gravity. Possible to form new structural materials from nodular cast iron.

Curreri, P. A.↗

Integrated Heat Switch/Oxide Sorption Compressor

Thermally-driven, nonmechanical compressor uses container filled with compressed praseodymium cerium oxide powder (PrCeOx) to provide high-pressure flow of oxygen gas for driving closed-cycle Joule-Thomson-expansion refrigeration unit. Integrated heat switch/oxide sorption compressor has no moving parts except check valves, which control flow of oxygen gas between compressor and closed-cycle Joule-Thomson refrigeration system. Oxygen expelled from sorbent at high pressure by evacuating heat-switch gap and turning on heater.

Bard, Steven↗

Synthesis, characterization and evaluation of CO-oxidation catalysts for high repetition rate CO2 TEA lasers

An extremely active class of noble metal catalysts supported on titania was developed and fabricated at Hughes for the recombination of oxygen (O2) and carbon monoxide (CO) in closed-cycle CO2 TEA lasers. The incipient wetness technique was used to impregnate titania and alumina pellets with precious metals including platinum and palladium. In particular, the addition of cerium (used as an oxygen storage promoter) produced an extremely active Pt/Ce/TiO2 catalyst. By comparison, the complementary Pt/Ce/ gamma-Al2O3 catalyst was considerably less active. In general, chloride-free catalyst precursors proved critical in obtaining an active catalyst while also providing uniform metal distributions throughout the support structure. Detailed characterization of the Pt/Ce/TiO2 catalyst demonstrated uniform dendritic crystal growth of the metals throughout the support. Electron spectroscopy for Chemical Analysis (ESCA) analysis was used to characterize the oxidation states of Pt, Ce and Ti. The performance of the catalysts was evaluated with an integral flow reactor system incorporating real time analysis of O2 and CO. With this system, the transient and steady-state behavior of the catalysts were evaluated. The kinetic evaluation was complemented by tests in a compact, closed-cycle Hughes CO2 TEA laser operating at a pulse repetition rate of 100 Hz with a catalyst temperature of 75 to 95 C. The Pt/Ce/TiO2 catalyst was compatible with a C(13)O(16)2 gas fill.

Moser, Thomas P.↗

LEO effects on candidate solar cell cover materials

In 1984, the LDEF (Long Duration Exposure Facility) was placed in LEO (Low Earth Orbit) for a mission planned to last approximately one year. Due to a number of factors, retrieval was delayed until 1990. An experiment, prepared under the direction of JPL, consisted of a test plate with thirty (30) individual thin silicon solar cell/cover samples. The covers consisted of conventional cerium doped microsheet platelets and potential candidate materials, such as FEP Teflon, silicon RTV's, glass resins, polyimides, and a silicone-polyimide copolymer encapsulant. The effects of the LDEF mission environment (micrometeorite/debris impacts, atomic oxygen, UV, and particulate radiation) on the samples are discussed.

Stella, Paul M.↗

AVIRIS as a tool for carbonatite exploration: Comparison of SPAM and Mbandmap data analysis methods

Data acquired with the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) of the Mountain Pass, San Bernadino County, California, area were analyzed to evaluate the use of narrow-band imaging data for carbonatite exploration. Carbonatites are igneous carbonate-rich rocks that are economically important in part because they are the major source for rare-earth minerals. Because the 224 AVIRIS spectral channels have a nominal spectral resolution of 10 nm, narrow absorption features such as those displayed by the rare-earth elements neodymium (Nd) and samarium (Sm) may be detected. The Mountain Pass region encompasses a well-exposed sequence of sedimentary, metamorphic, and igneous rocks, including an alkalic carbonatite intrusion. The carbonatite was emplaced in Precambrian granitic rocks that are fault bounded by a thick suite of Paleozoic, sedimentary rock, predominantly dolomite. The carbonatite stock, the major source of light rare-earth elements (REE) in the United States, affords the opportunity to test AVIRIS capabilities for detecting REE absorption features. Nd-bearing minerals display narrow, sharp and distinctive spectral features at 580, 740, 800, and 870 nm. Minerals bearing Sm display similarly sharp features near 1090, 1250, 1410, and 1550 nm. The more common REE, lanthanum and cerium, do not display absorption features in the visible/near-infrared region in their natural oxidation states.

Kingston, Marguerite J.↗

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Thompson, David W.↗

Impact of Solar Array Designs on High Voltage Operations

As power levels of advanced spacecraft climb above 25 kW, higher solar array operating voltages become attractive. Even in today s satellites, operating spacecraft buses at 100 V and above has led to arcing in GEO communications satellites, so the issue of spacecraft charging and solar array arcing remains a design problem. In addition, micrometeoroid impacts on all of these arrays can also lead to arcing if the spacecraft is at an elevated potential. For example, tests on space station hardware disclosed arcing at 75V on anodized A1 structures that were struck with hypervelocity particles in Low Earth Orbit (LEO) plasmas. Thus an understanding of these effects is necessary to design reliable high voltage solar arrays of the future, especially in light of the Vision for Space Exploration of NASA. In the future, large GEO communication satellites, lunar bases, solar electric propulsion missions, high power communication systems around Mars can lead to power levels well above 100 kW. As noted above, it will be essential to increase operating voltages of the solar arrays well above 80 V to keep the mass of cabling needed to carry the high currents to an acceptable level. Thus, the purpose of this paper is to discuss various solar array approaches, to discuss the results of testing them at high voltages, in the presence of simulated space plasma and under hypervelocity impact. Three different types of arrays will be considered. One will be a planar array using thin film cells, the second will use planar single or multijunction cells and the last will use the Stretched Lens Array (SLA - 8-fold concentration). Each of these has different approaches for protection from the space environment. The thin film cell based arrays have minimal covering due to their inherent radiation tolerance, conventional GaAs and multijunction cells have the traditional cerium-doped microsheet glasses (of appropriate thickness) that are usually attached with Dow Corning DC 93-500 silicone adhesive. In practice, these cover glasses and adhesive do not cover the cell edges. Finally, in the SLA, the entire cell and cell edges are fully encapsulated by a cover glass that overhangs the cell perimeter and the silicone adhesive covers the cell edges providing a sealed environment. These three types of blanket technology have been tested at GRC and Auburn. The results of these tests will be described. For example, 15 modules composed of four state-of-the-art 2x4 cm GaAs solar cells with 150 pm cover glasses connected in two-cell series strings were tested at high voltage, in plasma under hypervelocity impact. A picture of one of the modules is shown in figure 1. These were prepared by standard industry practice from a major supplier and had efficiencies above 18%. The test results and other fabrication factors that influenced the tests will be presented. In addition, results for SLA segments tested under the same conditions will be presented. Testing of thin film blankets at GRC will also be presented. Figure 1 : Typical GaAs Solar Cell Module These results will show significant differences in resistance to arcing that are directly related to array design and manufacturing procedures. Finally, the approaches for mitigating the problems uncovered by these tests will be described. These will lay the foundation for future higher voltage array operation, even including voltages above 300-600 V for direct drive SEP applications.

Brandhorst, Henry W., Jr.↗

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

Flytzani-Stephanopoulos, Maria↗

Stabilized tin-oxide-based oxidation/reduction catalysts

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D.↗

Compact Rare Earth Emitter Hollow Cathode

A compact, high-current, hollow cathode utilizing a lanthanum hexaboride (LaB6) thermionic electron emitter has been developed for use with high-power Hall thrusters and ion thrusters. LaB6 cathodes are being investigated due to their long life, high current capabilities, and less stringent xenon purity and handling requirements compared to conventional barium oxide (BaO) dispenser cathodes. The new cathode features a much smaller diameter than previously developed versions that permit it to be mounted on axis of a Hall thruster ( internally mounted ), as opposed to the conventional side-mount position external to the outer magnetic circuit ("externally mounted"). The cathode has also been reconfigured to be capable of surviving vibrational loads during launch and is designed to solve the significant heater and materials compatibility problems associated with the use of this emitter material. This has been accomplished in a compact design with the capability of high-emission current (10 to 60 A). The compact, high-current design has a keeper diameter that allows the cathode to be mounted on the centerline of a 6- kW Hall thruster, inside the iron core of the inner electromagnetic coil. Although designed for electric propulsion thrusters in spacecraft station- keeping, orbit transfer, and interplanetary applications, the LaB6 cathodes are applicable to the plasma processing industry in applications such as optical coatings and semiconductor processing where reactive gases are used. Where current electrical propulsion thrusters with BaO emitters have limited life and need extremely clean propellant feed systems at a significant cost, these LaB6 cathodes can run on the crudest-grade xenon propellant available without impact. Moreover, in a laboratory environment, LaB6 cathodes reduce testing costs because they do not require extended conditioning periods under hard vacuum. Alternative rare earth emitters, such as cerium hexaboride (CeB6) can be used in this configuration with possibly an even longer emitter life. This cathode is specifically designed to integrate on the centerline of a high-power Hall thruster, thus eliminating the asymmetries in the plasma discharge common to cathodes previously mounted externally to the thruster s magnetic circuit. An alternative configuration for the cathode uses an external propellant feed. This diverts a fraction of the total cathode flow to an external feed, which can improve the cathode coupling efficiency at lower total mass flow rates. This can improve the overall thruster efficiency, thereby decreasing the required propellant loads for different missions. Depending on the particular mission, reductions in propellant loads can lead to mission enabling capabilities by allowing launch vehicle step-down, greater payload capability, or by extending the life of a spacecraft.

Watkins, Ronald↗

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D.↗

A persistently low level of atmospheric oxygen in Earth’s middle age

Resolving how Earth surface redox conditions evolved through the Proterozoic Eon is fundamental to understanding how biogeochemical cycles have changed through time. The redox sensitivity of cerium relative to other rare earth elements and its uptake in carbonate minerals make the Ce anomaly (Ce/Ce*) a particularly useful proxy for capturing redox conditions in the local marine environment. Here, we report Ce/Ce* data in marine carbonate rocks through 3.5 billion years of Earth’s history, focusing in particular on the mid-Proterozoic Eon (i.e., 1.8 – 0.8 Ga). To better understand the role of atmospheric oxygenation, we use Ce/ Ce* data to estimate the partial pressure of atmospheric oxygen (pO2) through this time. Our thermodynamics-based modeling supports a major rise in atmospheric oxygen level in the aftermath of the Great Oxidation Event (~ 2.4 Ga), followed by invariant pO2 of about 1% of present atmospheric level through most of the Proterozoic Eon (2.4 to 0.65 Ga).

Xiao-Ming Liu↗

Removing Contamination From Genesis Sapphire Collectors By Polishing

The Array Collectors of the Genesis spacecraft collected bulk solar wind (SW), as well as three subsets of SW (fast, slow, and coronal mass ejection) in a variety of materials. In all cases the SW implant peaked within < 0.2 microns of the surface. So, when the sample return capsule crashed on landing, cleaning the surfaces for analysis became an extremely difficult, but imperative, task. One collector material was “sapphire”, commercial single crystal corundum. Only ~7.7% of the Genesis Array collectors were sapphire (SAP) but a much higher percentage survived the crash. In fact, surviving bulk SW sapphire collectors have an average area ~10x that of their silicon counterparts since SAP is physically tough, and hard (MOHS 9, by definition) as well as is chemically inert. So, SAP is a good candidate for analytical techniques for measuring SW that require clean areas larger than a millimeter; e.g., synchrotron TXRF and INAA. It is also possible to measure SW in SAP using laser ablation and secondary ion mass spectrometry (SIMS) and, recently, more researchers are choosing to analyze sapphire. Thus, removing surface contamination from SAP could enable many research projects. This report extends the task presented in Schmeling et al. ([4]) that used polishing compounds to remove contamination from Genesis sapphire. It focuses on how polishing with their two top candidates (colloidal silica and cerium oxide) affects the SW layer in SAP.

Genesis solar wind↗

REE chemistry and Sm-Nd systematics of late Archean weathering profiles in the Fortescue Group, Western Australia

Two weathering profiles, each consisting of an upper, sericite-rich zone and a lower, chlorite-rich zone, are preserved between flows of the Mt. Roe Basalt in the Fortescue Group, Hamersley Basin, Western Australia. REE concentrations in samples from these two profiles, which originally developed ca 2,760 Ma, show large variations depending on stratigraphic position. LREE abundances and (La/Yb)N are greatest at depths of 3-6 m below the paleosurface of the Mt. Roe #1 profile and are somewhat lower in samples above this level. The LREEs reach concentrations 6-9 times greater than in the underlying basalt, and thus appear to have been mobilized downward in the paleosol and concentrated in its middle part. LREE concentrations in the #2 profile show a similar distribution but with a sharp increase in all REE concentrations within 50 cm of the paleosurface. The distinction between the REE profiles in the two paleosols may be related to the difference in the overlying material. The #1 paleosol is overlain by a few meters of sediments and then by basalt, whereas the #2 paleosol is directly overlain by basalt. The LREEs appear to have been mobilized both during chemical weathering of the parental basalt and during later lower-greenschist-facies metamorphism and metasomatism of the paleosols. Remobilization of the REEs during the regional metamorphism of the Fortescue Group is confirmed by a whole-rock Sm-Nd reference isochron of Mt. Roe #1 samples with an age of 2,151 +/- 360 Ma. Variable initial 143Nd/144Nd values of unweathered basalt samples which may represent the paleosol protolith prevents a confident determination of the magnitude of LREE mobility. Both the initial mobilization of the REEs during weathering and the metasomatic remobilization appear to have taken place under redox conditions where Ce was present dominantly as Ce3+, because Ce anomalies are not developed within the sericite zone samples regardless of concentration. Europium anomalies in the paleoweathering profile are somewhat variable and were probably modified by mobilization of Eu2+ at metamorphic conditions. In all samples, the HREEs appear to have been relatively immobile and correlate with Al, Ti, Cr, V, Zr, and Nb. Sm-Nd systematics and REE patterns of four unweathered basalt samples indicate derivation of the Mt. Roe Basalts from a heterogeneous and enriched source having epsilon Nd between -4.0 and -7.4. Initial 143Nd/144Nd values of these basalts are even lower than those reported by NELSON et al. (1992) for Fortescue Group basalts and indicate a substantial crustal component in the generation of Mt. Roe Basalts.

NASA Discipline Exobiology↗

Electron-microscopic cytochemical localization of diamine and polyamine oxidases in pea and maize tissues

An electron-microscopic cytochemical method was used to localize diamine oxidase (DAO) in pea and polyamine oxidase (PAO) in maize (Zea mays L.). The method, based on the precipitation of amine-oxidase-generated H2O2 by CeCl3, was shown to be specific for DAO and PAO and permitted their localization in plant tissues with a high degree of resolution. Both enzymes are localized exclusively in the cell wall. Both DAO- and PAO-activity staining is most intense in the middle lamellar region of the wall and in cells exhibiting highly lignified walls. The oxidases could provide H2O2 for peroxidase-mediated cross-linking reactions in the cell wall and may, in this capacity, play a role in the regulation of plant growth.

NASA Program Space Biology↗