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At least 19 records

The effective thermal conductivity of an adsorbent - Praseodymium cerium oxide

The results of an experimental study to determine the effective thermal conductivity of praseodymium cerium oxide are reported. Praseodymium cerium oxide is an adsorbent used in the development of adsorption compressors for spaceborne refrigeration systems. A guarded-hot-plate apparatus was built for this study. Measurements were carried out for mean temperatures ranging from 300 to 600 C under a vacuum of 10 exp -5 torr. For the temperature range studied, the effective thermal conductivity increased from 0.14 to 0.76 W/m per C with increasing temperature, while displaying a cubic temperature dependency.

Secary, J. J.↗

Determining the Source of Water Vapor in a Cerium Oxide Electrochemical Oxygen Separator to Achieve Aviator Grade Oxygen

More than a metric ton of water is transported to the International Space Station (ISS) each year to provide breathing oxygen for the astronauts. Water is a safe and compact form of stored oxygen. The water is electrolyzed on ISS and ambient pressure oxygen is delivered to the cabin. A much smaller amount of oxygen is used each year in spacesuits to conduct Extra Vehicular Activities (EVAs). Space suits need high pressure (>1000 psia) high purity oxygen (must meet Aviator Breathing Oxygen "ABO" specifications, >99.5% O2). The water / water electrolysis system cannot directly provide high pressure, high purity oxygen, so oxygen for EVAs is transported to ISS in high pressure gas tanks. The tanks are relatively large and heavy, and the majority of the system launch weight is for the tanks and not the oxygen. Extracting high purity oxygen from cabin air and mechanically compressing the oxygen might enable on-board production of EVA grade oxygen using the existing water / water electrolysis system. This capability might also benefit human spaceflight missions, where oxygen for EVAs could be stored in the form of water, and converted into high pressure oxygen on-demand. Cerium oxide solid electrolyte-based ion transport membranes have been shown to separate oxygen from air, and a supported monolithic wafer form of the CeO2 electrolyte membrane has been shown to deliver oxygen at pressures greater than 300 psia. These supported monolithic wafers can withstand high pressure differentials even though the membrane is very thin, because the ion transport membrane is supported on both sides (Fig 1). The monolithic supported wafers have six distinct layers, each with matched coefficients of thermal expansion. The wafers are assembled into a cell stack which allows easy air flow across the wafers, uniform current distribution, and uniform current density (Fig 2). The oxygen separation is reported to be "infinitely selective" to oxygen [1] with reported purity of 99.99% [2]. Combined with a mechanical compressor, a Solid Electrolyte Oxygen Separator (SEOS) should be capable of producing ABO grade oxygen at pressures >2400 psia, on the space station. Feasibility tests using a SEOS integrated with a mechanical compressor identified an unexpected contaminant in the oxygen: water vapour was found in the oxygen product, sometimes at concentrations higher than 40 ppm (the ABO limit for water vapour is 7 ppm). If solid electrolyte membranes are really "infinitely selective" to oxygen as they are reported to be, where did the water come from? If water is getting into the oxygen, what other contaminants might get into the oxygen? Microscopic analyses of wafers, welds, and oxygen delivery tubes were performed in an attempt to find the source of the water vapour contamination. Hot and cold pressure decay tests were performed. Measurements of water vapour as a function of O2 delivery rate, O2 delivery pressure, and process air humidity levels were the most instructive in finding the source of water contamination (Fig 3). Water contamination was directly affected by oxygen delivery rate (doubling the oxygen production rate cut the water level in half). Water was affected by process air humidity levels and delivery pressure in a way that indicates the water was diffusing into the oxygen delivery system.

Graf, John↗

Coated silicon comprising material for protection against environmental corrosion

In accordance with an embodiment of the invention, an article is disclosed. The article comprises a gas turbine engine component substrate comprising a silicon material; and an environmental barrier coating overlying the substrate, wherein the environmental barrier coating comprises cerium oxide, and the cerium oxide reduces formation of silicate glass on the substrate upon exposure to corrodant sulfates.

Hazel, Brian Thomas↗

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↗

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↗

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↗

Catalysts for the decomposition of hydrazine and its derivatives and a method for its production

Catalysts of various types are used to decompose hydrazine and its derivatives. One type of catalyst is made as follows: the aluminum is dissolved out of an alloy of cobalt or nickel/aluminum so that a structure is produced that is chemically active for the monergol and that has a large active surface. The objective was to avoid difficulties and to create a catalyst that not only has a short start time but that can also be manufactured easily and relatively inexpensively. The solution to this task is to coat the base structure of the catalyst with oxides of copper, cobalt and cerium or oxides of copper, cobalt and cerite earth.

Sasse, R.↗

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.↗

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.↗

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.↗

Grain-boundary phases in hot-pressed silicon nitride containing Y2O3 and CeO2 additives

Auger electron spectroscopy in conjunction with X-ray powder diffraction and scanning electron microscopy is used to analyze the grain-boundary phases of Y2O3- and CeO2-doped Si3N4 hot-pressed materials in order to demonstrate that the additives concentrate predominantly in the grain boundaries of Si3N4 in the form of various oxynitride phases. A high oxygen content observed in sample fracture surfaces was found to be consistent with the existence of an oxygen-enriched phase in the grain boundaries. The presence of yttrium and cerium in the fracture surfaces and an overall increase in the O/N ratio imply that the additive oxides are predominantly concentrated in the intergranular phases.

Guha, J. P.↗

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.↗

New alloys to conserve critical elements

Previous studies and surveys on availability of domestic reserves have shown that chromium is a most critical element within the U.S. metal industry. More precisely, the bulk of chromium is consumed in the production of stainless steels, specifically Type 304 stainless steel (304SS) which contains 18% Cr. The present paper deals with means of reducing chromium in commercial stainless steels by substituting more abundant or less expensive elements with the intent of maintaining the properties of 304SS. The discussion focuses on some of the oxidation and corrosion properties of new substitute stainless steels with only 12% Cr, which represents a potential saving of 33% of the chromium consumed in the production of 304SS. The alloying elements substituted for Cr in 304SS are selected according to their potential for protective oxide formation during high-temperature oxidation; these are Al, Si, Ti, Y, and misch metal which is 99.7% rare-earth metals containing 50 to 55% cerium. Other alloying elements to impart corrosion resistance are Mn, Mo, and V.

Stephens, J. R.↗

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.↗

The Role of Entrained Surface Oxides in RS-PM Aluminum Alloys on Resultant Structures and Properties

The RS-PM aluminum alloys which show less than anticipated toughness properties were studied. After eliminating negative variables such as sodium and potassium in lithium containing alloys, hydrogen in all Al alloys, and trapped impurities from the atomization processing the data pointed to fine oxides, as the primary cause of poor toughness properties. The oxide content of aluminum powders increases with: decreasing powder size, deviations from spherical powder shapes, exposure to moist atmospheres either during atomization or in subsequent powder handling, and alloy compositions which contain significant amounts of lithium, magnesium, cerium, and other reactive elements.

Grant, N. J.↗

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↗

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↗