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At least 595 records · Page 33

A sputtering derived atomic oxygen source for studying fast atom reactions

A technique for the generation of fast atomic oxygen was developed. These atoms are created by ion beam sputtering from metal oxide surfaces. Mass resolved ion beams at energies up to 60 KeV are produced for this purpose using a 150 cm isotope separator. Studies have shown that particles sputtered with 40 KeV Ar(+) on Ta2O5 were dominantly neutral and exclusively atomic. The atomic oxygen also resided exclusively in its 3P ground state. The translational energy distribution for these atoms peaked at ca 7 eV (the metal-oxygen bond energy). Additional measurements on V2O5 yielded a bimodal distribution with the lower energy peak at ca 5 eV coinciding reasonably well with the metal-oxygen bond energy. The 7 eV source was used to investigate fast oxygen atom reactions with the 2-butene stereoisomers. Relative excitation functions for H-abstraction and pi-bond reaction were measured with trans-2-butene. The abstraction channel, although of minor relative importance at thermal energy, becomes comparable to the addition channel at 0.9 eV and dominates the high-energy regime. Structural effects on the specific channels were also found to be important at high energy.

Ferrieri, Richard A.↗

On the effect of the Fe(2+)/Fe(3+) redox couple on oxidation of carbon in hot H3PO4

Oxidation studies of graphite:glassy carbon composites have been carried out at 1 and 4.7 atm. pressures in conc. H3PO4 in the presence and absence of iron ions. The concentration of the acid was varied over 85-100 wt pct, and of the iron ions over 30-300 ppm; the temperature varied over 190-210 C. Unlike the effect of Fe, which has been observed to increase the corrosion of carbon in sulphuric acid, the corrosion in phosphoric acid was observed to be slightly decreased or not at all affected. This result arises because of the catalytic reduction of the oxidized surface groups of carbon by Fe(2+) ions. The catalytic reduction is possible because under the experimental conditions the redox potential of the Fe(2+)/Fe(3+) couple is lower than the open-circuit voltage of carbon.

Dhar, H. P.↗

Seasonal cycling of sulfur and iron in porewaters of a Delaware salt marsh

An extensive pore water data set has been gathered in the Great Marsh, Delaware over various seasons, salinities, and tides. The data all point to a complimentary redox cycle for sulfur and iron which operates seasonally and tidally. Surface oxidizing conditions prevail in summer, with more reducing conditions at depth during the winter. During the spring tides which flood the marsh, pyrite oxidation occurs releasing excess dissolved iron (II) and sulfate to the porewaters, and precipitating authigenic solid iron phases. The redox conditions in the porewaters of the upper zone during the summer is poised between mildly oxidizing and mildly reducing conditions as shown by pE calculations. This redox environment and intermediate iron-sulfur redox species may be important for the stimulation of plant growth (photosynthesis) and sustenance of a viable microbial community (heterotrophy and chemoautropy).

Luther, George W., III↗

Vertical O(sub 3) distribution as a diagnostic for eddy diffusion profile

A model study of the distribution of ozone on Mars is presented. It is showed that knowledge of the vertical ozone distribution, such as could be obtained from ultraviolet measurements from an orbiter, could be used to infer vertical transport rates at various levels in the atmosphere. The dependence of the vertical distribution of O(sub 3) on the height variation of eddy diffusion coefficient is illustrated. Ozone abundance is a valuable diagnostic for other climatological parameters. In addition, the sensitivity of O(sub 3) distribution to eddy diffusion may aid in determining the role of surface oxidation and recombination processes and lead to a better understanding of the volatiles released or adsorbed cyclically in the Martian regolith.

Tyler, A. L.↗

The search for and identification of amino acids, nucleobases and nucleosides in samples returned from Mars

An investigation of the returned Mars samples for biologically important organic compounds, with emphasis on amino acid, the puring and pyrimidine bases, and nucleosides is proposed. These studies would be conducted on subsurface samples obtained by drilling past the surface oxidizing layer with emphasis on samples containing the larges quantities of organic carbon as determined by the rover gas chromatographic mass spectrometer (GCMS). Extraction of these molecules from the returned samples will be performed using the hydrothermal extraction technique described by Cheng and Ponnamperuma. More rigorous extraction methods will be developed and evaluated. For analysis of the extract for free amino acids or amino acids present in a bound or peptidic form, aliquots will be analyzed by capillary GCMS both before and after hydrolysis with 6N hydrochloric acid. Establishment of the presence of amino acids would then lead to the next logical step which would be the use of chiral stationary gas chromatography phases to determine the enatiomeic composition of the amino acids present, and thus potentially establish their biotic or abiotic origin. Confirmational analyses for amino acids would include ion-exchange and reversed-phase liquid chromatographic analysis. For analyses of the returned Mars samples for nucleobases and nucleosides, affinity and reversed-phase liquid chromatography would be utilized. This technology coupled with scanning UV detection for identification, presents a powerful tool for nucleobase and nucleoside analysis. Mass spectrometric analysis of these compounds would confirm their presence in samples returned form Mars.

Gehrke, Charles W.↗

Lithologic mapping of mafic intrusions in East Greenland using Landsat Thematic Mapper data

The East Greenland Tertiary Igneous Province contains a variety of intrusive and extrusive rock types. The Skaergaard complex is the most well known of the intrusive centers. Landsat thematic mapping (TM) was used in conjunction with field spectrometer data to map these mafic intrusions. These intrusions are of interest as possible precious metal ore deposits. They are spectrally distinct from the surrounding Precambrian gneisses. However, subpixel contamination by snow, oxide surface coatings, lichen cover and severe topography limit the discrimination of lithologic units within the gabbro. Imagery of the Skaergaard and surrounding vicinity, and image processing and enhancement techniques are presented. Student theses and other publications resulting from this work are also listed.

Naslund, H. Richard↗

ESCA study of Kapton exposed to atomic oxygen in low earth orbit or downstream from a radio-frequency oxygen plasma

The ESCA spectra of Kapton polyimide film exposed to atomic oxygen O(3P), either in low earth orbit (LEO) on the STS-8 Space Shuttle or downstream from a radio-frequency oxygen plasma, were compared. The major difference in surface chemistry induced by the two types of exposure to O(3P), both of which caused surface recession (etching), was a much larger uptake of oxygen by Kapton etched in the O2 plasma than in LEO. This difference is attributed to the presence of molecular oxygen in the plasma reactor and its absence in LEO: in the former case, O2 can react with radicals generated in the Kapton molecule as it etches, become incorporated in the etched polymer, and thereby yield a higher steady-state 'surface oxidation' level than in LEO.

Golub, Morton A.↗

Transient oxidation of single-crystal beta-NiAl

The transient oxidation of beta-NiAl in air at 800 C and 1100 C has been studied using electron microscopy. The oxide scale consists predominantly of metastable Al2O3 phases. Theta-Al2O3 is the major oxide phase within 10.0 hr of oxidation at 800 C and 0.1 hr at 1100 C. The scales form epitaxially on (001) sub beta and (012) sub beta specimens throughout the transient stage, whereas the degree of preferred oxide orientation decreases with oxidation time on (011) sub beta and (111) sub beta specimens. The orientation relationships reflect the small mismatch between parallel close-packed directions in the metal and in the cation sublattice of the oxides. The correlation of distinctive oxide surface morphologies with internal structural defects indicates the strong tendency of the Al2O3 scale to grow via short-circuit diffusion paths.

Doychak, J.↗

Applications of Landsat Thematic Mapper and ground-based spectrometer data to a study of the Skaergaard and other mafic intrusions of East Greenland

Landsat TM data have been used in conjunction with field spectrometer data to map the lithologic units associated with a series of gabbroic intrusions in the East Greenland Tertiary Igneous Province. The general lack of vegetation combined with the difficulty of access to these intrusions make them ideal candidates for lithologic mapping using remote sensing techniques. In addition, these bodies are of interest as possible precious metal ore deposits. The intrusions are spectrally distinct from the surrounding Precambrian gneisses; however, subpixel contamination by snow, oxide surface coatings, and lichen cover and severe topography limit the discrimination of lithologic units within the gabbro. The spectral nature of the surface contaminants was evaluated with a Barringer Hand Held Ratioing Radiometer (HHRR). These HHRR data indicate that bare rock exposures have distinct TM signatures for each lithologic unit but that even small amounts of subpixel contamination are enough to mask these differences because of the large differences between the TM signatures of the rocks and the contaminants.

Birnie, Richard W.↗

ESCA study of several fluorocarbon polymers exposed to atomic oxygen in low earth orbit or within or downstream from a radio-frequency oxygen plasma

The ESCA (electron spectroscopy for chemical analysis) spectra of films of Tedlar, tetrafluoroethylene-hexafluoropropylene copolymer (in the form of a Teflon FEP coating on Kapton H, i.e., Kapton F), and polytetrafluoroethylene (Teflon or Teflon TFE), exposed to atomic oxygen O(3P) either in LEO on the STS-8 Space Shuttle or within or downstream from a radio-frequency oxygen plasma, were compared. The major difference in surface chemistry of Tedlar induced by the various exposures to O(3P) was a much larger uptake of oxygen when etched either in or out of the glow of an O2 plasma than when etched in LEO. In contrast, Kapton F exhibited very little surface oxidation during any of the three different exposures to O(3P), while Teflon was scarcely oxidized.

Golub, Morton A.↗

Could organic matter have been preserved on Mars for 3.5 billion years?

About 3.5 Gyr ago, when it is thought that Mars and earth had similar climates, biological evolution on earth had made considerable progress, such that life was abundant. It is therefore surmised that prior to this time period, the advent of chemical evolution and subsequent origin of life occurred on earth and may have occurred on Mars. Analysis for organic compounds in the soil buried beneath the Martian surface may yield useful information regarding the occurrence of chemical evolution and possibly biological evolution. Calculations based on the stability of amino acids lead to the conclusion that remnants of these compounds, if they existed on Mars 3.5 Gyr ago, might have been preserved buried beneath the surface oxidizing layer. For example, if phenylalanine, an amino acid of average stability, existed on Mars 3.5 Gyr ago, then 1.6 percent would remain buried today. Martian soil may exist from remnants of meteoritic and cometary bombardment, assuming that 1 percent of the organics survived impact.

Kanavarioti, Anastassia↗

The effect of nitrogen on xenon ion engine erosion

Erosion studies were performed on a 30-cm diameter J-series ion engine modified for operation on xenon propellant. The erosion rates of molybdenum and tantalum badges placed at different locations within the discharge chamber were measured as a function of the percentage of nitrogen (by mass) added to the xenon propellant. Reductions in the erosion rates of these badges of a factor of 8 to 50 were observed at nitrogen addition fractions between 0.5 to 2.0 percent. Reductions in cathode-side baffle erosion were achieved by adding nitrogen to the xenon propellant or by increasing the cathode orifice diameter. Analyses show that no significant degradation in ion engine performance should be expected at these nitrogen mass fractions. XRD, XPS and Auger analyses indicate the existence of nitrogen and nitrides in the surface of some but not all of the badges used in the tests where nitrogen was added to the xenon. Difficulty in identifying surface nitrides in the samples may be due to the existence of surface oxides and contaminants, or to the small thicknesses of the nitride layers.

Garner, Charles E.↗

Titanium aluminides - Surface composition effects as a function of temperature

Results are presented from an AES investigation of the surface characteristics of pure Ti, Ti-14Al-21Nb (alpha-2 aluminide), and Ti-33Al-6Nb-1.4Ta (gamma aluminide) under ultrahigh vacuum conditions over the 20-1000 C temperature range. The observed variations in surface composition are noted to be dramatic and indicative of a direct relationship between the amount of retained oxygen and carbon on the surface and the quantity of Al in that surface's vicinity. While TiO2 was the main surface oxide for pure Ti and the alpha-2 and gamma aluminides, only metallic peaks were observable at 600 C; at 1000 C, metallic Al and Ti were observed.

Outlaw, R. A.↗

Paleobiomarkers and defining exobiology experiments for future Mars experiments

Mars is a cold, dry planet with an oxidizing surface bombarded by ultraviolet and ionizing radiation, making prospects for an extant Mars biota bleak. Yet, it is suggested that early Earth and early Mars were similar enought that life may have evoled on Mars. If life did evolve on Mars, what evidence for its existence might we find? What constitutes a Martian paleobiomarker, and how can we distinguish such a marker from abiotically produced substances? The topics studied to answer this question include carbon and nitrogen cycling, as well as the stability and relative abundance of their intermediates in microbially dominated ecosystems. The microbially dominated ecosystems studied are the crytoendolithic microbial community living within sand rocks, the endoevaporite microbial community living inside salt crystals, and the microbial communities living beneath perennially ice-covered lakes and hypersaline ponds. The nitrogen cycle of these communities ranges from simple, where only assimilation occurs, to the more complex, where a complete cycle occurs. The carbon cycle of these communities appears to be complete.

Mancinelli, R. L.↗

Venus: The case for a wet origin and a runaway greenhouse

To one interested in atmospheric evolution, the most intriguing aspect of our neighboring planet Venus is its lack of water. Measurements made by Pioneer Venus and by Several Venera spacecraft indicate that the present water abundance in Venus' lower atmosphere is of the order of 20 to 200 ppmv, or 3 x 10( exp -6) to 3 x 10 (exp -5) of the amount of water in Earth's oceans. The exact depletion factor is uncertain, in part because of an unexplained vertical gradient in H2O concentration in the lowest 10 km of the venusian atmosphere, but the general scarcity of water is well established. The interesting question, then, is: Was venus deficient in water when it formed and, if not, where did its water go? The conclusion that Venus was originally wet is consistent with its large endowment of other volatiles and with the enhanced D/H ratio in the present atmosphere. The most likely mechanism by which Venus could have lost its water is by the development of a runaway or moist greenhouse atmosphere followed by photodissociation of water vapor and escape of hydrogen to space. Climate model calculations that neglect cloud albedo feedback predict the existence of two critical transitions in atmospheric behavior at high solar fluxes: (1) at a solar flux of approximately 1.1 times the value at Earth's orbit, S(o), the abundance of stratospheric water vapor increases dramatically, permitting rapid escape of hydrogen to space (termed a moist greenhouse) and (2) at a solar flux of approximately 1.4 S(o), the oceans vaporize entirely, creating a true runaway greenhouse. If cloudiness increases at high surface temperatures, as seems likely, and if the dominant effect of clouds is to cool the planet by reflecting incident solar radiation, the actual solar flux required to create moist or runaway conditions would be higher than the values quoted above. Early in solar system history, solar luminosity was about 25 percent to 30 percent less than today, putting the flux at Venus' orbit in the range of 1.34 S(o) to 1.43 S(o). Thus, it is possible that Venus had liquid water on its surface for several hundred million years following its formation. Paradoxically, this might have facilitated water loss by sequestering atmospheric CO2 in carbonate rocks and by providing an effective medium for surface oxidation.

Kasting, J. F.↗

Desulfurization Of Gas-Turbine Blades

Sulfur removed from nickel-base superalloy used to make gas-turbine blades by heating alloy and simultaneously subjecting it to sputtering by directed Ar(Sup+) ions from ion gun or from glow discharge. Reduction of sulfur content of superalloy by factor of 10 increases lifetime of turbine blade made of alloy by similar factor, because stability of protective surface oxide formed during operation of turbine increased.

Outlaw, Ronald A.↗

The friction and wear of ceramic/ceramic and ceramic/metal combinations in sliding contact

The tribological characteristics of ceramics sliding on ceramics are compared to those of ceramics sliding on a nickel based turbine alloy. The friction and wear of oxide ceramics and silicon-based ceramics in air at temperatures from room ambient to 900 C (in a few cases to 1200 C) were measured for a hemispherically-tipped pin on a flat sliding contact geometry. In general, especially at high temperature, friction and wear were lower for ceramic/metal combinations than for ceramic/ceramic combinations. The better tribological performance for ceramic/metal combinations is attributed primarily to the lubricious nature of the oxidized surface of the metal.

Sliney, Harold E.↗

Matrix isolation studies of the interactions of BF3 with water and substituted diethyl ethers. Chemical ionization mass spectrometric determination of the proton affinity of (CF3CH2)2O

BF3 was co-condensed with H2O, D2O, (C2H5)2O, (CF3CH2)2O, and (C2F5)2O in excess argon at 15 K. Infrared spectra of BF3/water isolated in solid argon provided a more complete analysis of the BF3--H2O complex than previously published. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis (2,2,2-trifluorodiethyl) ether, and no observable interaction with perfluorodiethyl ether. Thus, the ether data indicate a clear trend between strength of interaction with BF3 and the degree of F substitution. To support and explain the emerging relationship between interaction strength and the basicity of the oxygen-containing molecule, the proton affinity of (CF3CH2)2O was measured using chemical ionization mass spectrometry. The implications of the results for lubricant/metal oxide surface interactions are discussed.

Ball, David W.↗