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Indigenous Carbon Embedded in Apollo 17 Black Volcanic Glass Surface Deposits

The assessment of indigenous organic matter in returned lunar samples was one of the primary scientific goals of the Apollo program. The levels of such organic material were expected to be and found to be small. Previous work on this topic includes Murphy et al. [1] who reported the presence of anthropogenic organics with sub-ppm concentrations in Apollo 11 fines. In Apollo 12 samples, Preti et al. [2] detected low levels, < 10 ppb or below, of more complex organic material that may have been synthesized by abrupt heating during analysis. Kvenvolden et al. [3] detected porphyrin-like pigments at the ng to pg level in an Apollo 11 bulk sample. Hodgson et al. [4] and Ponnamperuma et al. [5] suggested that most if not all porphyrins were synthesized from rocket fuel during module landing. Chang et al. [6] reported indigenous carbon ranging from 5-20 g/g in the form of metal carbides in Apollo 11 fines. Hare et al. [7] reported amino acids at he 50 ng/g level in Apollo 11 samples but suggested the results may be explained as contamination. More recently, Clemett et al. [8] reported simple polycyclic aromatic hydrocarbons at concentrations of < 1ppm in an Apollo 16 soil. Low concentrations of lunar organics may be a consequence not only of its paucity, but also its heterogeneous distribution. If the sample size required for a measurement is large relative to the localization of organics, detection is limited not by ultimate sensitivity but rather by the ability to distinguish an indigenous signature from background contamination [9].

Thomas-Keprta, Kathie L.↗

Indigenous Carbonaceous Phases Embedded Within Surface Deposits on Apollo 17 Volcanic Glass Beads

The assessment of indigenous organic matter in returned lunar samples was one of the primary scientific goals of the Apollo program. Prior studies of Apollo samples have shown the total amount of organic matter to be in the range of approx 50 to 250 ppm. Low concentrations of lunar organics may be a consequence not only of its paucity but also its heterogeneous distribution. Several processes should have contributed to the lunar organic inventory including exogenous carbonaceous accretion from meteoroids and interplanetary dust particles, and endogenous synthesis driven by early planetary volcanism and cosmic and solar radiation.

Thomas-Keprta, K. L.↗

High atmospheric NO(x) levels and multiple photochemical steady states

The rate of removal of atmospheric NO(x) compounds at different NO(x) levels is estimated using a one-dimensional photochemical model. NO(x) removal by wet deposition, surface deposition, and thermochemical processes is examined. NO(x) removal rates at different surface NO mixing ratios are calculated and the data are analyzed. It is revealed that at low NO(x) levels NO(x) is photochemically converted to HNO3 by either wet or dry deposition; however, at high NO(x) levels formation of HNO3 is inhibited due to the disappearance of tropospheric ozone and OH, and the NO(x) is removed by rainout of N2O4 and N2O5, surface deposition of NO and NO2, and direct dissolution of NO and NO2 in rainwater. The effects of NO(x) mixing ratios greater than 10 to the -7th on the ozone and climate are investigated.

Kasting, J. F.↗

Emission FTIR analyses of thin microscopic patches of jet fuel residue deposited on heated metal surface

Deposits laid down in patches on metal strips in a high pressure/high temperature fuel system simulator operated with aerated fuel at varying flow rates were analyzed by emission FTIR in terms of functional groups. Significant differences were found in the spectra and amounts of deposits derived from fuels to which small concentrations of oxygen-, nitrogen-, or sulfur-containing heterocyclics or metal naphthenates were added. The spectra of deposits generated on strips by heating fuels and air in a closed container were very different from those of the flowing fluid deposits. One such closed-container dodecane deposit on silver gave a strong surface-enhanced Raman spectrum.

Lauer, J. L.↗

Ion-Plated Soft Metallic Films Reduce Friction and Wear

Ion plating is ion-assisted or glow-discharge surface-deposition technique. In this process, ions or energetic atoms transfer energy, momentum, and charge to substrate and deposited surface film. Process controlled to modify physical characteristics of surface, subsurface chemical conditions, and surface and subsurface microstructures as well. Ion plating with such soft, thin metallic films as gold, silver, or lead has great potential for producing self-contained lubricating surfaces. Such films reduce friction, wear, and corrosion on sliding or rotating mechanical surfaces used in wide range of environments.

Spalvins, T.↗

Friction surfacing and cold spray deposition for surface crack repair in austenitic stainless steels

Two technologies, friction surfacing (FS) and cold spray deposition (CSD), have been investigated for field repair of cracks in 304L austenitic stainless steel. Both technologies are low-heat-input, solid-state technologies that do not introduce the detrimental effects of solidification, such as compositionally segregated microstructures and shrinkage stresses. Friction surfacing was performed using a 304L stainless steel rod over the substrate of the same material. Further, the process was performed at a high spindle speed of 20,000 RPM allowing for process forces below 500N to be used effectively. Spherical gas-atomized 304L stainless steel powder, in size range of 25–44 µm, was used as feedstock powder for the cold spray process for deposition on 304L substrates. Both technologies showed leak-tight crack repair capabilities on ~30–50 µm wide simulated through-crack specimens based on helium leak tests.

36 MATERIALS SCIENCE↗

A morphological study of silicon carbide prepared by chemical vapor deposition

Surface morphologies of SiC deposits obtained via chemical vapor deposition (CVD) were studied as functions of substrate surface temperature and the concentration of the silicon and carbon source material, methyltrichlorosilane. Substrates of graphite and alpha-SiC crystals were used. Explanations of the observed morphologies on graphite substrates and their marked changes with temperature are given in terms of chemical kinetics and mass transport arguments. The results of thermodynamic calculations were used to help explain the observed morphologies of the deposits on alpha-SiC substrates.

Tsui, P.↗

Carbon nanotubes decorated with Pt as a viable electrocatalyst system using electrochemical atomic layer deposition

Surface limited redox replacement (SLRR) is an electrochemical deposition method designed to deposit metal thin films, typically onto other metals, that are mere monolayers in thickness, where such low dimensions allows catalyst-support interactions to affect catalyst efficiency. Here we explore the growth of Pt, using iterative Cu-mediated SLRR cycles, directly onto carbon nanotubes (CNTs) which are potentially good candidates as electrocatalyst supports due to their electrical conductivity and chemical resistance. Here scanning electron microscope images showed that Pt grew as nanoparticles, and hydrogen underpotential deposition from cyclic voltammetry showed that the active surface area approached an asymptotic value around eight iterations. Catalytic activity, measured using the oxygen reduction reaction, reached a maximum at ten iterations. Both are shown to be influenced by the growth mode, but electrochemical modeling indicates that the trend in activity is also due to a change in activation energy, possibly due to changes in Pt electronic structure due to interactions with the CNTs. Durability cycling showed a greater than 85% retention of surface area for the first 10,000 cycles of accelerated stress testing but decayed steadily to about 50% after 30,000 cycles. This performance may be related to the phenomenon that limits surface area growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Coatings on Lunar Volcanic Glasses

We are undertaking a detailed study of surface deposits on lunar volcanic glass beads. These tiny deposits formed by vapor condensation during cooling of the gases that drove the fire fountain eruptions responsible for the formation of the beads. Volcanic glass beads are present in most lunar soil samples in the returned lunar collection. The mare-composition beads formed as a result of fire-fountaining approx.3.4-3.7 Ga ago, within the age range of large-scale mare volcanism. Some samples from the Apollo 15 and Apollo 17 landing sites are enriched in volcanic spherules. Three major types of volcanic glass bead have been identified: Apollo 15 green glass, Apollo 17 orange glass, and Apollo 17 "black" glass. The Apollo 15 green glass has a primitive composition with low Ti. The high-Ti compositions of the orange and black glasses are essentially identical to each other but the black glasses are opaque because of quench crystallization. A poorly understood feature common to the Apollo 15 and 17 volcanic glasses is the presence of small deposits of unusual materials on their exterior surfaces. For example, early studies indicated that the Apollo 17 orange glasses had surface enrichments of In, Cd, Zn, Ga, Ge, Au, and Na, and possible Pb- and Zn-sulfides, but it was not possible to characterize the surface features in detail. Technological advances now permit us to examine such features in detail. Preliminary FE-TEM/X-ray studies of ultramicrotome sections of Apollo 15 green glass indicate that the surface deposits are heterogeneous and layered, with an inner layer consisting of Fe with minor S and an outer layer of Fe and no S, and scattered Zn enrichments. Layering in surface deposits has not been identified previously; it will be key to defining the history of lunar fire fountaining.

Wentworth, Susan J.↗

Differential Deposition for Surface Figure Corrections in Grazing Incidence X-Ray Optics

Differential deposition corrects the low- and mid- spatial-frequency deviations in the axial figure of Wolter-type grazing incidence X-ray optics. Figure deviations is one of the major contributors to the achievable angular resolution. Minimizing figure errors can significantly improve the imaging quality of X-ray optics. Material of varying thickness is selectively deposited, using DC magnetron sputtering, along the length of optic to minimize figure deviations. Custom vacuum chambers are built that can incorporate full-shell and segmented Xray optics. Metrology data of preliminary corrections on a single meridian of full-shell x-ray optics show an improvement of mid-spatial frequencies from 6.7 to 1.8 arc secs HPD. Efforts are in progress to correct a full-shell and segmented optics and to verify angular-resolution improvement with X-ray testing.

X-Ray Optics↗

Io - A surface evaporite deposit

A model is suggested for Io's surface composition involving evaporite salt deposits, rich in sodium and sulfur. According to this model, these deposits were produced as a result of the migration of salt-saturated aqueous solutions to Io's surface from a warm or hot interior followed by loss of the water to space. This model satisfies cosmochemical constraints based on Io's initial composition, current density, and thermal history. Salt-rich assemblages are easily derivable from the leaching of carbonaceous chondritic material. The chemical and optical properties of such deposits, after modification by irradiation, can be used to explain Io's overall albedo and spectral reflectance, its dark reddish poles, and the observed sodium emission as well as or better than other currently suggested materials.

Fanale, F. P.↗

An evaluation of the regional acid deposition model surface module for ozone uptake at three sites in the San Joaquin Valley of California

Plants and soils act as major sinks for the destruction of tropospheric ozone, especially during daylight hours when plant stomata open and are thought to provide the dominant pathway for the uptake of ozone. The present study, part of the California Ozone Deposition Experiment, compares predictions of the regional acid deposition model ozone surface conductance module with surface conductance data derived from eddy covariance measurements of ozone flux taken at a grape, a cotton, and a grassland site in the San Joaquin Valley of California during the summer of 1991. Results indicate that the model (which was developed to provide long-term large-area estimates for the eastern United States) significantly overpredicts the surface conductance at all times of the day for at least two important types of plant cover of the San Joaquin Valley and that it incorrectly partitions the ozone flux between transpiring and nontranspiring components of the surface at the third site. Consequently, the model either overpredicts or inaccurately represents the observed deposition velocities. Other results indicate that the presence of dew does not reduce the rate of ozone deposition, contradicting to model assumptions, and that model assumptions involving the dependency of stomata upon environmental temperature are unnecessary. The effects of measurement errors and biases, arising from the presence of the roughness sublayer and possible photochemical reactions, are also discussed. A simpler model for ozone surface deposition (at least for the San Joaquin Valley) is proposed and evaluated.

Massman, W. J.↗

Monitor senses amount of contamination deposited on surfaces

Monitoring device detects and indicates directly the amount of contamination deposited on a surface. It uses an optical system in conjunction with a reliable collimated light source and associated electronics. Change in its output signal is proportional to change in the optical absorption characteristics of the sample plate surface.

Sheehy, R. N.↗

Outgassing Measurements for Three Materials, Combined with Vacuum Ultraviolet Radiation Illumination of the Volatile Condensable Materials

The photolysis of three organic materials, by vacuum ultraviolet (VUV) radiation, has been quantified using 15-MHz temperature-controlled quartz microbalances (TQCM's). The rate at which molecular species, released from the individual samples, condensed on two TQCM s was measured for periods of up to 139.9-hours. The individual samples were heated in an effusion cell and the emitted molecular species collected on a pair of TQCM's which were maintained at -40 degrees Celsius. At several points during the deposition measurement, the deposition surface of one TQCM was illuminated by a 30 Watt deuterium lamp, and the loss of material from that surface was observed. V W illumination of the TQCM, concurrent with condensation, reduced the rate that material was lost from the deposition surface. These measurements present a contrasting picture of molecular deposition, in the presence of VUV, to that presented by other investigators who observed an enhanced rate of molecular deposition, when the deposition surface was illuminated by VUV.

Albyn, Keith↗

Sierpinski Structure and Electronic Topology in Bi Thin Films on InSb(111)B Surfaces

Deposition of Bi on InSb(111)B reveals a striking Sierpinski-triangle (ST)-like structure in Bi thin films. Such a fractal geometric topology is further shown to turn off the intrinsic electronic topology in a thin film. Relaxation of a huge misfit strain of about 30 to 40% between Bi adlayer and substrate is revealed to drive the ST-like island formation. A Frenkel-Kontrova model is developed to illustrate the enhanced strain relief in the ST islands offsetting the additional step energy cost. Besides a sufficiently large tensile strain, forming ST-like structures also requires larger adlayer-substrate and intra-adlayer elastic stiffnesses, and weaker intra-adlayer interatomic interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗