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Space Weathering in the Fine Size Fractions of Lunar Soils: Soil Maturity Effects

The effects of space weathering on the optical properties of lunar materials have been well documented. These effects include a reddened continuum slope, lowered albedo, and attenuated absorption features in reflectance spectra of lunar soils as compared to finely comminuted rocks from the same Apollo sites. However, the regolith processes that cause these effects are not well known, nor is the petrographic setting of the products of these processes fully understood. A Lunar Soil Characterization Consortium has been formed with the purpose of systematically integrating chemical and mineralogical data with the optical properties of lunar soils. Understanding space-weathering effects is critical in order to fully integrate the lunar sample collection with remotely-sensed data from recent robotic missions (e.g., Lunar Prospector, Clementine, and Galileo) We have shown that depositional processes (condensation of impact-derived vapors, sputter deposits, accreted impact material, e.g., splash glass, spherules, etc.) are a major factor in the modification of the optical surfaces of lunar regolith materials. In mature soils, it is the size and distribution of the nanophase metal in the soil grains that has the major effect on optical properties. In this report, we compare and contrast the space-weathering effects in an immature and a mature soil with similar elemental compositions. For this study, we analyzed <10 micron sieve fractions of two Apollo 17 soils, 79221 (mature, Is/FeO = 81) and 71061 (immature, Is/FeO = 14). Details of the sieving procedures and allocation scheme are given else where. The results of other detailed chemical, mineralogical, and spectroscopic analyses of these soil samples are reported elsewhere. A representative sample of each soil was embedded in low-viscosity epoxy, and thin sections (about 70nm thick) were obtained through ultra microtomy. The thin sections used for these analyses typically contained cross sections of up to 500 individual grains. The thin sections were studied using a JEOL 2010 transmission electron microscope (TEM) equipped with a thin window energy-dispersive X-ray (EDX) spectrometer. An individual thin section was selected from each soil, and for each grain in the section we determined (1) the elemental composition by EDX; (2) whether the grain was crystalline or glassy using electron diffraction and darkfield imaging; (3) the presence or absence of rims and accreted material; and (4) the distribution of nanophase Fe where present. Most of the categories are self-evident; however, we divide the agglutinate derived material into agglutinitic glass (glass with approximately the same composition as the bulk soil that contains nanophase Fe with or without vesicles) and agglutinate fragments, which are composed of crystalline grains and agglutinitic glass. Lithic fragments are defined as polymineralic grains with no glass. Pyroxene grains have been divided into high- and low-Ca groups. As expected, there are a number of differences in the petrography of the <10-microns fractions of 79221 and 71061 given the great difference in their respective maturities, but we focus here on two major distinctions: agglutinate content and the number of grains with micropatina. Slightly over 50% of the particles in 79221 consist of agglutinitic glass and agglutinate fragments, while the remainder are predominantly crystalline mineral grains. The agglutinic glass particles contain abundant nanophase Fe and vesicles. Angular particles are rare, with most showing smooth, rounded exteriors, Of the mineral grains analyzed thus far, over 90% of the grains have amorphous rims that contain nanophase Fe (these rims are believed to have formed by vapor deposition and irradiation effects). The nanophase Fe in these rims probably accounts for a significant fraction of the increase in Is/FeO measured in these size fractions. In addition to the rims, the majority of particles also show abundant accreted material in the form of glass splashes and spherules that also contain nanophase Fe. In stark contrast, the surfaces of the mineral grains in the 71061 sample are relatively prisitine, as only about 14% of the mineral grains in the sample exhibited amorphous rims. Furthermore, the mineral particles are more angular and show greater surface roughness than in the mature sample. Accreted material on particle surfaces is rare. Agglutinitic material is a major component of the 71061 sample; however, nanophase Fe and vesicles are not as well developed as in the 79221 sample. It is now recognized that nanophase Fe is probably the main agent in modifying the optical properties of lunar soil grains. The most important result of this study is the observation that in the fine size fractions of mature soils, nearly every grain has nanophase Fe within 100 run of the particle surface. (Additional Information contained in original)

Keller, L. P.↗

Influence of the microstructure on the corrosion behavior of magnetron sputter-quenched amorphous metallic alloys

The microstructure and corrosion behavior of magnetron sputter deposited amorphous metallic films of (Mo6ORu40)82B18 under varying sputtering atmospheres have been investigated. The microstructural details and topology of the films have been studied by scanning electron microscopy and correlated with the deposition conditions. By reducing the pressure of pure argon gas, the characteristic features of rough surface and columnar growth full of vertical voids can be converted into a mirror-smooth finish with very dense deposits. Films deposited in the presence of O2 or N2 exhibit columnar structure with vertical voids. Film deposited in pure argon at low pressure show remarkably high corrosion resistance due to the formation of a uniform passive surface layer. The influence of the microstructure and surface texture on the corrosion behavior is discussed.

Thakoor, A. P.↗

Development of sputtering process to deposit stoichiometric zirconia coatings for the inside wall of regeneratively cooled rocket thrust chambers

Thermal barrier coatings of yttria stabilized zirconia and zirconia-ceria mixtures were deposited by RF reactive sputtering. Coatings were 1-2 mils thick, and were deposited on copper cylinders intended to simulate the inner wall of a regeneratively cooled thrust chamber. Coating stoichiometry and adherence were investigated as functions of deposition parameters. Modest deposition rates (approximately 0.15 mil/hr) and subambient sustrate temperatures (-80 C) resulted in nearly stoichiometric coatings which remained adherent through thermal cycles between -196 and 400 C. Coatings deposited at higher rates or substrates temperatures exhibited greater oxygen deficiences, while coatings deposited at lower temperatures were not adherent. Substrate bias resulted in structural changes in the coating and high krypton contents; no clear effect on stoichiometry was observed.

Busch, R.↗

Application of ESCA to the determination of stoichiometry in sputtered coatings and interface regions

X-ray photoelectron spectroscopy was used to characterize radiofrequency sputter deposited films of several refractory compounds. Both the bulk film properties such as purity and stoichiometry and the character of the interfacial region between the film and substrate were examined. The materials were CrB2, MoS2, Mo2C, and Mo2B5 deposited on 440C steel. It was found that oxygen from the sputtering target was the primary impurity in all cases. Biasing improves the film purity. The effect of biasing on film stoichiometry is different for each compound. Comparison of the interfacial composition with friction data suggests that adhesion of these films is improved if a region of mixed film and iron oxides can be formed.

Wheeler, D. R.↗

Application of ESCA to the determination of stoichiometry in sputtered coatings and interface regions

X-ray Photoelectron Spectroscopy (XPS) was used to characterize radiofrequency sputter deposited films of several refractory compounds. Both the bulk film properties such as purity and stoichiometry and the character of the interfacial region between the film and substrate were examined. The materials were CrB2, MoS2, Mo2C, and Mo2B5 deposited on 440C steel. It was found that oxygen from the sputtering target was the primary impurity in all cases. Biasing improves the film purity. The effect of biasing on film stoichiometry is different for each compound. Comparison of the interfacial composition with friction data suggests that adhesion of these films is improved if a region of mixed film and iron oxides can be formed.

Wheeler, D. R.↗

Design and Operation of a Fast, Thin-Film Thermocouple Probe on a Turbine Engine

As a demonstration of technology maturation, a thin-film temperature sensor probe was fabricated and installed on a F117 turbofan engine via a borescope access port to monitor the temperature experienced in the bleed air passage of the compressor area during an engine checkout test run. To withstand the harsh conditions experienced in this environment, the sensor probe was built from high temperature materials. The thin-film thermocouple sensing elements were deposited by physical vapor deposition using pure metal elements, thus avoiding the inconsistencies of sputter-depositing particular percentages of materials to form standardized alloys commonly found in thermocouples. The sensor probe and assembly were subjected to a strict protocol of multi-axis vibrational testing as well as elevated temperature pressure testing to be qualified for this application. The thin-film thermocouple probe demonstrated a faster response than a traditional embedded thermocouple during the engine checkout run.

thermocouples↗

Thin Film Catalyst Layers for Direct Methanol Fuel Cells

One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.

Witham, C. K.↗

Ion beam sputter etching and deposition of fluoropolymers

Fluoropolymer etching and deposition techniques including thermal evaporation, RF sputtering, plasma polymerization, and ion beam sputtering are reviewed. Etching and deposition mechanism and material characteristics are discussed. Ion beam sputter etch rates for polytetrafluoroethylene (PTFE) were determined as a function of ion energy, current density and ion beam power density. Peel strengths were measured for epoxy bonds to various ion beam sputtered fluoropolymers. Coefficients of static and dynamic friction were measured for fluoropolymers deposited from ion bombarded PTFE.

Banks, B. A.↗

Ion beam sputter etching and deposition of fluoropolymers

Fluoropolymer etching and deposition techniques including thermal evaporation, RF sputtering, plasma polymerization, and ion beam sputtering are reviewed. Etching and deposition mechanisms and material characteristics are discussed. Ion beam sputter etch rates for polytetrafluoroethylene (PTFE) were determined as a function of ion energy, current density and ion beam power density. Peel strengths were measured for epoxy bonds to various ion beam sputtered fluoropolymers. Coefficients of static and dynamic friction were measured for fluoropolymers deposited from ion bombarded PTFE.

Banks, B. A.↗

Durability Issues for the Protection of Materials from Atomic Oxygen Attack in Low Earth Orbit

Low Earth orbital atomic oxygen is capable of eroding most polymeric materials typically used on spacecraft. Solar array blankets, thermal control polymers, and carbon fiber matrix composites are readily oxidized to become thinner and less capable of supporting the loads imposed upon them. Protective coatings have been developed that are durable to atomic oxygen to prevent oxidative erosion of the underlying polymers. However, the details of the surface roughness, coating defect density, and coating configuration can play a significant role as to whether or not the coating provides long duration atomic oxygen protection. Identical coatings on different surface roughness surfaces can have drastically different durability results. Examples and analysis of the causes of resultant differences in atomic oxygen protection are presented. Implications based on in-space experiences, ground laboratory testing, and computational modeling indicate that thin film vacuum-deposited aluminum protective coatings offer much less atomic oxygen protection than sputter-deposited silicon dioxide coatings.

Banks, Bruce↗

Surface acoustic wave/silicon monolithic sensor/processor

A new technique for sputter deposition of piezoelectric zinc oxide (ZnO) is described. An argon-ion milling system was converted to sputter zinc oxide films in an oxygen atmosphere using a pure zinc oxide target. Piezoelectric films were grown on silicon dioxide and silicon dioxide overlayed with gold. The sputtered films were evaluated using surface acoustic wave measurements, X-ray diffraction, scanning electron microscopy, Auger electron spectroscopy, and resistivity measurements. The effect of the sputtering conditions on the film quality and the result of post-deposition annealing are discussed. The application of these films to the generation of surface acoustic waves is also discussed.

Kowel, S. T.↗

Carbon Shields for Intercalated Fiber Conductors

Stability in air increased by depositing amorphous carbon. Initially graphite fibers intercalated (insertion of atoms or molecules between graphite layers). Next, conductor coated with diamondlike amorphous carbon. Coating applied in same chamber as intercalation reaction or alternate deposichamber is used. Deposition of carbon accomplished by any number of techniques. tion Ion-beam sputter-deposition and RF plasma techniques have been used, but dc plasma and others work also. Potential uses include conductive epoxy composites, tether conductors, signal wire, and power cables.

Banks, B. A.↗

NSTAR Extended Life Test Discharge Chamber Flake Analysis

The Extended Life Test (ELT) of the NASA Solar Electric Propulsion Technology Readiness (NSTAR) ion thruster was concluded after 30,352 hours of operation. The ELT was conducted using the Deep Space 1 (DS1) back-up flight engine, a 30 cm diameter xenon ion thruster. Post-test inspection of the ELT engine revealed numerous contaminant flakes distributed over the bottom of the cylindrical section of the anode within the discharge chamber (DC). Extensive analyses were conducted to determine the source of the particles, which is critical to the understanding of degradation mechanisms of long life ion thruster operation. Analyses included: optical microscopy (OM) and particle length histograms, field emission scanning electron microscopy (FESEM) combined with energy dispersive spectroscopy (EDS), and atomic oxygen plasma exposure tests. Analyses of the particles indicate that the majority of the DC flakes consist of a layered structure, typically with either two or three layers. The flakes comprising two layers were typically found to have a molybdenum-rich (Mo-rich) layer on one side and a carbon-rich (C-rich) layer on the other side. The flakes comprising three layers were found to be sandwich-like structures with Mo-rich exterior layers and a C-rich interior layer. The presence of the C-rich layers indicates that these particles were produced by sputter deposition build-up on a surface external to the discharge chamber from ion sputter erosion of the graphite target in the test chamber. This contaminant layer became thick enough that particles spalled off, and then were electro-statically attracted into the ion thruster interior, where they were coated with Mo from internal sputter erosion of the screen grid and cathode components. Atomic oxygen tests provided evidence that the DC chamber flakes are composed of a significant fraction of carbon. Particle size histograms further indicated that the source of the particles was spalling of carbon flakes from downstream surfaces. Analyses of flakes taken from the downstream surface of the accelerator grid provided additional supportive information. The production of the downstream carbon flakes, and hence the potential problems associated with the flake particles in the ELT ion thruster engine is a facility induced effect and would not occur in the space environment.

deGroh, Kim K.↗

Effects of microstructure and nonstoichiometry on electrical properties of vanadium dioxide films

Voided growth structures of sputter-deposited films affect strongly their optical and electrical properties. Vanadium dioxide is an interesting material to study effects of film microstructure and nonstoichiometry on electrical properties because its phase transition makes it possible to investigate electrical behavior both in a semiconducting phase and in a metallic phase. Vanadium oxide films were deposited with different vanadium oxygen ratios for substrate temperatures between 250 and 550 C by dc reactive magnetron sputtering. The resistivity ratios between a semiconducting phase and a metallic phase are limited to 1000 order by voided boundaries and oxygen vacancies. The voided boundaries are defined by columnar structure and agglomerated grain growth. The results emphasize the necessity of a combination of deposition to obtain the film with a favorable structure and postdeposition annealing to control the film stoichiometry.

Kusano, Eiji↗

Tribological properties of sputtered MoS sub 2 films in relation to film morphology

Thin sputter deposited MoS2 films in the 2000 to 6000 A thickness range have shown excellent lubricating properties, when sputtering parameters and substrate conditions are properly selected and precisely controlled. The lubricating properties of sputtered MoS2 films are strongly influenced by their crystalline-amorphous structure, morphology and composition. The coefficient of friction can range from 0.04 which is effective lubrication to 0.4 which reflects an absence of lubricating properties. Visual screening and slight wiping of the as-sputtered MoS2 film can identify the integrity of the film. An acceptable film displays a black-sooty surface appearance whereas an unacceptable film has a highly reflective, gray surface and the film is hard and brittle.

Spalvins, T.↗

Tribological properties of sputtered MoS2 films in relation to film morphology

Thin sputter-deposited MoS2 films with thicknesses ranging from 2000 to 6000 A have shown excellent lubricating properties when sputtering parameters and substrate conditions are properly selected and controlled. The lubricating properties are strongly influenced by the crystalline-amorphous structure, morphology, and composition of the films. The coefficient of friction can range from 0.04 (which is effective lubrication) to 0.4 (no lubricating action).

Spalvins, T.↗

On the sputter alteration of regoliths of outer solar system bodies

Several processes that are expected to occur when the porous regoliths of outer solar system bodies (without atmospheres) are subjected to energetic ion bombardment are discussed. The conclusions reached in much of the literature addressing sputtering are quantitatively or qualitatively incorrect because effects of soil porosity have been neglected. It is shown theoretically and experimentally that porosity reduces the effective sputtering yield of a soil by more than an order of magnitude. Between 90 and 97% of the sputtered atoms are trapped within the regolith, where they are factionated by differential desorption. Experiments indicate that more volatile species have higher desorption probabilities. This process is the most important way in which alteration of chemical and optical properties occurs when a regolith is sputtered. When a basic silicate soil is irradiated these effects lead to sputter-deposited films enriched in metallic iron, while O, Na and K are preferentially lost. The Na and K are present in the atmosphere above the sputtered silicate in quantities much greater than their abundances in the regolith. Icy regoliths of SO2 should be enriched in elemental S and/or S2O. This prediction is supported by the probable identification of S2O and polysulfur oxide bands in the IR spectra of H-sputtered SO2 reported by Moore. When porous mixtures of water, ammonia and methane frosts are sputtered, the loss of H and surface reactions of C, N and O in the deposits should produce complex hydrocarbons and carbohydrates, some of which may be quite dark. Such reactions may have played a role in the formation of the matrix material of carbonaceous chondrites prior to agglomeration.

Hapke, Bruce↗

Physical processes in directed ion beam sputtering

The general operation of a discharge chamber for the production of ions is described. A model is presented for the magnetic containment of both primary and secondary or Maxwellian electrons in the discharge plasma. Cross sections were calculated for energy and momentum transfer in binary collisions between like pairs of Ar, Kr, and Xe atoms in the energy range from about 1 eV to 1000 eV. These calculations were made from available pair interaction potentials using a classical model. Experimental data from the literature were fit to a theoretical expression for the Ar resonance charge exchange cross section over the same energy range. A model was developed that describes the processes of conical texturing of a surface due to simultaneous directed ion beam etching and sputter deposition of an impurity material. This model accurately predicts both a minimum temperature for texturing to take place and the variation of cone density with temperature. It also provides the correct order of magnitude of cone separation. It was predicted from the model, and subsequently verified experimentally, that a high sputter yield material could serve as a seed for coning of a lower sputter yield substrate. Seeding geometries and seed deposition rates were studied to obtain an important input to the theoretical texturing model.

Robinson, R. S.↗