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At least 433 records · Page 24

Erosion Behavior of Ti-hBN Multifunctional Coatings in A Custom-Made Planetary Test Rig at Extreme Lunar Temperatures

Spacecraft landings and takeoffs on the lunar surface, along with extreme temperature variations between day and night (-196 to 150° C), cause high-velocity dust impacts and erosion, resulting in the premature failure of structures. Ti/2 vol% hBN coatings were deposited using atmospheric (APS) and vacuum plasma spray (VPS) using cryo-milled powder feedstock to protect the structural components. The erosion performance of coatings at extreme lunar temperature regimes (-150 to 150° C) was evaluated in a custom-made planetary erosion test rig (PETR) at low (50 mph) and high impact velocities (250 mph). The mass loss of VPS coatings was reduced by 50% compared to the APS coatings and 40% compared to the Ti6Al4V substrate. The cryogenic temperature induces brittleness in the material, rendering it susceptible to extreme conditions of material loss. The particle impact-deformation behavior was captured using a high-speed camera to study the erosion mechanism. This analysis revealed chipping in substrates and brittle APS coatings, while particles rebounding and embedding were observed in VPS coatings. Energy calculations, aided by particle trajectory tracking from the high-speed camera, have conclusively shown that VPS coatings absorb 5–10% more energy than APS coatings during erosion tests. A modified erosion index was developed incorporating the fracture toughness and temperatures. New erosion models for brittle and ductile target materials are proposed for developing erosion-resistant material systems.

Abhijith Kunneparambil Sukumaran↗

The Distribution of Titanium in Lunar Soils on the Basis of Sensor and In Situ Data Fusion

A variety of remote-sensing measurements have been used to map the distribution of elements on the Moon as a means of providing constraints on the processes from which its crust and major terranes originated. Discussed here is Ti, which is incorporated into refractory minerals such as ilmenite during the latter stages of differentiation, and is thus a most useful element for understanding mare basalt petrogenesis. One of the earliest Ti maps showed Ti variations in nearside maria on the basis of groundbased spectral reflectance measurements. A map of Ti derived from gamma-ray measurements on Apollo 15 and 16 was produced at about the same time, and was improved upon considerably by Davis and coworkers, who effectively removed sources of spurious variation from Fe and Al or REE (e.g., Th) interference, and calibrated Ti on the bases of landing-site soil averages. In recent years, spectral reflectance measurements from Clementine have been used by Lucey and coworkers to produce global Ti distribution maps as well. As we indicated previously, the Lucey and Davis maps agree to first order. Meanwhile, we are using the concept of sensor data fusion to combine measurements from the AGR (Apollo gamma-ray) and CSR (Clementine Spectral Reflectance) techniques with ground truth from lunar soils to utilize the differences between the two maps to understand the distribution of Ti within lunar soil components, as we have done with Fe. This technique should be verified and applied on Lunar Prospector gamma-ray measurements of Ti, as the calibrated data become available within the next couple of years. Lunar Ti is found principally in the mineral ilmenite, and is associated with certain components of lunar soil: crystalline Ilmenite mineral fragments and high Ti-bearing glass. All data indicate that Ti is associated with maria and mafic minerals. In AGR and CSR datasets, Ti is highest on the nearside and in the maria, particularly in southern Serenitatis/northern Tranquillitatis and northwestern Procellarum. Unlike CSR-derived values, AGR Ti values show modest increase (up to 0.7%) on the northern farside. Both techniques show a primarily unimodal distribution with a shoulder in the high Ti direction and a primary mode at approximately 0.2% (0.15% for CSR and 0.25% for AGR data), but the AGR Ti data have more structure in the shoulder, including an apparent minor mode at 1.2% Ti, representing non-highland areas. Recalibrating the two datasets on the basis of matching the peaks and range on the histograms would not account for this additional structure in the AGR data. Low Ti areas, which occur predominantly on the farside, are not represented well in the lunar sample collection, although several meteorites thought to be of lunar highland origin show Ti abundances averaging about 0.2%. (Error bars on AGR Ti values are about 0.5%.) Gamma-ray measurements reflect intrinsic Ti surface composition, regardless of the physical or chemical state of Ti. Lucey and coworkers have attempted to produce an equivalent bulk Ti map by normalizing the spectral feature at 415 nm to remove the effects of physical variations from soil to soil. The normalization is based on laboratory measurements of available samples, primarily nearside maria, and is undoubtedly optimized for the proportions in which Ti- components are found in these soils. In particular, mare soils tend to have a much higher proportion of opaque mineral grains, which appears to be well correlated with Ti abundance. The relationship between Ti abundance and proportion of Ti-bearing glass (weighted for Ti abundance) is not as direct. Also shows the relationship between landing site soil average, AGR, and CSR Ti abundances (with CSR filtered to match resolution and field of view of AGR data). AGR Ti values show the best agreement with Ti soil averages, CSR Ti values being somewhat higher in high-Ti soils, and lower in low-Ti soils. These results would tend to support the argument that the technique for deriving Ti from the CSR measurements is optimized for one of the primary Ti-bearing components, most likely opaque mineral grains, and is thus over-compensating and reporting higher Ti values in mare areas, and underreporting Ti in highland areas with much lower proportions of opaque mineral grains. More information is contained in original.

Clark, P. E.↗

Global Geochemical Variation on the Lunar Surface: A Three-Element Approach

We present a method for displaying the relative abundances of three important elements (Th, Fe, and Ti) on the same map projection of the lunar surface. Using Th-, Fe-, and Ti-elemental abundances from orbital geochemical data and assigning each element a primary color, a false-color map of the lunar surface was created. This approach is similar to the ternary diagram approach presented by Davis and Spudis with some important differences, discussed later. For the present maps, Th abundances were measured by the Lunar Prospector (LP) Gamma-Ray Spectrometer(GRS).The new LPGRS low-altitude dataset was used in this analysis. Iron and Ti weight percentages were based on Clementine spectral reflectance data smoothed to the LP low altitude footprint. This method of presentation was designed to aid in the location and recognition of three principal lunar compositions: ferroan anorthosite (FAN), mare basalts (MB), and the Mg suite/ KREEP-rich rocks on the lunar surface, with special emphasis on the highlands and specific impact basins. In addition to the recognition of these endmember rock compositions, this method is an attempt to examine the relationship between elemental compositions that do not conform readily to previously accepted or observed endmember rocks in various specific regions of interest, including eastern highlands regions centered on 150 deg longitude, and a northern highlands Th-rich region observed. The LP low-altitude data has full width at half-maximum spatial resolution of about 40 km. The Clementine spectral reflectance datasets were adapted using an equal-area, gaussian smoothing routine to this footprint. In addition, these datasets, reported in weight percent of FeO and of Ti02, were adjusted to Fe and Ti weight percentages. Each dataset was then assigned one of the three primary colors: blue for Th, red for Fe, and green for Ti. For each element, the data range was normalized to represent the ratio of each point to the maximum in the dataset. (To view the color table, go to http://cass.jsc.nasa.gov/meetings/moon99/pdf/8033.pdf.) The full range of lunar longitudes is represented, but due to the lack of coverage of the Clementine data for latitudes > 70 deg and <-70 deg, the data for these regions is excluded. The differences between this approach and the ternary diagram approach of Davis and Spudis eliminate some of the uncertainty and ambiguity of the ternary diagram approach. Rather than using a ratio of Th to Ti normalized to CI chondritic ratios, and a ternary diagram with ternary apexes located at specific endmember compositional values, elemental compositions were used independently, eliminating the errors resulting from dividing numbers that can have high uncertainties, especially at low concentration. The three elements used in this method of presentation were chosen for several reasons. One reason for the inclusion of Th in this study is that it is an accurate indicator of KREEP. Iron and Ti concentrations are both low in highland regolith, causing any small fluctuations in Th to stand out very well. In addition, Fe and Ti are good compositional indicators of different mare basalts. Mixed with red for Fe, the green for Ti produces a yellow signal in high-Ti basalts. While universally high in Fe relative to the surrounding highlands, mare basalts have a diverse range of Ti values, making Ti concentration a valuable asset to the classification and identification of different basalt types. Finally, an important constraint in element selection is the availability of the global data, both from LP and Clementine results. Data for Th, Fe, and Ti are among the highest quality of existing lunar remote-sensing data. In addition, LP data for Fe and Ti will become available, enabling these data to be incorporated into the analysis. Using upper-limit values for end member rock compositions calculated from Korotev et al., attempts were made to locate the different endmember compositions of terranes on this diagram. Most strikingly, ferroan anorthosite (Th < and = 0.37 micro g/g; Fe (wt%)< and =2.29; Ti (wt%) < and = 0.22), which should appear as an almost black, reddish color, does not appear on the diagram at any noticeable frequency. Based on this analysis, the suggestion of extensive FAN regions on the lunar surface is not strong, especially at the presently accepted values for Fe and Th. However, to make sure this effect is not due to systematic errors, a thorough investigation of the precision, accuracy, and uncertainties of the Fe, Ti, and Th abundances needs to be carried out, especially at low concentrations. A particular region of interest is an area of high Th concentrations relative to Fe and Ti content north and east of Humboldtianum Crater. First observed by Lawrence et al., this region does not coincide with any visible impact structure and comprises one of the closest approximations to pure blue (high Th, very low Ti and Fe) on the lunar surface. Such an elemental composition does not lend itself readily to classification, and presents something of an anomaly. More detailed analysis of this region is needed to understand its structure and origin. There seems to be a longitudinal asymmetry in the Th concentrations of the highlands regolith. High-Th, low-Ti, and Fe regions are located between 135 deg and 180 deg longitude and between -30 deg and +30 deg latitude. While the Th levels are not high enough to attract attention in a single elemental display, the variation in the abundance of Th relative to Fe and Ti abundances can be clearly seen. The composition that these data suggest is not well represented in the sample return suite. In addition, these regions were largely missed by the Apollo orbital ground tracks, which only covered the outer edge of the areas of interest. The LP orbital Th data represent the first information about the Th concentrations in these regions of the highlands. Additional information contained in original.

Thomsen, D. R.↗

Atomic-Scale Structure and Non-Stoichiometry of Meteoritic Hibonite: A Transmission Electron Microscope Study

Hibonite (CaAl_12O_19) is a common refractory mineral in Ca-Al-rich inclusions (CAIs) in primitive meteorites. Transmission electron microscope (TEM) studies have identified enigmatic planar defects in different occurrences of hibonite in the Allende meteorite that give rise to strong streaking along c* in electron diffraction patterns. Atomic resolution high-angle annular dark-field (HAADF) imaging and energy-dispersive X-ray (EDX) analyses were used to determine the nature and origin of these planar features. HAADF images of hibonite grains reveal lamellar intergrowths of common 1.6 nm spacing, and less commonly 2.0 and 2.5 nm spacings, interspersed in stoichiometric hibonite showing 1.1 nm (002) spacing. Stoichiometric hibonite consists of alternating Ca-containing (“R”) and spinel-structured (“S”) blocks stacked in a sequence RS. In contrast, the 1.6 nm layers result from a doubled S block such that the stacking sequence is RSS, while in the widest defect observed, the stacking sequence is RSSSS. These intergrowths are epitaxial and have coherent, low-strain boundaries with the host hibonite Meteoritic hibonite shows common Ti and Mg substitution for Al in its structure. Atomic-resolution EDX maps of hibonite grains in the Allende CAI confirm the preferred site occupancy of Mg on tetragonal M3 sites in S blocks and of Ti on trigonal bipyramidal M2 and octahedral M4 sites in R blocks. Mg is highly concentrated, but Ti is absent in the planar defects where wider S blocks show Al-rich compositions compared to stoichiometric MgAl_2O_4 spinel. Therefore, Mg likely played the major role in the formation and metastability of planar defects in hibonite. Electron energy loss spectroscopy data from the Ti L_2,3 edge show the presence of mixed Ti oxidation states with ~ 15–20% of Ti as Ti^(3+) in hibonite, suggesting a direct substitution of Ti^(3+) ↔ Al^(3+) in hibonite. The remaining ~ 80–85% of Ti is present as Ti^(4+) and corresponding EDX analyses are consistent with the well-known coupled substitution 2Al^(3+) ↔ Ti^(4+) + Mg^(2+) being the major mechanism for Ti and Mg substitution in hibonite. The formation of planar defects in hibonite occurred during high-temperature nebular condensation or melting/crystallization processes. The occurrence of non-stoichiometric hibonite in the Allende CAI deviates from the mineral formation sequence predicted from equilibrium condensation models. Overall, our atomic resolution TEM observations signify non-equilibrium, kinetic-controlled crystal growth during the high-temperature formation of refractory solids in the early solar nebula.

hibonite↗

Further characterization of spectral features attributable to titanium on the moon

The following transitions are observed in the electronic absorption spectra of lunar titanaugites: Fe(2+) spin-allowed and spin-forbidden crystal field; Ti(3+) spin allowed and Jahn-Teller split crystal field; Ti(3+)-Ti(4+) CT; Fe(2+)-Ti(4+) CT; and O(2-)-Fe(2+), Ti(3+), Ti(4+) CT. Of these, the transitions involving Ti(3+) are unique to lunar or nonferric-bearing titanaugites. All titanaugites have the Fe(2+) crystal field and Fe(2+)-Ti(4+) CT transitions in common. These features in the diffuse reflectance spectra of lunar materials give rise to the '1.0 band' and to the observed absorption around 0.5-0.6 micron, respectively. Since regolith contains a variety of phases with coexisting Fe(2+), Ti(3+), and Ti(4+) ions, several metal-metal charge transfer processes are possible.

Burns, R. G.↗

The effects of ion implantation on the tribology of perfluoropolyether-lubricated 440C stainless steel couples

The lubricating lifetime of thin films of a perfluoropolyether (PFPE) based on hexafluoropropene oxide in the presence of ion implanted 440C stainless steel is presented. Stainless steel discs, either unimplanted or implanted with N2, C, Ti, Ti + N2, or Ti + C had a thin film of PFPE (60-400 A) applied to them reproducibly (+/- 20 percent) and uniformly (+/- 15 percent) using a device developed for this study. The lifetimes of these films were quantified by measuring the number of sliding-wear cycles required to induce an increase in the friction coefficient from an initial value characteristic of the lubricated wear couple to a final, or failure value, characteristic of an unlubricated, unimplanted couple. The tests were performed in a dry nitrogen atmosphere (less than 1 percent RH) at room temperature using a 3 N normal load with a relative sliding speed of 0.05 m/s. The lubricated lifetime of the 440C couple was increased by an order of magnitude by implanting the disc with Ti. Ranked from most to least effective, the implanted species were: Ti; Ti+C; unimplanted; N2; C approximately equals Ti+N2. The mechanism postulated to explain these results involves the formation of a passivating or reactive layer which inhibits or facilitates the production of active sites. The corresponding surface microstructures induced by ion implantation, obtained using x-ray diffraction and conversion electron Mossbauer spectroscopy, ranked from most to least effective in enhancing lubricant lifetime were: amorphous Fe-Cr-Ti; amorphous Fe-Cr-Ti-C + TiC; unimplanted; epsilon-(Fe,Cr)(sub x)N, x = 2 or 3; amorphous Fe-Cr-C approximately equals amorphous Fe-Cr-Ti-N.

Shogrin, Bradley↗

Fractionation of Iron and Titanium Isotopes By Ilmenite and the Isotopic Compositions of Lunar Magma Ocean Cumulates

Basaltic volcanism on the Moon produced low- and high-Ti mare basalt suites that are also distinct with respect to their iron, titanium, and magnesium iso- topic compositions. Here, the equilibrium fractionation of Fe and Ti isotopes between ilmenite and melt was experimentally investigated in order to evaluate the role of ilmenite in generating the isotopic compositional variability among the lunar mare basalts. Ilmenite crystallization experiments were conducted using two bulk compositions: an ilmenite-saturated basaltic andesite and an ilmenite-saturated Apollo 14 black glass, and the Fe and Ti isotopic compo- sitions of the experimental ilmenites and glass (quenched melt) were analyzed using solution MC-ICPMS after hand-picking. Additionally, Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements on synthetic ilmenite were conducted and compared to previous NRIXS measurements on synthetic lunar glasses in order to derive temperature-dependent equilibrium ilmenite-melt Fe isotopic fractionations. Experimentally determined ilmenite-melt fractionations were then incorporated into a lunar magma ocean crystallization model that tracks the major element and isotopic compositional evolution of lunar magma ocean cumulates and residual liquid. There is good agreement between the Fe equilibrium isotopic fractionation measured by NRIXS and the laboratory equili- bration experiments, and we find that the isotopic fractionation is sensitive to il- menite compositional differences (0 vs. 10% Fe3+). Further, the light Ti isotopic composition of ilmenite relative to the melt (∆49Ti ilmenite-melt = −0.09 ± 0.03h at 1100°C) is consistent with the higher coordination of Ti in ilmenite relative to melts and results of previous studies. The modeled Ti isotopic compositions for lunar magma ocean cumulates display Ti isotopic variability sufficient to explain the low- and high-Ti mare basalt sources. However, the difference in Fe isotopic composition between the low- and high-Ti mare basalts cannot be attributed solely to ilmenite fractionation. Instead, Fe isotopic fractionation by additional products of lunar magma ocean crystallization, such as clinopy- roxene, is required to generate the inferred Fe and Mg isotopic variability in the lunar mantle. Alternatively, the Fe and Mg isotopic compositions of the lunar mare basalts may indicate Fe-Mg interdiffusion has occurred in the Ti- rich component of the mare basalt source regions via reaction between ilmenite cumulates and the olivine- and pyroxene-rich lunar mantle.

Kelsey Prissel↗