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NASA NTRS2023

STXM-C-XANES, IR Microspectroscopy, and Raman Microspectroscopy Analysis of Organic Matter in the Chwichiya 002 C3.00-Ungrouped Chondrite

Chwichiya 002 is a C3.00-ungrouped carbonaceous chondrite discovered in Western Sahara in 2018. The presence of hydrated phases in Chwichiya 002 was not confirmed by XRD analysis, and only a faint water and Si-O band attributed to phyllosilicate were observed by infrared transmission spectroscopy, indicating a very low degree of aqueous alteration (Meteoritical Bulletin, 2020). The structural order of polycyclic aromatic hydrocarbons evaluated by Raman spectroscopy indicates that the effect of thermal metamorphism is less severe than in the Semarkona meteorite, an LL3.00 ordinary chondrite (Meteoritical Bulletin, 2020). Chiwichiya 002 is a very primitive carbonaceous chondrite and an important information source for the early stage of the evolution of organic matter in the solar system. In this study, we investigated the molecular structure and distribution of organic matter in Chiwichiya 002 by Carbon X-ray Absorption Near Edge Structure (C-XANES) analysis using a Scanning Transmission X-ray Microscope (STXM). The STXM-C-XANES analysis has a spatial resolution of 20~100 nm and can observe the spatial distribution of organic materials in microstructures. In addition, to investigate the degree of thermal metamorphism of the organic matter, micro-IR, and micro-Raman spectroscopic analyses were performed. In addition, the Murchison CM2 chondrite was also analyzed for comparison. To evaluate contamination during analytical procedures, antigorite, which was heated in air at 500°C for 5 hours to eliminate organic matter was also analyzed in the same manner. The samples were milled into 100 nm-thick, thin sections using a Focused Ion Beam (FIB), and C-XANES spectra were obtained using the STXM at the High Energy Accelerator Research Organization, Photon Factory (PF), BL-19B. The obtained C-XANES spectra were smoothed and then fitted with Gaussian functions using the method of Le Guillou et al. (2018). The C-XANES showed that the ratio of oxygenated functional group (ketone, phenolic) carbons in Chwichiya 002 was lower than in Murchison, whereas the ratio of aliphatic carbons was almost the same. This may reflect the low degree of aqueous alteration of Chwichiya 002. In addition, contamination peaks were detected at 287.3-287.7 eV and 288.3-288.7 eV in the C-XANES spectra of some of the antigorite samples. The source of these peaks is under investigation. Raman spectroscopic analysis showed that the intensity ratio of the D band to the G band of Chwichiya 002 was slightly higher than that of Murchison. IR absorption spectra showed aromatic absorption at 1630 cm -1 , but there was little absorption due to aliphatic C-H around 2900 cm -1 . These results suggest that the organic matter in Chwichiya 002 may be more heated than in Murchison.

Chwichiya 002↗
NASA NTRS1977

Shock glass veins in some lunar and meteoritic samples - Their nature and possible origin

Glassy veinlets, 15 microns to 1 mm thick and now in part devitrified, cut through breccias 67915, 67936, and 67955 from Outhouse Rock, and similar veins have been found in several other lunar samples and in meteorites. The veins have features suggesting injection of extremely hot material, possibly at several thousands degrees of superheat, presumably from an impact event. The vein compositions are very similar but not identical to the bulk compositions of the host rocks. Two mechanisms of injection are considered feasible-injection of hot liquid and injection of hot particulate matter (resembling a 'fluidized bed'), but neither mechanism fully explains all details of the occurrences.

Roedder, E.↗
NASA NTRS2012

The Violent Early Solar System, as Told by Lunar Sample Geochronology

One of the legacies of the samples collected by the Apollo and Luna missions is the link forged between radiometric ages of rocks and relative ages according to stratigraphic relationships and impact crater size-frequency distributions. Our current understanding of the history of the inner solar system is based on the relative chronology of individual planets, tied to the absolute geochronology of the Moon via these important samples. Samples from these nearside locations reveal a preponderance of impact-disturbed or recrystallized ages between 3.75 and 3.95 billion years. Argon and lead loss (and correlated disturbances in the Rb-Sr system) have been attributed to metamorphism of the lunar crust by an enormous number of impacts in a brief pulse of time, called the Lunar Cataclysm or Late Heavy Bombardment. Subsequent high-precision geochronometric analyses of Apollo samples and lunar highlands meteorites show a wider range of ages, but very few older than 4 Ga. The paucity of ancient impact melt rocks has been interpreted to mean that either that most impact basins formed at this time, or that ejecta from the large, near-side, young basins dominates the Apollo samples. Selenochronology is getting more complicated: new results question meaning of sample ages, crater counts, crater production functions, and the solar system itself. Improved geological mapping of lunar geologic units and boundaries using multiple remote sensing datasets. High-resolution image-based crater counting of discrete geologic units and relating them to location. Improved understanding of the regolith thickness and its global variation (GRAIL). Tying the sampling of impact-melt rocks to the lunar impact flux. Using improved techniques (magnetic fields, diffusion studies, isotopic analysis) on existing samples. New sample return from benchmark craters, particularly SPA, which appears in 2013 Decadal Survey.

Cohen, Barbara↗
NASA NTRS2010

Online Simulations of Global Aerosol Distributions in the NASA GEOS-4 Model and Comparisons to Satellite and Ground-Based Aerosol Optical Depth

We have implemented a module for tropospheric aerosols (GO CART) online in the NASA Goddard Earth Observing System version 4 model and simulated global aerosol distributions for the period 2000-2006. The new online system offers several advantages over the previous offline version, providing a platform for aerosol data assimilation, aerosol-chemistry-climate interaction studies, and short-range chemical weather forecasting and climate prediction. We introduce as well a methodology for sampling model output consistently with satellite aerosol optical thickness (AOT) retrievals to facilitate model-satellite comparison. Our results are similar to the offline GOCART model and to the models participating in the AeroCom intercomparison. The simulated AOT has similar seasonal and regional variability and magnitude to Aerosol Robotic Network (AERONET), Moderate Resolution Imaging Spectroradiometer, and Multiangle Imaging Spectroradiometer observations. The model AOT and Angstrom parameter are consistently low relative to AERONET in biomass-burning-dominated regions, where emissions appear to be underestimated, consistent with the results of the offline GOCART model. In contrast, the model AOT is biased high in sulfate-dominated regions of North America and Europe. Our model-satellite comparison methodology shows that diurnal variability in aerosol loading is unimportant compared to sampling the model where the satellite has cloud-free observations, particularly in sulfate-dominated regions. Simulated sea salt burden and optical thickness are high by a factor of 2-3 relative to other models, and agreement between model and satellite over-ocean AOT is improved by reducing the model sea salt burden by a factor of 2. The best agreement in both AOT magnitude and variability occurs immediately downwind of the Saharan dust plume.

Colarco, Peter↗
NASA NTRS1992

Early Archean spherule beds of possible impact origin from Barberton, South Africa: A detailed mineralogical and geochemical study

The Barberton Greenstone belt is a 3.5- to 3.2-Ga-old formation situated in the Swaziland Supergroup near Barberton, northeast Transvaal, South Africa. The belt includes a lower, predominantly volcanic sequence, and an upper sedimentary sequence (e.g., the Fig Tree Group). Within this upper sedimentary sequence, Lowe and Byerly identified a series of different beds of spherules with diameters of around 0.5-2 mm. Lowe and Byerly and Lowe et al. have interpreted these spherules to be condensates of rock vapor produced by large meteorite impacts in the early Archean. We have collected a series of samples from drill cores from the Mt. Morgan and Princeton sections near Barberton, as well as samples taken from underground exposures in the Sheba and Agnes mines. These samples seem much better preserved than the surface samples described by Lowe and Byerly and Lowe et al. Over a scale of just under 30 cm, several well-defined spherule beds are visible, interspaced with shales and/or layers of banded iron formation. Some spherules have clearly been deposited on top of a sedimentary unit because the shale layer shows indentions from the overlying spherules. Although fresher than the surface samples (e.g., spherule bed S-2), there is abundant evidence for extensive alteration, presumably by hydrothermal processes. In some sections of the cores sulfide mineralization is common. For our mineralogical and petrographical studies we have prepared detailed thin sections of all core and underground samples (as well as some surface samples from the S-2 layer for comparison). For geochemical work, layers with thicknesses in the order of 1-5 mm were separated from selected core and underground samples. The chemical analyses are being performed using neutron activation analysis in order to obtain data for about 35 trace elements in each sample. Major elements are being determined by XRF and plasma spectrometry. To clarify the history of the sulfide mineralization, sulfur isotopic compositions are being determined.

Koeberl, Christian↗
NASA NTRS2019

An Investigation into the Grain Structure of Impact Ice

To design effective anti-icing and de-icing technology for aircraft, scientists and engineers must obtain a fundamental understanding of the microstructural characteristics of impact ice. This study investigates the effects of icing parameters, such as airspeed and liquid water content (LWC), on impact ice microstructure near the interface to a metal substrate. Ice samples were accreted in the NASA Glenn Icing Research Tunnel and tested in the NASA Revolutionary Icing Materials Evaluation Laboratory. A microtome was used to shave down the ice to a thickness of < 1 mm for examination under a microscope. Samples were imaged at multiple magnifications using bright field imaging. The average grain size was determined for each sample in accordance with ASTM standard methods, and relationships between airspeed, LWC, and grain size were identified. It was observed that the average grain area in a given cross-section was linearly related to the distance of the cross-section from the metal surface. Finally, the effects of annealing and sublimation on the microstructure were also explored. Results show significant variation in the grain structure, suggesting a means by which icing condition influences adhesion strength.

grain↗
NASA NTRS1975

Development of a high efficiency thin silicon solar cell

Variations in temperatures used in experimental processing and their effect on the resulting solar cell performance parameters were investigated. Diffusion temperature variation results in a fairly distinct optimum cell performance for diffusion temperatures in the immediate vicinity of 850 C. An additional effort was also devoted to redesign of the matallization gridline pattern for both minimum light blockage and minimum fill factor alteration due to series resistance. Efforts on improvement of tantalum oxide antireflection coatings were undertaken. Fifty 2 cm x 2 cm cells having a range of thicknesses have been submitted as the first sample group. These cells were processed under conditions tentatively identified during this first contractual quarter's experiments as being optimal for resulting cell performance.

Lindmayer, J.↗
NASA NTRS1977

Silicon web process development

Thirty-five (35) furnace runs were carried out during this quarter, of which 25 produced a total of 120 web crystals. The two main thermal models for the dendritic growth process were completed and are being used to assist the design of the thermal geometry of the web growth apparatus. The first model, a finite element representation of the susceptor and crucible, was refined to give greater precision and resolution in the critical central region of the melt. The second thermal model, which describes the dissipation of the latent heat to generate thickness-velocity data, was completed. Dendritic web samples were fabricated into solar cells using a standard configuration and a standard process for a N(+) -P-P(+) configuration. The detailed engineering design was completed for a new dendritic web growth facility of greater width capability than previous facilities.

Duncan, C. S.↗
NASA NTRS1989

The effect of composition and cooling rate on the structure of rapidly solidified (Fe, Ni)3Al-C alloy

The quench rate-metastable structure dependence in the Fe-20Ni-8Al-2C wt pct alloy has been experimentally studied. The nonequilibrium gamma-prime and gamma phases were noted in foils 65-100 microns thick, while at higher quench rates (thinner samples) the matrix was found to be in a disordered fcc gamma phase with kappa carbide precipitates. With the addition of silicon to the alloys, the nonequilibrium gamma-prime and gamma structures are observed at higher cooling rates.

Myers, S. A.↗
NASA NTRS1990

Stored mafic/ultramafic crust and early Archean mantle depletion

Both early and late Archean rocks from greenstone belts and felsic gneiss complexes exhibit positive epsilon(Nd) values of +1 to +5 by 3.5 Ga, demonstrating that a depleted mantle reservoir existed very early. The amount of preserved pre-3.0 Ga continental crust cannot explain such high epsilon values in the depleted residue unless the volume of residual mantle was very small: a layer less than 70 km thick by 3.0 Ga. Repeated and exclusive sampling of such a thin layer, especially in forming the felsic gneiss complexes, is implausible. Extraction of enough continental crust to deplete the early mantle and its destructive recycling before 3.0 Ga ago requires another implausibility, that the sites of crustal generation of recycling were substantially distinct. In contrast, formation of mafic or ultramafic crust analogous to present-day oceanic crust was continuous from very early times. Recycled subducted oceanic lithosphere is a likely contributor to present-day hotspot magmas, and forms a reservoir at least comparable in volume to continental crust. Subduction of an early mafic/ultramafic oceanic crust and temporary storage rather than immediate mixing back into undifferentiated mantle may be responsible for the depletion and high epsilon(Nd) values of the Archean upper mantle.

Chase, Clement G.↗
NASA NTRS1995

The rate of pyrite decomposition on the surface of Venus

We report the results of a detailed experiment study of the kinetics and mechanism of pyrite (FeS2) chemical weathering under Venus surface conditions. Pyrite is thermodynamically unstable on the surface of Venus and will spontaneously decompose to pyrrhotite (Fe7S8) because the observed S2 partial pressure in the lower atmosphere of Venus is lower than the S2 vapor pressure over coexisting pyrite and pyrrhotite. Pyrite decomposition kinetics were studied in pure CO2 and CO2 gas mixtures along five isotherms in the temperature range 390-531 C. In all gas mixtures studied, pyrite thermally decomposes to pyrrhotite (Fe7S8), which on continued heating loses sulfur to form more Fe-rich pyrrhotites. During this process the pyrrhotites are also being oxidized to form magnetite (Fe3O4), which converts to maghemite (gamma-Fe2O3), and then to hematite (alpha-Fe2O3). The reaction rates for pyrite thermal decomposition to pyrrhotite were determined by measuring the weight loss. The thickness of the unreacted pyrite in the samples provided a second independent reaction rate measurement. Finally, Mossbauer spectra done on 42 of the 115 experimental samples provided a third set of independent reaction rate data. Pyrite decomposition follows zero-order kinetics and is independent of the amount of pyrite present. The rate of pyrite decomposition is apparently independent of the gas compositions used and of the CO2 number density over a range of a factor of 40. The derived activation energy of approximately 150 kJ/mole is the same in pure CO2, two different CO-CO2 mixtures, and a ternary CO-SO2-CO2 mixture. Based on data for a CO-CO2-SO2 gas mixture with a CO number density approximately 10 times higher than at the surface of Venus and a SO2 number density approximately equal to that at the surface of Venus, the rate of pyrite destruction on the surface of Venus varies from about 1225 +/- 238 days/cm at the top of Maxwell Montes (approximately 660 K) to about 233 +/- 133 days/cm in the plains of Venus (approximately 740 K). These lifetimes are very short on a geological time scale and show that pyrite cannot exist on the surface of Venus for any appreciable length of time.

Fegley, B., Jr.↗
NASA NTRS1995

Evaluation of Thermal Control Coatings and Polymeric Materials Exposed to Ground Simulated Atomic Oxygen and Vacuum Ultraviolet Radiation

Numerous thermal control and polymeric samples with potential International Space Station applications were evaluated for atomic oxygen and vacuum ultraviolet radiation effects in the Princeton Plasma Physics Laboratory 5 eV Neutral Atomic Oxygen Facility and in the MSFC Atomic Oxygen Drift Tube System. Included in this study were samples of various anodized aluminum samples, ceramic paints, polymeric materials, and beta cloth, a Teflon-impregnated fiberglass cloth. Aluminum anodizations tested were black duranodic, chromic acid anodize, and sulfuric acid anodize. Paint samples consisted of an inorganic glassy black paint and Z-93 white paint made with the original PS7 binder and the new K2130 binder. Polymeric samples evaluated included bulk Halar, bulk PEEK, and silverized FEP Teflon. Aluminized and nonaluminized Chemfab 250 beta cloth were also exposed. Samples were evaluated for changes in mass, thickness, solar absorptance, and infrared emittance. In addition to material effects, an investigation was made comparing diffuse reflectance/solar absorptance measurements made using a Beckman DK2 spectroreflectometer and like measurements made using an AZ Technology-developed laboratory portable spectroreflectometer.

Kamenetzky, R. R.↗
NASA NTRS2007

Genesis Contingency Planning and Mishap Recovery: The Sample Curation View

Planning for sample preservation and curation was part of mission design from the beginning. One of the scientific objectives for Genesis included collecting samples of three regimes of the solar wind in addition to collecting bulk solar wind during the mission. Collectors were fabricated in different thicknesses for each regime of the solar wind and attached to separate frames exposed to the solar wind during specific periods of solar activity associated with each regime. The original plan to determine the solar regime sampled for specific collectors was to identify to which frame the collector was attached. However, the collectors were dislodged during the hard landing making identification by frame attachment impossible. Because regimes were also identified by thickness of the collector, the regime sampled is identified by measuring fragment thickness. A variety of collector materials and thin films applied to substrates were selected and qualified for flight. This diversity provided elemental measurement in more than one material, mitigating effects of diffusion rates and/or radiation damage. It also mitigated against different material and substrate strengths resulting in differing effects of the hard landing. For example, silicon crystal substrates broke into smaller fragments than sapphire-based substrates and diamond surfaces were more resilient to flying debris damage than gold. The primary responsibility of the curation team for recovery was process documentation. Contingency planning for the recovery phase expanded this responsibility to include not only equipment to document, but also gather, contain and identify samples from the landing area and the recovered spacecraft. The team developed contingency plans for various scenarios as part of mission planning that included topographic maps to aid in site recovery and identification of different modes of transport and purge capability depending on damage. A clean tent, set-up at Utah Test & Training Range to control the environment for processing the sample return capsule and cleanly installing a nitrogen purge to the canister, was used to control the environment for extracting collector fragments from the damaged canister and to document and package over 10,000 collector fragments.

Stansbery, E. K.↗
NASA NTRS2004

Effects of Various Wavelength Ranges of Vacuum Ultraviolet Radiation on Teflon FEP Film Investigated

Teflon Fluorinated Ethylene Propylene (FTP) films (DuPont) have been widely used for spacecraft thermal control and have been observed to become embrittled and cracked upon exposure to the space environment. This degradation has been attributed to a synergistic combination of radiation and thermal effects. A research study was undertaken at the NASA Glenn Research Center to examine the effects of different wavelength ranges of vacuum ultraviolet (VUV) radiation on the degradation of the mechanical properties of FEP. This will contribute to an overall understanding of space radiation effects on Teflon FEP, and will provide information necessary to determine appropriate techniques for using laboratory tests to estimate space VUV degradation. Research was conducted using inhouse facilities at Glenn and was carried out, in part, through a grant with the Cleveland State University. Samples of Teflon FEP film of 50.8 microns thickness were exposed to radiation from a VUV lamp from beneath different cover windows to provide different exposure wavelength ranges: MgF2 (115 to 400 nm), crystalline quartz (140 to 400 nm), and fused silica (FS, 155 to 400 nm). Following exposure, FEP film specimens were tensile tested to determine the ultimate tensile strength and elongation at failure as a function of the exposure duration for each wavelength range. The graphs show the effect of ultraviolet exposure on the mechanical properties of the FEP samples.

Dever, Joyce A.↗
NASA NTRS1981

Compositional inhomogeneities in a single Icelandic tholeiite flow

New trace element analyses of 25 basalt samples from a vertical traverse in an 11 m thick flow of Icelandic tholeiite show compositional differences which exceed analytical uncertainties and are random with respect to height. These variations suggest a short-range segregation model in which the amounts of phenocrysts, groundmass materials, and residual liquid vary randomly in different samples of the flow; a least-squares method is applied to determine if these variations reflect different proportions of crystallizing phases and residual liquid. Monte Carlo computations indicate that short-range segregation results in inhomogeneity of a magnitude of interflow compositional differences; this causes incoherence in elements with different geochemical behaviors while preserving coherence in elements of similar behavior.

Lindstrom, M. M.↗
NASA NTRS2012

Rugged, Portable, Real-Time Optical Gaseous Analyzer for Hydrogen Fluoride

Hydrogen fluoride (HF) is a primary evolved combustion product of fluorinated and perfluorinated hydrocarbons. HF is produced during combustion by the presence of impurities and hydrogen- containing polymers including polyimides. This effect is especially dangerous in closed occupied volumes like spacecraft and submarines. In these systems, combinations of perfluorinated hydrocarbons and polyimides are used for insulating wiring. HF is both highly toxic and short-lived in closed environments due to its reactivity. The high reactivity also makes HF sampling problematic. An infrared optical sensor can detect promptly evolving HF with minimal sampling requirements, while providing both high sensitivity and high specificity. A rugged optical path length enhancement architecture enables both high HF sensitivity and rapid environmental sampling with minimal gaseous contact with the low-reactivity sensor surfaces. The inert optical sample cell, combined with infrared semiconductor lasers, is joined with an analog and digital electronic control architecture that allows for ruggedness and compactness. The combination provides both portability and battery operation on a simple camcorder battery for up to eight hours. Optical detection of gaseous HF is confounded by the need for rapid sampling with minimal contact between the sensor and the environmental sample. A sensor is required that must simultaneously provide the required sub-parts-permillion detection limits, but with the high specificity and selectivity expected of optical absorption techniques. It should also be rugged and compact for compatibility with operation onboard spacecraft and submarines. A new optical cell has been developed for which environmental sampling is accomplished by simply traversing the few mm-thick cell walls into an open volume where the measurement is made. A small, low-power fan or vacuum pump may be used to push or pull the gaseous sample into the sample volume for a response time of a few seconds. The optical cell simultaneously provides for an enhanced optical interaction path length between the environmental sample and the infrared laser. Further, the optical cell itself is comprised of inert materials that render it immune to attack by HF. In some cases, the sensor may be configured so that the optoelectronic devices themselves are protected and isolated from HF by the optical cell. The optical sample cell is combined with custom-developed analog and digital control electronics that provide rugged, compact operation on a platform that can run on a camcorder battery. The sensor is inert with respect to acidic gases like HF, while providing the required sensitivity, selectivity, and response time. Certain types of combustion events evolve copious amounts of HF, very little of other gases typically associated with combustion (e.g., carbon monoxide), and very low levels of aerosols and particulates (which confound traditional smoke detectors). The new sensor platform could warn occupants early enough to take the necessary countermeasures.

Pilgrim, Jeffrey↗
NASA NTRS1983

The diffusivity of hydrogen in Nb stabilized stainless steel

The evolution of hydrogen from 347 stainless steel has been studied by using a real time dynamic technique under ultrahigh vacuum conditions. Auger electron spectroscopy was used to determine the surface composition as a function of time and temperature. The surface film on the electropolished samples was found to be approximately 15 A thick and consisted of a carbon-oxygen complex and a metal oxide (FexOy). Upon heating to 400 C, the carbon-oxygen complex desorbed as CO and the remaining oxygen and carbon began to incorporate. Also at this temperature sulfur began to diffuse out of the bulk to the surface and at approximately 800 C formed a complete monolayer. At 900 C, carbon and oxygen virtually disappeared, leaving the monolayer of sulfur as the only surface contaminant. The hydrogen diffusivity was found to follow closely the equation D = 7.01 x 10 to the -7th exp(-48.0/RT) sq m per second over the entire temperature range studied, thus indicating that hydrogen evolution is not significantly affected by the changing surface composition. The somewhat higher value of the diffusivity obtained in this work compared to past measurements in austenitic stainless steels may indicate the importance of sample preprocessing and ultrahigh vacuum conditions in minimizing the effects of surface layers.

Outlaw, R. A.↗
NASA NTRS1992

Ellipsometric study of oxide films formed on LDEF metal samples

The optical constants of samples of six different metals (Al, Cu, Ni, Ta, W, and Zr) exposed to space on the Long Duration Exposure Facility (LDEF) were studied by variable angle spectroscopic ellipsometry. Measurements were also carried out on portions of each sample which were shielded from direct exposure by a metal bar. A least-squares fit of the data using an effective medium approximation was then carried out, with thickness and composition of surface films formed on the metal substrates as variable parameters. The analysis revealed that exposed portions of the Cu, Ni, Ta, and Zr samples are covered with porous oxide films ranging in thickness from 500 to 1000 A. The 410 A thick film of Al2O3 on the exposed Al sample is practically free of voids. Except for Cu, the shielded portions of these metals are covered by thin non-porous oxide films characteristic of exposure to air. The shielded part of the Cu sample has a much thicker porous coating of Cu2O. The tungsten data could not be analyzed.

Franzen, W.↗