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NASA NTRS1993

The role of CO2 in weathering reactions and the presence of S2 on Venus: Implications for the pyrite stability field

The stability of pyrite has become the focal point of study, since regions of low radio thermal emissivity were detected during the Pioneer Venus and Magellan radar mapping missions of Venus. Thermodynamic calculations and experimental studies have been performed assuming CO2 is a major contributor to the weathering of sulfides, as CO2 is the major gas species in the Venusian atmosphere. The purpose of the present study, however, is to demonstrate that CO2 is a non-reactive gas and that a minor species, S2, is the most important gas in determining whether pyrite is stable in the high radar reflectivity regions.

Straub, Darcy W.↗

NASA NTRS1994

Overcharge and overdischarge protection of ambient temperature secondary lithium cells

A cathode additive is provided for protecting an ambient temperature secondary lithium cell from overcharging or overdischarging. The cathode additive is chosen to create an upper voltage plateau which is slightly higher than a characteristic charge cutoff voltage of the cathode of the cell. The cathode additive additionally creates a lower voltage plateau which is slightly lower than the characteristic discharge cutoff voltage of the cell. Preferably, the cathode additive is a transition metal oxide or a sulfide and may, for example, include a mixture of Li2Mn2O4 and Li(0.1)MoO2.

Huang, Chen-Kuo↗

NASA NTRS1994

Solventless, curable fluid oligomeric systems for high performance microwave, acoustical and mechanical applications

While establishing the basis for a 'Technology 2000' product plan several years ago we plugged in the usual factors contributing toward product success: price/performance justifiable; profitable, warranting high quality maintenance, enhancement, and specific property improvement; narrow inventory requirements; and raw material integrable backwards with easily variable properties (molecular weight, functionality, and isomer control). We resolved this by selecting radical functional, low molecular weight polybutadiene liquid polymers. Encouraged by the need for solid rocket binders, several companies embarked on various perceptions of binder performance requirements over four decades ago. Initially dominated by progress of liquid polysulfides, soon a few settled primarily upon polybutadiene based binders. Such an approach in a few instances was exploited quite viably with a series of functional group terminated liquid polybutadienes: hydroxyl, mercaptan, carboxyl, vinyl, and amine. Good results are obtained for oligomers, liquid polymers, and their hybrids. The only significant limits on compounded products has been solvent resistance and oxidative sensitivity, unless sufficient proportion of sulfide or nitrile moiety is incorporated. For convenience, they have been grouped under the trademarks Nylane, Seamax, Oligomax, and Castomax.

Lefave, G. M.↗

NASA NTRS1993

Deposition rates of oxidized iron on Mars

The reddened oxidized surface of Mars is indicative of temporal interactions between the Martian atmosphere and its surface. During the evolution of the Martian regolith, primary ferromagnesian silicate and sulfide minerals in basaltic rocks apparently have been oxidized to secondary ferric-bearing assemblages. To evaluate how and when such oxidized deposits were formed on Mars, information about the mechanisms and rates of chemical weathering of Fe(2+)-bearing minerals has been determined. In this paper, mechanisms and rates of deposition of ferric oxide phases on the Martian surface are discussed.

Burns, R. G.↗

NASA NTRS1994

Copper-containing ceramic precursor synthesis: Solid-state transformations and materials technology

Three copper systems with relevance to materials technology are discussed. In the first, a CuS precursor, Cu4S1O (4-methylpyridine)(sub 4)- (4-MePy), was prepared by three routes: reaction of Cu2S, reaction of CuBr-SMe2, and oxidation of copper powder with excess sulfur in 4-methylpyridine by sulfur. In the second, copper powder was found to react with excess thiourea (H2NC(S)NH2) in 4-methylpyridine to produce thiocyanate (NCS(-)) complexes. Three isolated and characterized compounds are: Cu(NCS)(4-MePy)(sub 2), a polymer, (4-MePy-H)(Cu(NCS)(sub 3)(4-MePy)(sub 2)), a salt, and t-Cu(NCS)(sub 2)(4-MePy)(sub 4). Finally, an attempt to produce a mixed-metal sulfide precursor of Cu and Ga in N-methylimidazole (N-MeIm) resulted in the synthesis of a Cu-containing polymer, Cu(SO4)(N-MeIm). The structures are presented; the chemistry will be briefly discussed in the context of preparation and processing of copper-containing materials for aerospace applications.

Hepp, Aloysius F.↗

NASA NTRS1993

The anaerobic degradation of organic matter in Danish coastal sediments - Iron reduction, manganese reduction, and sulfate reduction

A combination of porewater and solid phase analysis as well as a series of sediment incubations are used to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). Solid phase data are integrated with incubation results to define the zones of the various oxidation processes. At S(9), surface Mn enrichments of up to 3.5 wt pct were found, and with such a ready source of Mn, dissimilatory Mn reduction was the only significant anaerobic process of carbon oxidation in the surface 10 cm of the sediment. At S(4) and S(6), active Mn reduction occurred; however, most of the Mn reduction may have resulted from the oxidation of acid volatile sulfides and Fe(2+) rather than by a dissimilatory sulfate. Dissolved Mn(2+) was found to completely adsorb onto sediment containing fully oxidized Mn oxides.

Canfield, Donald E.↗

NASA NTRS1993

Trace elements in mineral separates of the Pena Blanca Spring aubrite - Implications for the evolution of the aubrite parent body

A detailed chemical study is conducted of the Pena Blanca Spring aubrite in order to clarify both the origin of the aubrite parent body (APB) and its relation to the enstatite chondrites. The distribution of REE among aubritic minerals cannot be the result of fractional distillation, which would occur if high degrees of partial melting had occurred on the APB. The REE distributions instead indicate a complete equilibrium of oldhamite and other phases, so that a brief nonequilibrium melting episode must have led to the segregation of metal and sulfides.

Lodders, K.↗

NASA NTRS1994

Formation of chondrules and CAIs by nebular processes

Chondrules are essential components of most chondritic meteorites. Carbonaceous chondrites, with the exception of CI chondrites, contain 30-50% chondrules, ordinary and enstatite chondrites even more. A better understanding of chondrule formation will therefore lead to an improved understanding of the origin of meteorites. Most studies of chondrules are, however, concerned with their texture and mineralogy. As chondrules, by definition, passed through a molten stage, their present texture and mineralogy can only provide information on conditions of crystallization from a melt and the subsequent solid-state cooling history. Information concerning chondrule formation is contained in their chemical and isotopic composition. The two most important observations relevant to the chemistry of the chondrules are their generally low Fe content and the large compositional variability of chondrules from a single meteorite, reflected in major variations of Mg/Si ratios, of Al and other refractory element abundances, total Fe, metal (Fe, Ni), and sulfide. This large compositional variability is surprising considering the uniform and nearly solar composition of bulk chondrites, which, in some cases, consist of more than 90% of chondrules.

Palme, H.↗

NASA NTRS1994

Chondrule precursors and cooling paths: The sulfur evidence

The behavior of moderately volatile elements (Na and S) is controversial but critical in understanding chondrule precursors and heating processes. Sulfide appeared to be present in most chondrules, but S should have been vaporized during chondrule formation. In fact, S is extensively redistributed in the course of metamorphism, and its abundance at the end of chondrule formation can only be inferred from the least equilibrated chondrites. Our study of 530 chondrules from Renazzo (CR2) and Semarkona (LL3.0) shows partial volatilization of S during chondrule formation and our melting experiments define conditions for total loss or partial retention of S.

Zanda, B.↗

NASA NTRS1994

Advances in polycrystalline thin-film photovoltaics for space applications

Polycrystalline, thin-film photovoltaics represent one of the few (if not the only) renewable power sources which has the potential to satisfy the demanding technical requirements for future space applications. The demand in space is for deployable, flexible arrays with high power-to-weight ratios and long-term stability (15-20 years). In addition, there is also the demand that these arrays be produced by scalable, low-cost, high yield, processes. An approach to significantly reduce costs and increase reliability is to interconnect individual cells series via monolithic integration. Both CIS and CdTe semiconductor films are optimum absorber materials for thin-film n-p heterojunction solar cells, having band gaps between 0.9-1.5 ev and demonstrated small area efficiencies, with cadmium sulfide window layers, above 16.5 percent. Both CIS and CdTe polycrystalline thin-film cells have been produced on a laboratory scale by a variety of physical and chemical deposition methods, including evaporation, sputtering, and electrodeposition. Translating laboratory processes which yield these high efficiency, small area cells into the design of a manufacturing process capable of producing 1-sq ft modules, however, requires a quantitative understanding of each individual step in the process and its (each step) effect on overall module performance. With a proper quantification and understanding of material transport and reactivity for each individual step, manufacturing process can be designed that is not 'reactor-specific' and can be controlled intelligently with the design parameters of the process. The objective of this paper is to present an overview of the current efforts at MMC to develop large-scale manufacturing processes for both CIS and CdTe thin-film polycrystalline modules. CIS cells/modules are fabricated in a 'substrate configuration' by physical vapor deposition techniques and CdTe cells/modules are fabricated in a 'superstrate configuration' by wet chemical methods. Both laser and mechanical scribing operations are used to monolithically integrate (series interconnect) the individual cells into modules. Results will be presented at the cell and module development levels with a brief description of the test methods used to qualify these devices for space applications. The approach and development efforts are directed towards large-scale manufacturability of established thin-film, polycrystalline processing methods for large area modules with less emphasis on maximizing small area efficiencies.

Lanning, Bruce R.↗

NASA NTRS1994

Semi-volatiles at Mercury: Sodium (Na) and potassium (K)

Several lines of evidence now suggest that Mercury is a planet rich in moderately-volatile elements such as Na and K. Recent mid-infrared spectral observations of Mercury's equatorial and mid-latitude region near 120 degrees mercurian longitude indicate the presence of plagioclase feldspar. Spectra of Mercury's surface exhibit spectral activity similar to labradorite (plagioclase feldspar with NaAlSi3O8: 30-50 percent) and bytownite (NaAlSi3O8: 10-30 percent). These surface studies were stimulated by the relatively large abundance of Na and K observed in Mercury's atmosphere. An enhanced column of K is observed at the longitudes of Caloris Basin and of the antipodal terrain. Extreme heating at these 'hot' longitudes and severe fracturing suffered from the large impact event could lead to enhanced outgassing from surface or subsurface materials. Alternatively, sputtering from a surface enriched in K could be the source of the observed enhancement. Recent microwave measurements of Mercury also give indirect evidence of a mercurian regolith less FeO-rich than the Moon. An anomalously high index of refraction derived from the whole-disk integrated phase curve of Danjon may also be indicative of surface sulfides contributing to a regolith that is moderately volatile-rich. The recent exciting observations of radar-bright spots at high latitudes also indicate that a substance of high volume scattering, like ice, is present in shadowed regions. Other radar-bright spots have been seen at locations of Na enhancements on the atmosphere. All combined, these pieces of evidence point to a planet that is not severely depleted in volatiles or semi-volatiles.

Sprague, A.↗

NASA NTRS1994

Dimethylsulfide oxidation over the tropical South Atlantic: OH and other oxidants

The general course of events in the formation of a marine cloud begins with the emission of species which can eventually serve as nuclei around which water can condense to form a cloud droplet. In remote marine regions, cloud condensation nuclei (CCN) are primarily composed of sulfate, in either its acid or ammonium salt form. Most sulfate in these regions is the product of atmospheric oxidation of dimethyl sulfide (DMS), a reduced sulfur gas that is released by phytoplankton at the ocean surface. Therefore, in order to effectively quantify the links in the cloud-formation cycle, one must begin with a well-defined description of the atmospheric chemistry of DMS. The intent of this project has been to initiate development of a comprehensive model of the chemistry and dynamics responsible for the formation of clouds in the remote marine boundary layer. The primary tool in this work has been the Global/Regional Atmospheric Chemistry Event Simulator (GRACES), a global atmospheric chemistry model, which is under development within the Atmospheric Chemistry and Dynamics Branch of NASA-Ames Research Center. In this effort, GRACES was used to explore the first chemical link between DMS and sulfate by modeling the diurnal variation of DMS.

Hemming, Brooke L.↗

NASA NTRS1995

Natural and orbital debris particles on LDEF's trailing and forward-facing surfaces

Approximately 1000 impact craters on the Chemistry of Meteoroid Experiment (CME) have been analyzed by means of Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Analysis (EDXA) to determine the compositional make-up of projectile residues. This report completes our systematic survey of gold and aluminum surfaces exposed at the trailing-edge (A03) and forward-facing (A11) LDEF sites, respectively. The major categories for the projectile residues were (1) natural, with diverse subgroups such as chondritic, monomineralic silicates, and sulfides, and (2) man made, that were classified into aluminum (metallic or oxide) and miscellaneous materials (such as stainless steel, paint flakes, etc). On CME gold collectors on LDEF's trailing edge approximately 11 percent of all craters greater than 100 micron in diameter were due to man-made debris, the majority (8.6 percent) caused by pure aluminum, approximately 31.4 percent were due to cosmic dust, while the remaining 58 percent were indeterminate via the analytical techniques utilized in this study. The aluminum surfaces located at the A11 forward-facing site did not permit analysis of aluminum impactors, but approximately 9.4 percent of all craters were demonstratably caused by miscellaneous debris materials and approximately 39.2 percent were the result of natural particles, leaving approximately 50 percent which were indeterminate. Model considerations and calculations are presented that focus on the crater-production rates for features greater than 100 micron in diameter, and on assigning the intermediate crater population to man-made or natural particles. An enhancement factor of 6 in the crater-production rate of natural impactors for the 'forward-facing' versus the 'trailing-edge' CME collectors was found to best explain all observations (i.e., total crater number(s), as well as their computational characteristics). Enhancement factors of 10 and 4 are either too high or too low. It is also suggested that approximately 45 percent of all craters greater than 100 micron in diameter are caused by man-made impactors on the A11 surfaces. This makes the production rate for craters greater than 100 micron in diameter, resulting from orbital debris, a factor of 40 higher on the forward-facing sides as opposed to the trailing-edge direction.

Hoerz, Friedrich↗

NASA NTRS1993

The US Geological Survey, digital spectral reflectance library: version 1: 0.2 to 3.0 microns

We have developed a digital reflectance spectral library, with management and spectral analysis software. The library includes 500 spectra of 447 samples (some samples include a series of grain sizes) measured from approximately 0.2 to 3.0 microns. The spectral resolution (Full Width Half Maximum) of the reflectance data is less than or equal to 4 nm in the visible (0.2-0.8 microns) and less than or equal 10 nm in the NIR (0.8-2.35 microns). All spectra were corrected to absolute reflectance using an NBS Halon standard. Library management software lets users search on parameters (e.g. chemical formulae, chemical analyses, purity of samples, mineral groups, etc.) as well as spectral features. Minerals from sulfide, oxide, hydroxide, halide, carbonate, nitrate, borate, phosphate, and silicate groups are represented. X-ray and chemical analyses are tabulated for many of the entries, and all samples have been evaluated for spectral purity. The library also contains end and intermediate members for the olivine, garnet, scapolite, montmorillonite, muscovite, jarosite, and alunite solid-solution series. We have included representative spectra of H2O ice, kerogen, ammonium-bearing minerals, rare-earth oxides, desert varnish coatings, kaolinite crystallinity series, kaolinite-smectite series, zeolite series, and an extensive evaporite series. Because of the importance of vegetation to climate-change studies we have include 17 spectra of tree leaves, bushes, and grasses.

Clark, Roger N.↗

NASA NTRS1995

Solid film lubricants and thermal control coatings flown aboard the EOIM-3 MDA sub-experiment

Additional experimental data were desired to support the selection of candidate thermal control coatings and solid film lubricants for the McDonnell Douglas Aerospace (MDA) Space Station hardware. The third Evaluation of Oxygen Interactions With Materials Mission (EOIM-3) flight experiment presented an opportunity to study the effects of the low Earth orbit environment on thermal control coatings and solid film lubricants. MDA provided five solid film lubricants and two anodic thermal control coatings for EOIM-3. The lubricant sample set consisted of three solid film lubricants with organic binders one solid film lubricant with an inorganic binder, and one solid film lubricant with no binder. The anodize coating sample set consisted of undyed sulfuric acid anodize and cobalt sulfide dyed sulfuric acid anodize, each on two different substrate aluminum alloys. The organic and inorganic binders in the solid film lubricants experienced erosion, and the lubricating pigments experienced oxidation. MDA is continuing to assess the effect of exposure to the low Earth orbit environment on the life and friction properties of the lubricants. Results to date support the design practice of shielding solid film lubricants from the low Earth orbit environment. Post-flight optical property analysis of the anodized specimens indicated that there were limited contamination effects and some atomic oxygen and ultraviolet radiation effects. These effects appeared to be within the values predicted by simulated ground testing and analysis of these materials, and they were different for each coating and substrate.

Murphy, Taylor J.↗

NASA NTRS1994

Coccolithophorid blooms in the global ocean

The global distribution pattern of coccolithophrid blooms was mapped in order to ascertain the prevalence of these blooms in the world's oceans and to estimate their worldwide production of CaCO3 and dimethyl sulfide (DMS). Mapping was accomplished by classifying pixels of 5-day global composites of coastal zone color scanner imagery into bloom and nonbloom classes using a supervised, multispectral classification scheme. Surface waters with the spectral signature of coccolithophorid blooms annually covered an average of 1.4 x 10(exp 6) sq km in the world oceans from 1979 to 1985, with the subpolar latitudes accounting for 71% of this surface area. Classified blooms were most extensive in the Subartic North Atlantic. Large expanses of the bloom signal were also detected in the North Pacific, on the Argentine shelf and slope, and in numerous lower latitude marginal seas and shelf regions. The greatest spatial extent of classified blooms in subpolar oceanic regions occurred in the months from summer to early autumn, while those in lower latitude marginal seas occurred in midwinter to early spring. Though the classification scheme was effcient in separating bloom and nonbloom classes during test simulations, and biogeographical literature generally confirms the resulting distribution pattern of blooms in the subpolar regions, the cause of the bloom signal is equivocal in some geographic areas, particularly on shelf regions at lower latitudes. Standing stock estimates suggest that the presumed Emiliania huxleyi blooms act as a significant source of calcite carbon and DMS sulfur on a regional scale. On a global scale, however, the satellite-detected coccolithophorid blooms are estimated to play only a minor role in the annual production of these two compounds and their flux from the surface mixed layer.

Brown, Christopher W.↗

NASA NTRS1994

Mn-Cr isotopic systematics of individual Chainpur chondrules

Twenty-eight chondrules separated from Chainpur (LL3.4) were surveyed for abundances of Mn, Cr, Na, Fe, Sc, Hf, Ir, and Zn by Instrumental Neutron Activation Analysis (INAA). Six, weighting 0.6-1.5 mg each, were chosen for Scanning Electron Microscopy (SEM)/Energy Dispersive X-ray (EDX) and high-precision Ce-isotopic studies. LL-chondrite-normalized (Mn/Fe)(sub LL) and (Sc/Fe)(sub LL) were found to be useful in categorizing them. Five chondrules (CH-16, -17, -18, -23, and -28) were in the range 0.5 less than (Mn/Fe)(sub LL) less than 1. 4 and 0.5 less than (Sc/Fe)(sub LL) less than 1.4. The sixth (CH-25) had (Mn/Fe)(sub LL) and (Sc/Fe)(sub LL) ratios of 0.40 and 8.1, respectively, and was enriched in the refractory lithophile elements Sc and Hf and the refractory siderophile element Ir by 2.7 and 4.4x LL abundances respectively. SEM/EDX of exterior surfaces of the chondrules showed they consisted of varying proportions of low- and high-Ca pyroxenes, olivine, glass, kamacite/taenite, and Fe-sulfides. Chromium-53/chromium-52 for the six chondrules and bulk Chainpur (WR) are presented. Chromium-54/chromium-52 is close to terrestrial and does not correlate with Mn/Cr. We provisionally ignore the possibility of initial Cr isotopic heterogeneities among the chondrules. Omitting both the CH-25 and WR data, a linear regression gives initial (Mn-53/Mn-55)(sub I) = 8 +/- 4 x 10(exp -6), corresponding to chondrule formation at Delta(t)(sub LEW) = -9 +/- 4 Ma prior to igneous crystallization of the LEW 86010 angrite. If initial (Mn-53/Mn-55)(sub 0) in the solar system were as high as approximately 4.4 x 10(exp -5) when Allende CAI formed, our data suggest Chainpur chondrules formed approximately 9 Ma later, in qualitative agreement with 'late' I-Xe formation ages for most Chainpur chondrules.

Nyquist, L.↗

NASA NTRS1994

Carbonates in the Kaidun chondrite

Kaidun is a remarkable chondrite breccia fall containing lithic clasts that span a wide range of chondrite groups including C and E chondrites, as well as having clasts with characteristics not yet found in existing chondrite samples. The dominant lithology in Kaidun appears to be CR chondritic, consonant with recent O isotope data. The carbonates in Kaidun are presented as one mineralogical basis for comparing it to the other hydrated chondrites and to better understand its relative alteration history. The four polished thin sections of Kaidun studied contained a variety of lithologies that we classified into four groups -- CR, E, CM-like, and dark inclusions (DIs). DIs contain sulfide and magnetite morphologies that superficially resemble CI chondrites, and some of the previously reported CI lithologies in Kaidun may be what we term DIs. Carbonates were found in all lithologies studied. Carbonates in Kaidun are similar in composition to those in CR chondrites. Some of the DIs in Kaidun, previously characterized as CI, have carbonates similar to those in CR chondrites and are unlike those in CI or CM chondrites. Most carbonates in Kaidun and CR chondrites are calcites, some of which formed at temperatures above 250 C. Dolomite is less common and some may be metastable. Alteration temperatures in the Renazzo CR chondrite were estimated to be approximately 300 C, based on O isotope fractionation between phyllosilicates and magnetite. Temperatures of up to 450 C were proposed for the alteration of a CR-like dark inclusion in Kaidun, based on the presence of hydrothermal pentlandite veins. The alteration temperatures for Kaidun and the other CR chondrites are considerably higher than those suggested for CI or CM parent bodies.

Weisberg, M. K.↗