Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “sulfide”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 757 records · Page 42

A three-dimensional study of metal grains in equilibrated, ordinary chondrites

Metal particles in Guarena (H6), Colby (L6) and St. Severin (LL6) were studied by optical microscopy and by electron microprobe analysis. Observations from successive polished sections through the metal particles show that kamacite and taenite grains, which often appear to be isolated particles, are connected directly or by intervening sulfides. Also tetrataenite rims are widest when adjacent to sulfide or kamacite. These observations indicate that transfer of Ni during cooling when kamacite-taenite phase growth takes place does not occur through the silicate phases but proceeds through metal and sulfide phases or along grain boundaries. By utilizing the central Ni content of taenite grains from successive sections, metallographic cooling rates were determined more precisely than by using one arbitrary section. Cooling rates determined in this manner for Guarena, Colby, and St. Severin are 4.3 K, 4.0 K, and 1.0 K per million years, respectively.

Willis, J.↗

Development of advanced thermoelectric materials

The development of an advanced thermoelectric material for radioisotope thermoelectric generator (RTG) applications is reported. A number of materials were explored. The bulk of the effort, however, was devoted to improving silicon germanium alloys by the addition of gallium phosphide, the synthesis and evaluation of lanthanum chrome sulfide and the formulation of various mixtures of lanthanum sulfide and chrome sulfide. It is found that each of these materials exhibits promise as a thermoelectric material.

Source record↗

Sulfur diagenesis in marine sediments

Bacterial sulfate reduction occurs in all marine sediments that contain organic matter. Aqueous sulfide (HS-, H2S), one of the initial products of bacterial sulfide reduction, is extremely reactive with iron bearing minerals: sulfur is fixed into sediments as iron sulfide (first FeS and then Fe2S2). A working definition is given of sulfur diagenesis in marine sediments. Controls and consequences of sulfate reduction rates in marine sediments are examined.

Goldhaber, M.↗

Structure and physiology of Beggiatoa and Thiothrix

Reggiatoa and Thiothrix are genera of filamentous, colorless, sulfide oxidizing bacteria. These organisms are microaerophilic, oxidizing sulfide to sulfur in the presence of oxygen. The sulfur accumulates in intracellular sulfur globules - the outstanding morphological feature of these bacteria. Some strains are able to further oxidize the sulfur to sulfate aerobically or reduce the sulfur to sulfide anaerobically. This metabolic versatility makes these bacteria important links in aquatic sulfur cycles.

Schmidt, T. M.↗

Effects of SO2 and SO3 on the Na2SO4 induced corrosion of nickel

The effects of SO2 and SO3 in the environment on the hot-corrosion behavior of Ni in the temperature range 750-950 C has been studied. Below the melting point of Na2SO4 (884 C), rapid corrosion takes place by formation of a Na2SO4-NiSO4 melt which can penetrate the porous oxide scale and give rise to sulfide information by coming in contact with the metal. The distribution of the sulfides depends on the SO2 level in the ambient gas. Continued corrosion occurs by a sulfidation-oxidation mechanism. At temperatures above the melting point of Na2SO4, accelerated degradation occurs via dissolution of the surface scale, followed by reprecipitation of the oxide in a nonprotective form.

Misra, A. K.↗

Theoretical studies of the low-lying states of ScO, ScS, VO, and VS

Bonding in the low-lying states of ScO, ScS, VO, and VS is theoretically studied. Excellent agreement is obtained with experimental spectroscopic constants for the low-lying states of ScO and VO. The results for VS and ScS show that the bonding in the oxides and sulfides is similar, but that the smaller electronegativity in S leads to a smaller ionic component in the bonding. The computed D0 of the sulfides are about 86 percent of the corresponding oxides, and the low-lying excited states are lower in the sulfides than in the corresponding oxides. The CPF method is shown to be an accurate and cost-effective method for obtaining reliable spectroscopic constants for these systems.

Bauschlicher, Charles W., Jr.↗

Stable carbon and sulfur isotopes as records of the early biosphere

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

Desmarais, David J.↗

Microbial reduction of manganese oxides - Interactions with iron and sulfur

Alteromonas putrefaciens (strain MR-1) is capable of rapid Mn(IV) reduction under conditions of neutral pH and temperatures characteristic of the Oneida Lake, New York, sediments from which it was isolated. MR-1 also reduces Fe(3+) to Fe(2+), and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe(2+) and sulfide act as rapid reductants of Mn. The addition of Fe(3+) or thiosulfate to cultures of MR-1 in the presence of oxidized Mn increases the rate and the extent of Mn reduction relative to that observed in the absence of Fe(3+) or thiosulfate. Furthermore, when Fe(3+) and Mn oxides are present conjointly, Fe(2+) does not appear until the reduction of the oxidized Mn is complete. These results demonstrate that the observed rates of Fe(2+) and sulfide production may underestimate the total rates of Fe and sulfate reduction in those environments containing oxidized Mn. These results also demonstrate the potential impact that a single microbe can exert on sediment geochemistry, and provide the basis for preliminary models of the complexity of microbial and geochemical interactions that occur.

Myers, Charles R.↗

Corrosion Prevention in Copper Combustion Chamber Liners of Liquid Oxygen/Methane Booster Engines

Prior research conducted by United Technologies Research Center and Rockwell International Rocketdyne Division encountered severe copper corrosion while flowing hydrocarbon fuels through copper cooling tubes. These experimental results have very important implications for the development of low-cost, regeneratively cooled, oxygen/hydrocarbon bipropellant booster engines. Aerojet TechSystems undertook a program sponsored by NASA/Lewis Research Center in 1986 with two objectives: (1) to define the corrosive interaction process that occurs between hydrocarbon fuels and copper combustion chamber liner materials, using both static and dynamic test methods, and (2) to identify and demonstrate protective measures against this corrosive process. The results of the first program task demonstrated that the most damaging corrosive process was caused by trace amounts of sulfur-containing impurities in the hydrocarbon fuel which react with the copper chamber liner material to form cuprous sulfide (Cu2S), as reported in Paper No. AlAA 88-3215. Experiments were conducted which demonstrated this corrosive process with Mil-Spec RP-1, propane, and methane fuels in contact with OFHC, NASA-Z, and ZrCu coppers. The preliminary results of the second program task demonstrated that electrodeposited gold and platinum coatings held promise of preventing corrosion of copper chamber liners by methane contaminated with sulfur-containing impurities, as reported in Paper No. AIAA 89-2738. Experiments were conducted which demonstrated greatly reduced corrosion of copper by hydrogen sulfide (H2S) and methyl mercaptan (CH3SH) as measured impurities in methane. This paper presents the concluding, confirmatory results from the second program task. The efficacy of a protective gold coating on NASA-Z copper cooling channel walls was conclusively demonstrated. Tests were conducted in the Aerojet Carbothermal Test Facility which provide realistic simulations of booster engine cooling channel conditions such as temperature, pressure, flow velocity, and heat flux. Dynamic test series were performed with methane containing 5 and 10 ppm (by volume) hydrogen sulfide. Gold-plated and unplated copper alloy specimens were evaluated. The tests demonstrated that gold coatings were effective in preventing corrosion of the copper. Posttest metallographic examinations of the unplated specimens showed severe corrosion as a result of reaction with the sulfur containing contaminant in the fuel. In contrast, posttest metallographic examination of the gold-coated specimens showed no corrosion under similar operating conditions. The findings from metallurgical and chemical analyses of the copper specimens, chemical analysis of the methane, and description of all test conditions are provided. Conclusions are reached as to the efficacy of the plating methods and the effectiveness of the metal coatings in the prevention of corrosion in hydrocarbon-fueled booster engine combustion chamber liners.

S D Rosenberg↗

Effect of space exposure on pyroelectric infrared detectors

Twenty pyroelectric type infrared detectors were flown onboard the Long Duration Exposure Facility (LDEF). The detector chips were of three different pyroelectric materials: lithium-tantalate, strontium-barium-niobate, and triglycine-sulfide. The experiment was passive; no measurements were taken during the flight. Performance of the detectors was measured before and after flight. Postflight measurements revealed that detectors made of lithium-tantalate and strontium-barium-niobate suffered no measureable loss in performance. Detectors made of triglycine-sulfide suffered complete loss of performance, but so did the control samples of the same material. Repoling of the triglycine-sulfide failed to revive the detectors.

Robertson, James B.↗

Lunar sulfur

Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

Kuck, David L.↗

Evolution of ore deposits on terrestrial planets

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

Burns, R. G.↗

A preliminary study of the variability and magnitude of the flux of biogenic sulfur gases from a New Hampshire salt marsh

Salt marshes have highly variable spatial and temporal fluxes of hydrogen sulfide, carbonyl sulfide, methane thiol, dimethyl sulfide, and carbon disulfide (H2S, COS, MeSH, DMS, and CS2, respectively). This variability was tested at nine emission sites in a New Hampshire, USA salt marsh: three replicates in each of three vegetation zones, Spartina alterniflora, S. patens, and a transition zone. Three sites were sampled simultaneously, either within or across vegetation zones, using a dynamic flux chamber technique. Difficulties with calibration and field equipment resulted in fluxes with maximum absolute uncertainties of greater than plus or minus 200 percent. However, the relative uncertainty between subsequent samples was closer to plus or minus 20 percent. Chambers are expected to affect the natural flux of gases by altering the humidity, temperature, and composition of the gas inside the chamber. Summertime fluxes are highest for all gases except COS which demonstrated evidence of a springtime peak. A summertime background flux of 5 to 100 x 10(exp -9) g S/m(sup -2) min was observed for all gases, while S alternifora fluxes of MeSH and DMS were approximately 8 fold and approximately 100 fold higher than S. patens, respectively. DMS and MeSH fluxes were higher during the day than at night. Evidence of COS uptake by plants was observed. CS2 appeared to be the quantitatively least important sulfur gas emitted. Improved laboratory and sample collection techniques and further data collection in the field will yield information on the details of salt marsh variability, will improve estimates of the error associated with single flux measurements, and will allow a more accurate estimation of sulfur fluxes from salt marshes based on vegetation and area coverage data. Inability to control the temperature and humidity inside of the chamber remain significant problems with the chamber design.

Morrison, Michael Cope↗

Sulfate reduction and other sedimentary biogeochemistry in a northern New England salt marsh

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Hines, Mark E.↗

Emissions of sulfur gases from wetlands

Data on the emissions of sulfur gases from marine and freshwater wetlands are summarized with respect to wetland vegetation type and possible formation mechanisms. The current data base is largest for salt marshes inhabited by Spartina alterniflora. Both dimethyl sulfide (DMS) and hydrogen sulfide (H2S) dominate emissions from salt marshes, with lesser quantities of methyl mercaptan (MeSH), carbonyl sulfide (COS), carbon disulfide (CS2) and dimethyl disulfide (DMDS) being emitted. High emission rates of DMS are associated with vegetation that produces the DMS precursor dimethylsulfonionpropionate (DMSP). Although large quantities of H2S are produced in marshes, only a small percentage escapes to the atmosphere. High latitude marshes emit less sulfur gases than temperate ones, but DMS still dominates. Mangrove-inhabited wetlands also emit less sulfur than temperate S. alterniflora marshes. Few data are available on sulfur gas emissions from freshwater wetlands. In most instances, sulfur emissions from temperate freshwater sites are low. However, some temperate and subtropical freshwater sites are similar in magnitude to those from marine wetlands which do not contain vegetation that produces DMSP. Emissions are low in Alaskan tundra but may be considerably higher in some bogs and fens.

Hines, Mark E.↗

Fragments of ancient lunar crust: Ferroan noritic anorthosites from the descartes region of the Moon

Noritic anorthosite clasts from breccia 67016 have bulk compositions similar to that of the upper crust of the Moon and petrogenetic affinities with pristine ferroan anorthosites. Rb-Sr and Sm-Nd isotopic compositions of mineral separates from one of these clasts suggest very old (greater than or = 4.4 Ga) ages, but interpretation of these data is complicated by the multi-stage history of the clasts which involved magmatic crystallization, brecciation, subsolidus recrystallization, and sulfide metasomatism. These clasts record some of the earliest events on the Moon, including early crust formation, accretionary bombardment, and degassing of the lunar interior. Modal analyses of these clasts show they are now composed of about 70 percent plagioclase, 28 percent pyroxene, 2 percent troilite, and minor amounts of ilmenite and chromite. No metallic iron, phosphates, or other trace phases were observed. Olivine is very rare, occurring only as relicts within secondary troilite+pyroxene intergrowths which may reflect reaction of olivine with sulfurous vapors. PIXE proton microprobe analyses of the sulfides show that the metasomatism was accompanied by enrichments of Cu, Zn, Ni, Se, and Sb. The clasts have been only mildly shocked since the observed texture was established. Major and minor element mineral compositions are very homogeneous and strikingly similar to those of pristine ferroan anorthosites. Pyroxene compositions indicate equilibration temperatures of 850-900 C. Except for the sulfide and chalcophile element metasomatism, these clasts appear to be essentially monomict and probably represent a noritic member of the ferroan anorthosite suite. Their low Ni contents and Ni/Co ratios are consistent with the interpretation of these clasts as igneous rocks which have escaped mixing with meteoritic material.

Norman, M. D.↗

Gas exchange in wetlands: Controls and remote sensing

This project was directed toward the quantification of fluxes of gaseous biogenic sulfur compounds from freshwater wetlands. These compounds (primarily hydrogen sulfide (H2S), dimethyl sulfide (DMS), and carbonyl sulfide (OCS)) have been implicated in the regulation of planetary albedo by the formation of microscopic atmospheric aerosols when they oxidize, and the further role of these aerosols as cloud condensation nuclei (CCN). The role of continental sources and sinks for these compounds is poorly understood. The present study was undertaken to quantify the source and sink strength of high latitude wetlands, and to delineate factors that regulate this flux.

Hines, Mark E.↗

Troilite formation kinetics and growth mechanism in the solar nebula

Troilite formation via the reaction Fe(s) + H2S(g) + H2(g) is the major mechanism for S retention in grains in the solar nebula. Thermodynamic calculations predict that troilite condenses from a solar composition gas. We present experimental results on the kinetics and growth of troilite crystals on Fe metal at temperature (450-650 C) and composition (50-1000 ppm H2S in H2) conditions similar to those in the solar nebula. The fraction of Fe reacted (based on gravimetric data) is plotted at 450, 505, 575, and 650 C. The thickness change of unreacted iron (measured by optical microscopy) is plotted at 575 and 650 C vs. time. the weight change per unit area varies as the square root of time at the lower temperatures and varies linearly with time at the highest temperature. The growth behavior along the lower isotherms is due to diffusion. This behavior suggests sulfide diffusion to the metal-sulfide interface and suggests Fe(2+) diffusion to the sulfide-gas interface. The reaction along the highest isotherm appears to be interface controlled. The formation of troilite crystals is a rapid process forming measurable layers in a few hours. The crystalgrowth is complicated. Initially there are intergrowths of troilite into the pure Fe metal. As the reaction progresses two distinct layers of troilite crystals form. One is in contact with the Fe metal and consists of small randomly oriented crystals with pore space between them. The outermost layer contains large crystals that are all oriented in the same direction. The intergrowth layer is much smaller at 650 C than at 575 C. This suggest that FeS nucleation is inhibited at the higher temperature, accounting for the initially slower reaction rate. Once nucleated, the reaction kinetics are apparently controlled by the growth of the crystals at the interface.

Lauretta, D. S.↗