Search NASA⌕ Search

SEARCH · Search NASA

Results for “COPPER 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 91 records · Page 5

Cu site differentiation in tetracopper(I) sulfide clusters enables biomimetic N 2 O reduction

Copper clusters feature prominently in both metalloenzymes and synthetic nanoclusters that mediate catalytic redox transformations of gaseous small molecules. Such reactions are critical to biological energy conversion and are expected to be crucial parts of renewable energy economies. However, the precise roles of individual metal atoms within clusters are difficult to elucidate, particularly for cluster systems that are dynamic under operating conditions. Here, we present a metal site-specific analysis of synthetic Cu 4 (μ 4 -S) clusters that mimic the Cu Z active site of the nitrous oxide reductase enzyme. Leveraging the ability to obtain structural snapshots of both inactive and active forms of the synthetic model system, we analyzed both states using resonant X-ray diffraction anomalous fine structure (DAFS), a technique that enables X-ray absorption profiles of individual metal sites within a cluster to be extracted independently. Using DAFS, we found that a change in cluster geometry between the inactive and active states is correlated to Cu site differentiation that is presumably required for efficient activation of N 2 O gas. More precisely, we hypothesize that the Cu δ+ ∙∙∙Cu δ- pairs produced upon site differentiation are poised for N 2 O activation, as supported by computational modeling. These results provide an unprecedented level of detail on the roles of individual metal sites within the synthetic cluster system and how those roles interplay with cluster geometry to impact the reactivity function. We expect this fundamental knowledge to inform understanding of metal clusters in settings ranging from (bio)molecular to nanocluster to extended solid systems involved in energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The use of ERTS-1 images in the search for large sulfide deposits in the Chagai District, Pakistan

The author has identified the following significant results. Visual examination of color composites was tested under relatively ideal conditions for direct detection of large hydrothermal sulfide deposits at the low-grade porphyry copper deposit at Saindak, western Chagai District, Pakistan. The Saindak deposit is characterized by an elongate zone of easily eroded sulfide-rich rock surrounded by a resistant rim of hornfels and propylitically altered rock. The geomorphic features related to the Saindak deposit are easily distinguished on ERTS-1 images. Attempts to detect a color anomaly using false-color composites were not successful. About 36,000 square km of the western Chagai District were examined on false-color composites for direct evidence of large sulfide deposits. New geologic information acquired from the images was used in conjunction with the known geology to evaluate two previously known proposed areas and to suggest seven additional targets for field checking, one of which is proposed on the basis of tonal anomaly alone. The study also showed that Saindak-type deposits are not likely to be present in some extensive areas of the Chagai District; and also that a rim like that at Saindak does not form if regional metamorphism has increased the resistance of the country rock to erosion.

Schmidt, R. G.↗

Studies of the mechanisms of turbine fuel instability

The formation of insoluble deposits in a Jet A, a Diesel, and a model fuel (1/10 v/v tetralin/dodecane) was studied. Experiments were conducted using glass containers at 394 K with an air/fuel ratio of 14/1. The effects of addition of ppm levels of various compounds on deposit formation were evaluated. Nitrogen heterocycles were shown to produce a basicity dependent acceleration of deposition. Thiols and thiophene were shown to increase deposition while sulfides and disulfides act as inhibitors. Copper metal and its salts also promote deposition. Results of various instrumental analyses of deposits and development of a high performance liquid chromatographic method for monitoring deposit precursors are discussed.

Daniel, S. R.↗

Hydrocarbon-fuel/combustion-chamber-liner materials compatibility

The results of dynamic tests using methane and NASA-Z copper test specimen under conditions that simulate those expected in the cooling channels of a regeneratively cooled LOX/hydrocarbon booster engine operating at chamber pressures up to 3000 psi are presented. Methane with less than 0.5 ppm sulfur contamination has little or no effect on cooling channel performance. At higher sulfur concentrations, severe corrosion of the NASA-Z copper alloy occurs and the cuprous sulfide Cu2S, thus formed impedes mass flow rate and heat transfer efficiency. Therefore, it is recommended that the methane specification for this end use set the allowable sulfur content at 0.5 ppm (max). Bulk high purity liquid methane that meets this low sulfur requirement is currently available from only one producer. Pricing, availability, and quality assurance are discussed in detail. Additionally, it was found that dilute sodium cyanide solutions effectively refurbish sulfur corroded cooling channels in only 2 to 5 minutes by completely dissolving all the Cu2S. Sulfur corroded/sodium cyanide refurbished channels are highly roughened and the increased surface roughness leads to significant improvements in heat transfer efficiency with an attendant loss in mass flow rate. Both the sulfur corrosion and refurbishment effects are discussed in detail.

Homer, G. David↗

Identification of geostructures of continental crust, particularly as they relate to mineral-resource evaluation

The authors have identified the following significant results. As a precursor to the ERTS-1 investigation, the spatial relationship of geostructures seen on Nimbus IDCS photographs to the distribution of mineralized areas in Alaska and western Canada was analyzed to determine the possible metallogenic significance of the geostructures. In Canada, mercury and porphyry molybdenum deposits are closely associated with strong northwest-trending fault systems; the development of mineralized regions seems related to major crustal zones or fractures trending southwestward across the Cordillera from the Precambrian shield. In Alaska, comparison of the northeast- and northwest-trending set of possible crustal structures shown on the Nimbus photo, with the distribution of known mineral deposits suggests a similar relationship. The mineralized region of massive sulfides in Prince William Sound and upper Copper River areas and of porphyry coppers in the Nabesna area forms a broad northeast-trending belt possibly related to the Minto Arch on the Shield. The belt of metalliferous deposits in the western Alaska Range follows a comparable northeast trend. Mercury deposits, suggested by many to be fault-controlled, together with most tin and tungsten deposits, occupy a northeast-trending belt between the Bristol Bay-Mackenzie Bay linear and extensions of a linear along the lower Yukon River. This belt intersects the northwest-trending Canadian belt of similar deposits in the Fairbanks area.

Gryc, G.↗

Development of Biological and Electrochemical Technologies for the Clean Extraction of Copper and Critical Materials from Low Grade Ores

As we transition toward renewable energy resources and electrification, there will be an increasing demand for critical materials, including copper. While copper is currently mined in the US, processing capacity is not sufficient, and intermediate mining products are shipped to Asia for further processing. The goal of this research was to develop a transformative hydrometallurgical process for the production of copper from low-grade ores that would eliminate the need for smelting and would increase the domestic processing capacity in the US, The project initially focused on the electrochemical reduction of copper concentrate using vanadium, followed by the biological oxidation to produce a stream compatible with existing solvent extraction and electrowinning operations. We discovered an efficient electrochemical process that could produce copper salts from concentrate without the need for biological oxidation, and this technology has been licensed and spun-off into a start-up company. The microbes involved in the current state-of-the-art bioleaching processes were genetically modified to introduced a number of new traits, including increased sulfur oxidation, salt-tolerance, and binding of other critical metals such as cobalt, molybdenum, rhenium, and the rare earth elements. The project was extended to also explore the electrochemical oxidation of copper concentrate using cerium which would potentially eliminate production of hydrogen sulfide that occurs with the reductive leaching process. This technology was found to have slower kinetics, however could it still be developed as an alternative process for domestic copper production and has been found to be applicable to other critical minerals.

42 ENGINEERING↗

Stable Anode–Free All–Solid–State Lithium Battery through Tuned Metal Wetting on the Copper Current Collector

A stable anode-free all-solid-state battery (AF-ASSB) with sulfide-based solid-electrolyte (SE) (argyrodite Li 6 PS 5 Cl) is achieved by tuning wetting of lithium metal on “empty” copper current-collector. Lithiophilic 1 µm Li 2 Te is synthesized by exposing the collector to tellurium vapor, followed by in situ Li activation during the first charge. The Li 2 Te significantly reduces the electrodeposition/electrodissolution overpotentials and improves Coulombic efficiency (CE). During continuous electrodeposition experiments using half-cells (1 mA cm –2 ), the accumulated thickness of electrodeposited Li on Li 2 Te–Cu is more than 70 µm, which is the thickness of the Li foil counter-electrode. Full AF-ASSB with NMC811 cathode delivers an initial CE of 83% at 0.2C, with a cycling CE above 99%. Additionally, cryogenic focused ion beam (Cryo-FIB) sectioning demonstrates uniform electrodeposited metal microstructure, with no signs of voids or dendrites at the collector-SE interface. Electrodissolution is uniform and complete, with Li 2 Te remaining structurally stable and adherent. By contrast, an unmodified Cu current-collector promotes inhomogeneous Li electrodeposition/electrodissolution, electrochemically inactive “dead metal,” dendrites that extend into SE, and thick non-uniform solid electrolyte interphase (SEI) interspersed with pores. Density functional theory (DFT) and mesoscale calculations provide complementary insight regarding nucleation-growth behavior. Unlike conventional liquid-electrolyte metal batteries, the role of current collector/support lithiophilicity has not been explored for emerging AF-ASSBs.

36 MATERIALS SCIENCE↗

Auger analysis of oxygen and sulfur interactions with various metals and the effect of sliding on these interactions

Various gases were adsorbed to copper, aluminum, and chromium surfaces. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Chemisorption was conducted on static surfaces and during dynamic friction experiments. An Auger cyclindrical mirror analyzer was used to monitor surface films. The sulfur containing gases adsorbed readily to all surfaces. Exposures of as little as 0.000001 (torr)(sec) (1 langmuir) were sufficient to reduce friction. Sliding contact did not affect chemisorption of copper or aluminum but did affect chemisorption to chromium surfaces. Oxygen removed sulfur films from all surfaces at room temperature (23 C). Gaseous exposures were from 0.000001 to 0.01 (torr)(sec) (1 to 10,000 langmuirs).

Buckley, D. H.↗

Liquid Copper and Iron Production from Chalcopyrite, in the Absence of Oxygen

Clean energy infrastructure depends on chalcopyrite: the mineral that contains 70% of the world’s copper reserves, as well as a range of precious and critical metals. Smelting is the only commercially viable route to process chalcopyrite, where the oxygen-rich environment dictates the distribution of impurities and numerous upstream and downstream unit operations to manage noxious gases and by-products. However, unique opportunities to address urgent challenges faced by the copper industry arise by excluding oxygen and processing chalcopyrite in the native sulfide regime. Through electrochemical experiments and thermodynamic analysis, gaseous sulfur and electrochemical reduction in a molten sulfide electrolyte are shown to be effective levers to selectively extract the elements in chalcopyrite for the first time. We present a new process flow to supply the increasing demand for copper and byproduct metals using electricity and an inert anode, while decoupling metal production from fugitive gas emissions and oxidized by-products.

36 MATERIALS SCIENCE↗

Doping-modulated strain control of bifunctional electrocatalysis for rechargeable zinc–air batteries

Changes in the local atomic arrangement in a crystal caused by lattice-mismatch-induced strain can efficiently regulate the performance of electrocatalysts for zinc–air batteries (ZABs) in many manners, mainly due to modulated electronic structure configurations that affect the adsorption energies for oxygen-intermediates formed during oxygen reduction and evolution reactions (ORR and OER). However, the application of strain engineering in electrocatalysis has been limited by the strain relaxation caused by structural instability such as dissolution and destruction, leading to insufficient durability towards the ORR/OER. In this work, we propose a doping strategy to modulate the phase transition and formation of self-supported cobalt fluoride–sulfide (CoFS) nanoporous films using a low amount of copper (Cu) as a dopant. This well-defined Cu–CoFS heterostructure overcomes the obstacle of structural instability. Our study of the proposed Cu–CoFS also helps establish the structure–property relationship of strained electrocatalysts by unraveling the role of local strain in regulating the electronic structure of the catalyst. As a proof-of-concept, the Cu–CoFS electrocatalyst with doping-modulated strain exhibited superior onset potentials of 0.91 V and 1.49 V for the ORR and OER, respectively, surpassing commercial Pt/C@RuO 2 and benchmarking non-platinum group metal (non-PGM) catalysts. ZABs with the Cu–CoFS catalyst delivered excellent charge/discharge cycling performance with an extremely low voltage gap of 0.5 V at a current density of 10 mA cm –2 and successively 0.93 V at a high current density of 100 mA cm –2 and afforded an outstanding peak power density of 255 mW cm –2 .

25 ENERGY STORAGE↗

Environmental Durability of Coated GRCop-84 Copper Alloys

An advanced Cu-8(at.%)Cr-4%Nb alloy developed at NASA's Glenn Research Center, and designated as GRCop-84, is currently being considered for use as liners in combustor chambers and nozzle ramps in NASA s future generations of reusable launch vehicles (RLVs). However, past experience has shown that unprotected copper alloys undergo an environmental attack called "blanching" in rocket engines using liquid hydrogen as fuel and liquid oxygen as the oxidizer. Potential for sulfidation attack of the liners in hydrocarbon-fueled engines is also of concern. As a result, protective overlay coatings alloys are being developed for GRCop-84. The oxidation behavior of several new coating alloys has been evaluated. GRCop-84 specimens were coated with several copper and nickel-based coatings, where the coatings were deposited by either vacuum plasma spraying or cold spraying techniques. Coated and uncoated specimens were thermally cycled in a furnace at different temperatures in order to evaluate the performance of the coatings. Additional studies were conducted in a high pressure burner rig using a hydrocarbon fuel and subjected to a high heat flux hydrogen-oxygen combustion flame in NASA s Quick Access Rocket Exhaust (QARE) rig. The performance of these coatings are discussed.

Raj, Sai V.↗

The Explorer XVI Micrometeoroid Satellite: Description and Preliminary Results for the Period December 16, 1962 Through January 13, 1963

Explorer XVI (1962 Beta Chi l) data that have been analyzed for the period between December 16, 1962 (launch date), and January 13, 1963, indicate that the orbit achieved was close to the predicted orbit. Ten punctures of annealed 0.001-inch-thick beryllium-copper have been used to determine a puncture rate of 0.035 per square foot per day in this material. One puncture of a 0.002-inch-thick sample has also occurred in this period. A tentative evaluation of the puncture rate for the 0.001-inch beryllium-copper in terms of the rate for an equivalent thickness of aluminum has been attempted, and the result has been compared with two different puncture rate estimates. The three micrometeoroid impact detecting systems are operating. Counting rates for the high- and low-sensitivity systems were close to anticipated values near the end of one week. Two of the 0.001-inch-steel-covered grid detectors have been punctured, but none of the 0.003- or 0.006-inch-steel-covered grid detectors have indicated punctures. One of the cadmium sulfide cells indicates three punctures of the 0.00025-inch Mylar cover. None of the 0.002- or 0.003-inch-copper-wire cards have indicated a break in the period covered. Telemetry temperatures were initially higher than expected although they remained well within operating limits. Sensor temperatures have remained within the expected bounds.

Micrometeoroid↗

Crystalline phase transitions and water-soluble complexes of copper(Ⅰ) 2-hydroxyethanethiolate

We report the coordination polymer copper(I) 2-hydroxyethanethiolate, (CuSCH 2 CH 2 OH) n , though insoluble in all common solvents, dissolved readily in basic aqueous solutions of the thiolate anion (HOCH 2 CH 2 S – ) of 2-mercaptoethanol to form a single species: the tetranuclear cluster [Cu 4 (μ-SCH 2 CH 2 OH) 6 ] 2– . From this solution were grown X-ray quality single crystals of copper(I) 2-hydroxyethanethiolate. This compound underwent a hitherto unknown crystal phase transition at ca. 6 °C, from point group P2 1 2 1 2 1 to Pna2 1 , with noticeable changes in the geometry of the Cu-S layer and in the orientation of the alkylthiolate side chains. When the bulky base tetrabutylammonium hydroxide was employed in the aqueous thiolate solution used to dissolve (CuSCH 2 CH 2 OH) n , the water-soluble polynuclear copper(I) complex bis(tetrabutylammonium) hexakis(μ-2-hydroxyethanethiolato) tetracuprate(I), [(C 4 H 9 ) 4 N] 2 [Cu 4 (μ-SCH 2 CH 2 OH) 6 ], could be isolated as X-ray quality crystals. Structural characterization of this complex revealed a tetrahedral arrangement of copper(I) centers with thiolates bridging the edges of the tetrahedra. On standing, this complex degraded to a larger polynuclear Cu(I) sulfide cluster.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The application of remote sensing in geobotanical exploration for metal sulfides

A field study was conducted in Mineral, VA in 1980-82 to test the suitability of remote sensing techniques for geobotanical exploration. It was found that on trees growing over lead sulfide deposits, buds opened later and leaves were smaller than on trees growing on soils with background levels of lead and copper. This difference in leaf growth could be detected in remotely sensed data. In the spring, the smaller leaf size of metal-stressed trees resulted in a greater contribution from the soil and bark to the total reflectance imaged by the sensor. In the fall, the leaves of metal-stressed oaks sensed earlier than surrounding vegetation, which was also detected in remotely sensed data. It is concluded that vegetation growing on lead sulfide deposits has a shorter growing season than surrounding vegetation on unmineralized soil and that remotely sensed data collected at either end of the growing season can be used to locate geobotanical anomalies associated with these deposits.

Masuoka, E. J.↗

The catalytic removal of ammonia and nitrogen oxides from spacecabin atmospheres

Investigations were made on methods for the removal of ammonia and to a lesser extent nitrogen oxides in low concentrations from air. The catalytic oxidation of ammonia was studied over a temperature range of 250 F to 600 F and a concentration range 20 ppm to 500 ppm. Of the catalysts studied, 0.5 percent ruthenium supported on alumina was found to be superior. This material is active at temperatures as low as 250 F and was found to produce much less nitrous oxide than the other two active catalysts, platinum on alumina and Hopcalite. A quantitative design model was developed which will permit the performance of an oxidizer to be calculated. The ruthenium was found to be relatively insensitive to low concentrations of water and to oxygen concentration between 21 percent and 100 percent. Hydrogen sulfide was found to be a poison when injected in relatively large quantities. The adsorption of ammonia by copper sulfate treated silica gel was investigated at temperatures of 72 F and 100 F. A quantitative model was developed for predicting adsorption bed behavior.

Gully, A. J.↗

Influence of various surface pretreatments on adherence of sputtered molybdenum disulfide to silver, gold, copper, and bronze

Solid film lubricants of radio frequency sputtered molybdenum disulfide (MoS2) were applied to silver, gold, copper, and bronze surfaces that had various pretreatments (mechanical polishing, sputter etching, oxidation, and sulfurization). Optical and electron transmission micrographs and electron diffraction patterns were used to interpret the film formation characteristics and to evaluate the sputtering conditions in regard to the film and substrate compatibility. Sputtered MoS2 films flaked and peeled on silver, copper, and bronze surfaces except when the surfaces had been specially oxidized. The flaking and peeling was a result of sulfide compound formation and the corresponding grain growth of the sulfide film. Sputtered MoS2 films showed no peeling and flaking on gold surfaces regardless of surface pretreatment.

Spalvins, T.↗

Cubanite - A new sulfide phase in CI meteorites

Cubanite (CuFe2S3) previously unobserved in meteorites, has been discovered in two carbonaceous chondrites, Orgueil and Alais. The association of this mineral with low-copper pyrrhotite suggests that it formed in a low-temperature environment on the meteorite parent body.

Macdougall, J. D.↗