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Copper sulfide-cadmium sulfide thin film solar cells under simulated orbital conditions, including thermal cycling, constant illumination and temperature effects
Recent advances in copper chalcogenide-based nanocrystals (NCs), copper sulfide, and copper selenide derived nanostructures, have drawn considerable attention. However, reports of crystal phase and shape engineering of binary or ternary copper telluride NCs remain rare. Here, a colloidal hot-injection approach for producing binary copper/tin telluride, and ternary copper tin telluride NCs with controllable compositions, crystal structures, and morphologies is reported. Here, the crystal phase and growth behavior of these tellurides are systematically studied from both experimental and theoretical perspectives.
Detection of radioactive isotopes of polonium is important for understanding natural processes, management and assessment of radioactive waste, and nuclear forensics applications. Further, the most common methods for preparation of polonium samples for alpha spectrometry are electrodeposition and spontaneous deposition which are time consuming. Here, we compare three approaches utilizing rapid microprecipitation from bismuth phosphate, copper sulfide, or tellurium alongside traditional spontaneous deposition methods. From these experiments, results show that copper sulfide microprecipitation recoveries are similar to spontaneous deposition on silver and less time consuming with an approximate five-fold decrease in preparation time, including in the presence of complex matrices like seawater.
Nanoscale semiconductors, known as quantum dots (QDs), possess unique size-tunable optical and electrical properties. With continued research into quantum information storage and quantum communication, the need for near-infrared single photon emitters and absorbers has gained prominence. Lead sulfide QDs have only recently been explored as a reliable near-infrared single photon emitters with the addition of a protective cadmium sulfide shell. Despite the increased air and room temperature stability of these QDs, long photon emission times have limited widespread application. This work examines the enhanced photon emission due to the Purcell effect provided by the layering of copper sulfide. In particle, this work synthesized lead sulfide cores in the 10 nm range, successfully layered cadmium sulfide through cation exchange, and attempted the cation exchange of copper sulfide, as identified with near-infrared absorbance spectra, transmission electron microscopy, and photoluminescence spectra.
Barrier formation studies of copper sulfide and cadmium sulfide in photovoltaic cells
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Diogenites are typically highly brecciated orthopyroxenites that contain 84-100 vol.% orthopyroxene. Common accessory minerals include olivine, chromite, Ca-pyroxene, plagioclase, silica, troilite and Fe-Ni metal. Metal and sulfides are minor phases in diogenites with an average abundance of < 1 vol.% and 0-2 vol.% respectively. However their presence is important, as they could provide information on T-fO2-fS2 conditions and the evolution of the diogenite parent magma during crystallization and/or later metamorphism. We have examined the occurrence of Fe-Ni metal and sulfides in thin sections of several diogenites including, Johnstown, Manegaon, Roda, Shalka, Bilanga, and Tatahouine using optical microscopy and the electron microprobe. Here, we describe three features of metals and sulfides that are common in most of these diogenites. These are: i) The widespread occurrence of pentlandite associated with copper and copper sulfide minerals; ii) Textural evidence that at least some of the metal and sulfide occurring interstitially between, and as inclusions within, orthopyroxene formed from an early immiscible sulfide-oxide liquid; iii) That this sulfide- oxide liquid subsequently fractionated into assemblages containing either Fe-Ni metal, troilite, and chromite or pentlandite, troilite, and copper-bearing sulfide.
Nanoparticles (NPs) and their colloidal aggregates are ubiquitous and play important roles in the transport and release of metals. Knowledge of their dissolution rates and aggregation behavior in solution are crucial for better prediction of their fate in biogeochemical cycling, ecotoxicity, and environmental remediation. There are however significant technical challenges to accurately obtain such information as a result of the heterogeneity and highly dynamic transformation exhibited by NPs, particularly at relatively low particle concentrations in aqueous systems. Here, we quantitatively examine the simultaneous dissolution and aggregation behavior of metal sulfide NPs using single-particle inductively coupled plasma mass spectrometry (spICP–MS). We focus on nickel sulfide (NiS), with additional data presented for copper sulfide (CuS) and cobalt sulfide (CoS). The kinetics of metal release (dissolution and disaggregation) of NiS was fastest under strongly oxidizing conditions (from 0.04 to >3 min –1 with H 2 O 2 ) and were slower under near-neutral (HEPES buffer/H 2 O) and acidic (1 mM HNO 3 ) conditions (≤0.006 min –1 ). Metal release kinetics in HNO 3 was not faster than in H 2 O or HEPES, suggesting that the solution pH has an influence over both the dissolution kinetics of individual particles and the NP aggregation states, which in combination affect metal release rates over time. Between different metal sulfides, the measured metal release rates were largely consistent with predictions based on the crystallinity, solubility products, and specific surface areas of the NPs, following an order of CoS > NiS > CuS. Here, the spICP–MS approach described here can be easily applied to the characterization of metal release and aggregation of other NPs at low concentrations (~10 5 particles/mL) typically found in natural environments.
With recent advances in unconventional drilling technology in the US and around the world, the risks of environmental contamination and exposure due to technologically enhanced naturally occurring radioactive materials (TENORM) from fracking wastes have also surfaced. Although the Permian Basin (southeastern New Mexico, western Texas) has long been a modest producer of oil, the advent of fracking technology a decade ago turned it into hot property for producers. A 2018 assessment of undiscovered, technically recoverable continuous oil and gas resources by the U.S. Geological Survey estimates an average 46.3 billion barrels of oil and 281 trillion cubic feet of gas. This is likely to increase the use of unconventional drilling and TENORM generation. TENORM concentrations in oil and gas exploration and production waste can be several hundred to several thousand times higher than background TENORM concentrations. Both the thorium and uranium decay chains contribute to airborne radionuclides arising from the radon gas escaping the ground and subsequently decaying as airborne particulates. Additionally, radon decay products {sup 210}Pb and {sup 210}Po can build up in scale on the internal surfaces of oil and gas handling pipes and in sludge in refineries, becoming potential inhalation and ingestion hazards for workers. Furthermore, southeastern NM is also home to world's only licensed and operating transuranic nuclear waste repository, the DoE's Waste Isolation Pilot Plant (WIPP). Plutonium isotopes ({sup 239+240}Pu) and {sup 241}Am, are expected to account for more than 99% of the total radioactivity scheduled for disposal in the WIPP repository. Thus, an improved understanding of the environmental fate and transport of TENORM, liberated by unconventional drilling, is essential to assess how best to protect individuals and the environment. In this context, accurate measurement of TENORM and actinides in environmental and biological samples is essential. In this presentation, a new sequential method for the separation and pre-concentration of actinides (Pu, Am, Np) and TENORM (Po, U and Th) derived from oil and gas exploration is proposed. The TEVA method involves a rapid co-precipitation step to remove matrix interferences from the samples, followed by plutonium oxidation state adjustment to Pu (IV) and an incubation period of ∼ 1 hour at 50-60 deg. C to allow the resultant Po (II) to oxidize into Po(IV). The polonium, neptunium, thorium and plutonium are then separated on a TEVA column, while americium and uranium are separated on a TRU column. After separation, the alpha counting source was prepared by micro-precipitation with copper sulfide (CuS) for polonium and neodymium fluoride (NdF{sub 3}) for actinides. The efficiency and reliability of the procedures were tested by analyzing filter, drinking water and frack sand samples. The method is simple, robust and can be performed quickly with excellent removal of interferences, high chemical recovery and very good alpha peak resolution. (authors)
The mineralogy and isotopic composition of sulfur found in hydrothermal deposits associated with five groups of vents along the ridge axis of the East Pacific Rise near 21 deg N latitude are investigated. Solid samples of mixed sulfides and sulfates from mounds, chimneys and the surrounding sediment as well as fresh basaltic glass were examined with a portable X-ray fluorescence spectrometer and by scanning electron microscopy, X-ray diffractometry, and electron microprobe analysis. For the three vents of exit temperature close to 350 C, the chimneys are found to be rich in copper sulfides, while for those of temperatures around 300 C, zinc sulfide is found to predominate. The major sulfides found in the chimneys include wurtzite, chalcopyrite, pyrite and cubanite, with anhydrite the dominant sulfate. Significant mineralogical differences are found between active and inactive vents. The isotopic composition of sulfur in anhydrites from active vents is observed to be close to that of sea water and consistent with a derivation from sea water sulfate. The isotopic composition of sulfur in the sulfide minerals is explained in terms of precipitation from solutions with reduced sulfur derived from basalts or basaltic magmas, and sea water sulfate. Finally, the deposits are interpreted as the results of the mixing of H2S-dominated hydrothermal fluids with cold sea water near the sea floor.
A materials compatibility and thermal stability investigation was conducted using five common liquid hydrocarbon fuels and two structural materials. The tests were performed at the NASA Glenn Research Center Heated Tube Facility under environmental conditions similar to those encountered in regeneratively cooled rocket engines. Scanning-electron microscopic analysis in conjunction with energy dispersive spectroscopy (EDS) was utilized to characterize the condition of the tube inner wall surface and any carbon deposition or corrosion that was formed during selected runs. Results show that the carbon deposition process in stainless steel tubes was relatively insensitive to fuel type or test condition. The deposition rates were comparable for all fuels and none of the stainless steel test pieces showed any signs of corrosion. For tests conducted with copper tubing, the sulfur content of the fuel had a significant impact on both the condition of the tube wall and carbon deposition rates. Carbon deposition rates for the lowest sulfur fuels (2 ppm) were slightly higher than those recorded in the stainless steel tubes with no corrosion observed on the inner wall surface. For slightly higher sulfur content (25 ppm) fuels, nodules that intruded into the flow area were observed to form on the inner wall surface. These nodules induced moderate tube pressure drop increases. The highest sulfur content fuels (400 ppm) produced extensive wall pitting and dendritic copper sulfide growth that was continuous along the entire tube wall surface. The result of this tube degradation was the inability to maintain flow rate due to rapidly increasing test section pressure drops. Accompanying this corrosion were carbon deposition rates an order of magnitude greater than those observed in comparable stainless steel tests. The results of this investigation indicate that trace impurities in fuels (i.e. sulfur) can significantly impact the carbon deposition process and produce unacceptable corrosion levels in copper based structural materials.
Copper chalcogenide nanocrystals find applications in photovoltaic inks, bio labels, and thermoelectric materials. We reveal insights in the nucleation and growth during synthesis of anisotropic Cu 2 ZnSnS 4 nanocrystals by simultaneously performing in situ X-ray absorption spectroscopy (XAS) and small-angle X-ray scattering (SAXS). Real-time XAFS reveals that upon thiol injection into the reaction flask, a key copper thiolate intermediate species is formed within fractions of seconds, which decomposes further within a narrow temperature and time window to form copper sulfide nanocrystals. These nanocrystals convert into Cu 2 ZnSnS 4 nanorods by sequentially incorporating Sn and Zn. Real-time SAXS and ex situ TEM of aliquots corroborate these findings. Our work demonstrates how combined in situ X-ray absorption and small-angle X-ray scattering enables the understanding of mechanistic pathways in colloidal nanocrystal formation.
Additive manufacturing of polymers is a widely used and growing technology throughout the DOE complex. Composite filaments for Fused Deposition Modeling (FDM) printers are commonly used to enhance material properties such as mechanical strength, operating temperature and chemical resistance. Radio luminescent properties were added to 3D filaments by impregnating clear poly(ethylene terephthalate)-glycol (PETG) with X-ray scintillator powder. X-ray scintillators have unique, narrow emission spectra which can be imaged with low light DSLR cameras, photomultiplier tubes, or spectrometers. Filament Production: 1. Pellets are loaded into the hopper. 2. Temperature and extrusion speed are set on extruder. 3. Extruder turned on and filament is pulled from nozzle along air path to cool. 4. Spooler drive speeds set. 5. Filament is inserted through Filameasure then guided along drive wheels and into traverse. 6. Parameters adjusted to obtain 1.75 mm diameter 7. Filament is inserted into spooler wheel. Traverse speed set and slip nut adjusted to make tight and even roll. From Raw Materials to Printed Part: Clear PETG pellets were dipped in ZnS:Cu scintillator powder to coat pellets. Coated and uncoated pellets were mixed together before inserting into hopper. Filament showed trace amounts of powder and luminesced under UV light. Powder distribution is random and not reproducible thus providing a unique identification marker potentially useful for national security applications. Multiple X-ray scintillators can be arranged in a panel to discriminate incident X-ray photon energies. Variable panel arrangement: pixelated, layered, solid from homogenous filament. Ratio of emission intensities. Response varies with incident photon energy. Spectrally separate scintillators. Scintillators: Yttrium Oxide Europium Doped - Red, Gadolinium Oxysulfide Terbium Doped - Green, Barium Magnesium Aluminate Europium Doped - Blue, Zinc Sulfide Copper Doped - Green. Powder concentrations will need to be increased in the filament for use in the energy discriminating panel. Homogeneity in the filament will be a challenge that can be solved by turning the pellets into a powder and mixing it with scintillator powder prior to extrusion. The panels will be tested using x-ray booths and button sources such as Am-241, Cs-137, and Co-60.
Abstract Anode‐free all solid‐state batteries (AF‐ASSBs) employ “empty” current collector with three active interfaces that determine electrochemical stability; lithium metal – Solid electrolyte (SE) interphase (SEI‐1), lithium – current collector interface, and collector – SE interphase (SEI‐2). Argyrodite Li 6 PS 5 Cl (LPSCl) solid electrolyte (SE) displays SEI‐2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W‐Cu) controls the three interfaces and allows for state‐of‐the‐art electrochemical performance in half‐cells and fullcells. AF‐ASSB with NMC811 cathode achieves 150 cycles with Coulombic efficiency (CE) above 99.8%. With high mass‐loading cathode (8.6 mAh cm −2 ), AF‐ASSB retains 86.5% capacity after 45 cycles at 0.2C. During electrodeposition of Li, gradient Li‐Mg solid solution is formed, which reverses upon electrodissolution. This promotes conformal wetting/dewetting by Li and stabilizes SEI‐1 by lowering thermodynamic driving force for SE reduction. Inert refractory W underlayer is required to prevent ongoing formation of SEI‐2 that also drives electrochemical degradation. Inert Mo and Nb layers likewise protect Cu from corroding, while Li‐alloying layers (Mg, Sn) are less effective due to ongoing volume changes and associated pulverization. Mechanistic explanation for observed Li segregation within alloying Li x Mg layer is provided through mesoscale modelling, considering opposing roles of diffusivity differences and interfacial stresses.
The development of nanomaterials often relies on wet-chemical synthesis performed in reflux setups using round-bottom flasks. Here, an alternative approach to synthesize nanomaterials is presented that uses glass tubes designed for NMR analysis as reactors. This approach uses less solvent and energy, generates less waste, provides safer conditions, is less prone to contamination, and is compatible with high-throughput screening. The benefits of this approach are illustrated by an in breadth study with the synthesis of gold, iridium, osmium, and copper sulfide nanoparticles.