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At least 37 records · Page 2

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

Advancing GRCop-based Bimetallic Additive Manufacturing to Optimize Component Design and Applications for Liquid Rocket Engines

Additive manufacturing (AM) is advancing many applications of component design for liquid rocket engines. The ability to rapidly design and manufacture components has provided significant opportunities for development and flight programs across the propulsion industry. AM has demonstrated significant advantages that include cost and schedule savings in addition to performance improvements through new design opportunities. While these performance advantages can be in the characteristics of complex design features, they can also be in the form of new materials. AM has been demonstrated in these various component applications using a variety of metal alloys, many of which are traditional alloys for extreme environments. Additional developments were completed using AM to provide new alloys and maturing these material uses for high performance applications. Almost all of the prior developments across component applications have focused on single-alloys in these AM processes. NASA and industry partners have focused in recent years to advance processing to create bimetallic and multicomponent AM processes and materials. The role of multi-alloy AM offers advantages since it can further optimize weight, optimize reliability and performance by increasing the strength to weight ratio of a component, and can optimize materials for various engineering requirements. This is particularly important in liquid rocket engine combustion devices that must reject heat in high heat flux environments yet maintain adequate structural margins under high operational pressure. NASA has been exploring several AM processes, materials, and applications for combustion devices, specifically combustion chambers, injectors, nozzles, and ignition systems. These components require fine geometric features for internal flow or cooling functionality. They experience high thermal gradients across thin-walls and must survive high pressures and temperatures from propellants and the combustion process. A copper-based alloy is normally used to provide high thermal conductivity, but at the detriment of increased weight if used as a single alloy in an AM chamber. Various AM processes were demonstrated on these components using a copper-based alloy/superalloy bimetallic solution. The AM processes being explored individually and in combination for bimetallic applications include Laser Powder Bed Fusion (L-PBF), Laser Powder Directed Energy Deposition (LP-DED), and cold spray. The combination of bimetallic material combinations explored in this research include copper-based material primarily and superalloys, Inconel 625 or NASA HR-1. The various aspects of the additive manufacturing processes and challenges, materials characterization, and the testing of bimetallic components in a relevant environment will be discussed.

Additive Manufacturing

Advancing GRCop-based Bimetallic Additive Manufacturing to Optimize Component Design and Applications for Liquid Rocket Engines

Additive manufacturing (AM) is advancing many applications of component design for liquid rocket engines. The ability to rapidly design and manufacture components has provided significant opportunities for development and flight programs across the propulsion industry. AM has demonstrated significant advantages that include cost and schedule savings in addition to performance improvements through new design opportunities. While these performance advantages can be in the characteristics of complex design features, they can also be in the form of new materials. AM has been demonstrated in these various component applications using a variety of metal alloys, many of which are traditional alloys for extreme environments. Additional developments were completed using AM to provide new alloys and maturing these material uses for high performance applications. Almost all of the prior developments across component applications have focused on single-alloys in these AM processes. NASA and industry partners have focused in recent years to advance processing to create bimetallic and multicomponent AM processes and materials. The role of multi-alloy AM offers advantages since it can further optimize weight, optimize reliability and performance by increasing the strength to weight ratio of a component, and can optimize materials for various engineering requirements. This is particularly important in liquid rocket engine combustion devices that must reject heat in high heat flux environments yet maintain adequate structural margins under high operational pressure. NASA has been exploring several AM processes, materials, and applications for combustion devices, specifically combustion chambers, injectors, nozzles, and ignition systems. These components require fine geometric features for internal flow or cooling functionality. They experience high thermal gradients across thin-walls and must survive high pressures and temperatures from propellants and the combustion process. A copper-based alloy is normally used to provide high thermal conductivity, but at the detriment of increased weight if used as a single alloy in an AM chamber. Various AM processes were demonstrated on these components using a copper-based alloy/superalloy bimetallic solution. The AM processes being explored individually and in combination for bimetallic applications include Laser Powder Bed Fusion (L-PBF), Laser Powder Directed Energy Deposition (LP-DED), and cold spray. The combination of bimetallic material combinations explored in this research include copper-based material primarily and superalloys, Inconel 625 or NASA HR-1. The various aspects of the additive manufacturing processes and challenges, materials characterization, and the testing of bimetallic components in a relevant environment will be discussed.

Additive Manufacturing

Exploration for porphyry copper deposits in Pakistan using digital processing of Landsat-1 data

Rock-type classification by digital-computer processing of Landsat-1 multispectral scanner data has been used to select 23 prospecting targets in the Chagai District, Pakistan, five of which have proved to be large areas of hydrothermally altered porphyry containing pyrite. Empirical maximum and minimum apparent reflectance limits were selected for each multispectral scanner band in each rock type classified, and a relatively unrefined classification table was prepared. Where the values for all four bands fitted within the limits designated for a particular class, a symbol for the presumed rock type was printed by the computer at the appropriate location. Drainage channels, areas of mineralized quartz diorite, areas of pyrite-rich rock, and the approximate limit of propylitic alteration were very well delineated on the computer-generated map of the test area. The classification method was used to evaluate 2,100 sq km in the Mashki Chah region. The results of the experiment show that outcrops of hydrothermally altered and mineralized rock can be identified from Landsat-1 data under favorable conditions.

Schmidt, R. G.

Hydrogen and oxygen sensor development

A reliable and low cost gas sensor was investigated for instantaneously detecting H2 in N2, H2 in air, and O2 in N2. The major portion of the research was spent in developing a sensor which would instantaneously detect H2 to + or - 50 ppm even in the presence of trace amounts of other gases. The experimental procedures used to provide the performance characteristics for the various oscillators are discussed describing the equipment with help of schematics and photographs where applicable. The resulting performance is given in graphical form. In some cases both hydrogen and helium may be present and since both of them effect gas sensors similarly, a method was found to determine the concentration of each. The methods developed are grouped into the following four broad categories: pure metal response, variation in heat conductivity, reduction methods, and exotic processes. From the above it was decided for the present to use a copper oxide reduction process as this process was demonstrated to be capable of determining the concentrations of hydrogen and helium respectively in a gas mixture with air or nitrogen.

Farber, E. A.

Fabricating Copper Nanotubes by Electrodeposition

Copper tubes having diameters between about 100 and about 200 nm have been fabricated by electrodeposition of copper into the pores of alumina nanopore membranes. Copper nanotubes are under consideration as alternatives to copper nanorods and nanowires for applications involving thermal and/or electrical contacts, wherein the greater specific areas of nanotubes could afford lower effective thermal and/or electrical resistivities. Heretofore, copper nanorods and nanowires have been fabricated by a combination of electrodeposition and a conventional expensive lithographic process. The present electrodeposition-based process for fabricating copper nanotubes costs less and enables production of copper nanotubes at greater rate.

Yang, E. H.

Low Cost, Upper Stage-Class Propulsion

The low cost, upper stage-class propulsion (LCUSP) element will develop a high strength copper alloy additive manufacturing (AM) process as well as critical components for an upper stage-class propulsion system that will be demonstrated with testing. As manufacturing technologies have matured, it now appears possible to build all the major components and subsystems of an upper stage-class rocket engine for substantially less money and much faster than traditionally done. However, several enabling technologies must be developed before that can happen. This activity will address these technologies and demonstrate the concept by designing, manufacturing, and testing the critical components of a rocket engine. The processes developed and materials' property data will be transitioned to industry upon completion of the activity. Technologies to enable the concept are AM copper alloy process development, AM post-processing finishing to minimize surface roughness, AM material deposition on existing copper alloy substrate, and materials characterization.

Vickers, John

Dual interfacial H-bonding-enhanced deep-blue hybrid copper–iodide LEDs

Solution-processed light-emitting diodes based on non-toxic copper–iodide hybrids are a compelling solution for efficient and stable deep-blue lighting, owing to their tunability, high photoluminescence efficiency and environmental sustainability. Here we present a hybrid copper–iodide that shows near-unity photoluminescence quantum yield (99.6%) with an emission wavelength of 449 nm and colour coordinates (0.147, 0.087), alongside its emission mechanism and charge transport characteristics. Here, we use the thin film of this hybrid as the sole active emissive layer to fabricate deep-blue light-emitting diodes and subsequently enhance the device performance through a dual interfacial hydrogen-bond passivation strategy. This synergetic surface modification approach, integrating a hydrogen-bond-acceptor self-assembled monolayer with an ultrathin polymethyl methacrylate capping layer, effectively passivates both heterojunctions of the copper–iodide hybrid emissive layer and optimizes charge injections. We achieve a maximum external quantum efficiency of 12.57%, a maximum luminance of 3,970.30 cd m −2 with colour coordinates (0.147, 0.091) and an excellent operational stability (half-lifetime) of 204 hours under ambient conditions. We further showcase a large-area device of 4 cm 2 that maintains high efficiency. Our findings reveal the potential of copper–iodide-based hybrid materials for applications in solid-state lighting and display technologies, offering a versatile strategy for enhancing device performances.

14 SOLAR ENERGY

High intensity copper atom beam - Preliminary results

The development of a nozzle which gas-dynamically accelerates neutral copper atoms at controlled energy levels and flux rates suitable for the investigation of inelastic copper atom collision processes is reported. Preliminary test data demonstrate that vapor-deposited rhenium nozzles do not degrade in the presence of copper vapor at high temperatures. Operation with high purity helium gas at nozzle stagnation temperatures in the range 2650-2700 K and total stagnation pressures from 1/4 to 2 atm with continuous copper atom flux rates of approximately 10 to the 18th power per second has been maintained, for a total time of 8-1/2 h to date.

Kelly, A. J.

Upstream Extraction of Tellurium from Copper Concentrates

A major barrier to increasing CdTe PV module production is the availability of tellurium (Te), an element necessary to manufacture CdTe PV cells that currently has a very limited supply. Most Te is obtained from ore extracted for copper mining, but the current processing methods only extract 3-4% of the available Te in this ore, with the rest being discarded during other processing steps. This project aims to increase Te supply by developing an innovative extraction method that will recover more Te from the copper ore earlier in the process. This method will also extract toxic elements like antimony and arsenic, making the copper mining process more environmentally friendly.

14 SOLAR ENERGY

Ceruloplasmin copper induces oxidant damage by a redox process utilizing cell-derived superoxide as reductant

Oxidative damage by transition metals bound to proteins may be an important pathogenic mechanism. Ceruloplasmin (Cp) is a Cu-containing plasma protein thought to be involved in oxidative modification of lipoproteins. We have previously shown that Cp increased cell-mediated low-density lipoprotein (LDL) oxidation by a process requiring cell-derived superoxide, but the underlying chemical mechanism(s) is (are) unknown. We now show that superoxide reduction of Cp Cu is a critical reaction in cellular LDL oxidation. By bathocuproine disulfonate (BCS) binding and by superoxide utilization, we showed that exogenous superoxide reduces a single Cp Cu atom, the same Cu required for LDL oxidation. The Cu atom remained bound to Cp during the redox cycle. Three avenues of evidence showed that vascular cells reduce Cp Cu by a superoxide-dependent process. The 2-fold higher rate of Cp Cu reduction by smooth muscle cells (SMC) compared to endothelial cells (EC) was consistent with their relative rates of superoxide release. Furthermore, Cp Cu reduction by cells was blocked by Cu,Zn superoxide dismutase (SOD1). Finally, the level of superoxide produced by EC and SMC was sufficient to cause the amount of Cu reduction observed. An important role of Cp Cu reduction in LDL oxidation was suggested by results showing that SOD1 inhibited Cp Cu reduction and LDL oxidation by SMC with equal potency, while tumor necrosis factor-alpha stimulated both processes. In summary, these results show that superoxide is a critical cellular reductant of divalent transition metals involved in oxidation, and that protein-bound Cu is a substrate for this reaction. The role of these mechanisms in oxidative processes in vivo has yet to be defined.

NASA Discipline Regulatory Physiology

Method for the preparation of thin-skinned asymmetric reverse osmosis membranes and products thereof

A method for preparing water insoluble asymmetric membranes from water soluble polymers is discussed. The process involves casting a film of the polymer, partially drying it, and then contacting it with a concentrated solution of a transition metal salt. The transition metal ions render the polymer insoluable and are believed to form a complex with it. Optionally, the polymer is crosslinked with heat or radiation. The most preferred polymer is poly(vinyl alcohol). The most preferred complexing salt is copper sulfate. The process and the metal ion linked membranes are discussed. The membranes are reverse osmosis membranes.

Wydeven, T. J.

Texturing Copper To Reduce Secondary Emission Of Electrons

Ion-beam process produces clean, deeply textured surfaces on copper substrates with reduced secondary electron emission. In process, molybdenum ring target positioned above and around copper substrate. Target potential repeatedly switched on and off. Switching module described in "High-Voltage MOSFET Switching Circuit" (LEW-15986). Useful for making collector electrodes for traveling-wave-tube and klystron microwave amplifiers, in which secondary emission of electrons undesirable because of reducing efficiency.

Jensen, Kenneth A.

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.

First-Principles Study on the Role of Cu and Cl-Based Dopants in NiO

Utilization of wide band gap oxide-based materials in thin-film solar energy technologies has increased in recent years. Among the numerous candidate oxide materials, NiO has shown many desirable optoelectronic properties that are applicable to thin-film PV technologies such as cadmium telluride PV. However, one critical factor requiring further investigation is the p-type doping behavior of NiO, specifically when the cadmium telluride solar cell undergoes conventional processes such as copper doping and chlorine-based activation treatment. The previous literature has shown a large degree of variability in hole concentrations in NiO when copper is used as the primary dopant. This study uses first-principles computational modeling based on density functional theory coupled with defect equilibria calculations to quantitatively explore the role of copper and chlorine-based extrinsic dopants in the p-type doping activity of NiO. The study reveals the importance of extrinsic dopants and their binding interactions with nickel vacancies to effectively p-dope NiO. It is suggested that both the formation of V Ni + Cu Ni and V Ni + Cl O defect pairs under a supersaturated state of NiO are potential mechanisms for increasing hole densities. On the other hand, the production of 2Cu Ni severely limits the effectiveness of p-doping in NiO, even in the presence of the aforementioned defect pairs. Furthermore, the study provides a guideline for experimentalists interested in using copper or chlorine species to understand how to controllably p-dope NiO during thin-film synthesis.

chlorine

Deciphering electrocatalysts with multimodal operando approaches

Here, the electrocatalytic processes of a copper catalyst during nitrate electroreduction are unveiled by correlated operando microscopy and spectroscopy. Catalysts are vital to the modern chemical industry, yet their development has largely relied on trial-and-error approaches. Optimizing catalysts requires a fundamental understanding of their structure–chemical property behaviour under operational conditions. However, operando characterization remains challenging, especially for reactions occurring in the complex and dynamic liquid environments of electrochemical systems. Over the past decade, the rapid development of in situ and operando environmental transmission electron microscopy (ETEM) and microelectromechanical system (MEMS)-based closed-cell holders, enabling environmental studies within the vacuum environment of transmission electron microscopy (TEM), has substantively advanced understanding of heterogeneous catalysis, notably for gas-phase reactions. In situ ETEM enables the direct observation of the catalyst evolution in terms of structure, morphology and chemical state at the nano-to-atomic scale, providing insights into their correlation with catalytic performance.

36 MATERIALS SCIENCE