Cohesion of copper and steel repeatedly fractured and rejoined in vacuum
Cohesion of clean metal surfaces in space environment - fracture-rejoin experimental technique and cohesion data for copper and steel
METAL SURFACE↗
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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↗
Thermal emittance enhancement of graphite-copper composites for high temperature space based radiators
Graphite-copper composites are candidate materials for space based radiators. The thermal emittance of this material, however, is a factor of two lower than the desired emittance for these systems of greater than or equal to 0.85. Arc texturing was investigated as a surface modification technique for enhancing the emittance of the composite. Since the outer surface of the composite is copper, and samples of the composite could not be readily obtained for testing, copper was used for optimization testing. Samples were exposed to various frequencies and currents of arcs during texturing. Emittances near the desired goal were achieved at frequencies less than 500 Hz. Arc current did not appear to play a major role under 15 amps. Particulate carbon was observed on the surface, and was easily removed by vibration and handling. In order to determine morphology adherence, ultrasonic cleaning was used to remove the loosely adherent material. This reduced the emittance significantly. Emittance was found to increase with increasing frequency for the cleaned samples up to 500 Hz. The highest emittance achieved on these samples over the temperature range of interest was 0.5 to 0.6, which is approximately a factor of 25 increase over the untextured copper emittance.
Rutledge, Sharon K.↗
Thermal emittance enhancement of graphite-copper composites for high temperature space based radiators
Graphite-copper composites are candidate materials for space based radiators. The thermal emittance of this material, however, is a factor of two lower than the desired emittance for these systems of greater than or equal to 0.85. Arc texturing was investigated as a surface modification technique for enhancing the emittance of the composite. Since the outer surface of the composite is copper, and samples of the composite could not be readily obtained for testing, copper was used for optimization testing. Samples were exposed to various frequencies and currents of arcs during texturing. Emittances near the desired goal were achieved at frequencies less than 500 Hz. Arc current did not appear to play a major role under 15 amps. Particulate carbon was observed on the surface, and was easily removed by vibration and handling. In order to determine morphology adherence, ultrasonic cleaning was used to remove the loosely adherent material. This reduced the emittance significantly. Emittance was found to increase with increasing frequency for the cleaned samples up to 500 Hz. The highest emittance achieved on these samples over the temperature range of interest was 0.5 to 0.6, which is approximately a factor of 25 increase over the untextured copper emittance.
Rutledge, Sharon K.↗
Effect of Inert, Reducing, and Oxidizing Atmospheres on Friction and Wear of Metals to 1000 F
Experiments were conducted in inert, reducing, and oxidizing atmospheres to determine their influence on the friction and wear properties of various metals. Nitrogen, argon, forming gas (10 volume percent H2, 90 volume percent N2), and various concentrations of oxygen in nitrogen were used. A 3/16-inch-radius hemispherical rider under a load of 1000 grams contacted the flat surface of a rotating disk. The surface speed employed was 35 feet per minute. The presence of surface oxides is vitally important to the protection of metals in sliding contact. Extremely high friction and excessive wear were encountered in the absence of these oxides. In some instances (electrolytically pure copper), the removal of the surface oxides resulted in mass welding of the specimens in sliding contact. Extremely small quantities of oxygen are sufficient to provide protection of metal surfaces; for example, with 440-C stainless steel, 0.03 volume percent oxygen was found to be adequate.
Buckley, Donald H.↗
Repairing sealing surfaces on aluminum castings
Approach using stylus nickel plating instead of copper and cadmium plating has simplified repair procedure. Damaged sealing surfaces are stylus nickelplated in one step. Superficial scratches and porous areas are removed more easily from repaired surface by simply lapping sealing areas to required finish. Although method is aimed for aerospace components, it may be easily incorporated into conventional aluminumcasting technology. One-step repair can be considered for cast-aluminum automobile and aircraft engines to reduce time and costs.
Hanna, T. L.↗
Solar reduction of carbon dioxide on copper-tin electrocatalysts with energy conversion efficiency near 20%
Abstract Copper catalysts modified with tin have been demonstrated to be selective for the electroreduction of carbon dioxide to carbon monoxide. However, such catalysts require the precise control of tin loading amount. Here, we develop a copper/tin-oxide catalyst with dominant tin oxide surface being formed via a spontaneous exchange reaction between sputtered tin and copper oxide. Even though the surface of this catalyst is tin-rich, it achieves an excellent performance towards carbon monoxide production in a flow cell. This contrasts with copper/tin-oxide prepared via atomic layer deposition since it yields selectivity towards carbon monoxide only on a copper-rich surface. Mechanism studies reveal that the tin sites on the tin-rich copper/tin-oxide surface achieve a suitable binding with adsorbed carbon monoxide under the presence of copper. Powered by a triple-junction solar cell, the copper/tin-oxide based electrolyzer sets a new benchmark solar-to-chemical energy conversion efficiency of 19.9 percent with a Faradaic efficiency of 98.9 percent towards carbon monoxide under simulated standard air mass 1.5 global illumination.
14 SOLAR ENERGY↗
Surface roughness and finishing techniques in selective laser melted GRCop-84 copper for an additive manufactured lower hybrid current drive launcher
Not Available
Seltzman, A. H. (ORCID:0000000277252981)↗
Electrode Surface Heating with Organic Films Improves CO 2 Reduction Kinetics on Copper
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thermo-Mechanical Distortion of Tungsten-Coated Steel During High Heat Flux Testing Using Plasma Arc Lamps
An experimental setup and a test section were designed and fabricated for high heat flux testing (HHFT) of neutron-irradiated specimens using water-wall plasma arc lamps. Because of the radiological considerations and limitations of reactor irradiation, the size of the test articles was limited to disks less than 10 mm in diameter. The specimen was clamped onto an actively cooled block, and clamping allowed the insertion of several thermocouples on the back surface of the specimen through a copper (Cu) block. Five vacuum plasma sprayed tungsten (W)–coated F82H steel specimens were subjected to HHFT. Surface profilometry measurements, which were conducted after HHFT, revealed central bowing of the top W surface. This type of residual distortion occurred for all of the specimens, and the larger the specimens were, the larger was the distortion.In an attempt to understand specimen distortion and address the science questions related to the testing of subsize specimens during HHFT, a simplified thermo-mechanical model was developed. By using a measured temperature in the Cu as an isothermal boundary condition, the model eliminated the need for coupling cooling fluid flow models with stress models, greatly simplifying the analysis. The main variable in the proposed model is hC, i.e., the thermal contact conductance between the F82H and the Cu washer. Inelastic properties, including hardening properties, were considered for F82H steel and Cu. Numerical simulation results demonstrated a buildup of residual deformation during HHFT and a very complex state of stress and deformation during typical heat flux (HF) cycling. Additionally, hoop stress evolution during a high heat flux cycle reveals that F82H at an interface with W would be mainly in compression during HF application and experienced a transition to a tension state during cooldown. Also, specimen distortion evolves during each HF cycle, as the specimen bows downward during HF application and upward during the cooldown period between HF cycles. The final specimen distortion, i.e., upward bowing of the specimen center, was qualitatively predicted for hC values of 4000 to 5000 W/(m 2 ·K). This hC range of values, for which bulging is obtained, is at the lower spectrum of the range of values for hC, consistent with the low thermal contact conductance expected from the unpolished F82H surface.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Revealing the Predominant Surface Facets of Rough Cu Electrodes under Electrochemical Conditions
Metal electrodes with rough surfaces are frequently found to convert CO or CO 2 to hydrocarbons and oxygenates with high selectivity and at high reaction rates in comparison with their smooth counterparts. The atomic-level morphology of a rough electrode is likely one key factor responsible for its comparatively high catalytic selectivity and activity. However, few methods are capable of probing the atomic-level structure of rough metal electrodes under electrocatalytic conditions. As a result, the nuances in the atomic-level surface morphology that control the catalytic characteristics of these electrodes have remained largely unexplored. Because the C≡O stretching frequency of atop-bound CO (CO atop ) depends on the coordination of the underlying metal atom, the IR spectrum of this reaction intermediate on the copper electrode could, in principle, provide structural information about the catalytic surface during electrolysis. However, other effects, such as dynamic dipole coupling, easily obscure the dependence of the frequency on the surface morphology. Further, in the limit of low CO atop coverage, where coupling effects are small, the C≡O stretching frequencies of CO atop on Cu(111) and Cu(100) facets are virtually identical. Therefore, on the basis of the C≡O stretching frequency, it is not straightforward to distinguish between these two ubiquitous surface facets, which exhibit vastly different CO reduction activities. Herein, we show that key features of the atomic-level surface morphology of rough copper electrodes can be inferred from the potential dependence of the line shape of the C≡O stretching band of CO atop . Specifically, we compared two types of rough copper thin-film electrodes that are routinely employed in the context of surface-enhanced infrared absorption spectroscopy (SEIRAS). We found that copper films that are electrochemically deposited on Si-supported Au films (CuAu–Si) are poor catalysts for the reduction of CO to ethylene in comparison to copper films (Cu–Si) that are electrolessly deposited onto Si crystals. As quantified by differential electrochemical mass spectrometry (DEMS), the onset potential for ethylene is ~200 ± 65 mV more cathodic for CuAu–Si than that for Cu–Si. To reveal the origin of the disparate catalytic properties of Cu–Si and CuAu–Si, we probed the surfaces of the electrodes with cyclic voltammetry (CV) and SEIRAS. The CV characterization suggests that the (111) surface facet predominates on CuAu–Si, whereas the (100) facet is more common on Cu–Si. SEIRAS reveals that the line shape of the C≡O stretching of CO atop is composed of two bands that are attributable to CO atop on terrace and defect sites. The different surface structures manifest themselves in the form of starkly different potential dependences of the line shape of the C≡O stretching mode of CO atop on the two types of electrodes. With a simple Boltzmann model that considers the different adsorption energies of CO atop on terrace and defect sites, and the resulting CO atop populations on terrace and defect sites, we deduced that the observed electrode-specific potential dependence of the line shape is consistent with the presence of different predominant terrace sites on the two types of films. This strategy for assessing the atomic-level morphology is not restricted to SEIRAS but could also be applied to the C≡O stretching bands recorded with surface-enhanced Raman spectroscopy (SERS), which is suitable for probing a wide range of rough copper electrodes. Therefore, with this work, we establish the potential dependence of the C≡O stretching band of CO atop as a probe of the atomic-level surface structure of rough metal electrodes under electrochemical conditions. When it is coupled with complementary techniques, this methodology provides essential structural information for further improvement in the reaction selectivity of rough metal electrodes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Nano-engineered Multiwall Carbon Nanotube-copper Composite Thermal Interface Material for Efficient Heat Conduction
Efforts in integrated circuit (IC) packaging technologies have recently been focused on management of increasing heat density associated with high frequency and high density circuit designs. While current flip-chip package designs can accommodate relatively high amounts of heat density, new materials need to be developed to manage thermal effects of next-generation integrated circuits. Multiwall carbon nanotubes (MWNT) have been shown to significantly enhance thermal conduction in the axial direction and thus can be considered to be a candidate for future thermal interface materials by facilitating efficient thermal transport. This work focuses on fabrication and characterization of a robust MWNT-copper composite material as an element in IC package designs. We show that using vertically aligned MWNT arrays reduces interfacial thermal resistance by increasing conduction surface area, and furthermore, the embedded copper acts as a lateral heat spreader to efficiently disperse heat, a necessary function for packaging materials. In addition, we demonstrate reusability of the material, and the absence of residue on the contacting material, both novel features of the MWNT-copper composite that are not found in most state-of-the-art thermal interface materials. Electrochemical methods such as metal deposition and etch are discussed for the creation of the MWNT-Cu composite, detailing issues and observations with using such methods. We show that precise engineering of the composite surface affects the ability of this material to act as an efficient thermal interface material. A thermal contact resistance measurement has been designed to obtain a value of thermal contact resistance for a variety of different thermal contact materials.
Ngo, Quoc↗
Interpretation of aircraft multispectral scanner images for mapping of alteration with uranium mineralization, Copper Mountain, Wyoming
NS-001 multispectral scanner data (0.45-2.35 micron) combined as principal components were utilized to map distributions of surface oxidation/weathering in Precambrian granitic rocks at Copper Mountain, Wyoming. Intense oxidation is found over granitic outcrops in partly exhumed pediments along the southern margin of the Owl Creek uplift, and along paleodrainages higher in the range. Supergene(?) uranium mineralization in the granites is localized beneath remnant Tertiary sediments covering portions of the pediments. The patterns of mineralization and oxidation are in agreement, but the genetic connections between the two remain in doubt.
Conel, J. E.↗
Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction
Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO2 reduction reaction (CO2RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu2O nanocubes to polycrystalline metallic Cu nanograins under CO2RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions.
Yang, Yao↗
Detection of lack of fusion using opaque additives, phase 2
Plasma-sprayed copper coatings were developed to protect the aluminum surfaces of spacecraft structures from oxidation, as well as to provide a means of reliable nondestructive X-ray inspection of possible incomplete weldment penetration. Sixty day storage tests of coated aluminum samples indicated the promise of long-term oxidation protection, but revealed no advantage in detecting penetration defects. Delta-scan techniques were used, and peen plating as a means of applying copper to the aluminum surface was investigated.
Cook, J. L.↗
Abiotic manganese oxide formation induced by light and copper-driven Fenton chemistry
Redox-active transition metals such as manganese (Mn) and copper (Cu) frequently coexist in surface water systems, where their interactions can significantly influence contaminant fate and water quality. It is widely known that the oxidation of Mn 2+ (aq) to Mn(IV) oxide solids is driven mainly by biotic processes in which Cu 2+ serves as an inhibitor of Mn oxidation. However, Cu 2+ can also trigger Fenton reactions to produce reactive oxygen species (ROS) capable of promoting the abiotic Mn oxidation (i.e., without the involvement of biological organisms), through an alternative natural pathway that remains overlooked in water. In this study, we found that the abiotic oxidation of Mn 2+ can be facilitated by the co-existence of sunlight and Cu 2+ . By contrasting Cu 2+ with other divalent cations, such as Ca 2+ , Mg 2+ , and Zn 2+ , this investigation highlights the distinct role of Cu 2+ in promoting Mn oxidation. Moreover, the study elucidated how light induces ROS to trigger Cu-driven photo-Fenton reactions and identified the roles of ROS in Mn oxidation. Chemical-Fenton reactions (i.e., the interaction between Cu and H 2 O 2 in the absence of light) were also examined for their contribution to the Cu-driven Mn photo-oxidation, supporting the involvement of Fenton chemistry in Mn oxidation. By elucidating the novel photochemical mechanism of Mn oxide formation, our findings advance the understanding of heavy metal interactions in aqueous environments and highlight the intricate roles of Cu 2+ in affecting elemental cycling and the evaluation of heavy metal contamination in water resources. This discovery also underscores the critical contribution of co-existing Fenton-active metals in forming Mn oxide solids.
Abiotic Mn oxidation↗
Impact of UV-induced ozone and low-energy Ar + -ion cleaning on the chemical structure of Cu(In,Ga)(S,Se) 2 absorber surfaces
Dry buffer layer deposition techniques for chalcopyrite (CIGSSe)-based thin-film solar cells lack the surface-cleaning characteristics of the commonly used CdS or Zn(O,S) wet-chemical bath deposition. Here, a UV-induced ozone and/or a low-energy Ar + -ion treatment could provide dry CIGSSe surface cleaning steps. To study the impact of these treatments, the chemical surface structure of a CIGSSe absorber is investigated. For this purpose, a set of surface-sensitive spectroscopic methods, i.e., laboratory-based x-ray photoelectron spectroscopy and x-ray-excited Auger electron spectroscopy, is combined with synchrotron-based soft x-ray emission spectroscopy. After treatment times as short as 15 s, the UV-induced ozone treatment decreases the amount of carbon adsorbates at the CIGSSe surface significantly, while the oxygen content increases. This is accompanied by the oxidation of all absorber surface elements, i.e., indium, selenium, sulfur, and copper. Short (60 s) low-energy Ar + -ion treatments, in contrast, primarily remove oxygen from the surface. Longer treatment times also lead to a removal of carbon, while extremely long treatment times can also lead to additional (likely metallic) Cu phases at the absorber surface as well.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Recognition of the geologic framework of porphyry deposits on ERTS-1 imagery
The author has identified the following significant results. Photointerpretation methods have been most successfully applied in the less vegetated test sites where several previously unknown geologic features have been recognized and known ones extended. Northwest mid-Tertiary faults in the ELY, Nevada area are observed to offset north-trending ranges and abruptly terminate older Mesozoic structures. In the Ray, Arizona area the observed patterns of fault and fracture systems appear to be related to the locations of known porphyry copper deposits. In the Tanacross, Alaska area a number of regional circular features observed may represent near surface intrusions and, therefore, permissive environments for copper porphyries.
Wilson, J. C.↗