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At least 37 records · Page 2

High-temperature, low-cycle fatigue of advanced copper-base alloys for rocket nozzles. Part 2: NASA 1.1, Glidcop, and sputtered copper alloys

Short-term tensile and low-cycle fatigue data are reported for five advance copper-base alloys: Sputtered Zr-Cu as received, sputtered Zr-Cu heat-treated, Glidcop AL-10, and NASA alloys 1-1A and 1-1B. Tensile tests were performed in argon at 538 C using an axial strain rate of 0.002/sec. Yield strength and ultimate tensile strength data are reported along with reduction in area values. Axial strain controlled low-cycle fatigue tests were performed in argon at 538C using an axial strain rate of 0.002/sec to define the fatigue life over the range from 100 to 3000 cycles for the five materials studied. It was found that the fatigue characteristics of the NASA 1-1A and NASA 1-1B compositions are identical and represent fatique life values which are much greater than those for the other materials tested. The effect of temperature on NASA 1-1B alloy at a strain rate of 0.002/sec was evaluated along with the effect of strain rates of 0.0004 and 0.01/sec at 538 C. Hold-time data are reported for the NASA 1-1B alloy at 538 C using 5 minute hold periods in tension only and compression only at two different strain range values. Hold periods in tension were much more detrimental than hold periods in compression.

Conway, J. B.

Dataset from Manuscript: CO2 Electroreduction on Borated Copper Surfaces: Boron Active Sites, not Copper

(1) hcoverage-gcga: .db files with structures and data from GCGA sampling at various potentials (2) hcoverage-gcdft/vaspSC-finished.db: .db file with GCDFT calculations and structures on the sub-ensemble of various H coverages on CuB(3) int_ts: Optimized structures of intermediates and transition states for HER (H26.db and H39.db for LC and HC respectively), B migration (H33.db and H34.db), and CORR (H26.db and H39.db for LC and HC respectively)

Boron

Sub-Nanometer Nanoclusters of Copper Atop Single-Atom Copper Moieties toward Electrochemical CO 2 Hydrogenation to Methane

The electrochemical CO 2 reduction (eCO 2 R) offers a compelling route for converting CO 2 into value-added fuels and chemicals. Among CO 2 -derived products, methane (CH 4 ) occupies a distinct position, serving both as a key intermediate for emerging cascade electro-oxidation to oxygenates and as a strategically important extraterrestrial fuel that can be generated in situ from off-planet CO 2 resources. Although Cu-based catalysts capable of selectively producing CH 4 have been reported, they seldom sustain high selectivity at practically relevant current densities. Here, we created a single-step co-pyrolysis strategy toward generating and anchoring Cu sub-nanometer clusters (Cu SNC ) atop Cu-N x single-atom (SA) motifs embedded within N-doped carbon (NC), with controllable nanostructures through tuning of the synthesis parameters. Complementary spectroscopic analyses and density functional theory (DFT) calculations help reveal a structure−activity correlation that could guide the catalyst design. The Cu SNC @NC sample synthesized at 550 °C pyrolysis temperature (best described and modeled as Cu 3 -CuN 4 domains) represents the most effective combination of cluster size, metal-nitrogen coordination, and adsorption energetics needed to selectively promote CH 4 generation versus other eCO 2 R products. Incorporating pulsed electrolysis and hydrophobicity-modulated transport tuning at the triple-phase boundary (TPB) further enhanced CH 4 production achieving a partial CH 4 current density of ∼321 mA cm −2 , 53% Faradaic efficiency (FECH 4 ), and less than 4% combined FE for other eCO 2 R products, simplifying downstream CH 4 purification or upgrading. This work establishes generalizable principles for controlling Cu cluster atomicity and metal−nitrogen coordination, both of which are recognized determinants of CH 4 -efficient eCO 2 R.

CH4 production

High temperature, low-cycle fatigue of copper-base alloys in argon. Part 1: Preliminary results for 12 alloys at 1000 F (538 C)

Short-term tensile evaluations at room temperature and 538 C and low-cycle fatigue evaluations at 538 C are presented for the following materials: Zirconium copper-annealed, Zirconium copper-1/4 hard, Zirconium copper-1/2 hard, Tellurium copper-1/2 hard, Chromium copper-SA and aged, OFHC copper-hard, OFHC copper-1/4 hard, OFHC copper-annealed, Silver-as drawn, Zr-Cr-Mg copper-SA, CW and aged, Electroformed copper-30-35 ksi, and Co-Be-Zr- copper-SA, aged. A total of 50 tensile tests and 76 low-cycle fatigue tests were performed using a strain rate of 0.2 percent per second.

Conway, J. B.

Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

Philipp, W. H.

A Copper-Binding Peptide with Therapeutic Potential against Alzheimer′s Disease: From the Blood–Brain Barrier to Metal Competition

Alzheimer’s disease (AD) is the most common form of dementia worldwide. AD brains are characterized by the accumulation of amyloid-β peptides (Aβ) that bind Cu 2+ and have been associated with several neurotoxic mechanisms. Although the use of copper chelators to prevent the formation of Cu 2+ -Aβ complexes has been proposed as a therapeutic strategy, recent studies show that copper is an important neuromodulator that is essential for a neuroprotective mechanism mediated by Cu 2+ binding to the cellular prion protein (PrPC). Therefore, in addition to metal selectivity and blood–brain barrier (BBB) permeability, an emerging challenge for copper chelators is to prevent the formation of neurotoxic Cu 2+ -Aβ species without perturbing the neuroprotective Cu 2+ -PrPC interaction. Previously, we reported the design of a tetrapeptide (TP) that withdraws Cu 2+ from Aβ(1–16) and impacts the Cu 2+ -induced aggregation of Aβ(1–40). In this study, we improved the drug-like properties of TP in a BBB model, evaluated the metal selectivity of the optimized peptide (TP*), and tested its effect on Cu 2+ coordination to PrPC and proteins involved in copper trafficking, such as copper transporter 1 and albumin. Our results show that changing the stereochemistry of the first residue prevents TP degradation in the BBB model and coadministration of TP with a peptide that increases BBB permeability allows its passage through the BBB model. TP* is highly selective toward Cu 2+ in the presence of Zn 2+ ions, transfers Cu 2+ to copper-trafficking proteins, and forms a ternary TP*-Cu 2+ -PrP species that does not perturb the physiological conformation of PrP and displays only a minor impact in the neuroprotective Cu 2+ -dependent interaction of PrPC with the N-methyl-d-aspartate receptor. Overall, these results show that TP* displays desirable features for a copper chelator with therapeutic potential against AD. Moreover, this is the first study that explores the effect of a Cu 2+ chelator with therapeutic potential for AD on Cu 2+ coordination to PrPC (an emerging key player in AD pathology), integrating recent knowledge about metalloproteins involved in AD with the design of copper chelators against AD.

60 APPLIED LIFE SCIENCES

Thermotransport in liquid aluminum-copper alloys

A thermotransport study was made on a series of liquid aluminum-copper alloys which contained from trace amounts to 33 weight percent copper. The samples in the form of narrow capillaries were held in known temperature gradient of thermotransport apparatus until the stationary state was reached. The samples were analyzed for the concentration of copper along the length. Copper was observed to migrate to the colder regions in all the samples. The heat of transport, Q*, was determined for each composition from a plot of concentration of copper versus reciprocal absolute temperature. The value of Q* is the highest at trace amounts of copper (4850 cal/gm-atom), but decreases with increasing concentration of copper and levels off to 2550 cal/gm-atom at about 25 weight percent copper. The results are explained on the basis of electron-solute interaction and a gas model of diffusion.

Bhat, B. N.

Effect of oxygen, methyl mercaptan, and methyl chloride on friction behavior of copper-iron contacts

Sliding friction experiments were conducted with an iron rider on a copper disk and a copper rider on an iron disk. The sputter cleaned iron and copper disk surfaces were saturated with oxygen, methyl mercaptan, and methyl chloride at atmospheric pressure. Auger emission spectroscopy was used to monitor the surfaces. Lower friction was obtained in all experiments with the copper rider sliding on the iron disk than when the couple was reversed. For both iron and copper disks, methyl mercaptan gave the best surface coverage and was most effective in reducing friction. For both iron and copper disks, methyl chloride was the least effective in reducing friction. With sliding, copper transferred to iron and iron to copper.

Buckley, D. H.

Effect of copper impurity on polycrystalline silicon solar cells

The presence of copper impurity, up to 10 to the 15th atoms/cc, in single crystal silicon has been shown to have no deleterious effect on the p-n junction solar cell performance. However, in polycrystalline silicon, copper atoms tend to migrate to the defect sites because of the structural sensitive properties of copper. This study was undertaken to investigate the influence of this behavior of copper impurity on the performance of p-n junction solar cells fabricated from structurally imperfect silicon. Two sets of polycrystalline silicon substrates containing copper were examined. In one set of samples, copper was incorporated during growth, whereas in the other, copper was diffused. Solar cells were fabricated on both the sets of substrates by a standard process. Dark and light I-V and spectral response characteristics of the cells were measured and compared with copper-free polycrystalline silicon solar cells. The results and the model are discussed.

Daud, T.

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

Cu(II) Stability and UV-Induced Electron Transfer in a Metal–Organic Hybrid: An EPR, DFT, and Crystallographic Characterization of Copper-Doped Zinc Creatininium Sulfate

Single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopic experiments, complemented by quantum chemical DFT calculations, were carried out on the copper-doped metal–organic hybrid and Tutton salt analogue zinc creatininium sulfate to determine its crystal structure, to characterize the electronic structure of the doped Cu(II) binding site, and to propose a pathway for an excited-state, proton-coupled electron transfer (PCET) process in UV-exposed crystals. The crystal structure is isomorphous to that of cadmium creatininium sulfate, which has the transition ion, not in direct coordination with the creatinine, but forming a hexahydrate complex, which is bridged to a creatininium through an intervening sulfate ion. The EPR g (2.446, 2.112, 2.082) and copper hyperfine (A Cu : -327, -59.6, 10.8 MHz) tensor parameters are consistent with doped copper replacing host zinc in the metal–hexahydrate complex. These parameters are similar to those observed for copper hexahydrate in doped Tutton salt systems at low temperature, where the unpaired electron occupies mainly the copper 3d x 2 –y 2 orbital. At room temperature in the Tutton systems, vibration couplings stemming from a dynamic Jahn–Teller effect cause tensor averaging which results in a reduction in their maximum g-tensor and hyperfine tensor values. However, like for the doped isomorphous Cd creatinine crystal, the Cu(II) EPR exhibits little, or no room temperature averaging compared to its low temperature pattern. Samples exposed to 254 nm UV light generate a carbon-centered free radical species, characterized by an isotropic g-tensor (g = 2.0029) and an alpha-proton hyperfine coupling (-24 -14 +4 G). These parameters identify it as a creatinine radical cation formed by the oxidative release of one of its C2 methylene hydrogens. DFT calculations confirm the unpaired electronic structures of both the Cu(II) site and free radical. The growth in radical concentration with an increase in the UV exposure time coincides with a decrease in the copper EPR signal, indicating a coupled light-induced oxidation reduction process. A comparison of the crystal structure with the EPR parameters and DFT results provides evidence for a UV-induced PCET.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Formate-Induced Dissolution and Reprecipitation of a Copper Electrocatalyst during Electrochemical CO 2 Reduction Reaction

Catalyst size, morphology, and crystal structure play crucial roles in determining the activity and selectivity of electrochemical CO 2 reduction reactions, which are known to change during the reaction process. A comprehensive understanding of how, when, and why these parameters evolve under operational conditions is essential for developing stable, efficient, and selective catalysts. In this study, we reveal that formate, one of the reaction products, contributes to the degradation of copper catalysts through a ligand-assisted dissolution mechanism. Utilizing in situ electrochemical atomic force microscopy and ex-situ scanning and transmission electron microscopies, we observed a significant reduction in the size of copper nanoparticles, which decreased from over 30 nm to less than 10 nm in diameter within 60 min of CO 2 RR. The temporal production of formate correlated with the particle size changes. Furthermore, analysis of the electrolyte using inductively coupled plasma optical emission spectroscopy confirmed the dissolution of copper nanoparticles. Control experiments involving various reaction products (H 2 , CO, and HCOO – ) demonstrated that formate significantly promotes copper dissolution, thereby highlighting its role in the ligand-assisted dissolution mechanism of copper electrocatalysts. In conclusion, our findings provide critical insights into copper catalyst behavior during electrochemical CO 2 reduction, facilitating the design of more resilient and effective electrocatalysts.

Catalysts

Investigating the Effects of Copper Impurity Deposition on the Structure and Electrochemical Behavior of Hydrogen Evolution Electrocatalyst Materials

Electrolysis of impure water (such as seawater) has recently garnered research interest as it may enable hydrogen production at reduced costs. However, the tendency of impurity ions and other species to degrade electrocatalysts and membranes within an electrolyzer is a serious challenge. Here, we investigate the effects of copper impurities of varying concentrations on the hydrogen evolution reaction (HER) using platinum electrocatalysts. A decrease of current density is observed with an increasing copper concentration. By comparing the effect of ionic impurities on current density at different concentrations, we gain insight into how impurities can interfere with the HER at different potentials. Surface characterization of the electrodes reveals differences in the morphology and extent of copper deposition on HER-active platinum vs inactive gold electrodes. This enables an improved understanding of how copper nucleates and grows on the two types of electrodes under different electrochemical conditions while also confirming deposition in low-concentration cases, as present in seawater. The results indicate that copper electrodeposition competes with the HER, and the nature of copper electrodeposition varies depending on the electrocatalytic activity of the electrode. This study provides insight toward catalyst design that can withstand the effects of impurity-induced degradation over extended use.

08 HYDROGEN