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At least 307 records · Page 17

Adhesion characteristics of aromatic thermosetting copolyester and glass fiber laminates with copper foils for improved circuit boards

Copper foils are the vital elements used in microelectronic devices. Adequate adhesion between copper foils to various substrates, such as Si, SiO 2 and polyimide, is crucial to functional electronic devices. Liquid-crystalline polymers (LCPs) can be used as substrates for these modules as well as the adhesive to copper foils. The adhesion between aromatic thermosetting copolyester (ATSP)/fiberglass fabric (GF) laminates and copper foils was characterized by peel strength tests. It was found that ATSP/GF laminates with copper foil using ATSP oligomers as adhesive showed a highest average peel strength of 711 N · m -1 . Scanning electron microscope (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed an excellent bond between the composite and the copper foil interface. Failure occurred between the backside of the copper foil and the ATSP/GF laminates in the peeling test and the mechanism is discussed. Finally, thermogravimetic analyzer (TGA) indicated a thermal stability up to 371°C for ATSP/GF composite substrate and a glass transition temperature of over 400°C as determined by peak in tan δ during Dynamic Mechanical Analysis (DMA).

36 MATERIALS SCIENCE↗

Nanoparticle-enhanced absorptivity of copper during laser powder bed fusion

We report laser powder bed fusion (LPBF) of pure copper for thermal and electrical applications is hampered by its low near-infrared absorptivity and high thermal diffusivity. These material properties make it very difficult to localize the thermal energy needed to produce high density 3D printed parts. Modification of metal powders via nanoparticle additives is a promising approach to increasing absorptivity, but the effect of nanoparticles on absorptivity and melting behavior during LPBF is not well understood. In this study, we developed an in situ calorimetry system to measure effective absorptivity during LPBF on copper substrates. We decorated copper substrates using three nanoparticle systems (CuS, TiB 2 , multilayer graphene flakes) and demonstrated an enhanced absorptivity of the decorated substrates relative to pure copper. Graphene nanoflakes resulted in the highest improved absorption relative to pure copper from 0.09 to 0.48, due to their stability at high laser scanning powers. A thermomechanical model with convective heat transfer provided confidence in the measurements by reproducing the experimental melt pool traces. Full 3D cylindrical prints demonstrated an improvement in relative density of the copper-graphene powder prints (in the range of 0.930–0.992), relative to that of as-purchased copper powder prints (in the range of 0.854–0.972). This work provides a fundamental study of nanoparticle-enabled LPBF of highly reflective metals and demonstrates a viable route for expanding the library of reliably printable metals.

36 MATERIALS SCIENCE↗

Microstructure and thermal properties of copper–diamond composites with tungsten carbide coating on diamond particles

An effective method for preparing tungsten carbide coating on diamond surfaces was proposed to improve the interface bonding between diamond and copper. The WC coating was formed on the diamond surfaces with a reaction medium of WO{sub 3} in mixed molten NaCl–KCl salts and the copper–diamond composites were obtained by vacuum pressure infiltration of WC-coated diamond particles with pure copper. The microstructure of interface bonding between diamond and copper was discussed. Thermal conductivity and thermal expansion behavior of the obtained copper–diamond composites were investigated. Results indicated that the thermal conductivity of as-fabricated composite reached 658 W m{sup −} {sup 1} K{sup −} {sup 1}. Significant reduction in coefficient of thermal expansion of the composite compared with that of pure copper was obtained. - Highlights: • WC coating was successfully synthesized on diamond particles in molten salts. • WC coating obviously promoted the wettability of diamond and copper matrix. • WC coating greatly enhanced the thermal conductivity of Cu–diamond composite. • The composites are suitable candidates for heat sink applications.

36 MATERIALS SCIENCE↗

Shape-dependent bactericidal activity of copper oxide nanoparticle mediated by DNA and membrane damage

Highlights: • Spherical and sheet shaped copper oxide nanoparticles were synthesized. • Physical characterizations of these nanoparticles were done by TEM, DLS, XRD, FTIR. • They showed shape dependent antibacterial activity on different bacterial strain. • They induced both membrane damage and ROS mediated DNA damage in bacteria. - Abstract: In this work, we synthesized spherical and sheet shaped copper oxide nanoparticles and their physical characterizations were done by the X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering. The antibacterial activity of these nanoparticles was determined on both gram positive and gram negative bacterial. Spherical shaped copper oxide nanoparticles showed more antibacterial property on gram positive bacteria where as sheet shaped copper oxide nanoparticles are more active on gram negative bacteria. We also demonstrated that copper oxide nanoparticles produced reactive oxygen species in both gram negative and gram positive bacteria. Furthermore, they induced membrane damage as determined by atomic force microscopy and scanning electron microscopy. Thus production of and membrane damage are major mechanisms of the bactericidal activity of these copper oxide nanoparticles. Finally it was concluded that antibacterial activity of nanoparticles depend on physicochemical properties of copper oxide nanoparticles and bacterial strain.

36 MATERIALS SCIENCE↗

Evaluation of Copper Chelation Therapy in a Transgenic Rat Model of Cerebral Amyloid Angiopathy

Cerebral amyloid angiopathy (CAA) is characterized by the accumulation of the amyloid β (Aβ) protein in blood vessels and leads to hemorrhages, strokes, and dementia in elderly individuals. Recent reports have shown elevated copper levels colocalized with vascular amyloid in human CAA and Alzheimer’s disease patients, which have been suggested to contribute to cytotoxicity through the formation of reactive oxygen species. Here, we treated a transgenic rat model of CAA (rTg-DI) with the copper-specific chelator, tetrathiomolybdate (TTM), via intraperitoneal (IP) administration for 6 months to determine if it could lower copper content in vascular amyloid deposits and modify CAA pathology. In this work, results showed that TTM treatment led to elevated Aβ load in the hippocampus of the rTg-DI rats and increased microbleeds in the wild type (WT) animals. X-ray fluorescence microscopy was performed to image the distribution of copper and revealed a surprising increase in copper colocalized with Aβ aggregates in TTM-treated rTg-DI rats. Unexpectedly, we also found an increase in the copper content in unaffected vessels of both rTg-DI and WT animals. These results show that IP administration of TTM was ineffective in removing copper from vascular Aβ aggregates in vivo and increased the development of disease pathology in CAA.

36 MATERIALS SCIENCE↗

Evaluation of Copper Catalytic Effects in Cable Insulation Polymers

This paper summarizes work performed to evaluate a phenomenon that occurs in electrical cable insulation polymers subjected to accelerated aging while in contact with copper metal. This effect, commonly known as the copper catalytic effect, is a result of chemical reactions that occur when copper ions diffuse into insulation polymers. This diffusion process is observed in various types of polymeric materials exposed to elevated temperatures and happens at the interface between the insulation and metallic components (e.g., conductor, shielding, etc.) in a cable. This polymer-metal interaction has only been observed in cables constructed with copper components (i.e., no interactions observed in cables with aluminum or other metal conductor/shielding) and results in a significant catalytic effect that increases the oxidation rate (e.g., aging) of the material. Under this research, the copper catalytic effects observed in cross-linked polyethylene, cross-linked polyolefin and ethylene propylene rubber insulated cables subjected to thermal accelerated aging were evaluated. These evaluations involved applying infrared spectroscopy, microscopy, and energy dispersive X-ray spectroscopy cross-sectional depth profiling to obtain an in-depth understanding of the aging characteristics of the materials under accelerated conditions. Based on the results of these assessments, the copper catalytic effect can have a significant impact on the mechanical, thermal, chemical, and electrical properties of cable insulation polymers. Here, the results acquired from this research provided the information needed to characterize the copper catalytic effects observed in these polymers, analyze how this phenomenon affected the polymer degradation process, and compare and understand the differences in the properties of the materials.

42 ENGINEERING↗

Effects of Copper Chelation on BRAF V600E Positive Colon Carcinoma Cells

High affinity copper binding to mitogen-activated protein kinase kinase 1 (MAP2K1, also known as MEK1) allosterically promotes the kinase activity of MEK1/2 on extracellular signal regulated kinases 1 and 2 (ERK1/2). Consequently, copper-dependent activation of the mitogen-activated (MAP) kinase pathway has a role in promoting tumor growth. Conversely, copper chelation may represent a possible therapeutic approach for a specific subset of tumors characterized by activating mutations in the serine/threonine protein kinase V-Raf Murine Sarcoma Viral Oncogene Homolog B1 (BRAF), such as the V600E, occurring within the kinase domain (BRAF V600E ). Tetrathiomolybdate (TM) is a specific copper chelating agent currently used for the treatment of Wilson’s disease and in preclinical studies for the management of metastatic cancers owing to its anti-angiogenic and anti-inflammatory properties. We evaluated in vitro and in vivo the effects of copper depletion achieved by pharmacological treatment with TM in human colorectal cells bearing the BRAF V600E mutation in comparison with BRAF wild type cells. We provide evidence that selective copper chelation differentially affects proliferation, survival and migration of colon cancer cells bearing the BRAF V600E mutation compared to BRAF wt acting via differential phosphorylation levels of ERK1/2. Moreover, tetrathiomolybdate treatment was also effective in reducing the clonogenic potential of colon cancer BRAF V600E cells resistant to BRAF pharmacological inhibition. In conclusion, these results support further assessment of copper chelation therapy as an adjuvant therapy for inhibiting the progression of colon cancers containing the BRAF V600E mutation.

60 APPLIED LIFE SCIENCES↗

Corrosion Resistance and Durability of Superhydrophobic Copper Surface in Corrosive NaCl Aqueous Solution

Artificial superhydrophobic copper surfaces play an important role in modern applications such as self-cleaning and dropwise condensation; however, corrosion resistance and durability often present as major concerns in such applications. In this study, the anti-corrosion properties and mechanical durability of superhydrophobic copper surface have been investigated. The superhydrophobic copper surfaces were achieved with wet chemical etching and an immersion method to reduce the complexity of the fabrication process. The surface structures and materials were characterized using scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectrometer (FTIR). The corrosion resistance and mechanical properties of the superhydrophobic copper surface were characterized after immersing surfaces in a 3.5 wt % NaCl solution. The chemical stability of the superhydrophobic copper surface in the NaCl solution for a short period of time was also evaluated. An abrasion test and an ultrasound oscillation were conducted to confirm that the copper surface contained durable superhydrophobic properties. In addition, an atomic force microscope was employed to study the surface mechanical property in the corrosion conditions. The present study shows that the resulting superhydrophobic copper surface exhibit enhanced corrosion resistance and durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Role of Grain Size on Neutron Irradiation Response of Nanocrystalline Copper

The role of grain size on the developed microstructure and mechanical properties of neutron irradiated nanocrystalline copper was investigated by comparing the radiation response of material to the conventional micrograined counterpart. Nanocrystalline (nc) and micrograined (MG) copper samples were subjected to a range of neutron exposure levels from 0.0034 to 2 dpa. At all damage levels, the response of MG-copper was governed by radiation hardening manifested by an increase in strength with accompanying ductility loss. Conversely, the response of nc-copper to neutron irradiation exhibited a dependence on the damage level. At low damage levels, grain growth was the primary response, with radiation hardening and embrittlement becoming the dominant responses with increasing damage levels. Annealing experiments revealed that grain growth in nc-copper is composed of both thermally-activated and irradiation-induced components. Tensile tests revealed minimal change in the source hardening component of the yield stress in MG-copper, while the source hardening component was found to decrease with increasing radiation exposure in nc-copper.

36 MATERIALS SCIENCE↗

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↗

Novel catalysts with multivalence copper for organic pollutants removal from wastewater with excellent selectivity and stability in Fenton‐like process under neutral pH conditions

Abstract Fenton‐like reaction has been widely used for organics degradation. However, most Fenton‐like reaction works at low pH range (pH < 4) with uncontrollable selectivity of hydroxyl radicals from H 2 O 2 activation, and unsatisfied catalyst stability, which is compromised advanced oxidation performance for water/wastewater treatments. In this work, to solve the drawbacks, novel copper catalysts were fabricated via hydrogen reduction/calcination of Cu 2+ ‐supported Al/MCM‐41 with precisely controllable copper valence state. Compared with catalysts with monovalence copper (i.e., CuO, Cu, and Cu 2+ ), the obtained catalysts with multivalence copper present higher selectivity, excellent stability towards •OH radical pathways, and outperformance in p CBA degradation efficiency at neutral state. In addition, the fabricated catalysts also exhibited excellent phenol removal efficiency (75.5%) and H 2 O 2 utilization efficiency (47.9%) within neutral environment. Moreover, the degradation efficiency of phenol approaches to 100% within only 2 h. The catalyst also shows good stability for organic pollutants removal, which shows good potential in catalytic oxidation for phenolic compounds‐containing wastewater in Fenton‐like reaction, especially under neutral pH conditions. Practitioner Points Multivalence copper presents great potentials for organic compounds removal at neutral condition. Multivalence copper shows higher selectivity toward •OH and good stability at neutral condition. Multivalence copper exhibiters outperformed phenol removal efficiency at neutral condition.

Li, Haitao↗

Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy

Nanostructured copper cathodes are among the most efficient and selective catalysts to date for making multicarbon products from the electrochemical carbon dioxide reduction reaction (CO 2 RR). We report an in situ X-ray absorption spectroscopy investigation of the formation of a copper nanocube CO 2 RR catalyst with high activity that highly favors ethylene over methane production. The results show that the precursor for the copper nanocube formation is copper(I)-oxide, not copper(I)-chloride as previously assumed. A second route to an electrochemically similar material via a copper(II)–carbonate/hydroxide is also reported. In conclusion, this study highlights the importance of using oxidized copper precursors for constructing selective CO 2 reduction catalysts and shows the precursor oxidation state does not affect the electrocatalyst selectivity toward ethylene formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper-containing glass ceramic with high antimicrobial efficacy

Hospital acquired infections (HAIs) and the emergence of antibiotic resistant strains are major threats to human health. Copper is well known for its high antimicrobial efficacy, including the ability to kill superbugs and the notorious ESKAPE group of pathogens. We sought a material that maintains the antimicrobial efficacy of copper while minimizing the downsides – cost, appearance and metallic properties – that limit application. Here we describe a copper-glass ceramic powder as an additive for antimicrobial surfaces; its mechanism is based on the controlled release of copper (I) ions (Cu 1+ ) from cuprite nanocrystals that form in situ in the water labile phase of the biphasic glass ceramic. Latex paints containing copper-glass ceramic powder exhibit ≥99.9% reduction in S. aureus, P. aeruginosa, K. aerogenes and E. Coli colony counts when evaluated by the US EPA test method for efficacy of copper-alloy surfaces as sanitizer, approaching that of benchmark metallic copper.

36 MATERIALS SCIENCE↗

Copper-sulfenate complex from oxidation of a cavity mutant of Pseudomonas aeruginosa azurin

Metal–sulfenate centers are known to play important roles in biology and yet only limited examples are known due to their instability and high reactivity. Herein we report a copper–sulfenate complex characterized in a protein environment, formed at the active site of a cavity mutant of an electron transfer protein, type 1 blue copper azurin. Reaction of hydrogen peroxide with Cu(I)–M121G azurin resulted in a species with strong visible absorptions at 350 and 452 nm and a relatively low electron paramagnetic resonance g z value of 2.169 in comparison with other normal type 2 copper centers. The presence of a side-on copper–sulfenate species is supported by resonance Raman spectroscopy, electrospray mass spectrometry using isotopically enriched hydrogen peroxide, and density functional theory calculations correlated to the experimental data. In contrast, the reaction with Cu(II)–M121G or Zn(II)–M121G azurin under the same conditions did not result in Cys oxidation or copper–sulfenate formation. Structural and computational studies strongly suggest that the secondary coordination sphere noncovalent interactions are critical in stabilizing this highly reactive species, which can further react with oxygen to form a sulfinate and then a sulfonate species, as demonstrated by mass spectrometry. Engineering the electron transfer protein azurin into an active copper enzyme that forms a copper–sulfenate center and demonstrating the importance of noncovalent secondary sphere interactions in stabilizing it constitute important contributions toward the understanding of metal–sulfenate species in biological systems.

Sieracki, Nathan A.↗

SU-E-T-10: A Dosimetric Comparison of Copper to Lead-Alloy Apertures for Electron Beam Therapy

Purpose: To evaluate dosimetric differences of copper compared to conventional lead-alloy apertures for electron beam therapy. Methods: Copper apertures were manufactured by .decimal, Inc. and matching lead-alloy, Cerrobend, apertures were constructed for 32 square field sizes (2×2 – 20×20 cm{sup 2}) for five applicator sizes (6×6–25×25 cm{sup 2}). Percent depth-dose and off-axis-dose profiles were measured using an electron diode in water with copper and Cerrobend apertures for a subset of aperture sizes (6×6, 10×10, 25×25 cm{sup 2}) and energies (6, 12, 20 MeV). Dose outputs were measured for all field size-aperture combinations and available energies (6–20 MeV). Measurements were taken at 100 and 110 cm SSDs. Using this data, 2D planar absolute dose distributions were constructed and compared. Passing criteria were ±2% of maximum dose or 1-mm distance-to-agreement for 99% of points. Results: A gamma analysis of the beam dosimetry showed 93 of 96 aperture size, applicator, energy, and SSD combinations passed the 2%/1mm criteria. Failures were found for small field size-large applicator combinations at 20 MeV and 100-cm SSD. Copper apertures showed a decrease in bremsstrahlung production due to copper's lower atomic number compared to Cerrobend (greatest difference was 2.5% at 20 MeV). This effect was most prominent at the highest energies with large amounts of shielding material present (small field size-large applicator). Also, an increase in electrons scattered from the collimator edge of copper compared to Cerrobend resulted in an increased dose at the field edge for copper at shallow depths (greatest increase was 1% at 20 MeV). Conclusion: Apertures for field sizes ≥6×6 cm{sup 2} at any energy, or for small fields (≤4×4 cm{sup 2}) at energies <20 MeV, showed dosimetric differences less than 2%/1mm for more than 99% of points. All field size-applicator size-energy combinations passed 3%/1mm criteria for 100% of points. Work partially funded by .decimal, Inc. (Sanford, FL)

07 ISOTOPE AND RADIATION SOURCES↗

Methanobactin and the Link between Copper and Bacterial Methane Oxidation

Methanobactins (mbs) are low-molecular-mass (<1,200 Da) copper-binding peptides, or chalkophores, produced by many methane-oxidizing bacteria (methanotrophs). These molecules exhibit similarities to certain iron-binding siderophores but are expressed and secreted in response to copper limitation. Structurally, mbs are characterized by a pair of heterocyclic rings with associated thioamide groups that form the copper coordination site. One of the rings is always an oxazolone and the second ring an oxazolone, an imidazolone, or a pyrazinedione moiety. The mb molecule originates from a peptide precursor that undergoes a series of posttranslational modifications, including (i) ring formation, (ii) cleavage of a leader peptide sequence, and (iii) in some cases, addition of a sulfate group. Functionally, mbs represent the extracellular component of a copper acquisition system. Consistent with this role in copper acquisition, mbs have a high affinity for copper ions. Following binding, mbs rapidly reduce Cu 2+ to Cu 1+ . In addition to binding copper, mbs will bind most transition metals and near-transition metals and protect the host methanotroph as well as other bacteria from toxic metals. Several other physiological functions have been assigned to mbs, based primarily on their redox and metal-binding properties. Here, we examine the current state of knowledge of this novel type of metal-binding peptide. We also explore its potential applications, how mbs may alter the bioavailability of multiple metals, and the many roles mbs may play in the physiology of methanotrophs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of Copper Birnessite, Cu x MnO y ·nH 2 O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry

This report describes the first detailed electrochemical examination of a series of copper birnessite samples under lithium-based battery conditions, allowing a structure/function analysis of the electrochemistry and related material properties. To obtain the series of copper birnessite samples, a novel synthetic approach for the preparation of copper birnessite, Cu x MnO y ·nH 2 O is reported. The copper content (x) in Cu x MnO y ·nH 2 O, 0.28 >= x >= 0.20, was inversely proportional to crystallite size, which ranged from 12 to 19 nm. The electrochemistry under lithium-based battery conditions showed that the higher copper content (x = 0.28) and small crystallite size (similar to 12 nm) sample delivered similar to 194 mAh/g, about 20% higher capacity than the low copper content (x = 0.22) and larger crystallite size (similar to 19 nm) material. In addition, Cu x MnO y ·nH 2 O displays quasi-reversible electrochemistry in magnesium based electrolytes, indicating that copper birnessite could be a candidate for future application in magnesium-ion batteries.

25 ENERGY STORAGE↗

Secondary electron emission characteristics of molybdenum-masked, ion-textured OFHC copper

A method for producing a uniform, highly textured surface on oxygen-free, high conductivity (OFHC) copper by ion bombardment using sputtered molybdenum as a texture-inducing masking film was developed and used to provide samples for study. The purpose was to develop a basically OFHC copper surface having very low secondary electron emission characteristics. Surfaces having low secondary electron emission are a requirement for the electrodes of very high efficiency multistage depressed collectors (MDC's). Such MDC's are used in microwave amplifier traveling wave tubes for space communications and other applications. OFHC copper is the material most commonly used for MDC electrodes because it has high thermal conductivity, it is easy to machine, and its fabrication and brazing procedures are well established. However, its untreated surface displays relatively very high levels of secondary electron emissions. Textured OFHC copper samples were tested for true secondary electron emission and relative reflected primary electron yield at primary electron beam energy levels from 200 to 2000 eV and at direct (0 deg) to oblique (60 deg) beam impingement angles. The test results for three of the samples, each of which was processed in a slightly different way, are compared with each other and with test results for a machined OFHC copper sample. Although the textured samples are not represented here as having been processed optimally, their measured secondary electron emission characteristics are significantly lower than those of the untreated OFHC copper sample over the range of conditions studied. Importantly, the relative reflected primary electron yield of one of the textured samples is conspicuously lower than that of the others. Clearly, with further development, the molybdenum-masked ion-textured OFHC copper surface will be a promising material for high-efficiency MDC electrodes.

Curren, Arthur N.↗