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At least 433 records · Page 24

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

Highlights: • A Brønsted acidic ILs was used to leach Cu from WPCBs for the first time. • The particle size of WPCBs has significant influence on Cu leaching rate. • Cu leaching rate was higher than 99% under the optimum leaching conditions. • The leaching process can be modeled with shrinking core model, and the E{sub a} was 25.36 kJ/mol. - Abstract: In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO{sub 4}), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO{sub 4} can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cytochrome b561, copper, β-cleaved amyloid precursor protein and niemann-pick C1 protein are involved in ascorbate-induced release and membrane penetration of heparan sulfate from endosomal S-nitrosylated glypican-1

Ascorbate-induced release of heparan sulfate from S-nitrosylated heparan sulfate proteoglycan glypican-1 takes place in endosomes. Heparan sulfate penetrates the membrane and is transported to the nucleus. This process is dependent on copper and on expression and processing of the amyloid precursor protein. It remains unclear how exogenously supplied ascorbate can generate HS-anMan in endosomes and how passage through the membrane is facilitated. Here we have examined wild-type, Alzheimer Tg2576 and amyloid precursor protein (-/-) mouse fibroblasts and human fetal and Niemann-Pick C1 fibroblasts by using deconvolution immunofluorescence microscopy, siRNA technology and [S{sup 35}]sulfate-labeling, vesicle isolation and gel chromatography. We found that ascorbate-induced release of heparan sulfate was dependent on expression of endosomal cytochrome b561. Formation and nuclear transport of heparan sulfate was suppressed by inhibition of β-processing of the amyloid precursor protein and formation was restored by copper (I) ions. Membrane penetration was not dependent on amyloid beta channel formation. Inhibition of endosomal exit resulted in accumulation of heparan sulfate in vesicles that exposed the C-terminal of the amyloid precursor protein externally. Endosome-to-nucleus transport was also dependent on expression of the Niemann-Pick C1 protein. We propose that ascorbate is taken up from the medium and is oxidized by cytochrome b561 which, in turn, reduces copper (II) to copper (I) present in the N-terminal, β-cleaved domain of the amyloid precursor protein. Re-oxidation of copper (I) is coupled to reductive, deaminative release of heparan sulfate from glypican-1. Passage through the membrane may be facilitated by the C-terminal, β-cleaved fragment of the amyloid precursor protein and the Niemann-Pick C1 protein. - Highlights: • Cytochrome b561 is a mediator of ascorbate-induced release of heparan sulfate from glypican-1 in endosomes. • Beta-cleavage of the amyloid precursor protein is required for release and membrane penetration of heparan sulfate. • The Niemann-Pick C1 protein is involved in membrane penetration.

60 APPLIED LIFE SCIENCES↗

The CopC Family: Structural and Bioinformatic Insights into a Diverse Group of Periplasmic Copper Binding Proteins

The CopC proteins are periplasmic copper binding proteins believed to play a role in bacterial copper homeostasis. Previous studies have focused on CopCs that are part of seven-protein Cop or Pco systems involved in copper resistance. These canonical CopCs contain distinct Cu(I) and Cu(II) binding sites. Mounting evidence suggests that CopCs are more widely distributed, often present only with the CopD inner membrane protein, frequently as a fusion protein, and that the CopC and CopD proteins together function in the uptake of copper to the cytoplasm. In the methanotroph Methylosinus trichosporium OB3b, genes encoding a CopCD pair are located adjacent to the particulate methane monooxygenase (pMMO) operon. The CopC from this organism (Mst-CopC) was expressed, purified, and structurally characterized. The 1.46 Å resolution crystal structure of Mst-CopC reveals a single Cu(II) binding site with coordination somewhat different from that in canonical CopCs, and the absence of a Cu(I) binding site. Furthermore, extensive bioinformatic analyses indicate that the majority of CopCs in fact contain only a Cu(II) site, with just 10% of sequences corresponding to the canonical two-site CopC. Accordingly, a new classification scheme for CopCs was developed, and detailed analyses of the sequences and their genomic neighborhoods reveal new proteins potentially involved in copper homeostasis, providing a framework for expanded models of CopCD function.

59 BASIC BIOLOGICAL SCIENCES↗

ATCUN-like Copper Site in βB2-Crystallin Plays a Protective Role in Cataract-Associated Aggregation

Cataract is the leading cause of blindness worldwide, and it is caused by crystallin damage and aggregation. Senile cataractous lenses have relatively high levels of metals, while some metal ions can directly induce the aggregation of human γ-crystallins. Here, for this work, we evaluated the impact of divalent metal ions in the aggregation of human βB2-crystallin, one of the most abundant crystallins in the lens. Turbidity assays showed that Pb 2+ , Hg 2+ , Cu 2+ , and Zn 2+ ions induce the aggregation of βB2-crystallin. Metal-induced aggregation is partially reverted by a chelating agent, indicating the formation of metal-bridged species. Our study focused on the mechanism of copper-induced aggregation of βB2-crystallin, finding that it involves metal-bridging, disulfide-bridging, and loss of protein stability. Circular dichroism and electron paramagnetic resonance (EPR) revealed the presence of at least three Cu 2+ binding sites in βB2-crystallin, one of them with spectroscopic features typical for Cu 2+ bound to an amino-terminal copper and nickel (ATCUN) binding motif, which is found in Cu transport proteins. The ATCUN-like Cu binding site is located at the unstructured N-terminus of βB2-crystallin, and it could be modeled by a peptide with the first six residues in the protein sequence (NH 2 -ASDHQF-). Isothermal titration calorimetry indicates a nanomolar Cu 2+ binding affinity for the ATCUN-like site. An N-truncated form of βB2-crystallin is more susceptible to Cu-induced aggregation and is less thermally stable, indicating a protective role for the ATCUN-like site. EPR and X-ray absorption spectroscopy studies reveal the presence of a copper redox active site in βB2-crystallin that is associated with metal-induced aggregation and formation of disulfide-bridged oligomers. Our study demonstrates metal-induced aggregation of βB2-crystallin and the presence of putative copper binding sites in the protein. Whether the copper-transport ATCUN-like site in βB2-crystallin plays a functional/protective role or constitutes a vestige from its evolution as a lens structural protein remains to be elucidated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transport properties of zigzag graphene nanoribbon decorated with copper clusters

Using non-equilibrium green function with density functional theory, the present study investigates the transport properties of decorated zigzag graphene nanoribbon with a copper cluster. We have represented the decoration of zigzag graphene nanoribbon with single copper atom and cluster containing two and three copper atoms. In all the cases, copper atoms tend to occupy the edge state. In addition, we have shown that copper can alter the current-voltage characteristic of zigzag graphene nanoribbon and create new fluctuations and negative differential resistance. These alternations are made due to discontinuity in the combination of orbitals along the graphene nanoribbon. Decoration alters these discontinuities and creates more visible fluctuations. However, in low bias voltages, the changes are similar in all the cases. The study demonstrates that in the decorated zigzag graphene nanoribbon, the edge states are the main states for transporting electron from one electrode to another.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nanocarbon-copper thin film as transparent electrode

Researchers seeking to enhance the properties of metals have long pursued incorporating carbon in the metallic host lattice in order to combine the strongly bonded electrons in the metal lattice that yield high ampacity and the free electrons available in carbon nanostructures that give rise to high conductivity. The incorporation of carbon nanostructures into the copper lattice has the potential to improve the current density of copper to meet the ever-increasing demands of nanoelectronic devices. We report on the structure and properties of carbon incorporated in concentrations up to 5 wt. % (∼22 at. %) into the crystal structure of copper. Carbon nanoparticles of 5 nm–200 nm in diameter in an interconnecting carbon matrix are formed within the bulk Cu samples. The carbon does not phase separate after subsequent melting and re-solidification despite the absence of a predicted solid solution at such concentrations in the C-Cu binary phase diagram. This material, so-called, Cu covetic, makes deposition of Cu films containing carbon with similar microstructure to the metal possible. Copper covetic films exhibit greater transparency, higher conductivity, and resistance to oxidation than pure copper films of the same thickness, making them a suitable choice for transparent conductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Gold-Copper alloy “nano-dumplings” with tunable compositions and plasmonic properties

The unique yet tunable optical properties of plasmonic metal nanoparticles have made them attractive targets for a wide range of applications including nanophotonics, molecular sensing, catalysis etc. Such diverse applications that require precisely stable / reproducible plasmonic properties depend sensitively on the particle morphology ie. the shape, size and constituents. Herein, we systematically study the size / shape controlled synthesis of gold-copper “dumpling” shaped alloy nanoparticles by simultaneous reduction of gold and copper salts in the PVP-methanol solute-solvent system, by effectively utilizing the efficient but mild reduction as well as capping abilities of Poly (N-vinylpyrrolidone). Introduction of copper salts not only yielded the alloy nanoparticles, but also slowed down the growth process to maintain high mono-dispersity of the new shapes evolved. Copper and gold has different lattice constants (0.361 and 0.408 nm respectively) and hence doping/addition/replacement of copper atoms to gold FCC unit cell introduces strain into the lattice which is key parameter to the shape evolution in anisotropic nanoparticles. Synthesized alloy nanoparticles were characterized by UV-visible absorption spectroscopy, XRD and TEM imaging.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Direct write of copper-graphene composite using micro-cold spray

Direct write of a new class of composite materials containing copper and graphene in the powder phase is described. The composite was synthesized using batch electroless plating of copper for various times onto Nano Graphene Platelets (NGP) to control the amount of copper deposited within the loosely aggregated graphene powder. Copper deposition was confirmed by both Focused Ion Beam (FIB) and Auger electron spectroscopic analysis. A micro-cold spray technique was used to deposit traces that are ∼230 μm wide and ∼5 μm thick of the formulated copper/graphene powder onto a glass substrate. The deposited traces were found to have good adhesion to the substrate with ∼65x the copper bulk resistivity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Structural hierarchy of nanocarbon in copper covetics

Here, we prepared 0.4 wt.% carbon infused copper (i.e., copper covetic, CuCv) by electronbeam melting and deposited ≈18 nm-thick films of the CuCv on a substrate by electron-beam evaporation. Helium ion microscopy (HIM) and scanning transmission electron microscopy (STEM) were used to study the characteristics of the carbon nanostructure in the CuCv bulk and thin films. HIM observation of the fracture and ion-polished surface of bulk CuCv revealed ripple structures that are associated with carbon nanoribbons formed in the copper matrix. STEM high angle annular dark field (HAADF) imaging and energy dispersive X-ray spectroscopy (EDX) mapping indicated that carbon nanoparticles and carbon-rich pathways are interconnected to form a carbon-rich network in the CuCv films. High-resolution transmission electron microscopy and STEM electron energy loss spectroscopy (EELS) suggest that the carbon nanoparticles are composed of highly distorted graphenic carbon sheets, bond to copper matrix, and likely provide means for superior electrical and thermal conduction. In this letter, we report structural hierarchy and representations of carbon nanostructure in copper covetics at different scales.

36 MATERIALS SCIENCE↗

SU-C-213-05: Evaluation of a Composite Copper-Plastic Material for a 3D Printed Radiation Therapy Bolus

Purpose: To evaluate a novel 3D printed bolus fabricated from a copper-plastic composite as a thin flexible, custom fitting device that can replicate doses achieved with conventional bolus techniques. Methods: Two models of bolus were created on a 3D printer using a composite copper-PLA/PHA. Firstly, boluses were constructed at thicknesses of 0.4, 0.6 and 0.8 mm. Relative dose measurements were performed under the bolus with an Attix Chamber as well as with radiochromic film. Results were compared to superficial Attix Chamber measurements in a water equivalent material to determine the dosimetric water equivalence of the copper-PLA/PHA plastic. Secondly, CT images of a RANDO phantom were used to create a custom fitting bolus across the anterolateral scalp. Surface dose with the bolus placed on the RANDO phantom was measured with radiochromic film at tangential angles with 6, 10, 10 flattening filter free (FFF) and 18 MV photon beams. Results: Mean surface doses for 6, 10, 10FFF and 18 MV were measured as a percent of Dmax for the flat bolus devices of each thickness. The 0.4 mm thickness bolus was determined to be near equivalent to 2.5 mm depth in water for all four energies. Surface doses ranged from 59–63% without bolus and 85–90% with the custom 0.4 mm copper-plastic bolus relative to the prescribed dose for an oblique tangential beam arrangement on the RANDO phantom. Conclusion: Sub-millimeter thickness, 3D printed composite copper-PLA/PHA bolus can provide a build-up effect equivalent to conventional bolus. At this thickness, the 3D printed bolus allows a level of flexure that may provide more patient comfort than current 3D printing materials used in bolus fabrication while still retaining the CT based custom patient shape. Funding provided by an intra-department grant of the University of Minnesota Department of Radiation Oncology.

60 APPLIED LIFE SCIENCES↗

Enhancement of Nitrous Oxide Emissions in Soil Microbial Consortia via Copper Competition between Proteobacterial Methanotrophs and Denitrifiers

Unique means of copper scavenging have been identified in proteobacterial methanotrophs, particularly the use of methanobactin, a novel ribosomally synthesized, post-translationally modified polypeptide that binds copper with very high affinity. The possibility that copper sequestration strategies of methanotrophs may interfere with copper uptake of denitrifiers in situ and thereby enhance N 2 O emissions was examined using a suite of laboratory experiments performed with rice paddy microbial consortia. Addition of purified methanobactin from Methylosinus trichosporium OB3b to denitrifying rice paddy soil microbial consortia resulted in substantially increased N 2 O production, with more pronounced responses observed for soils with lower copper content.

59 BASIC BIOLOGICAL SCIENCES↗

Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å, c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Preparation and electrical conductivity of graphitic carbon-infused copper alloys

By electron-beam (e-beam) melting, we prepared 0.4 wt% carbon-infused copper (CuCv4), and a copper control without carbon addition (CuCv0). Scanning electron microscopy and helium ion microscopy (HIM) were performed on the as-solidified surface, fracture surface, and ion-polished surface of the CuCv4 sample. The results revealed that graphitic carbon flakes cover the as-solidified surface, and carbon nanoparticles and clusters exist in the fracture and ion-polished surfaces. HIM on the ion-polished surface revealed a unique ripple-shaped feature, which is possibly associated with the infusion of carbon nanoribbons in the copper matrix. The bulk densities were measured to be 8.86 and 8.53 g/cm 3 , which correspond to relative densities of 98.9% and 96.4% for the CuCv0 and CuCv4 samples, respectively. Also, apparent electrical conductivities were measured to be 56.9 and 57.5 MS/m, respectively, for the e-beam melted CuCv0 and CuCv4 samples. These values correspond to true electrical conductivities of 100.5% IACS (International Annealed Copper Standard) and 107.4% IACS after correction for the porosity. Thus, our results reveal remarkable promise of using covetic copper for the next generation conductors in energy applications from microelectronic devices to high-power transmission cables.

36 MATERIALS SCIENCE↗

Print-Consistency and Process-Interaction for Inkjet-Printed Copper on Flexible Substrate

Printed electronics is a fastest growing and emerging technology that have shown much potential in several industries including automotive, wearables, healthcare, and aerospace. Its applications can be found not only in flexible but also in large area electronics. The technology provides an effective and convenient method to additively deposit conductive and insulating materials on any type of substrate. Comparing with traditional manufacturing processes, which involves chemical etching, this technology also comes to be relatively environmental friendly. Despite its status, it is not without its challenges. Starting from the material being compatible in the printer equipment to the point of achieving fine resolutions, and with excellent properties are some of the challenges that printed electronics face. Among the myriad of printing technologies such as Aerosol Jet, micro-dispensing, gravure printing, screen printing, Inkjet printing, Inkjet has gained much attention due to its low-cost, low material consumption, and roll-to-roll capability for mass manufacturing. The technology has been widely used in home and office, but recently gained interest in printed electronics in a research and development setting. Conductive materials used in Inkjet printing generally comprises of metal Nanoparticles that need to be thermally sintered for it to be conductive. The preferred metal of choice has been mostly silver due to its excellent electrical properties and ease in sintering. However, silver comes to be expensive than its counterpart copper. Since copper is prone to oxidation, much focus has been given towards photonic sintering that involves sudden burst of pulsed light at certain energy to sinter the copper Nanoparticles. With this technique, only the printed material gets sintered in a matter of seconds without having a great impact on its substrate, due to which it is also preferred in low temperature applications. With all the knowledge, there is still a large gap in the process side with copper where it is important to look how the print process affects the resolution of the print along with the effect of post-print processes on electrical and mechanical properties. In this paper, a copper Inkjet ink is utilized for understanding the effect of Inkjet print parameters on the ejected droplet and its resolution. Post-print process is also quantified using a photonic sintering equipment for excellent electrical and mechanical properties. To demonstrate the complete process, commercial-off-the-shelf components will also be mounted on the additively printed pads via Inkjet. Statistically, control charting technique will be utilized to understand the capability of the Inkjet process.

printed electronics↗

Cu K-edge X-ray Absorption Spectroscopy Reveals Differential Copper Coordimation Within Amyloid-beta Oligomers Compared to Amyloid-beta Monomers

The fatal neurodegenerative disorder Alzheimer's disease (AD) has been linked to the formation of soluble neurotoxic oligomers of amyloid-{beta} (A{beta}) peptides. These peptides have high affinities for copper cations. Despite their potential importance in AD neurodegeneration few studies have focused on probing the Cu{sup 2+/1+} coordination environment within A{beta} oligomers. Herein we present a Cu K-edge X-ray absorption spectroscopic study probing the copper-coordination environment within oligomers of A{beta}(42) (sequence: DAEFRHDSGYEVHHQKLVFFAEDVGSNKGAIIGLMVGGVVIA). We find that the Cu{sup 2+} cation is contained within a square planar mixed N/O ligand environment within A{beta}(42) oligomers, which is similar to the copper coordination environment of the monomeric forms of {l_brace}Cu{sup II}A{beta}(40){r_brace} and {l_brace}Cu{sup II}A{beta}(16){r_brace}. Reduction of the Cu{sup 2+} cation within the A{beta}(42) oligomers to Cu{sup 1+} yields a highly dioxygen sensitive copper-species that contains Cu{sup 1+} in a tetrahedral coordination geometry. This can be contrasted with monomers of {l_brace}Cu{sup I}A{beta}(40){r_brace} and {l_brace}Cu{sup I}A{beta}(16){r_brace}, which contain copper in a dioxygen inert linear bis-histidine ligand environment [Shearer and Szalai, J. Am. Chem. Soc., 2008, 130, 17826]. The biological implications of these findings are discussed.

59 BASIC BIOLOGICAL SCIENCES↗

Atomistic-Scale Simulations on Graphene Bending Near a Copper Surface

Molecular insights into graphene-catalyst surface interactions can provide useful information for the efficient design of copper current collectors with graphitic anode interfaces. As graphene bending can affect the local electron density, it should reflect its local reactivity as well. Using ReaxFF reactive molecular simulations, we have investigated the possible bending of graphene in vacuum and near copper surfaces. We describe the energy cost for graphene bending and the binding energy with hydrogen and copper with two different ReaxFF parameter sets, demonstrating the relevance of using the more recently developed ReaxFF parameter sets for graphene properties. Moreover, the draping angle at copper step edges obtained from our atomistic simulations is in good agreement with the draping angle determined from experimental measurements, thus validating the ReaxFF results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flexible Copper Metal Circuits via Desktop Laser Printed Masks

A novel process is demonstrated that produces patterns of electrically conductive copper on a flexible polyimide film substrate using standard desktop laser printed toner and near room temperature aqueous chemistry. The laser toner acts as a mask to selectively block the ion exchange self-metallization (IESM) reduction reaction that forms nanoscale silver or palladium coatings at the polyimide surface. The silver or palladium IESM coating is then used as a catalyst for electroless deposition of copper. Under appropriate conditions, the copper is deposited selectively on top of the catalyst layer. The resulting copper layer has a measured sheet resistance as low as 0.3 Ohms/sq. Electrical isolation was measured between copper traces spaced as close as 300 microns, and high conductivity was measured along traces with widths as low as 200 microns. The minimum pattern size appears to be limited primarily by the resolution of the laser toner pattern, as the IESM metal layer was observed to follow the contours of individual toner particles. Here, the process avoids the use of high temperature, vacuum, and organic solvents and is thus suitable for very low cost prototyping or distributed manufacturing of simple electronic devices.

36 MATERIALS SCIENCE↗

Design, fabrication, simulation, and testing of additively manufactured lattice-based copper heat sinks

Here, this study investigates the potential advantages of lattice structure-based bound metal material extrusion (MEX) 3D printing for fabricating high-performance copper heat sinks. Copper powder-filled polymer filaments, with a copper content of > 90 wt.%, were developed specifically for the bound metal MEX 3D printing process. Three types of structures—planar, strut, and surface lattices—were 3D printed to facilitate efficient heat transfer pathways within the heat sinks. Subsequent post-processing steps, including polymer removal and sintering, were performed to achieve dense copper parts. Hot isostatic pressing was further employed to enhance the sintered density from 93 to 98%. Finite element analysis (FEA) simulations were conducted to assess the heat transfer efficiency of the designs, and heat transfer experiments were performed using a custom setup to validate the simulation results. Additionally, this research explores the use of extended hold times during pre-sintering and a reduced atmosphere to enhance the %IACS values (electrical conductivity) and thermal performance of the bound metal MEX 3D printed copper heat sinks. The investigation combines experimental analysis, including simulations and heat transfer experiments, to gain insights into the structure-material property relationships and optimize the thermal performance of the printed heat sinks.

Ajjarapu, Kameswara Pavan Kumar [Oak Ridge Nationa↗