Showing papers on "Copper published in 2001"

Anomalously increased effective thermal conductivities of ethylene glycol-based nanofluids containing copper nanoparticles

Abstract: It is shown that a “nanofluid” consisting of copper nanometer-sized particles dispersed in ethylene glycol has a much higher effective thermal conductivity than either pure ethylene glycol or ethylene glycol containing the same volume fraction of dispersed oxide nanoparticles. The effective thermal conductivity of ethylene glycol is shown to be increased by up to 40% for a nanofluid consisting of ethylene glycol containing approximately 0.3 vol % Cu nanoparticles of mean diameter <10 nm. The results are anomalous based on previous theoretical calculations that had predicted a strong effect of particle shape on effective nanofluid thermal conductivity, but no effect of either particle size or particle thermal conductivity.

Particle Size Effects on the Electrochemical Performance of Copper Oxides toward Lithium

Abstract: The electrochemical reactivity of tailor-made or CuO powders prepared according to the polyol process was tested in rechargeable Li cells. To our surprise, we demonstrated that CuO, a material well known for primary Li cells, and could reversibly react with 1.1 Li and 2 Li ions per formula unit, respectively, leading to reversible capacities as high as 400 mAh/g in the 3-0.02 V range. The ability of copper oxide-based Li cells to retain their capacity upon numerous cycles was found to be strongly dependent on the particle size, and the best results (100% of the total capacity up to 70 cycles) were obtained with 1 μm and CuO particles. Ex situ transmission electron microscopy data and in situ X-ray experiments show that the reduction mechanism of by Li first involved the formation of Cu nanograins dispersed into a lithia matrix, followed by the growth of an organic coating that partially dissolved upon the subsequent charge while Cu converted back to nanograins. We believe that the key to the reversible reactivity mechanism of copper oxides or other transition metal oxides toward Li is the electrochemically driven formation of highly reactive metallic nanograins during the first discharge, which enables the formation-decomposition of upon subsequent cycles. © 2001 The Electrochemical Society. All rights reserved.

Shuttles and muscles: linear molecular machines based on transition metals.

Abstract: Transition-metal-containing rotaxanes can behave as linear motors at the molecular level. The molecules are set into motion either by an electrochemical reaction or using a chemical signal. In a first example, a simple rotaxane is described that consists of a ring threaded by a two-coordination-site axle. The ring contains a bidentate ligand, coordinated to a copper center. The axle incorporates both a bidentate and a terdentate ligand. By oxidizing or reducing the copper center to Cu(II) or Cu(I) respectively, the ring glides from a given position on the axle to another position and vice versa. By generalizing the concept to a rotaxane dimer, whose synthesis involves a quantitative double-threading reaction triggered by copper(I) complexation, a molecular assembly reminiscent of a muscle is constructed. By exchanging the two metal centers of the complex (copper(I)/zinc(II)), a large-amplitude movement is generated, which corresponds to a contraction/stretching process. The copper(I)-containing rotaxane d...

Deposition of conformal copper and nickel films from supercritical carbon dioxide.

Abstract: Device-quality copper and nickel films were deposited onto planar and etched silicon substrates by the reduction of soluble organometallic compounds with hydrogen in a supercritical carbon dioxide solution. Exceptional step coverage on complex surfaces and complete filling of high-aspect-ratio features of less than 100 nanometers width were achieved. Nickel was deposited at 60°C by the reduction of bis(cyclopentadienyl)nickel and copper was deposited from either copper(I) or copper(II) compounds onto the native oxide of silicon or metal nitrides with seed layers at temperatures up to 200°C and directly on each surface at temperatures above 250°C. The latter approach provides a single-step means for achieving high-aspect-ratio feature fill necessary for copper interconnect structures in future generations of integrated circuits.

Superconductivity of powder-in-tube MgB2 wires

Abstract: A new class of `powder-in-tube' Mg-B superconducting conductors has been prepared using two different methods: an in situ technique where an Mg + 2B mixture was used as a central conductor core and reacted in situ to form MgB2, and an ex situ technique where fully reacted MgB2 powder was used to fill the metal tube. Conductors were prepared using silver, copper and bimetallic silver/stainless steel tubes. Wires manufactured by the in situ technique, diffusing Mg to B particles experienced ~25.5% decrease in density from the initial value after cold deformation, due to the phase transformation from Mg + 2(β-B)→MgB2 all with hexagonal structure. A comparative study of the intergranular current and grain connectivity in wires was conducted by AC susceptibility measurements and direct four point transport measurements. Using a SQUID magnetometer, magnetization versus magnetic field (M-H) curves of the round wires before and after sintering and reactive diffusion were measured at 5 K and in magnetic fields up to 5 T to define the Jcmag. The direct current measurements were performed in self field at 4.2 K. A comparison between zero-field-cooled (ZFC) and field-cooled (FC) susceptibility measurements for sintered Ag/MgB2, and reacted Cu/Mg + 2B conductors revealed systematic differences in the flux pinning in the wires which is in very good agreement with direct high transport current measurements.

Copper and Copper Alloys

Abstract: This book is a comprehensive guide to the selection and applications of copper and copper alloys, which constitute one of the largest and most diverse families of engineering materials. The handbook includes all of the essential information contained in the 20-volume ASM Handbook series, as well as important reference information and data from a wide variety of ASM publications and industry sources. In addition to extensive property data for wrought, cast, and powder-metallurgy products, this book provides practical information on the casting, forming, joining, machining, and finishing of copper alloys. The principles of physical metallurgy, including the relationships among heat treatment, structure, and properties, are also examined. Specifications for copper and its alloys are cross referenced in useful tabular form. Recent alloy developments - such as low-lead free-machining alloys, high-strength alloys with resistance to corrosion in hot 'sour' environments, and thermally stable, high-conductivity electronic packaging materials-are also reviewed. Contents: Metallurgy, alloys, and applications Fabrication and finishing Metallurgy, microstructures, and phase diagrams: Metallography and microstructures of copper alloys and beryllium-copper alloys Solidification structures Phase diagrams. Engineering properties and service characteristics Appendices.

Deactivation of supported copper metal catalysts for hydrogenation reactions

Abstract: Laboratory and industrial results are used to elucidate the general features of the deactivation of supported copper metal catalysts in hydrogenation reactions. Hydrogenations with copper catalysts are milder than with their nickel or platinum counterparts, and they have selectivities that are exploited commercially. They are used in single stream plants for production of hydrogen via the low-temperature water shift gas reaction, and for methanol manufacture from synthesis gas, and also in hydrogenation of speciality organic compounds. Common catalyst types are based on Cu/Cr 2 O 3 (copper chromite) or Cu/ZnO formulations that contain stabilisers and promoters such as alkaline earth oxides and Al 2 O 3 . These have several roles, including inhibition of sintering, and poison traps that prevent poisoning of the active metal surface. The best understood are Cu/ZnO formulations that have improved sulphur resistance due to formation of thermodynamically stable ZnS. Copper catalysts are susceptible to thermal sintering via a surface migration process and this is markedly accelerated by the presence of even traces of chloride. Care must be, therefore, taken to eliminate halides from copper catalysts during manufacture, and from the reactants during use. Operating temperatures must be restricted, usually to below 300°C when catalyst longevity is important with large catalyst volumes. Water can soften some Cu/ZnO formulations during use, and cause particle breakage that leads to high-pressure drop and maldistribution of flow through large catalyst beds and impaired performance. Commercial copper catalysts are not acidic, and since they operate under mild conditions, carbon deposition (coking) is uncommon. However, conventional site blocking poisoning with sulphur compounds, and particularly by H 2 S, is common. The initial phase involves interaction with surface hydroxyl groups and elimination of water. Sulphur is retained strongly on the catalyst, and when partially sulphided they can exhibit selectivity in hydrogenation of organic hydrogenations. A variety of other sulphur compounds, and some chlorinated organic compounds, can cause complete deactivation or enhanced selectivity.

Copper Delivery by Metallochaperone Proteins

Abstract: Copper is an essential element in all living organisms, serving as a cofactor for many important proteins and enzymes. Metallochaperone proteins deliver copper ions to specific physiological partners by direct protein-protein interactions. The Atx1-like chaperones transfer copper to intracellular copper transporters, and the CCS chaperones shuttle copper to copper,zinc superoxide dismutase. Crystallographic studies of these two copper chaperone families have provided insights into metal binding and target recognition by metallochaperones and have led to detailed molecular models for the copper transfer mechanism.

A Novel Method of Etching Copper Oxide Using Acetic Acid

Abstract: The removal of copper oxide using acetic acid at low temperatures was investigated. Acetic acid removes a variety of copper oxides, including cuprous oxide, cupric oxide, and cupric hydroxide without attacking the underlying copper film. The removal of these oxides was determined by X-ray photoelectron spectroscopy. Acetic acid can tolerate up to 4 vol % water dilution without hindering the oxide removal while producing an oxide-free surface. However, if a deionized water rinse is performed after an acetic acid treatment, a surface film of cupric hydroxide forms immediately. An acetic acid treatment at 35°C without a water rinse removes the native copper oxide and produces an oxide-free, streak-free copper surface.

New Electric Double-Layered Magnetic Fluids Based on Copper, Nickel, and Zinc Ferrite Nanostructures

Abstract: We report on stable colloidal aqueous suspensions of magnetic nanostructures made of copper, nickel, and zinc ferrites. These magnetic fluids could represent a new alternative for biological applications. The basic steps of the nanoparticles synthesis, their chemical surface treatment, and their peptization in a stable colloidal sol are given. Their chemical composition is carefully checked, and X-ray diffraction patterns provide both their mean size and a structural characterization. Magnetization results obtained at 300 K are presented and discussed.

Implication of the microstructure of binary Cu/ZnO catalysts for their catalytic activity in methanol synthesis

Abstract: Binary Cu/ZnO catalysts with varying molar ratios (90/10 through 10/90) were studied under methanol synthesis conditions at 493 K and at atmospheric pressure. The methanol synthesis activity of the catalysts was correlated to their specific Cu surface area (N2O reactive frontal chromatography, N2O RFC) after reduction in 2 vol% H2 at 513 K. Activity data were supplemented with a detailed analysis of the microstructure, i.e., crystallite size and strain of the reduced Cu and the ZnO phases after reduction using X-ray diffraction line profile analysis. The estimated copper surface area based on a spherical shape of the copper crystallites is in good agreement with data determined by N2O RFC. A positive correlation of the turnover frequency for methanol production with the observed microstrain of copper in the Cu/ZnO system was found. The results indicate a mutual structural interaction of both components (copper and zinc oxide) in the sense that strained copper particles are stabilized by the unstrained state of the zinc oxide microcrystallites. The observed structural deformation of ZnO in samples with higher Cu loading can originate, for instance, from epitaxial bonding of the oxide lattice to the copper metal, insufficient reduction or residual carbonate due to incomplete thermal decomposition during reduction. Additional EXAFS measurements at the Cu K and the Zn K edge show that about 5% ZnO are dissolved in the CuO matrix of the calcined precursors. Furthermore, it is shown that the microstructural changes (e.g., size and strain) of copper can be traced back to the phase composition of the corresponding hydroxycarbonate precursors.

Semiconducting system and production method

Abstract: The object of the present invention is to prevent rise of resistance due to oxidation of the copper wiring and diffusion of copper. The above object can be attained by the present invention providing a semiconductor device which contains a wire protective film 1 covering the top of the copper wiring 2 formed in the insulation film and a barrier film surrounding the side and bottom of the copper wiring; wherein the wire protective film and/or barrier film is formed with cobalt alloy film containing (1) cobalt, (2) at least one of chromium, molybdenum, tungsten, rhenium, thallium and phosphorus, and (3) boron, as in the case of other embodiments.

Old iron, young copper: from Mars to Venus.

Abstract: Iron and copper are metals which play an important role in the living world. From a brief consideration of their chemistry and biochemistry we conclude that the early chemistry of life used water soluble ferrous iron while copper was in the water-insoluble Cu(I) state as highly insoluble sulphides. The advent of oxygen was a catastrophic event for most living organisms, and can be considered to be the first general irreversible pollution of the earth. In contrast to the oxidation of iron and its loss of bioavailability as insoluble Fe(III), the oxidation of insoluble Cu(I) led to soluble Cu(II). A new iron biochemistry became possible after the advent of oxygen, with the development of chelators of Fe(III), which rendered iron once again accessible, and with the control of the potential toxicity of iron by its storage in a water soluble, non-toxic, bio-available storage protein (ferritin). Biology also discovered that whereas enzymes involved in anaerobic metabolism were designed to operate in the lower portion of the redox spectrum, the arrival of dioxygen created the need for a new redox active metal which could attain higher redox potentials. Copper, now bioavailable, was ideally suited to exploit the oxidizing power of dioxygen. The arrival of copper also coincided with the development of multicellular organisms which had extracellular cross-linked matrices capable of resisting attack by oxygen free radicals. After the initial 'iron age' subsequent evolution moved, not towards a 'copper age', but rather to an 'iron-copper' age. In the second part of the review, this symbiosis of iron and copper is examined in yeast. We then briefly consider iron and copper metabolism in mammals, before looking at iron-copper interactions in mammals, particularly man, and conclude with the reflection that, as in Greek and Roman mythology, a better understanding of the potentially positive interactions between Mars (iron) and Venus (copper) can only be to the advantage of our species.

Synthesis of Silver and Copper Nanoparticles in a Water-in-Supercritical-Carbon Dioxide Microemulsion

Abstract: Nanometer-sized silver and copper metal particles can be synthesized by chemical reduction of Ag+ and Cu2+ ions dissolved in the water core of a water in supercritical fluid carbon dioxide microemulsion. Sodium cyanoborohydride and N,N,N‘,N‘-tetramethyl-p-phenylenediamine are effective reducing agents for synthesizing these metal nanoparticles in the microemulsion. Formation of the metal nanoparticles was monitored spectroscopically using a high-pressure fiber-optic reactor equipped with a CCD array UV−vis spectrometer. Silver and copper nanoparticles synthesized in the microemulsion showed characteristic surface plasmon resonance absorption bands centered at 400 and 557 nm, respectively. Diffusion and distribution of the oxidized form of the reducing agent between the micellar core and supercritical CO2 appeared to be the rate-determining step for the formation of the silver nanoparticles in this system.

The stability of Cu/ZnO-based catalysts in methanol synthesis from a CO2-rich feed and from a CO-rich feed

Abstract: Water produced during methanol synthesis from a CO 2 -rich feed (CO 2 /CO/H 2 ) accelerated the crystallization of Cu and ZnO contained in a Cu/ZnO-based catalyst to lead to the deactivation of the catalyst. A small amount of silica added to the catalyst greatly improved the catalyst stability by suppressing the crystallization of Cu and ZnO. On the other hand, the catalysts both with and without silica were only slightly deactivated during methanol synthesis from a CO-rich feed containing a higher concentration of CO, because only a small amount of water was produced during the reaction, so no remarkable crystallization of Cu and ZnO contained in the catalyst occurred.

Highly effective conversion of CO2 to methanol over supported and promoted copper-based catalysts: influence of support and promoter

Abstract: In this study, gallium-promoted copper-based catalysts prepared by impregnation methods on silica and ZnO supports, were examined for the hydrogenation of CO 2 to methanol. The surface characteristics of catalysts depended on the support and were related to their catalytic performance. Silica-supported catalysts tested at reaction temperatures between 523 and 543 K were highly selective and stable. The selectivity to methanol was around 99%, the conversion to CO was very low and negligible amounts of hydrocarbons were formed. The use of hydrophobic silica enhanced the performance of the catalyst in terms of activity, selectivity and stability. The modification of properties of copper particles is related to the presence of very small particles of Ga 2 O 3 on the surface.

Structure, strain, and reorganization energy of blue copper models in the protein

Abstract: The copper coordination geometry in the blue copper proteins plastocyanin, nitrite reductase, cucumber basic protein, and azurin has been studied by combined density functional (B3LYP) and molecular mechanical methods. Compared to quantum chemical vacuum calculations, a significant improvement of the geometry is seen (toward the experimental structures) not only for the dihedral angles of the ligands but also for the bond lengths and angles around the copper ion. The flexible Cu–SMet bond is well reproduced in the oxidized structures, whereas it is too long in some of the reduced complexes (too short in vacuum). The change in the geometry compared to the vacuum state costs 33–66 kJ/mol. If the covalent bonds between the ligands and the protein are broken, this energy decreases by ∼25 kJ/mol, which is an estimate of the covalent strain. This is similar to what is found for other proteins, so the blue copper proteins are not more strained than other metalloproteins. The inner-sphere self-exchange reorganization energy of all four proteins are ∼30 kJ/mol. This is 30–50 kJ/mol lower than in vacuum. The decrease is caused by dielectric and electrostatic effects in the protein, especially the hydrogen bond(s) to the cysteine copper ligands and not by covalent strain. (Less)

Surface properties and catalytic activity of ferrospinels of nickel, cobalt and copper, prepared by soft chemical methods

Abstract: Ferrospinels of nickel, cobalt and copper and their sulphated analogues were prepared by the room temperature coprecipitation route to yield samples with high surface areas. The intrinsic acidity among the ferrites was found to decrease in the order: cobalt>nickel>copper. Sulphation caused an increase in the number of weak and medium strong acid sites, whereas the strong acid sites were left unaffected. Electron donor studies revealed that copper ferrite has both the highest proportion of strong sites and the lowest proportion of weak basic sites. All the ferrite samples proved to be good catalysts for the benzoylation of toluene with benzoyl chloride, copper and cobalt ferrites being much more active than nickel ferrite. The catalytic activity for benzoylation was not much influenced by sulphation, but it increased remarkably with calcination temperature of the catalyst. Surface Lewis acid sites, provided by the octahedral cations on the spinel surface, are suggested to be responsible for the catalytic activity for the benzoylation reaction.

XPS and TPR examinations of γ-alumina-supported Pd-Cu catalysts

Abstract: Alumina-supported palladium-copper catalysts, which promote liquid-phase nitrate reduction, have been prepared according to different impregnation sequences of γ-Al 2 O 3 support and characterized by X-ray photoelectron spectroscopy (XPS), X-ray induced Auger electron spectroscopy (XAES) and temperature-programmed reduction (TPR). Analysis of Pd XPS/XAES spectra reveals that palladium is present on the γ-alumina support in the metallic form. Copper is reduced at lower temperatures in the presence of palladium particles compared to the CuO/γ-Al 2 O 3 sample. Due to the low copper content in catalysts ( σ Cu ≈10 14 atoms cm −2 ), the XPS/XEAS spectral features of reduced copper species are quite different from those of bulk copper. As shown by TPR and XPS/XAES data, formation of highly dispersed Pd-Cu bimetallic clusters is suggested. It was discovered by means of TPR analysis that the catalyst preparation in which the γ-alumina support is impregnated first by copper salt, results in higher formation of the Pd-Cu alloy.

Synthesis of organic monolayer-stabilized copper nanocrystals in supercritical water.

Abstract: When water is heated and pressurized above the critical point, it becomes a suitable solvent to employ organic capping ligands to control and stabilize the synthesis of nanocrystals. Without alkanethiol ligands, Cu(NO3)2 hydrolyzes to form polydisperse copper(II) oxide particles with diameters from 10 to 35 nm. However, in the presence of 1-hexanethiol, X-ray photoelectron spectroscopy, selected area electron diffraction, and transmission electron microscopy reveal the formation of copper nanocrystals ∼7 nm in diameter. The use of a different precursor, Cu(CH3COO)2, leads to particles with significantly different morphologies. A mechanism is proposed for sterically stabilized nanocrystal growth in supercritical water that describes competing pathways of hydrolysis to large oxidized copper particles versus ligand exchange and arrested growth by thiols to produce small monodisperse Cu nanoparticles.