Investigating the surface of particles of ultradispersed copper powders obtained by gas-phase condensation

Ultradispersed powders of metal copper obtained by evaporation-condensation technology are investigated. It is shown that, depending on the evaporation rate, various dispersities and degrees of agglomeration of copper powders are attained with the conservation of the weight fraction of copper in them no lower than 99.0%. It is established using the XPES method that a 5- to 6-nm-thick CuO layer (on the surface of which there is a Cu₂O layer up to 1 nm thick) is always present on the surface of Cu particles of all powders under consideration. It is assumed that, because of a low residual air pressure in industrial installations, the surface layer of copper oxidizes to the lower oxide Cu₂O during the evaporation of metal, while oxide CuO is formed as a result of the decomposition of Cu₂O during the condensation of copper particles. The smaller the particle size of the powder is, the higher the content of oxides is.     

Cathodic reduction process of Al–Cu–Y alloy in fluoride-oxide eutectic system via molten salt electrolysis

Al-Cu-Y alloys were prepared by molten salt electrolysis in fluoride-oxide system composed of electrolyte(Na_3 AlF_6-AlF_3-LiF-MgF_2) and oxide(Al_2 O_3-CuO-Y_2 O_3). Cathodic reduction process of Al_2 O_3,CuO and Y_2 O_3 were analyzed by cyclic voltammetry and chronoamperometry. Components and phase composition of alloy samples prepared by potentiostatic electrolysis were characterized by scanning electron microscopy and energy dispersive spectroscopy. The results show that the Al-Cu-Y alloy can be prepared in the AIF_3-NaF-5 wt%LiF-5 wt%MgF2(NaF/AlF_3 = 2.2, molecular ratio) eutectic system with mixed oxide(Al_2 O_3-CuO-Y_2 O_3) through 2 h at the conditions of a temperature of 1208 K, cell voltage3.0 V, cathode current density 0.7 A/cm~2. Al(Ⅲ) and Cu(Ⅱ) ions can be reduced to zero valence Al(0) and Cu(0) directly on carbonaceous electrode surface by instantaneous nucleation, respectively, the reduction process is controlled by diffusion. The reduction potential of Y(Ⅲ) ions is close to the active ions of fluoride melts, but strengthened phase AI3 Y can be formed through electrochemical reduction and alloyed process with active Al(Ⅲ) and Cu(Ⅱ) ions, meanwhile, the Al_2 Cu and Al_3 Y phases are distributed at the grain boundary of Al matrix.     

Characterization of Cu-SiO2 Composite Synthesized by Hydrogen Reduction of Chalcopyrite Concentrate Followed by Acid Leaching

A Ghatshila chalcopyrite concentrate (average particle size, 50 μm) containing primarily CuFeS₂ and SiO₂ (Cu 16 pct, Fe 26 pct, S 14 pct, Si 5 pct, and O 33 pct) was reduced by a stream of hydrogen in a horizontal tube furnace at 1323 K (1050 °C), producing a mixture of Cu (26 pct), SiO₂, Fe₂O₃, Fe₃O₄, Cu₂O, and Fe. Subsequent acid leaching with 1 M HCl solution of the reduction product removed all iron oxides and iron, and other impurities too, leaving a Cu (53.3 pct) + SiO₂ mixture, with a small percentage of Cu₂O in it. This result compares well with the predicted final mixture of Cu (59 pct)-SiO₂ based on a mass balance on the starting concentrate. Elemental chemical analyses were done by energy-dispersive X-ray spectroscopy, which were crosschecked by atomic absorption spectroscopy in the majority of cases. The phase identification and microstructural characterization of Cu-SiO₂ mixtures were done by X-ray diffraction, Fourier transform infrared spectroscopy, Rietveld analysis, scanning electron microscopy, and high-resolution transmission electron microscopy (HRTEM). It was found that Cu-SiO₂ composites were formed in the final product, with a copper grain size of 385 nm.     

Effect of focused solar power on the structure and phase composition of a copper-based material

The change in the content, structure, and microhardness at a depth of the scale layer, which forms on the copper-based material under focused solar radiation, is studied. The formation of a structure with an external layer of CuO, Fe₂O₃, NiO oxides and mixed Cu₃WO₆ oxide (spinel type) with high microhardness H_μ = 29.4 GPa is shown. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 3–4 (454), pp. 20–25, 2007.     

Promotional effect of CO pretreatment on CuO/CeO2 catalyst for catalytic reduction of NO by CO

The CuO/CeO2 catalysts were investigated by means of X-ray diffraction(XRD),laser Raman spectroscopy(LRS),X-ray photoelectronic spectroscopy(XPS),temperature-programmed reduction(TPR),in situ Fourier transform infrared spectroscopy(FTIR) and NO+CO reaction.The results revealed that the low temperature(150 °C) catalytic performances were enhanced for CO pretreated samples.During CO pretreatment,the surface Cu+/Cu0 and oxygen vacancies on ceria surface were present.The low valence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation.These effects in turn led to higher activities of CuO/CeO2 for NO reduction.The current study provided helpful understandings of active sites and reaction mechanism in NO+CO reaction.     

Corrosion and Oxidation Behavior of Zr58Cu22Fe4Co4Al12 Metallic Glass

The pitting corrosion behavior of melt spun ribbon made at a wheel speed of 20 ms in 3.5 wt% NaCl solution and nonisothermal and isothermal oxidation behavior of 2 mm diameter rod samples of newly developed Zr₅₈Cu₂₂Fe₄Co₄Al₁₂ bulk metallic glass have been studied. The pitting corrosion is more on the air side as compared to the wheel side mainly due to the presence of air pockets. The pitted regions are enriched with copper suggesting dealloying effect due to its noble nature. The alloy shows very good oxidation resistance compared to some of the exiting bulk metallic glass forming alloys. The oxidation leads to the formation of mainly tetragonal ZrO₂ with the presence of monoclinic ZrO₂, mixture of CuO and Cu₂O and Al₂O₃. Copper in the alloy oxidized progressively with the appearance of white flowery globule shape which later forms interconnected faceted CuO network.     

Hydrolytic stripping of single and mixed metal-versatic solutions

Hydrolytic stripping is the process whereby metal ions in a loaded solvent extractant are directly precipitated as oxides or hydroxides by hydrolysis with water, typically at 130° to 200 °C. Hydrolytic stripping tests were carried out in sealed tubes at 200 °C on Versatic 10 solutions of Mg, Ca, Sr, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Cd, singly and in mixtures. Single solutions of Fe, Ni, Cu, Mg, and Mn precipitated αFe₂O₃, Ni(OH)₂, CuO + Cu₂O, Mg(OH)₂, and γMn₂O₃, respectively, during testing. Several mixtures of iron with other metals precipitated magnetic spinel ferrites, MFe₂O₄. No other combinations of metals formed crystallographically distinctive mixed oxides.     

Synthesis,phase study and magnetic characterisation of Co50Fe40Cu10 ternary alloy nanopowders prepared by mechanochemical alloying process

Abstract

Mechanical milling and hydrogen reduction of pure oxide mixture and magnetic characterisation of Co–Fe–Cu ternary alloy nanopowders were investigated. A powder mixture of Co₃O₄, CuO and Fe₂O₃ with Co₅₀Fe₄₀Cu₁₀ stoichiometry was first milled by a high energy planetary ball mill and then reduced in a hydrogen reduction system.

The optimum condition of the reduction under the hydrogen atmosphere was 650°C and 1 h. The X-ray diffraction patterns exhibit that the powder has ordered bcc structure with b2–bcc space group and 2·87 Å lattice parameter. Mean crystallite sizes calculated from X-ray diffraction results and mean particle size observed from electron microscopes were over 75 nm. Magnetic evaluation of ternary alloy nanopowders showed a saturation magnetisation value about 143 Am² kg^–1 and a low coercivity value of 0·93 Am^–1.     

Oxidation of molten copper matte

An amount of 80 mg of molten copper matte of a pseudo-ternary Cu₂S-FeS-Fe system contained in a slender alumina sample tube was oxidized at 1503 and 1533 K in a mixed O₂-Ar gas stream and the oxidation path was followed, comparing the overall rate of oxidation with the gaseous diffusion in the sample tube. The following successive reactions were found to be controlled by gas diffusion. Initially, Fe was oxidized to form FeO. After the melt composition reached a pseudo-ternary Cu₂S-FeS-FeO system, FeS was oxidized to form FeO. As the amount of FeO increased, Fe₃O₄ was also formed and subsequently Cu was produced by the oxidation of Cu₂S. In the latter stage, the Cu was oxidized, and the final product under the condition of gas diffusion control was composed of Cu₂O, Fe₃O₄, and CuFeO₂. On the other hand, the rate of formation of Fe₂O₃, CuO, and CuFe₂O₄ was much slower and they were not formed during the oxidation duration where the overall rate of oxidation was controlled by gas diffusion.     

Development of Kinetic Model for Reactions Between Cu-Containing Multicomponent Slag and Liquid Sulfide Using Coupled Reaction Model

Copper smelting slag contains less than 2 mass pct of Cu oxide and 30–50 mass pct of Fe_xO. Each year, the grade of copper ore decreases, while the amount of slag generated in the copper smelting process increases. In this study, a coupled reaction model to simulate the reaction between multicomponent slag and FeS-based matte was developed using reported thermodynamic data and double-film theory for the recycling of copper smelting slag. The activity coefficients of oxides in the multicomponent slag were calculated using a regular solution. The activity coefficients of Cu₂O in the slag and those of FeS, Cu₂S, and CaS in the FeS-based matte used previously reported data. The behaviors of Cu in slag and matte were confirmed by comparing the simulated results and the reported solubility of Cu in the slag in the temperatures ranging from 1473 K to 1573 K. In addition, the effect of the input amount of FeS on the copper content of the slag was verified by comparing the results of reaction model to experimental results. Using the reaction model, the influences of the initial ratio of FeO/SiO₂ of the slag, temperature, and matte composition on the behaviors of Cu in the slag and matte were investigated.     

Precursor Dependent Structural Phase Evolution in Hydrothermally Prepared Cu<Subscript>2</Subscript>O Octahedrons and Cu Micro-Flakes and Their Structural and Optical Properties

Cuprous oxide (Cu₂O) and metallic copper particles with different microstructures have been prepared by a single-step hydrothermal method by using copper acetate monohydrate and sodium hydroxide as precursors, d-glucose as reducing agent, and poly (vinylpyrrolidone) as stabilizing agent. It was found that the concentration of the NaOH in the reactant solution played a significant role in the structural phase formation of the product. Further, it was also optimized to get either the single phase of Cu₂O or Cu or the mixed phase of Cu₂O and Cu depending on the NaOH content in the reaction mixture. The product material was systematically investigated by x-ray diffraction (XRD), Rietveld refinement, UV–Vis, Raman spectroscopies, scanning electron microscopy (SEM), and X-ray energy dispersive spectroscopy (XEDS). A thorough analysis of the XRD patterns in a standard method as well as by Rietveld refinement have shown the cubic phases for both Cu₂O and Cu. The same phases have been retained in the mixed phase sample also. Optical band gap was determined through Tauc plot to be 1.95 eV. Microstructural studies by SEM showed that the Cu particles were formed as micro flakes whereas the Cu₂O particles were formed with the well-defined octahedral morphology. The XEDS analysis confirmed the chemical composition in Cu₂O. This work reports the dependence of NaOH concentration in the reactant solution on the type of product (single phase or a mixed phases of Cu₂O and Cu) and their structural and optical properties.     

New leaching agents for oxides. The reaction of metal oxides with the mixed non-aqeous systems: dimethyl sulphoxide-sulphur dioxide,dimethyl formamide-sulphur dioxide and acetonitrile-sulphur dioxide

The metal oxides MgO, V₂O₅, CrO₃, MnO₂, CoO, CuO, Cu₂O, and ZnO react with the mixed non-aqueous system dimethyl sulphoxide (DMSO)-sulphur dioxide to form metal disulphates as final products. Other oxides (SnO₂, PbO₂, La₂O₃, and Ag₂O) react with the mixed solvent, but it has not been possible to characterise the final products. The oxides TiO₂, Cr₂O₃, Fe₂O₃, Co₃O₄, NiO, MoO₃, and Al₂O₃ do not react with the mixed solvent. The same differentiating behaviour is shown by dimethyl formamide (DMF)-sulphur dioxide, but products of indeterminate composition are obtained. DMF-SO₂ reduces the oxides of copper to copper metal. The system acetonitrile-sulphur dioxide reacts only with the oxides of copper. Likely mechanisms for the reactions are discussed.     

Oxidation Behavior of CuZr-Based Glassy Alloys at 400 °C to 500 °C in Dry Air

The oxidation behavior of the Cu_47.5Zr_47.5Al₅ (Cu3) and Cu₄₇Ti₃₄Zr₁₁Ni₈ (Cu4) bulk metallic glasses (BMGs) was studied over the temperature range of 400 °C to 500 °C in dry air. The oxidation kinetics of both alloys generally followed a multistage parabolic-rate law, and the steady-state parabolic-rate constants (k _p values) fluctuated with temperature for the Cu3 BMG, but increased with increasing temperature for the Cu4 BMG. The scales formed on the BMGs were strongly dependent on the temperature and alloy composition, and were composed primarily of tetragonal-ZrO₂ (t-ZrO₂) and minor amounts of Al₂O₃, Cu₂O, and CuO at 400 °C for the Cu3 BMG, while the monoclinic-ZrO₂ (m-ZrO₂) phase is present at T ≥ 425 °C, and the Cu₂O phase is absent at 500 °C. Conversely, the scales formed on the Cu4 BMG consisted exclusively of CuO at 400 °C, while minor amounts of t-ZrO₂, TiO₂, and ZrTiO₄ formed at 425 °C to 450 °C, and TiO was also detected at higher temperatures. It was found that both amorphous Cu3 and Cu4 substrates transformed into different crystalline phases, and were strongly dependent on temperature and duration of time. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred during the TMS Annual Meeting February 25–March 1, 2007, in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

Experimental Liquidus Studies of the Pb-Cu-Si-O System in Equilibrium with Metallic Pb-Cu Alloys

Phase equilibria of the Pb-Cu-Si-O system have been investigated in the temperature range from 1073 K to 1673 K (800 °C to 1400 °C) for oxide liquid (slag) in equilibrium with solid Cu metal and/or liquid Pb-Cu alloy, and solid oxide phases: (a) quartz or tridymite (SiO₂) and (b) cuprite (Cu₂O). High-temperature equilibration on silica or copper substrates was performed, followed by quenching, and direct measurement of Pb, Cu, and Si concentrations in the liquid and solid phases using the electron probe X-ray microanalysis has been employed to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-“CuO_0.5”-SiO₂ plane for presentation purposes. The present study is the first-ever systematic investigation of this system to describe the slag liquidus temperatures in the silica and cuprite primary phase fields.     

Interfacial Reaction during Friction Stir Welding of Al and Cu

Commercially pure copper was joined to a 1050 aluminum alloy by friction stir welding. A specific configuration where the tool pin was fully located in the aluminum plate was chosen. In such a situation, there is no mechanical mixing between the two materials, but frictional heating gives rise to a significant thermally activated interdiffusion at the copper/aluminum interface. This gives rise to the formation of defect-free joints where the bonding is achieved by a very thin intermetallic layer at the Cu/Al interface. Nanoscaled grains within this bonding layer were characterized using transmission electron microscopy (TEM). Two phases were identified, namely, Al₂Cu and Al₄Cu₉ phases. The nucleation and growth of these two phases are discussed and compared to the standard reactive interdiffusion reactions between Cu and Al.     

Influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 for NO reduction by CO

In order to investigate the influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 catalyst for NO reduction by CO,two series of catalysts(xCuyMn/Ce and xCu/yMn/Ce) were prepared by co-impregnation and stepwise-impregnation methods,and characterized by means of X-ray diffraction(XRD),Raman spectra,H2-temperature programmed reduction(H2-TPR),in situ diffuse reflectance infrared Fourier transform spectra(in situ DRIFTS) techniques.Furthermore,the catalytic performances of these catalysts were evaluated by NO+CO model reaction.The obtained results indicated that:(1) The catalysts acquired by co-impregnation method exhibited stronger interaction owing to the more sufficient contact among each component of the catalysts compared with the catalysts obtained by stepwise-impregnation method,which was beneficial to the improvement of the reduction behavior;(2) The excellent reduction behavior was conducive to the formation of low valence state copper species(Cu+/Cu0) and more oxygen vacancies(especially the surface synergetic oxygen vacancies(SSOV,Cu+-□-Mn(4–x)+)) during the reaction process,which were beneficial to the adsorption of CO species and the dissociation of NO species,respectively,and further promoted the enhancement of the catalytic performance.Finally,in order to further understand the difference between the catalytic performances of these catalysts prepared by co-impregnation and stepwise-impregnation methods,a possible reaction mechanism(schematic diagram) was tentatively proposed.     

Kinetics and Mechanism of High-Temperature Oxidation in Air of Au - Cu Alloy

We have used thermogravimetry to study the kinetics of high-temperature (up to 800 °C) oxidation of the alloy 58.3 mass% Au - 41.7 mass% Cu with isothermal heating of the specimens. Using petrographic analysis of the oxide layers, we determined the reaction products. We have shown that up to 200 °C, the indicated alloy is not oxidized at all. More rapid oxidation of the alloy is observed at temperatures above 400 °C. Up to 500 °C, an inner layer consisting of Cu₂O predominates in the two-layer scale on the alloy, while the outer CuO layer has a significantly smaller thickness. At 600 °C, the upper layer of scale contains Cu₂O while the lower layer contains Cu₂O and gold. At higher temperatures, all the way up to 800 °C, the scale is two-layer as before but its upper layer contains CuO while its lower layer contains Cu₂O and small gold rods distributed in that oxide. Thus we have established three oxidation regions characterized by different scale phase compositions and different mechanisms for the process, mainly due to transition from an ordered state of the alloy (intermetallic AuCu₃) to a completely disordered solid solution of gold in copper. We used the Arrhenius equation to calculate the apparent activation energy for oxidation: E₁ = 20.4 kJ/mole for the temperature range 400–500 °C and E₂ = 9.5 kJ/mole for 600–800 °C. __________ Translated from Poroshkovaya Metallurgiya, Nos. 7–8(444), pp. 85–91, July–August, 2005.     

Directional Solidification and Liquidus Projection of the Sn-Co-Cu System

This study investigates the Sn-Co-Cu ternary system, which is of interest to the electronics industry. Ternary Sn-Co-Cu alloys were prepared, their as-solidified microstructures were examined, and their primary solidification phases were determined. The primary solidification phases observed were Cu, Co, Co₃Sn₂, CoSn, CoSn₂, Cu₆Sn₅, Co₃Sn₂, γ, and β phases. Although there are ternary compounds reported in this ternary system, no ternary compound was found as the primary solidification phase. The directional solidification technique was applied when difficulties were encountered using the conventional quenching method to distinguish the primary solidification phases, such as Cu₆Sn₅, Cu₃Sn, and γ phases. Of all the primary solidification phases, the Co₃Sn₂ and Co phases have the largest compositional regimes in which alloys display them as the primary solidification phases. There are four class II reactions and four class III reactions. The reactions with the highest and lowest reaction temperatures are both class III reactions, and are L + CoSn₂ + Cu₆Sn₅  =  CoSn₃ at 621.5 K (348.3 °C) and L + Co₃Sn₂ + CoSn = Cu₆Sn₅ at 1157.8 K (884.6 °C), respectively.     

Effect of CuO species and oxygen vacancies over CuO/CeO2 catalysts on low-temperature oxidation of ethyl acetate

The catalytic oxidation of ethyl acetate(EA) was studied over CuO/CeO₂ catalysts which were prepared by ball milling with different precursors(copper oxide,cerium acetate,cerium dioxide,copper acetate and cerium hydroxide).The CuO/CeO₂ catalyst(O-A) prepared with copper oxide and cerium acetate as precursors shows very high catalytic activity that 100% EA conversion is achieved at low temperature of 220℃.It is found that specific surface area(112.8 m²/g),particle...     

Oxidation of copper ultrafine powders and nanopowders produced by vapor phase condensation

The oxidation of copper nanopowders fabricated by metal evaporation and condensation is studied. It is found that, in contrast to the oxidation of bulk copper samples, the oxidation of nanopowders can provide the formation of a CuO surface layer on copper particles in a reactor, bypassing the stage of Cu₂O formation. The Cu₂O oxide that forms on the surface of unoxidized copper powder particles spontaneously transforms almost completely into a more thermodynamically stable phase (CuO oxide) during storage in air under natural conditions.