Room-temperature diffusion in Cu/Ag thin-film couples caused by anodic dissolution

Thin, 100-nm films of first silver and then copper were deposited consecutively onto inert substrates by magnetron sputter deposition. Constant anodic current densities were applied at room temperature to dissolve the outer copper film to varying depths. The 50Cu/50Ag interface, derived from the auger electron spectroscopic concentration-depth profile, initially moved into the copper toward the outer dissolving surface, indicating enhanced diffusion of copper into silver. After longer times at all anodic current densities, the interface reversed and moved back toward the underlying silver-rich layer, indicating that eventually diffusion of silver into copper predominated. The reversal time was inversely proportional to the anodic current density. These effects are explained by anodic formation of subsurface vacancies which migrate as divacancies to the copper/silver interface where they affect interface movements by the well-known Kirkendall mechanism. Calculated diffusivities up to 10⁻¹² cm²/s at maximum anodic current densities of 900 μA/cm² are dramatically above any that are normally observed at room temperature.     

Electrotransport and diffusion of Co,Fe, and Ag in γ-Cerium

Electrotransport mobilities and diffusion coefficients were obtained for radiotracer impurities of Fe, Co, and Ag in Ce. The iron and cobalt moved toward the anode with mobilities of ～10^?3 cm²/v-s in the range of 550° to 650°C. The silver moved to the cathode with mobilities of ～10^?5 cm²/v-s in the range of 600° to 700°C. The, diffusion coefficients obtained fit an Arrhenius equationD=D _o e ^?ΔH/RT with the following parameters: Fe:D _o=3.3×10^?4, ΔH=4.6 kcal/mole Co:D _o=10^?2, ΔH=11 kcal/mole Ag:D _o=1.4, ΔH=28 kcal/mole The results are compared with other rare-earth diffusion data, and the possibility of a substitutional-interstitial diffusion mechanism, is considered.     

The electrochemical oxidation of chalcopyrite in ammoniacal solutions

The anodic dissolution of chalcopyrite in ammoniacal solutions was investigated using electrochemical methods. At low overvoltages, the formation of a copper deficient sulfide layer, Cu_1-xFeS₂ through a charge transfer reaction is proposed based upon the dependence of the rest or open circuit potential on solution composition and the presence of a Tafel region of appropriate slope. In addition, a current peak that occurs at 10⁻⁴ A/cm² is a function of the square root of the voltage scanning speed and is explained in terms of a charge transfer reaction. At larger overvoltages, constant potential experiments and mass balances performed at various anodic potentials indicate that the dissolution is consistent with the overall reaction, CuFeS₂ + 4NH₃ + 9OH^- = Cu(NH₃) ₄ ⁺² + Fe(OH)₃ + S₂O ₃ ⁼ + 3H₂O +9e ^-, although some copper may be released to solution in the cuprous state and some ferrous iron has been identified in the product film. Currentvs time data taken during constant potential experiments were found to obey a linear rate relationship. This was interpreted in terms of the formation of a layer of constant thickness which is corroded at the outer interface at the same rate it is formed at the inner interface.. The model proposed is typical of the corrosion of some metals. An examination of the polarization curves shows the dissolution reaction to be first order with respect to [OH^-]. The lack of dependence on [Cu²⁺] indicates that the catalytic effect of cupric ion during oxygen pressure leaching is related only to the cathodic reduction of O₂ in agreement with the results of previous investigations.     

Electrotransport and diffusion of iron and silver in α-yttrium

The electrotransport mobilities and diffusion coefficients were determined for iron and silver impurities in yttrium. The mobility of iron increased from 1.2 x10^-4 cm²/V-s at 900°C to 7.4X10^-4 cm²/V-s at 1330°C. The silver mobility ranged from 8.1X10^-6 cm²/V-s at 905°C to 6.4 x 10^-5 cm²/V-s at 1095°C. The iron movement was anode-directed, and the silver movement was cathode-directed. The diffusion coefficients obtained fit an Arrhenius equationD = D₀e-ΔH/RT with the following values: Fe:D ₀ = 1.8 x 10^-2 cm²/s ΔH = 85 kJ/mol (20 kcal/mol); Ag:D ₀ = 5.4 x 10^-3 cm²/s ΔH = 77 kJ/mol (18 kcal/mol). A substitutional-interstitial mechanism previously proposed for anomalously high diffusion rates of impurities in cerium and lanthanum is also proposed for yttrium.     

Electrochemical behavior of the dissolution of gold-silver alloys in cyanide solutions

The dissolution behavior of gold and silver from Au/Ag alloys in aerated cyanide solutions has been investigated using rotating disc electrodes. The variables studied included concentration of cyanide, oxygen partial pressure, and rotating speed of the disc. The dissolution potential and the rate of dissolution were obtained in view of the anodic and cathodic current-potential relationships. The results were discussed in terms of the mixed potential theory. The results showed that the dissolution rate of gold and silver from the alloys was partially controlled by chemical reaction but largely controlled by transport of either oxygen or cyanide, depending on their relative concentrations under the experimental conditions employed in this study. The diffusion coefficient of free cyanide, D_cn ^?, was found to be (1.25 ± 0.05) X 10^?5 cm²/s. The diffusion coefficient of oxygen, $D_{O_2 } $ , was calculated to be (1.29 ± 0.02) X 10^?5 cm²/s.     

Absorption of gaseous oxygen by liquid cobalt,copper, iron and nickel

An experimental investigation of the rates of oxygen solution in molten cobalt, copper, iron and nickel was carried out using pure oxygen and a constant-volume Sieverts’ method. It was found that the volume of gaseous oxygen which initially reacted with the inductively stirred metals was strongly dependent on the physical nature of the oxide film which formed during the first stage of reaction. The initial temperature of the molten iron, cobalt, and nickel was 1600°C, and for copper was 1250°C. For initial oxygen pressures above the melt of about one atmosphere both molten iron and copper, which formed liquid surface oxides, initially absorbed nearly 20 cm³ (STP) O₂/cm² of melt surface area, while molten cobalt and nickel, which formed solid oxides, absorbed about 6 cm³ (STP) O₂/cm² under the same experimental conditions. For approximately 30 s after the initial reaction between these liquid metals and gaseous oxygen, the oxygen absorption rate was proportional to the square root of the oxygen pressure above the melt, and proportional to the melt surface area, but independent of melt volume. The rate-limiting step for oxygen absorption by liquid iron, cobalt and copper can be described by dissociative adsorption of oxygen molecules at the gas/oxide interface. After 30 s of reaction, the rate of oxygen absorption became less dependent on the oxygen pressure above the melt. This indicated that the rate-controlling step was changing from a surface reaction to growth of the oxide layer by cationic diffusion in the bulk oxide. The oxidation rate of liquid nickel appears to be too complex to be described by models for dissociative adsorption of oxygen molecules at the gas/oxide interface and parabolic growth of the oxide layer. The formation of a thin layer of nickel oxide which allows oxygen to migrate through cracks or grain boundaries may be responsible for the relatively high oxygen absorption rate compared to that of liquid cobalt. R. H. RADZILOWSKI, formerly a Graduate Studient at The University of Michigan     

Absorption of gaseous oxygen by liquid cobalt, copper, iron and nickel

An experimental investigation of the rates of oxygen solution in molten cobalt, copper, iron and nickel was carried out using pure oxygen and a constant-volume Sieverts' method. It was found that the volume of gaseous oxygen which initially reacted with the inductively stirred metals was strongly dependent on the physical nature of the oxide film which formed during the first stage of reaction. The initial temperature of the molten iron, cobalt, and nickel was 1600‡C, and for copper was 1250‡C. For initial oxygen pres-sures above the melt of about one atmosphere both molten iron and copper, which formed liquid surface oxides, initially absorbed nearly 20 cm³ (STP) O₂/cm² of melt surface area, while molten cobalt and nickel, which formed solid oxides, absorbed about 6 cm³ (STP) 0₂/cm² under the same experimental conditions. For approximately 30 s after the initial reaction between these liquid metals and gaseous oxygen, the oxygen absorption rate was proportional to the square root of the oxygen pressure above the melt, and pro-portional to the melt surface area, but independent of melt volume. The rate-limiting step for oxygen absorption by liquid iron, cobalt and copper can be described by dissocia-tive adsorption of oxygen molecules at the gasJoxide interface. After 30 s of reaction, the rate of oxygen absorption became less dependent on the oxygen pressure above the melt. This indicated that the rate-controlling step was changing from a surface reaction to growth of the oxide layer by cationic diffusion in the bulk oxide. The oxidation rate of liquid nickel appears to be too complex to be described by models for dissociative ad-sorption of oxygen molecules at the gasJoxide interface and parabolic growth of the oxide layer. The formation of a thin layer of nickel oxide which allows oxygen to migrate through cracks or grain boundaries may be responsible for the relatively high oxygen ab-sorption rate compared to that of liquid cobalt. Formerly a Graduate Student at The University of Michigan     

Studies on the application of copper(I)-ammune sulphate electrolytes in copper electrorefining

The electrolysis of a copper(I)-ammine sulphate electrolyte between copper electrodes has been investigated. A sealed cell and a solution containing 30 g/kg Cu, 95 g/kg NH₃ and 95 g/kg SO₄ were used.Current efficiencies (cathodic and anodic), at current densities over 100 A/m², were higher than 95% and were practically independent of the electrolysis variables (25–55°, 100–500 A/m² and 70–130 g/kg of NH₃ solution).It was shown that at temperatures over 40°C the energy consumption for electrorefining is lower in the copper(I)-ammine electrolyte than in a typical acidic electrolyte.Contributions to the energy consumption from the electrode processes and the resistance of the electrolyte have been determined from the experimental data.     

Lattice and grain-boundary diffusion of phosphorus in commercially-pure copper

The diffusion rates of phosphorus in 3 batches of commercially-pure copper with different impurity content have been determined in the temperature range 574 to 1046° using the tracer-sectioning technique. There is clear evidence of grain-boundary diffusion occurring below 720°. The three activation energies and preexponential factors obtained for volume diffusion areQ _l = 1.43 eV, 1.44 eV, 1.43 eV;Dqi = 7.02 × 10^-3 cmVs, 7.98 x 10^-3 cm²/s, 4.38 × 10^-3 cm²/s. For grain-boundary diffusion the respective average values are Q_b = 0.70 eV and D_obδ≈ 4.2× 10^-7 cm3/s.     

A Method for the Estimation of the Interface Temperature in Ultrasonic Joining

Ultrasonic joining of copper foil to 1100 aluminum sheet at nominal joining temperatures of 298 K to 413 K (25 °C to 140 °C) for 1.25 second caused significant copper diffusion into the aluminum sheet, indicating very high diffusivity (D) values of 1.54 × 10^?13 to 2.22 × 10^?13 m²/s. The D values reflect high excess vacancy concentrations caused by the rapid plastic deformation in the joining surfaces. A method is presented to estimate the actual values of interface temperature from the diffusion data and expected values of vacancy concentrations. The estimated values of interface temperature were about 390 to 410 deg below the equilibrium melting point of aluminum, and in agreement with reported experimental values.     

The kinetics of atomic diffusion to stacking faults and the related special problems in cold-worked alpha brasses

The diffusion kinetics of solute atoms to the stacking fault layers were investigated by the Laplace transformation method in binary homogeneous alloys. The room temperature annealing kinetics of stacking faults in cold-worked alpha brasses, which were studied by an X-ray diffraction technique, were analyzed in terms of the present theoretical findings. The chemical diffusivities in cold-worked (filings) Cu−10Zn and Cu−22.7Zn alpha brasses were determined as equal to 1.7×10⁻²¹ and 1.5×10⁻¹⁹ cm²/s at room temperature (300 K), respectively. Finally, the concentration of athermal monovacancies was estimated in plastically deformed Cu−10Zn (the particle size 20 μm) and Cu−22.7Zn (the particle size 75 μm) alloys and was found to be about 2.0×10¹⁹ and 3.0×10¹⁹ cm⁻³, respectively.     

Effect of added cobalt ion on electro-deposition of copper from sulfate bath using graphite and Pb–Sb anodes

Effect of added Co²⁺(aq) on copper electro-deposition was studied using Pb–Sb and graphite anodes and a stainless steel cathode. The presence of added Co²⁺(aq) in the electrolyte solution was found to decrease the anode and the cathode potentials. The optimum level of Co²⁺(aq) concentration in the electrolyte, with respect to the maximum saving of power consumption was established. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) were used to study the influence of added Co²⁺(aq) on the anodic and the cathodic processes in a copper sulfate-sulfuric acid electrolyte. The oxygen-evolution potential is depolarised at lower current densities (≤ 150 A/m²) and attains saturation at [Co²⁺]_o ? 600 ppm; whilst at higher current densities (≥ 300 A/m²) it is depolarised with [Co²⁺]_o ≥ 300 ppm. The presence of Co²⁺ promoted the deposit of a smoother and brighter copper cathode as measured by surface reflectivity. X-ray diffraction (XRD) showed that added Co²⁺ changed the preferred crystal orientations of the copper deposits. Scanning electron microscopy (SEM) indicated that the surface morphology of the copper deposited in the presence of added Co²⁺ has well-defined grains. Analysis of cathode copper deposits found negligible cobalt.     

Lime-enhanced carbon monoxide reduction of cuprous sulfide

Kinetic studies were conducted on the carbon monoxide reduction of cuprous sulfide powder in the presence of lime as a function of quantity of lime in the charge, CO flowrate, temperature, and time of reduction and particle size of the sulfide. Lime was found to enhance drastically the rate of reduction as well as reduce the COS emission into the off-gas to negligible levels. Both temperature and flowrate of the reducing gas were found to influence the reduction rate, and best results were obtained at 1273 K and at a CO flowrate of 3.33 cm³ s⁻¹. The overall reaction seems to be governed by the intrinsic kinetics of the Cu₂S-CO reaction. Kinetic analysis reveals the observance of the Valensi’s equation, indicating diffusional control through the product layer formed over reacting Cu₂S particles. The calculated experimental activation energy of 169.6 kJ/mole in the termperature range of 1123 to 1273 K is in good agreement with that reported in the literature for sulfur diffusion in copper. A critical comparison has been made of the lime-scavenged reduction of Cu₂S by different reagents, namely, hydrogen, carbon monoxide, and carbon.     

Diffusion in the titanium-nickel system: II. calculations of chemical and intrinsic diffusion coefficients

Diffusion coefficients in the Ti-Ni system have been calculated by the aid of equations given by Sauer and Freise, and Wagner. Values for the TiNi (50 at. pct Ni) phase were found to be:D ^u (cm²/s) = 0.0020 exp - 142,000/R for the temperature range between 650 and 940°C. The heat of activation, expressed in J/mol, has an accuracy of ±6000. For the β-Ti(Ni) phase containing 6 at. pct Ni the temperature dependence of the diffusion coefficient is expressed by:D ^u (cm²/s) = 0.0688 exp - 141,000/RT. The uncertainty in the energy of activation is ±12000 J/mol. No clear variation of the diffusion coefficient with concentration could be detected. It was found that Ni is by far the fastest moving component in β-Ti(Ni), Ti₂Ni and TiNi (at least in the composition range between 50 and 53 at. pct Ni). Values ofD _Ni/D _Ti have been calculated with an equation derived by van Loo. The significance of the calculated values is critically examined. By means of a practical example it is shown that the calculated ratio of the intrinsic diffusion coefficients can be extremely sensitive to slight variations in the position of the marker interface.Diffusion coefficients in the Ti-Ni system have been calculated by the aid of equations given by Sauer and Freise, and Wagner. Values for the TiNi (50 at. pct Ni) phase were found to be:D ^u (cm²/s) = 0.0020 exp - 142,000/R for the temperature range between 650 and 940°C. The heat of activation, expressed in J/mol, has an accuracy of ±6000. For the β-Ti(Ni) phase containing 6 at. pct Ni the temperature dependence of the diffusion coefficient is expressed by:D ^u (cm²/s) = 0.0688 exp - 141,000/RT. The uncertainty in the energy of activation is ±12000 J/mol. No clear variation of the diffusion coefficient with concentration could be detected. It was found that Ni is by far the fastest moving component in β-Ti(Ni), Ti₂Ni and TiNi (at least in the composition range between 50 and 53 at. pct Ni). Values ofD _Ni/D _Ti have been calculated with an equation derived by van Loo. The significance of the calculated values is critically examined. By means of a practical example it is shown that the calculated ratio of the intrinsic diffusion coefficients can be extremely sensitive to slight variations in the position of the marker interface. This paper is based on a Thesis submitted by G. F. BASTIN in fulfillment of requirements for the degree of Doctor in Technological Sciences.     

Charge transfer at Fe/FeO(CaF2) electrodes at 1450 ‡C: Exchange current density,electrode capacitance,diffusivity

The kinetics of the electrode reaction Fe = Fe _slag ²⁺ + 2e ^- has been investigated using the single and double pulse techniques. It was found that the exchange current densities are very large increasing from 2 to 10 A cm^-2 in the range of Fe²⁺-concentration from 2 · 10^-6 to 30 · 10^-6 mole cm⁻³. The electrode capacitance increases from 50 ΜF cm^-2 approximately linearly with the square root of Fe²⁺-concentration. An attempt was made to explain the concentration dependent part of the capacitance in terms of a model involving electrosorption of the speciesFe _ad ⁿ⁺ at the slag/iron interface. If the adsorbed iron ions are the intermediates in a consecutive charge transfer mechanism, the rate determining step is the transfer of iron between the adsorbed layer and the slag. On the other hand, it may be possible that the transfer is in one step with adsorption occurring in parallel. Formerly with Max-Planck Institut für Eisenforschung, D-4000 Düsseldorf, Germany     

Kinetics of disilicide layer growth at the interface of tungsten with molten copper, silver, and tin saturated with silicon

The kinetics of WS₂ layer growth at the interface of tungsten with molten metals saturated with silicon is studied. Research is performed at 1200°C using melts based on copper, silver, and tin. It was established that WSi₂ layer growth in these melts obeys a “parabolic” rule but the corresponding growth rate constants differ markedly, i.e., from 3.4·10^?11 m²/sec (melt based on copper) to 1.5·10^?13 m²/sec (melts based on silver and tin). The reasons for this difference are discussed.     

Some observations on the electrical and thermal properties of the slag-skin region in the electroslag remelting process

An unsteady-state method has been used to determine the electrical resistivity and overall heat-transfer coefficient,U, of the interface region, liquid slag/slag-skin/copper wall, in an electroslag furnace. The value ofU is found to have a slight dependence on slag temperature, slag composition, and slag-skin thickness. It is postulated that the major resistance to the transfer of heat across this composite interface lies in the discontinuity between the slag-skin and the mold wall. The numerical value ofU is found to be approximately 10⁻² cal · cm⁻² s⁻¹ °C⁻¹ for the range of conditions. The electrical resistivity of the interface is found to be a sensitive function of mold wall face temperature. The application of these results to a small ESR furnace is discussed.     

On the kinetics of oxidation of liquid copper and copper-sulfur alloys by carbon dioxide

The rates of transfer of oxygen between CO₂-CO gas mixtures and liquid copper and copper-sulfur alloys have been studied by a steady-state electrochemical technique. For sulfur-free stagnant copper, and under the conditions of the experiments, the rates are shown to be controlled by the diffusion of oxygen in the metal. The resulting diffusivities are in close accord with the bulk of the previous determinations. At high sulfur concentrations, the rate is found to be controlled by an interfacial reaction which is first order with respect to the pressure of CO₂ and inversely proportional to the sulfur concentration. The rate constant, in mole (at. pct)cm⁻² s⁻¹ atm⁻¹, is approximately 8 × 10⁻⁹ at 1146°C. Formerly a Graduate Student.     

Steady-state cellular solidification of Al-Cu Reinforced with alumina fibers

The steady-state directional solidification of aluminum-4.5 wt pct copper and aluminum-1.0 wt pct copper alloys reinforced with parallel,continuous, closely spaced alumina fibers is investigated under growth conditions that produce a plane front or cells in corresponding unreinforced alloys. Specimens were designed to have a central reinforced region surrounded by unreinforced metal of the composite matrix composition. Each was produced by pressure infiltration, subsequently remelted, directionally solidified, and quenched to reveal the liquid/solid metal interface. Both unreinforced and composite sections were characterized to determine solidification front morphology and degree of microsegregation. In the unreinforced portion of the samples, the transition from plane-front to cellular solidification was observed to correspond to a coefficient of diffusion of copper in liquid aluminum of 5 − 10⁻⁹ m² − s⁻¹, in agreement with published values. Cell lengths, analyzed using a finite-difference model of microsegregation, are in agreement with the Bower-Brody-Flemings (BBF) model for cell tip undercooling. In the composite portion of the samples, the alloys solidify free of lateral microsegregation for all solidification conditions investigated, in agreement with theory. The shape of the liquid/solid metal interface near the fibers indicates a much lower fiber/liquid metal interfacial energy than fiber/solid metal interfacial energy. In the composite, plane front solidification is therefore not observed even when plane front solidification obtains in the unreinforced alloy. It is shown that geometrical constraint imposed on deep cells by the fibers causes significant increases in cell tip undercoolings, in agreement with current analyses of deep cell solidification.