Intramolecular synergistic effect of glutamic acid, cysteine and glycine against copper corrosion in hydrochloric acid solution

The corrosion protection of copper by glutamic acid, cysteine, glycine and their derivative (glutathione) in 0.5 M hydrochloric acid solution has been studied by the electrochemical impedance spectroscopy and cyclic voltammetry. The inhibition efficiency of the organic inhibitors on copper corrosion increases in the order: glutathione > cysteine > cysteine + glutamic acid + glycine > glutamic acid > glycine. Maximum inhibition efficiency for cysteine reaches about 92.9% at 15 mM concentration level. The glutathione can give 96.4% inhibition efficiency at a concentration of 10 mM. The molecular structure parameters were obtained by PM3 (Parametric Method 3) semi-empirical calculation. The intramolecular synergistic effect of glutamic acid, cysteine and glycine moieties in glutathione is attributed to the lower energy of the lowest unoccupied molecular orbital (E_LUMO) level and to the excess hetero-atom adsorption centers and the bigger coverage on the copper surface.     

Titanium nitride diffusion barrier for copper metallization on gallium arsenide

The diffusion properties of Cu, Cu/titanium nitride (TiN) and Cu/TiN/Ti metallization on GaAs, including as-deposited film and others annealed at 350-550 °C, were investigated and compared. Data obtained from X-ray diffractometry, resistivity measurements, scanning electron microscopy, energy dispersive spectrometer and Auger electron spectroscopy indicated that in the as-deposited Cu/GaAs structure, copper diffused into GaAs substrate, and a diffusion barrier was required to block the fast diffusion. For the Cu/TiN/GaAs structure, the columnar grain structure of TiN films provided paths for diffusion at higher temperatures above 450 °C. The Cu/TiN/Ti films on GaAs substrate were very stable up to 550 °C without any interfacial interaction. These results show that a TiN/Ti composite film forms a good diffusion barrier for copper metallization with GaAs.     

Effects of trace zirconium on the initiation and propagation behavior of fatigue cracks in Cu–6Ni–2Mn–2Sn–2Al alloy

The effects of trace Zr on the fatigue behavior of Cu–6Ni–2Mn–2Sn–2Al alloy were studied through the initiation and growth behavior of a major crack. When stress amplitude was less than σ_a = 350 MPa, the fatigue life of Zr-containing alloys was about 2 times larger than that of alloy without Zr. When σ_a = 400 MPa, the effects of Zr addition on fatigue life disappeared. Increased fatigue life due to Zr addition resulted from an increase in crack initiation life and microcrack growth life. Zr addition generated strengthened grain boundaries (GBs) that developed from the precipitation of SnZr compounds. Strengthened GBs contributed to the increase in crack initiation life. The effects of Zr addition on fatigue behavior were discussed with relation to the behavior of microcracks.     

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.     

The assistance of microwave process in sludge stabilization with sodium sulfide and sodium phosphate

After industrial wastewater sludge passed through an acid-extraction process to reclaim most of the copper ions in it, the residue may still need to be treated by stabilization technologies. The common method for the stabilization of hazardous waste in Taiwan is by cement solidification. However, this method has the disadvantage of an increase in waste volume. In this study, it was tried to combine the advantages of sulfur anions and phosphate anions with the characteristics of microwave energy to offer a new method which can avoid the disadvantage of cement solidification. From the results, it was found that the assistance of heating in sludge stabilization with additives was effective. Huge amounts of additives were saved. Compared with the assistance of the traditional electrical-heating in sludge stabilization with additives, that of the microwave process saved much time and was more powerful. However, when the reaction time was longer, a re-leaching situation would occur. The hybrid microwave process, a procedure of leading an inert gas into the microwave process, could overcome the disadvantage of the microwave process with regard to the long reaction time. Finally, a modified hybrid microwave process which reduced the use of gas was performed and recommended.     

In situ ellipsometric study of copper growth on silicon

Thin copper films are of high interest for interconnect applications. However, optical studies, such as ellipsometry, of metallic thin films are still rare as the measurements are difficult to interpret due to the lack of a transparent range and often island-like growth at very low coverages. We investigated by in situ spectroscopic ellipsometry the growth of thermally evaporated thin copper films on silicon substrates from 0.5 nm to more than 100 nm, a thickness for which bulk-like response is observed. A strong change in the optical response was observed for films thinner than 10 nm as a result of plasmonic effects. The data at each thickness was modeled by employing the effective medium approximation theory. Besides the layer thickness and the void filling fraction, giving the film density, we obtained information about the mean free path of electrons in the thin films and compared it to single crystals. Cu oxidation was studied by deliberately introducing oxygen or air in the chamber, leading to a fast and pronounced change in the optical response. The data analysis provides detailed information on film thickness and quality.     

Dielectric/metal/dielectric structures using copper as metal and MoO3 as dielectric for use as transparent electrode

Transparent conductive oxide/metal/oxide, where the oxide is MoO₃ and the metal is Cu, is realized and characterized. The films are deposited by simple joule effect. It is shown that relatively thick Cu films are necessary for achieving conductive structures, what implies a weak transmission of the light. Such large thicknesses are necessary because Cu diffuses strongly into the MoO₃ films. We show that the Cu diffusion can be strongly limited by sandwiching the Cu layer between two Al ultra-thin films (1.4 nm). The best structures are glass/MoO₃ (20 nm)/Al (1.4 nm)/Cu (18 nm)/Al (1.4 nm)/MoO₃ (35 nm). They exhibit a transmission of 70% at 590 nm and a resistivity of 5.0 · 10^− 4 Ω cm. A first attempt shows that such structures can be used as anode in organic photovoltaic cells.     

A Methodology For Design And Operation Of Heap Leaching Systems

Leaching is a hydrometallurgical activity widely used in mineral processing, both for metallic and non-metallic ores, and in soil remediation. The dissolution of valuable species by heap leaching is strongly dependent on the design and operating variables, so the study of the influence of these variables on recovery and their optimization for the best performance are attractive tasks for the development of the mining industry. In this work, a methodology is developed that enables the planning and design of leaching systems. This methodology uses a proposed superstructure and a mathematical model to analyze the system behavior and determine the optimal design and operating conditions. The model was generated with a Mixed Integer Nonlinear Programming (MINLP) approach and solved by different solvers under GAMS® software (General Algebraic Modelling System). The Spatial Branch-and-Bound (SBB) solver obtained the global optimum in the shortest times. Based on a case of study for copper leaching, it is demonstrated that the procedure allows achieving optimal design and operational conditions.     

Effect of iron as alloying element on electrochemical behaviour of 90∶10 Cu–Ni alloy

Abstract

Copper–nickel alloys have been used in many applications in marine environments, because of their excellent corrosion and biofouling resistance. In this study, the effects of iron as an alloying element on the corrosion behaviour of copper–10 wt-% nickel alloy in artificial saline solutions and natural sea water were investigated. Synthetic copper–nickel alloys were prepared in an induction furnace under an argon–7 vol.-% hydrogen atmosphere in cylindrical boron nitride crucibles. They were then homogenised at 950°C for 10 h under the same protective atmosphere. Linear sweep polarisation, cyclic polarisation, Tafel extrapolation and cyclic voltammetry techniques were performed in this investigation. Following the electrochemical measurements, the corrosion products and the passive film were analysed using a field emission scanning electron microscope (FE-SEM), electron probe microanalysis, energy dispersive spectrometry (EDS), wavelength dispersive spectrometry (WDS) and X-ray diffraction (XRD). The electrochemical behaviour of the synthetic Cu–Ni–Fe alloys depends on maintaining iron in a single phase in the solid solution (the maximum amount of iron that can be used was 1·5 wt-%). Quenching improves the electrochemical behaviour of synthetic Cu–Ni–Fe alloys containing relatively high iron content. The outer layer of the passive film is porous in the absence of iron, but when iron is added, the pores disappear and cracks appear. When no sulphate is present in the solution, the passive film formed on synthetic Cu–Ni–Fe alloys consists entirely of chlorides, and Fe₂O₃. In the presence of sulphate, FeS and NiS were detected in the corrosion film.

On a utilisé les alliages de cuivre–nickel à de nombreuses fins en milieux marins, grâce à leur excellente résistance à la corrosion et à l’incrustation biologique. Dans cette étude, on a examiné l’effet du fer en tant qu’élément d’alliage sur le comportement de corrosion d’un alliage de cuivre–10% en poids de nickel dans des solutions salines artificielles et dans de l’eau de mer naturelle. On a préparé des alliages synthétiques de cuivre–nickel dans un four à induction dans une atmosphère d’argon–7% en volume d’hydrogène dans des creusets cylindriques de nitrure de bore. On les a ensuite homogénéisés à 950°C pendant 10 heures sous la même atmosphère protectrice. Dans cette investigation, on a utilisé des techniques de polarisation linéaire à balayage, de polarisation cyclique, d’extrapolation de Tafel et de voltampérométrie cyclique. Après les mesures électrochimiques, on a analysé les produits de corrosion et le film passif en utilisant un microscope à balayage électronique à champs par émission d’ions (FE-SEM), la microanalyse par électrons, la spectrométrie des rayons X à dispersion d’énergie (EDS), la spectrométrie dispersive en longueur d’onde (WDS) et la diffraction des rayons X (XRD). Le comportement électrochimique des alliages synthétiques de Cu-Ni-Fe dépend du maintien du fer en une phase unique dans la solution solide (la quantité maximale de fer que l’on pouvait utiliser étant de 1·5% en poids). La trempe améliore le comportement électrochimique des alliages synthétiques de Cu–Ni–Fe ayant une teneur relativement élevée en fer. La couche extérieure du film passif est poreuse en l’absence de fer, mais lorsque l’on ajoute du fer, les pores disparaissent et des fissures apparaissent. Lorsqu’il n’y a pas de sulfate dans la solution, le film passif formé sur les alliages synthétiques de Cu–Ni–Fe consiste entièrement en chlorures et en Fe₂O₃. En présence de sulfate, on détecte du FeS et du NiS dans le film de corrosion.