SORPTION EQUILIBRIUM OF COPPER BY PARTIALLY-COAGULATED CALCIUM ALGINATE GEL

The sorption equilibrium of dissolved copper by spherical partially-coagulated gels of calcium alginate was investigated in this work. The gels were formed by dispensing a viscous algin (food grade sodium alginate from kelp) solution with a multi-tip dispenser into 0.05 M CaCl₂ solution in a loop fluidized bed reactor. The resultant semi-rigid spherical gels were then transferred to another reactor operated batch wise to absorb dissolved copper at low concentrations (10-40 ppm). When the concentration of the inert neutral salt NaNO₃, added to the reactor fluid was 0.01 M, the amount of copper absorbed was found to be substantially higher than that at 0.1 MNaN0₃. The conventional Langmuir's model based on the concentration of copper in solution yielded different values of conditional stability constant at different ionic strengths in the reactor fluid. However, by defining the copper-binding stability constant on the basis of copper activity in the gel phase with the competition from calcium for metal binding sites taken into account, a unique copper-binding stability constant and a unique calcium-binding stability constant were obtained. The numerical procedure for estimating the activity of copper in the gel fluid was modified from Jang et al. Water Research, 1990, in press).     

EFFECTS OF NONIONIC SURFACTANTS ON PERFORMANCE OF COPPER CHEMICAL MECHANICAL POLISHING

During copper chemical mechanical polishing (Cu-CMP), the physical properties of slurry, such as the dispersion and suspension stability of abrasives, the interaction between particles and the polished surface, and the rheological characteristics, greatly affect the planarization efficiency. In this study, several nonionic surfactants were added to change the aforementioned physical characteristics of slurry and Cu-CMP performance. Their effects were investigated. The experimental results showed that Al₂O₃ slurry with 300 ppm Triton DF-16 could enhance the wettability of the Cu surface and stabilize the dispersion of abrasives in the slurry. Therefore, the passivation reaction on the Cu surface during CMP would occur uniformly, and the removal of particles during post cleaning could be improved. Cu CMP using the slurry with an adequate amount of nonionic surfactants, Triton DF-16, is proposed to reduce the surface roughness, enhancing the planarity.     

[Cu_2(Gly—GlyO)_2(OH)_2(4,4—bpy)]·9H_2O配合物合成、晶体结构研究

采用Gly—GlyOH,4,4＇—联吡啶与Cu(NO_3)_2·H_2O在二次水溶液中反应,合成出以4,4＇—bpy为中继基,Gly—Glyo为螯环新型双核铜配合物。经X射线单晶结构分析确定该配合物品体的化学结构式:[(H_2NCH_2CONHCH_2COO) Cu(OH) (C_(10)H_8N_2)Cu(OH) (H_2NCH_2CONHCH_2COO)]·9H_2O.晶体属于三斜晶系,P_空间群,晶胞参数a=1.1412nm,b=1.2298nm,C=1.4269nm,α=113.82°,β=101.91°,y=103.64°,V=1.6747nm~3,Z=2。衍射数据是在Nicolet XRD R3型四圆衍射仪上收集,结构参数经块矩阵最小二乘法精修后,最终一致性因子R值为0.068,RW值为0.057。     

Some phthalazin derivatives as non toxic corrosion inhibitors for copper in sulphuric acid

Phthalazin derivatives were tested as corrosion inhibitors of copper in 1 M H₂SO₄ using electrochemical polarization and weight loss techniques. This study monitored the evolution of the inhibitory effect of the phthalazin derivatives, according to their substituents. A significant decrease in the corrosion rate of copper was observed in the presence of the investigated inhibitors. The inhibition efficiency (%I) increases with increasing inhibitor concentration. The potentiodynamic polarization data indicated that, the inhibitors were of mixed type, but the cathodic effect is more pronounced. The slopes of the cathodic and anodic Tafel lines are approximately constant and independent on the inhibitor concentration. The mechanism of inhibition was discussed in the light of the chemical structure of the undertaken inhibitors. The adsorption on the copper surface follows the Langmuir isotherm model.     

Process development for the removal of copper from wastewater using ferric/limestone treatment

The removal of copper from wastewater by ferric/limestone coagulation followed by screen filtration was carried out at a laboratory scale. The optimum coagulant (FeCl₃) dose and working pH were 50 mg// of Fe(m) and pH 7.5, respectively, through jar tests. For the efficient removal of copper from wastewater, we developed a novel process including the co-precipitation of copper with FeCl₃, alkalization in a limestone aeration bed, and separation of precipitates in a sedimentation tank coupled with internal stainless steel screen filter. The performance results showed that removal of copper from the solution was over 99.5%. The pH was effectively maintained over 7.5 in limestone bed during the whole process. Ferric hydroxide/copper aggregates were removed over 99% by stainless steel screen filter of 1,450 mesh. Periodic air backwashing alleviated fouling of the filter surface.     

Electrochemical behaviour of copper/LDPE composites in the simulated uterine solution

Two metal/insulator composites, copper/low-density polyethylene (LDPE) microcomposites and copper/LDPE nanocomposites, were prepared in a uniform metal mass fraction. The corrosion characteristics of the two composites in the simulated uterine solution have been studied by cyclic voltammetry, potentiodynamic polarization measurement and electrochemical impedance spectroscopy. Results obtained during this study show that there are obvious differences on the corrosive rates and mechanisms between the two materials. The nanocomposites have stable corrosive reaction, hardly passivation, low corrosion rate and high transformation ratio of copper to soluble cupric ions compared with microcomposites, which indicate that the nanocomposites are perfect to be the novel material for intrauterine device. The corrosion behaviour of the microcomposites was controlled by both the processes of the pervasion of Cu²⁺ and the transfer of the charge, while that of the nanocomposites was only controlled by the transfer of the charge. This paper also compared the corrosion behaviours of the composites and bulk copper in the simulated uterine solution, there were more insoluble subproducts in the corrosion process of bulk copper than the composites. Further, the electrochemical method in this study is proved to be useful to characterize the corrosion behaviour of high electrical resistivity materials.     

The role of temperature in copper electrocrystallization in ammonia-chloride solutions

This paper presents the analysis of temperature effect on the copper electrocrystallization process from the stainless steel/Cu(II)-Cu(I)-NH₄Cl-NH₃-H₂O system. Electrochemical techniques and scanning electron microscopy with energy dispersion spectroscopy were employed. An increment in temperature had a favorable effect in increasing the kinetic and nucleation parameters, favoring the copper reduction on the stainless steel substrate. From the chronoamperometric study, it was possible to find the transfer coefficient (α), which does not have a significant variation with temperature, and the exchange current density (i₀) for different temperatures, where a 50.63 kJ/mol value was estimated for the activation energy. The potentiostatic study suggested the presence of two processes involved: an electron transfer reaction and a 3D nucleation—growth process, under combined charge transfer and diffusion limitations. In addition, an important current contribution could be accounted for on the basis of the existence of a capacitive component in the system. This capacitive behavior was associated to the oxide layer (Cr₂O₃)-chloride interactions on the stainless steel surface. Current transients analyses at different potentials, based on the models of: Milchev (low overpotential), Scharifker-Mostany (SM) and Heermann-Tarallo (HT) (high overpotential) allowed to obtain the values of nucleation parameters, such as: the nucleation rate constant (A), the active nucleation sites number (N₀), the stationary nucleation rate (I_st = A × N₀) and the nuclei saturation number (N_s). Finally, the deposits obtained were analyzed by SEM, showing an acceptable correlation between the nucleation parameters and morphology of the deposits obtained. An increment in temperature favored the growth of the cluster before the coalescence occurred.     

Polyaniline for corrosion prevention of mild steel coupled with copper

Polyaniline emeraldine base/epoxy resin (EB/ER) coating was investigated for corrosion protection of mild steel coupled with copper in 3.5% NaCl solution. EB/ER coating with 5-10 wt% EB had long-term corrosion resistance on both uncoupled steel and copper due to the passivation effect of EB on the metal surfaces. During the 150 immersion days, the impedance at 0.1 Hz for the coating increased in the first 1-40 days and subsequently remained constant above 10⁹ Ω cm², whereas that for pure ER coating fell below 10⁶ Ω cm² after only 30 or 40 days. Immersion tests on coated steel-copper galvanic couple showed that EB/ER coating offered 100 times more protection than ER coating against steel dissolution and coating delamination on copper, which was mainly attributed to the passive metal oxide films formed by EB blocking both the anodic and cathodic reactions. Salt spray tests showed that 100 μm EB/ER coating protected steel-copper couple for at least 2000 h.     

Cyclic oxidation processes during anodizing of Al-Cu alloys

The influence of copper on the morphologies of porous anodic alumina has been investigated under current and voltage control using a sputtering-deposited Al-2.7 at.% Cu alloy and a commercial AA 2024-T3 aluminium alloy anodized in either sulphuric acid electrolyte or the same electrolyte but with addition of tartaric acid. The findings indicate that film development involves repeated formation of embryo cells of anodic alumina at the metal/film interface. During the initial stages of anodizing at constant voltage, cell formation is accompanied by current peaks in the current-time response. The porosity of the resultant films has a lateral aspect due to the layering of embryo cells. The thickness of individual layers is proportional to the formation voltage, with a ratio of the order 1 nm V⁻¹. The cell formation is accompanied by enrichment of copper in the alloy, incorporation of copper species into the anodic film, in low amounts relative to the alloy, and evolution of oxygen. These processes disrupt the formation of the classical pore morphology, characteristic of high purity aluminium, due to continuous formation of fresh embryo cells and re-direction of pores. The main effect of the tartaric acid addition to the sulphuric acid was to reduce the rate of anodizing of the alloys at constant voltage by about 10-20%.     

Catalytic activity of dispersed CuO phases towards nitrogen oxides (N2O, NO, and NO2)

A systematic reactivity study of N₂O, NO, and NO₂ on highly dispersed CuO phases over modified silica supports (SiO₂–Al₂O₃, SiO₂–TiO₂, and SiO₂–ZrO₂) has been performed. Different reaction paths for the nitrogen oxide species abatement were studied: from direct decomposition (N₂O) to selective reductions by hydrocarbons (N₂O, NO, and NO₂) and oxidation (NO to NO₂). The oxygen concentration, temperature, and contact time, were varied within suitable ranges in order to investigate the activity and in particular the selectivity in the different reactions studied. The support deeply influenced the catalytic properties of the active copper phase. The most acidic supports, SiO₂–Al₂O₃ and SiO₂–ZrO₂, led to a better activity and selectivity of CuO for the reactions of N₂O, NO, and NO₂ reductions and N₂O decomposition than SiO₂–TiO₂. The catalytic results are discussed in terms of actual turnover frequencies starting from the knowledge of the copper dispersion values.