Characterization of copper-silicon nitride composite electrocoatings

Silicon nitride particles were incorporated to electrolytic copper by co-electrodeposition in acidic sulfate bath, aiming the improvement of its mechanical resistance. Smooth deposits containing well-distributed silicon nitride particles were obtained. The current density did not show significant influence on incorporated particle volume fraction, whereas the variation of particle concentration in the bath had a more pronounced effect. The microhardness of the composite layers was higher than that of pure copper deposits obtained under the same conditions and increased with the increase of incorporated particle volume fraction. The microhardness of composites also increased with the increase of current density due to copper matrix grain refining. The composite coatings were slightly more corrosion resistant than pure copper deposits in 3.5% NaCl solutions.

Do Larvae and Ovipositing Chironomus riparius (Diptera: Chironomidae) Females Avoid Copper-Contaminated Environments?

Studies on the avoidance behavior of aquatic organisms to contaminants have confirmed that such behavior can be relevant in field situations. However, almost all toxicity tests involve the forced exposure of organisms to toxicants. In particular, despite the importance of Chironomus riparius Meigen larvae in sediment toxicity testing, only a few studies on avoidance behavior have been performed. This study investigated the ability of different life stages of C. riparius, including ovipositing females, first-, second-, and fourth-instar larvae, to avoid copper-contaminated environments. Ovipositing females were given a choice between a control and copper solution (1.3 mg Cu l(-1)). First-instar larvae were provided with a choice between a control and a copper (2.0 mg Cu l(-1))-spiked sediment. Both second- and fourth-instars were exposed to a copper gradient (0.38-3.4 mg Cu l(-1)) in a flow-through system. None of the life stages avoided copper, even though the highest concentrations caused lethal effects on midges. The avoidance behavior of C. riparius is not a sensitive endpoint to assess copper sublethal toxicity.

Separation of silica from bauxite via froth flotation

This paper reports an innovative development: concentrating gibbsite via reverse froth flotation in order to obtain a metallurgical-grade bauxite concentrate. Tailings from an industrial plant have undergone attrition scrubbing and desliming; the quartz silica contained in the tailings has undergone flotation. Starch was used as a depressant, and ether-amine as the cationic collector. Optimum pH is around 10.0. In pilot plant scale, a metallurgical-grade concentrate was obtained by assaying 42.3% available alumina with an alumina/insoluble silica mass ratio of 11.1. It contained the gibbsite and the iron and titanium bearing minerals. The concentrate was further upgraded by magnetic separation, leading to 54.0% available alumina, with an alumina/insoluble silica mass ratio of 12.6 at an overall available alumina recovery of 69.3% in the final concentrate (non-magnetic product). (C) 2008 Elsevier Ltd. All rights reserved.

Electrochemical impedance spectroscopy investigation of the electrochemical behaviour of copper coated with artificial patina layers and submitted to wet and dry cycles

Due to rain events historical monuments exposed to the atmosphere are frequently submitted to wet and dry cycles. During drying periods wetness is maintained in some confined regions and the corrosion product layer, generally denominated patinas, builds up and gets thicker. The aim of this study is to use electrochemical impedance spectroscopy (EIS) to investigate the electrochemical behaviour of pure copper coated with two artificial patina layers and submitted either to continuous or to intermittent immersion tests, this latter aiming to simulate wet and dry cycles. The experiments were performed in 0.1 mol dm(-3) NaCl solution and in artificial rainwater containing the most significant pollutants of the city of Sao Paulo. The results of the continuous immersion tests in the NaCl solution have shown that the coated samples behave like a porous electrode with finite pore length. On the other hand, in the intermittent tests a porous electrode response with semi-infinite pore length can be developed. The results were interpreted based on the model of de Levie and a critical comparison with previous interpretations reported in the literature for similar systems is presented. (C) 2011 Elsevier Ltd. All rights reserved.

Chemical characterization and anticorrosion properties of corrosion products formed on pure copper in synthetic rainwater of Rio de Janeiro and Sao Paulo

This work aims to characterize corrosion products formed on copper samples exposed to synthetic rainwater of Rio Janeiro and Sao Paulo. XRD and XPS were employed to determine their composition, while electrochemical techniques were used to evaluate their protective properties. XRD and XPS indicated the thickening of the corrosion layer with time. Electrochemical results showed that the protectiveness of the corrosion layer depends on the solution composition. Based on our findings a corrosion mechanism for copper in simulated rainwater is proposed where the role of NH(4)(+) ions in the cuprite layer partial regeneration is taken into account. (C) 2009 Elsevier Ltd. All rights reserved.

Corrosion behavior of carbon steel protected with single and bi-layer of silane films filled with silica nanoparticles

The electrochemical behaviour of carbon steel coated with bis-[trimethoxysilylpropyl]amine (BTSPA) filled with silica nanoparticles in naturally aerated 0.1 mol L-1 NaCl solutions was evaluated. The coating was prepared by adding different concentrations of silica nanoparticles (100, 200, 300, 400 and 500 ppm) to the hydrolysis solution and then a second layer without silica nanoparticles was applied. The electrochemical behavior of the coated steel was evaluated by means of open-circuit potential (E-OC), electrochemical impedance spectroscopy (EIS) and polarization curves. Surface characterization was made by atomic force microscopy (AFM), and its hydrophobicity assessed by contact angle measurements. EIS diagrams have shown an improvement of the barrier properties of the silane layer with the silica addition, which was further improved on the bi-layer system. However, a dependence on the filler concentration was verified, and the best electrochemical response was obtained for samples modified with 300 ppm of silica nanoparticles. AFM images have shown a homogeneous distribution of the silica nanoparticles on the sample surface; however particles agglomeration was detected, which degraded the corrosion protection performance. The results were explained on the basis of the improvement of the barrier properties of the coating due to the filler addition and on the onset of defective regions on the more heavily filled coatings allowing easier electrolyte penetration. (C) 2007 Elsevier B.V. All rights reserved.

Study of copper electrodeposition mechanism from a strike alkaline bath prepared with 1-hydroxyethane-1,1-diphosphonic acid through cyclic voltammetry technique

Copper strike baths are extensively used in metal plating industry as they present the ability to plate adherent copper layers on less-noble metal substrates such as steel and zinc die castings. However, in the last few years, due to environmental controls and safety policies for operators, the plating industry has been interested in replacing the toxic cyanide copper strike baths with environmentally friendly baths. A broad bibliographic review showed that the published papers, referring to the new nontoxic copper strike baths, are patents, having little or no emphasis focused on electrodeposition mechanisms. Therefore, it was decided to study the copper electrodeposition mechanism from a strike alkaline bath prepared with one of the most nontoxic chelating agents cited in many patents which is the 1-hydroxyethane-1,1-diphosphonic acid, known as HEDP. This acid forms very stable water soluble complexes with Cu(2+) ions, thus cupric sulfate was used for preparing the plating bath. The results obtained through a cyclic voltammetry technique showed that Cu(2+) ion reduction to Cu from an HEDP electrodeposition bath occurs via a direct reduction reaction without a formation of Cu(+) intermediates. (C) 2010 Elsevier Ltd. All rights reserved.

Effect of Charge Asymmetry on Adsorption and Phase Separation of Polyampholytes on Silica and Cellulose Surfaces

The relation between the properties of polyampholytes in aqueous solution and their adsorption behaviors on silica and cellulose surfaces was investigated. Four polyampholytes carrying different charge densities but with the same nominal ratio of positive to negative segments and two structurally similar polyelectrolytes (a polyacid and a polybase) were investigated by using quartz crystal microgravimetry using silica-coated and cellulose-coated quartz resonators. Time-resolved mass and rigidity (or viscoelasticity) of the adsorbed layer was determined from the shifts in frequency (Delta f) and energy dissipation (Delta D) of the respective resonator. Therefore, elucidation of the dynamics and extent of adsorption, as well as the conformational changes of the adsorbed macromolecules, were possible. The charge properties of the solid Surface played a crucial role in the adsorption of the studied polyampholytes, which was explained by the capability of the surface to polarize the polyampholyte at the interface. Under the same experimental conditions, the polyampholytes had a higher nominal charge density phase-separated near the interface, producing a soft, dissipative, and loosely bound layer. In the case of cellulose substrates, where adsorption was limited, electrostatic and polarization effects were concluded to be less significant.

Biogenic modified silica as a sorbent of cadmium ions: Preparation and characterization

This work describes the preparation and characterization of biogenic modified silica from rice hull ash and its use as a sorbent of cadmium ions. Thus, an agro-industrial residue has been used to produce a new adsorbent product which is able to remove toxic elements. Mesoporous biogenic silica was obtained by alkaline extraction of sodium silicate by hydrolysis with the sol-gel process, and it was modified with salen using 1,2-dichloroethane as a spacer. The surface area of the silica was measured by nitrogen adsorption/desorption analysis. Surface modification was measured by Fourier transform infrared spectroscopy. The degree of functionalization was obtained by elemental analysis. This work showed that biogenic modified silica can be produced in aqueous media from rice hull ash using a simple method, providing an alternative method for adsorbent preparation. Thermogravimetric analysis showed that the salen-modified silica is stable up to 209 C. The modified silica displays appropriate structural characteristics for an adsorbent. The cylindrical pores, open at both ends, allow free diffusion of cadmium ions to the adsorption sites on the silica surface. The surface modification increases cadmium adsorption on the silica surface 100-fold. The salen-modified silica showed specific adsorption for Cd2+ of 44.52 mg/g SiO2 at cadmium concentration of 100 mg/l.

Annual and polyetic progression of citrus canker on trees protected with copper sprays

The effects of copper sprays on annual and polyetic progress of citrus canker, caused by Xanthomonas citri subsp. citri, in the presence of the Asian citrus leafminer (Phyllocnistis citrella), were evaluated in a study conducted in a commercial orchard in northwest Parana state, Brazil, where citrus canker is endemic. Nonlinear monomolecular, logistic and Gompertz models were fitted to monthly disease incidence data (proportion of leaves with symptoms) for each treatment for three seasons. The logistic model provided the best estimate of disease progress for all years and treatments evaluated and logistic parameter estimates were used to describe polyetic disease dynamics. Although citrus canker incidence increased during each of the seasons studied, it decreased over the whole study period, more so in copper-treated trees than in water-sprayed controls. Copper treatment reduced disease incidence compared with controls in every year, especially 2004-2005, when incidence was ca. 10-fold higher in controls than in treated plots (estimated asymptote values 0 center dot 82 and 0 center dot 07, respectively). Copper treatment also reduced estimated initial disease incidence and epidemic growth rates every year.

Copper sprays and windbreaks for control of citrus canker on young orange trees in southern Brazil

The benefit of windbreaks and copper sprays for control of citrus canker caused by Xanthomonas axonopodis pv. citri was investigated in a commercial citrus orchard located in a citrus canker endemic area in southern Brazil. Control of canker was evaluated as incidence and severity of lesions on foliage and by the effect on premature leaf and fruit drop for three production seasons. Effect of the treatments on fruit production was evaluated as incidence of citrus canker on prematurely abscised fruits and harvested fruits. Copper application significantly reduced damage to foliage and fruit, while windbreaks made little contribution to disease control. Copper sprays increased fruit yield for 3 years. This could be attributed to lower incidence of fruit with lesions and fewer fruits abscised due to canker infection. Incidence and severity on the leaves were inversely related to the number of fruits harvested per tree and directly related to the number of fruits abscised per tree. Published by Elsevier Ltd.

Bacterial stimulation of copper phytoaccumulation by bioaugmentation with rhizosphere bacteria

Copper contaminated areas pose environmental health risk to living organisms. Remediation processes are thus required for both crop production and industrial activities. This study employed bioaugmentation with copper resistant bacteria to improve phytoremediation of vineyard soils and copper mining waste contaminated with high copper concentrations. Oatmeal plant (Avena sativa L) was used for copper phytoextraction. Three copper resistant bacterial isolates from oatmeal rhizosphere (Pseudomonas putida A1 Stenotrophomonas maltophilia A2 and Acinetobacter calcoaceticus A6) were used for the stimulation of copper phytoextraction. Two long-term copper contaminated vineyard soils (Mollisol and Inceptisol) and copper mining waste from Southern Brazil were evaluated. Oatmeal plants substantially extracted copper from vineyard soils and copper mining waste. As much as 1549 mg of Cu kg(-1) dry mass was extracted from plants grown in Inceptisol soil. The vineyard Mollisol copper uptake (55 mg Cu kg(-1) of dry mass) in the shoots was significantly improved upon inoculation of oatmeal plants with isolate A2 (128 mg of Cu kg(-1) of shoot dry mass). Overall oatmeal plant biomass displayed higher potential of copper phytoextraction with inoculation of rhizosphere bacteria in vineyard soil to the extent that 404 and 327 g ha(-1) of copper removal were respectively observed in vineyard Mollisol bioaugmented with isolate A2 (S. maltophilia) and isolate A6 (A. calcoaceticus). Results suggest potential application of bacterial stimulation of phytoaccumulation of copper for biological removal of copper from contaminated areas. (C) 2010 Elsevier Ltd. All rights reserved.

Nutrition in bean plants and anthracnose intensity in function of silicon and copper application.

Nutrition in bean plants and anthracnose intensity in function of silicon and copper application. The objective of this work was to evaluate the effect of calcium silicate and copper sulfate on anthracnose intensity and nutrition of bean plants. The experiment was conducted using an experimental design in randomized blocks following a 4 x 4 factorial arrangement , (four levels of calcium silicate and four levels of copper sulfate) and two additional treatments (plants without inoculation and plants sprinkled with Benomyl). Four evaluations of the incidence and severity of anthracnose were done, in addition to measuring, total leaf area. At the end of the evaluations, incidence: and data were integrated over time, obtaining the area under disease progress curve (AUDPC). Contents of N, P, K, Ca, Mg, B, Cu, Fe, Mn, Zn, Si and lignin were determined in the aerial Part. A linear decrease of the intensity AUDPC was observed with the increase of the doses of calcium silicate. The severity AUDPC was influenced by the doses of copper, obtaining a reduction of 35% on the higher dosage. The supply of silicon and copper altered the content of the K, mg, S, Zn, Ca and Si in the aerial part of the bean plants.

Copper salt-catalyzed homo-coupling reaction of potassium alkynyltrifluoroborates: a simple and efficient synthesis of symmetrical 1,3-diynes

The copper-catalyzed dimerization of alkynyltrifluoroborates proceeds readily with good yields. The homo-coupling reaction can be effected in DMSO, in the open air, using Cu(OAc)(2) as catalyst in the absence of any other additives. A variety of functional groups are tolerated. (C) 2008 Elsevier Ltd. All rights reserved.

Bioavailability of dietary sodium copper chlorophyllin and its effect on antioxidant defence parameters of Wistar rats

BACKGROUND: There has been growing interest in sodium copper chlorophyllin (Cu-Chl) as a food colourant and supplement owing to its beneficial biological activities. Studies have revealed that this green pigment inhibits experimental carcinogenesis and interacts with proteins and genotoxic agents. Health-related activities have also been associated with the prevention of lipid peroxidation. However, intestinal absorption of this pigment has been considered insignificant, raising questions of whether eventual biological properties are related to pre- or post-absorptive actions. In this study, intestinal absorption of Cu-Chl and its appearance in serum and organs were estimated by high-performance liquid chromatography analysis in rat feeding experiments. The effect of ingested Cu-Chl on lipid peroxidation was analysed by measuring thiobarbituric acid-reactive substances and antioxidant enzyme activities in hepatic and brain tissues of oxidative stress-induced rats. RESULTS: The two main components of commercial Cu-Chl, namely Cu-chlorin e(6) and Cu-chlorin e(4), showed different digestive behaviours, and only Cu-chlorin e4 was found in serum, liver and kidneys. Antioxidant activity in vivo could be observed in brain and seemed to be related to in situ protection but not to antioxidant enzyme modulation. CONCLUSION: As at least one of the major components of Cu-Chl is effectively absorbed, further pharmacolkinetic studies are encouraged to access absorption rates and the role of ingested copper chlorophyllins in mammals. (C) 2009 Society of Chemical Industry