EFFECT OF THE ADDITION OF CR AND NB ON THE MICROSTRUCTURE AND ELECTROCHEMICAL CORROSION OF HEAT-TREATABLE AL-ZN-MG ALLOYS

The effect of the addition of Cr and Nb on the microstructure and the electrochemical corrosion of the weldable, high-strength and stress corrosion cracking (SCC) resistant Al-5%Zn-1.67%Mg-0.23%Cu alloy (H) has been studied. Combined additions of the alloying elements, J (with Nb), L (with Cr) and O (with Cr and Nb) and different heat treatments, ST (cold-rolled), A (annealed), F (quenched), B (quenched and aged) and C (quenched in two steps and aged), to obtain different microstructures and hardness have been performed. To correlate the electrochemical corrosion with the microstructure of the specimens, corrosion potential (E(cor)) measurements in different chloride solutions were performed and optical microscopy, SEM, TEM and EDX were applied. In chloride solutions containing dissolved O-2 or H2O2, the present alloys were polarized up to the pitting attack. It was shown that the E(cor) measurements were very sensitive to the alloy composition and heat treatment, increasing in the order H < J < L < O < Al (for a given heat treatment) and F < A approximate to ST < B < C (for a given alloy). The MgZn2 precipitates of the annealed (A) and cold-rolled (ST) specimens were dissolved in chloride solutions containing oxidizing agents and pitting attack was shown to develop in the cavities where the precipitates were present. In the specimens B and C, the compositions of the precipitate free zones was found to be equal to that of the matrix solid solution and preferential intergranular attack was not evident, this being in agreement with their SCC resistance. The addition of Cr and Nb increased the pitting corrosion resistance. The effects of Cr and Nb were additive, that of Cr being predominant, either, in the E(cor) shift or in the increase in the pitting corrosion resistance.

Electrochemical behavior of the N-nosyl-protected amino acids in N,N-dimethylformamide

The electrochemical reduction of serine, glycine, and leucine protected by the 4-nitrobenzenesulfonyl, group in N,N-dimethylformamide at mercury cathode occurs at two steps. The first one at -0.8 V vs. SCE, after a one-electron transfer, leads the anion radical formation that dimerizes and adsorbs at electrode. In the second step at -1.4 V, an instable dianion forms which then cleaves. The mechanism is discussed.

Inhibiting effect of citric acid on the pitting corrosion of tin

Potentiostatic and potentiodynamic studies were carried out to establish the inhibiting effects of citric acid on the pitting corrosion of tin. The critical potential (E-crit), which leads to pitting or general corrosion, was determined in sodium perchlorate solution in the pH range 1.0 to 4.0. Pit nucleation and growth, at pH 4.0, can be described by instantaneous nucleation followed by progressive nucleation. The results show that the minimum acid concentration needed to inhibit pitting of tin is 10(-2) M. Pitting occurrence by direct interaction between metal and perchlorate anions was observed.

THE INFLUENCE OF THE ELECTROCHEMICAL TREATMENT ON CU-AL-AG ALLOYS IN DEAERATED 0.5M NAOH

The effect of consecutive cyclic polarization in de-aerated 0.5 M NaOH solutions on the surface microstructure of mechanically polished Cu-Al-Ag alloys of different compositions and heat treatments has been studied using optical microscopy, SEM and EDS. The current peaks of the cyclic polarization curves do not depend on the alloy composition in the composition range studied. The repetitive potential scans between H2 and O2 evolution in alkaline media lead to preferential dissolution of aluminium, the roughness and phase composition of the surface of the alloys changing significantly. The quasistationary I-E curves of the different Cu-Al-Ag alloys studied consist in the superposition of the quasistationary I-E curves of high-purity Cu and Ag, the EDS microanalysis showing that aluminium is not present on the surface of the alloy in these conditions.

Electrochemical oxidation of an acid dye by active chlorine generated using Ti/Sn(1-x)Ir O-x(2) electrodes

The generation of active chlorine on Ti/Sn(1-x)Ir (x) O-2 anodes, with different compositions of Ir (x = 0.01, 0.05, 0.10 and 0.30 ), was investigated by controlled current density electrolysis. Using a low concentration of chloride ions (0.05 mol L-1) and a low current density (5 mA cm(-2)) it was possible to produce up to 60 mg L-1 of active chlorine on a Ti/Sn0.99Ir0.01O2 anode. The feasibility of the discoloration of a textile acid azo dye, acid red 29 dye (C.I. 16570), was also investigated with in situ electrogenerated active chlorine on Ti/Sn(1-x)Ir (x) O-2 anodes. The best conditions for 100% discoloration and maximum degradation (70% TOC reduction) were found to be: NaCl pH 4, 25 mA cm(-2) and 6 h of electrolysis. It is suggested that active chlorine generation and/or powerful oxidants such as chlorine radicals and hydroxyl radicals are responsible for promoting faster dye degradation. Rate constants calculated from color decay versus time reveal a zero order reaction at dye concentrations up to 1.0 x 10(-4) mol L-1. Effects of other electrolytes, dye concentration and applied density currents also have been investigated and are discussed.

Relation between ambient humidity and ionic conductivity of poly(thionaphtheneindole): Behaviour as an amperometric humidity sensor

The electrical characteristics of oxidized poly(thionaphtheneindole) were investigated as a function of ambient relative humidity (r.h.). The current flowing through a pressed pellet of material between two massive gold electrodes plotted against voltage gives a wave-shaped curve with a halfwave potential at V = similar to 3 V. The current recorded at 4 V (plateau of the wave) is a sigmoidal function of r.h, with the inflexion point at similar to 60%. An interpretation of these findings is given, based on the influence of water on the dielectric constant of the material and on acid-base equilibrium between poly(thionaphtheneindole) and water, from which protons are produced. The behaviour of poly (thionaphtheneindole) as the active component of an amperometric humidity sensor is also reported.

Electrochemical study of perchlorate reduction at tin electrodes

The electrochemical behaviour of tin in de-aerated sodium perchlorate was studied using potentiodynamic and potentiostatic techniques. Tin behaviour in sodium perchlorate has been complicated unexpectedly by the reduction of the perchlorate anion. It is shown that the reduction process takes place within a potential region comprising the negative side of the double layer region and the positive side of the hydrogen region (-0.7 less than or equal to E less than or equal to -1.3 V). The presence of oxide on the electrode surface favours the reduction reaction, which may occur in two steps: the formation of basic tin(II) chloride followed by its reduction, producing chloride.

BIOSENSORS FOR GLUCOSE NEEDLE-SHAPED FOR IN-VIVO MONITORING

Different procedures for obtaining a needle biosensor for the determination of glucose to be inserted subcutaneously in vivo, have been compared. Platinum wires with a diameter of 75 mum, teflon-coated were inserted in hypodermic needles and fixed with a two-component epoxy resin. Using a dip-coating procedure, several layers were deposited on electrodes. The first coating was cellulose acetate, the second was immobilized glucose oxidase (GOD) mixed with bovine serum albumin (BSA) and glutaraldheyde, the third coating was a polyurethane coating obtained with commercially available products. A large number of electrodes have been tried and statistically evaluated but they seem to be affected by poor reproducibility evidenced by a large spreading in successive calibration curves. Then, the polyurethane coating has been replaced by a thin polycarbonate membrane salinized and fixed on the tip of the needle. Reproducible results were achieved and first results of in vivo measurements on rabbits are reported.

Mass/charge balance as a tool to estimate dimensional change in polypyrrole-based actuators

The deconvolution of the voltammograms of polypyrrole electrochemistry has proved to be possible through the electrochemical quartz crystal microbalance data using the F(dm/dQ) function. This deconvolution allows the evolution of the thickness of the polypyrrole films during their redox processes to be estimated and therefore, the mechanical contraction/decontraction of this polymer as a function of the ionic exchange processes can be evaluated. (c) 2005 Elsevier B.V. All rights reserved.

(5,10,15,20-Tetra(4-pyridil)porphinato)manganes(III) acetate modified by four mu(3)-oxo-triruthenium acetate clusters: synthesis, characterization, electrochemical behavior and catalytic activity

A novel supermolecule constituted by four mu(3)-oxo-triruthenium acetate clusters coordinated to manganese(III)-meso -tetra(4-pyridil)porphyrin acetate ([MnTPyP]CH3COO) has been synthesized. Characterization has been performed by UV-Vis and H-1 NMR spectroscopy. The electrochemical behavior (cyclic voltammetry and spectroelectrochemistry) in N,N'-dimethylformamide has been analyzed in terms of five redox processes: three related to peripheral clusters (Ru-IV,Ru-III,Ru-III/Ru-III,Ru-III,Ru-III/Ru-III,Ru-II,Ru-II) and two centered on the Mn-porphyrin core ((MnP)-P-III/(MnP)-P-II/(MnP2-)-P-II). A direct comparison has been performed between MnTCP and MnTPyP as catalysts for the cyclooctene and cyclohexane oxidation reactions. The improved selectivity exhibited by the supramolecular catalyst for cyclohexane oxidation has been ascribed to electronic effects on the oxomanganese(V) porphyrin species induced by the four peripheral clusters, in the formal (RuRuRuIII)-Ru-IV-Ru-III oxidation state. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Polyol-mediated synthesis of ultrafine tin oxide nanoparticles for reversible Li-ion storage

A simple, cheap and versatile, polyol-mediated fabrication method has been extended to the synthesis of tin oxide nanoparticles on a large scale. Ultrafine SnO2 nanoparticles with crystallite sizes of less than 5 nm were realized by refluxing SnCl2 . 2H(2)O in ethylene glycol at 195 degrees C for 4 h under vigorous stirring in air. The as-prepared SnO2 nanoparticles exhibited enhanced Li-ion storage capability and cyclability, demonstrating a specific capacity of 400 mAh g(-1) beyond 100 cycles. (c) 2006 Elsevier B.V. All rights reserved.

Gold electrodes from recordable CDs

Gold electrodes are widely used in electrochemistry and electroanalytical chemistry. The notable performance when used in stripping analysis of many ionic species and the extraordinary affinity of thio compounds for its surface make these electrodes very suitable for many applications. This paper reports a simple and novel way to construct gold electrodes (CDtrodes) using recordable CDs as the gold source. The nanometer thickness of the gold layer of recordable disks (50-100 mm) favors the construction of band nanoelectrodes with areas as small as 10(-6) cm(2). The plane surface can be easily used for the construction of conventional-sized gold electrodes for batch or now injection analysis or even to obtain electrodes as large as 100 cm(2). The low price of commercial recordable CDs allows a one way use. The evaluation and applicability of these electrodes in the form of nanoelectrodes, in batch and associated with flow cells, are illustrated in this paper.

A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrocatalytic study of an electrode modified with Reactive Blue 4 dye covalently immobilized on amine-functionalized silica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)