Electrochemical decomposition of cyanides on tin dioxide electrodes in alkaline media

The electrochemical oxidation of cyanide in alkaline media was studied at different pH levels on SnO2 doped with Sb supported on titanium, at 25 degrees C, the electrooxidation of CN- at constant current follows a first-order rate law with a half life of t(1/2) = 35 min on SnO2-SbOx electrodes and t(1/2) = 69 min on SnO2-SbOx-RuO2 electrodes, in K2SO4(aq), pH 12, the reaction rate increases with the applied current and tends to reach a plateau when j > 20 mA cm(-2), In the pH range 10-13.5 the reaction rate diminishes as pH is increased owing to an increasing competition between CN- and OH- ions for the electrode surface. Addition of chloride to the solution does not alter the rate law but increases the reaction rate, A mechanism is proposed to explain the observed behaviour

Electrochemical studies of copper-aluminum-silver alloys in 0.5 M H2SO4

The electrochemical behavior in 0.5 M H2SO4 at 25 degreesC of a Cu-Al(9.3 wt%)-Ag(4.7 wt%) alloy submitted to different heat treatments and an annealed Cu- Al(9.7 wt%)-Ag(34.2 wt%) were studied by means of open circuit potential (E-mix) measurements, potentiodynamic polarizations and cyclic voltammetry. SEM and EDX microanalysis were used to examine the changes caused by the electrochemical perturbations. The steady state potentials observed for the studied samples were correlated in terms of the phases present in the alloys surface. The resulting E/I potentiodynamic profiles were explained in terms of the potentiodynamic behavior of pure copper and pure silver. The presence of aluminum decreased the extent of copper oxidation. In the apparent Tafel potential region, two anodic Tafel slopes were obtained: 40 mV dec(-1) in the low potential region and 130 mV dec(-1) in the high potential region, which were related with the electrochemical processes involving copper oxidation. (C) 2001 Elsevier B.V. Ltd. All rights reserved

Electrochemical behavior of cobalt oxide coatings on cold-rolled steel in alkaline sodium sulfate

The electrochemical behavior of a coating of cobalt oxide on cold-rolled steel in alkaline sodium sulfate was Studied using the electrochemical techniques of open-circuit potential measurements and electrochemical impedance spectroscopy. The coating was prepared at different annealing temperatures ranging from 350 to 750 degreesC and characterized by SEM, EDX and XRD. Below 550 degreesC the composition of the coating was basically of Co3O4. At 750 degreesC CoO was formed and big cracks appeared on the film exposing an inner layer of iron oxides. Analysis of the EIS data is very difficult because of the complexity of the interface structure. It can be inferred that the charge transfer resistance of the coatings prepared at 350 and 450 C were higher than those for the coatings prepared at temperatures above 550 degreesC. (C) 2002 Published by Elsevier B.V. Ltd

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 behaviour of heat-treated Al-Zn-Mg alloys in chloride solutions containing sulphate

The electrochemical corrosion and passivation of Al-5Zn-1.7Mg-0.23Cu-0.053Nb alloys, submitted to different heat treatments (cold-rolled, annealed, quenched and aged, and quenched in two steps and aged), in sulphate-containing chloride solutions, has been studied by means of cyclic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The cyclic polarization curves showed that sulphate addition to the chloride solution produced a poor reproducible shift of the breakdown potential to more positive potentials. The repassivation potentials, much more reproducible, and practically separating the passive from the pitting potential region, were slightly displaced in the negative direction with that addition. When the alloys were potentiodynamically polarized in the passive potential region, sulphate was incorporated in the oxide film, thus precluding chloride ingress. In addition, Zn depletion was favoured, whereas Mg losses were avoided. Different equivalent circuits corresponding to different alloys and potentials in the passive and pitting regions were employed to account for the electrochemical processes taking place in each condition. This work shows that sulphate makes these alloys more sensitive to corrosion, increasing the fracture properties of the surface layer and favouring the pitting attack over greater areas than chloride alone. (C) 2002 Elsevier B.V. Ltd. All rights reserved

Potentiodynamic behaviour of CuA1Ag alloys in NaOH: a comparative study related to the pure metals electrochemistry

The mechanism of electrochemical oxidation of surface reformed CuA1Ag alloys having different composition of heat treatment, in 0.5 M NaOH was studied by means of cyclic polarization, constant potential electrolysis, ICP, AA, SEM and EDX. The surface reformation consisted of a repetitive triangular potential sweep (RTPS) between H 2 and O 2 evolution at 100 mV s -1 in the working solution itself, performed in order to increase the electrode roughness and obtain a quasi-stationary I/E profile in which the potentiodynamic behaviour of copper and silver was clearly revealed. The alloys suffer aluminum dealloying after such an RTPS. The quasi-stationary cyclic polarization curve exhibits a multiplicity of current peaks which have been related to the electrochemical reactions involving the pure alloying elements. Complex potential perturbation programmes in regions having different anodic and cathodic limits allowed the study of the mechanism of the electrochemical oxidation of the surface reformed alloys and the compare with that corresponding to the pure metals. The basic differences between the electro-oxidation processes of the surface reformed CuA1Ag alloys with respect to those established for the high purity alloying metals are the splitting of the peaks corresponding to the formation of the Cu(I) and Ag(I) species. © 1991

Electrochemical stability of SnO2-based coated Ti electrodes

The electrochemical behavior of SnO2-SbOx, based electrodes, with and without the addition of RuO2, was studied by cyclic voltammetry, service life measurements and electrochemical impedance spectroscopy in 0.5 M H2SO4 the physical characteristics of these materials were investigated using SEM, EDX and XRD. The resulting cyclic voltammograms obtained using SnO2-SbOx, and SnO2-SbOx-RuO2(x), x = 30, 5, 1 and 0.4 % showed that the OER overpotential decreased with the addition of RuO2. In the repetitive triangular potential voltammetry applied to the SnO2 electrode without and with RuO2 (1%), a higher anodic current is observed during the first potential scan; it is explained in terms of the oxidation of the Ti substrate. The addition of 1% RuO2 increased the service life from 8 to 20 hours at 10 mAcm(-2), while at 50 mAcm(-2) this increase was from 1 to 8 hours. AC Impedance diagrams obtained for the Ti/SnO2-SbOx and Ti/SnO2-SbOx-RuO2 electrodes at the rest potential and at a potential in the OER region can be explained by a single equivalent circuit containing two elements in series. The results showed that the charge transfer resistance and the resistance of the oxide film are lower in the oxide film containing RuO2. Surface analysis of Ti/SnO2-SbOx, revealed that it is relatively porous and formed by clusters of small particles. The Ti/SnO2-SbOx-RuO2 (1%) film is more compact, though. XRD analysis showed that a Sn1-xTixO2 oxide is formed on the Ti/SnO2-SbOx with 1% and without RuO2 electrodes

Electrochemical behavior of metallic chromium in chloride media

The electrochemical behavior of metallic chromium in aqueous solutions containing chloride ions at different pH was studied by means of open-circuit potential vs. time measurements, cyclic voltammetry and electrochemical impedance spectroscopy. The composition of the surface oxides was analyzed by XPS. For solutions with pH3 the mechanism changes. XPS analysis revealed that Cr2O3 basically constitutes the passive layer