Pta Sumodjo

Electrochemical behaviour of copper electrode in concentrated sulfuric acid solutions

The electrochemical behaviour of copper in 6.0 mol 1−1 sulfuric acid at 30°C, was studied by means of the potentiodynamic method. At low potential sweep rates, v < 200 m V s−1, the data reveal that the anodic process is basically constituted of copper dissolution and a film formation which inhibits further metal oxidation and which may undergo further dissolution. For higher potential sweep rates, a modification in the passivation region of the voltammogram is observed. It can be ascribed to a change in the passivation mechanism which possibly involves different surface species. The kineticrelationships derived from the potentiodynamic I/E curves obtained at low v suggest a film formation via a dissolution/precipitation mechanism.

Electrochemical studies with tin electrodes in citric acid solutions

The electrochemical behaviour of tin in 0.5 M citric acid solution (pH=1.8) was studied by means of the potentiodynamic method. TheE-I profiles show an anodic current peak associated with a dissolution of the metal and the formation of a passivating film, and two cathodic current peaks which are related to the reduction of soluble Sn(II) species and reduction of the film. During the potential sweep in the cathodic direction, an anodic current peak can be observed and is interpreted in terms of a reactivation process. The data suggest that the passivation of tin in this medium occurs by a dissolution-precipitation mechanism. Depending on the potential sweep rate, the process is controlled either by mass transport or by the solution resistance in the pores of the film.

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

Abstract 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 °C and characterized by SEM, EDX and XRD. Below 550 °C the composition of the coating was basically of Co 3 O 4 . At 750 °C 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 °C.

Electrochemical studies with a Cu–5wt.%Ni alloy in 0.5 M H2SO4

The electrochemical behavior of the annealed Cu–5wt.%Ni alloy in 0.5 M H2SO4 was studied by means of open-circuit potential (EOCP) measurements, cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and quasi-stationary linear potential sweep. The hydrodynamics of the system was also studied. This material is constituted by a single α1 phase. The anodic behavior of a Cu–Ni alloy in H2SO4 consists fundamentally on the electrodissolution of Cu, its main component, and the formation of a sulfur-containing passive layer. The presence of Ni decreases the rate of Cu oxidation, mostly at high positive potentials. The impedance spectra, obtained for the unrotating electrode, can be interpreted in terms of a simple charge-transfer reaction across a surface layer. When the electrode is rotated, the occurrence of an inductive loop evidenced the existence of an adsorbed layer. All the resistance estimated from the proposed equivalent circuits diminished with the electrode rotation rate, emphasizing the influence of ion transport in the overall electrode process. The system presented two anodic Tafel slopes: 40 mV dec−1 for E 275 mV. A Tafel slope of 40 mV dec−1 evidences that copper dissolution can be interpreted in terms of the mechanism proposed by Mattsson and Bockris. The second Tafel suggests that at potentials more positive than 275 mV, copper dissolves according to a mechanism that considers the disproportionation of adsorbed Cu(I) species.

Influence of the heat treatment in the electrochemical corrosion of Al-Zn-Mg alloys

The localized corrosion of Al-(5.03%)Zn-(1.67%)Mg-(0.23%)Cu alloys and high purity Al has been studied using electrochemical techniques, optical microscopy, SEM and EDX. The samples were previously submitted to different heat treatments in which coherent and incoherent MgZn2 precipitates with different distribution and aggregation degree were produced. The influence of NaCl and Na2SO4, dissolved oxygen, immersion time and convection were studied. In NaCl solutions, pitting potentials for the alloys were more negative than for aluminium, indicating an increase in their susceptibility to localized corrosion. Moreover, annealed and cold-rolled alloys presented more negative pitting and repassivation potentials than those submitted to age hardening with direct or interrupted quenching. In annealed and cold-rolled samples, pit nucleation and propagation takes place in the zones where MgZn2 is accumulated. In the case of the age-hardened alloys, a double pitting behaviour is observed, the first one in the magnesium and zinc enriched regions and the second in the matrix. While the cold water quenched alloy is susceptible to stress corrosion craking, the alloy submitted to the interrupted quenching process is less susceptible to intergranular attack. The sulphate ion shifts the pitting potential of aluminium and the alloys by chloride towards more positive values because it impedes local accumulations of the latter.

Electrochemical behaviour of heat-treated AlZnMg 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.

Electrochemical dissolution and passivation of tin in citric acid solution using electron microscopy techniques

Abstract The electrochemical behaviour of tin in 0.5 M citric acid solution was studied by electron microscopy techniques in addition to the potentiodynamic method. The observed electrochemical dissolution is quite similar to pure chemical dissolution when metallographic practices are used and takes place distinctly between the grains. The film growing process follows a dissolution/precipitation mechanism. The local reactivation process occurs primarily along the tin grain boundaries locations.

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

Abstract The electrochemical behavior in 0.5 M H 2 SO 4 at 25°C 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.

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 (Ecor) measurements in different chloride solutions were performed and optical microscopy, SEM, TEM and EDX were applied. In chloride solutions containing dissolved O2 or H2O2, the present alloys were polarized up to the pitting attack. It was shown that theEcor 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 ≈ 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 theEcor shift or in the increase in the pitting corrosion resistance.

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

Dep. de Quimira Fundamental Inst. de Quimica Univ. de Sao Pualo, C.P. 20780, 01498 -Sao Paulo