Portugaliae
Electrochimica Acta

Inside the construction industry, in the area of sea water retention structures, the chlorides contamination is a main cause of the corrosion, because in the concrete they could form macro cells upon repairing and applying a mortar free of this ion, forming anodes in the repaired zones, and thus increasing corrosion. In the reinforcements are commonly formed corrosion products because the concrete is exposed to mechanical, physical, chemical or biological conditions that commit and shorten their performance. As a consequence, it is important to determine their useful life and that of the made repairs, using electrochemical techniques that allow determining the level of protection, the effect of the macro cells in the corrosive process of the reinforcement, and the mechanism of deterioration in the structures. The present work was carried out using six beams with preoxided reinforcements, six precracking and one beam blank. After curing, those beams were exposed to accelerated cycles of deterioration for causing the cracking of the concrete, making possible to observe their electrochemical behaviour. The tests carried out were corrosion potential and corrosion rate, through the resistance to the polarization technique.

This work describes the determination of pentachlorophenol (PCP) in pure and polluted waters by square wave voltammetry (SWV) and the influence of the electrode potential on PCP oxidation on boron doped diamond (BDD) electrodes. Measurements carried out in solutions of the Britton-Robinson buffer with pH = 5.5 revealed a single oxidation peak at 0.80 V vs. Ag/AgCl for PCP in a process that is controlled by the adsorption of the species. The detection limits obtained were 5.5 mg L-1 in pure water and 15.5 mg L-1 for water taken from a local creek, respectively. Controlled potential electrolyses were carried at 0.9, 2.0 and 3.0 V vs. Ag/AgCl and the solutions analysed by SWV, HPLC, chloride ion selective electrode and UV-vis spectroscopy. At low positive potential (0.9 V), the formation of an adherent film on the electrode surface involving the transference of 1 electron per PCP molecule was observed. At potentials close to the onset of O2 evolution (2.0 V), the formation of the corresponding quinone was detected. Electrolyses carried out well into the region of oxygen evolution (3.0 V) lead to the total combustion of PCP to CO2 and H2O as well as to the release into solution of 5 Cl- ions per PCP molecule destroyed.

LiMn2O4 is an attractive 4 V positive material in lithium rechargeable batteries owing to its favourable electrochemical characteristics besides its economic and environmental advantages. However, problems of limited cyclability, especially at elevated temperatures, have limited the utility and commercialization of this cathode material. Stabilization of the LiMn2O4 spinel structure has been sought to be realized by doping the spinel with suitable cations. In this paper, the results of an exploratory research on the capacity and cyclability of LiMn2O4 cathodes simultaneously doped with Cr3+ and Mg2+ are reported. LiMgy1Cry2Mn2-y1-y2O4 spinels with y1 = 0.00, 0.05, 0.10, 0.20, 0.25 and 0.30 and y2 (0.3 - y1) were synthesized by a solid-state fusion method. While Mg2+ bestows a positive effect on cyclability, it leads to a considerable reduction in capacity due to the oxidation of Mn3+ to the inactive Mn4+ as a result of charge compensation. Cr3+ on the other hand, leads only to half as much reduction in capacity while according added stability to the structure. Any expectation of a synergistic effect by Cr3+ and Mg2+ ions was belied by these findings.

The transfer of acetylcholine cation through a monolayer of a lipid, dipalmitoylphosphatidylcholine, formed at a polarized water | 1,2-dichloroethane interface has been studied using electrochemical impedance spectroscopy. The ion transfer process was characterized at different levels of interfacial coverage. From measurement of the cyclic voltammograms and double layer capacitance it was found that cation transfer through dipalmitoylphosphatidylcholine monolayers was cation and phospholipid concentration dependent. An increase on current intensity and capacitance values was observed at more positive potentials due to the transfer of acetylcholine across the interface in the absence or presence of lipid in the organic phase. The thermodynamic and kinetic parameters were also accessed from electrochemical impedance measurements.

Corrosion inhibition of 3-phenyl hydrazonoacetyl acetone derivatives on electrodeposited tellurium and palladium in nitric acid was measured by using electrochemical method. Polarization curves showed that these compounds are cathodic inhibitors. The inhibition appears to function through general adsorption following the Flory-Huggins adsorption isotherm. The rate of corrosion depends on the nature of the inhibitor and its concentration, mode of interaction with the metal surface, molecular size, formation of complexes and the active center in the molecules and its electron charge density. Also, ΔGoads. values were calculated. The reaction rate was found to be proportional to the absolute value of the Hammett constant (s).

Formation of complexes of alkaline-earth cations with crown ethers containing an anthraquinone unit (AQ18C6 and AQ21C7) was investigated in methanol and acetonitrile solutions. Stability constants of the resulting complexes were estimated by means of potentiometric methods. The results obtained show the formation of complexes of the LM2+ type for all alkaline-earth ions; for the larger cations, (Sr2+ and Ba2+) and in excess of ligand, L2M2+ complexes were also detected. The most stable complexes were obtained with Ba2+ cation and for both ligands. The binding strength for the cations towards AQ18C6 and AQ21C7 ligands and in both solvents, increased in the order, Mg2+ < Ca2+ < Sr2+ < Ba2+. The results of this study suggest that on the 1:1 complexes, the size of the cation and its fit into the macrocyclic internal cavity of the ligand was a dominant factor on the coordination binding. The number of donor atoms in the ring of the macrocycle does not affect the binding strength and the AQ18C6 complexes have larger stability than the corresponding AQ21C7 complexes. The presence of an anthraquinone unit on the structure of the crown ether induced a decrease of the cation binding strength. The external carbonyl group of the ligand molecules was not involved on the coordination to the cation. Considering the two solvents, the complexes were more stable on acetonitrile, the solvent of weaker solvating capacity.

The corrosion behavior of pure copper rotating cylinder electrode (RCE) exposed to 3% NaCl or artificial seawater prepared as Vätäänen nine salt solution (VNSS) has been studied using electrochemical impedance spectroscopy (EIS) and polarization techniques. EIS experiments for copper RCE were carried out at different rotation rate from 0 rpm to 1600 rpm. Polarization resistance (Rp) values were obtained from both EIS and polarization experiments. Excellent agreement between impedance and polarization data is observed. RCE experiments demonstrated that Ecorr and corrosion rate for copper depend linearly on rotation speed r0.7. The results obtained showed that EIS is a powerful electrochemical method to follow the change of corrosion mechanisms.

A few 1-aryl-2,5-dithiohydrazodicarbonamides and their triphenyltin and dibutyltin complexes have been studied as corrosion inhibitors for mild steel in dimethyl sulphoxide containing HCl at 25 ºC using electrochemical polarisation technique. Among dithiohydrazodicarbonamides, ethoxyphenyl derivative exhibited maximum inhibition efficiency (IE) followed by benzyl and phenyl analogues. The same order of IE was observed in their corresponding organotin complexes; however, IE of a complex was found to be significantly higher than that of the constituents ligand. All organotin complexes behaved predominantly as cathodic inhibitors. Triphenyltin complexes proved to be better corrosion inhibitors than their dibutyltin analogues.

The objective of the present work is the study and optimization of a voltammetric methodology to determine palladium traces and ultratraces, with the purpose of being able to establish the environmental levels of this element and to verify if a contamination takes place starting from the gases of escape of the vehicles equipped with catalytic converters. The voltammetric determination of palladium is based in the formation of a complex of palladium with dimethylglyoxime that adsorbes actively on the surface of a hanging mercury drop electrode, for then to be reduced when making the square wave potential sweep. The quantification is made by the method of standard additions. The study of interferences demonstrated that Na+, Mg2+, K+, Ca2+, Zn2+, Cu2+ and Al3+ are not even interferences at the level of 10 mg/L. The detection and quantification limits of the methodology are respectively 10 ng/L and 33 ng/L, with a sensibility of (4.3±0.8)*102 nA L/ng.

Studies of the corrosion evaluation of SS-304 stainless steel exposed in aqueous lithium bromide solution have been carried out applying the electrochemical noise technique, polarization curves and the weight loss method. The test temperatures were 50, 60 and 70 °C, and the exposure time was for fifteen days. The main objective was to determine the corrosion rates and the type of corrosion that SS-304 suffers under the mentioned conditions with the purpose of evaluating its application to heat pumps/transformers. The results showed that at the three test temperatures the type of corrosion was a mixed and pitting process. At 60 °C, it was observed some anodic peaks at the fifth day of exposure, indicating pitting nucleation. From 7 to 12 days a regular and continue pitting process was observed, and then the corrosion process became in generalized type. At 70 °C, some isolated and medium intensity peaks were observed, presenting behaviour of some mixed and pitting corrosion. The resistance noise was calculated through a statistical analysis, and then the Stern-Geary equation and Faraday Law were applied to determine the mass loss, which was compared to that obtained from weight loss method. Tafel slopes were determined from experimental polarization curves. To support the metallic oxidation carried out on the stainless steel surface, atomic absorption analysis was made to the solution corrosion products.

One of the main limiting factors of the electrocoagulation, as a process of treatment for remotion of contaminants from residual waters, is not knowing the degree of interaction of some variables which could significantly affect the system. The electrode passivation is one of them once its presence limits the emission of metallic ions and consequently the treatment time is increased as well as cost, and remotion efficiency is decreased. In the present work potentiodynamic and potentiostatic curves were used to observe the behaviour of current density vs. pH, electrical conductivity, distance between electrodes, auxiliary electrode area and applied potential difference. We found out that all the above variables influence the current density, that passivation is at 50 mV, independently of all the other variables, and that at 2000 mV, only is observed when pH = 2 and high electrical conductivities.

The electrochemical behaviour of five different complexes of cobalt with 2,4-bis(trimethylsilylethynyl)thiophene was studied, concluding that the presence of aromatic ligands gives rise to electronic communication effects that allow to define them as molecular wires. The stability of the compounds and of the products of oxidative and reductive charge transfers increases at a temperature of -30 °C.

Inconel 600 has been designed to heat resistance. It is used in the chemistry industry, food industry and, of course, in the production of electric energy, among others. The goal of this project was to decrease the costs in the equipments and pipes deterioration by prolonging their lifetime, controlling and preventing their deterioration by means of appropriated and programmed maintenance, but above all knowing the mechanism and kinetic of corrosion that affects them. We used polarization curves to evaluate the effect of wild culture isolated from a traditional thermoelectric plant located northern Mexico. The studied culture was isolated by enrichment cultures in two phases, in a selective medium for sulfate-reductive bacteria in environmental temperature. It was selected for being thermo resistant and promising the largest influence in the corrosion rate. Inconel 600 keeps a multiple protection control until week 7, then it becomes an anodic protection control and later it becomes unstable to these cultures.

For stainless steel 316 evaluation, reinforced concrete samples (12x12x25 cm), using four carbon steel bars and/or 316 stainless steel and two graphite reference electrodes were carried out. The concrete has resistance of 00 Kg/cm2 and a water/cement ratio of 0.65. The samples were exposed to an artificial environment of 5% of saline concentration and carbon dioxide, evaluating periodically the state of the samples in each environment. Electrochemical evaluations, such as potential measurement vs. Cu/CuSO4 electrode and polarization resistance were carried out. In addition, the cyclical polarization of stainless steel samples in pore solution (pH = 13.40) with different chloride concentration (0%, 0.5% and 5% chloride concentration) were evaluated. Stainless steel exposed for 6477 hours in saline environments showed very low corrosion rate for stainless steel, while carbon steel showed corrosion rate from moderate to high. Galvanic couples (stainless steel-carbon steel) showed intermediate corrosion rate. In carbonation environments low corrosion rate were detected for both materials. With cyclical polarization with 5% NaCl, corrosion products and pitting were observed.

Poly-N-vinylcarbazole (PNVCz) can be obtained by two different ways: when the reaction takes place through the vinyl group of the monomer, a white, linear-chain polymer, with interesting photoconducting properties, is obtained. When the polymerization occurs through the aromatic rings, the main product is a green, cross-linked polymer. Polymerization of N-vinylcarbazole (NVC) is possible by electrochemical oxidation. Direct anodic oxidation leads mainly to the green form of the polymer. Protons released from the initial oxidation of the aromatic rings, induce the polymerization through the vinyl group. Indirect electrolysis, making use of an intermediate to achieve oxidation of the monomer, is also possible. In particular, the electrochemical generation of Ce(IV) allows to increase selectivity towards the linear-chain polymer, and can be the basis for the development of a new process, involving the anodic oxidation, in aqueous phase, of Ce(III) to Ce(IV), which will activate the polymerization reaction through the vinyl group. This work presents results from initial characterization, by cyclic voltammetry, of the reacting system. The anodic polymerization of the monomer (NVC) was carried out in acetonitrile, using sodium perchlorate as supporting electrolyte, in the presence and in the absence of cerium salts. The voltammetric response of Ce(III) in aqueous phase, as a possible initiator for the polymerization, is also presented.

In the present study we have made the numeric simulation by finite elements of the cathodic protection by printed current system for the buried duct. The built model was based on the steel carbon type SAE-AISI 1015, and this steel is the constituent material of the duct. This work allowed analyzing the potential distribution in the proposed project and the parameters that more influence the variation of this potential. Those parameters were such as resistivity of the soil, distance between cathode and anode, position of the anode, potential and diameter of the cathode. As a result it was verified that the resistivity of the electrolyte and the distance cathode/anode influence significantly the distribution of the potential of the projected system of cathodic protection.

The reinforced concrete is a versatile and resistant material and it is used in several construction projects; for this reason the improvement of concrete properties and protection of the reinforced steel against corrosion is an active research area. Diverse methods are applied on the steel or on the concrete to protect them. The present investigation is directed towards the development and performance evaluation against corrosion of the reinforcement concrete, containing two different fly ash and blast furnace slag mixtures, in saline environments, and the corrosive evaluation was performed by electrochemical noise technique. The results show an improvement of the steel reinforcement corrosion resistance.

The development of mathematical models and the simulation of cathodic protection systems applied to buried tubing are presented. The solution of partial differential equations is obtained by numerical methods like finite elements and boundary elements. The purpose is developing a quantitative method of potential distribution prediction on the surface of the buried structure, covering aspects like selection of materials, geometric configuration and design of the system. As verification problems were used the problem of the square tank, and the problem of the cylindrical container. Finally two cases of buried structures are presented.

Fue evaluado un método voltamperométrico con preconcentración adsortiva y catálisis, utilizando el electrodo de gota suspendida de mercurio, para la determinación simultánea de ultratrazas de platino y rodio. Las condiciones óptimas establecidas fueron obtenidas luego de la optimización secuencial, consiguiéndose obtener una linealidad hasta los 6.00 ng/L de platino y los 0.7 ng/L de rodio. Los límites de detección y de cuantificación obtenidos son 4.0 ng/L y 10 ng/L para platino y 1.0 ng/L y 3.0 ng/L para el rodio.