Portugaliae
Electrochimica Acta

Pt nanoparticle-multi walled carbon nanotubes nanocomposites supported on titanium substrate (Pt-MWCNTs/Ti) were prepared by co-electrodeposition method. This composite catalyst was characterized by scanning electron microscopy (SEM), energy dispersive spectrum (EDS), and electrochemical methods. The SEM images reveal that nanostructures are distributed at the surface of the titanium plate. Electro-oxidation of methanol was investigated in acidic media on Pt-MWCNTs/Ti electrodes via cyclic voltammetric analysis in the mixed 0.1 M methanol and 0.1 M H2SO4 solutions. The Pt-MWCNTs/Ti catalyst has good electro-catalytic activity for methanol oxidation. This novel Pt-MWCNTs/Ti catalyst can be used repeatedly and exhibits stable electro-catalytic activity for the methanol oxidation.

The present work describes the preparation and characterization of polyvinyl chloride membrane doped with methyl-salin ionophore. This electrode was successfully used for selectivity and high sensibility of monohydroxiphosphate in aqueous solution. 1 µM detection limit of mono-hydrogen phosphate was obtained by using dibutyl phthalate and o-nitrophenyl octyl ether-poly vinyl chloride membrane in dynamic solution. The co-existence of a large excess of salts did not interfere with the detection in case of o-nitrophenyl octyl ether-poly vinyl chloride membrane that maked this selective electrode more adequate for the monohydrogen detection. Also, a highly selective and sensitive dihydrogen phosphate sensor was fabricated by autoassembly of polyvinyl chloride into silicium nitride gate of ISFET.

Susceptibility of mild steel to corrosion attack has restricted its industrial applications, despite its numerous advantageous characteristics. Comparison of the inhibitive tendency of a mixture of zinc gluconate (ZG) and ferrous gluconate (FG) on the corrosion behavior of mild steel in acid and saline media was investigated using electrochemical and weight loss techniques. The FG:ZG ratio was dosed from 0.5:0.5 to 2.0:2.0 g/v at an interval of 0.5:0.5. The surface morphology of the corroded mild steel samples was evaluated by high resolution scanning electron microscope equipped with energy dispersive spectroscopy (HR-SEM/EDS). Experimental results indicated that the combined inhibitor significantly reduced the corrosion rates of mild steel, with the maximum inhibition efficiency (IE) of 100% and 48% at 28 ºC in the presence of 1.5:1.5 g/v concentrations in 3.5 % NaCl and 0.5 M H2SO4 solutions, respectively. The SEM micrographs of the inhibited samples show a clearly reduced surface degradation as opposed to the surface morphology without inhibitor. Potentiodynamic polarization curves studies showed that the combined inhibitor is a mixed type inhibitor for mild steel corrosion in 3.5 % sodium chloride and 0.5 molar sulphuric acid solutions. From the set of experimental data it was found that the combined inhibitor reduced the corrosion rate through an adsorption process and obeyed Langmuir’s adsorption isotherm in chloride medium and Freundlich adsorption isotherm in sulphuric acid medium at all concentrations and temperature studied. Good synergism exists between FG and ZG. The results obtained from potentiodynamic polarization are consistent with the results of the weight loss method. Synergistic performance of inhibitors was perfect in saline medium. From the analysis of grey relational grade model, the significant concentration ratios were indentified. The results showed the influence of synergistic FG:ZG at a concentration of 1.5 g/v on the corrosion rate of mild steel. Predicted results were found to be in good agreement with experimental results.

This paper aims at investigating the influence of process parameters on micro hardness of metal matrix / material particle coated steel plates. The electro deposition parameters such as current density, pH of bath, bath temperature, Al particles concentration in the bath and agitation speed were considered for this study. Nickel matrix / aluminum particle composite coatings were prepared from a Watt’s bath by electro-codeposition method. The Taguchi method was used to establish the relationship between the process parameter and response variable, micro hardness of the coated plate. L27 Taguchi orthogonal design was employed for conducting the experiments. The micro-hardness of the deposits was examined using a Vickers micro-hardness tester with the payload of 100 g for 10 sec of indentation period. Signal-to-noise ratio and analysis of variance were employed to determine the significance of the process parameter. The surface morphologies of coating and vol. % of Al particles in deposits were analyzed using optical and scanning electron microscope observations.

Corrosion behavior of aluminum in 0.1 M HCl, 0.1 M HClO4 and 0.05 M H2SO4 solutions was studied using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results showed that the rate of corrosion of aluminum was arranged in the order: HCl > HClO4 > H2SO4. Lupine extract is an effective green inhibitor for the corrosion of aluminum in acidic solutions. The inhibition efficiency of the extract was found to increase with increasing the concentration of the extract. The obtained results showed that the lupine extract is effective in the order HClO4 > HCl > H2SO4. Theoretical fitting of the corrosion data to the Kinetic-thermodynamic model was tested to clarify the nature of adsorption.

The discoloration of the food colorant E131 (Patent Blue V) by K2S2O8 and KIO3 was investigated by spectrophotometric method. The discoloration is first order with respect to the food colorant and the oxidants. The discoloration rate constant increases with the increase in initial concentration of the oxidant and temperature; whereas discoloration decreases with the increase in concentration of E131 and chloride ion. In the presence of persulfate, Cu(II) and Fe(II) have a catalytic effect on discoloration but Ni(II) has not. The thermodynamic parameters (Ea, ∆H#, ∆S#, ∆G#) of the discoloration in the presence and absence of Cu(II) and Fe(II) are calculated.

The aim of this work was to study the effect of gadolinium content on the corrosion behavior of magnesium alloys in 1 wt.% NaCl solution at 21.5 (±0.5) °C. Four Mg-Gd alloys, namely Mg-2 wt.% Gd, Mg-5 wt.% Gd, Mg-10 wt.% Gd, and Mg-15 wt.% Gd, were studied. Weight loss measurements, potentiodynamic tests, electrochemical impedance spectroscopy, XR diffraction, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDS) were performed on the four Mg-Gd samples. The results showed the influence of the Gd content on the corrosion behavior of these alloys in 1wt.% NaCl solution. The corrosion resistance of the Mg-Gd alloys was improved with the introduction of 10 wt.% Gd in Mg matrix. Thus, weight loss and electrochemical measurements revealed the better corrosion resistance for Mg-10 wt.% Gd alloy. Further addition of Gd exceeding 10 wt.% in a magnesium matrix reduces the corrosion resistance of Mg-alloy and induces an incremental increase in the corrosion rate.

The essential oil of Artemisia herba alba has been extracted and tested as an inhibitor of lead corrosion in 0.1 M Na2CO3 medium, using stationary and transient electrochemical techniques. The results obtained show that the essential oil of Artemisia reduces the corrosion rate. The effectiveness of inhibition increases with the oil concentration to reach 77 % with 2000 ppm. The effect of temperature was also studied.

The redox properties of the 1,10-phenanthroline containing Robson type symmetrical macrocyclic dicopper(II) complex [Cu2L(H2O.phen)2](ClO4)2 1 (L = μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo-[19.3.1.18 19,13,21] he p t a c o s a-1(24) , 2, 7, 9, 11, 13(26), 14, 19, 21(25), 22-decaene-25,26-diolate) and of its dicopper(II) precursor [Cu2L(H2O)2](ClO4)2 2 have been investigated by cyclic voltammetry and controlled potential electrolysis in different organic solvents. They exhibit two consecutive reversible one-electron reductions assigned to the CuIICuII  CuICuII  CuICuI cathodic processes. The results suggest that, in solution, phenanthroline does not coordinate to the metal in complex 1, but its H-bonding interaction with the water ligands can be preserved.

Nickel coatings were obtained from Watts bath containing sodium dodecyl sulfate (SDS) or polyvinylpyrrolidone (PVP) surfactants by direct current plating. The influence of electrolysis parameters, temperature, current density, concentration of surfactants and pH on the nickel deposits brightness is investigated through a multiple linear regression model with interaction. The models obtained fitted very well the experimental data. ANOVA statistical analysis shows that all design factors are significant, and the brightness of nickel deposits obtained from bath containing PVP is more sensitive to the changes in the factors levels. The electrochemical behaviour of baths was discussed; the results revealed an inhibitive effect exerted by both SDS and PVP. We have also found that the brightness and the inhibition are well linked and directly proportional. In addition, the corrosion resistance of the nickel coatings was slightly improved, especially with PVP. Finally, the optimization analysis showed that PVP could efficiently and eco-friendly substitute SDS as an additive of nickel electroplating.

In this work, electrocoagulation (EC) was used to treat meat industry (frigorific) wastewater. Effects of EC process variables such as distance between electrodes and potential on the removal efficiency of chemical oxygen demand (COD), were examined. Two factors with three levels response surface design coupled with response surface methodology (RSM) were employed to optimize the EC process variables. Second order polynomial models were developed for the responses and three dimensional (3D) response surface plots were used to study the interactive effects of the process variables on the EC efficiency. Experimental results showed that EC treatment, using a potential of 40 V and electrodes with a 3 cm gap between them, presented a COD removal of over 90% for the meat industry wastewater.

Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were used to measure the corrosion rate of aluminium in 0.1 M HCl in the absence and presence of different concentrations of chitosan. Inhibition efficiency up to 90% in the presence of 0.028 g/L chitosan was achieved. Increasing the concentration of chitosan shifted the breakdown potential, Eb, of aluminium to more noble values and inhbitied the pitting corrosion of aluminium. Measurements of the break potential, Eb, and the electrical double layer capacity (Qdl) indicated that chitosan is adsorbed at the aluminium/solution interface.

The application of combined chemical coagulation and electrochemical oxidation processes to treat a leachate from an intermunicipal sanitary landfill was evaluated. Chemical coagulation (CC) experiments were performed with lime (Ca(OH)2), and the influence of the lime concentration, stirring speed and assay duration were studied. In the electrochemical oxidation (EO) assays, a boron-doped diamond anode was used, and two applied current intensities were tested. It was also evaluated the influence of the lime concentration used in the CC pre-treatment on the EO performance. In the CC assays, the highest COD removals were obtained for lime concentrations of 20 and 25 g L-1, at 100 rpm stirring speed, during 2 h. In the CC+EO combined treatment the highest removals were obtained at the applied current intensity of 0.6 A, being the influence of the lime concentration used in the pre-treatment almost insignificant. The highest current efficiency was obtained for the combined treatment with EO assays performed at 0.4 A.

The effect of linseed oil (LO) on the corrosion of carbon steel in 1 M HCl solution was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) technique and weight loss measurements. The inhibiting action increases with the concentration of the tested inhibitor. The highest efficiency (98.2%) is obtained at 3g/L of LO. The influence of temperature on the corrosion behavior of carbon steel in 1 M HCl, with the addition of LO was also studied. The obtained data from EIS measurements were analyzed to model the corrosion inhibition process through an appropriate equivalent circuit model; a constant phase element (CPE) has been used. Polarization measurements show also that LO acts as a good mixed inhibitor. The inhibition process is attributed to the formation of an adsorbed film of the inhibitor on the metal surface which protects the metal against corrosion. LO is adsorbed on the steel surface according to a Langmuir isotherm adsorption model. The results obtained showed that the linseed oil could serve as an effective green inhibitor of the corrosion of carbon steel in hydrochloric acid medium.

A new quaternary Ni–Fe–P–C composite coating was deposited on copper substrates by an electrodeposition process. The morphology, structure and composition of the prepared electrode were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) pattern, and energy dispersive X-ray spectroscopy (EDX). The activity of the composite coating toward hydrogen evolution reaction (HER) was evaluated on the basis of the steady-state polarization Tafel curves and electrochemical impedance spectroscopy (EIS) in 1 M NaOH at temperature of 298 K. The experimental results revealed that the HER activity of the Ni Fe P C coatings was enhanced compared with both ternary coatings of Ni P C and Ni-Fe C. The source of its activity was found from its high surface area and its intrinsic properties. It was sufficient to assume the Volmer–Heyrovský mechanism with the Heyrovský reaction as the rate-determining step to explain the experimental data. Besides the high electrocatalytic activity, excellent chemical and electrochemical stability were observed for Ni Fe P C composite coating toward the HER in 1 M NaOH at 298 K.

The present research article deals with the study of corrosion behavior of Ni-P-TiO2 composite coating. The TiO2 composite coating is deposited on the mild steel substrate. Corrosion behavior of the TiO2 composite coatings after heat treatment at various annealing temperatures (300 °C, 400 °C, and 500 °C) is evaluated with the help of potentiodynamic polarization test using 3.5% NaCl solution. The electrochemical parameters, corrosion potential (Ecorr) and corrosion current density (Icorr), are optimized for maximum corrosion resistance using Taguchi based grey relational analysis. The coating parameters, namely, nickel sulphate, sodium hypophosphite, concentration of TiO2 particles and annealing temperature are considered as main design factors. The analysis of variance (ANOVA) revealed that the annealing temperature and concentration of TiO2 particles have significant influence on the corrosion behavior of the composite coating. The microstructure characterization of the coating is conducted using scanning electron microscopy, energy dispersive X-ray analysis and X-ray diffraction analysis. The Ni-P-TiO2 composite coating exhibits nodular structure with uniform incorporation of titanium particles and converts into the crystalline structure after heat treatment.

The aim of present study is to establish the not known divalent state of praseodymium and samarium in non-aqueous medium at 298.15 K and atmospheric pressure. Potentiostatic and galvanostatic methods were used to characterize the divalent states of both lanthanides. Under the specified experimental conditions, samarium and praseodymium showed two reduction steps at glassy carbon electrode in non-aqueous medium. Cathodic and corresponding anodic peak potential and peak currents were calculated for samarium and praseodymium ions at different scan rates. The results also suggest that the scan rate has great influence on the behaviour of both lanthanides. Diffusion coefficient (D x cm2/sec) and heterogeneous forward rate constant (kºfhxcm/sec) have been evaluated. Transition time (tau) has also been evaluated for Pr(III)/Pr(II), Pr(II)/Pr(0) coupled systems, suggesting that the system is approaching from irreversible with increasing the scan rates. The effects of changing the scan rate and donor number on the electrochemical behavior of both lanthanides have been examined at 298.15 K and atmospheric pressure.

Concrete is one of the most widely used engineering materials for construction. Its durability is a major problem affecting the service life of the engineering structures. Various technologies such as cathodic protection and the use of corrosion inhibitors are used to improve the durability of reinforced concrete. Various organic and inorganic inhibitors, and also extracts of natural products have been used as corrosion inhibitors. Corrosion resistance of rebars has been evaluated by electrochemical studies such as polarization study and AC impedance spectra. The protective films formed on the metal surface have been analyzed by NMR, FTIR spectra, SEM, AFM and XRD.

The electrochemical corrosion behaviour of an electrodeposited Ni–28wt.%Al composite coating was characterized after 24 h and 72 h immersion periods in 3.5% NaCl solution, using electrochemical and surface probe techniques. Open circuit potential (OCP) and potentiodynamic polarization revealed that the Al particles modify the electrochemical corrosion behaviour of the Ni coating by shifting its EOCP more negatively and increasing its anodic dissolution current density, after 24 h immersion in 3.5% NaCl solution. Compared with the Ni coating, the composite can exhibit well–reduced anodic current density and slightly increased cathodic current with immersion up to 72 h. XPS characterization showed that a high rate of water adsorption and rapid formation of a continuous Ni(OH)2 initially occurs on the composite surface which, however, readily thickens during prolonged immersion time and promotes the corrosion product enrichment with Al2O3. This greatly decreased the rate of corrosion and susceptibility to pitting for the Ni–28wt.%Al composite after 72 h immersion in 3.5% NaCl solution.

Five different water soluble terpolymers, namely polyvinyl alcohol-g-poly(acrylamide-vinylsulfonate), polyvinyl alcohol-g-poly(acrylic acid-vinylsulfonate), polyvinyl alcohol-g-poly(acrylamide-vinyl benzene sulfonate), polyvinyl alcohol-g-poly(acrylic acid-vinyl benzene sulfonate) and polyvinyl alcohol-g-poly(vinylsulfonate-vinyl benzene sulfonate), have been designed, developed and tested for their efficacy to control N-80 steel corrosion in 10 % HCl, 3.5 % NaCl and simulated well water. The terpolymer characterization was carried out by FTIR. The inhibitors were tested by potentiodynamic and impedance techniques. The inhibitors were also tested in static and dynamic conditions at 55±5 °C, for 6 hours immersion period by weight loss method. Acrylamide terpolymers rendered the best inhibition efficiency in all the studied systems. The results provided a preliminary validation of the inhibitor such that they can be optimised and used for corrosion in oil and gas industries.