Portugaliae
Electrochimica Acta

The main objective of this work is to study the behavior of copper corrosion in nitric acid medium (2 M) for the evaluation and comparison of the corrosive power of the essential oil of Thymus Satureoides. To do this, we used weight loss and polarization techniques. The results show that the recovery rate of copper corrosion decreases in the presence of the essential oil tested. In a second step, we performed tests on the major component of the oil and the results obtained showed that the activity of the essential oil of thyme is clearly not related to it’s major constituent. On the other hand, it is clear from this study that the inhibition efficiency increases with the concentration of inhibitors to reach 89.04% at 1200 ppm for the essential oil of thyme and 69.72% at 1600 ppm for borneol. The adsorption isotherm and the activation energy were also determined.

A different approach for protecting the aluminium in 1M HCl is done by strengthening the surface oxide film of aluminium with nickel titanate particles. Weight loss methods, open circuit potential measurements and polarization techniques are used to measure the corrosion behaviour of aluminium samples. The corrosion rate of nickel titanate deposited aluminium shows lower values compared to pure aluminium in HCl medium. The intermixing of aluminium oxide with nickel titanate enhances the corrosion resistance property of the aluminium oxide layer on the surface of aluminium and thereby reduces the coulombic and non-coulombic loss of metal.

The ultrasonic measurements of solutions of uranyl caprylate and laurate in a mixture of 50/50 benzene-dimethylsulphoxide (V/V) have been used to determine the critical micellar concentration, ultrasonic velocity and various acoustic parameters at different temperatures. The results confirm that there is a significant interaction between uranyl soaps and the mixed organic solvent molecules.The values of critical micellar concentration of uranyl caprylate and laurate are in good agreement with those obtained from conductivity measurements.

The inhibition efficiency of sodium gluconate (SG)–Zn2+ system in controlling corrosion of carbon steel in sea water has been evaluated by weight-loss method. The formulation consisting of 250 ppm of SG and 75 ppm of Zn2+ has 98% IE. Influence of duration of immersion on the IE of SG-Zn2+ has been evaluated. The mechanistic aspects of corrosion inhibition have been investigated by polarization study and AC impedance spectra. The protective film has been analysed by FTIR and luminescence spectra. The surface morphology and the roughness of the metal surface have been analysed by atomic force microscopy. The protective film consists of Fe2+ - SG complex and Zn(OH)2. It is found to be UV – fluorescent.

Metal matrix composites are heterogeneous systems containing matrix and reinforcement. Their physical and mechanical properties can be tailored according to requirement. They are used in automobile, aircraft and marine industries because of their increased corrosion resistance. In this paper weight loss corrosion test, open circuit potential test and potentiostat test are conducted on AL6061/ Red Mud metal matrix composites in different concentrated neutral chloride solutions like sodium chloride solutions. Composites are prepared by liquid melt metallurgy technique using vortex method. Composites containing 2, 4 and 6 percent of red mud are prepared according to ASTM standards. Specimens are machined and made ready by standard metallographic methods. Weight loss corrosion studies, open circuit potential studies and potentiostat studies, are carried out in 0.035, 0.35 and 3.5% solutions of sodium chloride. The corrosion rate decreases with increase in the exposure time for all specimens in all corrodents in all the methods of testing. Corrosion rate also decreases with the increase in reinforcement content of the composites. Hence the composites can be used for the manufacture of the equipments used in marine environment so that they lost long.

Based on the energy form waste concepts we present here our results of the study of utilizing waste tea dust for preparing carbon, called the biocarbon. Tea dust after decocting has been selected as a low cost source of producing the carbon. Un-activated and activated carbons are produced by heating the tea waste around 250 oC for 2 h. For the first time, boric acid (H3BO3) has been reported through this work as a chemical agent for activating the selected biowaste. After physical characterization, the biocarbons have been tested in 3M KOH electrolyte solution for the possible application as electrodes in electrochemical double layer capacitors (EDLCs). Cyclic voltammetric studies with boric acid activated carbon of tea show slight improvement in the capacitance values over un-activated tea derived carbon. The study suggests that boric acid may be used as an activating agent for producing activated carbons.

The degradation of Acid Red I dye (ARI) and Luganil Blue N (LBN) has been studied by electrochemical treatment methods. The efficiency of cathode materials such as platinum, copper, zinc, lead, graphite, nickel, steel and titanium metals on the degradation of Luganil Blue N and Acid Red I dyes were investigated. The suitable cathode material was chosen and other parameters such as current density, and NaCl and dye concentrations were optimized. The electrolysis process was monitored by UV-Vis spectrophotometer and measuring chemical oxygen demand of the electrolyzed solutions. The overall COD removal efficiencies reached as high as 74.24% and 87% for ARI and LBN, respectively.

The chemical reaction of rhodamine B by electro-generated species using Pt and BDD electrodes was performed. The product(s) of this chemical reaction are related to the supporting electrolyte and electrolysis time. The rate of discoloration is affected by the current density, initial pH, temperature, and the nature of the supporting electrolyte. However, the initial dye concentration and the ionic strength did not show any significant effect on both electrodes. Discoloration of the dye and mineralization were not observed in presence of sulfate and nitrate with the Pt electrode, but occurred slowly with the BDD electrode. In the presence of KCl and KBr, the discoloration was very fast with both electrodes, and was accompanied with partial degradation. In the presence of KCl, the colorless rhodamine B solution turned rose after several hours of being set at rest.

The effect of synthesized 1,1'-propane-1,3-diylbis[3-(chloromethyl)-5-methyl-1H-pyrazole], dimethyl 1,1'-butane-1,4-diylbis(5-methyl-1H-pyrazole-3-carboxylate) and 1,1'-butane-1,4-diylbis[3-(chloromethyl)-5-methyl-1H-pyrazole] on corrosion of C38 steel in hydrochloric acid solution has been investigated in the temperature range from 298 K to 328 K by weight loss, potentiodynamic polarization method and modelled with an equivalent electric circuit. All the compounds exhibited more than 90% anticorrosion activity, the highest is 96 % by 1,1'-butane-1,4-diylbis[3-(chloromethyl)-5-methyl-1H-pyrazole], and it has been shown that the inhibition efficiencies increased with the concentration of the inhibitors, remaining almost constant in a wide temperature range. Potentiodynamic polarization studies suggested that it is a predominance cathodic type. Nyquist plots showed depressed semicircles with their centre below the real axis. The adsorption on the C38 steel surface followed the Langmuir adsorption isotherm. The thermodynamic parameters for dissolution were investigated at different concentrations and temperature. The theoretical study by modelling the molecules of these inhibitors has been performed by considering the Density Functional Theory (DFT) using the Gaussian 03W suite of programs that can calculate the different quantum parameters such as EHOMO, ELUMO, ΔEHOMO, ELUMO, and µ dipolar moment, allowing us to confirm the results found by the gravimetric and electrochemical methods.

Gas chromatography mass spectrophotometer (GCMS) analysis of Ficus tricopoda gum indicated the presence of 4.75, 56.15, 32.10 and 7.00 % of camphene, sucrose, 2-methylene cholestan-3-ol and 7-hexadecenal, respectively. Several stretching and bending vibrations were observed in the Fourier transformed infra-red (FTIR) spectrum of the gum. Physicochemical examinations of the gum revealed that it is pale yellow in colour, mildly acidic, ionic and display characteristics of sour taste. The solubility of the gum in water was found to increase with increase in temperature. Knowledge of the chemical constitution of the gum (hence chemical structures of its constituents) was useful in predicting the corrosion inhibition potential of Ficus tricopoda (FT) gum. Consequently, the gum was found to be a good adsorption inhibitor for the corrosion of aluminum in solution of H2SO4. The adsorption of the gum (which, followed first order kinetic) was found to be endothermic at FT gum critical concentration of 0.3 g/L and exothermic at concentrations above the critical limit. The short coming of the Langmuir adsorption model in describing the existent of interaction between the molecules of the gum was complimented by the Frumkin and Dubinin-Radushkevich adsorption models. Calculated values of activation and free energies of activation indicated that the adsorption of Ficus tricopoda gum on Al surface exhibited both physical and chemical adsorption mechanism.

The inhibition efficiency [IE] of an aqueous extract of eclipta alba leaves in controlling corrosion of carbon steel in sea water [Thondi, Tamil Nadu, India] has been evaluated by weight loss method. The weight loss study reveals that the formulation consisting of 6 mL of EAE (Eclipta Alba extract ) and 25 ppm of Zn2+ has 92% inhibition efficiency in controlling corrosion of carbon steel in sea water. Polarization study reveals that EAE and Zn2+ system functions as a mixed type inhibitor. AC impedance spectra reveal that a protective film is formed on the metal surface. The nature of the metal surface has been analysed by FTIR spectra and AFM analysis.

It was evaluated the technical viability of mercury removal by electrodeposition from vegetal biomass samples obtained from mining zones which had 10±0.3 µgHg g-1. Each sample was treated by mixed acid to destroy the organic matter and liberate the metal in its inorganic form for the later removal of Hg by means of a cell of electrolysis with a rotary electrode of copper as cathode. Mercury concentration was determined by Cold Vapor Atomic Absorption Spectrophotometry (CVAAS). Response surface methodology (RSM) was applied to evaluate the simple and combined effects of three independent parameters (voltage, time and concentration) on the removal efficiency and optimizing the operating conditions. Analysis of variance showed a high coefficient of determination (r2 = 0.925) indicating that the second order regression model explains 92.5 % of the variability in results. The maximum efficiency of removal (91.2 %) predicted by the model was found for the initial concentration of 1.0 µg mL-1, 66.6 mins and 34.3 V. Model Validation was carried out under the following conditions: 1.0 µg mL-1, 60 mins and 30 V, which are close to the maximum efficiency with a removal percentage of 87.1 %.

The effect of some mono-,bis -and tris-azo dyes compounds on the dissolution of mild steel in 1.0 M HCl solution was studied using weight loss and potentiodynamic polarization measurements. The inhibition efficiency was found to increase with increasing concentration of the inhibitors and with decreasing temperature. The adsorption of different azo dyes on the mild steel surface obeys the Langmuir adsorption isotherm. Polarization studies indicate that the compounds used are mixed type inhibitors. The thermodynamic functions of adsorption processes were calculated from weight loss at different temperatures data and were used to analyze the inhibitor mechanism. The surface morphology of the mild steel specimens was evaluated using SEM and EDAX analysis. To provide an evidence for the formation of the complex, UV-VIS spectra of solutions were investigated. From previous results (I.E.%, ∆Gads., SEM, EDAX and UV-VIS spectra) are likely to get into the possiblity of configure the complex on the mild steel surface.

The effect of the extract of Lupinus varius l. on corrosion of Al in 1 M NaOH solution using the weight loss technique was investigated. Lupinus varius l. extract inhibited the corrosion of Al in 1 M NaOH solution and the inhibition efficiency increased with increasing the concentration of the extract and decreased with increasing temperature. The adsorption of the inhibitor molecules on Al surface was in accordance with Langmuir and Temkin adsorption isotherms. A first-order kinetic relationship with respect to Al was obtained with and without the extract from the kinetics treatment of the data.

This paper reports an experimental study of corrosion characteristics of electroless Ni-P-TiO2 nanocomposite coatings. Coating process parameters are optimized for maximum corrosion resistance based on L9 Taguchi orthogonal design with four process parameters, viz., concentration of nickel source solution, concentration of reducing agent, concentration of TiO2 powder and bath temperature. Corrosion behavior of the electroless Ni-P-TiO2 nanocomposite coatings was evaluated in 3.5 wt.% NaCl aqueous solution by using polarization technique. Scanning electron microscope (SEM) and Energy dispersive X-ray spectroscopy (EDS) analysis were used for studying the surface morphology and chemical composition of the electroless Ni-P-TiO2 nanocomposite coatings. The results showed that incorporation of TiO2 in coating causes increasing of corrosion resistance and improves surface morphology. Finally, optimum conditions were achieved as, concentration of nickel source solution: 50 g L-1, concentration of reducing agent: 10 g L-1, concentration of TiO2 powder: 10 g L-1, and bath temperature of 85 °C.

The corrosion behaviour of welded maraging steel in hydrochloric acid solutions was studied over a range of acid concentration and solution temperature by electrochemical techniques like Tafel extrapolation method and electrochemical impedance spectroscopy. The corrosion rate of welded maraging steel increases with the increase in temperature and concentration of hydrochloric acid in the medium. The energies of activation, enthalpy of activation and entropy of activation for the corrosion process were calculated. The surface morphology of the corroded sample was evaluated by surface examination using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS).

An investigation about the corrosion resistance of SS316L alloys in artificial blood plasma environments in presence and absence of amoxicillin has been carried out by using electrochemical techniques. Tested alloys included 18% Cr, 12% Ni, 2.5% Mo, <0.03 C, balance iron, using artificial blood plasma solution. Electrochemical techniques included potentiodynamic polarization curves, linear polarization resistance and AC impedance spectroscopy. Different techniques have shown that generally speaking, SS316L alloys show a more corrosion resistance in artificial blood plasma in the presence of 100 ppm amoxicillin than in the presence of 50 ppm of amoxicillin and in the absence of amoxicillin. Their corrosion resistance is increased as the quantity of amoxicillin is increased in artificial blood plasma.

Aluminium is the most widely used non ferrous metal. It is very needful to prevent this metal from corrosion .Corrosion inhibitors are one of the widely used methods to control corrosion. The purpose of this paper is to make people aware of organic corrosion inhibitors. Organic inhibitors are mainly present in natural products. It has been found that plant extracts and natural products show inhibition efficiency up to 98%. They are also non –toxic, eco- friendly, very cheaper. In the present work, natural products are used at various conditions and their inhibition efficiency is calculated by different methods; they obey various adsorption isotherms; the protective films formed by the inhibitors are analyzed by techniques such as electrochemical methods, FTIR, HPLC-RP, SEM, EDS.

A modified electrode is fabricated by the electrodeposition of polyaniline-polystyrene sulphonate composite onto the carboxylated graphene modified graphite electrode for the detection of hydrogen peroxide (H2O2). The modified electrode displayed excellent catalytic response to the reduction of hydrogen peroxide in neutral pH. It was found that the presence of carboxylated graphene in the sensor system could effectively increase the electron transfer rate and stability. The modified electrode was characterized by cyclic voltammetry, electrochemical impedance spectroscopy and atomic force microscopy. Chronoamperometric studies showed the linear relationship between the reduction peak current and the concentration of H2O2 in the range 25 to 350 μM (R = -0.995) with the detection limit of 1×10-6 mol/L (S/N=3). Further, electrochemical analysis of H2O2 in the presence of common interferents such as dopamine, uric acid and ascorbic acid with the modified electrode reveals that there is no overlapping signal from the interferents.

Chlorophenols are a group of special interest due to their high toxicity and low bio degradability. Advanced oxidation process constitutes a promising technology for the treatment of wastewaters containing non-easily removable organic compounds. Several electro chemical processes are based on mediated electro chemical oxidation. The present study envisages the utility of electro-fenton and photo-fenton process for the degradation of parachlorophenol from aqueous solution by the electro oxidation under acidic condition. Experiments were carried out under batch recirculation conditions with stainless steel as cathodes and RuO2 coated titanium expanded mesh as anodes. Electrolysis was carried out with various current densities and flow rate using mediated electro chemical oxidation process with fenton mediator (Fe2+ / Fe3+ + H2O2). Extent of dehydration and reduction in COD was studied as a function of applied current, electrolysis time and concentration of ferrous ion. The electrolysis was carried at optimised conditions to achieve efficiencies higher than 80%.