Portugaliae
Electrochimica Acta

Three quaternary ammonium bromides were investigated as mild steel corrosion inhibitors in 1 M HCl. Two investigation methods were applied: electrochemical impedance spectroscopy (EIS) and polarization resistance (Rp method). The experimental impedance data showed capacitance frequency distribution, which imposed the introduction of a constant phase element, instead of a pure capacitance. Adequate structural models were advanced, to describe the interfacial processes. The models parameters values were determined. The resistance values found by impedance spectroscopy were compared to those of the polarization resistance provided by the Rp method. The inhibition efficiency of the investigated compounds was evaluated by both applied methods. The comparison of the investigated compounds’ protective properties outlined the best among them.

Catechol, which underwent electrochemical oxidation to produce o-benzoquinone, as Michael acceptor, taking part in a nucleophilic attack by dimethylamine, has been studied in an aqueous solution, with various pH values, different electrodes and different dimethylamine concentrations, using cyclic voltammetry, controlled potential coulometry and differential pulse voltammetry. The participation of o-benzoquinone reaction with dimethylamine, at higher nucleophiles concentrations, in the second potential’s scan, was observed. The products generated from the reaction were assumed to be 4-(dimethylamino)benzene-1,2-diol, which underwent electrons transfer at more negative potentials than those from catechol. Catechol pH effect, in dimethylamine presence, was studied by varying pH values from 3 to 9. The reaction was strongly influenced by pH, as well as by dimethylamine concentration. The reaction was mostly favorable in 150 mM of dimethylamine and 2 mM of catechol in a neutral medium. In both acidic and basic conditions, the reaction was not favored, due to amine protonation and hydroxylation. The reaction mechanism was of the ECE type, followed by the diffusion process.

The electrocatalytic property of electrode materials is the key for getting high cell current and low overvoltage of a fuel cell from fuels electro-oxidation. The bridge between laboratory scale fuel cell development and its fully commercialization is the development of inexpensive but energetic electrode materials. The catalytic actions of an electrode substrate are strongly influenced by the morphology and the grain fineness of the deposited materials. The present investigation aims at finding the effect of electrode deposition mode viz. direct current and pulse current coating, to produce an electrodeposited substrate that can deliver the highest current in a direct ethanol fuel cell. Nickel (Ni) is one of such non precious materials which has been produced through electro synthesis by both pulse current (PC) and direct current (DC) coating. It has been found that the morphology of the deposited is highly influenced by the current density, duty cycle, electrolyte chemistry and right selection of deposition potential on the cathodic polarization curve around the Tafel lines. Electrochemical characterization has been done by cyclic voltammetry (CV), chronoamperometry (CA) and potentiodynamic polarization (PD) studies. The substrate of the electrodeposited material has also been characterized by X-Ray Diffraction analysis (XRD), Energy Dispersive X-Ray Analysis (EDXA) and Scanning Electron Microscope (SEM). It has also been found that the electro synthesis by pulse current coating at pre-selected deposition potential, right at the end of Tafel region, at 40 ºC temperature and 150 second deposition time, gives the highest delivering current of ethanol fuel oxidation.

The inhibiting effect of Ailanthus altissima aqueous extract, as a corrosion inhibitor for Zn in a 0.5 M HCl solution, has been evaluated by weight loss (WL), hydrogen evolution (HE), potentiodynamic polarization (PP), electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. Obtained results showed that this extract offered good protection against Zn corrosion, and exhibited high inhibition efficiencies. The IE was found to increase with an increasing extract dose. Results revealed that this extract acted as a mixed-type inhibitor, and adsorbed onto the Zn surface following Temkin isotherm. Obtained results were justified from the study of surface morphology.

This paper deals with the theory and kinetics of oxalic acid electrochemical oxidation, in an acidic solution containing sodium chloride, using a manganese dioxide rotating cylinder anode. Voltammetric and galvanostatic electrolysis techniques were used. The voltametric study shows a higher anodic wave corresponding to chlorine oxidation on the MnO2 electrode, prevailing oxalic acid indirect oxidation. Galvanostatic electrolysis studies confirmed that the rate constant is affected by chloride concentration, current density, agitation and temperature. Electrochemical oxidation rate was found to be a pseudo-first order kinetic process. A strongly linear relationship between the rate constant and chloride concentration was observed, while polynomial relations, with respect to current density and temperature, were found. The activation energy was found to be 14.541 kJ/mol, which suggests a diffusion control kinetic step in oxalic acid degradation. The findings of the present research validate that oxalic acid incineration can be successfully carried out on a MnO2 anode, in NaCl presence.

Thymus Sahraouian essential oil (TSEO), as a new corrosion eco-friendly inhibitor, has been used to protect mild steel in 1 M HCl. Weight loss, three potentiodynamic polarization methods (Tafel, Stern and Stern-Geary), and electrochemical impedance spectroscopy measurements were undertaken to evaluate corrosion inhibition by TSEO. TSEO acted as an efficient corrosion inhibitor for mild steel in 1 M HCl, and its inhibition efficiency increased with a concentration of 77.82 % at 2 g L-1. The polarization curves revealed that TSEO acted as a mixed type inhibitor, with predominant anodic action. The EIS studies were fitted to a suitable equivalent circuit model, at 293 K, only reflecting a one-time constant characteristic of a charge transfer process. Besides, the higher is the temperature the lowest is the inhibiting efficiency. The kinetic parameters were in favour of an electrostatic character of TSEO components adsorption onto the mild steel surface, and adsorption followed the Langmuir isotherm model. Micrographic scanning electron microscopy and energy dispersive X-ray spectroscopy analyses confirmed the formation of a protective adsorbed film upon the mild steel surface.

Conducting polypyrrole was synthesized, and applied with a paint coating on a low carbon steel sample. By using linear polarization technique, the corrosion rates of uncoated and painted low carbon steel samples, in 3.5 wt% NaCl, were determined, and found to be 5 mpy and 0.1 mpy, respectively. The uncoated and conducting polypyrrole coated steel samples were immersed in a simulated carbonated concrete pore solution, and electrochemical studies were carried out. The shift of corrosion potential in the positive direction implies that the polypyrrole coating gives corrosion protection to low carbon steel, in the anodic direction. As compared to uncoated low carbon samples, polypyrrole coated low carbon steel samples exhibited higher impedance values, but their corrosion resistance decreased with increasing chloride ions in a carbonated pore solution.

This work investigates the effectiveness of the ethanol extract of Phyllanthus amarus (EEPA) as a possible green corrosion inhibitor for aluminum in a HCl solution, using weight loss, linear and potentiodynamic polarization methods, in order to evaluate the inhibition efficiencies of the plant extract, at various concentrations. Scanning electron microscopy and Fourier transformed infra red spectroscopy were used to study the surface morphology and engagement of functional groups in the corrosion inhibition process. The results obtained at 303 K from weight loss, linear polarization resistance and potentiodynamic polarization methods recorded an inhibition efficiency that ranged from 56.65 to 69.17, 65.00 to 93.93 and from 51.38 to 79.96 %, respectively. Generally, the inhibition efficiency increased with higher concentrations, but decreased with a rise in temperature. The potentiodynamic study revealed that EEPA acted as a mixed type inhibitor, and formed an insoluble film, which protected the metal against corrosion. Examination of micrographs in the inhibitor presence and absence also confirmed the role of the protective film in blocking the corrosion active sites on the metal surface. Spectra analysis obtained from Fourier transformed infra-red study indicated that EEPA was adsorbed onto the aluminum surface via C=O and OH functional groups. The inhibitor adsorption was spontaneous, exothermic, and supported the physical adsorption mechanism. Calculated quantum chemical parameters for EEPA constituents revealed that Phyllanthusin D is the most active corrosion inhibitor in the compound. HOMO and LUMO diagrams of Phyllanthusin D supported the findings from FTIR analysis.

In the present work, we present the first study about the effect of Chamaerops humilis L. extract on the behavior of reinforcement steel in a carbonated concrete pore solution (pH≈9). This study has been realized using electrochemical measurements: open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS). The phytochemical screening was used to reveal the presence of some phyto-constituents in the plant extract. The Folin–Ciocalteu method and the AlCl3 coloration were used to determine the total phenolic and flavonoid contents, respectively. Results show that the plant extract has a beneficial effect on the development of a passive layer. The extract plays an important role in the corrosion potential evolution, and in the polarization resistance increase. The inhibition efficiency of the plant extract is close to 60% at a concentration of 0.75 g/L. Corrosion parameters also changed with exposure time.

The goal of our work is to develop, study, characterize and apply new epoxy macromolecular matrices in the coating process, and to optimize them in the conservation of marine heritage. Epoxy resins are technologically and nano-technologically compatible thermosetting macromolecule matrices, which are easy to use, thanks to their structures and viscosimetric and rheological properties, able to protect the heritage subject to atmospheric corrosion. In this paper, we tested the synthesized, crosslinked and formulated novel macromolecular nanoglycidyl trihydrazine 4,4,4-tripropoxy ethylene tribisphenol A (NGTHTPETBA), used as an anti-corrosive coating for E24 steel in 3.5% NaCl. In order to evaluate the inhibiting performance of the NGTHTPTBAE coating for E24 steel corrosion, and to examine its coating behavior, we applied the different E1(NGTHTPETBA/MDA) and E2(NGTHTPETBA/MDA/PN) formulations. The stationary and transient electrochemical studies are very revealing.

Benzyl dimethyl dodecyl ammonium chloride-zinc ion system, as quaternary ammonium salt (QA-Zn+2), was investigated as corrosion inhibitor for carbon steel in a 2.0 M sodium chloride solution, by different techniques such as weight loss, open circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopic techniques. The inhibition efficiency of the used system (QA-Zn+2) increases with increasing mixed inhibitor concentrations and with rising temperatures. A synergistic effect exists between QA and Zn+2. Potentiodynamic polarization curves indicate that the used system mainly acts as an anodic mixed inhibitor. The polarization resistance values were (Rp) increased, and the interface capacitance (Cdl) was decreased in the mixed inhibitor system (QA- Zn+2) presence, more than in the case of individual inhibitors. The corrosion inhibition is due to the adsorption of (QA-Zn+2) onto the metal surface, and the formation of a barrier film that separates the metal from the corrosive medium. The maximum inhibition efficiency of 98% was obtained at 200 QA and 50 ppm Zn+2 of the mixed inhibitor system, due to a synergistic effect.

The inhibitive action of Piper guineense (uziza leaf) extract on the corrosion of mild steel in a 2 M H2SO4 medium has been studied using weight loss method. The collected leaf samples were rigorously grounded and squeezed, with the resultant gel extract used for the weight loss determination at 1.0%, 2.0%, 3.0%, 4.0% and 5.0% v/v concentrations, respectively. Therefore, rectangular mild steel coupons in a 2 M H2SO4 solution were also employed to determine the amount of weight loss in the absence and presence of Piper guineense extract at temperatures of 303 K, 313 K and 323 K. The results show that mild steel corrosion inhibition increases with increasing concentrations of Piper guineense extract, showing greater efficiency at higher temperatures of 313 K and 323 K. Moreover, Piper guineense extract can effectively perform as a green and non-toxic inhibitor for mild steel corrosion in acidic environments.

Concrete is one of the most commonly used construction materials, but there is a need to develop a new and sustainable technology to make it more affordable. With the advancement in technology, concrete is no longer seen as a composite of three elements (binder, aggregate, and water). The distinctive workability properties of SCC make it unique in the concrete industry. This review has assessed the materials, strength and rheological properties of agricultural waste, industrial waste and mineral additives in SCC production. The effect of the utilization of these additives and replacements on structural, mechanical and rheological properties of SCC has been studied. This review has revealed that the use of both industrial and agricultural waste enhances the strength properties of SCC. Additionally, the use of agricultural waste improves the rheological properties of fresh concrete. The utilization of expansive materials should be discouraged in SCC production. This review has revealed that SCC developments ensure a good balance between deformability and stability. It is therefore recommended that SCC is utilized in pavement construction, particularly when high axle load is expected.

In this study, Fenton, photo-Fenton, electro-Fenton, anodic oxidation and heterogeneous photocatalysis advanced oxidation processes (AOPs) have been applied to degrade reactive yellow 17 (RY17) dye in an aqueous solution. Comparison of these techniques for oxidation efficiency was undertaken. The results showed better performance with the use of a heterogeneous photocatalysis process. Degradation efficiency was observed in the order: heterogeneous photocatalysis > photo-Fenton = electro-Fenton > anodic oxidation > Fenton. Even though complete RY17 dye degradation has been observed with heterogeneous photocatalysis, photo-Fenton and electro-Fenton processes, the heterogeneous photocatalysis process has showed complete RY17 dye removal within 30 min, whereas in the case of photo-Fenton and electro-Fenton processes, no RY17 was detected after 60 min. Fenton and anodic oxidation processes have required more time for complete RY17 degradation. The RY17 degradation kinetics was studied and compared in all processes. The results showed higher rate constant values for heterogeneous photocatalysis (kapp = 0.2 min−1), photo-Fenton (kapp = 0.126 min−1) and electro-Fenton (kapp = 0.122 min−1) processes.

The chemical composition of Jatropha curcas seeds oil was determined using chromatography gas (GC/MS) analysis after the esterification of fatty acids to methyl ester (FAME). The obtained results show that the average yield of Jatropha curcas seeds oil reached a maximum value of 50%. The seeds oil fatty acids carbon chain was composed of palmitic, oleic and linoleic acids. The percentage of unsaturated fatty acids reached a value of 77%.The new developed formulation containing Jatropha curcas seeds oil (labeled as JAC) was tested as a friendly iron corrosion inhibitor in an acidic medium by potentiodynamic polarization and Electrochemical Impedance Spectroscopy (EIS) techniques. The surface analysis was performed using Scanning Electron Microscopy (SEM). The electrochemical measurements show that the JAC formulation is a mixed type inhibitor. The obtained inhibition efficiency results increase with higher inhibitor concentrations, to attain a maximum value of 97% at 250 ppm. Furthermore, the protective effect is reinforced by increasing the immersion time and the rotation speed of the working electrode.

Experimental electrochemical methods, combined with Monte Carlo simulations, have been employed to investigate the possibility of using 1-decyl-2-(decylthio)-1H-benzimidazole (T2) as corrosion inhibitor for mild steel in a 1 M HCl medium. This inhibitor was found to be of the mixed type. The results derived from EIS indicate that the charge transfer resistance has increased with the increase in the inhibitor concentration. The inhibitory mechanism was explored by the potential of zero charge (Epzc) measurement at the solution/metal interface. The inhibitor adsorption has followed Langmuir adsorption isotherm. Surface morphology results showed the compound adsorbed film on a mild steel surface. The molecule interactions with the mild steel surface were simulated based on Monte Carlo simulation approach using Fe(111) crystal surface as a representative metallic surface.

An expired drug with non-toxic characteristics has been evaluated as a corrosion inhibitor for mild steel alloy. The corrosion inhibition efficiency of the expired ethambutol drug in a 0.5 M HCl solution has been studied using weight loss, electrochemical impedance spectroscopy (EIS), electrochemical polarization, scanning electron microscopy (SEM) and molecular dynamics (MD) techniques. The results showed that the drug provides appreciable inhibition efficiency, more than 95% at the higher concentration, i.e., 1000 ppm. The Tafel polarization plots have shown that the expired drug acted as a mixed type inhibitor. Langmuir adsorption isotherm, along with physiochemical mode of interaction, has proved that the corrosion inhibition process accords with the isotherm. The outcomes obtained from all the experimental techniques and theoretically obtained information are in good correlation. MD simulations reveal that the studied compound adsorbs onto the surface of mild steel in the planar orientation.

Essential oil of Juniperus phoenicea (Cupressaceae) is extracted from the natural plant collected in Morocco. Extracted by distillation, its inhibiting action on the corrosion of mild steel in 1 M acidic media has been investigated by weight loss and various electrochemical techniques. Obtained results reveal that this naturally occurring substance is a very good inhibitor. The inhibition efficiency was found to increase with the oil content, attaining 83% at 1500 ppm. The oil of Juniperus phoenicea acts as a mixed-type inhibitor. The adsorption isotherm and the thermodynamic data of adsorption and activation are herein determined and discussed.

The purpose of our work is to improve the corrosion and mechanical shocks resistance of aluminium in the batteries, we have chosen tin as an element of addition by combining it with the aluminum and forming an Al-Sn alloy. By means of potentiodynamic polarization, electrochemical impedance spectroscopy, hardness evolution and optical microscopy, we have been able to study the effect of the tin addition on the corrosion of aluminum in NaCl as well as on its hardness and crystalline structure. We have also studied the influence of the electrolyte’s concentration in the battery (NaCl) and of temperature on the corrosion resistance of aluminum. The results obtained showed that the addition of tin have reduced significantly the corrosion rate of aluminum and increase its hardness. This means that the lifetime and the performance of the battery will be increased as well.

The objective of our work is to study, develop, characterize and apply a new epoxy macromolecular matrix in coatings, and their optimization for the conservation of marine heritage. Epoxy resins are technologically and nano-technologically compatible thermosetting macromolecule matrices that are easy to implement, according to their structures, viscosimetric and rheological properties, for the protection of the heritage possibly subject to atmospheric corrosion. In this sense, we have tested the new macromolecular binder, hexaglycidyl ethylene of methylene dianiline (HGEMDA), crosslinked and formulated for studying the behavior of steel coatings in a marine environment. In order to evaluate HGEMDA coating performance, we have studied its adsorption behavior onto the surface of corroded steel, and explained the interactions between the coating macromolecule and the steel surface. The coating effect on E24 steel was studied by quantum chemical calculations. The adsorption of HGEMDA onto the surface of E24 steel has been well described by the Quantitative Structure of Relation Property model (QSPR). The stationary and transient electrochemical studies are very interesting, since the prediction of the coating behavior was performed by the semi-empirical PM6, DFT methods and the method of three Becke compounds of parameter (UB3LYP), based on 6-311 G. All our calculations were performed using Gaussian software (03).