Portugaliae
Electrochimica Acta

The corrosion inhibition and adsorption of ethanol extracts of leaves (LV), stems (ST) and roots (RT) of Rotula aquatica plant for mild steel in H2SO4 solutions were investigated using conventional weight loss, gasometric techniques, electrochemical polarizations and electrochemical impedance spectroscopy. The results showed that all the three extracts of Rotula aquatica plant performed well as inhibitor for the corrosion of steel in sulphuric acid media and the inhibition efficiencies of the extract follow the trend RT > LV > ST. Inhibition efficiencies increased with increasing concentration of the plant extracts but decreased with the temperature rise for all cases. Both the cathodic hydrogen evolution and the anodic dissolution of mild steel were inhibited, hence the active molecules of all the extracts studied acted as mixed type corrosion inhibitors.

Electrochemical reduction of boron from boron containing fluoroborate species present in KCl (81.54 mol%)-KF (18.45 mol%)-NaBF4 (1.67x10-4 mol cm-4) melt on a platinum electrode was studied by cyclic voltammetry and chronoamperometry. These studies were carried out over the temperature range 1073 – 1123 K. Boron-containing electroactive species is shown to reduce quasi-reversibly at low scan rates (ν < 0.1 Vs-1) and irreversibly at higher scan rates (> 0.1 V s-1) through a single-step three-electron process (B(III) + 3e → B). The transfer and diffusion coefficients of the electroactive species were measured for sodium fluoroborate in KCl-KF melt over the temperature range 1073 – 1123 K.

Inhibition effect of poly 3-dodecyloxy aniline polymeric surfactant (PC12H) on the corrosion of aluminum in 0.5 M HCl solution was investigated using potentiodynamic polarization technique under different experimental conditions. Inhibition efficiency and thermodynamic functions for dissolution and adsorption of PC12H are compared with Poly 3-(dodecyloxy sulfonic acid) aniline (PC12SO3H) to explain the effect of terminal side chain on the corrosion protection. Data show that the presence of –SO3H as a terminal group in PC12SO3H decreases the inhibition efficiency from 88.7%, in case of PC12H, to 55.1% in case of PC12SO3H. Quantum chemical calculations were performed on PC12H and PC12SO3H to investigate the relationship between the molecular structures and their inhibition efficiencies.

The present article considers an experimental study of tribo-corrosion behavior of electroless Ni–P coatings in alkaline environment sliding against alumina. The study of wear and friction behaviour is carried out using different load and sliding speed with the help of a pin-on-disk tribometer. The wear rate increases with decrease in sliding speed and increase in the applied load. The friction coefficient initially decreases with increase in the applied load and then remains at nearly steady level at higher applied load. Also, it is found that the friction coefficient is lower at higher sliding speed. The friction coefficient does not change with the sliding duration after the initial transient running-in time. The coating is characterized using scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD) analysis. The wear mechanism is also studied and has been found to be mostly abrasive in nature.

The inhibitive effect of aqueous extract of leaves of Polyalthia longifolia on the corrosion of mild steel was studied using the gravimetric (weight loss) method at the temperatures 303 and 318 K. The results show that the aqueous extract of Polyalthia longifolia leaves inhibited the corrosion of mild steel in dilute H2SO4 solution. It was found that the inhibition efficiency increased with inhibitor concentration and decreased with rise in temperature. Values of the activation energy of the inhibited corrosion reaction range between 45.40 kJ/mol and 62.22 kJ/mol. This is much higher than the 25.74 kJ/mol obtained for the blank. The adsorption of the extract was spontaneous and occurs according to Flory-Huggins adsorption isotherm. The corrosion inhibition of Polyalthia longifolia leaves extract was attributed to the adsorption of phytochemical molecules present in the extract onto the surface of the mild steel. Physical adsorption mechanism has been proposed for the adsorption of the inhibitor.

An ion selective membrane sensor from dioctyl phthalate as a plasticizer in a polymeric matrix of polyvinyl chloride (PVC) and β-cyclodextrin as an ionophore was constructed and evaluated according to IUPAC recommendations. Linear Nernstian response of DPPH• within the concentration ranges of 10−6 to 10−2 mol L−1 was obtained with average recovery 99.87±0.617. Nernstian slope of 58.5 mV/decade with excellent selectivity over the pH range of 3-8 was observed. The suggested method was standardized using butylated hydroxyl anisole (BHA). The 50% radical scavenging activity (IC50) determined by the proposed sensor correlated well with that of the common spectrophotometric method based on scavenging of 2,2-diphenyl-1-picrylhydrazyl (DPPH•). An algorithm implemented in Microsoft Visual Basic® 6.0 was used for calculating (IC50) values which are 7.38 μg/mL ± 0.35, 89.98 μg/ mL ± 0.45 and 1.45 mg/ mL ± 1.50 for BHA, Paracetamol and Dipyridamole, respectively. The proposed sensor represents a simple and reproducible tool for measuring DPPH• scavenging activity of Paracetamol and Dipyridamole in bulk powder, pharmaceutical formulations and simulated intestinal fluid (SIF) without sophisticated separation techniques.

The inhibition effect of 2- amino, 5- ethyl- 1, 3, 4 thiadiazole (TTD) compound on the corrosion of type 304 stainless steel in 3 M H2SO4 test solution was investigated using potentiodynamic polarization, weight loss techniques and open circuit potential measurements. Results showed TTD to be very effective with an average inhibition efficiency of 98% from weight loss analysis and 87% from polarization test. Data from open circuit potential measurement are well within passivation potentials at specific concentrations of TTD. Scanning electron microscopy showed the effect of the inhibiting compound on the surface topography of the steel, while X - ray diffractometry determined the phase compounds formed on the surface due to inhibitor adhesion. Adsorption of the compound was determined to obey the Langmuir isotherm model. Thermodynamic calculations showed the inhibition process occurred through chemisorption mechanism and results from statistical analysis revealed the overwhelming influence of inhibitor concentration over exposure time on the inhibition performance of the compound.

Poly para aminophenol (PpAP)/Al2O3 composite was prepared by in situ chemical polymerization of para aminophenol using ammonium persulphate as an oxidizing agent in an aqueous medium containing anionic surfactants like DBSA (dodecyl benzene sulphonic acid) and SDS (sodium dodecyl sulphate) at 0 ˚C. The synthesized composites were characterized by UV–VIS-NIR spectroscopy, FTIR, XRD and TGA. The inhibiting effect of synthesized composites on the corrosion of mild steel in 1 M HCl solution has been investigated by different techniques like potentiodynamic polarization and electrochemical impedance spectroscopy methods for four different concentrations ranging from 50 to 300 mg/L. The results indicated that the corrosion inhibition efficiency increased on increasing composites concentration till 200 mg/L and decreased on further increasing concentration. It has been found that PpAP/Al2O3-DBSA has got higher corrosion protection efficiency than that of PpAP/ Al2O3-SDS. Polarization studies reveal that composites act as a mixed type corrosion inhibitor and adsorption follows Langmuir adsorption isotherm.

The electrochemical properties of rhodium(III) 1-3 and iridium(III) 4-6 complexes containing bis(pyrazolyl)alkane ligands [MCp*Cl(R2C(3,5-R’2pz)2)]X (M = Rh (1) or Ir (4), R = R’ = H, X = Cl; M = Rh (2) or Ir (5), R = H, R’ = Me, X = Cl; M = Rh (3) or Ir (6), R = Me, R’ = H, X = OTf; pz = pyrazolyl; Cp* =h5-C5Me5) were investigated by cyclic voltammetry and controlled potential electrolysis. They exhibit two sequential irreversible reductions assigned to the M(III) -> M(II) and M(II) ->M(I) reductions, which are dependent on the methylation of the bis(pyrazolyl)alkane ligands.

The inhibition performance of a non-oxidising surfactant, namely cetyl trimethyl ammonium bromide (CTAB), and its co-adsorption behaviour with zinc ion on carbon steel in well water was studied by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), weight loss, as well as atomic force microscopy (AFM) and scanning electron microscopy. Results indicated that the formulation acted as an anodic inhibitor. Adsorption of the used inhibitor led to a reduction in the double layer capacitance and an increase in the charge transfer resistance. A synergistic effect was also observed for the studied inhibitor with Zn(II) in weight loss measurements and electrochemical studies.

The inhibition effect of Mentha pulegium extract (MPE) on the acid corrosion of carbon steel in 1 M HCl solution was investigated using weight loss, potentiodynamic polarisation, and electrochemical impedance spectroscopy. The results show that the Mentha pulegium extract is a good inhibitor, and that the inhibition efficiency depends on the concentration of the plant extract. Efficiency is higher than 88 % for 33% Mentha pulegium extract. Polarization measurements also show that Mentha pulegium extract is a good mixed inhibitor. The remarkable inhibition efficiency of MPE was discussed in terms of blocking of the electrode surface by adsorption of inhibitor molecules through active centres. Mentha pulegium extract is adsorbed on the carbon steel surface according to the Temkin adsorption model. The effect of temperature on the corrosion behaviour of carbon steel in 1 M HCl with addition of 33% MPE was studied in the temperature range 308-338 K. SEM also confirmed the adsorption of MPE on carbon steel surface.

In this study polypyrrole (PPy) bilayers films were electrodeposited onto SAE 4140 steel. The inner layer was electropolymerized in the presence of molibdate and nitrate and the outer layer in a solution containing sodium bis (2-ethylhexyl) sulfosuccinate (AOT). The electrosynthesis was done under potentiostatic conditions. The corrosion protection properties of the films were examined in sodium chloride solution by open circuit measurements, linear polarization and electrochemical impedance spectroscopy (EIS). The bilayer coatings present an improved anticorrosive performance with respect to single PPy films.

Electroreduction properties of salicylic (SA) and acetylsalicylic (ASA) acids were investigated at platinum electrode using the voltammetry method. Cyclic voltammograms (CV) of the tested compounds were used in determining half-wave potential (E1/2) - the parameter describing the anti-reductive properties. The content of active substances (SA and ASA) in the selected pharmaceuticals (salicylic alcohol, Bayer aspirin, etopirin and polopirin) was examined with the application of electrochemical and spectrophotometric methods.

Examination of the physical (colour, odour, pH, solubility in various solvents) and chemical (GCMS and FTIR) characteristics of Ficus benjamina gum revealed that the gum is yellowish in colour, mildly acidic and ionic in nature. Major constituents of the gums were found to be sucrose and d-glucose, which constituted 60.92 % of their chemical constituents, while various carboxylic acids [(albietic acid (1.00%), hexadecanoic acid (4.41 %), 9-octadecanoic acid (1.00 %), octadecanoic acid (3.01 %), oleic acid (0.10 %), octadecanoic acid (9.12 %) and 6,13-pentacenequinone (20.43 %)] accounted for the remaining constituents. Functional groups identified in the gum were found to be those typical for other carbohydrates. From the knowledge of the chemical structures of compounds that constitute the gum, the corrosion inhibition potentials of the gum were ascertained and from weight loss analysis, the gum was found to be an active inhibitor against the corrosion of aluminum in solutions of tetraoxosulphate (VI) acid. The gum acted as an adsorption inhibitor that favours the mechanism of chemical adsorption and supported the Frumkin and Dubinin-Radushkevich adsorption models.

Electrochemical monitoring techniques were employed in this study to assess anticorrosion performance of Phyllanthus muellerianus leaf-extract on concrete steel-reinforcement in 0.5 M H2SO4, used for simulating industrial/microbial environment. For this, steel-reinforced concretes admixed with different concentrations of the natural plant leaf-extract were partially immersed in the acidic test-solution and subjected to electrochemical monitoring of corrosion potential, corrosion current and corrosion rate. Test responses analysed as per ASTM G16¬-95 R04, showed that the corrosion rate correlated, r = 84.93%, ANOVA p-value = 0.0403, with the leaf-extract concentration admixed in concrete and the ratio of the standard deviation of potential to the standard deviation of current. These identified the 0.3333% Phyllanthus muellerianus (per weight of cement) with optimum effectiveness at inhibiting steel-reinforcement corrosion both by the experimental model, η = 91.662.51%, and by the prediction from the correlation fitting model, η = 85.5414.44%. Fittings of both the experimental and the predicted data followed the Flory–Huggins and the Frumkin adsorption isotherms which suggest prevalent mechanism of physical adsorption (physisorption) of the extract on steel-rebar surface. These support the use of Phyllanthus muellerianus as environmentally-friendly admixture for inhibiting concrete steel-reinforcement corrosion in the industrial/microbial service-environment.

The influence of cathode material on the electrochemical degradation of methyl orange (MO), methylene blue (MB) and malachite green (MG) dyes was investigated. The cathode materials used were platinum (Pt), copper (Cu), zinc (Zn) and aluminum (Al). The electrochemical activity of the selected dyes on the metal cathodes was examined by cyclic voltammetry (CV). The electrochemical treatment was carried out in both divided and undivided cells. The degradation process was monitored by UV-Visible spectroscopy and chemical oxygen demand (COD) measurement. The influence of pH on discoloration and degradation of dyes was studied. The power consumption and current efficiency of the treatment process involving different cathode materials was computed and compared. The role of cathode material in the degradation of dyes has been established.

The degradation of Alizarin Red S by electro-generated species using Pt and BDD electrodes was performed. The results were explained by the generation of OH* radical, S2O82− at BDD electrode and active chlorine species at Pt electrode. The slow degradation is affected by the current density, initial pH, temperature, initial dye concentration and the nature of the supporting electrolyte. However, the ionic strength showed a negligible effect on both electrodes. In the presence of KCl, the intermediates produced during the degradation are similar at both electrodes. In the presence of sulfate (at BDD electrode), the rate and the mechanism of the degradation are different from those in the presence of KCl. TOC analysis showed total mineralization of AR S.

The perovskite BaPb0.9Sb0.1O3 was prepared through the ceramic route and, after being chemical, structural and electrochemically characterized, it was used in the electrochemical oxidation of guaiacol, using Na2SO4 as electrolyte, at current densities of 5 and 10 mA cm-2 and initial guaiacol concentrations of 50, 100 and 200 mg L-1. The guaiacol degradation was followed by UV-Visible absorbance measurements, Chemical Oxygen Demand (COD) tests and Dissolved Organic Carbon (DOC) analysis. The combustion efficiency was also determined. Results have shown COD removals between 40 and 85 % and DOC removals from 34 to 66 % after 120 h assays. The absolute COD and DOC removals increase with guaiacol initial concentration and applied current density. The mineralization tendency, measured as the combustion efficiency, was maximum for the applied current density of 10 mA cm-2 and a guaiacol initial concentration of 200 mg L-1.

The influence of 2,6-bis-(hydroxy)-pyridine (P1), 2,6-bis-(chloro)-pyridine (P2) and diethyl 1,1’-(pyridine-2,6-diyl)bis(5-methyl-1H-pyrazol2-3-carboxylate ( P3) on the corrosion of steel in 1 N HCl solution has been studied by weight loss measurements, potentiodynamic and impedance spectroscopy methods. The inhibiting action increases with the concentration of these compounds to attain 91,5% at 10-3 M for P3. We note good agreement between gravimetric and electrochemical methods. The polarisation measurements show also that the pyridines act essentially as mixed inhibitors and the cathodic curves indicate that the reduction of proton at the steel surface happens with an activating mechanism. The temperature effect on the corrosion behaviour of iron in 1 M HCl without and with these inhibitors at different concentrations was studied in the temperature range from 313 to 353 K, and allows deducing the apparent activation energy, enthalpy and entropy of the dissolution process and the free energy were determined and discussed. The inhibitors were adsorbed on the iron surface according to the Langmuir adsorption isotherm model at different temperatures and some thermodynamic data for the adsorption process are calculated. The experimental study has been finished by quantum theoretical study; the quantum chemical calculations, based on DFT methods at B3LYP/6-31G** level of theory, were performed, by means of the GAUSSIAN 03 set of programs. Structural parameters, such as the frontier molecular orbital energies (EHOMO and ELUMO), gap of energy E, charge distribution, absolute hardness η and softens , fraction of electrons N transferred from pyridine molecules to steel, as well as electronic parameters such as Mulliken atomic populations have been determined. The objective of this quantum theoretical treatment is to attempt to find relationships between their molecular and electronic structures and inhibition efficiency.

The inhibition action of the Pyrazolone Derivative (PYR) on the corrosion of mild steel in 0.5 M sulphuric acid was investigated by weight loss, polarization, impedance and SEM. Results obtained revealed that PYR performed excellently as corrosion inhibitor with efficiency of 91% at 11 ppm at 298 K. Its adsorption on mild steel obeys Langmuir and Temkin isotherm. Polarization curves indicate that PYR behaves as mixed type. The value of ∆G°ads indicates the spontaneous physisorption of PYR. The SEM results confirm the presence of a protective surface layer over the mild steel surface. The reactivity of the compound was analysed through theoretical calculation.