Portugaliae
Electrochimica Acta

Abstract A new corrosion inhibitor, namely, 1H-1,2,4-triazol-4-amine, 3, 5-diphenyl-N-(phenyl methylene) (HTADP), has been synthesised, and its inhibiting action on ordinary steel corrosion in an acidic media has been investigated by weight loss and various electrochemical techniques. The obtained results revealed that this organic compound is a very good inhibitor. Its inhibition efficiency (IE) exceeded 90%, even at very low concentrations. HTADP was able to reduce steel corrosion more effectively in 1 M HCl. Potentiodynamic polarization studies showed that HTADP is a mixed type inhibitor, predominantly influenced by the cathodic process. The adsorption of this inhibitor onto the ordinary steel surface in 1 M HCl was found to follow the Langmuir’s adsorption isotherm. The adsorption and activation thermodynamic data were determined and discussed. A protective film was formed on the steel surface, which changed the processes at the metal-solution interface. Keywords: corrosion, steel, inhibition, adsorption and acidic media.

Abstract Mild steel (MS) corrosion inhibition by Terminalia mantaly (TM), in 1.0 M HCl, was studied using weight loss and linear polarization methods, at different reaction conditions. Gas chromatography-mass spectrometry (GC-MS) was used to determine the possible extract components. Fourier transformed infrared spectroscopy (FTIR) and optical microscopy were used to investigate the interaction of the plant extract phytochemicals with the MS surface. The obtained results revealed that the inhibition efficiency percentage (IE%) increased with a decrease in the TM concentration, and decreased with a rise in temperature (T). The IE% also decreased as the hydrochloric acid (HCl) concentration increased. Inhibition occurred through the TM phyto-molecules adsorption onto the MS surface. The corrosion inhibition kinetics followed a zero order reaction, and it was uni-molecular. The linear polarization showed that TM is a mixed-type inhibitor. Gibb’s free energies values confirmed a spontaneous process, while TM adsorption onto the MS surface was found to obey physisorption, aligning with the Langmuir’s and El-Awady’s adsorption isotherm models. Keywords: Terminalia mantaly, activation energy, corrosion, Gibb’s free energy, linear polarization and MS.

Abstract Ethylenediamine (EDA), diethylenetriamine (DETA) and N,N,N',N'-tetrakis (2-hydroxypropyl) ethylenediamine (THPrED) are used relatively often in galvanic processes. Tetra-substituted derivatives, such as N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine, (THEtED) are quite biologically stable and hardly degradable. In recent years, much attention has been devoted to electrochemical oxidation, using anodes with a high over-potential of O2 evolution, such as the boron-doped diamond (BDD). DETA and THPrED electrochemical treatment using a BDD anode was herein studied. The degradation efficiency of the amines was evaluated under different current intensities and reaction times. To determine the products formed in the oxidation process, ion chromatography (IC) was used. A high decrease in the current between the first and the second CV scan indicated the polymer film formation on the BDD electrode surface. Hydroxyl radicals formed at a potential of about 2 V and higher caused further oxidation of the electrode reaction products. It was found that NH4+, CH3-COOH, N2, EDA, CO2 and NO3- were formed in a short reaction time, and at low current intensity. The mineralization occurred during substrates electrolysis, due to rapid DETA and THPrED decomposition. After 180 min of reaction, αTOC and αN values for DETA were 94% and 18%, respectively. For THPrED, αTOC was 98.6% and αN was 43.6%. Therefore, the electrochemical approach was considered a very promising method in practical application for the treatment of wastewater containing amines. Keywords: EDA, DETA, THPrED, hydroxyl radicals, BDD anode, direct and mediated oxidation and mineralization.

Abstract A graphene oxide-triazole hybrid anti-corrosive coating was done by fabricating a triazole derivative – 2-(5-mercapto-4-((3-nitrophenyl)amino)-4H-1,2,4-triazol-3-yl)isoindoline-1,3-dione (4-NBT) on a graphene oxide (GO) coated Cu electrode. The GO-4-NBT hybrid coating effect on the Cu surface corrosion behavior was electrochemically monitored through cyclic voltammetry (CV), potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). The fabrication of a protective coating was done in two steps. Firstly, GO was electrochemically deposited on the Cu electrode in two different aggressive media (1 M HCl and 0.1 M Na2SO4), separately. Secondly, different 4-NBT concentrations were employed to reinforce GO corrosion resistant properties. CV studies revealed that GO-4-NBT effectively suppressed the metal oxidation and oxygen reduction. EIS studies suggested that the electrochemical process on the Cu surface with GO and GO-4-NBT was charge transfer controlled. The corrosion inhibition efficiency (IE) measured by PDP and EIS was enhanced with a related raise in 4-NBT concentration. Electrochemical studies revealed that the GO-4-NBT was a mixed type of inhibitor that predominantly inhibited the anodic reaction, especially in the case of 0.1 M Na2SO4. Adsorption studies further indicated the involvement of a stable and spontaneous adsorption mechanism, most probably by chemisorption. GO-4-NBT has shown significant corrosion protection activity in 0.1 M Na2SO4. Keywords: GO-4-NBT, Cu electrode, anti-corrosion coating, electrochemical studies by, PDP and EIS, and adsorption studies.

Abstract The use of pesticides has been increased in recent years, to enhance crops productivity, which may lead to a serious global concern of environmental pesticides monitoring. Isoproturon (IPU: 3-(4-isopropylphenyl)-1,1-dimethylurea) is an herbicide widely used in wheat crops. However, when it enters in the ecosystem, it is heavily toxic to humans. Thus, there is an urgent need to develop sensitive and selective IPU detection methods. In the present work, a novel polymethylmethacrylate/ferrite (PMMA/M(FexOy)) polymer nanocomposite (PNC) modified glassy carbon electrode (GCE) was developed for IPU detection. The PNC/GCE surface morphology was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). PNC electrochemical characterization (EC) was performed by cyclic voltammetry (CV) that showed a quasi-reversible redox behavior. PNC/GCE demonstrated an excellent square wave voltammetric (SWV) response towards IPU, with a limit of quantification (LOQ) of 1.98 × 10-7 M, and a limit of detection (LOD) of 6.5 × 10-8 M, in 1 M HClO4 (perchloric acid), at pH 2.0. EC investigations reflected a peak current that was linearly related to IPU concentrations, with a high detection sensitivity. It also showed much better CV and SWV IPU responses than those of a bare GCE, and further environmental stability, without a high influence of common interfering ions. Keywords: IPU, PPMA/M(FexOy), EC, CV and SWV.