In the present work, the inhibitive action of natural propolis on bronze corrosion in a weakly acidic solution containing Na2SO4 and NaHCO3 at pH 5 was evaluated using multiscale electrochemical techniques, namely potentiodynamic polarization, electrochemical impedance spectroscopy and scanning vibrating electrode technique measurements. The major constituents of propolis were identified by HPLC. Surface characterization was performed by SEM-EDX and AFM analysis. Experiments were performed as a function of the propolis concentration and immersion time in the corrosive electrolyte. The obtained results showed that propolis presents good anticorrosive properties on bronze, acting as a mixed-type inhibitor, but its protective effectiveness is time-dependent. The highest inhibiting efficiency of 98.9% was obtained in the presence of 100 ppm propolis, after about 12 h of exposure to inhibitor-containing electrolyte through the stabilization of Cu2O on the bronze surface. The inhibitive properties of propolis on bronze corrosion are likely due to the adsorption of its main constituents (flavonoids and phenolic compounds), through the oxygen atoms in their functional groups and aromatic rings, which have been evidenced by FT-IR spectra. The adsorption of propolis on bronze was found to follow Langmuir adsorption isotherm.
An oxadiazole derivative with functional groups favouring its adsorption on copper surface, namely 5-(4-Pyridyl)-1,3,4-oxadiazole-2-thiol, has been explored as potential inhibitor of copper corrosion in 3.5 wt.% NaCl. Electrochemical evaluation by electrochemical impedance spectroscopy, potentiodynamic polarization and SVET reveals inhibition efficiencies exceeding 99%. Surface microscopy inspection and spectroscopic analysis by Raman, SEM-EDX and XPS highlight the formation of a compact barrier film responsible for long-lasting protection, that is mainly composed of the organic molecules. Machine Learning algorithms used in combination with Raman spectroscopy data were used successfully for the first time in corrosion studies to allow discrimination between corroded and inhibitor-protected metal surfaces. Quantum Chemistry calculations in aqueous solution and Molecular Dynamic studies predict a strong interaction between copper and the thiolate group and an extensive coverage of the metal surface, responsible for the excellent protection against corrosion.
The dissolution of the main metals (Cu, Zn, Sn, Pb and Fe) found in waste printed circuit boards (WPCBs) was investigated by electrochemical corrosion measurements (potentiodynamic polarization and electrochemical impedance spectroscopy (EIS)) in different bromide-based systems that could be used as lixiviants in hydrometallurgical route of metals recovery. The analysis of the corrosion products was carried out by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. All measurements showed that the addition of bromine in the electrolyte favors to great extents the dissolution process of all studied metals as compared to bromine-free electrolytes. In the investigated experimental conditions, the highest dissolution rates of the metals were obtained in acidic KBr solution containing 0.01 mol/L bromine and they decreased in the following order: Zn >> Sn > Pb > Fe > Cu. The XRD and XPS chemical assessment allowed the identification of the dissolution products formed on the metallic surfaces after exposure to the electrolytes. They consisted mainly of oxides in the case of Cu, Zn, Sn and Fe, while the presence of PbBr2 was also noticed on the lead surface. Based on the results of EIS and surface investigations, several models explaining the corrosion behavior of the metals were proposed and discussed. The obtained results demonstrate that all studied metals could be successfully leached using brominated solutions, providing a viable alternative for the selective and efficient recovery of the base metals from WPCBs through a multi-step hydrometallurgical processing route.
The purpose of this study was to review the physicochemical characterization of Romanian honey and propolis and their antifungal effect on different strains. As an indicator of environmental pollution, lead exceeded the allowed limits in two study areas. The relationship between the acidity and electrical conductivity of polyfloral honey and the antioxidant activity with the total content of phenolics and flavonoids was investigated. The antifungal activity of 13 polyfloral honey and propolis samples from North-West and Central Romania and 12 samples from Alba County was investigated against six fungal strains: Aspergillus niger, Aspergillus flavus, Candida albicans, Penicillium chrysogenum, Rhizopus stolonifer, Fusarium oxysporum. All honey and propolis samples exhibited an antifungal effect. The most sensitive strains were P. chrysogenum and R. stolonifer for honey and P. chrysogenum and F. oxisporumn for propolis. A two-way analysis of variance was used to evaluate the correlations between the diameter of the inhibition zones for the strains and the propolis extracts. Statistical analysis demonstrated that the diameter of the inhibition zone was influenced by the strain type and the geographical origin of honey and propolis. Pearson’s correlation coefficient shows a significant positive linear relationship between the diameter of the inhibition zone and the flavonoid and phenol concentration of honey and propolis, respectively.
Electrochemical impedance spectroscopy (EIS) and SEM‐EDX observations were used to evaluate the inhibiting effect of four thiadiazole derivatives, i.e. 2‐mercapto‐5‐amino‐1,3,4‐thiadiazole (MAT), 2‐mercapto‐5‐methyl‐1,3,4‐thiadiazole (MMeT), 2‐mercapto‐5‐acetylamino‐1,3,4‐thiadiazole (MAcAT) and 2‐mercapto‐5‐phenylamino‐1,3,4‐thiadiazole(MPhAT) on the corrosion of naked and artificially patinated bronze surface exposed to an acidic solution (pH 3) that simulates a strongly polluted rainfall. For comparison reasons, the inhibiting effect of benzotriazole (BTA) was also examined. In an attempt to better understand the influence of solution pH on the adsorption of the thiadiazole derivatives and to correlate their structural and electronic characteristics with the experimental inhibition efficiencies, quantum chemical calculations were performed starting with thiadiazole and its protonated derivatives. Finally, a possible inhibition mechanism of the thiadiazole protonated species on bronze corrosion was proposed. It was concluded that MMeT and MAT allow the stabilization of the patina layer, leading to the protection of the bronze substrate and their effectiveness significantly increase with the immersion time.
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