Electrochemical and spectroscopic evidences of corrosion inhibition of bronze by a triazole derivative

The electrochemical behavior of the bronze (Cu-8Sn in wt%) was investigated in 3% NaCl aqueous solution, in presence and in absence of a corrosion inhibitor, the 3-phenyl-1,2,4-triazole-5-thione (PTS). The inhibiting effect of the PTS was evidenced for concentrations higher than 1 mM for the cathodic process whereas its effect was clearly seen with a concentration as low as 0.1 mM for the anodic process. A significant positive shift of the corrosion potential was also observed, and its inhibiting effect increased with both its concentration and the immersion time of the sample. From voltammetry and electrochemical impedance spectroscopy experiments, the inhibiting efficiency of the PTS was found to be in the 94-99% range for 1 mM concentration. Scanning electron microscopy and X-ray energy dispersion analysis of the specimen surface show the presence of sulphur on the surface. Raman micro-spectrometry study confirms the protective effect of the PTS in aqueous solution through three types of interactions with the electrode, namely the adsorption of the inhibitor in a flat configuration, the formation of copper-thiol molecules, and when copper is released, the formation of a polymeric complex.     

Protection of bronze covered with patina by innoxious organic substances

Cultural bronze artefacts are exposed in indoor or outdoor environment. They often suffer of a substantial alteration due to an increasing atmospheric pollution. In this work, we propose the use of some innoxious compounds as corrosion inhibitors of bronze objects covered with patina. The bronze used was Cu-6Sn (in wt.%). This composition was selected after a preliminary work on several archaeological bronzes found in Transylvania, Romania, dated from the Late Neolithic to Roman periods. First, an artificial patina was formed on Cu-6Sn bronze under potential regulation, in 0.2 g L⁻¹ NaHCO₃ + 0.2 g L⁻¹ Na₂SO₄ aqueous solution (pH 8), during 4 days. A pale blue to green patina was obtained and characterized using EDS and Raman spectroscopy. Then, four innoxious organic substances were examined as corrosion inhibitors: 5 mM 4-methyl-1-(p-tolyl)-imidazole (TMI), 10 mM 1-phenyl 4-methyl-imidazole (PMI), 1 mM 2-mercapto 5-R-acetylamino-1,3,4-thiadiazole (MAcT), 1 mM 2-mercapto 5-R-amino-1,3,4-thiadiazole (MAT), and for comparison 1 mM benzotriazole (BTA). The impedance spectra collected showed, for all of them, three depressed capacitive loops. On the basis of these capacitance values, these loops were allocated to the surface film with ionic conduction, the double layer capacitance with the charge transfer resistance, and the oxidation-reduction process involving the surface patina. TMI and MAcT were found to be efficient inhibitors though their performances are significantly lower than that of BTA.     

Preventive knock protection technique for stationary SI engines fuelled by natural gas

In a combined heat and power (CHP) plant, spark ignition engines must operate at their maximum power to reduce the pay back time. Because of environmental and economic concerns, engines are set with high compression ratios. Consequently, optimal operating conditions are generally very close to those of knock occurrence and heavy knock can severely damage the engine piston.There are two main protection techniques: the curative one commonly used by engine manufacturers and well documented in the literature and the preventive one based on a knock prediction according to the quality of the supplied gas. The indicator used to describe gas quality is the methane number (MN). The methane number requirement (MNR) of the engine is defined, for an engine set (spark advance, air-fuel ratio, and load), as the minimum value of MN above which knock free operation is ensured. To prevent knock occurrence, it is necessary to adapt the engine tuning according to variable gas composition. The objective of the present work is to validate the concept of knock preventive protection. First, a prediction of MNR according to engine settings (ES) is computed through a combustion simulator composed of a thermodynamic 2-zone model. Predicted MNR are compared to experimental results performed on a single-cylinder SI gas engine and show good agreement with numerical results (uncertainty below 1 point). Then, the combustion simulator is used to generate a protection mapping. At last, the knock preventive protection was successfully tested.     

Electrical Conductivity and Complex Impedance Analysis of Ba<Subscript>2</Subscript>CrMo<Subscript>0.8</Subscript>W<Subscript>0.2</Subscript>O<Subscript>6</Subscript> Double Perovskite

Electrical properties of Ba ₂CrMo_0.8W_0.2O₆ double perovskite were investigated using admittance spectroscopy technique. According to impedance analysis, the material was modeled by an electrical equivalent circuit. Such analysis proves the presence of relaxation phenomenon in the compound. We also found that ac conductivity follows the Jonscher universal power law. Conduction process is found to be dominated by the thermally activated small polaron (SPH). The activation energy values, inferred from dc conductivity and from the temperature dependence of relaxation time, are closed to each other. Such result indicates that conduction process and relaxation phenomenon are related to the same defect.     

Magnetic resonance imaging of multiple myeloma]

The possible involvement of lipid peroxidation (LPO) in the lead-induced inhibition of type I iodothyronine 5'-monodeiodinase activity (5'-D) has been worked out in chicken liver. Lead nitrate (1.5 mg per bird per day) for 30 days increased the lipid peroxidative process with a concomitant decrease in 5'-D activity in chicken liver. Also, a significant decrease in serum triiodothyronine (T3) concentration and an increase in serum thyroxine (T4) concentration were observed. The data suggest that lead-induced inhibition of type I 5'-D activity in chicken liver is mediated through the lipid peroxidative process.     

Determination of the combustion properties of natural gases by pseudo-constituents

This paper presents a methodology for a rapid determination of important natural gas combustion properties (lower heating value, Wobbe index and the stoichiometric air-fuel ratio) using easily detectable physical properties. It is possible to determine natural gas composition by measuring two physical properties and using specific ternary diagrams (CH₄-C₂H₆-C₃H₈ and CH₄-C₂H₆-N₂). The first part of the work deals with the selection of two physical properties from a group comprising thermal conductivity, refraction index, and speed of sound. Then, in the second part, a sensor using the best couple of physical property is used to determine the ternary pseudo-constituents of the gas mixture. The model and the sensor are applied to specific situations such as the online determination of LHV. The error on the combustion properties of natural gas is less than 1% over the gases considered in the present study and over about 20 typical gases supplied over Europe. The effect of small errors in the measurement of physical properties has also been highlighted.     

The inhibiting effect of 3-methyl 1,2,4-triazole 5-thione on corrosion of copper in 3% NaCl in presence of sulphide

The effect of sulphide addition to the corrosion of copper in 3% NaCl was studied. The concentration of sulphide was remained rather low, up to 10 ppm. The effect of sulphide to copper corrosion is controversial in the literature and worth to verify by means of various experimental techniques. The polarization curves, plotted from a potential close to the open circuit one to negative or to positive direction indicated a decrease of corrosion current density, explained in the literature by the protective effect of CuS. In contrast, a quartz crystal microbalance, with electro-deposited copper indicated the increase of corrosion rate with increasing sulphide ion concentration. The EIS measurements showed also an acceleration of corrosion rate by addition of sulphide ions in sodium chloride solution. It is concluded that the presence of sulphide ions in the seawater accelerates the corrosion of copper. To protect the copper structure from the corrosion in presence of sulphide as pollutants, the anticorrosion effect of a new molecule, 3-methyl 1,2,4-triazole 5-thione was examined. The action of this molecule results in the reduction of the both anodic and cathodic current density, and its inhibiting efficiency reached a value of 90% at the concentration of 10 mM.     

Evaluation of some non-toxic thiadiazole derivatives as bronze corrosion inhibitors in aqueous solution

The inhibiting effect of four innoxious thiadiazole derivatives (2-mercapto-5-amino-1,3,4-thiadiazole (MAT), 2-mercapto-5-acetylamino-1,3,4-thiadiazole (MAcAT), 2-mercapto-5-methyl-1,3,4-thiadiazole (MMeT) and 2-mercapto-5-phenylamino-1,3,4-thiadiazole (MPhAT)) on bronze corrosion in an aerated solution of 0.2 g L⁻¹ Na₂SO₄ + 0.2 g L⁻¹ NaHCO₃ at pH 5 was studied by potentiodynamic voltammetry and electrochemical impedance spectroscopy.The corrosion parameters determined from the polarisation curves indicate that the addition of the investigated thiadiazole derivatives decreases both cathodic and anodic current densities, due to an inhibition of the corrosion process, through the adsorption of thiadiazoles on the bronze surface. The inhibiting effect of the investigated organic compounds appears to be more pronounced on the anodic process than on the cathodic one and, except for the case MPhAT, it is enhanced by the increases of the inhibitors’ concentration.The adsorption of the thiadiazole derivatives on bronze was confirmed by the presence of the nitrogen atoms in the EDX spectra of the bronze exposed to inhibitor-containing solutions.The magnitude of polarisation resistance values and, consequently, the inhibition efficiencies are influenced by the molecular structure of thiadiazole derivatives. The strongest inhibition was noticed in the presence of compounds with phenyl amino- or amino-functionalities in their molecules. The maximum protection efficiencies were obtained by addition of: 5 mM MAT (95.9%), 1 mM MAcAT (95.7%), 5 mM MMeT (92.6%) and 0.1 mM MPhAT (97%). EIS measurements also revealed that the inhibitor effectiveness of the optimal concentrations of thiadiazole is time-dependent.