Corrosion control of Cu-Ni alloys in neutral chloride solutions by amino acids

The corrosion inhibition of Cu-Ni alloys was investigated in aqueous chloride solutions using amino acids as environmentally safe materials. The corrosion rate was calculated in absence and presence of the corrosion inhibitor using polarization and impedance techniques. The inhibition efficiency of the different amino acids was also calculated.The experimental results have shown that a simple amino acid like glycine can be used as efficient corrosion inhibitor for the Cu-Ni alloys in neutral chloride solutions. An inhibition efficiency of about 85% could be achieved at very low concentrations of the amino acid (0.1 mM). For low Ni content alloy (Cu-5Ni), 2.0 mM cysteine shows a remarkable high (∼96%) corrosion inhibition efficiency. The experimental impedance data were fitted to theoretical data according to a proposed equivalent circuit model for the electrode/electrolyte interface, and the mechanism of the corrosion inhibition process was suggested. Different adsorption isotherms were tested and the corrosion inhibition process was found to depend on the adsorption of the amino acid molecules and/or the deposition of corrosion products on the alloy surface. The adsorption free energy of cysteine on Cu-5Ni (−37.81 kJ mol⁻¹) reveals a strong physical adsorption of the inhibitor on the alloy surface.     

In situ impedance study of the Y-Ni thin film under electrochemical hydrogenation

A thin film of yttrium Y (150 nm) protected by a 6 nm coating of nickel Ni on a glass substrate was completely hydrogenated in a 1 M NaOH electrolyte at a constant negative current until the transparent Y tri-hydride phase was achieved and hydrogen gas evolution from the electrode began. A series of impedance measurements were performed in situ during the electrochemical experiment to study the properties of the system as dependent on hydrogenation degree and time of relaxation. The equivalent electrical circuit (EEC) simulations were performed with a Randles-like scheme R₀[R₁CPE₁], where R₀ is the thin film electrode resistance, R₁ the charge transfer resistance and CPE₁ is the capacitive constant phase element. The behavior of all the components of the EEC undergoes a clear transition when the hydrogenation degree of the electrode is approximated to its maximum value (H to Y ratio 2.7) and electrochemical process changes from hydrogen uptake to hydrogen evolution.     

Polymeric sol–gel coatings as protective layers of aluminium alloys

Sol–gel route is an emerging technology to synthesize coatings of a wide variety of properties taylored. In this work three low temperature cured coatings has been studied to evaluate their protective properties in order to be used as protective barrier coatings for aluminium alloys with potential architectural and automotive applications. These three coatings are novel modified silane nanocomposites coatings obtained mixing two sols separately prepared: a pre-hydrolysed 3-glycidyloxypropyl trimethoxysilane (GPTS) with acidic catalyst and another obtained from tetraethylorthosilicate/methyltriethoxysilane (TEOS/MTES). Particulated coatings were obtained by addition of 25 wt.% particles of Aerosil 300 and Aerosil R972, respectively. The protective properties of the coatings were evaluated by electrochemical impedance spectroscopy (EIS) which showed notably differences among them not only from the protective viewpoint but the hydrophobic nature of the coatings and the controlling corrosion mechanism in each case.     

Dielectric loss and phase transition of sodium potassium niobate ceramic investigated by impedance spectroscopy

The dielectric permittivity of Na_0.80K_0.20NbO₃ ceramic was investigated by impedance spectroscopy. The dielectric characterization was performed from room temperature to 800 °C, in the frequency range 5 Hz–13 MHz. The bulk permittivity was derived by the variation of the imaginary part of the impedance as a function of reciprocal angular frequency. The permittivity values as a function of temperature showed two maxima. The first maximum is very similar at 200 °C and the second one positioned at around 400 °C, which was associated to Curie’s temperature. The evolution of the complex permittivity as a function of frequency and temperature was investigated. At low frequency dispersion was investigated in terms of dielectric loss. The Na_0.80K_0.20NbO₃ showed a dissipation factor between 5 and 40 over a frequency range from 1 to 10² kHz.     

Mechanism of hydrogen adsorption/absorption at thin Pd layers on Au(1 1 1)

Hydrogen adsorption and absorption at thin palladium deposits of 0.8-10 monolayers (ML) on Au(1 1 1) was studied in 0.1 M H₂SO₄ and HClO₄ using cyclic voltammetry, ac voltammetry, and impedance spectroscopy in the absence and in the presence of poison, crystal violet. Hydrogen adsorption on palladium is more reversible in sulfuric acid than in perchloric acid but it occurs at potentials 30 mV more positive in latter. The charge-transfer resistance exhibits a minimum at ∼0.27 V versus RHE and decreases with increasing in Pd deposit thickness in both acids. Adsorption capacitance at 0.8 ML Pd reaches maximum at the same potential. At other deposits the pseudo-capacitance starts to increase at lower overpotentials indicating the beginning of absorption, even at 2 ML Pd. The double layer capacitance is similar for all the deposits in sulfuric acid and it has a sharp maximum at 0.27 V versus RHE. In perchloric acid a broad maximum is observed. Crystal violet inhibits hydrogen adsorption but makes hydrogen absorption more reversible. The results suggest a fast direct hydrogen absorption mechanism that proceeds in parallel with slower hydrogen adsorption and indirect absorption.     

Multiply subtractive Kramers-Kronig relations for impedance function of concrete

The impedance function of concrete is considered and multiply subtractive Kramers-Kronig relations and sum rules are given for the impedance function. It is proposed that multiply subtractive Kramers-Kronig relations provide better convergence, and thus increase the reliability of numerical analysis of impedance of concrete than the conventional Kramers-Kronig relations.     

Characterization of self-assembled monolayers of iron and cobalt octaalkylthiosubstituted phthalocyanines and their use in nitrite electrocatalytic oxidation

Cobalt and iron phenylthiosubstituted phthalocyanines have been deposited on Au electrode surfaces through the self-assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric and impedance techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of nitrite. The electrocatalytic parameters of the cobalt and iron phenylthiosubstituted phthalocyanines deposited on Au electrodes in nitrite solution were studied. Nitrite overpotentials which are lower than ever reported were obtained in this work for the iron phenylthiosubstituted phthalocyanines with very high stability.     

Investigation of mass transport in gas diffusion layer at the air cathode of a PEMFC

In a polymer electrolyte membrane fuel cell (PEMFC), slow diffusion in the gas diffusion electrode may induce oxygen depletion when using air at the cathode. This work focuses on the behavior of a single PEMFC built with a Nafion^® based MEA and an E-TEK gas diffusion layer and fed at the cathode with nitrogen containing 5, 10 and 20% of oxygen and working at different cell temperatures and relative humidities. The purpose is to apply the experimental impedance technique to cells wherein transport limitations at the cathode are significant. In parallel, a model is proposed to interpret the polarization curves and the impedance diagrams of a single PEMFC. The model accounts for mass transport through the gas diffusion electrode. It allows us to qualitatively analyze the experimental polarization curves and the corresponding impedance spectra and highlights the intra-electrode processes and the influence of the gas diffusion layer.     

Aging characteristics of high-power lithium-ion cells with LiNi0.8Co0.15Al0.05O2 and Li4/3Ti5/3O4 electrodes

The impedance rise that results from the accelerated aging of high-power lithium-ion cells containing LiNi_0.8Co_0.15Al_0.05O₂-based positive and graphite-based negative electrodes is dominated by contributions from the positive electrode. Data from various diagnostic experiments have indicated that a general degradation of the ionic pathway, apparently caused by surface film formation on the oxide particles, produces the positive electrode interface rise. One mechanistic hypothesis postulates that these surface films are components of the negative electrode solid electrolyte interphase (SEI) layer that migrate through the electrolyte and separator and subsequently coat the positive electrode. This hypothesis is examined in this article by subjecting cells with LiNi_0.8Co_0.15Al_0.05O₂-based positive and Li_4/3Ti_5/3O₄-based negative electrodes to accelerated aging. The impedance rise in these cells was observed to be almost entirely from the positive electrode. Because reduction products are not expected on the 1.55 V Li_4/3Ti_5/3O₄ electrode, the positive electrode impedance cannot be attributed to the migration of SEI-type fragments from the negative electrode. It follows then that the impedance rise results from mechanisms that are “intrinsic” to the positive electrode.     

Impedance spectroscopy study of hardened Portland cement paste

In this paper, the differential impedance analysis (DIA) has been applied to the study of the dielectric properties of hardened Portland cement paste. Two time constants are found in the impedance spectra obtained in the frequency region form 100 kHz to 15 MHz. One time constant has been attributed to the solid matrix and the other one to the liquid phase filling the pores. The effect of the cement paste-electrodes interface has been quantified using two different experimental set-ups. Measurements using direct contact between electrodes and cement paste have been compared with measurements using an air gap technique in which the specimen “floats” between the electrodes. The two referred time constants have been found in both types of measurements. The influence of drying on the dielectric parameters is also studied.