Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and Co–Ni alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co–Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdO _x in methanol. The kinetics of the hydrogen evolution reaction (HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade^–1 for the Tafel slope, suggesting that the HER follows the Volmer–Heyrovsky mechanism. The values of exchange current density (i _o) are in the range 1–10 mA cm^–2 for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i _o) and energy transfer coefficient () have been calculated by employing a nonlinear least square-fitting program.     

双电层电容器用沥青焦基活性炭的制备工艺条件对其孔结构及电化学性能的影响

以沥青焦为原料，KOH为活化剂在不同的工艺条件下制备了双层电容器用活性炭电极材料。分别考察了活化剂用量、活化时间、以及加入Cu、Ni催化活化等工艺条件对活性炭孔结构及作为双电层电容器电极的电化学性能的影响。结果表明：在实验范围内增加KOH用量及活化时间，活性炭的比表面积和比电容增加，比电容最高达到247F／g。添加Cu、Ni催化活化后活性炭的比表面积及比电容增加，高功率放电性能明显改善。     

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.     

Model reference adaptive impedance control in Cartesian coordinates for physical human–robot interaction

In this paper, a nonlinear model reference adaptive impedance controller is proposed and tested. The controller provides asymptotic tracking of a reference impedance model for the robot end-effector in Cartesian coordinates applicable to rehabilitation robotics or any other human–robot interactions such as haptic systems. The controller uses the parameters of a desired stable reference model which is the target impedance for the robot’s end-effector. It also considers uncertainties in the model parameters of the robot. The asymptotic tracking is proven using Lyapunov stability theorem. Moreover, the adaptation law is proposed in joint space for reducing the complexity of its calculations; however, the controller and the stability proof are all presented in Cartesian coordinates. Using simulations and experiments on a two DOFs robot, the effectiveness of the proposed controller is investigated.     

Development and characterization of silicone/phosphorus modified epoxy materials and their application as anticorrosion and antifouling coatings

Epoxy resin is chosen for our present study owing to its exceptional combination of properties such as easy processing, high safety, excellent solvent and chemical resistance, toughness, low shrinkage on cure, good electrical, mechanical and corrosion resistance with excellent adhesion to many substrates. This versatility in formulation made epoxy resins widely applied for surface coatings, adhesives, laminates, composites, potting, painting materials, encapsulant for semiconductor and insulating material for electric devices. There are numerous paint/coating systems based on epoxy resin available for corrosion and fouling prevention. They however are not completely satisfactory in field applications, where high corrosion, fouling and flame resistance are required. The demand for epoxy resin as corrosion/fouling resistant coatings is restricted mainly due to its inferior characteristics like poor impact strength, high rigidity, and moisture absorbing nature besides inadequate flame retardant properties. It is for this reason that silicones and phosphorus-based compounds are used as modifier in this work by intercrosslinking network mechanism (ICN) to obtain epoxy resin with desired properties ideally suitable for field applications for preventing corrosion and fouling with flame retardantancy. The present work involves the development of solvent free silicone/phosphorus modified epoxy coating systems, since solvent free coating systems are widely used for numerous applications due to their lower cost per unit film thickness, freedom from fire and pollution hazard and ability to provide better performance. For the development of coating systems, epoxy resin (X) serves as base material, hydroxyl terminated polydimethylsiloxane (HTPDMS) as modifier, γ-aminopropyltriethoxysilane (γ-APS) as crosslinking agent and dibutyltindilaurate (DBTDL) as catalyst. Polyamidoamine (A), aromatic amine adducts (B) and phosphorus-containing diamine (C) were used as curing agents. The study also describes the evaluation of corrosion resistant behaviour of unmodified epoxy and siliconized epoxy coatings by potentiodynamic polarization method, electrochemical impedance spectroscopy (EIS), salt-spray and antifouling tests. The results are discussed.     

Electrochemical investigation of LiNi0.5Mn1.5O4 thin film intercalation electrodes

This work provides kinetic and transport parameters of Li-ion during its extraction/insertion into thin film LiNi_0.5Mn_1.5O₄ free of binder and conductive additive. Thin films of LiNi_0.5Mn_1.5O₄ (0.2 μm thick) were prepared on electronically conductive gold substrate utilizing the electrostatic spray deposition technique. High purity LiNi_0.5Mn_1.5O₄ thin film electrodes were observed with cyclic voltammetry, to exhibit very sharp peaks, high reversibility, and absence of the 4 V signal related to the Mn³⁺/Mn⁴⁺ redox couple. The electrode subjected to 100 CV cycles of charge/discharge delivered a capacity of 155 mAh g⁻¹ on the first cycle and sustained a good cycling behavior while retaining 91% of the initial capacity after 50 cycles. Kinetics and mass-transport of Li-ion extraction at LiNi_0.5Mn_1.5O₄ thin film electrode were investigated by means of electrochemical impedance spectroscopy. The apparent chemical diffusion coefficient (D_app) value determined from EIS measurements changed depending on the electrode potential in the range of 10⁻¹⁰-10⁻¹² cm² s⁻¹. The D_app profile shows two minimums at the potential values close to the peak potentials of the corresponding cyclic voltammogram.     

On the observation of inductive high-frequency impedance behaviour during the electrodeposition of Au—Sn alloys

Inductive high-frequency impedance behaviour is often observed in metal electrodeposition systems. This behaviour is typically attributed to equipment limitations or non-idealities in the cell set-up and electrical connections. Such instrumental artefacts would nevertheless be relevant to a frequency range which is expected to be well above that in which inductive behaviour is in fact observed (down to a few tens of Hz). In this paper some results on an acidic Au—Sn electrodeposition system are reported. Electrochemical impedance and potentiostatic transients were measured. These results suggest that the high-frequency inductive behaviour may be related to metal nucleation processes. A correlation is proposed between the pseudo-inductive potentiostatic nucleation transients and the pseudo-inductive behaviour of the impedance spectra.     

The Effect of Aluminum Ions on the DC Etching of Aluminum Foil

A study has been made of the electrochemical etching of 99.99% aluminum foils at a current density of 50 mA cm^–2in AlCl₃–HCl solutions (1 m Cl^–) at 80 °C. The solutions were made by dissolving metallic aluminum into 1m HCl solution, to give a Cl^– concentration of 1 m. The number density of etch tunnels and the homogeneity of tunnel length decreased, and the mean pit size and its standard deviation increased with increasing Al³⁺ concentration. The results were discussed based on potential transients at a current density of 50 mA cm^–2, current–potential curves at a scan rate of 10 m Vs^–1 and electrochemical impedance spectra.     

Electrochemical anticorrosion performance evaluation of Al2O3 coatings deposited by MOCVD on an industrial brass substrate

Alumina (Al₂O₃) coatings of different thickness were deposited on OT59 brass substrate (BS) using the metal organic chemical vapour deposition (MOCVD) technique to evaluate the corrosion performance by EIS measurements. The used precursor was dimethyl-aluminium-isopropoxide. Electrochemical characterizations of the deposited films were performed in a standard very aggressive acidic solution (aerated 1N H₂SO₄ at 25 °C up to 168 h of immersion time) by means of direct current method (Tafel curves) and electrochemical impedance spectroscopy (EIS). The Rutherford backscattering spectroscopy (RBS) indicated that the films are very pure with the correct Al₂O₃ stoichiometry, while the IR absorption spectra showed that the films did not contain any OH groups. The surface film morphology was investigated by atomic force microscopy (AFM) and displayed a globular texture. The films were very smooth, with a maximum root mean square roughness, for example, of 14 nm for a 0.96 μm thick coating. The EIS data confirmed, as expected, that a 2.40 μm Al₂O₃ layer ensures the best corrosion protection after 168 h of immersion in the very acidic environment used.     

Passivation and pitting corrosion of nanostructured Sn-Ni alloy in NaCl solutions

The passivation and pitting corrosion of tin-nickel alloy (34% Ni-66% Sn) in NaCl solution was studied using potentiodynamic, cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques complemented by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of concentration of the chloride ion, the switching potential, scans rate and pH on the electrochemical behavior of Sn-Ni alloy is discussed. The data indicate that the corrosion rate and the pitting corrosion of Sn-Ni alloy increases by the increasing of chloride ion concentration. The observed corrosion resistance of electrodeposited Sn-Ni alloy is due to the formation of a thin passive film from tin and nickel oxides.