Effect of oxide film on oxygen reduction current for the platinum-cobalt alloy electrodes in PEFC

Effect of surface oxide on Pt-Co alloy electrodes on the oxygen reduction reaction (ORR) was investigated in 0.5 M sulfuric acid solution by electrochemistry, ellipsometry, laser Raman scattering spectroscopy, and XPS. The oxide as thick as 1-2 nm increases the overpotential of ORR and falls down efficiency of PEFC. The thickness of the oxide films is precisely determined by ellipsometry. The oxide film 1.9 nm thick was formed on Pt-50 mol% Co electrode by constant potential oxidation at 1.20 V and the film 1.5 nm thick remains on the electrode at 0.6 V at which ORR already starts. The remaining oxide decreases the current density of ORR and increases the overpotential. On pure Pt electrode, the similar influence of the oxide film was observed.     

Corrosion and corrosion inhibition of Cu-20%Fe alloy in sodium chloride solution

The electrochemical behavior of copper (Cu), iron (Fe) and Cu-20%Fe alloy was investigated in 1.0 M sodium chloride solution of pH 2. The effect of thiourea (TU) addition on the corrosion rate of the Cu-20%Fe electrode was also studied. Open-circuit potential measurements (OCP), polarization and electrochemical impedance spectroscopy (EIS) were used. The results showed that the corrosion rates of the three electrodes follow the sequence: Cu < Cu-20%Fe < Fe. Potentiostatic polarization of the Cu-20%Fe electrode in the range −0.70 V to −0.45 V (SCE), showed that iron dissolves selectively from the Cu-20%Fe electrode surface and the rate of the selective dissolution reaction depends on the applied potential. At anodic potential of −0.45 V, thiourea molecules adsorb at the alloy surface according to the Langmuir adsorption isotherm. Increasing thiourea concentration (up to 5 mM), decreases the selective dissolution reaction and the inhibition efficiency η reach 91%. At [TU] > 5 mM, the dissolution rate of the Cu-20%Fe electrode increases due to formation of soluble thiourea complexes. At cathodic (−0.6 V), the inhibition efficiency of thiourea decreases markedly owing to a decrease of the rate of the selective dissolution reaction and/or desorption of thiourea molecules. The results indicated that thiourea acts mainly as inhibitor of the selective dissolution reaction of the Cu-20%Fe electrode in chloride solution.     

The influence of the conditions of the ZrO2 passive film formation on its properties in 1 M NaOH

In this paper, results of the potentiodynamic-potentiostatic formation of a homogeneous, passive films of ZrO₂ onto a Zr electrode in 1 M NaOH solution at different potentials (2.0, 4.0, 6.0 and 8.0 V vs. SCE) are presented. The properties of such films were investigated by EIS measurements at different potentials. After fitting the EIS spectra by an appropriate equivalent circuit, the capacitance (C_pf) and resistance (R_pf) of these films were determined. All films were found to become insulators at the potentials equal and/or more positive than 2.0 V, with their thicknesses increasing linearly with the potential from about 7 nm at 2.0 V to about 20 nm at 8.0 V. In the potential range 0.8 V < E < 2.0 V a transition from a semiconducting to insulating behaviour has been recorded for all films (except for the one formed at 2.0 V). The donor densities (N_sc) for all films, as well as their flat band potentials (E_fb) and their thicknesses of the space charge layer (d_sc), were determined from the corresponding Mott-Schottky plots (MS) recorded in the potential range (0.0 V < E < 0.8 V), where all films behaved as n-type semiconductors.     

Passivation oxide film on Nd-Fe-B permanent magnets in borate buffer solution by ellipsometry

The passivation of Nd-Fe-B permanent magnet was investigated in neutral borate solution at pH 8.4. The thickness of the passive oxide film on the magnets was measured by ellipsometry and the composition was estimated by glow discharge optical emission spectroscopy (GD-OES).The passivation of the magnets takes place in the potential range between −0.2 and 1.0 V vs. Ag/AgCl/Sat. KCl. In the potential range, current density decays to the lower than 10⁻⁶ A cm⁻² after potentiostatic oxidation for 1800 s. The passive oxide film growth is assumed to be optically simulated from a model with a homogeneous film with complex refractive index, N = 2.1 − j0.086. The thickness estimated from the refractive index linearly increases with potential from 3.6 nm at −0.2 V to 7.8 nm at 1.0 V. The passive film growth follows the ionic migration model under high electric field, i.e., the Cabrera-Mott growth model. The ionic conductivity estimated from the model is about κ = 1.7 × 10⁻¹⁶ Ω⁻¹ cm⁻¹. The passive oxide film is preferentially composed of iron oxide/hydroxide. Boron and neodymium are, respectively, concentrated at the surface of the oxide film and at the inner layer in the oxide film.     

Self-healing mechanism of a protective film prepared on a Ce(NO3)3-pretreated zinc electrode by modification with Zn(NO3)2 and Na3PO4

Self-healing mechanism of a protective film against corrosion of zinc at scratches in an aerated 0.5 M NaCl solution was investigated by polarization measurements, X-ray photoelectron spectroscopy (XPS) and electron-probe microanalysis (EPMA). The film was prepared on a zinc electrode by treatment in a Ce(NO₃)₃ solution and addition of aqueous solutions containing 9.98 or 19.9 μg/cm² of Zn(NO₃)₂ · 6H₂O and 55.2 μg/cm² of Na₃PO₄ · 12H₂O. After the coated electrode was scratched with a knife-edge crosswise and immersed in the NaCl solution for many hours, polarization measurements, observation of pit formation at the scratches, XPS and EPMA were carried out. This film was remarkably protective and self-healing against zinc corrosion on the scratched electrode. The cathodic and anodic processes of zinc corrosion were markedly suppressed by coverage of the surface except for scratches with a thin Ce₂O₃ layer containing a small amount of Ce⁴⁺ and the surface of scratches with a layer composed of Zn₃(PO₄)₂ · 4H₂O, Zn(OH)₂ and ZnO mostly.     

Multicycle chronoammetry of RRDE in the investigation of the anodic oxide formation

The method of multicycle chronoammetry of RRDE makes it possible to obtain separately the partial currents of metal electrode ionization, anodic oxide formation and chemical oxide dissolution. The method is tested for Ag∣Ag₂O∣OH⁻(H₂O) system. In the range of low anodic potentials (0.48 ÷ 0.51 V) the process of active silver dissolution prevails; the phase formation current rapidly drops. At higher potentials (0.52 ÷ 0.53 V) the phase formation current prevails and noticeably exceeds the rate of the chemical oxide dissolution. The thickness of Ag₂O film rapidly increases; and the net phase formation current is close to 100%.     

Effect of bias voltage on microstructure and properties of Ti-doped graphite-like carbon films synthesized by magnetron sputtering

Ti-doped graphite-like carbon (GLC) films with different microstructures and compositions were fabricated using magnetron sputtering technique. The influence of bias voltages on microstructure, hardness, internal stress, adhesion strength and tribological properties of the as-deposited GLC films were systemically investigated. The results showed that with increasing bias voltage, the graphite-like structure component (sp² bond) in the GLC films increased, and the films gradually became much smoother and denser. The nanohardness and compressive internal stress increased significantly with the increase of bias voltage up to −300 V and were constant after −400 V. GLC films deposited with bias voltages in the range of -300--400 V exhibited optimum adhesion strength with the substrates. Both the friction coefficients and the wear rates of GLC films in ambient air and water decreased with increasing voltages in the lower bias range (0--300 V), however, they were constant for higher bias values (beyond −300 V) . In addition, the wear rate of GLC films under water-lubricated condition was significantly higher for voltages below −300 V but lower at high voltage than that under dry friction condition. The excellent tribological performance of Ti-doped GLC films prepared at higher bias voltages of −300--400 V are attributed to their high hardness, tribo-induced lubricating top-layers and planar (2D) graphite-like structure.     

Prevention of passive film breakdown and corrosion of iron in 0.1 M KClO4 with and without Cl by covering with an ultrathin two-dimensional polymer coating and healing treatment in 0.1 M NaNO3

A two-dimensional polymer coating, the self-assembled monolayer of 16-hydroxy hexadecanoate ion HO(CH₂)₁₅ modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃ was prepared on the passivated iron electrode and further, the passive film was healed by additional treatment in 0.1 M NaNO₃. This electrode was immersed in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ to 1 × 10⁻² M of Cl⁻. Protection of passive film against breakdown by covering the electrode with the polymer coating was examined by monitoring the open-circuit potential during immersion in the solutions for many hours to determine the time for passive film breakdown, t_bd. Repeated polarization measurements were carried out during immersion in these solutions for obtaining the protective efficiency, P. The t_bd value of the passivated, polymer-coated and healed electrode in 0.1 M KClO₄ solutions with and without Cl⁻ increased with a decrease in the concentration of Cl⁻. No breakdown occurred on the electrode during immersion in 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ of Cl⁻ for 360 h. The P values were extremely high, more than 99.9% before t_bd, indicating complete protection of iron from corrosion. The effect of healing treatment in 0.1 M NaNO₃ on passive film breakdown was investigated by electron-probe microanalysis.     

Influence of fluoride ion on the electrochemical behaviour of β-Ti alloy for dental implant application

The corrosion behaviour of Ti-15Mo alloy in 0.15 M NaCl containing 0.01, 0.03, 0.06 and 0.5 M NaF is evaluated and its protective ability is compared with that of CP-Ti and Ti-6Al-4V alloy, to ascertain their suitability for dental implant application. The steady state current density of CP-Ti and, Ti-15Mo and Ti-6Al-4V alloys in 0.15 M NaCl containing 0.03 M NaF at 200 mV vs. SCE is found to be 1, 2 and 6 μA/cm², respectively, which indicate that all of them could offer a better corrosion resistance in the potential range that could exists in the oral environment.     

Effects of pretreatment on the aluminium etch pit formation

The effect of chemical pretreatments on the electrochemical etching behavior of aluminium was investigated with the topographic studies of surface and the analysis of initial potential transients. Two-step pretreatments with H₃PO₄ and H₂SiF₆ result in a high density of pre-etch pits on aluminium surface by the incorporation of phosphate ion inside the oxide film and the removal of surface layer by aggressive fluorosilicic acid solution. It generates a high density of etch pits during electrochemical etching and results in the capacitance increase of etched Al electrode by expanding the surface area, up to 61.3 μF/cm² with the pretreatment solution of 0.5 M H₃PO₄ at 65 °C and 10 mM H₂SiF₆ at 45 °C.     

Determination of electrochemical parameters and corrosion rate for carbon steel in un-buffered sodium chloride solutions using a superposition model

Corrosion of carbon steel in un-buffered NaCl solutions was studied applying linear potential sweep technique to a rotating disk electrode. Current-potential curves were obtained from linear potential sweep at a rate of 1 mV s⁻¹ in solution with concentrations in the range 0.02-1 M NaCl and rotation rates in the range 170-370 rad s⁻¹, at 22 °C. Potential sweeps, which were conducted in the potential range −700 to −100 mV/SHE, were started from the cathodic limit in order to approach the measurement of corrosion under rust-free conditions. Polarization curves were analyzed with a superimposition model developed ad hoc and implemented in a computer program, which enabled determining the corrosion rate and kinetics parameters of the underlying anodic and cathodic sub-processes. The anodic sub-process, dissolution of iron, was well described in terms of a pure charge transfer controlled reaction, while the cathodic sub-process, oxygen reduction on iron, was well described in terms of mixed mass transfer and charge transfer control. Increase of electrode rotation rate increases the limiting current of oxygen reduction, which results in an enhanced corrosion rate of carbon steel. Increase of NaCl concentration has a dual effect: the limiting current of oxygen reduction decreases as a result of the influence of NaCl concentration on solution viscosity and the anodic dissolution of iron increases due to the influence of NaCl on pitting formation. However, this last mechanism predominates and a net increase in carbon steel corrosion rate is observed in this case.     

Hydrogen transport and embrittlement in 300 M and AerMet100 ultra high strength steels

This paper describes how hydrogen transport affects the severity of hydrogen embrittlement in 300 M and AerMet100 ultra high strength steels. Slow strain rate tests were carried out on specimens coated with electrodeposited cadmium and aluminium-based SermeTel 1140/962. Hydrogen diffusivities were measured using two-cell permeation and galvanostatic charging methods and values of 8.0 × 10⁻⁸ and 1.0 × 10⁻⁹ cm² s⁻¹ were obtained for 300 M and AerMet100, respectively. A two-dimensional diffusion model was used to predict the hydrogen distributions in the SSR specimens at the time of failure. The superior embrittlement resistance of AerMet100 was attributed to reverted austenite forming around martensite laths during tempering.     

Evidence of caffeine adsorption on a low-carbon steel surface in ethanol

Different electrochemical methods have been employed in order to confirm the ability of caffeine (1,3,7-trimethylxanthine) to adsorb to low-carbon steel in ethanol solutions and thereby inhibit the corrosion process. The interaction between the organic compound and the electrode surface was dependent on the electrode potential and the maximum interaction was observed at −0.30 V (Ag/AgCl). The presence of the organic compound adsorbed on a low-carbon steel electrode surface was confirmed by comparing the voltammograms, Tafel plots and EIS curves of the electrode in the absence and presence of caffeine. The standard free energy of adsorption confirms a spontaneous chemical adsorption step.     

Cathodic reduction of the duplex oxide films formed on copper in air with high relative humidity at 60 °C

The cathodic reduction of duplex air-formed oxide film on copper was performed at a constant current density of i_c = −50 μA cm⁻² in deaerated 0.1 M KCl solution to investigate the sequence of cathodic reduction of each oxide layer and its mechanism. The single-phase thick CuO film on copper was also cathodically reduced at i_c = −50 μA cm⁻² or −2.5 mA cm⁻². The surface characterizations of the air-formed oxide film and single-phase CuO film before cathodic reduction and after partial or complete cathodic reduction were performed by XPS and X-ray diffraction, respectively.The two plateau regions appeared in the potential vs. time curve during cathodic reduction of the duplex air-formed oxide film on copper, while one plateau region was observed in the potential-time curve during cathodic reduction of the single-phase CuO film on copper. The potential in the first plateau region for the air-formed film coincided with that in the plateau region for the CuO film. The results of XPS and X-ray diffraction suggested that in the first plateau region, the outer CuO layer is directly reduced to metallic Cu, while in the second plateau region, the inner Cu₂O layer is reduced to metallic Cu.     

Effect of underpotential deposition of lead on polarization behavior of nickel in acidic perchlorate solutions at room temperature

The effect of Pb²⁺ on polarization behavior of nickel has been investigated in 0.1 M NaClO₄ + 10⁻² M HClO₄ + x M PbO solutions (x = 0, 10⁻⁵, 10⁻⁴, 10⁻³) at room temperature. The cyclic voltammogram has suggested that Pb²⁺ degrades the stability of the passive film on Ni. The corrosion potential of Ni shifted to the more noble direction and the anodic current peak of Ni dissolution decreased with increasing Pb²⁺ concentration in solution, indicating that Pb²⁺ suppresses significantly the anodic dissolution. The underpotential deposition (UPD) of lead on Ni in the potential range more noble than −0.215 V (SHE) corresponding to the equilibrium potential of the Pb²⁺ (10⁻³ M)/Pb electrode was confirmed by XPS and GDOES analyses. The anodic Tafel slope, b⁺, of Ni dissolution changed from b⁺ = 40 mV decade⁻¹ in the absence of Pb²⁺ to b⁺ = 17 mV decade⁻¹ in the presence of 10⁻⁴ or 10⁻³ M Pb²⁺, which was ascribed to the increase in active sites of Ni surface emerged as a result of electrodesorption of Pb adatoms. The roles of Pb adatoms in active dissolution and active/passive transition of Ni were discussed from the above results.     

Corrosion prevention of passivated iron in 0.1 M NaCl by coverage with an ultrathin polymer coating and healing treatment in 0.1 M NaNO3

An ultrathin, ordered and two-dimensional polymer coating was prepared on a passivated iron electrode by modification of 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Subsequently, the electrode was healed in 0.1 M NaNO₃. Protection of passivated iron against passive film breakdown and corrosion of iron was examined by monitoring of the open-circuit potential and repeated polarization measurements of the polymer-coated and healed electrode in an aerated 0.1 M NaCl solution during immersion for many hours. Localized corrosion was markedly prevented by coverage with the polymer coating and the healing treatment in 0.1 M NaNO₃. Prominent protection of iron from corrosion in 0.1 M NaCl was observed before the breakdown occurred. The electrode surface covered with the healed passive film and polymer coating was analyzed by contact angle measurement, X-ray photoelectron spectroscopy and electron-probe microanalysis.     

Electrochemical studies of steel in cement mortar containing chloride and micro-silica

Steel electrodes have been exposed for 3.5 years in cement mortar with and without chloride and ELKEM micro-silica. Corrosion potentials in mortar without Cl⁻ varied between −0.1 and +0.06 V(SCE), indicating passivity. One percentage of cement weight of Cl⁻ reduced the corrosion potentials to about −0.2 V(SCE). Micro-silica in chloride containing mortar increased the severity of corrosion the first year. However, after 2 years exposure reduction of interconnected porosity and increased resistivity caused by 15% micro-silica, raised the corrosion potentials and counteracted chloride-attack.The polarisation resistance was undefined, the apparent values varying with the technique and parameters used.     

Surface characterization of passive film formed on nitrogen ion implanted Ti-6Al-4V and Ti-6Al-7Nb alloys using SIMS

The aim of this paper is to study the effect of N⁺ ion implantation on corrosion and phase formation on the implanted surfaces of Ti-6Al-4V and Ti-6Al-7Nb alloys. Nitrogen ion was implanted on Ti-6Al-4V and Ti-6Al-7Nb alloys at an energy of 70 and 100 keV, respectively using a 150 keV accelerator at different doses ranging from 5 × 10¹⁵ to 2.5 × 10¹⁷ ions/cm². Electrochemical studies have been carried out in Ringer’s solution in order to determine the optimum dose that can give good corrosion resistance in a simulated body fluid condition. The implanted surfaces of such modified doses were electrochemically passivated at 1.0 V for an hour. Secondary ion mass spectroscopy was used to study and characterize titanium oxide and titanium nitride layers produced on implanted surface and to correlate them with the corrosion resistance. The nature of the passive film of the implanted-passivated specimen was compared with the unimplanted-passivated as well as as-implanted specimens.     

Direct modification of a passivated iron electrode with alkyltriethoxysilanes for preventing passive film breakdown in a borate buffer containing 0.1 M of chloride ion

A passive film on an iron electrode was modified with alkyltriethoxysilanes directly. In order to examine the protective ability of the modified passive film against breakdown, the pitting potential, E_pit was measured by anodic polarization of the modified electrode in a borate buffer solution (pH 8.49) containing 0.1 M of Cl⁻. The value of E_pit for the modified electrode shifted in the positive direction from that of the unmodified electrode, indicating prevention of passive film breakdown. The modified passive film was not broken down in the passive and transpassive regions of polarization curve in some cases. However, many current spikes appeared in the all curves of the modified electrodes. The modified surface of passivated electrode was characterized by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement. There were defects and clusters of associated water within the modified film and hence, Cl⁻ could permeate through the defects, leading to appearance of current spikes and occurrence of breakdown.     

Polypyrrole electrodeposited on copper from an aqueous phosphate solution: Corrosion protection properties

Highly adherent and homogenous polypyrrole films were electrodeposited at copper from a dihydrogen phosphate solution. The polypyrrole films were electrosynthesized in the overoxidized state by cycling the copper electrode from -0.4 to 1.8 V (SCE) in a pyrrole-containing phosphate solution. The growth of the polypyrrole films was facilitated by the initial oxidation of the copper electrode in the phosphate solution to generate a mixed copper-phosphate, copper oxide or hydroxide layer. This layer was sufficiently protective to inhibit further dissolution of the copper electrode and sufficiently conductive to enable the electropolymerization of pyrrole at the interface, and the generation of an adherent polypyrrole film.Potentiodynamic polarization measurements, Tafel analyses and open-circuit potential data revealed that the polypyrrole coating effectively protects the copper substrate from corrosion in a chloride solution. However, the corrosion protection properties were reduced with longer immersion times.