Preparation of a 16-hydroxyhexadecanoate ion self-assembled monolayer on a zinc electrode coated with hydrated cerium(III) oxide

A self-assembled monolayer (SAM) of 16-hydroxyhexadecanoate ion was prepared on a zinc electrode coated with a hydrated cerium(III) oxide Ce₂O₃ layer. The protective efficiency, P of the duplex film composed of the Ce₂O₃ layer and the SAM was examined by polarization measurement of the zinc electrode in aerated 0.5 M NaCl. The P value of the HOC₁₆A⁻ SAM on the Ce₂O₃-coated electrode was only a little higher than that of the Ce₂O₃-coated one. The contact angle of the surface covered with the film with a drop of water was far higher than the value of the HOC₁₆A⁻ SAM on passivated iron, suggesting that HOC₁₆A⁻ was partly adsorbed on the Ce₂O₃ surface via both and OH groups in a looped orientation. Because this orientation must be changed to an extended orientation during immersion in 0.5 M NaCl, some defects appeared within the SAM in places, resulting in a poor enhancement of P. The film structure was characterized by X-ray photoelectron and FTIR reflection spectroscopies.     

Protection of zinc from corrosion by coverage with a hydrated cerium(III) oxide layer and ultrathin polymer films of a carboxylate self-assembled monolayer modified with alkyltriethoxysilanes

Ultrathin films of one- and two-dimensional polymers were prepared on a zinc electrode coated with a hydrated cerium(III) oxide Ce₂O₃ layer by modification of a 16-hydroxyhexadecanoate ion self-assembled monolayer (SAM) with alkyltriethoxysilanes. The protective efficiency, P of the film was determined by polarization measurements of the electrodes bare and covered with the polymer films in an oxygenated 0.5 M NaCl solution. The respective P values for the one-dimensional polymers of the HOC₁₆A⁻ SAM modified with octyltriethoxysilane C₈H₁₇Si(OC₂H₅)₃ (C₈TES) and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃ (C₁₈TES) were 94.4 and 95.1%. The values for the two-dimensional polymers of the HOC₁₆A⁻ SAM modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅)₃Si(CH₂)₂Si(C₂H₅)₃ plus C₈TES and C₁₈TES were 95.4 and 96.5%, respectively, indicating higher than those of the one-dimensional polymers. Structures of the polymer films were characterized by contact angle measurement with a drop of water and X-ray photoelectron and FTIR reflection spectroscopies.     

Self-assembled monolayers of carboxylate ions on passivated iron for preventing passive film breakdown

Self-assembled monolayers (SAMs) of carboxylate ions C_n−1H_2n−1CO₂⁻ (C_nA⁻) with the carbon number, n=12-18 and 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ (HOC₁₆A⁻) were prepared on an iron electrode previously passivated in a borate buffer at pH 8.49 by treatment in aqueous solutions of their sodium salts for many hours. Breakdown of the passive film on the electrode coated with the SAM was examined by anodic polarization measurement in the borate buffer containing 0.1 M of Cl⁻. The pitting potentials of the passivated electrodes coated with the SAMs of C_nA⁻ and HOC₁₆A⁻ shifted toward a more positive potential than that of the uncoated electrode, indicating prevention of passive film breakdown by blocking diffusion of Cl⁻ through the SAM to defects of the passive film. No breakdown was observed over the potential range of the passive region by coverage of the passive film with the SAM in some cases. The SAMs on the passive film were characterized by contact angle measurements and X-ray photoelectron and Fourier transform infrared reflection spectroscopies.     

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.     

Electrochemical behavior of tin in sodium borate solutions and the effect of halide ions and some inorganic inhibitors

The corrosion of tin electrode in sodium borate (Na₂B₄O₇) solutions was investigated using cyclic voltammetry and potentiostatic current transient techniques. In absence of halide ions, the E/j response exhibits active/passive transition. The active region involves one anodic peak corresponding to the formation of Sn(OH)₂ and/or SnO. Addition of Cl⁻, Br⁻ or I⁻ (C ? 0.01 M) ions inhibits the active dissolution of tin, but higher concentrations enhance the active dissolution and tend to breakdown the passive film and induce pitting attack. The effect of , , and as inorganic inhibitors on the pitting corrosion of tin in (0.1 M Na₂B₄O₇ + 0.1 M NaCl) solution has also been studied. The presence of these anions (except ) inhibits pitting corrosion. Chronoamperometry measurements showed that nucleation of pit takes place after an incubation time (t_i). The rate of pit nucleation () increases with increasing halide ions concentration and applied potentials, but decreases with increasing the concentration of the inorganic inhibitors (except ). The inhibition efficiency of these inhibitors decreases in the order:

     

Protection of passivated iron from corrosion in 0.1 M KClO4 with and without Cl by coverage with a two-dimensional polymer film of carboxylate ion self-assembled monolayer

A film of two-dimensional polymer was prepared on an iron electrode passivated in a borate buffer solution at pH 8.49, derivatized with 16-hydroxyhexadecanoate ion and then modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. The protective ability of the polymer film adsorbed on passivated iron was examined by polarization measurement in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ and 1 × 10⁻³ M of Cl⁻. The values of the open-circuit potential, E_oc were monitored with the immersion time, t in these solutions. The E_oc value of the passivated electrode in 0.1 M KClO₄ was maintained high, more than −0.2 V/SCE in the initial region of t up to 10 h, indicating the presence of a passive film on the electrode. Thereafter, E_oc decreased to −0.4 V/SCE abruptly, exhibiting breakdown of the passive film. The value of the passivated electrode covered with the polymer film remained almost constant around −0.04 V/SCE during immersion for 45 h. The protective efficiency, P (%) of the polymer film on passivated iron was extremely high, more than 99.9% unless the passive film was broken down, indicating complete protection of iron against corrosion. The times for breakdown on the passivated electrode and polymer-coated one diminished with an increase in the concentration of Cl⁻. The polymer-coated surface was analyzed by electron-probe microanalysis after immersion in 0.1 M KClO₄ for 24 h.     

Effect of the strain rate on stress corrosion crack velocities in face-centred cubic alloys. A mechanistic interpretation

Constant extension rate tests on smooth samples, with strain rate (SR) values from 10⁻⁶ s⁻¹ up to 20 s⁻¹, were used to study stress corrosion cracking (SCC) systems in face-centred cubic alloys. It was found that by increasing the SR a monotonic increase of the (crack propagation rate) takes place. It was also observed that the slope α in vs. plots had different values for different SCC morphologies. Intergranular SCC is more steeply accelerated by SR, α_IG=0.5-0.7, than transgranular SCC, α_TG=0.2-0.3. The differences found between intergranular SCC and transgranular SCC were analysed under the light of the available SCC mechanisms.     

Complete protection of a passive film on iron from breakdown in a borate buffer containing 0.1 M of Cl by coverage with an ultrathin film of two-dimensional polymer

An ultrathin film of two-dimensional polymer was prepared on a passivated iron electrode by modification of a 16-hydroxyhexadecanoate ion self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. This film prevented passive film breakdown examined by potentiodynamic anodic polarization of the coated electrode in the borate buffer solution containing 0.1 M of Cl⁻. Neither current spikes nor the pitting potential was observed in the passive and transpassive regions of polarization curve. The anodic current density was decreased in these regions markedly, implying hindrance to permeation of Cl⁻ and water through the film. Structure of the film was clarified by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement with a drop of water. Electron-probe microanalysis of the passivated surface coated with the film after anodic polarization scanning up to the transpassive region revealed that the polymer film prevents pit initiation by an attack on the passive film with Cl⁻.     

Prevention of passive film breakdown on iron in a borate buffer solution containing chloride ion by coverage with a self-assembled monolayer of hexadecanoate ion

Breakdown of a passive film on iron in a borate buffer solution (pH 8.49) containing 0.1 M of Cl⁻ was suppressed by coverage of the passive film surface with a self-assembled monolayer (SAM) of hexadecanoate ion C₁₅H₃₁CO₂⁻ (C₁₆A⁻). The pitting potential of an iron electrode previously passivated in the borate buffer at 0.50 V/SCE increased by treatment in an aqueous solution of sodium hexadecanoate for many hours, indicating protection of the passive film from breakdown caused by an attack on defects of the film with Cl⁻. No breakdown occurred over the potential range of the passive region by coverage with the SAM of C₁₆A⁻ in some cases. Structures of the passive film and the monolayer were characterized by X-ray photoelectron and Fourier transform infrared reflection spectroscopies and contact angle measurement with a drop of water.     

Breakdown of passive film on nickel in borate solutions containing halide anions

The effect of Cl⁻, Br⁻ and I⁻ anions as aggressive agents on the anodic behaviour of nickel electrode in deaerated Na₂B₄O₇ solutions have been investigated by galvanostatic polarization technique. Lower concentrations of the halide anions have no effect on the mechanism of nickel passivation. An increase in the halide anions concentration causes oscillation of the potential in the oxygen evolution region. This could be attributed to the destruction of the passivity by halide anions and repassivation of the film by anodic current and/or OH⁻ anions. Higher aggressive anion concentrations cause breakdown of the passive film and initiated pitting corrosion. As the temperature increases, the breakdown potential is shifted towards the more negative direction. On the other hand, as the pH of the solution increases, the breakdown potential is shifted toward more positive direction, indicating increased protection of the passive film. The activation energy, , of the oxide film formation in the presence of Cl⁻ anions was calculated and was found to be 21 kJ/mol.     

Preparation of a one-dimensional polymer film on passivated iron by modification of a carboxylate ion self-assembled monolayer with octyltriethoxysilane for preventing passive film breakdown

A self-assembled monolayer (SAM) of 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻(HOC₁₆A⁻) has been prepared on an iron electrode passivated in a borate buffer solution (pH 8.49) in the preceding paper. In this work, the HOC₁₆A⁻ SAM on the passivated electrode was modified with octyltriethoxysilane C₈H₁₇Si(OC₂H₅)₃ to form a film composed of one-dimensional polymer. Prevention of passive film breakdown was examined by anodic polarization measurements of the electrodes uncoated and coated with the modified SAM in the borate buffer containing 0.1 M of Cl⁻. The pitting potential, E_pit of the coated electrode shifted from that of the uncoated electrode in the positive direction, indicating prevention of passive film breakdown. The anodic current density was decreased in the passive and transpassive regions by coverage with the modified SAM. Neither current spikes nor E_pit was observed in the curve of the passive region in some cases, demonstrating complete protection of the passive film against breakdown in the Cl⁻ solution. The modified SAM on the electrode was characterized by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement.     

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.     

Improvement of healing treatment with NaNO3 for a passivated iron electrode covered with an ultrathin polymer coating to prevent iron corrosion in some solutions containing aggressive anions

An ultrathin and ordered polymer coating was prepared on a passivated iron electrode by modification of a 16-hydroxyhexadecanoate ion self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octyltriethoxysilane C₈H₁₇Si(OC₂H₅)₃. Further, the passivated and polymer-coated electrode was healed by treatment in 1.0 M NaNO₃ for 4 h. Prevention of passive film breakdown and iron corrosion for the passivated, polymer-coated and healed electrode was examined by monitoring of the open-circuit potential and repeated polarization measurements in oxygenated 0.1 M KClO₄, 0.1 M Na₂SO₄ and 0.1 M NaCl for many hours. The values of the time for passive film breakdown, t_bd were >240, 22.2 and 9.5 h in these solutions, respectively. The protective efficiencies for the electrode were extremely high, more than 99.9% before t_bd, indicating complete protection of substrate iron against corrosion in these solutions, unless passive film breakdown occurred. The presence of on the passive surface by treatment in 1.0 M NaNO₃ was detected by X-ray photoelectron and FTIR reflection spectroscopies. The self-healing activity of adsorbed to suppress passive film breakdown was discussed.     

Environmental factors affecting the corrosion behavior of reinforcing steel. IV. Variation in the pitting corrosion current in relation to the concentration of the aggressive and the inhibitive anions

The pitting corrosion current of reinforcing steel is measured under natural corrosion conditions in Ca(OH)₂ solutions in presence of Cl⁻ as aggressive ions and as inhibiting anions. The corrosion current starts to flow after an induction period which depends on solution composition (concentration, pH and presence or absence of the aggressive and the inhibiting anions). The limiting corrosion currents increase with increasing the Cl⁻ ion concentration and decrease with increasing the pH and inhibiting ions concentration. The inhibition efficiency of the studied inhibiting ions increases in the following order: , and depends on the way by which the inhibitor is added to the solution. Injection of the inhibiting anions in solution causes repassivation of the pre-formed pits through competition with Cl⁻ ions for adsorption sites on metal oxide surface. The adsorbability constant and the free energy of repassivation of the inhibiting anions are calculated.     

Inhibitive effect of diethylcarbamazine on the corrosion of mild steel in hydrochloric acid

Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), weight loss measurements and atomic force microscopy techniques were used to investigate the inhibitory effect of diethylcarbamazine (DECM) on corrosion of mild steel in HCl solution. The inhibitor showed >90% inhibition efficiency at 5.01 × 10⁻⁴ M. Results obtained revealed that inhibition occurs through adsorption of inhibitor molecules on metal surface without modifying the mechanism of corrosion process. Potentiodynamic polarization studies suggested that it is a mixed type inhibitor, predominantly controls cathodic reaction. Activation parameters (E_a, ΔH and ΔS) and thermodynamic parameters (, and ) were calculated to investigate mechanism of inhibition.     

Corrosion of niobium in sulphuric and hydrochloric acid solutions at 75 and 95 °C

New Pourbaix diagrams were calculated at 25, 75 and 95 °C for the Nb-H₂O system. The species and were considered. Potentiodynamic polarization and mass loss experiments (14 days) were conducted in concentrated H₂SO₄ (20, 40 and 80 wt%) and HCl (20 and 38 wt%) solutions at 75 and 95 °C. Nb forms a metastable pentoxide (Nb₂O₅) in H₂SO₄ and HCl solutions which dissolves as . Corrosion rates decrease between the 40% and the 80% H₂SO₄ solutions. SEM micrographs show generalized pitting in the 20% and 40% H₂SO₄ solutions. Mass loss corrosion rates did not exceed 306 μm/yr. Corrosion rates estimated by Tafel extrapolation were within two orders of magnitude of those measured by mass loss and it is shown that this finding is consistent with the thickening of the oxide.     

Preparation of a two-dimensional polymer film on passivated iron by modification of a carboxylate ion self-assembled monolayer with alkyltriethoxysilanes for preventing passive film breakdown

The effect of an ultrathin, regularly arranged polymer film on prevention of passive film breakdown on iron in the presence of chloride ion was investigated. The film of two-dimensional polymer was prepared by modification of a 16-hydroxyhexadecanoate ion self-assembled monolayer adsorbed on a passivated iron electrode with 1,2-bis(triethoxysilyl)ethane(C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octyltriethoxysilane C₈H₁₇Si(OC₂H₅)₃. The pitting potentials of the passivated electrodes bare and covered with the polymer film were determined by anodic polarization measurements in a borate buffer solution containing 0.1 M of Cl⁻. The pitting potential of the coated electrode was higher than that of the uncoated one, indicating prevention of passive film breakdown. No breakdown was observed over the potential range in the passive and transpassive regions by covering the passive film with the well-arranged two-dimensional polymer film. The film was characterized by X-ray photoelectron and FTIR reflection spectroscopies and measurement of the contact angle with a drop of water.     

Voltammetric current oscillations due to general and pitting corrosion of tantalum: Implications for electrochemical-mechanical planarization

Anodic corrosion of Ta is examined for potential applications in electrochemical-mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of (or Br⁻) to form mechanically weak surface-oxide films, followed by mechanical removal of the latter. The voltammetric currents exhibit oscillatory behaviour with frequencies that are signature attributes of localised pitting by Br⁻ or general surface corrosion by . SEM, voltammetry, and impedance spectroscopy are used to probe these corrosion mechanisms. Apart from their relevance for ECMP, the results also address certain fundamental aspects of pitting and general corrosion of valve metals.