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.     

Evaluation of the corrosion performance of coil-coated steel sheet as studied by scanning electrochemical microscopy

This work focuses on the investigation of the very early stages of the degradation of coil-coated galvanized steel sheet through swelling and blistering during exposure to chloride-containing aqueous solutions and the possible effect of the zinc-based metallic coating on the degradation at these very early stages. Three types of coil-coated steel whose difference was in the zinc-based metallic coating, namely galvanized, galfan and aluzinc, were considered. Scanning electrochemical microscopy (SECM) operating in the feedback mode was employed to image topographic changes when the samples were left at their spontaneous open circuit potential. Swelling of the coating and nucleation of blisters were observed for all the samples when they were exposed to naturally aerated 0.1 M KCl solution within 24 h exposure. Conversely, featureless and flat surfaces were found when the samples were either exposed to 0.1 M K₂SO₄ or to 10 mM KCl. For chloride concentrations of 0.1 M and above the chloride ions were observed to promote coating degradation nearly immediately upon immersion in the electrolyte.     

Electrochemical response of AlNiLa amorphous and devitrified alloys

The electrochemical response of Al_94−xNi₆La_x alloys (x = 4, 5, 6, 7) after different stages of devitrification was studied in 0.05 M Na₂SO₄ as well as in different concentrations [0.001 M, 0.01 M and 0.1 M] NaCl solutions. Complementary crystallization studies were carried out to elucidate the composition dependent phase evolution in these alloys. It was observed that the primary crystallization did not cause any deterioration in the corrosion resistance of the alloys as compared to the amorphous alloys. In the case of Al₈₇Ni₆La₇, there was actually an improvement in the passivating ability in benign media. The various primary crystalline phases in the different alloys investigated did not cause different electrochemical responses. However, the onset of secondary crystallization caused a reduction in the corrosion resistance in the NaCl media through a loss in passivating ability of all the alloys. This is due to increased galvanic activity as well as the loss of the amorphous phase.     

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.     

Corrosion behavior of Cr/Cu-coated Mg alloy (AZ91D) in 0.1 M H2SO4 with different concentrations of NaCl

An electroplating process was proposed for obtaining a protective Cr/Cu deposit on the two-phase Mg alloy AZ91D. The corrosion behavior of Cu-covered and Cr/Cu-covered AZ91D specimens was studied electrochemically in 0.1 M H₂SO₄ with different NaCl concentrations. Experimental results showed that the corrosion resistance of an AZ91D specimen improved significantly after Cr/Cu electrodeposition. The corrosion resistance of Cr/Cu-covered AZ91D decreased with increasing NaCl concentration in 0.1 M H₂SO₄ solution. After immersion in a 0.1 M H₂SO₄ with a NaCl-content above 3.5 wt.%, the surface of Cr/Cu-covered AZ91D suffered a few blisters. Cracks through the Cr deposit provided active pathways for corrosion of the Cu and the AZ91D substrate. Formation of blisters on the Cr/Cu-covered AZ91D surface was confirmed based on the results of an open-circuit potential test, which detected an obvious potential drop from noble to active potentials.     

An ultrathin polymer coating of carboxylate self-assembled monolayer adsorbed on passivated iron to prevent iron corrosion in 0.1 M Na2SO4

For preparing an ultrathin two-dimensional polymer coating adsorbed on passivated iron, a 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer (SAM) was modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Protection of passivated iron against passive film breakdown and corrosion of iron was investigated by monitoring of the open-circuit potential and repeated polarization measurements in an aerated 0.1 M Na₂SO₄ solution during immersion for many hours. The time required for passive film breakdown of the polymer-coated electrode was markedly higher in this solution than that of the passivated one, indicating protection of the passive film from breakdown by coverage with the polymer coating. The protective efficiencies of the passive film covered with the coating were extremely high, more than 99.9% in 0.1 M Na₂SO₄ before the passive film was broken down, showing prominent cooperative suppression of iron corrosion in the solution by coverage with the passive film and polymer coating. The polymer-coated surface was characterized by contact angle measurement and electron-probe microanalysis (EPMA). Prevention of passive film breakdown and iron corrosion for the polymer-coated electrode healed in 0.1 M NaNO₃ was also examined in 0.1 M Na₂SO₄.     

Electrochemical reactivity, surface composition and corrosion mechanisms of the complex metallic alloy Al3Mg2

A corrosion mechanism is proposed for Al₃Mg₂, based on electrochemical tests, XPS, and depth profiling using XPS and ToF-SIMS. After short (∼2 min) solution exposure, the surface consists of a surface film above dealloying. The dealloying is attributed to selective Mg dissolution and the surface rearrangement of Al into islands, although the metallic Al could alternatively be formed by two reduction reactions. The surface film thickness was ∼10 nm. After exposure to ultra-pure water, the composition was AlMg_1.3O_0.2(OH)_5.1 corresponding to Al(OH)₃·1.1 Mg(OH)₂·0.2MgO. After exposure to 0.01 M Na₂SO₄, the composition was AlMg_0.2O_0.4(OH)_2.5 corresponding to Al(OH)₃·0.1Al₂O₃·0.2MgO. Longer exposure produced a thicker surface film, more pronounced metallic Al islands and more MgH₂. Three possibilities are identified for MgH₂ formation. Al(OH)₃ formation is attributed to a precipitation reaction. Bulk nanoporous Al₃Mg₂ formation is predicted to be possible by Mg dealloying of Mg₁₇Al₁₂.     

Poly(N-methylaniline) coatings on stainless steel by electropolymerization

Poly(N-methylaniline) (PNMA) coatings have been electropolymerized on 304 stainless steel alloy by potentiodynamic, galvanostatic and potentiostatic synthesis techniques from aqueous solutions of 0.1 M N-methylaniline (NMA) and 0.3 M oxalic acid. Characterization of PNMA coatings was carried out by cyclic voltammetry, UV-Vis and FTIR spectroscopy techniques. Corrosion behavior of PNMA coated stainless steel electrodes was investigated using linear anodic potentiodynamic polarization, Tafel test, chronoamperometry and electrochemical impedance spectroscopy (EIS) techniques in 0.5 M aqueous HCl solutions. Corrosion test results showed that PNMA coatings possessed protection to uncoated stainless steel against corrosion.     

Corrosion behaviour of dc magnetron sputtered Fe1−xMgx alloy films in 3 wt% NaCl solution

Fe_1−xMg_x alloy films (with x ? 43.4 at.% Mg) were deposited by dc magnetron sputtering onto glass slide substrates. The objective of this study was to characterise the corrosion properties of these alloys in saline solution for application as new friendly environmentally sacrificial coatings in the protection of steel structures. The morphological and structural properties of the alloys were systematically studied prior to electrochemical experiments, and then the degraded surfaces were analysed to determine the composition and nature of corrosion products. Alloys with <25  at.% Mg were single-phase body-centred cubic (bcc) with enlarged lattice parameters, whereas for magnesium contents above 25 at.%, amorphisation occurred. The reactivity of the alloys in saline solution is strongly dependent on the Mg content and the alloy structure. The incorporation of magnesium leads to an open circuit potential shift of the alloy towards more negative values, that confers an attractive interest of these alloys as sacrificial coatings. A transition in corrosion activity is observed at 25 at.% Mg from which the reactivity decreases with the magnesium content increase. The evolution of the alloy corrosion behaviour is discussed in terms of structural and corrosion products evolution versus magnesium content.     

Corrosion behaviour of Cu-10Sn bronze in aerated NaCl aqueous media - Electrochemical investigation

Investigation of the electrochemical behaviour of Cu-10Sn (wt.%) alloy has been conducted in aerated aqueous chloride solutions and compared to that of pure Cu and Sn. Cathodic and anodic bronze behaviours have been investigated in function of the chloride concentrations (0.1-0.001 M), the rotation speed of the electrode and the potential sweep rate after 1-h immersion time in open-circuit conditions. At the corrosion potential, the corrosion behaviour appears determined by the charge-transfer controlled reduction of oxygen and the mixed charge- and mass-transfer controlled electrodissolution. In 0.1 M NaCl solution, three anodic regions are evidenced corresponding to: (I) a dissolution part from Eoc value, (II) a maximum current region corresponding to peaks formation and (III) a large current plateau. A partial protective effect of the corrosion product layer is observed at high anodic potential. It has been interpreted as the result of a 3D growth mechanism involving the formation of stable tin species in the layer according to a “pore resistance model”. Results on synthetic alloy are compared with those obtained on an archaeological bronze with a similar composition immersed in the same medium. Equivalent interface behaviour is evidenced between the synthetic and the archaeological bronzes.     

2,2′-Dithiobis(3-cyano-4,6-dimethylpyridine): A new class of acid corrosion inhibitors for mild steel

The title compound (PyS)₂ has been synthesized and its inhibiting action on the corrosion of mild steel in 1-5 M H₂SO₄ solutions at 35-50 °C has been investigated by polarization resistance (R_p), polarization curves and electrochemical impedance spectroscopy (EIS). (PyS)₂ showed excellent performance and its efficiency did not affect either by increasing the acid concentration or rise of temperature. Polarization curves indicated that (PyS)₂ behaves mainly as anodic inhibitor in 1 M H₂SO₄ solutions and as a mixed-type inhibitor in 3 and 5 M H₂SO₄ solutions at different temperatures. Adsorption of (PyS)₂ on the steel surface followed Temkin’s adsorption isotherm with a very high negative value of the free energy of adsorption . The activation parameters of the corrosion process were calculated. EIS showed that the charge transfer controls the corrosion process in the uninhibited and inhibited solutions.     

Evaluation of hydrogen absorption behaviour during acid etching for surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys

The hydrogen absorption behaviour during acid etching for the surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys has been investigated on the basis of the surface morphology, electrochemical behaviour and hydrogen thermal desorption analysis. To simulate the conventional acid etching for the improvement of the biocompatibility of Ti alloys, the specimens are immersed in 1 M HCl, 1 M H₂SO₄ or 0.5 M HCl + 0.5 M H₂SO₄ aqueous solution at 60 °C. Upon immersion, commercial pure Ti absorbs substantial amounts of hydrogen irrespective of the type of solution. In H₂SO₄ or HCl + H₂SO₄ solutions, the hydrogen absorption occurs for a short time (10 min). For Ti-6Al-4V alloy, no hydrogen absorption is observed in HCl solution, whereas hydrogen absorption occurs in other solutions. For Ni-Ti superelastic alloy, the amount of absorbed hydrogen is large, resulting in the pronounced degradation of the mechanical properties of the alloy even for an immersion time of 10 min, irrespective of the type of solution. The hydrogen absorption behaviour is not necessarily consistent with the morphologies of the surface subjected to corrosion and the shift of the corrosion potential. The hydrogen thermal desorption behaviour of commercial pure Ti and Ni-Ti superelastic alloy are sensitively changed by acid etching conditions. The present results suggest that the evaluation of hydrogen absorption is needed for each condition of acid etching, and that the conventional acid etching often leads to hydrogen embrittlement.     

In situ gravimetry of nickel thin film during potentiodynamic polarization in acidic and alkaline sulfate solutions

The passivation process of nickel thin films during potentiodynamic polarization in acidic and alkaline sulfate solutions was analyzed by an electrochemical quartz crystal microbalance (EQCM) to separate the partial current density of nickel dissolution through the passive film, i_Ni²⁺, and the partial current density of film growth, i_O^2-. The values of i_Ni²⁺ and i_O^2- during potentiodynamic polarization (20 mV s⁻¹) in the passive potential region could be separated by comparing the mass change rate and net polarization current as a function of electrode potential. It is found that i_Ni²⁺ is larger than i_O^2- in pH 3.0, 0.5 M sulfate solution, while the situation reverses in pH 12, 0.5 M sulfate solution. The sulfate concentration dependences of i_Ni²⁺ and i_O^2- in pH 3.0, sulfate solution were significant as compared to those in pH 12, sulfate solution.     

Electrochemical behaviour of recasting Ni-Cr and Co-Cr non-precious dental alloys

Corrosion behaviour of dental alloys in artificial saliva was studied using different chemical and electrochemical techniques. The order of corrosion rate for the three alloys in artificial saliva is: wironit < wirolloy < wiron99. This order agrees with the results of chemical studies for determining the cumulative ion concentration using ICP/MS. The open-circuit potential of wirolloy is more positive than wiron99. The higher corrosion rate of wiron99 compared to wirolloy is due to presence of high concentration of Mo. Increasing casting number leads to decrease R_ct value and increasing C_dl.     

A comparative study on the corrosion behaviour of 304 austenitic stainless steel in sulfamic and sulfuric acid solutions

Potentiodynamic polarization and EIS have been employed to compare the corrosion behaviour of 304 stainless steel in NH₂SO₃H and H₂SO₄ solutions. Corrosion tests were carried out as a function of the acid’s concentration (0.1-0.5 M) and solution temperature (20-60 ^oC). The corrosion rate is higher in H₂SO₄ than in H₂NSO₃H in all concentrations and temperatures. Values of the activation energy (E_a) revealed that the corrosion process is faster in H₂SO₄ than in NH₂SO₃H solution. EIS data showed that the display of Nyquist plots, and hence the mechanism of corrosion, depends not only on the acid concentration but also on the solution temperature. In 0.1 M concentration, the equivalent circuits R_e(R_ctQ_dl) and R_e(R_ctQ_dl)(RQ)_ads describe the corrosion systems in H₂NSO₃H and H₂SO₄ solutions respectively. At concentrations ?0.2 M, the equivalent circuit R_e(R_ctQ_dl)Q_diff is applicable. Adsorption of the counter ion of the acid on the steel surface and the stability of the surface complex may explain the observed corrosion rates.     

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.     

Effect of surface finishing of a Zr-based bulk metallic glass on its corrosion behaviour

Zr-based metallic glasses passivate spontaneously, but exhibit also a certain pitting susceptibility. On the example of the Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈ alloy studied in 0.01 M Na₂SO₄ + x M NaCl (x = 0-0.1) electrolytes it is demonstrated that the surface finishing state and the pre-exposure conditions can significantly influence the free corrosion and anodic polarisation behaviour. Mechanical fine-polishing procedures can lead to extremely smooth topographies but also to Cu enrichment at the surface. This yields a pronounced Cu dissolution at low anodic polarisation prior to stable passivity and increases the pitting initiation susceptibility as compared to mechanically ground surface states.     

Inhibitive effect of sodium eperuate on zinc corrosion in alkaline solutions

The effect of sodium eperuate prepared from Wallaba (Eperua falcata Aubl) extract on zinc corrosion was investigated in alkaline solutions with chloride ions (i.e., simulated concrete pore solutions) by using electrochemical techniques. Sodium eperuate inhibits the corrosion of zinc in 0.1 M NaCl solutions with pH 9.6. As its concentration increases to 1 g/L, the inhibition efficiency reaches approximately 92%. In alkaline solutions with pH 12.6, sodium eperuate has no adverse effect on passivity of zinc, and retards the chloride attack. These suggest that sodium eperuate is an effective inhibitor for the protection of zinc in alkaline environments.     

The influence of yttrium (Y) on the corrosion of Mg-Y binary alloys

Corrosion of Mg-Y alloys was studied using electrochemical evaluations, immersion tests and direct observations. There were two important effects. In 0.1 M NaCl, the corrosion rate increased with increasing Y content due to increasing amounts of the Y-containing intermetallic. In 0.1 M Na₂SO₄, the corrosion rate decreased with increasing Y content above 3%, attributed to a more protective surface film, despite the intermetallic. The corrosion rate evaluated by electrochemical impedance spectroscopy was somewhat smaller than that evaluated from H evolution as expected from the Mg corrosion mechanism. A mechanism is proposed for filiform corrosion. Direct in situ corrosion observations revealed that a predominant feature was hydrogen evolution from particular parts of the alloy surface.     

Influence of rare earth metals on the characteristics of anodic oxide films on aluminium and their dissolution behaviour in NaOH solution

The characteristics of oxide films on Al and Al1R alloys (R = rare earth metal = Ce, Y) galvanostatically formed (at a current density of 100 μA cm⁻²) in borate buffer solution (0.5 M H₃BO₃ + 0.05 M Na₂B₄O₇·10H₂O; pH = 7.8) were investigated by means of electrochemical impedance spectroscopy. EIS spectra were interpreted in terms of an “equivalent circuit” that completely illustrate the Al(Al1R alloy)/oxide film/electrolyte systems examined. The resistance of the oxide films was found to increase on passing from Al to Al1R alloys while the capacitance showed an opposite trend. The stability of the anodic oxide films grown in the borate buffer solution on Al and Al1R alloys was investigated by simultaneously measuring the electrode capacitance and resistance at a working frequency of 1 kHz as a function of exposure over a period of time to naturally aerated 0.01 M NaOH solution. Analyses of the electrode capacitance and resistance values indicated a decrease in chemical dissolution rate of the oxide films on passing from Al to Al1R alloys.