Localised dissolution of iron in buffered and non-buffered chloride containing solutions

Pitting corrosion of pure iron was studied by using conventional samples, and artificial pit electrodes. Experiments were conducted in solutions of 0.01, 0.1 and 1 mol dm⁻³ NaCl at pH values of 7, 10, 11 and 12; and in borate buffer solutions with the same chloride concentrations and pH 8.7 and 9.2. Four times higher concentration of borate salt was required to reach inhibiting capacity of the hydroxyl anions, as determined via pitting potentials. From measurements of solution resistance, the increase in local conductivity due to dissolved corrosion products exuded from the pit was calculated for each bulk solutions. For the artificial pit electrodes, contribution of the borate species to the internal pit solution conductivity in low chloride solution was associated with the difference between transition potential, E_T, values for buffered and non-buffered solutions, and this contribution was also used to explain the non-linear dependence of E_T on [Cl⁻]. Further analysis was conducted using the concept of the critical i.x parameter for stable pit propagation.     

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.     

Film Growth and Dissolution of Iron Ions at passive iron in neutral solutions containing chloride

The passivating oxide layer on iron grows by transfer of oxygen ions from the solution into the oxide. As expected theoretically, the dissolution rate of iron ions increases with the growth rate of the layer. In neutral solution the current efficiency for oxide growth is larger than in acid solutions. By addition of chloride to the solution the current efficiency is further enhanced, because chloride catalyzes the transfer of oxygen ions more strongly than the transfer of iron ions. Chloride in the solution does not change the ionic conductivity of the oxide to a measurable extent. During galvanostatic polarization in solutions containing chloride, fluctuations of the potential and of the dissolution rate of Fe(II) are observed. The frequency of the fluctuations increases with current density and chloride concentration.     

The effect of carbon within corrosion pits of iron in chloride solutions

Iron artificial pits have been used in this work to investigate the effect of a carbon-based black layer that can form within a pit during iron dissolution in HCl solutions. Commercial purity iron (99.5%) and high purity iron (99.99+%) have been compared, and a black layer has been observed only in the 99.5% iron pit. It has been found that the formation of a black layer within an iron artificial pit is potential dependent: it can form at applied voltages below 0.2?V(SCE), but not at 0.6?V(SCE). The presence of a black layer can decrease the rate of mass transport inside a pit, which may help to maintain the aggressive acidic solution in an active pit. This effect has been characterised quantitatively via potentiostatic and potential step methods. In addition, the black layer has also been found to induce a small extra resistance in the solution.     

Investigation of the major reduction reaction occurring during the passivation of galvanized steel rebars

The corrosion behaviour of zinc plates immersed in calcium hydroxide saturated solutions in the presence of oxygen, air and nitrogen, respectively, was studied. The corrosion resistance was monitored by potentials and corrosion rate measurements. The results obtained were confirmed by further data collected on galvanized rebars embedded in concrete and stored in different curing environments. The results clearly show that oxygen is the main oxidizing agent and indeed not water for the rapid formation of an effective passivation layer on zinc coating.     

In situ monitoring the effects of a magnetic field on the open-circuit corrosion states of iron in acidic and neutral solutions

The effects of a 0.4 T horizontal magnetic field (HMF) on the open-circuit corrosion states of iron in static aqueous solutions are studied by in situ monitoring the responses of two electrochemical parameters to the applied magnetic field, i.e. the open-circuit potential (OCP) and the current under potentiostatic polarization. The applied magnetic field makes the OCP shift in the noble direction. Withdrawing the magnetic field causes a negative shift of the OCP in acidic solutions, but it does not cause any significant change of OCP in neutral solutions. Imposing a magnetic field induces a cathodic current for iron that was previously potentiostatically polarized at the OCP without magnetic field. Withdrawing the magnetic field induces an anodic current for iron that was previously potentiostatically polarized at the OCP with the magnetic field. The magnetic field effect is more significant in the acid solutions than in the salt solutions. The magnetic field effects on the oxygen reduction and on the activation-controlled iron dissolution reaction are found to be insignificant. The magnetic field effect on the hydrogen reduction reaction on iron in acidic solutions is demonstrated. Results show the possibility that a magnetic field would affect the hydrogen evolution by enhancing the electron-transfer process that has been categorized in the classical electrochemistry kinetics to be the rate-determining process. The memory effect of the magnetic field on the electrochemical reaction is identified and discussed.     

A study of the inhibition of iron corrosion in HCl solutions by some amino acids

The performance of three selected amino acids, namely alanine (Ala), cysteine (Cys) and S-methyl cysteine (S-MCys) as safe corrosion inhibitors for iron in aerated stagnant 1.0 M HCl solutions was evaluated by Tafel polarization and impedance measurements. Results indicate that Ala acts mainly as a cathodic inhibitor, while Cys and S-MCys function as mixed-type inhibitors. Cys, which contains a mercapto group in its molecular structure, was the most effective among the inhibitors tested, while Ala was less effective than S-MCys. The low inhibition efficiency recorded for S-MCys compared with that of Cys was attributed to steric effects caused by the substituent methyl on the mercapto group. Electrochemical frequency modulation (EFM) technique and inductively coupled plasma atomic emission spectrometry (ICP-AES), were also applied to make accurate determination of corrosion rates. Validation of the Tafel extrapolation method for measuring corrosion rates was tested. Rates of corrosion rates (in μm y⁻¹) obtained from Tafel extrapolation method are in good agreement with those measured using EFM and ICP methods. Some theoretical studies, including molecular dynamics (MD) and density functional theory (DFT), were also employed to establish the correlation between the structure (molecular and electronic) of the three tested inhibitors and the inhibition efficiency. Adsorption via hydrogen bonding was discussed here based on some theoretical studies. Experimental and theoretical results were in good agreement.     

Inhibition effects of LAB and LABS on iron corrosion in chlorine solutions at different temperatures

In this study, the corrosion of iron is studied using gravimetric and potentiodynamic polarization method at different temperatures and at pH 9 level in 0.1 M NaCl solutions containing different concentrations of linear alkyl benzene (LAB) and linear alkyl benzene sulphonate (LABS). Potentiodynamic polarization experiments show that corrosion rate in presence and absence of LAB and LABS increases with increasing temperature from 303 to 338 K. The corresponding activation energies are determined. Moreover, the protective film formation on metal surface is investigated by means of FTIR. It has been concluded from the results that LABS is more effective in preventing iron corrosion than LAB.     

N-Phenylcinnamimide and some of its derivatives as inhibitors for corrosion of lead in HCl solutions

The anodic and cathodic polarization behavior of lead electrode was studied galvanostatically in HCl solutions of various concentrations. Increasing the acid concentration enhances the rate of the anodic dissolution of the metal and the rate of hydrogen evolution reaction, with anodic and cathodic Tafel slopes equal to 30 and 115 ± 5 mV decade⁻¹, respectively. The effect of addition of N-phenylcinnamimide and some of its derivatives, N-(p-nitrophenyl)cinnamimide, N-(p-methylphenyl)cinnamimide, and N-(p-methoxyphenyl)cinnamimide, as inhibitors on the kinetic of the anodic and cathodic reactions of lead in 0.1 M HCl solutions was also studied. These compounds inhibit both the rate of anodic dissolution and the rate of hydrogen evolution reactions without affecting the Tafel slopes. This result indicates that the used compounds were of mixed-type. The inhibition efficiency of these additives increases in the order: N-(p-nitrophenyl)cinnamimide < N-phenylcinnamimide < N-(p-methylphenyl)cinnamimide < N-(p-methoxyphenyl)cinnamimide. The equilibrium constant and the free energy of adsorption process have been calculated and discussed.     

Effect of high gradient magnetic fields on the anodic behaviour and localized corrosion of iron in sulphuric acid solutions

The influence of high gradient magnetic fields on the anodic dissolution of iron in sulphuric acid solutions and the localization of the corrosion attack is investigated by means of potentiodynamic and potentiostatic polarization experiments and subsequent surface profile analysis. A localization of the material loss is observed in every potential region of the anodic Fe dissolution except from the passive region. The impact of the magnetic field on the anodic current density and the localization of the corrosion attack are explained by the action of the Lorentz force and the magnetic field gradient force.     

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.     

Localisation of oxygen reduction sites in the case of iron long term atmospheric corrosion

In different fields of civil engineering and cultural heritage, the corrosion behaviour of century old ferrous artefacts must be accurately evaluated, especially under uncontrolled conditions. This approach requires an understanding of the role played by the several hundred micrometre thick corrosion layers formed on ancient metals. Combining the study of historical mild steels and a new re-corroding experiment using isotopic tracers, we show here that mechanisms controlling corrosion kinetics differ according to the nature and the organisation of various microscopic phases, leading to a decoupling of anodic and cathodic reaction or to a homogeneous corrosion.     

Quantum chemistry study on the effect of Cl ion on anodic dissolution of iron in H2S-containing sulfuric acid solutions

The effect of Cl⁻ ion on the anodic dissolution of iron in H₂SO₄ solutions containing low H₂S level has been studied by electrochemical polarization curve measurements. The total energy and binding energy of the competitive adsorption for Cl⁻ and HS⁻ ions have been calculated with CNDO/2 method, as well as the net charge distribution of iron atoms at an anodic potential. The results showed that certain concentration of Cl⁻ ion inhibit the anodic reaction of iron accelerated by HS⁻. However, when Cl⁻ ion reached saturated adsorption, it began to promote the anodic reaction of iron due to the increased negative charge of iron atoms.     

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.     

Inhibition of iron corrosion in acid solutions by Cefatrexyl: Behaviour near and at the corrosion potential

The corrosion inhibition of iron in HCl, HClO₄, H₂SO₄ and H₃PO₄ solutions (1M for each) by cefatrexyl has been studied by polarization resistance (R_p) and electrochemical impedance spectroscopy (EIS) at the corrosion potential. The results obtained at 30 °C revealed that cefatrexyl acts as a weak inhibitor in HCl solution while it shows excellent inhibition performance in the remaining acids. Adsorption of cefatrexyl in HCl solution obeys Langmuir’s isotherm with a very low value of the free energy of adsorption (physisorption) while its adsorption in the other acids follows Temkin’s isotherm with very high negative values of (chemisorption). Data obtained from EIS measurements were analyzed to model the corrosion inhibition process through appropriate equivalent circuit models. The calculated values of the apparent activation energy (E_a) and the pre-exponential factor (λ) indicate that cefatrexyl blocks nearly the whole active centers of iron surface in H₃PO₄ solution even at elevated temperatures. The inhibition mechanism of cefatrexyl was discussed.     

Electrochemical characteristics of zirconium oxide treated Type 304 stainless steels of different surface oxide structures in high temperature water

Electrochemical polarization analyses were conducted to investigate the impact of different oxide structures on corrosion resistance of ZrO₂-treated Type 304 stainless steel specimens in high temperature water. All specimens were pre-oxidized in high temperature water containing either 300 ppb dissolved oxygen or 50 ppb dissolved hydrogen, followed by a hydrothermal deposition treatment with ZrO₂ nanoparticles. Experimental results revealed that the corrosion potentials and corrosion current densities on the ZrO₂-treated specimens were lower than those on the untreated ones, and the decreases in these parameters were more distinct on the ZrO₂-treated specimens with oxides developed under dissolved oxygen condition.     

Copper corrosion inhibition in O2-saturated H2SO4 solutions

Corrosion inhibition of copper in O₂-saturated 0.50 M H₂SO₄ solutions by four selected amino acids, namely glycine (Gly), alanine (Ala), valine (Val), or tyrosine (Tyr), was studied using Tafel polarization, linear polarization, impedance, and electrochemical frequency modulation (EFM) at 30 °C. Protection efficiencies of almost 98% and 91% were obtained with 50 mM Tyr and Gly, respectively. On the other hand, Ala and Val reached only about 75%. Corrosion rates determined by the Tafel extrapolation method were in good agreement with those obtained by EFM and an independent chemical (i.e., non-electrochemical) method. The chemical method of confirmation of the corrosion rates involved determination of the dissolved Cu²⁺, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of chemical analysis. Nyquist plots exhibited a high frequency depressed semicircle followed by a straight line portion (Warburg diffusion tail) in the low-frequency region. The impedance data were interpreted according to two suitable equivalent circuits. The kinetics of dissolved O₂ reduction and hydrogen evolution reactions on copper surface were also studied in O₂-saturated 0.50 M H₂SO₄ solutions using polarization measurements combined with the rotating disc electrode (RDE). The Koutecky-Levich plot indicated that the dissolved O₂ reduction at the copper electrode was an apparent 4-electron process.     

Carbon steel corrosion under anaerobic–aerobic cycling conditions in near-neutral pH saline solutions – Part 1: Long term corrosion behaviour

A corrosion mechanism has been developed to describe tubercle formation along pipeline steels during successive anaerobic–aerobic cycles. Small concentrations of O₂ under nominally anaerobic conditions can lead to the separation of anodes and cathodes. Under subsequent aerobic conditions localized corrosion is then promoted by O₂ reduction on the general magnetite-covered surface. Subsequently, the conversion of magnetite to maghemite passivates the general surface, and focuses corrosion within one major tubercle-covered pit. On switching from aerobic to anaerobic conditions, corrosion is temporarily supported by the galvanic coupling of lepidocrocite (γ-FeOOH) reduction (to γ-Fe-OH·OH) to steel dissolution primarily within the tubercle-covered pit.     

Long-term corrosion of rebars embedded in aerial and hydraulic binders - Parametric study and first step of modelling

The prediction of long-term behaviour of reinforced concrete structures involved in the nuclear industry requires a phenomenological modelling of the rebars corrosion processes. Previous analytical characterisation of archaeological artefacts allowed to identify a typical layout constituted of four layers (the metal, the dense product layer, the transformed medium and the binder). Additional experiments leaded to identify the long-term corrosion mechanisms. Following these results, this paper proposes an analytical model of long-term corrosion of rebars embedded in concrete. This modelling is considering the kinetic of oxygen diffusion through the system and its consumption at the metal/dense product layer interface as a function of concrete water saturation degree. Corrosion products thicknesses estimated with the model are then compared to corrosion product thicknesses measured on archaeological artefacts. A parametric study is performed and demonstrates that the oxygen diffusivity and the kinetic constant of the cathodic reaction affect in a wide range the model results.