Effects of solution pH and Cl on electrochemical behaviour of an Aermet100 ultra-high strength steel in acidic environments

In this work, the effects of solution pH and Cl⁻ on the electrochemical behaviour of an Aermet100 ultra-high strength steel in 0.5 M (Na₂SO₄ + H₂SO₄) solution were studied by polarization curve and electrochemical impedance spectroscopy (EIS) measurements, combined with scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) characterization. The results show that, when solution pH is below 4, the steel is in the active dissolution state, and corrosion current decreases with the increase of pH. There exists a critical pH value, above which the steel is passivated. Moreover, the oxides and hydroxides of Fe, Co, Ni and Cr are the primary components of the passive film. With addition of Cl⁻, pits are initiated on the steel electrode.     

Long-term anticorrosion behaviour of polyaniline on mild Steel

Anticorrosion performances of polyaniline emeraldine base/epoxy resin (EB/ER) coating on mild steel in 3.5% NaCl solutions of various pH values were investigated by electrochemical impedance spectroscopy (EIS) for 150 days. In neutral solution (pH 6.1), EB/ER coating offered very efficient corrosion protection with respect to pure ER coating, especially when EB content was 5-10%. The impedance at 0.1 Hz of the coating increased in the first 1-40 immersion days and then remained constant above 10⁹ Ω·cm² until 150 days, which in combination with the observation of a Fe₂O₃/Fe₃O₄ passive film formed on steel confirmed that the protection of EB was mainly anodic. In acidic or basic solution (pH 1 or 13), EB/ER coating also performed much better than pure ER coating. However, these media weakened the corrosion resistance due to breakdown of the passive film or deterioration of the ER binder.     

Influence of pH on the passivation behavior of 254SMO stainless steel in 3.5% NaCl solution

The potentiodynamic polarization measurement of 254SMO stainless steel (UNS 31254) was conducted in 3.5% NaCl solutions with pH ranging from 0.1 to 5. The results indicated that this stainless steel offered excellent pitting corrosion resistance in corrosive environments. Further, it also exhibited various features on the polarization curves in different pH solutions. The electrochemical constant-potential passivation treatment performed at different pH followed by XPS analysis revealed that the primary constituents of the outermost layer of the passive films formed in the weak (pH 5) and strong (pH 0.8) acid solutions are iron oxides and Cr₂O₃ and Cr(OH)₃, respectively. Molybdenum oxides, primarily in the six-valence state, existed in the outermost layer of the passive film. Only very weak signals corresponding to that of nickel oxides were detected in the film formed in the weak acid (pH 5) solution. The ICP-MS analyses indicated selective dissolution of a significant amount of Fe and a few Mo and Ni ions during the passivation treatment in the strong acid (pH 0.8) solution. No Cr dissolution was observed; this indicated that the Cr in the film is relatively stable. XPS depth profiling results showed that a similar bilayer-structured film was formed in both the solutions (pH 0.8 and 5); the outer layer of this film is primarily composed of Cr(OH)₃ and Mo(VI), and the inner layer, Cr₂O₃ and Mo(IV). The results of the examinations of passive film formations and dissolution by XPS and ICP-MS were consistent with the polarization curves.     

The growth mechanism of CO2 corrosion product films

Carbon steel usually has high corrosion rate in water with dissolved CO₂ however the steel surface can be covered by protective corrosion product film. Therefore the carbon steel can be widely used in oil and gas industry. This paper discusses the structure, electrochemistry performances, initiation and growth of protective corrosion product films. A duplex layer structure of FeCO₃ films was found by electrochemical impedance spectrum (EIS). The physical and chemical situations of solution near carbon steel surface were investigated by ultraviolet spectrophotometry and chronopotentiometry. According to crystallography the growth mechanisms of protective CO₂ corrosion product films were discussed.     

Atmospheric corrosion monitoring of a weathering steel under an electrolyte film in cyclic wet–dry condition

Electrochemical Impedance Spectroscopy (EIS) and film thickness measurements have been employed to study the corrosion monitoring of steel under an electrolyte film in wet–dry cycles simulating a coastal atmosphere. The results indicate that within each cycle, the corrosion rate increases during drying process due to an increase in Cl⁻ concentration and an enhancement of oxygen diffusion by thinning out of the electrolyte. As corrosion process proceeds, the corrosion rate increases greatly and reaches a maximum. During subsequent corrosion stage, the corrosion rate decreases greatly and keeps at a low value due to the formation of a stable rust layer.     

Electrochemical impedance studies of the initial-stage corrosion of 310S stainless steel beneath thin film of molten (0.62Li, 0.38K)2CO3 at 650 °C

Electrochemical impedance spectroscopy (EIS) has been used to study the initial-stage corrosion of 310S stainless steel beneath thin film of molten (0.62Li, 0.38 K)₂CO₃ at 650 °C in air. Two-electrode system is used to fabricate molten-salt film. The thickness of molten salt approximated from electrolyte resistance decreases rapidly until it is smaller than 6 mg/cm². The appearance of diffusion-related impedance at the end of the test is linked to the severe loss of molten salt which causes twisted diffusion paths. More molten salt on the surface of 310S causes a longer lithiation process and more profound degradation of the oxide film.     

Effect of antimony on the corrosion behavior of low-alloy steel for flue gas desulfurization system

The alloying effect of Sb in a new low-alloy steel for the purpose of FGD materials was investigated by potentiodynamic polarization, linear polarization resistance measurement, electrochemical impedance spectroscopy (EIS) and weight loss measurements in an aggressive solution of 16.9 vol.% H₂SO₄ + 0.35 vol.% HCl (modified green death solution) at 60 °C, pH −0.3. All measurements confirmed the marked improvement in the corrosion behavior of the low-alloy steel via the addition of a small amount of Sb, particularly for the 0.10Sb steel. Pitting corrosion was detected by scanning electron microscopy (SEM) on the surface of blank steel and 0.05Sb steel, but not 0.10Sb steel, after weight loss measurements. X-ray photoelectron spectroscopy (XPS) analysis of the corroded surfaces after EIS and linear polarization measurements showed that the decrease in corrosion rates was due to the formation of a protective Sb₂O₅ oxide film on the surface of the Sb-containing steels. Moreover, the addition of 0.10% Sb stimulated the development of high corrosion inhibiting, Cu-containing compounds which further inhibited the anodic and cathodic reactions.     

Poly(ortho-ethoxyaniline) in corrosion protection of stainless steel

Corrosion protection of stainless steel (13% Cr) coated with poly(ortho-ethoxyaniline) (POEA) has been investigated. The layers of POEA were synthesised from sulphuric and phosphoric acid solutions by means of cyclic voltammetry. The protecting properties of the layers in supporting electrolytes were investigated by monitoring the open circuit potential (E_oc) vs. time, and by electrochemical impedance spectroscopy (EIS). It was found that polymer layers provide corrosion protection, i.e. they help to stabilise the potential of the metal in the passive potential region. The protective properties of POEA layers have shown to be superior to polyaniline (PANI) layers, which is explained by a denser morphology of POEA. The behaviour of POEA obtained on stainless steel, examined by EIS, is different from the one obtained for POEA on Pt electrode. The registered resistance in the case of POEA on stainless steel represents the charge transfer resistance at polymer/solution interface, i.e. the polymer resistance. These measurements show that a part of the layer is reduced, i.e. that there is an interaction between polymer layer and stainless steel. EIS measurements prove the influence of monomer on stainless steel oxide formation and suggest that polymer is partly incorporated into the oxide film.     

Investigation on carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water

The carbon dioxide corrosion behaviour of HP13Cr110 stainless steel in simulated stratum water is studied by potentiodynamic curve and electrochemical impedance spectroscopy (EIS); the micro-structure and composition of the corrosion scale formed at high-temperature and high-pressure are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that 13Cr stainless steel is in passive state in the stratum water, the passive current density increases and the passive potential region decreases with increasing temperature. The corrosion scale formed at high-temperature and high-pressure is mainly composed of iron/chromium oxides and a little amount of FeCO₃.     

Electrochemical behaviour of high nitrogen stainless steel in acidic solutions

The electrochemical behaviour of high nitrogen stainless steel in acidic solutions was studied by potentiodynamic polarization, EIS, Mott-Schottky and XPS. The passive film formed in neutral NaCl solution was very stable, but the stability of the film decreased with the addition of H₂SO₄ into the solution. The passive film formed in acidic Na₂SO₄ has a superior protective ability than that in acidic NaCl solution. The stability of the film formed in tested solution decreased with increase of applied potentials. The film formed on steel surface was of n-type semiconductor. Chloride penetration mechanism was proposed for the observed passive film breakdown.     

Evolution of dissolution processes at the interface of carbon steel corroding in a CO2 environment studied by EIS

The evolution of interfacial phenomena during CO₂ corrosion of C1018 carbon steel was characterized by EIS (Electrochemical Spectroscopy Impedance) and LPR (Linear Polarization Resistance). Turbulent conditions were simulated by a channel flow cell with deoxygenated 3 wt.% NaCl solution at 80 °C and pH 6 during 158 h. EIS helped in the characterization of the dynamic mechanism during the formation of the unprotective porous Fe₃C layer, and subsequent precipitation of the protective FeCO₃ layer inside the cementite. The experimental response of the active states at the interface was characterized by electrical passive elements with constant phase parameter analogs showing good agreement with the experimental results.     

XPS analysis of the passive film formed on austenitic stainless steel coated with conductive polymer

Improvement of the passivation behavior of Type 304 austenitic stainless steel (SS) by coating with conductive polymers (CPs), like polyaniline (PANI) and poly(o-phenylenediamine) (PoPD), followed by exposure in an acid solution has been demonstrated. The passive films formed on SSs (after peeling off the polymer layer) are compared with those formed during anodic polarization under the same exposure condition. The passive films beneath the CPs are thicker and less hydrated than those formed on uncoated stainless steel. The polymer layer enhances the enrichment of chromium and nickel in the entire passive oxide, forming a more protective film than that formed during anodic polarization. The elemental distribution within the passive film is different in the two modes of passivation. The type of the polymer influences on the composition of the passive film. The best passivation is obtained by PoPD, with the passive film resulting in significant resistance of the SS to pitting corrosion in the 3% NaCl solution. The oxide film of this steel is characterized, in its inner and outer layers, by the highest ratio of Cr(OH)₃/Cr₂O₃ and the lowest content of iron species.     

Gamma-radiation-induced corrosion of carbon steel in neutral and mildly basic water at 150 °C

The effect of γ-radiation on the kinetics of carbon steel corrosion has been investigated by characterizing the oxide films formed on steel coupons at 150 °C and at two pH values. Results show that continuous irradiation enhances surface oxide formation with the type of oxide formed dependant on the solution pH. For experiments at 150 °C and a [OH⁻] equivalent to that for pH_{25 °C} = 10.6, the surface oxide on carbon steel after γ-irradiation was non-porous and uniform, and no localized corrosion was observed. This oxide, however, appears to be susceptible to brittle fracture during cooling. Raman spectroscopy of the surface film indicates that it is a mixture of the phases of Fe₃O₄ and γ-Fe₂O₃. In contrast, at 150 °C with [OH⁻] equivalent to neutral pH_{25 °C}, metal dissolution is significant and the surface oxide film is very porous. Raman spectra show that this oxide film is also composed of a mixture of Fe₃O₄ and γ-Fe₂O_3. The results from this work combined with previously reported electrochemical studies of the same system as a function of pH and temperature can be used to deconvolute the effects of radiation, pH and temperature on the nature of the corrosion process.     

Surface characterization and corrosion behavior of 70/30 Cu-Ni alloy in pristine and sulfide-containing simulated seawater

The corrosion behavior of the 70/30 Cu-Ni alloy in stagnant, aerated pristine and sulfide-containing simulated seawater as a function of exposure time was investigated with polarization curve measurement and electrochemical impedance spectroscopy (EIS). It was demonstrated that the compact protective oxide film formed on the 70/30 Cu-Ni alloy resulted in the decrease of corrosion rate in aerated pristine seawater; while the corrosion rate of 70/30 Cu-Ni alloy in aerated sulfide-containing seawater increased dramatically due to the catalysis of the sulfide ions or sulfide scale for both the cathodic and anodic reactions. The impedance spectra and the corresponding equivalent circuits confirmed that a duplex layer of a surface film was formed on the 70/30 Cu-Ni alloy in aerated pristine seawater after a period of time and that the inner layer was responsible for the good resistance of the alloy; while only a porous and non-protective corrosion product layer formed on the 70/30 Cu-Ni alloy in aerated sulfide-containing seawater, which made small values of charge transfer resistance (R_ct) to last for a abnormally long time by interfering with the growth of the protective oxide film. The composition of the surface film on the alloy in pristine and sulfide-containing seawater for different exposure times were investigated thoroughly by XPS. It was found that the duplex corrosion product layer formed on the alloy in pristine seawater was composed of an inner Cu₂O and an outer CuO layer. The porous and non-protective corrosion product layer formed on the alloy in aerated sulfide-containing seawater was a mixture of CuCl, Cu₂S, NiS, Cu₂O and NiO with trace amounts of CuO and Ni(OH)₂ and that the most significant component was Cu₂S. In addition, SEM was used to analyze the topography of the 70/30 Cu-Ni alloy in both solutions after different exposure times.     

Copper(II) 8-hydroxyquinolinate 3D network film with corrosion inhibitor embedded for self-healing corrosion protection

This work presents a self-healing protective coating for copper. The complex coating is composed of copper(II) 8-hydroxyquinolinate (Cu(8HQ)₂) 3D network film storing corrosion inhibitor as base layer and epoxy as top layer covering on the base layer. The results of EIS and polarization curves reveal the self-healing effect of Cu(8HQ)₂ 3D network film with corrosion inhibitor embedded. After being scratched with a knife-edge, the complex coating rapidly releases inhibitor embedded in 3D network structure to suppress the corrosion process. The scratch on the coating is covered with inhibitor adsorption film and the anodic activity is restrained.     

Corrosion processes of Mg–Y–Nd–Zr alloys in Na2SO4 electrolyte

The corrosion behavior of Mg–Y–Nd–Zr (WE43 commercial alloy) was investigated in Na₂SO₄ electrolyte using potentiodynamic polarization curves, X-Ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) depth profiles, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS) analyzes. SEM and EDS data show that Nd-rich precipitates are mainly located at the grains boundaries. Zr/Y-rich zones are distributed inside the most of the grains. XPS study indicates a depletion of Mg on surface that could be attributed to Mg dissolution and an enrichment of the addition element oxides. XPS and ToF-SIMS analyzes demonstrate that the corrosion films are made up of a magnesium hydroxide (Mg(OH)₂) outer layer and an inner layer containing magnesium oxide (MgO), yttrium oxide (Y₂O₃) and hydroxide (Y(OH)₃), mixed with a small amount of MgH₂, zirconium oxide (ZrO₂) and neodymium oxide (Nd₂O₃). The Y₂O₃ and Y(OH)₃ signals increase slightly in the inner layer towards the corrosion film/alloy interface. Unlike these compounds, ZrO₂ and Nd₂O₃ compound signals are constant inside the inner layer. It is concluded that: (i) neodymium, zirconium and yttrium play a key role in the slightly improved corrosion resistance of the alloy and (ii) the cathodic reaction is slower on WE43 than on pure Mg and AZ91.     

Corrosion mechanism of Mo/Nd16Fe71B13/Mo film in a simulated marine atmosphere

This study describes the corrosion mechanism of Mo/Nd₁₆Fe₇₁B₁₃/Mo film induced by sodium chloride particles in 80% relative humidity (RH) environment. The deliquescence of sodium chloride particles on the Mo/Nd₁₆Fe₇₁B₁₃/Mo film caused the step by step attacks. Initial loosening of the Mo layer allows permeation of electrolyte into Nd–Fe–B layer, resulting in cavitations of electrolyte and subsequent film failure. The second failure step involves corrosion of Nd element in the Nd–Fe–B layer, with Fe element remaining beneath the corrosion product. Corrosion of Fe constitutes the third-step failure, forming a mixture of Nd and Fe corrosion product.     

Effects of hydrogen on the anodic behavior of Alloy 690 at 60 °C

Polarization and electrochemical impedance spectroscopy (EIS) measurements, Mott-Schottky (M-S) analysis and X-ray photoelectron spectroscopy (XPS) were used to investigate the effects of hydrogen on the anodic behavior of a one-dimensionally (1D) 25% cold worked (CW) Alloy 690 thermal treated (TT) in a boric acid and sodium sulphate solution at 60 °C. The pre-hydrogen-charged specimen exhibited a higher anodic current than that of the uncharged specimen below the transpassive potential. The charged hydrogen can be trapped in the metal. Electrochemical impedance spectroscopy (EIS) showed that the resistance capacitance loop of the hydrogen-charged specimen was significantly smaller than that of the uncharged specimen. Mott-Schottky analyses indicated that the passive film formed on Alloy 690 at −0.2 V_SCE was an n-type semiconductor, with a p-n hetero-junction at 0.2 V_SCE. Charged hydrogen increased the carrier density and the thickness of the passive film both at −0.2 V_SCE and 0.2 V_SCE. The Ni/Cr ratio in the surface film decreased after hydrogen charging, indicating that charged hydrogen could enhance the oxide film growth by increasing the OH⁻ (O²⁻) concentrations through its reaction with vacancies.     

Corrosion and passivation mechanism of chromium diboride coatings on stainless steel

The corrosion resistance of fully crystalline CrB₂ coatings magnetron sputtered onto AISI 316L stainless steel was tested in acidic solutions. CrB₂ coatings showed excellent corrosion protection, but suffered a breakdown when an anodic potential of greater than about +1 V (SHE) was applied to the surface in a 1 M HCl electrolyte. The coating failure at high potentials is attributed to transpassive dissolution of the coating at volume defects, enabling the electrolyte to reach the underlying 316L substrate, resulting in its rapid corrosion and subsequent fracturing of the coating. Electrochemical data and potential-pH (Pourbaix) diagrams, constructed from thermodynamic data, indicate that the corrosion resistance of CrB₂ is due to the formation of a Cr(III) oxide passive film in the absence of activation corrosion.     

Kinetics of H2O2 reaction with oxide films on carbon steel

The nature of carbon steel surfaces in 0.01 M borate solutions (pH 10.6) have been characterized using a range of electrochemical techniques and ex situ analyses such as Raman and Auger spectroscopy. Their subsequent behaviour on exposure to 10⁻³ M H₂O₂-containing solutions has also been studied. The anodically oxidized carbon steel surfaces have been characterized according to three regions: (I) the potential range <−0.5 V (vs SCE), when the surface is active and covered by Fe^II/Fe^III oxide/hydroxide; (II) the potential range −0.5 V to 0.0 V when the surface is passivated by an outer layer of Fe^III oxide/hydroxide over the inner layer of Fe^II/Fe^III oxide/hydroxide; and (III) potentials >0 V when further growth of the underlying layer appears to lead to minor film breakdown/restructuring. The addition of H₂O₂ to films grown in the passive region or above (II and III) leads initially to a degradation of the outer layer allowing increased growth of the inner layer. Subsequently, the outer passivating layer is repaired and passivity re-established. These changes appear to be confirmed by Raman spectroscopy.