Evaluation of the corrosion resistance of Ni-Co-B coatings in simulated PEMFC environment

The corrosion resistance behavior of Ni-Co-B coated carbon steel, Al 6061 alloy and 304 stainless steel was evaluated in simulated proton exchange membrane fuel cell (PEMFC) environment. The phase structure of the NiCoB based alloy was determined by Rietveld analysis. The PEMFC environment was constituted of 0.5 M H₂SO₄ at 60 °C and the evaluation techniques employed included potentiodynamic polarization, linear polarization resistance, open circuit potential measurements and electrochemical impedance spectroscopy. The results showed that in all cases the corrosion resistance of the Ni-Co-B coating was higher than that of the uncoated alloys; about two orders of magnitude with respect to carbon steel and an order of magnitude compared to 304 stainless steel. Except for the uncoated 304 type stainless steel, the polarization curves for the coated specimens did not exhibit a passive region but only anodic dissolution. The corrosion potential value, E_corr, was always nobler for the coated samples than for the uncoated specimens. This was true for the stainless steel in the passive region, but in the active state for the carbon steel and Al 6061 alloy. The corrosion of the underlying alloy occurred due to filtering of the solution through coating defects like microcracks, pinholes, etc. During the filtering process the E_corr value of the coating decreased slowly until it reached a steady state value, close to the E_corr value of the underlying alloy.     

Effect of amino acids containing sulfur on the corrosion of mild steel in phosphoric acid solutions containing Cl<Superscript>−</Superscript>, F<Superscript>−</Superscript> and Fe<Superscript>3+</Superscript> ions: Behavior under polarization conditions

The effect of cysteine (RSH), methionine (CH₃SR), cystine (RSSR) and N-acetylcysteine (ACC) on the corrosion behavior of mild steel in 40% H₃PO₄ solution without and with Cl⁻, F⁻, Fe^3‰+ and their ternary mixture was studied using both potentiostatic and electrochemical impedance (EIS) techniques under anodic and cathodic polarization conditions. The inorganic additives stimulate the overall corrosion reaction while the amino acids inhibit it with a predominant effect on the dissolution of iron. Both RSH and ACC are adsorbed according to Temkin’s isotherm while adsorption of RSSR and CH₃SR follows Frumkin and Langmuir isotherms respectively. The standard free energy of adsorption (ΔG ) was found to be in the order: RSSR > RSH ≅ ACC > CH₃SR. The binary mixtures of Cl⁻ or F⁻ with RSH or CH₃SR are the best inhibitors (IE > 90%) while those containing ferric ions or blend I and amino acids are not good corrosion inhibitors. EIS measurements showed that the cathodic reaction, hydrogen evolution, is charge transfer controlled while the anodic one, iron dissolution, is a complex process.     

Electrochemical study of carbon steel corrosion in buffered acetic acid solutions with chlorides and H2S

In this work, the corrosion behavior of SAE 1018 carbon steel in buffered acetic acid (HAc) solutions containing chlorides, with and without H₂S, was studied. Polarization curves obtained by different electrochemical techniques, indicate negligible modification of anodic slopes when adding H₂S; however, the cathodic branch is more sensitive showing an accelerated reduction reaction in the presence of H₂S. Interface characterization was performed by electrochemical impedance technique (EIS) in the absence and presence of H₂S and near to the corrosion potential (E_corr). Analysis of results shows no film of corrosion products, since the impedance spectra characteristics indicate a great activity of steel in the solutions studied, with differences only at low frequencies. The adsorbed complexes formed in the solution containing HAc, acetate and chlorides control the corrosion process and prevent passive film formation, even in the presence of H₂S.     

Corrosion inhibition of mild steel in sulfamic acid solution by S-containing amino acids

R_p, potentiodynamic polarization curves and EIS techniques were applied to study the effect of five S-containing amino acids on the corrosion of mild steel in 5% sulfamic acid solution at 40 °C. The compounds are effective inhibitors and the inhibition efficiency follow the order: N-acetylcysteine (ACC) > cysteine (RSH) > S-benzylcysteine (BzC) > cystine (RSSR) ≅ methionine (CH₃SR). The inhibitors affect the anodic dissolution of steel by blocking the anodic sites of the surface. EIS measurements indicated that charge transfer is the rate determining step in the absence and presence of the inhibitors and the steel/solution interface can be represented by the equivalent circuit R_s(R_ctQ_dl). Adsorption of RSH, CH₃SR and RSSR follows the Langmuir model while the Temkin isotherm describes the adsorption of ACC and BzC. From the application of the Flory–Huggins isotherm, the number of water molecules displaced by the adsorbing inhibitor molecules was estimated. The potential of zero charge pzc of mild steel without and with the inhibitors is calculated and the mechanism of corrosion inhibition is discussed in the light of the molecular structure.     

Protection of stainless steel by polyaniline films against corrosion in aqueous environments

Polyaniline (PANI) thin films were electrochemically deposited by cyclic voltammetry on stainless steel electrode previously covered by a thin film of polyvinyl acetate (PVAc). The corrosion resistance of PANI covered stainless steel substrates was estimated by using potentiodynamic polarization curves and its linear polarization resistance (LPR) was measured in 0.5 M H₂SO₄, 0.5 M NaCl and 0.5 M NaOH aqueous solutions at room temperature. The results indicate that the PANI-PVAc films did improve the corrosion resistance of the stainless steel in NaOH, behaving even worst, in the case of PANI film, than the uncoated substrate. In H₂SO₄ both PANI and PANI-PVAc coatings gave good protection for the stainless steel electrode, with a slightly better performance of PANI-PVAc than PANI. In NaCl solution both PANI and PANI-PVAc films provided a good protection against corrosion. The better performance of PANI-PVAc coatings for corrosion protection in basic media may be due to its major chemical stability compared to simple PANI films, which lose their conductivity in high pH solutions. The E _corr (free corrosion potential) value of the coated substrate was in the passive region of the uncoated substrate in acidic environment but in the active region in neutral or basic environment.     

Influence of molybdenum on the anodic dissolution of iron in acidic solutions

The anodic dissolution of pure iron and binary iron-molybdenum alloys (10 and 20 wt% Mo) in molar H₂SO₄ and HCl solutions was studied by d.c. polarization and a.c. impedance techniques. Molybdenum additive influences both the steady state polarization curves and the impedance spectra in the two media, the impact being stronger for the Fe-20 wt % Mo alloy. In general, two-slope polarization curves are obtained for the alloys; impedance spectra exhibit two time constants in addition to the charge transfer one implying the existence of two reaction intermediates. Differences between spectra measured in H₂SO₄ and HCl are discussed. A kinetic model advanced on the basis of literature data for pure iron and molybdenum was able to reproduce quantitatively both the steady state and a.c. impedance results for both alloys in the two media. Kinetic parameters for the anodic dissolution of Fe-Mo alloys are thereby determined.     

Effect of H2S on the CO2 corrosion of carbon steel in acidic solutions

The objective of this study is to evaluate the effect of low-level hydrogen sulfide (H₂S) on carbon dioxide (CO₂) corrosion of carbon steel in acidic solutions, and to investigate the mechanism of iron sulfide scale formation in CO₂/H₂S environments. Corrosion tests were conducted using 1018 carbon steel in 1 wt.% NaCl solution (25 °C) at pH of 3 and 4, and under atmospheric pressure. The test solution was saturated with flowing gases that change with increasing time from CO₂ (stage 1) to CO₂/100 ppm H₂S (stage 2) and back to CO₂ (stage 3). Corrosion rate and behavior were investigated using linear polarization resistance (LPR) technique. Electrochemical impedance spectroscopy (EIS) and potentiodynamic tests were performed at the end of each stage. The morphology and compositions of surface corrosion products were analyzed using scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The results showed that the addition of 100 ppm H₂S to CO₂ induced rapid reduction in the corrosion rate at both pHs 3 and 4. This H₂S inhibition effect is attributed to the formation of thin FeS film (tarnish) on the steel surface that suppressed the anodic dissolution reaction. The study results suggested that the precipitation of iron sulfide as well as iron carbonate film is possible in the acidic solutions due to the local supersaturation in regions immediately above the steel surface, and these films provide corrosion protection in the acidic solutions.     

Evaluation of some bipyridinium dihalides as inhibitors for low carbon steel corrosion in sulfuric acid solution

Inhibition of low carbon steel (LCS) corrosion in 0.5 M H₂SO₄ solution by three bipyridinium dihalides (TMbPyBr₂, HMbPyBr₂ and MPhbPyCl₂) was evaluated by potentiodynamic polarization curves, EIS and SEM techniques. The effectiveness of the inhibitors is ranked as follows: MPhbPyCl₂ ≅ TMbPyBr₂ > HMbPyBr₂. The compounds behave as mixed-type inhibitors and their adsorption on the steel surface obeys the Langmuir adsorption isotherm. EIS measurements indicate that charge transfer controls the corrosion of steel in the absence and presence of the inhibitors and the equivalent circuit R_e(R_ctQ_dl) represents the electrode/solution interface either at the corrosion potential or at −75 and 30 mV versus E_corr. The compounds show maximum inhibition efficiency at 35 °C. The mechanism of corrosion inhibition was discussed in the light of the molecular structure of the bipyridinium salts.     

Effect of bromide ions on the corrosion behavior of tantalum in anhydrous ethanol

The electrochemical behaviors of Ta in Et₄NBr ethanol solutions were investigated using potentiodynamic polarization, cyclic voltammetry, potentiostatic current-time transient and impedance techniques. The potentiodynamic anodic polarization curves did not exhibit active dissolution region due to the presence of thin oxide film on the electrode surface, which was followed by pitting corrosion as a result of passivity breakdown by the aggressive attack of Br⁻ anions. The pitting potential (E_b) decreased with the increase of solution temperature and Br⁻ concentration, but increased with increasing potential scan rate and water concentration. The incubation time derived from potentiostatic current-time transients decreased with increasing potentials. The impedance spectra exhibited two time constants for all the potentials and the resistance of passive layer decreased with increasing potential.     

Study on the corrosion behavior of reinforcing steel in simulated concrete pore solutions using in situ Raman spectroscopy assisted by electrochemical techniques

In situ Raman spectroscopy, electrochemical impedance spectroscopy (EIS) and polarization curves were used to study the corrosion behavior of reinforcing steel in simulated concrete pore (SCP) solutions (saturated Ca(OH)₂ solutions). Results indicated that the reinforcing steel remained passive in chloride-free SCP solutions. However, the anodic polarization curve of the steel did not exhibit a stable passive region in the SCP solution with 0.5 M NaCl, the corrosion current density exceeded 0.1 μA cm⁻², the steel surface was unstable with chloride attack and localized corrosion appeared on it with FeCO₃ and Fe₂O₃ as the main corrosion products.     

Localized passivity breakdown of iron in chlorate- and perchlorate-containing sulphuric acid solutions: A study based on current oscillations and a point defect model

Current oscillations are used to study the effect of chlorate and perchlorate ions on the iron passivity in sulphuric acid solutions. Quasi steady-state current-potential and potentiostatic current-time curves show the emergence of complex current oscillations, besides the simple periodic ones attributed to general corrosion occurring across the passive-active transition of the Fe|0.75 M H₂SO₄ electrochemical system. The complex current oscillations arising at the iron passive state are indicative of pitting corrosion. Experimental results support that pitting is due to chlorides produced via the reduction of chlorates and perchlorates by ferrous ions either during the active phase of current oscillations or in the passive phase during the H⁺-catalyzed dissolution of the oxide. Thus, chloride is the aggressive ion that causes pitting corrosion and not chlorates and perchlorates themselves. Chloride production induced via the reduction of perchlorates is much slower than that induced by chlorates. A point defect model (PDM) is employed to explain the oxide growth and its breakdown induced by general and pitting corrosion.     

Effects of nanocrystallization on the corrosion behavior of 309 stainless steel

Nanocrystallized (NC) 309 stainless steel (309SS) coating has been fabricated on glass substrate by DC magnetron sputtering. The coating, with an average grain size less than 50 nm, had ferritic (bcc) structure rather than the austenitic (fcc) structure of the bulk steel. The electrochemical corrosion behavior of the NC coating and the bulk steel in solutions of 0.25 M Na₂SO₄ + 0.05 M H₂SO₄ and 0.5 M NaCl + 0.05 M H₂SO₄ was investigated by using potentiodynamic polarization, potentiostatic polarization and AC impedance techniques. The results showed that the corrosion behavior of the NC 309SS coating and 309SS bulk steel depended on the composition of the solutions. In the Na₂SO₄ solution there was only a little difference between the corrosion resistance of the passive films on the NC coating and the bulk steel. However, in the solution with chloride ions, the localized corrosion resistance of 309SS was greatly enhanced by nanocrystallization due to the formation of a compact and stable passive film on the NC coating. The electronic structure of the passive film formed on the NC coating and on the bulk steel was analyzed by means of capacitance measurements, and a corrosion mechanism is proposed.     

Oxidative dissolution of pyrite in acidic media

The pyrite oxidative dissolution in air-saturated (AS), H₂O₂, and Fe³⁺ solutions at pH 2.5 and 25 °C was investigated by electrochemical and aqueous batch experiments. The corrosion current density (i _corr) increases from AS solution to Fe³⁺ and H₂O₂ solutions. For the same oxidant, i _corr increases when the concentration of the oxidant increases. Similar variation was observed for the corrosion potential (E _corr). Electrochemical impedance spectroscopy measurements have indicated that in AS and H₂O₂ solutions, the charge transfer is the rate determining step of pyrite oxidative dissolution. In the presence of Fe _(aq) ³⁺ , both the charge transfer process and mass transfer caused by the diffusion of oxidant or reaction products across the interface of electrode control the mineral oxidative dissolution. The corrosion current densities of oxidative dissolution measured by electrochemical methods are higher than those estimated from dissolution rates determined by aqueous bath experiments. The observed differences suggest that the mechanism of polarized electrode oxidation is different by the mechanism of pyrite oxidation under open circuit conditions.     

Dodigen 213-N as corrosion inhibitor for ASTM 1010 mild steel in 10% HCL

This article describes a study of the behavior of a mixture of amines and amides, commercially known as Dodigen 213-N (D-213 N), as a corrosion inhibitor for ASTM 1010 mild steel in 10% w/w HCl solution. The concentration range used was 1 × 10⁻⁵ M to 8 × 10⁻⁴ M. The weight loss and electrochemical techniques used were corrosion potential measurement, anodic and cathodic polarization curves, and electrochemical impedance spectroscopy (EIS). The solution temperature was 50 ± 1 °C and it was naturally aerated. The corrosion potential values shifted to slightly more positive values, thus indicating mixed inhibitor behavior. The anodic and cathodic polarization curves showed that D-213 N is an effective corrosion inhibitor, since both the anodic and the cathodic reactions were polarized in comparison with those obtained without inhibitor. For all concentrations the cathodic polarization curves were more polarized than the anodic ones. The inhibition efficiency was in the range 75–98%, calculated from values of weight loss and corrosion current density, i _corr, obtained by extrapolation of Tafel cathodic linear region.     

Effect of alternating voltage passivation on the corrosion resistance of duplex stainless steel

Potentiodynamic polarization and E _corr versus t curves were obtained, together with electrochemical impedance spectroscopy (EIS) measurements, in order to understand the effects of alternating voltage (AV) passivation on the corrosion resistance of duplex stainless steel (DSS). SEM, EDS and XPS were employed to further investigate the influence of AV passivation on the properties of the passive film. The results of the electrochemical measurements showed that AV passivation significantly improved the corrosion resistance of DSS. SEM images indicated that the surface exhibited a unique morphology after AV passivation treatment, and XPS results suggested that AV passivation greatly increased the thickness of the passive film. Furthermore, significant chromium enrichment and a higher ratio of Fe³⁺/Fe²⁺ were observed in the passive film after AV passivation. Mott–Schottky results confirmed that AV passivation had a strong influence on the semiconducting properties of the passive film.     

Influence of H+ and Cl− ions on inhibitive performance of poly(aniline) for iron corrosion in acid

The inhibition effect of poly(aniline) on pure iron corrosion in 1M HCl and with various H⁺ ions and Cl^? ions concentrations was investigated by the polarization and electrochemical impedance spectroscopy methods. The results showed that poly(aniline) suppressed both cathodic and anodic processes of iron dissolution in 1M HCl by its adsorption on the iron surface according to Langmuir's adsorption isotherm. The inhibition efficiency of poly(aniline) was found to increase with the inhibitor concentrations. Further, it was observed that, there was no significant variation in corrosion potential (E_corr) values in the presence of inhibitors suggesting that, this polymer behaved as mixed type inhibitor. Similar studies for the inhibitor at 500 ppm in various concentrations of H⁺ and Cl^? ions, have shown that the inhibition efficiency decreases with decrease in concentrations of H⁺ ions and Cl^? ions in aqueous solution. It reveals that, the adsorption of inhibitor on iron surface is by more cationic form of inhibitor and higher efficiency at higher H⁺ and Cl^? ions is due to enhanced adsorption of cat ionic form of inhibitor molecules. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Electropolishing of metals in alcoholic solution of sulphuric acid

The potentiodynamic polarization curves of iron, nickel, cobalt, molybdenum, copper and iron-nickel and cobalt-nickel alloys were measured in the polishing solution of 1M H₂SO₄ in CH₃OH. The above mentioned metals and alloys may be divided into three groups: metals and alloys with high dissolution rate in the active state in which the polishing follows immediately behind the active dissolution region (Fe, Co and Ni-Fe and NiCo alloys with a low nickel content), metals and alloys with low passivating current density that become passive at first and the polishing takes place behind the region of localized corrosion (nickel and NiFe and NiCo alloys with a high nickel content) are metals that are polished in the transpassive region (molybdenum).     

碳钢在Na2CO3-NaHCO3溶液中的阳极极化行为

使用动电位极化技术研究了碳钢在Na₂CO₃-NaHCO₃溶液中的阳极极化行为，测试结果表明，阳极极化曲线上存在着两个电流峰和两个钝化区.与在NaHCO3溶液中相比，碳钢在Na₂CO₃-NaHCO₃溶液中的极化曲线上的第一个钝化区变得更宽.当增加NaHCO₃浓度后，两个峰值电位均往正方向移动，表明碳钢的钝化能力降低.研究发现，第二个电流峰对应的电位与NaHCO₃浓度的对数呈良好的线性关系.根据铁在Na₂CO₃-NaHCO₃溶液中的腐蚀热力学，推测该峰处发生的反应可能是：3FeCO₃+4H₂O---Fe₃O₄+3HCO^-₃+5H⁺+2e.XPS分析表明铁电极表面主要由二价铁和三价铁的氧化物组成，进一步支持了以上反应.     

Inhibition of steel corrosion by potentiodynamic deposition of poly(N-methyl carbazole)

Poly(N-methyl carbazole) (PNMeCz) coating was deposited on 304 type stainless steel (SS) by electropolymerization of N-methyl carbazole monomer in tetrabutylammonium perchlorate containing acetonitrile solution using cyclic voltammetry. PNMeCz coating was characterized by attenuated total reflectance-Fourier transform infrared spectroscopy, scanning electron microscopy, thickness, conductivity, and contact angle measurements. Corrosion performance of the polymer-coated steel electrodes was investigated in 1 M H₂SO₄ solution using open circuit potential–time (E_ocp–t) curves, potentiodynamic polarization, and electrochemical impedance spectroscopy techniques. PNMeCz coating was found to provide anodic protection to the substrate and significantly reduce the corrosion rate of SS in acidic medium.     

Effect of some polymeric materials on the corrosion behaviour of tin in succinic acid solution

The anodic behaviour and corrosion of tin in various concentrations (0.05–0.7M) of succinic acid were studied using cyclic voltammetry. The potentiodynamic anodic polarization curves exhibit active/passive transition. The active dissolution of tin involves one anodic peak. The cathodic curve exhibits one cathodic peak corresponding to the reduction of the passive layer. The ratio of the anodic charge/cathodic charge is more than unity indicating that the passive layer is very thin and the dissolution products are mainly soluble species. Additions of some polyethylene glycols to the succinic acid solution decrease the anodic peak current and shift the peak potential in the negative direction. These changes depend on the concentration and molecular weight of the polyethylene glycol added. The effect of the inhibitors decreases in the following order: (PEG)₆₀₀₀ > (PEG)₄₀₀₀ > (PEG)₁₂₀₀. The inhibition efficiency decreases with increase in temperature, suggesting physical adsorption.