Electrochemical corrosion characteristics of type 316 stainless steel in simulated anode environment for PEMFC

The corrosion behavior of type 316 stainless steel in simulated anode environment for proton exchange membrane fuel cell (PEMFC), i.e., dilute hydrochloric acid solutions bubbled with pure hydrogen gas at 80 °C, was investigated by using electrochemical measurement techniques. The main purpose is to offer some fundamental information for the use of stainless steels as bipolar plate material for PEMFC. Both polarization curve and electrochemical impedance spectroscopy (EIS) measurements illustrate that 316 stainless steel cannot passivate spontaneously in the simulated environments. The absorbed (and/or adsorbed) hydrogen atoms from cathodic corrosion reactions on the steel surface may deteriorate the passivity and corrosion resistance. The oxidation of these hydrogen atoms gives rise to a second current peak in the anodic polarization curve, and the current increases with immersion time. EIS spectra also reveal that a porous corrosion product layer formed on the steel surface during the active dissolution in the test solutions. 316 stainless steel exhibits the similar corrosion behavior in sulfate ions containing dilute hydrochloric acid solution.     

Modification of titanium oxide layer by calcium and phosphorus

The aim of the study was to investigate the possibility of calcium and phosphorus ion implantation into an oxide film applied onto titanium during anodic passivation. The corrosion resistance of modified titanium in Tyrode's physiological solution has been identified. Anodic oxidation was carried out in two solutions. The first contained 20 g dm⁻³ NaH₂PO₂ in 4.3 M H₃PO₄ (K1), whereas the other, 20 g dm⁻³ Ca(H₂PO₂)₂ in 4.3 M H₃PO₄ (K2). Voltage of 100 and 150 V was applied. It has been found out that it is possible to incorporate Ca and P into the emerging passive layer. The application of the voltage of 150 V makes it very porous. It has been also demonstrated that titanium so modified presents higher resistance to corrosion in the investigated environment than titanium not modified in Tyrode's solution.     

Electropolymerization of poly(N-ethyl aniline) on mild steel: Synthesis, characterization and corrosion protection

Poly(N-ethylaniline) (PNEA) coatings on the mild steel electrode were synthesized by electrochemical oxidation of N-ethylaniline using aqueous oxalic acid solutions as reaction medium. Electrodeposition was carried out by potentiodynamic, potentiostatic and galvanostatic synthesis techniques. Smooth, adhesive and thick PNEA coatings on mild steel could be electrosynthesized during sequential scanning of the potential region between −0.5 and 1.4 V versus SCE, with scan rate of 20 mV s⁻¹. The electrodeposited coatings were characterized by cyclic voltammetry, FT-IR and UV-vis techniques. Corrosion behavior of PNEA coated steels was investigated by linear anodic potentiodynamic polarization technique and Tafel test. Anodic potentiodynamic polarization results showed that electrodissolution current value of PNEA coated steel decreased about 90% compared to that of the uncoated steel in 0.5 M H₂SO₄ aqueous solution. Tafel plots showed also strong decrease of corrosion current for the PNEA coated electrode compared to the uncoated steel electrode in 3% NaCl as corrosive medium.     

Corrosion control of Cu-Ni alloys in neutral chloride solutions by amino acids

The corrosion inhibition of Cu-Ni alloys was investigated in aqueous chloride solutions using amino acids as environmentally safe materials. The corrosion rate was calculated in absence and presence of the corrosion inhibitor using polarization and impedance techniques. The inhibition efficiency of the different amino acids was also calculated.The experimental results have shown that a simple amino acid like glycine can be used as efficient corrosion inhibitor for the Cu-Ni alloys in neutral chloride solutions. An inhibition efficiency of about 85% could be achieved at very low concentrations of the amino acid (0.1 mM). For low Ni content alloy (Cu-5Ni), 2.0 mM cysteine shows a remarkable high (∼96%) corrosion inhibition efficiency. The experimental impedance data were fitted to theoretical data according to a proposed equivalent circuit model for the electrode/electrolyte interface, and the mechanism of the corrosion inhibition process was suggested. Different adsorption isotherms were tested and the corrosion inhibition process was found to depend on the adsorption of the amino acid molecules and/or the deposition of corrosion products on the alloy surface. The adsorption free energy of cysteine on Cu-5Ni (−37.81 kJ mol⁻¹) reveals a strong physical adsorption of the inhibitor on the alloy surface.     

Investigation of the anodic behavior of Al current collector in room temperature ionic liquid electrolytes

We have investigated the anodic behaviors of aluminum as a cathodic current collector for lithium ion batteries in several kinds of room temperature ionic liquids (RTILs) and EC + DMC solutions containing LiN(CF₃SO₂)₂ by cyclic voltammetry (CV), chronoamperometry (CA), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry and chronoamperometry data showed that the current density for aluminum foil with the RTIL electrolytes was less than that of aluminum foil in the EC + DMC solutions. Besides, much corrosion pits appeared on the aluminum foil surface after the electrochemical measurement in the EC + DMC solutions, while they were not observed on the aluminum foil with the RTIL electrolytes, suggesting that aluminum current collector was stable in the RTIL electrolytes. Further research by EDX and XPS analysis revealed that a good passivating film composed mainly of the products from the oxidation between aluminum and the anions of the RTIL electrolytes on the aluminum foil surface after the anodic polarization which suppressed the aluminum corrosion.     

Electrochemical and quantum chemical study of purines as corrosion inhibitors for mild steel in 1 M HCl solution

The purines and its derivatives, such as, guanine, adenine, 2,6-diaminopurine, 6-thioguanine and 2,6-dithiopurine, were investigated as corrosion inhibitors for mild steel in 1 M HCl solution by weight loss measurements, electrochemical tests and quantum chemical calculations. The polarization curves of mild steel in the hydrochloric acid solutions of the purines showed that both cathodic and anodic processes of steel corrosion were suppressed. The Nyquist plots of impedance expressed mainly as a depressed capacitive loop with different compounds and concentrations. For all these purines, the inhibition efficiency increased by increasing the inhibitor concentration, and the inhibition efficiency orders are 2,6-dithiopurine > 6-thioguanine > 2,6-diaminopurine > adenine > guanine with the highest inhibiting efficiency of 88.0% for 10⁻³ M 2,6-dithiopurine.The optimized structures of purines, the Mulliken charges, molecular orbital densities and relevant parameters were calculated by quantum chemical calculations. The quantum chemical calculation results inferred that the adsorption belong to physical adsorption, which might arise from the π stacking between the π electron of the purines and the metal surface.     

Poly(N-ethylaniline) coatings on 304 stainless steel for corrosion protection in aqueous HCl and NaCl solutions

Poly(N-ethylaniline) (PNEA) coatings were grown by potentiodynamic synthesis technique on 304 stainless steel (SS) alloy from 0.1 M of N-ethylaniline (NEA) in 0.3 M oxalic acid solution. Characterization of adhesive and electroactive PNEA coatings was carried out by cyclic voltammetry, FT-IR spectroscopy and scanning electron microscopy (SEM) techniques. The protective properties of PNEA coatings on SS were elucidated using linear anodic potentiodynamic polarization, Tafel and electrochemical impedance spectroscopy (EIS) test techniques, in highly aggressive 0.5 M HCl and 0.5 M NaCl solutions. Linear anodic potentiodynamic polarization test results proved that PNEA coating improved the degree of protection against pitting corrosion in HCl and NaCl solutions. Tafel test results showed that PNEA coating appears to enhancement protection for SS in 0.5 M NaCl and 0.5 M HCl solutions. However, according to long-term EIS results, PNEA coating is better for the protection of SS electrodes during the long immersion period in NaCl compared to that in HCl medium.     

Enhanced corrosion resistance properties of radiofrequency cold plasma nitrided carbon steel: Gravimetric and electrochemical results

Cold plasma nitriding treatment was performed to improve the corrosion resistance of C38 carbon steel. Nitriding process was conducted using a radiofrequency nitrogen plasma discharge for different times of treatment on non-heated substrates. The modification of the corrosion resistance characteristic of the C38 steel due to the treatment in acid medium (1 M HCl) were investigated by gravimetric and electrochemical tests such as potentiodynamic polarisation curves and electrochemical impedance spectroscopy (EIS). It was shown that the plasma nitriding treatment improves the corrosion resistance. Indeed, in the gravimetric tests, nitrided samples showed lower weight loss and lower corrosion rate in comparison to untreated one. In the Tafel polarisation tests, the nitrided samples showed greatly reduced corrosion current densities, anodic dissolution and also retarded the hydrogen evolution reaction. Using EIS method, an adequate structural model of the interface was used and the values of the corresponding parameters were calculated and discussed. The results obtained from weight loss and electrochemical studies were in reasonable agreement. X-ray photoelectron spectroscopy (XPS) was carried out to establish the mechanism of corrosion inhibition of nitrided C38 steel in 1 M HCl medium. The enhancement of the corrosion resistance is believed to be related to the iron nitride compound layer formed on the C38 steel surface during plasma nitriding, which protected the underlying metal from corrosive attack in the aggressive solutions.     

Surface analysis of inhibitor films formed by 1-aminoanthraquinones on API 5L-X60 steel in diesel-water mixtures

Three long chain fatty acid substituted aminoanthraquinone (AAQ) were synthesized in the laboratory and evaluated as corrosion inhibitors for steel (API 5L-X60) in diesel-water mixtures at room temperature by weight loss and electrochemical studies. Potentiodynamic polarization studies carried out at room temperature on steel (API 5L-X60) in diesel with water containing 120 ppm of chloride and 50 ppm of aminoanthraquinone (AAQ) derivative showed that all the investigated compounds are of anodic type. The results obtained indicate that 1-aminoanthraquinone derivatives are good corrosion inhibitors in diesel-water mixtures. Oleic acid substituted aminoanthraquinone was found to be the best corrosion inhibitor. It exhibited 92% inhibition efficiency against the corrosion of API 5L-X60 steel in diesel-water mixtures. The surface analysis by AFM indicates the adsorption of synthesized inhibitors on the metal surface.     

Eco friendly inhibitor for corrosion inhibition of mild steel in phosphoric acid medium

The inhibition effect of Zenthoxylum alatum plant extract on the corrosion of mild steel in 20, 50 and 88% aqueous orthophosphoric acid has been investigated by weight loss and electrochemical impedance spectroscopy (EIS). Plant extract is able to reduce the corrosion of steel more effectively in 88% phosphoric acid than in 20% phosphoric acid. The effect of temperature on the corrosion behaviour of mild steel in 20, 50 and 88% phosphoric acid with addition of plant extract was studied in the temperature range 50-80 °C. Results on corrosion rate and inhibition efficiency have indicated that this extract is effective up to 70 °C in 88% phosphoric acid medium. Surface analysis (XPS and FT-IR) was also carried out to establish the mechanism of corrosion inhibition of mild steel in phosphoric acid medium.     

Influence of 8-aminoquinoline on the corrosion behaviour of copper in 0.1 M NaCl

The corrosion behaviour of copper in aerated 0.1 M NaCl solution in presence of 8-aminoquinoline (8-AQ), using open circuit potential (OCP) measurements, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) measurements and atomic force microscopy (AFM), was studied. The measurements revealed that the effect of 8-AQ is dependent on its concentration. For concentrations up to 10⁻³ M, the organic compound displaces the corrosion potential following no trend and also reduces the anodic current. In contrast, for concentrations higher than 10⁻³, 8-AQ reduces markedly both, the anodic and cathodic currents and consequently, the corrosion current density of copper. After 9 days of exposure in chloride solution, containing the organic compound, potentiodynamic polarization analyses showed a significant reduction in the anodic response and a less significant reduction in the cathodic response, which is associated with a film formed at the copper surface of about 10 μm in thickness and visually observed by a colour change of the copper surface.In order to elucidate the most likely interaction between the 8-AQ molecule and the different molecular structures probably present on copper surfaces in chloride solutions, some results obtained from theoretical calculations are presented. The following molecular structures were considered: CuCl molecule, CuCl₂⁻ complex, and little copper clusters defect representation built as five atoms on C_4v symmetry. Thus, based on the geometric, energetic, frontier orbital, and Total Electronic Density analysis done for the optimized states found for the systems investigated, we suggest that the most probable interaction of 8-AQ proceeds above CuCl units and free copper sites.     

Synthesis and characterization of poly(aniline) and poly(o-anisidine) films in sulphamic acid solution and their anticorrosion properties

Poly(o-anisidine) (POA) and polyaniline (PANI) coatings were synthesized on platinum (Pt) surface and stainless steel (SS) in monomer containing 0.50 M sulphamic acid (SA) solution by means of cyclic voltammetry (CV) technique. Meanwhile, poly(o-anisidine) film was also deposited with a different scan rate on SS electrode. The behaviour of PANI and POA films obtained on stainless steel examined by CV was different from the one obtained for PANI and POA on Pt electrode. The corrosion performances of PANI and POA coatings in 3.5% NaCl solution were investigated with anodic polarization technique and electrochemical impedance spectroscopy (EIS). EIS measurements verified the effect of monomers and that of scan rate on corrosion inhibition of coatings on SS electrode. The results showed that POA film synthesized at low scan rate exhibited an effective anticorrosive property on SS electrode. POA synthesized at low scan rate and PANI coatings provided a remarkable anodic protection to SS substrate for longer exposure time than the one observed for POA coating produced at high scan rate as well as that of bare SS electrode.     

12-Aminododecanoic acid as a corrosion inhibitor for carbon steel

The inhibiting effect of 12-aminododecanoic acid (AA) on corrosion of carbon steel (CS) was investigated in hydrochloric acid of different pH, temperatures and over a prolonged period of time, and also in some other selected corrosive solutions. It was found that AA inhibits both partial corrosion reactions, with a slightly stronger inhibition of the anodic corrosion reaction. The corrosion protection mechanism is by formation of a surface-adsorbed AA monolayer that offers a hydrophobic barrier to transport of solvated corrosive ions to the surface. A maximum inhibition efficiency of 98.8 ± 0.5% was achieved in 0.5 M HCl. The adsorption of AA onto the CS surface was described by the Langmuir adsorption isotherm. The corresponding standard Gibbs energy of adsorption was calculated to be −26 kJ mol⁻¹. Polarization modulation infrared reflection absorption spectroscopy measurements revealed that the adsorbed AA monolayer is amorphous, which is due to the high heterogeneity of the CS surface.     

Corrosion protection of 1Cr18Ni9Ti stainless steel by polypyrrole coatings in HCl aqueous solution

Electrically conducting polypyrrole (Ppy) coatings doped with sodium dodecylsulfate (SDS) have been deposited on 1Cr18Ni9Ti stainless steel by anodic polymerization from aqueous solutions of pyrrole and sodium dodecylsulfate. The corrosion behavior of Ppy coated steel was investigated in 0.3 M HCl aqueous solution at room temperature by a combination of electrochemical measurement techniques and scanning electron microscopy. The steel is in active state at the open circuit potential and suffers from pitting corrosion when the polarization potential is higher than 210 mV versus SCE. The Ppy coating can increase the corrosion potential of the steel by more than 600 mV versus SCE, and the pitting corrosion potential by more than 500 mV versus SCE. Fifty-day exposure experiments indicated that the Ppy coating shows high stability, and can inhibit effectively the corrosion of the steel.     

Effect of 2-amino-3-mercaptopropanoic acid (cysteine) on the corrosion behaviour of low carbon steel in sulphuric acid

The effect of cysteine (cys) on the corrosion of low carbon steel (LCS) in sulphuric acid solution was investigated using electrochemical and scanning electron microscopy (SEM) techniques. Electrochemical impedance spectroscopy (EIS) results reveal that the presence of cys at low concentrations (0.1-0.5 mmol L⁻¹) promoted the LCS corrosion process, whereas an inhibiting effect was observed at higher concentrations (1.0-5.0 mmol L⁻¹), which was enhanced on deaeration of the test solution. Polarization results revealed that cys actually inhibited the cathodic process at all concentration but exerted a stimulating effect on the anodic metal dissolution reaction. Despite the cathodic inhibiting effect, the polarization resistances at low cys concentrations were less than that in the blank acid. This suggests that the anodic reaction was the predominant influence determining the corrosion rates in the presence of cys. This has been discussed vis-à-vis the catalytic effect of the Fe-cys complex, which turns the Fe surface more electrochemically active.     

Anisotropic corrosion of iron in pH 1 sulphuric acid

Anisotropic corrosion behaviour of a single grain of pure iron in 0.05 mol dm⁻³ sulphuric acid (pH 1) was investigated by a simple polarization technique. Both corrosion potential and corrosion current were found to be dependent on crystallographic orientation of the iron grain. A high corrosion current flowed on a grain showing a relatively noble corrosion potential, although both cathodic and anodic Tafel slopes were independent of the orientation. It was shown that cathodic hydrogen evolution reaction (HER) governed the corrosion reaction on the iron grain. Covalent bonding of Fe and H and coverage of H on Fe seem to play important roles in the HER and anisotropic corrosion behaviour of pure iron.     

Corrosion resistance of plasma-anodized AZ91D magnesium alloy by electrochemical methods

Anodic coatings formed on magnesium alloys by plasma anodization process are mainly used as protective coatings against corrosion. The effects of KOH concentration, anodization time and current density on properties of anodic layers formed on AZ91D magnesium alloy were investigated to obtain coatings with improved corrosion behaviour. The coatings were characterized by scanning electron microscopy (SEM), electron dispersion X-ray spectroscopy (EDX), X-ray diffraction (XRD) and micro-Raman spectroscopy. The film is porous and cracked, mainly composed of magnesium oxide (MgO), but contains all the elements present in the electrolyte and alloy. The corrosion behaviour of anodized Mg alloy was examined by using stationary and dynamic electrochemical techniques in corrosive water. The best corrosion resistance measured by electrochemical methods is obtained in the more concentrated electrolyte 3 M KOH + 0.5 M KF + 0.25 M Na₃PO₄·12 H₂O, with a long anodization time and a low current density. A double electrochemical effects of the anodized layer on the magnesium corrosion is observed: a large inhibition of the cathodic process and a stabilization of a large passivation plateau.     

Corrosion properties of electrodeposited cobalt in sulfate solutions containing chloride ions

The corrosion properties of electrodeposited pure cobalt were investigated in deaerated 0.5 M Na₂SO₄ solutions at pH 5, 7, 10 and 13 by using polarization techniques. The effect of chloride concentration (0.01 and 0.1 M NaCl) was also studied. The results showed that increasing pH shifted the anodic polarization curves to more negative potentials. At pH 5 and 7, cobalt exhibited active dissolution without any distinctive transition to passivation. However, at pH 10, the metal surface was partially passivated and anodic current increased sharply at approximately −0.2 V_SCE and the corroded surface revealed several well-defined pits. On the other hand, at pH 13, a clear passivation region was observed within the potential range of −0.5 to 0.6 V_SCE. With increasing chloride concentrations of 0, 0.01, and 0.1 M at pH 10, both the anodic current and the number of pits on the cobalt surface were gradually increased. X-ray photoelectron spectroscopic investigations showed that the cobalt surface was covered mostly with cobalt hydroxide after anodic polarization at pH 10 in 0.1 M NaCl.     

Electrochemical synthesis of polypyrrole (PPy) and PPyǀmetal composites on copper electrode and investigation of their anticorrosive properties

This study reports corrosion protection behaviour of various metal cations electrodeposited onto polypyrrole (PPy) coated copper (Cu) electrode. Before electropolymerization of pyrrole, the Cu electrode was passivated in 0.1 M oxalic acid via cyclic voltammetry method. After the coating process, metal cation electrodeposition onto PPy coating was carried out in 10⁻² M CuCl₂, ZnCl₂, FeCl₂ and NiCl₂ solutions. Corrosion behaviour of uncoated, PPy and PPy|metal coated Cu electrodes was studied in 0.1 M H₂SO₄ solution by using potentiodynamic polarization, chronoamperometric and impedance spectroscopic measurements. Surface morphologies were examined by scanning electron microscope (SEM). All the electrochemical measurements were in good agreement showing that metal electrodeposited PPy coated Cu electrodes have a higher corrosion resistance. Furthermore, SEM results show that while all the samples have a homogeneous distribution of metal cations, zinc and nickel have a much better homogeneous distribution compared to copper and iron. It was found that the best corrosion protection is provided by PPy|Zn and PPy|Ni coatings and there is a significant increase in their polarization resistance with increasing amounts of electrodeposited cations.     

Corrosion of tin in aqueous solutions of mono-, Di- and trichloroacetic acids

The corrosion behaviour of tin in stagnant mono-, di- and trichloroacetic acids solutions in the pH range 1–6 and at concentrations 4.0 to 5 × 10^?4 M was investigated. The results indicate behaviour that is generally the same but there is some dependence on the acid concentration and the pH value. In 4.0 to 10^?2 M solutions, the corrosion rate (W) increased with increasing acid concentration and decreasing pH value from 1 to 4 as follows: log W=a+b log C, where b=0.70, 0.42 and 0.35 for tri-, di- and mono-chloroacetic acids respectively. At high concentrations 4.0 to 10^?2 M and in the pH range 1–6, the steady state corrosion potential shifted in the negative direction with increase of acid concentration accompanied by an increase in the corrosion rate, indicating that the corrosion process becomes anodically controlled by the complexing of Sn²⁺ ions with organic acid anions and that the order of aggressiveness is mono-<di-<trichloroacetic acids. In dilute solutions (10^?2 to 5.10^?4 M) in the pH range 1–6 the steady state potential shifted in the noble direction with increase of acid concentration (accompanied by a remarkable decrease in the corrosion rate). Corrosion inhibition in dilute solutions was attributed to film formation on the surface of tin which may result from the hydrolysis of tin species.