Long-term corrosion of copper in a dilute anaerobic sulfide solution

The mechanism of corrosion of oxygen-free copper has been studied in stagnant aqueous sulfide solutions using corrosion potential and electrochemical impedance spectroscopy (EIS) measurements. Film structure and composition were examined on surfaces and on cross-sections prepared by focused ion beam (FIB) milling using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Experiments were conducted in anaerobic 5 × 10⁻⁵ mol dm⁻³ Na₂S + 0.1 mol dm⁻³ NaCl solutions for exposure periods up to 4000 h (∼167 days) to mimic (at least partially) the conditions that could develop on a copper nuclear fuel waste container in a deep geologic repository. The corrosion film formed was a single cellular Cu₂S layer with a non-uniform thickness. The film thickness increased approximately linearly with immersion time, which implied that the sulfide film formed on the Cu surface is non-protective under these conditions up to this exposure time. The film growth process was controlled by HS⁻ diffusion partially in the aqueous solution in the pores in the cellular sulfide film and partially in the bulk of the aqueous solution.     

Electrochemical corrosion behavior of hot-rolled steel under oxide scale in chloride solution

In this work, electrochemical corrosion behavior of a hot-rolled steel with oxide scale was investigated in chloride solution through electrochemical measurements and surface characterization. Results demonstrated that the presence of a layer of compact oxide scale would protect the underlying steel from corrosion attack. Upon immersion in chloride solution, oxide scale on the steel surface is reduced, resulting in increase of electrode activity and corrosion rate of the steel. With the further immersion, the insolvable corrosion product and/or new oxide form to accumulate on the electrode surface, enhancing the electrode resistance and decreasing the corrosion of the steel. The amount of dissolved oxygen affects the corrosion of steel. With the increasing concentration of oxygen, there is more compact corrosion product and/or new oxide generating on electrode surface.     

Electrochemical impedance of two-phase Ni-Ti alloys during corrosion in eutectic (0.62Li, 0.38K)2CO3 at 650 °C

The corrosion of two-phase Ni-10Ti and Ni-15Ti in molten (0.62Li, 0.38K)₂CO₃ at 650 °C under the atmosphere of air has been studied by electrochemical impedance spectroscopy (EIS). The impedance spectra for both Ni-10Ti and Ni-15Ti are composed of a semi-circle at high-frequency port and a line at low-frequency port indicating a diffusion-controlled reaction. The corrosion of the alloys produces an external scale composed of NiO and TiO₂, and a wide internal oxidation region. An equivalent circuit representing the features of the corrosion of the alloys was proposed to fit the impedance spectra, and electrochemical parameters in the equivalent circuit were also calculated.     

Influence of microstructure and composition on the corrosion behaviour of Mg/Al alloys in chloride media

The influence of the microstructure and aluminium content of commercial AZ31, AZ80 and AZ91D magnesium alloys was evaluated in terms of their corrosion behaviour in an aerated 3.5 wt.% NaCl solution at 25 °C. The corrosion process was monitored by electrochemical impedance spectroscopy (EIS). The surface was characterized by scanning electron microscopy (SEM), scanning Kelvin probe force microscopy (SKPFM) and low-angle X-ray diffraction (XRD). The extent of corrosion damage was strongly dependent on the aluminium content and alloy microstructure. Two key factors were observed for the lowest corrosion rates, which occurred for the AZ80 and AZ91D two-phase alloys: the aluminium enrichment on the corroded surface for the AZ80 alloy, and the β-phase (Mg₁₇Al₁₂), which acted as a barrier for the corrosion progress for the AZ80 and AZ91D alloys. Surface potential maps suggested that, between the β-phase and the α-matrix, the galvanic coupling was not significant.     

Electrochemical impedance spectroscopy and corrosion behaviour of Al2O3-Ni nano composite coatings

In this paper, the results on the electrochemical impedance spectroscopy and corrosion properties of electrodeposited nanostructured Al₂O₃-Ni composite coatings are presented. The nanocomposite coatings were obtained by codeposition of alumina nanoparticles (13 nm) with nickel during plating process. The coating thickness was 50 μm on steel support and an average of nano Al₂O₃ particles inside of coatings at 15 vol.% was present. The structure of the coatings was investigated by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure. The electrochemical behavior of the coatings in the corrosive solutions was investigated by polarization potentiodynamic and electrochemical impedance spectroscopy methods. As electrochemical test solutions 0.5 M sodium chloride and 0.5 M potassium sulphate were used in a three electrode open cell. The corrosion potential is shifted to more negative values for nanostructured coatings in 0.5 M sodium chloride. The polarization resistance in 0.5 M sodium chloride decreases in 24 h, but after that increases slowly. In 0.5 M potassium sulphate solution the polarization resistance decreases after 2 h and after 30 h of immersion the polarization resistance is higher than that of the beginning value. The corrosion rate calculated by polarization potentiodynamic curves obtained after 30 min from immersion in solution is smaller for nanostructured coatings in 0.5 M potassium sulphate (4.74 μm/year) and a little bit bigger in 0.5 M sodium chloride (5.03 μm/year).     

Electrochemical noise and impedance study of aluminium in weakly acid chloride solution

The electrochemical noise (EN) characteristics of pure aluminium in unbuffered potassium chloride solution and with acetic acid/sodium acetate buffer at pH 5.4 and 4.3 have been analysed to throw light on the influence of pH and of the presence of buffer at the aluminium surface on chloride ion-induced corrosion. Comparison has been made with results obtained by electrochemical impedance spectroscopy (EIS) and quantitative deductions made concerning the values of the noise resistance and the magnitude of the electrochemical impedance. Deviations between results obtained by the two experimental techniques are discussed.     

Electrochemical impedance spectroscopic investigation of the role of alkaline pre-treatment in corrosion resistance of a silane coating on magnesium alloy, ZE41

The protective performance of the coatings of bis-1,2-(triethoxysilyl) ethane (BTSE) on ZE41 magnesium alloy with different surface pre-treatments were evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 0.1 M sodium chloride solution. Electrical equivalent circuits were developed based upon hypothetical corrosion mechanisms and simulated to correspond to the experimental data. The morphology and cross section of the alloy subjected to different pre-treatments and coatings were characterized using scanning electron microscope. A specific alkaline pre-treatment of the substrate prior to the coating has been found to improve the corrosion resistance of the alloy.     

Electrochemical behaviour of heat-treated AlZnMg alloys in chloride solutions containing sulphate

The electrochemical corrosion and passivation of Al5Zn1.7Mg0.23Cu0.053Nb alloys, submitted to different heat treatments (cold-rolled, annealed, quenched and aged, and quenched in two steps and aged), in sulphate-containing chloride solutions, has been studied by means of cyclic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The cyclic polarization curves showed that sulphate addition to the chloride solution produced a poor reproducible shift of the breakdown potential to more positive potentials. The repassivation potentials, much more reproducible, and practically separating the passive from the pitting potential region, were slightly displaced in the negative direction with that addition. When the alloys were potentiodynamically polarized in the passive potential region, sulphate was incorporated in the oxide film, thus precluding chloride ingress. In addition, Zn depletion was favoured, whereas Mg losses were avoided. Different equivalent circuits corresponding to different alloys and potentials in the passive and pitting regions were employed to account for the electrochemical processes taking place in each condition. This work shows that sulphate makes these alloys more sensitive to corrosion, increasing the fracture properties of the surface layer and favouring the pitting attack over greater areas than chloride alone.     

Electrochemical impedance characterization of FeSn2 electrodes for Li-ion batteries

This work reports the electrochemical characterization of a micro-scale FeSn₂ electrode in a lithium battery. The electrode is proposed as anode material for advanced lithium ion batteries due to its characteristics of high capacity (500 mAh g⁻¹) and low working voltage (0.6 V vs. Li). The electrochemical alloying process is studied by cyclic voltammetry and galvanostatic cycling while the interfacial properties are investigated by electrochemical impedance spectroscopy. The impedance measurements in combination with the galvanostatic cycling tests reveal relatively low overall impedance values and good electrochemical performance for the electrode, both in terms of delivered capacity and cycling stability, even at the higher C-rate regimes.     

Effect of nano-ZnO particles on the corrosion resistance of polyurethane-based waterborne coatings immersed in sodium chloride solution via EIS technique

Nano-composite coatings were formed by incorporating 3 wt% nano-ZnO in a polyurethane-based waterborne coating. The nano-ZnO based composite coatings were applied on standard phosphated steel panels by cathodic electrodeposition. The electrodeposited nano-composite coatings were then baked for 20 min at 165 °C. To investigate the corrosion resistance of the coatings, the coated panels were immersed in 3.5 wt% NaCl solutions for 2880 h (120 days). The improvement in corrosion performance of the composite coatings was evaluated using electrochemical impedance spectroscopy technique. It was found that the films containing nano-sized ZnO particles show a corrosion resistance of 2 orders of magnitude higher than that of the neat films.     

Electrochemical corrosion study of Sn–3Ag–3Cu solder alloy in NaCl solution

The corrosion behaviour of Sn–3Ag–3Cu (at%) alloy was investigated in 0.1 M NaCl solution by potentiodynamic polarization and impedance spectroscopy measurements and compared with that of the Sn–3Ag–0.5Cu (at%) solder employed in the packaging of some microelectronic components and devices. Scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) were used to characterize the samples prior to and after the electrochemical tests. Results showed that in NaCl solution the corrosion resistance of the Sn–3Ag–3Cu alloy was better than that of the Sn–3Ag–0.5Cu solder. The presence of tin oxychlorides or oxyhydroxychlorides was detected at the surface of both alloys investigated after the electrochemical tests. The better corrosion behaviour of the Sn–3Ag–3Cu alloy compared to the Sn–3Ag–0.5Cu solder can be ascribed to a more adherent and compact corrosion products layer.     

Effect of naturally formed oxide films and other variables in the early stages of Mg-alloy corrosion in NaCl solution

The influence of initial surface conditions on the subsequent corrosion behaviour of AZ31 and AZ61 magnesium alloys in 0.6 M NaCl solution has been studied using electrochemical impedance spectroscopy. For obtaining the different surface conditions, some of the specimens were immersion tested with the surface in the as-received condition, while others were tested immediately after mechanical polishing, and part of the polished specimens after six months of exposure to the laboratory atmosphere. Considering the evolution of the high-frequency capacitive arc of the Nyquist diagram, whose diameter is related to the corrosion process, a clear effect of the initial surface conditions is observed only in the early stages of testing. This effect is especially significant for the freshly polished specimens.     

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.     

Effect of Al content on the corrosion behavior of Mg-Al alloys in aqueous solutions of different pH

The effect of systematic increase of Al content on the electrochemical behavior of the Mg-Al alloys in aqueous solutions of different pH was investigated. Different electrochemical methods such as open-circuit potential measurements, polarization techniques and electrochemical impedance spectroscopy, EIS, were used to investigate the electrochemical behavior of the alloys in aqueous solutions. The results have shown that Mg-5Al is easily corroded due to the microgalvanic effect between α-phase and β-phase, its corrosion rate is even higher than that of Mg itself. The increase of Al content increases the corrosion resistance of the alloy due to the formation of the β-phase (Mg₁₇Al₁₂) together with the Mg α-phase. The ranking of the corrosion rate of these alloys was Mg-5Al > Mg > Mg-10Al ≅ Mg-15Al. The corrosion rates of the alloys in acidic solutions are pronouncedly high compared to those measured in neutral or basic solutions. The impedance measurements are in consistence with the polarization techniques and the impedance data were fitted to theoretical data obtained according to an equivalent circuit model describing the electrode/electrolyte interface.     

Electrochemical anticorrosion performance evaluation of Al2O3 coatings deposited by MOCVD on an industrial brass substrate

Alumina (Al₂O₃) coatings of different thickness were deposited on OT59 brass substrate (BS) using the metal organic chemical vapour deposition (MOCVD) technique to evaluate the corrosion performance by EIS measurements. The used precursor was dimethyl-aluminium-isopropoxide. Electrochemical characterizations of the deposited films were performed in a standard very aggressive acidic solution (aerated 1N H₂SO₄ at 25 °C up to 168 h of immersion time) by means of direct current method (Tafel curves) and electrochemical impedance spectroscopy (EIS). The Rutherford backscattering spectroscopy (RBS) indicated that the films are very pure with the correct Al₂O₃ stoichiometry, while the IR absorption spectra showed that the films did not contain any OH groups. The surface film morphology was investigated by atomic force microscopy (AFM) and displayed a globular texture. The films were very smooth, with a maximum root mean square roughness, for example, of 14 nm for a 0.96 μm thick coating. The EIS data confirmed, as expected, that a 2.40 μm Al₂O₃ layer ensures the best corrosion protection after 168 h of immersion in the very acidic environment used.     

Electrochemical synthesis of polyindole on 304-stainless steel in LiClO4–acetonitrile solution and its corrosion performance

The use of electrochemically synthesized polyindole (PIN) film was investigated for protective coating on 304-stainless steel (SS). Polyindole was deposited via anodic oxidation of the corresponding monomer, indole in acetonitrile (ACN) solution containing LiClO₄. It provided an adherent and stable coating on SS. The corrosion performance of coated and uncoated SS was investigated in 3.5% NaCl solution using electrochemical impedance spectroscopy (EIS), anodic polarization curves and open-circuit potential–time (E_ocp–t) diagrams. These tests demonstrated that PIN coating provided important barrier effect to SS for important immersion times in aggressive medium.     

Electrochemical and spectroscopic evidences of corrosion inhibition of bronze by a triazole derivative

The electrochemical behavior of the bronze (Cu-8Sn in wt%) was investigated in 3% NaCl aqueous solution, in presence and in absence of a corrosion inhibitor, the 3-phenyl-1,2,4-triazole-5-thione (PTS). The inhibiting effect of the PTS was evidenced for concentrations higher than 1 mM for the cathodic process whereas its effect was clearly seen with a concentration as low as 0.1 mM for the anodic process. A significant positive shift of the corrosion potential was also observed, and its inhibiting effect increased with both its concentration and the immersion time of the sample. From voltammetry and electrochemical impedance spectroscopy experiments, the inhibiting efficiency of the PTS was found to be in the 94-99% range for 1 mM concentration. Scanning electron microscopy and X-ray energy dispersion analysis of the specimen surface show the presence of sulphur on the surface. Raman micro-spectrometry study confirms the protective effect of the PTS in aqueous solution through three types of interactions with the electrode, namely the adsorption of the inhibitor in a flat configuration, the formation of copper-thiol molecules, and when copper is released, the formation of a polymeric complex.     

Evaluation of mechanically treated cerium (IV) oxides as corrosion inhibitors for galvanized steel

The use of cerium salts as corrosion inhibitors for hot dip galvanized steel has been object of a numerous studies in the last few years. The role of cerium ions as corrosion inhibitors was proved: cerium is able to block the cathodic sites of the metal, forming insoluble hydroxides and oxides on the zinc surface. This fact leads to a dramatic decrease of the cathodic current densities and, therefore, to a reduction the overall corrosion processes. On the other hand, the potential of cerium oxides as corrosion inhibitors was also proposed. However, the real effectiveness of this kind of anticorrosive pigments has not been clarified yet.In this work cerium (IV) oxides are considered as corrosion inhibitors for galvanized steel. The corrosion inhibition mechanism of mechanically treated (milled) CeO₂ alone and in combination with milled SiO₂ nanoparticles was investigated. For this purpose milled CeO₂, CeO₂ and SiO₂ milled together and milled SiO₂ particles were studied as corrosion inhibitors in water solution. Therefore, the different mechanically treated particles were dispersed in 0.1 M NaCl solution to test their effectiveness as corrosion inhibitors for galvanized steel. The galvanized steel was immersed in the different solutions and the corrosion inhibition efficiency of the different particles was measured by means of electrochemical techniques. For this purpose, electrochemical impedance spectroscopy (EIS) measurements were carried out, monitoring the evolution of the corrosion processes occurring at the metal surface with the immersion time in the solution. The effect of the different pigments was also investigated by carrying out anodic and cathodic polarization measurements. The polarization curves were acquired under conditions of varied pH. The experimental measurements suggest that the mechanical treatment performed on the SiO₂ and CeO₂ particles promote the formation of an effective corrosion pigment. The tests evidence also the beneficial effect of the CeO₂ milled particles when used in combination with the mechanically treated SiO₂ particles. It was proved that in alkaline conditions the effect of the mechanically treated CeO₂ and SiO₂ particles is dramatically increased.     

Corrosion inhibition of steel in sodium chloride solution by undoped polyaniline epoxy blend coating

In this study an undoped polyaniline (PAni) was synthesized by chemical oxidative polymerization with ammonium persulfate as an oxidizing reagent. The synthesized PAni was used as a corrosion inhibitive pigment in an epoxy matrix. The corrosion protection performance of steel coated panels in 3.5% sodium chloride solution was evaluated via determination of open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS). It was found that after 300 days of immersing the resistance of coating was about 4 × 10⁵ Ω cm². The OCP was shifted to the noble region due to the passivation effect of PAni pigment. Besides, the phase angle (theta) at 10 kHz was stable around 87 ± 1° during immersion period. Results revealed that PAni pigmented paint showed acceptable protection against the corrosion of carbon steel in 3.5% sodium chloride solution.     

Electrochemical behavior of magnesium alloys AZ91D,AZCe2, and AZLa1 in chloride and sulfate solutions

The influence of Cl⁻ and SO₄²⁻ on the electrochemical behavior of AZ91D, AZCe2, and AZLa1 was studied. For all alloys, there was a current plateau in the anodic polarization curves in Na₂SO₄ solutions. In 0.5% NaCl solution, there was a small current plateau, whereas there was none in the 3.5% and 5% NaCl solutions. This indicated that SO₄²⁻ is less aggressive than Cl⁻. The range of the current plateau decreased with increasing SO₄²⁻ concentration. For all alloys, the high frequency capacitive loop in the Nyquist plots decreased with increasing concentration consistent with the decrease in corrosion resistance with increasing Cl⁻ and SO₄²⁻ concentration.