Electrochemical behaviour of cobalt in aqueous solutions of different pH

A systematic study of the corrosion and passivation behaviour of cobalt in aqueous solutions of different pH was carried out. Open circuit potential measurements, polarization experiments and electrochemical spectroscopic (EIS) investigations were employed. The experimental results show that the metal surface is always covered by a native passive film which consists of CoO. The formation of the oxide film obeys a two-electron charge transfer process. The dissolution of the barrier film is controlled by the pH of the solution. In neutral and basic solutions the barrier film is stable. In these media a barrier film thickening with the formation of secondary layer is considered. In acidic solutions, the passive film is unstable and dissolves via a pure chemical process. The mechanism of the corrosion and passivation processes taking place at the electrode/electrolyte interface in the different solutions is discussed. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to confirm the electrochemical measurements and the suggested mechanisms.     

Effect of curing on the corrosion protective properties of thin organosilane films on aluminium

Film properties and corrosion protection given by thin organosilane films (bis-1,2-(triethoxysilyl)ethane: BTSE) on aluminium were investigated as a function of curing. The thickness was determined using spectroscopic ellipsometry (SE). Impedance spectra, modelled by an electrical equivalent circuit, show three time constants. The variation of the elements in these three time constants as a function of the immersion time in a NaCl solution indicate the structure of the film after curing. It can be concluded that the barrier properties of the organosilane films are influenced more by the curing temperature than by the curing time.     

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.     

Effect of postreatment on the corrosion behaviour of tartaric-sulphuric anodic films

Unclad and clad AA2024 T3 specimens were anodised in a chromium-free tartaric-sulphuric acid bath (TSA) and subsequently postreated by different processes including impregnation in a cold, concentrated chromate solution, Cr-free hot-water sealing, and dichromate hot-water sealing. The purpose of this work is to evaluate the effectiveness of the classical postreatments used in the aircraft industry on the TSA-anodic films and their corrosion resistance behaviour. TSA-anodic films were characterised by scanning electron microscopy (SEM) and their thicknesses were measured by SEM and the eddy current method. Electrochemical impedance spectroscopy (EIS) was used to characterise the barrier and porous layers, and jointly with potentiodynamic polarisation allowed the evaluation of corrosion resistance parameters with immersion time in NaCl solution for anodised and postreated specimens. In all cases the postreatments increased the resistance of the barrier layer against degradation. However, the NaCl electrolyte easily penetrated TSA-anodised porous layers when they were not postreated, while penetration was slightly more difficult in cold-postreated specimens. The effective pore plugging was observed in the sealed TSA specimens resulting in an improved corrosion resistance. On the other hand, unsealed clad AA2024 specimens showed a self-sealing process of the TSA-anodic layer, which was slower for the cold chromate solution-postreated specimens.     

EIS evaluation of the filiform corrosion of aluminium coated by a cataphoretic paint

Filiform corrosion is mainly considered as a cosmetic attack and is undesirable in most applications. The initiation and propagation of the filaments are related to different parameters such as the presence of defects, the permeability of the coating to water and oxygen, the adherence of the paint system and the presence of salts.

The aim of this work is to study the behaviour of painted aluminium samples towards filiform corrosion or delamination. The 6082 Aluminium alloy was selected and the samples were covered with a cataphoretic epoxy primer without lead (PPG Industries France). Prior to the application of the electrocoat, the samples were pre-treated by a commercial Zr/Ti or chromate conversion treatment or simply etched with a commercial acid etching product.

Filiform corrosion was studied by the normalized test (ISO/DIS 4623): painted and scratched samples were inoculated in HCl and exposed in a constant humidity chamber at 40 °C and 82% RH for 3 weeks. After exposure the samples were subjected to a visual and optical microscopic examination.

Electrochemical impedance spectroscopy was used to study the sensitivity to filiform corrosion. The operating mode of this test is similar to the normalized one. The samples were scratched before inoculation for 1 h in HCl and then exposed to the humidity chamber for a maximum of 4 days. The samples were tested by EIS in an acidified 0.1 M Na₂SO₄ electrolyte solution. The resulting impedance spectra were analyzed with an appropriate equivalent electrical circuit which allows the evaluation of the exposed metallic surface area, directly related to the extent of filiform corrosion or delamination. Different parameters were varied: the exposure time in the humidity chamber; the immersion time in the electrolyte sulphate solution as well as its pH and the coating thickness.     

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.     

Effect of WC on electrodeposition and corrosion behaviour of chromium coatings

To study the effect of WC particles on corrosion behaviour of chromium coating steel samples were plated in Cr(VI) baths with various concentrations of WC. XPS, EPM and XRD were used to study the chemical composition, morphology and texture of the coatings. The corrosion behaviour was studied at different exposure times in solution containing 0.01 mol L^–1 H₂SO₄ + 0.5 mol L^–1 Na₂SO₄ using cyclic voltammetry and impedance spectroscopy. Cyclic polarization measurements suggest that WC particles slow down the processes of passive film dissolution and penetration of aggressive ions to the substrate. Electrochemical impedance spectroscopy (EIS) was used to reveal the details of the corrosion process at the solution/electrode interface. The simulation of EIS data with a proposed equivalent circuit model made it possible to obtain quantitative valuation of the Y₀ (Q_c), Y₀ (Q_s) and R_pore parameters, reflecting corrosion behaviour of samples at the solution/electrode interface. Samples plated in a Cr(VI) bath with WC provided better resistance to corrosion than those plated in a bath without WC. Analysis of the data obtained suggests that WC particles enhance corrosion resistance due to the microstructural features of the coatings.     

Influence of different anions on the behaviour of aluminium in aqueous solutions

The influence of chloride, sulfate and perchlorate anions on the behaviour of native oxide layers on aluminium is investigated using electrochemical techniques. Due to its influence on the open circuit potential and the cathodic side of the polarization curve the oxygen concentration has been carefully controlled. Two kinds of attack on a commercially pure aluminium (99.5 wt %) have been observed. In all the investigated 0.5 M Cl^–, 0.5 M ClO^– ₄ and 0.5 M SO^2– ₄ aqueous solutions the metal is corroded around the iron and silicon containing precipitates, but only in Cl^– and ClO^– ₄ solutions is crystallographic pitting observed. Comparison with high purity aluminium (99.99 wt %) shows that pitting corrosion is not influenced by the presence of impurities in the aluminium alloys, but by the presence of anions in solution. The pH and/or oxygen concentration determine whether or not the pitting potential coincides with the corrosion potential.     

Zn-Fe合金镀层黑色钝化工艺研究Ⅱ--工艺条件的优化及钝化膜耐蚀性能的研究

在钝化膜组成成分研究的基础上，详细研究了工艺条件对Zn-Fe合金钝化膜耐蚀性的影响，从而得到了最佳的工艺条件。对Zn-Fe合金钝化膜性能进行了测试，并采用5％NaCl中性溶液浸泡试验对Zn镀层、Zn-Fe合金镀层及Zn-Fe-TiO2复合镀层黑色钝化膜的耐蚀性进行了比较。结果表明，经黑色钝化后，Zn-Fe合金镀层及Zn-Fe-TiO2复合镀层的耐蚀性都有很大的提高；Zn-Fe合金镀层的耐蚀性是纯锌镀层的3倍多，而Zn-Fe-TiO2复合镀层的耐蚀性是Zn-Fe合金镀层的2倍多，是纯锌镀层的5倍左右。     

Role of alloyed silicon and some inorganic inhibitors in the inhibition of meta-stable and stable pitting of Al in perchlorate solutions

The study of both meta-stable and stable pitting events on the surface of pure Al and three Al–Si alloys, namely (Al + 6%Si), (Al + 12%Si) and (Al + 18%Si) alloys, was carried out in deaerated neutral NaClO₄ solutions of various concentrations (10⁻⁴–10⁻² M). Measurements were carried out under the effect of various experimental conditions using potentiodynamic anodic polarization and potentiostatic techniques. The results presented below showed that meta-stable pits (appeared as oscillations in current) form at potentials close to the pitting potential (E _pit) and during the induction time for stable pit formation. Various factors affecting the rate of meta-stable and stable pits were studied. The presence of Si as an alloying element in Al reduces the rate of formation of meta-stable pits, corresponding to a reduction in the probability of developing stable pits, and an increase in the pitting potential results. The inhibitive effects of chromate, silicate, molybdate and tungstate on pitting corrosion in Al were also studied. Results obtained showed that these known inhibitors retard both meta-stable and stable pitting events. This makes attainment of stable pit growth more difficult in presence of these inhibitors.

Influence of alloying additives on corrosion and hydrogen permeation through commercial aluminium in alkaline solution

The influence of alloying additives on the extent of corrosion and hydrogen permeation through aluminium of different grades such as 2S, 3S, 26S and 57S, in 0.01 M NaOH has been investigated using weight loss measurements and electropermeation. It is found that the extent of self corrosion and hydrogen permeated through different grades of commercial aluminium follow the order: 3S > 2S > 26S > 57S. The influence of incorporating zinc and indium either alone or in combination on self corrosion and permeation current has also been studied. It is found that ternary alloys of both 26S and 57S containing zinc and indium give considerably lesser values of self corrosion rate and permeation current.     

Effect of heat treatment on corrosion and electrochemical behaviour of AZ91D magnesium alloy

An AZ91D ingot in the as-cast condition was homogenized by solution treatment and then aged for various periods of time. The microstructures produced were studied in detail and the phase volume fraction was measured quantitatively. The Corrosion resistance of all the different microstructures was studied in 3.5% NaCl solution through weight loss measurement in constant immersion conditions and potentiodynamic polarization experiments. The corroded surfaces were analysed using SEM and XRD. The volume fraction of the phase was found to have a significant influence on the corrosion behaviour. The T4 condition improved the corrosion resistance of AZ91D alloy compared to the T6 heat treatment. The results support the idea of microgalvanic coupling between cathodic phase and anodic matrix.     

Corrosion Behaviour of Ti–6Al–4V Alloy in Concentrated Hydrochloric and Sulphuric Acids

Open-circuit potential, polarization and electrochemical impedance spectroscopy (EIS) measurements were used to investigate the corrosion behaviour of Ti–6Al–4V alloy in H₂SO₄ and HCl solutions. The corrosion rate of the alloy was found to increase with increasing acid concentration. The corrosion behaviour of the alloy was compared to that of pure titanium in both acids. The results showed that the alloy is more corrosion resistant than pure titanium in the investigated solutions. The apparent activation energies of the corrosion process for titanium are lower than those of the alloy in the same solutions, which reflects the higher corrosion resistance of the alloy.     

双氧水钝化对碳钢耐腐蚀行为的研究

以硫酸铜点滴实验的时间作为判据,通过正交试验对双氧水钝化体系工艺进行改进,试验优选出最优工艺配方为：双氧水质量分数为0．5％、三乙醇胺体积分数为0．15％,磷酸三钠质量浓度2g／L、钝化液pH为9．6、钝化温度40℃、钝化时间6h。电化学测试结果表明,双氧水钝化对碳钢整体的耐腐蚀性能有很大提高。     

Effect of powder painting procedures on the filiform corrosion of aluminium profiles

In this work, the filiform corrosion behaviour of powder painted aluminium profiles was studied, and the coating barrier properties together with adhesion to the substrate were analysed. Samples coated with a traditional painting procedure (one powder layer application followed by curing), and other samples coated using a special cycle to obtain wood grain effect were compared using accelerated filiform corrosion tests. Moreover, in order to better understand the degradation mechanisms of painted metal substrates, thermal stresses were applied to accelerate the natural weathering. The effects of the thermal aging were analysed by electrochemical impedance spectroscopy.     

Electrochemical behaviour and corrosion of lead in some carboxylic acid solutions

The electrochemical behaviour and corrosion of lead in various concentrations of acetic, lactic (0·01 M –1·0 M ), oxalic and tartaric (0·01 M –0·15 M ) acid solutions were studied at 25°C by a potentiodynamic method. The lead anode is readily soluble both in acetic and lactic acid solutions up to 2000 mV. In these two acid solutions, the anodic dissolution of lead increases with increases in the acid concentration and the dissolution process is under charge transfer control. Lactic acid is more corrosive than acetic acid. However, in oxalic and tartaric acid solutions, the E/i profiles depend on the acid concentration. Above a certain specific concentration, the profiles exhibit an anodic current peak associated with a dissolution of the metal and the formation of a passivating lead salt film and a cathodic peak which is related to the reduction of the film. The active dissolution of the lead increases with the acid concentration, the scan rate and stirring of the solution. The passivation of lead in these two acid solutions occurs by a dissolution–precipitation mechanism and the process is controlled by diffusion. X-ray diffraction analysis confirmed the presence of a passivating salt film (either lead oxalate or lead tartrate) on the electrode surface. © 1998 SCI     

The study of aluminium corrosion in acidic solution with nontoxic inhibitors

The inhibitory activity of some substituted N-arylpyrroles on aluminium corrosion in hydrochloric acid was studied in relation to inhibitor concentration, using potentiodynamic and impedance spectroscopy techniques. All investigated compounds were found to act as cathodic-type inhibitors and inhibition was ascribed to the adsorption of inhibitor onto the electrode surface. The inhibiting efficiency of the additives depended on the inductive power of the groups attached to the benzene and/or pyrrole ring. The carbaldehyde group showed better inhibiting power due to additional condensation on the electrode surface. The impedance results analysed in terms of the polarization resistance showed that the EIS technique can be successfully applied in the determination of corrosion resistance in systems where the corrosion kinetics are not simple.     

Macrosegregation and microstructure dendritic array affecting the electrochemical behaviour of ternary Al–Cu–Si alloys

The aim of the present study is to evaluate the electrochemical corrosion behaviour of ternary as-cast Al–Cu–Si alloys. Electrochemical impedance spectroscopy (EIS), potentiodynamic anodic polarization techniques and an equivalent circuit analysis were used to evaluate the corrosion resistance in a 0.5 M NaCl solution at 25 °C. It was found that silicon and copper contents, which are affected by position in casting due to macrosegregation, and the dendrite arm spacing, can play an interdependent role on the corrosion behaviour. For the region with predominant Cu inverse segregation, i.e., close to the casting surface, the Cu content is the driving-force leading to a decrease in the corrosion resistance, but the favorable effect of the fineness of the dendritic array has also to be taken into account. However, from secondary dendrite arm spacings of about 15 μm up to coarser dendritic arrays, the Si particles seem to be the driving-forces related to the corrosion resistance and for these cases coarser microstructures were shown to improve the corrosion resistance.     

Effect of nitrate ions on the corrosion of stellite in permanganate media

The dissolution behaviour of stellite #3 in two oxidizing agents of equivalent acidity namely, permanganic acid (HMnO₄) and a mixture of nitric acid and potassium permanganate (NP) was evaluated. The presence of nitrate in the permanganate formulation was found to reduce its efficiency for oxidizing stellite. Electrochemical polarization and impedance studies were carried out at 90 °C in NP and HMnO₄. The redox potential of both the oxidizing agents favoured transpassive dissolution of chromium from the alloy. In NP, only the chromium depleted inter-phase boundary was attacked while most of the chromium rich carbide phases were intact. In contrast, in HMnO₄, uniform corrosion of the surface was observed. The impedance response was found to change with duration of exposure. The nitrate ions in permanganate were found to promote the repassivation of the surface. HMnO₄ was found to be a better formulation for dissolving cobalt from the alloy as compared to NP.     

Effect of biofouling on corrosion behaviour of grade 2 titanium in Mandapam seawaters

Titanium has the ability to withstand extremely high seawater velocities with negligible corrosion. The inherent passive nature of the metal favours the attachment of bio-organisms more. In this paper the biofouling characteristics and the influence of macrofouling on grade 2 titanium have been investigated in the Palk Bay waters of Mandapam (India) over a period of a year.This work comprises both field exposure as well as laboratory studies. The deposits on titanium were analyzed with the XRD technique. Green algae such as Cladophorapsis zoolengeri, Cheatomorpha area, Chlorodesmis hillibrandii, Enteromorpha intestinalis, Cladophora species and red algae species of Hypnea valentiae, and animals such as bryozoans and barnacles 4 mm in size were identified on the titanium metal surface. The effect of macrofouling on corrosion of titanium was investigated by both impedance and polarization techniques. Titanium experienced negligible corrosion in seawater exposure with an appreciable fouling load of 0.4527 kg.m⁻²y⁻¹.