Ricardo M. Souto

Origins of pitting corrosion

Abstract Corrosion of metals and alloys by pitting constitutes one of the very major failure mechanisms. Pits cause failure through perforation and engender stress corrosion cracks. Pitting is a failure mode common to very many metals. It is generally associated with particular anions in solution, notably the chloride ion. The origin of pitting is small. Pits are nucleated at the microscopic scale and below. Detection of the earliest stages of pitting requires techniques that measure tiny events. This paper describes techniques designed to do this and discusses the measurements that result. Some metals show preferential sites of pit nucleation with metallurgical microstructural and microcompositional features defining the susceptibility. However, this is not the phenomenological origin of pitting per se, since site specificity is characteristic only of some metals. A discussion is presented of mechanisms of nucleation; it is shown that the events are microscopically violent. The ability of a nucleated event to survive a series of stages that it must go through in order to achieve stability is discussed. Nucleated pits that do not propagate must repassivate. However, there are several states of propagation, each with a finite survival probability. Several variables contribute to this survival probability. Examples are shown of several metals and some common features of their behaviour are discussed. It is shown that for some systems, the pit sites can be deactivated.

Degradation characteristics of hydroxyapatite coatings on orthopaedic TiAlV in simulated physiological media investigated by electrochemical impedance spectroscopy.

This paper concentrates on the degradation characteristics of hydroxyapatite (HA) coatings on orthopaedic Ti-6Al-4V alloy while immersed in Ringers salt solution, which were investigated by electrochemical impedance spectroscopy. Electrochemical impedance spectroscopy measurements were used to in situ characterize the electrochemical behavior of the passivated alloy covered with HA during aging in Ringers solution. Comparison of the electrochemical data for the coated material with that for the uncoated metal substrate was also performed. The characteristic feature that describes the electrochemical behavior of the coated material is the coexistence of large areas of the coating itself with pores where the substrate is exposed to the aggressive media. The interpretation of results was thus performed in terms of a two-layer model of the film, in which the precipitation of hydrated oxide or phosphate compounds seals the pores left by the ceramic coating. The blocking effect due to salt precipitation inside the pores produces an enhancement of the resistance values, thus effectively diminishing the metal ion release in the system.

Electrochemical characteristics of steel coated with TiN and TiAlN coatings

Abstract The corrosion protection characteristics of titanium nitride (TiN) and titanium–aluminum nitride (TiAlN) coatings produced on cemented carbon steel targets were investigated in aqueous sodium chloride solution. All coatings were produced by cathodic arc plasma deposition. The results indicated that it was possible to follow the corrosion behavior of the coated systems over a period of 300–900 h of immersion. It was found that the TiN and TiAlN coatings had a lower corrosion rate (current density), about three orders of magnitude lower than the untreated steel substrates. The metal substrate was actually passive in these experimental conditions, and exhibited an electrochemical impedance response that could be described by means of the same equivalent circuit than for the coating. Nevertheless, the analysis of the impedance parameters allowed for direct information concerning the enhancement of the corrosion resistance of the coated system as compared to the passive uncoated metal substrate to be extracted. The major corrosion mechanism for the coated samples arises from electrolyte penetration in the pores of the deposits, which may eventually lead to the development of localized forms of corrosion.

Electrochemical behaviour of copper in aqueous moderate alkaline media, containing sodium carbonate and bicarbonate, and sodium perchlorate

The voltammetric polarization of Cu specimens in Na2CO3, NaHCO3 and NaClO4 solutions (8-12pH range) has been investigated. Voltammetry data were complemented with SEM and electron microprobe analysis. Results are found to be in agreement with the passivation model developed for Cu in plain NaOH solutions. For the latter the process can be described in terms of two steps, namely, at low potentials the initial formation of a Cu2O thin layer followed by the growth of a massive Cu2O layer, and at higher potentials the appearance of a CuO-Cu(OH)2 layer. These processes are accompanied by the formation of soluble Cu species. Beyond a certain potential which increases with the solution pH, copper pitting takes place. This model can be extended to Cu in carbonate/bicarbonate containing solutions by considering that Cu carbonates precipitate as long as soluble ionic Cu species are produced, without interfering appreciably with the formation of Cu oxides. The appearance of copper carbonate species is enhanced when pitting corrosion sets in. The precipitation of Cu carbonates occurs principally around pits. Cu pitting, although it is observed for all solutions, becomes more noticeable at the lowest pH values. At a constant pH, the density of pits increases in the order NaClO4 > NaHCO3 > Na2CO3. The influence of the electrolyte composition on Cu pitting is closely related to the blockage capability for pit nucleation and growth of the corresponding copper salts. Passivation in the Cu2O-Cu(OH)2 region hinders pitting corrosion.

The formation of anodic layers on annealed copper surfaces in phosphate-containing solutions at different pH

Resume The electrochemical behaviour of Cu in different phosphate buffers is studied through electrochemical techniques combined with scanning electron microscopy and energy dispersive X-ray analysis. At pH 6.0 and 8.0 the onset of passivation is due to the anodic formation of a basic Cu(II) phosphate, whereas at pH 11.5 the passivating layer corresponds to a duplex Cu(I) oxide-Cu(II) oxide layer. The potentiostatic anodic current transients can be reproduced by a model involving the initial growth of a thin anodic layer and the simultaneous electrodissolution of Cu. The electrodissolution of passivated Cu takes place through the passivating layer. This reaction contributes to the thickening of the outer part of the passivating layer.

Investigation of the corrosion resistance characteristics of pigments in alkyd coatings on steel

Pigments are added to polymeric coatings for enhancing the protective characteristics of the barrier films that are deposited on metal surfaces to prevent corrosion. Electrochemical impedance spectroscopy (EIS) measurements were performed on carbon steel specimens coated with alkyd primers containing different pigments. Corrosion monitoring was carried out in immersion tests in 3.0 wt.% NaCl solution open to air at room temperature. Changes in the impedance characteristics of the systems were found to occur as a function of the exposure time in all the cases, though their evolution with time showed marked differences which derived directly from nature of the pigments contained in the alkyd primers. The impedance response of the coatings was found to correspond to a porous film presenting localized electrochemically reactive areas, though pigments may facilitate additional resistance to the protective film, the extent of which was found to depend on the nature of the pigment. In this way, the best results were found for the alkyd primer containing aluminium powder.

Resistance of metallic substrates protected by an organic coating containing aluminum powder

The corrosion behavior of an epoxy primer containing aluminum powder (10 vol.%) applied on carbon steel and on galvanized steel was examined by electrochemical impedance spectroscopy (EIS). The data show that this coating is more protective when applied onto carbon steel substrates, and that on galvanized steel thicker coatings allow to achieve similar protection levels as those obtained for carbon steel. These effects are probably due to aluminum pigments providing a cathodic protection of the substrate, and to the resulting products precipitating inside the pores of the polymeric coating. Three stages can be distinguished during exposure of the coated specimens. Upon immersion of the coated samples in the test solution, a pre-saturated stage is observed. After a certain period of immersion, which strongly depends on the thickness of the applied coating, a saturation stage is reached in which an effective protection of the metallic substrate against corrosion is achieved. Finally, at sufficiently long exposure times, swelling through the coating eventually leads to the detachment of the coating.

Some experiments regarding the corrosion inhibition of copper by benzotriazole and potassium ethyl xanthate

It has recently been reported that the association of benzotriazole with potassium ethyl xanthate (BTA + KEX) exhibits good inhibitive properties against the corrosion of copper in aqueous solutions containing 0.1 M NaCl [ 1,2]. Moreover, it has been shown that this selective composition appears to be one of the best of its type for avoiding the localized corrosion of copper [2]. These previous studies were mainly preliminary investigations intended to establish the experimental conditions for a synergistic inhibiting effect for copper corrosion, whilst this communication reports new results related to the formation of a surface complex and the nature of the passive film formed on copper. The effectiveness of the resulting protective film against corrosion in environments which do not contain a BTA + KEX reservoir is also investigated.

Application of AC-SECM in Corrosion Science: Local Visualisation of Inhibitor Films on Active Metals for Corrosion Protection†

The suitability of frequency-dependent alternating-current scanning electrochemical microscopy (4D AC-SECM) for investigation of thin passivating layers covering the surface of corrosion-inhibited metals has been demonstrated. Inhibition of copper corrosion by benzotriazole (BTAH) and methylbenzotriazole (MBTAH), which are effective inhibitors for this metal under many environmental conditions, was investigated. Strong dependencies were found for the AC z-approach curves with both the duration of the inhibitor treatment and the frequency of the AC excitation signal applied in AC-SECM. Both negative and positive feedback behaviours were observed in the AC approach curves for untreated copper and for Cu/BTAH and Cu/MBTAH samples. Negative feedback behaviour occurred in the low-frequency range, whereas a positive feedback effect was observed at higher frequencies. A threshold frequency related to the passage from negative to positive regimes could be determined in each case. The threshold frequency for inhibitor-modified samples was found always to be significantly higher than for the untreated metal, because the inhibitor film provides electrical insulation for the surface. Moreover, the threshold frequency increased with increasing surface coverage by the inhibitor. 4D AC-SECM was successfully applied to visualizing spatially resolved differences in local electrochemical activity between inhibitor-free and inhibitor-covered areas of the sample.

In Situ Scanning Electrochemical Microscopy (SECM) Detection of Metal Dissolution during Zinc Corrosion by Means of Mercury Sphere‐Cap Microelectrode Tips

This work presents a scanning electrochemical microscopy (SECM)-based in situ corrosion probing methodology that is capable of monitoring the release of zinc species in corrosion processes. It is based on the use of Hg-coated Pt microelectrodes as SECM tips, which offer a wider negative potential range than bare platinum or other noble-metal tips. This allows for the reduction of zinc ions at the tip to be investigated with low interference from hydrogen evolution and oxygen reduction from aqueous solutions. The processes involved in the corrosion of zinc during its immersion in chloride-containing solutions were successfully monitored by scanning the SECM tip, set at an adequate potential, across the sample either in one direction or in the X-Y plane parallel to its surface. In this way, it was possible to detect the anodic and cathodic sites at which the dissolution of zinc and the reduction of oxygen occurred, respectively. Additionally, cyclic voltammetry (CV) or constant potential measurements were used to monitor the release of zinc species collected at the tip during an SECM scan.