Delaminated areas beneath organic coating: A local electrochemical impedance approach

Local electrochemical impedance mapping was used to investigate delamination phenomena at the steel/epoxy-vinyl primer interface. The delamination occurred from an artificial defect(cutter scribing) and from ageing in a salt spray chamber. The samples were taken from the salt spray chamber after 20, 30 and 50 days of exposure. To observe delamination after ageing, the corrosion product layers were removed by a cathodic polarization at −1.5 V/SCE for 4 h. A non-aged reference sample was tested for comparison. Mapping was performed at 5 kHz. Initiation and propagation of the delamination were clearly observed. The delaminated surface areas measured by visual observations after the removal of the coating were lower than those determined by local electrochemical impedance mapping. The delamination mechanisms were discussed with reference to literature data

Comparison of local electrochemical impedance measurements derived frombi-electrode and microcapillary techniques

In the present paper, local electrochemical impedance spectrawere obtained on a 316L stainless steel from two configurations: a dual microelectrode (bi-electrode) and microcapillaries. With the bi-electrode, the local impedance measurements were made from the ratio of the applied voltage to the local current density calculated from the application of the ohm’s law. With the use of microelectrochemical cells, the specimen surface area in contact with the electrolyte is limited by the use of glass microcapillaries and the local impedance was defined fromthe ratio of the local potential to the local current restricted to the analysed surface area. Differences and similarities observed in local impedance spectra obtained with the two configurations were describe

Spectroscopie d'impédance electrochimique locale : caracterisation de la de lamination des peintures et de la corrosion des alliages Al-Cu

Ce travail est consacré à l'étude, au développement et à différentes applications de la spectroscopie d'impédance électrochimique locale ou SIEL. La première partie de ce mémoire se focalise sur la description et le développement de la SIEL tant d'un point de vue expérimental que théorique. La seconde partie présente trois applications différentes dans lesquelles la SIEL apporte des informations déterminantes. La première application est consacrée à l'étude du CPE (constant phase element). Cet élément, bien que régulièrement utilisé dans l'interprétation des diagrammes d'impédance électrochimique, garde une signification physique vague. Les mesures de SIEL ont montré que le CPE pouvait être interprété comme une distribution locale de résistances et de capacités en 2 ou 3 dimensions. Les études suivantes se rapportent au domaine de la corrosion et de la protection des matériaux. L'une d'entre elle est axée sur l'observation de la délamination se produisant à l'interface métal/peinture. La SIEL s'est avérée être une technique performante pour visualiser et mesurer la surface délaminée de manière non destructive. Les résultats obtenus ont permis de confirmer le mécanisme de délamination proposé par Funke. Puis, une autre étude est consacrée à la corrosion des alliages Al-Cu, et plus particulièrement aux couplages galvaniques se produisant entre la matrice, principalement constituée d'aluminium, et des particules intermétalliques grossières riches en cuivre. L'approche utilisée a consisté à préparer des alliages et des couples modèles et à les étudier à l'aide de diverses techniques dont la SIEL. Les résultats obtenus ont permis de proposer une approche nouvelle des phénomènes de corrosion par couplage galvanique. ABSTRACT : This work is devoted to the study, the development and different applications of the local electrochemical impedance spectroscopy, or LEIS. The first part of the thesis is focussed on the description and the development of LEIS, from both an experimental and a theoretical point of view. The second part presents three different applications in which the LEIS brings determining informations. The first is devoted to the study of the CPE (constant phase element). Currently used for impedance diagram interpretation, the physical meaning of this element is not clear. The LEIS measurments showed that the CPE could be explained by a local distribution of resistances and capacitances into two or three dimensions. The following studies refer to the corrosion and the corrosion protection of metals. One of them investigates the delamination occurring at the steel/coating interface. The LIES proved to be a powerful technique to visualize and to measure the delaminated areas in a nondestructive way. The results confirm the delemination mechanism proposed by Funke. The last part of the thesis is devoted to the study of the Al-Cu alloy corrosion and, more particularly, to the galvanic coupling occurring between the aluminium matrix and the copper-rich coarse intermetallics particles. The approach used consisted in preparing couples with the model alloys and investigating them using LEIS and other techniques. The results allowed an original approach of the corrosion phenomena by galvanic coupling to be proposed

CPE analysis by local electrochemical impedance spectroscopy

Constant-phase elements (CPE) are used extensively in equivalent electrical circuits for fitting of experimental impedance data. The CPE behavior is generally attributed to distributed surface reactivity, surface inhomogeneity, roughness or fractal geometry, electrode porosity, and to current and potential distributions associated with electrode geometry. In this work, different electrochemical systems showing the CPE dependence in the high-frequency range for the overall impedance were considered. Local electrochemical impedance spectroscopy was found to provide a good means for assessing the influence of local variations on the CPE behavior seen in global impedance measurements. A separation between 2D and 3D distributions could be easily observed. In the case of a 2D distribution (AZ91 Mg alloy), the origin of the CPE behavior was the distribution of high-frequency resistance associated with the geometry of the disk electrode; whereas, the capacitance was independent of position. In the case of the aluminium electrode, the CPE behavior could be attributed to a combination of 3D and 2D distributions. Geometric distributions can play a significant role in the impedance response of electrochemical systems, and these distributions can lead to CPE behavior

Galvanic Coupling Between Pure Copper and Pure Aluminum Experimental Approach and Mathematical Model

The corrosion behavior of a pure aluminum/pure copper couple in a weakly conductive sulfate solution was investigated. Potential and current distributions on the surface of the model couple at the beginning of immersion were obtained by solving the Laplace equation using a finite element method (FEM) algorithm. The potential distribution predicted by the calculations was checked using a Ag/AgCl microreference electrode. A good agreement was found between experimental and theoretical results. It was shown that the reaction occurring at the copper electrode was oxygen reduction, while aluminum remote from the Al/Cu interface remained in the passive state. Moreover, calculations predicted a large cathodic current, related to an increase in oxygen reduction, restricted to copper at the Al/Cu interface. This led to a local pH increase reaching values higher than 9, allowing the dissolution of aluminum to occur close to the interface. Combining these data with optical and scanning electron microscope observations after 24 h of immersion in the sodium sulfate solution allowed a three-step mechanism to be proposed to explain the corrosion damage, and particularly the presence of a copper deposit on the aluminum surface, some distance from the Al/Cu interface, a phenomenon currently observed in commercial copper-rich aluminum alloys

Corrosion protection of carbon steel by an epoxy resin containing organically modified clay

This study focusses on the use of montmorillonite clay (MMT) treated with an organic compound (aminotrimethylphosphonic acid (ATMP)) and dispersed in an epoxy resin to improve corrosion protection of carbon steel. X-ray diffraction was performed to verify that the individual silicate layers were separated and dispersed in the epoxy resin. Corrosion resistance of the coated steel was evaluated by electrochemical impedance spectroscopy (EIS) and local electrochemical impedance spectroscopy (LEIS). Three systems were tested: the epoxy clear-coat, the epoxy resin containing 2 wt.% clay and the epoxy resin containing 2 wt.% clay modified byATMP (ATMP-modified clay). From conventional EIS, it was shown that the incorporation of clay or ATMP-modified clay in the epoxy matrix significantly improved the barrier properties of the coating. The corrosion resistance of the carbon steel coated by the epoxy resin containing ATMP-modified clay was higher than that obtained for the system containing non-treated clay. Local electrochemical measurements performed on scratched samples revealed the inhibitive role of ATMP at the carbon steel/coating interface

Contribution to a better understanding of different behaviour patterns observed with organic coatings evaluated by electrochemical impedance spectroscopy

In the present paper, three different coatings (epoxy, alkyd, polyurethane paints) were characterized by electrochemical impedance measurements, permeability tests, free-standing film impedance and local impedance measurements. The increase in resistance with immersion time of alkyd paint was linked to the nature of the polymeric network and not to phenomena occurring at the metal/paint interface. For polyurethane paint, local impedance was not able to detect defects in the paint, which was attributed to the fact that the defects are smaller than those observed in alkyd paint and also that they are less active and homogeneously distributed through the coating. Although electrochemical impedance methods (global and local) are excellent tools to monitor the behaviour of organic coatings, these techniques alone are not sufficient to screen different paints

Determination of the sensitized zone extension in welded AISI 304 stainless steel using non-destructive electrochemical techniques

Extension of sensitized zone (SZ) in welded AISI 304 stainless steel was determined by two non-destructive electrochemical tests: double loop electrochemical potentiokinetic reactivation technique (DLEPR) and local electrochemical impedance spectroscopy (LEIS). Welding was carried out using the shielded metal arc with two selected welding energies: the first one (0.7 kJ mm¡1) does not promote the sensitization of the 304 steel and it constitutes the reference sample and the second one (2.2 kJ mm¡1) which leads to the precipitation of chromium carbides in the grain boundaries after the welding process. The non-destructive DLEPR and LEIS tests allowed the length of the SZ to be determined and a good agreement between the two techniques and the microstructure of the two welded samples was shown. The presence of an inductive loop on the local impedance diagrams seems to reflect a galvanic coupling between the weld string (anode) and the welded stainless steel plates (cathode) which will be very prejudicial to a good corrosion resistance of the welded system. The results showed that the two electrochemical tests could be applied in practical cases in industrial field

Spectroscopie d'impédance electrochimique locale (caracterisation de la delamination des peintures et de la corrosion des alliages Al-Cu)

Ce travail est consacré à l'étude, au développement et à différentes applications de la spectroscopie d'impédance électrochimique locale ou SIEL. La première partie de ce mémoire se focalise sur la description et le développement de la SIEL tant d'un point de vue expérimental que théorique. La seconde partie présente trois applications différentes dans lesquelles la SIEL apporte des informations déterminantes. La première application est consacrée à l'étude du CPE (constant phase element). Cet élément, bien que régulièrement utilisé dans l'interprétation des diagrammes d'impédance électrochimique, garde une signification physique vague. Les mesures de SIEL ont montré que le CPE pouvait être interprété comme une distribution locale de résistances et de capacités en 2 ou 3 dimensions. Les études suivantes se rapportent au domaine de la corrosion et de la protection des matériaux. L'une d'entre elle est axée sur l'observation de la délamination se produisant à l'interface métal/peinture. La SIEL s'est avérée être une technique performante pour visualiser et mesurer la surface délaminée de manière non destructive. Les résultats obtenus ont permis de confirmer le mécanisme de délamination proposé par Funke. Puis, une autre étude est consacrée à la corrosion des alliages Al-Cu, et plus particulièrement aux couplages galvaniques se produisant entre la matrice, principalement constituée d'aluminium, et des particules intermétalliques grossières riches en cuivre. L'approche utilisée a consisté à préparer des alliages et des couples modèles et à les étudier à l'aide de diverses techniques dont la SIEL. Les résultats obtenus ont permis de proposer une approche nouvelle des phénomènes de corrosion par couplage galvaniqueThis work is devoted to the study, the development and different applications of the local electrochemical impedance spectroscopy, or LEIS. The first part of the thesis is focussed on the description and the development of LEIS, from both an experimental and a theoretical point of view. The second part presents three different applications in which the LEIS brings determining informations. The first is devoted to the study of the CPE (constant phase element). Currently used for impedance diagram interpretation, the physical meaning of this element is not clear. The LEIS measurments showed that the CPE could be explained by a local distribution of resistances and capacitances into two or three dimensions. The following studies refer to the corrosion and the corrosion protection of metals. One of them investigates the delamination occurring at the steel/coating interface. The LIES proved to be a powerful technique to visualize and to measure the delaminated areas in a nondestructive way. The results confirm the delemination mechanism proposed by Funke. The last part of the thesis is devoted to the study of the Al-Cu alloy corrosion and, more particularly, to the galvanic coupling occurring between the aluminium matrix and the copper-rich coarse intermetallics particles. The approach used consisted in preparing couples with the model alloys and investigating them using LEIS and other techniques. The results allowed an original approach of the corrosion phenomena by galvanic coupling to be proposed.TOULOUSE-ENSIACET (315552325) / SudocSudocFranceF

Delaminated areas beneath organic coating: A local electrochemical impedance approach

International audienceLocal electrochemical impedance mapping was used to investigate delamination phenomena at the steel/epoxy-vinyl primer interface. The delamination occurred from an artificial defect(cutter scribing) and from ageing in a salt spray chamber. The samples were taken from the salt spray chamber after 20, 30 and 50 days of exposure. To observe delamination after ageing, the corrosion product layers were removed by a cathodic polarization at −1.5 V/SCE for 4 h. A non-aged reference sample was tested for comparison. Mapping was performed at 5 kHz. Initiation and propagation of the delamination were clearly observed. The delaminated surface areas measured by visual observations after the removal of the coating were lower than those determined by local electrochemical impedance mapping. The delamination mechanisms were discussed with reference to literature data