Local and global electrochemical impedances applied to the corrosion behaviour of an AZ91 magnesium alloy

The electrochemical behaviour of an AZ91 magnesium alloy was investigated in a low aggressive medium by means of local and global electrochemical impedance measurements. The results were compared to those obtained on a pure magnesium sample. It was possible to show the individual contribution of each phase constituting the alloy, and it was observed that the corrosion mechanism of the two phases was the same, controlled by the Mg dissolution. However, local impedance diagrams clearly indicated that the kinetics dissolution of the b-phase was slower than that of the a-phase, which was in good agreement with SEM observations

An Impedance Investigation of the Mechanism of Pure Magnesium Corrosion in Sodium Sulfate Solutions

The corrosion behavior of pure magnesium in sodium sulfate solutions was investigated using voltammetry and electrochemical impedance spectroscopy with a rotating disk electrode. The analysis of impedance data obtained at the corrosion potential was consistent with the hypothesis that Mg corrosion is controlled by the presence of a very thin oxide film, probably MgO, and that the dissolution occurs at film-free spots only. This hypothesis was substantiated both by the superposition of the EIS diagrams, obtained for different immersion times and for two Na2SO4 concentrations once normalized, and by use of scanning electrochemical microscopy in the ac mode to sense the local conductivity of the material. On the basis of the electrochemical results, a model was proposed to describe magnesium corrosion at the open-circuit potential. Simulation of the impedance diagrams was in good agreement with the experimental results

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

Influence of flow on the corrosion inhibition of carbon steel by fatty amines in association with phosphonocarboxylic acid salts

This work was carried out to study the inhibition mechanism of a carbon steel in a 200 mg l−1 NaCl solution by a non-toxic multi-component inhibitor used for water treatment in cooling circuits. The inhibitive formulation was composed of 50 mg l−1 fatty amines associated with 200 mg l−1 phosphonocarboxylic acid salts. Steady-state current–voltage curves, obtained with a rotating disc electrode, revealed that the properties of the protective layer were dependent on the electrode rotation rate and on the immersion time. The cathodic process of oxygen reduction was not modified in the presence of the inhibitive mixture. As expected, the current densities increased when the rotation rate was increased. In the anodic range, original behaviour was observed: the current densities decreased when the electrode rotation rate increased. The morphology and the chemical composition of the inhibitive layers allowed the electrochemical results to be explained. Two distinct surface areas were visualised on the metal surface and the ratio between the two zones was dependent on the flow conditions. This behaviour was attributed to a mechanical effect linked to centrifugal force. XPS analysis revealed that the formation of a chelate between the phosphonocarboxylic acid salt molecules and the iron oxide/hydroxide was enhanced by the increase of the electrode rotation rate

Localized approach to galvanic coupling in an aluminum–magnesium system

The corrosion behavior of a pure aluminum/pure magnesium couple in a weakly conductive sodium 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 algorithm. Magnesium acted as the anode of the system while oxygen and water were reduced on aluminum. Calculations predicted a large current peak at the Al/Mg interface related to a local increase in both Mg dissolution and oxygen and water reduction on aluminum, leading to a local pH increase. Optical and scanning electron microscope observations confirmed the strong dissolution of magnesium concomitantly with depassivation of aluminum at the Al/Mg interface. Local electrochemical impedance spectroscopy showed the detrimental effects of the galvanic coupling both on aluminum and magnesium

Positron detection in silica monoliths for miniaturised quality control of PET radiotracers

We demonstrate the use of the miniaturised Medipix positron sensor for detection of the clinical PET radiotracer, [⁶⁸Ga]gallium-citrate, on a silica-based monolith, towards microfluidic quality control. The system achieved a far superior signal-to-noise ratio compared to conventional sodium iodide-based radio-HPLC detection and allowed real-time visualisation of positrons in the monolith

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

An electrochemical and surface analytical study of the formation of nanoporous oxides on niobium

In the present paper, the anodization of Nb in mixed sulphate + fluoride electrolytes resulting in the formation of a nanoporous oxide film has been studied. Chronoamperometry and electrochemical impedance spectroscopy have been employed to characterise in situ the kinetics of the oxidation process. In addition, the evolution of the layer structure and morphology has been followed by ex situ scanning electron microscopy. Particularly, local electrochemical impedance spectroscopy has been used to discern between the mesoscopic 2D and 3D distributions of time constants at the electrode surface. The similarity between local and global impedance spectra during anodic oxidation of Nb demonstrates the presence of an inherent 3D distribution of the high-frequency time constant, which is interpreted as in-depth variation of the steady state conductivity of the passive film. The experimental and calculational results are discussed in relation to the micro- and nanoscopic structure of the formed oxide

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