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Abstract: Local electrochemical impedance spectroscopy provides a powerful tool for the investigation of surface heterogeneities on electrode surfaces. However, measurements are greatly influenced by geometry-induced frequency dispersion. In order to account for this frequency dispersion, both simulations and experiments were performed to explore the influence of a recessed electrode on the local and global impedance response. The calculations presented here demonstrated that the depth of the recessed electrode required to achieve a uniform primary current distribution was twice the electrode radius. The calculations provide guidelines for design of LEIS measurements, and were in good agreement with results obtained for a stainless steel disk electrode in a Na2SO4 electrolyte. [Copyright &y& Elsevier]

Abstract: A new Ce, Zr and Nb-based conversion coating was designed for AZ91 and AM50 magnesium alloys. The corrosion protection provided by this coating was evaluated by electrochemical measurements (polarization curves, electrochemical impedance spectroscopy) in Na2SO4 electrolyte, and accelerated atmospheric corrosion tests (humid, SO2 polluted air, and salt spray). Its chemical composition was characterized by X-ray photoelectron spectroscopy (XPS). Electrochemical measurements showed that Mg alloys treated during 24h in the Ce–Zr–Nb conversion bath exhibit: (i) increased corrosion potential, (ii) decreased corrosion and anodic dissolution current densities, and (iii) increased polarization and charge transfer resistances. The accelerated corrosion tests revealed excellent atmospheric corrosion resistance for all Ce–Zr–Nb-treated samples, with or without an additional layer of epoxy–polyamide resin lacquer or paint. XPS analysis showed that the coating includes CeO2, Ce2O3, ZrO2, Nb2O5, MgO, and MgF2 as main components. No significant modification of the chemical composition was observed after cathodic and anodic polarization in Na2SO4. This new coating provides improved corrosion resistance, and excellent paint adhesion. It offers an alternative to the chromate conversion coating for magnesium alloys. [Copyright &y& Elsevier]

Electrochemical methods(cyclic voltammetry (CV), potential steps, and electrochemical impedance spectroscopy) were successfully combined with in situ reflectometry measurements for a detailed analysis of the passive layer evolution as a function of the electrode potential. Interestingly, both EIS and surface reflectivity allowed a film thickness in the nanometer range to be readily determined. In addition, transient analyses of the reflectivity simultaneously recorded with CVs show the formation of both Fe2O3 and Fe3O4 oxides. The image analysis showed that the steel surface reactivity is heterogeneous and presents micrometric islands coated with a thicker oxide layer than the surrounding surface. The in situ combination of these techniques thus offers a powerful analytical description of the interface on a local scale and its transient response to a perturbation. [ABSTRACT FROM AUTHOR]

The adsorption of a model protein, the bovine serum albumin (BSA), on plasma-deposited silver nanocomposite thin films was investigated in situ by quartz crystal microbalance (QCM) and ex situ by X-ray photoelectron spectroscopy (XPS). For comparison, BSA adsorption was also studied on pure silver sample and on the polymeric matrix without silver nanoparticles. Both techniques showed that BSA adsorption systematically occurred, regardless of the chemical composition of the solid surface. BSA adsorption was found to be a fast and irreversible process. For the adsorbed BSA layer characterization, a general island model was considered. The height of the protein islands ( h ) and their surface coverage ( γ ) were estimated from combined QCM and XPS data. On the polymeric matrix, the surface coverage was low whereas on pure silver sample and on the nanocomposite film, it was significantly increased. From QCM measurements, mass loss at a constant rate, ascribed to the release and dissolution of Ag particles from the nanocomposite film into the surrounding solution, was observed before and after BSA adsorption, with two different associated rates. The decrease of the silver release rate after BSA adsorption is explained by silver particles coverage by protein islands. BSA molecules adsorbed on silver nanoparticles have a “blocking” effect, decreased the rate of silver nanoparticle release. However, silver dissolution as Ag + ions may still occur. [ABSTRACT FROM AUTHOR]

Copper alloys, often used in cooling circuits of industrial plants using seawater as coolant, can be affected by biocorrosion induced by biofilm formation. Extracellular polymeric substances (EPS) produced by bacteria play a fundamental role in the different stages of biofilm formation, maturation and maintenance. The influence of loosely bound (LB) and tightly bound (TB) EPS, extracted from marine Pseudomonas NCIMB 2021, on the electrochemical behaviour of 70Cu–30Ni (wt.%) alloy in static artificial seawater (ASW) and on the chemical composition of oxide layers was studied by combined electrochemical measurements (polarization curves, EIS) and surface analysis (XPS, ToF-SIMS). Results were compared with those obtained in the presence of bovine serum albumin (BSA), a model protein. Compared to 70Cu–30Ni alloy in static ASW without biomolecules, for which a thick duplex oxide layer (outer redeposited Cu 2 O layer and inner oxidized nickel layer) is shown, the presence of BSA, TB EPS and LB EPS leads to a mixed oxide layer (oxidized copper and nickel) with a lower thickness. In the biomolecules-containing solutions, this oxide layer is covered by an adsorbed organic layer, mainly composed of proteins. A model is proposed to analyse impedance data obtained at the corrosion potential. The fitting procedure of impedance diagrams allows extracting the anodic charge transfer resistance, from which the corrosion current density can be calculated. The results show a slow-down of the anodic reaction in the presence of biomolecules (BSA, TB EPS and LB EPS), and a corrosion inhibition effect by LB EPS and to a lesser extent by BSA. No detrimental effect is evidenced with TB EPS. [ABSTRACT FROM AUTHOR]

Abstract: Copper alloys often used in cooling circuits of industrial plants can be affected by biocorrosion induced by biofilm formation. The objective of this work was to study the influence of protein adsorption, which is the first step in biofilm formation, on the electrochemical behavior of 70Cu–30Ni (wt.%) alloy in static artificial seawater and on the chemical composition of oxide layers. For that purpose, electrochemical measurements performed after 1h of immersion were combined to surface analyses. A model is proposed to analyze impedance data. In the presence of bovine serum albumin (BSA, model protein), the anodic charge transfer resistance deduced from EIS data at Ecorr is slightly higher, corresponding to lower corrosion current. Without BSA, two oxidized layers are shown by XPS and ToF-SIMS: an outer layer mainly composed of copper oxide (Cu2O redeposited layer) and an inner layer mainly composed of oxidized nickel, with a global thickness of ~30nm. The presence of BSA leads to a mixed oxide layer (CuO, Cu2O, Ni(OH)2) with a lower thickness (~10nm). Thus, the protein induces a decrease of the dissolution rate at Ecorr and hence a decrease of the amount of redeposited Cu2O and of the oxide layer thickness. [Copyright &y& Elsevier]

Abstract: Two different mathematical formulas for estimating effective capacitance from Constant-Phase-Element (CPE) parameters, taken from the literature, are associated unambiguously with either surface or normal time-constant distributions. Application to different systems are used to illustrate the importance of using the correct formula that corresponds to a given type of distribution. Experiments and simulations are used to show that the effective capacitance obtained for a normal distribution yields correct values for the film thickness under conditions where the local resistivity does not vary significantly. When the local resistivity varies considerably over the thickness of a film, the experimental frequency range may preclude observation of the capacitance contribution of a portion of the film, resulting in under prediction of the film thickness. [Copyright &y& Elsevier]

Abstract: An XPS investigation was carried out of the surface films, formed by exposure to ultrapure water, on mechanically ground Mg and the two Mg–Al intermetallic compounds: Al3Mg2 and Mg17Al12. The mechanically ground Mg surface had a film of MgO at the Mg metal surface covered by a Mg(OH)2 layer, formed by the reaction of the MgO with water vapour in the air. Upon immersion in ultrapure water, this film converted to a duplex film with an inner MgO layer next to the Mg metal and an external porous hydroxide layer. For both intermetallics, the XPS data is consistent with (i) preferential dissolution of Mg and (ii) a 10nm thick film on the surface after immersion in ultrapure water; the film composition on Al3Mg2 was whilst on Mg17Al12 the composition was . [Copyright &y& Elsevier]