An electrochemical method for measuring localized corrosion under cathodic protection

 A new method has been developed to measure metal corrosion rates and their distribution under cathodic protection (CP). This method uses an electrochemically integrated multi-electrode array to take local measurements of cathodic current density while simulating a continuous metallic surface. The distribution of cathodic current densities obtained under CP was analyzed to estimate the anodic current component at each electrode of the array. Corrosion patterns determined by this new method have shown good correlation with visual inspection and surface profilometry of the multi-electrode array surface.

Monitoring cathodic shielding and corrosion under disbonded coatings

This work presents a novel corrosion monitoring probe designed for simulating the conditions developed under disbonded coatings and for measuring current densities and their distribution over a simulated pipeline surface. The probe’s concept was experimentally evaluated via immersion tests under Cathodic Protection (CP) in high resistivity aqueous solution. Under the disbonded area, anodic currents as well as cathodic currents were both measured. Anodic current densities were used to calculate metal losses by means of Faraday’s law. Calculated corrosion patterns were compared with corrosion damage observed at the probe’s surface after a period of test. The probe’s working principles are explained in terms of simple electrochemistry.

Cyclopalladated complexes containing 2-C 6 R 4 PPh 2 ligands (R = H, F): one-electron electrochemical reduction leading to metal–carbon σ-bond cleavage via palladium( i )

Three new ortho -metallated palladium complexes, [Pd(O,O’-hfacac)(κ2-2-C6F4PPh2)] (11), [Pd2(O,O’hfacac)2(μ-2-C6F4PPh2)2](12) and [Pd(O,O’-hfacac)(κC-2-C6F4PPh2)(PPh3)] (13) (hfacac = hexafluoroace-tylacetonate), have been prepared and fully characterised. The electrochemical reductions of complexes 11–13, together with those of other cyclopalladated complexes containing 2C6R4PPh2 ligands (R = H, F) were studied by cyclic, rotating disk and microelectrode voltammetry. Evidence for the one-electron reduction of [PdI(κ2-2-C6F4PPh2)(PPh2Fc)] (6) was obtained from coulometric analysis, although the product is unstable and undergoes further chemical processes. Preparative electro-reduction of [Pd2(μ-Br)2(κ2-2-C6F4PPh2)2] (7) in CH2Cl2 causes reductive cleavage of its Pd–C σ-bonds and formation of the complex [PdBr2{PPh2(2-C6F4H)}2](14); possible mechanisms are discussed.

Electrochemical method for studying localized corrosion beneath disbonded coatings under cathodic protection

This paper presents a new method for measuring localized corrosion under disbonded coatings by means of an electrochemical sensor, denoted differential aeration sensor (DAS). It measures the distribution of electrochemical currents over an electrode array surface partially covered by a crevice that simulates a disbonded coating. The DAS has been evaluated using immersion tests at open circuit and under cathodic protection (CP) conditions. Under both conditions, anodic as well as cathodic current densities were detected within the crevice. A fundamental understanding for the detection of anodic currents under CP has been explained in terms of basic electrochemistry. Based on the current distribution data provided by the sensor, two different analysis methods have been used to estimate corrosion and its distribution. These methods consisted of a direct application of Faraday's Law to the anodic currents detected by the array, and on a sensor-specific method denoted corrected currents' method. It has been demonstrated that under diffusion controlled conditions this latter method produces a better corrosion estimation than the direct application of Faraday's Law. The corrected currents' method allowed the estimation of corrosion patterns outside the crevice under CP. Good correlation between electrochemical calculations and surface profilometry results has been obtained.

Electrochemical impedance spectroscopy as a tool to measure cathodic disbondment on coated steel surfaces: capabilities and limitations

The disbondment of protective organic coatings under excessive cathodic protection potentials is a widely reported coating failure mechanism. Traditional methods of evaluating cathodic disbondment are based on ex situ visual inspection of coated metal surfaces after being exposed to standard cathodic disbondment testing conditions for a long period of time. Although electrochemical impedance spectroscopy (EIS) has been employed as an effective means of evaluating various anti-corrosion properties of organic coatings; its application for assessing the cathodic disbondment resistance of coatings has not been sufficiently exploited. This paper reports an experimental study aimed at developing EIS into a tool for in situ measurement and monitoring of cathodic disbondment of coatings. A clear correlation between EIS parameters and the disbonded coating areas has been confirmed upon short term exposure of epoxy-coated steel electrodes to cathodic disbondment conditions; however the degree of this correlation was found to decrease with the extension of exposure duration. This observation suggests that EIS loses its sensitivity with the propagation of coating disbondment, and that in order to achieve quantitative determination of the coating cathodic disbondment localized EIS measurements are required to measure the parameters related to local disbonded areas.

Understanding the effectiveness of cathodic protection under disbonded coatings

© 2015 Elsevier Ltd. All rights reserved. Factors affecting the effectiveness of cathodic protection under disbonded coatings were studied using a partially covered two dimensional electrode array that simulates a crevice under a disbonded coating and allows for the mapping of electrochemical currents under the influence of cathodic protection (CP). This technique enabled the study of the effects of major factors, including crevice gap size, solution conductivity and applied CP potential on the distribution and evolution of CP currents over the electrode array surface. The effect of each of these factors on the overall current distribution profile has been explained using a new electrochemical model. This model suggests that, despite the detrimental effect of cathodic shielding, the steel under disbonded areas could still be protected, independent of the crevice geometry and solution resistivity, by means of concentration polarization instead of direct electrochemical polarization. A set of conditions for maintaining CP potentials more negative than -850 mVCSE along disbonded coating areas was deduced from the proposed model and validated against potential profiles available in the literature. The possible practical implications of the current mapping technique used in this study for developing in-situ CP monitoring sensors has also been discussed.

Quantifying the effects of major factors affecting the effectiveness of cathodic protection of pipelines

electrical interference signals on CP and steel corrosion using newly designed electrochemical corrosion cells; as well as to monitoring cathodic disbondment of coatings using electrochemical impedance spectroscopy. Typical results from using these new techniques for measuring stray current corrosion and for probing the cathodic disbondment of pipeline coatings have been briefly discussed.

Molecular pathogenesis of H5 highly pathogenic avian influenza: the role of the haemagglutinin cleavage site motif

The emergence of H5N1 highly pathogenic avian influenza has caused a heavy socio-economic burden through culling of poultry to minimise human and livestock infection. Although human infections with H5N1 have to date been limited, concerns for the pandemic potential of this zoonotic virus have been greatly intensified following experimental evidence of aerosol transmission of H5N1 viruses in a mammalian infection model. In this review, we discuss the dominance of the haemagglutinin cleavage site motif as a pathogenicity determinant, the host-pathogen molecular interactions driving cleavage activation, reverse genetics manipulations and identification of residues key to haemagglutinin cleavage site functionality and the mechanisms of cell and tissue damage during H5N1 infection. We specifically focus on the disease in chickens, as it is in this species that high pathogenicity frequently evolves and from which transmission to the human population occurs. With >75% of emerging infectious diseases being of zoonotic origin, it is necessary to understand pathogenesis in the primary host to explain spillover events into the human population.

Communication - an approach to measuring local electrochemical impedance for monitoring cathodic disbondment of coatings

An electrochemically integrated multi-electrode array has been used for monitoring and visualizing the cathodic disbondment of
defective coatings by measuring local electrochemical impedance. Compared with the conventional electrochemical impedance and
local current measurement approaches, this new approach significantly enhances the sensitivity of detecting the propagation of
coating disbondment by eliminating the effects of the dominating low impedance regions, such as those that arise at coating defects,
and thus increases the visibility of higher impedance regions deep in the disbonded coating. Furthermore, it facilitates the probing
of electrode processes and mechanisms in selected local electrode regions.

Investigating effects of potential excursions and pH variations on cathodic protection using new electrochemical testing cells

Excursion from safe cathodic protection (CP) potentials occurs on buried steel pipelines due to various forms of electrical interferences such as stray currents. Variations in pH can also occur over some pipeline sections such as seashore and river crossing pipes. Currently, the exact effects of potential excursion and the pH on CP efficiency have not been sufficiently quantified preliminary due to difficulties in measuring these effects. In this work, these effects have been investigated using electrochemical cells designed to mimic the high resistivity and pH conditions observable over underground steel pipes, including a new electrochemical cell that has been designed to facilitate the effective simulation and control of pH, potential excursion and other CP testing parameters. The pH has been shown to be a key factor affecting the patterns of corrosion and CP efficiency. Localised corrosion has been found to be the dominating form of corrosion under potential excursions conditions.

Pathogenesis of avian influenza: role of the haemagglutinin cleavage site motif

 The pathogenicity of highly pathogenic avian influenza viruses (HPAIVs) is highly dependent on the presence of a polybasic haemagglutinin cleavage site (HACS) motif. This study demonstrated that HPAIV replication in chickens occurs primarily in vascular endothelium and is modulated by the molecular composition of the HACS motif.

Electrochemical methods for monitoring localized corrosion under cathodic protection

This research proposes two new electrochemical methods for measuring corrosion rates and their distribution under cathodic protection (CP). These methods were incorporated into a corrosion monitoring sensor that grow a great interest in the Australian energy pipeline industry.

In situ measurement of pipeline coating integrity and corrosion resistance losses under simulated mechanical strains and cathodic protection

A novel experimental assembly consisting of a specially designed tensile testing rig and a standard electrochemical flat cell has been designed for simulating buried high pressure pipeline environmental conditions in which a coating gets damaged and degrades under mechanical strain, and for studying the influence of mechanically induced damages such as the cracking of a coating on its anti-corrosion property. The experimental assembly is also capable of applying a cathodic protection (CP) potential simultaneously with the mechanical strain and environmental exposure. The influence of applied mechanical strain as well as extended exposure to the corrosive environment, coupled with the application of CP, has been investigated based on changes in electrochemical impedance spectroscopy (EIS). Preliminary results show that the amplitude of the coating impedance decreases with an increase in the applied strain level and the length of environmental exposure. The EIS characteristics and changes are found to correlate well with variations in coating cracking and degradation features observed on post-test samples using both optical microscopy and scanning electron microscopy. These results demonstrate that this new experimental method can be used to simulate and examine coating behaviour under the effects of complex high pressure pipeline mechanical, electrochemical and environmental conditions.

Occurrence of anodic current and corrosion of steel in aqueous media under fluctuating cathodic protection potentials

Excursion of cathodic protection (CP) potential from the designed "safe" CP level resulting from various forms of electrical interference signals are observed rather frequently in industrial applications, in particular in the pipeline industry; however, the influence of such potential fluctuations on the corrosion behavior of steel under CP conditions does not yet appear to be fully understood. In this work, the effects of anodic transients that periodically shift the potential of a CP protected steel electrode from-1,200 mVAg/AgCl to-750 mVAg/AgCl on the corrosion of a steel electrode in aqueous media was investigated using square wave polarization. Anodic currents were measured that lasted for significant periods of time upon stepping the CP potential up to a less cathodic potential at various frequencies (1 h, 30 s, 10 s, 5 s, and 1 s). Part of such anodic currents is found to cause steel corrosion, and this is explained on the basis of understanding the Fe/H2O equilibrium.

Cleavage of Ru-C(aryl) bond of a four-membered ortho-metalated ruthenium(II) organometallics by mercaptopyrimidine and pyridine-2,6-dicarboxylate ligands: spectroscopic, structural and computational studies

The heterogeneous phase reaction of Ru(η2-RL)(PPh3)2(CO)Cl (1) with 2-mercaptopyrimidine(pymSH) and pyridine-2,6-dicarboxylate(dipic) ligands afforded the complexes of the type Ru(PPh3)(CO)(pymS)2 (2) and Ru(PPh3)2(CO)(dipic) (3) in excellent yield respectively. The chelation of pymS/dipic is attended with the cleavage of Ru-O, Ru-Cl and Ru-C(aryl) bonds and the RL ligand is no longer coordinated with the metal center in the products. The spectral (UV-Vis, IR, 1H NMR) and electrochemical data of the complexes are included. In dichloromethane solution both 2 and 3 display one quasi-reversible RuIII/RuII cyclic voltammetric response with E1/2 in the range 1.15-1.50 V vs Ag/AgCl. Structure determinations of 2 and the solvate 3·CH3CN have revealed distorted octahedral RuCN2S2P coordination sphere for 2 and RuCNO2P2 coordination sphere for 3·CH3CN. For 2 the pairs (P, N), (S, S) and (C, N) define the three trans directions whereas for 3·CH3CN those pairs are (P, P), (C, N) and (O, O). The electronic structures and the absorption spectra of 2 and 3 are also scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analysis.