The Mechanism of Hydrogen Evolution During Anodic Polarization of Aluminium

AbstractIn this work, a model to account for the superfluous hydrogen evolution mechanism during anodic polarization of Al is proposed. The model is based on the assumption that the simultaneous presence of an anodic current, produced at some distance from the corrosion front, and of conditions that promote local depassivation such as, for example, the presence of chlorides, induces localized rupture of the pre-existing oxide/hydroxide film. This local depassivation leads to the formation of regions where the electrolyte is either in contact with the metal or separated only by a poorly protective salt film. Here, due to the large potential difference available, hydrogen evolves. The model is validated via electrochemical polarization assisted with in-situ image visualization of pure Al and Al/Cu system in experimental conditions that promote stable oxide film formation or induce local film rupture. Hydrogen streams from the active corrosion sites, increasing upon anodic polarization, are observed only in the presence of a depassivating media (chloride) and a remote cathodic current, provided either via galvanic coupling to copper or via external polarization

Correlation between electrochemical impedance measurements and corrosion rate of magnesium investigated by real-time hydrogen measurement and optical imaging

The corrosion behaviour of magnesium in chloride-containing aqueous environment was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) performed simultaneously with real-time hydrogen evolution measurements and optical imaging of the corroding surface. The potentiodynamic investigation revealed substantial deviations from linearity in close proximity of the corrosion potential. In particular, differences in the slope of the current/potential curves were observed for small polarizations above or below the corrosion potential. These observations, suggest that the usual method based on the use of the Stern–Geary equation to convert a value of resistance into a value of corrosion current is inadequate. Nonetheless, a very good correlation between values of resistances estimated by EIS and corrosion currents obtained from real-time hydrogen measurement was found. Real-time hydrogen measurement also enabled, for the first time, direct measurement of an ‘apparent’ Stern–Geary coefficient for magnesium. In order to rationalize the complex behaviours experimentally observed, an electrical model for the corroding magnesium surface is presented

Correlation between electrochemical impedance measurements and corrosion rate of magnesium investigated by real-time hydrogen measurement and optical imaging

The corrosion behaviour of magnesium in chloride-containing aqueous environment was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) performed simultaneously with real-time hydrogen evolution measurements and optical imaging of the corroding surface. The potentiodynamic investigation revealed substantial deviations from linearity in close proximity of the corrosion potential. In particular, differences in the slope of the current/potential curves were observed for small polarizations above or below the corrosion potential. These observations, suggest that the usual method based on the use of the Stern–Geary equation to convert a value of resistance into a value of corrosion current is inadequate. Nonetheless, a very good correlation between values of resistances estimated by EIS and corrosion currents obtained from real-time hydrogen measurement was found. Real-time hydrogen measurement also enabled, for the first time, direct measurement of an 'apparent' Stern–Geary coefficient for magnesium. In order to rationalize the complex behaviours experimentally observed, an electrical model for the corroding magnesium surface is presented

a mathematical description accounting for the superfluous hydrogen evolution and the inductive behaviour observed during electrochemical measurements on magnesium

Abstract When electrochemical techniques are used to probe the surface of corroding magnesium with the aim of obtaining quantitative information on the corrosion process, two peculiarities are generally observed: i) with anodic polarization, the rate of hydrogen evolution increases instead of decreasing and ii) during electrochemical impedance spectroscopy measurements, an inductive contribution is often observed at the low-frequency end of the spectra. The presence of these two phenomena clearly has an impact on the methodology that should be applied to correctly estimate corrosion rates from electrochemical data. The aim of this work is to provide a general mathematical description of the corroding magnesium surface that, under minimal a priori assumptions regarding the reaction kinetics, can account simultaneously for both superfluous hydrogen evolution and inductive response. The mathematical results are consistent with the suggestion that the superfluous hydrogen evolution is mainly related to the increase of the surface of the active corrosion front during anodic polarization. Further, the obtained results show that the inductive response is expected when, at the corrosion front, oxidation of magnesium proceeds faster than hydrogen evolution

T-stress solutions for through-wall circumferential cracks in straight pipes under bending

© 2017 The Authors. This paper reports the results of an extensive series of finite element calculations to provide normalised T-stress solutions for through-wall cracked pipes under bending for a range of crack sizes and pipe radius to wall thickness ratios. Comparisons with the limited solutions in the literature are used to give confidence in the numerical solutions obtained, which are shown to be sensitive to mesh refinement. The results are provided in a form that is suitable for use in practical constraint based defect assessment approaches.Engineering and Physical Sciences Research Council under grant reference EP/K007815/1

Stress corrosion cracking of additively manufactured alloy 625

Laser bed powder fusion (LPBF) is an additive manufacturing technology for the fabrication of semi-finished components directly from computer-aided design modelling, through melting and consolidation, layer upon layer, of a metallic powder, with a laser source. This manufacturing technique is particularly indicated for poor machinable alloys, such as Alloy 625. However, the unique microstructure generated could modify the resistance of the alloy to environment assisted cracking. The aim of this work was to analyze the stress corrosion cracking (SCC) and hydrogen embrittlement resistance behavior of Alloy 625 obtained by LPBF, both in as-built condition and after a standard heat treatment (grade 1). U-bend testing performed in boiling magnesium chloride at 155 and 170◦C confirmed the immunity of the alloy to SCC. However, slow strain rate tests in simulated ocean water on cathodically polarized specimens highlighted the possibility of the occurrence of hydrogen embrittlement in a specific range of strain rate and cathodic polarization. The very fine grain size and dislocation density of the thermally untreated specimens appeared to increase the hydrogen diffusion and embrittlement effect on pre-charged specimens that were deformed at the high strain rate. Conversely, heat treatment appeared to mitigate hydrogen embrittlement at high strain rates, however at the slow strain rate all the specimens showed a similar behavior