Numerical modelling of the electrochemical behaviour of 316L stainless steel based upon static and dynamic experimental microcapillary-based techniques

Microcapillary-based techniques allow the selection and interrogation of single metallurgical sites and are therefore becoming increasingly popular to investigate the electrochemical behaviour of metallic phases and non-metallic heterogeneities in alloys. This study has been carried out to assess the differences between current measurements made using a 'closed' microcapillary system (the electrochemical microcell technique) with current measurements derived from a flowing 'open' microcapillary droplet cell (the scanning droplet cell). The experimental results were compared with calculations derived from a model system adopting a finite element approach. The corrosion system consists of four parallel electrochemical reactions: three cathodic reactions (the oxygen reduction reaction, the hydrogen evolution reaction and water dissociation) and one anodic reaction (metal dissolution reaction). Comparative experimental results have shown there is a large discrepancy between the magnitudes of the cathodic current obtained by the two techniques. The results of this study allow an assessment of the parameters responsible for the mass transport and distribution of species in the closed and open systems. Critical parameters (for example, microcell crevice geometry, specimen surface-capillary gap distance, etc.) which lead to significant modifications of the curves were then identified using the numerical simulation. (C) 2008 Elsevier Ltd. All rights reserved.