While it has long been known that water flow can influence non-uniform corrosion of copper pipe (Rushing 2002, Marshall 2004), it has never previously been considered a primary contributor to the problem. This work is the first to describe a fundamentally important phenomenon in aqueous non-uniform corrosion: flow electrification. A conceptual framework for flow electrification was developed from prior work on non-aqueous fluid flow in pipes, where the primary concern was prevention of electrical explosions. Thereafter, a series of experiments was aimed at monitoring flow electrification, quantifying its practical effects, and examining aspects of non-uniform copper corrosion in real situations. Under conditions with little or no flow, in a high pH and high chlorine water known to cause pinholes in copper pipes, while water chemistry influenced corrosion, non-uniform corrosion was not sustained. But when flowrates were higher, flow electrification contributed to severe and sustained non-uniform corrosion, with the most serious attack manifested in the first section of pipe that encountered the flowing water. The magnitude of flow electrification increased with chlorine concentration, pH and flowrate. Containers dosed with inhibitors such as zinc or phosphate experienced lower electrification, current, voltage, scale resistance, and corrosion potential measurements when compared to a control without an inhibitor. Additionally, systems dosed with inhibitors had reduced rate of chlorine decay, weight loss, pit density and/or maximum depth. Zinc orthophosphate had the largest positive impact on electrochemical measures of pitting. However, experimental studies suggested that if zinc orthophosphate was dosed to a system for a period of time, and dosing was then stopped, very serious pitting could occur. A practical case study seemed to strongly confirm this hypothesis in one system. The presence of sulfides caused the separation of anode and cathode along a pipe section, from electrification, to reverse relative to what was observed in the system with high chlorine and high pH. Below a certain level of sulfides, electrification ceased. It seems likely, based on measurement of electrochemical potential (Ecorr) in waters of this type as a function of sulfide concentration, that the onset of pitting would be associated with decreasing Ecorr with time. If so, the fundamental basis of tracking Ecorr rise with time to predict pitting propensity would be invalidated. Electrochemical noise programs were applied to try to differentiate between systems of low and high pitting propensity. Amplitudes of potential noise and current noise measurements drastically increased with the presence of sulfides or chlorine, confirming that tracking electrochemical noise may indicate the presence of a pitting agent. However, the electrochemical noise measurements are at best, an indirect indicator of copper pitting, and their interpretation is complicated by the co-occurrence of flow electrification. Attempts were made to apply these insights to a case study examining pitting in two real waters in Maryland and to examine the effects of orthophosphate, chlorination, chloramination and enhanced coagulation on copper pitting propensity. Tracking of Ecorr suggested that the control water (without phosphate) had the greatest pitting propensity. The free chlorine system with orthophosphate maintained Ecorr values below the control signifying that the presence of phosphate lowered the corrosion propensity. Waters with chloramine and phosphate had the lowest Ecorr values and also had the least variability in Ecorr due to the stability of the disinfectant. There is considerable ambiguity in the results, since the copper pipes exposed to the waters in question did not develop serious pitting over the several months of the study. / Master of Science

Avec la nouvelle génération d'avions composites, une attention est portée sur les systèmes de carburant vis-à-vis de la prévention des décharges électrostatiques (ESD) durant les phases de remplissage des réservoirs. La plupart des travaux réalisés en aéronautique a été menée sur des réservoirs métalliques. Toutefois, l'introduction des matériaux composites a soulevé de nouvelles interrogations, puisque ces matériaux peuvent avoir un comportement différent des métaux vis-à-vis de l'électrisation par écoulement, qui justifient pleinement de nouvelles analyses. Afin de définir correctement les structures des réservoirs et leur protection contre les risques ESD, il est crucial de comprendre comment un empilement complexe de matériaux se comporte en termes de création de charge lorsque ces matières sont en contact avec un carburant d'avion. La structure de ces matériaux et leurs propriétés électriques contrôlent le potentiel électrique atteint dans le réservoir à travers un équilibre entre la production, l'accumulation et la fuite des charges électriques. Ce potentiel peut dépasser le point d'éclair du mélange air/vapeurs de carburant et provoquer une inflammation. Diverses mesures de protection peuvent être adoptées pour contrôler ce phénomène, comme utiliser des additifs antistatiques dans les carburants, des réservoirs métalliques à la masse ou encore des réservoirs faits de matériaux non métalliques mais ne favorisant pas l'accumulation de charges. C'est principalement en réponse à cette dernière solution que ce travail est orienté afin de guider vers le choix optimaux des matériaux et une meilleure définition des structures du réservoir. / With the new generation of composite aircrafts an attention is carried out on fuel systems with respect to prevention of electrostatic discharges (ESD) during the filling phases of the tanks. Most of the work realized in aeronautics (during the 60's) was conducted on metallic fuel tanks. However, the introduction of composite materials has raised new questions, since those materials can have a different behavior than metallic ones with respect to flow electrification, which fully justify new analyses. In order to properly define the tank structures and their protection against ESD hazards, it is crucial to understand how a complex stack of materials (conductive or not, multilayered or homogeneous, painted or not) constituting a fuel tank behaves with respect to the mechanisms of charge creation by flow electrification when these materials are in contact with aviation fuel. The structure of these materials and their electrical properties control the electric potential reached in the tank through a balance between the production, accumulation and leakage of the electrical charge. This potential may exceed the flash point of the fuel vapors/air mixture and induce ignition. Various protective measures can be adopted to control this phenomenon such as using antistatic additives in the fuels, lowering the rates ofthe fuel injection inside the tank, using only bonded metallic tanks or tanks made of non-metallic materials which do not favor charge accumulation or local charge trapping. It is majorly in response to the latter solution that this work is oriented in order to guide optimum choices of materials and a better definition of the tank structures.

Lorsqu'un solide est en contact avec un liquide, des phénomènes physico-chimiques conduisent à polariser l'interface. Deux zones de charge, de signe opposé, apparaissent à cette interface, une dans le solide et l'autre dans le liquide, formant ainsi la double couche électrique (DCE). Par rapport à la littérature existante, l’originalité de ce travail est de s’intéresser à la DCE à l’interface acier inoxydable 304L /film passif d’oxyde/ solution de NaCl (0.01M) en couplant des caractérisations électrochimiques, électriques et physiques. Une méthodologie de caractérisation par voie électrochimique en utilisant les méthodes de spectroscopie d’impédance (SIE) et de voltammétrie cyclique (CV) a été mise au point pour accéder à deux paramètres: la capacité effective et la densité surfacique de charge. Des modifications de la concentration de l'électrolyte, du potentiel appliqué et de l'état de surface ont ensuite été réalisées : la capacité effective de la DCE dépend principalement de la concentration et du potentiel et la densité surfacique de charge croît avec la concentration. Dans la gamme étudiée, la rugosité a une faible influence sur la capacité effective mesurée. Des analyses physico-chimiques de la surface ont permis de caractériser les films passifs formés sur l'acier, sans révéler de différences significatives entre les surfaces avant et après immersion. Un autre paramètre caractéristique de la DCE, la densité volumique de charge à la paroi, a été aussi déterminé par la méthode d'électrisation par écoulement du liquide. Les 3 méthodes de caractérisation (SIE, CV et électrisation) confirment l'influence de la concentration sur les caractéristiques de la DCE. / When a metal is immersed in an electrolyte, a charge distribution is created at the interface and a potential is set up across the two phases. The separation between charges give rise to what are known as electric double layers (EDL). Compared to the usual solid/liquid interfaces investigated in the literature, this study is dedicated to the EDL at the stainless steel 304L / passive film / NaCl (0.01M) interface by combining electrochemical, electrical and physical methods. First, a methodology has been set up to characterise the EDL by the electrochemical methods: Electrochemical Impedance Spectroscopy (EIS) and cyclic voltammetry (CV). Both the effective capacity and the surface charge density were evaluated. Then, several parameters were investigated such as the electrolyte concentration, the applied potential and the influence on the EDL of the surface preparation. The results showed that the double layer capacitance depends mainly on the concentration of the electrolyte and on the applied potential. The roughness seems to have a poor influence on the measured capacitance. Various physico-chemical analysis were performed in order to characterise the passive films formed at the surface: no significant difference could have been evidence between the surfaces before and after immersion. Finally, the volume charge density was also determined by the liquid flow electrification measurement. Whatever the characterization techniques used (EIS, CV or flow electrification), the same trend was observed with regard to the influence of the concentration on the characteristics of the EDL.

A l'interface solide-liquide, des réactions physicochimiques conduisent à polariser l'interface et à former la double couche électrique (DCE). La circulation du liquide transporte une partie des charges électriques de la DCE et conduit au phénomène d'électrisation par écoulement. Dans les transformateurs de puissance, constitués, entre autres, d'huile minérale et de carton d'isolement, le phénomène d'électrisation est suspecté d'être à l'origine de certaines défaillances et accidents. Dans cette problématique de risque, de nombreuses études ont été menées et ont permis de mettre en évidence l'influence de paramètres significatifs : nature des matériaux, humidité des matériaux, géométrie et vitesse de l'écoulement, température. Peu d'études se sont concentrées sur l'influence du champ électrique, en particulier les champs continus (DC). Même si le champ électrique généré dans les équipements de puissance est principalement alternatif (AC), il n'en est pas moins vrai que des champs électriques continus (DC) résiduels peuvent être présents, en particulier dans les dispositifs H.V.D.C (High Voltage Direct Current). L'objet du travail s'inscrit dans ce contexte et a pour but, dans une approche à la fois expérimentale et numérique, d'apporter des éléments de réponse sur le développement et le transport des charges de la double couche électrique sous contrainte de champ électrique externe. / At the solid-liquid interface, physicochemical reactions lead to the polarization of the interface and to the formation of an electrical double layer (EDL). The process of flow electrification is due to the convection of part of the electrical charges located in the EDL. In power transformers within which mineral oil and pressboard are commonly used for cooling and electrical insulation, a flow electrification phenomenon is suspected to be responsible of failures. In this hazard assessment problematic, many studies have been made and allowed identifying the influence of significant parameters: nature of materials, moisture level of materials, flow geometry and velocity, temperature. Few studies have focused on the influence of the electric filed, particularly the continuous electric fields (DC). Even though the electric field generated within power transformers is mainly alternating (AC), it is nonetheless true that residual DC electric fields may be detected (e.g. High Voltage Direct Current appartus). This present work fits in this context and aims at providing, both through an experimental and numerical approach, some answers on the development and the transport of charges from the electrical double layer under external electric field stresses.