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No description available.

No description available.

No description available.

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Non-uniform corrosion of copper and brass in potable water systems poses both economic and environmental problems associated with premature plumbing failures and release of metals. With respect to copper pitting corrosion, it was found that forensic testing (i.e., in pipe-loops) is the only investigative technique that can closely mimic conditions found in real water systems and produce unambiguous results; and, if used in combination with electrochemical techniques, it may also provide some mechanistic insights into the pitting process. Using pipe-loops, it was demonstrated that copper pitting in aggressive water qualities (i.e., chlorinated, high pH and low alkalinity) is deterministic and reproducible. Additionally, the effects of various chemical and physical factors on pitting were investigated. Overall, increased flow velocity and frequency, increased chlorine residual and decreased hardness were found to accelerate pitting; whereas increased phosphate and silica were found to decelerate pitting. Several mitigation strategies for copper pitting in aggressive water were further investigated, and experimental data were interpreted utilizing electrochemical theory to evaluate specific effects on the initiation and propagation phases of pitting. Surprisingly, it was found that decreased chlorine may delay pit initiation, however, even relatively low levels of chlorine may eventually initiate and propagate pits. Increased alkalinity appears to decelerate pit growth, but does not prevent pit initiation. NOM can delay pit initiation and propagation, although the potential for DBP formation in chlorinated waters makes inhibition by NOM an unfavorable alternative. At sufficient dosages, phosphate and silica corrosion inhibitors may completely stop pitting, consistent with the success of several field trials. At very low dosages, phosphate and silica may actually accelerate pinhole failures, so these inhibitors should not be under-dosed. While brass alloys exist that can limit dezincification problems, they are not always utilized in potable water applications due to high costs, and so dezincification is a re-emerging issue in some countries, including the US. Little research has been conducted in the past several decades regarding the effects of water chemistry, and almost no work has addressed the roles of physical factors associated with real plumbing systems. Thus, a comprehensive review of these topics was conducted. To better understand the effects of some factors associated with specific plumbing installations on dezincification and other brass corrosion types, a series of pipe-loop studies was carried out. It was confirmed that increased oxidant delivery rates to cathodic surfaces, either via increased oxidant concentration or increased flow velocity, can increase corrosion rates. Several key differences were observed with respect to corrosion of brass located in copper plumbing tube systems as opposed to plastic. When copper tubes contribute copper ions to water, brass corrosion becomes more selective for zinc; but if galvanic connections are made between the copper tubes and brass, selectivity for zinc is reduced while overall corrosion rates are accelerated. As opposed to copper tubing, plastic maintains oxidant (e.g., free chlorine) levels, and may thereby increase brass corrosion and build-up of corrosion by-products. Finally, it was found that increased temperature can significantly increase lead leaching from brass. Following recent outbreaks of brass dezincification failures, NSF/ANSI Standard 14 has been revised to require that all NSF 14-listed brass is dezincification resistant, as certified by satisfactory results from an accelerated test method (ISO 6509). Various brasses were tested using this method as well as a longer-term jar method utilizing real potable water. Results of the two tests were in good agreement with respect to dezincification, specifically; but some inconsistencies were observed with respect to uniform corrosion and lead leaching. / Ph. D.

Water chemistry and fluid velocity are factors that can perpetuate certain types of non-uniform pitting corrosion in copper tube, specifically in waters with high chlorine and a high pH. These two parameters can further act synergistically to alter pitting propensities in copper pipes subjected to this type of water. A preliminary short-term experiment considered pitting propensity in copper pipe as a function of water chemistry. This study used a water chemistry that had been documented to promote and sustain pitting in copper tube that further developed into fully penetrating pinhole leaks. Modifications to this base water chemistry found that dosing a chloramine disinfect (rather than free chlorine) or the addition of silica greatly reduced corrosion activity and pitting propensity on copper pipes. In another short-term experiment, copper pitting propensity was considered as a function of fluid velocity. A number of different fluid velocities were tested in several different pipe diameters using the same documented pitting water. Velocity was observed to significantly increase pitting propensity in all pipe diameters considered. At the highest fluid velocity tested (11.2 fps) a pinhole leak formed in ¼â tubing after only 2 months of testing. Larger pipe diameters were also found to increase the likelihood of forming deeper pits on the pipe surface at the same fluid velocity. Chlorine was a driving factor in corrosion for preliminary tests conducted using this pitting water. The reduction of chlorine to chloride is believed to be the primary cathodic reaction limiting the overall rate of corrosion in this type of water. As such, a subsequent study considered the relationship between the rate of chlorine reduction and corresponding corrosion activity. Chlorine reduction or demand rates were found to be good indicators for pitting propensity and corrosion activity for this particular type of water. All preceding work led to the development and design of a large scale, long-term, copper pitting study. A matrix of 21 unique conditions tested various water chemistries, flow conditions, corrosion inhibitors, and galvanic connections of copper pipes to other metallic plumbing materials. The severity of pitting corrosion was observed to be dramatically decreased by lower free chlorine residual concentrations, high alkalinity, and sufficient doses of copper corrosion inhibitors such as natural organic matter, silica, and orthophosphate. Pitting severity was consequently observed to increase at a low alkalinity, indicating that this parameter has a significant effect on corrosion reactions. Furthermore, the addition of aluminum solids to the base pitting water chemistry dramatically increased the formation of tubercle mounds on the inside of the copper pipes in contact with the waster. Aluminum solids have been observed to be a vital constituent for sustaining pit growth in this specific water at lower pHs, however, the role of this constituent at the high pH levels tested in this study was previously unknown. From simple visual observation, aluminum solids appear to increase the aggressiveness of this water even at higher pHs. / Master of Science

L’objectif de ce travail de thèse a été d’évaluer les propriétés inhibitrices de corrosion d’un traitement multifonctionnel utilisé dans l’industrie pétrolière. Dans la première partie de la thèse, l’influence des conditions hydrodynamiques, du temps d’immersion et de la température sur les processus de corrosion de l’acier API 5L-X65 en milieu CO2 en l’absence d’inhibiteur a été étudiée par des mesures électrochimiques (courbes de polarisation, courbes de Levich et spectroscopie d’impédance électrochimique) avec une électrode à disque tournant. A partir de ces essais, la vitesse de corrosion a été calculée pour les différentes conditions expérimentales. L’analyse couplée des résultats électrochimiques et des analyses de surface suggèrent la formation d’une couche de produits de corrosion, principalement de carbonate de fer qui recouvre la surface du métal et conduit à la diminution de la vitesse de corrosion quand le temps d’immersion, la vitesse de rotation et la température augmentent. La deuxième partie de la thèse a été consacrée à l’évaluation d’un traitement multifonctionnel contre la corrosion. Ce traitement est composé principalement de produits extraits de l’Aloe Vera (gel de l’Aloe Vera et « acibar »). Ces produits ont été choisis car ils empêchent la formation simultanée d’hydrates et de carbonate de calcium. Ces composés « verts », ainsi que la dodécylamine, qui est un inhibiteur de corrosion commercial, ont été testés à l’aide des mesures électrochimiques et par perte de masse afin de comparer leur efficacité et d’évaluer un possible effet de synergie lorsqu’ils sont utilisés en mélange. Les produits testés séparément ont un pouvoir protecteur comparable et il n’a pas été mis en évidence d’effet de synergie. En revanche, il a été montré que les composés sont compatibles entre eux. Ceci constitue un point très important pour l’utilisation de ces traitements qui permettent d’augmenter la fiabilité et la rentabilité pour la production du pétrole et du gaz. / The objective of this work was to evaluate the corrosion inhibitive properties of a multifunctional treatment used in the petroleum industry. In the first part of the thesis, the influence of hydrodynamic conditions, immersion time and temperature on the corrosion process of API 5L-X65 steel in CO2 medium in absence of inhibitor was studied by electrochemical measurements (polarization curves, Levich curves and electrochemical impedance spectroscopy) with a rotating disk electrode. From these tests, the corrosion rate was calculated for different experimental conditions. The analysis of the electrochemical results and surface analyses suggest the formation of a layer of corrosion products, mainly iron carbonate which covers the metal surface and leads to the decrease of the corrosion rate when the immersion time, the rotation speed and temperature increase. The second part of this work was devoted to the evaluation of a multifunctional treatment against corrosion. The treatment is mainly composed Aloe Vera extracts (Aloe Vera gel and "acibar”). These products were chosen because they prevent the simultaneous formation of hydrates and calcium carbonate. These "green" compounds and dodecylamine, which is a commercial corrosion inhibitor, were tested using electrochemical measurements and by mass loss in order to compare their efficiency and to evaluate a possible synergistic effect when they are used as a mixture. The products tested separately have a similar efficiency and did not reveal any synergistic effect. However, it was shown that the compounds are compatible. This is an important point for the use of these treatments which can increase the reliability and profitability for the production of oil and gas.

Ce travail a été consacré au développement de nouveaux microréservoirs d'inhibiteurs de corrosion à base de ressources naturelles minérales (les argiles marocaines de types beidellite et palygorskite), et organiques (le chitosane et l'acide heptanoïque) pour être utilisés en tant que charges anticorrosion dans les peintures. Dans les réservoirs de type beidellite, le stockage des inhibiteurs de corrosion a été réalisé soit en saturant les espaces interfoliaires par des cations inhibiteurs de corrosion tels que Ca2+ ou Ce3+, soit en modifiant les charges des feuillets argileux par intercalation du biopolymère chitosane afin d'adsorber des composés anioniques comme les ions heptanoate (C7-). Dans les réservoirs de type palygorskite, le stockage est basé sur le greffage d'un alkoxysilane sur les sites silanols de surface permettant d'adsorber les composés inhibiteurs via des sites NH3+. Après avoir caractérisé les matériaux avant et après fonctionnalisation par différentes techniques analytiques, les performances d'inhibition de corrosion du zinc et d'un acier doux en milieu NaCl ont été évaluées et comparées à celles du composé commercial dihydrogénotriphosphate d'aluminium (TPA) en utilisant des techniques électrochimiques stationnaires et dynamiques. Globalement, le revêtement organique à base de la beidellite modifiée au C7- montre une meilleure protection de l'acier électrozingué que le revêtement au TPA. De même, le revêtement organique comportant la palygorskite greffée au C-7 présente une performance d'inhibition de la corrosion de l'acier doux très intéressante par rapport au revêtement au TPA, sur environ 400 h d'immersion / This work was devoted to the development of new micrometric tanks of corrosion inhibitors based on mineral natural resources (Moroccan beidellite and palygorskite clays), and organic (chitosan and heptanoic acid) to be used as corrosion inhibitor tanks in the paintings. In the reservoirs of beidellite type, the storage of corrosion inhibitors made either by saturating the interlamellar areas by corrosion inhibitors cations such as Ca2+, or Ce3+, or by modifying the electrostatic charge of clays by intercalation of chitosan biopolymer in order to adsorb anionic compounds as heptanoate ions (C7-. In palygorskite type tanks, storage is based on the grafting of an alkoxysilane on the surface silanol sites to adsorb compounds via NH3+ sites. After characterizing materials before and after functionalization by several analytical techniques, the performance of corrosion inhibitors on zinc and mild steel in NaCl medium was evaluated and compared to those of commercial compound aluminium dihydrogen triphosphate (TPA) using stationary and dynamic electrochemical techniques. Overall, the organic coating containing modified C7- beidellite shows better protection of zinc than TPA compound. Similarly, C7- grafted palygorskite coating presents a very interesting performance of corrosion inhibition of mild steel corrosion compared to the coating with TPA, during approximately 400 h of immersion