Le traitement de la corrosion constitue un enjeu économique, environnemental et de sécurité sanitaire. Plus largement utilisée à l’échelle industrielle, la protection par revêtements consiste à isoler le métal du milieu agressif par une couche adhérente, continue et imperméable. Ils doivent répondre à trois propriétés majeures : 1) être fortement adhérent au substrat métallique, 2) posséder de bonnes propriétés barrière pour limiter la pénétration de l’eau et des espèces agressives et 3) apporter un rôle d’inhibition de la corrosion. Cependant, la protection des surfaces métalliques par les techniques actuelles génère une pollution notable liée à l’usage de chromates. L’utilisation de polymères biosourcés et solubles en milieu aqueux serait un challenge et contribuerait à préserver l’environnement. Les polysaccharides comme le chitosane sont des macromolécules biodégradables et respectueuses de l'environnement possédant des propriétés d’anticorrosion et sont donc des alternatives envisageables. Ces travaux de thèse portent sur le développement de revêtements anticorrosion à base de chitosane. Le chitosane possède deux points faibles pour être utilisé comme revêtement contre la corrosion : 1) une adhésion insuffisante sur la surface des matériaux et 2) un caractère hydrophile. En conséquence, le chitosane a été modifié chimiquement afin d’augmenter son adhésion et ses propriétés barrières. Afin d’améliorer son adhésion sur des substrats métalliques, des groupements de type acide phosphonique ont été ajoutés via la réaction de Kabachnik-Fields sur le chitosane. L’élaboration d’un chitosane possédant des fonctions catéchol a été également discutée. Dans un premier temps, le chitosane modifié a été testé et caractérisé par spectroscopie d’impédance électrochimique (SIE) en tant qu’inhibiteur de corrosion puis des revêtements à partir de ce même chitosane ont été réalisés et leurs protections contre la corrosion ont été évaluées. Deux approches de mise en forme des revêtements ont été testées : par dip-coating et par la technique Layer-by-Layer (LbL). Différentes voies de fonctionnalisation du chitosane ont également été présenté afin d’augmenter les propriétés barrière du revêtement. La chimie de phthaloylation du chitosane a été décrite puis le greffage de chaînes hydrophobes a été étudié. / Corrosion treatment is an economic, environmental and health safety issue. More widely used on an industrial scale, coating protection consists in isolating the metal from the aggressive medium by an adherent, continuous and impermeable layer. They must have three major properties: 1) be strongly adherent to the metallic substrate, 2) have good barrier properties to limit the penetration of water and aggressive species and 3) provide a role in inhibiting corrosion. However, the protection of metal surfaces by current techniques generates significant pollution due to the use of chromates. The use of bio-based and soluble polymers in aqueous media would be a challenge and would contribute to preserving the environment. Polysaccharides such as chitosan are biodegradable and environmentally friendly macromolecules with anticorrosive properties and are therefore possible alternatives. These theses focus on the development of anticorrosion coatings based on chitosan. Chitosan has two weak points for use as a coating against corrosion: 1) insufficient adhesion on the surface of the materials and 2) hydrophilicity. As a result, chitosan has been chemically modified to increase its adhesion and barrier properties. In order to improve its adhesion on metal substrates, phosphonic acid groups have been added via the Kabachnik-Fields reaction on chitosan. The development of a chitosan with catechol functions was also discussed. Initially, the modified chitosan was tested and characterized by electrochemical impedance spectroscopy (EIS) as a corrosion inhibitor and coatings based on the same chitosan were made and their corrosion protection evaluated. Two approaches of coating elaborations were tested: dip-coating and Layer-by-Layer (LbL). Different ways of functionalizing chitosan have also been presented to increase the barrier properties of the coating. Phthaloylation chemistry of chitosan was described and hydrophobic chain grafting was studied.

This project involved the improvement of several properties of the current “universal” primer coating sold by Kelly-Moore Paint Company. This formulation is an all purpose primer used both for interior and exterior applications. However, its corrosion resistance has room for improvement. The addition of sodium nitrite, an aminocarboxylate salt, and a zinc phosphate-based additive were all tested as corrosion inhibitors. In addition, during the project the coating binder was changed to improve adhesion. After a systematic experimental program, a new “universal” primer with increased corrosion resistance and adhesion was formulated. A direct to metal top coat formulation sold by Kelly-Moore Paint Company was reformulated in order to produce a coating with better corrosion resistance and gloss retention. Five new latexes were investigated. Each formulation was tested for several properties including adhesion to metal substrates, water immersion resistance, accelerated UV exposure resistance, and outdoor exposure resistance. This effort resulted in a formulation that showed promise as a replacement for the current product; however, its adhesion was inadequate. Further work is needed to improve this coating.

L'objectif de ces travaux de thèse a été de développer un système de protection anticorrosion sur alliages d'aluminium 2024 en combinant le procédé sol-gel à la technique de dépôt par électrophorèse (ou EPD). Dans cette optique, nous nous sommes intéressés à l'évaluation du couplage de la technique de dépôt par EPD, technique offrant l'avantage de réaliser des dépôts à la fois épais, couvrants et homogènes en épaisseur même sur pièces complexes, au procédé sol-gel, bien connu et fortement prometteur pour développer des revêtements anti-corrosion performants. Le travail de thèse s'est focalisé sur la réalisation de dépôts par électrophorèse à partir d'un sol hydride, chargé ou non en particules de boehmite (NPs), et sur l'étude de différents paramètres électrophorétiques (paramètres à la fois liés au medium et au procédé lui-même). Nous avons ensuite cherché à connaître les propriétés des revêtements mis en forme par EPD (propriétés anti-corrosion et perméabilité des films en particulier) via des caractérisations électrochimiques (étude par Spectroscopie d'Impédance Electrochimique (SIE), électrode à disque tournant (EDT)). Ces dernières études ont été réalisées sur alliage d'aluminium 2024 (AA2024), dans un premier temps, puis sur substrat modèle (substrat inerte tel que l'or (Au)) dans le but d'évaluer la réponse électrochimique intrinsèque du revêtement. Dans un premier temps, nous avons pu obtenir par EPD et de façon répétable, des dépôts homogènes et d'épaisseurs contrôlées sur AA2024 et Au. La croissance de ces dépôts est à la fois le résultat de la migration des NPs et de l'augmentation du pH interfacial, provoqué par l'électrolyse de l'eau mais responsable, à terme, d'une redissolution du film. Ce phénomène de redissolution/décollement a pu néanmoins être limité en modulant la forme du signal électrique (application d'un potentiel périodique). Aussi, nous avons démontré que la quantité de NPs présente dans le sol précurseur joue un rôle clé dans les épaisseurs de dépôts obtenues (des épaisseurs dans la gamme 7 à 20 µm ont pu être atteintes en doublant uniquement la concentration en NPs vectrices dans le sol précurseur). En ce qui concerne le comportement électrochimique des différents systèmes mis en forme par EPD, la modélisation des spectres SIE, via le logiciel Z view, montre que les propriétés barrières des revêtements chargés tendent à se dégrader plus vite avec le temps d'immersion que pour ceux obtenus sans particules. Nous avons finalement cherché à mesurer la perméabilité des films électrophorétiques via un dispositif de type électrode à disque tournant (EDT). Les résultats obtenus ont montré que le coefficient de perméabilité kf des films électrophorétiques évolue fortement, dès les premières heures d'immersion, et augmente d'autant plus que le système est chargé en NPs. / The realisation of organic/inorganic coatings on metal substrates, prepared by sol-gel route and shaped by electrophoretic deposition (EPD), is a new combined process which has been the subject of only few studies. EPD technique offers an easy control of the thickness and morphology of the film even on substrates of complex shape, which are the main challenges for all kinds of deposition techniques used in various industrial fields. Moreover, sol-gel route has been extensively studied as a potential alternative pre-treatment to prepare a variety of materials with versatile applications from anti-corrosion to anti-wear. So, coupling these two techniques is one way to obtain both benefits on a same system. In this work, the electrophoretic deposition was performed on AA2024 from an aqueous sol suspension containing sol-gel boehmite nanoparticles (NPs). The influence of the applied voltage and deposition time on the deposit thickness was studied. The effect of the concentration of NPs, added in the precursor sol, on the thickness was also investigated. It is shown that an increase in the applied voltage and deposition time increased the thickness of the deposit film (from 2 to 11 µm). However, for a same voltage, increasing the concentration of NPs in the precursor sol, progressively increases the coating thickness (Figure 1.) and appears as a key parameter to adjust the coating thickness. Finally, it was demonstrated that a perfect control of the microstructure and the deposit thickness was achievable, thanks to both EPD parameters and sol properties. The electrochemical properties of the electrophoretic coatings are then studied by Electrochemical Impedance Spectroscopy (EIS) and by rotating disk electrode and showed that the permeability of the coatings increased with the particles concentration.

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No description available.

L’objectif de ces travaux est d’étudier les effets d’une irradiation ultrasonore haute fréquence (500 kHz) sur la synthèse électrochimique de polymères conducteurs en milieu aqueux. Les ultrasons favorisent la réaction de polymérisation électrochimique en augmentant le transport des espèces électroactives vers l’électrode. Ils engendrent des films plus compacts, présentant une topographie plus fine et plus homogène. Les effets chimiques engendrés par la propagation de l’onde acoustique permettent un meilleur taux de dopage des films. Néanmoins, leur conductivité électrique se trouve légèrement diminuée, dû à une dégradation des chaînes polymères par l’activité cavitationelle. La possibilité de contrôler les propriétés de morphologie fut mise à profit dans différentes applications comme celles des capteurs pH potentiométriques ou des revêtements anti-corrosion. Pour de telles applications, utilisant ces films en tant que couche fonctionnelle, les surfaces obtenues en présence d’irradiation ultrasonore mènent à de meilleurs résultats. Une technique de masquage sélectif à base d’ultrasons focalisés a également été développée afin d’élaborer un substrat biphasique laissant présager d’intéressantes applications biologiques / This study deals with the effects of high frequency ultrasound (500 kHz) irradiation on the electrochemical synthesis of conducting polymers in aqueous media. Ultrasound favors electrochemical polymerization reaction by improving mass transfer of electroactive species towards the electrode. It leads to films more compact, presenting a thinner and more homogeneous topography. Chemical effects generated by the acoustic wave propagation enable a higher doping level for the films. However, their electrical conductivity is slightly reduced, due to partial degradation of polymer chains by cavitational activity. The possibility to control morphological properties was used in different applications such as potentiometric pH sensors or anti-corrosion coatings. For such applications, using these films as functional layers, the irradiated coatings lead to better results. A selective masking technique, based on focused ultrasound, has been developed as well in order to elaborate a biphased substrate permitting interesting biological applications

Filmes inorgânicos de ZrO2 e filmes híbridos orgânico-inorgânicos de ZrO2-PMMA, preparados pelo método sol-gel, foram estudados como protetores contra a corrosão de aço inoxidável em meio ácido. Os sóis foram preparados a partir de uma solução submetida à irradiação de ultra-som e contendo o alcóxito metálico correspondente como precursor, álcool como solvente e ácido acético glacial como agente quelante para modificar a reatividade do alcóxito metálico. Várias concentrações de PMMA foram adicionadas aos sóis e estes foram caracterizados através de reometria, espectroscopia na região do infravermelho (FTIR), calorimetria explanatória diferencial (DSC) visando estudar a evolução de suas características morfológicas durante o envelhecimento. Os filmes de ZrO2 e ZrO2-PMMA foram depositados, utilizando-se a técnica de imersão, sobre lâminas de aço inoxidável 316L (AISI 316L), densificados a 200&#176C e o tempo de tratamento térmico foi variado de 5 a 180 minutos. Os filmes foram caracterizados por espectroscopia de reflexão especular na região do infravermelho; a morfologia, composição e textura superficiais foram determinadas por microscopia eletrônica de varredura (MEV), dispersão de energia de raios X (EDS) e perfilometria, respectivamente. curvas de polarização potenciodinâmica a 1 mVs-1 foram usadas para estudar a eficiência dos diferentes recobrimentos na proteção do AISI 316L contra a corrosão em soluções de H2SO4 0,5 mol.L-1. Os resultados mostram que os filmes híbridos ZrO2-PMMA aumentam em média 30 vezes o tempo de vida do substrato em relação aos filmes puramente inorgânicos. / ZrO2 inorganic and ZrO2-PMMA hybrids organic-inorganic films, obtained by the sol-gel method, were studied in order to determine their properties as protective layers against corrosion of stainless steel in acid media. The sol was prepared from a sonocatalyzed solution containing the appropriate metal alkoxide as precursor, alcohol as solvent, and glacial acid acetic as chelant agent to modify the reactivity of the metal alkoxide and PMMA was added into these sols. Reology, infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were employed to determine the evolution of structural changes during aging time. The ZrO2 and ZrO2-PMMA films were deposited on stainless steel by dip-coating technique and heat treated at 200&#176C at times of heating ranging from 5 to 180 minutes. The films were characterized by FTIR reflection spectroscopy, scanning electronic microscopy, X-ray dispersive energy and profilometry to determine the surface morphology, composition and texture, respectively. Potentiodynamic polarization curves (PPC) at 1 mVs-1 were used to study the efficiency on the protection of AISI 316L against corrosion in H2SO4 0,5 mol.L-1, showing that ZrO2-PMMA increase in a factor up 30 the life time of substrate.

Filmes inorgânicos de ZrO2 e filmes híbridos orgânico-inorgânicos de ZrO2-PMMA, preparados pelo método sol-gel, foram estudados como protetores contra a corrosão de aço inoxidável em meio ácido. Os sóis foram preparados a partir de uma solução submetida à irradiação de ultra-som e contendo o alcóxito metálico correspondente como precursor, álcool como solvente e ácido acético glacial como agente quelante para modificar a reatividade do alcóxito metálico. Várias concentrações de PMMA foram adicionadas aos sóis e estes foram caracterizados através de reometria, espectroscopia na região do infravermelho (FTIR), calorimetria explanatória diferencial (DSC) visando estudar a evolução de suas características morfológicas durante o envelhecimento. Os filmes de ZrO2 e ZrO2-PMMA foram depositados, utilizando-se a técnica de imersão, sobre lâminas de aço inoxidável 316L (AISI 316L), densificados a 200&#176C e o tempo de tratamento térmico foi variado de 5 a 180 minutos. Os filmes foram caracterizados por espectroscopia de reflexão especular na região do infravermelho; a morfologia, composição e textura superficiais foram determinadas por microscopia eletrônica de varredura (MEV), dispersão de energia de raios X (EDS) e perfilometria, respectivamente. curvas de polarização potenciodinâmica a 1 mVs-1 foram usadas para estudar a eficiência dos diferentes recobrimentos na proteção do AISI 316L contra a corrosão em soluções de H2SO4 0,5 mol.L-1. Os resultados mostram que os filmes híbridos ZrO2-PMMA aumentam em média 30 vezes o tempo de vida do substrato em relação aos filmes puramente inorgânicos. / ZrO2 inorganic and ZrO2-PMMA hybrids organic-inorganic films, obtained by the sol-gel method, were studied in order to determine their properties as protective layers against corrosion of stainless steel in acid media. The sol was prepared from a sonocatalyzed solution containing the appropriate metal alkoxide as precursor, alcohol as solvent, and glacial acid acetic as chelant agent to modify the reactivity of the metal alkoxide and PMMA was added into these sols. Reology, infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were employed to determine the evolution of structural changes during aging time. The ZrO2 and ZrO2-PMMA films were deposited on stainless steel by dip-coating technique and heat treated at 200&#176C at times of heating ranging from 5 to 180 minutes. The films were characterized by FTIR reflection spectroscopy, scanning electronic microscopy, X-ray dispersive energy and profilometry to determine the surface morphology, composition and texture, respectively. Potentiodynamic polarization curves (PPC) at 1 mVs-1 were used to study the efficiency on the protection of AISI 316L against corrosion in H2SO4 0,5 mol.L-1, showing that ZrO2-PMMA increase in a factor up 30 the life time of substrate.

No description available.

Nonwetting surfaces including superhydrophobic (SHS) and liquid infused surfaces (SLIPS) exhibit diverse exceptional characteristics promoting numerous application opportunities. Engineered textured surfaces demonstrate multiple features including drag reduction, fouling reduction, corrosion resistance, anti-fogging, anti-icing, and condensation enhancement. Integrating these properties, nonwetting surfaces have shown significant potential in improving the efficiency of energy applications. The first part of the thesis work aims at developing a fundamental mathematical understanding of the wetting process on the solid surface followed by presenting fabrication methodologies specifically focused on metallic substrates. The second part of this thesis presents an exhaustive survey on recent advancements and researches about features of nonwetting surfaces that could be implemented in major industrial applications. To establish how realistically these features could enhance the real-life applications, the third part of this work investigates the dynamic performance and economic benefits of using textured surfaces fabricated using an electrodeposition process for condenser tubes in thermoelectric power plants. The textured surfaces are expected to provide enhanced performance by deterring fouling and promoting dropwise condensation of the steam on the shell side. Using a thermal resistance network of a shell and tube condenser, detailed parametric studies are carried out to investigate the effect of various design parameters on the annual condenser performance measured in terms of its electric energy output of a representative 550 MW coal-fired power plant. A cost modeling tool and a new Levelized cost of condenser (LCOC) metric have been developed to evaluate the economic and performance benefits of enhanced condenser designs. The LCOC is defined as the ratio of the lifetime cost of the condenser (and associated costs such as coating, operation and maintenance) to the total electric energy produced by the thermoelectric power plant. The physical model is coupled with a numerical optimization method to identify the optimal design and operating parameters of the textured tubes that minimizes LCOC. Altogether, the study presents the first effort to construct and analyze enhanced condenser design with textured tube surfaces on annual thermoelectric power plant performance and compares it against the baseline condenser design with plain tubes. / Master of Science / Liquid repellant surfaces have attracted lots of attention due to their numerous promising characteristics including promoting condensation, drag reduction, prohibiting fouling/deposition, corrosion, and fog/dew harvesting. These attributes have the potential to inspire a variety of applications for these surfaces in power plants, automotive and aviation industries, oils/organic solvents clean-up, fuel cells, solar panels, membrane distillation, stone/concrete protection, surgical fabrics, and biological applications, to name a few. Some of these applications have reached their potential for real-life implementation and more are still at the research phase needing more experimental and fundamental studies to get them ready. The first part of this study presents the fundamentals of the wetting process. Next, fabrication methods for metallic surfaces have been explored to identify the most scalable and cost-effective approaches which could be administered in large scale industrial applications. A comprehensive review of recent publications on features of nonwetting surfaces has been carried out and presented in the second part of this thesis. To establish how realistically these features could enhance the real-life applications of a thermo-economic a performance model is developed for a powerplant condenser in the third section. Through a simple and cost-effective electrodeposition process, the common condenser tubes are modified to achieve textured tubes with superhydrophobic properties. The influence of using textured tubes on the plant's performance and its economic benefits are investigated to predict the potential promises of nonwetting surfaces.