Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation of crosslinks. Straight chain hydrocarbons were used as model compounds to investigate the regioselectivity of vinyltrimethoxysilane grafting. To stabilize the water-sensitive grafted products, the methoxy groups were substituted using phenyllithium. It was found that this reaction must be carried out for a minimum of three days to ensure full substitution. The grafted products were then separated on a weight basis using semi-preparative HPLC. Analysis of the di-grafted fraction using edited HSQC and HSQC-TOCSY NMR showed that radical propagation occurs via 1,4- and 1,5-intramolecular hydrogen shifts along the hydrocarbon backbone, resulting in multiple grafts per backbone. Post-combustion carbon capture targets CO₂ emissions from large point sources for capture and sequestration. A new class of potential carbon capture agents known as reversible ionic liquids (RevILs) has been synthesized and evaluated in terms of potential performance parameters (e.g. CO₂ capacity, viscosity, enthalpy of regeneration). These RevILs are silylated amines, which react with CO₂ to form a salt comprising an ammonium cation and a carbamate anion that is liquid at room temperature. Structural modifications of the basic silylamine skeleton result in drastic differences in the performance of the resulting RevIL. Systematic variation of the silylated amines allowed determination of a structure-property relationship, and continued iterations will allow development of an ideal candidate for scale-up. The properties and potential applications of gold nanoparticles (AuNP) are highly dependent on their size and shape. These properties are commonly controlled during liquid-phase synthesis through the use of capping agents, which must be removed following synthesis. Reverse micelles can also be used to control the morphology of AuNP during their synthesis. When RevILs are used in the formation of these reverse micelles, either as the disperse phase or as the surfactant, the built-in switch can be used to release the nanoparticles following their synthesis. This release on command could decrease the post-synthetic steps required to clean and purify AuNP prior to use. We have successfully synthesized AuNP using a number of different RevILs.

Ce travail de thèse porte sur l'élaboration de particules de polymère magnétiques capables de capter et relarguer différents microorganismes par des interactions électrostatiques non spécifiques. Des nanoparticules d'oxyde de fer cationiques stabilisées par des contre-ions nitrate ont été synthétisées par coprécipitation de sels de fer. La surface de la maghémite obtenue a été modifiée par voie sol-gel avec un organosilane présentant une fonction méthacrylate pour permettre son incorporation covalente dans des particules de latex par des réactions de copolymérisation. Ces particules ont été obtenues par polymérisation radicalaire en dispersion, en émulsion ou en miniémulsion du méthacrylate de méthyle ou du styrène, conduite en présence de maghémite. Les interactions entre celle-ci et le stabilisant rendent difficile la formation de latex magnétiques par polymérisation en dispersion. En revanche, la polymérisation en (mini-)émulsion permet, selon la technique de dispersion des oxydes de fer utilisée avant polymérisation, l'obtention de particules de latex de 140 à 650 nm, dont la fraction magnétique varie entre 2 et 37 % et contient jusqu'à 91 % de maghémite. La distribution de taille est toutefois large. Les particules magnétiques ainsi obtenues ont été ensuite fonctionnalisées directement au cours de la polymérisation en émulsion par l'introduction de co-monomères chargés, de polyélectrolytes ou de polyamphotères réamorçables. Ces deux derniers types de polymère sont obtenus par polymérisation RAFT. Leur capacité de capture/relargage a été évaluée sur des systèmes modèles à base de silice. Les polyamphotères donnent de bons résultats sur de nombreux microorganismes / This thesis describes the synthesis of magnetic latexes which are able to capture and release various microorganisms via non-specific and electrostatic interactions. Cationic iron oxide nanoparticles stabilized by nitrate counterions were synthesized by the co-precipitation of iron salts in water. The surface of the asobtained maghemite was then modified by a sol-gel process using a methacrylate-functionalized organosilane, in order to incorporate the iron oxide nanoparticles into latex particles by copolymerization reactions. Magnetic particles were obtained by dispersion, emulsion or miniemulsion polymerization of styrene or methyl methacrylate, performed in the presence of iron oxide. Due to the interaction between the stabilizers and iron oxides, dispersion polymerization was not a suitable approach. On the other hand, (mini-)emulsion polymerization led to a large range of particle diameters (140 – 650 nm), according to the process used to disperse iron oxides prior to the polymerization. These latexes contained between 2 and 37 % of magnetic particles, incorporating up to 91% of iron oxide. But the size distribution remained quite broad in all cases. The functionalization of the as-prepared magnetic particles was then undertaken by the introduction of either a charged co-monomer or polyelectrolytes or polyampholytes reactivable during the polymerization process. These kinds of polymers were synthesized by RAFT polymerization. Their ability to capture and release microorganisms was tested on silica-based model systems. Polyampholytes displayed good results on several microorganisms

De nouveaux précurseurs borates-triéthoxysilanes comprenant le closo-decahydrodecaborate ont été préparés et immobilisés dans la silice. L'introduction des groupements trialkoxysilyles sur les clusters (NH4)2B10H10, a été réalisée par condensations électrophiles faisant appel à des réactifs nucléophiles dans des conditions douces, tout en épargnant l'utilisation d'électrophiles ou de catalyseurs coûteux. Les borates-trialkoxysilanes obtenus ont été caractérisés par RMN 1H, 13C, 11B, 29Si, 31P, IRTF, analyse élémentaire et spectroscopie de masse. Comme preuve de concept, ces précurseurs ont été incorporés de manière covalente dans les pores d'une silice mésoporeuse, SBA-15. Tous les matériaux hybrides mésoporeux et modifiés avec du borate-triéthoxysilane ont été caractérisés par RMN solide 11B et 29Si, DRX, MET, les analyses élémentaires et étude de l'adsorption d'azote (méthode BET). Les précurseurs silylés-borate ont été combinés avec des nanoparticules de silice pour une utilisation éventuelle dans BNCT, où des NPs d'environ 100 nm ont été synthétisées comprenant deux types de centres luminescents différents. FITC silylé (isothiocyanate de fluorescéine) et complexe Eu (III) silylé ont été respectivement immobilisés dans des nanoparticules de silice par le procédé sol-gel. Les deux types de nanoparticules luminescentes ont été fonctionnalisés par les groupes silylés-borates et caractérisés par RMN du solide 11B, 31P et 29Si, DLS, MET, analyses élémentaires, d'adsorption d'azote et spectrophotométrie. / New borate-triethoxysilane precursors comprising the closo-decahydrodecaborate cluster were prepared and immobolized into hybrid silica materials. The synthesis of silylated clusters starting from (NH4)2B10H10 and silane precursors R-Si(OEt)3 through Electrophilic Induced Nucleophilic Reactions was performed under mild conditions, the silylated clusters were analyzed by 1H, 13C, 11B, 29Si, 31P NMR, IR, elemental analyses and mass spectroscopy ES-ESI. As a proof of concept, the borate-triethoxysilane precursors were covalently incorporated into the pores of mesoporous silica, SBA-15 type. All mesoporous materials modified with borate-triethoxysilane were characterized by 11B and 29Si solid state NMR, XRD, TEM, elemental analyses and Nitrogen sorption studies. The silylated-borate precursors were combined with dye-doped silica nanoparticles for possible future use in BNCT technique, where ~100 nm nanoparticles were synthesized comprising two different types of luminescent centers. Silylated FITC (fluorescein isothiocyanate) and silylated Eu(III) complexes were embedded into silica nanoparticles through sol-gel process. Both types of luminescent nanoparticles were functionalized with the silylated-borate clusters and characterized by 11B, 31P and 29Si solid state NMR, DLS, TEM, elemental analyses, Nitrogen sorption studies and spectrophotometer.

La structure et les propriétés rhéologiques de nanocomposites élastomère (BR ou SBR)/silice ont été étudiées dans cette thèse dans le but de mieux comprendre, par la suite, l’origine des défauts volumiques qui peuvent être observés à l’extrusion de ces mélanges. Des mélanges modèles simplifiés ont été réalisés au laboratoire et majoritairement étudiés dans ce travail de thèse. La structure de ces nanocomposites a été caractérisée par des mesures de taux d’élastomère lié, des analyses en RMN ainsi que des observations microscopiques (MEB ou MET). Ces dernières ont souligné l’existence de microstructures similaires pour les mélanges à base de BR dans la gamme de températures et de vitesses de mélangeage étudiée. A première vue, l’absence de différence quant à la distribution ou la dispersion des charges suggère donc que les différences de propriétés rhéologiques résident davantage dans les interactions gomme/charges. Les analyses en RMN ont, quant à elles, permis la détermination des taux de greffage du silane incorporé aux mélanges pour coupler les charges aux chaines élastomères. Il a été observé qu’une augmentation de la température de mélangeage favorise le greffage du silane. Les analyses RMN ont également mis en évidence la présence de réactions de pré-réticulation. Les taux de greffage ont alors pu être reliés aux conditions de mélangeage, via l’établissement d’une loi corrélant les taux de greffage silane/BR à un paramètre d’équivalence temps-température. Ce dernier est représentatif de l’histoire thermique subie par le mélange lors de sa préparation. La structure des mélanges a été corrélée aux propriétés rhéologiques caractérisées par des mesures en rhéologie dynamique, en fluage et en élongation. Les temps de relaxation moyens ou l’indice de strain hardening « SHI », issus de ces mesures, ont montré une augmentation avec la croissance des taux de greffage déterminés en RMN. Ces comparaisons ont également mis en évidence l’impact de la vitesse de mélangeage dont l’augmentation tend à diminuer le rhéoépaississement. Il existe donc au cours du mélangeage une compétition entre les réactions de greffage et les phénomènes de rupture qui induisent respectivement une croissance ou une réduction de la taille des amas d’agrégats connectés ; ces derniers étant à l’origine de l’augmentation du rhéoépaississement. Un modèle rendant compte de cette compétition a été proposé afin d’estimer l’évolution du SHI en fonction du taux de greffage et de la vitesse de mélangeage. Pour finir, les propriétés rhéologiques ont été comparées aux défauts volumiques caractérisés par profilométrie. Cette comparaison a mis en évidence l’existence de lois uniques reliant ces descripteurs rhéologiques au niveau de bosselage / The structure and rheological properties of elastomer (BR or SBR)/silica nanocomposites were studied in this work in order to understand the causes of volume defects observed during blends extrusion. Simplified model blends were prepared in laboratory internal mixer and mainly studied in this work. Nanocomposites structure was characterized by bound rubber measurements, NMR analysis and microscopic observations (SEM or TEM). These last observations have highlighted the existence of similar microstructures for BR blends in the range of studied mixing temperature and speeds. At first sight, the absence of difference in the fillers distribution or dispersion suggests that silica/rubber interactions have main impact on rheological properties. NMR analysis allowed the determination of silane grafting rate. TESPT silane was incorporated in blends to couple fillers to elastomer chains. It has been observed that the mixing temperature increase promotes the grafting of the silane. NMR analysis also demonstrated the presence of pre-crosslinking reactions. Grafting rates were then connected to the mixing conditions, through the establishment of a law correlating the silane/BR grafting rate to a time-temperature equivalence parameter. This parameter is representative of the thermal history undergone by the blend during its preparation. Blend structure was correlated to rheological properties characterized by dynamical rheology, creep and elongation measurements. Relaxation times or strain hardening index "SHI", determined thanks to these measurements, increase with the growth of grafting rate. These evolutions have also highlighted the impact of the mixing speed on rheological properties. The increase of mixing speed tends to reduce the shear thickening. Therefore, a competition between the grafting reactions and breaking phenomena occurs during blending. Grafting and breaking phenomena respectively induce growth or reduction of the size of connected aggregates clusters. The latter are responsible of the increase in the strain hardening. A model accounting for this competition has been proposed to estimate the evolution of SHI as a function of grafting and mixing speed. Finally, rheological properties were compared to volume defects characterized by profilometry. This comparison showed the existence of unique laws correlating these rheological descriptors to the intensity of volume instabilities

No description available.

Part I. The syntheses of a series of stable ferrocenylsilane compounds and their corresponding polyradical cations are reported. Electron spin properties of these molecules were investigated by cyclic voltammetry, ESR, and magnetic susceptibility measurements. All the compounds presented, showed significant electronic communication (>100 mV) between the redox centers by CV. Part II. Baeyer-Villiger oxidation of (1,9-dimethyl-PCU-8,11-dione) was performed using m-chloroperoxybenzoic acid in 1:2 molar ratios. The product obtained was the corresponding dilactone 113. The structure of the reaction products was established unequivocally via single crystal X-ray diffraction methods. The reaction of the 1,9-dimethyl-PCU-8,11-dione with 1:1 molar ratio of m-chloroperoxybenzoic acid produced again the dilactone 113, and not the expected monolactone 114. Ceric ammonium nitrate (CAN) promoted oxidation reaction of 1,9-dimethyl-PCU-8,11-dione afforded a mixture of dimethylated lactones, which indicated unique reaction mechanism pathways. These individual isomers, 115 and 116, have been isolated from these mixtures via column chromatography by using silica gel as adsorbent followed by fractional recrystallization of individual chromatography fractions. Structures of these pure products have been established unequivocally by application of single crystal X-ray crystallographic methods.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

La corrosion des canalisations métalliques pour le transport de gaz ou d’hydrocarbures est un problème critique qui peut avoir des répercussions financières et environnementales très importantes. Les revêtements polyoléfines tricouches sont largement utilisés pour préserver l’intégrité des structures. Ils sont constitués d’une sous couche mince époxy, d’une couche mince d’adhésif et d’une couche épaisse le plus souvent en polyéthylène. Ce système de revêtement bénéficie de très bonnes qualités d'adhérence. Néanmoins, des cas de décollements de ces revêtements à l’interface époxy/acier ont été constatés sur des pipelines en service depuis quelques années seulement, alors que la durée minimale de vie escomptée des tubes dans le sol est de quelques dizaines d’années. Ces décollements pourraient être dus à une dégradation progressive des liaisons interfaciales entre le primaire époxy et la surface métallique, associée à la présence de contraintes interfaciales importantes entre les différentes couches de l'assemblage. Cette étude vise alors d'une part à proposer des solutions permettant d’aboutir à la meilleure performance en vieillissement de la liaison adhésive, et d'autre part à quantifier les niveaux de contraintes au sein de la canalisation en acier revêtue depuis sa mise en œuvre, jusqu'à sa mise en service.Les liaisons interfaciales dépendant nécessairement de la préparation de surface de l’acier, des procédés de nettoyage ont été testés afin d’évaluer leur influence sur l’adhérence initiale et la durabilité des assemblages. Les préparations de surface permettent d'obtenir un degré de propreté et une rugosité. Ces deux éléments maximisent les forces de liaison et donc l'adhérence du revêtement. Le revêtement résiste alors mieux dans des environnements agressifs. Tous les procédés de nettoyage testés ont conduits à des niveaux de propreté équivalents du substrat en acier. Les essais effectués sur substrats polis miroir ont mis en évidence qu’une rugosité est nécessaire pour améliorer la durabilité des assemblages. La rugosité permet d'obtenir des adhérences supérieures à celles sur substrats polis miroir, de ralentir les effets du vieillissement humide et donc de prolonger la durée de vie du système. Il a été mis en évidence que les fortes rugosités étaient particulièrement bénéfiques pour les adhérences sèches. Par contre, au-delà d’une certaine rugosité, l’augmentation de la rugosité ne s’accompagne pas d’une amélioration significative de l’adhérence humide. Une étude sur l’apport des traitements de surface a aussi été menée. L’addition d’un traitement de surface a peu d’impact sur les adhérences initiales des assemblages, en comparaison avec une préparation de surface classique. Par contre les traitements de surfaces améliorent considérablement les adhérences humides, et donc la durabilité des assemblages. Notre travail prouve que le traitement aminosilane est un candidat potentiel en vue du remplacement du traitement toxique de chromatation, référence en matière de traitements de surface dans l'industrie des pipelines et dont l'utilisation sera interdite dans un futur proche compte tenu de l'évolution de la réglementation. Dans de bonnes conditions d'application et associé avec des primaires époxy appropriés, les adhérences sèches et humides obtenues avec les silanes sont comparables (voire supérieures) à celles de la chromatation.Par ailleurs, la modélisation par éléments finis du système tricouches a permis de préciser les niveaux de contraintes aux interfaces résultant de la mise en œuvre et de prévoir leur évolution au cours du temps et du vieillissement humide. / External Corrosion can weaken underground steel pipelines and render them unsafe for transporting oil or gas. Premature damage of this network could lead to dramatic financial and environmental consequences. Three layers polyolefin coatings composed by a fusion bonded epoxy, a modified polyolefin adhesive and a thick polyolefin topcoat, are the most widely systems used to preserve the structure integrity. This protective coating system presents excellent adhesion. Nevertheless, in some specific cases, loss of adhesion has been observed at steel/epoxy interface on operating pipelines on shorter period than their expected lifetime of about fifty years. This disbonding can be assigned to the progressive degradation of interfacial bonds between the epoxy primer and the metallic surface combined to substantial interfacial stresses between the different layers of the assembly. This study thus aims both to provide solutions to achieve the best ageing performance of the adhesive bond, and secondly to quantify the stress levels in a coated steel pipe since coating manufacturing to pipeline commissioning.Given that interfacial bonds depend necessarily on steel surface preparation, cleaning methods were compared to appraise their influence on assemblies dry and wet adhesion. Surface preparations allow to achieve a level of cleanness and to create a surface roughness. These two elements maximize binding forces and therefore the adhesion of the coating. The coating is thus more resistant to aggressive environments. All cleaning process have led to equivalent level of cleanness of steel substrate. Experiments carried out on mirror polished steel substrates highlighted that a surface roughness is necessary to improve joints durability. Roughness allows to obtain higher adhesion compared to mirror polished steel substrates, slows the effects of humid ageing and thus contributes to extend the durability of the system. It has been demonstrated that a high roughness is particularly beneficial for dry adhesion. By cons, beyond a certain roughness, increasing the surface roughness does not lead to significant improvement of wet adhesion. The benefits of surface treatments were also investigated. The addition of a surface treatment has little impact on dry adhesion in comparison with a conventional surface preparation. However, surface treatments substantially enhance the adhesion strength in wet stage, and therefore increase the durability of the assemblies. We also demonstrate that aminosilane surface treatments are competitive alternatives to traditional chromate conversion, which is the surface treatment of reference in pipeline industry, and whose use will be prohibited in a near future considering changes in legislation. Under good conditions of application and associated with appropriate fusion bonded epoxy, dry and wet adhesion obtained with silane surface treatments are comparable (or even higher ) than those obtained with chromate surface treatments.Furthermore, finite element modeling has allowed to specify interfacial stresses levels inside the assembly resulting from coating's manufacturing process and to predict their evolution over time and during wet ageing.

Para avaliar o efeito de diferentes tratamentos superficiais sobre a resistência ao cisalhamento da união entre uma liga metálica (Co-Cr-Mo - Remanium CD) e uma resina composta (Z-250) e analisar o tipo de fratura durante a separação dos espécimes, sessenta discos metálicos foram fundidos, regularizados e polidos, submetidos a quatro ciclos térmicos (vácuo, 960ºC, 8 minutos) e divididos aleatoriamente em seis grupos. Cada grupo recebeu um tipo de tratamento: Grupo ASB: Asperização com ponta diamantada (No 3118); Grupo ASI: Asperização e aplicação do silano (3M); Grupo AAP: Asperização e aplicação do Alloy Primer (Kuraray); Grupo JSB: Jateamento com óxido de alumínio (50µm, 75lib/pol2); Grupo JSI: Jateamento e aplicação do silano; Grupo JAP: Jateamento e aplicação do Alloy Primer. Todos os espécimes receberam aplicação do adesivo Single Bond e da resina Z-250 (3M), foram armazenados em água deionizada a 37ºC por 24 horas e separados em ensaio de cisalhamento. Os resultados e desvio-padrão de cada grupo, expressos em MPa foram: ASB: 12,708±2,962; ASI: 16,343±2,714 e AAP: 16,723±2,666; JSB: 25,958±5,650; JSI: 28,185±3,322; JAP: 28,670±3,246. Os maiores valores foram produzidos pelos grupos jateados (JSB, JSI e JAP); o silano e o Alloy primer aumentaram a retentividade entre a resina Z-250 e a liga de Co-Cr-Mo, independente da textura superficial e sem apresentar diferença entre os mesmos; todos os espécimes apresentaram falha adesiva na interface testada. / To evaluate the effect of different surface treatments on shear bond strength between a metallic alloy (Co-Cr-Mo - Remanium CD) and a composite resin (Z-250) and to evaluate the fracture mode after testing, sixty disks were casted, polished, submitted to four thermal cycles (960ºC/8min) and divided randomly in six groups. Each group received a different type of treatment: Group ASB: roughen with diamond bur (No 3118); Group ASI: roughen and application of a ceramic Primer; Group AAP: roughen and application of a metallic Primer; Group JSB: Sandblasting with 50 µm aluminum oxide (75lib/pol2); Group JSI: Sandblasting and application of a ceramic Primer; Group JAP: Sandblasting and application of a metallic Primer. All the specimens received the application of an adhesive (Single Bond) and a composite resin (Z-250 /3M). The groups were stored in distilled water at 37ºC during 24 hours and submitted to shear bond strength test. The results and the standard deviation of each group (expressed in MPa) were: JSB: 25,958±5,650; JSI: 28,185±3,322; JAP: 28,670±3,246; ASB: 12,708±2,962; ASI: 16,343±2,714 and AAP: 16,723±2,666. The highest values were obtained by the sandblasted groups (JSB, JSI e JAP). In spite of the surface, ceramic primer and alloy primer increased the retention between the composite resin Z-250 and the Co-Cr-Mo alloy without statistical differences on the results; all of the specimens showed adhesive failures.

A crescente preocupação com o desenvolvimento sustentável, aliada com uma maior conscientização com relação à preservação do meio ambiente, tem incentivado pesquisas com a finalidade de encontrar substitutos ambientalmente amigáveis para os eficientes sistemas à base de cromo hexavalente (Cr6+), que são empregados como pré-tratamento em ligas de alumínio de alta resistência utilizadas na indústria aeronáutica. Neste trabalho, o desempenho do silano BTSE (Bis-1,2-(trietoxisilil) etano) como método de proteção contra a corrosão da liga de alumínio 2024-T3 foi investigado utilizando técnicas de caracterização eletroquímicas, microestruturais e químicas. Para melhorar as propriedades anticorrosivas do sistema, a camada de silano foi modificada pela introdução de aditivos, tendo sido estudados também sistemas em bi-camada. Efeitos das condições de cura (tempo e temperatura) do BTSE e da quantidade de modificantes sobre as propriedades dos substratos revestidos também foram avaliados. Para os estudos eletroquímicos, realizados em solução de NaCl 0,1 M, foram empregadas a espectroscopia de impedância eletroquímica (EIS) e curvas de polarização potenciodinâmica anódica e catódica. As técnicas de caracterização morfológica e microestrutural foram microscopia de força atômica (AFM), microscopia eletrônica de varredura (SEM) e medidas de ângulo de contato. A caracterização da composição e do estado químico da camada foi realizada usando as espectroscopias por energia dispersiva de Raios-X (EDS), de infravermelho (IR) e de fotoelétrons excitados (XPS). Os resultados dos ensaios de corrosão mostraram que a adição dos modificantes à camada de BTSE melhora o desempenho anticorrosivo do sistema, o qual também teve seu comportamento melhorado quando utilizado em forma de bi-camada. Verificou-se que um excesso de aditivos tende a deteriorar as propriedades protetoras do silano, e que o aumento do tempo e da temperatura de cura é benéfico para as propriedades anticorrosivas dos diferentes sistemas. Os resultados dos ensaios de caracterização química e microestrutural também detectaram que os modificantes contribuem para uma melhor cobertura do substrato pela camada de silano, assim como para uma maior reticulação da mesma, sem, no entanto, modificar sua estrutura química e física. / The increasing concern with sustainable development, allied with a stronger awareness with environmental preservation, has stimulated researches in order to find environmentally friendly substitutes to replace the efficient hexavalent chromium-based pre-treatment systems (Cr6+) used to protect high-strength aluminium alloys employed in the aircraft industry. In this work, the performance of BTSE (bis-1, 2-(triethoxysilyl) ethane) as a protection method against corrosion of aluminium alloy 2024-T3 was investigated using electrochemical, microstructural and chemical characterization techniques. In order to improve the system anticorrosion properties, modifiers were added to the silane layer, and bi-layers systems were also tested. The effects of the silane curing conditions (time and temperature) and of the modifiers amounts on the properties of the layers were also evaluated. Electrochemical impedance spectroscopy (EIS) and anodic and cathodic potentiodynamic polarization curves were employed for the electrochemical studies, which were performed in 0.1 M NaCl solution. For microstructural and morphological characterization, atomic force microscopy (AFM), scanning electron microscopy (SEM) and contact angle measurements were used. The chemical state and the composition of the different layers were evaluated using X-ray photoelectrons (XPS), infrared (IR) and X-ray dispersive energy (EDS) spectroscopy. The results of the corrosion studies have shown that the addition of modifiers to the BTSE layer improves its anticorrosion performance, which was also improved in the bi-layers systems. It was also verified that addition of modifiers excess hinders the performance of the layers, as well as that increasing curing time and temperature are beneficial to the anticorrosion properties of the systems. The results of the different chemical and microstructural analyses showed that the modifiers contribute to better substrate coverage by the silane layer, as well as to a more complete reticulation. However, this does not imply in modifications of the chemical and physical structure of the layer.