The design of functional materials with complex properties is very important for different applications, such as coatings, microelectronics, biotechnologies and medicine. It is also crucial that such kinds of materials have a long service lifetime. Unfortunately, cracks or other types of damages may occur during everyday use and some parts of the material should be changed for the regeneration of the initial properties. One of the approaches to avoid the replacement is utilization of self-healing materials. The aim of this thesis was to design a self-repairable material with superhydrophobic and switchable properties using colloidal particles. Specific goals were the synthesis of colloidal particles and the preparation of functional surfaces incorporated with the obtained particles, which would exhibit a repairable switching behavior and repairable superhydrophobicity. In order to achieve these goals, first, methods of preparation of simple and functional colloidal particles were developed. Second, the behavior of particles at surfaces of easy fusible solid materials, namely, paraffin wax or perfluorodecane, was investigated.

Le manuscrit porte sur l'élaboration de couches minces ayant des propriétés barrières aux liquides, aux gaz et aux ultra-violets. Pour réaliser nos différents systèmes, la technologie plasma à décharge à barrière diélectrique à la pression atmosphérique (DBD) a été utilisée. Dans la première partie, des films polymère plasma à base de 1H, 1H, 2H, 2H, Perfluorodecyl acrylate ont été développé. En fonction des paramètres plasma une surface dîtes superhydrophobe en une étape a été obtenue grâce à l'obtention d'un film composé de nanoparticules fluorés. La seconde partie des travaux a consisté à développer des films barrières aux gaz à partir de l'hexamethyldisiloxane. Ainsi, des films minces SiOx et multicouches SiOxHyCz/SiOx ont pu être obtenue afin d'améliorer les performances barrières de substrat PET et PEN. Enfin, l'obtention de film barrière aux UV a consisté à une croissance in-situ de nanoparticules de dioxyde de titane (TiO2) à partir du film polymère plasma. La matrice polymère constitué d'une structure siloxane et aminée plasma joue le rôle de nano-réacteur pour la croissance de cristaux de TiO2. / This works presents the development of plasma-polymrized surfaces for superhydrophobic, gas barrier and UV attenuation properties. These functional coatings have been deposited by means of atmospheric pressure dielectric barrier discharge (DBD). The first part deals on the plasma polymerization of the de 1H, 1H, 2H, 2H, Perfluorodecyl acrylate. According to the plasma parameters, surperhydrophobic coatings have obtained on several substrates. Morphologies analysis have shown the formation of fluorinate nanoparticles. The second part of the work was to develop gas barrier films from hexamethyldisiloxane. Thus, SiOx thin films and SiOxHyCz / SiOx multilayers have been obtained in order to improve the barrier performance of PET and PEN substrate. Finally, obtaining UV barrier film was to an in-situ growth of nanoparticles of titanium (TiO2) dioxide from the plasma polymer filin. The plasma polymer acts as a nano-reactor for the growth of TiO2 nanoparticles

Made available in DSpace on 2016-12-12T20:15:50Z (GMT). No. of bitstreams: 1 Jorge Batista - resumo.pdf: 37444 bytes, checksum: 8f8f7a4b6f5f96a5fc6085e5128c66c2 (MD5) Previous issue date: 2013-03-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The control of surface wettability is an issue of great scientific interest because of the large number of applications both as hydrophobic to hydrophilic surfaces, such as medical instruments, fluidic microdevices, coating for microdevices, manipulation of nanoparticles, microscale motors, lubricants, waterproofing surfaces and even instruments for domestic use. The objectives of this work are to compare the values obtained in experiments with surfaces of well-defined topography with available theoretical models and characterize the transition between hydrophobic and superhydrophobic surfaces with the proposition of configurations and criteria that lead to a better understanding of the wettability and superhydrophobic surfaces production, in the light of the energy minimization. / O controle da molhabilidade de superfícies é um tema de grande interesse científico em função da grande quantidade de aplicações, tanto para superfícies hidrofílicas quanto hidrofóbicas, como é o caso de instrumentos médicos, microdispositivos fluídicos, recobrimento para microdispositivos, manipulação de nanopartículas, motores em microescala, lubrificantes, impermeabilização de superfícies e mesmo em instrumentos de uso doméstico. Os objetivos deste trabalho são comparar os valores obtidos em experimentos com superfícies de topografia bem definida com os modelos teóricos disponíveis e caracterizar a transição entre superfícies hidrofóbicas e superhidrofóbicas, com a proposição de configurações e critérios que levem a um melhor entendimento da molhabilidade e da produção de superfícies superhidrofóbicas, sob a luz da minimização de energia.

Water droplets tend to bead up on rough or textured hydrophobic surfaces by trapping air on the crevices underneath resulting in “Cassie” state of wetting. When a textured hydrophobic surface is immersed in water, the resulting underwater “Cassie” state can lead to significant drag reduction. The entrapped air pockets act as shear free regions and the composite interface consisting of alternate no slip and no shear regions thus formed can deliver substantial drag reduction during flow. The magnitude of drag reduction depends not only on the fractional coverage of air on the surface, but also on the size of the air pockets, with larger sized air pockets facilitating larger drag reduction. It is a common observance that Lotus leaf when kept immersed in water for a few minutes loses its water repellency due to the loss of entrapped air on the surface. Underwater Cassie state on textured hydrophobic surfaces is also not sustainable because of the depletion of air pockets caused by the diffusion of trapped air into water. This causes the drag reduction to diminish with time. Rate of diffusion of air across the water–air interface depends on the concentration gradient of air across the interface. Under flow conditions, removal of entrapped air is further enhanced by convection, leading to more rapid shrinkage of the air pockets. In order to sustain the Cassie state, it is thus necessary to continuously supply air to these air pockets. In this work, we explore the possibility of supplying air to the cavities on the textured surface inside a microchannel by controlling the solubility of air in water close to the surface. The solubility is varied by i) Controlling the absolute pressure inside the channel and ii) Localized heating of the surface To trap uniform air pockets, a textured surface containing a regular array of blind holes is used. The textured surface is generated by photo etching of brass and is rendered hydrophobic through a self-assembled monolayer. The sustainability of the underwater Cassie state of wetting on the surface is studied at various flow conditions. The air trapped on the textured surface is visualized using total internal reflection based technique, with the pressure drop (or drag) being simultaneously measured. Water which is initially saturated with air at atmospheric conditions, when subjected to sub-atmospheric pressures within the channel becomes supersaturated causing the air bubbles to grow in size. Further growth causes the bubbles to merge and eventually detach from the surface. The growth and subsequent merging of the air bubbles leads to a substantial increase in the pressure drop because as the air pockets grow in size, they project into the flow and start obstructing the flow. On the other hand, a pressure above the atmospheric pressure within the channel makes the water undersaturated with air, leading to gradual shrinkage and eventual disappearance of air bubbles. In this case, the air bubbles do cause reduction in the pressure drop with the minimum pressure drop (or maximum drag reduction) occurring when the bubbles are flush with the surface. The rate of growth or decay of air bubbles is found to be significantly dependent on the absolute pressure in the channel. Hence by carefully controlling the absolute pressure, the Cassie state of wetting can be sustained for extended periods of time. A drag reduction of up to 15% was achieved and sustained for a period of over 5 hours. Temperature of water also influences the solubility of air in water with higher temperatures resulting in reduced solubility. Thus locally heating the textured hydrophobic surface causes the air bubbles to grow, with the rate of growth being dependent on the heat input. The effect of trapped air bubbles on thermal transport is also determined by measuring the heat transfer rate through the surface in the presence and absence of trapped air bubbles. Even though the trapped air bubbles do cause a reduction in the heat transfer coefficient by about 10%, a large pressure drop reduction of up to 15% obtained during the experiments helps in circumventing this disadvantage. Hence for the same pressure drop across the channel, the textured hydrophobic surface helps to augment the heat transfer rate. The experiments show that, by varying the solubility of air in water either by controlling the pressure or by local heating, underwater Cassie state of wetting can be sustained on textured hydrophobic surfaces, thus delivering up to 15% drag reduction in both cases for extended periods of time. The results obtained hold important implications towards achieving sustained drag reduction in microfluidic applications.

Smooth fluorocarbon plasma polymer films have been for a long time considered for fabrication of hydrophobic and slippery coatings. Interest in fluorocarbon materials was also supported by their excellent self-lubricant, dielectric properties and chemical inertness. This thesis is focused on development of new methods for fabrication of fluorocarbon plasma polymes, which could combine the chemical composition and the physical structure necessary for reaching superhydrophobic character of coatings. Poly(tetrafluoroethylene) was the subject material. RF magnetron sputtering using gas aggregation cluster source was the method adapted to fabricate fluorocarbon nanostructured films with chemical composition close to conventional bulk PTFE, but with high degree of cross- linking and branched structure. A model of growth of such plasma polymer nanostructures was discussed.

The design of functional materials with complex properties is very important for different applications, such as coatings, microelectronics, biotechnologies and medicine. It is also crucial that such kinds of materials have a long service lifetime. Unfortunately, cracks or other types of damages may occur during everyday use and some parts of the material should be changed for the regeneration of the initial properties. One of the approaches to avoid the replacement is utilization of self-healing materials. The aim of this thesis was to design a self-repairable material with superhydrophobic and switchable properties using colloidal particles. Specific goals were the synthesis of colloidal particles and the preparation of functional surfaces incorporated with the obtained particles, which would exhibit a repairable switching behavior and repairable superhydrophobicity. In order to achieve these goals, first, methods of preparation of simple and functional colloidal particles were developed. Second, the behavior of particles at surfaces of easy fusible solid materials, namely, paraffin wax or perfluorodecane, was investigated.

Ce travail de thèse décrit la préparation de deux types de films de polymères : i) des films nanocomposites à base de silice pyrogénée aux propriétés superhydrophobes et ii) des films LbL auto-assemblés, incluant tous deux des dérivés de poly(2,3,4,5,6-pentaflurostyrene) (PPFS), utilisés comme briques élémentaires. La stratégie utilisée ici consiste à exploiter les nombreux avantages que présente la réaction de substitution du fluor en position para du PPFS avec un thiol, pour générer de nouveaux dérivés aux propriétés ajustables. Ainsi, le premier volet de la thèse a consisté à introduire des chaînes de PPFS de façon covalente à la surface de silice pyrogénée par une stratégie dite de «grafting through» en utilisant la polymérisation radicalaire contrôlée par le voir nitroxydes, en présence de PS-DEPN comme macroamorceur. La cinétique de polymérisation du PFS avec et sans particules silice a été étudiée dans divers solvants, différentes particules hybrides de silices modifiées en surface par une couronne de PPFS ont été préparé. Ensuite, un thiol perfluoré (perfluorodecanethiol:PFDT) a été utilisé pour modifier le PPFS, considéré dans ce cadre comme matrice hôte pour la préparation des nanocomposites et pour modifier le PPFS présent à la surface des particules de silice. A partir de là, un large panel de films nanocomposite a été préparé à partir des différentes combinaisons possibles de polymère hôte (PPFS ou PPFS-PFDT) et de charges inorganiques de silice (modifiées par le PPFS ou par le PPFS-PFDT). Les propriétés de mouillabilité ainsi que la morphologie de surface de chaque film ont été analysées et il en résulte que certains films présentent un caractère superhydrophobe. Le deuxième volet de la thèse a porté sur la modification du PPFS par des thiols porteurs de fonctions acide carboxylique, toujours par la réaction de substitution décrite précédemment. Différents dérivés de PPFS carboxylés de DS variés ont été synthétisés. Leur habilité à développer des liaisons hydrogène avec un polymère modèle accepteur de liaison H (la poly(4-vinyl pyridine) (P4VP)) a été étudiée. Il en ressort que dépendamment de la nature du solvant, des mélanges miscibles ou des complexes interpolymères ont ensuite été formés. Des solutions de complexes préformés ont été successivement déposées par spin-coating pour construire des films. De plus, des films multicouches LbL stabilisés par des liaisons H entre le PPFS carboxylé et la P4VP ont été élaborés and il a été démontré que la nature du solvant de dépôt, ainsi que le taux de modification du PPFS, impactent fortement le mécanisme de croissance, l’épaisseur du film et les caractéristiques de surface, en termes de topologie et de mouillabilité. / This work describes the preparation of two kinds of thin polymer films : i) self-cleaning silica-based (nano)composites films and ii) LbL self-assembling films, both including poly(2,3,4,5,6-pentaflurostyrene) (PPFS) derivatives, as building blocks. The cornerstone of the approach is to exploit the thiol-para fluoro substitution reaction to PPFS chains in order to generate derivatives with tailored properties. In this frame, PPFS chains were anchored onto the surface of vinyl-functionalized fumed silica nanoparticles by nitroxide-mediated polymerization (NMP) in presence of PS-DEPN as macro-initiator via a “grafting through” strategy. The kinetics of NMP of PFS were investigated in presence and without silica in various solvents and well-characterized hybrid silica particles containing different polymer grafting weight were declined. Then, perfluorodecanethiol (PFDT) was employed to modify PPFS, considered as the host polymer matrix, and to functionalize PPFS chains tethered to silica particles. A large panel of (nano)composite films from the different possible host matrix/silica particles combinations was prepared. The wettability and the surface morphology of each film were discussed, as a function of the host structure (PPFS or PPFS-PFDT with different DS) and silica (modified with PPFS or PPFS-PFDT), as well as the silica content. It results that superhydrophobic features can be reached. Subsequently, PPFS was modified by using carboxylic acid mercapto modifier via the thiol-para fluoro coupling. Various carboxylated PPFS derivatives differing in the degree of substitution (DS) were prepared and their ability to develop H-bonds in solution with a model strong H-bond acceptor partner (poly(4-vinyl pyridine) (P4VP)) was investigated. Dependently on the nature of the solvent, a miscible blend or interpolymer complexes (IPC) were achieved. IPC-containing solutions were used to successfully fabricate spin-assisted films. Furthermore, H-bonds mediated LbL self-assembly multilayer films involving carboxylated PPFS and P4VP were prepared and it was evidenced that the nature of the deposition solvent as well as the extent of the modification (quantified by the DS), impact the growth mechanism, the thickness and the surface features, in terms of topology and wettability.

No description available.

Wood is a renewable resource and versatile material used in tasks ranging from tools and furniture to advanced engineering structures. Although wood is light, mechanically robust, environmentally friendly, and abundant, some inherent properties of wood, such as degradation due to moisture and UV radiation from sunlight, are less desirable for extended service life and dimensional stability. In this dissertation, a novel surface modification of wood is explored by depositing nano-sized titania particles on wood veneers and cross-laminated timber (CLT) blocks by liquid-precursor flame spray pyrolysis to confer reversible wettability switching and enhanced durability to UV irradiation. The reaction between a flame source and a titanium precursor in isopropyl alcohol under controlled air pressure created a micrometer-scale thin TiO2 coating on wood that turns the treated wood superhydrophobic with a water contact angle (WCA) of >=150°. Morphological studies suggest the coating is comprised of sub-100 nm TiO2 individual and aggregated particles, creating a very porous microstructure. The coating consists of TiO2 rich in the anatase phase (>60%) with an average crystal size of 18 and 32 nm for the anatase and rutile phases, respectively. The wettability switching characteristics of the surface of TiO2-wood veneers from superhydrophobicity to superhydrophilicity (WCA ~0°) and again back to superhydrophobicity are examined through UV exposure (0.0032 W/m2), WCA measurements, and vacuum drying at ~0.14 mbar. The color and gloss spectrometry results of the TiO2-treated CLT samples indicate that the coating offered better resistance to discoloration and gloss change than the uncoated samples during the 8-week accelerated weathering conditions. The data shows that the FSP-treated CLT samples were more than two times more effective in preventing discoloration and changes in natural luster, as evidenced by the significant differences in L*, a*, b*, and gloss values. Moreover, the FSP treatment might have played a role in preventing weathering defects, such as splits and cracks. In addition, the FSP-treated CLT specimens were able to reduce variability in the samples more effectively than the control group. Overall, the findings of the study indicate that liquid-precursor FSP has the potential to serve as a facile, economically viable, and less energy-intensive approach to modify wooden surfaces for improved hydrophobicity, as well as to provide shielding against the deteriorating impacts of UV radiation and moisture exposure. Keywords: wood modification, flame spray pyrolysis, titania coating, superhydrophobic coating, particle deposition, wettability switching

No description available.