Ce travail de thèse a pour objet l’étude d’organogélifiants bis(urée) originaux de faible masse moléculaire (LMWG), intégrant ou non des unités fluorescentes pyrènes. Il intègre les aspects liés à la synthèse organique de ces systèmes, l’étude de leur capacité de gélification pour des solvants variés, la caractérisation des édifices auto-assemblés correspondants -en particulier à l’aide de méthodes spectroscopiques et de microscopies variées-, et enfin la mise en œuvre d’une méthode originale de structuration par alignement des fibres auto-assemblées. Deux premiers organogélifiants bis(urée) modèles ont été synthétisés et leur aptitude à geler de multiples solvants ainsi que la structuration des auto-assemblages correspondant ont été étudiées en détail (RMN, microscopies optiques et électroniques). L’étude de l’alignement des fibres résultantes a été réalisée avec succès en utilisant un gabarit, par remplissage des pores d’une membrane d’alumine, puis dissolution de cette dernière. Une seconde série d’organogélifiants bis(urée), intégrant cette fois une, deux ou encore trois unités fluorescentes pyrène a été synthétisée. L’intégration covalente de cette unité dans nos gels s’est révélée intéressante à plusieurs titres. D’abord, celle-ci joue le rôle de sonde interne permettant une caractérisation approfondie de la structuration des édifices auto-assemblés à l’aide des spectroscopies d’absorption et d’émission en fonction de la température. Cette unité participe par ailleurs à la robustesse des objets nanostructurés, comme remarquablement mis en évidence dans les gels hybrides associant les gélifiants tris(pyrényles) de symétrie C3, soit à un gélifiant porteur de deux unités pyrène ou soit à un dérivé accepteur-π d’électrons, introduit dans le milieu. / This thesis focuses on the study of original bis(urea) low molecular weight organogelators (LMWG), integrating or not fluorescent pyrene units. This study integrates organic synthesis of these systems, study of their gelling capacity for various solvents, characterization of the corresponding self-assembled structures through various spectroscopic and microscopy techniques, and finally implementation of an original structuring method by alignment of the self-assembled fibers. Two first model bis(urea) organogelators were synthesized and their ability to gel multiple solvents as well as the structuration of the corresponding self-assemblies have been studied in detail (NMR, optical and electron microscopy). Alignment of the resulting fibers has been successfully performed using a template method, by filling the pores of an alumina membrane, followed by dissolution of the latter. A second series of bis(urea) organogelators, which incorporate one, two or three pyrene fluorescent units was synthesized. The integration of this unit in our gels has proved useful in several ways. First, it acts as an internal probe for further characterize the resulting self-assembled structures, using variable temperature absorption and emission spectroscopies. The pyrene unit also contributes to the robustness of the nanostructured objects, as remarkably evidenced in hybrid gels involving tris(pyrenyl) C3 symmetry gelators associated to either a bis(pyrenyl) gelator or to a π-acceptor derivative.

No description available.

This dissertation describes the preparation of a novel inorganic membrane for hydrogen permeation and its application in a membrane reactor for the study of the methane steam reforming reaction. The investigations include both experimental studies of the membrane permeation mechanism and theoretical modeling of mass transfer through the membrane and simulation of the membrane reactor with 1-D and 2-D models. A hydrothermally stable and hydrogen selective membrane composed of silica and alumina was successfully prepared on a macroporous alumina support by chemical vapor deposition in an inert atmosphere at high temperature. Before the deposition of the silica-alumina composite, multiple graded layers of alumina were coated on the alumina support with a mean pore size of 100 nm by the sequential application of three boehmite sols with gradually decreasing sol particle sizes of 630, 200 and 40 nm, respectively. The resulting supported composite alumina-silica membrane had high permeability for hydrogen in the order of 10-7 mol m-2 s-1 Pa-1 at 873 K with a H2 /CH4 selectivity of 940 and exhibited much higher stability to water vapor at the high temperature of 873 K. In addition, the same unusual permeance order of Heï¼ H2ï¼ Ne previously observed for the pure silica membrane was also observed for the alumina-silica membrane, indicating that the silica structure did not change much after introduction of the alumina. The permeation of hydrogen and helium through vitreous glass and silica membranes was modeled using ab initio density functional calculations. Comparison of the calculated activation energies to those reported for vitreous glass (20—40 kJ mol -1) indicated the presence of 5- and 6-membered siloxane rings, consistent with the accepted structure of glass as a disordered form of cristobalite. The experimental studies of the steam reforming of methane were examined at various temperatures (773-923 K) and pressures (1-20 atm) with a commercial Ni/MgAl2O4 catalyst in a hydrogen selective silica-alumina membrane reactor and compared with a packed bed reactor. One-dimensional and two-dimensional modeling of the membrane rector and the packed bed reactor were performed at the same conditions and their performances were compared with the values obtained in the experimental study. Improved methane conversions and hydrogen yields were obtained in the membrane reactor compared to the packed bed reactor at all temperatures and pressures. From the two modeling studies, it was also found out that the two-dimensional model performed better in the membrane reactor case especially at higher pressures. / Ph. D.

Les membranes d'alumine nano-poreuses suscitent depuis quelques années un grand intérêt dans la synthèse de nano-objets. Ces membranes présentent des pores très verticaux naturellement organisés en un réseau hexagonal (structure en nid d'abeilles). Le diamètre des pores peut varier entre 20 et 200nm espacés de 60 à 540nm et l'épaisseur de la membrane peut varier de 100nm à plusieurs centaines de µm. Durant ces travaux de thèse, deux approches ont été envisagées pour synthétiser des nano-structures. La première consiste à utiliser ces membranes comme nano-réservoirs. La couche barrière formée au fond de la membrane dont l'épaisseur est environ égale au diamètre des pores est diminuée à 10nm par voie chimique. Puis des dépôts de divers matériaux (Au, Co, Si) ont été réalisés dans des membranes avec des pores de 180nm et 40nm préalablement dégazées. Ces objets 3D ont été fabriqués sous ultra-vide (10-10 mbar), concfinés à l'intérieur des nano-réservoirs, transparents aux électrons. Les études en TEM permettent d'avoir accès à la morphologie des nanoparticules, qui se révèlent être cristallines, selon plusieurs directions cristallographiques. En vue plane, perpendiculairement à l'interface, pour ceux déposés au fond du nano-réservoir et en vue transverse pour ceux déposés sur les parois. Il a par ailleurs été possible de réaliser des études de recuits in-situ en température (RT à 1000° C) dansle TEM pour des particules d'or. La seconde approche repose sur l'utilisation des membranes ouvertes comme masque pour l'évaporation. Cette technique permet de dupliquer le motif de la membrane sur le substrat préalablement nettoyé pour former un réseau de nanoparticules correspondant au matériau déposé. Nous avons réalisé de manière reproductible, sous ultravide,des réseaux de plots d'or à l'aide de membranes dont le diamètre des pores est de 180 nm / The nanoporous alumina membrane rise in recent years a great interest in the synthesis of nanoobjects. These membranes have pores naturally very vertical organized in a hexagonal lattice(honeycomb structure). The pore diameter may vary between 20 and 200nm spaced 60 to 540nmand the thickness of the membrane can vary from 100nm several hundred microns. During this thesis work, two approaches have been explored to synthesize nano-structures. The first is touse these membranes as nano-tanks. The barrier layer formed at the bottom of the membrane whose thickness is about equal to the diameter of pores is reduced to 10nm by chemical etching. Then deposits from materials (Au, Co, Si) were performed in membranes with pores of 180nmand 40nm previously degassed. These 3D objects have been produced under ultra-high vacuum(10-10 mbar), confined within nano-tanks, transparent to electrons. TEM studies allow accessto the morphology of nanoparticles, which are proving to be crystallin, according to several crystallographic directions. In plane view perpendicular to the interface for those deposited atthe bottom of the nano-tank and cross-sectional view for those deposited on the walls. It has also been possible to perform studies of in-situ annealing (RT to 1000° C) in TEM of Au particles. The second approach relies on the use of membranes opened as an evaporation mask. This technique allows to duplicate the pattern of the membrane to the substrate previously cleaned, to form a network of nanoparticles corresponding to the material deposited. We have achieved reproducible, gold dot arrays, under UHV conditions using membranes with a pore size of 180 nm.

This study focuses on fabrication of dry adhesives mimicking gecko adhesion. We also look into the origin of the supreme adhesion of geckos, which have inspired the fabrication of fibrillar dry adhesives during the last decade or so. In principle, the superior material properties of ??-keratin (the main material comprising the fibrillar feature on gecko toe pads) along with the hierarchical high aspect-ratio fibrillar structure of geckos??? foot pad have enabled geckos to stick readily and rapidly to almost any surface in both dry and wet conditions. In this research, non-sticky fluoropolymer (Teflon AF) resembling ??-keratin rigidity and having an extremely low surface energy and dielectric constant was applied to fabricate a novel dry adhesive consisting of extremely high aspect-ratio nanopillars (200 nm in diameter) terminated with a fluffy top nanolayer. Both the nanopillars and the terminating layer were fabricated concurrently by replica-molding using a nanoporous anodic aluminum oxide membrane as the mold. In particular, upon infiltration of Teflon AF melt into the anodic aluminum oxide nanopores, the polymer melt fingered over the pore walls. The fingerlike structure formed during infiltration, subsequently collapsed after removal of the mold, developing a unique sheet-like nanostructure on top of the base nanopillars. Concurrent fabrication of the terminating nanostructure helps the fabrication of extremely high aspect-ratio (27.5???225) nanopillars which, up to an aspect-ratio of 185, neither collapse at the tip nor bundle. In order to fabricate nanopillars of different topographical properties, in our first approach, the height of the nanopillars as well as the size and density of the terminating nanostructure are carefully controlled by adjusting the processing temperature. Following that, a novel replica-molding technique for fabrication of bi-level Teflon AF nanopillars is reported. The developed technique relies on the concurrent heating and cooling of the Teflon AF melt which filled vertically-aligned alumina nanochannels. Unlike conventional polymer infiltration methods which consist of filling the mold by only heating the polymer above its glass transition temperature, in our novel method, the polymer melt is also simultaneously cooled down during the infiltration process. Concurrent cooling of the Teflon AF melt allows control over the interfacial instabilities of the polymer thin film, which forms ahead of the polymer melt upon its infiltration into the alumina nanochannels. Doing so, the geometrical properties of the subsequently developed peculiar fluffy nanostructure ??? after removal of the mold ??? on top of the extremely high aspect-ratio Teflon AF nanopillars (~25 ??m tall) are modified. In this project, we have also shown that the adhesion of the fabricated dry adhesives for the most part arises from electrostatic interactions of the applied polymer. In other words, Teflon AF, having an exceptional potential for developing electric charges at its surface upon contact with other materials via the so-called contact electrification phenomenon, can develop significant electrostatic interactions at its surface upon contact. In the current thesis, tribological results were discussed in detail to clarify the contribution of the structural properties of the fabricated dry adhesives toward their remarkable adhesion and friction forces generated via contact electrification. Nanopillars of specific geometrical properties have achieved remarkable adhesion and friction strengths, up to ~2.1 N/cm2 and 17 N/cm2, respectively (up to ~2.1 and 1.7 times larger than those of a gecko toe pad). It is commonly accepted that the adhesive performance of other synthetic bio-inspired dry adhesives is due to the formation of van der Waals interactions at the tip or side of the dry adhesives fibrils with the substrate they are brought into contact with. However, what has been usually neglected in this connection is that electrostatic interactions may also be developed at the contact between any two materials via the familiar contact electrification phenomenon. Although contact electrification is common and can have a large influence on interfacial interaction forces, its impact on adhesive properties of synthetic dry adhesives has been overlooked. Our results on adhesion of bi-level Teflon AF nanopillars, which can generate strong adhesion forces relying on electrostatic interactions arising from contact electrification, have brought to light again the idea that charging the surface of dry adhesives, specifically polymeric ones, can play a very crucial role in their adhesive behavior. From this perspective, the main reasons that have caused this lack of attention to this concept and the possible contributions of contact electrification to interfacial interactions of polymeric dry adhesives, other than bi-level Teflon AF nanopillars, are also thoroughly discussed in this thesis. Besides synthetic fibrillar dry adhesives, the possibility of the occurrence of contact electrification and its contribution to the supreme dry adhesion of geckos have also been overlooked for several decades. In this research, by the simultaneous measurement of electric charges and adhesion forces that gecko toe pads develop on two distinct substrates (a sticky and a non-sticky one), we have shown that the toe pads generate significantly large amounts of electric charge on both substrates. More importantly, we have found that there is a direct correlation between the contact electrification-driven electrostatic forces and the measured adhesion forces. Otherwise stated, we have shown that what makes the difference that geckos stick strongly to one surface and not to the other are the electrostatic interactions arising from contact electrification, and not van der Waals interactions, which have been considered as the prime source of adhesion of geckos for many years.

Made available in DSpace on 2014-12-17T14:07:09Z (GMT). No. of bitstreams: 1 JoseFTJ_TESE.pdf: 4834280 bytes, checksum: 1a618560296186081bd6c34117d226be (MD5) Previous issue date: 2012-07-04 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Thin commercial aluminum electrolytic and passed through reactions was obtained with anodic alumina membranes nanopores. These materials have applications in areas recognized electronic, biomedical, chemical and biological weapons, especially in obtaining nanostructures using these membranes as a substrate or template for processing nanowires, nanodots and nanofibers for applications noble. Previous studies showed that the membranes that have undergone heat treatment temperature to 1300? C underwent changes in morphology, crystal structure and optical properties. This aim, this thesis, a study of the heat treatment of porous anodic alumina membranes, in order to obtain and to characterize the behavior changes structures during the crystallization process of the membranes, at temperatures ranging between 300 and 1700? C. It was therefore necessary to mount a system formed by a tubular furnace resistive alumina tube and controlled environment, applying flux with special blend of Ag-87% and 13% N2, in which argon had the role of carrying out the oxygen nitrogen system and induce the closing of the pores during the densification of the membrane. The duration of heat treatment ranged from 60 to 15 minutes, at temperatures from 300 to 1700? C respectively. With the heat treatment occurred: a drastic reduction of porosity, grain growth and increased translucency of the membrane. For the characterization of the membranes were analyzed properties: Physical - thermogravimetric, X-ray diffraction, BET surface area; morphological - SEM, EDS through compositional and, optical absorbance, and transmittance in the UV-VIS, and FTIR. The results using the SEM showed that crystallization has occurred, densification and significant changes in membrane structure, as well as obtaining microtube, the BET analysis showed a decrease in specific surface area of the membranes has to 44.381 m2.g-1 to less than 1.8 m2.g-1 and in the analysis of transmittance and absorbance was found a value of 16.5% in the range of 800 nm, characteristic of the near infrared and FTIR have confirmed the molecular groups of the material. Thus, one can say that the membranes were mixed characteristics and properties which qualify for use in gas filtration system, as well as applications in the range of optical wavelength of the infra-red, and as a substrate of nanomaterials. This requires the continuation and deepening of additional study / L?minas delgadas de alum?nio comercial passaram por rea??es eletrol?ticas e obtiveram-se membranas de alumina an?dica com nanoporos. Estes materiais t?m reconhecidas aplica??es nas ?reas eletr?nicas, biom?dicas, qu?micas e biol?gicas, principalmente, na obten??o de nanoestruturas utilizando estas membranas como substrato ou molde para processamento de nanofios, nanopontos e nanofibras para aplica??es nobres. Estudos anteriores apontaram que as membranas que passaram por tratamentos t?rmicos at? a temperatura de 1300? C, sofreram altera??es na morfologia, na estrutura cristalina e nas propriedades ?pticas. O objetivo deste trabalho foi o estudo do tratamento t?rmico de membranas de alumina an?dica porosas, com o intuito de obter e caracterizar as altera??es de comportamento das estruturas, durante o processo de cristaliza??o das membranas, em temperaturas que variaram entre 300 e 1700? C. Assim, foi necess?rio montar um sistema formado por um forno resistivo tubular e tubo de alumina com ambiente controlado, aplicando fluxo com mistura especial de Ar-87% e N2-13%, no qual o arg?nio teve o papel de carrear o oxig?nio para fora do sistema e o nitrog?nio de induzir o fechamento dos poros, durante a densifica??o das membranas. A dura??o dos tratamentos t?rmicos variou de 60 a 15 minutos, para as temperaturas de 300 at? 1700? C respectivamente. Com o tratamento t?rmico ocorreu redu??o dr?stica da porosidade, crescimento do gr?o e aumento da translucidez da membrana. Para a caracteriza??o das membranas, foram feitas an?lises das propriedades: f?sica - termogravim?trica; difra??o de raios-X, ?rea superficial BET; morfol?gica - MEV, composicional atrav?s do EDS; e, ?ptica - transmit?ncia e absorb?ncia no UV-VIS e FTIR. Os resultados por meio do MEV mostraram que ocorreu cristaliza??o, densifica??o e mudan?as significativas na estrutura das membranas, bem como, a obten??o de microtubo; a an?lise de BET constatou uma diminui??o na ?rea superficial espec?fica das membranas que passou de 44,381m2.g-1, para menos de 1,8m2.g-1; na an?lise de transmit?ncia e absorb?ncia foi encontrado um valor de 16,5 % na faixa de 800nm, caracter?stico do infravermelho pr?ximo e no FTIR foram confirmadas os grupos moleculares do material. Assim, pode-se afirmar que as membranas apresentaram caracter?sticas mistas e propriedades que as qualificam para o uso em sistema de filtra??o de gases, bem como, de aplica??es ?ticas na faixa do comprimento de onda do Infravermelho, e como substrato de nanomateriais. Isto requer a continuidade e aprofundamento em estudos complementares

Made available in DSpace on 2014-12-17T14:57:41Z (GMT). No. of bitstreams: 1 JoseFTJ.pdf: 1695651 bytes, checksum: 0a95ed624ef6e5342ad90e1b6193878e (MD5) Previous issue date: 2007-12-17 / This a study on the achievement of alumina membranes by the method of anodizing. From this method got up a layer of aluminum oxide on the anodic metal, who presented the basic properties necessary for the application as a support for the production and acquisition of nanomaterials, such as porosity nano and resistance to high temperature, and other properties, as resistance to corrosion, and chemical, high ranking of the structure and pore size of the pores. The latter, ranging from 10 to 100nm depended on the electrolyte used, which in this study was the H2SO4. To remove all remaining aluminum, it is a bath of dissolution with HCl and CuCl where the residual aluminum has been withdrawn, and the deep pores were opened after chemical treatment with NaOH. After the dissolution, the membranes were calcined at temperatures of 300, 600 and 900? C, and sintered at temperatures of 1200 and 1300? C to win mechanical strength, porosity and observe the desired crystallization. Then went through analyses of composition through X-ray diffraction and morphology of the microstructure through a scanning electron microscope. The method was effective for obtaining alumine membranes applied in the processes of production of materials in nano / Trata de um estudo sobre a obten??o de membranas de alumina atrav?s do m?todo da anodiza??o. A partir deste m?todo obteve-se uma camada de ?xido an?dico sobre o alum?nio met?lico, que apresentou as propriedades b?sicas necess?rias ? aplica??o como suporte para produ??o e obten??o de nanomateriais, tais como: porosidade nanom?trica e resist?ncia a altas temperaturas, al?m de outras propriedades, como resist?ncia ? corros?o, e qu?mica, alta ordena??o da estrutura dos poros e tamanho dos poros. Este ?ltimo, variando de 10 at? 100nm dependeu do eletr?lito usado, o qual neste estudo foi o H2SO4. Para retirar todo alum?nio restante, procedeu-se um banho de dissolu??o com HCl e CuCl no qual o alum?nio residual foi retirado, e os poros profundos foram abertos ap?s o tratamento qu?mico com NaOH. Ap?s a dissolu??o, as membranas foram calcinadas nas temperaturas de 300, 600 e 900? C, e sinterizadas nas temperaturas de 1200 e 1300? C para ganhar resist?ncia mec?nica, porosidade desejada e observar a cristaliza??o. Em seguida passou por an?lises de composi??o atrav?s da Difra??o de Raios-X e morfologia da microestrutura por meio de um microsc?pio eletr?nico de varredura. O m?todo se mostrou eficiente para obten??o de membranas de alumina aplicadas nos processos de produ??o de materiais em escala nanom?trica

Les substrats structurés aux échelles micrométriques et nanométriques sont intéressants pour des applications biomédicales, par exemple dans des puces à ADN/protéines, pour la miniaturisation des « lab-on-chip » ou pour préparer des implants permettant le contrôle de l'adhésion de cellules. Dans la dernière décennie des études ont montrées, que les cellules vivantes peuvent détecter la présence de nano-structures sur les substrats sur lesquels elles adhèrent. Bien que ces mécanismes soient étudiés depuis une dizaine d'années, les mécanismes fondamentaux sont encore en cours d'études. Tant pour une étude au niveau fondamental que dans le but d'applications concrètes, il est important de développer des techniques simples pour structurer des substrats sur de grandes surfaces. Nous avons réalisé une nouvelle méthode alliant un faible coût de fabrication et la biocompatibilité pour structurer et biofonctionnaliser des substrats à l'échelle nanométrique en utilisant des membranes d'alumine poreuses comme masque. Les membranes d'alumine poreuses, préparées par électrochimie, sont naturellement organisées en un réseau hexagonal sur une surface de quelques cm². Nous les utilisons comme masque pour la structuration de surfaces. Des trous réguliers sont gravés dans le substrat à travers les membranes d'alumine poreuses. Ce substrat est ensuite utilisée lors d'une application biologique : une bicouche lipidique est déposée sur le substrat structuré pour imiter les hétérogénéités de la membrane cellulaire. La mobilité de la bicouche est étudiée par corrélation de spectroscopie de fluorescence à rayon variable. Une autre série d'expériences est faite en utilisant des membranes d'alumine poreuses comme masque d'évaporation pour créer des réseaux organisés d'îlots d'organo-silanes. Deux molécules sont utilisées elles possèdent soit une fonction amine réactive soit une longue chaîne carbonée inerte. La bio-fonctionnalisation est ensuite effectuée en utilisant la fonction amine pour accrocher un anticorps. Des études sont effectuées en parallèle, sur des substrats bio-fonctionnalisés à l'échelle micrométrique grâce au micro-contact printing. Le but de cette étude est de mettre au point une biochimie de surface permettant le contrôle de l'adhésion de cellules immunitaires, avec le but de transférer ensuite la biochimie à l'échelle nanométrique. / Substrates patterned at the micro-scale and nano-scale are interesting for biomedical applications, for example, in DNA/protein nano-arrays, for miniaturized lab-on-chip applications or for making smart implants that can control adhesion of cells. In the last decade, some studies showed that living cells can detect nano-scale structures on substrates to which they adhere. Although this behaviour has been observed now for over a decade, the fundamental detection mechanism is still under investigation. Both for fundamental studies and for applications, it is important to develop facile techniques to pattern substrates on a large scale. We have realized a novel technique for patterning and bio-functionalizing substrates at the nano-scale using porous anodic alumina membranes as masks. The ordered porous anodic alumina membranes, prepared by classical electro-chemistry, are naturally organized in an hexagonal array over surface area of few square centimeters. Here we use them as mask for surface patterning. To create an array of nano holes, the substrate is dry etched through the alumina pores. In a biologically relevant application, a lipid bilayer is deposited on the patterned substrate to mimic a heterogeneous cell membrane. The mobility of the bilayer is studied by fluorescent correlation spectroscopy. In a different set of experiments, the porous alumina membranes are used as evaporation mask to create an organized array of alkyl-silane islands - either with a short carbon chain and with a reactive amine group or with a long carbon chain and non-reactive. Afterwards, biochemical functionalization is achieved by exploiting the amino-function of the amino-silane to bind an antibody. In parallel, we have started some studies of adhesion on a pattern substrate at micro-scale with immunological cells. The substrate is pattern by micro contact printing and the cell adhesion is observed by RICM. The aim of this studies is to prepare the biochemistry for the immunological cells adhesion, with the aim or transferring this to the nano-scale.

No description available.