Esta dissertação versa sobre o estudo de filmes híbridos orgânicos-inorgânicos do tipo ormosil com heteropoliânions do tipo Keggin. O heteropoliânion usado nesse trabalho foi: H3PW12O40 enquanto o ormosil foi obtido a partir do processo sol-gel usando tetraetilortossilicato (TEOS) como agente formador da rede 3D de silicatos e organossilanos contendo grupos oxirana e grupos básicos de Lewis nitrogenados. Realizaram-se testes do uso de Poli (dimetilsiloxano), bis (3-aminopropil) terminados (PDMSa) como agentes modificadores nos filmes. Foram obtidos filmes autossuportados e suportados em lâminas de vidro aluminossilicato. O PDMSa e o silano contendo o grupo oxirana levaram a uma queda na rugosidade média quadrática dos filmes como demonstrado nas micrografias obtidas por Microscopia Eletrônica de Varredura (MEV). Medidas de ângulos de contato estático da água sobre os filmes e de Espectroscopia de Fotoelétrons Excitados por Raios-X mostraram que há segregação do PDMSa ou do silano contendo o grupo oxirana na superfície dos filmes, entretanto os filmes com maior ângulo de contato são aqueles contendo PDMSa. Medidas de Espectroscopia de Absorção na Região do Infravermelho (IV) e Espectroscopia de Ressonância Magnética Nuclear com Rotação em Ângulo Mágico no Estado Sólido (RMN) mostraram que ormosis contendo silanos com grupo amino levam a parcial decomposição dos heteropoliânions, enquanto ormosis contendo silanos com o o grupo nitrila resultam em menor taxa de decomposição. Nos ormosis contendo igual proporção em número de moles destes dois silanos observou-se que estes dois grupos devem estar muito próximos e interagindo entre si via ligação de hidrogênio o que resultou numa queda ainda maior da taxa de decomposição. Os ormosis com silanos dotados de grupos oxirana e nitrila apresentaram maior sensibilidade a radiação UV, ou seja, a maior variação de absorbância e menor tempo de retorno à cor original. Estes filmes mostraram reprodutibilidade e não perderam sua atividade fotocrômica após serem submetidos a 10 ciclos sucessivos de irradiação com UV. Os filmes mostraram resposta linear da função de refletância com a dose de radiação UVB na faixa de 0,80 até 69 MED. Desta forma nós demonstramos a possibilidade de se obter filmes fotocrômicos reprodutíveis e estáveis e como controlar sua sensibilidade usando o processo sol-gel. / This thesis aim to study the organic-inorganic hybrid films of the organosilanes with heteropolyanions of the Keggin type. The heteropolyanion used in this study was H3PW12O40 while the ormosil was obtained by the sol-gel process using tetraethylortossilicate (TEOS) to build the 3D silicate network and organosilanes bearing the oxirane and Basic Lewis nitrogenated groups. Poly (dimethylsiloxane), terminated with (3-aminopropyl) groups, (PDMSa) was essayed as modifiers agents in the film. The films were supported on aluminosilicate glass substrates and self-suported ones. PDMSa or oxirane bearing silanes addition results on smoother filmes reporting lower mean square root roughness based on electron micrographies obtained by Scanning Electron Microscopy (SEM). Water static contact angle measurements and X-ray Photoemission Spectroscopy (XPS) pointed out the surface segregation of the PDMSa and oxirane bearing silane, however higher contact angles were observed for the PDMSa based films. InfraRed Absorption Spectroscopy (IR) and Magic Angle Spinning Nuclear Magnetic Resonance spectroscopy (MAS NMR) results demonstrate that in ormosis with silanes bearing amino groups there was phosphotungstic acid decomposition while in ormosis with nitrile groups such decomposition is much less pronounced. For mixed ormosis with even proportion of amino and nitrile bearing silanes those functional groups are close enough to interact through hydrogen bonding resulting on even lower decomposition of the Phosphotungstate oxocluster. Those films with nitrile functional groups showed higher photochromic activity and faster bleaching time. The films showed high reproducibility and did not loose their photochromic activity after ten cycles of UV irradiation. The films bearing nitrile functionality showed linear response of the reflectance function as a function of the irradiation dose between 0,80 and 69 MED. Therefore, it was demonstrated the possibility to use sol-gel process to obtain photochromic ormosis.

Depuis quelques décennies, les matériaux composites organique/inorganique font l’objet de nombreux travaux de recherches. En raison de leurs propriétés uniques et intermédiaires entre les deux mondes minérales et organiques, ces matériaux sont d’un grand intérêt pour des nombreuses applications tel que le domaine, d’optique, la microfluidique, la microélectronique…, La synthèse de ce type des matériaux est réalisée à moindre coût en deux étapes : La synthèse du réseau inorganique est effectué par procédé sol-gel , tant qu’à la partie organique des compositions de type résines négatives et positives possède la particularité d’être photo-réticulables sous irradiation (UV et visible). Parallèlement, est apparue la lithographie par écriture laser (spot de quelques microns). Elle s’avère très pertinente pour la mise au point d’un procédé pour lequel des objets de petites dimensions (quelques Microns) et de petites surfaces sont à réaliser car elle permet de s’affranchir de la fabrication de masques. Cette technique associée aux résines négatives, n’est pas idéale pour la fabrication d’objets de grandes surfaces en raison de temps de fabrication induits trop long. Il est, par exemple, extrêmement compliqué et couteux d’utiliser l’écriture Laser pour la réalisation de dispositifs microfluidiques. En effet, la création de canaux de taille micronique nécessite une très grande surface à insoler. Il est donc bien plus pertinent de travailler sur l’association de l’écriture laser avec une résine de type positive. L’objectif principal de ce travail est la synthèse, l’optimisation et mise en œuvre d’un matériau hybride photosensible de type résine positive : Application à la fabrication des capteurs microfluidiques. Notre choix s’est porté sur le poly(amic acid) PAA de masse molaire 2340 g/mol comme partie organique, connu pour ces bonnes propriétés mécaniques et sa grande stabilité thermique. Le travail est centré d’une part, sur la synthèse d’une résine positive photosensible à la longueur d’onde utilisée (365 nm) à base du polymère PAA. En général, les PAA sont très solubles dans une solution alcaline aqueuse, dû à la présence d’acide carboxylique. Afin d’améliorer le contraste entre la partie insolée et non insolée après le développement, un inhibiteur de dissolution 1,3,5-tris[(2-vinyloxy)ethoxy]benzène (TVEB) est greffé au PAA via la fonction vinyl éther. Ce dernier permet la réduction de la teneur en acide carboxylique dans le motif répétitif du polymère et comme conséquence diminuer la dissolution de la partie non insolée. D’autre part, la synthèse du matériau hybride à base de la résine photosensible optimisée, est réalisée par greffage d’un précurseur ORMOSIL le 4-vinyléther-phenyltriéthoxysilane (VEPTES) pré-hydrolysé par procédé sol-gel comme partie inorganique à notre polymère. Afin d'optimiser le matériau, une étude structurale a été réalisée depuis la synthèse du solution jusqu'à l'obtention des dépôts et enfin la création des canaux microfluidiques. Une amélioration significative au niveau des propriétés mécaniques et thermiques est notée au niveau du polymère par ajout d’une partie minérale. / In recent decades, the organic / inorganic composite materials are the subject of many research works. Because of their unique properties and intermediate between inorganic and organic worlds, these materials are of great interest for many applications such as the area, optical, microfluidics, microelectronics ... The synthesis of this type of materials is carried out at a lower cost in two stages: The synthesis of inorganic network is made by sol-gel process, as well as the organic part of the negative and positive resin type compositions has the particularity of being photo-crosslinked under irradiation ( UV and visible).Meanwhile, the lithography by laser writing has appeared (spot a few microns). It is particularly appropriate for the development of a method for which small objects (a few microns) and small surfaces are to achieve because it eliminates the production of masks. This technique associated with negative resins, is not ideal for manufacturing large objects surfaces due to induced production time too long. It is, for example, be extremely complicated and expensive to use writing laser for producing microfluidic devices. Indeed, the creation of micron-sized channels requires a very large surface area to be exposed. It is therefore more appropriate to work on the combination of laser writing with a resin positive type. The main objective of this work is the synthesis, optimization and implementation of a photosensitive hybrid material resin positive type: Application to the fabrication of microfluidic sensors. Our choice fell on the poly(amic acid) PAA with molar mass of 2340 g/mol as an organic part, known for its good mechanical properties and high thermal stability.The work focuses on a part, on the synthesis of a positive photosensitive resin at the wavelength used (365 nm) based on the PAA polymer. In general, PAA are very soluble in an aqueous alkaline solution, due to the presence of carboxylic acid. In order to improve the contrast between the irradiated and unirradiated part after the development, an dissolution inhibitor 1,3,5-tris [(2-vinyloxy) ethoxy] benzene (TVEB) is grafted to the PAA via the vinyl ether function. This allows the reduction of the carboxylic acid content in the repeating unit of the polymer and as a consequence reduces the dissolution of the non-exposed part.On the other part, the synthesis of the hybrid material based on the optimized photosensitive resin is formed by grafting a precursor ORMOSIL 4-vinylether-phenyltriethoxysilane (VEPTES) pre-hydrolyzed by sol-gel method as the inorganic part to our polymer. In order to optimize the material, a structural study was conducted for the synthesis of the solution until the deposits and the creation of microfluidic channels. A significant improvement in mechanical and thermal properties is recorded at the polymer by adding an inorganic portion.

In organic-inorganic hybrid compounds an organic and an inorganic component are combined to form either a coordination or an ionic material. Relevant to the current study are hybrid materials composed of an organic part that contains one or more functional groups, for example amine, amide or carboxylic acid functional groups, and a metal halide inorganic portion. These functional materials display a range of interesting and desired properties, as evidenced from numerous literature reports on their properties. In order to utilise these properties in applications, a detailed understanding of the way that the crystal structure influences the properties of a material is required. However, before this step can be achieved, it is necessary to obtain information on the structural trends of the materials, and to use the approach of crystal engineering to identify robust supramolecular synthons that may afford structural control and prediction. The aim of the current study was to investigate the synthesis and crystal structures of hybrid materials, both ionic and coordination, composed of divalent transition metal halides and the organic components 4-aminobenzoic acid, 4-aminobenzamide and isonicotinic acid, and to identify the structural trends and crystal engineering synthons displayed by these materials. A secondary objective was the preliminary identification of properties exhibited by selected materials, in order to decide on the suitability of the materials for detailed future property investigations. Part of the work describes the investigation of the structural characteristics of coordination materials prepared by the combination of the organic and inorganic components. Five novel crystal structures of coordination materials were determined, and these are compared with six related coordination structures reported in the literature. Two of the novel structures display interesting one-dimensional coordination polymers, one of which has never been reported previously in the literature. The molecular and structural characteristics of both the novel and the literature coordination structures are presented in detail, and this discussion includes a description of the coordination geometry, the molecular geometry, packing trends, hydrogen bonding interactions and aromatic interactions. A comparison study across the three families of organic components in which the structural trends, hydrogen bonding interactions, aromatic interactions, ligand geometry and coordination modes are compared, is included. The results of the synthesis of the coordination materials by means of a mechanochemical method are presented, and the products afforded by this method are compared with those prepared via solution crystallisation. Finally, the results of preliminary studies of the thermal and electronic propertries of the materials are presented and interpreted. The combination of the hybrid components as cations and anions to form ionic materials yielded nine novel structures, and these were compared with five related ionic structures reported in the literature. The novel structures include three polar structures that contain the 4-ammoniumbenzamide cation, and to our knowledge no structures containing this cation have ever been reported in the literature, hence a significant contribution to the structural knowledge of perhalometallate salts of 4-ammoniumbenzamide is made by this study. In addition two novel structures display interesting one-dimensional and two-dimensional polymeric anions, respectively, are reported. The discussion of the novel and literature ionic structures includes a description of the molecular geometry of each of the components, the identification of packing trends, and an analysis of the hydrogen bonding and aromatic interactions occurring in the structures. The structures of all three families of organic components are compared, and trends in structural type, anion geometry, water inclusion, hydrogen bonding and functional group recognition are presented. In addition, a detailed analysis of robust crystal engineering synthons occurring in these structures is presented. Lastly the results of preliminary property investigations of the thermal and electronic properties of the materials are presented and discussed / Dissertation (MSc)--University of Pretoria, 2011. / Chemistry / unrestricted

Cette thèse décrit la préparation de matériaux hybrides organiques-inorganiques aux propriétés ciblées. Dans la première partie de ce travail, le procédé sol-gel a été couplé aux techniques d'auto-assemblage pour la préparation de matériaux hybrides organiques-inorganiques. Cette combinaison est d'un grand intérêt, non seulement d'un point de vue fondamental, mais aussi parce qu'elle permet la production de nouveaux matériaux hybrides fonctionnels à structuration hiérarchique. Deux familles ont été étudiées, avec deux types de liens : urée ou uréthane. L'influence de paramètres tels que la longueur des chaînes alkyle et alkylène et le solvant sur la nanostructure a été analysée. Le comportement hystérétique d'une classe des matériaux à liens uréthane a été exploité. Dans la seconde partie de ce manuscrit, le procédé sol-gel a été utilisé pour préparer des électrolytes hybrides organiques-inorganiques composés de biohybrides siloxane/poly(e-caprolactone) à liens uréthane, contenant des proportions fortement variables de triflate de potassium dans un cas, et un mélange de triflates de lithium et d'europium dans l'autre exemple. Dans les deux cas, des prototypes de dispositifs électrochromes ont été construits, avec une structure sandwich constituée de quatre couches comprenant deux couches externes formées de films d'oxyde conducteur transparent, un film électrochrome d'oxyde de tungstène (WO3) et une couche active conductrice d'ions constituée des échantillons d'ormolyte. Les transmittances optiques moyennes, les contrastes de couleur et les temps de réponse associés aux processus de coloration/décoloration ont été déterminés. Le changement de couleur a été quantifié dans le prototype à base du mélange Li/Eu.Le carbonate de calcium (CaCO3) est un composé minéral très important dans la Nature, qui peut exister sous six formes polymorphiques différentes. Parmi elles, la phase amorphe (ACC) métastable est utilisée par beaucoup d'organismes comme intermédiaire transitoire pour former des objets composés de monocristaux de calcite ou d'aragonite à morphologie élaborée. L'ACC a un potentiel inédit dans le domaine de l'orthopédie étant donné sa vitesse de croissance, son caractère immunogène et les propriétés mécaniques des os qui en dérivent. Dans cette étude, nous avons utilisé une méthode de synthèse faisant appel à la poly(vinylpyrrolidone) pour retarder la cristallisation de l'ACC et à plusieurs liquides ioniques et tensio-actifs pour changer la morphologie de calcite. / This thesis is focused on the preparation of organic-inorganic hybrid systems with targeted properties. In the first part of the work, the sol-gel process and self-assembly techniques were employed for the preparation of organic-inorganic hybrid materials. This combination is of great interest, not only from the fundamental point of view, but also because it allows the production of novel functional and hierarchically structured hybrid materials. Two families of materials were obtained, featuring two different types of cross links: urea and urethane. The influence of parameters such as the alkyl and alkylene chain length and the solvent on the nanostructure was analyzed. In the second part of the work the sol-gel method was used to prepare organic-inorganic hybrid electrolytes composed of novel di-urethane cross-linked poly(e-caprolactone)/siloxane biohybrids incorporating a wide range of potassium triflate concentration in one example and a mixture of lithium triflate and europium triflate in the other example. In both cases prototype ECDs have been constructed using a four layer-sandwich configuration comprising two outermost layers composed of transparent conducting oxide (TCO) films, an EC film of tungsten oxide (WO3) and an IC active layer of selected ormolyte samples. The average optical transmittance, colour contrast, optical density and device response time associated with the colouring/bleaching processes have been determined. The colour change has been quantified in the prototype based on the Li/Eu mixture. Calcium carbonate (CaCO3) is an important biomineral in Nature, that can exist in six different polymorphic forms. Among them, the metastable amorphous CaCO3 phase (ACC) is used in many organisms as a transient intermediate to form single crystals of calcite and aragonite with elaborate shapes. ACC has a tremendous potential in the orthopedic field. Herein we have employed poly(vinylpyrrolidone) to retard the crystallization of ACC. In addition, several ionic liquids and surfactants were employed to tune the morphology of calcite.

付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 新制・課程博士 / 博士(工学) / 甲第23227号 / 工博第4871号 / 新制||工||1760(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 田中 一生, 教授 秋吉 一成, 教授 古賀 毅 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Epoxy resins have been broadly used in the industry for adhesives, laminates, coatings, composites, encapsulation of electronic devices, printed circuit boards, etc. Despite their excellent adhesion to different materials, heat and chemical resistance and good mechanical properties, they also exhibit few drawbacks like brittleness, high thermal expansion coefficient (CTE), poor resistance to crack initiation and growth. Therefore, the thesis is focused on the preparation of epoxy-silica hybrid materials exhibiting improved thermomechanical properties compared to the neat epoxides, without impairing their beneficial features. The main synthetic route of epoxy-silica hybrids' preparation has been the sol-gel process of alkoxysilanes, allowing either in-situ formation of high purity and homogeneity silica particles or creation of various siloxane structures in a form of liquid (sol) silica-based precursors. The sol-gel method, on one hand, helps to omit too high viscosity of nanofiller suspension and energy-intensive nanofiller dispergation problems, but on the other hand, is often associated with necessity to use solvents and to remove formed volatiles. Therefore, in the first part of the thesis, a simple solvent-free sol-gel procedure, enabling to minimize the side-effect of solvent evaporation and...

Organic-inorganic polymer hybrids containing butyl stannoxane dodecamer cages (Sn_POSS) as nano-building blocks were prepared and investigated. Sn_POSS was employed as a linear, crosslinking or non-bonding molecularly blended unit. For this purpose, it was synthesized with two acrylamido, primary- or secondary amino, or with two additional non- functional groups, which were attached via ionic-bonded sulfonate substituents. The nano- building block was then incorporated in matrices such as PS, PAOS, PETA, PEMA, PHEMA and PPO-based epoxies (the latter with different mesh sizes). Sn_POSS reinforces the studied matrixes by filler-filler interactions (self-assembly to nano-domains). Specific interactions of the ionic bonds of Sn_POSS with suitable pendant groups of the matrixes also can generate reinforcement and suppress filler aggregation. Moreover, the Sn_POSS can undergo several types of chemical reactions like heat-induced oligomerization, dissociation of the ionic substituents, acidolysis of the Sn-butyl bonds, as well as radical reactions of the latter. The influence of ionically bonded cages on the hybrids' morphology, as well as their ability of dissociation and short-distance migration in the polymer network at elevated temperature, was evaluated by TEM, IR and NMR analyses. The mechanical...

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20402号 / 工博第4339号 / 新制||工||1672(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 中條 善樹, 教授 澤本 光男, 教授 古賀 毅 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24586号 / 工博第5092号 / 新制||工||1975(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 秋吉 一成, 教授 大塚 浩二, 教授 田中 一生 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The recent increased availability of additional wavelengths in the telecommunications window of about 1300-1600 nm has generated an interest in new optical materials and devices that can operate outside the normally used regions of 840 nm, 1310 nm, and 1550 nm. Specifically, methods to amplify fiber optical data transmission in the regions where there is limited or no existing methods to achieve amplification is of interest in the chemistry and photonic communities. Raman gain is one method that has been proposed to passively amplify optical data transmission through a distributed process. Amplification is obtained through a nonlinear light scattering process where an optical wave is amplified at the expense of a higher frequency pump wave. Multiple wavelengths can be evenly amplified simultaneously in a desired region by specific selection of one or more pump wavelengths. Herein, the synthesis and characterization of new hybrid inorganic/organic sol-gels and monomers capable of producing broad wavelength Raman scattering over a spectral range of 1200-1670 nm are presented. The synthetic methodology developed facilitates the systematic approach to produce sol-gel derivatives with functional groups known to be strongly Raman scattering. Additionally, a method to synthesize and characterize a large number of different compounds using a combinatorial approach was demonstrated. Thio based derivatives of sulfonyldiphenol, isopropylidenediphenol, and triallyloxy triazine were synthesized in addition to thio derivatives of poly(hydroxystyrene). Micro-Raman spectra of the hybrid sol-gels, thiobased derivatives, and IR spectra of select sol-gel monomers were obtained.