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.

O titânio comercialmente puro (Ti-Cp) e suas ligas destacam-se como biomateriais metálicos devido a sua biocompatibilidade sendo amplamente utilizados. Buscando aprimorar o sucesso clínico dos implantes de Ti-Cp em longo prazo, é necessário revestir a sua superfície, proporcionando uma eficiente ancoragem mecânica do implante com o tecido ósseo. Dentre os diversos revestimentos superficiais destacam-se os revestimentos híbridos orgânicos-inorgânicos à base de precursores alcóxidos de silício, obtidos via processo sol-gel. Para que ocorra uma satisfatória adesão do revestimento no substrato, precisa-se levar em consideração a natureza e a preparação da superfície metálica antes da aplicação deste revestimento. Na etapa inicial do trabalho, pré-tratamentos superficiais foram propostos previamente à aplicação dos revestimentos buscando aumentar a aderência entre o titânio e este revestimento híbrido. Utilizou-se três diferentes pré-tratamentos na superfície do Ti-Cp: o "piranha" (ácido sulfúrico e peróxido de hidrogênio), o "kroll" (ácido fluorídrico, ácido nítrico e água) e o "hidróxido de sódio". Em sequência, aplicou-se por processo de dip-coating sobre as superfícies tratadas, um revestimento híbrido produzido a partir dos precursores alcóxidos de silício tetraetoxisilano (TEOS) e metiltrietoxisilano (MTES), obtido pelo processo de sol-gel. Em uma segunda etapa, sobre a superfície do Ti-Cp com o pré-tratamento superficial que proporcionou uma maior aderência do revestimento híbrido ao titânio, aplicou-se por dip-coating, um revestimento híbrido à base de precursores alcóxidos de silício TEOS e MTES com adição de partículas de hidroxiapatita buscando aprimorar a diferenciação celular sobre o revestimento híbrido. O pré-tratamento com o hidróxido de sódio promove o melhor resultado dentre os pré-tratamentos, pois o revestimento híbrido aplicado posteriormente apresenta recobrimento regular e adesão ao substrato de Ti-Cp. Os resultados morfológicos por MEV-FEG mostraram um revestimento híbrido com boa dispersão da hidroxiapatita e um recobrimento regular e adesão ao substrato de Ti-Cp. Nos resultados biológicos Ti-Cp revestido com TEOS/MTES com a presença de partículas de hidroxiapatita obteve uma adesão celular semelhante ao Ti-Cp sem tratamento. Porém este mesmo revestimento não propiciou a proliferação e diferenciação celular. Os resultados indicaram que a combinação de fatores como a sua superfície hidrofóbica (91°) e a presença da hidroxiapatita no revestimento tornou a superfície desorganizada, acarretando em uma superfície com comportamento desfavorável para o desenvolvimento das células-tronco mesenquimais. / Commercially pure titanium (cp-Ti) and its alloys stand out among the metallic materials due to their biocompatibility being widely used in biomaterials. In order to improve the clinical success of cp-Ti implants in the long term, it is necessary to coat the surface, providing an efficient mechanical anchoring of the implant with the bone tissue. Among the various surface coatings are the hybrid coatings based on silicon alkoxide precursors, obtained by the sol-gel process, however, considering the nature and the preparation of the metal surface prior to the application of this coating. In the initial stage of the work, surface pre-treatments were proposed prior to the application of the coatings seeking to increase the adhesion between the titanium and this hybrid coating. Three different pretreatments were used on the cp-Ti surface: "piranha" (sulfuric acid and hydrogen peroxide), "kroll "(hydrofluoric acid, nitric acid and water) and "sodium hydroxide". Subsequently, a hybrid coating produced by the tetraethoxysilane silicon (TEOS) and methyltriethoxysilane (MTES) precursors obtained by the sol-gel process was applied by the dip-coating process onto the treated surfaces. In a second step, on the surface of the cp-Ti with the surface pretreatment that gave a greater adhesion of the hybrid coating to the titanium, dip-coating, a hybrid coating based on precursors silicon alkoxides TEOS and MTES with the addition of hydroxyapatite particles to enhance cell differentiation on the hybrid coating. Pretreatment with sodium hydroxide promotes the best result among the pre-treatments, since the hybrid coating applied afterwards presents regular coating and adhesion to the cp-Ti substrate. The morphological results by SEM-FEG showed a hybrid coating with good dispersion of the hydroxyapatite and a regular coating and adhesion to the cp-Ti substrate. In the biological results Ti-Cp coated with TEOS / MTES with the presence of hydroxyapatite particles obtained a cell adhesion similar to Ti-Cp without treatment. However, this same coating did not promote cell proliferation and differentiation. The results indicated that the combination of factors such as its hydrophobic surface (91°) and the presence of the hydroxyapatite encapsulated in the coating rendering the surface disorganized led to a surface with unfavorable behavior for the development of mesenchymal stem cells.

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

As atuais condições ambientais tem direcionado o foco de muitas pesquisas para o reaproveitamento de resíduos agroindustriais na obtenção de novos materiais. Entre estes resíduos, destacam-se as fibras naturais, como o bagaço de cana-de-açúcar, principalmente por apresentarem características importantes para as aplicações industriais: de origem renovável, biodegradável e de baixo custo. A celulose extraída de fibras vegetais revela-se como uma alternativa promissora para a produção de materiais híbridos orgânico-inorgânicos com propriedades multifuncionais e amplas aplicações. Este trabalho busca primeiramente à obtenção de híbridos celulose/óxido de alumínio hidratado a partir do tratamento e modificação da celulose extraída do bagaço de cana-de-açúcar e sua posterior aplicação na produção de membranas. As fibras de celulose foram tratadas com clorito de sódio em meio ácido e com a mistura de ácidos nítrico e acético, com objetivo de verificar a influência do tratamento químico da celulose nas propriedades térmicas dos híbridos formados. O Al2O3.nH2O foi preparado pelo método da precipitação convencional partindo-se do alumínio metálico. As celuloses tratadas e o Al2O3.nH2O foram caracterizados por DRX, FTIR, TG, DSC e MEV. O tratamento químico das fibras de celulose não interferiu na estabilidade térmica e no processo de combustão das celuloses. Os híbridos foram produzidos nas proporções de 5, 10, 15 e 20% de óxido hidratado e caracterizados por DRX, TG, DSC, Calorimetria de Combustão e MEV/EDS. Os resultados obtidos mostraram uma boa interação entre as fibras de celulose e o óxido de alumínio hidratado. As análises de calorimetria de combustão e de DSC em ar sintético permitiram observar que o Al2O3.nH2O agiu como um agente retardante de chamas. A proporção definida para a produção de membranas foi 95Cel/05Al2O3.nH2O. Membranas de celuloses puras e dos híbridos 95CelA/05Al2O3.nH2O e 95CelB/05Al2O3.nH2O foram produzidas nos sistemas solventes de NaOH/ureia e NaOH/tioureia e caracterizadas por DRX, TG, DSC e MEV/EDS. A dissolução das fibras de celulose nos sistemas solventes promoveram a conversão da celulose tipo I (nativa) em celulose tipo II (regenerada). As membranas preparadas com os híbridos 95CelA/05Al2O3.nH2O e 95CelB/05Al2O3.nH2O em NaOH/ureia e 95CelA/05Al2O3.nH2O em NaOH/tioureia apresentaram maior estabilidade térmica e resistência à combustão que as membranas de celulose. / The current environmental conditions has directed the focus of much research for the reuse of industrial residues in obtaining new materials. Among these residues, there are the natural fibers such as sugarcane bagasse, mainly because of the important features for industrial applications: source renewable, biodegradable and low cost. Cellulose extracted from plant fibers revealed as a promising alternative for the production of organic-inorganic hybrid materials with multifunctional properties and broad applications. This paper seeks primarily to obtain hybrids cellulose/hydrous aluminum oxide from the treatment and modification of cellulose extracted from crushed sugarcane and its subsequent application in the production of membranes. Cellulose fibers were treated with sodium chlorite in acid and a mixture of nitric and acetic acids, in order to verify the influence of the chemical treatment of cellulose in the thermal properties of hybrids formed. The Al2O3.nH2O was prepared by the conventional precipitation method starting from metallic aluminum. The treated pulps and Al2O3.nH2O were characterized by XRD, FTIR, TG, DSC and SEM. The chemical treatment of cellulose fibers did not affect the thermal stability of the combustion process celluloses. Hybrids were produced in proportions of 5, 10, 15 and 20% hydrated oxide and characterized by XRD, TG, DSC Calorimetry Combustion and SEM / EDS. The results showed a good interaction between the cellulose fibers and hydrated aluminum oxide. Analyses of combustion calorimetry and DSC in synthetic air propose that the Al2O3.nH2O acted as a flame retardant agent. The set ratio for the production of membranes was 95Cel/05Al2O3.nH2O. Pure cellulose membranes and hybrid 95CelA/05Al2O3.nH2O 95CelB/05Al2O3.nH2O and solvent systems were produced in NaOH/urea and NaOH/thiourea and characterized by XRD, TG, DSC and SEM/EDS. The dissolution of cellulose fibers in solvent systems promoted conversion of cellulose I type (native) type II cellulose (regenerated).The membranes prepared from the hybrids 95CelA/05Al2O3.nH2O and 95CelB/05Al2O3.nH2O in NaOH/urea 95CelA/05Al2O3.nH2O in NaOH/thiourea showed higher thermal stability and resistance to combustion the membranes.

Abstract This thesis conducts a comprehensive investigation of the of the physical chemistry related to the TEOS-based porous materials prepared by so-gel approach and develops the fast qualification technology for the hydrolysis and condensation reaction of sol-gel process. The porous materials were prepared by introducing a polymer polyethylene glycol (PEG) into sol-gel after different aging times and with different drying and annealing processes. The effects of pH and addition of PEG on sol-gel derived SiO2 powders for purification of ethanol are studied. The methods and results of this work provide valuable reference for the development of other functional materials such as low k dielectric materials. In the first part, the long-term behavior of the hydrolysis and condensation reaction of the tetraethoxysilane (TEOS) pre-solution at different pH values with and without addition of polyethyleneglycol (PEG) for various aging times was characterized by liquid 1H, 13C, and 29Si NMR spectroscopy.The experimental results demonstrate that alcohol was generated in the TEOS pre-solutions with and without addition of PEG at pH 3 and pH 9 after aging, implying the occurrence of hydrolysis and condensation. The rate of hydrolysis and condensation for the TEOS pre-solution at pH 3 was found to follow the trend of the pre-solution with PEG 2000 > pre-solution with PEG 200 > pre-solution without PEG. However, after adding PEG, the oxygen atom of the deprotonated silanol group (siloxy) of the hydrolyzed TEOS pre-solution at pH3 acted as a reaction center. The result indicates that the oxygen atom is more susceptible to electrophilic attack, resulting in an increased reaction rate. Consequently, the rate of hydrolysis and condensation for of the TEOS pre-solution at pH 9 follows a different order: pre-solution with PEG 200 > pre-solution without PEG > presolution with PEG 2000. The slowest reaction rate of the TEOS pre-solution when adding PEG 2000 is related to the tangled chains of PEG 2000 which sterically reduces the hydrolysis and condensation reaction. This work shows that the correlation between the pH and aging time on hydrolysis and condensation reaction of the TEOS pre-solution can be effectively monitored by liquid 1H NMR spectroscopy, supported by 13C and 29Si liquid NMR spectra. The data obtained should assist optimizing the pH, polymer type/size/concentration and the aging time in the preparation of polymer modified TEOS sols In the second part, SiO2 powders were prepared by the sol-gel in combination with oven-drying method before and after annealing.The experimental result demonstrates the rate of hydrolysis and condensation occurs at a fast rate in TEOS with and without adding PEG at pH3 than in any other pH levels. Because free space can lead to the vaporization of H2O, the ionization of ammonia decreases (i.e., reduction the amount of hydroxide ion), which arises from the rate of hydrolysis and condensation decreases when TEOS at pH9. After attaching PEG, the oxygen atom of the deprotonated silanol group (siloxy) for of the hydrolyzed TEOS pre-solution at pH 3 acted as a reaction center. The result indicates the oxygen atom is more susceptible to electrophilic attack, resulting in an increased reaction rate. Thus, a maximum in the powder yield is reached for TEOS pre-solution with and without adding PEG at pH 3. The SiO2 powder with adding PEG of higher molecular weight presents higher adsorption capacities, pertaining to a greater amount of hydrophilic hydroxyl groups of PEG with higher molecular weight. After annealing, the surface area of SiO2 powder prepared from the TEOS pre-solutions increases as compared with powder without adding PEG and enhances the adsorption of water. A potential absorbent SiO2 powders for producing purified ethanol suitable for fuel and industrial use, can be fabricated by using sol-gel route by careful selection of pH and PEG molecular weight. In addition, during the preparation and characterization of these materials, some interesting phenomena were observed, which are academically valuable. For instance, some samples show very narrow 1H MAS spectra and yet has high 1H-29Si CPMAS sensitivety. This phenomenon suggests us that CPMAS sensitivety may be improved by a new route, i.e., by properly preparing the sample so that CP efficiency is enhanced.

Solubility-based membrane separation, in which the more soluble species preferentially permeates across the membrane, has attracted considerable recent attention due to both economic and environmental concerns. This solubility-selective mode is particularly attractive over a diffusivity-selective mode in applications in which the heavier species are present in dilute concentrations. Examples include the recovery of volatile organic components (VOCs) from effluent streams and the removal of higher hydrocarbons from natural gas. Recently, nanocomposites have shown great promise as possible membrane materials for solubility-selective separations. The chemical derivatization of inorganic mesoporous substrates has been explored to synthesize organic-inorganic nanocomposite membranes. The most exciting feature of this approach is that it enables the rational engineering of membrane nano-architecture with independent control over the free volume and chemistry to create membranes with highly customizable permselectivity properties. In this study, we synthesized the organic-inorganic nanocomposite membranes by decorating the surfaces of commercially available mesoporous alumina substrates, and surfactant-templated highly ordered mesoporous silicate thin films placed on commercially available macroporous inorganic substrates, with a selective organic material that is physically or chemically anchored to the porous surfaces. Hyperbranched melamine-based dendrimers, with nanometer dimension and chemical composition designed to target certain components, were used as filling agents. We evaluated these membranes for several environmentally relevant separations, such as the recovery of the higher hydrocarbon from air and the removal of trace VOCs from air or water, while exploring the impact of organic oligomer size, chemistry, and surface coverage, as well as substrate pore size and structure, on membrane performance. First, we did a model study to verify the feasibility of dendrimer growth inside mesopores by using ordered mesoporous silica. Alumina-ordered mesoporous silica (alumina-OMS) hybrid membranes were prepared as new inorganic porous substrates. Finally, we synthesized dendrimer-ceramic nanocomposite membranes by growing several generations of melamine-based dendrimers with diverse functional groups directly off the commercial alumina membranes. Composite membranes show very high propane/nitrogen selectivity up to 70.

The objective of this thesis is to integrate the optical waveguide and single mode fiber in a passive alignment way on a silicon bench. This technique can reduce the complexity of packaging the individual components and increase yield of the module in order to achieve the goal of the mass production. In this module, buried waveguide structure was used for light guidance. A 1.31µm semiconductor laser was used as the input light source. Light signal launched by semiconductor laser is transferred through the buried waveguide into the single mode fiber. This module structure is consisted of two major parts, namely, the buried waveguide and the silicon bench. Buried optical Waveguide uses SO2 as the bottom cladding. Conventional photolithography procedures and etching technique were used to form a trench on the SiO2 cladding. The waveguide core was fabricated by coating the organic-inorganic hybrid materials into the trench. Finally, an organic-inorganic hybrid materials with a refractive index smaller than that of the core is used as the top cladding. The silicon benches were obtained by etching V-groove and saw-cutting U-groove on the silicon substrates for fixing the fiber. The patterning of buried waveguide and silicon V-groove were fabricated by a single optical mask procedure. Therefore accurate alignment between the waveguide and the single mode fiber can be obtained.

In this study, organic-inorganic hybrid materials were prepared from polyurethane and boehmite. It was achieved by polymerizing monomers in the presence of functional nano-particles of boehmite with cyanate groups. The produced polyurethane organic-inorganic hybrid materials with enhanced mechanical properties were used for coating applications. Plate-like boehmite nano-particles were produced by hydrothermal process from aluminum hydroxide which was first ground in a high energy ball-mill, and then, processed hydrothermally under pressure and high temperature in a reactor. The surface morphology and crystal structure of boehmite were investigated by Scanning Electron Microscopy and X-Ray Diffraction analyses, respectively. The molecular structures of boehmite particles were investigated by Fourier Transform infrared spectroscopy. Furthermore, Brunauer-Emmett-Teller analysis and Photon Correlation Spectroscopy analysis were carried out to determine the surface area and the size of particles. Then, plate-like boehmite nano-particles were functionalized by the reaction of their hydroxyl groups with 1,6-hexamethylene diisocyanate and 4,4&rsquo / -methylene diphenyl diisocyanate. Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, Differential Thermal Analysis-Thermal Gravimetric Analysis, and elemental analysis were performed for both functionalized and non-functionalized particles to confirm the functionalization of the particles. The polyester polyol used in the production of polyurethane was synthesized from 1,4-butanediol and adipic acid (PE-PO-1), and phthalic anhydride (PE-PO-2). Molecular structure of the polyester polyols was confirmed by Fourier Transform Infrared Spectroscopy analysis and molecular weight of the polymers were determined by end group analysis. Then, the produced functionalized nano-particles and polyester polyols were used for producing polyurethane organic-inorganic hybrid materials. Furthermore, polyurethane polymer and polymer-nonfunctionalized boehmite organic-inorganic hybrids were also synthesized for property comparison. Hardness, impact resistance, scratch resistance, abrasion resistance, and gloss property of the samples were determined. It was observed that mechanical properties of organic-inorganic hybrid materials improved significantly. The hardness of the PU produced with PE-PO-1 increased from 82 to 98 Persoz, and the hardness of the PU produced with PE-PO-2 increased from 52 to 78 Persoz when one weight percentage functionalized boehmite was used. The impact resistance of the coatings was found to depend on the type of the polyols used in PU but not in the inorganic component. Therefore PE-PO-2 used PU has higher impact resistance than PE-PO-1 used PU. Scratch resistance of the coatings improved from 2B to 2H when using functionalized boehmite. Abrasion resistance of PUs produced with PE-PO-1 increased from 2 to 10 l/micrometer and abrasion resistance of PUs produced with PE-PO-2 increased from 12 to 20 l/micrometer by addition of functionalized boehmite.

The purpose of the work is to employ molecular simulation to further extend the understanding of Self-Assembled Monolayers (SAMs), especially as it relates to three particular applications: organic-inorganic composite membranes, surface treatments in Micro-Electro-Mechanical Systems (MEMS) and organic-surface-modified Ordered Mesoporous Materials (OMMs). The first focus area for the work is the use of SAMS in organic-inorganic composite membranes for gas separations. These composite membranes, recently proposed in the literature, are based on the chemical derivatization of porous inorganic surfaces with organic oligomers. Our simulations achieve good qualitative agreement with experiment in several respects, including the improvement in the overall selectivity of the membrane and decrease in the permeance when increasing the chain length. The best improvement in the overall solubility selectivity is reached when the chains span throughout the pore. The second application focus is on the use of SAMs as coatings in MEMS devices. The work focuses on the modeling of adhesion issues for SAM coatings at the molecular level. It is shown that as the chain length is increased from 4 to 18 carbon atoms, the adhesion forces between two monolayers at the same separations decreases. The third application focus is on the use of SAMs for tailoring surface and structural properties of OMMs, in particular, porous silicas. A molecular study of structural and surface properties of a silica material with a 5 nm pore size, modified via chemical bonding of organosilanes with a range of sizes (C4, C8 and C18) is presented. Grand canonical MC simulations are employed to obtain nitrogen adsorption isotherms for unmodified and modified MCM-41 material models. Furthermore, the density profiles of alkyl chains and nitrogen molecules are analyzed to clarify the differences in the adsorption mechanisms in unmodified and modified materials. The position of the capillary condensation steps gradually shifted to lower pressure values with the increase in size of the bonded ligands, and this shift was accompanied by a gradual disappearance of the hysteresis loop. As the length of the bonded ligands is increased, a systematic decrease in the pore diameter is observed and the multi-layer adsorption mechanism in modified model materials diminishes.

O processamento de peles para a fabricação de couro utiliza uma mistura complexa de substâncias - dentre elas, os taninos - que torna o tratamento de águas residuais difícil e oneroso. Vários estudos estão sendo conduzidos na tentativa de melhorar o tratamento e até mesmo reutilizar o efluente tratado. Neste trabalho foi avaliado o desenvolvimento de adsorventes funcionais sintetizados pelo método solgel e dotados de impressão molecular, para adsorção de compostos de taninos. Por serem de fácil preparação, os materiais híbridos obtidos viabilizam a sua produção para o uso como sólidos adsorventes. A caracterização dos materiais híbridos orgânico-inorgânico obtidos foi realizada por análise de Porosimetria de nitrogênio (BET), Espalhamento de raios-X a baixo ângulo (SAXS), Espectroscopia de refletância difusa no UV-vis (DRS), Espectroscopia de infravermelho com transformada de Fourier (FT-IR) e Potencial Zeta (PZ). As características estruturais e texturais dos materiais híbridos gerados variaram para cada rota sol-gel e processo de extração de template empregado, resultando em materiais com diferentes capacidades de adsorção. As sílicas sem funcionalização não foram capazes de adsorver os compostos de tanino em solução aquosa, enquanto que as sílicas funcionalizadas com APTES demonstraram sua potencialidade como adsorvente para os compostos testados, atingindo remoções superiores a 80%. Diferenças nas capacidades de adsorção entre as sílicas funcionalizadas com e sem impressão molecular também foram observadas, onde a sílica sem impressão apresentou uma adsorção superior de taninos, indicando que mais estudos são necessários para encontrar um processo de extração eficiente do template. É importante salientar que as sílicas que obtiveram a maior capacidade de adsorção, puderam adsorver os compostos de taninos por vários ciclos consecutivos. / The processing of hides for leather manufacturing uses a complex mix of chemicals that makes the wastewater treatment difficult and costly. Several studies are being conducted in attempt to improve the treatment and even reuse the treated effluent. This study evaluated the development of functional adsorbent synthesized by the molecular imprinting method in a sol-gel matrix, for adsorbing tannin compounds. Easy to prepare, hybrid materials obtained enable their production for use as solid adsorbents. The characterization of organic-inorganic hybrid materials obtained was performed by nitrogen porosimetry analysis (BET), small-angle X-ray scattering (SAXS), diffuse reflectance spectroscopy (DRS), Fourier-Transform Infrared Spectroscopy (FT-IR) and Zeta Potential (PZ). The structural and textural characteristics of hybrid materials ranged for each sol-gel route and template employed extraction process resulting in materials with different adsorption capacities. The silicas without functionalization were unable to adsorb the tannin compounds in aqueous solution, whereas the silica functionalized with APTES demonstrated the potential of the adsorbent for the tested compounds, with removals above of 80%. Differences in adsorption capacities between functionalized silica with and without molecular imprinting were observed where the unprinted silica had a higher adsorption of tannins, indicating that more studies are needed to find a process of efficient template extraction to improve adsorption capacity to the imprinted materials. Further, the silicas with improved adsorption capacity could adsorb the tannin compounds for several consecutive cycles of adsorption.