Materiais biocerâmicos são constituídos por elementos encontrados normalmente no organismo e por esse motivo são empregados na área médica, principalmente para a fabricação de implantes dentários e aplicação ortopédica. A partir do tipo de ligação realizada com o organismo, o biocerâmico é classificado em inerte, reabsorvível e bioativo, sendo esse último dividido em vidro bioativo, hidroxiapatita e vitrocerâmico. O material vitrocerâmico exibe propriedades únicas devido a sua microestrutura específica, variedade de composições e propriedades mecânicas adequadas. Entre as possíveis composições, o sistema CaO-MgO-SiO2 exibe bioatividade devido a concentração de cálcio e silício que podem estimular os genes responsáveis pela proliferação de osteoblastos. A presença de magnésio eleva as propriedades mecânicas e a osteointegração devido a interações na superfície da cerâmica com os osteoblastos, possibilitando a formação de hidroxiapatita (HA) e consequentemente ligações diretas com o tecido vivo. Para este trabalho foram realizadas sínteses empregando sol-gel combinado com coprecipitação e sol-gel convencional, para comparação dos produtos obtidos. Os pós cerâmicos sintetizados foram caracterizados por DRX, MEV, BET e as cerâmicas foram testadas para determinação de bioatividade e citotoxicidade in vitro. A formação de HA na superfície das cerâmicas confirmou a bioatividade e observou-se que as amostras não são citotóxicas. Portanto, pôde-se concluir que a partir das metodologias aplicadas foi possível sintetizar pós cerâmicos que exibiram propriedades semelhantes, com potencial aplicação na área médica. / Bioceramic materials are constituted by elements normally found in the body and are therefore used in the medical field, mainly for the manufacture of dental implants and orthopedic application. From the type of binding performed with the organism, the bioceramic is classified as inert, resorbable and bioactive, the latter being divided into bioactive glass, hydroxyapatite and glass-ceramic. The glassceramic material exhibits unique properties due to its specific microstructure, variety of compositions and suitable mechanical properties. Among the possible compositions, the CaO-MgO-SiO2 system exhibits bioactivity due to the concentration of calcium and silicon that can stimulate the genes responsible for the proliferation of osteoblasts. The presence of magnesium increases the mechanical properties and the osseointegration due to interactions on the surface of the ceramic with the osteoblasts, allowing the formation of hydroxyapatite (HA) and consequently direct connections with the living tissue. In this work, syntheses were performed using sol-gel combined with coprecipitation and conventional sol-gel methods for comparison of the obtained products. The synthesized ceramic powders were characterized by XRD, SEM and BET, and the ceramics were submitted for tests of in vitro bioactivity and cytotoxicity. The formation of HA on the surface of the ceramics confirmed the bioactivity and no cytotoxicity was observed in the samples. Therefore, it was possible to conclude that using proposed methodologies it was possible to synthesize ceramic powders that exhibited similar properties, with potential application in the medical area.

Die vorliegende Arbeit beschäftigt sich mit der Synthese und Charakterisierung mesoporöser monolithischer Silica und deren Hybridmaterialien mit Ionischen Flüssigkeiten (ILs, ionic liquids). Zur Synthese der Silicaproben wurde ein Sol-Gel-Verfahren, ausgehend von einer Präkursorverbindung wie Tetramethylorthosilicat angewendet. Der Katalysator mit der geringsten Basizität führte zum Material mit der kleinsten Porengröße und der größten spezifischen Oberfläche. Eine Kombination von porösen Silica mit ILs führt zur Materialklasse der Silica-Ionogele. Diese Hybridmaterialien verbinden die Eigenschaften eines porösen Festkörpers mit denen einer IL (Leitfähigkeit, weites elektrochemisches Fenster, gute thermische Stabilität) und bieten vielfältige Einsatzmöglichkeiten z.B. in der Katalyse- Solar- und Sensortechnik. Um diese Materialien für ihren Verwendungszweck zu optimieren, bedarf es deren umfassenden Charakterisierung. Daher wurde in der vorliegenden Arbeit das thermische Verhalten von Silica-Ionogelen unter Verwendung verschiedener 1-Ethyl-3-methylimidazolium [Emim]-basierter ILs untersucht. Interessanterweise zeigen die untersuchten ILs deutliche Änderungen in ihrem thermischen Verhalten, wenn diese in porösen Materialien eingeschlossen werden (Confinement). Während sich die untersuchten reinen ILs durch klar unterscheidbare Phasenübergänge auszeichnen, konnten für die entsprechenden Hybridmaterialien deutlich schwächer ausgeprägte Übergänge beobachtet werden. Einzelne Phasenübergänge wurden unterdrückt (Glas- und Kristallisationsübergänge), während z.B. Schmelzübergänge in verbreiterten Temperaturbereichen, zum Teil als einzeln getrennte Schmelzpeaks beobachtet wurden. Diese Untersuchungen belegen deutliche Eigenschaftsänderungen der ILs in eingeschränkten Geometrien. Über Festkörper-NMR-Spektroskopie konnte außerdem gezeigt werden, daß die ILs in den mesoporösen Silicamaterialien eine unerwartet hohe Mobilität aufweisen. Die ILs können als quasi-flüssig bezeichnet werden und zeigen die nach bestem Wissen höchste Mobilität, die bisher für vergleichbare Hybridmaterialien beobachtet wurde. Durch Verwendung von funktionalisierten Präkursoren, sowie der Wahl der Reaktionsbedingungen, kann die Oberfläche der Silicamaterialien chemisch funktionalisiert werden und damit die Materialeigenschaften in der gewünschten Weise beeinflußt werden. In der vorliegenden Arbeit wurde der Einfluß der Oberflächenfunktionalität auf das thermische Verhalten hin untersucht. Dazu wurden zwei verschiedene Möglichkeiten der Funktionalisierung angewendet und miteinander verglichen. Bei der in-situ-Funktionalisierung wird die chemische Funktionalität während der Sol-Gel-Synthese über ein entsprechend funktionalisiertes Silan mit in das Silicamaterial einkondensiert. Eine postsynthetische Funktionalisierung erfolgt durch Reaktion der Endgruppen eines Silicamaterials mit geeigneten Reaktionspartnern. Um den Einfluß der physikalischen Eigenschaften der Probe auf die Reaktion zu untersuchen, wurden pulverisierte und monolithische Silicamaterialien miteinander verglichen. Im letzten Teil der Arbeit wurde die Vielfältigkeit, mit der Silicamaterialien postsynthetisch funktionalisiert werden können demonstriert. Durch die Kenntnis von Struktur-Eigenschaftsbeziehungen können die Eigenschaften von Silica-Ionogelen durch die geeignete Kombination von fester und mobiler Phase in der gewünschten Weise verändert werden. Die vorliegende Arbeit soll einen Beitrag zur Untersuchung dieser Beziehungen leisten, um das Potential dieser interessanten Materialien für Anwendungen nutzen zu können. / This work describes the synthesis and characterization of mesoporous monolithic silica and its hybrid materials with ionic liquids (ILs). For synthesis of the silica samples a sol-gel method was used. The catalyst with the weakest basicity leads to the material with the smallest pore size and the largest specific surface area. Combination of porous silica with ILs yields silica-ionogels. These hybrid materials combine the properties of porous solids with the properties of ILs (which is e.g. high conductivity, wide electrochemical stability window, and good thermal stability) and therefore offer a variety of possible applications like catalysis, solar and sensing. To optimize these materials for specific applications there is a need to understand their structure-composition-property relations. For this reason the thermal behavior of silica-ionogels was studied using different 1-ethyl-3-methylimidazolium [Emim]-based ILs. Interestingly the ILs show a clear change in their thermal behavior upon confinement in porous silica. Whereas the pure ILs show distinct phase transitions, the hybrid materials exhibit considerably weaker phase transitions. Phase transitions are suppressed (glass- and crystallization phase transitions); melting transitions show multiple melting peaks. Furthermore solid-state NMR also shows that ILs in mesoporous silica exhibit unusual high mobility. The confined ILs can therefore be classified as quasi-liquid and represents to our best knowledge the highest mobility observed so far in ionogels. By using functionalized silane precursors and different reaction conditions the silica surface was chemically functionalized which further changes the material properties. In a final approach a post-synthetic functionalization was performed by reaction of the selected groups of a silica material with suitable reactants. To study the effect of the physical appearance on the characteristics of the final material, powdered and monolithic samples were studied. In the last part of the work the versatility of post-synthetic silica functionalization was demonstrated. The current work contributes to a better understanding of structure-property correlations, to improve the potential of these interesting materials for possible applications.

The objective of this work was to develop a novel enzyme immobilization scheme for supported lipase sol-gels and to evaluate the potential of the immobilized biocatalyst for the production of biodiesel in a packed bed reactor. Two sources of lipase (EC 3.1.1.3 triacylglycerol hydrolase) were used in this study and the transesterification of methanol and triolein to produce glycerol and methyl oleate was used as a model reaction of biodiesel production. A commercially available form of immobilized lipase, Novozym® 435, was used as a basis for comparison to the literature. Upon establishing a lipase sol-gel formulation technique, the experimental methodology for the transesterification reaction using Novozyme® 435 was developed. Subsequently, a series of inert materials were considered based on their suitability as supports for immobilized lipase sol-gels and the synthesis of methyl oleate. The value of a supported lipase sol-gel is to improve the activity and stability of the enzyme and develop an immobilized biocatalyst that is practical for use under packed bed reactor conditions. Of the six support materials considered (6-12 mesh silica gel, Celite® R633, Celite® R632, Celite® R647, anion exchange resin, and Quartzel® felt), the diatomaceous earth supports (Celite® R633, R632 and R647) exhibited high enzymatic activity, were thermally stable, and possessed high sol-gel adhesion. From the three types of diatomaceous earth considered, Celite® R632 supported lipase sol-gels were identified as the most promising supported lipase sol-gels for methyl oleate production via transesterification. Upon further evaluation, the Celite® R632 lipase sol-gels were found to achieve high methyl oleate percent conversions, glycerol-water absorption was only significant at glycerol levels higher than 75%, and the immobilized lipase had high stability upon storage at 4°C for 1.5 years. To determine the effects of methanol and glycerol inhibition as well as temperature on the reaction kinetics, a ping-pong bi-bi kinetic model was developed and validated over a range of methanol concentrations and temperatures. The optimal methanol concentration for the conditions tested was in the range of 1.3 M to 2.0 M, and increased with increasing temperature. The model developed was consistent with the experimental data and confirmed that glycerol inhibition and the presence of products had significant effects on the reaction kinetics. The methyl oleate production capabilities of the Celite® supported lipase sol-gel were investigated using a packed bed reactor and compared with Novozym® 435 under similar operating conditions. A kinetic and mass transfer based model was developed for the reactor system using a novel efficiency correlation to account for the effect of glycerol on the enzymatic activity. Increasing the flow rate (1.4 mL/min to 20 mL/min) increased the reaction rate, presumably due to the reduction of the glycerol inhibition effect on the immobilized biocatalyst. The Celite® supported lipase sol-gel was found to have superior performance over Novozym® 435 both under batch stirred tank reaction conditions and in a packed bed reactor (83% conversion for Celite® sol-gel vs. 59% conversion for Novozym® 435 at 20 mL/min in the packed bed reactor). Based on the results obtained, Celite® supported lipase sol-gels exhibited good performance for the transesterification of triolein with methanol to produce methyl oleate in both batch and packed bed reactors, and warrant further exploration for the enzymatic production of biodiesel.

The objective of this work was to develop a novel enzyme immobilization scheme for supported lipase sol-gels and to evaluate the potential of the immobilized biocatalyst for the production of biodiesel in a packed bed reactor. Two sources of lipase (EC 3.1.1.3 triacylglycerol hydrolase) were used in this study and the transesterification of methanol and triolein to produce glycerol and methyl oleate was used as a model reaction of biodiesel production. A commercially available form of immobilized lipase, Novozym® 435, was used as a basis for comparison to the literature. Upon establishing a lipase sol-gel formulation technique, the experimental methodology for the transesterification reaction using Novozyme® 435 was developed. Subsequently, a series of inert materials were considered based on their suitability as supports for immobilized lipase sol-gels and the synthesis of methyl oleate. The value of a supported lipase sol-gel is to improve the activity and stability of the enzyme and develop an immobilized biocatalyst that is practical for use under packed bed reactor conditions. Of the six support materials considered (6-12 mesh silica gel, Celite® R633, Celite® R632, Celite® R647, anion exchange resin, and Quartzel® felt), the diatomaceous earth supports (Celite® R633, R632 and R647) exhibited high enzymatic activity, were thermally stable, and possessed high sol-gel adhesion. From the three types of diatomaceous earth considered, Celite® R632 supported lipase sol-gels were identified as the most promising supported lipase sol-gels for methyl oleate production via transesterification. Upon further evaluation, the Celite® R632 lipase sol-gels were found to achieve high methyl oleate percent conversions, glycerol-water absorption was only significant at glycerol levels higher than 75%, and the immobilized lipase had high stability upon storage at 4°C for 1.5 years. To determine the effects of methanol and glycerol inhibition as well as temperature on the reaction kinetics, a ping-pong bi-bi kinetic model was developed and validated over a range of methanol concentrations and temperatures. The optimal methanol concentration for the conditions tested was in the range of 1.3 M to 2.0 M, and increased with increasing temperature. The model developed was consistent with the experimental data and confirmed that glycerol inhibition and the presence of products had significant effects on the reaction kinetics. The methyl oleate production capabilities of the Celite® supported lipase sol-gel were investigated using a packed bed reactor and compared with Novozym® 435 under similar operating conditions. A kinetic and mass transfer based model was developed for the reactor system using a novel efficiency correlation to account for the effect of glycerol on the enzymatic activity. Increasing the flow rate (1.4 mL/min to 20 mL/min) increased the reaction rate, presumably due to the reduction of the glycerol inhibition effect on the immobilized biocatalyst. The Celite® supported lipase sol-gel was found to have superior performance over Novozym® 435 both under batch stirred tank reaction conditions and in a packed bed reactor (83% conversion for Celite® sol-gel vs. 59% conversion for Novozym® 435 at 20 mL/min in the packed bed reactor). Based on the results obtained, Celite® supported lipase sol-gels exhibited good performance for the transesterification of triolein with methanol to produce methyl oleate in both batch and packed bed reactors, and warrant further exploration for the enzymatic production of biodiesel.

Neste trabalho, estudou-se a síntese por sol-gel da ferrita de cobalto (CoFe2O4), variando-se a temperatura de tratamento térmico do xerogel. Nitrato de ferro e nitrato de cobalto foram utilizados como fonte de cátions e ácido cítrico como mineralizador. Os produtos obtidos, tratados a 750, 800 e 850°C, tiveram sua microestrutura e propriedades magnéticas investigadas no intuito de encontrar correlações entre as condições de síntese, as posições ocupadas pelos cátions dentro da estrutura espinélio do composto e as propriedades magnéticas medidas. Estudos de difratometria de raios X exibiram reflexões características da estrutura espinélio, o que sugere que o tratamento térmico não afetou significativamente a estrutura cristalina do material. Uma fração secundária de hematita também foi observada. As ferritas apresentaram área superficial específica (por BET) de aproximadamente 4 m².g-1. Imagens por MEV indicam que o material apresenta-se aglomerado. Quanto às propriedades magnéticas, um máximo de coercividade de 1405.2 Oersted foi encontrado para a amostra tratada a 800°C. Espectros Mößbauer indicaram um baixo grau de inversão nos espinélios formados, o que é incomum para a ferrita de cobalto. Subtraindo do espectro obtido por Mößbauer o excesso de ferro na forma de hematita, há um forte indicativo que a ferrita foi sintetizada de maneira sub-estequiométrica deficiente em ferro. / We herein report a study on the sol-gel synthesis of cobalt ferrite (CoFe2O4) and the effect of treatment temperature on the product outcome. Iron nitrate and cobalt nitrate were used as cation sources and citric acid as mineralizer. Products treated at 750, 800 and 850°C had their microstructure and magnetic properties assessed in order to correlate their synthesis conditions, the positions in which the cations are inserted in the spinel structure and the magnetic behavior displayed by the ferrites. X-ray diffractometry studies exhibit the characteristic reflections of spinel group materials, suggesting that the thermal treatment does not sensibly affect the crystalline structure of the material. A secondary fraction of hematite was also observed. The ferrites exhibit a specific surface area (from BET) of approximately 4 m².g-1. SEM images indicate the material forms agglomerates. As to the magnetic properties, a maximum of 1405.2 Oersted was achieved for the sample treated at 800°C. Mößbauer spectra indicate a fairly low inversion degree in the synthesized materials, which is rather unusual for cobalt ferrite. After deducting the iron fraction present in the form of hematite, there are strong indications that cobalt ferrite was synthesized as a substoichiometric iron-deficient spinel.

Le projet de thèse a pour but de synthétiser de nouveaux matériaux siliciques à microstructure contrôlée en utilisant des procédés de polycondensation à basse température, et de développer de nouvelles approches de microfabrication 3D à haute résolution par excitation bi-photonique d’une formulation sol-gel. La synthèse de matériaux microstructurés est ici centrée sur le procédé sol-gel, impliquant des réactions d’hydrolyse-polycondensation. Les mtériaux les plus étudiés par ces approches en particulier dans le cadre d’un contrôle de la porosité sont préparés à partir de tetraéthoxide de silicium (TEOS)/ Le matériau est structuré généralement par des agent moléculaires structurants (« templates ») tels que les composés tensioactifs. Ces derniers sont en général éliminés, après condensation des silanols, par traitement thermique ou lavage afin de libérer la porosité et générer la structuration. Cette étape d’élimination des agents structurants est souvent problématique, en particulier au niveau industriel, car elle utilise soit des hautes températures, soit des quantités importantes de solvants. Il y a un enjeu important à développer des approches de microstructuration s’affranchissant de ces agents moléculaires structurants, cela représentant le principal objectif de cette thèse.Deux stratégies sont abordées aux cours de ce travail de recherche. La première implique l’utilisation de précurseurs organosilylés donc la structure moléculaire permet une microstructuration du matériau synthétisé. Cette partie explore l’utilisation de précurseurs de la famille des silsesquioxanes et leur transformation vers les matériaux. La deuxième approche propose d’évaluer pour la première fois l’utilisation de l’excitation biphotonique pour contrôler l’étape de condensation sol-gel par modification de pH au point focal d’un laser et ainsi apporter une résolution micrométrique à la structuration du matériau / The main goal of this research was the synthesis of new siliceous materials with controlled microstructures, using low-temperature polycondensation process, and develop the new approach towards 3D microfabrication under two-photon excitation of a sol-gel formulation. Synthesis of microstructured materials is based on the sol-gel process, i.e. hydrolytic polycondensation. Most known siliceous materials with controlled microstructure are synthesized from tetraethoxysilane (TEOS). The materials are generally structured by structuring molecular agents ("templates") such as surfactant compounds, which are then removed by heat treatment or washing with appropriate solvents. This stage of removal of structuring agents is often problematic, particularly at the industrial level, because it uses either high temperatures or large amounts of solvents. Therefore, new methods to obtain materials with controlled porosity without the need to use templates are still being developed. Two strategies are discussed during this research work. First one involved the use of organosilicon precursors with a define structure that at molecular level modify the structure of the final materials. The use of well-defined precursors (silsesquioxanes), in appropriate proportions, allows the control of the porosity of the obtained silica materials. The second approach investigated in this work is the local photo-induced structuration of silicon based pre-hydrolyzed precursors under two-photon excitation allowing high 3D resolution

Ce travail de thèse porte la synthèse et la caractérisation d’un luminophore rouge inorganique sans terres rares de formulation Na2SiF6 : Mn4+. Un protocole de synthèse originale des matrices fluorures A2MF6 : Mn4+ (A = Na, K ; M = Si, Ti) par un procédé sol-gel a ainsi été mis au point. Cette synthèse brevetée et industrialisable permet d’obtenir des composés avec un rendement quantique absolu supérieur à 50% sous excitation LED bleue. Plusieurs analyses structurales, microstructurales, et à sondes locales ont permis de caractériser précisément les composés synthétisés. Le deuxième volet important de ce travail a été la construction d’une enceinte de vieillissement permettant de suivre l’évolution des propriétés de luminescence des luminophores en fonction du temps sous l’effet combiné d’un stress hydrique, thermique et photonique. Les mesures, entièrement automatisées, nous ont permis d’établir des lois cinétiques de dégradation du flux lumineux à partir desquels des facteurs de maintenance (L90, L70, L50, etc…) ont pu être déterminés. De plus, un mécanisme de dégradation de cette famille de luminophores a été proposé. Finalement, un prototype d’éclairage à base de LEDs bleues intégrant une couche de conversion constituée des luminophores Na2SiF6 : Mn4+ et YAG : Ce3+, Gd3+ a conduit à des caractéristiques très prometteuses. / This PhD work deals with the synthesis and characterization of a rare earth-free inorganic red phosphor of Na2SiF6: Mn4+ formulation. An original synthesis protocol of fluoride matrices A2MF6: Mn4+ (A = Na, K, M = Si, Ti) by a sol-gel process has been developed. This patented and industrializable synthesis allows to obtain compounds with an absolute quantum yield greater than 50% under blue LED excitation. Several structural, microstructural and local probe analyzes have made it possible to precisely characterize the synthesized compounds. The second important part of this work was the design of an aging chamber to follow the evolution of phosphor luminescence properties as a function of time under the combined effect of hydrous, thermal and photonic stress. Measurements, fully automated, allowed us to establish kinetic laws of luminous flux degradation from which maintenance factors (L90, L70, L50, etc. ...) could be determined. Moreover, a degradation mechanism of this family of phosphors has been proposed. Finally, a blue LED lighting prototype incorporating a conversion layer consisting of Na2SiF6: Mn4+ and YAG: Ce3+, Gd3+ phosphors led to very promising characteristics.

Com o objetivo de desenvolver novos revestimentos mais protetores e quantificar a resistência à corrosão resultante, estudou-se a adição de caulinita em novos revestimentos híbridos a base de silanos sobre a liga de alumínio AA7075. Os revestimentos com silanos aqui estudados diferem dos relatados anteriormente na literatura, os quais usualmente contém cargas minerais apenas para a liberação de inibidores de corrosão, enquanto que os revestimentos desenvolvidos no presente estudo contém caulinita lamelar com a finalidade de barreira de difusão para espécies corrosivas. Para tanto, estudou-se primeiramente a esfoliação da caulinita e produção de filmes finos (2-3μm) por diferentes rotas de preparação pelo processo sol-gel, obtendo-se os melhores resultados com o processo envolvendo acidificação final. Os revestimentos e as partículas de caulinita processada foram caracterizados por microscopia ótica, microscopia de varredura eletrônica e difração de raios-X. A resistência à corrosão foi estudada por voltametria cíclica e cronoamperometria, em potencial aplicado entre o potencial de pite e o de repassivação. A maior resitência à corrosão por pites foi obtida para os revestimentos contendo 3% em massa de caulinita, seguido dos com 33% em massa. Estudou-se também preliminarmente a permeação de H2O no revestimento por medidas rápidas de capacitância, após exposição cíclica em soluções contendo cloreto seguidas de secagem, sendo esta metodologia empregada até o momento apenas para tintas bem mais espessas (≈ 300μm). Observou-se que o método é aplicável para medidas no primeiro ciclo de absorção de H2O, concluindo-se que após a primeira exposição, o cloreto continua difundindo, diminuindo o tempo de resistência ao pite. / Aiming to develop more protective new coatings and to quantify the resulting corrosion resistance, new hybrid coatings based on silanes with the addition of kaolinite were produced and applied on the AA7075 aluminum alloy. The studied silane coatings differ from those reported previously in the literature that usually contain mineral fillers to release corrosion inhibitors, since we here developed silane coatings contain lamellar kaolinite as a barrier against the diffusion of corrosive species. For this, we first studied the exfoliation of kaolinite, and production of thin coating (2-3μm) by different preparation routes of the sol-gel process, obtaining the best results with the process of final acidification. Coatings and processed kaolinite particles were characterized by optical microscopy, scanning electron microscopy and X-ray diffraction. The corrosion resistance was evaluated by cyclic voltammetry and chronoamperometry at potentials between that of the repassivation and of the pitting of the substrate alloy. The greatest pitting resistance was obtained for coatings with 3% kaolinite addition, followed by the ones with 33%. The permeation of H2O into the coating was also preliminarily studied by fast capacitance measurements after cyclic exposure to solutions containing chloride followed by drying, a methodology that up to date was only used for much thicker paints (≈ 300μm). It was concluded that in chloride media this method is only applicable for measurements in the first cycle, as after the first exposure, chloride ions continuously permeate into the coating during the drying phase, greatly reducing the time to pit nucleation.

Neste trabalho, estudou-se a síntese por sol-gel da ferrita de cobalto (CoFe2O4), variando-se a temperatura de tratamento térmico do xerogel. Nitrato de ferro e nitrato de cobalto foram utilizados como fonte de cátions e ácido cítrico como mineralizador. Os produtos obtidos, tratados a 750, 800 e 850°C, tiveram sua microestrutura e propriedades magnéticas investigadas no intuito de encontrar correlações entre as condições de síntese, as posições ocupadas pelos cátions dentro da estrutura espinélio do composto e as propriedades magnéticas medidas. Estudos de difratometria de raios X exibiram reflexões características da estrutura espinélio, o que sugere que o tratamento térmico não afetou significativamente a estrutura cristalina do material. Uma fração secundária de hematita também foi observada. As ferritas apresentaram área superficial específica (por BET) de aproximadamente 4 m².g-1. Imagens por MEV indicam que o material apresenta-se aglomerado. Quanto às propriedades magnéticas, um máximo de coercividade de 1405.2 Oersted foi encontrado para a amostra tratada a 800°C. Espectros Mößbauer indicaram um baixo grau de inversão nos espinélios formados, o que é incomum para a ferrita de cobalto. Subtraindo do espectro obtido por Mößbauer o excesso de ferro na forma de hematita, há um forte indicativo que a ferrita foi sintetizada de maneira sub-estequiométrica deficiente em ferro. / We herein report a study on the sol-gel synthesis of cobalt ferrite (CoFe2O4) and the effect of treatment temperature on the product outcome. Iron nitrate and cobalt nitrate were used as cation sources and citric acid as mineralizer. Products treated at 750, 800 and 850°C had their microstructure and magnetic properties assessed in order to correlate their synthesis conditions, the positions in which the cations are inserted in the spinel structure and the magnetic behavior displayed by the ferrites. X-ray diffractometry studies exhibit the characteristic reflections of spinel group materials, suggesting that the thermal treatment does not sensibly affect the crystalline structure of the material. A secondary fraction of hematite was also observed. The ferrites exhibit a specific surface area (from BET) of approximately 4 m².g-1. SEM images indicate the material forms agglomerates. As to the magnetic properties, a maximum of 1405.2 Oersted was achieved for the sample treated at 800°C. Mößbauer spectra indicate a fairly low inversion degree in the synthesized materials, which is rather unusual for cobalt ferrite. After deducting the iron fraction present in the form of hematite, there are strong indications that cobalt ferrite was synthesized as a substoichiometric iron-deficient spinel.

O material SiO2/Nb2O5 (SiNb) foi preparado pelo método sol-gel e empregado como adsorvente para remoção do corante Violeta Cristal. O material foi caracterizado utilizando isotermas de adsorção/dessorção de nitrogênio, espectroscopia FTIR, pHpzc, e SEM-EDS. A análise isotérmica de N2 revelou a presença de micro e mesoporos na amostra de SiNb com área superficial específica de 747 m2g−1. No processo de adsorção do corante foram avaliados parâmetros como pH, temperatura, tempo de contato, e concentração do corante no processo. O valor de pH inicial da solução do corante que levou a uma máxima adsorção foi 7. A cinética de adsorção e equilíbrio para a adsorção do corante foram representadas por ordem-geral e Liu, respectivamente. A capacidade máxima de adsorção do corante com o adsorvente SiNb, na temperatura de 303K, foi de 116mg g-1. Dois efluentes de corantes foram simulados e usados para verificar a aplicabilidade do material SiNb para tratamento de efluentes, sendo que o adsorvente se mostrou muito eficiente na descoloração desses efluentes. / In this dissertation, SiO2/Nb2O5 (SiNb) material was prepared using sol–gel method and employed as adsorbent for removal of crystal violet dye (CV). The material was characterized using nitrogen adsorption–desorption isotherms, FTIR spectroscopy, pHpzc, and SEM-EDS. The analysis of N2 isotherms revealed the presence of micro- and mesopores in the SiNb sample with specific surface area 747 m2 g−1. For the dye adsorption process, variations of parameters such as of pH, temperature, contact time, and concentration of dye of the process were evaluated. The optimum initial pH of the CV dye solution was 7.0. The adsorption kinetic and equilibrium data for CV adsorption were suitably represented by the general-order and Liu models, respectively. The maximum adsorption capacity of the CV dye by SiNb was achieved at 303 K, which attained 116 mg g−1at this temperaure. Dye effluents were simulated and used to check the applicability of the SiNb material for treatment of effluents – the material showed very good efficiency for decolorization of dye effluents.