L'objectif général de cette thèse est de transformer les déchets ultimes et dangereux contenant des métaux lourds, en matières minérales chimiquement stables. L'augmentation de la production des ordures ménagères (OM) est un problème qui concerne et préoccupe le monde entier. Parmi les différentes méthodes de traitement des déchets municipaux, l'incinération est une technologie qui peut fournir une solution efficace et respectueuse pour l'environnement. Le problème de ce traitement est la production de REFIOM. Les REFIOM peuvent contenir de grandes quantités de composés métalliques toxiques et est considéré comme un déchet dangereux ce qui oblige à les mettre en décharges classées. Trois types de matériaux pour l'immobilisation du plomb et du cadmium ont été étudiés : les vitrocéramiques, les céramiques frittées et les géopolymères. Nous sommes parvenus à synthétiser une base de vitrocéramique à partir de cendres incinérées purs et nous avons diminué sa volatilisation lors de sa production. Des résultats prometteurs ont été obtenus pour la vitrocéramique Ca-Mg-Si-O qui a incorporé durablement une quantité élevée de cadmium dans les structures cristallines et le plomb dans la structure amorphe. La phase cristalline est plus résistante à l'attaque acide en raison de son incorporation dans une matrice vitreuse qui génère une double protection. Ses travaux ouvrent la possibilité de créer cette matrice en ajoutant des oxydes commerciaux aux résidus d'incinération. Nous avons étudié la céramique frittée à base du système Ba-Mg-Ti-O. Nous avons obtenu les trois phases minérales présentées dans la céramique SYNROC (hollandite, pérovskite et rutile) où le cadmium substitue le magnésium tandis que le plomb a occupé le site appartenant au baryum. La céramique frittée est satisfaisante en termes d'immobilisation des métaux lourds avec de bonnes propriétés physiques. Pour produire des géopolymères résistants à partir de REFIOM, il est avantageux d'utiliser un rapport L/S = 1,2 et de les sécher à température ambiante. Il a été observé que le frittage influence le taux de réorganisation structurelle avec l'apparition de la phase sodalite ( Na4Si3Al3O12Cl), qui se compose de tunnels où les métaux lourds peuvent être incorporés. Le plomb et le cadmium restent largement en dessous de la limite des normes TCLP. Le traitement thermique à plus de 500°C augmente la densité de l'échantillon. Lorsque les REFIOM sont mélangés avec d'autres types de déchets tels que des MIOM ou du calcin, il est possible d'augmenter la résistance chimique et mécanique. Nous avons conclu que les trois matrices de stockages étudiées offrent de bonne perspective pour l'immobilisation du plomb et du cadmium / The overall objective of this thesis is to transform ultimate and hazardous waste containing heavy metals, into chemically stable mineral materials. The increasing municipal solid waste (MSW) generation is a problem ranging to global concern. Among various MSW treatment methods, incineration is a technology, which may provide an efficient and environmental friendly solution. Problem of this treatment is the production of fly ash. Fly ash may contain large amounts of toxic metal compounds and is considered as hazardous waste with obligation of final disposal into specialized landfills. Three types of materials for immobilization of lead and cadmium have been investigated: glass ceramics, sintered ceramics and geopolymers. We manage to synthetize a glass-ceramic based purely on the incinerated ashes and to decrease the volatilization during its production. Promising results have been obtained for Ca-Mg-Si-O bearing glass-ceramic with high sustainable incorporation of cadmium into crystalline structures and lead into an amorphous structure. Crystalline structure was evaluated being more resistant against acid attack because of its embedding into a glass matrix that generates a double protection. The future research should be done on possibility obtaining this phase by addition of commercial oxides into fly ash. Sintered ceramic investigated was based on Ba-Mg-Ti-O system. We obtained three mineral phases presented in SYNROC (hollandite, perovskite and rutile) where cadmium substituted the site of magnesium while lead occupied the site belonging to barium. The sintered ceramic is satisfactory in terms of toxic elements incorporation and of chemical and mechanical resistance. For production of resistant geopolymer from fly ashes, it is favorable to use ratio L/S =1.2 and drying at room temperature. It was observed that sintering affects the rate of structural reorganization with apparition of sodalite phase (Na4Si3Al3O12Cl), which consists of tunnels where heavy metals can be incorporated. Lead and cadmium stay mainly below the limit of TCLP standards. The heat treatment over 500°C increases density of the sample. When fly ash mixed with other types of waste such as bottom ash or waste glass powder, it is possible to obtain a more resistant. It was found that all three matrices are a good prospect for a stabilization technique with respect to the major pollutants lead (Pb) and cadmium (Cd)

Solid oxide fuel cells (SOFC) in a flat-plate configuration require a hermetic seal between the fuel and air sides of the electrodes, and this seal must withstand a variety of thermally-induced stresses over the lifetime of the cell. In this study, quantitative microstructure-property relationships are developed to predict optimum seal structures for mechanical properties and thermal expansion coefficient criteria. These relationships are used to create an inverse approach to characterizing the processing method from the desired microstructure. The main focus of the work concentrates on providing tools to enable macroscopic property predictions from the constituent properties using homogenization techniques based on the individual phase properties and microstructure morphology. The microstructure is represented by two-point correlation functions. Statistical continuum mechanics models were then employed and developed to predict the mechanical and thermal properties of the material. The models enable the prediction of elastic modulus and coefficient of thermal expansion of the multi-phase material. The inelastic mechanical behavior was also studied, indicating microstructure dependence. These models will aid in predicting the a proper seal microstructure (with desired elastic stiffness, coefficient of thermal expansion, and viscoelastic behaviors) based on a desired level of crystallization glass-ceramic materials.

L'objectif du projet COMPTINN (COMPosites Tièdes INNovants) est d'obtenir des matériaux composites pouvant être utilisés sur de longues durées, à des températures comprises entre 150°C et 400°C, pour des applications structurales de l'aéronautique civile. Les travaux de thèse s'inscrivent dans un objectif de développement de matériaux thermostructuraux mis au point par un procédé industrialisable pour la production de pièces en série, respectueux de l'environnement et économiquement viable. Les procédés d'élaboration choisis sont ceux utilisés pour la mise en œuvre des CMO (Composites à Matrice Organique) thermodurcissables en moule fermé et par voie liquide. Les procédés les plus conventionnels ont été sélectionnés : l'injection par transfert de résine (RTM : Resin Transfer Molding) et l'infusion de résine sous vide (LRI : Liquid Resin Infusion). Les constituants des composites sont d'une part une matrice vitrocéramique, issue d'une résine dérivée d'un système géopolymérique, et d'autre part des renforts 2D et 3D en fibres de carbone. La viscosité d'une résine est la propriété principale qui conditionne sa mise en œuvre par les procédés d'élaboration par la voie liquide. La résine utilisée étant une suspension dont la viscosité est relativement élevée, la faisabilité de l'élaboration de composites par RTM ou LRI est a priori délicate. Une attention particulière a donc été portée à la rhéologie de la résine. Les résultats de cette étude ont permis d'optimiser d'importants paramètres procédés. L'étude s'est ensuite dirigée vers l'élaboration et la caractérisation des composites. L'impact du procédé de mise en œuvre sur la microstructure et sur les propriétés thermomécaniques des composites a été évalué. L'influence d'autres paramètres procédés, tels que le taux de dilution de la résine, la direction d'imprégnation du renfort et le différentiel de pression, a été étudiée. / This research work is part of the collaborative project COMPTINN (Innovative composite materials for intermediate temperature applications). This project aims at enabling the manufacturing of competitive structural composites able to bear up continuous thermal exposure, such as in aircraft parts located close to engines. A new class of glass-ceramic matrices for structural composites was developed to reach this goal. These new matrices come from an inorganic thermosetting polymer derived from a geopolymeric system. Prepreg process is currently used to manufacture composites but these composites would be more competitive if they are produced by an easy and cost effective process technology. Liquid molding (LRI or RTM) seems to be a convenient solution. Two kinds of reinforcements were considered: a layup of several two-dimensional woven fabric plies and a three-dimensional preform.The rheological behaviour of the considered inorganic polymer was firstly investigated. The best conditions were identified to obtain the lowest viscosity of the resin in order to help the production of structural composite parts by liquid molding.Then, the research work investigates how changes in the manufacturing process impact the mechanical properties of the composites. A microstructural characterization helps to link the mechanical behavior to the processing route. The effects of varying several processing parameters have been studied such as the dilution rate of the resin, the impregnation direction or the pressure differential.

Made available in DSpace on 2016-06-02T20:18:11Z (GMT). No. of bitstreams: 1 2456.pdf: 6548607 bytes, checksum: 486173aee7443e35a2910af043a12256 (MD5) Previous issue date: 2009-04-03 / Universidade Federal de Sao Carlos / Bioactive materials have the ability to bond and to integrate with bone tissue by forming a biologically active bonelike apatite layer, which has chemical and structural properties equivalent to the mineral phase of living bone. This process is determined by chemical reactions, whose products also influence the attachment, the proliferation, the differentiation and the mineralizing capacity of bone cells. Cellular responses contribute to the bioactive behavior, which is known for being higher in glass materials. However, as low mechanical properties are also inherent characteristics of glasses, researchers from Federal University of Sao Carlos were stimulated to develop nucleation and growth thermal treatments for the obtainment of the Biosilicate®, a fully-crystallized bioactive glassceramic of the quaternary system P2O5-Na2O-CaO-SiO2. Although a high in vitro osteogenic potential of this novel glass-ceramic has been previously demonstrated, its in vivo effects have not been investigated yet. To contribute to this knowledge, two studies were developed. The first one aimed to investigate the in vivo biological performance of Biosilicate® in bone defects of rat tibias, by means of hystomorphometric and biomechanical analyses 20 days after the surgical procedure. This study revealed that the fully-crystallized Biosilicate® has good bone-forming and bone-bonding properties. Hence, the second study aimed to compare the kinetics of the bone reactions to two different granulometric distributions of this novel glass-ceramic. Although they were both efficient for bone formation, smaller-sized particles of Biosilicate® showed partial reabsortion, which was accompanied by a more pronounced osteogenic activity within the period of time studied. Since positive results were obtained, the search for scaffolds that could serve as supports for the guided bone regeneration had started. A third study preliminarily evaluated cell culture and cocultures in porous structures made of Biosilicate® and of other chemical compositions that were specifically developed for this purpose. The findings suggest that, when in adjusted conditions, the scaffolds can create favorable cellular responses for bone tissue engineering purposes. Taken togheter, these studies point to a promising potential and provide directives for the use of Biosilicate® in bone regenerative processes. / Materiais bioativos possuem a capacidade de se ligar ao tecido ósseo por meio da formação de uma interface apatítica que apresenta similaridade química e estrutural com a fase mineral dos ossos. Esse processo ocorre devido a uma série de reações químicas, cujos produtos também influenciam a adesão, a proliferação, a diferenciação e a capacidade de mineralização da matriz pelas células ósseas. As respostas celulares contribuem para o comportamento bioativo, que é conhecido por ter maiores índices em materiais vítreos. No entanto, como baixas propriedades mecânicas também são características inerentes aos vidros, pesquisadores da Universidade Federal de São Carlos foram estimulados a empregarem nucleação e tratamentos térmicos especiais para o desenvolvimento do Biosilicato®, uma vitrocerâmica biotiva, totalmente cristalina, pertencente ao sistema quaternário P2O5-Na2O-CaO-SiO2. Embora um elevado potencial osteogênico in vitro tenha sido demonstrado para esta vitrocerâmica, seus efeitos in vivo ainda não são conhecidos. Para auxiliar este entendimento, foram desenvolvidos dois estudos. O primeiro teve como objetivo investigar o desempenho biológico in vivo do Biosilicato® particulado em defeitos ósseos em tíbias de ratos, por meio de análises histomorfométricas e biomecânicas 20 dias após o procedimento cirúrgico. Este estudo evidenciou que o Biosilicato® parece favorecer a formação óssea in vivo e o estabelecimento de fortes ligações com o tecido neoformado. Com isso, o objetivo do segundo estudo foi comparar a cinética das reações ósseas frente a duas diferentes distribuições granulométricas desta nova vitrocerâmica. Embora ambas tenham sido eficientes para a formação óssea, as partículas de Biosilicato® com menores diâmetros demonstraram reabsorção parcial no período estudado, que foi acompanhada de uma maior atividade osteogênica. Com os resultados positivos obtidos nestas investigações, iniciou-se uma busca para o desenvolvimento de matrizes porosas que pudessem servir de suporte para a regeneração guiada do tecido ósseo. Um terceiro estudo preliminarmente avaliou monoculturas e coculturas celulares em matrizes porosas de Biosilicato® e de outras novas composições químicas desenvolvidas especificamente para este propósito. Os achados sugerem que, quando em condições adequadas, as matrizes avaliadas podem produzir respostas celulares favoráveis ao seu emprego na engenharia do tecido ósseo. Estes estudos, de maneira conjunta, apontam para um potencial promissor e fornecem diretrizes para o emprego do Biosilicato® no favorecimento de processos regenerativos ósseos.

Fundação de Amparo a Pesquisa no Estado do Rio Grande do Sul / The aim of this study was to investigate the effect of heat treatments on the flexural strength, surface roughness and crystalline structure of a leucite reinforced glass ceramic (IPS Empress CAD, Ivoclar Vivadent, Liechtenstein). A hundred fifty (150) discs were machined by CEREC inLab MC XL (Sirona, Alemanha) and distributed into five groups, n=30: C (control, no heat treatment), A-575 (annealed at 575°C during 15 min, followed by slow cooling and furnace opening at 200°C), A-790 (annealed at 790°C during 15 min, followed by slow cooling and furnace opening at 200°C), G (glazed at 790°C during 1,5 min, followed by fast cooling - immediate furnace opening) and GM (modified glaze, at 790°C during 1,5 min, followed by slow cooling and furnace opening at 200°C). Biaxial flexural strength was determined by the piston-on-three ball test (ISO 6872/2008). Weibull modulus (m) and characteristic strength (σ0) were calculated from the results. The surface roughness (Ra and Rz) was measured before and after the treatments. One specimen from each group was used for X-ray diffraction. A-790 produced the highest values of fracture strength (211.7 MPa). The values of σ0 obtained for the other tested regimens (A-575: 167.9 MPa, GM: 157.7 MPa and G: 153.7 MPa) were lower than those from the control group (187.7 MPa). The value of m was statistically similar between the groups. All heat treatments were able to reduce the mean roughness (Ra) of the specimens. The mean amplitude (Rz), showed a significant reduction only for the groups submitted to the annealing treatments (A-575 e A-790). The X-ray diffraction analysis revealed no changes in the crystalline phase (tetragonal leucite) of the material after the different heat treatments. Variations in the size of the leucite crystallites after thermal cycles were not significant. Thus, high values of fracture strength and decreased surface roughness for a leucite reinforced glass ceramic are achieved by annealing above the glass transition (Tg=625 ± 20ºC) after machining. This regimen (A-790) was capable to produce favorable structural reorganization of the material, without modifying its original crystalline structure. Annealing bellow the glass transition (A- 575) and thermal cycle for glazing (G and GM) significantly reduced the strength of the material. / A proposição deste estudo foi investigar o efeito de tratamentos térmicos na resistência flexural biaxial, na rugosidade superficial e na estrutura cristalina de uma vitrocerâmica reforçada por leucita (IPS Empress CAD, Ivoclar Vivadent, Liechtenstein). Para tanto, 150 discos foram obtidos por usinagem em equipamento CEREC inLab MC XL (Sirona, Alemanha) e distribuídos em cinco grupos, de n=30: C (controle, sem tratamento térmico), A-575 (annealing à 575°C por 15 min, seguido de resfriamento lento com abertura do forno em 200°C), A-790 (annealing à 790°C por 15 min, seguido de resfriamento lento com abertura do forno em 200°C), G (glazeamento à 790°C por 1,5 min, seguido de resfriamento rápido com abertura imediata do forno) e GM (glazeamento modificado à 790°C por 1,5 min, seguido de resfriamento lento com abertura do forno em 200°C). A resistência flexural dos discos foi determinada pelo teste piston-on-three ball, conforme normas da ISO 6872/2008 e os dados submetidos à análise de Weibull para cálculo do módulo de Weibull (m) e da resistência característica (σ0). A rugosidade superficial (Ra e Rz) antes e após os tratamentos foi mensurada. Um espécime de cada grupo foi utilizado para difração de raios-X. O regime A-790 produziu os maiores valores de resistência à fratura (211,7 MPa). Os valores de σ0 promovidos pelos demais ciclos testados (A-575: 167,9 MPa, GM: 157,7 MPa e G: 153,7 MPa) foram inferiores aos do grupo controle (187,7 MPa). O valor de m não diferiu significativamente entre os grupos. Todos os tratamentos térmicos foram capazes de reduzir a rugosidade média (Ra) dos espécimes. Já os valores de amplitude média do perfil (Rz), apresentaram redução significativa apenas para os grupos submetidos à annealing (A-575 e A-790). A análise de difração de raios-x revelou não ter havido mudanças de fase cristalina (leucita tetragonal) do material após os tratamentos térmicos. As alterações no tamanho dos cristalitos de leucita após a realização dos ciclos térmicos não foram expressivas. Sendo assim, maiores valores de resistência à fratura e diminuição da rugosidade superficial para uma vitrocerâmica reforçada por leucita puderam ser conseguidos através de annealing acima da transição vítrea (Tg=625 ± 20ºC) após a usinagem. Tal regime (A-790) foi capaz de produzir reorganização estrutural favorável do material, sem contudo modificar sua estrutura cristalina original. Annealing abaixo da transição vítrea (A-575) e regimes de glazeamento (G e GM) reduziram significativamente a resistência do material.

Made available in DSpace on 2016-12-08T17:19:18Z (GMT). No. of bitstreams: 1 Thais de Jesus Schmitt.pdf: 2052116 bytes, checksum: d868f1a9aaf1f2eadf918c40531c8101 (MD5) Previous issue date: 2012-06-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Recently, the traditional ceramics industry has developed great interest in obtaining pigments which may have firing temperature stable, so that the action of molten glass does not interfere with the final product. In the coating industry, whose selection is strongly influenced by the visual appearance of the decorated surface, the color is an important feature. In order to search for new pigments that replace or optimize the old, new synthetic methods has being studied, as well as new systems and the incorporation of pigments alternative raw materials. Thus, this work studied the possibility of use of industrial byproducts, rich in iron, in the synthesis of pigments encapsulated in glassy matrix. The by product from the surface treatment of sheet metal was evaluated and characterized by chemical composition, crystalline phases and morphology of particles. The residue was added to the glassy matrix, homogenized using conventional milling and calcined at temperatures of 700 ° C to 900 ° C for 15 minutes. The characterization of the pigments obtained were performed using XRD and SEM. The pigments were used in ceramic and enamel porcelain paste and observed by optical microscopy and SEM. The results showed that color development becomes effective when the pigment is incorporated into porcelain paste, because it is a less aggressive. Was concluded that the developed color is influenced by oxide content employed, milling conditions and the processing temperature. The results showed that the use of the pigment developed does not interfere in the microstructural characteristics of pigmented material. / Recentemente, na indústria cerâmica tradicional, tem havido um interesse crescente na obtenção da inclusão de pigmentos na qual a temperatura de queima seja estável de tal forma que ação dos vidros fundidos não interfiram no produto final. No setor de revestimento, cuja seleção é fortemente influenciada pelo aspecto visual da superfície decorada, a cor passa a ser uma importante característica. Com o intuito de buscar novos pigmentos que substituam ou otimizem os já conhecidos, novos métodos de síntese estão sendo pesquisados, bem como novos sistemas pigmentantes e a incorporação de matérias primas alternativas. Desta forma, no presente trabalho, procurou-se estudar a possibilidade de aproveitamento de subprodutos industriais, ricos em ferro, na síntese de pigmentos encapsulados em matriz de vidro. O subproduto que é proveniente, do processo de tratamento superficial de chapas metálicas foi avaliado. O subproduto foi caracterizado quanto a sua composição química, fases cristalinas presentes e morfologia das partículas. O resíduo foi adicionado à matriz vítrea, sendo posteriormente homogeneizados, utilizando moagem convencional e seguidos de calcinação nas temperaturas de 700°C até 900°C por 15 minutos. As caracterizações dos pigmentos obtidos foram realizadas através de difratometria de raios X e microscopia eletrônica de varredura. Os pigmentos foram aplicados em esmalte cerâmico e em massa porcelânica. Posteriormente, foram realizadas análises de microscopia ótica e eletrônica de varredura. Os resultados evidenciaram que o desenvolvimento da cor torna-se efetivo quando o pigmento é incorporado em massa porcelânica, por se tratar de um meio menos agressivo. A coloração desenvolvida é influenciada por variáveis como o teor de óxido empregado, condições de moagem e temperatura de processamento. Os resultados mostraram ainda que a utilização do pigmento desenvolvido não interfere nas características microestruturais do material pigmentado.

Materiais vítreos e vitrocerâmicos bioativos podem ser usados particulados ou como scaffolds em diferentes tratamentos de defeitos ósseos. Tratamentos térmicos que possibilitam o desenvolvimento de scaffolds a partir de composições de vidros bioativos introduzem fases cristalinas em sua estrutura amorfa com potencial impacto na bioatividade e biocompatibilidade do material. O objetivo do presente estudo foi avaliar, qualitativa e quantitativamente, o desenvolvimento do fenótipo osteogênico de culturas de células osteoblásticas sobre substratos vítreos e vitrocerâmicos bioativos. Células MC3T3-E1 foram cultivadas em condições osteogênicas por períodos de até 21 dias sobre superfícies de Bioglass® 45S5, de duas preparações de vitrocerâmica bioativa e altamente cristalina, Biosilicato® e Biosilicato® para scaffold, e de borosilicato (vidro bioinerte). Foram avaliados, nos períodos de 7, 12 e 21 dias, morfologia celular, formação de matriz mineralizada e expressão de genes relacionados à osteogênese. Os resultados mostraram confluência das culturas sobre as superfícies de vidros e vitrocerâmicas, com progressiva formação de multicamadas celulares. A quantificação de vermelho de Alizarina revelou aumento de mineralização para culturas sobre materiais bioativos, com os maiores valores para Biosilicato® para scaffold. Expressão diferencial de genes foi observada nos 3 períodos de culturas sobre os materiais vítreo e vitrocerâmicos bioativos em comparação ao vidro bioinerte e sobre as vitrocerâmicas em comparação ao vidro bioativo. Os resultados permitem concluir que modificações em aspectos químicos de materiais vítreos e vitrocerâmicos, com efeitos sobre sua bioatividade, resultam em alteração do potencial osteogênico e do perfil de expressão gênica de células osteoblásticas in vitro. A maior atividade osteogênica sobre o Biosilicato® para scaffold permite considerar esse material um potencial candidato para aplicações em defeitos ósseos. / Bioactive glasses and glass-ceramics have been used as bone substitutes in either particulate or scaffold forms. Various thermal treatments that allow the development of scaffolds from bioactive glasses may create varied proportions of new crystalline phases in the amorphous phase with a potential impact on the bioactivity and biocompatibility of the material. The aim of the present in vitro study was to qualitatively and quantitatively evaluate the development of the osteogenic phenotype in osteoblastic cell cultures grown on bioactive glass and glass-ceramic surfaces. MC3T3-E1 cells, subclone 14, were cultured under an osteogenic condition for periods of up to 21 days on the following disc surfaces: Bioglass® 45S5 (bioactive glass), Biosilicate® (bioactive glass-ceramic), Biosilicate® as the material for scaffold preparation (Bio-sc, bioactive glass-ceramic), and borosilicate (bioinert glass). At days 7, 12, and 21 post-plating, cell morphology, mineralized matrix formation and the expression profile of genes associated with osteogenesis were evaluated. Epifluorescence of actin cytoskeleton and DAPI DNA stain revealed confluent cell cultures at day 7 for all groups, with progressive cell multilayering formation. The quantitative analysis of Alizarin red-stained cultures at day 21 revealed significantly enhanced mineralization in cultures grown on bioactive materials compared with the ones on borosilicate and the highest absorbance intensities for the Bio-sc group. Differential gene expression profiles were detected at the three time points evaluated in cultures grown on the bioactive materials in comparison with borosilicate, and on the glass-ceramics in comparison with Bioglass® 45S5. From the results presented, it can be concluded that changes in chemical characteristics of glass and glass-ceramic that may have an impact on their bioactivity index can affect the osteogenic potential and the gene expression profile of osteoblastic cells in vitro. The highest osteogenic activity on Bio-sc renders this material a good candidate for bone defect applications.

A preparação de vitrocerâmicas transparentes a base de SiO2-ZrO2 dopado com íons Eu3+ e Er3+ através da metodologia sol-gel foi o objetivo desta dissertação. São apresentados resultados estruturais e óticos deste sistema, em função de temperatura, tempo e composição (variando-se a concentração de zircônia). Os sóis foram preparados em meio ácido e deixados em repouso até evaporação total do solvente, obtendo-se assim monolitos amorfos, os quais foram submetidos a tratamentos a 900, 1000 e 1100ºC durante 2, 4 e 8 horas visando eliminação de resíduos orgânicos, moléculas de água, grupos hidroxilas e densificação do material. O processo de densificação com os tratamentos leva a formação inicial da fase tetragonal de ZrO2. Foi observado o crescimento de nanopartículas de ZrO2 com dimensão dependente do tempo e temperatura de tratamento térmico, além da composição do nanocompósito. As nanopartículas obtidas apresentam tamanho que variam entre 3,1 a 5,5 nm, observadas por microscopia eletrônica de transmissão. A partir da adição de 20% de óxido de zircônio é possível observar uma mistura de fases entre tetragonal e monoclínica, resultado este evidenciado principalmente por espectroscopia Raman. Neste trabalho, o íon Eu3+ foi usado como sonda estrutural e um possível luminóforo na região do vermelho. Íons lantanídeos encontram-se parcialmente distribuídos na rede amorfa à base de sílica, apresentando um tempo de vida do 5D0 de 1,5 ms e em óxido de zircônio, com um tempo de vida de 2,7 ms. À medida que ocorre cristalização, aumenta-se a proporção de íons no óxido de zircônio, sugerindo que os íons lantanídeos preferencialmente encontram-se distribuídos em regiões ricas de ZrO2. Todas as amostras dopadas com íons Er3+ apresentam emissão no infravermelho próximo, na região da banda C utilizada em telecomunicações. A emissão do íon Er3+ em 1532 nm, atribuída à transição 4I13/2 4I15/2, apresentou uma largura a meia altura que variou entre 29 a 56 nm, dependendo da composição e do tratamento térmico realizado. O tempo de vida (1/e) do estado excitado 4I13/2 é de 5,3 ms a 6,5 ms dependendo do tratamento térmico. / The preparation of transparent glass-ceramic based on the SiO2-ZrO2 doped with Eu3+ and Er3+ ions by the sol-gel methodology was the aim of this work. The structural and optical properties of the systems as a function of the time and temperature of annealing and also zirconium concentration are presented. The sol was prepared in acid solution and left in rest until total evaporation solvent, to obtaining the amorphous monoliths. The follow, the growthing of ZrO2 nanoparticles were induced and by the Transmission Electron Microscopy sizes between 3.1 and 5.5 nm were observed to be dependent to the time and temperature of annealing. The densification from the annealing at 900, 1000 and 1100ºC initially takes the formation of the tetragonal phase of ZrO2, and after 20 mol% of zirconium oxide is observed a mixture of phases between the tetragonal and monoclinic phase, result this evidenced by Raman spectroscopy. In this work the Eu3+ ion was used as a structural and possible luminescent material in the red region, displaying a life time value between 1.4 - 2.3 ms, for samples contend 0.3 mol% of Eu3+. The life time values increases as a function of time and temperature of annealing due the increase of the crystallinity of material that decreases the sites number of Eu3+ ions on the system. The Er3+ ions emission assigned to 4I13/2 4I15/2 localized around 1532 nm, showed a full width half maximum between 29 and 56 nm. The lifetime measurements were realized for Er3+ ions. The larger values of lifetime obtained are correspondent to samples with less crystalinity. Samples annealed in less temperatures show 5.3 ms of lifetime while samples annealed in higher temperatures show 6.5 ms of lifetime.

Ce travail de thèse concerne l'évaluation biologique et physico-chimique de deux biomatériaux : verre pure associé au risedronate (46S6-xRIS) et une vitrocéramique poreuse dopée avec l'oxyde de zinc et le nitrure de titane noté 46S6-10Zn-2Ti. Le premier est un matériau hybride composé du verre (46S6) et d'un bisphosphonate le risedronate à différentes teneurs (xRIS) avec x= 8, 12 et 20%. Le deuxième est une vitrocéramique ayant une porosité créée par l'élimination de N après calcination. Les analyses physico-chimiques après les tests in vitro du 46S6-xRIS montrent une modification de la cinétique de la bioactivité de ces composites selon la quantité de risedronate ajoutée au 46S6. Les analyses in vivo ont été aussi menées sur le 46S6-10Zn-2Ti. Cette vitrocéramique a été implantée dans des condyles fémoraux de rattes ostéoporotiques, phénomène créé par l'irradiation des rattes à différentes doses de rayons γ. L'investigation biologique après irradiation montre un déséquilibre entre la peroxydation lipidique et les enzymes antioxydants. L'implantation en site osseux avec le 46S6-10Zn-2Ti a permis la restauration de cette balance. L'étude histologique montre le rétablissement du tissu osseux. Cependant, celui ci décroit avec l'augmentation de la dose des rayons gamma. Pour l'exploration physico-chimique, plusieurs techniques complémentaires ont été utilisées pour évaluer la cinétique d'ossification. La bioconsolidation de notre vitrocéramique a été également évaluée après implantation chez des lapins. Le microscanner (mCT) montre la résorption du 46S6-10Zn-2Ti et l'osséo-intégration des cellules osseuses dans les pores du bio-implant alors que, l'étude histologique montre que le 46S6-10Zn-2Ti est presque totalement dégradé et remplacé par le tissue osseux. Le MEB met en évidence la dégradation du 46S6-10Zn-2Ti et son remplacement par un dépôt apatitique. Les spectres MAS-RMN du ³¹P et u ²⁹Si illustrent la dégradation progressive du 46S6-10Zn-2Ti en faveur du développement de l'apatite biologique. / This work focuses on the biological and physicochemical evaluations of two biomaterials: a bioactive glass associated to risedronate (46S6-xRIS) and a porous glass ceramic doped with zinc oxide and titanium nitride noted 46S6-10Zn-2Ti. The first is a hybrid material composed of bioactive glass (46S6) and a bisphosphonate, the risedronate with different contents (xRIS) with x=8, 12 and 20%. The second is a ceramic glass having a porosity, which has been created following the elimination of N after heating. Physicochemical analysis after the in vitro essays of 46S6-xRIS show the modification of the bioactivity kinetic of these composites proportional to the quantity of risedronate added to the 46S6. The in vivo analyses were also conducted in the 46S6-10Zn-2Ti. This glass ceramic was implanted in the femoral condyles of osteoporotic rats. This phenomenon was created after its irradiation at different doses of γ-rays. The biological investigations after irradiation show an imbalance between the lipid peroxidation and antioxidants enzymes. The implantation of 46S6-10Zn-2Ti in bone tissue restored the oxidative balance. The histological study manifests the restoration of bone tissue. However, this restoration decreased with the rising of γ-rays doses. For the physiochemical exploration, several complementary techniques were used to evaluate the kinetic of ossification. The porous glass ceramic was evaluated also in the bioconsolidation process after implantation in rabbit. The X-ray Micro-Computer Tomography (mCT) shows the resorption of the 46S6-10Zn-2Ti and the osseointegration of bones cells in the biomaterial pores. Moreover, the histological study illustrates that the degradation and the resoption of the 46S6-10Zn-2Ti is almost total. The SEM highlights the degradation of the 46S6-10Zn-2Ti and its replacement by an apatitic deposit. The MAS-NMR spectra of ³¹P and of ²⁹Si illustrate a progressive degradation of 46S6-10Zn-2Ti in favor of the development of a biological apatite.

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