The objective of this study was to investigate the stress corrosion behaviour of BioglassTM 4555 in order to predict the lifetime of the glass in use as a load-bearing prosthetic device. As part of this study, the development of BioglassTM and the medical tests conducted to assess the glass's biocompatibility are reviewed. The results of implant tests in laboratory animals which indicate that stress corrosion cracking of the glass may be a prohibitive factor to its use are presented. The theories of glass corrosion and stress corrosion cracking of silica based glasses are discussed and an extensive review of the literature presented. The corrosion behaviour of the glass was analysed and found to be similar to that obtained by previous workers. The depths of the corrosion layers were found to be smaller. This was attributed to alumina contamination of the glass. The fatigue parameters of the glass were measured by slow crack-growth studies and strength measurements in a corrosive solution simulating the physiological environment. The values of A and n in the equation relating crack velocity (v) and stress intensity (K1) v=AK1n, were found to be 1x10-173 and 30 respectively. Lifetime predictions for the glass were performed. It was determined that the glass was suitable for use as a prosthetic device if the maximum tensile stress encountered in vivo did not exceed 15MPa. / Thesis / Master of Engineering (ME)

O objetivo do presente estudo foi avaliar histologicamente e histomorfometricamente a resposta óssea a três composições de Biosilicato com diferentes fases de cristalização (Vítreo, 1F e 2F) comparando-as com o Bioglass®45S5, que foi empregado como controle. Cilindros de Biosilicato 2F, Biosilicato 1F, Biosilicato®vítreo e Bioglass®45S5 foram implantados em fêmur de coelhos e as amostras obtidas após 8 e 12 semanas da colocação, sendo as mesmas preparadas para análise histológica e histomorfométrica utilizando microscopia de luz. Nesses períodos foi avaliada a resposta óssea e o contato direto osso/implante na porção cortical e no canal medular do fêmur de todos os materiais. A maior quantidade de contato osso implante na região cortical, após 8 semanas, foi observada no material Biosilicato 2F, seguido pelo Biosilicato 1F, Bioglass®45S5 e Biosilicato®vítreo. A análise estatística não evidenciou diferença estatisticamente significante entre os materiais Biosilicato 1F e 2F (p=0,06). Entretanto, nesse período, esses materiais mostraram diferenças estatisticamente significantes em relação aos materiais Biosilicato®vítreo e Bioglass®45S5 (p=0,02). Após 12 semanas o Biosilicato 2F também apresentou os melhores resultados, seguido pelo Bioglass®45S5, Biosilicato®vítreo e Biosilicato 1F, sem contudo serem observadas diferenças estatisticamente significantes (p>0,05). Avaliando a porção medular no período de 8 semanas, observa-se maior formação óssea ao redor do implante de Biosilicato®vítreo, seguido pelos implantes de Bioglass®45S5, Biosilicato 2F e Biosilicato 1F. Decorridas 12 semanas, observa-se melhor resposta óssea nos implantes de Biosilicato 1F, seguido pelos implantes de Biosilicato 2F, Biosilicato®vítreo e Bioglass®45S5, sem contudo serem observadas diferenças estatisticamente significantes entre os materiais ou tempos analisados. Os resultados do presente trabalho demonstram o excelente comportamente biológico das cerâmicas de Biosilicato®. / The aim of this study was to investigate the histological and histomorphometric bone responses to three Biosilicate® with different crystal phases (Vítreo, 1F and 2F) compared to Bioglass®45S5 used as control. Rods of Biosilicate 2F, Biosilicate 1F, Biosilicate®vítreo, and Bioglass45S5 were implanted in rabbits femurs. Implants were harvested at 8 and 12 weeks and prepared for histological and histomorphometric analyses at light microscope level. At these periods bone response and bone-to-implant contact were evaluated at cortical and medullar portion. Considering bone-to-Implant contact at cortical portion Biosilicate 2F presented the highest bone formation, followed by Biosilicate 1F, Bioglass®45S5, and Biosilicate®vítreo (eight weeks). Biosiliacate 1F and 2F presented similar results with no statistic difference (p=0,06). However, in this period Biosilicate 2F demonstrated higher values than Bioglass®45S5 and Biosilicato®vítreo (p=0,02). After twelve weeks direct bone contact was similar between all tested materials (Biosilicate 2F > Bioglass®45S5 > Biosilicate®vítreo > Biosilicate 1F) with no statistically significant difference (p>0,05). When medullar portion was evaluated Biosilicate®vítreo presented a higher amount of new formed bone followed by Bioglass®45S5, Biosilicate 2F, and Biosilicate 1F (eight weeks). After twelve weeks Biosilicate 1F demonstrated the best result, followed by Biosilicate 2F, Biosilicate®vítreo, and Bioglass®45S5. No statistically significant difference between the materials or the periods was observed (p>0,05).All the Biosilicate® glassceramics appeared to have an excellent behavior at biological environment.

O objetivo do presente estudo foi avaliar histologicamente e histomorfometricamente a resposta óssea a três composições de Biosilicato com diferentes fases de cristalização (Vítreo, 1F e 2F) comparando-as com o Bioglass®45S5, que foi empregado como controle. Cilindros de Biosilicato 2F, Biosilicato 1F, Biosilicato®vítreo e Bioglass®45S5 foram implantados em fêmur de coelhos e as amostras obtidas após 8 e 12 semanas da colocação, sendo as mesmas preparadas para análise histológica e histomorfométrica utilizando microscopia de luz. Nesses períodos foi avaliada a resposta óssea e o contato direto osso/implante na porção cortical e no canal medular do fêmur de todos os materiais. A maior quantidade de contato osso implante na região cortical, após 8 semanas, foi observada no material Biosilicato 2F, seguido pelo Biosilicato 1F, Bioglass®45S5 e Biosilicato®vítreo. A análise estatística não evidenciou diferença estatisticamente significante entre os materiais Biosilicato 1F e 2F (p=0,06). Entretanto, nesse período, esses materiais mostraram diferenças estatisticamente significantes em relação aos materiais Biosilicato®vítreo e Bioglass®45S5 (p=0,02). Após 12 semanas o Biosilicato 2F também apresentou os melhores resultados, seguido pelo Bioglass®45S5, Biosilicato®vítreo e Biosilicato 1F, sem contudo serem observadas diferenças estatisticamente significantes (p>0,05). Avaliando a porção medular no período de 8 semanas, observa-se maior formação óssea ao redor do implante de Biosilicato®vítreo, seguido pelos implantes de Bioglass®45S5, Biosilicato 2F e Biosilicato 1F. Decorridas 12 semanas, observa-se melhor resposta óssea nos implantes de Biosilicato 1F, seguido pelos implantes de Biosilicato 2F, Biosilicato®vítreo e Bioglass®45S5, sem contudo serem observadas diferenças estatisticamente significantes entre os materiais ou tempos analisados. Os resultados do presente trabalho demonstram o excelente comportamente biológico das cerâmicas de Biosilicato®. / The aim of this study was to investigate the histological and histomorphometric bone responses to three Biosilicate® with different crystal phases (Vítreo, 1F and 2F) compared to Bioglass®45S5 used as control. Rods of Biosilicate 2F, Biosilicate 1F, Biosilicate®vítreo, and Bioglass45S5 were implanted in rabbits femurs. Implants were harvested at 8 and 12 weeks and prepared for histological and histomorphometric analyses at light microscope level. At these periods bone response and bone-to-implant contact were evaluated at cortical and medullar portion. Considering bone-to-Implant contact at cortical portion Biosilicate 2F presented the highest bone formation, followed by Biosilicate 1F, Bioglass®45S5, and Biosilicate®vítreo (eight weeks). Biosiliacate 1F and 2F presented similar results with no statistic difference (p=0,06). However, in this period Biosilicate 2F demonstrated higher values than Bioglass®45S5 and Biosilicato®vítreo (p=0,02). After twelve weeks direct bone contact was similar between all tested materials (Biosilicate 2F > Bioglass®45S5 > Biosilicate®vítreo > Biosilicate 1F) with no statistically significant difference (p>0,05). When medullar portion was evaluated Biosilicate®vítreo presented a higher amount of new formed bone followed by Bioglass®45S5, Biosilicate 2F, and Biosilicate 1F (eight weeks). After twelve weeks Biosilicate 1F demonstrated the best result, followed by Biosilicate 2F, Biosilicate®vítreo, and Bioglass®45S5. No statistically significant difference between the materials or the periods was observed (p>0,05).All the Biosilicate® glassceramics appeared to have an excellent behavior at biological environment.

Com os avanços tecnológicos ocorridos nas últimas décadas, tornou-se possível às diversas áreas do conhecimento melhorar a qualidade e expectativa de vida da população. Dentre as diversas áreas da Engenharia de Materiais, a de Biomateriais é a que está se destacando, vindo ao encontro das necessidades crescentes de melhorar a qualidade de vida da população. O uso de materiais que possam substituir partes ósseas vem sendo motivo de estudos há muitos anos. Para isto, os materiais têm que possuir propriedades químicas e mecânicas semelhantes às do organismo. Materiais como: cerâmicas, polímeros, metais ou até mesmo combinações entre eles vem sendo utilizados como biomateriais. Uma linha de materiais cerâmicos que se destaca é a de produtos à base de alumina, em função de suas características de biocompatibilidade e excelentes propriedades mecânicas. Na medicina, as próteses assumiram um papel importante, tanto na questão estética quanto na funcional. Os desafios nesta área, no intuito de descobrir novos materiais que possam substituir os existentes com desempenho satisfatório e custos mais acessíveis, tornam-se objetos de pesquisa em todo mundo. Na literatura existem poucos trabalhos que correlacionam bioatividade e propriedades mecânicas de cerâmicas à base de alumina, com relação à área médica. Para contribuir nesta questão, propôs-se um estudo tendo como base a alumina. O trabalho tem como objetivo desenvolver cerâmicas a base de alumina porosa, utilizando para isto o hidróxido de alumínio como nucleador de microporos. Resultados obtidos para o material mostram que a porosidade cresce com o aumento da concentração de hidróxido de alumínio na amostra. O preenchimento dos poros da matriz com biovidro tem por objetivo facilitar o processo de osteocondução. A vantagem do processo é a diminuição do tempo de recuperação para o paciente. Os resultados obtidos mostram que a adição de hidróxido de alumínio leva a uma porosidade maior nas amostras. Ensaios realizados verificaram que a concentração máxima de hidróxido é de 20 % em volume, e que concentrações maiores levam os corpos de prova a instabilidade. Os ensaios com o biovidro em forma de gel mostraram-se promissores, devido a facilidade para impregnação nos corpos de prova. Testes de bioatividade in vitro revelaram que o biovidro poderá ser utilizado como material bioativo, revelando um material útil no uso em próteses médicas. / With technological advances in the past decades, it became possible for various areas of knowledge to improve the quality and life expectancy of the population. Among the various areas of Materials Engineering, the Biomaterials is one that is emerging, coming to meet the growing needs to improve the quality of life. The use of materials that can replace bony parts has been subject of study for many years. For this, the materials have to possess chemical and mechanical properties similar to the body. Materials such as ceramics, polymers, metal or even combinations of them have been used as biomaterials. A line of ceramic materials that stands out is that of alumina-based products, due to their biocompatibility and excellent mechanical properties. In medicine, prosthetics played an important role in both aesthetics and functionality. The challenges in this area in order to discover new materials that can replace the existing performance and costs more affordable, they become objects of research worldwide. In the literature there are few studies that correlate bioactivity and mechanical properties of alumina ceramic base with respect to the medical field. To contribute to this issue, a proposed a study based on alumina. The work aims to develop ceramic-based porous alumina, using study has been aluminum hydroxide as nucleator of micropores. Results obtained for the material show that the porosity increases with increasing concentration of aluminum hydroxide in the sample. The filling of pores of the matrix with bioglass aims to facilitate the process of osteoconduction. The advantage of the process is to reduce the recovery time for the patient. The results show that the addition of aluminum hydroxide leads to a higher porosity in the samples. Tests carried out found that the maximum concentration of hydroxide is 20%, and higher concentrations lead to specimens instability. The tests with the bioglass gel have show promising due to ease of impregnation in the specimens. Bioactivity in vitro tests revealed that the bioglass can be used as a bioactive material, revealing a useful material for medical prostheses.

Com os avanços tecnológicos ocorridos nas últimas décadas, tornou-se possível às diversas áreas do conhecimento melhorar a qualidade e expectativa de vida da população. Dentre as diversas áreas da Engenharia de Materiais, a de Biomateriais é a que está se destacando, vindo ao encontro das necessidades crescentes de melhorar a qualidade de vida da população. O uso de materiais que possam substituir partes ósseas vem sendo motivo de estudos há muitos anos. Para isto, os materiais têm que possuir propriedades químicas e mecânicas semelhantes às do organismo. Materiais como: cerâmicas, polímeros, metais ou até mesmo combinações entre eles vem sendo utilizados como biomateriais. Uma linha de materiais cerâmicos que se destaca é a de produtos à base de alumina, em função de suas características de biocompatibilidade e excelentes propriedades mecânicas. Na medicina, as próteses assumiram um papel importante, tanto na questão estética quanto na funcional. Os desafios nesta área, no intuito de descobrir novos materiais que possam substituir os existentes com desempenho satisfatório e custos mais acessíveis, tornam-se objetos de pesquisa em todo mundo. Na literatura existem poucos trabalhos que correlacionam bioatividade e propriedades mecânicas de cerâmicas à base de alumina, com relação à área médica. Para contribuir nesta questão, propôs-se um estudo tendo como base a alumina. O trabalho tem como objetivo desenvolver cerâmicas a base de alumina porosa, utilizando para isto o hidróxido de alumínio como nucleador de microporos. Resultados obtidos para o material mostram que a porosidade cresce com o aumento da concentração de hidróxido de alumínio na amostra. O preenchimento dos poros da matriz com biovidro tem por objetivo facilitar o processo de osteocondução. A vantagem do processo é a diminuição do tempo de recuperação para o paciente. Os resultados obtidos mostram que a adição de hidróxido de alumínio leva a uma porosidade maior nas amostras. Ensaios realizados verificaram que a concentração máxima de hidróxido é de 20 % em volume, e que concentrações maiores levam os corpos de prova a instabilidade. Os ensaios com o biovidro em forma de gel mostraram-se promissores, devido a facilidade para impregnação nos corpos de prova. Testes de bioatividade in vitro revelaram que o biovidro poderá ser utilizado como material bioativo, revelando um material útil no uso em próteses médicas. / With technological advances in the past decades, it became possible for various areas of knowledge to improve the quality and life expectancy of the population. Among the various areas of Materials Engineering, the Biomaterials is one that is emerging, coming to meet the growing needs to improve the quality of life. The use of materials that can replace bony parts has been subject of study for many years. For this, the materials have to possess chemical and mechanical properties similar to the body. Materials such as ceramics, polymers, metal or even combinations of them have been used as biomaterials. A line of ceramic materials that stands out is that of alumina-based products, due to their biocompatibility and excellent mechanical properties. In medicine, prosthetics played an important role in both aesthetics and functionality. The challenges in this area in order to discover new materials that can replace the existing performance and costs more affordable, they become objects of research worldwide. In the literature there are few studies that correlate bioactivity and mechanical properties of alumina ceramic base with respect to the medical field. To contribute to this issue, a proposed a study based on alumina. The work aims to develop ceramic-based porous alumina, using study has been aluminum hydroxide as nucleator of micropores. Results obtained for the material show that the porosity increases with increasing concentration of aluminum hydroxide in the sample. The filling of pores of the matrix with bioglass aims to facilitate the process of osteoconduction. The advantage of the process is to reduce the recovery time for the patient. The results show that the addition of aluminum hydroxide leads to a higher porosity in the samples. Tests carried out found that the maximum concentration of hydroxide is 20%, and higher concentrations lead to specimens instability. The tests with the bioglass gel have show promising due to ease of impregnation in the specimens. Bioactivity in vitro tests revealed that the bioglass can be used as a bioactive material, revealing a useful material for medical prostheses.

This research provides a comprehensive investigation in understanding the effect of the addition of graphene nano-platelets (GNP) on the mechanical, tribological and biological properties of glass/ceramic composites. We investigated two kinds of materials namely amorphous matrices like glasses (silica, bioglass) and polycrystalline matrices like ceramics (alumina). The idea was to understand the effect of GNP on these matrices as GNP was expected to behave differently in these composites. Bioglass (BG) was also chosen as a matrix material to prepare BG-GNP composites. GNP can improve the electrical conductivity of BG which can be used further for bone tissue engineering applications. The effect of GNP on both electrical conductivity and bio-activity of BG-GNP composites was investigated in detail. There were three main problems for fabricating these novel nano-composites: 1) Production of good quality graphene; 2) Homogeneous dispersion of graphene in a glass/ceramic matrix and; 3) Retention of the graphitic structure during high temperature processing. The first problem was solved by synthesising GNP using liquid phase exfoliation method instead of using a commercially available GNP. The prepared GNP were ~1 μm in length with a thickness of 3-4 layers confirmed using transmission electron microscopy. In order to solve the second problem various processing techniques were used including powder and colloidal processing routes along with different solvents. Processing parameters were optimised to fabricate glass/ceramic-GNP composite powders. Finally in order to avoid thermal degradation of the GNP during high temperature processing composites were sintered using spark plasma sintering (SPS) technique. Fully dense composites were obtained without damaging GNP during the sintering process also confirmed via Raman spectroscopy. Finally the prepared composites were characterised for mechanical, tribological and biological applications. Interestingly fracture toughness and wear resistance of the silica nano-composites increased with increasing concentration of GNP in the glass matrix. There was an improvement of ~45% in the fracture toughness and ~550% in the wear resistance of silica-GNP composites with the addition of 5 vol% GNP. GNP was found to be aligned in a direction perpendicular to the applied force in SPS. In contrast to amorphous materials fracture toughness and scratch resistance of alumina-GNP composites increased only for small loading of GNP and properties of the composites decreased after a critical concentration. There was an improvement of ~40% in the fracture toughness with the addition of only 0.5 vol% GNP in the alumina matrix while the scratch resistance of the composite increased by ~10% in the micro-ductile region. Electrical conductivity of the BG-GNP composite was increased by ~9 orders of magnitude compared to pure BG. In vitro bioactivity tests performed on BG-GNP composites confirmed that the addition of GNP to BG matrix also improved the bioactivity of the nano-composites confirmed using XRD analysis. Future work should focus on understanding electrical and thermal properties of these novel nano-composites.

OBJECTIVES: To compare the amount of fluoride, calcium and phosphate release and recharge of a fluoride containing bioactive glass composite to a conventional resin composite and a resin modified glass ionomer cement at different time points. Furthermore, bond strength of a fluoride containing bioactive glass composite, a conventional flowable composite, and a resin modified glass ionomer cement to metal orthodontic brackets was evaluated. METHODS: A fluoride containing bioactive glass (BG) was synthesized using a sol-gel method and mixed homogeneously with an unfilled resin. For ion release and recharge, resin modified glass ionomer (RMGIC), Photac Fil Quick Aplicap (3M/ESPE) and flowable composite (Control), Filtek Supreme Ultra (Kerr), were used for comparison. Disc shape samples were fabricated using custom aluminum mold (1 mm in thickness and 9 mm in diameter, (n=5 for each material) and stored in 15 mL deionized water at 37°C until the testing time. The amounts of fluoride, calcium, and phosphate ions released were evaluated at different time points: 1 hour, 24 hours, 2 days, 3 days, 4 days, 5 days 6 days and 7 days. At each time point, all of the storage solution was extracted, and 7.5 mL was used for fluoride release measurement and the remaining 7.5 mL for calcium and phosphate ion release measurements. After solution extraction, the samples were replaced in 15 mL fresh deionized water at 37°C until the next sampling time point. Ionic recharge was performed with 5% sodium fluoride varnish (FluoroDose, Centrix) and MI paste plus (GC) following the ion release-testing period. An ion meter with a Fluoride ionic selective electrode were used to determine fluoride concentration. A Microwave-Plasma Atomic Emission Spectrometer (MP-AES) was used to test the concentration of the calcium and phosphate. For the shear bond strength test, rectangular shaped ceramic samples with the dimensions of 2 mm x 12 mm x 14 mm (Vita Mark II, Vita) were fabricated. Standard edgewise-metal brackets (American Orthodontics) were bonded to the center of the ceramic samples using tested material (n=10 for each material). Excess material was removed, and the cementing materials were polymerized from each side for 20 seconds. Specimens were either stored in water for 24 hours at 37o C or went under thermocycling for 5000 cycles. After the storage period, the specimens were subjected to shear bond strength test using an Instron universal machine at a crosshead speed of 0.5mm/min. Loads to failure were recorded to calculate shear bond strength. Comparison of released/recharged ions and shear bond strength were done by ANOVA and Tukey-Kramer HSD (α = 0.05) using JMP Pro 13. RESULTS: RMGIC showed significantly higher fluoride release and recharge than BG composite and the control. BG showed significantly higher Ca and P ion release compared to RMGIC followed by composite. RMGIC and BG showed significant ion recharge capability compared to composite. For the shear bond strength, the control composite showed significantly higher shear bond strength than BG composite followed by RMGIC. Thermocycling significantly increase bond strength for RMGIC and control but not for BG composite. CONCLUSIONS: 1. A fluoride containing bioactive glass composite was fabricated that showed the ability of ion release and recharge. 2. There was a significant difference in the amount of ion release and recharge among tested materials at different time points. 3. Favorable fluoride, calcium and phosphate ion release and recharge of BG composite were maintained over the testing period. 4. BG composite showed favorable bond strength to orthodontic metal brackets. 5. Thermocycling had a significant influence in bond strength for the materials tested except for BG composite. / 2020-07-18T00:00:00Z

Bioactive glasses react with the human physiological solution in control of their biofunctionality. The stress state in bioactive glasses determines the chemomechanical reaction and their biofunctionality. Using the microindentation technique, the effect of the indentation deformation on the surface damage and material dissolution of 45S5 bioglass was investigated. The indentation-induced residual stresses were calculated. Complete anelastic recoveries of the indentation depths and the impression marks were observed for the first time, which was likely driven by the stored strain energy over the anelastic deformation zone. The indentation-induced local surface damages were revealed before and after the immersion tests in phosphate buffer solution (PBS). The growth of the cracks in the PBS solution displayed the stress-corrosion behavior with the crack-growth speed being a linear function of the indentation load. 45S5-bioglass was crystallized at temperature of 650 ºC. Microindentation technique also was used to study the localized mechanical behavior of the crystallized 45S5-bioglass. The crystallization had little effect on the indentation hardness, and the indentation hardness of the crystallized 45S5-bioglass is the same as that of the corresponding material in vitreous state. The fracture toughness is about 3 times less than that of annealed 45S5-bioglass in vitreous state, suggesting the preference of using bioactive glasses of vitreous state in the implant applications. Also, the effect of crystallization on the material dissolution was examined in phosphate buffer solution. We also studied the growth and mechanical behaviors of the Ca-P precipitate layers formed on 45S5 bioglass in simulated body fluid. The thickness of the Ca-P precipitate layers was proportional to the square root of the immersion time, and the ratio of Ca/P in the Ca-P precipitate layers increased with the immersion time and approached 1.67, corresponding to the stoichiometric hydroxyapaptite (HA).Using the indentation technique, the indentation behavior of the Ca-P precipitate layers was investigated. The indentation hardness of the HA layers formed in SBF was found to be 0.40 GPa, and the contact modulus was 12.0 GPa. The contact modulus of 12.0 GPa is close to that of cortical bone. In this thesis, the primary mechanical properties of the non-crystalline and crystalline bioglass 45S5 were revealed. The relationship between the dissolution rate and localized residual stresses are discussed. With such knowledge, the evaluation of implants with respect to manufacturing processes, control, and service conditions now has another variable to consider and evaluate against performance.

Les nanosciences représentent, actuellement, un domaine de recherche en pleine expansion grâce aux nombreuses applications auxquelles elles peuvent être associées, et en particulier à la course à la miniaturisation des systèmes. De plus, il a rapidement été montré que les propriétés physico-chimiques des matériaux à l’échelle nanométrique sont modifiées parfois de manière drastique, à cause par exemple des effets quantiques apparaissant à des tailles aussi petites, mais aussi en raison des effets de confinement. Le confinement de molécules ou de particules à l’échelle nanoscopique nécessite donc la fabrication de matériaux hôtes possédant ce qu’il convient d’appeler des sites de confinement, c’est-à-dire des sites possédant une taille voisine de celle du système à insérer. Ce type de matériau est désormais relativement connu, et deux familles monopolisent l’intérêt, à savoir la silice mésoporeuse, aussi et récemment utilisé, les verres bioactifs à base de silice ayant des caractéristiques contrôlées qui constituent des matériaux hôtes de confinement qui peuvent être immergés dans des fluides complexes tel que le plasma sanguin synthétique. Pour réaliser ces travaux on a besoins d’appliquer plusieurs techniques de caractérisations telles que la diffusion des Rayons X et des Neutrons, la Microscopie Electronique à Balayage et à Transmission, la spectroscopie Infrarouge à Transformé de Fourier etc...De plus, ces dernières années, des systèmes microfluidiques ont été utilisés pour élaborer des émulsions doubles, des microcapsules ou des microparticules, avec la particularité d’obtenir des populations très monodisperses par rapport à celles obtenues avec des techniques plus traditionnelles et de morphologie contrôlée. Dans le domaine pharmaceutique, ces capacités sont particulièrement intéressantes pour la synthèse de médicaments à libération contrôlée. Elles permettent d’obtenir des particules monodisperses de polymère encapsulantes pour lesquelles l’effet de relargage brutal est diminué et qui possèdent des vitesses de relargage plus lentes que celles observées avec des procédés de fabrication conventionnels. / Nanoscience currently represent a growing area of research through the many applications for which they may be associated, particularly in the race for miniaturization of systems. In addition, it was quickly demonstrated that the physico-chemical properties of nanoscale materials are sometimes changed drastically, for example because of quantum effects occurring at sizes as small, but also because of confinement effects .Confinement of molecules or particles at the nanoscale therefore requires the manufacture of host materials with what to call containment sites, that is to say, sites with a size close to that of the system insert. This type of material is now relatively well known, and two families monopolize the interest, ie the mesoporous silica, and also recently used bioactive glasses based on silica having controlled characteristics that are host materials containment can be immersed in complex fluids such as synthetic blood plasma.To do this work several characterization techniques we need to apply, including the spread of X-rays and neutrons, the Scanning Electron Microscopy and Transmission, Infrared spectroscopy Transformed Fourier etc ...Moreover, in recent years, microfluidic systems were used to prepare double emulsions, microcapsules or microparticles, with the particularity to obtain highly monodisperse populations compared to those obtained with more traditional and controlled morphology techniques. In the pharmaceutical field, these capabilities are particularly interesting for the synthesis of controlled release to drugs. They enable polymer monodisperse particles encapsulating why the sudden release effect is decreased and have slower release rates than those observed with conventional manufacturing processes

Le développement de matériaux biocompatibles permettant la vectorisation de principes actifs est particulièrement souhaitable dans le cadre de la réparation osseuse liée à certaines pathologies. Dans la première partie de ce mémoire, nous décrivons la synthèse et la caractérisation de verres de phosphates de calcium dopés avec du gallium qui est un agent inhibiteur de la résorption osseuse. Les modifications du réseau phosphate sont étudiées par RMN du 31P et les différents environnements locaux du Ga3+ sont mis en évidence par RMN du 71Ga en utilisant des conditions expérimentales spécifiques (très haut champ magnétique de 20T et rotation de l’échantillon ultra-rapide). Le comportement en solution de ces verres a été étudié par RMN et par ICP-AES. Les résultats obtenus indiquent qu’ils sont soumis à une dissolution quasi-congruente et que l’ajout de Ga3+ augmente leur durabilité chimique. La seconde partie de ce travail est dédiée à l’étude d’un verre bioactif utilisé en chirurgie réparatrice osseuse : le Bioglass® 45S5 (système SiO2-CaO-Na2O-P2O5). L’utilisation d’expériences RMN de double résonance a permis d’apporter des éléments de réponse sur le type d’association entre les groupements phosphates et le réseau silicate. Après immersion de ce verre dans un fluide physiologique simulé (SBF), un suivi quantitatif des espèces, initiales et formées à la surface du verre, a été réalisé par RMN. Les résultats obtenus par RMN et par d’autres techniques de caractérisation montrent que l’hydroxyapatite carbonatée se formant en surface du verre présente de grandes similitudes avec les apatites biologiques. / The development of biocompatible materials allowing the local delivery of specific drugs is of high interest to repair pathological bone defects. The first part of this manuscript describes the synthesis and the characterisation of calcium phosphates glasses doped with gallium, which is a bone resorption inhibitor. The nature of the phosphate network is probed by 31P NMR and the Ga3+ local environments are studied 71Ga NMR at very high magnetic field (20T) and ultra-fast spinning frequency. The leaching behaviour of these glasses is investigated by NMR and ICP-AES. The obtained results indicate that the glass dissolution is nearly congruent and that Ga3+ doping improves the chemical durability. The second part of this work is dedicated to the study of the Bioglass® 45S5 which is a bioactive glass (SiO2-CaO-Na2O-P2O5 glassy system) used in bone repair surgery. Double-resonance NMR experiments are used to obtain information about the association between the phosphate units and the silicate network. NMR analyses are also used to characterize quantitatively the various species formed at the glass surface after immersion into a simulated body fluid for varying periods. Results obtained from NMR and other characterization methods revealed that the carbonated hydroxyapatite formed at glass surface shows strong similarities with biological apatites.