Materiais dopados com o íon trivalente Tb apresentam intensa emissão no verde (5D4 → 7Fj, j = 3, 4, 5 e 6) e fraca na região UV-azul (5D3 → 7Fj , j = 4, 5 e 6). A emissão azul pode ocorrer a partir de excitação direta no UV (emissão Stokes) ou por upconversion (emissão anti-Stokes), após a excitação em 488 nm (excitação ressonante no nível 5D4 a partir do estado fundamental). Nesta dissertação analisamos as propriedades da luminescência do Tb3+ em vidros aluminosilicato de cálcio com baixa concentração de sílica. Para excitação em 325nm, verificou-se que a intensidade da luminescência verde aumenta linearmente com a concentração, enquanto a emissão azul é fortemente reduzida com o aumento da concentração de Tb3+ de 0,5 para 15,0% (% em peso). No caso da excitação em 488 nm, observou-se uma forte saturação das emissões verdes, para intensidades duas ordens de grandeza menores que o esperado. Por meio de um sistema de equações de taxa, mostramos que esse comportamento pode ser explicado pelo mecanismo de absorção do estado excitado (AEE) e, por uma seção de choque de absorção (5D4 → 5D3) aproximadamente duas ordens de magnitude maior do que a do estado fundamental (7F6 → 5D4). Nossos resultados sugerem que a relaxação cruzada envolvendo os níveis 5D4 e 5D3 não é o único mecanismo responsável pela depopulação do nível 5D3 , como tipicamente descrito na literatura. Processos de upconversion por luminescência cooperativa entre íons excitados (5D3: 5D3 ou 5D3: 5D4) e outros mecanismos que envolvem transferência de energia para níveis excitados superiores (4f5d, banda de transferência de carga, matriz hospedeira, defeitos, etc) podem desempenhar um papel significativo neste sistema. Medidas de Z-scan resolvidas no tempo com excitação em 488 nm foram realizadas e não-linearidades de altas ordens foram observadas (n2, n4, etc.). A partir do n2, valores de Δαp e Δσ da ordem de 10-25 cm3 e 10-20cm2 foram calculados, respectivamente. Este valor de Δαp é o mais alto já reportado em materiais dopados com TR, provavelmente devido à baixa energia dos níveis 4f5d para o íon Tb3+. / Trivalent Tb-doped materials exhibit strong emission in the green (5D4 → 7Fj, j = 3, 4, 5 e 6) and weak in the UV-blue (5D3 → 7Fj , j = 4,5 e 6). The blue emission can occur from direct UV excitation (Stokes emission) or by upconversion (anti-Stokes emission) through 488 nm excitation (resonant pump of 5D4 metastable level from the ground state). In this dissertation the luminescence properties of Tb3+ doped low silica calcium aluminosilicate glasses are reported and analyzed. The intensity of green luminescence increases proportionally to the concentration while the blue luminescence is strongly reduced with the increase of Tb3+ concentration from 0.5 up to 15.0 wt%. In the case of 488 nm excitation, a saturation behavior of the green emission is observed at intensities two orders of magnitude smaller than expected for bleaching of the ground state population. Using a rate equation model, we show that this behavior can be explained by an excited state absorption (ESA) from 5D4 to upper levels, with an absorption cross section two orders of magnitude larger than the ground state absorption. The effect of ESA could also be observed by the shortening of the green emission risetime with the increase of pump intensity. We infer that the CR is not the only loss mechanism responsible for the 5D3 depopulation. Cooperative upconversion from a pair of excited ions (5D3:5D3 or 5D3:5D4) and other mechanisms involving upper lying states (4f5d, charge transfer, host matrix, defects, etc.) may play a significant role. Time-resolved Z-scan measurements were also performed at 488 nm high order nonlinearities were observed (n2, n4, etc.). From n2, Δαp and Δσ of the order of 10-25 cm3 and 10-20cm2, respectively, were obtained. This Δαp value is the highest ever reported for a RE doped material, it seems to be due to the low energy value of the 4f5d state in Tb3+.

INTRODUÇÃO: A falta da correção óptica recentemente foi reconhecida como importante causa de baixa visão e parece ser um problema fácil de ser resolvido com o uso de óculos. No entanto, a falta da correção óptica é um problema complexo do seu diagnóstico ao tratamento, envolvendo a procura e alcance da assistência médica, além da confecção e uso dos óculos. OBJETIVOS: Determinar a frequência da necessidade de correção óptica em escolares; determinar a influência do absenteísmo no estudo da frequência da necessidade de correção óptica e suas causas; determinar o impacto da reconvocação dos faltosos na cobertura do atendimento oftalmológico; verificar cobertura oftalmológica prévia; verificar uso da correção óptica prescrita e causas de abandono de óculos. MÉTODO: Foi realizado um estudo transversal analítico. Escolares de 7 a 10 anos do ensino público de Guarulhos foram triados e encaminhados para exame oftalmológico na Campanha Olho no Olho 2006 e 2007. RESULTADOS: Foram triados 40.197 escolares e encaminhados 11.741 escolares com suspeita de problemas visuais. O absenteísmo na primeira convocação foi 42.5% e na reconvocação foi 62.2%. A Campanha alcançou 73.6% dos escolares encaminhados. A reconvocação ampliou a cobertura do projeto em 16.1%. A falta de orientação (não ter recebido aviso ou guia de encaminhamento) foi a razão mais frequente (35.6%) alegada para o não comparecimento, seguida de trabalho (20.6%) e doença (12.4%). A necessidade de óculos não foi fator associado ao comparecimento. Para 60.2% dos escolares foi a primeira oportunidade de exame ocular, sendo que 27.3% procuraram mas não tiveram acesso a consulta médica. Dos 1.379 escolares que já haviam feito exame, 48.3% utilizaram o SUS e 1.029 receberam prescrição de óculos em exame prévio. Destes, 899 (87.4%) fizeram os óculos e apenas 590 (57.3%) usavam os óculos no dia do exame. Dos óculos doados na Campanha, 84.7% dos escolares utilizavam a correção óptica após um ano. A estimativa da frequência da necessidade de correção óptica, na população estudada, foi de 6.9%. CONCLUSÕES: O erro refracional não corrigido foi a maior causa de baixa acuidade visual entre os escolares. A Campanha foi a primeira oportunidade de exame ocular para a maioria dos escolares. Existe uma parcela de pais que não leva seus filhos para exame, mesmo com oferecimento de facilidades (acesso, transporte, alimentação, duas oportunidades diferentes de exame gratuito realizado em fins de semana e doação de óculos). O absenteísmo poderia ser evitado em 87,1% dos casos, com melhor estruturação da primeira convocação. A reconvocação não é recomendada quando os recursos financeiros são escassos / INTRODUCTION: The lack of optical correction was recently recognized as an important cause of low vision and it seems to be an easy problem to be solved with the use of spectacles. However, it is a complex problem from its diagnosis to treatment, which includes medical assistance searching and finding, and spectacles acquisition and use. PURPOSES: To determine the frequency of optical correction need; to determine the impact of the recall of those absent in the ophthalmologic service coverage and its causes; to check the previous ophthalmologic coverage; to check the use of the prescribed optical correction and causes to neglect the use of spectacles. METHOD: An analytical cross-sectional study was conducted. Students between 7 and 10 years old of public education from Guarulhos were screened and referred to ophthalmologic exam in the Eye to Eye Campaign 2006 and 2007. RESULTS: 40.197 students were screened and 11.741 (29,2%) were referred with suspicion of visual problems. The absenteeism in the first call was 42.5% and in the recall 62.2%. The Campaign reached 73.6% of the referred students. The recall expanded the project coverage in 16.1%. The lack of guidelines (parents did not receive notification or referral guide) was the most frequent reason (35.6%) provided by parents for the non attendance, followed by work (20.6%) and disease (12.4%). The need of glasses was not related to the attendance. For 60.2% of the students, it was the first opportunity for ophthalmological exam, whereby 27.3% searched but did not have access to a medical visit. Among the 1.379 students who had already performed an exam, 48.3% used the Public Health System and 1.029 received prescription of glasses in the previous exam. From those, 899 (87.4%) made their glasses and only 590 (57.3%) were wearing glasses on the day of the exam. From the donated spectacles in the Campaign, 84.7% of the students were using the donated optical correction after one year. The estimate of optical correction need within the studied population was 6.9%. CONCLUSIONS: The uncorrected refractive error was the main cause of low visual acuity among students. The Campaign was the first opportunity of ocular exam for most of them. A significant number of parents did not take their children for ophthalmological exams, even when facilities (access, free transportation, meal, two different opportunities of free exam over the weekend and spectacle donation) were offered. For 87.1% of the absenteeism cases, the difficulties could have been overcome via improved structuring of the first call. A recall is not recommended when financial resources are low

Submitted by Izabel Franco (izabel-franco@ufscar.br) on 2016-10-06T13:50:45Z No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-20T16:14:11Z (GMT) No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-20T16:14:17Z (GMT) No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) / Made available in DSpace on 2016-10-20T16:14:23Z (GMT). No. of bitstreams: 1 TeseMM.pdf: 4347312 bytes, checksum: a5a64729ea719b0ac57b31c2cdeeb425 (MD5) Previous issue date: 2016-03-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this study, we present the production and characterization of a novel binary glass system: (100-x)SbPO4-xGeO2 where x = 30, 40, 50, 60, 70, 80 and 90 mol %. The dependence of GeO2 content on thermal, structural and optical properties were investigated by thermal analysis (DSC), Raman spectroscopy, UV-Visible absorption, infrared transmittance and M-lines techniques. Glass transition temperatures (Tg) shows an almost constant value around 400 °C when GeO2 content was increased. Thermal stability (ΔT = Tx-Tg) increases almost linearly with GeO2 content reaching a maximum value (300 °C). Ions Er3+ and Yb3+ were further incorporated into system SG in different proportions. Infrared and up-conversion emission processes were investigated. The emission spectra in the infrared region showed that the incorporation of Yb3+ ions into the glass composition increases the emission intensity at 1538 nm (4I13/2  4I15/2). The up-conversion processes showed a higher intensity emission at 522 nm and 544 nm (green) and 652 nm (red) regions and the emission mechanism has been the same as proposed in several works in literature. Finally, the glass sample showing the highest emission intensity at 1538 nm was chosen for micromachining using femtosecond laser. The waveguides having the lowest propagation losses were used for the optical internal gain proceeds. The best result obtained for internal gain at 1535 nm was around 1.7 dB/cm and this value is in agreement with other glass systems based on germanium and phosphates glasses present in literature. / Neste estudo, foi realizado a preparação e caracterização do sistema vítreo: (100-x) SbPO4-xGeO2 (SG), onde x varia entre 30 e 90% em mol. A dependência da concentração de GeO2 nas propriedades térmicas, ópticas e estruturais foram estudadas. O comportamento térmico foi investigado através da análise térmica (DSC), enquanto as propriedades estruturais foram estudadas por espectroscopia de espalhamento Raman. As propriedades ópticas foram avaliadas usando as espectroscopias na região do UV-Vis, infravermelho e M-Lines. No sistema SG a temperatura de transição vítrea (Tg) apresenta uma pequena variação e se encontra por volta de 400 °C quando a concentração de GeO2 foi alterada. O parâmetro de estabilidade térmica (ΔT = Tx-Tg) aumenta quase linearmente com o aumento da quantidade de GeO2, alcançando um valor máximo de 300 °C. Para o sistema SG foram incorporados ainda íons Er3+ e Yb3+ em diferentes proporções e as emissões na região do infravermelho e os processos de conversão ascendente de energia (upconversion) foram investigados. Os espectros de emissão na região do infravermelho mostram que a incorporação de íons Yb3+ na composição química do vidro, aumenta a intensidade de emissão em 1538 nm (4I13/2  4I15/2). Os processos de up-conversion mostram emissões de alta intensidade na região do verde (522 e 544 nm) e vermelho (652 nm), e os mecanismos das emissões foram estudados e propostos. Por fim, a amostra com a maior intensidade de emissão em 1538 nm foi escolhida para a realização da microfabricação de guias ópticos, usando lasers de femtossegundo. Os guias de onda que apresentaram as menores perdas por propagação, foram utilizados para as medidas de amplificação óptica.

Orientador: Keizo Yukimitu / Banca: Victor Ciro Solano Reynoso / Banca: Sandro Márcio Lima / Resumo: Neste trabalho foram estudados os vidros teluretos do sistema (20-x)Li2O-80TeO2- xWO3 com diferentes valores de x. Os resultados das medidas de DRX dos vidros como preparados confirmaram o comportamento amorfo das matrizes vitreas, e para os vidros tratados termicamente em diferentes temperaturas, acima de Tg, evidenciou-se a formacao das fases cristalinas durante o processo de cristalizacao. No vidro com x=0 (TL) foi observado a presenca das fases cristalinas -TeO2, -TeO2 e Li2Te2O5, e para os vidros com x=5 e 10 (TLW-5 e TLW-10) foi observado somente as duas primeiras fases cristalinas. Esse resultado sugere que o WO3 entra na estrutura como formador vitreo e inibe o crescimento da fase cristalina Li2Te2O5. Os parametros termicos, como a Tg, Tx e Tp, e o processo de cristalizacao dos vidros foram estudados por meio das medidas de DSC, e foram calculados os valores da energia de ativacao (E) e do parametro de Avrami. As curvas de DSC foram obtidas para taxas de aquecimento entre 2.5 e 12.5 K.mol-1 e particulas com tamanho 45-63 ƒÊm. A energia de ativacao e o indice de Avrami foram calculados para cada fase cristalina e os picos de DSC foram ajustados utilizando funcoes gaussianas. As curvas de DSC das amostras tratadas termicamente apresentaram os picos de cristalizacao, referentes a cada fase cristalina, separadamente. Nas curvas de DSC do vidro TLW-5 foram observados tres picos de cristalizacao, embora as medidas de DRX tenham apresentado apenas duas fases cristalinas. Deste modo, a existencia deste terceiro pico de cristalizacao nas curvas de DSC do vidro TLW-5 confirmam o processo de transformacao da fase -TeO2 em -TeO2, conforme sugerido pelos dados de DRX e tambem pelos espectros de FT-IR. Nos espectros de infravermelho das tres matrizes vitreas foram verificadas as bandas de absorcao referentes as vibracoes das unidades tetragonais TeO4 e as bandas referentes as ligacoes W-O. / Abstract: In this work the tellurite glasses of the system (20-x)Li2O-80TeO2-xWO3 with different x values were studied. The results of the XRD measurements for glasses as quenched confirmed the amorphous behavior of the glass matrix, and for the glasses thermally treated at different temperatures above Tg evidenced the phases crystalline formed during the crystallization process. In the glass with x=0 (TL) the presence of the -TeO2, -TeO2 and Li2Te2O5 crystalline phases was observed and for the glasses with x=5 and 10 (TLW-5 and TLW-10) were observed only the first two crystalline phases. This result suggests that WO3 enters in the structure as glass former and it inhibits the growth of the crystalline phase Li2Te2O5. The thermal parameters, as Tg, Tx and Tp, and the crystallization process of the glasses were studied through the DSC measurements, the values of the activation energy (E) and the Avrami’s parameter were calculated. The DSC curves were obtained for heating rates between 2.5 and 12.5 K.mol-1, and 45-63 ìm particles size. The activation energy and the Avrami’s parameter were calculated for each crystalline phase and the peaks of DSC were fitted using Gaussian functions. The DSC curves of the samples thermally treated showed the crystallization peaks, regarding each crystalline phase, separately. In the DSC curves of TLW- 5 glass three crystallization peaks were observed, although the measurements of XRD have presented only two crystalline phases. In this way the existence of this third crystallization peak in the DSC curves of the glass TLW-5 confirms the process of transformation of the phase -TeO2 in -TeO2, as suggested by XRD data and also for the FT-IR spectra. In the infrared spectra of the three glass matrix the absorption bands regarding the vibrations of the tetragonal units TeO4 and the bands regarding the connections W-O were observed. / Mestre

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / PbS quantum dots has been grown in oxide glasses by two distinct methodologies according to the dopants, using the fusing method at 1200ºC. The host glass matrices used were SNAB (SiO2.Na2CO3.Al2O3.B2O3) and SNABP (SiO2.Na2CO3.Al2O3.B2O3.PbO2), with PbS bulk and S (sulphur) added as dopants, respectively. Thermal treatments were applied in a systematic way in order to allow a controlled growth of quantum dots. Different experimental techniques were realized in order to study the growth kinetic of dots as a function of thermal treatment times and dopant concentrations. It was analyzed thermal properties of the glass matrices by Calorimetry Scanning Diferencial (DSC). Many techniques have allowed discussion of the optical properties by Optical Absorption (OA) and Photoluminescence (PL), morphologic properties by Atomic Force Microscopy (AFM), and structural properties by X-Ray Diffractometry (DRX) of the nanocrystals. Qualitative and quantitative analyse of the chemical composition of the samples has been possible by spectrometry of Fluorescence of Raios-X (FRX). Using the ] 4 4 [ . × p k r r method we were able to estimate the avarage diameter of the PbS quantum dots. Calculations of dispersion sizes of PbS quantum dots, from the AO bands, has been presented. We have found the dependence between the quantum dot gap and the dopant concentrations. The relation between the Stokes Shift and the average size of the PbS quantum dots was also presented. Through the previous results, we have defined the methodology referring the host glass matrix SNABP with S bulk added as the most favorable to the growth PbS quantum dots with low size dispersion. / Pontos Quânticos de PbS foram sintetizados em vidros à base de óxidos, a partir duas metodologias distintas quanto a dopagens, pelo método da fusão a 1200ºC. As matrizes vítreas hospedeiras utilizadas foram: SNAB (SiO2.Na2CO3.Al2O3.B2O3) e SNABP (SiO2.Na2CO3.Al2O3.B2O3.PbO2), e os dopantes adicionados à elas foram PbS bulk e S (enxôfre), respectivamente. Tratamentos Térmicos variados e adequados foram efetuados nestas amostras para permitir o crescimento controlado dos pontos quânticos de PbS. Com o objetivo de estudar e acompanhar a cinética de crescimento destes pontos em função dos tempos de tratamentos térmicos e das variadas concentrações de dopantes, foram efetuadas várias técnicas de caracterizações. Estas permitiram análises das propriedades térmicas dos vidros por Calorimetria Exploratória Diferencial (DSC); ópticas, por Absorção Óptica (AO) e Fotoluminescência (PL); morfológicas, por Imagens de Microscopia de Força Atômica (AFM); e estruturais, por Difratometria de Raios-X (DRX) dos referidos nanocristais. Análises qualitativas e quantitativas das composições químicas das amostras sintetizadas neste trabalho foram possíveis através da técnica de espectrometria de Fluorescência de Raios-X (FRX). Com o auxilio do método ] 4 4 [ . × p k r r , foi possível estimar o diâmetro médio dos pontos quânticos de PbS. Cálculos de dispersão de tamanhos ξ a partir da largura a meia altura (W) das bandas de AO e discussões sobre a dependência de energia e o tamanho médio dos pontos quânticos foram apresentados e discutidos. Mostrouse graficamente a relação de dependência entre o Gap dos pontos quânticos e as concentrações de dopantes adicionados às matrizes vítreas. Apresentou-se de forma gráfica a relação entre o deslocamento Stokes e o tamanho médio dos pontos quânticos de PbS. A partir de análises dos resultados obtidos, definiu-se então a metodologia correspondente à matriz SNABP dopada com S bulk como sendo a mais favorável para a formação e crescimento dos pontos quânticos de PbS com menor dispersão de tamanhos entre si. / Mestre em Física

Cette thèse porte sur l’étude du processus de cristallisation de verres et l’élaboration de vitrocéramiques transparentes dans le visible. Ce travail a permis d’élaborer plusieurs vitrocéramiques complètement cristallisées et transparentes, ce qui constitue un résultat exceptionnel pour ce type de matériaux qui perd habituellement la transparence lors de la cristallisation. Ces matériaux originaux et novateurs ont fait l’objet d’un brevet sur des "Céramiques transparentes" (dépôt en France N° 1161025 et extension internationale PCT N° EP2012/074171) et de plusieurs articles (cf. page 162). Plusieurs verres dans les systèmes oxydes de terres rares-oxydes d’alcalino-terreux-Al2O3-SiO2 ont été élaborés au moyen d’un lévitateur aérodynamique couple a un chauffage par laser puis étudiés. Une recherche de la composition optimale du verre d’aluminosilicate d’yttrium parent qui permettrait d’avoir un maximum de cristaux de YAG sans formation d’impuretés lors de la cristallisation a été menée. L’étude de la cristallisation du YAG a partir des verres d’aluminosilicates d’yttrium choisis, réalisée principalement par RMN et diffraction des rayons X, a montré que les ions de silicium initialement présents dans la matrice vitreuse se trouvent incorporés dans les cristaux de YAG formes, en substitution des ions d’aluminium des sites tétraédriques. Les conséquences structurales de cette incorporation dans le YAG ont été étudiées. En particulier, la réduction de la maille cubique du YAG et des liaisons des sites tétraédriques a été mise en évidence par DRX et affinement Rietveld. Par RMN, la présence d’aluminium en coordinence IV, V et VI a été détectée dans le verre parent. Pour ce système, il est remarquable que la cristallisation du verre d’aluminate d’yttrium puisse avoir lieu au-dessous de sa température de transition vitreuse. Ce phénomène rarement rapporté pourrait être expliqué par la tendance élevée du verre à cristalliser et par la capacité de Si4+ à s’incorporer dans les cristaux de YAG comme cette étude le démontre. L’avancement de la cristallisation par recuit du verre au-dessous de Tg a été suivi ainsi que l’absorbance et la diffusion de l’irradiation IR par les vitrocéramiques en se basant sur le modèle de Rayleigh-Guns-Debye. Cette étude a révélé l’influence de la différence de l’indice de réfraction entre le verre et les cristaux sur la diffusion de la lumière. Les images MET et MEB de ces vitrocéramiques montrent des cristaux de YAG de tailles comprises entre 500 nm et 1300 nm. La cristallisation d’une autre famille de verres de terres rares a été étudiée. Il s’agit de verres d’aluminate de lanthane et de borate de lanthane. Dans les deux cas, une cristallisation démarrant à partir de la surface a été observée et étudiée. La cristallisation des phases LaAlO3 et LaBO3 dans ces verres a été suivie par DRX (Haute Température). L’ajout de SiO2 à la composition La2O3-Al2O3 a été nécessaire pour élaborer un verre avec un four classique. Une étude de cristallisation poussée a été également menée sur de nouveaux verres d’aluminates d’alcalinoterreux. Cette étude a compris une caractérisation des vitrocéramiques formées ainsi que la résolution de la structure de deux nouveaux polymorphes de BaAl4O7 formés par cristallisation des verres en se servant de la diffraction électronique, neutronique et synchrotron. Une étude par RMN de l’évolution de l’environnement de l’oxygène durant le recuit a été réalisée et a permis de mettre en évidence la présence des entités d’oxygène tri-coordinées dans les verres d’aluminate de baryum. Ce travail nous a finalement permis d’élaborer plusieurs vitrocéramiques complètement cristallisées et transparentes, ce qui constitue un résultat exceptionnel. La luminescence de ces vitrocéramiques a été caractérisée et les raisons de leur transparence sont discutées à la lumière de leurs microstructures. / This thesis concerns the crystallization and the structural study of different alumino-silicate glasses. This study has led to several completely crystallized and transparent glass-ceramics, which is an original result for this type of material that usually loses transparency during crystallization. These innovative materials were the subject of a patent entitled “Transparent ceramics” (French deposit number: N° 1161025 and international extension number : PCT N° EP2012/074171) and different articles (cf. page 162). Numerous glasses in the systems rare earth oxides, alkaline earth oxides-Al2O3-SiO2 were prepared by an aerodynamic levitator coupled to a laser heating system and studied. The study of the YAG crystallization from the yttrium alumino-silicate glasses was achieved mainly by double resonance 27Al/29Si NMR spectroscopy and by (lab and synchrotron) X-ray diffraction. This study showed that the silicon ions that are initially present in the glassy matrix are incorporated during crystallization in the formed YAG crystals on the 4-fold coordination Al site. The structural consequences of this incorporation were studied. In particular, the reduction of the YAG cubic lattice and the bonds of the tetrahedral sites have been evidenced. Upon post synthesis annealing, the glass was observed to exhibit crystallization below the glass transition temperature. This unusual behaviour was examined using XRD and infrared spectroscopy to follow crystallinity and optical absorbance as a function of annealing treatment. This rarely reported phenomenon could be explained by the high tendency of our glass to crystallize compared to glasses elaborated by classical furnaces and by the ability of Si4+ to be accommodated into the YAG crystal structure as we have demonstrated. This study also revealed the influence of the refractive index difference between the glass and the crystals on the scattering of light. TEM and SEM images show that the YAG crystals sizes range between 500 nm and 1300 nm. Furthermore, the crystallization of a family of lanthanum aluminate and lanthanum borate glasses was studied. In both cases, the crystallization started from the surface. The formation of LaAlO3 LaBO3 phases in these glasses was followed by XRD (High Temperature). The addition of SiO2 to the Al2O3-La2O3 composition was found necessary for the vitrification with a conventional oven. Finally, a crystallization study was also conducted on new alkaline-earth aluminate glasses. This study included a characterization of the parent glasses with the formed glass-ceramics and the structure resolution of two new polymorphs of BaAl4O7 formed by crystallization, using electron neutron and synchrotron diffraction. An NMR study of the environment evolution of the oxygen during annealing was performed. This allowed to evidence the presence of tri-coordinated oxygen entities in the parent glasses. This work has finally allowed us to develop fully crystallized and transparent glass-ceramics, which is an exceptional result. The luminescence of these glass-ceramics was characterized and the reasons for their transparency were discussed in light of their microstructures.

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.

Au cours de ce travail, essentiellement expérimental, nous nous sommes intéressés à la relaxation structurale dans un verre silicaté que nous avons analysé et interprété en terme de dynamique hétérogène. Expérimentalement, nous avons couplé les informations obtenues par différentes spectroscopies qui sondent des échelles spatiales allant du nm (Raman, Infrarouge) à une centaine de nanomètres (Brillouin). Numériquement, nous avons décomposé les fonctions de relaxation obtenues par les différentes spectroscopies et nous avons mis en évidence l’existence de plusieurs échelles temporelles ainsi existantes. A longue distance, les expériences in situ Brillouin effectuées le long d’une rampe de chauffage et des isothermes montrent que (i) les phonons acoustiques sont affectés par le recuit et (ii) la dynamique de relaxation est hétérogène à l’approche de la transition vitreuse. Ainsi, contre toute attente cette hétérogénéité est très fortement dépendante du parcours suivi en température. A courte et moyenne distance, les mesures in situ Raman à hautes température sur des rampes de chauffe et des isothermes, montrent que la relaxation structurale affecte l’ordre spatiale du réseau silicaté. Le couplage des analyses en composantes individuelles et principales a permis d’identifier deux processus de relaxation attribués respectivement à la relaxation du fond continu et des entités Qn. Par des mesures in situ d’Emissivité Infrarouge dans le liquide et grâce à un modèle proche du modèle binaire l’abondance des espèces Qn lors des processus de relaxation et cristallisation a été obtenue. Un mécanisme d’activation de la relaxation à grande distance par une re-polymérisation locale est mis en évidence. Ce même mécanisme est un précurseur de la cristallisation. / Résumé en cours de rédaction

Ces travaux de thèse portent sur la synthèse et purification de matériaux vitreux utilisés pour le développement de fibres optiques à profils opto-géométriques variés, adaptées à la génération de supercontinuum (SC) entre 1 et 5 μm.Concernant la purification, plusieurs pistes ont été suivies, le meilleur résultat étant obtenu pour la purification du système vitreux TeO2-ZnO-Na2O au moyen du fluorure de zinc. Les mesures d'atténuation sur fibre mono-indice révèlent l'élimination presque complète des absorptions liées aux groupements OH entre 3 et 4 μm (taux d'impuretés OH dans la matrice inférieur à 1 ppm massique). Ces verres purifiés sont utilisés pour la fabrication de fibres optiques microstructurées (FOMs). Un élargissement spectral couvrant la fenêtre 0.6 μm - 3.3 μm est obtenu dans une fibre effilée à coeur suspendu. Aussi, une source compacte basée sur la génération de SC dans une FOM en tellurite est développée et appliquée à la détection de gaz (du méthane) entre 2 et 3 μm. Cependant un phénomène de vieillissement, lié à une interaction du coeur de la fibre avec la vapeur d'eau atmosphérique via la microstructure, et entraînant une augmentation des pertes optiques entre 3 et 4 μm, est mis en évidence dans ces fibres à coeur suspendu. Pour pallier ce problème, des fibres tout-solide à saut d’indice sont développées. La méthode de fabrication des préformes en verre, combinant les techniques de built-in casting et de rod-in-tube, est alors adaptée aux techniques de purification. Une fibre à saut d'indice à petit coeur en verres TNaGZ et TZNF purifiés a notamment été étirée et utilisée pour la génération d’élargissements spectraux dans différents régimes de dispersion. / This PhD thesis work focuses on the synthesis and purification of vitreous materials used for the development of waveguides with varied profiles, dedicated to supercontinuum (SC) generation between 1 and 5 μm.Concerning the purification of tellurite glasses, several leads were followed, but best results are obtained for the purification of the TeO2-ZnO-Na2O glassy system by the means of zinc fluoride. Attenuation measurements performed on several meter-long single-index fiber samples reveal the nearly complete elimination of water-related absorptions between 3 and 4 μm (OH ions concentration lower than 1 ppm mass.). Such water-purified glasses were firstly dedicated to microstructured optical fibers (MOFs) fabrication for SC generation. Spectral broadening between 0.6 and 3.3 μm is obtained in a suspended-core taper. Moreover, a compact source based on supercontinuum generation in tellurite MOFs is developed for a gas detection application in the 2-3 μm domain. However an aging process, due to water contamination and leading to the apparition of additional optical losses between 3 and 4 μm, has been identified in those suspended-core fibers. In order to avoid such transmission degradation, all-solid step-index fibers are developed. The preforms fabrication method, which combines the built-in casting and the rod-in-tube, is adapted to the purification techniques. An all-solid small-core waveguide made from purified TNaGZ and TZNF glasses is fabricated and moreover used for spectral broadening experiments in different dispersion regimes.

Neste trabalho foram realizadas análises estruturais de dois conjuntos de vidros metafosfatos ternários relevantes em potenciais aplicações: aluminofosfatos e álcalis mistos. Para os aluminofosfatos a análise estrutural tem por objetivo verificar a existência de comportamentos preferenciais da conectividade entre os grupos fosfatos e os átomos de Al, e verificar a possível extensão a estes sistemas ternários de princípios de ligação química e ordem local inferidos em fosfatos binários, sendo os sistemas estudados K(1-x)Alx(PO3)(2x+1) e Na(1-x)Alx(PO3)(2x+1) . Para os vidros de álcalis mistos, a análise estrutural tem por objetivo identificar se existe segregação ou mistura aleatória das duas espécies de cátions, e determinar quais modificações na ordem local de cada álcali são induzidas pela troca de espécies, sendo os sistemas estudados LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) e CsxLi(1-x)(PO3). As informações estruturais nestes vidros foram obtidas através de técnicas de Ressonância Magnética Nuclear (RMN) de estado sólido de 7Li, 23Na, 27Al, 31P, 87Rb e 133Cs. A conectividade entre a rede de fosfatos e os átomos de Al foi estudada utilizando informações a respeito da distribuição de espécies tetraédricas de fosfatos Q2m , sendo m = 0,1, 2 o número de pontes P-O-Al por tetraedro, obtidas através de RMN de 31P, e do número de coordenação médio do Al obtido através de RMN de 27Al. Da análise quantitativa da evolução das diferentes populações Q2m com a concentração de Al, juntamente com o número de coordenação médio do Al, foi possível verificar a existência de comportamentos preferenciais na organização estrutural: tetraedros fosfatos compartilham um vértice único (oxigênio não-ponte) com os poliedros de coordenação do Al. Esta organização de médio alcance é mantida até uma determinada concentração de Al, onde todo tetraedro forma uma ponte P-O-Al . A distribuição das espécies Q2m resultante é do tipo binária em função da concentração de Al: { Q20, Q21 } até concentrações intermediárias e { Q21, Q22 } para concentrações altas. Para os metafosfatos de álcalis mistos, o comportamento do desvio químico de 23 Na e 133Cs revela um efeito sistemático de aumento/decréscimo no tamanho do ambiente de coordenação ao redor dos álcalis em função da substituição. O ambiente de O dos álcalis de menor raio iônico resulta comprimido quando ocorre a substituição deste por uma espécie de raio iônico maior, e vice-versa. Com relação à distribuição dos álcalis na rede vítrea, as evoluções dos desvios químicos em função da substituição excluem a possibilidade de segregação dos álcalis ou separação de fase. A análise do acoplamento dipolar homonuclear de 23 Na, através da medida do segundo momento, revelou que a mistura de Na com o segundo álcali não é aleatória, existindo uma maior probabilidade de um Na ter outro Na como próximo vizinho. A correlação entre o grau de não-aleatoriedade na dispersão do Na e o incremento na magnitude do efeito de álcalis mistos na condutividade DC dos metafosfatos de Rb-Na, K-Na e Li-Na sugere que os fenômenos estão fundamentalmente relacionados. Esta seria a primeira evidência de vínculo entre uma propriedade estrutural da distribuição dos álcalis e o efeito de álcalis mistos de uma propriedade dinâmica. / In this work, the structure of two ternary metaphosphate glass systems was analyzed: aluminum-phosphates and mixed-alkali. The aim of the study in aluminum-phosphates is to determine the existence of preferential structural connectivities between phosphate groups and Al, and to verify the possible extension to these ternary glasses of principles of structural organization valid in binary phosphates. The aluminum metaphosphates studied here were K(1-x)Alx(PO3)(2x+1) and Na(1-x)Alx(PO3)(2x+1) . In mixed-alkali metaphosphates the goal of the structural analysis is the identification of the way in which alkali cations are distributed in the glass network (segregation versus random mixture), and to determine what kind of modification in the local order around the alkalis are induced by the substitution of species. The mixed-alkali metaphosphate studied here were LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) and CsxLi(1-x)(PO3). The structural information was obtained using solid-state Nuclear Magnetic Resonance (NMR) techniques of 7Li, 23Na, 27Al, 31P, 87Rb and 133Cs. The connectivity between the phosphate groups and Al was analyzed studying the populations of phosphate species Q2m, with m=0,1,2 being the number of P-O-Al bridges per tetrahedron, obtained using 31P-NMR, and considering the average coordination number of Al obtained by 27Al-NMR. Through the quantitative analysis of the evolution of the Q2m population with the Al concentration, it was possible to identify the existence of a preferential structural behavior: phosphate tetrahedra share only one common corner (non-bridging oxygen) with the coordination polyhedra around Al. This medium-range organization can be sustained up to a certain concentration of Al, to the point where every phosphate establishes a P-O-Al bridge. The resulting distribution of Q2m species can be identified as binary, as a function of the Al content: { Q20, Q21} up to intermediate concentrations and { Q21, Q22} for higher concentrations. In the mixed-alkali metaphosphates, the behavior of the 23Na and 133Cs chemical shift reveals a systematic increase/decrease in the average size of the coordination environment around the alkalis as a function of the substitution. The O environment around cations with the smaller ionic radius is compressed as this species is substituted by another alkali with bigger ionic radius, and vice-versa. With respect to the alkali distribution in the glass network, the observed evolution of the chemical shift as a function of the cation substitution excludes the possibility of segregation of alkalis or phase separation. The analysis of the 23Na homonuclear magnetic dipolar coupling, through the measurement of the second moment, revealed that the mixture at atomic scale of Na with the second alkali is not random, having a higher probability of a Na being close to other Na than to other alkali. The correlation between the degree of non-random dispersion of Na and the increment in the magnitude of the mixed alkali effect in the dc conductivity of Rb-Na, K-Na and Li-Na metaphosphates indicates a fundamental connection between both phenomena. This may be the first evidence of a relation between a structural property of the alkali distribution and the mixed alkali effect of a dynamical property.