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Rare earth ion doped glasses find applications in optical and photonic devices such as optical windows, laser, and optical amplifiers, and as model systems for immobilization of nuclear waste. Macroscopic properties of these materials, such as luminescence efficiency and phase stability, depend strongly on the atomic structure of these glasses. In this thesis, I have studied the atomic level structure of rare earth doped silicate and aluminophosphate glasses by using molecular dynamics simulations. Extensive comparisons with experimental diffraction and NMR data were made to validate the structure models. Insights on the local environments of rare earth ions and their clustering behaviors and their dependence on glass compositions have been obtained. In this thesis, MD simulations have been used to investigate the structure of Eu2O3-doped silica and sodium silicate glasses to understand the glass composition effect on the rare earth ions local environment and their clustering behaviors in the glass matrix, for compositions with low rare earth oxide concentration (~1mol%). It was found that Eu–O distances and coordination numbers were different in silica (2.19-2.22 Å and 4.6-4.8) from those in sodium silicate (2.32 Å and 5.8). High tendencies of Eu clustering and short Eu-Eu distances in the range 3.40-3.90 Å were observed in pure silica glasses as compared to those of silicate glasses with much better dispersed Eu3+ ions and lower probability to form clusters. The results show Eu3+ clustering behavior dependence on the system size and suggest for low doping levels, over 12,000 atoms to obtain statistical meaningful results on the local environment and clustering for rigid silica-based glasses. The structures of four cerium aluminophosphate glasses have also been studied using MD simulations for systems of about 13,000 atoms to investigate aluminum and cerium ion environment and their distribution. P5+ and Al3+ local structures were found stable while those of Ce3+ and Ce4+ ions, through their coordination numbers and bond lengths, are glass composition-dependence. Cerium clusters were found in the high cerium glasses.P5+ coordination numbers around cerium revealed the preference of phosphorus ions in the second coordination shell. Total structure factors from MD simulations and experimental diffraction results show a general agreement from comparison for all the cerium aluminophosphate glasses and with compositional changes up to 25 Å-1. Aluminum enters the phosphate glass network mainly as AlO4 and AlO5 polyhedra only connected through corner sharing to PO4 tetrahedra identified by Q11(1 AlOx), Q12(2 AlOx), Q21(1 AlOx), and Q22(2 AlOx) species.

Glasses in the system v₂o₅-Te0₂ were prepared at intervals throughout the glass-forming composition range. The vanadium valence state was varied for each composition by the addition of elemental tellurium to reduce the melt. A chemical analysis method was devised to determine the v⁴⁺:vtotal ratio. Conductivity and thermopower measurements were made as functions of composition, valence ratio and temperature. The conductivity was found to increase as the total vanadium content increased and to be 21/2 to 3 orders of magnitude greater than that of a v₂0₅-P₂0₅ glass of similar v₂o₅ content. A maximum in conductivity was observed as the vanadium valence ratio was varied. This maximum was shifted to values around v⁴⁺:vtotal = 0.2 from the theoretically predicted value of 0.5. At temperatures above 250 K the conductivity varied exponentially with temperature with activation energies in the range 0.25 to 0.40 eV. Below this temperature there was a continuous decrease in slope of the conductivity down to the lowest temperature at which measurements were made. Thermopower was found to be negative and temperature independent above 250 K, while below this temperature it decreased in an activated manner with an activation energy of 0.02 eV. As a function of valence ratio the thermopower followed the behaviour predicted by Heikes and Ure, with the exception that the change of sign occurred at v⁴⁺:vtot ratios of around 0.2, instead of the theoretically predicted value of 0.5. (iii) Measurements were made of the optical absorption coefficient as functions of photon energy, composition, valence ratio and temperature. Temperature and composition did not affect the absorption spectrum significantly except that an absorption band appeared below the fundamental absorption edge as the glasses were reduced. The high electric field and a.c. properties of the glasses were also measured. These are consistent with hopping conduction of carriers between v⁴⁺ and v⁵⁺ sites. This data gives indirect indications of an inhomogeneous glass structure.

Dans un environnement urbain pollué, les altérations qui affectent les verres du patrimoine dépendent de facteurs intrinsèques, extrinsèques et temporels. Afin de caractériser les altérations atmosphériques résultant des interactions entre ces différents facteurs une stratégie de recherche prenant en compte un environnement multiphasique, le matériau (composition et surface) et le temps a été mise en place. Pour ce faire une étude complémentaire est menée sur des verres de vitraux exposés plusieurs centaines d'année et de verres modèles exposés en site réel et altéré artificiellement en laboratoire. Une approche multi-instrumentale et multi-échelle a été mise en place. Elle a permis d'identifier des mécanismes d'évolution de la couche d'altération (CA) notamment par la formation de lamines concentriques de ~10 nm (anciens fronts d'altération probables). L'exploration de l'impact des eaux de ruissellement montre que l'évolution de l'épaisseur de CA est dépendante à la fois d'une cinétique de diffusion (√t) et de dissolution (t). Enfin l'influence indirecte des produits néoformés sur l'altération semble jouer un rôle majeur à la fois en condition de ruissellement, avec la présence de CaCO3 qui précipite le détachement des écailles, et en milieu abrité, où la présence de K2CO3 est mise en cause dans la dissolution du réseau vitreux / In a polluted urban environment, alterations affecting heritage glasses depend on intrinsic and extrinsic factors as well as time. In order to characterize the atmospheric alteration resulting from the interactions occurring between these factors, a research strategy has been set up, taking into account the multi-phase environment, the material (composition and surface) and time. In order to do so, a complementary study was conducted on stained glasses displaying several hundred years of alterations and model-glasses exposed in-situ for a few years or artificially altered in the lab. A multi-instrument and multi-scale approach was used in this study. It allowed the identification of the mechanisms responsible for the evolution of the leached layer (LL), especially the presence of concentric 10nm thick laminae (probable traces of alteration front). The exploration of the run-off impact on alteration shows a dependency of LL thickness on both diffusion type kinetics (√t) and dissolution kinetics. Finally, the indirect impact of neoformed alteration products seems to take a major part both in run-off conditions, CaCO3 hastens the scaling, and in sheltered conditions, where K2CO3 can be cause for glass network dissolution

Este trabalho teve como principal objetivo a síntese e o estudo do processo de cristalização dos sistemas vítreos B2O3-BaO-SiO2, e B2O3-BaO-SiO2-Al2O3, assim como do sistema B2O3-BaO-SiO2 dopado com cério e prata. Amostras do sistema B2O3-BaO-SiO2 contendo 8 e 15% de SiO2, amostras do sistema B2O3-BaO-SiO2-Al2O3 contendo 2, 4 e 8 mol% de Al2O3 e amostras do sistema B2O3-BaO-SiO2 contendo 15% de SiO2 dopada com cério e prata foram caracterizadas através da técnica de analise térmica diferencial (DTA), difração de raios X (DRX), microscopia óptica (MO), espectroscopia Raman, medidas de transmissão na região do ultra-violeta/visível e medidas de luminescência. O estudo do processo de cristalização revelou que em todas as amostras prevaleceu o mecanismo de cristalização superficial. O tratamento térmico em temperaturas acima de Tg e abaixo de Tc levou a formação de uma única fase cristalina, a fase beta -BaB2O4 (beta-BBO). A morfologia dos cristais da fase beta -BBO presentes na superfície das amostras vítreas depende da quantidade de SiO2 e Al2O3. A amostra dopada com cério e prata quando submetida a radiação proveniente de um laser de HeCd e a um posterior tratamento térmico a 400 ºC apresentou somente um efeito de fotosensibilidade superficial devido a alta absorção dos átomos de cério presentes na amostra. / The main purpose of this work was the synthesis and study of the crystallization process of B2O3-BaO-SiO2 and B2O3-BaO-SiO2-Al2O3 as well cerium and silver co-doped B2O3-BaO-SiO2 glassy systems. Samples of 8 and 15 mol% SiO2-containing B2O3-BaO-SiO2 system, 2, 4 and 8 mol% Al2O3-containing B2O3-BaO-SiO2-Al2O3 system and samples 15% mol % SiO2-containing B2O3-BaO-SiO2 system doped with cerium and silver were characterized by different techniques as differential thermal analysis (DTA), X-ray diffraction (XRD), optical microscopy (OM) and Raman spectroscopy. The study of the crystallization process showed that, in all the prepared samples, surface crystallization was the predominant mechanism. The heat treatment at temperatures above Tg and below Tc led to the formation of a single crystalline phase: beta-BaB2O4 (abbreviated as beta-BBO). The morphology of the crystals that appear at the glass surface depends on the amount of SiO2 and Al2O3 in the systems. When subjected to radiation from a HeCd laser and a subsequent heat treatment at 400 ºC, the glass system doped with cerium and silver, showed a photosensitivity effect on the surface due to high absorption of cerium atoms present on the glass sample.

Utilizando amostras de vidro aluminossilicato, 21SiO2·9Al2O3·58Tb2O3·4,0MgO·3,0B2O3·2,0ZnO·1,0Sb2O3 (mol%) e fluorfosfato, 7,49NaPO3·16,45MgF2·16,38CaF2·17,66SrF2·11,63BaF2·30,39AlF3 (mol%) adicionado de 8Tb2O3 e 0,5Ce2O (mol), foram realizadas medidas de absorção óptica, tempo de vida de emissões e luminescência nas faixas do ultravioleta e visível dos íons Tb3+. As eficiências quânticas das emissões para o íon Tb3+, 0,90 (90 %), para o vidro aluminossilicato e 0,69 (69 %), para o vidro fluorfosfato, foram determinadas a partir das razões entre os tempos de vida experimentais, obtidos da experiência de tempo de vida e os tempos de vida teóricos, obtidos das informações de absorção óptica e teoria de Judd- Ofelt. As informações de absorção óptica também possibilitaram identificar as prováveis excitações e emissões observadas nos espectros de luminescência em ambos os vidros estudados. Para determinação dos tempos de vida teóricos, foi necessário calcular as probabilidades de transições radiativas que dependem dos parâmetros de Judd-Ofelt, cujos valores encontrados foram 2 = (2,4 ± 0,2)10-19 cm2, 4 = (3,4 ± 0,3)10-20 cm2 e 6 = (1,5 ± 0,2)10-20 cm2, para o vidro aluminossilicato, e 2 = (7,7 ± 0,6)10-20 cm2, 4 = (0,61 ± 0,05)10-20 cm2 e 6 = (0,69 ± 0,06)10-20 cm2, para o vidro fluorfosfato. Tais valores mostraram-se compatíveis aos da literatura pesquisada, confirmando os valores satisfatórios das eficiências quânticas das emissões dos íons Tb3+. / Samples of glasses 21SiO2·9Al2O3·58Tb2O3·4,0MgO·3,0B2O3·2,0Si2O·2,0ZnO·1,0Sb2O3 (mole %) aluminosilicate and 7,49NaPO3·16,45MgF2·16,38CaF2·17,66SrF2·11,63BaF2·30,39AlF3 (mole %) fluorphosphate added of 8Tb2O3 and 0,5Ce2O (mole) were studied by optical absorption, luminescence and emissions lifetime measurements for the Tb3+ ions. The quantum efficiencies of the Tb3+ emissions, 0,90 (90 %), for the aluminosilicate glass and 0,69 (69 %), for the fluorphosphate glass, were determined using the emissions lifetimes and theoretical lifetimes, obtained from the experimental optical absorption data and Judd-Ofelt theory. The information obtained from the optical absorption spectra allowed the identification of the more likely excitations and emissions observed in the luminescence spectra of the glasses. For the determination of the theoretical lifetimes it was necessary to calculate the radiactive transition probabilities which are dependent of the Judd-Ofelt parameters, whose values were found as 2 = (2,4 ± 0,2)10-19 cm2, 4 = (3,4 ± 0,3)10-20 cm2 and 6 = (1,5 ± 0,2)10-20 cm2, for the aluminosilicate, and 2 = (7,7 ± 0,6)10-20 cm2, 4 = (0,61 ± 0,05)10-20 cm2 and 6 = (0,69 ± 0,06)10-20 cm2, for the fluorphosphate glasses. The results are in good agreement literature examined, and confirm the satisfactory values of the quantum efficiency for the Tb3+ emissions.

Há um crescente interesse científico e tecnológico voltado para compostos cristalinos de óxido de bismuto com óxidos de germânio, silício ou titânio, por exibirem propriedades eletro e magnetoópticas, fotocondutivas e piezoelétricas. Sistemas vítreos com propriedades similares a estes compostos são de alto interesse, devido ao baixo custo e facilidade no procedimento de preparação em relação aos monocristais. Este trabalho teve como finalidade analisar o efeito de adição de óxidos de boro e gálio, ao sistema binário composto por óxido de bismuto com óxidos de germânio. A amostra vítrea de composição 45BiO1.5:40BO1.5:15GeO2 (BBG-8), apresentou alta reprodutibilidade e estabilidade térmica (ΔT=132, Hr=0.34 e S=26.74), sendo assim, selecionada para o estudo da cristalização. As fases cristalizadas nesta amostra, durante tratamento térmico, foram determinadas por análises de difração de raios-X e medidas composicionais. Foram cristalizadas as fases Bi6B10O24 e Bi4Ge3O12, sendo a última, a fase de interesse para nosso estudo. Métodos térmicos foram utilizados no estudo da cristalização da fase Bi4Ge3O12, possibilitando a verificação da energia de ativação (≈ 54Kcal/mol) pelos métodos de Ozawa e Chen, e a direcionalidade do crescimento dos cristais (nmédio=1.12). A fim de obtermos mais informações a respeito de cristalização utilizamos óptica eletrônica. / The sillenite crystals, Bi12MO20 (M = Ge, Si, Ti), are interesting for applications such as optical memories, holography or optical phase conjugating devices. The eulytite crystals, Bi4M3O12, have been studied for their electro-optical, electromechanical and luminescence properties. These crystals am used as scintillators or, when doped with rare-earth elements, as laser materials. The study of glass systems, having properties similar to those crystals, is of high interest because of the lower cost and easier preparation procedures with respect to single crystals. The purpose of this work is the study of interaction of B2O3 and Ga2O3 with binary system Bi2O3-GeO2. The glassy sample BBG-8 (45BiO1.5:40BO1.5:15GeO2), was chosen far crystallition study, due to its high reproducibility and thermal stability. The presence of crystalline phases (Bi6B10O24 and Bi4Ge3O12), obtained after heat treatment, was investigated by powder X-ray diffraction and compositional analysis. The crystalline eulytite phase (Bi4Ge3O12) is an interest of our study. Thermal methods were used on the study of Bi4Ge3O12crystallization process of the sample BBG-8, and the value obtained, by means of Ozawa and Chen methods, was approximately 54Kcal/mol, and the directionality of crystal growth (n average) was equal to 1.12. To obtain further information on the crystallization mechanism we also performed microphotographic analysis.

Este trabalho apresenta um estudo sobre a modificação e cristalização superficial dos sistemas vítreos 40BaO-45B2O3-15TiO2 (BBT) e 42BaO-42B2O3-16SiO2 (BBS) utilizando a radiação proveniente de um laser modulado de CO2. Três diferentes parâmetros experimentais foram avaliados: a potência do laser, o tempo de exposição à radiação e a presença de micropartículas da fase ?-BaB2O4 (?-BBO) na superfície da amostra. As modificações causadas pela exposição das amostras à radiação laser foram caracterizadas através das técnicas de perfilometria, microscopia óptica, espectroscopia micro-Raman e difração de raios X. De uma maneira geral, os resultados mostram que a escolha adequada da potência do laser e do tempo de exposição à radiação leva a uma modificação superficial ou a uma modificação seguida da cristalização superficial da região exposta a radiação. A presença de micropartículas da fase ?-BBO na superfície da amostras influi de maneira significativa no processo de modificação e cristalização superficial. A presença dessas micropartículas induziu a cristalização da fase ?-BBO com um relativo alto grau de orientação preferencial na direção (006), permitindo a observação visual do efeito de geração de segundo harmônico em algumas amostras. Estudos de micro-fotoluminescência mostraram que o íon Sm3+ quando adicionado a matriz vítrea BBT apresenta um alto grau de desordem mesmo em amostras cristalizadas. No entanto, para a matriz BBS, este estudo mostra uma possível incorporação do íon terra-rara na região cristalizada. / This work describes a study regarding the permanent modification and/or crystallization of 40BaO-45B2O3-15TiO2 (BBT) and 40BaO-45B2O3-16SiO2 (BBS) glass compositions when exposed to a continuous CO2 laser beam radiation. The effect of three experimental parameters was evaluated: the laser power, the radiation time exposure and the presence of micro-particles of the ?-BaB2O4 crystalline phase on the glass sample surface prior to radiation. The geometry of permanent modification and the crystallization process were characterized by using the perfilometry, optical microscopy, Micro-Raman spectroscopy and X-ray diffraction (XRD) techniques. The results show that the surface modification and crystallization can be controlled by a suitable choice of the laser power and radiation time exposure. In all samples, it was observed that the presence of ?-BaB2O4 micro-particles on the sample surface affects significantly equally the permanent modification and the crystallization process. The preferential orientation of the ?-BaB2O4 on the (006) plane direction allowed the observation of a relative high intense second harmonic generation effect. The micro-photoluminescence study shows that the Sm3+ ion in BBT glass sample present a high degree of disorder, even in the crystallized samples. On the other hand, when added to the BBS glass sample, it seems that the Sm3+ ions are incorporated onto the crystallized region.

Vidros metálicos maciços fazem parte de um novo grupo de materiais de características distintas das ligas metálicas convencionais. O processamento dessas ligas ainda não foi bem consolidado nos centros de pesquisa brasileiros devido à dificuldade de processamento. Este trabalho descreve o desenvolvimento de um sistema de síntese e coquilhamento para a obtenção de vidros metálicos maciços. O sistema foi avaliado quanto ao desempenho e repetibilidade das amostras. A liga Cu46Zr42Al7Y5, formadora de vidro, foi processada e analisada através da caracterização por difração de raios-X (DRX), calorimetria exploratória diferencial (DSC) e microscopia eletrônica de varredura (MEV). Foram obtidas duas amostras com estrutura totalmente amorfa em espessuras médias de até 1,5 mm e uma amostra com aproximadamente 5,5 mm de espessura amorfa. A temperatura de transição vítrea observada foi igual às relatadas na literatura científica. Assim, o sistema desenvolvido mostrou-se eficiente para o controle da atmosfera, resfriamento rápido das amostras e outras variáveis que são obrigatórias para o sucesso na formação de estruturas amorfas em ligas por fundição. / Bulk metallic glasses are new materials with different features in comparison with conventional metallic alloys. The processing techniques of such alloys are still not consolidated in Brazilian research centers because of inherent processing difficulties. This work describes the development of a system for the synthesis and casting of bulk metallic glassy samples. The system was evaluated by its performance and alloys repeatability. The Cu46Zr42Al7Y5 alloy was processed and analyzed for the formation of amorphous structure through X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). It was produced two samples with fully amorphous structure at average thickness of 1.5 mm and one sample reaching around 5.5 mm of fully glassy structure. The same glass transition temperature reported on scientific literature was found in the alloys processed in the present work. Thus, the system has shown efficiency on atmosphere control, sample quenching and others important variables that are, by default, necessary to succeed in amorphous structure formation.

Foram estudados compósitos poluméricos e vidros fluoroindatos utilizando as espectroscopias de Ressonância Magnética Nuclear (RMN) pulsada e Ressonância Paramagnética Eletrônica (RPE). O estudo de RMN do 1H nos compósitos baseado no polímero polióxido de etileno e partículas de carbono permitiu diferenciar as mobilidades das cadeias poluméricas e identificar as contribuições destas fases. A partir das medidas de RPE foi possível sugerir uma interpretação das interações entre as partículas de carbono nos compósitos. Nos vidros fluoroindatos foi estudado o processo de cristalização, sendo acompanhada sua influência na relaxação nuclear do 19F. A cristalização foi observada por RPE nos vidros dopados com Cu2+, Mn2+ e Gd3+, sendo verificadas as alterações locais causadas por este processo. / Polymeric composites and fluoroindate glasses were studied using pulsed Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies. Study of the composite formed by the polymer poly-ethylene oxide and carbon particles allowed us to distinguish the mobilities of polimeric chains and to identify the contributions from different phases. From EPR measurements it was possible to suggest an interpretation of the interactions between carbon particles in the composites. The main objective in the fluoroindate glasses study was to follow the crystallzation process. The 19F NMR measurements allowed to the observation of the influence of this process in the nuclear relaxation. The crystallization was also tracked by EPR spectroscopy in the doped glasses with the paramagnetic ions Cu2+, Mn2+ and Gd3+. This was accomplished by observing the local alterations caused by that process.