Call number: LD2668 .T4 1985 O83 / Master of Science

It is important to optimize glass compositions for their specific purpose but also for the efficiency of the production process, the manufacturing of glass. This will be beneficial economically and environmentally. Today many processes and glass compositions are already optimized, but due to more strict legislation on toxic elements and substances there must be changes in many glass compositions. One of these elements is antimony; the oxide is used as fining agent to obtain a bubble free glass within a reasonable process time. One aim with this thesis is to obtain a deeper understanding of the fining mechanism in 20R2O-10MO-70SiO2 (R=Na and/or K, M = Ca and/or Ba, Mg, Sr) glasses in order to minimise the amount of Sb2O3. Another intention is to study the structure of 20R2O-10CaO-70SiO2 (R = Na, K) with Cu2+ as probe ion and thus get a deeper knowledge of the surrounding glass matrix.  The optical basicity scale is used to determine the acid/base character of the different glass compositions.   Fining efficiency results showed a remarkable increase of the number of remaining bubbles when the glass contains either approximately equal amounts of Na and K or Ca and Ba, Mg or Sr. The much higher number of bubbles in the potassium containing glasses compared to the sodium containing is explained by the increase in viscosity, the increase in optical basicity and thus lower oxygen activity. The differences in the fining efficiency when altering alkaline earth ions cannot be explained by the optical basicity values, it seems to be a more complicated situation.   This thesis also reports maximum in Vickers hardness and packing density as well as minimum in glass transition temperature for the mixed alkali glasses. The mixed alkaline earth glasses do not exhibit any clear nonlinear behaviour. Raman spectroscopy measurements showed a variation in the network connectivity which has a clear relation to the optical basicity of the different glass compositions. The combination of UV-Vis-NIR and X-ray absorption spectroscopy measurements showed that the coordination sphere for Cu(II) is a tetragonal distorted octahedron with two elongated Cu-O bonds along the z axis. There were no trends in the degree of tetragonal distortion, thus it was about the same for all the investigated glass compositions. Cu(I) is found to be coordinated by two oxygen ligands in mainly linear coordination sphere, evidenced from X-ray absorption spectroscopy.

Chalcogenide glasses and glass-ceramics present a high interest for the production of thermal imaging lenses transparent in the 3-5 μm and 8-12 μm windows. However, chalcogenide glasses are conventionally synthesized in sealed silica ampoules which have two major drawbacks. First, the low thermal conductivity of silica limits the sample dimensions and second the silica tubes employed are single use and expensive, and represent up to 30% of the final cost of the material. The present work therefore addresses the development of innovative synthesis methods for chalcogenide glass and glass-ceramics that can present an alternative to the silica tube route. The method investigated involves melting the raw starting elements in reusable silica containers. This method is suitable for the synthesis of stable chalcogenide glasses compositions such as GeSe₄ but uncontrolled crystallization and homogenization problems are experienced for less stable compositions. The second approach involves preparation of amorphous chalcogenide powders by ball milling of raw elements. This mechanosynthesis step is followed by consolidation of the resulting powders to produce bulk glasses. Hot Uniaxial Pressing is suitable for compositions stable against crystallization. However, uncontrolled crystallization occurs for the unstable 80GeSe₂-20Ga₂Se₃ glass composition. In contrast consolidation through Spark Plasma Sintering (SPS) allows production of bulk glasses in a short duration at relatively low temperatures and is appropriate for the synthesis of unstable glasses. A sintering stage of only 2 min at 390°C is shown to be sufficient to obtain infrared transparent 80GeSe₂-20Ga₂Se₃ bulk glasses. This method enables the production of lenses with a 4-fold increase in diameter in comparison to those obtained by melt/quenching technique. Moreover, increasing the SPS treatment duration yielded infrared transparent glass-ceramics with enhanced mechanical properties. This innovative synthesis method combining mechanosynthesis and SPS has been patented in the framework if this study. The controlled etching of 80GeSe₂-20Ga₂Se₃ glass-ceramics in acid solution yields nanoporous materials with enhanced surface area. The porous layer created on the surface of the glass-ceramic is shown to play the role of anti-reflection coating and increase the optical transmission in the infrared range by up to 10%. These materials may have potential for the production of sensors with increased sensitivity in the infrared. The influence of indium and lead addition on the thermal and optical properties of the 80GeSe₂-20Ga₂Se₃ glass has also been assessed. Increased In or Pb contents tend to decrease the Tg of the glasses and shift the optical band gap toward higher wavelengths. A systematic ceramization study emphasizes the difficulty of controlling the crystallization for glasses in the systems GeSe₂-Ga₂Se₃-In₂Se₃ and GeSe₂-Ga₂Se₃-PbSe. No crystallization of the In₂Se₃ and PbSe crystalline phase was obtained. Finally, the possibility of producing rare-earth doped 80GeSe₂-20Ga₂Se₃ glass-ceramics transparent in the infrared region up to 16 μm is demonstrated. Enhanced photoluminescence intensity and reduced radiative lifetimes are observed with increased crystallinity in these materials.

Une nouvelle famille de vitrocéramiques, avec une microstructure inédite, a été fabriquée par une cristallisation contrôlée des verres dans le système GeSe2-Sb2Se3-CuI. L'influence de la composition et du processus de cristallisation des verres de base, sur la microstructure et sur l’intensité du photo-courant des vitrocéramiques a été étudiée. Une composition optimisée, le 40GeSe2-40Sb2Se3-20CuI, a été particulièrement étudiée avec des résultats suivants: (1) Après une étude systématique , il a été constaté que cette composition donne la plus forte intensité de photo-courant parmi tous les verres étudiés dans ce système pseudo-ternaire GeSe2-Sb2Se3-Cul. Il a été également démontré que le photo-courant généré par différentes vitrocéramiques est non seulement déterminé par la composition, mais aussi par la microstructure composite de la vitrocéramique, qui est déterminée par le processus de céramisation. Ce processus de céramisation a ensuite été optimisé. Par rapport au procédé de traitement thermique en deux étapes, le procédé en une seule étape à basse température est une stratégie plus appropriée pour obtenir une microstructure efficace, favorisant la séparation des charges, construisant des canaux conducteurs et donnant une intensité de photo-courant élevée dans la vitrocéramique. (2) La microstructure composite inédite, discutée ci-dessus est composée de micro-domaines conducteurs interconnectés, formées par des cristaux Sb2Se3 faiblement conducteur en forme de tiges, couverts par des nano-cristaux de Cu2GeSe3 beaucoup plus conducteurs. Le procédé le plus probable de la photo-génération efficace des charges est le suivant: les photons sont efficacement et essentiellement absorbés par Sb2Se3 ainsi que par Cu2GeSe3. Les hétérojonctions formées par les Sb2Se3 du type n et les Cu2GeSe3 du type p, favorisent la séparation de charges, tandis que les Cu2GeSe3 interconnectées et conductrices fournissent des canaux conducteurs et jouent ainsi le rôle de collecteur efficace de charges. Il en résulte ainsi une très longue durée de vie des porteurs de charge et un fort photo-courant. (3) La formation de nano-hétérojonctions entre les cristaux Sb2Se3 et Cu2GeSe3 dans un seul micro-domaine peut conduire à une séparation efficace des électrons et des trous photo-générés. Par conséquent, pour application photo-catalytique, il n’est pas nécessaire de former des canaux conducteurs (conducteurs interconnectés des micro-domaines) dans l'ensemble de la vitrocéramique. De plus, la formation de ces canaux conducteurs, nécessiterait une augmentation de la durée ou/et la température de recuit, pouvant conduire à une diminution de l'activité photo-catalytique à cause de la taille relativement grande des grains cristallins. Les vitrocéramiques optimisées montrent une bonne capacité de désamination oxydative et une forte activité photo-catalytique en général, démontrant ainsi son potentiel en tant que photo-catalyseur efficace. / A totally new family of glass ceramics with a unique microstructure was fabricated by controlling the crystallization of the GeSe2-Sb2Se3-CuI glass system. The influences of the material composition and the crystallizing process of the precursor glasses on the microstructure and photocurrent of the prepared glass ceramics were investigated. An optimized composition, 40GeSe2-40Sb2Se3-20CuI, was particularly studied with the following significant results: (1) After a systematic study, it was found that this particular composition shows the highest photocurrent density among all studied glasses in the pseudo-ternary GeSe2-Sb2Se3-CuI system. It is also demonstrated that the photocurrent generated by different glass ceramics is not only determined by the composition, but also by the composite microstructure of the glass ceramic, which is determined by the ceramisation process. This process was then carefully studied. Compared with the two-step heat treatment process, the single-step process at a low temperature is a more efficient strategy to build up an efficient composite microstructure, which promotes charge carrier separation and provides a conductive channel, leading to a high photocurrent intensity in the glass ceramic. (2) The above-mentioned unique composite microstructure is composed of interconnected conductive microdomains, formed by low conductive rod-like Sb2Se3 crystals, covered by relatively high conductive Cu2GeSe3 nanocrystals. The most likely process for efficient photogeneration of charges is proposed as follows: photons are efficiently and essentially absorbed by Sb2Se3 as well as by Cu2GeSe3, and then the heterojunction formed by n-type Sb2Se3 and p-type Cu2GeSe3 promotes the charge separation, whereas the oriented and relatively conductive Cu2GeSe3 aggregate provides a conductive channel and plays the role of efficient charge collector. This structure results in exceptionally long lifetime of charge carriers (around 16 µs) and high photocurrent (at least 100 times higher than any of Sb2Se3 and Cu2GeSe3 individually). (3) The formation of nano-heterojunctions between Sb2Se3 and Cu2GeSe3 crystals within a single conductive microdomain can fully lead to an efficient separation of photo-generated electrons and holes. Therefore, for the photocatalytic application, it is unnecessary to form conductive channels (interconnected conductive microdomains) in the whole glass ceramic. Moreover, in order to form conductive channels, the necessary increase of annealing time or/and temperature may decrease the photocatalytic activity due to its relatively large crystal grain size. The optimized glass ceramic exhibits a good oxidative deamination ability and high photocatalytic activity, demonstrating its potential as an efficient photocatalyst.

A falta de ordenamento atômico de longo alcance dos vidros metálicos produz propriedades superiores em comparação com as mesmas ligas em condição cristalina. Ligas amorfas à base de Zr se oxidam facilmente, tornando-se frágeis, além do aumento do oxigênio levar a um aumento na taxa crítica de resfriamento necessário para a formação de vidro. O presente estudo mostrou a influência do oxigênio e da taxa de resfriamento (representada pelo diâmetro da amostra) na formação de fases cristalinas em duas ligas amorfas baseadas em Zr: Zr48Cu46,5Al4Nb1,5 e Zr52,5Cu17,9Ni14,6Al10Ti5 (Vit 105). As amostras de cada liga foram produzidas por fusão à arco elétrico com coquilhamento em molde de cobre refrigerado à água obtendo-se amostras de 2, 3, 4, 5 e 6 mm de diâmetro. As técnicas de caracterização empregadas foram medidas de oxigênio em equipamento LECO pelo princípio de fusão em gás inerte, quantificação da fração amorfa por análise de imagem de microscopia ótica, identificação das fases cristalinas por difração de raios-X (DRX) convencional e síncrotron, realização de refinamento Rietveld para quantificação da fração amorfa pelo método do grau de cristalinidade no software TOPAS e da fração das fases cristalinas, análises de microscopias eletrônicas de varredura (MEV) e de transmissão (MET). A fração amorfa formada nas ligas tende a diminuir com o aumento do oxigênio e com o aumento do diâmetro da amostra. Foram criados os mapas de formação de fases para ambas as ligas, onde observou-se que a liga Vit 105 possui uma maior tendência de formação vítrea (TFV) do que a liga Zr48Cu46,5Al4Nb1,5. / The lack of long-range atomic ordering in metallic glasses produces better properties when compared with the same alloys in crystalline condition. Zr-based amorphous alloys easily oxidize and becomes brittle with oxygen increases, leading to an increase in the critical cooling rate required for glass formation. This study aimed to analyze the influence of oxygen and cooling rate (represented as sample diameter) on the crystalline phase formation in two amorphous alloys based on Zr: Zr48Cu46.5Al4Nb1.5 and Zr52.5Cu17.9Ni14.6Al10Ti5 (Vit 105). The samples were produced by electric arc-melting followed by suction casting in a water-cooled copper mold producing samples with 2, 3, 4, 5 and 6 mm in diameter. The characterization techniques used were: oxygen measurement in LECO equipment by the fusion inert gas principle, optical microscopy to amorphous fraction quantification by image analysis, conventional and synchrotron X-ray diffraction (XRD) to identification of crystalline phases by Rietveld refinement with quantification of the amorphous fraction by the degree of crystallinity method on TOPAS software along with quantification of crystalline phases, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The amorphous fraction formed in the alloys tended to decrease with increasing oxygen content and sample diameter. Phase formation maps were created for both alloys, where it was observed that Vit 105 alloy has a higher glass forming ability (GFA) than Zr48Cu46.5Al4Nb1.5 alloy.

A fotosensibilidade à radiação dos vidros fosfatos é uma propriedade que tem despertado grande interesse nas últimas décadas12. No presente trabalho, foi realizado um estudo sistemático e comparativo dos fenômenos fotoinduzidos por meio da caracterização de filmes do sistema (Sb(PO3)3)n - Sb2O3 quando dopados com óxido de cobre (CuO). Neste estudo, foram observadas as mudanças fotoestruturais e os efeitos causados por ação dos Raios-X. Os danos causados pela radiação sobre as amostras foram investigados através de medidas de perfilometria, Difração de Raio-X, EPR (Electron Paramagnetic Resonance) e SFG (Sum Frequency Generation) para a análise morfológica dos filmes, usadas para a compreensão das mudanças estruturais ocorridas. Além disso, foram realizadas medidas de absorção UV-Vis para a determinação de suas propriedades ópticas. Estudos recentes mostraram que o sistema vítreo (Sb(PO3)3)n - Sb2O3 sofre efeito de fotoclareamento e fotocontração, devido a irradiação com laser UV16. Nossos resultados mostraram que filmes do mesmo sistema vítreo dopados com 3%CuO, quando irradiados com Raio-X, apresentam efeito de fotoescurecimento, que foi observado visivelmente, e fotoexpansão, que foi confirmado por medidas de perfilometria. Ambos os efeitos, fotoescurecimento e fotoexpansão, ocorrem simultaneamente nos filmes irradiados e tem uma evidente dependência com a variação de parâmetros como espessura do filme e tempo de exposição à radiação / The photosensibility to radiation of phosphate glasses is a property that has attracted great interest in the last decades12. In this work, we realized a systematic and comparative study of the photoinduced phenomena through characterization of the doped copper oxide (CuO) (Sb(PO3)3)n-Sb2O3 system films. In this study, we observed the photostructural changes and the effects caused by X-ray. The radiation damage on the samples was investigated by measurements of profilometry, X-ray diffraction, EPR (Electron Paramagnetic Resonance) and SFG (Sum Frequency Generation) for morphological analysis, used for the understanding of the structural changes occurred. Besides that, we realized UV-Vis absorption measurements for the determination of its optical properties. Recents studies have shown the (Sb(PO3)3)n-Sb2O3 glassy system has photobleaching and photocontraction effects, when irradiated with UV laser16. Our results have shown that films of the same glassy system doped with 3%CuO, when irradiated with X-ray, show the photodarkening effect, which was visually observed, and photoexpansion, which was confirmed by profilometry measurements. Both effects, photodarkening and photoexpansion, occur simultaneously in the irradiated films and have a evident dependence with the parameters changes, as film thickness and radiation exposure time.

Esse trabalho descreve a caracterização térmica, estrutural e elétrica do sistema vítreo 50B203-(50-x)PbO-xLiF com x variando de 0,0 a 50,0. A técnica de calorimetria diferencial exploratória (DSC) foi utilizada na determinação das temperaturas características. A difratometria de raios x foi utilizada na detecção e identificação de fases cristalinas originadas durante a síntese ou durante o processo de aquecimento das amostras. As técnicas de espectroscopia Raman e Ressonância Magnética Nuclear (RMN) foram utilizadas na obtenção de informações estruturais da ordem a curto alcance em função da composição das amostras. A técnica de espectroscopia de impedância complexa foi utilizada na determinação das condutividades elétrica em função da quantidade de LiF e da temperatura. Amostras vítreas sem a presença de fases cristalinas foram obtidas para composições contendo no máximo 40moI % de LiF. Através da análise da medida de densidade, foi possível constatar que o aumento da quantidade de LiF leva a formação de uma estrutura mais aberta. A análise do espectro Raman das amostras vítreas mostrou que com o aumento da concentração de LiF, ocorre uma mudança significativa nas unidades estruturais borato presentes nas amostras. Na amostra vítrea contendo 40 mol% de LiF observou-se a existência de uma superunidade estrutural formada por diferentes unidades borato. Apesar dessa variação das unidades borato, as medidas de RMN do 11B mostraram que a razão entre as unidades trigonal B03 e tetraédrica B04 permanece praticamente constante em todo intervalo de composição analisada. A condutividade elétrica aumenta à medida que a concentração de LiF aumenta devido ao aumento do numero de portadores de carga. A 330°C uma condutividade de 3,55 x 10-5 S/cm foi medida para a amostra contendo 40 moI % de LiF. Utilizando as amostras contendo 40 e 45 mol% de LiF preparadas e caracterizadas durante a realização desse trabalho, foi possível construir um dispositivo para ser utilizado na demonstração do processo de condução elétrica em materiais vítreos condutores para alunos do ensino médio / This work describes the thermal, structural and electric characterization of 50B203-(50-x)PbO-xLiF glass system with x varying from 0,0 to 50,0. The differential scanning calorimetry (DSC) technique was used to determine the glass transition and the crystallization temperatures. The X-ray diffraction technique was used to detect and in the identification of the crystallized phases present on the glassy samples after the melt and during the heating. The Raman spectroscopy and the Nuclear Magnetic Resonance techniques were used in order to verify the structural changes induced by the substitution of PbO by LiF on the anionic borate units and on the B03/B04 species ratio. The impedance complex spectroscopy technique was used to evaluate the variation of the electrical conductivity and activation energy as a function of the LiF content. Homogenous glassy sample containing less than 45 mol % of LiF without any trace of crystallization were obtained. The analysis of the Raman spectra shows that as the amount of LiF increases the concentration of anionic borate species changes and that these changes are an indicative of the formation of B-F bonds. However, according to the 11B NMR data, these structural rearrangement should be of such nature that the ratio sup>[3]B/[4]B is near1y invariant. As expected, the electrical conduction increases as the amount of LiF increases because the number of carriers increases. At 330°C; , the conductivity varies from 3.93 x 10-10 (S/cm) for the sample without LiF to 3.55 x 10-5(S/cm) for the sample containing 40 mol % of LiF. The activation energy (Ea) varied respectively from 1.55 eV to 0.97 eV. Using the glassy samples with 40 and 45 mol% of LiF, we could built a set up that can be used to demonstrate the electrical conduction process on glass materials to high school students

Neste trabalho são apresentadas a síntese e caracterização das propriedades luminescentes dos sistemas vítreos TeO2-ZnO e TeO2-ZnO-PbO-Na2O dopados com íons de európio e térbio contendo nanopartículas (NPs) metálicas de prata, ouro e cobre, para aplicações em dispositivos fotônicos. Estes vidros possuem uma larga região de transmissão (350-6500 nm), elevada estabilidade química, resistências mecânica e térmica, baixa energia de fônon (em torno de 700 cm-1) e alto índice de refração (~ 2,0). Por meio de medidas de absorção óptica foi observada a incorporação dos íons de terras-raras na forma trivalente, responsável pelo fenômeno de luminescência nos vidros e a presença de bandas de absorção relacionadas à ressonância dos plasmons superficiais (RPS), localizadas em aproximadamente 490 nm (no caso das NPs de prata), em 500 nm (no caso das NPs de ouro) e em torno de 800 nm (no caso das NPs de cobre). A caracterização das NPs metálicas foi realizada por meio da Microscopia Eletrônica de transmissão auxiliada pelas técnicas de difração de elétrons e espectrometria de energia dispersiva (EDS) e permitiu a observação de NPs metálicas, cristalinas e de diversos formatos e tamanhos. As medidas de emissão foram realizadas excitando as amostras em 405 nm para as dopadas com Eu3+ e 377 nm para as amostras dopadas com Tb3+, por meio de um espectrômetro de fluorescência, com lâmpada de Xenon de pulsos de 2 a 3 s. Foram medidas bandas de emissão associadas à emissão do Eu3+ em 580 nm, 590 nm, 614 nm, 650 nm e 695 nm devidas às transições 5D07FJ (com J = 0 até 4). A banda situada em 614 nm, associada a uma transição de dipolo-elétrico é a mais intensa, por ser mais sensível às mudanças do campo local provocado pela presença das NPs metálicas. Para as amostras dopadas com Tb3+ foram observadas emissões em 485 nm, 550 nm, 590 nm e 623 nm, associadas às transições 5D47FJ (com J = 6 até 3), sendo a emissão em 550 nm associada também a uma transição de dipolo-elétrico e portanto a mais sensível às alterações do campo local provocado pela presença das NPs metálicas. Para as amostras codopadas com íons de Eu3+ e Tb3+, foram observados aumentos significativos da luminescência referente à emissão em 614 nm na presença de NPs de prata. A obtenção de aumento da luminescência dos íons de Eu3+ somente pela transferência de energia proveniente do Tb3+ não é um mecanismo trivial. Entretanto, foi observado em amostras preparadas com diferentes concentrações de íons aceitadores e doadores e intensificada também na presença de NPs de prata. Os aumentos ocorridos na luminescência são provavelmente causados pelo aumento do campo local nas proximidades dos íons de terras-raras e por processos de transferência entre as NPs metálicas e os íons de terras-raras. Nestes casos a distância entre os íons de terras-raras e as NPs está compreendida entre 5 nm e 20 nm. Portanto, a presença das NP desempenha um papel importante para o aumento da luminescência, permitindo o desenvolvimento de novos materiais com aplicações em nanofotônica. / This work presents the synthesis and characterization of luminescent properties of vitreous systems TeO2-ZnO e TeO2-ZnO-PbO-Na2O doped with ions of europium and terbium containing silver, gold and copper nanoparticles (NPs), for applications in photonic devices. These glasses have a large window transmission (350-6500 nm), chemical stability, mechanical and thermal resistance, low phonon energy (around 700 cm-1) and high refraction index (~2,0). The optical absorption measurement showed the incorporation of rareearths ions in the trivalent form, responsible for the luminescence phenomenon in the glasses and the presence of absorption bands related to the surface plasmons resonance (SPR), located in approximately 490 nm (in the case of silver NPs) in 500 nm (in the case of gold NPs) and around 800 nm (in the case of copper NPs). The characterization of the metallic NPs was perfomed with transmission electron microscopy (TEM) with the aid of electron diffraction and energy dispersive spectroscopy techniques that allowed the observation of metallic NPs, crystalline with several shapes and sizes. The measurements were made through with excitation of 405 nm for samples doped with Eu3+ and 377 nm for samples doped with Tb3+, using a fluorescence spectrometer, with Xenon lamp with pulses varying from 2 to 3 s. The bands associated to Eu3+ emission were measured at 580 nm, 590 nm, 614 nm, 650 nm and 695 nm due to the transitions 5D07FJ (with J = 0 to 4). The band situated at 614 nm related to electric dipole transition is the most intense because it is sensitive to changes in the local field, caused by the presence of metallic NPs. For samples doped with Tb3+ it was observed emissions at 485 nm, 550 nm, 590 nm and 623 nm, associated with the transitions 5D47FJ (with J = 6 to 3) being the 550 nm emission also related to electric dipole transition and consequently the most sensitive to changes in the local field, caused by the presence of metallic NPs. For the samples codoped with Eu3+ and Tb3+ ions it was observed significative enhancement of the luminescence at 614 nm emission in the presence of silver NPs. The achievement of the enhancement of the luminescence of Eu3+ ions only by energy transfer from Tb3+ is not a trivial mechanism. However, it was observed in samples prepared with different concentrations of acceptor and donors ions and intensified in the presence of NPs silver. The enhancement of the luminescence is probably caused by the increase of the local field around the rare earth ions and by processes of energy transfer between the metallic NPs and the rare earth ions. In these cases the distance between the rare earth ions and the metallic NPs ranges from 5 to 20 nm. Thus, the presence of metallic NPs plays an important role for the enhancement of the luminescence, allowing the development of new materials with application in photonic.

As amostras de vidro aluminoborato de bário (BABAL), obtido a partir da estrutura 20 Al2O3. 50 B2O3. 30 BaO mol% dopadas com manganês foram preparadas e caracterizadas pelas técnicas de absorção óptica (AO), ressonância paramagnética eletrônica (RPE) e termoluminescência (TL). O presente estudo está centrado nos íons manganês e nas suas interações com os vizinhos mais próximos que são os átomos de oxigênio e outros íons que o circundam dentro da matriz vítrea. As amostras do vidro BABAL não dopadas e irradiadas com radiação gama apresentam uma banda de absorção óptica com um máximo em 555 nm, a qual foi associada ao BOHC (boron hole center). As amostras do vidro BABAL dopadas com MnO e MnO2 não apresentaram uma mudança significativa com a radiação, pois a janela óptica relativamente reduzida não permite observar diretamente as principais transições referentes ao Mn2+. Para os vidros BABAL dopados com baixas dopagens de MnO2 (< 0,1 mol%) foi demonstrada a redução de Mn4+ para Mn3+ e posteriormente para Mn2+ até atingir a distribuição de equilíbrio nos estados de oxidação. Assim, a utilização dos diagramas de Tanabe e Sugano associados aos íons Mn2+ e Mn3+ em sítios octaédricos forneceram os resultados Mn2+=12610 ±100 cm-1 e Mn3+=21440 ±100 cm-1, respectivamente, para os vidros BABAL dopados com íons de manganês. Para os vidros Li2O.CaF2.B2O3 produzidos e caracterizados por Rao et al. calculamos a intensidade do campo cristalino, obtendo os resultados para o íon Mn2+ é 13740 ± 100 cm-1 e para o íon Mn3+ é 20030 ± 100 cm1-. Para o caso de amostras BABAL não irradiadas observou-se um aumento do pico de uma banda de absorção na região compreendidas entre os comprimentos de onda de 360 a 650 nm quando foram adicionadas quantidades crescentes de manganês. Aumentando a dopagem com MnO ocorreu um deslocamento do pico de 460 para 470 nm devido à introdução de pequenas distorções adicionais na estrutura da rede vítrea causado pela presença do íon Mn2+. As amostras dopadas com MnO2 apresentaram o mesmo comportamento para diferentes concentrações de dopantes, mas não apresentam deslocamento do pico central em 465 nm, mostrando que a adição dos íons Mn4+ introduz menores distorções à rede vítrea. O espectro RPE dos vidros BABAL dopado com MnO2 e MnO apresenta quatro ressonâncias (g1 = 5,1; g2 = 4,3; g3 = 3,0 e g4 = 2,0) que são consistentes com as impurezas contidas nestas amostras. A curva TL para as amostras irradiadas dos vidros BABAL dopados com manganês apresentou dois picos bem definidos às temperaturas de 140 0C e 302 0C, respectivamente, atribuídos ao centro de elétron do boro (BEC) e centro de buraco do boro (BOHC) e uma emissão mais fraca adicional em 4000C associado a BOHC´s na vizinhança de íons de manganês localizados no centro de unidades estruturais tetragonais. / Samples of barium aluminobonate (BABAL) glasses of composition 20 Al2O3. 50 B2O3. 30 BaO mole% doped with manganese were prepared and characterized using the techniques of optical absorption (OA), electron paramagnetic resonance (EPR) and thermoluminnescence (TL). This study is concerned about the different manganese ions and their interactions with the nearest neighboring atoms of oxygen and other ions present in the glassy matrix. The non-doped BABAL glass samples, after being gamma-irradiated show an OA maximum at the wavelength of 555 nm that was attributed to the boron-oxygen hole center (BOHC). The BABAL glass samples doped with MnO and MnO2 did not show a significant change on irradiation, because the relatively reduced optical gap did not allow to observe directly. The main transitions due to the Mn2+ ion. For the lower doping levels with MnO2 (<0.1mole%) it was demonstrated that Mn4+ was reduced to Mn3+ and then to Mn2+ until the equilibrium redox distribution was reached. Thus, using the Mn2+ and Mn3+. Tanabe-Sugano diagrams for sites having octahedral symmetry, the results of Mn2+=12610 ±100 cm-1 and Mn3+=21440 ±100 cm-1, respectively, for BABAL glasses doped with manganese. For the Li2O.CaF2.B2O3 glasses produced and characterized by Rao et al., we calculated the crystalline field parameters, yielding the results 13740 ± 100 cm-1 for the Mn2+ ion and 20030 ± 100 cm-1 for Mn3+ . Increasing manganese content in non-irradiated BABAL samples produced an increase of the absorption in the range of 360 to 650 nm and the peak shifted from 460 to 470 nm as a consequence of the introduction of small additional distortions in the glass amorphous lattice caused by the presence of Mn2+ ions. The samples doped with MnO2 presented the same behavior for different dopant concentrations but did not show any shift for the peak in 465 nm, showing that the Mn4+ ions introduce less distortion in the glass lattice. The EPR spectra of the BABAL glasses doped with MnO2 exhibit four resonances (g1=5.1; g2=4.3; g3=3.0 and g4=2.0), consistent with the manganese and iron impurities also present in the samples. The TL of the irradiated BABAL samples doped with manganese presented two well defined peaks at the temperatures of 140 0C and 302 0C, respectively, attributed to the boron-electron center (BEC) and BOHC and an additional weak emission at 400 0C that was associated to BOHC´s in the vicinity of manganese into tetrahedral structural units.

Este trabalho apresenta a caracterização espectroscópica de dois conjuntos de vidros sódio aluminofosfatos co-dopados com Yb3+ e Tm3+, na região do visível e infravermelho, preparados em atmosfera de nitrogênio e ambiente. Nestas amostras, os íons de Yb3+ são empregados como doadores eficientes, da excitação em 980nm, com transferência de energia subseqüente para os íons Tm3+. Os resultados são discutidos em termos do conteúdo de OH- presentes em cada conjunto das amostras, e em função da concentração Tm2O3. As propriedades radiativas foram analisadas usando a teoria de Judd Ofelt, e empregando os resultados experimentais e teóricos, foram avaliadas as eficiências quântica das luminescências (h) dos diversos níveis. Os resultados indicam que as amostras preparadas em atmosfera do N2, com um conteúdo de OH- menor, apresentam propriedades superiores do que aquelas preparadas em atmosfera ambiente. Entre estas propriedades destacamos a transmissão no infravermelho, a qual é 30% mais extensa, as intensidades de emissão são mais elevadas, e a diminuição dos efeitos de supressão da luminescência, caracterizando-os como materiais potenciais para a geração do laser alta potência, bem com conversão ascendente de energia eficiente. Também foram estudados os processos de transferência de energia, usando os modelos teóricos de Förster, Dexter e Miyakawa, calculando-se os parâmetros de transferência de energia. Os processos principais de transferência de energia analisados foram: migração da energia entre íons de Yb3+, transferência de energia entre íons Yb3+ e Tm3+, e interações com radicais OH-. Os resultados indicam que transferência de energia Yb-Tm favorece a emissão em 1800 nm, e não há nenhuma evidência da supressão da luminescência até concentração de 2% de Tm2O3. / This work presents a throughout near-infrared and visible spectroscopic characterization of two sets of Yb3+ and Tm3+ codoped sodium aluminophosphate glasses, prepared in nitrogen and ambient atmospheres. In these samples, the Yb3+ ions are employed as efficient sensitizers of 0.98 µm excitation, with subsequent energy transfer to Tm3+ ions. Results are discussed in terms of the inferred OH- content in each set of samples, and as a function of Tm2O3 concentration. Radiative properties are analyzed using Judd Ofelt theory, and by employing experimental and theoretical data, the fluorescence quantum efficiencies h of several levels are evaluated. Results indicate that samples prepared in N2 atmosphere, with lower OH- content, present superior properties than those prepared in ambient atmosphere. Among these properties are a 30% more extensive infrared transmission of the host matrix, higher emission intensities, and decreased quenching effects, characterizing them as potential materials for high power laser generation, as well as efficient upconversion. Also the energy transfer processes were studied, by using Förster, Dexter and Miyakawa theoretical models, the energy transfer parameters were calculated. The main ion-ion energy transfer processes analyzed were: energy migration among Yb3+ ions, energy transfer between Yb3+ and Tm3+ ions, and interactions with OH- radicals.The results indicated that Yb®Tm energy transfer favors 1.8 ?m emission, and there is no evidence of concentration quenching up to 2% Tm2O3 doping.