Thesis (M.A.)--Boston University / PLEASE NOTE: Boston University Libraries did not receive an Authorization To Manage form for this thesis or dissertation. It is therefore not openly accessible, though it may be available by request. If you are the author or principal advisor of this work and would like to request open access for it, please contact us at open-help@bu.edu. Thank you. / 2031-01-01

Neste trabalho foram estudadas duas composições vítreas, a saber: 30PbF2 - 15InF3 - 20GaF3 - 15ZnF2 - 20CaF2, chamada fluoroindogalato e 41,5Al2O3 - 47,4CaO - 7SiO2 - 4,1MgO, chamada LSCA ( do inglês Low Silica content Calcium Aluminate). A matriz de fluoroindogalato foi dopada com dois conjuntos de íons terras-raras: Tm3+ + Ho3+ e Er3++Yb3+, enquanto que a matriz LSCA foi dopada apenas com os íons Er3+:Yb3+. O objetivo do trabalho foi a caracterização destas matrizes como possíveis meios ativos para laser de estado sólido nas regiões de 2,0 µm (Ho3+) e 2,8µm (Er3+). Neste sentido, foram realizados os experimentos de absorção óptica, fotoluminescência e tempo de vida. A partir dos dados obtidos, foram calculados os parâmetros de intensidade de Judd-Ofelt, os microparâmetros de transferência de energia e o coeficiente de ganho óptico das transições eletrônicas 5I7→ 5I8 (Ho3+) e 4I11/2→ 4I13/2 (Er3+). A contribuição deste trabalho a espectroscopia de terras-raras em vidros está na caracterização destes íons em termos dos parâmetros de transferência de energia via os modelos de Dexter e Yokota e Tanimoto. Haja vista que tais dados não se encontram disponíveis na literatura especializada. Os resultados mostraram que ocorrem processos de transferência de energia de ordem mais alta que dipolo-dipolo nas interações Tm3+→ Tm3+ e Tm3+→ Ho3+. A transição 5I7 → 5I8 do Ho3+ apresenta coeficiente de ganho óptico positivo a partir da densidade de excitação de 1,2 kW/cm2. Os processos de transferência de energia Er3+→ Er3+ e Er3+→ Yb3+ ocorrem via mecanismo de dipolo-dipolo e a transição 4I11/2→ 4I13/2 do Er3+ não é auto-terminada na matriz de fluoroindogalato. O coeficiente de ganho óptico para esta transição é sempre positivo para qualquer densidade de excitação. . A matriz LSCA apresenta auto-terminação da transição 4I11/2→ 4I13/2 do Er3+, sendo portanto, necessária a inserção dos mecanismos de upconversion para a observação de ganho óptico nesta transição eletrônica / In this work two vitreous compositions were studied, that are: fluoroindogalate (30PbF2 - 15InF3 - 20GaF3 - 15ZnF2 - 20CaF22) and LSCA (41,5Al2O3 - 47,4CaO - 7SiO2 - 4,1MgO) - Low Silica Content Calcium Aluminates. The fluoroindogalate host was doped with two sets of rare earth ions: Tm3+ + Ho3+ and Er3++Yb3+, whereas the LSCA host was only doped with Er3+ and Yb3+ ions. The aim of the work was the characterization of these hosts as possible active media for solid state lasers in the spectral regions of 2,0 µm (Ho3+) and 2,8µm (Er3+). In this sense, optical absorption, photoluminescence and lifetime experiments were performed. From the resulting data, Judd-Ofelt intensity parameters, energy transfer microparameters and the electronic transitions 5I7→ 5I8 (Ho3+) and 4I11/2→ 4I13/2 (Er3+) optical gain coefficients were calculated. This work\'s contribution to the rare earth spectroscopy lies in the characterization of such ions in terms of the energy transfer parameters using the Dexter, and Yokota and Tanimoto models considering that these data are not available in the specialized literature. The results have shown that higher than dipole-dipole order processes occur in the interactions Tm3+→ Tm3+ and Tm3+→ Ho3+. The Ho3+ 5I7→ 5I8 transition presents positive optical gain coefficient starting from the excitation density of 1.2 kW/cm2. The energy transfer processes Er3+→ Er3+ and Er3+→ Yb3+ occur via dipole-dipole mechanism and the Er3+ 4I11/2→ 4I13/2 transition is not auto terminated in the fluoroindogalate host. The optical gain coefficient for this transition is always positive for any excitation density. The LSCA host presents auto termination of the Er3+ 4I11/2→ 4I13/2 making it necessary the insertion of upconversion mechanisms for the observation of the optical gain in this electronic transition

A busca de melhores características elétricas, acompanhada de crescentes evoluções tecnológicas e novos materiais passivantes para junções semicondutoras vem sendo bastante pesquisados nas últimas décadas. Existem dois tipos de passivação: por filmes finos ou por filmes espessos. No primeiro caso são realizadas deposições de óxido de silício, carbeto de silício, nitreto de silício, enquanto que no segundo caso faz-se uso de materiais como borrachas de silicone ou vidros. A escolha entre filme fino e filme espesso está relacionada diretamente ao custo/benefício e as características do dispositivo final. Na indústria de semicondutores de potência opta-se pelos filmes espessos devido às grandes dimensões dos dipositivos e ao custo do processo empregado nas linhas de produção. Os passivantes mais utilizados em semicondutores de potência são borrachas de silicone e vidros. Os vidros inorgânicos são mais estáveis a temperaturas elevadas do que as borrachas de silicone. Neste trabalho procuramos desenvolver e controlar um processo de passivação a vidro em junções semicondutoras de dispositivos de potência para que seja usado numa linha de produção de diodos retificadores de alta estabilidade. Existem diferentes tipos de vidros para esta aplicação como os vidros de Al-Pb-B-Si e os vidros de Zn-B-Si. No presente trabalho foi realizada uma comparação entre a influência da composição química dos vidros, a granulometria do pó (frita) deste vidro, com a tensão de ruptura e corrente de fuga dos diodos levando em conta o rendimento do processo. Observou-se que fritas de vidro de Al-Pb-B-Si com granulometrias mais finas resultam em tensões de ruptura maiores com um rendimento de produção de até 33% superior aos demais casos. As correntes de fuga , à temperatura ambiente, para fritas de vidro de Zn-B-Si e Al-Pb-B-Si com diferentes granulometrias, se mostrou pràticamente a mesma. / The search for better electrical properties, new passivating materials for semiconductors junctions and the process of obtaining those ones have being studied intensively in the latest decades. There are two types of passivation layers: thick film and thin film. The first one is obtained by the deposition of silicon oxides, silicon nitride or silicon carbide, while in the second one is obtained through the application of silicon rubber or glass over the exposed juntion. The decision of using one or another depends on cost/benefit and desired electrical properties of the devices. In the semiconductor power industry the thick films are frequently used because the devices dimensions are large and the cost of these processes are cheaper than those of thin films. Silicon rubber and glass are widely used by this industry. The silicon rubbers are materials that show temperature resistance up to 2000C. The inorganic glasses are more stables at high temperatures. In this work we developed a process of glass passivation for power semiconductors devices, controlled this process and it is in use in a production line of a semiconductor power device industry. There are a few glasses for this application where the two more widely used are Al-B-Pb-Si glass and Zn-B-Si glass. In this work it was compared the influence of the glass chemical composition as well as frit grain size of the glass, over the breakdown voltage and leakage current of the devices. It was observed that glasses of Al-B-Pb-Si with smaller grain size gave better values of breakdown voltage with a production yield bigger up to 33%. It was obtained leakage current values of the same magnitude, at ambient temperature, for both kinds of glasses with different grain sizes and composition.

We study dynamic phase transitions in the constant-volume and constant- pressure ensembles of two different systems: a one-dimensional system of diffusive hard particles and a three-dimensional glass-former of nearly-hard repulsive particles. The dynamic transitions are observed using ensembles of trajectories biased with respect to their dynamic activity, biasing to greater or lower activities than equilibrium allows us to sample different dynamic phases. We perform finite-size scaling of the transitions with respect to sys- tem size and observation time, and compare them to first-order phase tran- sitions. The two ensembles are not equivalent in the one-dimensional model. We compare our results to analytic predictions for diffusive systems in both the active and inactive phases, there are structural signatures for both dy- namic regimes. The active phases show hyperuniform ordering and the inac- tive regimes show jamming behaviour, local jamming in the constant-volume ensemble is achieved through phase separation. In the three-dimensional sys- tem we observe a dynamic transition to a glassy inactive phase, there is no obvious structural change and the structural relaxation time increases sig- nificantly. We take configurations from the active and inactive phases and subject them to a jamming protocol in order to compare the final density of the jammed packings. Previous work shows that the inactive phase of glass-forming systems have a different distribution of vibrational modes and a higher compressibility, this suggests that the jamming behaviour should differ between the two phases. We show that jammed packings generated from inactive configurations are denser than those generated from active configurations.

Imagens desenhadas com fuligem de fumaça sobre lâminas de vidro transparente, cujo conjunto sugere imagem em volume / Drawings with smoke dust on glass blades set suggesting volume

Thesis (Sc.D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Bibliography: leaves 274-279. / Sc.D.

Imagens desenhadas com fuligem de fumaça sobre lâminas de vidro transparente, cujo conjunto sugere imagem em volume / Drawings with smoke dust on glass blades set suggesting volume

No description available.

Glass-ceramic composites and nanocrystalline glass-ceramics containing barium titanate (BT) or potassium sodium niobate (KNN) ferroelectric phases have been studied, with particular regard to their use as dielectric energy storage materials. Barium borosilicate glass (BBS) was used as a sintering aid for BT and KNN, producing glass-ceramic composites. The temperatures required to achieve densification were reduced from 1400 to 1200 °C for BCZT (Ca, Zr-doped BT) and 1170 to 1050 °C for KBN (Bi, Na, K, Zr-doped KNN) by the use of glass additives. An unexpected observation, found in both BCZT and KBN systems, was the heterogeneous dissolution of dopant elements into the glass, inducing additional anomalies in the relative permittivity-temperature relationships. For BCZT, the orthorhombic-tetragonal phase transformation temperature shifted upwards to ≈ 50 °C, which was attributed to modification of the Ca/Zr ratio by preferential dissolution of Ca into the glass phase. Similarly, for KBN the dopant elements appeared to be leached into the liquid phase during sintering, resulting in relative permittivity-temperature characteristics similar to those of pure KNN. A modified BBS glass having various KNN contents was prepared by the conventional melt-quenching method and then heat-treated to induce crystallisation, producing nanocrystalline glass-ceramics. It is shown that crystallisation of an intermediate barium niobate phase initiates at temperatures in the region of 650 °C; this is subsequently converted into perovskite KNN together with a second phase of Ba3Nb5O15 at temperatures from 700 to 800 °C. The final crystallite size was in the region of 30±7 nm. The highest dielectric energy storage density of 0.134(4) J cm-3 was obtained for a glass-modified BT ceramic at an electric field level of 5 kV mm-1. However, the energy storage efficiency of the BT-based ceramics was relatively poor and they displayed a general tendency for saturation, indicating potentially poor performance at higher field levels. On the other hand, the KNN-based ceramics exhibited slightly lower energy storage density values, up to 0.108(1) J cm-3, but with much improved linearity and energy storage efficiency. Therefore, the latter is considered to be more suitable as energy storage dielectrics. The BBS-KNN glass-ceramics yielded relatively low energy storage density, 0.035(2) J cm-3, but the dielectric linearity and storage efficiency were similar to or better than those of the KNN ceramics, indicating good potential for use as energy storage dielectrics at very high electric field levels as a result of their nanocrystalline microstructures.

The British Museum holds one of the largest and most important collections of Late Antique gold glasses in the world, numbering over fifty pieces. However, the collection has never been fully examined or analysed and the standard reference works on the medium are well over 100 years old. This thesis uses the British Museum collection to offer a new and in-depth case study of gold glass which reconsiders the traditional but untested set of interpretations that have been in circulation since the mid-nineteenth century and before. Chapter One examines the history of gold glass scholarship from the late sixteenth century up until the present day. This serves to demonstrate where many of the frequently repeated assumptions regarding gold glass have their roots. Chapter Two gives a brief account of scholarship focusing on the British Museum collection. It then moves on to examine in detail the formation of the collection itself in the context of changing nineteenth-century attitudes to Late Antique art. Chapter Three for the first time defines the various sub-types of gold glass identifiable in the British Museum collection and incorporates a discussion of the first significant program of scientific analysis to be carried out on the medium. Chapter Four concentrates on the manufacture of gold glass and includes a detailed program of experimental reproduction. Chapters Five to Eight discuss in detail the range of iconography appearing on the gold glasses in the British Museum collection, reflective of the medium as a whole. Lastly, after examining the pattern of gold glass distribution and context, Chapter Nine draws together the preceding analysis to explore the possible workshop identity and chronology. The final Chapter concludes as to the function of gold glass in Late Antiquity.