• Refine Query
  • Source
  • Publication year
  • to
  • Language
  • 235
  • 187
  • 78
  • 52
  • 15
  • 14
  • 14
  • 14
  • 14
  • 14
  • 14
  • 6
  • 5
  • 4
  • 3
  • Tagged with
  • 787
  • 177
  • 160
  • 151
  • 143
  • 140
  • 137
  • 92
  • 81
  • 77
  • 70
  • 70
  • 60
  • 54
  • 54
  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
521

Magnetic phase transitions in Gd-rich metallic glasses

Jantan, Jaafar. January 1985 (has links)
Call number: LD2668 .T4 1985 J365 / Master of Science
522

Développement des bases théoriques nécessaires à la modélisation de la vitesse résiduelle d'altération en milieu aqueux des verres nucléaires AVM. / Development of basis necessary to model the aqueous residual alteration rate of AVM nuclear glasses

Thien, Bruno 03 December 2010 (has links)
En milieu aqueux, les verres nucléaires AVM présentent de grandes différences de comportement à l'altération, malgré de faibles variations de composition. La vitesse résiduelle d'altération de ces verres est contrôlée par deux phénomènes, qui sont la précipitation de phases secondaires de type hectorites alumineuses, qui en altérant le gel protecteur, augmentent la vitesse résiduelle d'altération du verre, et, la diffusion de l'eau à travers un gel plus ou moins protecteur. Le magnésium, contenu dans ces verres, facilite la précipitation de ces phases secondaires, mais s'incorpore également dans le gel, augmentant son pouvoir de passivation. La prédominance de l'un ou l'autre de ces phénomènes dépend de la composition initiale du verre, du pH de la solution, des conditions d'altération. Altérés en eau souterraine de stockage (riche en Mg et Ca), les verres AVM s'altèrent moins qu'en eau pure, et ce malgré la précipitation de phases secondaires. Le calcium s'incorpore dans le gel, à la place du sodium et du magnésium, augmentant son pouvoir de passivation. Nous avons adapté le modèle géochimique d'altération des verres GRAAL, aux verres AVM. Malgré ses limites, ce modèle nous permet de rendre compte des différences de comportement entre les verres AVM, selon leur composition, ainsi que de proposer un modèle opérationnel de l'altération des verres AVM. / During their aqueous alteration, AVM French nuclear glasses exhibit a large range of behaviour, in spite of a small range of composition. AVM glasses alteration rates are controlled by two phenomena: (i) precipitation of secondary phases, mostly aluminous hectorites, and (ii) diffusion of water across a more or less protective gel. The magnesium contained in these glasses increases the precipitation of these secondary phases, leading to a partial or total dissolution of the gel layer. This dissolution increases the glass alteration rates. On the other hand, Mg also incorporates in the gel, increasing his passivation properties. The predominance of one of these two phenomena depends on the initial composition of the glass, the pH of the solution, and the alteration conditions. In presence of Bure geological disposal site water (Mg and Ca rich), AVM glasses undergo less alteration than in initially pure water, in spite of larger amounts of secondary phase precipitates. This results from incorporation of calcium in the gel instead of sodium and magnesium, improving its passivating properties. We have adapted the geochemical GRAAL model for AVM glasses. In spite of its limitations, this model allows us to describe the differences of behaviour between these glasses, in function of their composition. Moreover, GRAAL can be proposed as a basis of a future operational model for predicting the alteration of AVM glasses.
523

Développement de guides d'onde IR à base de couches épaisses de verres tellurures pour l'interférométrie spatiale. / Development of IR waveguides based on telluride thick films for spatial interferometry.

Barthélémy, Eléonore 09 December 2010 (has links)
La mission Darwin, un projet d'interférométrie spatiale initié par l'ESA, nécessite l'utilisation de filtres modaux fonctionnant dans la gamme spectrale [6-20 µm]. Dans le cadre de ce travail, nous proposons la réalisation de filtres modaux basés sur des guides d'onde « tout tellurures » obtenus par la méthode d'empilement et de gravure. L'originalité de ce travail réside dans le fait que les guides réalisés sont de grandes dimensions (couches épaisses et profondeurs de gravure importantes), pour satisfaire aux exigences du projet. La première étape a donc consisté à choisir une méthode de dépôt qui permette d'obtenir des couches épaisses. La co-évaporation thermique a ainsi été mise en place et les paramètres de dépôt optimisés. Des couches d'épaisseur pouvant atteindre 17 µm, de bonne qualité (adhérentes, amorphes, denses et homogènes), transparentes de 6 à 20 µm et d'indice de réfraction contrôlé ont pu être obtenues. La gravure physique réactive (RIE) de ces couches, en utilisant un mélange gazeux CHF3/O2/Ar, a constitué la deuxième partie de ce travail. L'obtention de marches de profondeur pouvant dépasser 10 µm, présentant des profils de gravure de qualité, a été démontrée. Les différents guides d'onde IR réalisés ont été caractérisés optiquement après préparation de leurs faces d'entrée et de sortie. L'observation d'un bon confinement de la lumière sur un banc de guidage à λ = 10,6 µm et l'obtention d'un taux de réjection de 10-3 sur un banc d'interférométrie annulante nous ont permis de confirmer que les guides d'onde à base de couches tellurures et réalisés par la méthode d'empilement et de gravure constituaient une solution de choix en tant que filtres modaux pour l'interférométrie spatiale. / The Darwin mission, an interferometric spatial project initiated by ESA, requires modal filters being able to work in the whole spectral range [6-20 µm]. In the framework of this work, we propose the realization of modal filters based on waveguides obtained by stacking and etching chalcogenide films. The originality of this work lies in the fact that the realized waveguides have large dimensions (thick films and deep etching), to satisfy the project requirements. The first step consisted in choosing the deposition method which allows obtaining thick films. The thermal co-evaporation was setting up and the deposition parameters were optimized. Films with thickness which can reach 17 µm, of good quality (adhesive, amorphous, dense and homogeneous), transparent from 6 to 20 µm and with controlled refractive index were obtained. The physical reactive etching of these films, by using a gas mixture CHF3/O2/Ar, constituted the second part of this work. The obtaining of deep rib which can exceed 10 µm, presenting etching profiles of good quality was demonstrated. The elaborated IR waveguides were optically characterized after preparation of their entrance and exit faces. The observation of light confinement on a guiding bench at λ = 10.6 µm and the obtaining of a rejection rate of 10-3 on a nulling interferometry bench allowed confirming that the waveguides based on the stacking and etching of telluride films was a choice solution as modal filters for the spatial interferometry.
524

Two-dimensional colloidal systems : grain boundaries and confinement

Skinner, Thomas Olof Edwin January 2012 (has links)
The behaviour of colloidal particles in two-dimensional (2D) systems is addressed in real space and time using magnetic fields, optical tweezers and optical video microscopy. First, the fluctuations of a grain boundary in a 2D colloidal crystal are analysed. A real space analogue of the capillary fluctuation method is derived and successfully employed to extract the key parameters that characterise the grain boundary. Good agreement is also found with a fluctuation-dissipation based method recently suggested in simulation. Following on from analysis of the interface fluctuations, the properties of the individual grain boundary particles are analysed to investigate the long standing hypothesis that suggests that grain boundary particle dynamics are similar to those in supercooled liquids. The grain boundary particle dynamics display cage breaking at long times, highly heterogeneous particle dynamics and the formation of cooperatively moving regions along the interface, all typical behaviour of a supercooled liquid. Next, the frustration induced by confining colloidal particles inside a pentagonal environment is investigated. The state of the system is adjusted via two separate control parameters: the inter-particle interaction potential and the number density. A gradual crystalline to confined liquid-like transition is observed as the repulsive inter-particle interaction potential is decreased. In contrast, re-entrant orientational ordering and dynamical effects result as the number density of the confined colloidal particles is increased. Finally, the dynamics of colloidal particles distributed amongst a random array of fixed obstacle particles is probed as a function of both the mobile particle and fixed obstacle particle number densities. Increasing the mobile and the obstacle particle number density drives the system towards a glass transition. The dynamics of the free particles are shown to behave in a similar way to the normal glass transition at low obstacle density and more analogous to a localisation glass transition at high obstacle density.
525

Image Recognition Techniques for Optical Head Mounted Displays

Kondreddy, Mahendra 21 February 2017 (has links) (PDF)
The evolution of technology has led the research into new emerging wearable devices such as the Smart Glasses. This technology provides with new visualization techniques. Augmented Reality is an advanced technology that could significantly ease the execution of much complex operations. Augmented Reality is a combination of both Virtual and Actual Reality, making accessible to the user new tools to safeguard in the transfer of knowledge in several environments and for several processes. This thesis explores the development of an android based image recognition application. The feature point detectors and descriptors are used as they can deal great with the correspondence problems. The selection of best image recognition technique on the smart glasses is chosen based on the time taken to retrieve the results and the amount of power consumed in the process. As the smart glasses are equipped with the limited resources, the selected approach should use low computation on it by making the device operations uninterruptable. The effective and efficient method for detection and recognition of the safety signs from images is selected. The ubiquitous SIFT and SURF feature detectors consume more time and are computationally complex and require very high-level hardware components for processing. The binary descriptors are taken into account as they are light weight and can support low power devices in a much effective style. A comparative analysis is being done on the working of binary descriptors like BRIEF, ORB, AKAZE, FREAK, etc., on the smart glasses based on their performance and the requirements. ORB is the most efficient among the binary descriptors and has been more effective for the smart glasses in terms of time measurements and low power consumption.
526

Theory of fluctuations in disordered systems / Théorie des fluctuations dans les systèmes désordonnés

Urbani, Pierfrancesco 04 February 2014 (has links)
Dans cette thèse nous avons étudié de nombreux aspects de la théorie des systèmes désordonnés. En particulier, nous avons étudié les systèmes vitreux. La description détaillée des systèmes désordonnés et vitreux est un problème ouvert en physique de la matière condensée. Dans le cadre de la théorie de champ moyen pour les verres structuraux nous avons étudié la théorie des fluctuations proche de la transition vitreuse dynamique. L’étude des fluctuations peut etre fait avec le formalisme statique de la théorie de répliques. Nous avons fait cela en introduisant une théorie des champs pour la transition vitreuse à partir du potentiel microscopique entre les particules. Nous avons étudié dans ce cadre les fluctuations au niveau gaussien et nous avons évalués les exposants critiques dans ces approximations. Nous avons aussi étudié la région de validité de la prédiction gaussienne avec l’introduction d’un critère de Ginzburg pour la transition vitreuse. Les résultats que nous avons obtenues ne sont valides que dans la région β. Pour obtenir des resultats dans la région α nous avons étudié la pseudodynamique de Boltzmann que a été introduit par Franz and Parisi. Nous sommes parti des équations de Ornstein-Zernike et nous avons obtenu un ensemble d’équations dynamiques. En utilisant l’approximation Hypernetted Chain nous avons obtenu un ensemble complet d’équations qui sont très similaires aux équations de la théorie de mode-coupling. La troisième partie de la thèse porte sur l’étude des états amorphes des sphères dures en hautes dimensions. Pour obtenir les exposants dynamique dans ce cas, nous avons étudié la stabilité du diagramme de phase 1RSB (one-step-replica-symmetry-breaking). Nous avons découvert que ce diagramme de phase possède une région où la solution 1RSB est instable. La région où la solution 1RSB est instable est connectée avec la description théorique de la physique de jamming des sphères dures et nous avons montré que l’instabilité 1RSB est responsable d’une transition de phase en haute densité. Cette transition s’appelle la transition de Gardner. Nous avons cherché une solution 2RSB et nous avons vu qu’il existait un point en densité après lequel on peut avoir une solution 2RSB (et aussi fullRSB). Nous avons étudié le diagramme de phase 2RSB dans la limite de jamming où la pression devient infini. Après la solution 2RSB nous avons cherché à décrire la solution fullRSB. Nous avons écrit les équations fullRSB et nous avons découvert qu’elles sont identiques aux equations que l’on a dans le cas de un modèle de verres de spins qui s’appelle modèle de Sherrington et Kirkpatrick. Nous avons aussi étudié la solution numerique des équations fullRSB dans la limite de jamming. Cette solution montre beaucoup des choses intéressantes. La plus importante est le comportement du mean square displacement dans la limite de jamming. Si l’on regard les résultats numériques et éxperimentaux, il semble que le plateau de le mean square displacement s’approche a zero comme la pression à un exposant proche de −3/2. Nous avons vu que la solution numérique des équations fullRSB est en mesure de reproduire ce comportement. La quatrième partie de la thése a porté sur la dynamique de mode-coupling dans le régime où la transition vitreuse devient continue. / In this thesis we have studied many aspects of the physics of disordered and glassy systems. The first part of the work is about the theory of dynamical fluctuations in the beta regime. When a system undergoes a dynamical arrest, it can be studied by introducing an appropriate dynamical correlation function that plays the role of the order parameter of the transition. To understand the collective effects underlying the glass transition we have studied the fluctuations of the order parameter on a time scale where the system is relaxed in a typical metastable glassy state. To do this we have seen that coming from the glass phase the system develops critical fluctuations with a diverging correlation length at the mean field level. We have thus derived an effective field theory by focusing only on them. This field theory can be used firstly to derive the mode-coupling exponent parameter that controls the relaxation of the dynamical correlation function when the system relaxes in a metastable glassy state. Moreover we can give a Ginzburg Criterion that can be used to determine the region of validity of the Gaussian approximation. These considerations are valid in the beta regime. To clarify what happens in the alpha regime we have studied a quasi-equilibrium construction, called Boltzmann-Pseudodynamics, recently introduced in order to describe with static techniques the long time regime of glassy dynamics. We have extended this formalism to structural glasses by producing a new set of dynamical equations. We have done this in the simplest approximation scheme that is called Hypernetted Chain. Two results have been obtained : firstly, we have computed the mode-coupling exponent parameter and we have shown that it coincides with the one obtained with the formalism of the first part of the thesis ; secondly we have studied the aging regime and we have derived that the condition that determines the fluctuation-dissipation ratio is a marginal stability one. In the third part of the thesis we have studied the theory of amorphous states of hard spheres in high dimensions. Hard spheres provide simple models of glasses and they are extensively studied for the jamming transition. In our framework jammed states can be thought as infinite pressure limit of metastable glassy states. During the last years it has been derived a mean field theory of hard spheres based on the 1RSB assumption on the structure of the free energy landscape. However it has been realized that this construction is inconsistent for what concerns the property of the packings at jamming. In the present work we have firstly investigated the possibility of an instability of the 1RSB solution and we have actually found that the 1RSB solution is unstable in the jamming part of the phase diagram. At the same time we have been able to compute the mode-coupling exponent parameter for this system. In order to go beyond the 1RSB solution we have first tried a 2RSB ansatz and then a fullRSB solution. We have derived a set of variational equations that are very close to the ones that have been derived in the Sherrington-Kirkpatrick model. We have solved numerically the equations and we have shown that the fullRSB solution seems to predict that the plateau value of the mean square displacement scale as the pressure to a power close to 3/2 as it seems to be predicted by scaling arguments and in contrast with the 1RSB predictions that show a scaling with the inverse of the pressure. The last chapter of the thesis is on the mode-coupling theory when the glass transition is becoming continuous. We have been able to show that in such a situation a detailed characterization of the solution of the equations can be obtained in the long time regime.
527

Preparação de vidros boratos dos sistemas 50B2O315PbO(35-x)Li2OxNa2O e 50B2O315PbO(35-x)LiFxNaF e determinação do efeito dos alcalinos mistos / Preparation of borate glasses from 50B2O315PbO(35-x)Li2OxNa2O and 50B2O315PbO(35-x)LiFxNaF systems and the evaluation of the mixed alkali effect

Ferreira, Fábio Augusto de Souza 22 July 2010 (has links)
Diferentes vidros alcalinos têm sido desenvolvidos para serem usados como eletrólitos sólidos na fabricação de baterias e em sensores químicos devido a sua elevada condutividade iônica. Entretanto, um efeito deletério para os dispositivos surge quando dois íons alcalinos distintos se encontram em uma mesma matriz vítrea. O fenômeno conhecido na literatura como efeito dos alcalinos mistos (mixed-alkali effect (MAE), em inglês) provoca uma variação não-linear em certas propriedades físicas, especialmente na condutividade elétrica, levando ao aparecimento de um profundo mínimo (ou máximo, dependendo da propriedade em estudo), à medida que a concentração relativa dos dois íons alcalinos presentes na rede vítrea varia. O MAE foi descoberto há mais de 100 anos e até hoje a sua real origem não é conhecida. As pesquisas ganharam um novo impulso com a necessidade de miniaturizar e aumentar a eficiência das baterias, para atender a demanda dos novos equipamentos eletrônicos, e com o desenvolvimento da computação, especialmente dos programas de modelagem e dinâmica molecular. Neste trabalho o objetivo foi produzir vidros boratos dos sistemas 50B2O315PbO(35-x)Li2OxNa2O e 50B2O315PbO(35-x)LiFxNaF e determinar a ocorrência e a intensidade do MAE, procurando correlacionar com a possível mudança da estrutura local. Os vidros foram produzidos pelo método de fusão/moldagem em atmosfera aberta. O caráter não-cristalino foi determinado por difração de raios X e a caracterização estrutural foi realizada utilizando-se das técnicas espectroscópicas vibracionais de Infravermelho (IV) e Raman. O estudo das propriedades físicas dos vidros foi realizado mediante a utilização das técnicas de espectroscopia de impedância (caracterização elétrica), calorimetria exploratória diferencial (determinação dos eventos térmicos) e pelo método de Arquimedes (obtenção da densidade). / Different alkali glasses have been developed because exhibit a high ionic conductivity and can be used as solid electrolytes in the fabrication of devices such as batteries and chemical sensors. However, a deleterious effect emerges when two alkali ions are present in the same glassy matrix. The phenomenon, named of the mixed alkali effect (MAE), causes a nonlinear variation of certain physical properties, especially for the electrical conductivity, with the emergence of a deep minimum (or maximum, depending of the property under study). The effect was discovered more than 100 years ago and even today its real origin remain unknown. The research gained new impetus due to need to miniaturize and to increase the efficiency of the batteries to answer the demands of new electronic equipment and with the development of computing, especially of the modeling and dynamic molecular softwares. In this work the goal was to produce the borate glass systems 50B2O315PbO(35-x)Li2OxNa2O and 50B2O315PbO(35-x)LiFxNaF and to determine the occurrence and intensity of the MAE, seeking to correlate with the possible change of the local structure. The glasses were produced by melting/modeling method in open atmosphere. The structural characterization was performed using Infrared (IR) and Raman vibrational spectroscopies. The study of the physical properties was carried out by impedance spectroscopy (electrical characterization), differential scanning calorimetry (to get the thermal events) and Archimedes method (to obtain the density).
528

Estudo, análise e proposta de diretrizes a serem consideradas no projeto do produto óculos para o público infantil / Study, analysis and proposal of guidelines to consider in product design glasses for children

Chaves, Iana Garófalo 17 December 2014 (has links)
Os óculos se destacam por sua função social no atendimento das necessidades humanas, se considerados os indivíduos que dependem deste produto em sua condição de órtese. Este trabalho considera que para o público infantil, o projeto do produto de armações, demanda estudos e pesquisas, para propor resoluções técnicas, formais e estéticas adequadas, mas, sobretudo para captar os aspectos perceptivos, subjetivos e emocionais, que despertem a afeição desse segmento social com este objeto. A pesquisa teve como principal objetivo a definição e proposta de diretrizes para auxiliar no projeto do produto óculos para o público infantil. Para isto, foram utilizadas abordagens metodológicas do design, que consideram os indivíduos envolvidos como elementos centrais no processo do projeto, a exemplo do Design Centrado no Humano (DCH), adotado como estratégia fundamental no enfoque desta dissertação.A pesquisa presenta um levantamento histórico sobre o produto óculos e sobre as normas já existentes para o seu projeto; além de uma revisão sobre as abordagens metodológicas de design centradas nos indivíduos; e as coletas de dados considerando as crianças usuárias de óculos de 6 a 11 anos e as seguintes partes envolvidas, ou seja, os stakeholders - os responsáveis ou cuidadores; os oftalmopediatras e os atendentes das óticas. Para cada grupo foi definido um método a ser aplicado, com intuito de coletar informações sobre as diferentes visões do produto, considerando principalmente os aspectos emocionais e comportamentais envolvidos nas relações das crianças com as armações. Foram utilizados os procedimentos de storytelling e \'prototipar para empatia\', aplicados com as crianças; entrevistas individuais realizadas com oftalmopediatras e atendentes de óticas; e questionários com os cuidadores. A análise e a discussão dos resultados obtidos em cada um dos métodos foram confrontadas através de relações de triangulação, contribuindo para elencar as diretrizes para o projeto das armações, com conteúdose aspectos objetivos e subjetivos, referendando o uso das metodologias adotadas, e desta perspectiva de aproximação com as emoções de desejos das crianças em relação aos seus óculos, como fundamentais para a atuação em design de produto. / The glasses stands out for their social function in the attendance of human needs, if we consider whom depends on this product in orthoses condition. This research considered for the children audience, the demand for glasses design studies and research to propose technical, formal and appropriate aesthetic resolutions, but, especially to capture the perceptual, subjective and emotional aspects that arouse affection of this social segment with this object. The research aimed to define and propose guidelines to design glasses for children. The methodological approaches adopted considered the user and the individuals involved in the process as central elements in the design process, such as the study of Human Centered Design (HCD). The research presents historical study on the glasses and the existing standards for its project; the design methodologies geared to individuals, and the data collection considering children whom wear glasses of 6 to 11 years and the following third parties involved called stakeholders - the adults caregivers; the pediatric ophthalmology and the optical attendants. For each stakeholder was defined a method to be applied, aiming to collect information about the different views of the product, especially considering the emotional and behavioral relationships involved in children\'s issues with the frames. For the children were applied two methods, the storytelling and prototype for empathy; the individual interviews method was applied with pediatric ophthalmology and optical attendants and questionnaire method was applied with caregivers. The analysis and discussion of the results obtained in each method was compared using triangulation relationship, contributing to define the guidelines for design children glasses, based on the adopted methodology the guidelines has objective and subjective aspects in its contents, approaching of the children\'s emotions and wishes regarding their glasses, a very important issue for design this product.
529

Rare earth doped fluorophosphate glass and glass-ceramics: structure-property relations / Vidros e vitroceramicas dopados com terras raras: correlações entre estrutura e propriedades

Gonçalves, Tássia de Souza 03 September 2018 (has links)
Rare earth RE3+ doped fluorophosphates glasses and glass ceramics are among the most promising candidates for high efficiency laser generation in the near-infrared spectral region. Glass ceramics are polycrystalline materials of fine microstructure that are produced by the controlled crystallization (devitrification) of a glass. By developing fluorophosphate base glasses with appropriate compositions and by controlling crystal nucleation and growth in them, glass ceramics with special properties can be fabricated combining the advantages of fluorides (low phonon energy, low refractive indexes, extensive optical window, lower hygroscopicity) and oxides (high chemical and mechanical stability and high dopant solubility), resulting in enhancement of the RE3+ emissive properties. In this study, we present the synthesis by melting/quenting and structural/spectroscopic investigation of new glasses and glass ceramics with composition 25BaF225SrF2(30-x)Al(PO3)3xAlF3(20-z)YF3: zREF3, where x = 15, 20 or 25, RE = Er3+ an/or Yb3+ and Nd3+. A detailed structural investigation of a series of this glasses has been conducted, using Raman, solid-state nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies. / Vidros e vitrocerâmicas fluorofosfatos dopados com íons terras raras (TR3+) estão entre os candidatos mais promissores para a geração de laser de alta eficiência na região espectral do infravermelho próximo. As vitrocerâmicas são materiais policristalinos com microestrutura bem definida obtida a partir da cristalização controlada do vidro base. Desenvolvendo vidros base de fluorofosfato com composições apropriadas e controlando a nucleação e crescimento de cristais, vitrocerâmicas com propriedades especiais podem ser fabricadas combinando as vantagens dos fluoretos (baixa energia de fônons, baixos índices de refração, janela ótica extensa, baixa higroscopicidade) e óxidos (alta estabilidade química e mecânica e alta solubilidade dopante), resultando no aumento das propriedades emissoras dos íons TR3+. Neste estudo, apresentamos a síntese por fusão/resfriamento e investigação estrutural/espectroscópica de novos vidros e vitrocerâmicas com composição 25BaF225SrF2(30-x)Al(PO3)3xAlF3(20-z)YF3: zREF3, onde x = 15, 20 ou 25, RE = Er3+ an / ou Yb3+ e Nd3+. Uma investigação estrutural detalhada de uma série destes vidros foi conduzida utilizando espectroscopias Raman, de ressonância magnética nuclear de estado sólido (RMN) e de ressonância paramagnética eletrônica (EPR).
530

Estudo da mudança estrutural fotoinduzida em filmes de vidros a base de polifosfato de antimônio / Photoinduced strucural changes in amorphous films of antimony polyphosphate glasses

De Vicente, Fábio Simões 16 December 2004 (has links)
O objetivo deste trabalho é o estudo das Mudanças Estruturais Fotoinduzidas em filmes do sistema vítreo [Sb(PO3)3]n −Sb2O3 bem como a produção e caracterização do sistema vítreo em questão. Vidros de x[Sb(PO3)3]n−(100−x)Sb2O3 (5 ≤ x ≤ 40) foram produzidos pela fusão dos precursores Sb2O3 e [Sb(PO3)3]n a 900°C em cadinhos de carbono vítreo e em seguida vertidos e resfriados rapidamente em moldes de aço inox. Dessa forma foi possível obter vidros homogêneos e estáveis com dimensões de 1,0 x 1,0 x 0,5 cm3. A caracterização do sistema vítreo e parâmetros como região de formação vítrea e temperaturas características foram obtidos por meio de técnicas como DSC, Difração de Raios−X, FTIR, e MAS−NMR. A região de formação vítrea neste sistema ocorre para composições entre 10 ≤ x &#8804 25 sendo que para x = 5, x = 30, e x = 35 forma−se um vidro com pequena fração de microcristalinidade que apresenta coloração amarelada sendo visualmente transparente, já para x = 40 forma−se um vidro com maior fração de microcristalinidade e totalmente opaco. Este sistema vítreo possui interessantes propriedades como larga janela de transmitância (∼ 0,4 a 8 µm), alto índice de refração (n ∼ 2,0), baixa temperatura de fusão (Tf∼900 °C) e baixa temperatura de transição vítrea, (Tg∼300 °C). Filmes de x[Sb(PO3)3]n−(100−x)Sb2O3 foram produzidos por evaporação térmica dos vidros através de canhão de elétrons (EB−PVD) em um sistema não comercial de evaporação desenvolvido em nosso laboratório, onde conseguimos produzir de maneira eficiente e com boa qualidade óptica filmes de até 10 µm de espessura. Estes filmes apresentam um atípico fenômeno de fotocontração em torno de 8 % da espessura do filme, acompanhado de fotoclareamento após irradiação com laser UV em 350,7 nm. Além da caracterização a nível macroscópico do fenômeno de fotocontração (comportamento em função da potência e tempo de irradiação com laser UV) nossa atenção ficou voltada para o estudo desse efeito a nível estrutural, através de técnicas como Difração de Raios−X, XANES, FTIR, RPE, RBS e Holografia Óptica. Além da ampla caracterização mostramos a possibilidade de aplicação do material para holografia ou armazenamento óptico, redes de difração, e matrizes de microlentes. O efeito de fotocontração nos filmes foi notado devido ao fotoclareamento observado visualmente após a exposição ao UV e foi confirmado por medidas de perfilometria da região exposta ao UV. O efeito de fotoclareamento (simultâneo a fotocontração da superficie) ocorre gerando deslocamento de ∼ 30 nm do bandgap (3,58 eV, 347 nm) para maiores energias (4,01 eV, 310nm). Também observamos um pequeno deslocamento do bandgap para irradiações com λ.=482 e 460 nm. A fotocontração evolui não linearmente com o tempo e potência de irradiação. Depende também do tempo de exposição e da potência do laser, tendendo a saturação após 4 horas de exposição a 5 W⁄cm2 (100 mW) ou 2 horas de exposição a 15 W⁄cm2 (300 mw). O efeito de fotocontração tem forte dependência com a concentração de polifosfato de antimônio na composição dos filmes do sistema vítreo x[Sb(PO3)3]n−(100−x)Sb2O3. Filmes de 1,0 µ de espessura irradiados com 100 mW (5,0 W⁄cm2) por 4 horas (região de saturação) apresentam fotocontração (−ΔV⁄V) de até 8,0 % da espessura do filme (para x = 25) quando irradiados com laser UV (λ.=350 nm) Para x = 10 a contração é menor que 2,0 %, e para concentrações de polifosfato acima de 25 % efeito é diminuído drasticamente. A atmosfera na qual o filme é irradiado tem grande influência no efeito de fotocontração. Filmes de 20 % [Sb(PO3)3]n−80 % Sb2O3 (espessura: 1,0 µm)irradiado com laser UV por 4 horas a 100 mW (5,0 W⁄cm2) apresentaram fotocontração (−ΔV⁄V) de ∼ 8 % (∼ 50 % maior) em atmosfera de O2, 5 % no ar, e menor que 2 % para o vácuo, N2 e He. Apesar de se partir da evaporação dos vidros para produção dos filmes, a principal diferença de estrutura entre vidro e filme é que estes últimos apresentam estrutura com grande número de vazios intersticiais ao redor de unidades estruturais, o que não ocorre para os vidros. Nossos resultados mostraram efetivamente que o efeito de fotocontração em filmes irradiados com UV está relacionado com mudanças de estrutura de grupos fosfatos e efeitos fototérmicos cooperativos. Na parte de aplicações gravamos redes holográficas de relevo nos filmes estudados. Utilizando uma montagem tipo espelho de Lloyd para holografia foi possível gravar redes com período de 600 nm até 20 µm e medimos a eficiência de difração em tempo real utilizando um feixe de prova de laser He−Ne. As redes gravadas em filmes de filmes de 20% [Sb(PO3)3]n−80 % Sb2O3 com período de 20 µm de espessura apresentam eficiência de difração de 3 a 10,5 % para aproximadamente 1 hora de gravação e potencia variando de 50 a 600 mW (2,5 a 30 W⁄cm2), respectivamente. / The aim of this work is the study of the Photoinduced Structural Changes (PSC) in films of the [Sb(PO3)3]n −Sb2O3 glassy system, as well as the production and characterization of the glassy system. The glass samples x[Sb(PO3)3]n−(100−x)Sb2O3 (5 ≤ x ≤ 40) were produced by the melt−quenehing technique of suitable quantities of the precursors Sb2O3 and [Sb(PO3)3]n, fused at 900°C in glassy carbon crucibles and verted into stainless steel moulds. Homogeneous and stable glass plates of 1.0 x 1.0 x 0.5 cm3 were obtained. The characterization of the glass system and the obtaining of parameters such as the glass forming region and characteristic temperatures were possible through DSC, X−ray Diffraction, FTIR and MAS−NMR techniques. The studied glass system possess remarkable properties such as broad transmittance window (from 0.4 to 8.0 µm), high index of refraction (n ∼ 2.0), low melting temperature (Tf∼900 °C) and low glass transition temperature (Tg∼300 °C). The films were produced by electron beam physical vapor deposition (EB−PVD) of the glasses, in a non−commercial evaporation system developed in our laboratory, where is possible to produce high quality films with thickness of up to 10 µm. The films samples presented an atypical photocontraction behavior that consists of a decrease of up to 10 % in the thickness, accompanied of photobleaching after UV irradiation using a 350.7 nm laser line. Besides the macroscopic characterization of the photocontraction effect (behavior as function of the UV laser power density and irradiation time), our attention was focused on the study of the effect at structural level using techniques such as X−ray diffraction, XANES, FTIR, EPR, RBS and Optical Holography. In addition to the wide characterization we shown in this work the possibilities of application of this material for optical storage and holography, diffraction gratings, micro-lens array.

Page generated in 0.0551 seconds