Incorporation of PbF2 into Heavy Metal Oxide Borate Glasses. Structural Studies by Solid State NMR

A series of heavy metal oxide (HMO) glasses with composition 26.66B(2)O(3)-16GeO(2)-4 Bi2O3-(53.33-x)PbO-xPbF2 (0 <= x <= 40) were prepared and characterized with respect to their bulk (glass transition and crystallization temperatures, densities, molar volumes) and spectroscopic properties. Homogeneous glasses are formed up to x = 30, while crystallization of beta-PbF2 takes place at higher contents. Substitution of PbO by PbF2 shifts the optical band gap toward higher energies, thereby extending the UV transmission window significantly toward higher frequencies. Raman and infrared absorption spectra can be interpreted in conjunction with published reference data. Using B-11 and F-19 high-resolution solid state NMR as well as B-11/F-19 double resonance methodologies, we develop a quantitative structural description of this material. The fraction of four-coordinate boron is found to be moderately higher compared to that in glasses with the same PbO/B2O3 ratios, suggesting some participation of PbF2 in the network transformation process. This suggestion is confirmed by the F-19 NMR spectra. While the majority of the fluoride ions is present as ionic fluoride, similar to 20% of the fluorine inventory acts as a network modifier, resulting in the formation of four-coordinate BO3/2F- units. These units can be identified by F-19{B-11} rotational echo double resonance and B-11{F-19} cross-polarization magic angle spinning (CPMAS) data. These results provide the first unambiguous evidence of B-F bonding in a PbF2-modified glass system. The majority of the fluoride ions are found in a lead-dominated environment. F-19-F-19 homonuclear dipolar second moments measured by spin echo decay spectroscopy are quantitatively consistent with a model in which these ions are randomly distributed within the network modifier subdomain consisting of PbO, Bi2O3, and PbF2. This model, which implies both the features of atomic scale mixing with the network former borate species and some degree of fluoride ion clustering is consistent with all of the experimental data obtained on these glasses.

Magic Lantern Slides 2

According to Charles Musser, Huygens had two key innovations for his magic lantern: 1. Images painted on glass instead of etchings on mirrors. 2. An artificial light source was used instead of the reflection of sunlight. (20) Glass slides (often more than one) with hand drawn images are the standard aesthetic for these slides. They are then usually mounted in rectangular wooden frames approx. 4 x 7 inches with a 3 inch circular opening for the image. (Musser 30) The various mechanisms attached to the images are described in the Object Narrative section.

Magic Lantern Slides 4

According to Charles Musser, Huygens had two key innovations for his magic lantern: 1. Images painted on glass instead of etchings on mirrors. 2. An artificial light source was used instead of the reflection of sunlight. (20) Glass slides (often more than one) with hand drawn images are the standard aesthetic for these slides. They are then usually mounted in rectangular wooden frames approx. 4 x 7 inches with a 3 inch circular opening for the image. (Musser 30) The various mechanisms attached to the images are described in the Object Narrative section.

Magic Lantern Slides 1

According to Charles Musser, Huygens had two key innovations for his magic lantern: 1. Images painted on glass instead of etchings on mirrors. 2. An artificial light source was used instead of the reflection of sunlight. (20) Glass slides (often more than one) with hand drawn images are the standard aesthetic for these slides. They are then usually mounted in rectangular wooden frames approx. 4 x 7 inches with a 3 inch circular opening for the image. (Musser 30) The various mechanisms attached to the images are described in the Object Narrative section.

Magic Lantern Slides 3

According to Charles Musser, Huygens had two key innovations for his magic lantern: 1. Images painted on glass instead of etchings on mirrors. 2. An artificial light source was used instead of the reflection of sunlight. (20) Glass slides (often more than one) with hand drawn images are the standard aesthetic for these slides. They are then usually mounted in rectangular wooden frames approx. 4 x 7 inches with a 3 inch circular opening for the image. (Musser 30) The various mechanisms attached to the images are described in the Object Narrative section.

Thaumatrope (Magic Circle)

The thaumatrope consists of a circle of cardstock, 2.5 inches in diameter with 2 strings attached, one each at opposite points of the diameter. There were 2 images painted on the cardstock, one on each side, with their positions inverted. The outline of the image was usually printed and the color hand-painted in (Barnes 7).

Analysis of quality of experience in 3D video systems

Esta tesis presenta un estudio exhaustivo sobre la evaluación de la calidad de experiencia (QoE, del inglés Quality of Experience) percibida por los usuarios de sistemas de vídeo 3D, analizando el impacto de los efectos introducidos por todos los elementos de la cadena de procesamiento de vídeo 3D. Por lo tanto, se presentan varias pruebas de evaluación subjetiva específicamente diseñadas para evaluar los sistemas considerados, teniendo en cuenta todos los factores perceptuales relacionados con la experiencia visual tridimensional, tales como la percepción de profundidad y la molestia visual. Concretamente, se describe un test subjetivo basado en la evaluación de degradaciones típicas que pueden aparecer en el proceso de creación de contenidos de vídeo 3D, por ejemplo debidas a calibraciones incorrectas de las cámaras o a algoritmos de procesamiento de la señal de vídeo (p. ej., conversión de 2D a 3D). Además, se presenta el proceso de generación de una base de datos de vídeos estereoscópicos de alta calidad, disponible gratuitamente para la comunidad investigadora y que ha sido utilizada ampliamente en diferentes trabajos relacionados con vídeo 3D. Asimismo, se presenta otro estudio subjetivo, realizado entre varios laboratorios, con el que se analiza el impacto de degradaciones causadas por la codificación de vídeo, así como diversos formatos de representación de vídeo 3D. Igualmente, se describen tres pruebas subjetivas centradas en el estudio de posibles efectos causados por la transmisión de vídeo 3D a través de redes de televisión sobre IP (IPTV, del inglés Internet Protocol Television) y de sistemas de streaming adaptativo de vídeo. Para estos casos, se ha propuesto una innovadora metodología de evaluación subjetiva de calidad vídeo, denominada Content-Immersive Evaluation of Transmission Impairments (CIETI), diseñada específicamente para evaluar eventos de transmisión simulando condiciones realistas de visualización de vídeo en ámbitos domésticos, con el fin de obtener conclusiones más representativas sobre la experiencia visual de los usuarios finales. Finalmente, se exponen dos experimentos subjetivos comparando varias tecnologías actuales de televisores 3D disponibles en el mercado de consumo y evaluando factores perceptuales de sistemas Super Multiview Video (SMV), previstos a ser la tecnología futura de televisores 3D de consumo, gracias a una prometedora visualización de contenido 3D sin necesidad de gafas específicas. El trabajo presentado en esta tesis ha permitido entender los factores perceptuales y técnicos relacionados con el procesamiento y visualización de contenidos de vídeo 3D, que pueden ser de utilidad en el desarrollo de nuevas tecnologías y técnicas de evaluación de la QoE, tanto metodologías subjetivas como métricas objetivas. ABSTRACT This thesis presents a comprehensive study of the evaluation of the Quality of Experience (QoE) perceived by the users of 3D video systems, analyzing the impact of effects introduced by all the elements of the 3D video processing chain. Therefore, various subjective assessment tests are presented, particularly designed to evaluate the systems under consideration, and taking into account all the perceptual factors related to the 3D visual experience, such as depth perception and visual discomfort. In particular, a subjective test is presented, based on evaluating typical degradations that may appear during the content creation, for instance due to incorrect camera calibration or video processing algorithms (e.g., 2D to 3D conversion). Moreover, the process of generation of a high-quality dataset of 3D stereoscopic videos is described, which is freely available for the research community, and has been already widely used in different works related with 3D video. In addition, another inter-laboratory subjective study is presented analyzing the impact of coding impairments and representation formats of stereoscopic video. Also, three subjective tests are presented studying the effects of transmission events that take place in Internet Protocol Television (IPTV) networks and adaptive streaming scenarios for 3D video. For these cases, a novel subjective evaluation methodology, called Content-Immersive Evaluation of Transmission Impairments (CIETI), was proposed, which was especially designed to evaluate transmission events simulating realistic home-viewing conditions, to obtain more representative conclusions about the visual experience of the end users. Finally, two subjective experiments are exposed comparing various current 3D displays available in the consumer market, and evaluating perceptual factors of Super Multiview Video (SMV) systems, expected to be the future technology for consumer 3D displays thanks to a promising visualization of 3D content without specific glasses. The work presented in this thesis has allowed to understand perceptual and technical factors related to the processing and visualization of 3D video content, which may be useful in the development of new technologies and approaches for QoE evaluation, both subjective methodologies and objective metrics.

Structure and thermal properties of yttrium alumino-phosphate glasses

The structure and thermal properties of yttrium alumino-phosphate glasses, of nominal composition (Y2O3)(0.31-z)(Al2O3)(z)(P2O5)(0.69) with 0 less than or similar to z less than or similar to 0.31, were studied by using a combination of neutron diffraction, Al-27 and P-31 magic angle spinning nuclear magnetic resonance, differential scanning calorimetry and thermal gravimetric analysis methods. The Vickers hardness of the glasses was also measured. The data are compared to those obtained for pseudo-binary Al2O3-P2O5 glasses and the structure of all these materials is rationalized in terms of a generic model for vitreous phosphate materials in which Y3+ and Al3+ act as modifying cations that bind only to the terminal (non-bridging) oxygen atoms of PO4 tetrahedra. The results are used to help elucidate the phenomenon of rare-earth clustering in phosphate glasses which can be reduced by substituting Al3+ ions for rare-earth R3+ ions at fixed modifier content.

An examination of the calcium and strontium site distribution in bioactive glasses through isomorphic neutron diffraction, X-ray diffraction, EXAFS and multinuclear solid state NMR.

Strontium has been substituted for calcium in the glass series (SiO2)49.46(Na2O)26.38(P2O5)1.07(CaO)23.08x(SrO)x (where x = 0, 11.54, 23.08) to elucidate their underlying atomic-scale structural characteristics as a basis for understanding features related to the bioactivity. These bioactive glasses have been investigated using isomorphic neutron and X-ray diffraction, Sr K-edge EXAFS and solid state 17O, 23Na, 29Si, 31P and 43Ca magic-angle-spinning (MAS) NMR. An effective isomorphic substitution first-order difference function has been applied to the neutron diffraction data, confirming that Ca and Sr behave in a similar manner within the glass network, with residual differences attributed to solely the variation in ionic radius between the two species. The diffraction data provides the first direct experimental evidence of split Ca–O nearest-neighbour correlations in these melt quench bioactive glasses, together with an analogous splitting of the Sr–O correlations; the correlations are attributed to the metal ions correlated either to bridging or to non-bridging oxygen atoms. Triple quantum (3Q) 43Ca MAS NMR corroborates the split Ca–O correlations. Successful simplification of the 2 < r (A) < 3 region via the difference method has also revealed two distinct Na environments. These environments are attributed to sodium correlated either to bridging or to nonbridging oxygen atoms. Complementary multinuclear MAS NMR, Sr K-edge EXAFS and X-ray diffraction data supports the structural model presented. The structural sites present will be intimately related to their release properties in physiological fluids such as plasma and saliva, and hence the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimising material design.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO, 30 mol % CaO) for each of the calcium precursors. When CaCl was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.

Bioactive sol-gel glasses at the atomic scale:the complementary use of advanced probe and computer modeling methods

Sol-gel-synthesized bioactive glasses may be formed via a hydrolysis condensation reaction, silica being introduced in the form of tetraethyl orthosilicate (TEOS), and calcium is typically added in the form of calcium nitrate. The synthesis reaction proceeds in an aqueous environment; the resultant gel is dried, before stabilization by heat treatment. These materials, being amorphous, are complex at the level of their atomic-scale structure, but their bulk properties may only be properly understood on the basis of that structural insight. Thus, a full understanding of their structure-property relationship may only be achieved through the application of a coherent suite of leading-edge experimental probes, coupled with the cogent use of advanced computer simulation methods. Using as an exemplar a calcia-silica sol-gel glass of the kind developed by Larry Hench, in the memory of whom this paper is dedicated, we illustrate the successful use of high-energy X-ray and neutron scattering (diffraction) methods, magic-angle spinning solid-state NMR, and molecular dynamics simulation as components to a powerful methodology for the study of amorphous materials.

An analysis of facial description in static images and video streams

[ES]This paper describes an analysis performed for facial description in static images and video streams. The still image context is first analyzed in order to decide the optimal classifier configuration for each problem: gender recognition, race classification, and glasses and moustache presence. These results are later applied to significant samples which are automatically extracted in real-time from video streams achieving promising results in the facial description of 70 individuals by means of gender, race and the presence of glasses and moustache.