Structural models for yttrium aluminium borate laser glasses: NMR and EPR studies of the system (Y(2)O(3))(0.2)-(Al(2)O(3))(x)-(B(2)O(3))(0.8-x)

The structure of laser glasses in the system (Y(2)O(3))(0.2){(Al(2)O(3))(x))(B(2)O(3))(0.8-x)} (0.15 <= x <= 0.40) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as electron spin echo envelope modulation (ESEEM) of Yb-doped samples. The latter technique has been applied for the first time to an aluminoborate glass system. (11)B magic-angle spinning (MAS)-NMR spectra reveal that, while the majority of the boron atoms are three-coordinated over the entire composition region, the fraction of three-coordinated boron atoms increases significantly with increasing x. Charge balance considerations as well as (11)B NMR lineshape analyses suggest that the dominant borate species are predominantly singly charged metaborate (BO(2/2)O(-)), doubly charged pyroborate (BO(1/2)(O(-))(2)), and (at x = 0.40) triply charged orthoborate groups. As x increases along this series, the average anionic charge per trigonal borate group increases from 1.38 to 2.91. (27)Al MAS-NMR spectra show that the alumina species are present in the coordination states four, five and six, and the fraction of four-coordinated Al increases markedly with increasing x. All of the Al coordination states are in intimate contact with both the three-and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, non-segregated glass structure. (89)Y solid state NMR spectra show a significant chemical shift trend, reflecting that the second coordination sphere becomes increasingly ""aluminate-like'' with increasing x. This conclusion is supported by electron spin echo envelope modulation (ESEEM) data of Yb-doped glasses, which indicate that both borate and aluminate species participate in the medium range structure of the rare-earth ions, consistent with a random spatial distribution of the glass components.

Expanding the magic circle in pervasive casual play

Dissertação para obtenção do Grau de Doutor em Informática

Structural Characterization of Rare-Earth Doped Yttrium Aluminoborate Laser Glasses Using Solid State NMR

The structure of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-x)(Y(2)O(3))(x)} (0.1 <= x <= 0.25) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as Y-3d core-level X-ray photoelectron spectroscopy, (11)B magic-angle spinning (MAS) NMR spectra reveal that the majority of the boron atoms are three-coordinated, and a slight increase of four-coordinated boron content with increasing x can be noticed. (27)Al MAS NMR spectra show that the alumina species are present in the coordination states four, five and six. All of them are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, nonsegregated glass structure. For the first time, (89)Y solid state NMR has been used to probe the local environment of Y(3+) ions in a glass-forming system. The intrinsic sensitivity problem associated with (89)Y NMR has been overcome by combining the benefits of paramagnetic doping with those of signal accumulation via Carr-Purcell spin echo trains. Both the (89)Y chemical shifts and the Y-3d core level binding energies are found to be rather sensitive to the yttrium bonding state and reveal that the bonding properties of the yttrium atoms in these glasses are similar to those found in the model compounds YBO(3) and YAl(3)(BO(3))(4), Based on charge balance considerations as well as (11)B NMR line shape analyses, the dominant borate species are concluded to be meta- and pyroborate anions.

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Glasses in the SbPO4-WO3 system

Glasses in the binary system (100 - x)SbPO4-xWO3 (20 <= x <= 60, x in mol%) have been prepared and characterized. Differential thermal analysis (DTA) shows that the glass transition temperature, T-g increases from 412 degrees C, for samples containing 20 mol% of WO3 to 481 degrees C observed for glass containing 60 mol%. Sample containing 40 mol% in WO3 were observed to be the most stable against devitrification. The structural organization of the glasses has been studied by using Fourier transform infra-red (FTIR), Raman, P-31 Magic angle spinning (MAS) and spin echo nuclear magnetic resonance (NMR) spectroscopies. Results suggest two distinct networks comprising the glass structure, one with high SbPO4 content and the other characteristic of the highest WO3 content samples. The glasses present photochromic properties. Colour changes are observed for samples after exposure to ultraviolet or visible laser light. XANES, at L-1 absorption edge of tungsten, suggests partial reduction from W6+ to W5+ species during the laser irradiation. The photochromic effects and the colour changes, promoted by laser excitation, are reversible and easily removed by heat for during 1 h at 150 degrees C. Subsequent 'write/erase' cycles can be done without degradation of the glasses. (C) 2007 Elsevier B.V. All rights reserved.

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO3-x% MoO3 (0 <= x <= 70) glass-forming system by a modified melt method that allowed good optical quality samples to be obtained. The structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), Raman scattering, and solid-state nuclear magnetic resonance (NMR) for P-31, Na-23, and Mo-95 nuclei. Addition of MoO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures up to x = 45, suggesting a significant increase in network connectivity. For this same composition range, vibrational spectra suggest that the Mo6+ ions are bonded to some nonbridging oxygen atoms (Mo-O- or Mo=O bonded species). Mo-O-Mo bond formation occurs only at MoO3 contents exceeding x = 45. P-31 magic-angle spinning (MAS) NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. These sites are denoted as Q(2Mo)((2)), Q(1Mo)((2)), and Q(0Mo)((2)), respectively. For x < 0.45, the populations of these sites can be described along the lines of a binary model, according to which each unit of MoO3 converts two Q(nMo)((2)) sites into two Q((n+1)Mo)((2)) sites (n = 0, 1). This structural model is consistent with the presence of tetrahedral Mo(=O)(2)(O-1/2)(2) environments. Indeed, Mo-95 NMR data suggest that the majority of the molybdenum species are four-coordinated. However, the presence of additional six-coordinate molybdenum in the MAS NMR spectra indicates that the structure of these glasses may be more complicated and may additionally involve sharing of network modifier oxide between the network formers phosphorus and molybdenum. This latter hypothesis is further supported by Na-23{P-31} rotational echo double resonance (REDOR) data, which clearly reveal that the magnetic dipole-dipole interactions between P-31 and Na-23 are increasingly diminished with increasing molybdenum content. The partial transfer of modifier from the phosphate to the molybdate network former implies a partial repolymerization of the phosphate species, resulting in the formation of Q(nMo)((3)) species and accounting for the observed increase in the glass transition temperature with increasing MoO3 content that is observed in the composition range 0 <= x <= 45. Glasses with MoO3 contents beyond x = 45 show decreased thermal and crystallization stability. Their structure is characterized by isolated phosphate species [most likely of the P(OMo)(4) type] and molybdenum oxide clusters with a large extent of Mo-O-Mo connectivity.

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.