Tesis por compendio / Desde comienzos del siglo XXI, los sistemas de radiodifusión terrestre han sido culpados de un uso ineficiente del espectro asignado. Para aumentar la eficiencia espectral, los organismos de estandarización de TV digital comenzaron a desarrollar la evolución técnica de los sistemas de TDT de primera generación. Entre otros, uno de los objetivos principales de los sistemas de TDT de próxima generación (DVB-T2 y ATSC 3.0) es proporcionar simultáneamente servicios de TV a dispositivos móviles y fijos. El principal inconveniente de esta entrega simultánea son los diferentes requisitos de cada condición de recepción. Para abordar estas limitaciones, se han considerado diferentes técnicas de multiplexación. Mientras que DVB-T2 acomete la entrega simultánea de los dos servicios mediante TDM, ATSC 3.0 adoptó la Multiplexación por División en Capas (LDM). LDM puede superar a TDM y a FDM al aprovechar la relación de Protección de Error Desigual (UEP), ya que ambos servicios, llamados capas, utilizan todos los recursos de frecuencia y tiempo con diferentes niveles de potencia. En el lado del receptor, se distinguen dos implementaciones, de acuerdo con la capa a decodificar. Los receptores móviles solo están destinados a obtener la capa superior, conocida como Core Layer (CL). Para no aumentar su complejidad en comparación con los receptores de capa única, la capa inferior, conocida como Enhanced Layer (EL), es tratada como un ruido adicional en la decodificación. Los receptores fijos aumentan su complejidad, ya que deben realizar un proceso de Cancelación de Interferencia (SIC) sobre la CL para obtener la EL. Para limitar la complejidad adicional de los receptores fijos, las capas de LDM en ATSC 3.0 están configuradas con diferentes capacidades de corrección, pero comparten el resto de bloques de la capa física, incluido el TIL, el PP, el tamaño de FFT, y el GI. Esta disertación investiga tecnologías avanzadas para optimizar el rendimiento de LDM. Primero se propone una optimización del proceso de demapeo para las dos capas de LDM. El algoritmo propuesto logra un aumento de capacidad, al tener en cuenta la forma de la EL en el proceso de demapeo de la CL. Sin embargo, el número de distancias Euclidianas a computar puede aumentar significativamente, conduciendo no solo a receptores fijos más complejos, sino también a receptores móviles más complejos. A continuación, se determina la configuración de piloto ATSC 3.0 más adecuada para LDM. Teniendo en cuenta que las dos capas comparten el mismo PP, surge una contrapartida entre la densidad de pilotos (CL) y la redundancia sobre los datos (EL). A partir de los resultados de rendimiento, se recomienda el uso de un PP no muy denso, ya que ya han sido diseñados para hacer frente a ecos largos y altas velocidades. La amplitud piloto óptima depende del estimador de canal en los receptores (ej., se recomienda la amplitud mínima para una implementación Wiener, mientras que la máxima para una implementación FFT). También se investiga la potencial transmisión conjunta de LDM con tres tecnologías avanzadas adoptadas en ATSC 3.0: las tecnologías de agregación MultiRF, los esquemas de MISO distribuido y los de MIMO colocalizado. Se estudian los potenciales casos de uso, los aspectos de implementación del transmisor y el receptor, y las ganancias de rendimiento de las configuraciones conjuntas para las dos capas de LDM. Las restricciones adicionales de combinar LDM con las tecnologías avanzadas se consideran admisibles, ya que las mayores demandas ya están contempladas en ATSC 3.0 (ej., una segunda cadena de recepción). Se obtienen ganancias significativas en condiciones de recepción peatonal gracias a la diversidad en frecuencia proporcionada por las tecnologías MultiRF. La conjunción de LDM con esquemas de MISO proporciona ganancias de rendimiento significativas en redes SFN para la capa fija con el esquema de Alamouti. / Since the beginning of the 21st century, terrestrial broadcasting systems have been blamed of an inefficient use of the allocated spectrum. To increase the spectral efficiency, digital television Standards Developing Organizations settled to develop the technical evolution of the first-generation DTT systems. Among others, a primary goal of next-generation DTT systems (DVB-T2 and ATSC 3.0) is to simultaneously provide TV services to mobile and fixed devices. The major drawback of this simultaneous delivery is the different requirement of each reception condition. To address these constraints different multiplexing techniques have been considered. While DVB-T2 fulfilled the simultaneous delivery of the two services by TDM, ATSC 3.0 adopted the LDM technology. LDM can outperform TDM and FDM by taking advantage of the UEP ratio, as both services, namely layers, utilize all the frequency and time resources with different power levels. At receiver side, two implementations are distinguished, according to the intended layer. Mobile receivers are only intended to obtain the upper layer, known as CL. In order not to increase their complexity compared to single layer receivers, the lower layer, known as EL is treated as an additional noise on the CL decoding. Fixed receivers, increase their complexity, as they should performed a SIC process on the CL for getting the EL. To limit the additional complexity of fixed receivers, the LDM layers in ATSC 3.0 are configured with different error correction capabilities, but share the rest of physical layer parameters, including the TIL, the PP, the FFT size, and the GI. This dissertation investigates advanced technologies to optimize the LDM performance. A demapping optimization for the two LDM layers is first proposed. A capacity increase is achieved by the proposed algorithm, which takes into account the underlying layer shape in the demapping process. Nevertheless, the number of Euclidean distances to be computed can be significantly increased, contributing to not only more complex fixed receivers, but also more complex mobile receivers. Next, the most suitable ATSC 3.0 pilot configuration for LDM is determined. Considering the two layers share the same PP a trade-off between pilot density (CL) and data overhead (EL) arises. From the performance results, it is recommended the use of a not very dense PP, as they have been already designed to cope with long echoes and high speeds. The optimum pilot amplitude depends on the channel estimator at receivers (e.g. the minimum amplitude is recommended for a Wiener implementation, while the maximum for a FFT implementation). The potential combination of LDM with three advanced technologies that have been adopted in ATSC 3.0 is also investigated: MultiRF technologies, distributed MISO schemes, and co-located MIMO schemes. The potential use cases, the transmitter and receiver implementations, and the performance gains of the joint configurations are studied for the two LDM layers. The additional constraints of combining LDM with the advanced technologies is considered admissible, as the greatest demands (e.g. a second receiving chain) are already contemplated in ATSC 3.0. Significant gains are found for the mobile layer at pedestrian reception conditions thanks to the frequency diversity provided by MultiRF technologies. The conjunction of LDM with distributed MISO schemes provides significant performance gains on SFNs for the fixed layer with Alamouti scheme. Last, considering the complexity in the mobile receivers and the CL performance, the recommended joint configuration is MISO in the CL and MIMO in the EL. / Des de començaments del segle XXI, els sistemes de radiodifusió terrestre han sigut culpats d'un ús ineficient de l'espectre assignat. Per a augmentar l'eficiència espectral, els organismes d'estandardització de TV digital van començar a desenvolupar l'evolució tècnica dels sistemes de TDT de primera generació. Entre altres, un dels objectius principals dels sistemes de TDT de pròxima generació (DVB-T2 i el ATSC 3.0) és proporcionar simultàniament serveis de TV a dispositius mòbils i fixos. El principal inconvenient d'aquest lliurament simultani són els diferents requisits de cada condició de recepció. Per a abordar aquestes limitacions, s'han considerat diferents tècniques de multiplexació. Mentre que DVB-T2 escomet el lliurament simultani dels dos serveis mitjançant TDM, ATSC 3.0 va adoptar la Multiplexació per Divisió en Capes (LDM). LDM pot superar a TDM i a FDM en aprofitar la relació de Protecció d'Error Desigual (UEP), ja que tots dos serveis, cridats capes, utilitzen tots els recursos de freqüència i temps amb diferents nivells de potència. En el costat del receptor, es distingeixen dues implementacions, d'acord amb la capa a decodificar. Els receptors mòbils solament estan destinats a obtenir la capa superior, coneguda com Core Layer (CL). Per a no augmentar la seua complexitat en comparació amb els receptors de capa única, la capa inferior, coneguda com Enhanced Layer (EL), és tractada com un soroll addicional en la decodificació. Els receptors fixos augmenten la seua complexitat, ja que han de realitzar un procés de Cancel·lació d'Interferència (SIC) sobre la CL per a obtenir l'EL. Per a limitar la complexitat addicional dels receptors fixos, les capes de LDM en ATSC 3.0 estan configurades amb diferents capacitats de correcció, però comparteixen la resta de blocs de la capa física, inclòs el TIL, el PP, la grandària de FFT i el GI. Aquesta dissertació investiga tecnologies avançades per a optimitzar el rendiment de LDM. Primer es proposa una optimització del procés de demapeo per a les dues capes de LDM. L'algoritme proposat aconsegueix un augment de capacitat, en tenir en compte la forma de l'EL en el procés de demapeo de la CL. No obstant açò, el nombre de distàncies Euclidianes a computar pot augmentar significativament, conduint NO sols a receptors fixos més complexos, sinó també a receptors mòbils més complexos. A continuació, es determina la configuració de pilot ATSC 3.0 més adequada per a LDM. Tenint en compte que les dues capes comparteixen el mateix PP, es produeix una contrapartida entre la densitat de pilots (CL) i la redundància sobre les dades (EL). A partir dels resultats de rendiment, es recomana l'ús d'un PP no gaire dens, ja que ja han sigut dissenyats per a fer front a ecos llargs i altes velocitats. L'amplitud pilot òptima depèn de l'estimador de canal en els receptors (ex., es recomana l'amplitud mínima per a una implementació Wiener, mentre que la màxima per a una implementació FFT). També s'investiga la potencial transmissió conjunta de LDM amb tres tecnologies avançades adoptades en ATSC 3.0: les tecnologies d'agregació de MultiRF, els esquemes de MISO distribuït i els de MIMO colocalitzat. S'estudien els potencials casos d'ús, els principals aspectes d'implementació del transmissor i el receptor, i els guanys de rendiment de les configuracions conjuntes per a les dues capes de LDM. Les restriccions addicionals de combinar LDM amb les tecnologies avançades es consideren admissibles, ja que les majors demandes ja estan contemplades en ATSC 3.0 (ex., una segona cadena de recepció). S'obtenen guanys significatius per a la capa mòbil en condicions de recepció per als vianants gràcies a la diversitat en freqüència proporcionada per les tecnologies MultiRF. La conjunció de LDM amb esquemes MISO distribuïts proporciona guanys de rendiment significatius en xarxes SFN per a la capa fixa amb l'esquema d'Alamouti. / Garro Crevillén, E. (2018). Advanced Layered Divsion Multiplexing Technologies for Next-Gen Broadcast [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/105559 / Compendio

La caractérisation géochimique et isotopique des eaux souterraines de la « zone minéralisée de l’Entre-Deux-Mers » indique une origine commune de la minéralisation, directement liée à la minéralogie des formations captées par les forages.La géochimie montre que les interactions eau-roche sont majoritairement influencées par la présence d’évaporites, mais que d’autres interactions mettant en jeu des carbonates, des silicates et des argiles existent. Un modèle géochimique d’acquisition de la minéralisation reconstitue parfaitement la chimie des eaux souterraines à l’échelle de la zone d’étude. Ce modèle, construit en se basant sur la géochimie des eaux et sur la minéralogie des formations tertiaires du nord du Bassin aquitain, met à l’équilibre des eaux avec des formations carbonatées et évaporitiques. Afin de mieux comprendre la distribution latérale et verticale des formations tertiaires et leur minéralogie, une approche paléogéographique et sédimentologique a permis de localiser les différents horizons riches en sulfates et/ou en fluorures, mais aussi de comprendre leur origine de dépôt. En se basant sur l’hydrogéologie, la paléogéographie, la minéralogie et la géochimie, des hypothèses de répartition de la minéralisation à l’échelle du forage ont pu être testées. Les résultats de la modélisation couplée hydrodynamique–transport reconstituent la chimie des eaux prélevées par les forages de la « zone minéralisée de l’Entre-Deux-Mers ». Au vu de ces résultats, un modèle avec obturation des horizons riches en sulfates et en fluorures a été testé et les résultats obtenus ouvrent des perspectives pour des futures recherches. Ce travail a donc permis de comprendre l’origine de la minéralisation des eaux de « la zone minéralisée de l’Entre-Deux-Mers », mais aussi de proposer des améliorations et des perspectives pour une meilleure gestion d’une des principales ressources en eau potable de la Gironde. / Geochemical and isotopic characterizations of groundwaters in the "mineralized Entre-Deux-Mers area" indicate a common origin of the mineralization, directly linked to the mineralogy of the formations abstracted by drilling.Geochemistry shows that water-rock interactions are mainly influenced by the presence of evaporites, and that but that other interactions involving carbonates, silicates and clays exist. A geochemical model based on the water geochemistry and mineralogy of the Tertiary formations of northern Aquitaine Basin fix waters in equilibrium with evaporitic and carbonated formations. This model reconstitutes perfectly the groundwaters’ chemistry across the study area and explains the mineralization acquisition. Improving the understanding of the lateral and vertical distribution of tertiary formations and their mineralogy requires a sedimentological and paleogeographical approach. This approach allowed to locate the different layers rich in sulphates and/or fluoride and to understand also their origin.Based on hydrogeology, paleogeography, mineralogy and geochemistry, the distribution of the mineralization has been tested at the borehole scale. The results of this coupled hydrodynamic-transport modeling reconstitute the chemistry of the groundwaters in the "mineralized Entre-Deux-Mers area." A model, that considers the sealing of sulphates- and fluorides-rich layers has been tested and its results highlights future research perspectives. This work has allowed understanding the origin of the mineralization of the waters "of the mineralized Entre-Deux-Mers area" and also suggests improvements and prospects for sustainable management of a major drinking water resource in Gironde.

A potencialidade do eletrodo de cobre em meio alcalino foi demonstrada para o determinação de etanol a +0,6 V vs Ag/AgCl. A participação de espécies solúveis de Cu(III) no processo eletrocatalítico envolvendo a oxidação do etanol foi demonstrada por experimentos utilizando eletrodo disco-anel. A influência do potencial de pré-tratamento no sinal anódico foi investigada e correlacionada com a morfologia dos filmes formados na superfície do eletrodo por EDS (Energy Dispersive X-Ray Spectroscopy), indicando que as espécies de Cu(III) são originadas a partir da oxidação da camada de CuO. As medidas de etanol foram realizadas por amperometria em 0,6 V (vs Ag/AgCl). A repetibilidade das medidas utilizando padrão aquoso de etanol 0,05 % (v/v) foi de 3 % (v/v) e os limites de detecção e quantificação foram de 0,005 % (v/v) e 0,01 % (v/v), respectivamente. Nas condições experimentais otimizadas, o sensor amperométrico foi utilizado para o monitoramento da concentração de etanol no ar exalado (BrAC), que foi convenientemente coletado em um balão de borracha (V = 3 L) e introduzido em uma solução de NaOH 1 mol L-1 (V = 10 mL). O sensor apresentou uma faixa linear para concentrações de etanol em ar exalado na faixa de 0,26 – 130 mg L-1, operando de acordo com os parâmetros analíticos especificados na Legislação Brasileira para a quantificação de etanol no ar exalado em condutores de veículos automotores. A constante de eliminação de etanol do corpo humano também foi investigada e os resultados concordaram com os valores da literatura. Empregando-se eletrodos de Cu e Au foram também desenvolvidas outras metodologias para a quantificação de dipirona, glicose e ácido ascórbico e sistemas em fluxo. Estudos sobre o desenvolvimento e propriedades de um sistema gerador-coletor foram realizados e o dispositivo foi utilizado em titulações de substâncias redutoras com iodo gerado eletroquimicamente. / A copper disc working electrode in alkaline solutions was demonstrated to act as a suitable amperometric sensor for ethanol determination at +0.6 V vs Ag/AgCl. The participation of free-soluble Cu(III) species in the electrocatalytic process involving the anodic oxidation of ethanol has been demonstrated by rotating ring-disc electrode voltammetry. The influence of the pretreatment potential on the anodic signal was investigated and a correlation with the morphology of the electrode surface characterized by Energy Dispersive X-Ray Spectroscopy (EDS) indicated that the Cu(III) species is originated from the oxidation of a CuO layer. Ethanol measurements were performed in the amperometric mode at 0.6 V (vs Ag/AgCl). The repeatability of the measurements for a 0.05 % aqueous ethanol solution was estimated as 3 %, and the detection and quantification limits were determined as 0.005 % and 0.01 %, respectively. At the optimum experimental conditions, the amperometric sensor was used to monitor the concentration of ethanol in breath (BrAC), which was conveniently collected in a rubber air balloon (volume = 3 L) and introduced in a 1 mol L-1 NaOH working solution (volume = 10 mL). The sensor can measure a person\'s breath ethanol over the concentration range 0.26 - 130 mg L-1 by operating it according to an established protocol, of which the analytical parameters are specified by the Brazilian Legislation for BrAC measurements in drivers. The rate of ethanol degradation in the body was followed, and the results agree with predictions in the literature. Methodologies for the determination of dipyrone, glucose and ascorbic acid were also developed by using Cu and Au electrodes. Features of a dual-band electrochemical cell were investigated towards the development of a generator-collector system, which was employed in titrations with electrogenerated iodine.

Die besonderen Eigenschaften von Graphen ermöglichen das Design von elektronischen Bauteilen im Nanometerbereich. Graphen kann auf der Oberfläche von Siliziumkarbonat (SiC) durch das Ausdampfen von Si epitaktisch gewachsen werden. Ein detailliertes Verständnis der atomaren und elektronischen Struktur der Grenzschicht zwischen Graphen und SiC ist ein wichtiger Schritt um die Wachstumsqualität zu verbessern. Wir nutzen Dichtefunktionaltheorie um das Hybridsystem Graphen-SiC auf atomarer Ebene zu beschreiben. Experimentelle Arbeiten auf der Si Seite von SiC haben gezeigt, dass die Grenzschicht (ZLG) durch eine teilweise kovalent gebundene Kohlenstofflage wächst; darüber bildet sich die erste Graphenlage (MLG). Durch das Konstruieren eines ab initio Oberflächenphasendiagrams zeigen wir, dass sowohl ZLG als auch MLG Gleichgewichtsphasen sind. Unsere Ergebnisse implizieren, dass Temperatur- und Druckbedingungen für den selbstbegrenzenden Graphenwachstum existieren. Wir zeigen, dass sich das Doping und die Riffellung von epitaktischem Graphene durch H-Interkalation reduzieren. Im Experiment unterscheidet sich das Graphenwachstum auf der C Seite qualitativ von der Si Seite. Zu Beginn des Graphenwachstums wird eine Mischung verschiedener Oberflächenphasen beobachtet. Wir diskutieren die Stabilität dieser konkurierenden Phasen. Die atomaren Strukturen von einigen dieser Phasen, inklusive der Graphen-SiC Grenzschicht, sind nicht bekannt wodurch die theoretische Beschreibung erschwert wird. Wir präsentieren ein neues Model für die bisher unbekannte (3x3) Rekonstruktion, das Si Twist Model. Die Oberflächenenergie vom Si Twist Model und von der bekannten (2x2)c Phase schneiden sich direkt an der Grenze zur Graphitbildung. Dies erklärt die experimentell beobachtete Phasenkoexistenz zu Beginn des Graphenwachstums. Wir schlussfolgern, dass auf der C Seite der kontrollierte Graphenewachstum durch Si-reiche Oberflächenphasen blockiert wird. / Graphene with its unique properties spurred the design of nanoscale electronic devices. Graphene films grown by Si sublimation on SiC surfaces are promising material combinations for graphene applications. Understanding the atomic and electronic structure of the SiC-graphene interface, is an important step to refine the growth quality. In this work, density-functional theory is used to simulate the SiC-graphene interface on an atomistic level without empirical parameters. Experimental work has shown that on the Si face of SiC, a partially covalently bonded carbon layer, the zero-layer graphene (ZLG), grows. On top of the ZLG layer forms mono-layer graphene (MLG) as large ordered areas and then few-layer graphene. By constructing an ab initio surface phase diagram, we show that ZLG and MLG are at least near equilibrium phases. Our results imply the existence of temperature and pressure conditions for self-limiting growth of MLG key to the large-scale graphene production. H intercalation significantly reduces both the corrugation and the graphene doping. Our calculations demonstrate that unsaturated Si atoms in the ZLG influence the electronic structure of graphene. The situation on the C face of SiC is very different. The experimental growth of large areas of graphene with well defined layer thickness is difficult. At the onset of graphene formation a phase mixture of different surface phases is observed. We will address the stability of the different occuring surface phases. However, the atomic structure of some of the competing surface phases, as well as of the SiC-graphene interface, is unknown. We present a new model for the (3x3) reconstruction, the Si twist model. The surface energies of this Si twist model, the known (2x2)c adatom phase, and a graphene covered (2x2)c phase cross at the chemical potential limit of graphite, which explains the observed phase mixture. We argue that well-controlled graphene formation is hindered by Si-rich surface phases.

At some point during a creative action something clicks, suddenly the prospective problem solver just knows the solution to a problem, and a feeling of joy and relief arises. This phenomenon, called Eureka experience, insight, Aha moment, hunch, epiphany, illumination, or serendipity, has been part of human narrations for thousands of years. It is the moment of a subjective experience, a surprising, and sometimes a life-changing event. In this thesis, I narrow down this moment 1. conceptually, 2. experientially, and 3. temporally. The concept of emerging solutions has a multidisciplinary background in Cognitive Science, Arts, Design, and Engineering. Through the discussion of previous terminology and comparative reviews of historical literature, I identify sources of ambiguity surrounding this phenomenon and suggest unifying terms as the basis for interdisciplinary exploration. Tracking the experience based on qualitative data from 11 creative practitioners, I identify conflicting aspects of existing models of creative production. To bridge this theoretical and disciplinary divide between iterative design thinking and sequential models of creativity, I suggest a novel multi-layered model. Empirical support for this proposal comes from Dira, a computer-based open-ended experimental paradigm. As part of this thesis I developed the task and 40 unique sets of stimuli and response items to collect dynamic measures of the creative process and evade known problems of insightful tasks. Using Dira, I identify the moment when solutions emerge from the number and duration of mouse-interactions with the on-screen elements and the 124 participants' self-reports. I provide an argument for the multi-layered model to explain a discrepancy between the timing observed in Dira and existing sequential models. Furthermore, I suggest that Eureka moments can be assessed on more than a dichotomous scale, as the empirical data from interviews and Dira demonstrates for this rich human experience. I conclude that the research on insight benefits from an interdisciplinary approach and suggest Dira as an instrument for future studies.

Made available in DSpace on 2014-12-17T15:42:01Z (GMT). No. of bitstreams: 1 EdissonMJ.pdf: 6565731 bytes, checksum: 5d6fdd6db6fc25a30c6100d96fff1edc (MD5) Previous issue date: 2007-08-24 / TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800?C), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7?nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200?C, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400?C. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150?C, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase / Titanatos nanoestruturados, particularmente TiTanatos NanoTubulares (TTNT), foram sintetizados por tratamento hidrot?rmico alcalino de TiO2-anat?sio seguido de repetidas lavagens com diversos graus de troca prot?nica. Amostras de TTNT com diferentes teores de s?dio foram caracterizadas na forma de p? seco e ap?s calcina??o (200-800?C) por difra??o de raios-X, microscopia eletr?nica de varredura e transmiss?o, difra??o de el?trons, an?lise t?rmica, adsor??o de nitrog?nio e t?cnicas espectrosc?picas de infravermelho e de reflet?ncia difusa no UV-Vis?vel. Demonstrou-se que tais materiais de paredes multilamelares s?o trititanatos de f?rmula geral NaxH2−xTi3O7?nH2O, retendo ?gua entre as lamelas. A remo??o de s?dio da estrutura reduz a quantidade de ?gua contraindo o espa?o interlamelar levando, combinado a outros fatores, ao aumento da ?rea e do volume de poros espec?ficos. Os TTNTs s?o materiais mesoporosos com duas contribui??es principais: poros menores que 10 nm devido ao volume interno dos nanotubos e poros entre 5 e 60 nm devido aos espa?os interpart?cula. A composi??o qu?mica e a estrutura cristalina do TTNT n?o dependem do tamanho de cristalito do TiO2-anat?sio precursor, todavia este par?metro afeta significativamente a morfologia e as caracter?sticas texturais do produto nanoestruturado. Tal depend?ncia foi racionalizada atrav?s de um mecanismo de dissolu??o-recristaliza??o que leva em conta a velocidade de dissolu??o do TiO2 de partida e sua influ?ncia sobre a taxa de crescimento de nanofolhas intermedi?rias em rela??o ? taxa de seu curvamento a nanotubos. A estabilidade t?rmica do TTNT ? definida pelo teor de s?dio e em pequena extens?o pelo tipo de anat?sio de partida. Foi demonstrado que o TTNT ap?s perder a ?gua intercalada entre 100 e 200?C se transforma pelo menos parcialmente num hexatitanato NaxH2−xTi6O13 intermedi?rio ainda nanotubular. A transforma??o t?rmica do tri- e hexatitanato nanoestruturados ocorre em maior ou menor temperatura e segue diferentes rotas dependendo do teor de s?dio. No caso de alto s?dio sinterizam e crescem at? grandes cristais de Na2Ti3O7 e Na2Ti6O13 na forma de bast?es e fitas acima de 600?C. No caso da amostra protonizada evoluem para nanotubos de TiO2(B) que facilmente se convertem em nanobast?es de anat?sio acima de 400?C. Al?m de hidroxilas e acidez de Lewis t?picos dos ?xidos de tit?nio, os TTNTs apresentam uma pequena contribui??o de acidez prot?nica capaz de se coordenar com a piridina a 150?C, e que ? perdida ap?s sua calcina??o e transforma??o ? anat?sio. O ponto isoel?trico do TTNT variou dentro da faixa 2,5- 4,0, indicando o comportamento de um ?cido fraco. Apesar de se revelar um semicondutor exibindo banda de absor??o t?pica no espectro de UV-vis?vel com energia de bandgap ligeiramente superior ao do respectivo TiO2-anat?sio precursor, os TTNTs apresentaram baixo desempenho fotocatal?tico na degrada??o de corantes cati?nico e ani?nico. Concluiu-se que a causa fundamental reside em sua estrutura de titanato lamelar que, em rela??o ? forma TiO2, apresentaria maior probabilidade de recombina??o do par el?tron-lacuna (e-/h+), inibindo as rea??es de fotoxida??o. A transforma??o do TTNT prot?nico ? nanobast?es de anat?sio melhorou a atividade fotocatal?tica, por?m ainda sem atingir o mesmo desempenho do TiO2-anat?sio precursor

Ce travail de thèse présente l’étude du diagramme de phase des oxydes lamellaires NaxMoO2dans le cadre de la recherche de nouveaux matériaux. L’identification des transitionsstructurales au cours de l’intercalation et désintercalation électrochimique du sodium dans lesdomaines de composition ½ ≤ x ≤ 1 et ¼ < x ≤ ½ a été faite par électrochimie combinée à ladiffraction des rayons X in situ. Il a été montré que le profil très accidenté de la courbegalvanostatique résulte de multiples réarrangements structuraux au cours du cyclage.Notamment l’existence de nombreuses phases NaxMoO2 particulières a été mise en évidence,pour lesquelles des mises en ordre des ions sodium et des atomes de molybdène sont attendues.Des composés Na~1/2MoO2, Na~2/3MoO2 et NaMoO2 ont été synthétisés ex situ par voieélectrochimique ou chimique et leur caractérisation révèle des arrangements structurauxcomplexes, tel que des chaînes de clusters de molybdène dans les feuillets [MoO2] de NaMoO2. / This work concerns the investigation of the phase diagram of sodium layered oxides NaxMoO2in the search of new materials. Structural transitions upon sodium electrochemical(de)intercalation were studied by electrochemistry combined with in situ X-ray diffraction forcompositions ½ ≤ x ≤ 1 et ¼ < x ≤ ½. It was shown that the very undulating aspect of theelectrochemical curve results from multiple structural rerarrangements upon cycling. Especiallynumerous NaxMoO2 specific phases have been evidenced, for which sodium/vacancy orderingsas well as the formation of Mo-Mo bonds are expected. Na~1/2MoO2, Na~2/3MoO2 et NaMoO2compounds have been (electro)chemically synthesized and their structural characterizationreveals complex structures, such as chains of diamond-like molybdenum clusters in NaMoO2.

Ce travail présente la mise en oeuvre d’un protocole de synthèse de gradients deconcentration dans les oxydes lamellaires riches en Li et en Mn. Le but a été dedévelopper la formation d’oxydes lamellaires riches en Li et Mn au coeur des agrégatssphériques du matériau actif et, en se rapprochant de la surface, d’enrichir lacomposition de l’oxyde lamellaire en Co et en Ni, afin de combiner une forte densitéd’énergie (apportée par le coeur du gradient) et une excellente stabilité thermique etstructurale (apportée par la surface du gradient). La synthèse a été réalisée en deuxétapes, une co-précipitation pour former un carbonate de métaux de transition suivied’une calcination à haute température pour obtenir le matériau actif lithié. L’influencede différents paramètres (pH, débit d’injection, taille du réacteur, composition, …) surla nature du carbonate à gradient de concentration ainsi formé a été étudiée. De lamême façon, le contrôle du ratio Li/M (ici M = Ni, Co, Mn), de la température et de ladurée de calcination s’est révélé important pour parvenir à maintenir le gradient deconcentration dans le matériau lithié. Le ratio Li/M est également déterminant pourcontrôler la nature des matériaux obtenus (lamellaire - spinelle ou lamellaire –lamellaire). Des caractérisations extrêmement pointues, et complexes à mettre enoeuvre, ont été menées afin d’obtenir des informations pertinentes sur la distributiondes phases au sein des agrégats (composition et structure), de la surface au coeur dugradient : différentes techniques de microscopie (EPMA, MEB-EDX et FIB-STEM) ontainsi été largement utilisées. Les matériaux les plus intéressants ont été étudiés enbatteries Lithium-ion avec une électrode de graphite à la négative, les performancesélectrochimiques et la stabilité thermique à l’état chargé de la batterie sont largementdiscutées par rapport à l’état de l’art et notamment au matériau de coeur riche en Li eten Mn. / This work describes in details the implementation of the synthesis protocol for theformation of Li- and Mn-rich layered oxides with concentration-gradients. The purposewas to develop the synthesis of Li- and Mn-rich layered oxides in the bulk of sphericalaggregates of active material and, moving to the surface, to enrich the layered oxides’composition with Co and Ni, in order to combine a high energy density (provided bythe bulk) and an excellent thermal and structural stability (provided by the surface).The synthesis was performed in two steps, a coprecipitation to form a transition metalcarbonate followed by a calcination at high temperature to obtain the lithiated activematerial. The influence of several parameters (pH, feeding rate, size of the reactor,composition …) on the nature of the carbonates formed with concentration-gradientswas studied. Similarly, the control of the Li/M ratio (with M = Ni, Co, Mn) and of thetemperature and duration of calcination was revealed to be important to maintain theconcentration-gradient in the lithiated materials. The Li/M ratio is also the keyparameter to control the nature of the materials obtained (layered - spinel or layered -layered). Advanced characterizations, complex to be implemented, were performed inorder to obtain in-depth information on the distribution of phases within the aggregates(composition and structure), from the bulk to the surface: complementary microscopytechniques (EPMA, SEM-EDS and FIB-STEM) were widely used. The most interestingmaterials were studied in Lithium-ion batteries with graphite at the negative electrode,their electrochemical performance and the thermal stability in the charged state of thebattery were compared to the state of art, and particularly to the bulk Li and Mn-richlayered oxide.

Worldwide there is considerable concern over the effects of human activities on the quantity and quality of freshwater. Measurement of infiltration behaviour will be important for improving freshwater management. This study identifies that New Zealand has a sporadic history of measuring soil water movement attributes on a limited number of soil types, although the current practical demand should be large for management of irrigation, dairy farm effluent disposal, as well as municipal / domestic waste- and storm-water disposal. Previous research has demonstrated that infiltration behaviour is governed by the interplay between numerous mechanisms including hydrophobicity and preferential flow, the latter being an important mechanism of contaminant leaching for many NZ soils. Future characterisation will need to recognise the dynamic nature of these interactions, and be able to reliably characterise the key infiltration mechanisms. Since macropores are responsible for preferential flow, it is critical that infiltration studies use a representative sample of the macropore network. The aim of this project was to study the mechanisms governing the infiltration behaviour of a layered soil in large (50 x 70 cm) monolith lysimeters, where the connectivity of the macropore network remains undisturbed. Four lysimeters of the Gorge silt loam were collected, a structured soil with four distinct layers. On each lysimeter there were four separate infiltration experiments, with water applied under suctions of 0, 0.5, 1, and 1.5 kPa by a custom-built tension infiltrometer. Each lysimeter was instrumented with 30 tensiometers, located in arrays at the layer boundaries. There was also a field experiment using ponded dye infiltration to visually define preferential flowpaths. Analysis of dye patterns, temporal variability in soil matric potential (Ψm), and solute breakthrough curves all show that preferential flow is an important infiltration mechanism. Preferential flowpaths were activated when Ψm was above -1.5 kPa. During saturated infiltration, at least 97% of drainage was through the ‘mobile’ pore volume of the lysimeter (θm), estimated among the lysimeters at 5.4 – 8.7 % of the lysimeter volume. Early-time infiltration behaviour did not show the classical square-root of time behaviour, indicating sorptivity was not the governing mechanism. This was consistent across the four lysimeters, and during infiltration under different surface imposed suctions. The most likely mechanism restricting sorptivity is weak hydrophobicity, which appears to restrict infiltration for the first 5 – 10 mm of infiltration. Overall, the Gorge soil’s early-time infiltration behaviour is governed by the dynamic interaction between sorptivity, hydrophobicity, the network of air-filled pores, preferential flow and air encapsulation. Long-time infiltration behaviour was intimately linked to the temporal dynamics of Ψm, which was in turn controlled by preferential flow and soil layer interactions. Preferential flowpaths created strong inter-layer connectivity by allowing an irregular wetting front to reach lower layers within 2 – 15 mm of infiltration. Thereafter, layer interactions dominate infiltration for long-time periods, as Ψm in soil layers with different K(Ψm) relationships self-adjusts to try to maintain a constant Darcy velocity. An important finding was that Ψm rarely attained the value set by the tension infiltrometer during unsaturated infiltration. The results show that ‘true’ steady-state infiltration is unlikely to occur in layered soils. A quasi-steady state was identified once the whole column had fully wet and layer interactions had settled to where Ψm changes occurred in unison through each soil layer. Quasi-steady state was difficult to identify from just the cumulative infiltration curve, but more robustly identified as when infiltration matched drainage, and Ψm measurements showed each layer had a stable hydraulic gradient. I conclude that the in-situ hydraulic conductivity, K(Ψm), of individual soil layers can be accurately and meaningfully determined from lysimeter-scale infiltration experiments. My results show that K(Ψm) is different for each soil layer, and that differences are consistent among the four lysimeters. Under saturated flow the subsoil had the lowest conductivity, and was the restricting layer. Most interestingly this pattern reversed during unsaturated flow. As Ψm decreased below -0.5 to -1 kPa, the subsoil was markedly more conductive, and the topsoil layers became the restricting layers. All four soil layers demonstrate a sharp decline in K(Ψm) as Ψm decreases, with a break in slope at ~ -1 kPa indicating the dual-permeability nature of all layers.

<p>This dissertation considers packet-switched wireless networks for transmission of variable-rate layered hybrid video streams. Target applications are video streaming and broadcasting services. The work can be divided into two main parts.</p><p>In the first part, a novel quality-scalable scheme based on coefficient refinement and encoder quality constraints is developed as a possible extension to the video coding standard H.264. After a technical introduction to the coding tools of H.264 with the main focus on error resilience features, various quality scalability schemes in previous research are reviewed. Based on this discussion, an encoder decoder framework is designed for an arbitrary number of quality layers, hereby also enabling region-of-interest coding. After that, the performance of the new system is exhaustively tested, showing that the bit rate increase typically encountered with scalable hybrid coding schemes is, for certain coding parameters, only small to moderate. The double- and triple-layer constellations of the framework are shown to perform superior to other systems.</p><p>The second part considers layered code streams as generated by the scheme of the first part. Various error propagation issues in hybrid streams are discussed, which leads to the definition of a decoder quality constraint and a segmentation of the code stream to transmit. A packetization scheme based on successive source rate consumption is drafted, followed by the formulation of the channel code rate optimization problem for an optimum assignment of available codes to the channel packets. Proper MSE-based error metrics are derived, incorporating the properties of the source signal, a terminate-on-error decoding strategy, error concealment, inter-packet dependencies, and the channel conditions. The Viterbi algorithm is presented as a low-complexity solution to the optimization problem, showing a great adaptivity of the joint source channel coding scheme to the channel conditions. An almost constant image qualiity is achieved, also in mismatch situations, while the overall channel code rate decreases only as little as necessary as the channel quality deteriorates. It is further shown that the variance of code distributions is only small, and that the codes are assigned irregularly to all channel packets.</p><p>A double-layer constellation of the framework clearly outperforms other schemes with a substantial margin. </p><p>Keywords — Digital lossy video compression, visual communication, variable bit rate (VBR), SNR scalability, layered image processing, quality layer, hybrid code stream, predictive coding, progressive bit stream, joint source channel coding, fidelity constraint, channel error robustness, resilience, concealment, packet-switched, mobile and wireless ATM, noisy transmission, packet loss, binary symmetric channel, streaming, broadcasting, satellite and radio links, H.264, MPEG-4 AVC, Viterbi, trellis, unequal error protection</p>