The hyperfine interaction between carrier spins and nuclear spins is an important component in exploring spin-dependent properties in materials with strong spin orbit interaction.However hyperfine interaction has been less studied in bismuth (Bi), a heavy element exhibiting a strong Rashba-like spin-orbit interaction in its two-dimensional surface states due to the broken spatial inversion symmetry. In this dissertation we experimentally explore the carrier spin polarization due to transport under strong spin-orbit interaction and the nuclear polarization resulting from the relatively unexplored hyperfine interaction on Bi(111) films.The carrier and nuclear spin polarizations are expected to dynamically interact, a topic with ramifications to other materials where surface states with noteworthy properties play a role.To achieve this goal, an optimized van der Waals epitaxy growth technique for Bi(111) on mica substrates was developed and used, resulting in flat Bi surfaces with large grain sizes and a layered step height of 0.39±0.015 nm, corresponding to one Bi(111) bilayer height. A comparison between Bi(111) films grown on three different substrates (mica, InSb(111)B, and Si(111)) is discussed, for which scanning electron microscopy and atomic force microscopy are applied to obtain the structural and morphological characteristics on the film surface. Magnetotransport measurements are carried out to extract the transport properties of theBi(111) films. Using the high quality Bi(111) film deposited on mica, we develop quantum magnetotransport techniques as delicate tools to study hyperfine interaction. The approach is based on measuring quantum corrections to the conductivity due to weak antilocalization, which depend on the coherence of the spin state of the carriers. The carrier spin polarization is generated by a strong DC current in the Bi(111) surface states (here called the Edelstein effect), which then induces dynamic nuclear polarization by hyperfine interaction. Quantum transport antilocalization measurements in the Bi(111) thin-films grown on mica indicate a suppression of antilocalization by the in-plane Overhauser field from the nuclear polarization, and allow for the quantification of the Overhauser field, which is shown to depend on both polarization duration and the DC current magnitude. Various delay times between the polarization and the measurement result in an exponential decay of the Overhauser field, driven by relaxation time T1. We observe that in the Bi surface states, the appreciable electron density and strong spin-orbit interaction allow for dynamic nuclear polarization in the absence of an external magnetic field. / Doctor of Philosophy / This dissertation focuses on the heavy element bismuth (Bi), a semimetal with strong spin-orbit interaction at its two-dimensional surface. Given the challenge to grow high qualityBi(111) films, we present an optimized van der Waals epitaxy technique to grow Bi(111)films on mica substrates, which show a flat surface with large grain sizes and a layered step height of 0.391±0.015 nm, corresponding to one Bi(111) bilayer height. To demonstrate the high quality of the Bi(111) surface, a comparison of surface morphology was conducted among Bi(111) films deposited on three different substrates (mica, Si(111), and InSb(111)B),along with a comparison between their electronic transport properties. By applying a DC current on the high quality Bi(111) film on mica, a carrier spin polarization is established via mainly what we here call the Edelstein effect, which then induces dynamic nuclear polarization by hyperfine interaction and generates a non-equilibrium nuclear spin polarization without externally applied magnetic field. We quantified the Overhauser field from the nuclear polarization all-electrically by conducting quantum transport antilocalization experiments, which showed a suppression of antilocalization by the in-plane Overhauser field.Comparative measurements indicated that the magnitude of the Overhauser field depends onthe spin-polarizing DC current magnitude and the polarization duration. The experiments also show that antilocalization forms a sensitive probe for hyperfine interaction and nuclear polarization.

The focus of this thesis is the critical review of Additive Printing (AP) or 3D-printing, and optimization strategies for the introduction of new materials. During the course of tenure, four classes of solids were investigated to determine the hurdles presented from each system. Specifically, the investigation developed techniques for optimization of ink production, green-film deposition, and laser sintering parameters surrounding the Optomec AJP system (AJP). In the assessment, statistical experimental design, analysis and material characterization techniques have been utilized. Final recommendations disseminate current best practices for new ink and material development, along with factor analysis of input variables for phase and material properties, along with insights for future research of these systems. The first chapter provides a general introduction to the field of AP. The second chapter focuses specifically on Optomec aerosol-jet process (AJP) techniques, and expands the discussion to process parameters, information concerning the fabrication/characterization procedure followed for each system, and includes: a detailed description of the materials investigated. This is important because printing parameters, optimization, and approach may be divergent for optimization within each strain; and is meant as an aid to resolve some technical issues for future investigators. The third chapter is fully dedicated to the results concerning the fabrication and the characterization of amorphous boron powder to film. Chapter four discusses future research options, ideas and directions. Appendices are provided for any which wish to investigate the orthogonal arrays used, or the combinatorial effects resulting in the attributes of the material system final products. / Master of Science

[ES] A pesar de la tendencia actual hacia la electrificación del transporte por carretera, los motores de combustión interna alternativos han sido esenciales en este sector y se espera que sigan siendo una tecnología con notable presencia durante las próximas décadas. Los vehículos de pasajeros actuales basados en motores de combustión interna son más ecológicos que los utilizados hace años, aunque todavía queda trabajo por hacer. Los sistemas de postratamiento están enfocados a minimizar tanto como sea posible el impacto de los motores de combustión interna en términos de emisiones contaminantes. En el caso de los motores de encendido provocado, los catalizadores de tres vías representan la tecnología más extendida en las últimas décadas, debido a su compacidad y buena relación precio-prestaciones. Estos convertidores son capaces de oxidar hidrocarburos y monóxido de carbono al mismo tiempo que reducen los óxidos de nitrógeno. No obstante, para lograr su mejor eficiencia, el dosado debe controlarse con precisión en torno a condiciones estequiométricas. En este sentido, los sistemas electrónicos de gestión del motor son esenciales para aprovechar las características de estos convertidores. En particular, las estrategias de control y diagnóstico desempeñan un papel clave para lograr una reducción efectiva de las emisiones en el amplio rango de condiciones de operación que se dan en condiciones de funcionamiento reales. El desarrollo de estas estrategias es fundamental, especialmente teniendo en cuenta el bajo nivel de emisiones permitido por las normativas de emisiones actuales y la tendencia hacia cero emisiones. El propósito de esta tesis doctoral es analizar el comportamiento del sistema de postratamiento en condiciones específicas pero a la vez muy comunes en conducción real, y desarrollar estrategias que proporcionen una reducción adicional de las emisiones en sistemas basados en catalizador de tres vías. Con la popularización de pequeños motores turboalimentados de encendido provocado, ha aumentado el uso de estrategias de barrido de la cámara de combustión para mitigar los típicos problemas de falta de par a bajo régimen. Esta tesis analiza el impacto de los pulsos de cortocircuito en el catalizador y en las sondas ¿. El proceso de cortocircuito de aire fresco al escape tiene un impacto importante en la dinámica intraciclo de la composición de los gases de escape. En particular, los pulsos de monóxido de carbono e hidrógeno seguidos por los pulsos de aire fresco perturban el normal funcionamiento del sensor de oxígeno. Por lo tanto, se ha propuesto un nuevo método para estimar la tasa de cortocircuito abordo. Este método permite corregir la desviación sufrida por el sensor y, por lo tanto, ayuda a reducir la penalización en emisiones de este tipo de estrategias. Para mejorar la eficiencia del catalizador en condiciones transitorias, no solo se requiere un control preciso del dosado aguas arriba del catalizador, sino que también resulta imprescindible considerar el comportamiento dinámico del convertidor en sí mismo. Por ejemplo, el almacenamiento de oxígeno es un buen indicador del estado del catalizador, pero no se puede medir directamente mediante sensores. Por lo tanto, el desarrollo de modelos es clave en las estrategias de control actuales, para poder estimar abordo diferentes parámetros relacionados con el estado del catalizador. Varios modelos de catalizador se han desarrollado en esta tesis doctoral para lidiar con diferentes cuestiones, desde la predicción de los efectos de la condensación de agua en la evolución de la temperatura del catalizador justo después del arranque en frío, a la cuantificación del nivel de envejecimiento, pasando por el control óptimo de purga del catalizador. / [CA] Malgrat la tendència actual cap a l'electrificació del transport per carretera, els motors de combustió interna alternatius han sigut essencials en aquest sector i s'espera que continuen sent una tecnologia amb notable presència durant les pròximes dècades. Els vehicles de passatgers actuals basats en motors de combustió interna són més ecològics que els utilitzats fa anys, encara que hi ha treball per fer. Els sistemes de post-tractament estan enfocats a minimitzar tant com siga possible l'impacte dels motors de combustió interna en termes d'emissions contaminants. En el cas dels motors d'encés provocat, els catalitzadors de tres vies representen la tecnologia més estesa en les últimes dècades, pel fet que són compactes i posseeixen bona relació preu-prestacions. Aquests convertidors són capaços d'oxidar hidrocarburs i monòxid de carboni al mateix temps que redueixen els òxids de nitrogen. No obstant això, per a aconseguir la seua millor eficiència, el dosatge ha de controlar-se amb precisió entorn de condicions estequiomètriques. En aquest sentit, els sistemes electrònics de gestió del motor són essencials per a aprofitar les característiques d'aquests convertidors. En particular, les estratègies de control i diagnòstic exerceixen un paper clau per aconseguir una reducció efectiva de les emissions en l'ampli rang de condicions d'operació que es donen en condicions de funcionament reals. El desenvolupament d'aquestes estratègies és fonamental, especialment tenint en compte el baix nivell d'emissions permès per les normatives actuals i la tendència cap a zero emissions. El propòsit d'aquesta tesi doctoral és analitzar el comportament del sistema de post-tractament en condicions específiques però alhora molt comunes en conducció real, i desenvolupar estratègies que proporcionen una reducció addicional de les emissions en sistemes basats en catalitzador de tres vies. Amb la popularització de xicotets motors amb sobrealimentació d'encés provocat, ha augmentat l'ús d'estratègies de curtcircuit per a mitigar els típics problemes de falta de parell a baix règim. Aquesta tesi analitza l'impacte dels polsos de curtcircuit en el catalitzador i en les sondes ¿. El procés de curtcircuit d'aire fresc té un impacte important en la dinàmica intra-cicle de la composició dels gasos. En particular, els polsos de monòxid de carboni i hidrogen seguits pels polsos d'aire fresc pertorben el normal funcionament del sensor d'oxigen. Per tant, s'ha proposat un nou mètode per a estimar la taxa de curtcircuit del motor. Aquest mètode permet corregir la desviació patida pel sensor i, per tant, ajuda a reduir la penalització en emissions d'aquest tipus d'estratègies. Per a millorar l'eficiència del catalitzador en condicions transitòries, no solament es requereix un control precís del dosatge aigües amunt del catalitzador, sinó que també resulta imprescindible considerar el comportament dinàmic del convertidor en si mateix. Per exemple, l'emmagatzematge d'oxigen és un bon indicador de l'estat del catalitzador, però no es pot mesurar directament mitjançant sensors. Per tant, el desenvolupament de models és clau en les estratègies de control actuals, per poder estimar els diferents paràmetres relacionats amb l'estat del catalitzador. Diversos models de catalitzador s'han desenvolupat en aquesta tesi doctoral per a tractar diferents qüestions, des de la predicció dels efectes de la condensació d'aigua en l'evolució de la temperatura del catalitzador just després de l'arrencada en fred, a la quantificació del nivell d'envelliment, passant pel control òptim de porga del catalitzador. / [EN] In spite of the current tendency towards the electrification of the road transport, internal combustion engines have been essential in this sector and it is expected to continue being a technology with a noticeable presence during next decades. Current passenger cars based on internal combustion engines are greener than those used years ago, although it is still a developing process. Aftertreatment systems are aimed to minimize as much a possible the impact of internal combustion engines in terms of pollutant emissions. In case of spark-ignited engines, three-way catalytic converters represent the most widespread technology during last decades, due to their compactness and cost-performance. These converters are capable to oxidise hydrocarbons and carbon monoxide while simultaneously reducing nitrogen oxide. Nonetheless, to achieve their best efficiency, the air-to-fuel ratio must be accurately controlled close to stoichiometric conditions. In this sense, electronic engine management systems are essential to take advantage of the features of these converters. In particular, control and diagnosis strategies play a key role to achieve an effective emissions reduction under the wide range of operating conditions that arise in real driving conditions. The further development of this strategies is fundamental, especially taking into account the low emissions level allowed by current regulatory procedures and the trend towards zero emissions. The purpose of this dissertation is to analyse the behaviour of the aftertreatment system under very specific but at the same time very common conditions, and developing strategies that provide a further emissions reduction for systems based on three-way catalyst. With the popularization of small turbocharged spark-ignited engines, the use of scavenging strategies to solve the typical low-end torque issues has increased. This dissertation analyses the impact of the short-circuit pulses on both three-way catalyst and ¿ sensors. The short-circuit process has an important effect on the in-cycle dynamics of the exhaust gas composition. In particular, the carbon monoxide and hydrogen pulses followed by fresh air pulses cause a sensor bias. Thus a new method to on-line estimate the short-circuit rate has been proposed. This method allows to correct the sensor bias and, therefore, help to reduce the emissions penalty. To improve the TWC efficiency under transient conditions, not only an accurate air-to-fuel ratio control upstream of the converter is required, but also to consider the dynamic behaviour of the converter itself. For example, the oxygen storage is the main responsible for the converter dynamics, and thus, a good indicator of the catalyst state, but it cannot be directly measured. Hence the development of models is key in current control strategies, to on-line track different parameters related with the state of the converter. Several models have been derived in this dissertation in order to fulfil different requirements, from the prediction of water condensation effects on the temperature evolution inside the converter just after cold-start, to the quantification of the ageing level, through the optimal catalyst purge control, or the air-to-fuel ratio disturbances rejection. / Real Minuesa, M. (2020). Modelling, control and diagnosis of aftertreatment systems based on three-way catalyst in spark-ignited engines [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/137040

Yes / The Sustainable Development Goals (SDGs) present the emerging need to explore new ways of AgriFood production and food security as ultimate targets for feeding future generations. The study adopts a Design Science methodology and proposes Artificial Intelligence (AI) techniques as a solution to food security problems. Specifically, the proposed artefact presents the collective use of Agricultural Technology (AgriTech) drones inspired by the biomimetic ways of bird swarms. The design (artefact) appears here as a solution for supporting farming operations in inaccessible land, so as unmanned aerial devices contribute and improve the productivity of farming areas with limited capacity. The proposed design is developed through a scenario of drone swarms applying AI techniques to address food security issues. The study concludes by presenting a research agenda and the sectoral challenges triggered by the applications of AI in Agriculture. / European Union's H2020 research and innovation programme under the Marie Skłodowska-Curie grant (agreement No. 746667)

L’objectif de ce travail est d’établir des relations entre chimie d’interface et propriétés mécaniques dans les assemblages bimétalliques. Il met en évidence que les mécanismes qui contrôlent le développement d’une interface entre alliage Al-Si et renfort ferreux ou titane ont une influence majeure sur les propriétés mécaniques de cette interface. La caractérisation mécanique des interfaces est réalisée par un test de flexion 4 points sur des lames bimétallique élaborées par aluminiage au trempé sur lesquelles un raidisseur est rapporté par collage ou surmoulage. L’évolution de la chimie de la zone de réaction interfaciale est provoquée par un traitement thermique à 535°C à différents temps. La caractérisation des zones de réaction ainsi que des chemins de fissuration est réalisée par diffraction des rayons X et microsonde électronique. Pour les interfaces Fe/A-S7G03 brutes d’élaboration, avant traitement thermique, l’analyse des essais mécaniques conduit à l’obtention d’une valeur du taux de restitution d’énergie de 23 J/m2 qui correspond à la propagation d’une fissure dans la phase η−Al5Fe2(Si). En ce qui concerne les interfaces Ti/A-S7G03, leur force n’a pas permis la propagation d’une fissure dans les conditions de l’essai. A la suite d’un traitement thermique à 535°C, les interfaces Fe/A-S7G03 sont fragilisées par le mécanisme de croissance de la couche de réaction interfaciale qui conduit à l’apparition de porosités Kirkendall en son sein. A l’inverse, dans le cas des interfaces Ti/A-S7G03, aucun affaiblissement de l’interface n’est associé au traitement thermique en raison d’un mécanisme de croissance différent. / The objective of this work is to establish the relationships between interface chemistry and mechanical properties in bimetallic assemblies. It proves that the mechanisms which control the development of an interface between Al-Si alloy and titanium or ferrous reinforcement have a major influence on the mechanical properties of this interface. The mechanical characterization of these interfaces is performed by a 4-point bending test on the bimetallic plates elaborated by hot dip aluminizing on which a stiffener is joined by bonding or overmolding. The chemistry evolution of the interfacial reaction zone is induced by a heat treatment at 535 °C at different reaction times. The characterization of reaction zones and the crack paths is performed by X-ray diffraction and electron probe microanalysis. Before heat treatment, the analysis of mechanical tests performed on Fe/A-S7G03 interfaces leads to a value for the energy release rate of 23 J/m2 which corresponds to a crack propagation in the η- Al5Fe2 (Si) phase. As regards the Ti/A-S7G03 interfaces, their strength did not allow a crack propagation under the test conditions. After a heat treatment at 535°C, the Fe/A-S7G03 interfaces are weakened by the growth mechanism of interfacial reaction layer which leads to the appearance of Kirkendall voids within it. Conversely, in the case of Ti/A-S7G03 interfaces, the heat treatment is not associated with any weakening of the interfacial zone because of a different growth mechanism.

Ce travail de thèse ce focalise sur la croissance et la caractérisation de Nanofils (NFs) et de Microfils (µFs) de GaN. L'élaboration de telles structures est obtenue par épitaxie en phase vapeur d'organométalliques à partir de deux stratégies de croissances: l'une dite auto-organisée, réalisée sur substrat saphir, l'autre appelée sélective ou localisée, obtenue sur template GaN de polarité Ga. Quelque soit la stratégie employée, nous montrons que la croissance de structures verticales suivant l'axe c requièrent l'utilisation d'un flux de NH3 et d'un rapport V/III faible, lorsque nous les comparons avec les valeurs utilisées pour la réalisation de couches planaires de GaN. Les paramètres et les étapes de croissances ayant une influence sur le rapport d'aspect (hauteur/diamètre) sont étudiées et mises en évidence pour chacune des stratégies employées. Par ailleurs, les mécanismes de croissance ainsi que les propriétés structurales et optiques de ces objets sont caractérisés par MEB, MET, CL et µPL. En particulier, les expériences réalisées sur les µFs auto-organisés permettent d'observer et d'expliquer l'origine de la double polarité, de mettre en lueur la différence d'incorporation de dopants/d'impuretés entre les domaines Ga et N, d'identifier la présence de deux sections de propriétés électriques et optiques différentes, et de révéler la présence de deux types de résonances optiques: des Modes de galerie et des Modes de Fabry-Perot. D'autres part, nous étudions la courbure des dislocations vers les surfaces libres des NFs localisés et µFs auto-organisés, et pointons la présence de fautes d'empilement basales dans des régions de faibles dimensions. / This work focus on growth and characterization of GaN Nanowires (NWs) and Microwires (µWs). Such structures are obtained by Metal Organic Vapor Phase Epitaxy with two growth strategies: one called self-organized which is realized on sapphire, and the other named selective area growth which is obtained on a GaN Ga-polar template. Whatever the growth strategies employed, vertical growth of structures along the c axis requires the use of a low NH3 flux and V/III ratio, when they are compared with values used for planar growth of GaN. The influence of growth parameters and growth steps on aspect ratio (height/diameter) are studied and highlight for each growth strategies employed. Beside, growth mechanisms and structural and optical properties of such objects are characterized by SEM, TEM, CL and µPL. In particular, experiments realized on self-organized µWs enable us to observe and explain the origin of the double polarity, to highlight the dopants/impurities incorporation difference between Ga and N-domain, to identify two sections with differences in electrical and optical properties, and to reveal the presence of two types of optical resonances, identify as Whispering Gallery Modes and Fabry-Perot Modes. On the other hand, we study the bending of dislocations on free walls of localized NWs and self-organized µWs, and pointed out the presence of basal stacking faults in regions of small dimensions.

[pt] Vivemos a era da intimidade como espetáculo, como denominou a pesquisadora e professora Paula Sibilia, e como observamos na mídia e a cada clique dado na internet entre redes sociais, sites de celebridades, blogs, instagram, notícias e conversas. É a vez dos anônimos, das pequenas histórias, dos relatos cotidianos, e o ciberespaço surge como alternativa para aquisição de voz e lugar. Nesta pesquisa pretende-se abordar o cenário de escrita dos blogs abrindo uma reflexão sobre a importância da internet como forma de construção de história e memória, onde se registram tendências atuais de criação de identidade. Através de uma discussão analítico-crítica a respeito desse modo de fixação da escrita – território em constante transformação –, observam-se as características semelhantes e divergentes dos diversos autores e propostas destes espaços. Toma-se como objeto, principalmente, as escritas que se podem nomear poético-recordativas, que produzem um acervo de lembranças que circulam entre autores – professores, escritores, cantores, compositores, estudantes, atrizes, pais e mães – e entre incontáveis leitores, que delineiam, ambos, seus perfis e visitam-se nestes espaços, constituindo uma multiplicidade de perspectivas, entre as quais esta autora inclui-se com seus próprios blogs. Desloca-se o olhar investigativo entre estes espaços virtuais, formulando e debatendo uma série de questões: Como a plataforma virtual interfere na produção e recepção da escrita? Como e por quê se escreve? Como se lê? Que armas afetivo-intelectuais são utilizadas? O objetivo deste trabalho é contribuir para a caracterização de como a internet vem se inserindo na vida intelectual da atualidade. / [es] Vivimos en la era de la intimidad como espectáculo, como denominó la investigadora y profesora Paula Sibilia, y como observamos en los medios de comunicación y a cada click dado en internet entre redes sociales, sitios de celebridades, blogs, instagram, noticias y conversaciones. Es la vez de los anónimos, de las pequeñas historias, de los relatos cotidianos, y el ciberespacio surge como alternativa para adquisición de voz y lugar. En esta investigación se pretende abordar el escenario de la escritura de los blogs abriendo una reflexión sobre la importancia de internet como forma de construcción de la historia y de la memoria, donde se registran tendencias actuales de creación de la identidad. A partir de una discusión analítico-crítica acerca de ese modo de fijación de la escritura – territorio en constante cambio –, se observan características de similitudes y diferencias de los varios autores y propuestas de estos espacios. Serán objeto de análisis, principalmente, las escrituras que se pueden nombrarse poético-recordativas, que producen un acervo de recuerdos que circulan entre autores – profesores, escritores, cantantes, compositores, estudiantes, actrices, padres y madres – y entre incontables lectores, que delinean, ambos, sus perfiles y se visitan en estos que espacios, formando una multiplicidad de perspectivas, entre las cuales la autora de esta disertación se incluye con sus propios blogs. Se disloca la mirada investigativa entre estos espacios virtuales, formulando y debatiendo una serie de cuestiones: Cómo la plataforma virtual interfiere en la producción y recepción de la escritura? Cómo y por qué se escribe? Cómo se lee? Qué armas afectivo-intelectuales se utilizan? El objetivo de este trabajo es contribuir a la caracterización de cómo internet está incidiendo en la vida intelectual actual.

Estudamos neste trabalho o comportamento da impureza oxigênio em rede cristalina de silício, usando primeiramente o método INDO (lntermediate Neglect of Differential Overlap) com parametrização espectroscópica e incluímos os efeitos de muitos elétrons via Método CI-(Interacão de Configuração). Fazemos uma análise sobre as possíveis origens do posicionamento não-central (off-center) dessa impureza, - se decorrente de uma distorsão Pseudo Jahn-Teller: - se originária de um CR Reconstrução Química. Quando o átomo de Oxigênio é deslocado ao longo da direção [100] ocupa um sitio de mínimo absoluto. O oxigênio introduz no gap de banda um orbital anti-ligante de simetria a1 totalmente ocupado, situação semelhante à dos anti-sitios em materiais semi-condutores III-V. Estudamos também o comportamento dessa impureza quando a mesma é deslocada ao longo da direção [111], verificando que é criada uma posição de Instabilidade mas, os auto-valores têm comportamento não esperado para orbitais anti-ligantes. / In this work we studied the Oxygen impurity in Silicon. The calculations were performed using a semi-empirical method (INDO/S) with Configuration Interaction to account for many-electron effects. We analyse the origin of the off-center position for substitutional oxygen. Pseudo Jahn-Teller distortion or Chemical Rebonding effects. The oxygen introduces an a1 anti-bonding state in the forbidden band-gap similar to anti-site defects in III-V materials. To answer the question about distortion, we also studied oxygen dislocation in the (111) direction and we obtained a metastable state but his eigen-value has a non-expected behavior for anti-bonding orbitals.

A otimização de sistemas do tipo Ti-Si-X requer que os sistemas binários estejam constantemente atualizados. O sistema Ti-Si foi investigado experimentalmente desde a década de 50 e poucos estudos usaram os dados experimentais para calcular o diagrama de fases Ti-Si usando modelamento termodinâmico. A otimização mais recente do sistema Ti-Si foi realizada em 1998, descrevendo a fase Ti5Si3 como um intermetálico não estequiométrico contendo três sub-redes e mostrando a presença da fase intermetálica estequiométrica Ti3Si. Dada a recente disputa sobre a cinética de precipitação e a estabilidade das fases Ti3Si e Ti5Si3 nos sistemas Ti-Si e Ti-Si-X, o canto rico em titânio do sistema Ti-Si (estável e metaestável) foi otimizado no presente trabalho. Os limites de estabilidade de fases, os valores dos erros pelo método dos mínimos quadrados do procedimento de otimização e os desvios padrões relativos das variáveis calculadas foram discutidos para inspirar a realização de mais trabalhos experimentais para investigar as reações eutetóides estáveis e/ou metaestáveis, ?->? + Ti3Si e ?->? + + Ti5Si3; e para melhorar cada vez mais as otimizações termodinâmicas do diagrama de fases do sistema Ti-Si. / The thermodynamic optimization of Ti-Si-X systems requires that the binary systems are constantly updated. The Ti-Si system has been experimentally investigated since the 1950\'s and few investigations have used this experimental data to calculate the Ti-Si phase diagram using thermodynamic modeling. The most recent assessment of the Ti-Si system was performed in 1998, describing the Ti5Si3 phase as a non-stoichiometric intermetallic containing three sublattices and showing the presence of the stoichiometric Ti3Si phase. In the light of the dispute over the precipitation kinetics and stability of Ti3Si and Ti5Si3 phases in Ti-Si and Ti-X-Si systems, the present work assessed the Ti-rich corner of the stable (featuring Ti3Si phase) and metastable Ti-Si phase diagrams. The phase boundaries, the values of the error of the least-square method of the optimization procedure and the relative standard deviation of the calculated variables were discussed in order to inspire further experimental work to investigate the stable and/or metastable eutectoid reactions, ?->? + Ti3Si e ?->? +Ti5Si3, and to improve the thermodynamic assessments of the Ti-Si phase diagram.

Nesta tese, utilizamos técnicas de química quântica para o estudo de sistemas contendo átomos de silício e nitrogênio. Nesse contexto, o trabalho aqui apresentado procurou concentrar-se em três tópicos principais: aglomerados de silício e nitrogênio, a superfície Si(100) e a interação de um átomo de nitrogênio com essa superfície. Estudamos inicialmente os aglomerados de fórmula SiNN e Si3N2, onde procuramos caracterizar de forma rigorosa a estabilidade e a natureza das ligações químicas das várias espécies. Com relação ao sistema SiNN, os resultados utilizando cálculos de alto nível mostraram a necessidade de novos dados experimentais para a caracterização inequívoca dessa espécie. Além disso, obtivemos os primeiros resultados para as propriedades de quatro novas estruturas. Estudamos a estrutura de várias espécies com fórmula Si3N2, e obtivemos como mínimo global uma estrutura planar contendo apenas ligações Si-N. Para a simulação da superfície Si(100) utilizamos os aglomerados de fórmula Si9H12 e Si15H16. Apenas a metodologia do Funcional da Densidade indicou a existência de uma estrutura distorcida para o Si9H12. Os cálculos CASSCF mostraram a necessidade do uso de funções multideterminantais. Com relação ao aglomerado Si15H16, obteve-se uma estrutura distorcida com os dímeros alternados como a forma mais estável. Entretanto, o uso do CASSCF mostrou ser a forma simétrica a mais estável. Com base no estudo dos aglomerados Si9H12 e Si15H16, partimos para a investigação dos mecanismos envolvidos no processo de interação e incorporação de átomos de nitrogênio na superfície de silício. Estruturas com simetria de spin quarteto e dupleto foram estudadas, sendo os mecanismos bastante semelhantes, com o nitrogênio interagindo inicialmente com um dos silícios dímeros para em seguida poder formar duas outras estruturas, uma com o nitrogênio ligado aos dois silícios dímeros e outra com o nitrogênio inserido no interior do aglomerado. Esta última estrutura corresponde à forma mais estável. Os resultados mostram claramente que a reação é bastante favorável do ponto de vista energético. Questionamos também o uso de vínculos durante a otimização das estruturas por impedir um devido relaxamento apropriado dos átomos de silício da primeira e segunda camadas. / In this thesis, quantum chemical techniques were used to study molecular systems containing silicon and nitrogen atoms. ln this context, the work was concentrated on three main topics: silicon-nitrogen clusters, the Si(100) surface, and the interaction of a nitrogen atom with that surface. We studied initially the clusters SiNN and Si3N2, where we tried to characterize with rigour the stability and the nature of the chemical bonds of the various species. Concerning the system SiNN, using high level calculation, the results showed the necessity of new experimental data for the unequivocal characterization of this species. Moreover, the properties of four new structures were described for the first time in this study. The structures of various species with formula Si3N2 were studied, and the global minimum corresponds to a planar structure containing only Si-N bonds. For the simulation of Si(100) surface, the clusters Si9H12 and Si15H16 were used. Density Functional Theory predicted the existence of an asymmetric geometry for the Si9H12 cluster. The CASSCF calculations showed the necessity of using multideterminantal wave functions. Concerning the Si15H16 cluster, the most stable structure corresponds to a distorted one with alternated dimers. However, the CASSCF methodology showed that the symmetric structure is the most stable. Based on the results for the Si9H12 and Si15H16 clusters, we started to investigate the mechanism involved in the interaction and incorporation of a nitrogen atom into the silicon surface. Structures with quartet and doublet spin symmetry were studied, being their mechanisms very similar, with the nitrogen atom interacting initially with one silicon dimer; after that two other structures can be formed, one with the nitrogen bonded to two silicon dimers, and the other with the nitrogen bonded to one silicon dimer and two internal silicons. This last structure corresponds to the most stable species. The results show clearly that the reaction is very favorable energetically. The use of geometrical constraints during the optimization was questioned since it prevents the proper relaxation of the silicon atoms in the first and second layers.