Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work first we perform a study about the stability, and the electronic properties of SiC growth in the [111] direction when defects are present. We use the supercell method and the dangling bonds on the surface of the nanowire are saturated using hydrogen atoms. We also study antisites and substitutional oxygen impurity in this nanowire. For this study, we perform total energy and band structure calculations in order to find the most stable positions for the defects and the influence of defects on the electronic properties. The first principles calculations are based in the density functional theory (DFT). The Generalized Gradient Approximation (GGA) is used for the exchange-correlation term and the ion-electron interactions are replaced by norm-conserving fully separable Troullier-Martins pseudopotentials. For the calculations we use the SIESTA-code and the standard Kohn-Shan (KS) equations are solved in a fully selfconsistent way. The Khon-Sham orbitals are expanded using a linear combination of numerical pseudo-atomic orbitals (PAOs). All calculations use a split-valence double-zeta quality basis set enhanced with a polarization function. Our results show that the most stable antisite is a carbon atom occupying a silicon site (CSi). The substitutional oxygen impurity is most stable in a carbon site (OC). Both defects present a greater stability in the surface of the nanowire when compared with the core of the nanowire. The analysis of electronic structure of bands shows that these defects give rise to electronic levels localized in the band gap of the nanowire. Keywords: density functional theory; SiC nanowires, antisites, impurity. / Neste trabalho inicialmente realizamos um estudo da estabilidade e das propriedades eletrônicas de nanofios de SiC crescido na direção [111]. Foi utilizado o método de supercélula e as ligações pendentes da superfície do nanofio de SiC foram saturadas com átomos de H. Em seguida analisamos estes nanofios na presença de antissítios e impureza substitucional de oxigênio. Para estes defeitos procurou-se as posições energeticamente mais estáveis e as influências dos defeitos nas propriedades eletrônicas. Os cálculos teóricos foram de primeiros princípios fundamentados na Teoria do Funcional da densidade (DFT). Utilizamos para descrever o funcional de trocacorrelação a Aproximação do Gradiente Generalizado (GGA) e para a interação elétron-íon pseudopotenciais de norma conservada de Troullier-Martins. As densidades de carga são obtidas resolvendo as equações de Kohn-Sham, com as funções de onda de Khon-Sham expandidas em uma combinação linear de orbitais atômicos. Nossos resultados mostram que o antissítio mais estável é um átomo de carbono ocupando o sítio de um átomo de silício (CSi). A impureza substitucional de oxigênio apresenta uma maior estabilidade quando ocupando o sítio do átomo de carbono (OC). Ambos os defeitos são energeticamente mais estáveis na superfície do nanofio de SiC. A análise da estrutura eletrônica apresenta que níveis de defeitos podem estar presentes no gap do nanofio, porém nos sítios mais estáveis não observa-se níveis de defeitos no gap.

Made available in DSpace on 2016-08-03T12:21:16Z (GMT). No. of bitstreams: 1 DISSERTACAO FINAL.pdf: 844004 bytes, checksum: 8d3fa4b2650339ece711921dd082e593 (MD5) Previous issue date: 2011-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The composite work knows as I Enoch compound of five books reached much importance for Second Temple s Judaism(s) as well as for the Christianism(s) of first four centuries. For this intention in this research was test the contribution of Myth of Watchers (I Enoch 6-11) for the imaginary of demoniac in the synoptics, especially while impure spirit. To reach this object firstly we show the impact of Myth of Watchers in both Enochic and Judaic tradition, for ahead analyze its contribution for the imaginary of demoniac. After this, we present the presence of themes and ideas of this myth in some texts of New Testament. Proved this presence of the myth in Christian s communities, we analyze the characteristics and symbolic expressions that to paint the demoniac picture in the synoptics, asking for the relations that with daemons of the Judaic traditions. With the collection of images about demoniac of these traditions in the Second Temple period and its nearby relation with the Myth of Watchers, we conclude with the hypothesis that demoniac while calling of impure spirit bear marks and echoes of development of the Myth of Watchers in the Enoch traditions and in apocalyptic. Possibly we can to state that the images and ideas raised for reads of this myth was present in imaginary of the Christian s communities where the synoptics raised especially in the idea of daemons. Thus the influence of the Myth of Watchers doesn t resume itself at the literary utilitarism but is in environment of imaginary appropriate in manner very much dynamic and hidden. / A obra compósita conhecida como I Enoque, formada por cinco livros, logrou muita importância para os Judaísmos do segundo templo, como também para os Cristianismos dos primeiros quatro séculos. Por isso, a intenção dessa pesquisa foi testar a contribuição do Mito dos Vigilantes (I Enoque 6-11) para o imaginário do demoníaco nos sinóticos, em especial enquanto espírito imundo. Para esse intento, primeiramente apresentamos as influencias do Mito dos Vigilantes na tradição enoquita e judaica em geral, para depois analisarmos suas contribuições para o imaginário do demoníaco. Depois, mostramos a presença de temas e idéias desse mito em alguns textos neotestamentários. Comprovada a presença do mito nas comunidades cristãs, analisamos as características e expressões simbólicas que pintam o quadro demonológico nos sinóticos, perguntando pela possível relação com os demônios das tradições judaicas. Com o acúmulo de imagens dos seres malignos dessas tradições no período do segundo templo, e a sua próxima relação com o Mito dos Vigilantes, concluímos ser possível a hipótese de que o demoníaco ao ser chamado de espírito impuro trás indícios e ecos do desenvolvimento, nas tradições de Enoque e na apocalíptica, do Mito dos Vigilantes. Possivelmente, podemos afirmar que as imagens e idéias geradas pelas releituras desse mito permeavam o imaginário das comunidades cristãs que geraram os sinóticos, em especial na concepção dos demônios. Assim, a influência do Mito dos Vigilantes não se resume a utilização literária, mas está no âmbito do imaginário, apropriado de maneira muito mais sutil e dinâmica.

New NMR Tools for Impurity Analysis was written by Jane Power and submitted for the degree of Doctor of Philosophy in the Faculty of Engineering and Physical Sciences at the University of Manchester, on 31st March 2016.NMR spectroscopy is rich in structural information and is a widely used technique for structure elucidation and characterization of organic molecules; however, for impurity analysis it is not generally the tool of choice. While 1H NMR is quite sensitive, due to its narrow chemical shift range (0 - 10 ppm) and the high abundance of hydrogen atoms in most drugs, its resolution is often poor, with much signal overlap. Therefore, impurity signals, especially for chemically cognate species, are frequently obscured. 19F NMR on the other hand offers extremely high resolution for pharmaceutical applications. It exhibits far wider chemical shift ranges (± 300 ppm) than 1H NMR, and typical fluorinated drugs, of which there are many on the market, have only one or two fluorine atoms. In view of this, 19F NMR is being considered as an alternative for low-level impurity analysis and quantification, using a chosen example drug, rosuvastatin. Before 19F NMR can be effectively used for such analysis, the significant technical problem of pulse imperfections, such as sensitivity to B1 inhomogeneity and resonance-offset effects, has to be overcome. At present, due to the limited power of the radiofrequency amplifiers, only a fraction of the very wide frequency ranges encountered with nuclei such as fluorine can be excited uniformly at any one time. In this thesis, some of the limitations imposed by pulse imperfections are addressed and overcome. Two new pulse sequences are developed and presented, CHORUS and CHORUS Oneshot, which use tailored, ultra-broadband swept-frequency chirp pulses to achieve uniform constant amplitude and constant phase excitation and refocusing over very wide bandwidths (approximately 250 kHz), with no undue B1 sensitivity and no significant loss in sensitivity. CHORUS, for use in quantitative NMR, is demonstrated to give accuracies better than 0.1%. CHORUS Oneshot, a diffusion-ordered spectroscopic technique, exploits the exquisite sensitivity of the 19F chemical shift to its local environment, giving excellent resolution, which allows for accurate discrimination between diffusion coefficients with high dynamic range and over very wide bandwidths. Sulfur hexafluoride (SF6) is investigated and shown to be a suitable reference material for use in 19F NMR. The bandshape of the fluorine signal and its satellites is simple, without complex splitting patterns, and therefore good for reference deconvolution; in addition, it is sufficiently soluble in the solvent of choice, DMSO-d6.To demonstrate the functionality of the CHORUS sequences for low-level impurity analysis, 470 MHz 1H decoupled 19F spectra were acquired on a 500 MHz Bruker system, using a degraded sample of rosuvastatin, to reveal two low-level impurities. Using a standard Varian probe with a single high frequency channel, simultaneous 1H irradiation and 19F acquisition was made possible by time-sharing. Simultaneous 19F{1H} and 19F{13C} double decoupling was then performed using degraded and fresh samples of rosuvastatin, to reveal three low-level impurities (in the degraded sample) and low-level 1H and 13C modulation artefacts.

Doctor of Philosophy / Department of Chemistry / Mark D. Hollingsworth / The ferroelastic urea inclusion compound (UIC) of 2,10-undecanedione/urea exhibits a striking pseudoelastic memory effect. Although pseudoelasticity is possible for UICs containing only 2,10-undecanedione, introduction of a structurally similar guest impurity (2-undecanone) gives rise to rubber-like behavior, a form of pseudoelasticity. This phenomenon depends on both the crystal strain and the concentration of monoketone: above 13-14% 2-undecanone, pseudoelastic behavior is observed reliably, even at strains as high as 2.4%. The dramatic change in ferroelastic behavior over a small range of impurity content indicates that this is a critical threshold phenomenon. Because the impurity concentration has such a dramatic effect on domain switching, it was important to determine the sector-dependent patterns of incorporation of this relaxive impurity. Preliminary HPLC analyses of guest populations suggest that preferential incorporation of monoketone guests occurs between nonequivalent growth sectors, and that these patterns can be rationalized using a symmetry specific growth model. Birefringence mapping and HPLC studies of optically anomalous UICs containing mixtures of 2,9-decanedione and 2-decanone (which possess trigonal metric symmetry) suggest analogous patterns in guest incorporation and/or ordering that can also be rationalized. Although crystals of 2,9-decanedione/urea exhibit no ferroelastic strain at ambient temperature, they exhibit a proper ferroelastic phase transition near -170[degrees]C. It is proposed that differential perfection of domains gives rise to pseudoelasticity in UICs, and that relaxive impurities play an important role in the energetics of this process. Because ultrafast video studies of domain reversion kinetics demonstrate no clear correlation of observed rates with impurity content, it is proposed that the relaxive impurities facilitate spontaneous domain reversion by annealing stressed defect sites that would otherwise lead to irreversible or plastic domain switching. Following earlier work using synchrotron white beam X-ray topography, the driving force for domain reversion is thought to involve the presence of nanoscopic twins whose strain is epitaxially mismatched with neighboring daughter domains. The behavior of these nanoscopic twins was monitored with in-situ X-ray diffraction studies of stressed crystals, and this has led to a more thorough understanding of the role of these nanoscopic twins in the ferroelastic domain switching and rubber-like behavior in this class of materials.

Ce travail a pour but de comprendre les effets de deux principaux défauts liés à l’oxygène, les complexes bore-oxygène et les donneurs thermiques, sur les propriétés électriques et photovoltaïques du silicium. Plus particulièrement, les interactions des impuretés isovalentes, connues pour modifier la distribution spatiale de l’oxygène, avec ces défauts ont été étudiées. Deux protocoles expérimentaux ont d’abord été développés pour évaluer la dégradation de la durée de vie des porteurs de charge sous éclairement dans le silicium riche en fer. Ensuite, il a été mis en évidence que l’introduction de germanium et d’étain en très grande quantité dans le silicium n’influence pas de façon significative le rendement de conversion des cellules. Cependant, contrairement à ce qui a été récemment avancé dans la littérature, aucune limitation due au co-dopage au germanium ou à l’étain de la dégradation sous éclairement des performances photovoltaïques n’a été observée. Par contre, il a été montré que le carbone entraîne un ralentissement de la dégradation due aux complexes bore-oxygène. Egalement, contrairement à l’étain qui n’influence pas la génération des donneurs thermiques, le germanium conduit à un ralentissement de la formation de ces défauts. Une expression empirique a été proposée pour rendre compte de cet effet, et ce pour une large gamme de teneurs en germanium. Enfin, dans le silicium très dopé et très compensé, la génération des donneurs thermiques est identique au cas du silicium standard. Ceci constitue un résultat marquant puisqu’il permet de valider par l’expérience le fait que la formation des donneurs thermiques est limitée par la teneur en électrons. / This study aims at understanding the effects of two main defects related to oxygen, the boron-oxygen complexes (responsible for light-induced degradation of the carrier lifetime) and the thermal donors (among other things, responsible for variations of the conductivity), on the electric and photovoltaic properties of silicon. More precisely, the interactions of isovalent impurities, known for modifying the oxygen spatial distribution, with these defects were studied. Two experimental protocols were first developed to evaluate the light-induced degradation of the carrier lifetime in iron-rich silicon. Then, the introduction in silicon of germanium and tin in high quantity were shown not to significantly influence the conversion efficiency of the cells. However, contrary to recent studies from the literature, no reduction due to germanium co-doping or to tin co-doping of the light-induced degradation of the photovoltaic performances was observed. However carbon was shown to lead to a slowdown of the degradation due to boron-oxygen complexes. Moreover contrary to tin which has no influence on the thermal donor generation, germanium slows down their formation. An empirical expression has been proposed to take into account this effect for a large range of germanium concentrations. Eventually in highly doped and compensated silicon, the thermal donor generation is identical as in conventional silicon, which experimentally confirms that the thermal donor formation is limited by the electron density.

[pt] Esta dissertação apresenta resultados teóricos e experimentais relativos ao problema de clusterização de um conjunto de vetores (que possam ser interpretados como distribuições de probabilidade) com o objetivo de minimizar uma medida de impureza da partição resultante. Por meio de uma conexão entre o problema geométrico de k-médias e o problema de clusterização para minimizar a impureza ponderada de Gini da partição, prova-se que este último é NP-completo e APX-difícil. Também analisamos uma família de algoritmos para clusterização com base nas componentes dominantes (as maiores componentes) dos vetores a serem particionados. Mostra-se que, em alguns casos, dois desses algoritmos conseguem obter bons resultados em termos da entropia ponderada da partição resultante, em um tempo bem menor do que os algoritmos considerados como o estado da arte. / [en] We present theoretical and experimental results related to the problem of clustering a set of vectors (which can be interpreted as probability distributions) with the goal of minimizing a weighted impurity measure of the resulting partition. The problem of clustering while minimizing the weighted Gini impurity of the partition is shown to be NP-complete and APX-hard, via a connection with the geometrical k-means problem. We also analyze a family of algorithms for information-theoretic clustering that rely on the dominant (largest) component of the vectors to be clustered. These algorithms are shown to be very fast compared to the state of the art, while able to achieve comparable results in terms of the resulting partition s weighted entropy.

Prenumerationstjänster blir alltmer populära i dagens samhälle. En av nycklarna för att lyckas med en prenumerationsbaserad affärsmodell är att minimera kundbortfall (eng. churn), dvs. kunder som avslutar sin prenumeration inom en viss tidsperiod. I och med den ökande digitaliseringen, är det nu enklare att samla in data än någonsin tidigare. Samtidigt växer maskininlärning snabbt och blir alltmer lättillgängligt, vilket möjliggör nya infallsvinklar på problemlösning. Denna rapport kommer testa och utvärdera ett försök att förutsäga kundbortfall med hjälp av maskininlärning, baserat på kunddata från ett företag med en prenumerationsbaserad affärsmodell där prenumeranten får besöka live-event till en fast månadskostnad. De maskininlärningsmodeller som användes i testerna var Random Forests, Support Vector Machines, Logistic Regression, och Neural Networks som alla tränades med användardata från företaget. Modellerna gav ett slutligt träffsäkerhetsresultat i spannet mellan 73,7 % och 76,7 %. Därutöver tenderade modellerna att ge ett högre resultat för precision och täckning gällande att klassificera kunder som sagt upp sin prenumeration än för de som fortfarande var aktiva. Dessutom kunde det konstateras att de kundegenskaper som hade störst inverkan på klassifikationen var ”Använda Biljetter” och ”Längd på Prenumeration”. Slutligen kommer det i denna rapport diskuteras hur informationen angående vilka kunder som sannolikt kommer avsluta sin prenumeration kan användas ur ett mer affärsmässigt perspektiv. / In today’s world subscription-based online services are becoming increasingly popular. One of the keys to success in a subscription-based business model is to minimize churn, i.e. customer canceling their subscriptions. Due to the digitalization of the world, data is easier to collect than ever before. At the same time machine learning is growing and is made more available. That opens up new possibilities to solve different problems with the use of machine learning. This paper will test and evaluate a machine learning approach to churn prediction, based on the user data from a company with an online subscription service letting the user attend live shows to a fixed price. To perform the tests different machine learning models were used, both individually and combined. The models were Random Forests, Support Vector Machines, Logistic Regression and Neural Networks. In order to train them a data set containing either active or churned users was provided. Eventually the models returned accuracy results ranging from 73.7 % to 76.7 % when classifying churners based on their activity data. Furthermore, the models turned out to have higher scores for precision and recall for classifying the churners than the non-churners. In addition, the features that had the most impact on the model regarding the classification were Tickets Used and Length of Subscription. Moreover, this paper will discuss how churn prediction can be used from a business perspective.

The study, “Between honor and shame: Martyrdom in 2 Maccabees 6-7 within the socio-cultural arena”, presents a look at how the community viewed martyrdom in 2 Maccabees 6:18-7:42 from the perspective of honor and shame. The chief objective is to determine whether or not the community supported or challenged the notion of the martyrs’ death being either honorable or shameful. In order to reach a satisfactory conclusion to this objective, this study set as goals the identification of key themes which shed light upon the views of the community in regard to the martyrs, as well as the investigation of the community’s understanding of honor and shame found in 2 Maccabees 6:18-7:42. This study incorporates a contextual analytical method comprising of an analysis of sociocultural vocabulary, an analysis of the socio-cultural vocabulary within the Greek text of 2 Maccabees 6:18-7:42 and a synthesis of the analysis of both the socio-cultural and the Greek context. As criteria for the study of the socio-cultural context the aspects of sacred-profane, pure-impure, the patron-client relationship and the relationship between individual and group(s) are implemented. Core-findings of this study may be divided into two main categories: evidence in defence of an honorable conduct during death, and evidence in defence of the dishonorable manner of death. Evidence in defence of honorable conduct during death, are: • The martyrs remain completely loyal and devoted to God (their Chief-Patron), His laws and • the customs of the forefathers. • They are portrayed as being bodily whole. • They safeguard their set-apartness. • They remain pure – especially in the ritualistic sense. • As individuals belonging to the collected identity of various groups, the martyrs prove themselves loyal and honorable. Evidence in defence for the dishonorable manner in which the martyrs die, are: • Torture was deemed disgraceful by the community and would therefore degrade honor. • Mutilation went into the very fabric of the wholeness of the body by destroying the bodily unity, thereby disqualifying a person to come into the realm of the sacred. • Certain members of the community would regard the martyrs’ rejection of the lesser patrons’ favor as disrespectful and therefore as dishonorable conduct. Despite this evidence, it is still found that the community could remain undecided on how to judge the martyrs and martyrdom. Therefore, it is proposed, and successfully implemented, that an emotional argument might be the key to tipping the scale toward viewing the martyrs and martyrdom as honorable. It must therefore be concluded that the community would have indeed challenged the notion of martyrdom being honorable, for torture and mutilations in themselves, were regarded as being disgraceful. Yet the community would have been persuaded to accept the honor of the martyrs because of their honorable conduct and the emotional appeal made by the author of Maccabees. / Thesis (MA (Greek))--North-West University, Potchefstroom Campus, 2013.

Geological Carbon Storage (GCS) is considered as one of the key techniques to reduce the rate of atmospheric emissions of CO2 and thereby to contribute to controlling the global warming. A successful application of a GCS project requires the capability of the formation to trap CO2 for a long term. In this context, processes related to CO2 trapping and also possible leakage of CO2 to the near surface environment need to be understood. The overall aim of this thesis is to understand the flow and transport of CO2 through porous media in the context of geological storage of CO2. The entire range of scales, including the pore scale, the laboratory scale, the field experiment scale and the industrial scale of CO2 injection operation are addressed, and some of the key processes investigated by means of experiments and modeling.  First, a numerical model and laboratory experimental setup were developed to investigate the CO2 gas flow, mimicking the system in the near-surface conditions in case a leak from the storage formation should occur. The system specifically addressed the coupled flow and mass transport of gaseous CO2 both in the porous domain as well as the free flow domain above it. The comparison of experiments and modelling results showed a very good agreement indicating that the model developed can be applied to evaluate monitoring and surface detection of potential CO2 leakage. Second, the field scale CO2 injection test carried out in a shallow aquifer in Maguelone, France was analyzed and modeled. The results showed that Monte Carlo simulations accounting for the heterogeneity effects of the permeability field did capture the key observations of the monitoring data, while a homogeneous model could not represent them. Third, a numerical model based on phase-field method was developed and model simulations carried out addressing the effect of wettability on CO2-brine displacement at the pore-scale. The results show that strongly water-wet reservoirs provide a better potential for the dissolution trapping, due to the increase of interface between CO2 and brine with very low contact angles. The results further showed that strong water-wet conditions also imply a strong capillary effect, which is important for residual trapping of CO2. Finally, numerical model development and model simulations were carried out to address the large scale geological storage of CO2 in the presence of impurity gases in the CO2 rich phase. The results showed that impurity gases N2 and CH4 affected the spatial distribution of the gas (the supercritical CO2 rich phase), and a larger volume of reservoir is needed in comparison to the pure CO2 injection scenario. In addition, the solubility trapping significantly increased in the presence of N2 and CH4.

A pesquisa tem o intuito de explorar a noção de \"Presença\", que é amplamente estudada no campo das artes da cena e em performance art. Essa noção é emancipada a um dispositivo conceitual criativo nas áreas da música e de arte sonora. Passando por questionamentos acerca da performance musical, contrapõe o conceito de obra à ideia de impureza, que surge como um território propício para a investigação do conceito de presença. Para isso, é levantada uma definição desse conceito, balizada em estudos teatrais e filosóficos, que possibilitam a abertura de um campo de estudos em criação e performance sonora. Dentro desse contexto, são feitas reflexões sobre artistas que buscam relacionar seus trabalhos a elementos extramusicais, e que, de alguma forma, tangenciam o conceito de presença que fora delineado. / The research aims to explore the notion of \"presence,\" which is widely studied in the stage arts and performance art. This notion is emancipated to a creative conceptual device in the areas of music and sound art. Through discusses about the musical performance, the research opposes the concept of work to the idea of impurity, which appears as a breeding ground for the investigation of the concept of presence. Therefore, it is raised a definition of this concept, rooted by theatrical and philosophical studies, which allows the opening of a field of sound studies about performance and composition. In this context, reflections are made about artists who seek to relate their work to extramusical elements, and that, somehow, are related to the concept of presence that had been outlined by this research.