No description available.

<p>Advances in Magnetic Resonance Imaging (MRI) have been made possible through increased field strengths and innovations in radiofrequency (RF) coils. With increasing field strengths, unique challenges are presented in RF coil development, namely the suppression of common-mode currents present along the shields of the cabling that connect the RF coil to the MR scanner. These currents can lead to coupling with the coil, resulting in a reduction of coil sensitivity and signal-to-noise ratio. These currents can induce local electric fields that beyond a certain level can exceed SAR limits and even cause patient burns. Several cable trap designs exist to help address this problem; however, many of the existing designs, such as bazooka cable traps, are rigid and bulky. This leads to increased overall coil weight and impedes the flexibility of the cable. Improving upon these designs, a small, 3D-printed, lightweight elliptical cable trap is presented. The unique geometry makes it invisible to the MR scanner while maintaining significant mutual inductance that can produce up to 380 Ω on the cable. These structures were wrapped with stranded wire containing four breaks for tuning capacitors. 60 of these elliptical cable traps were placed along the length of a 139-cm cable, replacing the standard 4 bazooka cable traps. The results of B₁ distortion and heating tests showed that these elliptical baluns improve RF coil thermodynamic stability, produce less B₁ distortion, and reduce overall coil weight and bulk compared to a cable with four bazooka traps. </p>

Nous présentons d’abord une introduction au sujet des marches aléatoires en milieux aléatoires. Nous nous penchons en particulier sur les phénomènes de ralentissement, et plus précisément sur la propriété de vieillissement qu’exhibent plusieurs de ces systèmes lorsque les paramètres sont tels qu’ils conduisent l’environnement aléatoire à produire fréquemment des « pièges », soient des structures qui retiennent la marche aléatoire dans la même région de l’environnement pour de longues durées de temps. Nous illustrons ces notions à l’aide de résultats connus pour deux modèles. Nous présentons par la suite une preuve pour une propriété de vieillissement dans le cas de la marche aléatoire biaisée sur les conductances aléatoires à queues lourdes dans la grille infinie hyper-cubique à d dimensions, qui est le sujet d’un article en attente de publication. / We first present an introduction to the topic of random walks on random environments (RWRE). In particular, we look at slow-down phenomena and, more specifically, ageing properties exhibited by multiple such systems when parameters are chosen such that the random environment frequently produces large “traps”: structures that hold up the progress of the random walk by keeping it in the same region of the environment for long periods of time. We illustrate these behaviours by presenting known results for two such models. We then present a proof for an ageing property in the case of the biased random walk on heavy-tailed random conductances in the infinite hyper-cubic lattice in d dimensions; this is the subject of a research article pending publication.

Die vorliegende Arbeit befasst sich mit der Simulation und Modellierung organischer Feldeffekt-Transistoren (OFETs). Mittels numerischer Simulationen wurden detaillierte Untersuchungen zu mehreren Problemstellungen durchgeführt. So wurde der Einfluss einer exponentiellen Verteilung von Trapzuständen, entsprechend dem sogenannten a-Si- oder TFT-Modell, auf die Transistorkennlinien untersucht. Dieses Modell dient der Beschreibung von Dünnschicht-Transistoren mit amorphen Silizium als aktiver Schicht und wird teils auch für organische Transistoren als zutreffend angesehen. Dieser Sachverhalt wird jedoch erstmals in dieser Arbeit detailliert untersucht und simulierte Kennlinien mit gemessenen Kennlinien von OFETs verglichen. Insbesondere aufgrund der Dominanz von Hysterese-Effekten in experimentellen Kennlinien ist jedoch eine endgültige Aussage über die Gültigkeit des a-Si-Modells schwierig. Neben dem a-Si-Modell werden auch noch andere Modelle diskutiert, z.B. Hopping-Transport zwischen exponentiell verteilten lokalisierten Zuständen (Vissenberg, Matters). Diese Modelle liefern, abhängig von den zu wählenden Modellparametern, zum Teil ähnliche Abhängigkeiten. Möglicherweise müssen die zu wählenden Modellparameter selbst separat gemessen werden, um eindeutige Schlussfolgerungen über den zugrundeliegenden Transportmechanismus ziehen zu können. Unerwünschte Hysterese-Effekte treten dabei sowohl in Transistorkennlinien als auch in Kapazitäts-Spannungs- (CV-) Kennlinien organischer MOS-Kondensatoren auf. Diese Effekte sind bisher weder hinreichend experimentell charakterisiert noch von ihren Ursachen her verstanden. In der Literatur findet man Annahmen, dass die Umladung von Trapzuständen oder bewegliche Ionen ursächlich sein könnten. In einer umfangreichen Studie wurde daher der Einfluß von Trapzuständen auf quasistatische CV-Kennlinien organischer MOS-Kondensatoren untersucht und daraus resultierende Hysterese-Formen vorgestellt. Aus den Ergebnissen läßt sich schlussfolgern, dass allein die Umladung von Trapzuständen nicht Ursache für die experimentell beobachteten Hysteresen in organischen Bauelementen sein kann. Eine mögliche Erklärung für diese Hysterese-Effekte wird vorgeschlagen und diskutiert. In einem weiteren Teil der Arbeit wird im Detail die Arbeitsweise des source-gated Dünnschicht-Transistors (SGT) aufgezeigt, ein Transistortyp, welcher erst kürzlich in der Literatur eingeführt wurde. Dies geschieht am Beispiel eines Transistors auf der Basis von a-Si als aktiver Schicht, die Ergebnisse lassen sich jedoch analog auch auf organische Transistoren übertragen. Es wird geschlussfolgert, dass der SGT ein gewöhnlich betriebener Dünnschicht-Transistor ist, limitiert durch das Sourcegebiet mit großem Widerstand. Die detaillierte Untersuchung des SGT führt somit auf eine Beschreibung, die im Gegensatz zur ursprünglich verbal diskutierten Arbeitsweise steht. Ambipolare organische Feldeffekt-Transistoren sind ein weiterer Gegenstand der Arbeit. Bei der Beschreibung ambipolarer Transistoren vernachlässigen bisherige Modelle sowohl die Kontakteigenschaften als auch die Rekombination von Ladungsträgern. Beides wird hingegen in den vorgestellten numerischen Simulationen erstmalig berücksichtigt. Anhand eines Einschicht-Modellsystems wurde die grundlegende Arbeitsweise von ambipolaren (double-injection) OFETs untersucht. Es wird der entscheidende Einfluß der Kontakte sowie die Abhängigkeit gegenüber Variationen von Materialparametern geklärt. Sowohl der Kontakteinfluß als auch Rekombination sind entscheidend für die Arbeitsweise. Zusätzlich werden Möglichkeiten und Einschränkungen für die Datenanalyse mittels einfacher analytischer Ausdrücke aufgezeigt. Es zeigte sich, dass diese nicht immer zur Auswertung von Kennlinien herangezogen werden dürfen. Weiterhin werden erste Simulationsergebnisse eines ambipolaren organischen Heterostruktur-TFTs mit experimentellen Daten verglichen.

Transaldolase-Mangel (TALDO) ist ein extrem seltener, angeborener Stoffwechseldefekt, von dem weltweit nur 34 Fälle bekannt sind. Der Defekt geht auf den Verlust des Enzyms Transaldolase 1 aus dem nicht-oxidativen Pentosephosphat-Weg (nicht-oxPPW) zurück und äußert sich in einem weiten Spektrum klinischer Symptome. Die schwerwiegendsten Folgen sind Leber- und Nierenmangelfunktionen, die zum sehr frühen Tod führen können. Desweiteren leiden 15 % der Patienten an wiederkehrenden Infektionen. Neutrophile Granulozyten (Neutrophile) sind die häufigsten weißen Blutkörperchen im Menschen und essentiell für die angeborene Immunantwort gegen Infektionserreger. Ich habe hier funktionale Aspekte von TALDO-Neutrophilen untersucht. Der oxidative Pentosephosphat-Weg (oxPPW) stellt das Reduktionsäquivalent NADPH bereit, welches indirekt für die Entstehung von reactive oxygen species (ROS)-abhängigen Neutrophil Extracellular Traps (NETs) verantwortlich ist. Der Beitrag des nicht-oxPPW zur ROS-abhängigen NET-Bildung ist bislang nicht bekannt. In dieser Arbeit konnte ich für Neutrophile aus drei TALDO-Patienten eine jeweils komplett abwesende Entstehung ROS-abhängiger NETs und einen deutlich verringerten oxidativen Burst nach PMA-Stimulation zeigen. Um diese Beobachtungen in einem unabhängigen Modelsystem zu bestätigen, habe ich mit Hilfe des CRISPR-Cas9-Systems, ‚knock-out‘ Mutanten von Transaldolase 1 und dessen Partnerenzym Transketolase in der Neutrophil-ähnlichen Zelllinie PLB-985 hergestellt. Die dergestalt genetisch manipulierten Zellen waren nicht mehr zu PMA-induziertem Zelltod in der Lage. Dies ist somit der erste genetische Beweis für die Abhängigkeit des oxidativen Burst und der Bildung von NETs vom nicht-oxPPW. Diese Erkenntnis trägt zum einen zum mechanistischen Verständnis der NET-Entstehung bei und liefert zum anderen eine potentielle Erklärung für einige der bei TALDO beobachteten Symptome. Desweiteren wurden einige der metabolischen Erfordernisse für die Bildung von NETs mit Hilfe von Inhibitoren untersucht. Die erhaltenen Erkenntnisse zeigen, dass das initiale Maximum des oxidativen Bursts für NET-Bildung unerheblich ist und vielmehr die ROS-Generierung nach ca. 50 Minuten entscheidende Bedeutung für diese hat. / Transdaldolase 1-deficiency (TALDO) is a rare genetic disease with only 34 described cases globally. Transaldolase 1 is part of the non-oxidative pentose phosphate pathway (PPP) and its deficiency results in many clinical symptoms including kidney and liver failure, which can lead to early child-mortality. Some of these patients suffer from recurrent infections, for example in the respiratory tract. Neutrophils are the most abundant white blood cells and essential for the innate immune defence against bacterial and fungal pathogens. The PPP generates reduced NADPH that is crucial for the generation of superoxide by the NADPH oxidase NOX2. In turn, NOX2 is essential for neutrophil extracellular trap (NET) formation. NETs occur through the neutrophil-specific cell death netosis and consist of chromatin decorated with granular proteins. Here I report that neutrophils of three TALDO patients did not make NETs. Deletion of transaldolase 1, and its partner enzyme transketolase, in the neutrophil-like PLB-985 cell line reduced ROS generation and cell death. This confirms that transaldolase 1 is required for NET formation. We present, to the best of our knowledge, the first genetic evidence that the non-oxidative PPP is required for ROS generation and NET formation. Furthermore, some of the metabolic requirements for NET formation were assessed. The obtained data indicate that the initial peak of the oxidative burst is irrelevant for NET formation but the ROS generation after 50 minutes on the contrary has crucial significance.

Les granulocytes de faible densité (LDGs) sont un sous-type de neutrophiles mis en évidence initialement dans le sang de patients atteints de différentes maladies telles que le lupus érythémateux systémique ou le psoriasis. Cependant, des études rapportent également leur présence chez des individus sains. On connait mal à ce jour les caractéristiques des LDGs, notamment en ce qui a trait à leur profil inflammatoire. De plus, leur biogenèse demeure toujours mal connue. Mes travaux de maîtrise visaient à comparer les propriétés des LDGs à celles des neutrophiles de densité normale (NDNs). Pour ce faire, 8 chevaux atteints d’asthme équin sévère et 11 chevaux sains bien caractérisés ont été sélectionnés pour l’étude et sur lesquels des isolations de NDNs ainsi que des LDGs ont été réalisées. La morphologie des neutrophiles a ensuite été évaluée par microscopie optique. Le contenu en myéloperoxidase, un composant des granules primaires azurophiles des neutrophiles, et la présence de récepteurs du N-formylméthionine-leucyl-phénylalanine (fMLP-R) ont été évalués par cytométrie de flux et immunofluorescence, respectivement. Enfin, la capacité fonctionnelle de ces cellules à produire spontanément des pièges extracellulaires des neutrophiles (NETs) a été étudiée in vitro par microscopie confocale. Les résultats démontrent que le nombre de LDGs est augmenté dans le sang des chevaux asthmatiques lors d'exacerbation de la maladie. De plus, ces cellules présentent une morphologie différente puisqu’elles sont de taille plus petite et contiennent plus de fMLP-R que les NDNs. Le contenu en myéloperoxidase est cependant similaire dans les deux populations de neutrophiles. Enfin, les LDGs produisent plus de NETs, et sont plus sensibles aux stimuli activateurs que les NDNs. Ces caractéristiques sont similaires dans les 2 groupes de chevaux suggérant ainsi que ce sont des propriétés intrinsèques des LDGs et qu’ils représentent une population cellulaire préactivée et qui de plus, est majoritairement mature. Cette étude caractérise et compare pour la première fois les LDGs chez des animaux sains et ceux retrouvés chez des animaux atteints d’une maladie inflammatoire chronique. / Low-density granulocytes (LDGs) are a subset of neutrophils first described in the bloodstream upon pathological conditions. However, several studies also reported the presence of these cells in the blood of healthy patients. Whether LDGs characteristics, especially their enhanced pro-inflammatory profile, are specific to this subset of neutrophils and not related to disease states is unknown. Thus, we sought to compare the properties of LDGs to those of autologous normal-density neutrophils (NDNs), in both health and disease. We studied 8 horses with severe equine asthma and 11 healthy animals. Neutrophil morphology was studied using optical microscopy, and content in myeloperoxidase and N-formylmethionine-leucyl-phenylalanine receptors (fMLP-R) evaluated using flow cytometry and immunofluorescence, respectively. Confocal microscopy was used to determine their functional capacity to spontaneously release neutrophil extracellular traps (NETs) stimulating with phorbol-12-myristate-13-acetate (PMA). LDGs were smaller and contained more fMLP-R than NDNs, but myeloperoxidase content was similar in both populations of neutrophils. They also had an increased capacity to produce NETs, and were more sensitive to activation stimuli. These characteristics were similar in both healthy and diseased horses, suggesting that these are intrinsic properties of LDGs. Furthermore, these results suggest that LDGs represent a population of primed and predominantly mature cells. Our study is the first to characterize LDGs in health, and to compare their characteristics with those of animals with a naturally occurring disease.

This thesis is an investigation into the microeconomic mechanisms that govern some of the occupational choices faced by workers in Sub-Saharan Africa, and into the monetary and non-monetary returns to their decisions. Chapter 1 begins by exploring the decision process that leads workers to allocate themselves to different occupations within the economy. In particular, I investigate the role of risk-aversion in the allocation of workers between formal and informal jobs in Ghana, hence attempting to explain a fundamental dimension of duality through an investigation into workers' preferences. In my model of sectoral allocation risk-averse workers can opt between entering the free-entry informal sector and queuing for formal occupations. Conditional on identifying the riskier option, the model yields testable implications on the relationship between risk-aversion and workers' allocation. My testing strategy proceeds in two steps. First, using the first three waves of the Ghana Household Urban Panel Survey (GHUPS) dataset, I estimate expected income uncertainty and find it considerably higher in the informal sector than in formal employment. Second, using experimental data to elicit risk-attitudes I estimate the effect of risk-aversion on occupational choices and I find that, in line with the first result, more risk-averse workers are more likely to queue for formal jobs and less likely to be in the informal sector. The conclusion of the first chapter is that attitudes to risk should feature more prominently in models of sector allocation and in the design of labour market policies, in particular when those policies aim to impact workers' vulnerability to risk and uncertainty. Chapter 2 focuses on the largest occupational category in the Developing world, self-employed workers with small productive activities, and it tries to estimate the returns to different productive assets, namely physical capital, labour and human capital. These are the workers that form most of the informal sector analysed in chapter 1, which allows me to draw a direct link with the analysis so far. The chapter begins by specifying a model for the income-generating process grounded in the literature on firms' production and hence abridging the gap between the analysis of individual earnings and the study of firms' value added. Identification in the empirics is achieved by means of panel estimators that are suitable to address the endogeneity of input choices, which derives from both time-varying and time-invariant unobservable heterogeneity. The use of these estimators is made feasible by the length of the Ghanaian Household Urban Panel Survey dataset at CSAE. I also explore issues of endogeneity in the selection of different technologies, defined by their relative capital and labour intensity. Finally, I analyse the shape of returns to capital, with the aim to detect potential non-convexities in technology. The results show that capital and work-experience play the strongest role in income-generation, while the shares of value added attributed to labour and to formal schooling are low. Marginal returns to investment are high at low capital levels and they decrease very rapidly, pointing against the existence of non-convexities due to minimum scale requirements, but implying that real income gains resulting form micro-investment are modest. Chapter 3 returns to the issue of earnings uncertainty and risk-aversion explored in Chapter 1, but it now takes the allocation choice as given and explores the direct welfare implications of income uncertainty for worker's well-being. Namely, the chapter explores the relationship between income and welfare, with a particular attention on the link between income vulnerability and happiness. Using unique longitudinal data on life-satisfaction and labour market outcomes, I estimate an individual measure of vulnerability (defined as the probability of falling below a low-income threshold) and investigate its effect on well-being. After controlling for unobservable individual fixed effects, work-satisfaction, relative income and other relevant worker characteristics, I find a sizable impact of vulnerability, over and above the income effect. When I explore the mechanisms behind my results, I find that aspiration adaptation to current income may result in a transitory income effect. Moreover, using my direct measure of attitudes to risk from field-experiments (already used in chapter 1), I can test directly the hypothesis that more risk-averse agents suffer more heavily from a given increase in income vulnerability. Overall, my findings support policy interventions that aim to reduce vulnerability, as I expect such policies to have a 'direct' impact on agents' happiness given the prevailing attitudes to risk and uncertainty in the population. Finally, from the point of view of overall social welfare, my results suggest that non-Rawlsian growth models, whereby 'someone may be left behind', may fail to enhance general welfare, for high enough levels of risk-aversion in the population, if the risk of falling behind is sufficiently widespread.

O objetivo deste trabalho é analisar e comparar o comportamento quanto à resistência à corrosão, permeabilidade de hidrogênio e sua relação com a susceptibilidade ao trincamento induzido por hidrogênio de aços ARBL, em ambientes contendo H2S, enfatizando a influência da microestrutura. Foram realizados tratamentos térmicos de normalização e têmpera (em água) de dois tipos de tubos API 5L X65 para aplicação sour service, obtendo-se três condições com diferentes microestruturas para cada tubo. Assim, as duas amostras tais como recebidas apresentavam microestruturas de: ferrita/perlita e, o outro, ferrita/ferrita acicular; após tratamento de normalização os dois tipos de amostras apresentaram microestrutura de ferrita/perlita; e, por último, os aços que passaram por têmpera constituíram-se de martensita. O eletrólito empregado foi a solução A (ácido acético contendo cloreto de sódio) da norma NACE TM0284-2011, saturado com H2S. Os materiais foram submetidos a: ensaios de polarização linear para determinação da Resistência de Polarização (Rp), ensaios de permeabilidade de hidrogênio - baseado na ASTM G148-2003 - e ensaios de resistência ao trincamento induzido por hidrogênio (HIC) segundo a norma NACE TM0284-2011; exames em microscópio óptico e eletrônico de varredura para caracterização microestrutural, da morfologia da corrosão e do trincamento. Após os ensaios de polarização linear, foi observada uma diferença pequena dos valores de Rp entre as diferentes amostras estudadas, entre 120 ?.cm2 e 210 ?.cm2; dentro desta faixa, as microestruturas de martensita (aços temperados) apresentaram a menor resistência à corrosão. Foi realizado o tratamento dos dados obtidos por polarização linear com a metodologia desenvolvida por Mansfeld (1973) para cálculo da taxa de corrosão, observando mudanças nos declives de Tafel evidenciando a formação de produtos de corrosão. Apesar da formação destes produtos a taxa de corrosão não foi afetada, já que estes produtos são dissolvidos na solução A, oferecendo uma baixa proteção contra à corrosão. Nos ensaios de permeabilidade de hidrogênio foi utilizada uma célula modificada tipo Devanathan-Stachurski, com a solução A, com injeção de H2S no lado de geração de hidrogênio e 0,2M NaOH no lado de detecção. Foi realizado o tratamento dos dados com o método tlag, calculando a difusividade aparente, concentração de hidrogênio no metal e quantidade de sítios de ancoramento de hidrogênio. Também foi utilizado um método de ajuste da curva experimental com a equação obtida a partir da segunda lei de Fick para calcular a difusividade aparente. Foram comparados os valores obtidos com os dois métodos, obtendo-se resultados similares de difusividade aparente. As amostras temperadas foram as que apresentaram menor difusividade aparente, maior concentração de hidrogênio e maior número de sítios de ancoramento. Após o ensaio de resistência ao trincamento induzido por hidrogênio os exames em microscópio óptico mostraram que as amostras de tubos API 5L X65 como recebidas e normalizadas não apresentaram trincamento, já as amostras que passaram por tratamento de têmpera apresentaram trincas. A realização dos ensaios e tratamento dos dados permitiram observar a relação entre a quantidade de interface e a taxa de corrosão: assim a microestrutura martensítica apresenta a maior taxa de corrosão devido a maior quantidade de interfaces. A difusividade de hidrogênio também é afetada por esta mesma microestrutura, por ter maior quantidade de interface e maior número de discordâncias, apresentando menor difusividade aparente, maior concentração de hidrogênio e maior quantidade de sítios de ancoramento, tem-se que a microestrutura de martensita apresenta maior susceptibilidade ao trincamento induzido por hidrogênio. A nucleação e propagação das trincas nesta microestrutura depende de vários mecanismos que atuam simultaneamente: (i) nucleação das microtrincas, (ii) formação de H2 nas microcavidades com aumento da pressão local e (iii) migração de átomos de hidrogênio até a ponta da trinca diminuindo a força coesiva do reticulado facilitando a propagação. No entanto, esta relação entre microestrutura e HIC não pode ser generalizada, pois a susceptibilidade ao trincamento depende tanto da quantidade de sítios de ancoramento, como de sua energia de ligação, localização microestrutural e tamanho destes sítios. Outro fator importante é a presença de regiões de pouca ductilidade onde as trincas nucleadas tenham maior facilidade para sua propagação. Este trabalho contribuiu para o melhor entendimento dos mecanismos que levam à fragilização e danos provocados pelo hidrogênio, mostrando a relação entre microestrutura, corrosão, difusão e trincamento. Permitiu ampliar o conhecimento sobre os testes utilizados para avaliar o desempenho de aços microligados para aplicações em ambientes severos. / Pipelines produced from High Strength Low Alloy steels (HSLA) are a safe and cheap way to transport large quantities of petroleum and gas. HSLA steels offers mechanical and economic advantages. When HSLA steels are exposed to environments containing hydrogen sulphide (H2S), the steel can corrode and generate atomic hydrogen in the surface wich can diffuse and trapped, leading loss of mechanical properties and subsequent failures. The infrastructure to transport oil and gas represent a high cost investment, in adittion, they must be free from degradation processes that can causes severe health and environmental impacts. For this reason, the development of materials with high performance in aggressive environments is required. The aim of this study is to analyze and compare the corrosion behavior, hydrogen permeability and its relation with the susceptibility to Hydrogen Induced Cracking (HIC) of HSLA steels in environments containing H2S, with emphasis on the influence of microstructure. Normalizing and quenching heat treatments were applied in two different API 5L X65 pipelines for sour service. Three conditions were obtained (as received, normalized and quenched). The as received has a microstructure of ferrite / pearlite and ferrite / acicular ferrite, respectively; the microstructure of normalized specimens consist of ferrite / pearlite and finally quenched steels presented a microstructure of martensite. Solution A (acetic acid containing sodium chloride), according to NACE TM0284-2011 standard and saturated with H2S was used. The materials were tested by linear polarization technique, hydrogen permeability and Hydrogen Induced Cracking test (HIC). HIC tests were performed according to NACE TM0284-2011 standard. Optical microscope and scanning electron microscope were used for microstructural, corrosion and cracking characterization. Rp values show a slight difference between the different samples studied (120 ?.cm2 e 210 ?.cm2); the martensite microstructure (quenched) showed the lower corrosion resistance. Mansfeld (1973) method was used to calculate the corrosion rates from polarization curves. The Tafel slopes are differents between samples making evident the formation of corrosion products. Despite the growth of those corrosion products, the corrosion rate was not affected, since these products are dissolved in the solution A, providing a low corrosion protection. A modified Devanathan-Stachurski cell was used for the hydrogen permeability tests. It was used the solution A, with injection of H2S in the charging cell, and 0.1M NaOH solution on the oxidation cell. The hydrogen effective diffusivity, sub-surface concentration of atomic hydrogen at the charging side and number of hydrogen-trap sites were calculate by tlag method. Moreover, the experimental data were fitted using an equation derived from Fick\'s second law, in order to determinate the diffusion coefficient. The diffusion coefficient obtained from both methods were compare showing similar results. The quenching samples showed the lower diffusion coefficient, higher hydrogen concentration and number of trap sites. The steels in the as received and normalized conditins did not show cracks in Hydrogen Induced Cracking test; in the other hand, quenched samples presents cracks. The results shoed the relationship between the amount of interface and the corrosion rate. Being the martensitic microstructure the one with the higher corrosion rate. The diffusion coefficient in the martensitic microstructure, is a result of the high amount of interfaces and high dislocation density, leading to a lower diffusion coefficient, higher hydrogen concentration and number of trap sites. In the Hydrogen induced Cracking test the martensitic microstructure has shown the lower resistance to crack. The nucleation and propagation of the cracks in martensite depend of mechanisms that may act simultaneously: (i) nucleation of micro-cracks in preferential sites, (ii) formation of H2 in micro-cavities, with increase the local pressure, and (iii) hydrogen migration to the tip of the crack, decreasing the cohesive force in the lattice. However, the relationship between microstructure and Hydrogen Induced Cracking can not be generalized, since the susceptibility to cracking depends of several factors, like number of trap sites, binding trap energy, microstructural distribution and trap sizes. In addition, the presence of regions of low ductility can result in easy cracks nucleation and propagation. This thesis contributed to the understanding of the mechanisms that lead to hydrogen embrittlement and hydrogen damage, showing the relationship between microstructure, corrosion rate, diffusion and cracking, I ncreasing the scientific knowledge about the standard tests actually used to evaluate the performance of microalloyed steels in sour environments.

Neste trabalho abordamos os processos de perdas colisionais por mudança de estrutura fina e por escape radiativo. Estes processos são importantes por serem os principais fatores limitantes da densidade e da permanência de átomos confinados em armadilhas magneto-ópticas. A utilização do formalismo de Wigner nos possibilitou tratar a dinâmica dos graus de liberdade internos do sistema de forma puramente quântica, enquanto tratamos os graus de liberdade translacionais de maneira semiclássica. Com este formalismo deduzimos equações inéditas para uma colisão unidimensional e desenvolvemos um algoritmo, também inédito, para a resolução numérica de tais equações. / In this work we study the collision loss processes caused by fine-structure change and radiative escape. These processes are important because they limit the density and the confinement time of atoms in magneto-optical traps. The use of the Wigner-function formalism allows us to treat the internal degrees of freedom purely quantum mechanically, while treating the dynamics of the external degrees of freedom quasi-classically. This dissertation employs this formalism to derive for the first time, quasi-classical equations describing one-dimensional cold collisions, including dissipation due to spontaneous emission, and an algorithm, also for the first time, to solve numerically the mentioned set of coupled equations.

Made available in DSpace on 2016-12-23T14:04:28Z (GMT). No. of bitstreams: 1 Jairo Pinto de Oliveira.pdf: 2727767 bytes, checksum: 3b1352014d87848112176e085bb84c8d (MD5) Previous issue date: 2012-12-10 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Effluents are released daily into water bodies without any treatment with high levels of oil and grease (OG) and are a huge environmental problem. These residues are potentially available may be used for energy recovery, such as oil usage for the production of biodiesel. As the biggest barrier to the production of biodiesel involves the cost of raw materials, grease traps of restaurants, industries and wastewater treatment plants can be used as feedstock for biofuel production, since they have large amounts of oil and grease without cost. However, residual oils and greases contain high levels of free fatty acids (FFA) and as the preferred route for the production of biodiesel transesterification is alkaline, may be formed soap as a final product, impairing the separation of glycerol and decreasing the reaction yield. Thus, the acidic and enzymatic transesterification can present as promising alternatives, since it can catalyze the modification of both triglycerides and free fatty acids. The objective of this study was to investigate the possibility of using four types of oily waste sanitation (skimmings of grease from a University Restaurant, a Food Industry, a Station Wastewater Treatment and Sludge pits and septic tanks); characterize the physicochemical properties of oils and greases extracted and evaluate processes involving generation of biodiesel acid catalyst (H2SO4) and enzyme (immobilized Candida antarctica). The residues studied showed high levels of oil and grease and physicochemical characterization showed high levels of acidity, saponification and humidity. Were detected and quantified the major saturated and unsaturated fatty acids by High Performance Liquid Chromatography (HPLC). The production of biodiesel from raw materials from grease traps showed high levels of conversion, greater than or equal 90%, which shows that both catalysts (H2SO4 and lipase Candida antarctica) are presented in the efficient esterification of raw waste acidic. The best conversion was found to be 96.5% using the lipid material from the grease trap the University Restaurant UFES catalyzed enzymatically at 50 ° C and molar ratio of 1:9 (oil: alcohol) / Efluentes são lançados diariamente em corpos d água sem nenhum tipo de tratamento com elevados teores de óleos e graxas (OG) e constituem um enorme problema ambiental. Estes resíduos potencialmente disponíveis podem ser utilizados para o aproveitamento energético, como o uso de óleo para a produção de biodiesel. Como a maior barreira para produção de biodiesel envolve o custo de matéria prima, caixas de gordura de restaurantes, indústrias e de estações de tratamento de efluentes podem ser utilizados como matéria prima para produção de biocombustível, pois apresentam grandes quantidades de óleos e graxas sem nenhum custo. No entanto, óleos e graxas residuais contêm altos teores de ácidos graxos livres (AGL), e como a via preferencial para a produção de biodiesel é a transesterificação alcalina, pode ocorrer a formação de sabão como produto final, prejudicando a separação do glicerol e diminuindo o rendimento da reação. Desta forma, a transesterificação enzimática e ácida podem se apresentar como alternativas promissoras, visto que podem catalisar a modificação tanto de triglicerídeos como de ácidos graxos livres. O objetivo deste trabalho foi verificar a possibilidade de utilização de quatro tipos de resíduos oleosos do saneamento (Escumas de caixas de gordura de um Restaurante Universitário, de uma Indústria de Alimentos, de uma Estação de Tratamento de Efluentes e de Lodos de Fossas e Tanques Sépticos), caracterizar as propriedades físico-químicas dos óleos e graxas extraídos, bem como avaliar processos de geração de biodiesel envolvendo catalisador ácido (H2SO4) e enzimático (Candida antarctica imobilizada). Os resíduos estudados apresentaram altos teores de óleos e graxas e a caracterização físico-química mostrou elevados índices de acidez, saponificação e umidade. Foram detectados e quantificados os principais ácidos graxos saturados e insaturados por Cromatografia Líquida de Alta Eficiência (CLAE). A produção do biodiesel a partir das matérias primas provenientes de caixas de gordura apresentaram altos níveis de conversões, maior ou igual 90%, o que demonstra que ambos os catalisadores (H2SO4 e a lipase Candida antarctica) apresentam-se eficientes na esterificação de matérias primas residuais ácidas. A melhor conversão encontrada foi de 96,5% utilizando o material lipídico proveniente da caixa de gordura do Restaurante Universitário da UFES catalisado enzimaticamente a 50ºC e razão molar 1:9 (óleo:álcool)