Les composants de puissance à base de GaN sont connus par l’instabilité de leurs caractéristiques électriques, en particulier la tension de seuil et la résistance à l'état passant. Cela est dû aux effets des mécanismes de piégeage/de-piégeage des charges dans la structure. Le travail présenté dans ce mémoire se compose de deux grandes parties. Dans un premier temps, nous mettons en évidence l’effet d’un certain nombre de paramètres de commutation sur l'évolution de la résistance dynamique avec des cycles de commutation successifs. Nous analysons, en particulier, l’effet de la tension au blocage, la fréquence de commutation et la température sur l'évolution de la résistance dynamique. Dans un deuxième temps, nous présentons les résultats des essais de cyclage de puissance effectués en utilisant 80K de variation de température de jonction sur des puces de puissance MOS-HEMT Al2O3/AlGaN/GaN Normally-On. Ensuite, nous réalisons des caractérisations de pièges, basées sur des analyses de mesures de courants transitoires pendant le processus de vieillissement. Les résultats montrent qu’une dégradation irréversible affecte la tension de seuil avec une dérive vers des valeurs négatives. Ces dérives sont principalement attribuables au piégeage cumulatif avec des cycles de puissance, probablement induits par des électrons chauds, d’une manière progressive et non récupérable. / Power components based on GaN are known by the instability of their electrical characteristics, in particular the threshold voltage and the on-state resistance. This is due to the effects of trapping/de-trapping mechanisms in the structure. The work presented in this memoir consists of two main parts. At the first step, we highlight the effect of a number of switching parameters on the evolution of the dynamic resistance with successive switching cycles. In particular, we analyze the effect of blocking voltage, switching frequency and temperature on the evolution of dynamic resistance. In a second step, we present the results of power cycling tests performed using 80K of junction temperature swing on Normally-ON Al2O3/AlGaN/GaN MOS-HEMTs. Then, we perform trap characterizations, based on the analyses of transient current measurements, during the aging process. The results show that irreversible degradation affects threshold voltage with drift to negative values. These drifts were mainly attributed to cumulative trapping with power cycles, probably induced by hot electrons, in a progressive and non-recoverable way.

Capillary trapping plays a central role in the geological storage of CO2, oil recovery, and water soil infiltration. The key aim of this study is to investigate the impact of surface properties (wettability, roughness, heterogeneous mineral composition) on the dynamics of quasi-static fluid displacement process and capillary trapping efficiency in porous medium. We concluded that for homogeneous wet smooth glass beads surfaces, a transition in fluid displacement pattern occurs from a compact (for θ < 90°; imbibition process) to a fractal front-pattern (for θ > 90°; drainage process) leading to a crossover in capillary trapping efficiency from zero to maximum. The impact of surface roughness on capillary trapping efficiency was also studied, and an opposite trends in terms of wettability dependency was observed. Rough natural sands surfaces depicts a non-monotonous wettability dependency, i.e. a transition from maximal trapping (for θ < 90°) to no-trapping occurs (at θ = 90°), followed by an increase to medium trapping (for θ > 90°). For a fractional-wet media, the percolating cluster of hydrophobic sediments (connected hydrophobic pathways) characterize the fluid displacement pattern and trapping efficiency.

Dans cette thèse, nous étudions le problème de l'inférence bayésienne dans les graphes factoriels, en particulier les codes LDPC, quasiment résolus par les algorithmes de message-passing. Nous réalisons en particulier une étude approfondie du Belief Propagation (BP) dont la question de la sous-optimalité est soulevée dans le cas où le graphe factoriel présente des boucles. A partir de l'équivalence entre le BP et l'approximation de Bethe en physique statistique qui se généralise à l'approximation basée régions, nous détaillons le Generalized Belief Propagation (GBP), un algorithme de message-passing entre des clusters du graphe factoriel. Nous montrons par des expériences que le GBP surpasse le BP dans les cas où le clustering est réalisé selon les structures topologiques néfastes qui empêchent le BP de bien décoder, à savoir les trapping sets. Au-delà de l'étude des performances en termes de taux d'erreur, nous confrontons les deux algorithmes par rapport à leurs dynamiques face à des événements d'erreur non triviaux, en particulier lorsqu'ils présentent des comportements chaotiques. Par des estimateurs classiques et originaux, nous montrons que l'algorithme du GBP peut dominer l'algorithme du BP. / This thesis addresses the problem of inference in factor graphs, especially the LDPC codes, almost solved by message-passing algorithms. In particular, the Belief Propagation algorithm (BP) is investigated as a particular message-passing algorithm whose suboptimality is discussed in the case where the factor graph has a loop-like topology. From the equivalence between the BP and the Bethe approximation in statistical physics that is generalized to the region-based approximation, is detailed the Generalized Belief Propagation algorithm (GBP), a message-passing algorithm between clusters of the factor graph. It is experimentally shown to surpass the BP in the cases where the clustering deals with the harmful topological structures that prevents the BP from rightly decoding any LDPC code, namely the trapping sets. We do not only confront the BP and the GBP algorithms according to their performance from the point of view of the channel coding with the error-rate, but also according to their dynamical behaviors for non-trivial error-events for which both algorithms can exhibit chaotic beahviors. By means of classical and original dynamical quantifiers, it is shown that the GBP algorithm can overcome the BP algorithm.

Isoelectric trapping (IET) has become an accepted preparative-scale electrophoretic separation technique. However, there are still a number of shortcomings that limit its utility. The performance of the current preparative-scale IET systems is limited by the serial arrangement of the separation compartments, the difficulties in the selection of the appropriate buffering membranes, the effect of Joule heating that may alter separation selectivity and a lack of methods for the determination of the true, operational pH value inside the buffering membranes. In order to bolster the current membrane pH determination methods which rely on the separation of complex ampholytic mixtures, a fluorescent carrier ampholyte mixture was synthesized. The use of a fluorescent mixture allows for a reduced load of carrier ampholytes, thereby reducing a possible source of error in the pH determinations. A mixture of carrier ampholytes tagged with an alkoxypyrenetrisulfonate fluorophore was shown to have suitable fluorescence and ampholytic properties and used to accurately determine the pH of high pH buffering membranes under actual IET conditions. In a more elegant solution to the difficulties associated with pH determinations, a method utilizing commercial UV-transparent carrier ampholytes as the ampholyte mixture to be separated was developed. By using commercial carrier ampholytes and eliminating the need to synthesize, purify, and blend fluorescently tagged ampholytes, the new method greatly simplified the determination of the operational pH value of the buffering membranes. In order to address the remaining limitations, a new system has been developed that relies on (i) parallel arrangement of the electrodes and the collection compartments, (ii) a directionally-controlled convection system for the delivery of analytes, (iii) short anode-to-cathode distances, (iv) short intermembrane distances, and (v) an external cooling system. This system has been tested in four operational modes and used for the separation of small molecule ampholytic mixtures, for the separation of protein isoforms, and direct purification of a target pI marker from a crude reaction mixture.

No description available.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-16T14:17:49Z No. of bitstreams: 1 DANIELLE FREIRE DE ARAÚJO - TESE (PPGEQ) 2017.pdf: 4185527 bytes, checksum: e932aa4fa6aa33e42656b4c6d33e01b5 (MD5) / Made available in DSpace on 2018-08-16T14:17:49Z (GMT). No. of bitstreams: 1 DANIELLE FREIRE DE ARAÚJO - TESE (PPGEQ) 2017.pdf: 4185527 bytes, checksum: e932aa4fa6aa33e42656b4c6d33e01b5 (MD5) Previous issue date: 2017-08 / Capes / O presente trabalho teve como objetivo o estudo do aprisionamento de hidrogênio em aços da classe API 5L X60, X65 e X70, classificados como aços de alta resistência e baixa liga (ARBL). A respectiva implicação da difusão do hidrogênio, isto é, adsorvido e dissolvido na matriz metálica dos aços, o aprisionamento em defeitos microestruturais, foram abordados através do estudo da cinética de aprisionamento, com a determinação das taxas de liberação (k) e captura (p), da da obtenção da energia de aprisionamento (EA) e da densidade de sítios aprisionadores (N). Através da energia de aprisionamento, determinada via eletroquímica, foi possível fazer a caracterização dos típos de sítios aprisionadores, presentes nos materiais estudados, no qual se configurou a presença de sítios reversíveis e cuja característica microestrutural mostra a existência de contornos de grãos com fases de ferrita e perlita, identificadas após ataque químico com nital à 2% e pela microscopia óptica. Os resultados obtidos para os parâmetros cinéticos de aprisionamento são condizentes com os resultados encontrados na literatura e por análises de dessorção térmica para esses tipos de aços. / The objective of the present work was to study the hydrogen trapping in steel class API 5L X60, X65 and X70, classified as High-strength low-alloy (HSLA). The respective implication of the diffusion of hydrogen, i.e., adsorbed and dissolved in the metallic matrix of the steels, the trapping in microstructural defects, were approached through the study of the trapping kinetics, with the determination of the release (k) and capture (p ), The trapping energy (EA) and the density of trap sites (N). Through the trapping energy, determined by electrochemistry, it was possible to characterize the types of trap sites, present in the studied materials, in which the presence of reversible sites was configured and whose microstructural characteristic it shows the existence of grain boundaries, with phases of ferrite and perlite, identified after chemical attack with 2% nital and by optical microscopy. The results obtained for the kinetic entrapment parameters are consistent with the results found in the literature and by thermal desorption analysis for these types of steels.

Les nitrones sont de composés diamagnétiques qui additionnent les radicaux libres pour former des adduits nitroxyde détectables par résonance paramagnétique électronique (RPE). Récemment les nitrones linéaires telles que l’α-phényl-N-tert-butylnitrone (PBN) et ses dérivés ont été proposées comme nouvelles thérapeutiques dans des pathologies à stress oxydant. Dans ce contexte nous avons synthétisé une vingtaine de PPNs originales, dérivés β-phosphorylés de la PBN, dont le groupe phényle a été substitué par des groupes ayant des effets électroniques sur la fonction nitrone ou a été conçu de manière à former un fragment phénolique présent dans certains antioxydants naturels. Il s’agissait de combiner le bon outil de détection des radicaux que sont les PPNs aux éventuels effets antioxydants et donneurs de NO● de ces nitrones. Nous avons réalisé une évaluation des propriétés antioxydantes des nouvelles PPNs au moyen de différents tests biochimiques ainsi qu'une étude par RPE permettant de déterminer leur réactivité in vitro sur plusieurs types de radicaux libres d'intérêt biologique. Nous avons sélectionné les PPNs ayant les meilleures propriétés afin d'examiner leur impact pharmacologique dans un modèle d'endothélium aortique de rat soumis à un stress oxydant. Dans une deuxième partie, nous avons greffé sur certaines des PPNs synthétisées des chaînes alkyles de différentes longueurs dont la terminaison triphénylphosphonium confère à ces nitrones une affinité particulière pour la mitochondrie, principale source cellulaire de production radicalaire. Nous avons ensuite évalué par RPE la capacité de ces 5 nouvelles mito-PPNs à piéger les radicaux libres alkyle et alcoxy in vitro. / Nitrones are diamagnetic compounds commonly used as probes to monitor biological free radical formation by the spin trapping (ST)/electron paramagnetic resonance coupling (EPR). In addition the growing interest in the therapeutic potential of α-phenyl-N-tert-butylnitrone (PBN) derivatives led researchers to develop analogs having improved protective properties and bioavailability. Among these, PPNs are β-phosphorylated analogues of PBN which form more persistent spin adducts than PBN toward oxygen-centered radicals. In this context we have synthesized twenty new hybrid PPNs having their aromatic ring substituted either by groups which can bring electronic and steric effects to the nitrone function or mimic natural antioxidant moieties. We evaluated the antioxidant properties of the new PPNs with a series of specific assays and we used ESR to study PPNs properties in ST toward a wide array of biologically-relevant free radicals, and their intrinsic nitric oxide releasing properties. The most promising compounds were than tested as vasorelaxant and antioxidant free radicals detectors in rat aortic rings. Protection by PPNs was assessed by measuring vascular response preservation and biochemical indices in aortic tissue. The second purpose dealt with the synthesis of new mitochondrial targeted PPNs with the aim to reach the primary biological source of endogenous production of free radicals. Using EPR we have assessed their ability to scavenge alkyl and alkoxy free radicals in vitro which allowed us to envisage a potential use of this probe against lipid peroxidation at mitochondrial level.

The trophy hunting of African leopards Panthera pardus pardus may generate revenue to help foster their conservation. However, leopards are sensitive to hunting and populations decline if overharvested. The practice therefore requires careful management grounded in robust estimates of population density/status. Camera-trap surveys are commonly used to establish leopard numbers, and may guide harvest quotas. However, such surveys are limited over wide spatial scales and many African governments lack resources to implement them. In this thesis I explore the potential use of a harvest composition scheme applied to puma Puma concolor in North America, to monitor leopards. The method hinges on the susceptibility of different leopard cohorts to hunting and if this varies, then predictions can be made about harvest composition. Susceptibility is likely to be governed by space use, encounter rates with bait lures (a common method used to attract leopards to hunting hides) and hunter selectivity. Thus in this thesis I explore leopard susceptibility to these factors using a protected leopard population in northern Zululand, South Africa. In my first chapter I examine using scent lures in camera-trapping. Against a backdrop of a passive survey I show adult males, females and sub-adults are captured at similar rates compared to a passive survey using lures. The use of lures does not appear to violate closure assumptions or affect spatio-temporal patterning, but their use appears limited as density estimate precision is not improved. My second chapter examines ecological (likelihood of encountering a hunter) and anthropogenic (attractiveness to hunters) susceptibility of leopards to trophy hunting. I show that adult males are the most susceptible cohort to hunting (sub-adults least susceptible). I then take the incident rates from ecological and anthropogenic models and create a theoretical harvest composition using population parameters of protected leopards. My third data chapter departs from hunting susceptibility and examines determinants of leopard trophy package price across Africa. I show that factors such as trophy quality, outfitter leopard hunting reputation and hunt success have little impact on price determination. Instead, overall outfitter reputation and the number of charismatic species in a package are positively correlated with price. These results have important consequences on several sustainable leopard hunting schemes proposed in the literature.

This thesis explores the structures and dynamics of optically confined matter, ranging from single particle traps to complex optically bound colloidal arrays, investigating and quantifying the behaviour of each system. It begins with an introduction to optical manipulation techniques and a discussion of the development of the single beam gradient force trap, more commonly referred to as optical tweezers. Following this, the building of a single beam optical trap will be presented alongside a discussion of some of the key components in such a setup, before it is calibrated, allowing a demonstration of some of the techniques which are utilised later in the thesis. The optical trapping of aerosol droplets is an area of key importance in atmospheric chemistry, as optical tweezers provide a valuable and versatile tool for droplet manipulation and characterisation. Trapping single aerosol droplets is facilitated by using annular rather than conventional Gaussian beams, as will be demonstrated, with significant advantages in increasing the size range of trappable droplets, and improving their axial localisation. These improvements will be demonstrated experimentally with an in-depth comparison of Gaussian and annular beam trapping. These enhancements are also verified theoretically using a model developed by Burnham and McGloin, showing excellent agreement with experimental results. Ionic liquids, defined as organic salts with melting points below room temperature, are another area of great contemporary interest. They are highly tunable and so have been referred to as "designer solvents", and also have important applications as "green" solvents in organic chemistry. Trapping particles within these novel liquids allows a micro-rheological investigation of their properties to be conducted. This is demonstrated by determining the temperature dependent viscosity changes of these media, showing excellent agreement with previous macro-rheological studies. In addition, hydrodynamic effects such as Faxen's correction to viscous drag in proximity to a surface, and hydrodynamic coupling between pairs of colloids trapped in ionic liquids are demonstrated. Following these single and dual particle studies, this thesis continues with an investigation of the structures and dynamics of optically bound matter formed of larger numbers of particles. The behaviour of these optically bound structures is particularly sensitive to the number of particles involved, and so a counter-propagating evanescent field trap in conjunction with an inverted optical tweezers setup is utilised in order to controllably assemble these structures and study the factors affecting their behaviour. Initially one-dimensional chains of optically bound 3.5 um diameter silica particles are studied, allowing an implementation of Generalized Lorentz-Mie Theory (GLMT) to be developed through collaboration with Dr. Jonathan Taylor of The University of Glasgow. Experimental and theoretical insights allow further understanding of the processes involved in the formation of these structures. Having studied the behaviour of 3.5 um diameter silica particles in a counter-propagating evanescent wave trap, the effects of changing particle size and refractive index are presented by using smaller silica and melamine particles. These results are explained in terms of the increased importance of interference fringes in determining the arrangement of the optically bound structures of smaller particles, and due to the increased interaction of the melamine particles with the evanescent field as a result of the larger refractive index contrast between them and the trapping medium. The thesis then concludes with a study of the dynamics of the previously presented optically bound chains. Initially the diffusion of single particles in the evanescent field is compared to their freely-diffusing behaviour, quantifying the confining effect of the field. The addition of particles to the field then allows the diffusive behaviour to be studied as a function of particle number, and understood in terms of on-axis confinement by adjacent particles. The tilting of these optically bound chains relative to the inter-beam axis is also explored as a function of particle number, as is the rigidity of these chains. Finally a more complex, dynamic effect is presented, dubbed "Newton's Cradle", in which particles are ejected from the ends of the chains before returning and repeating this process. This behaviour is understood by utilising the previously developed GLMT simulations.

It has been proposed that coated gas microbubbles, currently used as ultrasound contrast agents could also be used as microscale sensors due to the sensitivity of their acoustic response to changes in their environment. However, their behaviour is not fully understood and there remains considerable scope for improving their characterisation. The aim of this thesis is to improve the theoretical description of microbubble dynamics under ultrasound excitation with the ultimate aim of assessing the regimes in which they could be exploited most effectively as sensors. Previous theoretical and experimental work relating to the confinement and acoustic excitation of microbubbles is reviewed. Specifically, optical trapping as a method for the isolation and manipulation of individual bubbles is studied for use in developing a sensor. An assessment of the existing models’ validity is undertaken. This is followed by the development of models for optical trapping of single microbubbles, and the coupled radial and translational motion of a microbubble under ultrasound excitation, which includes time dependent phenomena. The latter model is used to perform a sensitivity analysis to determine the uncertainty associated with using microbubbles as sensors. The potential for uniquely characterising the shell of the microbubble from experimental data is also assessed. Subsequent chapters present the results from a combination of computer simulations and experimental data, used to develop and assess the validity of the new models for describing microbubble behaviour. Particularly, the model is used to simulate the response of a dilute suspension of microbubbles undergoing large amplitude oscillations and single microbubbles undergoing lipid shedding. The optimal regimes in which microbubbles may be utilised as sensors for liquid physical properties and local pressure variations are then assessed. Finally, a summary of the conclusions and areas for further work is presented.