Les microsystèmes électromécaniques (MEMS) ont été développés dès le début des années 1980 en s'appuyant sur la technologie de l'industrie microélectronique. Ils ont d'abord été utilisés dans les accéléromètres et les airbags des automobiles. Depuis lors ils se diversifient et connaissent un important essor, notamment grâce à la rapidité De la réponse des matériaux piézoélectriques. La technologie des couches minces piézoélectriques a permis la miniaturisation et les déformations sous tensions d'actionnement plus faibles. Parmi les matériaux piézoélectriques, les films minces de PbZrTiO3 (PZT) morphotropique sont fréquemment utilisés pour leurs propriétés électromécaniques remarquables. Le PZT fabriqué par la voie sol-gel au CEA Leti est à l'état de l'art mondial. Dans le souci de continuer à être compétitif, plusieurs stratégies de R&D sont envisagées, notamment des études approfondies de la microstructure des films PZT pour l'optimiser, afin d'atteindre les propriétés ultimes du PZT. Dans ce but, cette thèse recherche les corrélations entre la microstructure et l'effet piézoélectrique du PZT. Le PZT morphotropique massif, apparu dans les années 1950, est un matériau bien étudié du point de vue microstructurale et piézoélectrique. Il existe plusieurs théories expliquant ses performances piézoélectriques au niveau microscopique. Pour citer les plus connues, le basculement de domaine des phases tétragonale et rhomboédrique, le réarrangement des nano-domaines rhomboédriques, la rotation de l'axe de polarisation dans la phase monoclinique et la transition de phase. Les films minces de PZT morphotropique sont apparus dans les années 1990. Leur microstructure diffère radicalement du PZT massif. Le PZT sol-gel étudié dans ce manuscrit, est contraint et possède une orientation préférentielle des cristaux, des domaines nanométriques et un gradient chimique de Zr et Ti dans l'épaisseur. Notre but est d'étudier les liens entre la microstructure complexe de ces films et leurs propriétés piézoélectriques en utilisant la caractérisation par diffraction des rayons X (DRX). Grace à l'accès au nano-faisceau à l'ESRF, nous avons pu étudier l'influence du gradient chimique de Zr/Ti sur la microstructure de PZT. Les résultats ont montré que la variation de concentration de Zr et Ti engendre une variation du rapport des phases tétragonale et rhomboédrique dans l'épaisseur de la couche. Cette variation suit les oscillations de Zr/Ti dans les films observées par SIMS. Cette observation montre la sensibilité de la microstructure sur la composition chimique. De même, il en résulte la possibilité d'améliorer l'homogénéité de composition du PZT et de ses performances. Car plus le PZT est homogène en composition, meilleurs sont ses coefficients piézoélectriques (d33, e31). Par la suite nous avons effectués des expériences in-situ sous champ électrique sur des capacités contenant le PZT avec le gradient de composition atténué. La microstructure de PZT a été affinée en utilisant la phase tétragonale et rhomboédrique. A 0V, on estime que le PZT contient 40% de phase rhomboédrique et 60% de phase tétragonale. A 30V, on n'observe plus que la présence de la phase rhomboédrique. Les résultats montrent une diminution de la proportion de phase tétragonale au profit de la phase rhomboédrique sous champ électrique. Pour finir nous avons étudié l'influence du gradient de concentration sur l'amplitude du changement de phase en analysant deux échantillons de gradient Zr/Ti différents par DRX in-situ. Nous avons pu montrer que plus l'échantillon est homogène chimiquement, plus il est sujet à la transition de phase sous champ électrique et plus il est performant piézoélectriquement. Finalement, afin d'améliorer les performances piézoélectriques des films PZT, nous proposons de fabriquer des films plus homogènes et plus riches en Ti pour amplifier la transition de phase dans les films. / MEMS have been developed since 1980, when they appeared as derivatives from the microelectronic industry. They were first used in accelerometers and car airbags. They have diversified since then and expanded. One of the main contributors to this expansion are piezoelectric materials. Among them, PbZrTiO3 (PZT) is widely used for its outstanding piezoelectric performances. Sol-gel PZT thin films fabricated at CEA are worldwide state of the art. In order to stay competitive, several R&D strategies have been developed. One of them is a detailed study of PZT microstructure in order to draw correlations with the piezoelectric effect in PZT films. The goal of this study is to optimize PZT microstructure aiming to reach its best piezoelectric properties. For this purpose, this thesis takes advantage of numerous studies performed on PZT bulk ceramics in order to analyze PZT thin films microstructure and its modifications with voltage. PZT bulk ceramics of morphotropic composition are now well known from the piezoelectric and microstructural point of view. There are several theories explaining the piezoelectric effect at the microscopic level, namely tetragonal and rhombohedral domain switching, rhombohedral nanodomains rearrangement, polarization axis rotation in the monoclinic phase and the phase transition.Morphotropic PZT thin films have emerged more recently. Their microstructure is very different from the bulk PZT. Indeed, sol-gel PZT films studied in this manuscript are stressed and contain preferred oriented nanoscale crystals and Ti/Zr composition gradient through the film thickness. Our goal is to study links between the complex microstructure of these films and their piezoelectric properties using X-ray diffraction (XRD).Thanks to the nano-beam at ESRF, we were able to study the influence of the Zr/Ti chemical gradient on the PZT microstructure. Our observations showed that the composition gradient gives rise to a variation of the tetragonal and rhombohedral phase ratio in the layer thickness. This variation follows Zr/Ti composition oscillations evidenced by SIMS. This experiment shows the sensitivity of PZT microstructure to the PZT chemical composition. At the same time, it suggests the possibility of improving the composition homogeneity of PZT and its performances. The more the PZT composition is homogeneous, the better the piezoelectric coefficients are.Then, we performed in-situ XRD under electric field experiments on a capacitor containing the PZT active layer with an attenuated Zr/Ti gradient. The PZT diffraction pattern was refined using the tetragonal and the rhombohedral PZT phases. At 0V PZT contains 40% of rhombohedral phase and 60% of tetragonal phase. At 30V, no tetragonal phase is observed any more. Results show an electric field induced phase transition from the tetragonal to the rhombohedral phase.Finally, we used in-situ XRD to study the influence of Zr/Ti composition gradient on the amplitude of the phase transition of two PZT samples with different Zr/Ti gradient. We showed that the more the sample is homogeneous in composition, the more phase transition it exhibits and the more it is performant.Finally, to improve the piezoelectric performances of PZT films, we propose to improve PZT compositional homogeneity and slightly increase the Ti content to promote the tetragonal phase in order to amplify the phase transition under voltage.

Novel and known metal organic frameworks with copper(II), sodium and 1,2,4,5-benzenetetracarboxylate were prepared by ambient precipitation, solvothermal and gel-synthesis methods, and characterized by single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, and thermogravimetry with FTIR evolved-gas analysis. Some of these complexes were investigated for guest inclusion properties with water (the original guest species), methanol, ethanol and pyridine. The gel-synthesis products were the most interesting. The novel threedimensional metal-organic framework complex Cu₂ Na(OH)L·7H₂O (where L=1,2,4,5-benzenetetracarboxylate) -formed by gel-synthesis- is a covalent three-dimensional metal organic framework polymer with open channels containing both guest water molecules and water molecules coordinated to sodium. The structure collapsed on dehydration, but was essentially restored to the original structure on rehydration in moist air. On exposure of the dehydrated material to methanol and ethanol vapour, significant uptake of these solvents was observed, and the resolvated structures closely resembled that of the parent material. On heating in dry nitrogen, small amounts of methanol and ethanol remained until about 280 °C, when loss of the remaining guest triggered decomposition of the framework. The related complex, Cu₂¼(OH)½ L·7½H₂O (or possibly Cu₂⅓ (OH)⅔L·8H₂O) -formed by gel-synthesis- had a different physical appearance to Cu₂Na(OH)L·7H₂O above, but had nearly identical X-ray diffraction pattern, mid-infrared spectrum and thermal behaviour. The novel complex Cu₄Na₄L₃·14H₂O -formed by gel-synthesis- is a covalent three-dimensional metal-organic framework with small channels containing both guest water molecules and water coordinated to sodium and copper. Upon dehydration the structure collapsed, but on rehydration in moist air the original structure was partly restored. The dehydrated material did not absorb methanol. Known two-dimensional polymeric complexes [Cu₂L·6H₂O]·4H₂O and [Cu₂L·4H₂O]·2H₂O were also obtained by gel-synthesis, and were characterized and investigated for guest inclusion properties. The structures of these complexes collapsed on dehydration, and were only partly restored on rehydration in saturated water vapour. The dehydrated materials did not absorb methanol. The two-dimensional polymeric mixed-ligand complex Cu₂(pyridine)₄·6H₂O -formed very slowly by gel-synthesis- was characterized by TG-FTIR, and was shown to undergo a complicated decomposition involving the loss of water and pyridine, carbon dioxide and carbon monoxide in various stages. Solvothermal synthesis did not yield materials suitable for single-crystal X-ray diffraction studies or inclusion studies, producing only an anhydrous or hemihydrate complex with the formula Cu₂L·0.65H2O. Ambient precipitation syntheses did not yield materials suitable for singlecrystal diffraction studies, forming products approximately equivalent to the complexes [Cu₂L·6H₂O]·4H₂O and Cu₂¼(OH)½L·7 ½H₂O above. During the course of the above study it was discovered that, on changing the DSC purge from nitrogen to argon, the normally exothermic carboxylate decompositions appeared to become endothermic. The effects of the supposedly inert atmospheres of argon and nitrogen on the decomposition-mechanism of copper(II) oxalate -a well-studied copper carboxylate- were therefore studied by DSC, TG, TG-FTIR and XRPD. DSC experiments were performed in nitrogen and argon at different flow-rates, in various mixtures of nitrogen and argon, and at various heating rates. Regardless of the proportions of nitrogen and argon, the DSC residues consisted mainly of copper metal, a small amount of copper(I) oxide (cuprite) and, in some circumstances, traces of copper(II) oxide (tenorite). Also, regardless of whether TG-FTIR experiments were performed under argon or nitrogen, the gaseous decomposition products consisted mainly of carbon dioxide, with traces of carbon monoxide being detected over part of the decomposition period. Various explanations for the thermal behaviour are discussed, and it is possible that small amounts of O2 or monatomic oxygen were given off during the decomposition under argon. The design and implementation of a low-cost prototype X-ray proportional counter detector system, consisting of a hybrid analog-digital computer built using commonly available electronic components, is presented. This system was designed to replace ageing discrete-transistor designs still in use in earlier X-ray diffractometers. The prototype performs the functions of pulse-shaping, pulseheight discrimination, counting and scaling, and provides both digital and scaled analog outputs.

Le Lanréotide est un octapeptide amphiphile cationique et un analogue thérapeutique de la somatostatine. Cette molécule synthétique a été conçue au sein de Beaufour-Ipsen comme thérapie contre l’acromégalie. Ce peptide révèle la propriété de former des nanotubes avec un haut degré de monodispersité en diamètre des tubes (244 Å) et épaisseur de la paroi (~18 Å) lorsqu’il est mélangé avec de l’eau pure à 10% (w/w). Le peptide forme des tubes emboîtés à plus haute concentration. Cette propriété d’auto-assemblage est utilisée pour concevoir un implant sous cutané à libération prolongée d’un mois : la Somatuline Autogel. Les gels de Lanréotide deviennent de plus en plus visqueux avec la concentration en peptide et cette viscosité limite la dose maximale injectable. L’ajout d’un adjuvant dans la formulation : le polyéthylène glycol (PEG600) à permit d’augmenter le temps de libération du peptide dans l’organisme tout en diminuant la viscosité du gel. Dans le but d’étudier l’effet du PEG600 sur l’auto-assemblage du Lanréotide, une étude structurale et thermodynamique est proposée. Cette étude est réalisée grâce à une approche par diagramme de phase systématique, par la technique de diffusion des rayons X et de modèles d’analyses des clichés, croisé par différentes techniques de caractérisations moléculaires. Cette étude révèle des interactions fortes du PEG avec le Lanréotide conduisant à la formation d’un complexe en solution. Ce complexe influe sur les équilibres entre deux phases du système biphasique, tube et intermédiaire du Lanréotide (rubans et dimères), ce qui pourrait jouer un rôle important dans les propriétés rhéologiques des gels. Enfin, il est montré qu’il est possible de réaliser la transition pratiquement totale du Lanréotide vers un dimère chimique conduisant à la formation de fibre type amyloïde. La simplicité du procédé de fabrication à température ambiante de ce dimère non actif dans l’organisme par un simple changement d’ordre d’addition des composants, fait de la compréhension des paramètres physico-chimiques de formations de ce dimère, un point capital du point de vue industriel. / The Lanreotide is an cationic octapeptide and a therapeutic analogue of the somatostatin. This synthetic molecule was designed by Beaufour Ipsen as a therapy against acromegaly. This peptide has the capacity to form monodisperse nanotubes with a high degree of monodispersity in diameter (244 Å) and wall thickness (~18 Å) when the peptide is mixed with pure water at 10% (w/w); embedded tubes are found at higher concentration. The viscosity of Lanreotide gels is strongly increasing with the peptide concentration, a property that limits the maximum injectable dose. The addition of a polymer (polyethylene glycol, PEG600) as an adjuvant in the formulation allows one to increase the release time in the organism to be treated and to decrease the gel viscosity. To study the effect of PEG600 on the self-assembly of the Lanreotide, a structural and thermodynamic work is proposed. This study is performed with a systematic phase diagram approach, by X-ray scattering and modeling of the scattering pattern and different experimental techniques at the molecular scale. This study reveals strong interaction between PEG and Lanreotide that form a complex in solution. This complex impacts the equilibrium state between two phases of the biphasic system, i.e., pure tubes and an intermediate state consisting of a mixture between ribbons and dimers of the Lanreotide. This result could play an important role for the gel’s rheological properties. Then, we demonstrate that it is possible to obtain an almost complete transition to a covalent dimer which yields the formation of amyloid fibers. To sum up, we discuss a new process for the fabrication of a dimer that is not active in the organism, this process being (i) based on a simple change of the order at which the components are added in solution and (ii) easy to implement at room temperature. Our findings could impact industrial applications.

xxv, 207 p. ; ill. (some col.) A print copy of this title is available from the UO Libraries, under the call number: SCIENCE QD172.T6 T87 2008 / A growing interest in the physics of complex systems such as in the transition-metal oxide family has exploded recently, especially in the last 20 years or so. One notable effect is the change in electrical resistivity of a system by orders of magnitude in an applied magnetic field, coined the "colossal magnetoresistance effect". In efforts to understand these types of effects, there has been an unveiling of a rich variety of phenomena in the field of strongly correlated electron physics that has come to dominate the current scientific times. Most notable is the competition of myriad types of order: magnetic, lattice, charge and orbital all self-organize to display a fascinating array of phases on a variety of length scales. Furthermore, it has become apparent that new probes are needed to grasp some of this physics that transcends current condensed matter theory, where much of the behavior of these types of systems has remained unexplored. We have developed a new technique to gain more information about the system than with conventional x-ray diffraction. By scattering highly coherent, low energy x-rays, we can measure manganite speckle: a "fingerprint' of the microscopic structure in the bulk. The coherence of the x-rays can further be used to elucidate new insight into the dynamics of these phases. We describe here a number of novel effects near the orbital order phase transition in a half-doped manganite. We observe a small fluctuating component in the scattered signal that is correlated with three effects: both a rapidly decreasing total signal and orbital domain size, as well as an abrupt onset of a broad background intensity that we attribute to the thermal production of correlated polarons. Our results suggest that the transition is characterized by a competition between a pinned orbital domain topology that remains static, and mobile domain boundaries that exhibit slow, spatiotemporal fluctuations. This study opens up a new chapter to the study of manganite physics as coherent x-ray scattering offers a new direction to understand the strange and exotic behavior demonstrated in the multifaceted manganites. / Adviser: Stephen Kevan

Les sprites sont de gigantesques phénomènes lumineux qui sont produits entre 40 et 90 km d’altitude généralement par des éclairs nuage-sol positifs. Les sprites sont des phénomènes très brefs (durée de quelques millisecondes) qui appartiennent à la famille des TLEs (évènements lumineux transitoires) et qui sont composés de structures filamentaires nommées streamers. Les streamers sont des filaments de plasma, qui se propagent à des vitesses allant jusqu’à ∼10⁷ m/s et qui possèdent des champs électriques très forts souvent proches de 150 kV/cm (champs réduit à la pression atmosphérique). Lors de ce travail, on a développé un modèle fluide de plasma qui simule les décharges streamers couplées avec un modèle simulant les émissions optiques afin d’étudier la physique des streamers, des TLEs et plus particulièrement des sprites dans le cadre de la mission spatiale TARANIS. Cette mission a pour objectif d’étudier le système Atmosphère-Ionosphère-Magnétosphère, et observera les TLEs et leurs émissions associées: électromagnétiques, optiques, et probablement radiations énergétiques depuis le nadir. Dans cette thèse, on propose d’étudier certains problèmes liés aux streamers et aux sprites qui sont cruciaux pour préparer la mission TARANIS. Plus particulièrement nous abordons certains mécanismes de production de radiations énergétiques par les streamers récemment proposés dans la littérature et nous développons une méthode qui permet de déterminer l’altitude, la vitesse et le champ électrique des streamers des sprites, à partir d’une analyse spectroscopique de leurs émissions optiques. Nos résultats renforceront donc le retour scientifique des futures missions spatiales observant les TLE depuis le nadir et particulièrement TARANIS. / Sprites are large optical phenomena usually produced between 40 and 90 km altitude generally by positive cloud-to-ground lightning (+CG). These are short lifetime phenomena (duration of few milliseconds) that belong to the family of transient luminous events (TLEs) and composed of complex filamentary structures called streamers. Streamers are non-thermal plasma filament, highly collisional, propagating with velocities up to 10⁷ m/s, and characterized with high electric fields at their heads often close to 150 kV/cm when scaled to ground level air. In this work, we have developed a streamer plasma fluid model coupled with an optical emission model to investigate the physics of streamers and sprites in the framework of the TARANIS space mission. TARANIS will observe TLEs from a nadir-viewing geometry along with their related emissions (electromagnetic and particles). In this dissertation, we investigate some mechanisms of emission of energetic radiation from streamers recently proposed in the literature and we present an original spectroscopic method to determine sprite streamers altitudes, velocities, and electric fields through their optical emissions. This method is especially useful for increasing the scientific return of space missions that have adopted nadir-based observation strategies.

O padrão ouro para a avaliação e o acompanhamento de desvios posturais é o exame radiológico. No entanto, a exposição à radiação ionizante aumenta o risco do desenvolvimento de câncer. Nessa perspectiva, se faz necessário o uso de métodos não invasivos com validade, repetibilidade e reprodutibilidade para mensurar os desvios posturais e acompanhar a sua progressão. Dessa maneira, o intuito do presente estudo foi verificar se o sistema Vert 3D fornece informações válidas referentes aos desvios posturais nos planos frontal e sagital de indivíduos de diferentes faixas etárias. Além disso, verificar a repetibilidade e a reprodutibilidade interavaliador do sistema Vert 3D nos planos sagital e frontal. Foi avaliada a postura sagital e frontal de 89 crianças de ambos os sexos e diferentes faixas etárias. A avaliação consistiu de duas etapas: exame radiológico e sistema Vert 3D. A primeira etapa foi realizada por um operador de raios X experiente e, a partir das imagens geradas, foram calculados os ângulos de Cobb nos planos sagital e frontal. A segunda etapa foi executada no mesmo dia por três avaliadores treinados no método e foram calculados os ângulos de deformidade do Vert 3D nos planos sagital e frontal e as flechas de escoliose do Vert 3D. O primeiro avaliador efetuou duas análises sucessivas, o segundo avaliador efetuou em seguida outras duas análises sucessivas e o terceiro avaliador efetuou a seguir uma única análise. Foram comparados e correlacionados os dados sucessivos de um mesmo avaliador para verificar a repetibilidade, os dados de diferentes avaliadores para verificar a reprodutibilidade interavaliador e entre os dados dos dois sistemas para verificar a validade do sistema Vert 3D. Para a repetibilidade no plano sagital, não houve diferença (p>0,05) e as correlações foram excelentes (ICC≥0,750, p<0,05). Para a reprodutibilidade interavaliador no plano sagital, não houve diferença (p>0,05) e as correlações foram satisfatórias (0,400<ICC<0,750, p<0,05) para a cifose de indivíduos de 6 a 10 anos e 16 a 18 anos e para a lordose de indivíduos de 11 a 15 anos e excelentes (ICC≥0,750, p<0,05) para a cifose de indivíduos de 11 a 15 anos e para a lordose de indivíduos de 6 a 10 e de 16 a 18 anos. E para a validade no plano sagital, houve diferença (p<0,05) e as correlações entre os ângulos de deformidade do Vert 3D (cifose e lordose) e os ângulos de Cobb (cifose e lordose) foram moderadas (0,400<r<0,699, p<0,05) para a cifose de indivíduos de 11 a 18 anos e para a lordose de indivíduos de 6 a 18 anos. Para a repetibilidade no plano frontal, não houve diferença (p>0,05) e as correlações foram satisfatórias (0,400<ICC<0,750, p<0,05) a excelentes (ICC≥0,750, p<0,05) para as flechas de escoliose do Vert 3D de indivíduos de 6 a 18 anos e para os ângulos de deformidade do Vert 3D (escoliose) de indivíduos de 11 a 18 anos. Para a reprodutibilidade interavaliador, não houve diferença (p>0,05) e as correlações foram satisfatórias (0,400<ICC<0,750, p<0,05) para as flechas de escoliose do Vert 3D de indivíduos de 6 a 18 anos e para os ângulos de indivíduos de 11 a 18 anos. E para a validade no plano frontal, houve diferença (p<0,05) entre os ângulos dos dois sistemas e as correlações foram moderadas (0,400<rho< 0,699, p<0,05) em relação à média das flechas de escoliose do Vert 3D à esquerda e à média dos ângulos de deformidade do Vert 3D à esquerda. Tendo em vista os resultados para repetibilidade e reprodutibilidade do Vert 3D nos planos sagital e frontal, o sistema pode ser utilizado para o acompanhamento das posturas sagital e frontal de indivíduos de 6 a 18 anos, a partir dos ângulos de deformidade do Vert 3D (cifose e lordose) e das flechas de escoliose do Vert 3D. Além disso, pode ser utilizado para o acompanhamento da postura frontal de indivíduos de 11 a 18 anos, a partir dos ângulos de deformidade do Vert 3D (escoliose). No entanto, na ausência de validade em relação ao padrão ouro, esse instrumento não pode ser utilizado para fins de avaliação dos ângulos de Cobb (cifose, lordose e escoliose). / The gold standard for the assessment and monitoring of postural deviations is the radiological examination. However, exposure to X-rays increases the risk to develop cancer. At this view, it is necessary the use of valid, repeatable and reproducible non-invasive methods to measure and monitor the progression of the postural deviations. Thus, the aim of this study was to verify if the Vert 3D system provides valid information regarding the postural deviations in frontal and sagittal planes of individuals of different age groups. Also, check the repeatability and inter-rater reliability of the Vert 3D system in sagittal and frontal planes. We evaluated the sagittal and frontal posture of 89 children of both sexes and different age groups. The evaluation consisted of two steps: radiological examination and Vert 3D system. The first step was performed by an experienced X-rays operator and from X-ray images were calculated Cobb angles in the sagittal and frontal planes. The second step was performed on the same day by three trained in the method evaluators. Was calculated the Vert 3D deformity angles in the sagittal and frontal planes and the Vert 3D scoliosis arrows. The first evaluator carried out two successive analyzes, the second evaluator then made two other successive analyzes and after the third evaluator made a single analysis. Were compared and correlated successive data of the each evaluator to verify repeatability, data from different evaluators to verify inter-rater reliability reproducibility and data from each system to verify the validity of Vert 3D system. For repeatability the in sagittal plane, was no difference (p>0.05) and the correlations were excellent (ICC≥0.750, p<0.05). For inter-rater reliability in the sagittal plane, was no difference (p>0.05) and the correlations were satisfactory (0.400 <ICC<0.750, p<0.05) for kyphosis in 6-10 years old and 16-18 years old individuals and for lordosis of 11-15 years old individuals and fine (ICC≥0.750, p<0.05) for kyphosis in 11-15 years old individuals 11 to 15 years and for lordosis in 6-10 years old and 16-18 years old individuals. And for validity in the sagittal plane, was significant differences (p<0.05) and the correlations between Vert 3D deformity angles (kyphosis and lordosis) and Cobb angles (kyphosis and lordosis) were moderate (0.400<r<0.699, p<0.05) for kyphosis in 11-18 years old individuals and for lordosis in 6-18 years old individuals. For the repeatability in the frontal plane, was no difference (p>0.05) and the correlations were satisfactory (0.400<ICC<0.750, p <0.05) to excellent (ICC≥0.750, p <0.05) for Vert 3D scoliosis arrows in 6-18 years old individuals and for Vert 3D deformity angles (scoliosis) in 11-18 years old individuals 11-18 years. For inter-rater reliability, was no difference (p>0.05) and the correlations were satisfactory (0.400<ICC<0.750, p<0.05) for Vert 3D scoliosis arrows in 6- 18 years old individuals and Vert 3D deformity angles (scoliosis) in 11-18 years old individuals. And for validity in the frontal plane, was significant differences (p<0.05) between the angles of the two systems and the correlations were moderate (0.400<rho<0.699, p<0.05) to the mean of Vert 3D scoliosis left arrows and the mean of Vert 3D deformity left angles (scoliosis). Considering the results for repeatability and inter-rater reliability of Vert 3D in both planes, the system can be used for monitoring the sagittal and frontal postures of 6-18 years old individuals 6-18 years from Vert 3D deformity angles (kyphosis and lordosis) and from Vert 3D scoliosis arrows. Moreover, it can be used for monitoring the frontal posture of 11-18 years old individuals from Vert 3D deformity angles (scoliosis). However, in the absence of validity related to the gold standard, the Vert 3D system cannot be used for diagnosis of Cobb angles (kyphosis, scoliosis, lordosis).

Revestimentos de zinco obtidos por imersão a quente têm sido amplamente utilizados em estruturas expostas em solos, águas naturais e atmosfericamente, devido a excelente resistência em meios de baixa agressividade. Nessas aplicações, as arestas de corte ficam expostas e estão mais susceptíveis à corrosão. Objetivando relacionar a microestrutura dos revestimentos com técnicas de microssondas eletroquímicas, para melhor entender os processos corrosivos de aços galvanizados, buscou-se uma nova metodologia para ampliar as fases e obter uma estrutura em camadas. Para a caracterização da morfologia dos revestimentos obtidos pelo processo de galvanização por imersão a quente (galvanized, galvannealed e galvalume) utilizou-se microscopia óptica e eletrônica de varredura com microanálise. Para verificar e analisar os mecanismos de corrosão das fases presentes nos revestimentos de zinco de forma localizada empregou-se a técnica de varredura por eletrodo vibratório (SVET) e microcélula capilar (MEC), e de forma complementar, para identificar os produtos de corrosão formados utilizou-se micro difração de raios X (μ-DRX). Os resultados demonstraram que a metodologia empregada neste estudo é adequada para avaliar as fases de forma individual ou conectadas galvanicamente, e assim identificar as fases mais ativas durante os processos corrosivos. Os resultados obtidos por microcélula complementam os mapeamentos de densidade de corrente obtidos por eletrodo vibratório, mostrando que os intermetálicos permanecem estáveis após os ensaios e a região mais ativa é o revestimento não intemperizado (polido) próximo à interface aço/revestimento. O revestimento que apresentou melhor resistência à corrosão em soluções contendo cloreto foi o Zn55Al. O espectro μ-XRD para o revestimento galvanized, indica a presença das fases zincita e Fe-α sobre o aço IF (interstitial free), mostrando que sob condições de OCP a superfície de aço IF foi protegida pelo revestimento apesar da sua grande área. Esta precipitação pode ainda proteger áreas de aço expostas aonde o revestimento foi danificado por arranhões ou na aresta de corte. / Hot-dip zinc coatings have been widely used in structures exposed to soils, natural water and atmosphere due to their excellent resistance in low aggressive media. In such applications, the cutting edges are exposed and more susceptible to corrosion. In order to correlate the microstructure of the coating with electrochemical microprobe techniques, a new methodology was developed to amplify the size of the phases and to obtain a layered structure. Optical microscopy and scanning electron microscopy were used to characterize the morphology of the coatings obtained by the hot dip galvanization process (galvanized, galvannealed e galvalume). Scanning vibrating electrode technique (SVET) and capillary microcell (MEC) were used to identify and study the corrosion mechanisms of the phases present in zinc coatings. The corrosion products were identified by X-ray micro-diffraction (μ-XRD). The results demonstrated that the methodology employed in this study is adequate to evaluate the phases individually or galvanically connected, thus identifying the most active phases during the corrosive processes. The results obtained by microcell complement the current density mappings obtained by vibrating electrode, showing that the intermetallics remain stable after the analysis and the most active region is the not wedered coating near the steel/coating interface. The coating that showed the best corrosion resistance in solutions containing chloride was the Zn55Al. The μ-XRD spectrum for the galvanized coating indicates the presence of zincite and Fe-α on the IF steel (interstitial free), showing that under OCP conditions the IF steel surface was protected by the coating despite its large area. This precipitation can further protect exposed steel areas where the coating has been damaged by scratches or at the cutting edge.

Thesis submitted in partial fulfilment of the requirements for the degree Doctor of Technology: Electrical, Electronic and Computer Engineering in the Faculty of Engineering at the Cape Peninsula University of Technology / This research investigates the effects of sub-10 MeV protons on coatings obtained from the pulsed laser ablation of W2B5/B4C. This is in an attempt to extend the bullet proof applications of W2B5/B4C to space radiation shielding applications, offering low cost and low mass protection against radiation including X-rays, neutrons, gamma rays and protons in low Earth orbit. The focus in this research, however, is on low energy protons. The associated problems addressed in this work are solar cell degradation and Single Event Upsets in high density semiconductor devices caused by low energy protons. The relevant constraints considered are the necessity for low cost, low mass and high efficiency solutions. The work starts with a literature review of the space environment, the interaction of radiation with matter, and on pulsed laser deposition as a technique of choice for the coating synthesis. This paves the way for the pulsed laser ablation of W2B5/B4C. The resulting coating is a solid solution of the form WC1-xBx which contains crystalline and amorphous forms. Two proton irradiation experiments are carried out on this coating, and the resulting effects are analysed. The effects of 900 keV proton irradiation were the melting and subsequent growing of nanorods on the surface of the coating, the lateral transfer of the proton energy across the coating surface, and the lateral displacement of matter along the coating surface. These effects show that the coating is a promising cost effective and low mass radiation shield against low energy protons. The effects of 1 MeV protons on this coating are the three-stage melting of rods formed on the coating surface, and further evidence of lateral transfer of energy across the coating surface. Optical measurements of this coating show that it is about 73% transparent in the Ultraviolet, Visible and near Infrared range. This allows it to be used as radiation shielding for solar cells, in addition to high density semiconductor devices, against low energy protons in low Earth orbit. Simulations show that based on coulombic interactions alone, the same level of protection coverglass offers to solar cells can be achieved with about half the thickness of WC1-xBx or less.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2016. / For decades, clays have been applicable as commercial catalysts mostly for cracking in petroleum industries. Clays are also used for development of useful catalysts for various other industrial applications. Hence, this work was aimed to synthesize clay-based catalysts from clay minerals (Kaolin, bentonite and talc) that will be active for the conversion of bioethanol to fuel hydrocarbons. Catalyst characterisation techniques employed on the samples produced in this work include the Energy Dispersive Spectroscopy (EDS), Scanning Electron Microscopy (SEM) and the X-Ray Diffraction pattern (XRD). All catalytic reactions were carried out in a fixed bed reactor (at fixed reaction condition of 6 hour and 350 ⁰C) and corresponding reaction products (liquid and gaseous) were analysed through a Gas Chromatograph- Flame Ionisation Detector (GC-FID) and Gas Chromatograph Mass Spectrometer (GC/MS). The activity of clays in their non-modified state was studied and they were all found active for bioethanol conversion to hydrocarbons. Bentonite was the most active catalyst with bioethanol of 84.95 % and this through subsequent beneficiation and acid-modification approach, led to increased bioethanol conversion of 87.3 %. EDS/SEM characterisation of the catalyst in line to the above modification and increased catalyst activity, revealed that the structural morphology of bentonite and the concentration of basic structural elements (in terms of Si/Al ratio) was increased.

O padrão ouro para a avaliação e o acompanhamento de desvios posturais é o exame radiológico. No entanto, a exposição à radiação ionizante aumenta o risco do desenvolvimento de câncer. Nessa perspectiva, se faz necessário o uso de métodos não invasivos com validade, repetibilidade e reprodutibilidade para mensurar os desvios posturais e acompanhar a sua progressão. Dessa maneira, o intuito do presente estudo foi verificar se o sistema Vert 3D fornece informações válidas referentes aos desvios posturais nos planos frontal e sagital de indivíduos de diferentes faixas etárias. Além disso, verificar a repetibilidade e a reprodutibilidade interavaliador do sistema Vert 3D nos planos sagital e frontal. Foi avaliada a postura sagital e frontal de 89 crianças de ambos os sexos e diferentes faixas etárias. A avaliação consistiu de duas etapas: exame radiológico e sistema Vert 3D. A primeira etapa foi realizada por um operador de raios X experiente e, a partir das imagens geradas, foram calculados os ângulos de Cobb nos planos sagital e frontal. A segunda etapa foi executada no mesmo dia por três avaliadores treinados no método e foram calculados os ângulos de deformidade do Vert 3D nos planos sagital e frontal e as flechas de escoliose do Vert 3D. O primeiro avaliador efetuou duas análises sucessivas, o segundo avaliador efetuou em seguida outras duas análises sucessivas e o terceiro avaliador efetuou a seguir uma única análise. Foram comparados e correlacionados os dados sucessivos de um mesmo avaliador para verificar a repetibilidade, os dados de diferentes avaliadores para verificar a reprodutibilidade interavaliador e entre os dados dos dois sistemas para verificar a validade do sistema Vert 3D. Para a repetibilidade no plano sagital, não houve diferença (p>0,05) e as correlações foram excelentes (ICC≥0,750, p<0,05). Para a reprodutibilidade interavaliador no plano sagital, não houve diferença (p>0,05) e as correlações foram satisfatórias (0,400<ICC<0,750, p<0,05) para a cifose de indivíduos de 6 a 10 anos e 16 a 18 anos e para a lordose de indivíduos de 11 a 15 anos e excelentes (ICC≥0,750, p<0,05) para a cifose de indivíduos de 11 a 15 anos e para a lordose de indivíduos de 6 a 10 e de 16 a 18 anos. E para a validade no plano sagital, houve diferença (p<0,05) e as correlações entre os ângulos de deformidade do Vert 3D (cifose e lordose) e os ângulos de Cobb (cifose e lordose) foram moderadas (0,400<r<0,699, p<0,05) para a cifose de indivíduos de 11 a 18 anos e para a lordose de indivíduos de 6 a 18 anos. Para a repetibilidade no plano frontal, não houve diferença (p>0,05) e as correlações foram satisfatórias (0,400<ICC<0,750, p<0,05) a excelentes (ICC≥0,750, p<0,05) para as flechas de escoliose do Vert 3D de indivíduos de 6 a 18 anos e para os ângulos de deformidade do Vert 3D (escoliose) de indivíduos de 11 a 18 anos. Para a reprodutibilidade interavaliador, não houve diferença (p>0,05) e as correlações foram satisfatórias (0,400<ICC<0,750, p<0,05) para as flechas de escoliose do Vert 3D de indivíduos de 6 a 18 anos e para os ângulos de indivíduos de 11 a 18 anos. E para a validade no plano frontal, houve diferença (p<0,05) entre os ângulos dos dois sistemas e as correlações foram moderadas (0,400<rho< 0,699, p<0,05) em relação à média das flechas de escoliose do Vert 3D à esquerda e à média dos ângulos de deformidade do Vert 3D à esquerda. Tendo em vista os resultados para repetibilidade e reprodutibilidade do Vert 3D nos planos sagital e frontal, o sistema pode ser utilizado para o acompanhamento das posturas sagital e frontal de indivíduos de 6 a 18 anos, a partir dos ângulos de deformidade do Vert 3D (cifose e lordose) e das flechas de escoliose do Vert 3D. Além disso, pode ser utilizado para o acompanhamento da postura frontal de indivíduos de 11 a 18 anos, a partir dos ângulos de deformidade do Vert 3D (escoliose). No entanto, na ausência de validade em relação ao padrão ouro, esse instrumento não pode ser utilizado para fins de avaliação dos ângulos de Cobb (cifose, lordose e escoliose). / The gold standard for the assessment and monitoring of postural deviations is the radiological examination. However, exposure to X-rays increases the risk to develop cancer. At this view, it is necessary the use of valid, repeatable and reproducible non-invasive methods to measure and monitor the progression of the postural deviations. Thus, the aim of this study was to verify if the Vert 3D system provides valid information regarding the postural deviations in frontal and sagittal planes of individuals of different age groups. Also, check the repeatability and inter-rater reliability of the Vert 3D system in sagittal and frontal planes. We evaluated the sagittal and frontal posture of 89 children of both sexes and different age groups. The evaluation consisted of two steps: radiological examination and Vert 3D system. The first step was performed by an experienced X-rays operator and from X-ray images were calculated Cobb angles in the sagittal and frontal planes. The second step was performed on the same day by three trained in the method evaluators. Was calculated the Vert 3D deformity angles in the sagittal and frontal planes and the Vert 3D scoliosis arrows. The first evaluator carried out two successive analyzes, the second evaluator then made two other successive analyzes and after the third evaluator made a single analysis. Were compared and correlated successive data of the each evaluator to verify repeatability, data from different evaluators to verify inter-rater reliability reproducibility and data from each system to verify the validity of Vert 3D system. For repeatability the in sagittal plane, was no difference (p>0.05) and the correlations were excellent (ICC≥0.750, p<0.05). For inter-rater reliability in the sagittal plane, was no difference (p>0.05) and the correlations were satisfactory (0.400 <ICC<0.750, p<0.05) for kyphosis in 6-10 years old and 16-18 years old individuals and for lordosis of 11-15 years old individuals and fine (ICC≥0.750, p<0.05) for kyphosis in 11-15 years old individuals 11 to 15 years and for lordosis in 6-10 years old and 16-18 years old individuals. And for validity in the sagittal plane, was significant differences (p<0.05) and the correlations between Vert 3D deformity angles (kyphosis and lordosis) and Cobb angles (kyphosis and lordosis) were moderate (0.400<r<0.699, p<0.05) for kyphosis in 11-18 years old individuals and for lordosis in 6-18 years old individuals. For the repeatability in the frontal plane, was no difference (p>0.05) and the correlations were satisfactory (0.400<ICC<0.750, p <0.05) to excellent (ICC≥0.750, p <0.05) for Vert 3D scoliosis arrows in 6-18 years old individuals and for Vert 3D deformity angles (scoliosis) in 11-18 years old individuals 11-18 years. For inter-rater reliability, was no difference (p>0.05) and the correlations were satisfactory (0.400<ICC<0.750, p<0.05) for Vert 3D scoliosis arrows in 6- 18 years old individuals and Vert 3D deformity angles (scoliosis) in 11-18 years old individuals. And for validity in the frontal plane, was significant differences (p<0.05) between the angles of the two systems and the correlations were moderate (0.400<rho<0.699, p<0.05) to the mean of Vert 3D scoliosis left arrows and the mean of Vert 3D deformity left angles (scoliosis). Considering the results for repeatability and inter-rater reliability of Vert 3D in both planes, the system can be used for monitoring the sagittal and frontal postures of 6-18 years old individuals 6-18 years from Vert 3D deformity angles (kyphosis and lordosis) and from Vert 3D scoliosis arrows. Moreover, it can be used for monitoring the frontal posture of 11-18 years old individuals from Vert 3D deformity angles (scoliosis). However, in the absence of validity related to the gold standard, the Vert 3D system cannot be used for diagnosis of Cobb angles (kyphosis, scoliosis, lordosis).