L’étude effectuée au cours de cette thèse a permis de caractériser numériquement les instabilités d’origine aérodynamique rencontrées dans un compresseur centrifuge dessiné par Turbomeca. Ce compresseur est composé d’une roue directrice d’entrée, d’un rouet centrifuge, d’un diffuseur radial et de redresseurs axiaux. Le module expérimental, dénommé Turbocel, sera accueilli au LMFA courant 2016. Le contenu de cette étude repose donc exclusivement sur des résultats numériques dont certains sont cependant comparés à des résultats expérimentaux partiels obtenus par Turbomeca sur une configuration proche. _ Le fonctionnement du compresseur est analysé à différentes vitesses de rotation, à partir de simulations RANS et URANS menées avec le code elsA. Du point de vue de la méthodologie, deux points importants sont à retenir :- Du fait du caractère transsonique de l’écoulement dans le rouet et le diffuseur radial à haut régime de rotation, les simulations RANS stationnaires ne permettent pas d’accéder à une description satisfaisante des phénomènes physiques. Cela est dû à l’utilisation d’un plan de mélange aux différentes interfaces rotor-stator qui a pour effet d’empêcher les ondes de choc de remonter à l’amont, et qui affecte tant la physique de l’écoulement que l’étendue de la plage de fonctionnement stable.- En-dessous d’un certain débit, les calculs URANS sur période machine révèlent que le comportement de l’étage n’obéit plus à la périodicité spatio-temporelle mono-canal. Une plage instable est alors obtenue à toutes les iso-vitesses simulées. A bas régime de rotation, une autre plage stable existe lorsque le compresseur est suffisamment vanné. L’étage retrouve alors une périodicité spatio-temporelle, à condition d’étendre le domaine de calcul dans le stator à deux canaux inter-aubes. En ce qui concerne les limites de stabilité de Turbocel, différentes évolutions sont décrites selon la vitesse de rotation considérée :- A haut régime de rotation, une basse fréquence commence à émerger près du point de rendement maximal et son intensité ne fait qu’augmenter jusqu.au pompage.- A bas régime, une signature basse fréquence comparable se manifeste près du point de rendement maximal mais disparaît passé un certain vannage, et n’est donc présente que sur une plage de débit délimitée. La seconde zone stable peut alors être numériquement parcourue jusqu.au pompage proprement dit. La signature basse fréquence est imputée à l’instauration d’une recirculation dans l’inducteur qui une fois établie est quasi-stationnaire. Les résultats numériques mettent en évidence que la source d’instabilité sévère sur Turbocel provient du diffuseur aubé. En fonction du point de fonctionnement, ce composant adopte des comportements différents, entre lesquels une certaine continuité existe, et ses performances chutent progressivement lorsque le débit diminue. Au final, les domaines de stabilité de l’étage de compression peuvent être reliés au type d’écoulement qui se développe dans le diffuseur radial, et apparaissent dictés par le diffuseur semi-lisse à haut régime de rotation. Enfin, afin d’étendre les plages de fonctionnement stable, une stratégie de contrôle basée sur l’aspiration de couche limite dans le diffuseur aubé a également été déterminée dans le cadre de cette thèse. Son évaluation fera l’objet d’études ultérieures sur Turbocel. / The present study aims at characterizing the aerodynamic instabilities involved in a centrifugal compressor designed by Turbomeca, by means of numerical simulation. This compressor is composed of inlet guide vanes, a centrifugal impeller, a radial vaned diffuser and axial outlet guide vanes. The test module, named Turbocel, will be delivered to the LMFA in 2016. Thus, the results presented in this manuscript are only based on CFD, although some of them are compared to experimental results obtained by Turbomeca on a close configuration.RANS and URANS simulations are performed for several rotational speeds, using the elsA software.Two methodological key points are to be emphasized:- As the flow in both the impeller and the radial diffuser is transonic at high rotational speed, steady RANS simulations cannot provide a satisfactory description of the physical phenomena taking place. This can be explained by the use of the mixing plane approach which prevents shock waves to extend upstream the rotor-stator interfaces, and which impacts the flow field predicted as well as the prediction of the stable operating range.- Below a given massflow rate, URANS simulations covering the spatial period of the compressor prove that the stage behavior does not obey to the single passage spatio-temporal periodicity anymore. An unstable operating range then appears at all the simulated rotational speeds. At low rotational speed, another stable range is however obtained if the compressor is further throttled’ A new periodicity arises on this massflow range, provided that the stator domain is extended to two neighboring blade passages. Concerning the stability domains of Turbocel, different evolutions are obtained depending on the rotational speed:- At high rotational speed, a low frequency phenomenon starts to develop near the peak efficiency point and its intensity keeps increasing until surge happens.- At low rotational speed, a low frequency signature also appears near the peak efficiency point, but it then vanishes when the compressor is further throttled, so that only a restricted operating range exhibits this instability. It then gives rise to a second stable operating range which can be described numerically, ending with surge itself. The low frequency signature is attributed to the enhancement of a flow recirculation in the inducer which, once fully established, is quasi-steady. The numerical results underline that the source of severe instability in the compressor comes from the vaned diffuser. Depending on the operating point, this component can adopt different behaviors, between which a relative continuity exists, and its performances decrease when the massflow rate decresases. The overall stage performances prove that at high rotational speed, the global stability is driven by the semi-vaneless diffuser and depends on the flow developing in the radial diffuser. Finally, in order to extend the stable operating range of the compressor, a flow control strategy based on boundary layer suction has also been determined in the diffuser. Its impact on the performances of Turbocel will be deeply studied later on.

Helical anchors, used widely to resist uplift loading for a variety of applications, including in transmission towers, pipelines, offshore structures, etc., are subjected to environmental cyclic loads that influence the anchor performance and may induce fatigue failure. However, the influence of cyclic loading on helical anchor behaviour is unknown. A comprehensive evaluation of the effect of cyclic loading on the load-displacement response of single-helix anchors in sandy soils is presented here, including an interaction diagram to help designers evaluate the impact of different conditions in cyclic loadings. The experimental work of this thesis includes geotechnical centrifuge modelling and field load tests. The centrifuge model tests were carried out with reduced scale models of helical anchors in sand, at IFSTTAR (Nantes, France). The field load tests were performed on helical anchors installed in a tropical residual soil of the Experimental Site of the University of São Paulo (São Carlos, Brazil). In addition, numerical modelling was used to predict the pre- and postcyclic responses of the single-helix anchors tested in a centrifuge. The main findings of this research are: (a) helical anchor behaviour is governed by helix bearing resistance, and no loss of helix bearing capacity was observed in the range of cyclic loadings tested, (b) the degradation of shaft resistance was noticed mainly during the first 100 cycles, when the accumulation of permanent displacements is more significant, (c) an interaction diagram showing the different conditions of cyclic stability is proposed from the results of the experimental data, (d) modified values of the bearing capacity factor in tension (Nq) are suggested for the estimation of post-cyclic uplift capacity of single-helix anchors in sand, (e) the installation effect of the anchor should be taken into account in the numerical model in order to obtain reliable predictions of the helical anchor performance. / As estacas helicoidais são largamente utilizadas para resistir a carregamentos de tração em uma variedade de aplicações como torres de linhas de transmissão de energia, dutos enterrados, estruturas offshore, etc. Estes tipos de estruturas são normalmente submetidos a carregamentos cíclicos que influenciam o desempenho de fundações por estacas helicoidais submetidas a esforços de tração, e podem induzir ruptura por degradação da capacidade de carga. Contudo, a influência do carregamento cíclico no comportamento das estacas helicoidais (ou ancoragens helicoidais, quando submetidas apenas a esforços de tração) é pouco conhecida. Uma avaliação abrangente do efeito de carregamentos cíclicos sobre o comportamento das ancoragens helicoidais é apresentada nesta tese, incluindo um diagrama de interação para auxiliar na avaliação do impacto de diferentes condições de carregamento cíclico. O trabalho experimental desta tese inclui modelagem em centrífuga geotécnica e ensaios de carregamento cíclico em estacas na grandeza real em campo. Os ensaios em centrífuga foram realizados com modelos reduzidos de estacas helicoidais em areia, no IFSTTAR (Nantes, França). Os ensaios de campo foram realizados em ancoragens helicoidais instaladas no solo residual tropical do Campo Experimental de Fundações da Universidade de São Paulo (São Carlos, Brasil). Além disso, modelos numéricos foram utilizados para simular os resultados do comportamento das ancoragens helicoidais ensaiadas em centrífuga nas condições pré- e pós-ciclos. Os principais resultados desta pesquisa são: (a) a capacidade de carga à tração da ancoragem helicoidal é controlada pela capacidade de carga da hélice, (b) a degradação da resistência por atrito lateral foi observada principalmente durante os primeiros 100 ciclos, período em que a acumulação dos deslocamentos permanentes é mais significante, (c) um diagrama de interação mostrando as diferentes condições de estabilidade cíclica é proposto a partir dos resultados experimentais em centrífuga, (d) valores modificados do fator de capacidade de carga em tração (Nq) são sugeridos para estimativa da capacidade pós-ciclos de ancoragens helicoidais com uma hélice em areia, (e) o efeito da instalação da ancoragem deve ser levado em consideração no modelo numérico para que se obtenha previsões confiáveis do desempenho de ancoragens helicoidais.

O monitoramento em campo de fundações em estacas metálicas helicoidais é baseado em correlações empíricas entre a capacidade de carga à tração e o torque medido durante a instalação. Nesta pesquisa é proposto um modelo teórico da relação entre o torque de instalação e a capacidade de carga à tração deste tipo de estaca em areias para ser utilizado como procedimento de controle durante a execução deste tipo de fundação. Para validar esta relação teórica e para avaliar o desempenho desta fundação em solos arenosos, foi realizado um programa experimental dividido em dois grupos: ensaios de campo e ensaios de laboratório. Em campo foram realizadas provas de carga à tração na Escola de Engenharia de São Carlos (EESC) e em Contagem (Minas Gerais). Os ensaios de laboratório foram divididos em três grupos. O primeiro corresponde aos ensaios de modelagem física em centrífuga realizados no Laboratoire Central des Ponts et Chaussées (LCPC) em Nantes, França. O segundo engloba ensaios de cisalhamento direto de interface entre o aço da hélice da estaca e diferentes areias, parte executada no LCPC e parte na EESC. O terceiro grupo refere-se a ensaios de torção de tubos de estacas metálicas helicoidais efetuados na EESC. A partir dos resultados dos ensaios, o modelo teórico proposto nesta tese foi verificado e mostrou-se adequado para estacas metálicas helicoidais profundas com diferentes dimensões e número de hélices instaladas em solos arenosos. Os resultados das provas de carga realizadas em centrífuga e em campo foram examinados por meio dos métodos existentes na literatura para estimativa de capacidade de carga à tração desenvolvidos para este tipo de fundação. Por meio dos resultados obtidos nos ensaios em centrífuga, constatou-se que nas estacas multi-hélices a porcentagem de capacidade de carga relativa à hélice da ponta aumenta de acordo com o diâmetro da hélice e com a densidade da areia. Nos ensaios de torção de fustes de estacas helicoidais observou-se que, para tubos de mesmo diâmetro e espessura, a ruptura se inicia a partir do mesmo valor de momento torçor aplicado, independentemente de conter ou não emenda. / Empirical correlations between installation torque and uplift capacity of helical screw piles are routinely used as a procedure for quality control on site of this type of foundation. In this work, a theoretical model of the relationship between uplift capacity and installation torque of deep helical screw piles in sand was presented to be used as a quality control method for this type of foundation. An experimental program of laboratory and field investigations was carried out in order to validate this theoretical relationship. The field study included uplift tests of full-scale piles installed at the Escola de Engenharia de São Carlos (EESC) and in Contagem (Minas Gerais). The laboratory tests were performed in the Laboratoire Central des Ponts et Chaussées (LCPC/ Nantes) and at the EESC. In the LCPC a program of centrifuge and direct shear interface tests was completed. A set of torsion tests on pile shafts and of direct shear interface tests were carried out at the EESC. The results showed that the theoretical model presented is applicable to different pile dimensions, number of helices, and sand relative density. The methods existing in the literature for estimating uplift capacity of helical screw piles were used to verify the results of uplift capacities measured in field and in centrifuge studies. The results of centrifuge modelling tests demonstrated that the fraction of uplift capacity corresponding to the bottom helix increases with helix diameter and sand density. The torsion tests showed that the failure of the pile shaft begins at the same torque magnitude in experiments on shafts with and without connections.

Les travaux de cette thèse portent sur le développement de nouvelles méthodologies de purification des peptides pharmaceutiques par chromatographie de partage centrifuge (CPC) dans le but de l'introduction de cette technique comme outil de R&D mais surtout de production en milieu industriel. Le caractère original de ces travaux porte essentiellement sur l'introduction de nouveaux systèmes de solvants et la mise au point de nouveaux procédés de purification en mode CPC co-courant. Les différents aspects liés à l'industrialisation des différents procédés de purification ont également été étudiés.La première partie des travaux a consisté en l'étude de quelques nouveaux aspects de l'intérêt de l'application du mode co-courant en chromatographie de partage centrifuge. Une méthodologie originale de purification des peptides tensioactifs non ioniques en mode CPC co-courant a été mise au point. Cette méthodologie a permis de résoudre les problèmes de perturbations hydrodynamiques et de perte de phase stationnaire engendrés par le caractère tensioactif de ces molécules et a été appliquée avec succès à la purification d'une cyclosporine modifiée douée d'une activité anti-virale et faiblement soluble dans les solvants usuellement utilisés en CLHP. Une étude fondamentale de l'effet du peptide sur le comportement hydrodynamique des deux phases lors de la séparation et la visualisation des modèles d'écoulement au sein de la colonne CPC a permis la mise en évidence du role de la ciclosporine modifiée dans la perturbation de la composition des phases du système chromatographique. D'autres aspects de l'intérêt du mode co-courant en CPC ont été étudiés lors de cette étude, notamment l'amélioration de la robustesse et de la résolution de la séparation.La seconde partie des travaux a porté sur le développement de nouveaux systèmes biphasiques de solvants particulièrement adaptés à la purification des peptides hydrophobes non-ioniques, notamment les intermédiaires de synthèse protégés, qui sont très faiblement solubles dans la plupart des solvants communs utilisés en chromatographie. Deux gammes quaternaire et quinaire de systèmes biphasiques de solvants, ainsi qu'un système biphasique ternaire ont été introduits. L'originalité de ces systèmes porte sur l'usage de solvants verts à fort caractère solvatant tel que le Methyl-THF et le cyclopentyl methyl ether (CPME). Les systèmes développés ont été efficacement utilisés pour la purification en CPC d'une exénatide protégée de 39 acides aminés et d'un peptide protégé de 8 acides aminés intermédiaire de la synthèse de la bivalirudine. Ces systèmes devraient être utiles pour une utilisation générale en CPC pour la séparation des peptides synthétiques hydrophobes libres ou protégés. / The work presented in this thesis deals with the development of new methodologies for the purification of pharmaceutical peptides by centrifugal partition chromatography (CPC) in order to introduce this technique as a tool for R & D but also in industrial production. The original character of this work relies on the introduction of new solvent systems and the development of new purification processes based on the co-current CPC mode. The different aspects of the process intensification and industrialization have also been studied.In the first part of the work, a study of some new aspects of the interest of the application of the stationary phase co-current mode in CPC is described. An original method for the purification of non-ionic tensioactive peptides in the co-current CPC mode was developed. This method has been successfully applied to the purification of a modified cyclosporine showing a therapeutic interest. This particular elution mode, taking advantage of the liquid nature of the stationary phase, appears to be an efficient solution to get round some hydrodynamic instabilities that sometimes appears during a purification intensification by CPC. A fundamental study of the effect of the peptide on the hydrodynamic behavior of the two phases in the separation and visualization of flow patterns within the CPC column allowed highlighting the role of the peptide in the disruption of phases composition of the chromatographic system. Other aspects of the interest of the co-current mode in CPC were investigated in this study, including the improvement of the efficiency and the resolution of the separation.The second part of the work focused on the development of new biphasic solvent systems particularly suitable for the purification of hydrophobic non-ionic peptides, including protected intermediates, which are very poorly soluble in the most common solvents used in chromatography. Two new scales of biphasic solvent systems showing a wide range of polarity and a ternary biphasic system were introduced to overcome solubility problems often encountered with synthetic hydrophobic protected peptides. The originality of these systems relies on the use of green solvents with high solvating character such as Methyl-THF and cyclopentyl methyl ether (CPME). The developed systems have been effectively used for the purification in CPC of a 39mer protected exenatide and and a 8mer protected peptide intermediate of bivalirudin synthesis.

Este trabalho apresenta o desenvolvimento de um método para garantir a proteção dos dados contra falhas de comunicação, em redes de sensores inteligentes sem fios. A rede sem fios foi empregada nos ensaios de modelos físicos reduzidos em centrífuga para estudar o comportamento das âncoras \"tartaruga\", utilizadas nas linhas de ancoragem de sistemas oceânicos para produção de óleo e gás em águas profundas. O emprego da tecnologia de redes de sensores sem fios tem aumentado em muitas áreas da sociedade, principalmente na engenharia. Dessa forma, muitos problemas estão sendo enfrentados e estudados pelos pesquisadores. Sobretudo no que diz respeito à interferência ambiental, relação de potência e alcance, integridade da informação, miniaturização dos dispositivos, autonomia de energia, limitação de algoritmos e vida útil. A inserção da tecnologia de redes de sensores inteligentes sem fios nos ensaios de modelos físicos reduzidos em centrífuga, além de ser inédita no Brasil, permitirá avanços significativos na determinação de parâmetros que, atualmente, são de difícil obtenção com tecnologias convencionais como os sistemas de aquisição de dados e controle que utilizam cabos e fios. Muitas vezes depara-se com a inconveniência do peso dos cabos e dificuldades de instalação dos dispositivos nos modelos, pela sua pouca portabilidade. / This work present a method development to guarantee of the integrity data in the wireless smart sensor networks, employed in centrifuge physical modeling tests of anchors used as fixing devices of deep water production oil and gas systems. The use of wireless smart sensor networks technology has been increasing in many engineering areas. In spite of this evidence, lots of problems are being faced and studied by the researchers, environmental interference, power and reach relations, integrity of the information, miniaturization of the devices, energy autonomy, algorithms and useful life. The use of the wireless smart sensor networks technology in the reduced physical models test in centrifuge, by first time in Brazil, will allow significant advances in the parameters determination. The conventional instrumentation presents inconvenience of the weight cables and difficulties of the devices in the models by limited portability.

Normalmente fundações diretas não são utilizadas em solos colapsáveis devido à falta de soluções econômicas e eficientes para melhorar essa condição crítica de terreno. Quando estes solos são inundados, a água afeta sua estrutura provocando uma redução de volume, e consequentemente grandes recalques nas fundações. Por outro lado, a maioria dos solos colapsíveis em regiões tropicais está sujeita a intenso intemperismo e laterização, os quais são responsáveis por melhorar as propriedades do solo após compactação. Por esta razão, solos lateríticos colapsíveis em forma compactada são comumente usados como aterros e materiais de construção em estradas, e têm sido empregados no Brasil para possibilitar a construção de fundações diretas. A pesquisa atual foi planejada para avaliar um aprimoramento desta técnica, que seria o uso de grupos de colunas de solos lateríticos compactados, ao invés de camadas compactadas de solo muito espessas, para permitir o uso de fundações diretas. Para este estudo, ensaios edométricos simples e duplos e de modelagem física em centrífuga foram conduzidos em um solo laterítico colapsível típico do sudeste brasileiro. Complementarmente, um modelo numérico foi ajustado, usando-se os resultados dos ensaios em centrífuga, para estimar a melhoria nas propriedades do solo reforçado. Por fim, os resultados experimentais mostraram que a técnica proposta pode reduzir os recalques de colapso induzidos por umedecimento do solo, e também melhorar o comportamento carga-recalque de fundações diretas apoiadas no solo investigado. / Normally, shallow foundations are not used in collapsible lateritic soils due to the lack of economic and efficient solutions to improve this critical ground condition. When these soils become wetted, the water breaks down soil arrangement and causes the soil to compress, and consequent large settlement of the foundations supported by them. In contrast, most collapsible soils in tropical regions are subject to intense weathering and laterization, which are responsible for good soil properties after compaction. For this reason, collapsible lateritic soils in compacted form are commonly used as fills and road construction materials, and have been utilised in Brazil to allow the construction of shallow foundations. The current research was designed in order to evaluate an enhancement of this technique, which is the use of groups of compacted lateritic soil columns, instead of very thick compacted soil layers, to allow the use of shallow foundations. For this study, single-point and double oedometer and physical model tests in centrifuge were conducted on a collapsible lateritic soil typical in the southeastern part of Brazil. Additionally, a numerical model was adjusted using the data from the centrifuge tests to estimate the improvement of the reinforced soil. The experimental results show that the proposed technique can reduce wetting-induced collapse settlements and also improve the loaddisplacement performance of shallow foundations in the soil investigated.

Thesis (Ph.D, Civil Engineering) -- Queen's University, 2011-01-31 20:52:11.162 / One of the most severe hazards for buried pipelines, which are sometimes referred to as lifelines due to their essential role in delivering vital resources, is the hazard due to Permanent Ground Deformation (PGD). Earthquake induced PGD can be caused by surface faulting, landslides and seismic settlement. In this thesis, the behaviour of buried pipelines subject to normal faulting has been experimentally investigated through a series of centrifuge tests performed on both continuous and jointed pipelines. Both pipe and soil displacements were measured using image analysis. Signal processing techniques were then developed to filter this data so as to enable the calculation of curvature and other aspects of the response from the observed pipe deformations. First, a series of centrifuge tests was conducted on continuous pipelines of varying materials, representing a wide range of pipe stiffness relative to the soil and investigating the effect of pipe stiffness relative to the soil on soil-pipe interaction. The experimentally derived p-y curves at different locations along the pipe were compared to the recommended soil-pipe interaction models in the relevant guidelines. These p-y curves showed that the central shearing region was not captured well with independent soil springs. The response of the pipelines predicted by the ALA (2001) guideline, however, was shown to match the experimental data within 50%. Two new simplified design approaches were then developed. The first features calculations based on simplified pressure distributions. The second featured peak curvature normalized using a characteristic length, ipipe, the distance from peak to zero moment. A series of centrifuge tests using brittle pipes was also performed. The pipes were buried at three different depths, and the post-failure fracture angle of the pipe was measured to be used as an input for design of liners. Based on the experimental data, a computationally efficient approach was developed to estimate the initial fracture angle which occurs immediately after the pipe breaks. The last series of centrifuge tests was conducted on jointed pipelines with five different joint stiffnesses to investigate the flexural behaviour of jointed pipelines under normal faulting. Based on the observed pipe response, a simplified kinematic model was proposed to estimate the maximum joint rotation for a given geometry, pipe segment length, and the magnitude of the imposed ground displacement. / Ph.D

Ce travail de thèse est une contribution à l’étude phytochimique par Chromatographie de Partage Centrifuge (CPC), de trois plantes utilisées en médecine traditionnelle au Soudan : Aristolochia bracteolata (plante entière), Ziziphus spina-christi (feuilles) et Hydnora abyssinica (rhizomes). Ce travail a permis de mettre au point trois méthodologies de purification par CPC, applicables au fractionnement des acides aristolochiques, des flavonoïdes ou des proanthocyanidols (PAC). Dans ce contexte, la première partie de ce manuscrit est consacrée aux notions générales portant sur la CPC. La deuxième partie porte sur l’étude d’Aristolochia bracteolata. Cette plante est utilisée en médecine traditionnelle, malgré la présence d'acides aristolochiques qui confèrent une néphrotoxicité élevée. Ce travail a permis de mettre au point une méthode innovante pour l’isolement et la purification, avec un très haut niveau de pureté, des acides aristolochiques I, II et IIIa à partir d’un extrait brut, en une étape par CPC en mode d’échange d’ions forts (SIX-CPC). L’acide aristolochique IIIa n’avait jamais été décrit dans cette plante auparavant. Ces résultats ont fait l’objet d’une publication en 2015 dans Separation and Purification Technology. Dans la troisième partie de cette thèse, la CPC a été appliquée à l’isolement de flavonosides présents dans Z. spina-christi. Nous appuyant sur l’expérience du laboratoire dans l’extraction par CPC des flavonosides du Ginkgo biloba, nous proposons une méthodologie de purification utilisant les systèmes de solvant biphasiques EtOAc/n-BuOH/MeOH/H2O et EtOAc/n-BuOH/H2O à différents ratios en fonction de la polarité des flavonosides. Dans la dernière partie, l’étude phytochimique de Hydnora abyssinica a mis en évidence la présence de PACs, polymères de hauts poids moléculaires de flavanols. La méthodologie de fractionnement CPC, précédée d’un pré-fractionnement sur résine LH-20, a permis l’isolement pour la première fois dans cette plante de la katsumadine et du rhodioloside. / This work was a contribution to the phytochemical study of three Sudanese medicinal plants: Aristolochia bracteolata (Whole plant), Ziziphus spina-christi (Leaves) and Hydnora abyssinica (Rhizomes). The specificity of this research program was to emphasize the application of Centrifugal Partition Chromatography (CPC) for the fractionation of these plants. Three specific CPC methodologies were developed for the purification of either aristolochic acids, flavonoids or proanthocyanidins (PACs). In this context, the first part of this manuscript was devoted to the presentation of the CPC methodology. The second part focused on the fractionation of crude extract of Aristolochia bracteolata. This plant is used in traditional medicine, in spite of the presence of aristolochic acids that confer a high nephrotoxicity. In this work was developed an innovating procedure for the isolation and purification in high purity of aristolochic acids I, II and IIIa, in one step from crude extract, using Strong Ions eXchange CPC (SIX-CPC). These results were published in 2015 in Separation and Purification Technology. In the third part, the flavonosides present in Z. spina-christi were isolated using CPC, either in normal or reverse elution mode, using two phases solvent systems EtOAc/n-BuOH/MeOH/H2O or EtOAc/n-BuOH/H2O with different ratios. In the last part, the phytochemical study of Hydnora abyssinica led to the fractionation of PACs, polymers of high molecular weight of flavanols. The CPC fractionation methodology, preceded by LH-20 resin pre-fractionation, allowed the isolation of katsumadine and rhodioloside.

Au-dessus d’une certaine température appelée température de trouble (Tc), les solutions aqueuses de la majorité des tensioactifs non ioniques polyéthoxylés se séparent en deux phases liquides en équilibre : la phase diluée et le coacervat. Grâce à la solubilisation micellaire de composés hydrophobes, amphiphiles ou même ioniques et à leur concentration dans le (faible) volume de coacervat, une extraction à deux phases aqueuses (extraction par point de trouble ou par coacervat)peut être réalisée et appliquée à des opérations de dépollution d'effluents industriels ou à la concentration ou encore à la séparation de substances à haute valeur ajoutée. L’extraction par point de trouble (CPE) est une technique relativement simple et écologique pour l'élimination des matières toxiques de l'environnement, qui s’est avérée efficace dans le traitement de divers contaminants (organiques et inorganiques dissous ou dispersés) de l’eau. Une première partie de cette thèse consiste à rappeler quelques notions sur la pollution industrielle des eaux et quelques généralités sur les tensioactifs (TA) et sur l’extraction liquide-liquide. Elle est suivie d’une description des réactifs, du matériel et des méthodes utilisées au cours de ce travail, comme préliminaire à la mise au point d'un procédé d'extraction par coacervat. Quelques propriétés thermodynamiques superficielles (adsorption) et d’association (micellisation) de deux tensioactifs non ioniques industriels (le Simulsol NW342 et le Tergitol 15-S-7) ont été déterminées. Les courbes de démixtion des systèmes binaires (eau/TA) ainsi que l’effet de divers additifs (sel, composés organiques, tensioactifs ioniques) sur le point de trouble sont étudiés. Le diagramme isotherme du système ternaire (eau/TA/ phénol) est tracé. Une application du modèle de Flory-Huggins-Rupert pour la prédiction des courbes de démixtion des tensioactifs non ioniques a été expérimentée. L’extraction à un seul contact, à partir de solutions modèles, utilise des alcools oxo éthoxylés biodégradables (Simulsol NW342 et Tergitol 15-S-7) pour des polluants organiques dissous (phénol, 1-phényléthanol et alcool benzylique) et un mélange de tensioactifs non ionique (Simulsol NW342) et ionique (SDS ou CTAB) pour des polluants métalliques solubles (plomb(II), molybdène(VI)). On cherche le meilleur compromis entre le pourcentage de soluté extrait (E%),la fraction volumique du coacervat (фv), et les pourcentages de soluté et de tensioactif restants dans la phase diluée (Xs,d et XTA, d), en utilisant un plan d'expériences de type Scheffé et un lissage empirique des courbes. Les résultats sont très prometteurs car les pourcentages d’extraction varient de 60 à 95% pour les solutés organiques et de 40 à 85% pour les solutés métalliques, les meilleures performances étant obtenues pour le phénol et le plomb. D’autre part, il est possible, en jouant sur le pH, d’améliorer les séparations et de recycler le tensioactif après désextraction des solutés. Les cinétiques d’extraction, de séparation et de clarification ont été aussi étudiées pour une meilleure compréhension de ces systèmes. Enfin, l’extraction continue du phénol à partir du mélange eau/4%Simulsol NW342/0,2%phénol (mass.) a été testée sur deux appareillages (extracteur centrifuge et mélangeurdécanteur)thermostatés. Dans un procédé multi-étagé à courants croisés sur un mélangeur-décanteur, on arrive à réduire la concentration du phénol à moins de 0,3ppm (concentration limite selon la législation) après six étages. / Above a certain temperature called cloud point (Tc), aqueous solutions of most nonionic polyethoxylated surfactants separate into two liquid phases in equilibrium: the dilute phase and the coacervate. Thanks to the micellar solubilization of hydrophobic, amphiphilic or even ionic compounds and their concentration in the low volume of coacervate, two-aqueous phase extraction (cloud-point or coacervate extraction) can be performed and applied to the removal of pollutants from aqueous industrial effluents or to the concentration or even separation of high added-value chemicals. Cloud point extraction (CPE) is a relatively simple and ecologically-safe technique for the removal of toxic materials from the environment; this process has proved efficient in treating water for various contaminants including dissolved or dispersed organic and inorganic chemicals. The first part of this thesis consists of recalling some notions on industrial wastewater, some generalities about surfactants (TA) and liquid-liquid extraction, followed by a description of all the reagents, materials and methods used in this work as a preliminary study of a coacervate extraction process. Some surface thermodynamic (adsorption) and association (micellization) properties of two industrial nonionic surfactants (Simulsol NW342 and Tergitol 15-S-7) were determined. The cloud point curves of water /TA binary systems are drawn and the effect of various additives (salt, organic compounds, ionic surfactants) on the cloud point is studied. The isothermal diagram of a water/TA/phenol ternary system is drawn. An application of the Flory-Huggins-Rupert model for the prediction of cloud point curves of nonionic surfactants is discussed. Single contact extraction, from model solutions, uses biodegradable polyethoxylated nonionic surfactants (Simulsol NW342 and Tergitol 15-S-7) for dissolved organic pollutants (phenol, 1-phenylethanol and benzyl alcohol) and mixed micelles of nonionic (Simulsol NW342) and ionic (SDS, CTAB) surfactants for soluble electolytes (lead (II), molybdenum (VI)). We search for the best compromise between the percentage of solute extracted (E%), the coacervate volume fraction (фc) and the percentages of solute and surfactant remaining in the dilute phase (Xs,d and XTA,d), These experimental results are subject to an empirical smoothing through a Scheffé-type experimental design, and an empirical curve fitting procedure. The results are very promising, due to the percentage of solute extracted, which varies between 60 and 95% for organic solutes and from 40 to 85% for electrolytes, the best performances being obtained for phenol and lead. On the other hand, it is possible, by adjusting pH, to improve the separation and recycle the surfactant after back-extraction. The kinetics of extraction yield and phase separation and clarification were also investigated for a better understanding of these systems. Finally, the continuous extraction of phenol from a model solution (water/4wt.% Simulsol NW342/0.2wt.% phenol) on two thermostated equipments (a centrifugal extractor and a mixer-settler) was attempted. In a multi-stage process on a cross-current mixer-settler, the concentration of residual phenol in the dilute phase could be reduced to less than 0.3 ppm (concentration allowed by standard European regulations) after six stages.

O monitoramento em campo de fundações em estacas metálicas helicoidais é baseado em correlações empíricas entre a capacidade de carga à tração e o torque medido durante a instalação. Nesta pesquisa é proposto um modelo teórico da relação entre o torque de instalação e a capacidade de carga à tração deste tipo de estaca em areias para ser utilizado como procedimento de controle durante a execução deste tipo de fundação. Para validar esta relação teórica e para avaliar o desempenho desta fundação em solos arenosos, foi realizado um programa experimental dividido em dois grupos: ensaios de campo e ensaios de laboratório. Em campo foram realizadas provas de carga à tração na Escola de Engenharia de São Carlos (EESC) e em Contagem (Minas Gerais). Os ensaios de laboratório foram divididos em três grupos. O primeiro corresponde aos ensaios de modelagem física em centrífuga realizados no Laboratoire Central des Ponts et Chaussées (LCPC) em Nantes, França. O segundo engloba ensaios de cisalhamento direto de interface entre o aço da hélice da estaca e diferentes areias, parte executada no LCPC e parte na EESC. O terceiro grupo refere-se a ensaios de torção de tubos de estacas metálicas helicoidais efetuados na EESC. A partir dos resultados dos ensaios, o modelo teórico proposto nesta tese foi verificado e mostrou-se adequado para estacas metálicas helicoidais profundas com diferentes dimensões e número de hélices instaladas em solos arenosos. Os resultados das provas de carga realizadas em centrífuga e em campo foram examinados por meio dos métodos existentes na literatura para estimativa de capacidade de carga à tração desenvolvidos para este tipo de fundação. Por meio dos resultados obtidos nos ensaios em centrífuga, constatou-se que nas estacas multi-hélices a porcentagem de capacidade de carga relativa à hélice da ponta aumenta de acordo com o diâmetro da hélice e com a densidade da areia. Nos ensaios de torção de fustes de estacas helicoidais observou-se que, para tubos de mesmo diâmetro e espessura, a ruptura se inicia a partir do mesmo valor de momento torçor aplicado, independentemente de conter ou não emenda. / Empirical correlations between installation torque and uplift capacity of helical screw piles are routinely used as a procedure for quality control on site of this type of foundation. In this work, a theoretical model of the relationship between uplift capacity and installation torque of deep helical screw piles in sand was presented to be used as a quality control method for this type of foundation. An experimental program of laboratory and field investigations was carried out in order to validate this theoretical relationship. The field study included uplift tests of full-scale piles installed at the Escola de Engenharia de São Carlos (EESC) and in Contagem (Minas Gerais). The laboratory tests were performed in the Laboratoire Central des Ponts et Chaussées (LCPC/ Nantes) and at the EESC. In the LCPC a program of centrifuge and direct shear interface tests was completed. A set of torsion tests on pile shafts and of direct shear interface tests were carried out at the EESC. The results showed that the theoretical model presented is applicable to different pile dimensions, number of helices, and sand relative density. The methods existing in the literature for estimating uplift capacity of helical screw piles were used to verify the results of uplift capacities measured in field and in centrifuge studies. The results of centrifuge modelling tests demonstrated that the fraction of uplift capacity corresponding to the bottom helix increases with helix diameter and sand density. The torsion tests showed that the failure of the pile shaft begins at the same torque magnitude in experiments on shafts with and without connections.