Este trabalho tem como objetivo preparar e avaliar membranas de Paládio em suporte cerâmico poroso de α-alumina, sinterizado a 1600ºC, utilizando os métodos sol-gel e de deposição química, electroless plating. Foram preparadas membranas, α-alumina/Pd, com uma e duas camadas de paládio na superfície externa do suporte cerâmico. O suporte cerâmico e as membranas foram caracterizados por análise morfológica através de Microscopia Eletrônica de Varredura (MEV), Espectroscopia por Dispersão de Energia (EDS), Porosimetria por Intrusão de Mercúrio e, a permeabilidade e seletividade dos gases H2, CH4 e CO2 a partir de um sistema de bancada. As imagens de MEV mostram uma superfície mais uniforme para a membrana com uma camada de paládio do que com duas camadas. Os testes de permeação de gases indicam que as membranas são seletivas, apresentando seletividade de ≈60% para H2/CO2 e ≈ 45% para H2/CH4 independente da espessura da camada de paládio depositada no suporte cerâmico. / This work aims to prepare and evaluate Palladium membranes on porous ceramic support of α-alumina, sintered at 1600ºC, using sol-gel and electroless plating technique. It were prepared membranes Pd/α-alumina, with one e two depositions of Pd in the external surface of ceramic support. The ceramic support and the membranes were characterized by morphological analysis through Scanning Electron Microscopy (SEM), Energy Dispersion Spectroscopy (EDS), mercury porosimetry and, the permeability and selectivity to H2, CH4 e CO2 from a bench system. The SEM images show that surface membrane is more uniform with one layer than two Pd layers. Gas permeability test suggest that the composite membranes possessed gas selectivity, and selectivity was of ≈60% for H2/CO2 gas and ≈45% for H2/CH4 gas, regardless of thickness of Pd layer.

Orientador: Marcelo Giannini / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-28T03:49:14Z (GMT). No. of bitstreams: 1 Sa_RenataBacelarCantanhedede_D.pdf: 1663244 bytes, checksum: ddbd6a5d390052ef93aca63cbdf510ab (MD5) Previous issue date: 2015 / Resumo: Este estudo avaliou o efeito de agentes cross-linking e a utilização de sistemas adesivos (SA) que não contém o monômero HEMA. No capítulo 1 foram avaliadas a resistência de união (RU) e o selamento dentinário (SD) após 24 horas e 6 meses de armazenamento em água. Para RU, foram avaliados 4 SA: um autocondicionante e um convencional contendo o monômero HEMA (Scotchbond Universal/SU e Prime & Bond Elect/PB), um autocondicionante e um convencional sem HEMA (G-Aenial/GA e All-Bond 3/AB) respectivamente. Cada SA foi subdividido em grupos baseados na biomodificação da dentina: controle (sem aplicação de agentes cross-linking), glutaraldeído 5% e proantocianidina 6,5% (PA). Após a aplicação dos adesivos com ou sem o uso de agentes cross-linking e aplicação do compósito, os dentes foram seccionados para obtenção de espécimes, os quais foram avaliados com o teste de microtração. O agente cross-linking que produziu os melhores resultados (PA) foi selecionado para o estudo de SD. Os espécimes foram preparados da mesma forma como descrito anteriormente. As mensurações de permeabilidade dentinária (PD) foram realizadas com a simulação da pressão pulpar através de uma coluna de água de 140 cm em 5 tempos (PD mínima: P min, PD máxima: P máx, PD após o uso do PA: PPA, PD após aplicação dos SA: PSA e PD após 6 meses: Parmazenado). Para o grupo controle, a mensuração difere na remoção da etapa correspondente a PPA, continuando com PSA e Parmazenado, respectivamente. No capítulo 2 foram avaliadas a RU, SD e micropermeabilidade de 4 SA: um convencional contendo HEMA (Adper Single Bond 2/SB), um adesivo de 3 passos que não contem HEMA no solução adesiva hidrófoba (AB) e dois autocondicionantes sem HEMA (GA e BeautiBond/BB). Os dentes foram preparados da mesma forma descrita no primeiro capítulo. A micropermeabilidade foi avaliada através da infiltração do corante amarelo de lúcifer na camada híbrida. Todas as metodologias foram avaliadas após 24 horas e 1 ano de armazenamento em saliva artificial. As mensurações de SD foram expressas em %. Os dados foram analisados com metodologia de modelos mistos para medidas repetidas para o primeiro capítulo e ANOVA 2 fatores e teste de Tukey (?=0,05). A RU produzida por PB, SU e AB não apresentou diferença entre eles e GA apresentou os menores valores em 24 horas. Todos SA apresentaram maiores RU com a aplicação do agente cross-linking PA em 24 horas, independentemente de possuírem HEMA na composição. Após armazenamento por 6 meses, SU e AB apresentaram redução da RU. PA e SA reduziram a permeabilidade da dentina e da interface dentina-resina, respectivamente. No segundo capítulo, AB apresentou maior RU seguido de SB e dos autocondicionantes (BB e GA) em 24 horas. GA apresentou o menor valor de RU após um ano, pois teve redução com o armazenamento. No SD em 24 horas, SB e AB selaram a dentina como a Pmin, enquanto BB não apresentou a mesma capacidade, porém manteve-se estável por um ano. Na avaliação da micropermeabilidade, ausência do HEMA não influenciou os resultados. Os resultados sugerem que a aplicação apenas do agente cross-linking PA pode produzir o selamento da dentina e aumentar a RU. Na segunda parte do estudo, o adesivo AB mostrou os melhores resultados nas análises de RU, SD e micropermeabilidade / Abstract: This study evaluated the effects of cross-linking agents and adhesive systems (AS) that not contain the monomer HEMA. In the chapter 1 the microtensile bond strength (BS) and dentin sealing (DS) after 24 hours and 6 months of water storage were evaluated. For BS teste, 4 groups AS were evaluated: a self-etch and one total-etch HEMA-containing adhesives (Scotchbond Universal/SU and Prime & Bond Elect/PB), one self-etch and one total-etch HEMA-free adhesives (G-Aenial/GA and All-Bond 3/AB). Each AS was divided into sub-groups based on dentin biomodification: control (no cross-linking agent application), 5% glutaraldehyde and 6.5% proanthocyanidin (PA). After adhesives application with or not cross-linking agent use, teeth were sectioned to obtain specimens, which were evaluated in microtensile bond strength test. The most promising dentin biomodification strategy (PA) was selected for DS study. The specimens were prepared in the same way as previous described. Permeability (PD) measurements study was carried out using a simulated pulpal pressure of 140 cm water column at 5 times of evaluation (minimum PD: Pmin, maximum PD: Pmax, PD after PA: PPA, PD after AS application: PAS and PD after 6 months: Pstored). For the control group, the measurements differ from PPA removal, continuing with PAS and Pstored, respectively. In the chapter 2, BS, DS and micropermeability of 4 AS: one total-etch HEMA-containing (Adper Single Bond 2/SB), one three-step etch-and-rinse adhesive that does not contain HEMA in hydrophobic solution (AB) and two self-etch HEMA-free (GA and BeautiBond/BB). The teeth were prepared in the same way as described in the chapter one. For micropermeability analysis the yellow lucifer was used and detected its penetration into the hybrid layer. All methods were tested after 24 hours and after 1 year of artificial saliva storage. DS measurements were expressed as %. The data were submitted to multiple comparisons using PROC MIXED for chapter one and two-way ANOVA and by Tukey¿s test (?=0.05) for chapter two. The BS of PB, SU and AB did not differ among them and GA showed the lowest values at 24 hours. PA cross-linking agent increased the BS for all at 24 hours, regardless the presence of HEMA. Storage for 6 months significantly decreased the BS for SU and AB. PA and AS decrease the permeability of the dentin and dentin-resin interface, respectively. In the chapter two, AB showed the highest values BS followed by SB and self-etch adhesives (BB and GA) at 24 hours. GA showed the lowest BS after one year because it was reduced. For DS, SB and AB sealed the dentin as Pmin, while BB and did not present the same ability, however kept stable after one year. The micropermeability revealed that the absence of HEMA did not influence the outcomes. Results suggested that PA cross-linking application alone was able to seal the dentin and increase the BS. In the second chapter, AB adhesive showed the best results in BS, DS and micropermeability analyses / Doutorado / Materiais Dentarios / Doutora em Materiais Dentários / 2011/11415-1, BEPE 2013/02386-3 / FAPESP

Orientador: Rosângela Barros Zanoni Lopes Moreno / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica e Instituto de Geociências / Made available in DSpace on 2018-08-28T12:56:20Z (GMT). No. of bitstreams: 1 Dominguez_LuciaGarcia_M.pdf: 8169227 bytes, checksum: 3b6d0e210f4dc8a2db3d9f8b9f93f6c0 (MD5) Previous issue date: 2015 / Resumo: A capacidade de armazenamento de hidrocarbonetos no reservatório depende do tipo de rocha e da estrutura dos poros. Uma das propriedades rocha-fluido mais estudadas é a permeabilidade relativa, ou seja, a medida da resistência ao escoamento que um fluido apresenta na presença de outro. A permeabilidade relativa é essencial para a avaliação dos processos de recuperação de hidrocarbonetos e previsão do escoamento multifásico de fluidos através do reservatório. A permeabilidade relativa depende de outros parâmetros que têm sido estudados por especialistas durante os últimos anos, como saturação dos fluidos, molhabilidade, tensão interfacial, estrutura porosa, temperatura, heterogeneidades e vazão de deslocamento. Em relação ao efeito da vazão de deslocamento na permeabilidade relativa, muitas pesquisas têm sido realizadas sem conseguir um acordo. Por tanto, a principal motivação deste estudo é a falta de conformidade na literatura. O foco do trabalho é encontrar se existe dependência da permeabilidade relativa com a vazão e avaliar este efeito em óleos de diferentes viscosidades. Foram realizados quinze testes de deslocamento em regime transiente a temperatura e vazão constantes. Os experimentos de laboratório foram executados com três plugues, cortados a partir de uma amostra única de rocha carbonática e saturados com três óleos de viscosidades diferentes, respetivamente. Foram utilizadas três vazões diferentes para cada amostra, que correspondem aos valores mínimo, máximo e intermediário de acordo o critério de dos Santos et al (1997) que visa balancear as forças viscosas, capilares e gravitacionais. Estas vazões foram variadas começando pela maior e diminuindo até a menor e posteriormente revertendo o ciclo, para observar se a sequência seguida influencia nos resultados. A análise dos resultados foi realizada mediante o método de Johnson-Bossler-Naumann para calcular as permeabilidades relativas ao óleo e à água. Sob as condições dos testes realizados, observou-se que as saturações e permeabilidades dos pontos terminais bem como as curvas de permeabilidade relativa, dependem da vazão. Além disso, pode-se observar que as variações foram diferentes dependendo da viscosidade do óleo utilizado. Deste modo, o óleo de menor viscosidade sempre se comportou de modo contrário ao de maior viscosidade e a mistura dos outros dois teve um comportamento intermediário. Este comportamento tem sido atribuído, nos óleos mais viscosos, a um aumento no ângulo de contato e consequente diminuição do número capilar em resposta à vazão mais elevada. Já nos óleos menos viscosos, a vazão não altera significativamente o ângulo de contato e, portanto, o número capilar aumenta com a vazão. Estas diferenças na variação do número capilar, dependendo do óleo utilizado, podem gerar as tendências diferentes nos resultados e explicar o desacordo na literatura / Abstract: The storability of hydrocarbons in the reservoir is dependent upon the rock formation and the pore structures. One of the main important rock-fluid property is the relative permeability, a measure of the flow resistance of one fluid in the presence of another one into the rock. Relative permeability depends on other parameters which have been studied by researchers during the years like fluid properties and saturation, wettability, interfacial tension, porous structure, temperature, heterogeneity and flow rate. Many researchers have focused on flow rate influence in relative permeability curves without obtaining agreement. Therefore, the main motivation for this study is the lack of conformity in the literature. The focus of the work is to find whether there is dependence of relative permeability with the flow and evaluate this effect in oils of different viscosities. Fifteen transient displacement tests were performed at constant temperature and flow rate. The laboratory experiments were performed with three plugs, cut from a single sample of carbonate rock and saturated with three fluids of different viscosities, respectively. Three different flow rates were used for each sample, corresponding to the minimum, maximum and intermediate according to dos Santos et al criterion (1997) which aims to balance the viscous, capillary and gravitational forces. These flow rates were varied starting with the largest and decreasing to the smallest, and subsequently reversing the cycle, to see if the next sequence influences the results. Experimental results were analyzed using JBN method (Johnson-Bossler-Naumann) to calculate oil and water relative permeability curves. Under the studied circumstances, it was observed that the end point saturations and permeabilities and the relative permeability curves depend on the flow rate. Moreover, variations were different depending on the viscosity of the oil used. Thus, the lower viscosity oil will always behave in a contrary manner to the higher viscosity and the mixture of the other two had an intermediate performance. This behavior has been attributed, for more viscous oils, to an increment in contact angle and thus diminution in the capillary number in response to the higher flow. Nevertheless in lower viscous oils, the flow rate does not alter significantly the contact angle and thus the capillary number increases with flow rate. These differences in the variation of the capillary number depending on the oil used may generate the differences on the results trends and explain the disagreement in the literature / Mestrado / Reservatórios e Gestão / Mestra em Ciências e Engenharia de Petróleo

Para melhor ação da MIC, é necessário que esta penetre no interior dos túbulos dentinários. Sendo assim, o objetivo deste trabalho foi avaliar a permeabilidade dentinária do sistema endodôntico observando a penetração da MICM (medicação intracanal marcada com Rodhamina B 1%) após o preparo biomecânico usando soluções irrigadoras, associadas ou não a irradiação com laser de diodo de alta potência 810 nm. Foram utilizados 72 pré-molares inferiores unirradiculares As amostras foram divididas em três grupos: I, II e III, compostos por 24 espécimes cada. Estes por sua vez, foram sub-divididos em três outros grupos, A, B e C de acordo com a substância química auxiliar utilizada no preparo biomecânico.Nas amostras do grupo A foi utilizado o hipoclorito de sódio (NaOCl) 2,5%; no grupo B o EDTA-T (ácido etilenodiamino tetracético dissódico) 17%; e no grupo C o NaOCl 2,5% e irrigação final com EDTA-T 17% por três minutos. Os canais das amostras do grupo I foram irradiados imediatamente após o preparo biomecânico, por sua vez as do grupo II foram irradiadas antes do preenchimento do canal com a MIC- M e o grupo III foi o grupo controle. Os dentes foram clivados e as imagens digitalizadas avaliadas no programa ImageLab. O protocolo que permitiu melhores resultados foi o realizado nas amostras do grupo IB - irrigação com EDTA-T seguido da MICM e irradiação intracanal.Os resultados obtidos foram submetidos a análise estatística. Concluiu-se que a realização dos protocolos do ensaio experimental promoveram alterações na capacidade de penetração do agente indicador. / To get a better action of MIC, it is necessary to penetrate into the teeths ducts. So, this search brings an evaluation of teeths permeability by the penetration of MIC-M (intracanal medication with Rhodamine 1%), after biomechanical instrumentation with chemical solutions associated or not to irradiation with laser of high power of diode 810 nm. It has been used 72 daily pay-molar inferiors with only one root. The samples had been divided in three groups: I, II and III, composed by for 24 specimens each. These in turn, had been subdivided in three other groups, A, B and C in accordance with the chemical substance used in the biomechanical instrumentation. Group A used the sodium hypochlorite (NaOCl) 2,5%; group B used EDTA-T 17%; and group C used NaOCl 2.5% and final irrigation with EDTA-T 17% during three minutes. Group I was radiated after the biomechanical preparation immediately, in group II the diode laser was applied before the full filling of the canal with the MIC and group III was the group that has controlled. The teeth had been bisected longitudinally, typed and the images evaluated in the ImageLab program. The protocol that showed the best results were in group IB irrigation with EDTA-T, followed by MIC-M and irradiation of root canal walls. The results obtained were submitted to statistical analysis. Our conclusion for this study is that the experimental protocols caused alterations on penetration ability of the indicator agent.

A Ressonância Magnética Nuclear (RMN) é uma das técnicas mais versáteis de investigação científica experimental, com destaque para o estudo da dinâmica, estrutura e conformação de materiais. Em particular, sua utilização na ciência do petróleo é uma de suas primeiras aplicações rotineiras. Metodologias desenvolvidas especificamente para atender esta comunidade científica mostraram-se desde cedo muito úteis, sendo o estudo da interação rocha/fluido uma de suas vertentes mais bem sucedidas. Desde então, importantes propriedades petrofísicas de reservatórios de óleo e gás têm sido determinadas e entendidas, tanto em laboratório quanto in-situ, nas próprias formações geológicas que armazenam esses fluidos. Entre estas propriedades, a permeabilidade, porosidade e molhabilidade de um reservatório figuram dentre as mais importantes informações estimadas. Com essa finalidade, a determinação e correlação dos possíveis efeitos que a interação rocha/fluido pode causar nos fenômenos de relaxação magnética e difusão molecular, tais como influência da susceptibilidade magnética e geometria do espaço poroso, foram estudados em onze rochas sedimentares retiradas de afloramentos, que possuem propriedades petrofísicas similares àquelas apresentadas por rochas reservatório de petróleo. Os resultados mostraram que os tipos de interação rocha/fluido, detectáveis pelos experimentos de RMN, são por sua vez influenciados pelas características geométricas e estruturais do meio poroso, sendo possível obter essas informações pelos resultados de RMN. Assim, este trabalho teve como objetivo principal estudar e estabelecer essas correlações, afim de se obter informações petrofísicas com maior acurácia e abrangência. Em particular, o estudo da razão T1/T2, que é a razão entre os tempos de relaxação longitudinal e transversal, típicos parâmetros envolvidos numa medida de RMN, mostrou ser um parâmetro útil no estabelecimento destas correlações. Ainda, diferentes metodologias para se medir estes e outros parâmetros de RMN foram estudadas e propostas, cuja interpretação conjunta mostrou ser fundamental para o entendimento dessas correlações. A permeabilidade das rochas, importante parâmetro que define as propriedades de transporte de fluidos dentro da matriz porosa, foi estimada aplicando-se essas metodologias propostas, mostrando excelentes resultados. Através do uso da técnica de RMN em estado-estacionário, esses resultados podem ser estendidos para a escala de well-logging, fato que aumenta consideravelmente a importância desses resultados. Uma vez consolidadas as medidas in-situ, as metodologias propostas deverão auxiliar a indústria de exploração e produção de petróleo a otimizar seus métodos e estratégias de produção, reduzindo seus custos e aumentando a vida útil de seus reservatórios. / The Nuclear Magnetic Resonance (NMR) technique is one of the most versatile techniques for scientific research, specially for the study of dynamics, structure and conformational of materials. In particular, its application in oil science is one of its first routine applications. Methodologies developed specifically to match this scientific community proved to be very useful, and the study of rock/fluid interactions is one of its most successful cases. Since then, important petrophysical properties of oil and gas reservoirs have been determined and understood both in the laboratory and inside the geological formations that store those fluids. Among these properties, the permeability, porosity and wettability of a reservoir formation are the most important information to be estimated. For this purpose, the determination and correlation of possible rock/fluid interaction effects that cause alterations on magnetic relaxation phenomena and molecular diffusion, such as the influence of the magnetic susceptibility and geometry of the porous space, were studied in eleven sedimentary rock cores taken from outcrops, since they have the same petrophysical properties presented by oil reservoir rocks. The results obtained confirmed that the types of rock/fluid interactions, detectable by the NMR experiments, are for instance influenced by the porous media geometry and structure, being possible so to obtain such information using those NMR results. Thus, the main goal of this work was the study and establishment of these correlations, in order to obtain petrophysical information with greater accuracy and comprehensiveness. In particular, the study of the T1/T2 ratio, which is the ratio of longitudinal and transverse relaxation times, common parameters strongly involved in a typical NMR measurement, was found to be useful in establishing those correlations. Moreover, different methodologies to measure this and other NMR parameters were studied and proposed, whose joint interpretation proved to be fundamental for the success of these correlations. The permeability of the rocks, an important parameter that controls the fluid transport properties inside the porous matrix, was estimated using the proposed methodologies, showing excellent results. Appling the steady-state NMR technique, those results could be extended to the well-logging scale, which could improve considerably the importance of that results. Once confirmed in measurements in-situ, the proposed methodologies will be able to help the production and exploration industry to optimize their production methods and strategies, thereby reducing production costs and increasing the reservoir lifetimes.

L'amélioration des sols est à l'origine une solution économique pour rendre un sol constructible, notamment par rapport aux méthodes de fondations profondes utilisant des pieux. L'amélioration de la compréhension du comportement du matériau provenant de soil-mixing ou jet-grouting connait un intérêt grandissant. Ces deux procédés consistent à mélanger le sol en place avec un liant hydraulique afin de former des colonnes ou des panneaux en "béton de sol". Les fondations spéciales ont connu ces dernières décennies un franc succès aux États-Unis, au Japon et dans les pays Scandinaves. En Europe les nouvelles priorités, pour la plupart liées à l'environnement, au coût de la construction et à la valorisation des matériaux encouragent les industriels à contribuer au développement technologique de la discipline. Certains procédés de mélange paraissent désormais suffisamment sophistiqués pour assurer la réalisation d'éléments structuraux tels que les fondations et les soutènements.Contrairement aux matériaux préfabriqués, à cause des incertitudes liées à l'hétérogénéité des sols, aux conditions environnementales et à la qualité du malaxage sur chantier, il reste toutefois difficile de prédire les propriétés du matériau obtenu. Un manque de règles et de recommandations semble également assez flagrant. Pour répondre au besoin de prédiction et de fiabilisation performantielle des bétons de sol l'objectif des travaux de thèse était donc d'étudier l'influence des paramètres de formulation sur les propriétés physiques et mécaniques du matériau. Les fortes quantités d'eau de gâchage nécessaires à l'obtention d'une consistance de BAP et la faible granulométrie des sols limitent les caractéristiques mécaniques de ces bétons. De par leur composition, les bétons de sol sont donc particulièrement sensibles au retrait de dessiccation et l'importante porosité de ces matériaux les aussi rend plus vulnérables aux agressions chimiques. L’objectif ultime des travaux de recherche était donc de déterminer des paramètres pour une meilleure visibilité de la durée de vie des ouvrages en béton de sol.L'approche béton suivie au laboratoire a consisté à étudier différents bétons de sol composés de sols "artificiels", d'un ciment CEM III/C, et avec un rapport E/C efficace constant. L'étude paramétrique met en évidence un pourcentage volumique d’argile dans le sol au-delà duquel la résistance diminue et la rigidité du matériau peut poser problème pour certaines utilisations structurelles. Les gains de résistance et de rigidité associés à l'augmentation du dosage en ciment sont également quantifiés. Les résultats montrent que l'endommagement par chargement mécanique dépend surtout du dosage en ciment. À partir des résultats expérimentaux, des relations mathématiques sont proposées pour la phase de dimensionnement. Divers essais de vieillissement accéléré permettent de définir des seuils pour les indicateurs de durabilité (porosité et la perméabilité à l'eau). L'analyse de la microstructure du matériau montre aussi l'importance de l'interface pâte-granulat et a permis d'identifier certains mécanismes de dégradation en lien avec les conditions d'exposition. Enfin, ce travail est complété par une étude du comportement à haute température. / Soil improvement initially has been used as an economical solution to make soil constructible, particularly in the context of deep foundation methods using piles. There has been growing interest to improve understanding of the behavior of soil-mixing and jet-grouting material, which consist of mixing the soil in place with a hydraulic binder in order to form columns or panels of "soilcrete". In recent decades, these special foundations have had a great success in the United States, Japan and the Scandinavian countries. In Europe, the environmental consciousness and the ongoing trend to reuse existing material to reduce cost of construction are driving companies to contribute to the technological development of this discipline. Some mixing processes now seem to be sophisticated enough to provide structural elements such as foundations and supports.Unlike prefabricated materials, it is difficult to predict the properties of the material obtained through deep soil mixing due to uncertainties related to soil heterogeneity, environmental conditions and the quality of mixing on site. The objective of the thesis work is to address this need for prediction and performantial reliability of soilcrete by studying the influence of the formulation parameters on the physical and mechanical properties of the material. The high quantities of mixing water necessary to obtain a BAP consistency and the small particle size of the soil limit the mechanical properties of the soilscretes and as a consequence, are particularly sensitive to desiccation shrinkage. Besides, the high porosity of these materials also makes them more vulnerable to chemical aggressions. The ultimate objective of the research is to determine parameters for a better visibility of the lifetime of concrete structures in the soil.The approach tested in the laboratory consists of studying different soilcretes composed of "artificial" soils, CEM III / C cement and with a constant W/C ratio. The parametric study reveals a proportion by volume of clay in the soil beyond which the resistance decreases and thus the stiffness of the material can be problematic for some structural uses. The increase in resistance and the associated stiffness of the soilcrete by increasing the cement dosage is also quantified. The results show that the damage by mechanical load depends mostly on the cement dosage. From the experimental results, mathematical relations are proposed for the dimensioning phase. Various tests of accelerated aging help define thresholds for the indicators of durability (porosity and water permeability). The analysis of the microstructure of the material also shows the importance of the paste-aggregate interface and made it possible to identify some mechanisms of degradation in relation to the exposure conditions. To conclude, this work is finalised by a study of the behavior at high temperature.

La connaissance des modalités d’absorption trans-épithéliale des molécules actives est un préalable indispensable à leur formulation rationnelle. Parmi les diverses méthodes in vitro disponibles, la technique de la chambre de perméation d’Ussing se distingue non seulement par une relative facilité de mise en œuvre, mais surtout la possibilité de déterminer de manière fiable les modalités de passage des molécules d'intérêt au travers de l'épithélium digestif (transport actif/passif, voies paracellulaire/transcellulaire, transports d’efflux, effets du métabolisme), ainsi que les caractéristiques électrophysiologiques et la viabilité du tissu.Nous présentons tout d'abord les principes généraux de la technique, les paramètres électriques utilisés en vue de l’interprétation des données physiologiques. Enfin, nous proposons une méthodologie pour l'évaluation du passage transmembranaire des molécules actives.La partie expérimentale du travail a eu pour objectif d'évaluer l'apport de cette approche du modèle lorsqu'il s'agit de mesurer l'impact des formulations des molécules d'intérêt (solutions, ou dispersions colloïdales) sur le flux d'absorption. Ainsi, dans un premier temps nous avons démontré pour deux molécules modèles, le paracétamol et la vitamine C, que la nature des solutions physiologiques mises en œuvre pouvaient avoir un effet important sur le fonctionnement électrophysiologique de la membrane, en modifiant notamment sa conductance, son intégrité et par voie de conséquence modifiant profondément la perméabilité transépithéliale. Dans un second temps, dans le cadre de travaux menés en collaboration, nous avons utilisé le modèle d’Ussing pour caractériser l'absorption des molécules d'intérêt lorsque celles-ci sont préalablement associées à divers systèmes colloïdaux. D'une part, nous avons ainsi montré que l'association du resvératrol, une molécule très hydrophobe, à des microémulsions permettait d'augmenter d'un facteur x6 à x11 le passage du transresvératrol par rapport au resvératrol natif. D'autre part, nous avons également montré que l'association d'une héparine de bas poids moléculaire, très hydrophile et naturellement très peu absorbée, mais associée à des nanoparticules de squalène permettait d’augmenter considérablement le flux d'absorption. En conclusion, l'ensemble de nos travaux montre l'intérêt du modèle d’Ussing lorsqu'on souhaite détailler les mécanismes physico-chimiques et biologiques par lesquels les nanoparticules sont susceptibles d'améliorer le passage digestif de molécules naturellement mal absorbées / One has to have the knowledge of the transepithelial absorption method for active molecules, as it is a necessity for rational formulation. Among various in vitro methods, the Ussing chamber technique stands out not only by its relative ease to implement, but mostly through the practical arrangements of the molecules through the digestive epithelium (active/passive transport, paracellular/transcellular, transport efflux, metabolic effects) and electrophysiological characteristics and viability of the tissue.Firstly, we will present the general principles of the technique, the electrical parameters used for the interpretation of physiological data. Eventually, we will suggest a methodology for evaluating the transmembrane passage of active molecules.The experimental part of the work is aimed to evaluate the contribution of this model approach when it comes to measuring the impact of the formulations of molecules (solutions or colloidal dispersions) on the flow of absorption.So initially we worked around with two molecule models, paracetamol and vitamin C, as the nature of physiological solutions implemented could have a significant effect on the electrophysiological function of the membrane, it could change its conductance, and therefore change its transepithelial permeability.Secondly, concerning the collaborative work, we used the Ussing model to characterize the absorption of molecules when they were previously associated with various colloidal systems. On the one hand, we have shown that the combination of resveratrol, a very hydrophobic molecule, has microemulsions which allow an increase by a factor from x6 to x11, the passage of transresveratrol compared to native resveratrol. Additionally, we also showed that the combination of heparin, a lower molecular weight, extremely hydrophilic and poorly absorbed, but when associated with squalene nanoparticles, makes it possible to significantly increase the absorption flow.As a conclusion, all our work shows through Ussing chamber model, that when one wants to detail the physico-chemical and biological mechanisms, the nanoparticles can indeed improve the digestive passage, for those molecules which are poorly absorbed naturally.

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第21958号 / 医博第4500号 / 新制||医||1037(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 中川 一路, 教授 松原 和夫, 教授 西渕 光昭 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22420号 / 工博第4681号 / 新制||工||1731(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 岸田 潔, 教授 三村 衛, 准教授 肥後 陽介 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

>Magister Scientiae - MSc / The area of concentration of this particular project is focused on the central part of the Bredasdorp Basin, block 9, offshore South Africa. Petrophysical evaluation of sandstone reservoirs of the F-0 tract offshore South Africa has been performed. The main aim of this study is to investigate the reservoir potential of this tract, using processed data of four wells which include; F-01, F-02, F-R1 and F-Sl. The data used for this evaluation include; wireline logs, conventional core data and special core analysis data (SCAL). Combining these laboratory results with wireline log examinations and core descriptions gives an idea of the sedimentary environment, sandstone properties and ultimately generates an effective model. Six facies were identified from the core, based on the grain size (facies 1, 2, 3, 4, 5 and 6). Facies 1 and 2 had the best reservoir rock qualities, whereas facies 3 to 6 are classified as poor or non - reservoir rock. These reservoirs are deposited in a shallow marine environment. Porosity and permeability are the two main properties which ultimately determine the quality of the reservoir. These two property measurements were taken from the routine core analysis and SCAL data and generated for the entire well using various methods. The Steiber equation was used to calculate the volume of clay from the gamma ray log. The average porosity for all four wells range between 0.5% to 17%. The minimum value recorded for permeability is 0.009mD and the maximum value is 235mD, even though permeability seems to have a broad range, the majority of the values recorded is less than lOmD. Based on these values, the reservoir rock properties are generally classified as moderate to fair. In some places, where the permeability is more than 100mD, the reservoir is classified as very good. Capillary pressure and conventional core data was compared to the log calculated water saturation models. The best fit model was the Indonesia model. The average water saturations range from 10% to 88 %. A total of eleven reservoir intervals were identified from the four wells based on the cut - off parameters. For an interval to be classified as a reservoir interval, the porosity should be equal or greater than 6%, water saturation equal or less than 35% and the volume of clay should be equal to or less than 40%. From the eleven intervals identified, four intervals contain gas and the remainder of the intervals identified are water bearing. The gross thickness of the reservoir ranges from 10m to 66m and net pay interval from 0.46m to 51.6m.