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Un milieu poreux ou un matériau poreux comprend deux régions interconnectées : une perméable par un gaz ou un liquide et l’autre imperméable. Beaucoup de substances naturelles comme les roches, le sol et les tissus biologiques (par exemple, os, bio-membranes) sont poreuses ainsi que les matériaux manufacturés comme les ciments et les céramiques, etc. Les matériaux poreux ont des applications technologiques importantes et nombreuses, par exemple, comme tamis moléculaires, catalyseurs ou senseurs chimiques. Il existe un nombre très important d’études en expérience et en théorie pour comprendre la structure des matériaux poreux ainsi que les propriétés des substances confinées dans ces matériaux. Dans leur travail de pionnier, Madden et Glandt ont proposé un modèle très simple pour l’adsorption de fluide dans des milieux poreux désordonnés. Dans ce modèle, on forme la matrice en prenant une configuration figée instantanément d’un système à l’équilibre (“quench” en anglais) et puis un fluide est introduit dans une telle matrice. Récemment, T. Patsahan, M. Holovko et W. Dong ont généralisé la “scaled particle theory” (SPT) aux fluides confinés et obtenu ainsi des équations d’état analytiques pour un fluide de sphère dure dans plusieurs modèles de matrice. Dans un premier temps, j’ai développé la version de la SPT pour un mélange de sphères dures additives confiné en milieu poreux. Les expressions pour les valeurs au contact de différentes fonctions de distribution ont été obtenues également. J’ai effectué aussi des simulations de Monte Carlo. Les résultats de ces simulations sont utilisés pour valider les résultats théoriques. Ensuite, j’ai étudié aussi la séparation de phase d’un mélange binaire des sphères dures non additives confiné dans un milieu poreux. Pour obtenir l’équation d’état, nous avons utilisé une théorie de perturbation en prenant un fluide de sphères dures additive comme système de référence. Les résultats donnés par cette théorie sont en bon accord avec les résultats de simulation Monte Carlo. / A porous medium or a porous material (called as frame or matrix also) usually consists of two interconnected rejoins: one permeable by a gas or a liquid, i.e., pore or void, and the other impermeable. Many natural substances such as rocks, soils, biological tissues (e.g., bio membranes, bones), and manmade materials such as cements, foams and ceramics are porous materials. Porous materials have important technological applications such as molecular sieve, catalyst, chemical sensor, etc. In recent years, there have been considerable investigations for understanding thoroughly the structure of these materials as well as the behavior of substances confined in them. Much effort (both experimental and theoretical) has been devoted to the study of porous materials. In their pioneering work, a very simple model for the fluid adsorption in random porous media was proposed by Madden and Glandt. The matrix in Madden-Glandt model is made by quenching an equilibrium system. Then, a fluid is adsorbed in such a matrix. Recently, T. Patsahan, M. Holovko and W. Dong have extended the scaled particle theory (SPT) to confined fluids and derived analytical equations of state (EOS) for a hard sphere (HS) fluid in some matrix models. In this thesis, using SPT method, I obtained the equation of state of additive hard-sphere (AHS) fluid mixtures confined in porous media. The contact values of the fluid-fluid and fluid-matrix radial distribution functions (RDF) were derived as well. The results of the contact values of the RDFs and the chemical potentials of different species were assessed against Monte Carlo simulations. Moreover, I analyzed also the fluid-fluid phase separation of non-additive hard sphere (NAHS) fluid confined in porous media. An equation of state is derived by using a perturbation theory with a multi-component fluid reference. The results of this theory are in good agreement with those obtained from semi grand canonical ensemble Monte Carlo simulations.

La mise en oeuvre de matériaux acoustiques est une méthode efficace et très utilisée pour réduire le bruit le long de sa propagation. Les propriétés acoustiques de nouvelles structures sandwich multifonctionnelles et de matériaux absorbants poreux sont étudiées dans la thèse. Les principales contributions de la thèse sont les suivantes: Les panneaux sandwich ont généralement d'excellentes propriétés mécaniques et un bon indice de perte en transmission sonore (STL), mais aucune capacité d'absorption acoustique. De nouvelles structures sandwich multifonctionnelles sont développées en intégrant des microperforations et des matériaux absorbants poreux aux panneaux sandwich ondulés et en nid d’abeilles conventionnels, structurellement efficaces pour obtenir de bons STL et de bonnes absorptions en basses fréquences. Le coefficient d'absorption acoustique (SAC) et la perte en transmission (STL) des panneaux sandwich ondulés sont évalués numériquement et expérimentalement en basse fréquence pour différentes configurations de perforations. Les modèles éléments finis (EF) sont construits en tenant compte des interactions vibro-acoustiques sur les structures et des dissipations d'énergie, visqueuse et thermique, à l'intérieur des perforations. La validité des calculs FE est vérifiée par des mesures expérimentales avec les échantillons testés obtenus par fabrication additive. Par rapport aux panneaux sandwich ondulés classiques sans perforation, les panneaux sandwich perforés (PCSPs) avec des perforations dans leur plaque avant présentent non seulement un SAC plus élevé aux basses fréquences, mais aussi un meilleur STL, qui en est la conséquence directe. L'élargissement des courbes des indices d’absorption et de transmission doit être attribué à la résonance acoustique induite par les micro-perforations. Il est également constaté que les PCSPs avec des perforations dans les plaques avant et les parois internes onduleés ont les fréquences de résonance les plus basses de tous les PCSPs. En outre, les performances acoustiques des panneaux sandwich en nid d'abeilles avec une plaque avant microperforée sont également examinées. Un modèle analytique est présenté avec l'hypothèse que les déplacements des deux plaques sont identiques aux fréquences inférieures à la fréquence de résonance des plaques. Le modèle analytique est ensuite validé par des modèles d'éléments finis et des résultats expérimentaux existants. Contrairement aux panneaux sandwich en nid d'abeilles classiques qui sont de piètres absorbeurs de bruit, les sandwichs en nid d'abeilles perforés (PHSPs) conduisent à un SAC élevé aux basses fréquences, ce qui entraîne en conséquence un incrément dans le STL basse fréquence. Les influences de la configuration du noyau sont étudiées en comparant les PHSPs avec différentes configurations de noyaux en nids d'abeilles. […] / Implementation of acoustic materials is an effective and popular noise reduction method during propagation. Acoustic properties of novel multifunctional sandwich structures and porous absorbing materials are studied in the dissertation. The main contributions of the dissertation are given as, Sandwich panels generally have excellent mechanical properties and good sound transmission loss (STL), but no sound absorption ability. Novel multifunctional sandwich structures are developed by integrating micro perforations and porous absorbing materials to the conventional structurally-efficient corrugated and honeycomb sandwich panels to achieve good SAC and STL at low frequencies. Low frequency sound absorption and sound transmission loss (STL) of corrugated sandwich panels with different perforation configurations are evaluated both numerically and experimentally. Finite element (FE) models are constructed with considerations of acousticstructure interactions and viscous and thermal energy dissipations inside the perforations. The validity of FE calculations is checked against experimental measurements with the tested samples provided by additive manufacturing. Compared with the classical corrugated sandwich panels without perforation, the perforated corrugated sandwich panels (PCSPs) with perforations in its face plate not only exhibits a higher SAC at low frequencies but also a better STL as a consequence of the enlarged SAC. The enlargement of SAC and STL should be attributed to the acoustical resonance induced by the micro perforations. It is also found that the PCSPs with perforations in both the face plates and corrugated cores have the lowest resonance frequencies of all the PCSPs. Besides, the acoustic properties of honeycomb sandwich panels with microperforated faceplate are also explored. An analytical model is presented with the assumption that displacements of the two faceplates are identical at frequencies below the faceplate resonance frequency. The analytical model is subsequently verified by finite element models and existing experimental results. Unlike classical honeycomb sandwich panels which are poor sound absorbers, perforated honeycomb sandwiches (PHSPs) lead to high SAC at low frequencies, which in turn brings about increment in the low frequency STL. Influences of core configuration are investigated by comparing PHSPs with different honeycomb core configurations. In order to enlarge the SAC bandwidth of perforated sandwich panels, porous absorbing materials are added to the cores of novel perforated sandwich panels. FE models are set up to estimate the SAC and STL of perforated sandwich panels with porous materials. Results show that perforated sandwich panels with porous material can provide SAC with broader bandwidth and lower resonance frequency than that without porous materials. Whereas the peak values in the SAC and STL curves are reduced due to the weakened acoustical resonance by the porous materials. […]

Peatlands cover a total area of approximately 3 million square kilometers and are one of the largest natural sources of atmospheric methane (CH4) and carbon dioxide (CO2). Most traditional methods used to estimate biogenic gas dynamics are invasive and provide little or no information about lateral distribution of gas. In contrast, Ground Penetrating Radar (GPR) is an emerging technique for non-invasive investigation of gas dynamics in peat soils. This thesis establishes a direct comparison between gas dynamics (i.e. build-up and release) of four different types of peat soil using GPR. Peat soil blocks were collected at peatlands with contrasting latitudes, including the Everglades, Maine and Minnesota. A unique two-antenna GPR setup was used to monitor biogenic gas buildup and ebullition events over a period of 4.5 months, constraining GPR data with surface deformation measurements and direct CH4 and CO2 concentration measurements. The effect of atmospheric pressure was also investigated. This study has implications for better understanding global gas dynamics and carbon cycling in peat soils and its role in climate change. / by Anastasija Cabolova. / Thesis (M.S.)--Florida Atlantic University, 2010. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2010. Mode of access: World Wide Web.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Materiais mesoporosos ordenados tipo SBA-15 possuem uma rede de canais e poros de tamanho bem definido na escala nanométrica. Essa arquitetura particular de poros torna esses materiais viáveis para encapsular uma variedade de compostos na matriz da sílica, resultando em um material promissor para uma gama de aplicações. Esses materiais, quando contêm óxidos de metais de transição, especialmente nanopartículas de óxido de ferro magnéticas, podem ser usados para algumas aplicações in vivo, tais como no aumento do contraste em imagens por ressonância magnética nuclear, reparo de tecidos, imunoensaio, hypertermia, e liberação de fármacos. Nesse trabalho, nanopartículas magnéticas encapsuladas em sílica mesoporosa foram preparados em duas etapas. Primeiro a magnetita foi sintetizada pelo método de oxidação-precipitação a partir de uma solução de sulfato de ferro, hidróxido de potássio e nitrato de potássio. Em seguida, as nanopartículas magnéticas foram revestidas com sílica mesoporosa pelo uso de um surfactante não-iônico copolímero em blocos como agente direcionador da estrutura. A caracterização dos materiais foi feita por difração de raios X, adsorção de gases, infravermelho, espectroscopia Mössbauer, espectrometria de energia dispersiva (EDS), microscopia eletrônica de varredura (MEV), microscopia eletrônica de transmissão (TEM), espectroscopia de fotoelétrons excitados por raios X (XPS) e medidas magnéticas. Os resultados revelaram uma estrutura bem ordenada de mesoporos do nanocompósito, sugerindo que a mesma pode ser descrita como mesoporos hexagonais separados por uma parede de sílica contínua, formando uma camada de revestimento sobre as nanopartículas magnéticas. Dos dados de difração de raios X, foi obtido o tamanho médio das partículas de magnetita, que foi de 38 nm. A espectroscpia Mössbauer mostrou que a magnetita é preservada na rota de síntese. Os dados de XPS aliados aos de TEM mostraram que a rede de sílica recobre as partículas de magnetita, formando um nanocompósito com tamanho médio de grãos de 138 nm. Por fim, foi feito o estudo da influência dessas partículas magnéticas na cinética de liberação de três fármacos-modelo: cisplatina, carboplatina e atenolol sob condições in vitro. A liberação foi estudada na ausência e na presença de um campo magnético externo, utilizando para tanto um magneto NdFeB de 0,25 T. A análise foi feita por estudos de mecanismos cinéticos e de modelos de difusão, revelando que o campo externo influencia pouco no processo de liberação dos fármacos. Ao considerar que as nanopartículas estão presas na estrutura, esse resultado é coerente. Então, foi feito um teste para verificar a influência de um campo alternado no perfil de liberação, que mostrou um resultado mais significativo para a liberação de cisplatina. Para explicar esse fato, foi proposto então um modelo de interação entre a mesma e o nanocompósito. / Ordered mesoporous materials like SBA-15 posses a network of channels and pores of well-defined size in the nanoscale range. This particular pore architecture makes them suitable for hosting a broad variety of compounds into the silica matrix, resulting in very promising material for a broad range of applications, including magnetic carriers for drug delivery. In this work, magnetic nanocomposites embedded into mesoporous silica were prepared in two steps. Firstly, magnetite was synthesized by oxidation-precipitation method from a solution of iron sulfate, potassium nitrate and potassium hydroxide. After this, the magnetic nanoparticles were coated with mesoporous silica by using nonionic block copolymer surfactants as structure-directing agents. Characterization of the materials was carried out by using X-ray diffraction (XRD), 57Fe Mössbauer spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), N2 adsorption, energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), XRay Photoeletron Spectroscopy (XPS) and magnetic measures. Our results revealed a wellordered mesopore structure of the nanocomposite, suggesting that the samples structure can be described as a honeycomb of hexagonal mesopores separated by continuous silica walls and the coating layer is distributed over the magnetic nanoparticles. The average size of magnetite particles obtained by XRD data was about 38 nm. Mössbauer spectroscopy showed that magnetite is preserved in the applied synthesis route. Both XPS data and TEM had shown that the silica recovers magnetite particles, forming a composite with particle sizeof 138 nm. Finally, the influence of these magnetic particles in the release kinetic was studied using drugs like cisplatin, carboplatin and atenolol; this study was made under in vitro conditions. The release was studied in absence and presence of a external magnetic field, using a NdFeB permanent magnet of 0,25 T. The kinetic mechanisms and diffusion models were investigated by the external field, and the results had showed a small influence of this parameter on the process of drug release. Considering that nanoparticles are coated by mesoporous silica, this result is expected. Then, a test was made to verify the influence of an oscillating field in the release profile and the results showed a more significant delivery for cisplatin. To explain this fact, an interaction model between this drug and the nanocomposite was proposed.

Made available in DSpace on 2015-03-04T18:50:58Z (GMT). No. of bitstreams: 1 Apresentacao.pdf: 260390 bytes, checksum: 1bc9756e919b0969a6e6dfc3777f7aad (MD5) Previous issue date: 2006-08-02 / Neste trabalho propomos uma nova formulação micromecânica para descrever escoamentos monofásicos em meios porosos viscoelásticos. Na abordagem proposta consideramos o meio poroso por dois níveis de porosidade (micro e macroporos), onde os efeitos de relaxação e fluência da matriz porosa são advindos da drenagem secundária do fluido residente nos microporos. A derivação do modelo macroscópico é obtida via técnicas de homogeneização de estruturas periódicas aplicadas à mudança a partir do modelo micromecânico composto por uma matriz poroelástica circundada por uma rede conexa de macroporos. Neste contexto o nosso principal resultado consiste na conjugação do modelo de suas escalas com a análise assintótica da formulação variacional do problema micromecânico posto no domínio da célula unitária periódica. Mostramos que esta combinação de técnicas fornece o decaimento dos núcleos de convolução das equações constitutivas homogeneizadas para as tensões efetivas da fase sólida e para a porosidade viscosa além de estabelecer a dependência constitutiva para o tempo de relaxação do processo de compactação secundária da matriz. Simulações numéricas são obtidas descretizando os problemas de célila locais via métoco de elementos finitos e ilustram as taxas de decaimento obtidas na análise

Le stéarate de butyle, un matériau de changement de phase biosourcé (MCP), a été encapsulés dans des matrices polymères (pullulane, lignine, hémicelluloses) par la technique des émulsions concentrées. Les matrices polymères ont été réticulées avec du trimetaphosphate de sodium (STMP) dans des conditions alcalines afin d’obtenir un réseau poreux interconnecté rigide. L’influence du processus de séchage sur les matériaux composites obtenus a été étudiée, indiquant la lyophilisation comme la technique la plus efficace. Des études de calorimétrie à balayage différentiel (DSC) ont permis de déterminer que l’encapsulation de stéarate de butyle dans des matrices polymères ne modifiait pas ses propriétés thermiques de changement de phase. Des essais de compression mécanique et de résistance à la déformation ont permis d'évaluer le potentiel des monolithes en tant que panneaux de stockage de chaleur installés directement dans des bâtiments et des serres.Les produits de réticulation par le STMP ont été identifiés et caractérisés par RMN solide du31P. Il a ainsi été possible de synthétiser des monolithes ayant différents taux de réticulation afin d’optimiser la formulation d'encapsulation de MCP. Les matrices polymères vidée de tous leurs contenus liquides ont été étudiées par microscopie électronique à balayage afin d’étudier leur structure poreuse (distribution de taille des pores). Cette nouvelle approche d’encapsulation en une étape apparaît comme efficace et devrait permettre un développement important des applications énergétiques. / Emulsion-templated polymer based (pullulan, lining and hemicelluloses) monoliths encapsulating butyl stearate as bio-based phase change material (PCM) were synthesized. Polymer-bases were crosslinked with sodium trimetaphosphate (STMP) under alkaline aqueous conditions leading to an interconnected porous network. The influence of the drying process on the obtained composite materials morphology was studied indicating freeze-drying as the most effective technique. Differential Scanning Calorimetry (DSC) studies allow to assess that encapsulation of butyl stearate onto matrices do not alter its phase change thermal properties. Mechanical compression and strain resistance tests allowed to evaluate monoliths potential as heat storage panels installed directly in buildings and greenhouses, STMP crosslinking products were identified by solid-NMR characterization, this allowed to synthetize monoliths at different crosslinking yields to find a formulation that improves PCM encapsulation. Polymer matrices were studied by scanning electron microscopy to identify the pore size distribution obtained in STMP crosslinked materials. This new one-step encapsulating approach appears as efficient and cost-effective and is expected to find a broad development in energy storage applications

Cette thèse porte sur le confort acoustique et, en particulier, sur les matériaux absorbants destinés au traitement des nuisances sonores dans le domaine de l’habitat. L’objectif est double : il s’agit de proposer un matériau bio-sourcé et absorbant dans la gamme des basses fréquences.Notre choix s’est porté sur un matériau poreux bio-sourcé basé sur la fabrication de céramiques poreuses. Il est constitué de cellulose homogène et isotrope. Son procédé de fabrication repose sur la construction d’une empreinte en polyméthacrylate de méthyle permettant un contrôle fin de sa structure interne. Ensuite, nous avons procédé à la caractérisation expérimentale de ses propriétés acoustiques et des paramètres intrinsèques du matériau. L’analyse de ces données, associée à la modélisation numérique, a permis de définir les caractéristiques physiques influant sur ses performances acoustiques et d’identifier les leviers d’amélioration de celles-ci.Enfin, une mise en œuvre de concepts empiriques est présentée, à savoir : (i) inclusion d’aérogel dans la matrice poreuse, (ii) exploitation de la double porosité dans deux configurations différentes, soit dans le cas d’un composite cellulose/aérogel, soit celui d’un matériau constitué d’un double réseau mésoporeux/microporeux et (iii) utilisation de matériaux à gradient de propriétés (interconnexions ou porosité). Pour chacune de ces trois approches, le procédé de fabrication et la caractérisation de ces nouveaux matériaux sont détaillés et leurs performances acoustiques sont discutées. / This thesis is about acoustic comfort and deals particularly with absorptive materials used to treat noise pollution in the housing environment. Our purpose is a double-sided one as the idea is to propose a bio based and absorptive material within the range of low frequencies.We have focused on porous bio based material on the same manufacturing process of porous ceramic. It is composed of homogeneous and isotropic cellulose. The making of a polymethyl methcrylate print enabling a thorough control of its internal structure. Then, we have dealt with the experimental characterization of its acoustic properties and of the intrinsic parameters of the material. The analysis of these data together with the numerical modelling permitted to define the physical characteristics having an influence on acoustic performances and to identify their means of improvement.Finally, the implementation of empirical means will be presented, namely: (i) the inclusion of aerogel in the porous mould, (ii) the exploitation of double porosity in two different configurations, either in the case of cellulose/aerogel composite, or the one of a material composed of a double mesoporous/microporous structure and (iii) the use of materials containing gradients of properties (interconnection or porosity). For each of these three approaches, the manufacturing process and the characterization of these new materials are detailed and their acoustic performances are discussed.

Ce travail a été réalisé dans le cadre du projet EcOBEx, qui consiste à réduire le bruit du groupe motopropulseur rayonné à l'extérieur par l'ajout d'écrans acoustiques dans le compartiment moteur du véhicule. Les écrans acoustiques sont fabriqués par thermocompression de matériaux poreux uniformes. Les propriétés et l'épaisseur du matériau évoluent en fonction du degré de compression subit par le matériau. L'objectif de ce travail est de proposer des lois pour prédire l'évolution des propriétés des matériaux à partir du taux de compression et de leurs valeurs initiales avant compression. Dans un premier temps, on s'intéresse aux paramètres du modèle de fluide équivalent de Johnson-Champoux-Allard-Lafarge (JCAL) : porosité, résistivité au passage d'air, tortuosité, longueurs caractéristiques visqueuse et thermique, perméabilité thermique statique. Des expressions analytiques sont proposées pour prédire la variation de ces paramètres en fonction de la compression. Elles sont développées à partir d'un modèle de matériaux fibreux à fibres cylindriques où les variations d'orientation des fibres induites par la thermocompression peuvent être prises en compte. Les résultats sont en bon accord avec les mesures effectuées sur deux types de matériaux (mousse à cellules ouvertes et fibreux). Un modèle empirique généralisé est finalement proposé pour la résistivité au passage d'air. Dans un deuxième temps, on s'attache aux paramètres élastiques dont la connaissance est essentielle pour prendre en compte la vibration du squelette. La méthode expérimentale quasistatique est d'abord appliquée pour étudier l'évolution du module de Young par rapport au taux de compression pour les fibres et les mousses. Une loi de puissance est alors proposée pour prédire ces variations. Enfin, une méthode inverse pour estimer les propriétés élastiques d'un matériau poroélastique orthotrope à partir d'une mesure vibratoire d'un écran tricouche thermo comprimé est proposée. Cette méthode permet de caractériser les propriétés élastiques du matériau poreux dans une situation proche de son application réelle / This work was carried out in the framework of the project EcOBEx, whose main objective was to reduce the passby noise by mean of acoustic shields in the engine compartment of the vehicle. The acoustic shields are manufactured by thermocompression of uniform porous materials. The material’s properties and thickness evolve according to the degree of compression experienced by the material. The objective of this work is to propose some laws to predict the evolution of the materials properties from their initial non compressed values and the compression rate. Firstly, we focus on the parameters of the Johnson-Champoux-Allard-Lafarge (JCAL) equivalent fluid model : porosity, air-flow resistivity, tortuosity, viscous characteristic lengths, thermal characteristic length, static thermal permeability. Some analytical expressions are proposed to predict the variation of these parameters as a function of compression. They are derived from a physical model of cylindrical fibres where the fibre orientation variations induced by the thermocompression can be taken into account. The results are in good agreement with the measurements made two types of materials (open cell foam and fibrous). A generalized empirical model is finally proposed for the air-flow resistivity.In a second part, we focus on the elastic parameters, which are necessary to take into account the vibration of the skeleton. The quasi-static experimental method is first applied to study the evolution of the Young’s modulus along the compression rate for fibrous and open cell foams. A power law is then proposed to predict these variations. Finally, an inverse method for estimating the elastic properties of an orthotropic poro-elastic material from a vibratory measurement of a thermocompressed three layer sandwich structure is proposed. This method allows us to characterize the elastic properties of a porous material in a situation close to its actual application.