Ce travail de thèse avait pour objectif de développer des capteurs électrochimiques, basés sur des réactions de transfert assistés d’ions aux interfaces liquide | liquide. Le dispositif électrochimique utilisé repose sur la formation d’une micro-interface entre l’eau et le 1,2-dichloroéthane (eau | DCE), obtenue par un micropore percé par un laser dans un film de polyimide. Cette micro-interface supportée a été conçue pour obtenir des mesures reproductibles et significatives. Parce que la pollution aquatique par les métaux lourds est considérée comme l'un des problèmes environnementaux les plus importants, nos études se sont particulièrement focalisées sur les transferts assistés de Pb(II) et de Cd(II), seuls ou en mélange, par le 8-Hydroxyquinoline (8-HQ), et de Ba(II)) par le 18-couronne-6 (18C6). La voltampérométrie cyclique a été utilisée pour comprendre les mécanismes de transfert ainsi que la détermination de la stœchiométrie des complexes formés. Des mesures complémentaires par spectrométrie de masse et spectrophotométrie UV-Visible ont permis de confirmer ces stœchiométries. L’ensemble de ces mesures montre clairement que le dispositif expérimental proposé est bien adapté pour quantifier électrochimiquement des espèces, même si elles ne sont pas électroactives. Dans des perspectives d’applications industrielles, nous avons démontré la possibilité et l’efficacité de la mise en œuvre d’un dispositif d’analyse en ligne. Ce procédé semble très prometteur en raison de sa simplicité et de son faible coût, avec la possibilité de réutiliser la solution organique pour une série de mesures. Enfin, nous avons également testé des réseaux de micropores à la place d’un seul micropore, dans le but d’accroître la sensibilité du dispositif. Nous avons montré clairement leur intérêt pour atteindre des valeurs de concentrations plus faibles et représentatives du domaine de l’environnement. Toutes les études menées au cours de cette thèse montrent comment le dispositif expérimental utilisé est prometteur et performant. / This thesis aims to develop electrochemical sensors based on ion assisted transfer reactions at liquid | liquid interfaces. The electrochemical device used is based on the formation of a micro-interface between water and 1,2-dichloroethane (water | DCE), obtained by a micropore drilled by a laser in a polyimide film. This micro-interface has been designed to obtain reproducible and meaningful measurements. Because water pollution by heavy metals is considered as one of the most important environmental problems, our studies focused particularly on assisted transfers of Pb (II) and Cd (II), alone or in mixture, by the 8-Hydroxyquinoline (8-HQ), and Ba (II)) by the 18-crown-6 ether (18C6). Cyclic voltammetry was used for understanding the mechanisms of transfer, and for determining the stoichiometry of the formed complexes. Complementary measurements by mass spectrometry and UV-visible spectrophotometry have confirmed these stoichiometries. All measures clearly show that the proposed experimental device is well suited for quantifying the electrochemically species, even if they are not electroactive.In prospects of industrial applications, we have demonstrated the feasibility and effectiveness of the implementation of the proposed device for online analysis. This process appears very promising because of its simplicity and its low cost, and with the possibility of reusing the organic solution for many measurements. Finally, in order to increase the sensitivity of the device, we also tested micropore arrays instead of a single micropore. We have clearly shown the interest in achieving lower concentrations values hence more representative of the environment. All studies in this thesis show how the used experimental device is promising and well performing.

Detection and identification of important biological targets, such as DNA, proteins, and diseased human cells are crucial for early diagnosis and prognosis. The key to discriminate healthy cells from the diseased cells is the biophysical properties that differ radically. Micro and nanosystems, such as solid-state micropores and nanopores can measure and translate these properties of biological targets into electrical spikes to decode useful insights. Nonetheless, such approaches result in sizable data streams that are often plagued with inherit noise and baseline wanders. Moreover, the extant detection approaches are tedious, time-consuming, and error-prone, and there is no error-resilient software that can analyze large data sets instantly. The ability to effectively process and detect biological targets in larger data sets lie in the automated and accelerated data processing strategies using state-of-the-art distributed computing systems. In this dissertation, we design and develop techniques for the detection and classification of biological targets and a distributed detection framework to support data processing from multiple bio-nano devices. In a distributed setup, the collected raw data stream on a server node is split into data segments and distributed across the participating worker nodes. Each node reduces noise in the assigned data segment using moving-average filtering, and detects the electric spikes by comparing them against a statistical threshold (based on the mean and standard deviation of the data), in a Single Program Multiple Data (SPMD) style. Our proposed framework enables the detection of cancer cells in a mixture of cancer cells, red blood cells (RBCs), and white blood cells (WBCs), and achieves a maximum speedup of 6X over a single-node machine by processing 10 gigabytes of raw data using an 8-node cluster in less than a minute, which will otherwise take hours using manual analysis. Diseases such as cancer can be mitigated, if detected and treated at an early stage. Micro and nanoscale devices, such as micropores and nanopores, enable the translocation of biological targets at finer granularity. These devices are tiny orifices in silicon-based membranes, and the output is a current signal, measured in nanoamperes. Solid-state micropore is capable of electrically measuring the biophysical properties of human cells, when a blood sample is passed through it. The passage of cells via such pores results in an interesting pattern (pulse) in the baseline current, which can be measured at a very high rate, such as 500,000 samples per second, and even higher resolution. The pulse is essentially a sequence of temporal data samples that abruptly falls below and then reverts back to a normal baseline with an acceptable predefined time interval, i.e., pulse width. The pulse features, such as width and amplitude, correspond to the translocation behavior and the extent to which the pore is blocked, under a constant potential. These features are crucial in discriminating the diseased cells from healthy cells, such as identifying cancer cells in a mixture of cells. / Ph. D.

En raison de l'exigence de protection de l'environnement, les briques d'argile cuites sont face à une nouvelle tendance de développement. Briques d'argile cuites ne sont pas seulement satisfaits de la mécanique force mais aussi augmentation de l'utilisation de l'énergie. La conductivité thermique est un paramètre très important mesurer l'utilisation de l'énergie. Sur le principe de garantir essentiellement propriétés mécaniques, la réduction de la conductivité thermique a été l'un des développements importants objectifs dans l'industrie du bâtiment.Basé sur l'analyse de la microstructure, les pores microscopiques ont un effet sur la macroscopie constantes élastiques et conductivité thermique. Micropores parallèles résultant de la production les méthodes provoquent l'isotropie transversale des briques d'argile cuites. Cependant, ce n'est pas clair que l'influence des micropores sur les propriétés macroscopiques. Bien que certains modèles étudié l'effet de la porosité sur les propriétés mécaniques des briques d'argile cuite, ces modèles sont empiriques et ont ignoré de nombreuses informations microscopiques. Un des buts de la thèse est d'analyser l'influence de la forme, l'orientation et la distribution spatiale de microscopique facteurs sur les propriétés mécaniques et la conductivité thermique afin de fournir une référence optimiser la micro-structure des briques d'argile cuites. / Due to the environmental protection requirement, fired clay bricks are facing new development tendency. Fired clay bricks are not only satisfied with mechanical strength but also rising energy utilization. Thermal conductivity is a very important parameter to measure the energy utilization. On the premise of guaranteeing the basically mechanical properties, reducing thermal conductivity has been one of important development goals in building industry.Based on the analysis of micro-structure, microscopic pores have an effect on macroscopic elastic constants and thermal conductivity. Parallel micropores resulting from producing methods cause the transverse isotropy of fired clay bricks. However, it is not clear that the influence of micropores on the macroscopic properties. Though some models studied the effect of porosity on mechanical properties of fired clay bricks, these models are empirical and ignored many microscopic information. One of the goals of the thesis is to analyze the influence of shape, orientation and spatial distribution of microscopic factors on mechanical properties and thermal conductivity in order to provide a reference to optimize the micro-structure of fired clay bricks.

La zone non saturée (ZNS) des sols contient de l'eau plus ou moins fortement retenue par succion capillaire. Concrètement, cette succion modifie la pression interne de l'eau capillaire et donc modifie ses propriétés thermodynamiques. De ce fait, la spéciation des solutés aqueux, la solubilité des gaz et des solides sont modifiées. Pour permettre de faire des bilans de masse à l'échelle des profils, on a utilisé les courbes de rétention en eau du sol, qui relient un volume d'eau porale à une gamme de succion capillaire. A cette dernière gamme sont associées les propriétés de la succion moyenne. Certains modèles de courbes de rétention sont spécialement adaptés au domaine des fortes succions et ils sont ici étudiés en détail. Leur utilisation permet de constater que les volumes retenus à des succions géochimiquement significatives peuvent atteindre plusieurs dizaines de litres par mètre cube de sol et ainsi participer au transfert de masse en profondeur. Plusieurs faits d'observations pourraient être re-interprétés par cette approche capillaire, comme les successions anormales de paragénèses dans certains régolites.<br />Des premières études de bilans de masse ont été réalisées en s'appuyant sur un modèle en double porosité, avec un domaine macroporal de percolation, et un domaine microporal de rétention. Ces deux zones sont couplées par des échanges diffusifs. Le modèle utilisé est celui des colonnes de transfert-réactif 1Dde PhreeqC, un des modèles géochimiques les plus courants. Les caractéristiques géochimiques des solutions capillaires sont calculées avec Thermo-ZNS, un logiciel de calculs thermodynamiques développé pour la ZNS au BRGM. Les résultats de simulation des colonnes mettent en évidence l'effet de la capillarité sur la stabilité des minéraux, la vitesse des réactions et la complexation de surface, consistant avec les observations naturelles de terrain.

A lixiviação de resíduos industriais e de mineração usualmente resultam em águas residuárias com pH extremamente ácido. Estes contaminantes podem migrar para o solo ou percolar através de barreiras de fundo em aterros de resíduos sólidos, perturbando a estrutura do solo e modificando a sua condutividade hidráulica. A adição de cimento Portland a este tipo de barreira pode ser uma opção para a neutralização do pH, buscando reduzir os impactos da lixiviação ácida nas águas subterrâneas. Embora muitos estudos abordem o comportamento de barreiras compactadas quando submetidas à ação dos mais diversos tipos de contaminantes, poucos tem explorado os aspectos microestruturais dos materiais componentes das barreiras e suas modificações ao longo do processo de percolação do contaminante. Neste contexto, este trabalho propôs a avaliação do comportamento microestrutural e macroestrutural de um solo argiloso residual compactado, com e sem a adição de cimento Portland (0, 1 e 2%), para fins de aplicação em barreiras impermeáveis sumetidas à ação de lixiviados ácidos. Os resultados motraram uma notável redução da condutividade hidráulica com a percolação de uma solução a 2% de ácido sulfúrico, a qual foi acompanhada pela ocorrência de recalques e redução do pH. Com relação à análise do tamanho e distribuição dos poros, pôde-se concluir que tanto a adição de cimento como a variação do peso específico de compactação, aliadas à ocorrência de recalques, contribuíram para a redução dos microporos e a consequente redução da condutividade hidráulica. Com relação às modificações químicas e mineralógicas, o ataque ácido promoveu principalmente a solubilização de Fe2O3 nas camadas superiores das amostras ensaiadas, porém não causou alterações significativas na estrutura dos argilominerais. Pode-se inferir que o peso específico de compactação não influenciou os resultados e que a adição de cimento contribuiu de maneira discreta para reduzir o impacto da percolação ácida, na medida em que produziu compostos de Ca e S nas camadas de meio e inferior das amostras, reduziu os microporos e retardou a solubilização de Fe2O3, a qual ocorreu principalmente nas camadas superiores das amostras ensaiadas. / The leaching of industrial and mining solid wastes usually result in wastewaters with extremely acidic pH, which might percolate into the ground or through bottom compacted barriers of landfills, disturbing soil structure and increasing hydraulic conductivity. The addition of Portland cement to containment barriers can be an option for pH neutralization, seeking to reduce the impact of acidic leachate to the groundwater. Although many studies have addressed the behavior of compacted barriers subjected to the action of several types of contaminants, a few have explored the microstructural aspects of barriers component materials and their modifications along the contaminant percolation process. In this context, this work proposed the evaluation of microstructural and macrostructural behavior of a compacted residual clayey soil, with and without the addition of Portland cement (0, 1, and 2%), for purposes of application in containment bottom submitted to acidic leachate percolation. The results showed a noticeable reduction in the compacted soil hydraulic conductivity during the percolation of a 2% sulfuric acid solution, which was accompanied by settlements and pH reduction. Regarding the determination of the size and distribution of pores, it can be concluded that both the addition of cement and the variation of specific weights, coupled with the occurrence of settlements, contributed to the reduction of micropores, which consequently resulted in hydraulic conductivity reduction. Concerning the chemical and mineralogical changes, the acidic attack mainly promoted the solubilization of Fe2O3 in the upper layers of the specimens tested but caused no significant modification in clay minerals structure. It can be inferred that the specific gravity did not influence the results and that the cement addition contributed discretely to reduce the acidic percolation impact, as it produced compounds of Ca and S in the middle and lower layers, reduced micropores, and slowly delayed Fe2O3 solubilization, which occurred mainly in the upper layers of the specimens tested.

A lixiviação de resíduos industriais e de mineração usualmente resultam em águas residuárias com pH extremamente ácido. Estes contaminantes podem migrar para o solo ou percolar através de barreiras de fundo em aterros de resíduos sólidos, perturbando a estrutura do solo e modificando a sua condutividade hidráulica. A adição de cimento Portland a este tipo de barreira pode ser uma opção para a neutralização do pH, buscando reduzir os impactos da lixiviação ácida nas águas subterrâneas. Embora muitos estudos abordem o comportamento de barreiras compactadas quando submetidas à ação dos mais diversos tipos de contaminantes, poucos tem explorado os aspectos microestruturais dos materiais componentes das barreiras e suas modificações ao longo do processo de percolação do contaminante. Neste contexto, este trabalho propôs a avaliação do comportamento microestrutural e macroestrutural de um solo argiloso residual compactado, com e sem a adição de cimento Portland (0, 1 e 2%), para fins de aplicação em barreiras impermeáveis sumetidas à ação de lixiviados ácidos. Os resultados motraram uma notável redução da condutividade hidráulica com a percolação de uma solução a 2% de ácido sulfúrico, a qual foi acompanhada pela ocorrência de recalques e redução do pH. Com relação à análise do tamanho e distribuição dos poros, pôde-se concluir que tanto a adição de cimento como a variação do peso específico de compactação, aliadas à ocorrência de recalques, contribuíram para a redução dos microporos e a consequente redução da condutividade hidráulica. Com relação às modificações químicas e mineralógicas, o ataque ácido promoveu principalmente a solubilização de Fe2O3 nas camadas superiores das amostras ensaiadas, porém não causou alterações significativas na estrutura dos argilominerais. Pode-se inferir que o peso específico de compactação não influenciou os resultados e que a adição de cimento contribuiu de maneira discreta para reduzir o impacto da percolação ácida, na medida em que produziu compostos de Ca e S nas camadas de meio e inferior das amostras, reduziu os microporos e retardou a solubilização de Fe2O3, a qual ocorreu principalmente nas camadas superiores das amostras ensaiadas. / The leaching of industrial and mining solid wastes usually result in wastewaters with extremely acidic pH, which might percolate into the ground or through bottom compacted barriers of landfills, disturbing soil structure and increasing hydraulic conductivity. The addition of Portland cement to containment barriers can be an option for pH neutralization, seeking to reduce the impact of acidic leachate to the groundwater. Although many studies have addressed the behavior of compacted barriers subjected to the action of several types of contaminants, a few have explored the microstructural aspects of barriers component materials and their modifications along the contaminant percolation process. In this context, this work proposed the evaluation of microstructural and macrostructural behavior of a compacted residual clayey soil, with and without the addition of Portland cement (0, 1, and 2%), for purposes of application in containment bottom submitted to acidic leachate percolation. The results showed a noticeable reduction in the compacted soil hydraulic conductivity during the percolation of a 2% sulfuric acid solution, which was accompanied by settlements and pH reduction. Regarding the determination of the size and distribution of pores, it can be concluded that both the addition of cement and the variation of specific weights, coupled with the occurrence of settlements, contributed to the reduction of micropores, which consequently resulted in hydraulic conductivity reduction. Concerning the chemical and mineralogical changes, the acidic attack mainly promoted the solubilization of Fe2O3 in the upper layers of the specimens tested but caused no significant modification in clay minerals structure. It can be inferred that the specific gravity did not influence the results and that the cement addition contributed discretely to reduce the acidic percolation impact, as it produced compounds of Ca and S in the middle and lower layers, reduced micropores, and slowly delayed Fe2O3 solubilization, which occurred mainly in the upper layers of the specimens tested.

A lixiviação de resíduos industriais e de mineração usualmente resultam em águas residuárias com pH extremamente ácido. Estes contaminantes podem migrar para o solo ou percolar através de barreiras de fundo em aterros de resíduos sólidos, perturbando a estrutura do solo e modificando a sua condutividade hidráulica. A adição de cimento Portland a este tipo de barreira pode ser uma opção para a neutralização do pH, buscando reduzir os impactos da lixiviação ácida nas águas subterrâneas. Embora muitos estudos abordem o comportamento de barreiras compactadas quando submetidas à ação dos mais diversos tipos de contaminantes, poucos tem explorado os aspectos microestruturais dos materiais componentes das barreiras e suas modificações ao longo do processo de percolação do contaminante. Neste contexto, este trabalho propôs a avaliação do comportamento microestrutural e macroestrutural de um solo argiloso residual compactado, com e sem a adição de cimento Portland (0, 1 e 2%), para fins de aplicação em barreiras impermeáveis sumetidas à ação de lixiviados ácidos. Os resultados motraram uma notável redução da condutividade hidráulica com a percolação de uma solução a 2% de ácido sulfúrico, a qual foi acompanhada pela ocorrência de recalques e redução do pH. Com relação à análise do tamanho e distribuição dos poros, pôde-se concluir que tanto a adição de cimento como a variação do peso específico de compactação, aliadas à ocorrência de recalques, contribuíram para a redução dos microporos e a consequente redução da condutividade hidráulica. Com relação às modificações químicas e mineralógicas, o ataque ácido promoveu principalmente a solubilização de Fe2O3 nas camadas superiores das amostras ensaiadas, porém não causou alterações significativas na estrutura dos argilominerais. Pode-se inferir que o peso específico de compactação não influenciou os resultados e que a adição de cimento contribuiu de maneira discreta para reduzir o impacto da percolação ácida, na medida em que produziu compostos de Ca e S nas camadas de meio e inferior das amostras, reduziu os microporos e retardou a solubilização de Fe2O3, a qual ocorreu principalmente nas camadas superiores das amostras ensaiadas. / The leaching of industrial and mining solid wastes usually result in wastewaters with extremely acidic pH, which might percolate into the ground or through bottom compacted barriers of landfills, disturbing soil structure and increasing hydraulic conductivity. The addition of Portland cement to containment barriers can be an option for pH neutralization, seeking to reduce the impact of acidic leachate to the groundwater. Although many studies have addressed the behavior of compacted barriers subjected to the action of several types of contaminants, a few have explored the microstructural aspects of barriers component materials and their modifications along the contaminant percolation process. In this context, this work proposed the evaluation of microstructural and macrostructural behavior of a compacted residual clayey soil, with and without the addition of Portland cement (0, 1, and 2%), for purposes of application in containment bottom submitted to acidic leachate percolation. The results showed a noticeable reduction in the compacted soil hydraulic conductivity during the percolation of a 2% sulfuric acid solution, which was accompanied by settlements and pH reduction. Regarding the determination of the size and distribution of pores, it can be concluded that both the addition of cement and the variation of specific weights, coupled with the occurrence of settlements, contributed to the reduction of micropores, which consequently resulted in hydraulic conductivity reduction. Concerning the chemical and mineralogical changes, the acidic attack mainly promoted the solubilization of Fe2O3 in the upper layers of the specimens tested but caused no significant modification in clay minerals structure. It can be inferred that the specific gravity did not influence the results and that the cement addition contributed discretely to reduce the acidic percolation impact, as it produced compounds of Ca and S in the middle and lower layers, reduced micropores, and slowly delayed Fe2O3 solubilization, which occurred mainly in the upper layers of the specimens tested.

No description available.

4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...