Les argiles sont des minéraux complexes présentant une porosité multi-échelles et une aptitude à gonfler sous atmosphère humide. Ces matériaux ont diverses applications en catalyse, dans le stockage des déchets, dans le bâtiment… Pourtant, les propriétés de l'eau confinées sont encore mal comprises, notamment en raison de la complexité de l'eau elle-même. Le but de ce travail est, en utilisant principalement les simulations moléculaires et les spectrométries vibrationnelles, de comprendre la structure et la dynamique de l'eau confinée dans les argiles.Afin d'évaluer la précision des modèles numériques pour décrire l'eau confinée dans les argiles, et pour comprendre l'origine de ses propriétés structurales et dynamiques, un large part de ce travail est consacrée aux briques constitutives de l'argile : l'eau pure, l'eau interfaciale et l'eau salée. A ce titre, on étudie les propriétés viscoélastiques de l'eau du domaine surfondu jusqu'à la température d'ébullition par dynamique moléculaire classique. On analyse aussi les propriétés de frottement près d'une surface type, et la précision des approches ab initio et des modèles de sels.Dans une seconde partie, on confronte ces résultats aux propriétés de l'eau confinée dans les argiles à basse température et à température ambiante, expérimentalement et numériquement. Les expériences consistent en des mesures exhaustives par spectrométrie d'absorption dans l'infrarouge moyen et lointain, tandis que les calculs sont des simulations de dynamique moléculaire classique. En particulier, on s'intéresse à l'existence de transitions de phases induites par le confinement ou les variations de température / Clay are complex minerals with a multiscale porosity and a remarkable ability to swell under humid atmosphere. These materials have many applications in catalysis, waste management, construction industry... However, the properties of confined water are still not fully understood, due in particular to the complexity of water itself. The aim of this work is, using mainly molecular simulations and vibrational spectroscopy, to understand the structure and the dynamics of water confined in clay minerals. To evaluate the accuracy of numerical models to describe water confined in clay minerals, and to understand the origin of its structural and dynamical properties, a large part of the work was devoted to the building blocks of clays: pure bulk water, water at the surface of a solid, and salt water. To this extent, the viscoelastic properties of water from the deeply supercooled regime to the boiling temperature were investigated using classical molecular dynamics. The evolution of the friction properties of water on a prototypical solid surface was also analyzed, and the accuracy of ab initio approaches and empirical salt models was studied.In a second part, those results were confronted to the properties of water confined in clay minerals at low and room temperature, studied both experimentally and numerically. Experimental work consisted mostly in extensive far- and -mid infrared absorption spectrometry measurements, whereas numerical work mainly consisted in empirical molecular dynamics simulations. Especially, the existence of confinement- or temperature-induced phase transitions of confined water was investigated

Ce travail s’inscrit dans le cadre de l’étude de liants aluminosilicatés que sont les géopolymères. La première partie de ce travail a consisté à caractériser la texture poreuse des géopolymères, par des techniques intrusives (porosimétrie à eau, adsorption-désorption d’azote, intrusion mercure) et non-intrusives (diffusion des rayons X et des neutrons aux petits angles). Le terme « texture poreuse » regroupe la forme et la taille des pores, le volume poreux, la surface spécifique et la connectivité des pores. En parallèle, l’évolution de la texture poreuse et des propriétés mécaniques a été suivie sur une période de deux ans, en évitant les échanges avec le milieu extérieur afin d’étudier l’évolution intrinsèque des géopolymères. La seconde étape a consisté à étudier les propriétés thermodynamiques, la structure et la dynamique de l’eau confinée dans la porosité, par calorimétrie différentielle à balayage basse température, par diffusion des neutrons et par des essais de migration. La structure poreuse des géopolymères est complexe, puisqu’il s’agit d’une porosité multi échelle, méso- et macroporeuse, essentiellement ouverte et connectée. Elle consiste en un réseau vermiculaire de mésopores et un réseau de macropores connecté via les mésopores. La taille caractéristique (comprise entre 4 et 10 nm environ) et le volume des mésopores dépendent de la formulation de la pâte de géopolymère, à savoir de la teneur en eau, du rapport molaire Si/Al et de la nature du cation compensateur de charge. Il a été montré que les géopolymères étudiés sont très poreux, la porosité représentant entre 40 et 50 % du volume total du matériau. Le volume mésoporeux représente entre 7 et 15 % du volume total, le reste étant attribué à un volume macroporeux. Au cours du temps, la porosité des géopolymères se ferme légèrement, ceci étant attribué à un mécanisme de dissolution-reprécipitation au niveau des murs de pores. Les propriétés mécaniques atteignent un maximum entre 7 et 10 jours, puis sont stables dans le temps lorsque les échantillons sont conservés à 20°C et à l’abri du séchage ou de la carbonatation de la solution porale. Par ailleurs, trois types d’eau ont été mises en évidence au sein des pores : (i) l’eau liée chimiquement et/physiquement à la surface des parois, (ii) l’eau libre confinée dans les mésopores, et (iii) l’eau libre dans les macropores. A l’échelle locale, les molécules d’eau possède une mobilité proche de celle de l’eau libre, tandis qu’à l’échelle macroscopique, une diminution d’un ordre de grandeur du coefficient de diffusion a été observé, avec un effet probable de la taille des mésopores. / In this study, we have investigated the porous network of geopolymers. The first step consisted in characterizing the structure of the porous network by the means of both intrusive experimental techniques (water porosimetry, gas sorption and mercury intrusion) and non-intrusive techniques (small-angle X-ray and neutron scattering). By the same time, the evolutions of the porous structure as well as the mechanical properties were followed over time. The second step was to determine the structure, the thermodynamics and the dynamics of water confined in the porosity by differential scanning calorimetry, quasi-elastic neutron scattering and migration tests.Geopolymer pore structure is a complex multi-scale porosity, a meso- and macroporous network, essentially open and connected. It consists in a vermicular mesoporous network which connects the macropores. The mesopore characteristic size depends on the formulation of the geopolymer paste and is ranged between about 4 and 10 nm. Geopolymer have a total pore volume comprised between 40 and 50 %, the mesoporous volume represents between 7 and 15 % of the material global volume. The majority of the pore volume is then attributed to macropores. A slight closure of porosity was observed with time and was attributed to a dissolution-precipitation mechanism occurring at pore wall interfaces. The mechanical properties reach a maximum within 10 days, and then are stable over time when the samples were kept from drying and carbonation and at the temperature of 20°C. Besides, three kinds of water were highlighted inside the porosity: (i) an interfacial water linked at the pore surfaces, (ii) free water inside the mésopores and (iii) free water inside macropores. At local time scale, the mobility of water was found close to the one of free water, and at the macroscopic scale, a decrease in diffusion coefficient of one order of magnitude was observed, together with an effect of mesopore size.

O método Umedecimento, Compactação e Secagem (UCOS) (1, 2, 3) produz, a partir de gesso e água, um material de elevada resistência mecânica: até 90 MPa na compressão. Este trabalho apresenta o estudo do comportamento mecânico deste material e como a água, a temperatura, as impurezas e a microestrutura influenciam no seu comportamento. Durante o estudo da adesão intercristalina, foi encontrada presença de água confinada e que é responsável por grande parte da resistência mecânica. Para auxiliar o estudo, foi desenvolvido outro método: Empacotamento Direto do Dihidrato (EDD). Nesta metodologia, é produzido um material com a mesma resistência, porém com algumas diferenças no comportamento mecânico diferente. Através da elevada resistência mecânica alcançada pelos métodos UCOS e EDD, as aplicações do gesso podem ser ampliadas desde que o gesso conformado por tais métodos possuam confiabilidade e segurança. Para avaliar as propriedades mecânicas, a confiabilidade e a segurança de tal material, realizou-se o estudo dos mecanismos tenacificadores e da mecânica da fratura. Os mecanismos tenacificadores estudados neste trabalho são: controle da microestrutura (aumento da superfície de ruptura), introdução de fibras poliméricas (distribuição da tensão na ponta da trinca, ramificação da ponta da trinca e contenção da abertura da trinca) e introdução de adesivo polimérico (melhora a adesão entre cristais e distribui melhor a tensão na ponta da trinca). Os resultados mostram que os compósitos de gesso reforçados com fibras poliméricas e/ou adesivo polimérico possuem elevada resistência e comportamentos mecânicos distintos para cada tipo de compósito e método de conformação. Concluímos que, com o conhecimento adquirido, é possível intervir no processamento e na microestrutura, além de poder incorporar elementos a esse material para atender às condições de uma determinada aplicação / The humidification, compaction and drying (Umedecimento, Compactação e Secagem UCOS) (1, 2, 3) method produces a high strength material from plaster and water: up to 90 MPa in compression. This work presents the study of mechanical properties of this material and how water, temperature, impurity and microstructure influence in its behavior. During the study of the intercrystalline adhesion force, we found the presence of confined water and that it accounts for great part of the strength. In order to aid the study, another method was developed: Direct Packaging of the Dihydrate (Empacotamento Direto do Dihidrato EDD). In this methodology, it produces a material with the same resistance, but with some difference in the mechanical behavior. Through the high strength reached by the UCOS and EDD methods, the plaster applications can be extended, since the set material by these methods are reliable and safe. In order to evaluate the mechanical properties, the reliability and the safety of these pieces, we performed the study of the fracture mechanics and the fracture toughening mechanisms. In this work, the studied toughening are: microstructure control (enlargement of the fracture surface), polymeric fiber reinforcement (tension distribution on the fracture tip, fracture tip deflection, and fiber bridging), and polymer adhesive reinforcement (they enhance the adhesion between crystals and better distribute the tension on the fracture tip). The results show that the plaster composites of polymeric fibers and/or polymer adhesive have high resistance, and different mechanical behaviors for each type of composite and setting method. Based on the acquired knowledge, we conclude that it is possible to interfere on the processing and on the microstructure, as well as reinforcements in this material to satisfy the needs of a specific application

O método Umedecimento, Compactação e Secagem (UCOS) (1, 2, 3) produz, a partir de gesso e água, um material de elevada resistência mecânica: até 90 MPa na compressão. Este trabalho apresenta o estudo do comportamento mecânico deste material e como a água, a temperatura, as impurezas e a microestrutura influenciam no seu comportamento. Durante o estudo da adesão intercristalina, foi encontrada presença de água confinada e que é responsável por grande parte da resistência mecânica. Para auxiliar o estudo, foi desenvolvido outro método: Empacotamento Direto do Dihidrato (EDD). Nesta metodologia, é produzido um material com a mesma resistência, porém com algumas diferenças no comportamento mecânico diferente. Através da elevada resistência mecânica alcançada pelos métodos UCOS e EDD, as aplicações do gesso podem ser ampliadas desde que o gesso conformado por tais métodos possuam confiabilidade e segurança. Para avaliar as propriedades mecânicas, a confiabilidade e a segurança de tal material, realizou-se o estudo dos mecanismos tenacificadores e da mecânica da fratura. Os mecanismos tenacificadores estudados neste trabalho são: controle da microestrutura (aumento da superfície de ruptura), introdução de fibras poliméricas (distribuição da tensão na ponta da trinca, ramificação da ponta da trinca e contenção da abertura da trinca) e introdução de adesivo polimérico (melhora a adesão entre cristais e distribui melhor a tensão na ponta da trinca). Os resultados mostram que os compósitos de gesso reforçados com fibras poliméricas e/ou adesivo polimérico possuem elevada resistência e comportamentos mecânicos distintos para cada tipo de compósito e método de conformação. Concluímos que, com o conhecimento adquirido, é possível intervir no processamento e na microestrutura, além de poder incorporar elementos a esse material para atender às condições de uma determinada aplicação / The humidification, compaction and drying (Umedecimento, Compactação e Secagem UCOS) (1, 2, 3) method produces a high strength material from plaster and water: up to 90 MPa in compression. This work presents the study of mechanical properties of this material and how water, temperature, impurity and microstructure influence in its behavior. During the study of the intercrystalline adhesion force, we found the presence of confined water and that it accounts for great part of the strength. In order to aid the study, another method was developed: Direct Packaging of the Dihydrate (Empacotamento Direto do Dihidrato EDD). In this methodology, it produces a material with the same resistance, but with some difference in the mechanical behavior. Through the high strength reached by the UCOS and EDD methods, the plaster applications can be extended, since the set material by these methods are reliable and safe. In order to evaluate the mechanical properties, the reliability and the safety of these pieces, we performed the study of the fracture mechanics and the fracture toughening mechanisms. In this work, the studied toughening are: microstructure control (enlargement of the fracture surface), polymeric fiber reinforcement (tension distribution on the fracture tip, fracture tip deflection, and fiber bridging), and polymer adhesive reinforcement (they enhance the adhesion between crystals and better distribute the tension on the fracture tip). The results show that the plaster composites of polymeric fibers and/or polymer adhesive have high resistance, and different mechanical behaviors for each type of composite and setting method. Based on the acquired knowledge, we conclude that it is possible to interfere on the processing and on the microstructure, as well as reinforcements in this material to satisfy the needs of a specific application

Le débat sur l'origine du comportement anormal de l'eau (H2O), que peut être dû, au niveau moléculaire, à sa capacité à former des réseaux de liaisons hydrogène, est encore ouvert. Les anomalies de le H2O sont fortement accentuées dans la région surfondue du diagramme de phase (PD). Beaucoup de simulations numérique ont expliqué cet comportement en suggérant l'existence d'une transition de phase liquide-liquide (LLPT) entre deux phases de densité différente: Low Density Liquid et High Density Liquid, séparées par une ligne de coexistence terminant sur un point critique (CP) (hypothèse de le 2°point critique). Malheureusement, ce CP, s'il existe, réside dans le No man's land, une région du PD difficile à explorer expérimentalement à cause de la cristallisation spontanée. Confiner H2O dans des géométries nanométrique peut abaisser la température de congélation, en ouvrant la possibilité d'entrer dans le No man's land et d'enquêter sur l'existence de LLPT. Nous avons étudié H2O confiné dans une matrice mésoporeuse (MCM-41), en mettant l'accent sur l'existence d'un minimum de densité (DM) à 210 K, qui devrait être directement lié au second CP supposé. Nos expériences ont exploité la spectroscopie infrarouge, la diffusion de neutrons à petit angle et la diffraction de neutrons sur une large gamme de Q. L'interprétation de nos résultats a conduit à conclure que dans le centre du pore de MCM-41 se forme une hétérophase solide, à une température proche a quelle prétendu par d'autres auteurs pour le DM. Donc l'approche expérimentale commune est faux et ce qui a été précédemment interprété comme un signe de DM à 210 K est en réalité dû au début d'un événement de cristallisation. / Le débat sur l'origine du comportement anormal de l'eau (H2O), qui peut être dû, au niveau moléculaire, à sa capacité à former des réseaux de liaisons hydrogène, est encore ouvert. Les anomalies du H2O sont fortement accentuées dans la région surfondue du diagramme de phase (PD). Beaucoup de simulations numérique ont expliqué cet comportement en suggérant l'existence d'une transition de phase liquide-liquide (LLPT) entre deux phases de densité différente: Low Density Liquid et High Density Liquid, séparées par une ligne de coexistence terminant sur un point critique (CP) (hypothèse de le 2°point critique). Malheureusement, ce CP, s'il existe, réside dans le No man's land, une région du PD difficile à explorer expérimentalement à cause de la cristallisation spontanée. Confiner H2O dans des géométries nanométrique peut abaisser la température de congélation, en ouvrant la possibilité d'entrer dans le No man's land et d'enquêter sur l'existence de LLPT. Nous avons étudié H2O confiné dans une matrice mésoporeuse (MCM-41), en mettant l'accent sur l'existence d'un minimum de densité (DM) à 210 K, qui devrait être directement lié au second CP supposé. Nos expériences ont exploité la spectroscopie infrarouge, la diffusion de neutrons à petit angle et la diffraction de neutrons sur une large gamme de Q. L'interprétation de nos résultats a conduit à conclure que dans le centre du pore de MCM-41 se forme une hétérophase solide, à une température proche a quelle prétendu par d'autres auteurs pour le DM. Donc l'approche expérimentale commune est faux et ce qui a été précédemment interprété comme un signe de DM à 210 K est en réalité dû au début d'un événement de cristallisation.

This thesis presents experimental and related theoretical studies of single layer graphene, bilayer graphene and single walled carbon nanotubes. The thesis is divided into three parts; the first part describes the phonon renormalization due to doping in two dimensional graphene and one dimensional carbon nanotubes. In the recent years, there is a tremendous interest both experimentally and theoretically, in the issues related to electron-phonon coupling in nanotubes and graphene. Theoretically, it is expected that the presence of Kohn anomalies in graphene and metallic nanotubes will result in significant changes in the self energy of phonons due to doping. In particular, with Fermi energy shift how the blockage of phonon decay (due to Pauli Exclusion Principle) into electron-hole excitations changes the phonon frequencies as well as its life time have been studied in details in the first part of the thesis. Since in graphene and metallic nanotubes, the momentum relaxation time of electrons is comparable to the phonon pulsation time, the phonon cannot be treated as a static perturbation and hence non-adiabatic effects are taken into account using time dependent perturbation theory. Electron-phonon coupling constant is also a key parameter to understand the mobility of carrier due to electron scattering by optical phonons at room temperature and limitation of the maximum current carrying capacity of graphene and nanotubes. All these parameters are determined in the first part of the thesis by performing in-situ transport and Raman measurements on graphene and nanotubes based field effect transistors. The second part of the thesis deals with the interaction of bio-molecules (nucleobases) with the nanotubes and graphene. The binding energies of various nucleobases with nanotubes and graphene have been calculated theoretically using quantum chemical and classical force field calculations, and experimentally from isothermal titration (micro) calorimetry. In this part we also present an experimental study on the dynamics of water confined inside the carbon nanotubes. Proton nuclear magnetic resonance studies have been used to probe the freezing and dynamics of the confined water inside 1.4 nm diameter single walled carbon nanotubes. We have observed that the confined water does not freeze up to 223K. The dynamics of confined water has been studied using pulsed field gradient technique. The decay of spin echo intensity as a function of gradient field shows characteristic features of water confined in unidimensional channels. From the decay profiles the mean squared displacement of water molecules is obtained for different diffusive times, showing an unambiguous evidence of single file diffusion of water molecules inside the nanotubes i.e mean squared displacement varying as square root of time. In the last part, we have developed carbon nanotube based vibration sensor and accelerometer to detect the vibrations of liquid and solid, respectively, using the property of voltage generation in nanotubes due to liquid flow.