The equilibrium “pore water in sediment–gas hydrate-former–bulk gas hydrate” was experimentally studied. This residual pore water corresponds to a minimal possible amount of water in the sediment, which is in thermodynamic equilibrium with both gas and the bulk hydrate phase. This pore water can be defined as non-clathrated water by analogy to unfrozen water widely used in geocryological science. The amount of non-clathrated water depends on pressure, temperature, type of sediment, and gas hydrate former. The presence of residual pore water influences the thermodynamic properties of hydrate-saturated samples. The paper’s purpose is to describe a new experimental method for determining the amount of non-clathrated water in sediments at different pressure/temperature conditions. This method is based on measuring the equilibrium water content in an initially air-dried sediment plate that has been placed in close contact with an ice plate under isothermal, hydrate-forming gas pressure conditions. This method was used to measure the non-clathrated water content in kaolinite clay in equilibrium with methane hydrate and CO2 hydrate at a temperature of –7.5o C in a range of gas pressures from 0.1 to 8.7 MPa for methane and from 0.1 to 2.5 MPa for CO2. Experimental data show that at the fixed temperature the non-clathrated water in hydrate-containing sediments sharply reduces when gas pressure increases. The experiment demonstrates that the non-clathrated water content strongly depends on temperature, the mineral structure of sediment, and the hydrate-forming gas.

The equilibrium “pore water in sediment–gas hydrate-former–bulk gas hydrate” was experimentally studied. This residual pore water corresponds to a minimal possible amount of water in the sediment, which is in thermodynamic equilibrium with both gas and the bulk hydrate phase. This pore water can be defined as non-clathrated water by analogy to unfrozen water widely used in geocryological science. The amount of non-clathrated water depends on pressure, temperature, type of sediment, and gas hydrate former. The presence of residual pore water influences the thermodynamic properties of hydrate-saturated samples. The paper’s purpose is to describe a new experimental method for determining the amount of non-clathrated water in sediments at different pressure/temperature conditions. This method is based on measuring the equilibrium water content in an initially air-dried sediment plate that has been placed in close contact with an ice plate under isothermal, hydrate-forming gas pressure conditions. This method was used to measure the non-clathrated water content in kaolinite clay in equilibrium with methane hydrate and CO2 hydrate at a temperature of –7.5o C in a range of gas pressures from 0.1 to 8.7 MPa for methane and from 0.1 to 2.5 MPa for CO2. Experimental data show that at the fixed temperature the non-clathrated water in hydrate-containing sediments sharply reduces when gas pressure increases. The experiment demonstrates that the non-clathrated water content strongly depends on temperature, the mineral structure of sediment, and the hydrate-forming gas.

Développer un matériau pour une application dans le domaine des lentilles de contact nécessite de satisfaire plusieursexigences, notamment sur la transparence optique, sur la stabilité chimique et thermique. En outre, puisque le matériauest directement en contact avec le tissu de l'oeil, il doit être mouillable, biocompatible, résistant à l'encrassementbiologique, et perméable à l'oxygène. La perméabilité à l'oxygène (Dk) est un paramètre important pour la conceptionde lentilles de contact. Ce paramètre représente la facilité qu’aura l’oxygène à diffuser à travers la lentille vers l’oeil.Dans ce contexte, nous décrivons deux voies de recherche sur une nouvelle formulation afin de répondre à ces critères. Dans une première approche, cette recherche est axée sur la synthèse d’hydrogels de morphologie spécifique, en particulier, sur la synthèse simultanée et/ou séquentielle de réseaux polymères interpénétrés (IPN) permettant d’obtenir unemorphologie à phases co-continues. Parmi les nombreux monomères biocompatibles, nous nous sommes focalisésinitialement sur la combinaison d'un acrylate fluoré (2,2,2 -trifluoroéthyl méthacrylate, TFEM) et de la 1 -vinyl-2 -pyrrolidone (NVP), ce système étant comparé à un IPN constitué d’un monomère siloxane (3-[tris (triméthylsiloxy)-silyle] méthacrylate de propyle], TRIS), bien connu dans le domaine des lentilles de contact en raison de ses bonnes propriétés de transport de l'oxygène. Dans une deuxième approche, ces systèmes sont considérés comme une référence et nous avons prospecté l’élaboration d’IPN à base d’alginate et d’acrylamide, ces hydrogels ayant démontré des propriétés attractives, en particulier les propriétés mécaniques. Plusieurs formulations de gels ont été préparées et l'influence de leur composition sur les propriétés d’intérêt est décrite. En effet, ces hydrogels sont caractérisés d’un point de vue chimique par spectroscopie IRTF, chromatographie couplée GC-MS et d’un point de vue morphologie par microscopie MEB afin de mettre en évidence une morphologie avec des phases co-continues. Les propriétés mécaniques sont aussi déterminées. La perméabilité à l’oxygène étant en partie liée aux propriétés de gonflement du gel, la calorimétrie différentielle à balayage (DSC) a permis de déterminer et de quantifier l’eau absorbée dans ses différents états thermodynamiques et ces données sont reliées aux mesures de perméabilité. Une autre partie de ce projet est centrée sur la simulation numérique des hydrogels et de leurspropriétés physico-chimiques telles que le gonflement dans l’eau et la diffusion de molécules de gaz. Nous avons utilisé la méthode de dynamique moléculaire (MD) avec le champ de force COMPASS afin de modéliser les polymères les plus communs dans le domaine des lentilles de contact. / To design a material for contact lens application, the candidate materials must satisfy several requirements, including theoptical transparency, the chemical and thermal stability. In addition, since the material is directly in contact with the eyetissue, it should be tear wettable, biocompatible, biofouling resistant and oxygen permeable. Oxygen permeability (Dk) isan important parameter for the contact lens design as it is representative of the lens ability to diffuse oxygen at the eye.In this context, we are following two ways for a new formulation answering to these constrains. First, this research is focusedon the simultaneous or two-step synthesis of IPNs (interpenetrating polymer network) as a means to obtain a cocontinuousphases structure. Among the available biocompatible monomers, the work was initially focused on the achievement of IPN's based on a fluorinated acrylate - TFEM (2,2,2-trifluoroethyl methacrylate) and the 1 -vinyl-2 -pyrrolidone (NVP). Such a system is compared to IPN's based on a siloxane monomer - TRIS (3 - [tris (trimethylsiloxy) silyl] propyl methacrylate]), well known in the field of contact lens thanks to its properties of oxygen transport. These systems are chosen as a reference. In a second part, our research was concentrated on the development of IPN based on alginate and polyacrylamide which have demonstrated attractive properties for biomedical applications, especially their mechanical properties. Several formulations of biocompatible hydrogels were prepared and the influence of their composition on the interest properties is described. These hydrogels are characterized from a chemical point of view by FTIR spectroscopy and GC-MS chromatography, from themorphological point of view by SEM microscopy in order to prove the presence of co-continuous phases. The mechanicalproperties were also investigated. The differential scanning calorimetry (DSC) was used to determine and quantify theabsorbed water in its various thermodynamic states. The oxygen permeability was measured by polarographicelectrochemical method and relations between this parameter and gel swelling and structural properties discussed. Anotherpart of the project is computational simulation of hydrogel systems and its physico-chemical properties. Especially, wewere focused on modeling of various physic-chemical processes in hydrogels such as their swelling in water anddiffusion of gases molecules. We used molecular dynamics method (MD) with the COMPASS force field to be able tomodel polymer systems widely used in contact lens field.