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With the widening and increasing use of nuclear energy, it is very important to design and build long-term deep geological repositories (DGRs) to manage radioactive waste. The disposal of nuclear waste in deep rock formations is currently being investigated in several countries (e.g., Canada, China, France, Germany, India, Japan and Switzerland). In Canada, a repository for low and intermediate level radioactive waste is being proposed in Ontario’s sedimentary rock formations. During the post-closure phase of a repository, significant quantities of gas will be generated from several processes, such as corrosion of metal containers or microbial degradation of organic waste. The gas pressure could influence the engineered barrier system and host rock and might disturb the pressure-head gradients and groundwater flows near the repository. An increasing gas pressure could also cause damage to the host rock by inducing the development of micro-/macro-cracks. This will further cause perturbation to the hydrogeological properties of the host rock such as desiccation of the porous media, change in degree of saturation and hydraulic conductivity. In this regard, gas generation and migration may affect the stability or integrity of the integrate barriers and threaten the biosphere through the transmitting gaseous radionuclides as long-term contaminants. Thus, from the safety perspective of DGRs, gas generation and migration should be considered in their design and construction. The understanding and modelling of gas migration within the host rock (natural barrier) and the associated potential impacts on the integrity of the natural barrier are important for the safety assessment of a DGR. Therefore, the key objectives of this Ph.D. study include (i) the development of a simulator for coupled modelling of gas migration in the host rock of a DGR for nuclear waste; and (ii) the numerical investigation of gas migration in the host rock of a DGR for nuclear waste in Ontario by using the developed simulator. Firstly, a new thermo-hydro-mechanical-chemical (THMC) simulator (TOUGHREACT-COMSOL) has been developed to address these objectives. This simulator results from the coupling of the well-established numerical codes, TOUGHREACT and COMSOL. A series of mathematical models, which include an elastoplastic-damage model have been developed and then implemented into the simulator. Then, the predictive ability of the simulator is validated against laboratory and field tests on gas migration in host rocks. The validation results have shown that the developed simulator can predict well the gas migration in host rocks. This agreement between the predicted results and the experimental data indicates that the developed simulator can reasonably predict gas migration in DGR systems. The new simulator is used to predict gas migration and its effects in a potential DGR site in Ontario. Valuable results regarding gas migration in a potential DGR located in Ontario have been obtained. The research conducted in this Ph.D. study will provide a useful tool and information for the understanding and prediction of gas migration and its effect in a DGR, particularly in Ontario.

Esta pesquisa in vitro avaliou a influência do aquecimento de diferentes agentes de acoplamento na resistência de união de um cimento resinoso (Panavia F2.0®/Kuraray Noritake. Japão) e uma zircônia (Y-TZP - YZ ). Inicialmente, placas de zircônia foram silicatizadas com o sistema Rocatec (3M / ESPE). Foram aplicados os agentes de acoplamento químico: Single Bond Universal (3M/ESPE); Monobond N (Ivoclar Vivadent) e Clearfil Ceramic Primer (Kuraray Co); após, foram aquecidos em um forno resistivo em diferentes temperaturas (750C e 1000C) por 5 min, antes da cimentação resinosa de um cilindro de resina composta previamente confeccionado (diam. 0,8 mm). Os grupos controle de cada agente de acoplamento foram mantidos à temperatura ambiente (240C). Metade dos corpos-de-prova foi submetida imediatamente ao teste de microcisalhamento (0,5 mm/min) realizado com auxílio de um fio ortodôntico e a outra metade envelhecida por meio de a 2.000 ciclos térmicos (50C e 550C), seguido de armazenamento em água destilada a 370 C por 2 meses, antes do ensaio mecânico. A análise de variância de três fatores (ANOVA) e o teste de Tukey (p?0,05) mostraram que o aquecimento dos agentes químicos de acoplamento produziu maiores valores de resistência de união entre o cimento e a zircônia. A resistência de união imediata foi superior para o Monobond N (30 MPa) e Single Bond Universal (32,5 MPa). Após o envelhecimento, houve redução da resistência de união em todos os grupos e o grupo Monobond N (16,9 MPa) apresentou resistência de união superior à dos demais. A associação de um tratamento térmico simples a um agente de acoplamento é válida para produzir resistência de união superior entre o cimento resinoso e a zircônia. / This in vitro study evaluated the influence of the heating different coupling agents on microshear bond strength between zirconia (Y-TZP-YZ ) and a resin cement (Panavia F2.0® / Kuraray Noritake, Japan). Initially, the zirconia blocks were silicoated with the Rocatec system (3M / ESPE). After, the chemical coupling agents were applied: Single Bond Universal (3M / ESPE); Monobond N (Ivoclar Vivadent) and Clearfil Ceramic Primer (Kuraray Co). They were then heated in a resistive furnace at different temperatures (750C and 1000C) for 5 min prior to resin cementation of a preformed resin composite cilinder (0.8 mm diameter). Control groups were maintained at room temperature (240C). Half of the specimens were immediately submitted to the microshear test (0.5 mm/min) performed with an orthodontic wire and the other half was subjected to 2,000 thermal cycles (50C and 550C), followed by storage in distilled water at 370C for 2 months before the microshear test. 3-way ANOVA and Tukey\'s test (p<0.05) showed that the heating of the chemical coupling agents produced higher bond strength between the ceramic and resin cement. Immediate bond strength was superior for Monobond N (30 MPa) and Single Bond Universal (32,5 MPa). After aging, there was reduction of bond strength in all groups and the Monobond N group (16,9 MPa) was superior to the others. The combination of a simple heat treatment with a coupling agent is valid to produce greater bond strength.

The objective of the study is to improve the interfacial adhesion between the wood fibers and thermoplastic matrix. Efforts were also directed towards improving manufacturing processes so as to realize the full potential of wood fibers as reinforcing fillers. Chemical coupling plays an important role in improving interfacial bonding strength in wood-polymer composites. A novel compatibilizer with isocyanate functional group was synthesized by grafting m-Isopropenyl –α –α –dimethylbenzyl-isocyanate (m-TMI) onto isotactic polypropylene using reactive extrusion process. The compatibilizer was characterized with respect to its nature, concentration and location of functional group, and molecular weight. There are two main process issues when blending polymers with incompatible filler: (1) creating and maintaining the target morphology, and (2) doing so with minimum degradation of fillers. A 28mm co-rotating intermeshing twin screw extrusion system was custom built and the design optimized for (1) blending biological fibers with thermoplastics, and (2) for melt phase fictionalization of thermoplastics by reactive extrusion. To assess the effect of inclusion of wood fibers in polypropylene composites, a series of polypropylene wood fiber/wood flour filled composite materials having 10 to 50 wt % of wood content were prepared using the co-rotating twin screw extrusion system. m-TMI-g-PP and MAPP were used as coupling agents. Addition of wood fibers, at all levels, resulted in more rigid and tenacious composites. The continuous improvement in properties of the composites with the increasing wood filler is attributed to the effective reinforcement of low modulus polypropylene matrix with the high modulus wood filler. Studies on were also undertaken to understand effect of particle morphology, type and concentration of coupling agent, and effect of process additives on mechanical properties. Composites prepared with m-TMI-grafted-PP were much superior to the composites prepared with conventionally used maleated polypropylene in all the cases. Non-destructive evaluation of dynamic modulus of elasticity (MoE) and shear modulus of wood filled polypropylene composite at various filler contents was carried out from the vibration frequencies of disc shaped specimens. The vibration damping behaviour of the composite material was evaluated. MoE and shear modulus were found to increase whereas damping coefficient decreased with the increasing filler content. Knowledge of moisture uptake and transport properties is useful in estimating moisture related effects such as fungal attack and loss of mechanical strength. Hence, a study was undertaken to asses the moisture absorption by wood filled polypropylene composites. Composites prepared with coupling agents absorbed at least 30% less moisture than composites without compatibilizer. Thermo-gravimetric measurements were also carried out to evaluate the thermal stability and to evaluate kinetic parameters associated with thermal degradation of wood fiber and wood flour filled polypropylene composites. The moisture absorption and thermal behaviour are described based on analytical models. High efficiency filler-anchored catalyst system was prepared by substituting of hydroxyl groups present on the cellulosic filler. The process involves immobilizing the cocatalyst onto the cellulosic filler surface followed by addition of metallocene catalyst and then polymerization of ethylene using this filler supported catalyst. The polymerization and composite formation takes place simultaneously. All the polymerization reactions were carried out in a high-pressure stirred autoclave. Effect of temperature, ethylene pressure, and cocatalyst to catalyst ratios (Al/TM ratios) were also studied. Studies on kinetics of polymerization showed that, higher Al/Zr ratio and higher temperature lead to higher polymerization rates but lower the molecular weight. A model incorporating effect of reaction parameter on polymerization rates has been developed.

[pt] Atrelado aos cenários cada vez mais complexos de extração de energia, o estudo de fenômenos acoplados em meios porosos - notadamente térmicos, hidráulicos, químicos e mecânicos - tem se apresentado como essencial na previsão de comportamento de meios geológicos no que diz respeito à disposição de rejeitos radioativos, armazenamento de dióxido de carbono, engenharia de reservatórios geotérmicos e geomecânica de reservatórios. Assim, este trabalho objetiva desenvolver um esquema de acoplamento termo-hidro-mecânico-químico iterativo visando a simulação do armazenamento geológico de dióxido de carbono, empregando um simulador de fluxo composicional (GEM) e um programa de análise de tensões (ABAQUS ou CHRONOS). A idealização das metodologias de acoplamento foi efetuada através dos processos hidro-mecânico, termo-hidro-mecânico e termo-hidro-mecânico-químico, bem como as validações e aplicações em casos reais. Os casos de validação, realizados empregando modelos simplificados monofásicos, apresentaram resultados satisfatórios quanto ao comportamento hidro-mecânico e termo-hidro-mecânico. Adicionalmente às validações, os esquemas termo-hidro-mecânico e termo-hidro-mecânico-químico foram aplicados em dois casos reais de armazenamento de CO2 apresentados na literatura, projeto In Salah (Argélia) e aquífero Utsira (Noruega), respectivamente. De maneira geral, os resultados encontrados, para ambos os casos estudados, representaram acuradamente as respostas encontradas em campo, fato que evidencia a qualidade, robustez e aplicabilidade dos esquemas de acoplamento propostos neste trabalho. / [en] Considering the increasingly complex scenarios of energy extraction, the study of coupled phenomena in porous media - notably thermal, hydraulic, chemical and mechanical - has been considered as essential in order to predict the behavior of geological media with regard to radioactive waste storage, CO2 geological storage, geomechanics of geothermal reservoirs and reservoir geomechanics. Thus, this work aims to develop a thermo-hydro-mechanical-chemical iterative coupling scheme in order to simulate the geological storage of CO2, employing a compositional flow simulator (GEM) and a stress analysis program (ABAQUS or CHRONOS). The idealization of the coupling methodologies was carried out through the processes hydro-mechanical, thermo-hydro-mechanical and thermo-hydro-mechanical-chemical, as well as the validations and applications in real cases. The validation cases, performed employing simplified single-phase models, presented satisfactory results regarding the hydro-mechanical and thermo-hydro-mechanical behaviors. Additionally to the validations, the thermo-hydro-mechanical and thermo-hydro-mechanical-chemical schemes were applied in two real cases of CO2 geological storage reported by the literature, In Salah project (Algeria) and Utsira aquifer (Norway), respectively. In general, the results found, in both cases studied, accurately represented the behavior observed in the field, which in turn highlights the accuracy, robustness and applicability of the coupling schemes proposed in this work.

Une dégradation des propriétés mécaniques des arcs surperélastiques en alliages à mémoire de forme à base NiTi, utilisés dans les traitements orthodontiques, a été observée après absorption d'hydrogène. L’effet de l’hydrogène a été étudié, dans un premier temps, sur le comportement global des arcs à l’aide des essais de traction et dans un deuxième temps, sur le comportement local à l’aide des essais de nanoindentation. Pour modéliser le comportement des AMFs après absorption d'hydrogène, une première approche a été proposée, en introduisant la dépendance des paramètres de la transformation martensitique à la concentration moyenne d'hydrogène, observée dans les courbes contrainte-déformation obtenues, dans un modèle existant dédié aux AMFs. Une deuxième approche consiste à proposer un modèle thermomécanochimique couplé. Pour ce faire, un nouveau potentiel thermodynamique est défini en introduisant la déformation chimique due à la présence de l'hydrogène et l'interaction de ce dernier avec les variantes de martensite. Des forces thermodynamiques sont déduites de ce potentiel et équilibrées en faisant intervenir les phénomènes dissipatifs : mécanique, thermique et chimique. L'exploitation du modèle proposé a nécessité le développement d'un élément fini spécifique adoptant la concentration d'hydrogène comme un degré de liberté supplémentaire qui prend en compte le couplage complet et la formulation proposée de l'équilibre thermique et chimique / A degradation of the mechanical properties of NiTi-based shape memory alloys superelastic archs, used in orthodontic treatments, was observed after hydrogen absorption. The effect of hydrogen was first investigated on the global behaviour of archs using tensile tests and secondly on the local behaviour using nanoindentation tests. A first approach to model the behavior of AMFs after hydrogen absorption has been proposed, by introducing the dependence of martensitic transformation parameters on the average hydrogen concentration, observed in the stress-strain curves obtained, in an existing dedicated model to SMA. A second approach is to propose a coupled thermomechanical model. A new thermodynamic potential is defined by introducing the chemical strain due to the presence of hydrogen and the interaction of the latter with martensite variants. Thermodynamic forces are deduced from this potential and balanced by involving mechanical, thermal and chemical dissipative phenomena. The exploitation of the proposed model required the development of a special finite element adopting the hydrogen concentration as an additional degree of freedom that takes into account the thermomechanical coupling and the proposed formulation of the thermal and chemical equilibrium

La réalisation de micro et nanomatériaux avec des propriétés contrôlées nécessite le développement de nouvelles voies d’élaboration dites ascendantes « ou Bottom-up ». Les travaux présentés dans ce manuscrit visent à maîtriser la formation d’agrégats de particules colloïdales et de cellules, avec des applications potentielles dans les domaines des biocapteurs, de la microélectronique, de l’optique et de l’ingénierie tissulaire. L’approche proposée pour assembler les particules en structures organisées se base sur l’emploi de la diélectrophorèse, reposant sur l’application d’un champ électrique non- uniforme. L’un des inconvénients de cette technique tient au caractère réversible des assemblages ainsi formés, l’annulation du champ électrique entrainant la redispersion des colloïdes. Afin d’apporter une solution à ce problème, il est possible de recourir à un couplage chimique pour maintenir la cohésion des structures formées dans le milieu liquide. Afin de mieux maîtriser le comportement diélectrophorétique et les réactions chimiques exploitées, des travaux de caractérisation électrique et chimique des particules manipulées ont été réalisés. D’autre part, différents types de microélectrodes ont été étudiées pour la génération du champ électrique nécessaire à l’assemblage. Une nouvelle filière technologique a été développée pour la réalisation de microélectrodes transparentes en ITO et leur intégration en système microfluidique, basée sur l’exploitation du pouvoir isolant d’une fine couche de PDMS micro-structurée. La méthode a été appliquée à la fabrication de microélectrodes « verticales » puis à la réalisation de matrices d’électrodes quadripolaires. Ces dernières ont permis d’obtenir des assemblages permanents de particules de polystyrène fluorescentes présentant des groupements carboxyliques en surface, en combinant l’emploi de la diélectrophorèse négative et l’utilisation d’un agent de couplage chimique (Jeffamine). Des agrégats de cellules HEK 293 ont également été réalisés par diélectrophorèse négative. Nous avons démontré qu’il était possible, sous certaines conditions, de préserver le caractère permanent des agrégats cellulaires après coupure du champ. / The design of micro and nanomaterials with controlled properties requires the development of new bottom- up assembly approaches. The work presented in this manuscript aims to control the formation of aggregates of colloidal particles and cells, with potential applications in the fields of biosensors, microelectronics, optics and tissue engineering. The proposed approach for assembling colloids into organized structures is based on the use of dielectrophoresis, a phenomenon observed when polarizable particles are placed in a non-uniform electric field. One of the drawbacks of this technique is the reversibility of the assemblies thus formed, the cancellation of the electric field causing the redispersion of the colloids. As a solution to this problem, we proposed to use a coupling agent to maintain the cohesion of the structures formed in the liquid medium. In order to better control the dielectrophoretic behavior and the chemical reactions exploited, electrical and chemical characterizations of the manipulated particles were carried out. Moreover, different types of microelectrodes have been studied for the generation of the electric field required for the assembly. A new approach has been developed for the fabrication of transparent micro patterned ITO microelectrodes and their integration in microfluidic systems, based on the exploitation of a thin micro-structured PDMS membrane used as an insulating layer. The method has been applied to the fabrication of "vertical" microelectrodes and of quadrupolar electrode arrays. The latter were used to obtain permanent assemblies of carboxylic acid functionalized, fluorescent, polystyrene particles, by combining negative dielectrophoresis with the use of a chemical coupling agent (Jeffamine). HEK 293 cell aggregates were also produced by negative dielectrophoresis. We have demonstrated that it was possible, under certain conditions, to preserve the permanent character of the cell aggregates after field removal.