[pt] No âmbito da indústria de petróleo e gás, a interrupção das linhas de produção e transporte devido à acumulação de compostos orgânicos e inorgânicos representa um desafio generalizado e significativo, resultando em consideráveis perdas financeiras e apreensões ambientais. Os hidratos de gás, particularmente enfatizados entre vários desafios relacionados à deposição inorgânica, apresentam uma questão complexa caracterizada pela formação de sólidos cristalinos à base de água, semelhantes ao gelo, ocorrendo sob condições de pressão elevada e baixas temperaturas que se formam quando moléculas leves de hidrocarbonetos e água se combinam para formar uma estrutura ordenada específica. A formação de hidrato começa na interface água-hidrocarboneto, o que destaca o papel crítico que a reologia interfacial desempenha neste processo. Apesar da importância desta interface na formação de hidratos, persiste uma lacuna na pesquisa, particularmente no emprego de abordagens de reologia de cisalhamento. Este estudo ajuda a preencher essa lacuna investigando as propriedades mecânicas e de fluxo da interface, utilizando um recurso em um reômetro rotacional, uma célula de anel de parede dupla, para controle preciso da temperatura. O ciclopentano serve como formador de hidrato, permitindo a experimentação sob condições atmosféricas. pressão e temperaturas variadas. Os protocolos exploram a temperatura e as concentrações de hidrocarbonetos, com ênfase no envolvimento dos cristais de gelo no início da formação de hidratos. Após a saturação completa da interface hidrocarboneto/água por hidratos, os módulos elásticos e viscosos interfaciais são obtidos através de varreduras de deformação para avaliar a fragilidade do filme de hidrato e resposta mecânica. Além disso, é examinado o impacto do tempo de envelhecimento e do tipo de cisalhamento (estático ou dinâmico) na rigidez do hidrato. Testes com inibidores termodinâmicos, como cloreto de sódio e monoetilenoglicol, demonstram extensão significativa do tempo de indução. Além disso, mudanças sistemáticas na taxa de cisalhamento são investigadas para compreender de forma abrangente sua influência nas características e propriedades do filme hidratado sob diversas condições de histórico de cisalhamento. No geral, esta pesquisa lança luz sobre as nuances da dinâmica da interface águahidrocarboneto na formação e mitigação de hidratos. / [en] Within the realm of the oil and gas industry, the disruption of production and transportation lines due to the accumulation of organic and inorganic compounds poses a widespread and significant challenge, resulting in considerable financial losses and environmental concerns. Gas hydrates, particularly emphasized among various challenges related to inorganic deposition, present a complex issue characterized by the formation of crystalline water-based solids, akin to ice, occurring under conditions of high pressure and low temperatures that arise when light hydrocarbon molecules and water combine to form a specific ordered structure. Hydrate formation begins at the water-hydrocarbon interface, highlighting the critical role interfacial rheology plays in this process. Despite the importance of this interface in hydrate formation, a research gap persists, particularly in the employment of shear rheology approaches. This study aids in bridging this gap by investigating the mechanical and flow properties of the interface, utilizing a resource in a rotational rheometer, a double-wall ring cell, for precise temperature control. Cyclopentane serves as the hydrate former, allowing experimentation under atmospheric pressure and varied temperatures. Protocols explore temperature and hydrocarbon concentrations, with an emphasis on the involvement of ice crystals in the early stages of hydrate formation. Following complete saturation of the hydrocarbon/water interface by hydrates, interfacial elastic and viscous moduli are obtained through strain sweeps to assess hydrate film fragility and mechanical response. Additionally, the impact of aging time and shear type (static or dynamic) on hydrate stiffness is examined. Tests with thermodynamic inhibitors, such as sodium chloride and monoethylene glycol, demonstrate a significant extension of the induction time. Furthermore, systematic changes in shear rate are investigated to comprehensively understand their influence on the characteristics and properties of the hydrated film under various shear history conditions. Overall, this research sheds light on the nuances of waterhydrocarbon interface dynamics in hydrate formation and mitigation.

In this research thermal properties enhancement of phase change material (PCM) using boron nitride nanomaterials such as nanoparticles and nanotubes is studied through experimental measurements, finite element method (FEM) through COMSOL 5.3 package and molecular dynamics simulations via equilibrium molecular dynamics simulation (EMD) with the Materials and Process Simulations (MAPS 4.3). This study includes two sections: thermal properties enhancement of inorganic salt hydrate (CaCl2∙6H2O) as the phase change material by mixing boron nitride nanoparticles (BNNPs), and thermal properties enhancement of organic phase change material (paraffin wax) as the phase change material via encapsulation into boron nitride nanotubes (BNNTs). The results of the proposed research will contribute to enhance the thermal transport properties of inorganic and organic phase change material applying nanotechnology for increasing energy efficiency of systems including electronic devices, vehicles in cold areas to overcome the cold start problem, thermal interface materials for efficient heat conduction and spacecraft in planetary missions for efficient thermal managements.

Dans cet ouvrage sera décrite la synthèse de nouveaux analogues du sialyl Lewis X (sLex). A cet effet, nous avons préparé une librairie d’analogues synthétisée à partir d’une approche mettant en jeu un «espaceur» acyclique permettant d’avoir un biais conformationnel que nous avons défini comme la stratégie ATC-B. Nous avions déjà démontré que certains analogues portant un groupe benzoate en C-2 et en C-4 du galactose présentent une activité 50 fois supérieure à celle du sLex. Nous avions par ailleurs démontré qu’en l’absence du benzoate en C-2, l’activité devient alors trois fois plus faible. A présent, il paraissait interessant de synthétiser des analogues ayant seulement un groupe benzoate en C-4 pour evaluer l’impact de ce groupement sur la puissance de nos analogues. Par le passé, nous avions également mis en évidence le rôle des esters sur l’activité des analogues portant un «espaceur» acyclique dans le cadre de la stratégie ATC-B. Nous effectuerons donc des variations à ce niveau pour en évaluer l’impact. Enfin, nous avons préparé une nouvelle famille d’analogues de type dimère. Ceux-ci seront constitués de 2 unités des composés monomériques synthétisés précédemment. La synthèse de ces dimères fera l’emploi de la «Click Chemistry». Cette étude nous mènera a vous présenter la synthèse de ces composés et la méthodologie employée. / This work describes the synthesis of novel sialyl Lewis X (sLex) analogues. To this end, we have prepared a library of analogues by implementing a strategy that makes use of an Acyclic Tether which allows for defined Conformational Bias (ATCB strategy). We have previously shown that analogues bearing a benzoate group at both positions C-2 and C-4 of the galactose exert an activity 50-fold greater than that of sLex. Indeed, removing the benzoate at position C-4 while keeping the one at C-2 led to a three fold decrease in potency. We are currently preparing the corresponding analogues that have the benzoate only at position C-4 in order to fully evaluate its impact on the potency of the analogue. We have also previously elucidated the role of esters on the activity of analogues that have acyclic tether as part of the ATC-B strategy. Variations have been made at the level of the ester and their impact has been evaluated. Lastly, we have prepared a novel family of analogues consisting of two identical monomeric subunits linked together. Synthesis of these dimers was performed via «Click Chemistry». This study describes the synthesis of the compounds and the methodology employed.

Made available in DSpace on 2017-07-21T20:42:35Z (GMT). No. of bitstreams: 1 rodrigoric.pdf: 9183178 bytes, checksum: 1d5fba078a589cbc1810eea245d1e019 (MD5) Previous issue date: 2006-10-31 / Mechanical alloying is a powder processing technique involving cold welding, fracturing mechanisms and rewelding of powder particles in a ball mill. The present work applied this technique with the purpose of processing titanium, niobium and tin alloys, through planetary ball mill and attritor mill. The atomic percentages of these elements were varied in six differents ways. The niobium hydrate was used on production of some alloys in study, with the purpose to observe the effects during the milling and on the alloys obtained after sintering. Differences between processing in planetary ball mill and attritor mill, as well the cold welding influences on the kinetic parameters of milling process were approached. The use of niobium hydrate result in a decrease of powders average crystallite size, and an increase of micro hardness of sintered alloys. This work obtained beta titanium alloys and alpha-beta titanium alloys in namometric sizes. The average crystallite size, for milled powders, was 7,6 nm. / Mecano-síntese é uma técnica de processamento em pó que envolve a soldagem a frio, mecanismos de fratura e a resoldagem das partículas de pós, em moinhos de bolas. O presente trabalho utilizou esta técnica com o propósito de processar ligas de titânio, nióbio e estanho, através de moinhos de bolas planetário e de atrito. As porcentagens atômicas destes elementos foram variadas de seis maneiras diferentes. O hidreto de nióbio foi utilizado na produção de algumas ligas em estudo, com o propósito de se observar os efeitos durante a moagem e na liga obtida após a sinterização. Diferenças entre o processamento em moinho de bolas planetário e o moinho de atrito, assim como as influências da soldagem a frio nos parâmetros cinéticos do processo de moagem, foram abordadas. O uso do hidreto de nióbio resultou na diminuição do tamanho médio de cristalito dos pós, e em um acréscimo na microdureza das ligas sinterizadas. Neste trabalho foram obtidas ligas de titânio beta e de titânio alfa-beta, em tamanhos nanométricos. O tamanho médio do cristalito, para os pós moídos, foi de 7,6 nm.

Localisation des molécules d'eau par RMN à l'état solide à la température de l'azote liquide ; mise en évidence d'un comportement conducteur protonique à partir de 235 K. Insertion redox de ferrocène conduisant au composé VOPO...

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Seafloor compliance is a non-intrusive geophysical method sensitive to the shear modulus of the sediments below the seafloor. A compliance analysis requires the computation of the frequency dependent transfer function between the vertical stress, produced at the seafloor by the ultra low frequency passive source-infra-gravity waves, and the resulting displacement, related to velocity through the frequency. The displacement of the ocean floor is dependent on the elastic structure of the sediments and the compliance function is tuned to different depths, i.e., a change in the elastic parameters at a given depth is sensed by the compliance function at a particular frequency. In a gas hydrate system, the magnitude of the stiffness is a measure of the quantity of gas hydrates present. Gas hydrates contain immense stores of greenhouse gases making them relevant to climate change science, and represent an important potential alternative source of energy. Bullseye Vent is a gas hydrate system located in an area that has been intensively studied for over 2 decades and research results suggest that this system is evolving over time. A partnership with NEPTUNE Canada allowed for the investigation of this possible evolution. This thesis describes a compliance experiment configured for NEPTUNE Canada’s seafloor observatory and its failure. It also describes the use of 203 days of simultaneously logged pressure and velocity time-series data, measured by a Scripps differential pressure gauge, and a Güralp CMG-1T broadband seismometer on NEPTUNE Canada’s seismic station, respectively, to evaluate variations in sediment stiffness near Bullseye. The evaluation resulted in a (- 4.49 x10-3± 3.52 x 10-3) % change of the transfer function of 3rd October, 2010 and represents a 2.88% decrease in the stiffness of the sediments over the period. This thesis also outlines a new algorithm for calculating the static compliance of isotropic layered sediments.

Seafloor compliance is a non-intrusive geophysical method sensitive to the shear modulus of the sediments below the seafloor. A compliance analysis requires the computation of the frequency dependent transfer function between the vertical stress, produced at the seafloor by the ultra low frequency passive source-infra-gravity waves, and the resulting displacement, related to velocity through the frequency. The displacement of the ocean floor is dependent on the elastic structure of the sediments and the compliance function is tuned to different depths, i.e., a change in the elastic parameters at a given depth is sensed by the compliance function at a particular frequency. In a gas hydrate system, the magnitude of the stiffness is a measure of the quantity of gas hydrates present. Gas hydrates contain immense stores of greenhouse gases making them relevant to climate change science, and represent an important potential alternative source of energy. Bullseye Vent is a gas hydrate system located in an area that has been intensively studied for over 2 decades and research results suggest that this system is evolving over time. A partnership with NEPTUNE Canada allowed for the investigation of this possible evolution. This thesis describes a compliance experiment configured for NEPTUNE Canada’s seafloor observatory and its failure. It also describes the use of 203 days of simultaneously logged pressure and velocity time-series data, measured by a Scripps differential pressure gauge, and a Güralp CMG-1T broadband seismometer on NEPTUNE Canada’s seismic station, respectively, to evaluate variations in sediment stiffness near Bullseye. The evaluation resulted in a (- 4.49 x10-3± 3.52 x 10-3) % change of the transfer function of 3rd October, 2010 and represents a 2.88% decrease in the stiffness of the sediments over the period. This thesis also outlines a new algorithm for calculating the static compliance of isotropic layered sediments.

Dans cet ouvrage sera décrite la synthèse de nouveaux analogues du sialyl Lewis X (sLex). A cet effet, nous avons préparé une librairie d’analogues synthétisée à partir d’une approche mettant en jeu un «espaceur» acyclique permettant d’avoir un biais conformationnel que nous avons défini comme la stratégie ATC-B. Nous avions déjà démontré que certains analogues portant un groupe benzoate en C-2 et en C-4 du galactose présentent une activité 50 fois supérieure à celle du sLex. Nous avions par ailleurs démontré qu’en l’absence du benzoate en C-2, l’activité devient alors trois fois plus faible. A présent, il paraissait interessant de synthétiser des analogues ayant seulement un groupe benzoate en C-4 pour evaluer l’impact de ce groupement sur la puissance de nos analogues. Par le passé, nous avions également mis en évidence le rôle des esters sur l’activité des analogues portant un «espaceur» acyclique dans le cadre de la stratégie ATC-B. Nous effectuerons donc des variations à ce niveau pour en évaluer l’impact. Enfin, nous avons préparé une nouvelle famille d’analogues de type dimère. Ceux-ci seront constitués de 2 unités des composés monomériques synthétisés précédemment. La synthèse de ces dimères fera l’emploi de la «Click Chemistry». Cette étude nous mènera a vous présenter la synthèse de ces composés et la méthodologie employée. / This work describes the synthesis of novel sialyl Lewis X (sLex) analogues. To this end, we have prepared a library of analogues by implementing a strategy that makes use of an Acyclic Tether which allows for defined Conformational Bias (ATCB strategy). We have previously shown that analogues bearing a benzoate group at both positions C-2 and C-4 of the galactose exert an activity 50-fold greater than that of sLex. Indeed, removing the benzoate at position C-4 while keeping the one at C-2 led to a three fold decrease in potency. We are currently preparing the corresponding analogues that have the benzoate only at position C-4 in order to fully evaluate its impact on the potency of the analogue. We have also previously elucidated the role of esters on the activity of analogues that have acyclic tether as part of the ATC-B strategy. Variations have been made at the level of the ester and their impact has been evaluated. Lastly, we have prepared a novel family of analogues consisting of two identical monomeric subunits linked together. Synthesis of these dimers was performed via «Click Chemistry». This study describes the synthesis of the compounds and the methodology employed.

Face à la finitude des ressources de la terre et de sa capacité d’absorption de la pollution, le développement d’écobétons pour un futur industrialisé durable représente un défi majeur de la science du béton moderne. En raison de sa nature hétérogène complexe, les propriétés macroscopiques du béton dépendent fortement des constituants de sa microstructure (ex. silicates de calcium hydratés [C–S–H], Portlandite, inclusions anhydres, porosité, agrégats, etc.). De plus, la nécessité d’une exploitation rapide et optimale des matériaux cimentaires émergents dans les applications industrielles demande de nos jours une meilleure compréhension de leurs particularités chimico-mécaniques à l’échelle micrométrique. Cette thèse vise à développer une méthode de pointe de couplage de la nanoindentation et de la spectroscopie quantitative aux rayons X à dispersion d'énergie (NI-QEDS), puis à fournir une caractérisation chimico-mécanique originale des phases microstructurales présentes dans les matrices réelles de ciments mélangés. La combinaison d’analyses NI-QEDS statistiques et déterministes a ainsi permis d’élargir la compréhension des systèmes avec ciment Portland et ajouts cimentaires (ACs) conventionnels ou alternatifs. Plus spécifiquement, l’étude des C–(A)–S–H (C–S–H incluant l’aluminium ou non) dans différents systèmes à base de ciments mélangés a montré des compositions différentes pour cet hydrate (variations dans les taux de Ca, Si, Al, S et Mg), mais ses propriétés mécaniques n’ont pas été significativement affectées par l’incorporation des ACs dans des dosages typiques. Les résultats présentés ont aussi démontré le rôle important des autres phases imbriquées dans la matrice de C–(A)–S–H, soit les inclusions anhydres dures (ex. le clinker et les ACs) et les autres hydrates tels que la Portlandite et les hydrates riches en aluminium (ex. les carboaluminates) avec des propriétés mécaniques plus élevées que celles des C–(A)–S–H. La thèse est basée sur cinq articles couvrant : (1) une analyse NI-EDS de systèmes incorporant des volumes élevés de pouzzolanes naturelles; (2) le développement de la méthode NI-QEDS; des analyses statistiques NI-QEDS (3) de systèmes avec cendres volantes et laitier, et (4) d’un système combinant ciment, calcaire et argile calcinée; et (5) une exploration déterministe NI-QEDS de systèmes conventionnels et alternatifs incorporant la poudre de verre, le métakaolin, le laitier ou la cendre volante. Finalement, en plus d’avancer les derniers modèles et méthodes micromécaniques, l’outil développé a fourni une perception chimico-mécanique originale des phases microstructurales et de leur arrangement. Le dévoilement de la signature chimico-mécanique de ces pâtes de ciments mélangés particulièrement complexes offre un savoir unique pour l’ingénierie des bétons de demain. / Abstract : Facing the limitedness of the earth’s resources and pollution absorption capacity, the development of eco-concrete for a sustainable industrialized future is one of the major challenges of modern concrete science. Due to its complex heterogeneous nature, the macro-scale properties of concrete strongly depend on the microstructure constituents (e.g., calcium-silicate-hydrates [C–S–H], Portlandite, anhydrous inclusions, porosity, aggregates, etc.). Moreover, the need for rapid and optimal exploitation of emerging binding materials in industrial applications urges today a better understanding of their chemo-mechanical features at the micrometer scale. This thesis aims at developing a state-of-the-art method coupling NanoIndentation and Quantitative Energy-Dispersive Spectroscopy (NI-QEDS), and providing an original chemo-mechanical characterization of the microstructure phases in highly heterogeneous matrices of real blended-cement pastes. The combination of statistical and deterministic NI-QEDS analysis approaches opened new research horizons in the understanding of Portland-cement systems incorporating conventional and alternative supplementary cementitious materials (SCMs). More specifically, the investigations of C–(A)–S–H (C–S–H including aluminum or not) in different blended-cement systems showed variable compositions for this hydrate (i.e., Ca, Si, Al, S and Mg contents), but the mechanical properties were not significantly affected by the incorporation of SCMs in typical dosages. The presented results also showed the important role of the other phases embedded in the C–(A)–S–H matrix, i.e., hard anhydrous inclusions (e.g., clinker and SCMs) and other hydrates such as Portlandite and Al-rich hydrates (e.g., carboaluminates) with mechanical properties higher than those of the C–(A)–S–H. The thesis is based on five articles focusing on: (1) the NI-EDS investigation of high-volume natural pozzolan systems; (2) the development of the NI-QEDS method; the statistical NI-QEDS analyses of (3) fly ash and slag blended-cement systems and of (4) a limestone-calcined-clay system; and (5) the deterministic NI-QEDS exploration of alternative and conventional systems incorporating glass powder, metakaolin, slag or fly ash. Finally, the developed tool not only advanced the latest micromechanical methods and models, but also provided original chemo-mechanical insights on the microstructure phases and their arrangement. Unveiling the chemo-mechanical signature of these highly-complex blended cement pastes further provided unique knowledge for engineering concretes for tomorrow.