Des photoamorceurs construits sur une chimie radicalaire originale sont développés. Les photopolymères présentent des avantages écologiques (pas de COV) et économiques. Ils sont utilisés dans les adhésifs, les encres, les revêtements, l’optique… Une première étude est réalisée sur la photopolymérisation radicalaire (FRP) en présence d’organoboranes. Sous l’action de la lumière, des radicaux boryles sont formés. Ces composés convertissent des radicaux peroxyle (stables) en radicaux boryles très réactifs sous air. Ils permettent ainsi une polymérisation radicalaire en milieu aéré. Avec l’ajout de colorant, la photopolymérisation a lieu sous lumière visible.Une seconde étude est menée sur la photopolymérisation cationique (FRPCP). Des sources d’irradiation douces (lampe halogène, LED,…), peu énergivores et peu coûteuses sont employées. Des composés photosensibles ayant de fortes propriétés d’absorption dans le visible sensibilisent les sels d’iodonium. Cette décomposition permet d’amorcer la polymérisation cationique sous faible intensité lumineuse.Enfin, la polymérisation radicalaire contrôlée/vivante induite par de la lumière UV et visible est présentée. Deux modes de polymérisation contrôlée sont discutés : la NMP2 (Nitroxide Mediated PhotoPolymerization) et l’ATRP2 (Atom Transfer Radical PhotoPolymerization). En NMP2, les alcoxyamines ont la particularité de se réactiver sous irradiation lumineuse. En ATRP2, de nouveaux complexes d’iridium et de fer ayant de bonnes propriétés d’absorption dans le visible sont employés comme photocatalyseurs. Les résultats montrent un caractère contrôlé/vivant lors de la photopolymérisation du MMA. / Photoinitiators constructed on an original radical chemistry are developed. Photopolymers have ecological advantages (no VOCs) and economic. They are used in adhesives, inks, coatings, optical...A first study is carried out on the radical curing (FRP) in the presence of boron molecules. Under light irradiation, boryls radicals are formed. These compounds convert peroxyl radicals (stable) in boryls radicals highly reactive under air. They allow a radical polymerization in aerated medium. With the addition of dye, the photopolymerization is carried out under visible light.A second study was conducted on the cationic curing (FRPCP). Soft radiation sources (halogen lamp, LED, ...), energy efficient and inexpensive are used. Photosensitive compounds having high absorption properties in the visible sensitize iodonium salts. This decomposition allows initiating the cationic polymerization under low light intensity.Finally, controlled/living radical polymerization induced by UV and visible light is presented. Two controlled polymerization methods are discussed: NMP2 (Nitroxide Mediated Photopolymerization) and ATRP2 (Atom Transfer Radical Photopolymerization). In NMP2, alkoxyamines have the particularity to be reactivated under light irradiation. In ATRP2, new iridium complexes and iron having good absorption properties in the visible range are used as photocatalysts. The results show a controlled/living character during the photopolymerization of MMA.

Les performances des filtres interférentiels répondent aujourd'hui à des spécifications de plus en plus exigeantes et permettent de repousser les limites physiques des instruments optiques dans lesquels ils sont intégrés. Au cours du processus de fabrication d'un filtre, il est évidemment primordial de maîtriser avec une très grande précision (typiquement sub-nanométrique) l'épaisseur optique des couches déposées. Ceci nécessite le recours à une mesure in situ des caractéristiques optiques de l’empilement tout au long de son dépôt.Dans le cadre de ce travail de thèse, nous avons développé un nouveau système de contrôle optique qui rend possible la mesure simultanée de la transmission d’un empilement, d’une part à une seule longueur d’onde, définie par l’utilisateur dans le domaine spectral compris entre 350 et 1000 nm (contrôle monochromatique présentant une résolution de 0,35 nm), et d’autre part sur l’ensemble de ce domaine spectral (contrôle large bande présentant une résolution de 3 nm). Ces deux mesures sont réalisées en 6 millisecondes à une cadence de 2 Hz (fréquence de rotation du porte-substrat), et ce, de manière parfaitement synchrone. En outre, grâce à la mise en place, dans le plateau porte-substrat, d’une voie de référence correspondant à une absence d’échantillon, ce dispositif de contrôle présente une très grande stabilité et une justesse meilleure que le pour mille. Enfin, une méthode numérique a été développée pour rendre possible une comparaison fiable des résultats fournis par les deux voies de mesure malgré la différence de leur résolution spectrale.Ce dispositif ouvre la voie à l’utilisation de plusieurs critères indépendants pour définir en temps réel l’instant précis où le dépôt d’une couche doit être arrêté (annulation de la dérivée de la transmission à une longueur d’onde, comparaison de cette transmission monochromatique à un niveau pré-défini, minimisation d’une fonction de mérite quantifiant l’écart entre le spectre mesuré et un spectre de référence défini par le calcul, respect d’une durée de dépôt utilisant une mesure optique in situ de la vitesse de dépôt). Il s’agit donc bien d’un contrôle multi-critère tout optique.La première application des potentialités de ce nouveau système a concerné la détermination des constantes optiques (indice de réfraction, coefficient d’extinction) d’un matériau diélectrique de haut indice, le pentoxyde de tantale. La méthode utilisée met en œuvre un enregistrement de l’évolution de la transmission spectrale de l’échantillon tout au long de la croissance de la couche (voie large bande) et un traitement, longueur d’onde par longueur d’onde, du profil temporel de cette évolution. Cette nouvelle méthode ne nécessite donc pas le choix a priori d’une loi de dépendance spectrale pour chacune de ces deux constantes optiques. Elle ouvre également la voie à une analyse de l’évolution de l’indice de réfraction d’une couche en fonction de l’épaisseur qui lui est assignée. Enfin, elle est transposable à des matériaux bas indice, comme, par exemple, la silice / The performances of complex interference filters meets today to exigent specifications and permit to enhance the physical limits of optical instruments in which they are integrated. During the manufacturing of a filter, it is obviously important to monitor with very high accuracy (typically sub-nanometric) the thickness of the deposited layers. This requires the use of an in situ measurement of the optical characteristics of the multilayer during the process.In the framework of this thesis, we have developed a new optical monitoring system which makes possible to achieve the simultaneous measurement of the transmittance of a multilayer filter, on one hand at a single wavelength defined by the user in the spectral range between 350 nm and 1000 nm (monochromatic monitoring with a resolution of 0.35 mm), and on the other hand on this whole spectral range at single shot (broadband monitoring with a resolution of 3 nm). These two measurements are made in 6 milliseconds at a rate of 2 Hz (corresponding to the rotation speed of the substrate holder), and are perfectly synchronized. In addition, the substrate holder tray is designed with a reference channel corresponding to a void position (without sample). Thanks to that configuration the monitoring system has a very high stability and accuracy better than 0.001. Finally, a numerical method has been developed to enable the comparison of the results provided by the two acquisition channels (monochromatic and broadband) taking into account the difference of their spectral resolution.This system opens the way for the use of several independent criteria to determine in real time the exact moment when the deposition of a layer must be stopped (turning point monitoring, trigger point monitoring, broadband monitoring, achievement with time monitoring using an optical in situ determination of the deposition rate). So this is indeed an all optical multi-criteria monitoring systems.This first application of this system has involved the determination of the optical constants (refractive index and extinction coefficient) of a high index dielectric material: the tantalum pentoxide. The method used is based on a recording of the evolution of the transmitted spectrum of a witness sample during the growth of the layer (broadband channel) and a processing, wavelength by wavelength, of the timing data profile of that evolution. This new method does not require any descriptive spectral dependence law for each of the two optical constants. It also paves the way for an analysis of the behavior of the refractive index of a layer in function of the thickness. Finally, it is applicable to low index materials, such as, for example, silica.

L’ère de l’exascale creusera encore plus l’écart entre la vitesse de génération des données de simulations et la vitesse d’écriture et de lecture pour analyser ces données en post-traitement. Le temps jusqu’à la découverte scientifique sera donc grandement impacté et de nouvelles techniques de traitement des données doivent être mises en place. Les méthodes in situ réduisent le besoin d’écrire des données en les analysant directement là où elles sont produites. Il existe plusieurs techniques, en exécutant les analyses sur les mêmes nœuds de calcul que la simulation (in situ), en utilisant des nœuds dédiés (in transit) ou en combinant les deux approches (hybride). La plupart des méthodes in situ traditionnelles ciblent les simulations qui ne sont pas capables de tirer profit du nombre croissant de cœurs par processeur mais elles n’ont pas été conçues pour les architectures many-cœurs qui émergent actuellement. La programmation à base de tâches est quant à elle en train de devenir un standard pour ces architectures mais peu de techniques in situ à base de tâches ont été développées.Cette thèse propose d’étudier l’intégration d’un système in situ à base de tâches pour un code de dynamique moléculaire conçu pour les supercalculateurs exaflopiques. Nous tirons profit des propriétés de composabilité de la programmation à base de tâches pour implanter l’architecture hybride TINS. Les workflows d’analyses sont représentés par des graphes de tâches qui peuvent à leur tour générer des tâches pour une exécution in situ ou in transit. L’exécution in situ est rendue possible grâce à une méthode innovante de helper core dynamique qui s’appuie sur le concept de vol de tâches pour entrelacer efficacement tâches de simulation et d’analyse avec un faible impact sur le temps de la simulation.TINS utilise l’ordonnanceur de vol de tâches d’Intel® TBB et est intégré dans ExaStamp, un code de dynamique moléculaire. De nombreuses expériences ont montrées que TINS est jusqu’à 40% plus rapide que des méthodes existantes de l’état de l’art. Des simulations de dynamique moléculaire sur des système de 2 milliards de particles sur 14,336 cœurs ont montré que TINS est capable d’exécuter des analyses complexes à haute fréquence avec un surcoût inférieur à 10%. / The exascale era will widen the gap between data generation rate and the time to manage their output and analysis in a post-processing way, dramatically increasing the end-to-end time to scientific discovery and calling for a shift toward new data processing methods. The in situ paradigm proposes to analyze data while still resident in the supercomputer memory to reduce the need for data storage. Several techniques already exist, by executing simulation and analytics on the same nodes (in situ), by using dedicated nodes (in transit) or by combining the two approaches (hybrid). Most of the in situ techniques target simulations that are not able to fully benefit from the ever growing number of cores per processor but they are not designed for the emerging manycore processors.Task-based programming models on the other side are expected to become a standard for these architectures but few task-based in situ techniques have been developed so far. This thesis proposes to study the design and integration of a novel task-based in situ framework inside a task-based molecular dynamics code designed for exascale supercomputers. We take benefit from the composability properties of the task-based programming model to implement the TINS hybrid framework. Analytics workflows are expressed as graphs of tasks that can in turn generate children tasks to be executed in transit or interleaved with simulation tasks in situ. The in situ execution is performed thanks to an innovative dynamic helper core strategy that uses the work stealing concept to finely interleave simulation and analytics tasks inside a compute node with a low overhead on the simulation execution time.TINS uses the Intel® TBB work stealing scheduler and is integrated into ExaStamp, a task-based molecular dynamics code. Various experiments have shown that TINS is up to 40% faster than state-of-the-art in situ libraries. Molecular dynamics simulations of up to 2 billions particles on up to 14,336 cores have shown that TINS is able to execute complex analytics workflows at a high frequency with an overhead smaller than 10%.

Using a hydrogen donor and a catalyst for upgrading and increasing oil recovery during in situ combustion is a known and proven technique. Based on research conducted on this process, it is clear that widespread practice in industry is the usage of tetralin as a hydrogen donor. The objective of the study is to find a cheaper hydrogen donor with better or the same upgrading performance. Decalin (C10H18) is used in this research as a hydrogen donor. The experiments have been carried out using field oil and water saturations, field porosity and crushed core for porous medium. Four in situ combustion runs were performed with Gulf of Mexico heavy oil, and three of them were successful. The first run was a control run without any additives to create a base for comparison. The next two runs were made with premixed decalin (5 percent by oil weight) and organometallic catalyst (750 ppm). The following conditions were kept constant during all experimental runs: air injection rate at 3.1 L/min and combustion tube outlet pressure at 300 psig. Analysis of the performance of decalin as a hydrogen donor in in-situ combustion included comparison of results with an experiment where tetralin was used. Data from experiments of Palmer (Palmer-Ikuku, 2009) was used for this purpose, where the same oil, catalyst and conditions were used. Results of experiments using decalin showed better quality of produced oil, higher recovery factor, faster combustion front movement and higher temperatures of oxidation. API gravity of oil in a run with decalin is higher by 4 points compared to a base run and increased 5 points compared to original oil. Oil production increased by 7 percent of OOIP in comparison with base run and was 2 percent higher than the experiment with tetralin. The time required for the combustion front to reach bottom flange decreased 1.6 times compared to the base run. The experiments showed that decalin and organometallic catalysts perform successfully in in situ combustion, and decalin is a worthy replacement for tetralin.

Thesis (M.S.)--West Virginia University, 2002. / Title from document title page. Document formatted into pages; contains viii, 100 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references (p. 80-96).

In Alberta, Canada, amongst its mixture of sand, clay, water and other minerals, the tar sand’s heavy and viscous component bitumen, a thick, sticky form of crude oil is extracted through two methods; open-pit mining for shallower deposits (<75 m), and in situ for deeper deposits (>75 m). This degree project consists of a comparison between these two extraction methods impact on air, nature and water, which all have been evaluated by reviewing and analyzing literature. Studies showed that in situ methods cause a higher impact on air than open-pit mining, through higher emissions of greenhouse gases and sulfur dioxide (SO2), and will surpass the carbon dioxide (CO2) emissions caused by the open-pit mines when the shallower, more accessible tar sands dwindle. Open-pit mining causes a higher impact on water due to its large tailing ponds that causes leakage of processing water and fine tailings, polyaromatic hydrocarbons (PAH: s) and these 13 following elements considered priority pollutants (PPE) by the US Environmental Protection Agency (EPA); antimony (Sb), arsenic (As), beryllium (Be), lead (Pb), cadmium (Cd), copper (Cu), chromium (Cr), mercury (Hg), nickel (Ni), selenium (Se), silver (Ag), thallium (Tl) and zinc (Zn). However studies remain unclear whether or not in situ methods are worse due to underground tailing ponds. Finally, when it comes to nature, open-pit mining causes a more direct environmental impact through deforestation, drainage of peat and wetland, and blasting of rock. In situ methods however, seem to cause more of a long term environmental impact through fragmentation. Dividing the landscape into smaller units through roads, wells, pipelines and seismic lines, leads to domestic biodiversity and homogenization of flora and fauna as unfavorable conditions is created for the nature’s wildlife. In conclusion, in situ methods causes a bigger impact on air than open-pit mining, while open-pit mining causes a bigger impact on water. Due to lack of time and resources, more research about the direct impact on nature is needed to fully evaluate which of the two extraction methods causes the least environmental impact.

In 1996-2000 during expeditions were found and described 123 Carum carvi habitats. Mostly common caraway is found in pasture type habitats of Cynosurion cristati confederation communities. Plants of Carum carvi cenopopulations are characterized by wide diversity of phenotypic traits strongly influenced by ecological conditions and anthropogenic activity in natural habitats. The most stable parameters are weight of 1000 fruit and biochemical composition of essential oil. Essential oil synthesis in fruits is positively affected by warm and dry weather at the stage of caraway flowering – fruit ripening, carvone content – by warm and wet weather. The identified morphological types of Carum carvi leaves were as follows: normal, dill and parsley. Early-season caraway forms in comparison to others distinguished for the lowest height, fruit weight and total yield, but had the highest carvone content in fruit essential oil. Pink petals are characteristic for early-season caraway cenopopulations. White petal color, greater pigments amount in leaves, higher fruit productivity, as well as essential oil and carvone output characterize medium late and late forms. Various caraway genotypes with different levels of leaf carotinoids, chlorophyll content and ratio, anthocianins amount in petals, different reaction to cold and lighting stress reveal specific adaptive plasticity of caraway. Caraway intercenopopulation genetic diversity was determined at the molecular level.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal / Pour respecter les droits d'auteur, la version électronique de cette thèse ou ce mémoire a été dépouillée, le cas échéant, de ses documents visuels et audio-visuels. La version intégrale de la thèse ou du mémoire a été déposée au Service de la gestion des documents et des archives de l'Université de Montréal.

Despite its many challenges and limitations the concept of in situ upgrading of informal settlements has become one of the most favoured approaches to the housing crisis in the ‘Global South’. Due to its inherent principles of incremental in situ development, prevention of relocations, protection of local livelihoods and democratic participation and cooperation, this approach is often perceived to be more sustainable than other housing approaches that often rely on quantitative housing delivery and top down planning methodologies. While this study does not question the benefits of the in situ upgrading approach, it seeks to identify problems of its practical implementation within a specific national and local context. The study discusses the origin and importance of this approach on the basis of a review of international housing policy development and analyses the broader political and social context of the incorporation of this approach into South African housing policy. It further uses insights from a recent case study in Cape Town to determine complications and conflicts that can arise when applying in situ upgrading of informal settlements in a complex local context. On that basis benefits and limitations of the in situ upgrading approach are specified and prerequisites for its successful implementation formulated. / Trotz vieler Herausforderungen und Beschränkungen gilt das Konzept des in situ upgrading informeller Siedlungen als eine der wichtigsten Herangehensweisen an die Wohnraumkrise im „globalen Süden“. Aufgrund seiner immanenten Prinzipien einer schrittweisen Entwicklung an Ort und Stelle, der Vermeidung von Umsiedlungen, dem Erhalt lokaler Existenzgrundlagen sowie demokratischer Beteiligung und Kooperation, wird oftmals angenommen, dass diese Herangehensweise nachhaltiger ist, als eine quantitativ ausgerichtete Wohnraumversorgung und Top-Down-Planungsansätze. Während diese Studie die Vorteile des in situ upgrading nicht in Frage stellt, zielt sie darauf ab, Probleme der praktischen Umsetzung dieses Ansatzes in einem spezifischen nationalen und lokalen Kontext zu identifizieren. Die Studie diskutiert die Herkunft und die Bedeutung des in situ upgrading auf der Grundlage einer Rückschau auf die Entwicklung internationaler Wohnraumpolitik und analysiert den politischen und sozialen Kontext der Einbettung dieses Ansatzes in die südafrikanische Wohnraumpolitik. Darüber hinaus macht sie sich Einblicke einer kürzlich durchgeführten Fallstudie in Kapstadt zunutze, um Probleme und Konflikte zu erfassen, die bei der Umsetzung des in situ upgrading in einem komplexen lokalen Kontext entstehen können. Auf dieser Grundlage werden die Vorteile wie auch die Beschränkungen des in situ upgrading näher spezifiziert und zentrale Voraussetzungen für eine erfolgreiche Umsetzung des Konzeptes formuliert.

Contamination of soils and groundwater with nitroaromatic compounds such as 2,4,6-trinitrotoluene (TNT) and dinitrotoluenes (DNTs) has drawn considerable attention due to widely distributed contamination sites and substantial efforts for cleanup. Two isomers of DNT, specifically 2,6-dinitrotoluene (2,6-DNT) and 2,4-dinitrotoluene (2,4-DNT), occur as soil and groundwater contaminants at former TNT production sites. The discovery of bacteria that use DNT isomers as electron donors has encouraged bioremediation at contaminated sites. Current work is extending the existing engineered bioremediation to naturally occurring in situ biodegradation and focuses on the application of natural attenuation (NA) as a remediation strategy for residual DNT at contaminated sites. More specifically this research evaluated factors influencing in situ bioremediation of DNTs and TNT in surface soils, vadose zones, and saturated medium. Applications involving surface soils and vadose zones investigated the potential of water infiltration to promote in situ bioremediation. Studies in saturated media were more applicable to NA. Factors that were also considered in studies conduced included: 1) the presence and distribution of degrading microbes in field soils (Barksdale, WI); 2) the dissolution and bioavailability of contaminants in historically contaminated soils; and 3) the effect of mixtures of contaminants (i.e., DNTs and TNT) on biodegradation processes. This research provided information useful for practitioners considering an in situ bioremediation NA as a remedial solution for contaminated sites. Under the condition simulating downflow of surface waters or rainwater, the rapid rate of DNT degradation could be facilitated by the availability of oxygen in the soil gas without concern of toxicity (i.e., nitrite evolution and pH drop) and addition of nutrients. As a result, in situ bioremediation or NA should be strongly considered as a remedial option for Barksdale soils and similar sites where relatively low concentrations of DNT isomers are present as contaminants. At TNT contaminated sites TNT was not mineralized by indigenous microorganisms despite oxidative biotransformation, and mixed culture capable of growth on DNT also could not develop the mineralization of TNT during DNT degradation. This suggests that the mixtures of contamination did not improve the potential for in situ TNT bioremediation.