Les matériaux à base de bore et d'azote présentent un grand potentiel et donc un grand intérêt pour des applications énergétique et en particulier dans le domaine du stockage de l'hydrogène. L'ammoniaborane (NH3BH3) s'est révélé, au milieu des années 2000, comme un matériau avec une grande capacité gravimétrique (19,6%m) et volumétrique (140 g.L-1) en hydrogène. Au cours de l'analyse de la bibliographie nous nous sommes aperçus que tous les travaux sur l'ammoniaborane portés sur sa déstabilisation thermique, nous avons donc choisi une approche originale en nous concentrant sur la stabilisation thermique de l'ammoniaborane. Mon travail de thèse a consisté à revisiter la synthèse de l'ammoniaborane pour en dégager les meilleurs paramètres de synthèse (précurseurs de bore et d'azote, solvant et température) possible en vue d'obtenir une température de début de déshydrogénation la plus haute possible. En effet, en faisant varier certains précurseurs nous avons pu observer une modification de la température de début de déshydrogénation et donc de la stabilité thermique de l'ammoniaborane. Après avoir déterminé les meilleurs paramètres de synthèses nous avons entrepris une étude thermique et thermolytique afin de comprendre quel(s) facteur(s) étai(en)t à l'origine de cette différence de stabilisation. Pour cela nous avons effectué une étude d'analyse thermogravimétrique couplée à un spectromètre de masse afin de déterminer le mécanisme de déshydrogénation et une étude en conditions isotherme afin de vérifier la stabilité des ammoniaboranes que nous avons synthétisés. Dans un troisième temps nous avons effectué une étude spectroscopique de surface, grâce à l'XPS et du matériau dans son ensemble, grâce à la RMN-MAS à l'état solide des noyaux de bore 11 et d'azote 15. Ces études nous ont permis de déterminer un nouveau mécanisme de déshydrogénation de l'ammoniaborane pour des expériences en conditions isotherme. / Boron and nitrogen based-materials offer a great potential and interest in energy applications and in particular in the field of hydrogen storage. The ammonia borane (NH3BH3) was revealed, in the mid 2000s, as a material with high gravimetric (19.6%m) and volumetric (140 g.L-1) capacities in hydrogen. During the analysis of the literature we realized that all studies on ammonia borane treated on its thermal destabilization, so we chose an original approach by focusing our work on the thermal stabilization of ammonia borane. My thesis work focused on the synthesis of ammonia borane to identify the best synthesis parameters (boron and nitrogen precursors, solvent, and temperature) for the highest possible onset temperature. Indeed, by varying some precursors we observed a change in the onset temperature and therefore in the thermal stability of the ammonia borane. After determining the best synthesis parameters we undertook thermal and thermolytic studies to understand which factor(s) is(are) responsible for the stabilization's differences. For this, we performed thermogravimetric analysis coupled to mass spectrometer studies to determine the dehydrogenation mechanism and studies in isothermal conditions to verify the stability of our ammonia boranes. Thirdly we performed a spectroscopic study by XPS and solid state MAS-NMR of boron 11 and nitrogen 15. These studies allowed us to identify a new mechanism of dehydrogenation of ammonia borane for experiments in isothermal conditions.

Ce manuscrit constitue la synthèse d'efforts visant à évaluer l'impact des composés oxygénés contenus dans des mélanges représentatifs de Biodiesel, sur leur tendance à la production de suie d'une part, et sur les propriétés physico-chimiques et la réactivité des suies d'autre part. Pour ce faire, une production stationnaire de particules de suie par un brûleur académique générant des flammes non-prémélangées a été mise en point. Dans un premier temps, nous avons montré que la teneur ainsi que la structure des additifs oxygénés à base d'ester méthylique affectent la formation de suie dans la flamme. Ainsi, les résultats ont démontré que l'efficacité d'un carburant à réduire la tendance à la production de suie en terme d'indice YSI est de plus en plus importante lorsque le contenu et/ou la longueur de la chaîne aliphatique carbonée de l'ester méthylique augmentent dans le carburant de référence. Dans un second temps, les suies " modèles " récupérées dans la région post-flamme ont été caractérisées puis comparées entre elles ainsi qu'avec une suie Biodiesel " réelle ". Les analyses ont montré que les suies issues des " surrogates " Biodiesel contenant la teneur en ester la plus élevée et la chaîne aliphatique carbonée la plus longue présentaient la distribution de taille la plus étroite, le diamètre des agrégats le plus petit, les teneurs en oxygène et en fraction organique soluble les plus faibles et étaient moins réactives. Enfin, nous avons observé que les suies " modèles " issue du brûleur académique de SANTORO et la suie " réelle " possèdent des propriétés physico-chimiques très proches et une réactivité similaire. / The aim of this work was to evaluate the effect of oxygenated compounds concentration and structure on sooting tendencies of surrogate Diesel and Biodiesel, and to investigate the properties and the oxidative reactivity of soot obtained by their combustion using an atmospheric axi-symmetric co-flow non-premixed flame burner. Results evidenced that ester functions contained in Biodiesel surrogates reduce soot production. This decrease was more pronounced when the concentration of the oxygenated additive investigated was higher. However, it has been determined that YSI decreases when the aliphatic carbon chain of the ester additive is longer. On the other hand, physico-chemical characterizations of the generated model soot revealed that oxygen and soluble organic fraction (SOF) content decreases when the amount of methyl ester based additives increases in the reference fuel. Moreover, the behavior towards oxidation indicated that the Biodiesel-derived soot was less reactive than the Diesel-derived one. Finally, it was noticed from the results obtained from laser granulometry and TPOs that the particle size distribution and the reactivity of model soot collected from the burner are in the same range of size and of maximum oxidation temperature as soot derived from a Diesel engine functioning under specific conditions and with different type of fuel blending.

Les zirconates titanates de plomb (PZT) suscitent un intérêt considérable pour plusieurs applications industrielles, au regard de leurs excellentes propriétés piézoélectriques et électromécaniques. Le contexte actuel de l’innovation technologique est la miniaturisation et l’allègement des produits ; c’est pour cette raison que de nombreuses études sont menées depuis une vingtaine d’années sur les techniques et les procédés de synthèse de ces matériaux piézoélectriques sous forme de couches minces tout en garantissant une fiabilité accrue. Dans ce contexte, l’étude menée dans le cadre de cette thèse, a visé l’optimisation du procédé d’élaboration de films minces piézoélectriques de PZT par pulvérisation cathodique magnétron en mode DC et en mode Rf, en vue d’obtenir des capteurs d’efforts piézoélectriques. La synthèse in situ et la cristallisation ex-situ des films élaborés, par recuit classique (CFA) ou recuit rapide (RTA) confirme une structure pérovskite du PZT, complétées par une série de caractérisations morphologiques et structurales. Les domaines ferroélectriques à l’origine des propriétés piézoélectriques sont correctement visualisés par PFM et le calcul du coefficient piézoélectrique d33 des couches synthétisées sur des substrats métalliques, est réalisé par interféromètre laser. En parallèle, une approche expérimentale est menée sur l’évolution des performances piézoélectriques des films de PZT d’une part en fonction du mode d’élaboration et d’autre part en fonction de la texturation des couches, assurée par des traitements thermiques de cristallisation. / Recently, PZTs thin films have been spotlighted for various applications owing to their excellent piezoelectric and electromechanical properties. Most of the existing coating methods have been explored for the deposition of PZT. In this work, amorphous Pb(ZrxTi1-x)O3 (PZT) thin films were prepared by pulsed DC and RF magnetron sputtering in order to device a piezoelectric force sensors. The structure of a perovskite phase of PZT thin films was successfully characterized and morphological characterizations were investigated. Ferroelectrics properties of PZT thin films were determined using Piezoresponse Force Atomic technique (PFM) while the functional response of the films was characterized by measurements of piezoelectric d33 coefficients. Additionally, the coating processes and the crystallization behavior at different temperatures, of amorphous PZT thin films during either conventional furnace annealing (CFA) or rapid thermal annealing (RTA) were studied to understand the evolution of piezoelectric properties of films.

Slow speed rotating machines are the mainstay of several industrial applications worldwide. They can be found in paper and steel mills, rotating biological contractors, wind turbines etc. Operational experience of such machinery has not only revealed the early design problems but has also presented opportunities for further significant improvements in the technology and economics of the machines. Slow speed rotating machinery maintenance, mostly related to bearings, shafts and gearbox problems, represents the cause of extended outages. Rotating machinery components such as gearboxes, shafts and bearings degrade slowly with operating time. Such a slow degradation process can be identified if a robust on-line monitoring and predictive maintenance technology is used to detect impending problems and allow repairs to be scheduled. To keep machines functioning at optimal levels, failure detection of such vital components is important as any mechanical degradation or wear, if is not impeded in time, will often progress to more serious damage affecting the operational performance of the machine. This requires far more costly repairs than simply replacing a part. Over the last few years there have been many developments in the use of Acoustic Emission (AE) technology and its analysis for monitoring the condition of rotating machinery whilst in operation, particularly on slow speed rotating machinery. Unlike conventional technologies such as thermography, oil analysis, strain measurements and vibration, AE has been introduced due to its increased sensitivity in detecting the earliest stages of loss of mechanical integrity. This programme of research involves laboratory tests for monitoring slow speed rotating machinery components (shafts and bearings) using AE technology. To implement this objective, two test rigs have been designed to assess the capability of AE as an effective tool for detection of incipient defects within low speed machine components (e.g. shafts and bearings). The focus of the experimental work will be on the initiation and growth of natural defects. Further, this research work investigates the source characterizations of AE signals associated with such bearings whilst in operation. It is also hoped that at the end of this research program, a reliable on-line monitoring scheme used for slow speed rotating machinery components can be developed.

The City of Winnipeg, located at the confluence of the Red and Assiniboine Rivers, has over 240 km of natural riverbank property. The increased frequency and magnitude of flooding along the Red and Assiniboine Rivers over the past decade appears to have influenced the number of slope failures along riverbank property, resulting in the loss of both public green space and privately owned land. The loss of private and public property adjacent to the river has led to the loss of valuable real estate and public parkland amenities. To ensure that riverbank property is preserved for future generations, the City of Winnipeg wants to increase the stability of certain reaches of publicly owned riverbank property along the Red and Assiniboine Rivers that are prone to slope movements. Extensive research has been conducted on slope stability problems in the Winnipeg area, but a transparent prioritization procedure for the remediation of riverbank stability problems has not existed. Therefore, a Riverbank Asset Management System (RAMS) was developed for publicly owned riverbank property to prioritize riverbank slope stability problems along the Red and Assiniboine Rivers. The RAMS provides the City of Winnipeg with a rational approach for determining risk levels for specific reaches of the Red and Assiniboine Rivers. The calculated risk levels allow the City to develop recommended response levels for slope stability remediation projects in a fiscally responsible manner with minimal personal and political influences. This system permits the City to facilitate timely and periodic reviews of priority sites as riverbank conditions and input parameters change. / May 2009

The City of Winnipeg, located at the confluence of the Red and Assiniboine Rivers, has over 240 km of natural riverbank property. The increased frequency and magnitude of flooding along the Red and Assiniboine Rivers over the past decade appears to have influenced the number of slope failures along riverbank property, resulting in the loss of both public green space and privately owned land. The loss of private and public property adjacent to the river has led to the loss of valuable real estate and public parkland amenities. To ensure that riverbank property is preserved for future generations, the City of Winnipeg wants to increase the stability of certain reaches of publicly owned riverbank property along the Red and Assiniboine Rivers that are prone to slope movements. Extensive research has been conducted on slope stability problems in the Winnipeg area, but a transparent prioritization procedure for the remediation of riverbank stability problems has not existed. Therefore, a Riverbank Asset Management System (RAMS) was developed for publicly owned riverbank property to prioritize riverbank slope stability problems along the Red and Assiniboine Rivers. The RAMS provides the City of Winnipeg with a rational approach for determining risk levels for specific reaches of the Red and Assiniboine Rivers. The calculated risk levels allow the City to develop recommended response levels for slope stability remediation projects in a fiscally responsible manner with minimal personal and political influences. This system permits the City to facilitate timely and periodic reviews of priority sites as riverbank conditions and input parameters change.

The City of Winnipeg, located at the confluence of the Red and Assiniboine Rivers, has over 240 km of natural riverbank property. The increased frequency and magnitude of flooding along the Red and Assiniboine Rivers over the past decade appears to have influenced the number of slope failures along riverbank property, resulting in the loss of both public green space and privately owned land. The loss of private and public property adjacent to the river has led to the loss of valuable real estate and public parkland amenities. To ensure that riverbank property is preserved for future generations, the City of Winnipeg wants to increase the stability of certain reaches of publicly owned riverbank property along the Red and Assiniboine Rivers that are prone to slope movements. Extensive research has been conducted on slope stability problems in the Winnipeg area, but a transparent prioritization procedure for the remediation of riverbank stability problems has not existed. Therefore, a Riverbank Asset Management System (RAMS) was developed for publicly owned riverbank property to prioritize riverbank slope stability problems along the Red and Assiniboine Rivers. The RAMS provides the City of Winnipeg with a rational approach for determining risk levels for specific reaches of the Red and Assiniboine Rivers. The calculated risk levels allow the City to develop recommended response levels for slope stability remediation projects in a fiscally responsible manner with minimal personal and political influences. This system permits the City to facilitate timely and periodic reviews of priority sites as riverbank conditions and input parameters change.

Neste trabalho foram produzidas dispersões aquosas poliuretânicas com formulações variadas, obtidas pelo processo em duas etapas. Na primeira etapa foi obtido um prepolímero e na segunda etapa, através da reação de extensão de cadeia foi obtido o polímero final. Nas sínteses foram empregados o diisocianato de isoforona (IPDI) e como polióis o poli(glicol propilênico) (PPG) e três diferentes tipos de polibutadieno líquido hidroxilado (HTPB) comerciais. A fim de possibilitar a dispersão dos poliuretanos em água, foi introduzido em sua estrutura o ácido dimetilolpropiônico (DMPA), que após neutralização com trietilamina (TEA) forneceu os sítios iônicos responsáveis pela estabilidade das dispersões em água. Como extensor de cadeia foi utilizado a hidrazina (HYD). As dispersões aquosas poliuretânicas obtidas foram avaliadas quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade. Os filmes formados a partir dessas dispersões foram avaliados quanto à sua aparência visual, propriedades mecânicas, estabilidade térmica por análise termogravimétrica (TGA) e espectroscopia na região do infravermelho (FTIR). Todas as dispersões obtidas apresentaram teor de sólidos totais entre 31 a 45% e tamanho de partícula na faixa de 70 a 221 nm. / In this work polyurethane aqueous dispersions with varied compositions, synthesized by a two steps process were produced. On the first step it was obtained a prepolymer and on the second one, by the reaction of chain extension with hydrazine (HYD) was obtained the final polymer. In the prepolymer synthesis, diisocyanate of isophorone (IPDI), poly(propylene glycol) (PPG), three different types of hydroxy-terminated polybutadienes (HTPB) and, in order to make possible the polyurethane dispersion in water, dimethylol propionic acid (DMPA), were employed. Afterwards the acid groups were neutralized with triethylamine (TEA) to provide the ionic groups responsible for the dispersion stability in water. The polyurethane aqueous dispersions produced in this work were evaluated through the solids content, particle size and viscosity. The films formed from these dispersions were characterized by their visual appearance, mechanical properties, thermal stability (TGA) and by infrared spectroscopy (FTIR). All the obtained dispersions presented solids content between 31 to 45 percent (m/m) and particle size between 70 to 221 nm.

La recherche de nouveaux matériaux absorbant les ondes électromagnétiques dans le domaine des hyperfréquences est devenue un enjeu majeur avec le développement croissant des moyens de communication et, corrélativement, le besoin de se prémunir efficacement contre la « pollution » électromagnétique (protection des équipements et des personnes). Dans ce manuscrit, nous nous intéressons à un matériau composite anisotrope constitué d'une matrice polymère chargée en particules ferromagnétiques aplaties appelées pétales. Ce type de composite suscite actuellement un intérêt grandissant dans la communauté grâce aux nombreux avantages qu'il présente (ajustement de la bande d'absorption en fonction de la nature et du rapport de forme des charges, faible épaisseur du revêtement). Le champ de cette étude s'est voulu relativement large afin d'avoir une vue d'ensemble des problématiques liées à ces composites à base de pétales et cela à plusieurs échelles. Dans un premier temps, une étude originale a été menée sur le pétale seul. Après des travaux préliminaires portant sur l'élaboration des pétales et leurs propriétés morphologiques, des caractérisations magnétiques statiques et dynamiques ont été réalisées sur un pétale unique. Le spectre de perméabilité obtenu met en évidence trois résonances. Une étude complémentaire menée sur des objets de mêmes dimensions élaborés par PVD et structurés par FIB a permis, par analogie, d'attribuer ces trois résonances respectivement aux domaines, aux parois et au vortex joignant les parois. Dans un second temps, une étude approfondie a été menée sur le composite complet. L'adaptation de la technique de perméamétrie par perturbation de spire a rendu possible la caractérisation fine et complète de matériaux composites épais avec ou sans champ magnétique statique appliqué et pour différentes directions de pompage. Celle-ci a permis de confirmer l'origine des différentes résonances malgré le désordre structurel caractéristique des milieux composites. Pour finir, une étude à vocation plus applicative a été réalisée établissant le lien fort entre la microstructure (porosité, orientation et taille des particules) et les propriétés électromagnétiques du composite. Le potentiel industriel, tant d'un point de vue de l'élaboration que des performances, a pu être démontré. / Research on new microwave absorbing materials has become a major issue with the growing development of wireless communications and, accordingly, the need to shield effectively from the electromagnetic "pollution" (protection of equipment and persons).In this manuscript, we focus on an anisotropic composite consisting of aligned ferromagnetic flakes embedded in a nonmagnetic matrix. There is currently a growing interest for this kind of composite in the community due to the many benefits it provides (adjustment of the absorption band as a function of both nature and flakes aspect ratio, thin composite coating). The scope of this study was deliberately relatively large in order to get an overview of issues related to these flakes composites at several scales. At first, an original study was conducted on a single flake. After preliminary work on the development of flakes and their morphological properties, static and dynamic magnetic characterizations were performed on a single flake. The permeability spectrum obtained shows three resonances. A complementary study on objects of the same size, produced by PVD and structured by FIB has, by analogy, attributed these three resonances to respectively, domains, domains wall and an embedded vortex (vortex linked with several domains walls).In a second step, the evolution of the shorted microstrip permeametry technique made possible the detailed and complete characterization of thick composites with or without a static magnetic field applied in different directions and for various pumping directions. This confirmed the origin of the different resonances despite the characteristic structural disorder of composite media.Finally, an applicative study was conducted establishing the strong link between the microstructure (porosity, particle size and orientation) and the electromagnetic properties of the composite. Taking into consideration both elaboration and performance point of views, the industrial potential of this composite has been demonstrated.

Neste trabalho foram produzidas dispersões aquosas poliuretânicas com formulações variadas, obtidas pelo processo em duas etapas. Na primeira etapa foi obtido um prepolímero e na segunda etapa, através da reação de extensão de cadeia foi obtido o polímero final. Nas sínteses foram empregados o diisocianato de isoforona (IPDI) e como polióis o poli(glicol propilênico) (PPG) e três diferentes tipos de polibutadieno líquido hidroxilado (HTPB) comerciais. A fim de possibilitar a dispersão dos poliuretanos em água, foi introduzido em sua estrutura o ácido dimetilolpropiônico (DMPA), que após neutralização com trietilamina (TEA) forneceu os sítios iônicos responsáveis pela estabilidade das dispersões em água. Como extensor de cadeia foi utilizado a hidrazina (HYD). As dispersões aquosas poliuretânicas obtidas foram avaliadas quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade. Os filmes formados a partir dessas dispersões foram avaliados quanto à sua aparência visual, propriedades mecânicas, estabilidade térmica por análise termogravimétrica (TGA) e espectroscopia na região do infravermelho (FTIR). Todas as dispersões obtidas apresentaram teor de sólidos totais entre 31 a 45% e tamanho de partícula na faixa de 70 a 221 nm. / In this work polyurethane aqueous dispersions with varied compositions, synthesized by a two steps process were produced. On the first step it was obtained a prepolymer and on the second one, by the reaction of chain extension with hydrazine (HYD) was obtained the final polymer. In the prepolymer synthesis, diisocyanate of isophorone (IPDI), poly(propylene glycol) (PPG), three different types of hydroxy-terminated polybutadienes (HTPB) and, in order to make possible the polyurethane dispersion in water, dimethylol propionic acid (DMPA), were employed. Afterwards the acid groups were neutralized with triethylamine (TEA) to provide the ionic groups responsible for the dispersion stability in water. The polyurethane aqueous dispersions produced in this work were evaluated through the solids content, particle size and viscosity. The films formed from these dispersions were characterized by their visual appearance, mechanical properties, thermal stability (TGA) and by infrared spectroscopy (FTIR). All the obtained dispersions presented solids content between 31 to 45 percent (m/m) and particle size between 70 to 221 nm.