A detailed study of the lithiation of iron phosphate as well as the development of a novel synthesis of lithium iron silicate as cathode material for lithium-ion batteries

Dans cette thèse nous démontrons le travail fait sur deux matériaux de cathodes pour les piles lithium-ion. Dans la première partie, nous avons préparé du phosphate de fer lithié (LiFePO4) par deux méthodes de lithiation présentées dans la littérature qui utilisent du phosphate de fer (FePO4) amorphe comme précurseur. Pour les deux méthodes, le produit obtenu à chaque étape de la synthèse a été analysé par la spectroscopie Mössbauer ainsi que par diffraction des rayons X (DRX) pour mieux comprendre le mécanisme de la réaction. Les résultats de ces analyses ont été publiés dans Journal of Power Sources. Le deuxième matériau de cathode qui a été étudié est le silicate de fer lithié (Li2FeSiO4). Une nouvelle méthode de synthèse a été développée pour obtenir le silicate de fer lithié en utilisant des produits chimiques peu couteux ainsi que de l’équipement de laboratoire de base. Le matériau a été obtenu par une synthèse à l’état solide. Les performances électrochimiques ont été obtenues après une étape de broyage et un dépôt d’une couche de carbone. Un essai a été fait pour synthétiser une version substituée du silicate de fer lithié dans le but d’augmenter les performances électrochimiques de ce matériau.

M'affirmer, ce n'est pas sorcier : programme visant à prévenir le risque de victimisation chez les enfants de maternelle en améliorant leur capacité à s'affirmer positivement

Rapport d'analyse d'intervention présenté à la Faculté des arts et sciences en vue de l'obtention du grade de Maîtrise ès sciences (M. Sc.) en psychoéducation.

Isolation and identification of native microalgae for biodiesel production

La demande croissante en carburants, ainsi que les changements climatiques dus au réchauffement planétaire poussent le monde entier à chercher des sources d’énergie capables de produire des combustibles alternatifs aux combustibles fossiles. Durant les dernières années, plusieurs sources potentielles ont été identifiées, les premières à être considérées sont les plantes oléagineuses comme source de biocarburant, cependant l’utilisation de végétaux ou d’huiles végétales ayant un lien avec l’alimentation humaine peut engendrer une hausse des prix des denrées alimentaires, sans oublier les questions éthiques qui s’imposent. De plus, l'usage des huiles non comestibles comme sources de biocarburants, comme l’huile de jatropha, de graines de tabac ou de jojoba, révèle un problème de manque de terre arable ce qui oblige à réduire les terres cultivables de l'industrie agricole et alimentaire au profit des cultures non comestibles. Dans ce contexte, l'utilisation de microorganismes aquatiques, tels que les microalgues comme substrats pour la production de biocarburant semble être une meilleure solution. Les microalgues sont faciles à cultiver et peuvent croitre avec peu ou pas d'entretien. Elles peuvent ainsi se développer dans des eaux douces, saumâtres ou salées de même que dans les terres non cultivables. Le rendement en lipide peut être largement supérieur aux autres sources de biocarburant potentiel, sans oublier qu’elles ne sont pas comestibles et sans aucun impact sur l'industrie alimentaire. De plus, la culture intensive de microalgues pour la production de biodiesel pourrait également jouer un rôle important dans l'atténuation des émissions de CO2. Dans le cache de ce travail, nous avons isolé et identifié morphologiquement des espèces de microalgues natives du Québec, pour ensuite examiner et mesurer leur potentiel de production de lipides (biodiesel). L’échantillonnage fut réalisé dans trois régions différentes du Québec: la région de Montréal, la gaspésie et le nord du Québec, et dans des eaux douces, saumâtres ou salées. Cent souches ont été isolées à partir de la région de Montréal, caractérisées et sélectionnées selon la teneur en lipides et leur élimination des nutriments dans les eaux usées à des températures différentes (10 ± 2°C et 22 ± 2°C). Les espèces ayant une production potentiellement élevée en lipides ont été sélectionnées. L’utilisation des eaux usées, comme milieu de culture, diminue le coût de production du biocarburant et sert en même temps d'outil pour le traitement des eaux usées. Nous avons comparé la biomasse et le rendement en lipides des souches cultivées dans une eau usée par apport à ceux dans un milieu synthétique, pour finalement identifié un certain nombre d'isolats ayant montré une bonne croissance à 10°C, voir une teneur élevée en lipides (allant de 20% à 45% du poids sec) ou une grande capacité d'élimination de nutriment (>97% d'élimination). De plus, nous avons caractérisé l'une des souches intéressantes ayant montré une production en lipides et une biomasse élevée, soit la microalgue Chlorella sp. PCH90. Isolée au Québec, sa phylogénie moléculaire a été établie et les études sur la production de lipides en fonction de la concentration initiale de nitrate, phosphate et chlorure de sodium ont été réalisées en utilisant de la méthodologie des surfaces de réponse. Dans les conditions appropriées, cette microalgue pourrait produire jusqu'à 36% de lipides et croitre à la fois dans un milieu synthétique et un milieu issu d'un flux secondaire de traitement des eaux usées, et cela à 22°C ou 10°C. Ainsi, on peut conclure que cette souche est prometteuse pour poursuivre le développement en tant que productrice potentielle de biocarburants dans des conditions climatiques locales.

Conservative upwind difference schemes for the Euler equations for real gas flows in a duct

In a recent paper [P. Glaister, Conservative upwind difference schemes for compressible flows in a Duct, Comput. Math. Appl. 56 (2008) 1787–1796] numerical schemes based on a conservative linearisation are presented for the Euler equations governing compressible flows of an ideal gas in a duct of variable cross-section, and in [P. Glaister, Conservative upwind difference schemes for compressible flows of a real gas, Comput. Math. Appl. 48 (2004) 469–480] schemes based on this philosophy are presented for real gas flows with slab symmetry. In this paper we seek to extend these ideas to encompass compressible flows of real gases in a duct. This will incorporate the handling of additional terms arising out of the variable geometry and the non-ideal nature of the gas.

Numerical study of 2D heat transfer in a scraped surface heat exchanger

A numerical study of fluid mechanics and heat transfer in a scraped surface heat exchanger with non-Newtonian power law fluids is undertaken. Numerical results are generated for 2D steady-state conditions using finite element methods. The effect of blade design and material properties, and especially the independent effects of shear thinning and heat thinning on the flow and heat transfer, are studied. The results show that the gaps at the root of the blades, where the blades are connected to the inner cylinder, remove the stagnation points, reduce the net force on the blades and shift the location of the central stagnation point. The shear thinning property of the fluid reduces the local viscous dissipation close to the singularity corners, i.e. near the tip of the blades, and as a result the local fluid temperature is regulated. The heat thinning effect is greatest for Newtonian fluids where the viscous dissipation and the local temperature are highest at the tip of the blades. Where comparison is possible, very good agreement is found between the numerical results and the available data. Aspects of scraped surface heat exchanger design are assessed in the light of the results. (C) 2003 Elsevier Ltd. All rights reserved.

Local oscillator phase lock under multipath for video deghoster systems

Under multipath conditions, standard Video Intermediate Frequency (VIF) detectors generate a local oscillator phase error and consequently produce a dispersed non-ideal detected video signal due to the presence of additional IF carriers. The dispersed video causes problems when attempting to identify and remove the multipath interference, or ghosts, by the use of Digital Signal Processing and digital filtering. A digital phase lock system is presented which derives the correct phase for synchronous detection in the presence of multipath by using correlation information that has already been calculated as part of the deghosting process. As a result, the video deghoster system is made simpler, faster and more economical.

Phosphorus loss from agricultural catchments: pathways and implications for management

The contribution non-point P sources make to the total P loading on water bodies in agricultural catchments has not been fully appreciated. Using data derived from plot scale experimental studies, and modelling approaches developed to simulate system behaviour under differing management scenarios, a fuller understanding of the processes controlling P export and transformations along non-point transport pathways can be achieved. One modelling approach which has been successfully applied to large UK catchments (50-350km2 in area) is applied here to a small, 1.5 km2 experimental catchment. The importance of scaling is discussed in the context of how such approaches can extrapolate the results from plot-scale experimental studies to full catchment scale. However, the scope of such models is limited, since they do not at present directly simulate the processes controlling P transport and transformation dynamics. As such, they can only simulate total P export on an annual basis, and are not capable of prediction over shorter time scales. The need for development of process-based models to help answer these questions, and for more comprehensive UK experimental studies is highlighted as a pre-requisite for the development of suitable and sustainable management strategies to reduce non-point P loading on water bodies in agricultural catchments.

The "Fair trade nation": market-oriented development in devolved European regions

Scholars have largely ignored the roles played by government and public sector institutions in the fair trade movement. This article addresses the knowledge gap through examining government involvement in fair trade networks in the context of European devolution and the localization of international development action. Proposing a relational view of fair trade networks, and considering the Fair Trade Nation as a social category for development, it highlights how power sources outside the centralized nation-state permit a political community to associate itself with fair trade. Research from Wales demonstrates that government acts in a leadership role rather than as regulator, conferring political voice and finance while enhancing its international credentials and contributing to the politics of nation-building. Our conclusion is cautious; campaigners celebrate political commitment to fair trade embodied within the category of the Fair Trade Nation, but evidence suggests that government reliance on the market as a vehicle for decentralized development action is limited by how the Fair Trade Nation is currently executed.

The role of horizontal resolution in simulating drivers of the global hydrological cycle

The role of atmospheric general circulation model (AGCM) horizontal resolution in representing the global energy budget and hydrological cycle is assessed, with the aim of improving the understanding of model uncertainties in simulating the hydrological cycle. We use two AGCMs from the UK Met Office Hadley Centre: HadGEM1-A at resolutions ranging from 270 to 60 km, and HadGEM3-A ranging from 135 to 25 km. The models exhibit a stable hydrological cycle, although too intense compared to reanalyses and observations. This over-intensity is explained by excess surface shortwave radiation, a common error in general circulation models (GCMs). This result is insensitive to resolution. However, as resolution is increased, precipitation decreases over the ocean and increases over the land. This is associated with an increase in atmospheric moisture transport from ocean to land, which changes the partitioning of moisture fluxes that contribute to precipitation over land from less local to more non-local moisture sources. The results start to converge at 60-km resolution, which underlines the excessive reliance of the mean hydrological cycle on physical parametrization (local unresolved processes) versus model dynamics (large-scale resolved processes) in coarser HadGEM1 and HadGEM3 GCMs. This finding may be valid for other GCMs, showing the necessity to analyze other chains of GCMs that may become available in the future with such a range of horizontal resolutions. Our finding supports the hypothesis that heterogeneity in model parametrization is one of the underlying causes of model disagreement in the Coupled Model Intercomparison Project (CMIP) exercises.

Playing Kant at the Court of King Arthur

This article contrasts the sense in which those whom Bernard Williams called ‘political realists’ and John Rawls are committed to the idea that political philosophy has to be distinctively political. Distinguishing the realist critique of political moralism from debates over ideal and non-ideal theory, it is argued that Rawls is more realist than many realists realise, and that realists can learn more about how to make a distinctively political vision of how our life together should be organised from his theorising, although it also points to a worrying tendency among Rawlsians to reach for inappropriately moralised arguments. G. A. Cohen’s advocacy of socialism and the second season of HBO’s The Wire are used as examples to illustrate these points.

Electrocatalysis of oxygen reduction on carbon-supported Pt-Co nanoparticles with low Pt content

The oxygen reduction reaction (ORR) was investigated on carbon-supported Pt-Co nanoparticle electrocatalysts with low Pt content in alkaline electrolyte. High resolution transmission electron microscopy, In situ X-ray absorption spectroscopy, and X-ray diffraction analysis evidenced large structural differences of the Pt-Co particles depending oil the route of the catalyst synthesis. It was demonstrated that although the Pt-Co materials contain low amounts of Pt, they show very good activities when the particles are formed by a Pt-rich shell and a Pt-Co core, which was obtained after submitting the electrocatalyst to a potential cycling in acid electrolyte. The high activity of this material was due to a major contribution from its higher surface area, as a result of the leaching of the Co atoms from the particle Surface. Furthermore, its high activity was ascribed to a minor contribution from the electronic interaction of the Pt atoms, at the particle surface, and the Co atoms located in the beneath layer, lowering the Pt cl-band center. As these electrocatalysts presented high activity for the ORR with low Pt content, the cost of the fuel cell cathodes could be lowered considerably. (c) 2009 Elsevier B.V. All rights reserved.

Hydrogen production by steam reforming of ethanol over Ni-based catalysts promoted with noble metals

The catalytic activity of Ni/La(2)O(3)-Al(2)O(3) Catalysts modified with noble metals(Pt and Pd) was investigated in the steam reforming of ethanol. The catalysts were characterized by ICP, S(BFT), X-ray diffraction, temperature-programmed reduction, UV-vis diffuse reflectance spectroscopy and X-ray absorption fine structure (XANES). The results showed that the formation of inactive nickel aluminate was prevented by the presence of La(2)O(3) dispersed on the alumina. The promoting effect of noble metals included a marked decrease in the reduction temperatures of NiO species interacting with the support. due to the hydrogen spillover effect, facilitating greatly the reduction of the promoted catalysts. it was seen that the addition of noble metal stabilized the Ni sites in the reduced state throughout the reaction, increasing ethanol conversion and decreasing coke formation, irrespective of the nature or loading of the noble metal. (C) 2009 Elsevier B.V. All rights reserved.

Modeling and simulation of the anode in direct ethanol fuels cells

Mathematical modeling has been extensively applied to the study and development of fuel cells. In this work, the objective is to characterize a mechanistic model for the anode of a direct ethanol fuel cell and perform appropriate simulations. The software Comsol Multiphysics (R) (and the Chemical Engineering Module) was used in this work. The software Comsol Multiphysics (R) is an interactive environment for modeling scientific and engineering applications using partial differential equations (PDEs). Based on the finite element method, it provides speed and accuracy for several applications. The mechanistic model developed here can supply details of the physical system, such as the concentration profiles of the components within the anode and the coverage of the adsorbed species on the electrode surface. Also, the anode overpotential-current relationship can be obtained. To validate the anode model presented in this paper, experimental data obtained with a single fuel cell operating with an ethanol solution at the anode were used. (C) 2008 Elsevier B.V. All rights reserved.

Nickel catalysts supported on ZrO2, Y2O3-stabilized ZrO2 and CaO-stabilized ZrO2 for the steam reforming of ethanol: Effect of the support and nickel load

Catalysts with various nickel loads were prepared on supports of ZrO2, ZrO2-Y2O3 and ZrO2-CaO, characterized by XRD and TPR and tested for activity in ethanol steam reforming. XRD of the supports identified the monoclinic crystalline phase in the ZrO2 and cubic phases in the ZrO2-Y2O3 and ZrO2-CaO supports. In the catalysts, the nickel impregnated on the supports was identified as the NiO phase. In the TPR analysis, peaks were observed showing the NiO phase having different interactions with the supports. In the catalytic tests, practically all the catalysts achieved 100% ethanol conversion, H-2 yield was near 70% and the gaseous concentrations of the other co-products varied in accordance with the equilibrium among them, affected principally by the supports. It was observed that when the ZrO2 was modified with Y2O3 and CaO, there were big changes in the CO and CO2 concentrations, which were attributed to the rise in the number of oxygen vacancies, permitting high-oxygen mobility and affecting the gaseous equilibrium. The liquid products analysis showed a low selectivity to liquid co-products during the reforming reactions. (c) 2007 Published by Elsevier B.V.

Production of hydrogen by ethanol steam reforming on Co/Al2O3 catalysts: Effect of addition of small quantities of noble metals

The catalytic performance of Co/Al2O3 catalysts promoted with small amounts noble metals (Pt, Pd, Ru, Ir) for steam reforming of ethanol (SRE) has been investigated. The catalysts were characterized by the energy dispersive X-ray, X-ray diffraction, BET surface area, X-ray absorption fine structure and temperature reduction programmed techniques. The results showed that the promoting effect of noble metals included a marked decrease of the reduction temperatures of both Co3O4 and cobalt surface species interacting with the support due to the hydrogen spillover effect, leading to a significant increase of the reducibilities of the promoted catalysts. The better catalytic performance for the ethanol steam reforming at 400 degrees C was obtained for the CoRu/Al2O3 catalyst, which presented an effluent gaseous mixture with the highest H, selectivity and the reasonable low CO formation. (C) 2007 Published by Elsevier B.V.