Ce travail de thèse a pour but d'étudier la fixation d'azote marine dans les environnements riches mais déficitaires en azote (N), comparé au phosphore (P) dans un rapport N:P<16, grâce à l'utilisation d'approches complémentaire en culture in vitro et sur le terrain in situ. La première partie de ce travail a consisté à évaluer la réponse de la fixation d'azote de la cyanobactérie unicellulaire diazotrophe Crocosphaera watsonii face à des concentrations micromolaires en azote inorganique dissous (DIN) supposées inhiber l'activité de fixation d'azote : - suite à un apport sporadique, ou, - après une longue période d'acclimatation. Les résultats de ces études n'ont pas permis d'observer une inhibition des activités de fixation d'azote de cet organisme, laissant supposer que ce processus pourrait être actif dans une zone de l'Océan ayant ces même caractéristiques biogéochimiques : le Sud Est Tropical de l'Océan Pacifique (ETSP). En effet, cette zone est une des trois plus grandes zones de minimum d'oxygène (OMZ) de l'Océan et d'intenses processus de pertes de N (dénitrification et anammox) y ont lieu, résultant en un déficit de N par rapport au P. Des études présumaient que des processus inverses, de gains de N par la fixation d'azote, pourraient y être actifs mais aucune mesure à l'échelle du bassin n'y avait été faite car la fixation d'azote n'était supposée se produire que dans les environnements oligotrophes, comme les gyres subtropicaux. Dans le cadre d'un projet international, des missions océanographiques ont pu avoir lieu dans cette zone en Février 2010 pendant un évènement El Niño et en Mars-Avril 2011 pendant un évènement La Niña. / The objectif of these thesis was to study dinitrogen fixation in marine environments rich but deficient of nitrogen (N) compared to phosphorus (P) in a ratio N:P<16, by using complementary approaches in culture in vitro and in the field in situ. The first part of this work was to evaluate the response of nitrogen-fixing unicellular Cyanobacteria Crocosphaera watsonii faced with micromolar concentrations of dissolved inorganic nitrogen (DIN) supposed to inhibit nitrogen fixation activity : - after sporadic input, or, - after a long period of acclimatization. The results of these studies have failed to observe the inhibition of nitrogen fixation activities of this organism, suggesting that this process could be active in an area of the Ocean with these same biogeochemical characteristics : the Eastern Tropical South Pacific (ETSP). Indeed, this area is one of the three largest oxygen minimum zones (OMZ) of the Ocean, where intense processes of N losses (denitrification and anammox) took place, resulting in a deficit of N compared to P. Studies assumed that the inverse process, gain of N by nitrogen fixation, could be active in the ETSP but no measurements across the basin have been performed because nitrogen fixation was assumed to occur only in oligotrophic environments, such as the subtropical gyres. In the framework of an international project, cruises took place in this area in February 2010 during a El Niño event and in March-April 2011 during a La Niña event. Results of these two cruises have confirmed that nitrogen fixation was unexpectedly active with an intensity comparable to those reported in oligotrophic areas.

This study examined the effect of an 8-week, progressive exercise intervention on neural responses, specifically N2 amplitude as a measure of inhibitory control, to pictures of food. Healthy women ages 18-44 years were randomized to a morning (AM) exercise group or evening (PM) exercise group. The AM group did moderate-to-vigorous intensity exercise on 4 days per week between 6:30 and 9:30 a.m. while the PM group had the identical volume of exercise between 6:30 and 9:30 p.m. Neural responses, eating behaviors, cardiovascular fitness outcomes, and body weight/composition were measured at baseline and after the 8-week intervention. The N2 amplitude in response to pictures of high- and low-calorie foods was assessed using electroencephalography during a go/no-go task. Dietary restraint, emotional eating, and external eating were assessed using the Dutch Eating Behavior Questionnaire. VO2peak, HRmax, and time to completion were measured during a maximal treadmill test. Body weight was measured on a digital scale, and body composition was measured using dual-energy x-ray absorptiometry. There was not a significant task (go, no-go) × group (AM, PM) × period (baseline, 8 weeks) interaction (F = 0.18; p = 0.677), but there was a main effect of exercise over 8 weeks (F = 6.26; p = 0.017) with increased N2 amplitude following the intervention. There was not a significant interaction as a function of picture type (high-calorie, low-calorie), task, group, and period (F = 0.52; p = 0.478). Changes in body weight and neural outcomes were not significantly associated with changes in eating behaviors for either group (ps < 0.05). There was a significant group × period interaction for body weight (F = 4.90; p = 0.032). Body weight increased by 0.79 ± 1.16 kg in the AM group and decreased by 0.21 ± 1.46 kg in the PM group (effect size = 0.77; CI = 0.15-1.35). There was not a significant group × period interaction for body fat percentage, total body fat or fat-free mass (ps < 0.05). When examining the main effect of exercise on cardiovascular fitness outcomes, VO2peak was not different (F = 1.80; p = 0.187), time-to-completion on treadmill increased (F = 6.51; p = 0.014), and HRmax during the treadmill test was significantly lower (F = 5.49; p = 0.025). This study suggests that 8 weeks of exercise training may increase the inhibitory response to pictures of both high- and low-calorie foods. However, time of day of exercise did not influence this response. Eight weeks of exercise training did not change self-reported dietary restraint, external eating, or emotional eating, and there was no correlation between these eating behaviors and inhibitory control. However, evening exercise was more beneficial for body weight than morning exercise. Given the novelty of this study and its results, additional studies on the influence of time of day of exercise on weight management are needed.

Ce travail s'inscrit dans le cadre de la recherche d'une alternative à l'utilisation du gaz hexafluorure de soufre (SF6) dans l'appareillage électrique Haute Tension et plus particulièrement les postes à isolation gazeuse. Ce gaz possède de bonnes propriétés diélectriques mais son potentiel de réchauffement global (GWP) est estimé à 23900 fois celui du dioxyde de carbone (CO2). Malheureusement, les gaz dits simples tels que l'azote (N2) présentent une tenue diélectrique deux à trois fois plus faible que celle du SF6. Dans le but d'améliorer la tenue diélectrique du système, on se propose d'appliquer sur les conducteurs un revêtement isolant à base de silicone constitué d'une sous-couche semi-conductrice d'épaisseur 0.5 mm et d'une couche isolante d'épaisseur 1.5 mm, afin de limiter ou supprimer le rôle des électrons du métal. Les essais diélectriques réalisés sous une tension de choc de foudre dans des conditions expérimentales proches de la pratique industrielle montrent qu'en présence de N2 la tenue diélectrique du système avec revêtement est régie par le gaz. Par conséquent, l'application du revêtement sur les conducteurs diminue la tenue diélectrique du système (effet capacitif). Ces essais montrent, cependant, qu'il est possible d'améliorer la tenue diélectrique du système avec le revêtement, en présence de SF6 en polarité négative. Les paramètres importants semblent être la propreté du gaz, le degré d'ionisation du gaz et surtout les charges qui se déposent à l'interface gaz-revêtement qui, dans certaines conditions, ont un effet bénéfique : ce dernier résultat donne une piste aux travaux futurs.

The aim of the study is to investigate matrix-fracture interaction, gas oil gravity drainage (GOGD) and diffusion mechanisms with CO2, N2 and CH4 gas injection in a fractured system. Effects of injected gas type, initial gas saturation and diffusion coefficient on oil recovery are studied by an experimental and simulation work. In the experimental study, Berea sandstone cores are placed in a core holder and the space created around the core is considered as a surrounding fracture. System is kept at a pressure of 250 psi by CO2, N2 and CH4 gases and at a reservoir temperature of 70 &deg / C. Experiments with cores having similar initial saturations resulted in the highest ndecane recovery in CO2 experiment followed by CH4 and N2. The highest solubility of CO2 in n-decane and density difference between CO2 and CO2-ndecane mixture are considered as the reason of results. CO2 injection tests with n-decane and brine saturated core with and without initial gas saturation indicate that availability of initial gas saturation in matrix increased recovery. A simulation study is continued using CMG (Computer Modeling Group Ltd.) WinProp (Microsoft Windows&trade / based Phase-Behavior and Fluid Property Program) and GEM (Generalized Equation-of-State Model Compositional Reservoir Simulator). Simulation results of CO2 experiment with initial gas show that dominant effect of GOGD decreases and diffusion becomes more effective at final production stages. Simulation study indicates an immediate, sharp decrease in oil saturation in matrix. Oil in matrix migrates into fractures and moves downward as a result of GOGD with gas injection.

Ce travail s'intéresse à la compréhension du comportement des flammes non-prémélangées issues d'un jet de méthane assisté par un coflow d'air dilué avec du CO2, ou d'autres gaz chimiquement inertes pour discriminer les différents phénomènes impliqués dans la dilution. Les phénomènes transitionnels, décrochage et extinction, quantifiés par des limites de stabilité, sont analysés à l'aide de grandeurs physiques représentatives. Le domaine de stabilité de flamme est limité par des surfaces 3D dans le domaine physique ( Qdiluant/Qair (taux de dilution), Uair (vitesse d'air), UCH4 (vitesse de méthane)), révélant un effet compétitif entre l'aérodynamique et la dilution. Des cartographies génériques de décrochage et d'extinction communes à tous ces diluants sont proposées. Des grandeurs liées à la stabilisation sont toutes soumises à des lois d'évolution auto-simlilaires. Il en ressort que la vitesse de propagation de flamme est l'élément clé du mécanisme de stabilisation lors de la dilution.

Dans cette thèse, des calculs ab initio et analytiques ont été effectués pour déterminer les surfaces d'énergie potentielle, de moment dipolaire et de polarisabilité des complexes de van der Waals faiblement liés CH4-N2 et C2H4-C2H4, pour une large gamme de distances intermoléculaires et de configurations, dans l’approximation des molécules en interaction rigides. Pour les calculs ab initio, la méthode CCSD(T), CCSD(T)-F12, ainsi que les méthodes moins couteuses MP2, MP2-F12, SAPT et DFT-SAPT ont été employées (pour toutes les méthodes,la base aug-cc-pVTZ a été utilisée). La correction BSSE a été prise en compte dans les calculs. Les calculs analytiques ont été réalisés dans le cadre de l'approximation classique aux grandes distances. Un modèle prenant en compte les effets d'échange dans la région des petits recouvrements des nuages électroniques des molécules en interaction a été suggéré pour décrire le moment dipolaire du complexe de van der Waals CH4-N2 sous une forme analytique, pour les grandes distances intermoléculaires incluant la région des puits de potentiel. Dans ce modèle, le moment dipolaire total est considéré comme résultant de la somme des contributions d'échange, d'induction et de dispersion. / In the present thesis both ab initio and analytical calculations were carried out for thepotential energy, dipole moment and polarizability surfaces of the weakly bound van der Waals complexes CH4-N2 and C2H4-C2H4 for a broad range of intermolecular separations and configurations in the approximation of the rigid interacting molecules. For ab initio calculations the CCSD(T), CCSD(T)-F12 and less computationally expensive methods such as MP2, MP2-F12, SAPT, DFT-SAPT were employed (for all methods the aug-cc-pVTZ basis set was used). The BSSE correction was taken into account during the calculations. The analytical calculations were performed in the framework of the classical long-range approximation. A model accounting the exchange effects in the range of small overlap of the electron shells of interacting molecules has been suggested to describe the dipole moment of the CH4-N2 van der Waals complexes in analytical form for large intermolecular separations including the range of potential wells. In this model the total dipole moment is considered to be the sum of exchange, induction and dispersion contributions.

Mesoporous γ-alumina is the most extensively used catalysts support in a wide range of catalytic processes. The usefulness of γ-alumina relies on its favorable combination of physical, textural, thermal, and chemical properties. Pore structure properties are among the most important properties, since high surface area and large pore volume enable higher loading of active catalytic phases, while design of pore size and pore size distribution is critical to optimize pore diffusional transport and product selectivity. In addition, accurate determination of surface area (SA), pore volume (PV) and pore size distribution (PSD) of porous supports, catalysts, and nanomaterials is vital to successful design and optimization of these materials and to the development of robust models of pore diffusional resistance and catalyst deactivation.In this dissertation, we report a simple, one-pot, solvent-deficient process to synthesize mesoporous γ-alumina without using external templates or surfactants. XRD, TEM, TGA and N2 adsorption techniques are used to characterize the morphologies and structures of the prepared alumina nanomaterials. By varying the aluminum salts or the water to aluminum molar ratio in the hydrolysis of aluminum alkoxides, γ-alumina with different morphologies and pore structures are synthesized. The obtained alumina nanomaterials have surface areas ranging from 210 m2/g to 340 m2/g, pore volumes ranging from 0.4 cm3/g to 1.7 cm3/g, and average pore widths from 4 to 18 nm. By varying the alcohols used in the rinsing and gelation of boehmite/bayerite precursors derived from a controlled hydrolysis of aluminum alkoxides, the average pore width of the γ-aluminas can be tuned from 7 to 37 nm. We also report improved calculations of PSD based on the Kelvin equation and a proposed Slit Pore Geometry model for slit-shaped mesopores of relatively large pore size (>10 nm). Two structural factors, α and β, are introduced to correct for non-ideal pore geometries. The volume density function for a log normal distribution is used to calculate the geometric mean pore diameter and standard deviation of the PSD. The Comparative Adsorption (αs) Method is also employed to independently assess mesopore surface area and volume.

Various nitrides, such as chromium nitride and titanium nitride, find extensive use in cutting tools, micromechanical devices, and medical implants due to their exceptional physical, mechanical, and chemical properties. These coatings exhibit superior hardness compared to high-speed steel and cemented carbide along with notable protective capabilities against corrosion and wear. These coatings have been successfully used to enhance the properties of cemented carbide and steel tools while safeguarding their surfaces. By adjusting deposition parameters like N2 gas pressure, the properties of PVD coatings can be tailored to effectively withstand specific dominant wear modes during machining. The study investigates and demonstrates that CrN coatings can be specifically engineered to have distinct mechanical and tribological properties by adjusting the N2 gas pressure, which enhances machining performance in cases where BUE formation occurs. A comprehensive coating characterization was conducted for each CrN coating studied. Wear performance assessments of the various CrN-coated WC tools were carried out during dry finish turning of SS 304. Additionally, high temperature coating characterization was performed for the best-performing in house deposited coating (nitrogen gas pressure of 4 Pa, bias voltage of -50 V) and a commercial coating, up to 450°C. The results highlighted the influence of N2 gas pressure on the structural, mechanical, and tribological properties of CrN coatings. The findings indicate that coatings with a comparatively low H/E ratio (while maintaining higher elastic modulus values), low roughness, moderate residual stress, high plasticity index, and high toughness exhibited superior performance when machining sticky materials and in high-temperature applications prone to adhesive wear and built-up edge (BUE) formation. Furthermore, high-temperature studies confirmed that the in-house coating retained a low H/E ratio, high plasticity index, high toughness, and low roughness, without compromising the hardness or elastic modulus values. In contrast, the commercial coating failed to retain its properties at higher temperatures. These high-temperature studies provide valuable insights for selecting CrN coatings tailored for machining materials that tend to adhere to the cutting tool and for high-temperature applications. / Dissertation / Master of Applied Science (MASc) / Coating properties such as hardness, residual stress, adhesive behaviour, elastic modulus, and roughness significantly affect tool performance and wear patterns, besides machining parameters and conditions. This research focuses on CrN coatings deposited by PVD cathodic arc deposition, adjusting the N2 gas pressure while keeping bias voltage constant. The research investigates and illustrates that CrN coatings can be specifically tailored (by adjusting the N2 gas pressure) to possess unique mechanical, and tribological properties that ameliorate machining performance in scenarios involving BUE formation. Three CrN coatings were deposited using the PVD technique by varying the N2 gas pressure. A thorough coating characterization was conducted for each of three in house deposited coatings and one commercially available coating. The wear behaviour of different CrN-coated WC tools was evaluated during dry finish turning of SS 304 to identify the best-performing coating. Lastly, high-temperature coating characterization was performed up to 450 ˚C for one in-house deposited coating (nitrogen gas pressure of 4 Pa, bias voltage of -50 V) and one commercial coating. The results showed that a coating that has low H/E ratio (without compromising elastic modulus), high plasticity index, high toughness, moderate residual stress and low roughness effectively minimizes issues related to sticking and BUE formation and retains coating properties at high temperatures.

No description available.

The soft x-rays (wavelengths less than 30 nm) emitted by the sun are responsible for the production of high energy photoelectrons in the D and E regions of the ionosphere, where they deposit most of their energy. The photoelectrons created by this process are the main drivers for dissociation of nitrogen ($N_2$) molecules in the altitude range below 200 km. The dissociation of $N_2$ is one of main mechanisms responsible for the production of nitric oxide (NO) at these altitudes. These processes are important to understand because NO plays a critical role in controlling the temperatures of various regions of Earth's atmosphere. In order to estimate the dissociation rate of $N_2$ we need its dissociation cross-sections. The dissociation cross-sections of $N_2$ due to inelastic collisions with electrons is primarily es- timated from the cross-sections of its excitation states (using predissociation factors) and dissociative ionization channels. Predissociation is the transition without emission of radi- ation from a stable excited state to an unstable excited state of a molecule that leads to dissociation. Unfortunately, the lack of cross-section data, particularly at high electron en- ergies and of higher excited states of N 2 and N 2 + , introduces uncertainty in the dissociation cross-section and subsequently the dissociation rate calculation, which leads to uncertainties in the NO production rate. We have updated a photoelectron model with thoroughly-revised electron impact cross- section data of all major species and experimentally determined predissociation factors. The dissociation rates of $N_2$ using this model are compared to the dissociation rates obtained using another existing (Solomon and Qian [2005]) model. A parameterized version of the updated dissociation rates are used in a one-dimensional global average thermospheric/ ionospheric model, ACE1D (Atmospheric Chemistry and Energetics), to obtain the updated production rates of NO. In the final chapter, we use the ACE1D model to show that the energies deposited by the solar soft x-rays in the lower thermosphere at altitudes between 100 -150 km affect the temperature of the Earth's thermosphere at altitudes well above 300 km. By turning off the input solar flux in the different wavelength bins of the model iteratively, we are able to demonstrate that the maximum change in exospheric temperature is due to changes in the soft solar x-ray bins. We also show, using the thermodynamic heat equation, that the molecular diffusion via non-thermal photoelectrons is the main source of heat transfer to the upper ionosphere/thermosphere. Moreover, these temperature changes and heating effects of the solar soft x-rays are comparable to that of the much stronger He II 30.4nm emission. Finally, we show that the uncertainties in the solar flux irradiance at these soft x-rays wavelengths result in corresponding uncertainties in the modeled exospheric temperature, and these uncertainties increase substantially with increased solar activity. / Doctor of Philosophy / The radiation from the sun covers a wide range of the electromagnetic spectrum. The soft x-rays with wavelengths less than 30 nm are the most energetic and variable part of the spectrum, and would have detrimental effects on humans were they not absorbed by the atmosphere. The absorption of soft x-rays by the Earth's atmosphere at altitudes near 100- 150 km creates ionized and energized particles. These energetic changes can affect and even damage the satellites in low Earth orbit, and can cause radio communication blackouts and radiation storms (large quantities of energetic particles, protons and electrons accelerated by processes at and near the Sun). Therefore, we need to have good models that can quantify these changes in order to correctly predict their effects on our atmosphere, and help to mitigate any harmful effects. The soft x-rays and the extreme ultraviolet (EUV) are responsible for ionization of the major neutral species, $N_2$ , $O_2$ and O, in the Earth's atmosphere, which leads to the production of ions and energetic photoelectrons. These high energy photoelectrons can cause further ion- ization, excitation and dissociation. We study the dissociation of $N_2$ by these photoelectrons to create neutral N atoms. The N atoms created via this process combine with the $O_2$ in the atmosphere to produce nitric oxide (NO), which is one of the most important minor constituents because of its role in regulating atmospheric heating/cooling. The production of NO peaks near 106 km altitude, where most of the energy of the soft x-rays are deposited. However, they also affect the temperature of the upper atmosphere well above this altitude. This is because the energy of the photoelectrons is conducted to the upper atmosphere by collisions of electrons and ions with ambient neutral atoms and molecules, thus increasing their temperature. In this study, we use modeling of soft x-ray irradiance, photoelectron ionization, excitation and dissociation rates and atmospheric neutral temperature to quantify the effects of soft x-rays on the Earth's atmosphere.