This study describes the development of a novel thin membrane exchange assembly (MEA) from a solid acid material, cesium hydrogen sulfate (CsHSO4), and from a composite anode electrocatalyst for electrolytic splitting of (100 %) H2S feed content gas operating at 135 kPa and 150 °C. A new class of anode electrocatalyst with the general composition, RuO2/CoS2, and an improved proton conductor, CsHSO4, have shown great stability and desired properties at typical operating conditions. This configuration demonstrated stable electrochemical operation for 24 h with a (100 %) H2S fuel stream at 423 K. This same system showed a maximum current density of (19 mA/cm²) at 900 mV. The performance of this new anode electrocatalyst when compared to that of Pt black investigated in a previous study showed an overall superiority in application. We have achieved a 30 % reduction in the overall system performance by fabricating a thin (200 µm) CsHSO4 electrolyte, which reduced the whole MEA thickness from 2.3 mm to 500 µm. The result of permeability measurements proved that this thin solid electrolyte is impermeable to H2S gas and physical integrity was preserved throughout the experimental period. Further resistance losses were compensated by using a high energy planetary milling system to enhance the ionic conductivity of CsHSO4. The difference in stability and electrochemical performance of these cells compared to that of Pt anode based systems is directly attributable to the anode materials developed in this project. Factorial experiments were used to characterize the effect of controllable process variables (electrolyte thickness, time, age of the electrolyte) on the cell current density and interfacial polarization resistances. As expected, cell current density and interfacial polarization resistances were a function of electrolyte thickness and age. Nevertheless, the effect of electrolyte thickness has a more prominent effect on the measured parameters. In addition, these experiments were used to identify regions of optimum system performance. Tafel plots were constructed to investigate the kinetic behavior of various anode based electrocatalysts. Exchange current densities, which are directly a measure of the electrochemical reaction, increased with RuO2/CoS2-based anodes. These experiments also suggested that high levels of feed utilization were possible using these materials. This was an impressive result considering the drastic improvement in electrochemical performance, current density, and sulfur tolerance compared to the other anode configurations.

Frequently, in evaluating plant deficiencies, one considers only those soil factors which are associated with the fertility of the soil-- mainly the levels of phosphorus, potash, nitrogen, and organic matter. A certain level of nutrition is essential for plant growth, but in order for the nutrients to exert their maximum influence on the productivity of the soil, it is equally important that a good soil environment be provided and maintained. A good environment requires that good physical conditions of soil, sir, and water be in balance.

Cette thèse a permis d’évaluer l’effet des changements de morphologie d’un matériau cimentaire soumis à un traitement thermique jusqu’à T (≤ 400°C). Pour cela, nous avons caractérisé expérimentalement le comportement mécanique (en compression uniaxiale, compression hydrostatique avec ou sans déviateur), poro-mécanique (modules d’incompressibilité Kb, Ks et coefficient de Biot b) et hydraulique (perméabilité au gaz), d’un mortier modèle E/C=0,5 suite à un cycle de chauffage/refroidissement. Les essais mécaniques multiaxiaux sont couplés aux mesures de perméabilité, qui servent d’indicateur de la progression de la fissuration du matériau sous contrainte. Nous avons également mis au point un essai original, permettant de quantifier le volume de l’espace poreux interconnecté sous chargement hydrostatique Pc. La création de porosité occluse sous l’effet d’un accroissement du confinement est confirmée, et ainsi la diminution de la rigidité de la matrice solide Ks avec Pc après traitement thermique T>200°C. Nous avons également identifié un effet bouchon (aucun passage de gaz) lors d’un chargement couplé, thermique et en compression hydrostatique du mortier mais aussi de bétons industriels (CERIB et ANDRA). Afin d’analyser l’évolution des propriétés mécaniques et poro-élastiques après traitement thermique, un modèle prédictif thermo-élasto-plastique avec endommagement isotrope et une approche micro-mécanique descriptive, intégrant la présence de micro-fissures, y sont couplés / This work investigates the effects of morphological changes of a cement-based material subjected to heat treatment (up to 400°C). For a model W/C=0.5 mortar, we have characterized experimentally hydraulic behaviour (gas permeability), mechanical behaviour (in uniaxial compression, hydrostatic compression with or without deviatoric stress) and poro-mechanical behaviour (incompressibility moduli Kb, Ks and Biot’s coefficient b) after a heating/cooling cycle. We have also developed an original experiment aimed at quantifying the accessible pore space volume under hydrostatic compression. The creation of occluded porosity under high confinement is confirmed, which justifies the observed decrease of solid matrix rigidity Ks under high confinement. A gas retention phenomenon was identified under simultaneous thermal and hydrostatic loadings for mortar, and industrial concretes (provided by CERIB and ANDRA). A predictive thermo-elasto-plastic model with isotropic damage and a micro-mechanical approach, which represents micro-cracking, are coupled in order to analyze or predict the evolution of mechanical and poro-elastic properties after heat cycling

MY-24 is an aristeromycin derivative previously shown to protect AG129 type I and II interferon receptor knockout mice from lethal challenge with Tacaribe virus (TCRV). TCRV is nonpathogenic to humans, but is closely related to the highly pathogenic New World arenaviruses that cause often-fatal viral hemorrhagic fever syndromes. Remarkably, MY-24 prevented mortality without reducing TCRV burden in the circulation or tissues. To investigate the mechanism by which MY-24 protects AG129 mice against TCRV infection, we first characterized the natural history of disease in the model with an emphasis on cytokine responses and vascular integrity to establish the best times to evaluate the effects of MY-24 treatment on host responses believed to contribute to pathogenesis and fatal outcome. We found that viral replication in the blood and in various tissues precedes a hyperproduction of proinflammatory mediators that may lead to the destabilization of the endothelial barrier and increased vascular leakage believed to contribute to terminal shock associated with severe cases of hemorrhagic fever. We also found slightly reduced virus titers in certain tissues from MY-24-treated mice, suggesting that there may be a weak antiviral effect; however, TCRV was not cleared from lung, spleen, brain or kidney in recovering animals out to 40 days post-infection, indicative of the establishment of chronic infection in mice that are able to survive the initial challenge. Neutralizing antibodies do not appear to play a major role in the antiviral effect of MY-24, whereas reductions in several key proinflammatory cytokines in mice treated with MY-24 may serve to reduce vascular leakage caused by TCRV infection.

Bentonite clay is widely used in barrier systems due to its low hydraulic conductivity and it high swell capacity. Exposure to inorganic solutions can cause significant increases in hydraulic conductivity, due to changes in the surface chemistry and fabric. This phenomenon can be attributed to a reduction in the thickness of the double layer, due to the cation exchange capacity of the clay. The clay can be modified with polymers to render it less susceptible to chemical attack. The treatment process allows the clay to be engineered to enhance specific properties, such as permeability and sorption. In the present study, engineered soils are prepared by sorbing organic polymers to the surface of Na-bentonite. Three classes, cationic, anionic and nonionic polymers are investigated. The sorbents are water-soluble compounds based on the polymerization of acrylamides (PAM). Mixing and sample preparation techniques are developed and discussed. The interaction of the polymeric compounds and the clay mineral surface are evaluated by testing the liquid limit, swell index and specific gravity of the soils. Permeability tests are performed to determine if the polymer treatment enhances the hydraulic performance of the clay when permeated with highly concentrated salt solutions. The effect of permeant, void ratio, initial wetting condition and preparation techniques are found to have a significant affect on the hydraulic conductivity.

Le mélanome cutané est l'un des cancers les plus agressifs et mortel capables de dissémination métastatique à distance. L’intravasation cellules tumorales dans le vaisseau sanguin dans les tumeurs primaires et l'extravasation sont des étapes importantes dans la formation de métastases. Ces étapes impliquent la perturbation de la barrière endothéliale par des cellules tumorales afin de faciliter leur migration transendothéliale et la colonisation métastatique. Cependant, le processus par lequel les cellules tumorales modulent l'intégrité des jonctions vasculaires est encore mal compris. Afin de déterminer les facteurs de perméabilité sécrétés par les cellules métastatiques, nous avons identifié la protéine matricielle SPARC comme un facteur critique contribuant à la perméabilité vasculaire et l'extravasation des cellules tumorales. Nous montrons que SPARC sécrété par les cellules de mélanome induit une perméabilité vasculaire via l'ouverture des jonctions intercellulaires des monocouches endothéliales et entraîne la migration transendothéliale de cellules de mélanome. In vivo, l’extinction de SPARC mène à une diminution drastique dans la colonisation à court et long terme des poumons et de la perméabilité des capillaires pulmonaires. A l’inverse, sa surexpression augmente les capacités d’extravasation et les métastases. / Cutaneous melanoma is one of the most aggressive cancers capable of distant and lethal metastatic spread. Tumor cell intravasation into blood vessel at primary tumor sites and subsequent extravasation are critical steps in the formation of metastases. These steps entail disruption of the endothelial barrier by tumor cells to facilitate their transendothelial passage and metastatic seeding. However, the way by which tumor cells modulate vascular junction integrity is still poorly understood. In an attempt to determine permeability factors secreted by metastatic cells, we identified the matricellular protein SPARC as a critical signaling factor that contributes to elevated vascular permeability and tumor cell extravasation. We show that SPARC released by melanoma cells enhances vascular leakiness by inducing opening of intercellular junctions of endothelial monolayers and drives melanoma cell transendothelial migration. In vivo vascular permeability and metastatic assays demonstrate that SPARC deficiency abrogates tumor-induced permeability of lung capillaries and prevents extravasation from blood vessels and metastasis, whereas overexpression of SPARC increases the lung metastatic potential of melanoma cells. Mechanistically, SPARC-induced endothelial gap formation and transmigration is dependent on vascular cell adhesion molecule (VCAM1) and p38 MAPK signaling pathway in endothelial cells. Importantly, blocking VCAM1 impedes melanoma cell extravasation. The clinical relevance of our findings is highlighted by the high levels of SPARC detected in tumor cells from human pulmonary melanoma lesions.

The control of excessive water production in oil and gas producing wells is of increasing importance to the field operator, primarily when trying to maintain the survivability of a mature field from shut in. During the last two decades many chemicals have been studied and applied under the name of relative permeability modifier (RPM) to combat this problem. These chemicals were mostly bullheaded individually into the affected zones, consequently their application resulted in low to medium success, particularly in treating reservoirs suffering from matrix flow. It has been found that the disproportionate permeability reduction depends on the amount of polymer dispersed or absorbed by the porous rock. If single polymers are employed to treat excessive water production in a matrix reservoir they cannot penetrate deep into the formation rock because the polymer will start to build as a layer on the surface of the rock grains. As a result the placement of polymer into the formation will no be piston like and the dispersion over the rock pores will be uneven. To improve water shutoff technology a method of injecting chemicals sequentially is recommended provided that the chemical’s viscosity is increasing successively with the chemicals injected. / Experimentally confirmed, injecting chemicals sequentially provides better results for conformance control. The value of post treatment water mobility is conspicuously lowered by the method of applying injecting chemicals sequentially in comparison with the single chemical injection method. For instance, the residual resistance factor to water (Frrw) at the first cycle of brine flushing for this method is approximately five times higher than the Frrw obtained by injecting only one single chemical. Furthermore, for the second cycle of brine flushing Frrw is still higher by a ratio of about 2.5. In addition to this improvement residual resistance factor to oil Frro for this method is less than two which has been considered as the upper limit for conformance control in matrix reservoir. Accordingly injecting chemical sequentially can be applied for enhancing relative permeability modifier performance in matrix reservoir.

Naturally fractured reservoirs have attracted an increased interest of exploration and production geophysics in recent years. In many instances, natural fractures control the permeability of the reservoir, and hence the ability to find and characterize fractured areas of the reservoir represents a major challenge for seismic investigations. In fractured and porous reservoirs the fluid affects elastic anisotropy of the rock and also causes significant frequency dependent attenuation and dispersion. In this study we develop a mathematical model for seismic wave attenuation and dispersion in a porous medium in a porous medium with aligned fractured, caused by wave induced fluid flow between pores and fractures. In this work fractures in the porous rock are modelled as very thin and highly porous layers in a porous background. Dry highly porous materials have low elastic moduli; thus dry skeleton of our system contains thin and soft layers, and is described by linear slip theory. The fluid saturated rock with high-porasity layers is described by equations of poroelasticity with periodically varying coefficients. These equations are analyzed using propagator matrix approach commonly used to study effective properties of layered system. This yields a dispersion equation for a periodically layered saturated porous medium taking into account fluid communication between pore spaces of the layers. Taking in this dispersion equation a limit of small thickness for high-porosity layers gives the velocity and attenuation as a function of frequency and fracture parameters. The results of this analysis show that porous saturated rock with aligned fractures exhibits significant attenuation and velocity dispersion due to wave induced fluid flow between pores and fractures. / At low frequencies the material properties are equal to those obtained by anisotropic Gassmann theory applied to a porous material with linear-slip, interfaces. At high frequencies the results are equivalent to those for fractures with vanishingly small normal slip in a solid (non-porous) background. The characteristic frequency of the attenuation and dispersion depends on the background permeability, fluid viscosity, as well as fracture density and spacing. The wave induced fluid flow between pores and fractures considered in this work has exactly the same physical nature as so-called squirt flow, which is widely believed to by a major cause of seismic attenuation. Hence, the present model can be viewed as a new model of squirt-flow attenuation, consistent with Biot’s theory of poroelasticity. The theoretical results of this work are also limited by the assumption of periodic distribution of fractures. In reality fractures may be distributed in a random fashion. Sensitivity of our results to the violation of the periodicity assumption was examined numerically using reflectivity modelling for layered poroelastic media. Numerical experiments for a random distribution of fractures of the same thickness still show surprisingly good agreement with theoretical results obtained for periodic fractures. However this agreement may break down if fracture properties are allowed to vary from fracture to fracture. The results of this thesis show how to compute frequency dependences of attenuation and velocity caused by wave induced fluid flow between pores and fractures. These results can be used to obtain important parameters of fractured reservoirs, such as permeability and fracture weakness, from attenuation measurements. The major requirement for the success of such an approach is that measurements must be made in over a relatively broad frequency range.

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Abstract not available