L’atmosphère est un milieu oxydant au sein duquel les réactions en phase homogène, initiées par des espèces radicalaires (OH notamment), sont prépondérantes. Le chlore atomique peut être l'oxydant le plus important de la couche limite marine à l'aube lorsque la concentration en radicaux OH est faible. L’atmosphère est aussi chargée en particules d’aérosol où des collisions réactives peuvent se produire à l’interface gaz/solide ou gaz/liquide. Il est donc important de prendre en compte les mécanismes élémentaires de chimie hétérogène pour une meilleure description des processus physico-chimiques atmosphériques. L’objectif de cette thèse est d’étudier la réactivité entre le chlore atomique et des particules représentatives des sels marins (NaCl et sels marins synthétiques). Des mesures ont également été effectuées avec du sulfate et du nitrate d’ammonium, composés majoritaires dans les particules secondaires issues de la condensation d’espèces gazeuses d’origine anthropique. Le principe consiste à mettre une phase gazeuse en contact avec une phase solide au sein d’un réacteur à écoulement à parois recouvertes couplé à un spectromètre de masse. Nous cherchons à mesurer la vitesse de réaction et à déterminer le coefficient de capture de ces réactions ainsi que les produits formés. Nous avons fait varier un certain nombre de paramètres : concentration des réactifs, température, présence ou non de vapeurs d’eau. L’analyse de la surface solide après réaction a été réalisée par des techniques de microscopie avancée (XPS, TOF SIMS). / The atmosphere is an oxidizing environment in which the homogeneous phase reactions initiated by radical species (OH in particular) are dominant. Atomic chlorine could be the most important oxidant in the marine boundary layer at dawn when the concentration of OH radicals is low. The atmosphere is loaded with aerosol particles, on the surface of which reactive collisions can occur at the gas / solid or gas / liquid interfaces. It is therefore important to take into account the basic mechanisms of heterogeneous chemistry for a better description of atmospheric chemical and physical processes. The objective of this thesis is to study the reactivity between chlorine atoms and particles representative of sea salts (NaCl and synthetic sea salts). Measurements have also been carried out with ammonium sulfate and nitrate particles, the major components in the secondary particles formed by the condensation of gaseous species of anthropogenic origin. The principle is to put a gas phase in contact with a solid surface in a coated wall flow tube reactor and microwave discharge coupled to a quadrupole mass spectrometer. The contact time between the two phases can be varied inside the reactor. In this work, we have measured the reaction rate and determined the uptake coefficient of these reactions and the possible products formed. Several parameters have been studied: the concentration, the temperature and the presence or absence of surface adsorbed water. The solid surface was analyzed after reaction by advanced microscopy techniques (XPS, TOF SIMS) during this study.

Des études cinétiques et des analyses de surface ont été effectuées sur la réaction multiphasique entre le gaz NO2 et des cristaux de NaCl en présence de molécules tensio-actives sous air humide. Ces études de laboratoire contribuent à la validation de processus de chimie atmosphérique suggérés par des campagnes de mesure sur des aérosols d’origine marine. Les vents provoquant des vagues à la surface des océans propulsent de nombreuses gouttelettes d’eau de mer dans la troposphère où elles se déshydratent partiellement et forment l’aérosol marin, constitué de particules de taille micrométrique comportant du NaCl et de nombreux composés mineurs dont des acides gras (stéarique, oléique). Les concentrations en particules peuvent dépasser 20 µg/m3 dans l’air des zones côtières. Des quantités énormes d’oxydes d’azote (NO, NO2) sont émises actuellement par les transports et le chauffage et leur concentrations peuvent dépasser 100 µg/m3 dans les zones fortement antropisées. Le passage de masses d’air d’origine marine dans des zones fortement urbanisées a des impacts négatifs sur la qualité des eaux continentales par des pluies chargées en nitrates et sur la qualité de l’air par des dégagements de gaz chlorés. La cinétique de la réaction montre que la capture de NO2 par NaCl est favorisée a des fortes humidités. Par contre un revêtement d’acides gras réduit peu la production de NaNO3 et l’émission de NOCl. Les études de surfaces par microimagerie Raman polarisée et microscopie à force atomique mettent en évidence des processus de précipitation et de migration de surface dans la production de nanocristaux de NaNO3 et le faible rôle protecteur des molécules tensio-actives. / In this laboratory work we studied an important atmospheric process typical of polluted costal regions: the heterogeneous reaction of a gaseous pollutant of mainly anthropogenic origin, NO2, on NaCl(100), taken as a surrogate for marine aerosol. Evidence of the presence of a native organic coating on field-collected marine aerosol particles inspired us to investigate the effect of insoluble fatty acids on the heterogeneous removal reaction of NOx in the marine boundary layer. The originality of this work consists in coupling reactivity studies with high spatial resolution surface analysis. The surface is followed, before and after reaction, via Raman micro-spectrometry and AFM techniques. Significant modifications in the morphology and orientation of the formed NaNO3 crystals on the surface are found as a function of humidity during the reaction. A thin organic coating on the salt surface is prepared and characterized. The reactivity of the coated/uncoated salt is measured in a static reactor where the gaseous phase composition can be monitored by FTIR spectrometry in different humidities (RH=0-80%). From NO2 and ClNO kinetics we can independently estimate both the uptake and the reaction probability coefficients. The presence of a palmitic or oleic acid coating slightly hinders the reactivity, especially in some humidities. By coupling all experimental information to a simple reactivity model which fits the experimental data well, we can conclude that the NO2/NaCl reaction directly releases a precursor of active chlorine atoms (ClNO) into the atmosphere, even at high humidities.

This diploma thesis is focused on combination of experimental study and computer modelling of diffusion processes in gel phases. The aim of experimental part of the diploma thesis was to test and optimize the setting of the diffusion coefficient in gel medium by using the method of horizontal diffusion cells, commonly used for study of diffusion processes through membranes. Specific description of experiments was to determinate the impact of presence of reactive component in inert hydro-gel carrier on final value of diffusion coefficient of low-molecular model diffusion probe. The defined dependencies were subsequently combined with computer simulation of diffusion process in a properly designed model in order to determinate the experimentally unavailable system parameters. The stated combination of both approaches was proved to be an appropriate instrument for studying of hydro-gels with a wide potential especially in the field of preparation of hydro-gel carriers with controlled release of active substances.

Calcium carbonate minerals (CaCO3) are important for our understanding of past marine conditions as well as tools for constructing paleoclimate. However, very little experimental work has been done to determine the influence of oxygen depletion on the geochemistry of CaCO3. To determine how oxygen depletion affects elemental incorporation and partitioning, aragonite was grown inorganically in artificial seawater at pressures of 1 atm and 5 bars (0.1%CH4-N2 mixture). Solution of Na2CO3 was used to induce aragonite precipitation. N2 was bubbled through solution in order to minimize oxygen content and iron powder was used to trap remaining O2. Experimental products (aragonite and fluid) were analyzed with ICP-MS, and isotope ratio mass spectrometer. Results suggest that Eh affects incorporation of Mn, S, Cu, and V into aragonite. No methane oxidation was observed.

Previous work has systematically and numerically demonstrated feasibility and performance benefits of the tension-element concept in golf club heads; however, higher fidelity models needed to be created and validated for this concept. There is a need for more accurate models for this concept to further investigate its performance benefits. Performance is measured in terms of impact efficiency of the ball and head and is referred to as coefficient of restitution (COR). COR is affected by the dynamic effective face stiffness and mass properties of the club. This thesis creates and validates high-fidelity, non-linear, dynamic finite element models for the tension-element golf club concept. These models predicted COR with less than one percent error when compared to dynamic experimentation results.

Numerical approaches have been conducted to investigate the effect of droplet deformation and internal circulation on droplet dynamics. Although droplet drag is a classical area of study, there are still theoretical gaps in understanding the motion of large droplets. In applications such as spray combustion, droplets of various sizes are generated and move with the flow. Large droplets tend to deform in the flow, and they have complex interactions with the flow because of this deformation. To better model spray, the physical understanding of droplets needs to be improved. Under spray conditions, droplets are subjected to a high-temperature-and-pressure environment, and the coupling between liquid and gas is enhanced. Therefore the deformation and internal circulation will affect the droplet drag coefficient more significantly than they would under atmospheric conditions. To study the mechanism of how droplet shape and internal circulation influence droplet dynamics, we have used direct numerical simulation (DNS) to simulate a droplet falling at its terminal velocity in high-pressure air. An in-house code developed for interface-capturing DNS of multiphase flows is employed for the simulation. The drag coefficient is calculated, and the results are consistent with the existing literature for slightly deformed droplets. The results show that the drag coefficient is directly related to the droplet deformation and droplet internal circulation. This paper also develops an analytical theory to account for the effect of the Weber number and fluid properties on droplet deformation. / Master of Science / This study investigates how larger droplets interact with airflow in spray conditions. Classical droplet drag models are not accurate under extreme conditions due to the neglect the droplet deformation and droplet internal circulation. To better understand droplet dynamics and to improve the accuracy of droplet models, direct numerical simulations were conducted. In our simulations, a non-evaporating falling droplet in high-pressure air was modeled. Results show a direct link between drag coefficient and droplet shape and internal flow. We also derived an analytical scaling law to explore the parameters related to droplet deformation. This research enhances our understanding of droplet dynamics in spray conditions.

No description available.

For concrete, a sustainable design requires considering both mechanical properties and durability. One of the major deterioration modes of reinforced concrete structures is the entry of chloride ions and corrosion of embedded metals, which is mainly controlled by diffusion as the mass transport mechanism. Therefore, it is pivotal to quantify the chloride diffusion coefficient of concrete, which controls the rate of chloride ingress. Several testing methods exist for quantifying diffusivity of concrete. However, the current test methods are time consuming and demanding. The primary goal of this study is to develop models for quantifying the chloride diffusion coefficient of concrete. As such, initially, the most recent and prevailing analytical models proposed in the scientific literature were critically reviewed and the parameters controlling the chloride diffusion coefficient of concrete were identified. Then, the cement degree of hydration of concrete – as a key parameter which controls the properties of concrete – its measurement methods, and the uncertainties associated with different quantification methods were scrutinized. Finally, three models were developed to quantify the chloride diffusivity of concrete. The first model quantifies the chloride diffusivity of concrete in terms of its electrical resistivity based on the modified Nernst-Einstein equation. The model accounts for the ionic concentration of the pore solution through the alkalis released due to hydration of cementing materials and the alkali uptake of hydration products, the pore solution conductivity, and the interaction between the ions in the pore solution. The second model, which provides a phenomenological relationship for chloride diffusivity of concrete in terms of its compressive strength, accounts for the tortuosity factor of the mixture, aggregate volume fraction, porosity, compressive strength, and cementing materials content and composition. The third model is developed based on the mixture constituents and the cement degree of hydration of concrete. The model accounts for tortuosity factor through the volume fraction of aggregate particles, the interfacial transition zone thickness and diffusivity, cementing materials type and chemical composition, bulk cement paste transport properties through water to cementing materials ratio, cement degree of hydration, supplementary cementing materials type and replacement levels. In order to assess the accuracy and precision of the proposed models, an experimental program was developed and conducted. The following variables were considered for the experimental program: the volume fraction of coarse aggregate, water to cementing materials ratio, total cementing materials content, and supplementary cementing materials type and replacement levels. The experimental results along with the reported data in the scientific literature were used to validate the proposed models. The results revealed the capability of the models to capture the documented observations, as well as the high accuracy and precision of the proposed models for quantifying the chloride diffusivity of concrete in a wide range of concrete mixtures composition and age. The developed models provide designers, practicing engineers and standard/code developers with accurate, precise and consistent models for quantifying the chloride diffusion coefficient of concrete as a direct measure of its durability. / Thesis / Doctor of Philosophy (PhD)

The behavior of aluminum alloy ship deck panels under the thermal loads of Vertical Take-off-and Landing (VTOL) capable aircraft has become a question of interest with the introduction of new primarily aluminum alloy ships to the U.S. Naval Fleet. This study seeks to provide an initial investigation of this question by examining the transient transfer of heat through aluminum alloy ship deck panels under application of the local heat transfer similar to that of a VTOL aircraft exhaust plume core in typical operation. In this study, a jet stream intended to replicate the key physics of the core of a VTOL aircraft plume was impinged onto the upper surface of aluminum alloy corrugated deck panel test specimen. Temperature measurements are taken via thermocouples on the face of the specimen opposite the impingement to evaluate heat transfer through the specimen. This data is used to assess the effects of variation in the geometry of the corrugation between specimen. Qualitative temperature distributions were also gathered on the impingement surface via thermal imaging. A quantitative assessment of the heat paths for transverse and vertical heat transfer was made based on a thermal resistance model, leading to a conceptual description of predominant heat flow paths in the specimen, specifically weld lines between the corrugation and the flat plate surfaces. In support of this, thermal images indicated that the weld lines provided paths for heat to be pulled away from the center of heat application more rapidly than over the rest of the surface. Ultimately, heat transfer through the specimen was found to be more dependent on the flow conditions than the variations in geometry of the deck panels due to the low variation in thermal resistance across the plate. A recommendation is made based upon this observation to use the deck panels similarly to heat exchanges by adding a small amount of through-deck airflow in the areas of high heat load. / Master of Science

When a gas turbine operates in a particle laden environment, such as a desert, small solid particles are ingested into the engine. The ingested sand particles can cause damage to engine components and reduce the service life of the engine. Particle ingestion causes the erosion of metal blades and vanes, and, if the firing temperature is hot enough, deposition of molten particles in the hot sections of the engine. Both deposition and erosion phenomena can severely reduce overall engine performance. The Coefficient of Restitution (COR) is a measure of the particle-wall interaction, and has been widely used to quantify particle rebound characteristics in past particle impact studies. This work investigates the effects of temperature on sand particle impact characteristics by measuring the COR and other deposition related impact parameters. The first study presented as part of the dissertation contains a description of a novel method used to measure COR using a Particle Tracking Velocimetry (PTV) method. This is combined with Computational Fluid Dynamics (CFD) flow field to allow for an accurate determination of the particle impact velocity. The methodology described in this paper allows for measurement of the COR in a wide range of test conditions in a relatively simple manner. The COR data for two different sizes of Arizona Road Dust (ARD) and one size of glass beads are presented in this paper. Target material was stainless steel 304 and the impact angle was varied from 25 to 85 degrees. The second study details the first quantification of the COR of san particles at elevated temperatures. Temperatures used in this study were 533 K, 866 K, and 1073 K. In this study the mass flow rate through the experimental setup was fixed. This meant that velocity and temperature were coupled. Target material for this study was stainless steel 304 and the impact angle was varied from 30° to 80°. The COR was found to decrease substantially at the temperatures and velocity increased. It was determined that the decrease in COR was almost certainly caused by the increase in velocity, and not the decrease in temperature. The third study contains COR results at elevated temperatures. Significant improvements from the method used to calculate COR in the first paper are described. The particle used for these tests was an ARD sand of 20-40 μm size. Target materials used were stainless steel 304 and Hastelloy X. The particles impinged on the target coupon at a velocity of 28m/s. Tests were performed at three different temperatures, 300 K (ambient), 873 K, and 1073 K to simulate temperatures seen in gas turbine cooling flows. The angle of impingement of the bulk flow sand on the coupon was varied between 30° and 80°. A substantial decrease in COR was discovered at the elevated temperatures of this experiment. Hastelloy X exhibited a much larger decrease in COR than does stainless steel 304. The results were compared to previously published literature. The final study also used the ARD size of 20-40 μm. The target material was a nickel alloy Hastelloy X. Experiments for this study were performed at a constant velocity of 70m/s. Various temperatures ranging from 1073 K up to and including 1323 K were studied. Particle angle of impact was varied between 30° and 80°. Significant deposition was observed and quantified at the highest two temperatures. The COR of the ARD sand at the highest temperatures was found not to change despite the occurrence of deposition. At elevated temperatures, many of the particles are not molten due to sand's non-homogenous and crystalline nature. These particles rebound from the target with little if any change in COR. / Ph. D.