<p> Atherosclerosis generally occurs near the branching in the arteries where there tends to be flow irregularities. A build up of fatty deposits (plaque) occurs in the blood vessel in such regions making it to lose its elasticity. Such hardening of the arteries and the narrowing of the lumen can cause severe atheromas and even high blood pressure and blockage of the vessels. It is observed in North America that nearly 47% of the deaths are caused due to cardiovascular diseases and hence determination of such regions becomes very critical and can be very beneficial if done at an earlier stage. In this thesis, we present: an approach to model the pulsating flow of blood through such an atherosclerosis affected region of the artery using finite element method and further discuss the statistical model used to implement the optimization techniques to estimate the region of maximum rigidity. Here within we present a numerical and non-invasive approach to predict such regions. The computational modeling is carried out under two categories: a. The mathematical model and b. The statistical model. </p> <p> The mathematical model which is the forward model, comprises of the artery and the cardiac muscle as hyperelastic material modeled with the neo-hookean model and the three dimensional Navier-Stokes equations solve for the blood flowing through it. We perform fluid dynamic analysis for the blood flowing through the vessel to compute the velocity at different time instances and mechanical analysis to compute the deformation of the artery which is a function of the elasticity of the vessel. The two models are interconnected to each other by boundary conditions as the normal component of the surface force provides the coupling between the two models. The shear modulus represents a measure of the elasticity of the vessel. We use linear spatial basis functions to model the shear modulus which spatially varies along the geometry of the vessel thus we have a region of atherosclerosis and the geometry shows the stenosis. The change in the shear modulus affects the velocity of blood through the vessel. </p> <p> In the statistical model, we propose an inverse computational model for estimating the elasticity profile of the arterial wall where we implement the inverse modeling approach to estimate the maximum shear modulus which helps us to predict the region of atherosclerosis. The velocity and the deformation obtained for a particular shear modulus from our COMSOL forward model provide the realistic simulated measurements that are made noisy by introduction of white Gaussian noise with different SNR and we try to estimate the shear modulus that minimizes the error-function. We use COMSOL with MATLAB for simultaneous iterative computations of velocity and deformation measurements by running the optimization code. We estimate these unknown parameters using optimization algorithm that minimizes the cost function of our model. For our estimation we use the least squares estimator and we derive the maximum likelihood estimator. The unconstrained optimization is carried out with Neider Mead Simplex Method and the Trust Region Method which uses only the function evaluations to find the minimum: making it a very robust algorithm and very efficient for problems that are nonlinear or have a number of discontinuities. Our preliminary results demonstrate significant change in velocity of the blood and occurrence of vortices in the region of less elasticity and the tendency of the artery to deform minimum in the hardened less elastic region. Our estimation results show that the parameters are identifiable. The mean square error of the estimate as a function of SNR shows accuracy of the estimation. </p> / Thesis / Master of Applied Science (MASc)

Tsunami is one of the most dangerous natural hazards in the coastal zone worldwide. Large tsunamis are relatively infrequent. Deposits are the only concrete evidence in the geological record with which we can determine both tsunami frequency and magnitude. Numerical modeling of sediment transport during a tsunami is important interdisciplinary research to estimate the frequency and magnitude of past events and quantitative prediction of future events. The goal of this dissertation is to develop robust, accurate, and computationally efficient models for sediment transport during a tsunami. There are two different modeling approaches (forward and inverse) to investigate sediment transport. A forward model consists of tsunami source, hydrodynamics, and sediment transport model. In this dissertation, we present one state-of-the-art forward model for Sediment TRansport In Coastal Hazard Events (STRICHE), which couples with GeoClaw and is referred to as GeoClaw-STRICHE. In an inverse model, deposit characteristics, such as grain-size distribution and thickness, are inputs to the model, and flow characteristics are outputs. We also depict one trial-and-error inverse model (TSUFLIND) and one data assimilation inverse model (TSUFLIND-EnKF) in this dissertation. All three models were validated and verified against several theoretical, experimental, and field cases. / Ph. D.

Snowmelt-dominated systems are a significant source of water supply for the Western United States. Changes in timing and duration of snowmelt are predicted to continue under climate change; however, the impact this change will have on water resources is not well understood. The ability to compare hydrologic processes across space and time is critical to accurately assess the physical and chemical response of headwater systems to climate change. This dissertation builds upon previous work by using long-term data from two snowmelt dominated catchments to investigate the response of hydrologic processes at different temporal and spatial scales. First, results from an hourly spatially-distributed energy balance snowmelt model were spatially and temporally aggregated to provide daily, catchment-wide snowmelt estimates, which, along with measured discharge and hydrochemical data were used to assess and compare hydrologic processes which occur on an annual scale in two headwater catchments for an eleven year study period. Second, the magnitude and timing of snowmelt, discharge fluxes and hydrochemical data were used to assess and compare inter-annual catchment response in two headwater catchments for an eleven year study period. Third, a pseudoinverse method was developed to compare mineral weathering fluxes in a series of nested sub-catchments over an eleven year study period. Advances from this work include the use of an independently-created energy balance snowmelt model for spatially-distributed hydrologic input for catchment-scale water balance, application of a quantifiable measure of catchment-scale hydrologic flux hysteresis and the development of a method to quantify and compare mineral weathering reactions between source waters across space and time. These methods were utilized to quantify and assess its role of dynamic storage in mitigating climate change response.

The aim of this thesis is preparation of inverse model catalyst CeOx/Pt(111) and its investigation using combination of surface physics methods and electrochemistry. New electrochemical cell was designed and built for electrochemical experiments. CeOx/Pt(111) samples were prepared and studied in UHV using STM and XPS methods. After that, samples were transferred to the electrolyte environment and studied by means of cyclic voltammetry and AFM. For high surface coverage of CeOx, new reaction was observed. We have identified this reaction as a combination of the reduction of cerium(IV) oxide by interaction with hydrogen adsorbed on the Pt(111) surface and oxidation of cerium(III) oxide by dissociative adsorption of water molecules. Powered by TCPDF (www.tcpdf.org)

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23455号 / 理博第4749号 / 新制||理||1681(附属図書館) / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)准教授 成瀬 元 助教 松岡 廣繁, 教授 生形 貴男 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Dans cette thèse, nous étudions la dynamique du plateau antarctique à l'aide d'observations in situ. Nous présentons la circulation de l'eau circumpolaire profonde modifiée (MCDW) sur le plateau, en Antarctique de l'est, au large de la Terre Adélie. Le plateau Adélie est actuellement présenté comme la seconde source majeure d'eau antarctique de fond (AABW). La MCDW est une source de chaleur, de sel et de nutriments pour le plateau Antarctique. Améliorer la connaissance de la circulation de la MCDW et le transport de chaleur associé sur le plateau Antarctique est primordial pour mieux comprendre la formation d'AABW, la fonte des glaciers et des plateformes glaciaires ; et l'activité biologique du plateau. Grâce à la mise en ¿uvre d'un modèle inverse sur le plateau Adélie, nous avons proposé un schéma de la circulation moyenne pendant l'été et nous avons estimé les flux de chaleur et d'eau douce associés depuis l'entrée du plateau jusqu'aux région côtière proche du glacier du Mertz. Nous avons pu mettre en évidence des interactions potentielles entre les masses d'eau intermédiaires et profondes, d'une part, et le glacier, d'autre part, mettant en jeu des taux de fonte compatibles avec des estimations antérieures. Une seconde partie de ce travail s'est concentrée sur la variabilité du courant de la fréquence inertielle à l'échelle de temps saisonnière. Nous avons montré avec des observations in situ un fort cycle saisonnier de l'intensité et de la structure du courant sur le plateau Adélie, déjà suggéré dans des études antérieures basées sur des simulations numériques. Le cycle saisonnier doit donc être appréhendé pour bien comprendre les processus sur le plateau. / In this thesis, we study the Antarctic shelf ocean dynamics using in situ observation. We study the circulation of the Modified Circumpolar Deep Water (MCDW) on the East Antarctic shelf off Adélie Land presently recognized as the second major source of AntArctic Bottom Water (AABW). The MCDW is a source of heat, salt and nutrients for the Antarctic shelf. Improved knowledge of the circulation of the MCDW and the associated heat transport on the Antarctic shelf is very important to better understand the AABW formation, the role of the oceanic ice shelf, glacier melting and the biological activity. Thanks to the inverse model implemented on the Adélie Land shelf, we propose a comprehensive scheme of the mean circulation in summer 2008 and we estimate the associated heat and freshwater transports through the shelf break and farther on the shelf toward the Mertz Glacier. We present evidences of ocean induced glacial melt involving interaction of the dense shelf water and the MCDW with the glacier. A second part of this work focuses on the variability of the current from the inertial to the seasonal time scale using mooring observations collected in the AD, we show that a strong seasonal cycle exists in the current heading and vertical structure, in agreement with earlier model results, which implies that the seasonal cycle should be properly taken into account to correctly understand shelf-ocean processes in this region.

No description available.

Concentration of Ce3+ is one of the most important parameters that influence the reactivity of ceria based catalyst. In this work we examine different experimental approaches for controlling Ce3+ concentration in cerium oxide model catalyst systems such as: i) influencing the stoichiometry of ceria, ii) introducing high valence doping agent, and iii) growing ultra thin ceria films with a strong metal substrate interaction. Structure, morphology and chemical state of prepared reduced ceria based systems were examined by means of surface science techniques: scanning tunneling microscopy, low-energy electron diffraction and X-ray photoelectron spectroscopy. In the present work an original method of ceria film reduction was introduced that allows stepwise control on stoichiometry and degree of film reduction (i). Further we introduce preparation procedures for well-ordered tungsten doped ceria model system (ii) and for the high quality 2D ultrathin ceria system on Cu (1 1 1) (iii). Preparation methods and model systems introduced in this work incorporate different physicochemical principles of Ce3+ induction and provide a variety of model systems useful for examining different effects that diversely prepared Ce3+ ions have on the activity of the catalyst.

Pour atteindre les objectifs de réduction de consommation et augmenter la flexibilité de la demande des bâtiments, il est nécessaire de disposer de modèles de prévision de charge de climatisation facilement diffusables sur site et performants qui permettent la mise en place de stratégies d’optimisation énergétique et d’effacement. Cette thèse compare plusieurs architectures de modèles inverses (« boite noire », « boite grise »). Un modèle semi-physique d’ordre 2 (R6C2) a été retenu pour prévoir la puissance de climatisation et la température intérieure moyenne en chauffage et en refroidissement. Il permet aussi d’interpréter des situations inédites (effacement), absentes de la phase d’apprentissage. Trois stratégies d’optimisation énergétique et d’effacement adaptées aux contraintes d’exploitation sont étudiées. La première permet d’optimiser la relance en chauffage afin de réduire la consommation et d’atteindre effectivement la température de confort le matin. La seconde stratégie optimise les températures de consigne sur une journée dans un contexte de prix variable de l’énergie, ceci afin de réduire la facture énergétique. Enfin, la troisième stratégie permet au bâtiment de s’effacer en limitant la charge tout en respectant des critères de confort spécifiés. Le modèle R6C2 et les stratégies ont été confrontés à un bâtiment réel (une école élémentaire). L’étude montre qu’il est possible de prévoir la puissance électrique et la température moyenne d’un bâtiment complexe avec un modèle mono-zone ; elle permet d’évaluer les stratégies développées et d’identifier les limites du modèle. / To reach the objectives of reducing the energy consumption and increasing the flexibility of buildings energy demand, it is necessary to have load forecast models easy to adapt on site and efficient for the implementation of energy optimization and load shedding strategies. This thesis compares several inverse model architectures ("black box", "grey box"). A 2nd order semi-physical model (R6C2) has been selected to forecast load curves and the average indoor temperature for heating and cooling. It is also able to simulate unknown situations (load shedding), absent from the learning phase. Three energy optimization and load shedding strategies adapted to operational constraints are studied. The first one optimizes the night set-back to reduce consumption and to reach the comfort temperature in the morning. The second strategy optimizes the set-point temperatures during a day in the context of variable energy prices, thus reducing the energy bill. The third strategy allows load curtailment in buildings by limiting load while meeting specified comfort criteria. The R6C2 model and strategies have been faced with a real building (elementary school). The study shows that it is possible to forecast the electrical power and the average temperature of a complex building with a single-zone model; the developed strategies are assessed and the limitations of the model are identified.

<p>The strong metal support interaction (SMSI) is among the best-known classes of metal-oxide interfacial interactions in heterogeneous catalysis, which is defined by the coverage of surface oxide on metal nanoparticles, forming a metal-oxide interface. However, there is limited insight in the atomic scale understanding of the structure of the SMSI oxide. In this work, surface science techniques including scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS) and low energy electron diffraction (LEED) were employed to investigate interfacial interactions in multiple catalytic systems, including ZnO-Pd, ZnO-Pt, and MoOx-Pt. To utilize the capabilities of the surface science techniques and to mimic a catalytic metal nanoparticle in SMSI state, ultrathin oxide films were prepared on metal single crystals as inverse model catalysts.</p> <p>The structural and chemical transformations of ultrathin zinc (hydroxy)oxide films on Pd(111) were studied under varying gas phase conditions (UHV, 5×10−7 mbar of O2 and D2/O2 mixture). Under oxidative conditions, zinc oxide forms partially hydroxylated bilayer islands on Pd(111). Sequential treatments of the submonolayer ZnOxHy films in D2/O2 mixture (1:4) at 550 K evoked structural transformations from bilayer to monolayer and to a PdZn near-surface alloy, in accompany with the reduction of Zn, demonstrating that zinc oxide as a non-reducible oxide, can spread on metal surface and show an SMSI-like behavior in the presence of hydrogen. A mixed canonical – grand canonical phase diagram revealed that the monolayer intermediate structure is a metastable structure formed during the kinetic transformation, and the near-surface alloys are stable under the D2/O2 conditions. Grand canonical phase diagram predicted that under real SMSI conditions zinc oxide films on Pd nanoparticles would be stabilized by hydroxylation with stoichiometries such as ZnOH and Zn2O3H3. Based on the experimental and theoretical observations, we propose that the mechanism of metal nanoparticle encapsulation involves both surface (hydroxy)oxide formation as well as alloy formation, depending on the environmental conditions.</p> <p>Hydroxylation plays a more important role in the ZnO/Pt(111) system. Different from Pd(111), zinc oxide tends to form monolayer graphite-like ZnO films on Pt(111) under oxidative conditions at submonolayer coverages. This structure is extremely susceptible to hydroxylation at room temperature, leading to spontaneous formation of honeycomb-like Zn6O5H5 films in hydrogen. The interaction of the two distinct structures with Pt were investigated by XPS, STM, and HREELS with CO, C2H4, and NO as probe molecules. Zn exhibits a partially reduced oxidation state in Zn6O5H5 and donates negative charge to surface Pt in the confined rings, leading to a switch from linear CO adsorption to bridged CO adsorption in accompany with a 50 cm-1 shift of ν(CO) towards lower frequencies. C2H4 readily forms ethylidyne (*CCH3) species at room temperature once adsorbed on Pt(111), while the formation of ethylidyne is weakened on the Zn6O5H5/Pt(111) surface. In summary, this study demonstrated a unique metal-hydroxide interaction, which serves as a novel approach for the modification of metal catalysts.</p> <p>The partial coverage of metal surfaces by oxides could be utilized to passivate specific sites of catalysts, improving the activity and stability. Herein, we studied the structure of surface Mo oxides on Pt(111) and Pt(544) using STM, XPS, and HREELS. At 0.08 ML coverage, Mo oxide tends to form 1~2 nm clusters and the majority of Mo is in +5 oxidation state. The Mo oxide clusters tend to aggregate near the monoatomic Pt steps, showing a higher local density compared to the wide terraces. Therefore, our results provide experimental evidence for the site-selective growth of Mo oxides at step sites, which could prevent the leaching of active component in catalysts under real reaction conditions.</p> <p>Overall, through atomic-level characterization of inverse model catalysts, we provided insights into the nature of metal-oxide interactions in multiple systems. The surface oxide films influence the property of metal surfaces in various ways, including migration, alloy formation, electronic perturbation, geometric confinement, and site-selective blocking. These findings emphasize the necessity of understanding the real structure of catalytic surfaces under different reaction conditions and shed light on rational design of oxide supported metal nanoparticle catalysts.</p>