Understanding the gas phase flow and transport of volatile organic compounds (VOCs) in unsaturated zones is indispensable to develop effective environmental remediation strategies, to create precautions for fresh water protection, and to provide guidance for land and water resources management. Atmospheric pressure and water table fluctuations are two important natural processes at the upper and lower boundaries of the unsaturated zone, respectively. However, their significance has been neglected in previous studies. This dissertation systematically investigates their influence on the gas phase flow and transport of VOCs in soil and ground water remediation processes using analytically and numerically mathematical modeling. New semi-analytical and numerical solutions are developed to calculate the subsurface gas flow field and the gas phase transport of VOCs in active soil vapor extraction (SVE), barometric pumping (BP) and natural attenuation taking into account the atmospheric pressure and the water table fluctuations. The accuracy of the developed solutions are checked by comparing with published analytical solutions under extreme conditions, newly developed numerical solutions in COMSOL Multiphysics and field measured data. Results indicate that both the atmospheric pressure and the tidal-induced water table fluctuations significantly change the gas flow field in active SVE, especially when the vertical gas permeability is small (less than 0.4 Darcy). The tidal-induced downward moving water table increases the depth-averaged radius of influence (ROI) for the gas pumping well. However, this downward moving water table leads to a greater vertical pore gas velocity away from the gas pumping well, which is unfavorable for removing VOCs. The gas flow rate to/from the barometric pumping well can be accurately calculated by our newly developed solutions in both homogeneous and multi-layered unsaturated zones. Under natural unsaturated zone conditions, the time-averaged advective flux of the gas phase VOCs induced by the atmospheric pressure and water table fluctuations is one to three orders of magnitude less than the diffusive flux. The time-averaged advective flux is comparable with the diffusive flux only when the gas-filled porosity is very small (less than 0.05). The density-driven flux is negligible.

Les études existantes s'intéressant au dimensionnement des structures paravalanches s'appuient généralement sur des signaux de force lissés dans le temps. Cependant, le caractère hétérogène de la neige en écoulement est responsable de fortes fluctuations systématiquement observées. Cette thèse a pour objectif de caractériser les fluctuations de force exercées sur un obstacle surversé par un écoulement granulaire. Des modélisations numériques par la méthode des éléments discrets sont mises en œuvre pour simuler l'interaction entre la neige, représentée par un ensemble plan de particules sphériques, et un mur immobile et indéformable. Une particularité de ce travail réside dans l'étude d'une gamme très large de régimes d'écoulement, de quasistatique à collisionnel. Deux systèmes modèles sont développés dans le but de focaliser la zone d’étude en amont de l’obstacle, et de permettre le contrôle des variables macroscopiques de l’écoulement (vitesse de cisaillement, pression de confinement, tailles des systèmes). Le premier confine les grains entre quatre parois dont l’une impose un cisaillement à vitesse constante, alors que les signaux de force sont mesurés sur la paroi faisant face au cisaillement. Le second système confine les grains entre deux parois (dont une cisaillante) et une condition aux limites périodique dans la direction du cisaillement, alors que le mur est immergé dans les grains. Chaque système est étudié via une analyse moyenne puis les fluctuations sont caractérisées à partir des signaux de force instantanés.Le nombre inertiel macroscopique construit sur la vitesse de cisaillement et la pression de confinement imposées au système s'avère être une variable de contrôle à la fois de la dynamique moyenne et des fluctuations dans les deux systèmes. Une loi empirique a été établie pour chacun des systèmes pour prédire la transmission de force moyenne sur l'obstacle en fonction du nombre inertiel macroscopique, et la mesure de grandeurs locales a révélé que la loi rhéologique µ(I) des milieux granulaires en écoulement est respectée quasiment partout. Les autocorrélations des signaux de force sur le mur à l'échelle mésoscopique ont révélé l'existence d'un effet mémoire des systèmes aux faibles nombres inertiels, disparaissant avec la transition vers le régime dense inertiel. Les distributions de forces à trois échelles spatiales différentes sont également contrôlées par le nombre inertiel macroscopique : aux régimes lents les distributions sont resserrées et approchent une forme Gaussienne, aux régimes rapides les distributions sont exponentielles. Des lois de probabilité log-normales tronquées à trois paramètres ont été établies afin de prédire de façon empirique les distributions de force sur l'obstacle.Ce travail contribue à approfondir les connaissances sur la composante moyenne et les fluctuations de force subies par un obstacle soumis à un écoulement granulaire. Les résultats obtenus permettent d'envisager la modélisation de systèmes gravitaires s'approchant des conditions réelles d'écoulements, permettant ainsi la comparaison avec des expérimentations de laboratoire dans le but de mieux dimensionner les structures de génie-civil. / The existing studies dealing with the design of civil-engineering structures against snow avalanches are generally based on force times series that are smoothed over time. However the strong heterogeneity of snow leads to systematic observations of a high level of force fluctuations. This PhD thesis aims at characterizing the force fluctuations exerted on an obstacle that is overflowed by a granular flow. Numerical simulations based on the discrete elements method are implemented to model the interaction between the snow, represented by an assembly of spherical particles, and a rigid motionless wall-like obstacle. A key feature of this work is the broad range of flow regimes investigated, from quasistatic to collisionnal. Two model systems are studied in order to focus on a zone restricted to the upstream of the obstacle, and to allow a full control of the macroscopic flow variables (shearing velocity, confinement pressure, system sizes). The first one confines the grains between four walls from which the top one imposes a constant shearing velocity while the force signals are measured on the wall facing the corresponding displacement. The second system confines the grains between a static bottom wall, a shearing top wall, and a periodic boundary condition in the shear direction, while the wall-like obstacle is fully immersed in the grains. Each system is studied through a time-averaged analysis then the fluctuations are characterized from the instantaneous force time series.The macroscopic inertial number built from the shear velocity and the confinement pressure imposed to the system turns out to be the main control variable of both the mean dynamics and the fluctuations in the systems. An empirical law has been established to predict the mean force transmission on the obstacle as a function of the macroscopic inertial number for each of the two systems, and the measurement of local strain and stress tensors revealed that the granular flow µ(I)-rheological law is respected nearly everywhere in the samples. The autocorrelations of force signals on the obstacle at the mesoscopic scale revealed the presence of a memory effect of both systems at low inertial numbers which vanishes with the transition from the quasistatic to the dense inertial flow regimes. The force distributions at three different spatial scales are also controlled by the macroscopic inertial number: for slow regimes the distributions are tightened and resemble Gaussian shapes, for fast regimes the distributions are rather exponential. Truncated log-normal probability density functions (with three parameters) have been established in order to predict empirically the force distributions on the obstacle.This work contributes to advance the knowledge on both the time-averaged and the fluctuating components of the force exerted on a wall subjected to a granular flow. The results enable to look forward with the modeling of gravity-driven systems approaching real flow conditions, thus allowing a comparison with laboratory experiments and full-scale measurements, with the aim of better designing of civil engineering structures impacted by avalanches.

Ce travail traite de la dynamique des flammes turbulentes prémélangées confinées et swirlées soumises à des perturbations de vitesses acoustiques. L'objectif général est d'acquérir une compréhension des mécanismes régissant la réponse de ces flammes et d'en tirer des méthodes de prévision des instabilités de combustion. Les écoulements swirlés sont d'abord examinés en termes de nombre de swirl et de nouvelles expressions sont données pour cette quantité. On traite notamment des effets de perturbations de vitesse et une expression est proposée qui tient compte des fluctuations de vitesses dans l'écoulement. Le système utilisé pour l'étude expérimentale comprend une cavité amont, un injecteur équipé d'un swirler et un tube à flamme transparent permettant la visualisation directe du mouvement de la flamme. Deux points de fonctionnement sont étudiés correspondant à des vitesses débitantes différentes. La cavité amont et le tube à flamme du brûleur peuvent être facilement changés pour étudier plusieurs configurations différentes. L'acoustique du brûleur est également analysée au moyen d'une approche de cavités couplées pour déterminer les fréquences de résonance du système en configuration non-réactive. Des expériences sont menées pour mesurer les fréquences propres du système et l'estimation du coefficient d'amortissement est réalisée à partir de la réponse du système à une modulation externe. Un critère de découplage des mode acoustiques est proposé. La dynamique de l'écoulement est examinée en termes de conversion de modes au niveau de la vrille (swirler) ou dans une grille d'aubes. Cette partie du travail, effectuée au moyen de simulations numériques montre que lorsqu'une grille ou une vrille sont soumis à une onde acoustique, le swirler donne naissance à une onde azimutale convective en plus de l'onde acoustique axiale transmise. Les deux types de swirlers, axial et radial, donnent lieu à ce mécanisme, un fait confirmé par des expériences. Il est montré que ce processus de conversion de mode a un impact important sur la dynamique de la flamme swirlée. La dynamique de la combustion est ensuite analysée en mesurant la fonction de transfert généralisée ainsi que les distributions de taux de dégagement de chaleur au cours du cycle d'oscillation. La fonction de transfert est utilisée pour déterminer la réponse de la flamme à des perturbations acoustiques se propageant dans l'écoulement en amont de la flamme. Il est aussi montré que le nombre de Strouhal est un groupe sans dimensions qui permet de caractériser la réponse de la flamme. La dynamique est également analysée au moyen d'un ensemble de diagnostics comprenant des sondes de pression, un photomultiplicateur et un vélocimètre laser Doppler. Un modèle pour la fonction de transfert linéaire de la flamme est dérivé théoriquement à partir d'une description de la flamme au moyen de l'équation pour une variable de champ G. Les mécanismes physiques de la réponse de la flamme sont identifiés : enroulement tourbillonnaire et fluctuations du nombre de swirl. L'enroulement tourbillonnaire est associé à l'onde acoustique transmise en aval du swirler et qui pénètre dans la chambre de combustion. Tandis que les fluctuations du nombre de swirl sont directement liées aux mécanismes de conversion de mode au swirler qui induit différentes vitesses pour les perturbations axiales et azimutales. L'enroulement tourbillonnaire enroule l'extrémité de la flamme tandis que les fluctuations du nombre de swirl agissent sur l'angle de la flamme. Ces deux mécanismes en compétition se combinent de manière constructive ou destructive conduisant à des gains faibles ou élevés dans la réponse de la flamme en fonction de la fréquence. Ces mécanismes sont retrouvés par simulation aux grandes échelles (LES). / This work is concerned with the dynamics of premixed confined turbulent swirling flames submitted to acoustic velocity disturbances. The general objective is to gain an understanding of the mechanisms governing the response of these flames and to derive predictive methods for combustion instabilities. Swirling flows are first reviewed in terms of swirl numbers and novel expressions for them are given. Perturbed form of the swirl number are suggested taking into account acoustic disturbances in the flow. The experimental system comprises an upstream manifold, an injector equipped with a swirler and a transparent flame tube allowing direct visualization of the flame motion. Two operating points are investigated corresponding to different bulk velocities. The upstream manifold and the flame tube of the burner can be easily change to test several configurations. The burner acoustic is also analyzed in term of coupled cavities approach to determined the resonant frequencies of the system in non reactive cases. Experiments are carried out to measure the system eigen frequencies and the estimate damping coefficient of the various burners arrangements. A criterion for decoupling acoustic mode is suggested. The flow dynamics is examined in terms of mode conversion occurring at the swirler or downstream an airfoil cascade. This part of the work, carried out with numerical simulations, shows that when submitted to an acoustic wave, a swirler gives rise to an azimuthal convective wave in addition to the transmitted acoustic wave. Both axial and radial swirlers are prone to this mechanism as confirmed by experiments. It is found that this mode conversion process has a strong impact on the flame dynamics in swirling flames combustors. Combustion dynamics is then analyzed by measuring the flame describing function (FDF) of this burner. This FDF is used to determine the response of the flame to acoustic velocity disturbances propagating on the upstream flow. It is shown that the Strouhal number is a suitable dimensionless group to characterize the swirling flame response. The flame dynamics is also analyzed with an ensemble of diagnostics including pressure probes, photomultipliers and laser Doppler velocimeter (LDV). A model for the linear swirling flame transfer function is derived theoretically. The physical mechanisms driving the response of the flame are identified : vortex rollup and swirl number fluctuations. The vortex rollup is associated to the acoustic wave transmitted downstream of the swirler and entering in the combustor while the swirl number fluctuations are directly linked to the mode conversion mechanisms downstream the swirler which induced different axial and azimuthal speeds upstream the flame. The rollup phenomena acts at the extremity of the flame while swirl number fluctuations act on the flame angle. These competiting mechanisms act constructively or destructively leading to low or high gains in the flame response depending on the frequency. These mechanisms are retrieved by large eddy simulations of the flame dynamics. Finally, an instability analysis is carried out by combining the experimental flame describing function (FDF) and an acoustic model of the combustor to determine the frequency and the amplitude of the velocity disturbances at the limit cycle. A good agreement between predictions and experiments is obtained in most cases indicating that the method is suitable subject to further developments.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15034号 / 工博第3183号 / 新制||工||1479(附属図書館) / 27495 / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 関口 秀雄, 教授 間瀬 肇, 教授 後藤 仁志 / 学位規則第4条第1項該当

In this work a Finite Difference Time Domain (FDTD) simulation is employed to explore local field enhancement, plasmonic coupling, and charge distribution patterns. This 3D simulation calculates the magnetic and electric field components in a large matrix of Yee cells using Maxwell’s equations. An absorbing boundary condition is included to eliminate reflection back into the simulation chamber, and a sample system of cells is checked for convergence. In the specific simulations considered here, a laser pulse of single wavelength is incident on a silicon substrate, travels through an embedded ZnO nanowire (NW) waveguide only (due to an Ag filter), then incites plasmonic coupling at the gap between an Au nanoparticle tip and an Au substrate, an Au nanoparticle (NP), or a trio of Au nanoparticles incident on an angled Si substrate. The angle between the axis of the NW and the normal of the substrate is varied from 0-60°. The NP perpendicular deflection with respect to the NW axis is also varied from -115 - 75 nm. The enhancement patterns reveal superior signal to noise ratio compared to Near Field Scanning Optical Microscopy (NSOM), three times smaller than the NP diameter 100 nm, as well as resolution and spot size of less than 50 nm. This method of Apertureless NSOM (ANSOM) using a NW waveguide grown on a transparent microcantilever therefore shows promise for imaging of single molecules incident on a substrate and NP-labeled cell membrane. / text

The work in this thesis concerns the estimation of the electromagnetic, elastodynamic and piezoelectric properties of homogenized composite materials (HCMs). A composite may be considered homogeneous if wavelengths are suficiently large in comparison to the size of the particles of each component material. This thesis examines HCMs constructed from two component materials and several methods of estimating the HCMs constitutive properties. Firstly, the Maxwell Garnett estimates and Bergman-Milton bounds on the electromagnetic properties of HCMs are examined. While both are widely used, we re-examine them, for isotropic dielectric HCMs, in light of recent advancements in material manufacture. Secondly, we examine the strong-property-fluctuation theory (SPFT). The SPFT estimate is calculated using iterations upon an initial ansatz, these iterations being dependent on statistical cumulants of the spatial distribution of the particles of the component materials. The zeroth-order SPFT estimate is identical to the first-order and both are taken to be identical to a comparison material. For the second-order estimate a two-point correlation function along with its associated correlation length are used to characterize the component materials' particle distribution. The general framework for the elastodynamic SPFT was established in 1999 by Zhuck and Lakhtakia. Here we further develop the elastodynamic SPFT for orthotropic HCMs, in order to undertake numerical studies. We simplify certain integrals in order to make them amenable to numerical computation. Also, we establish the piezoelectric SPFT for orthorhombic mm2 materials. The general theory is developed first in a manner analogous to the elastodynamic SPFT. We then implement a two-point covariance function, perform similar integral simplifications to those done in the elastodynamic SPFT and carry out numerical experiments. From the numerical studies it is clear that, for both the elastodynamic and piezoelectric HCMs, the lowest-order SPFT estimate is similar to that provided by the corresponding Mori-Tanaka formalism. It is also apparent that the second-order SPFT estimate provides a significant correction to the lowest-order estimate, which reflects dissipative losses due to scattering.

L'étude fine des fluctuations de courant dans les petites composantes électroniques est un excellent moyen de tester notre compréhension du transport électronique quantique. Lorsque la fréquence est suffisamment élevée, ce qui est mesuré en laboratoire n’est plus un courant d’électrons mais un champ électromagnétique causé par l’agitation des électrons. Faire un pont entre l’optique en terme de photons et l’électronique quantique est l’objectif dans le laboratoire de Bertrand Reulet. Ce mémoire de maîtrise traite des fluctuations de courant d’une jonction tunnel polarisée en courant et excitée avec une tension alternative dans les micro-ondes. La nouveauté dans ce projet provient du fait que les fluctuations de courant générées par la jonction tunnel ont été mesurées en phase et en quadrature avec l’excitation micro-onde envoyée sur l’échantillon. Il a été démontré qu’il est possible de faire un parallèle entre les fluctuations du courant électrique et l’optique quantique pour arriver à prédire le comportement de ces fluctuations en phase et en quadrature. De plus, la présence d’état comprimé ou «squeezé» sur l’une des quadratures du courant a été mesurée expérimentalement. Les résultats obtenus sont en parfait accord avec la théorie développée.

The implementation of a recently suggested class of structural change tests, which test for parameter instability in general parametric models, in the R language for statistical computing is described: Focus is given to the question how the conceptual tools can be translated into computational tools that reflect the properties and flexiblity of the underlying econometric metholody while being numerically reliable and easy to use. More precisely, the class of generalized M-fluctuation tests (Zeileis & Hornik, 2003) is implemented in the package strucchange providing easily extensible functions for computing empirical fluctuation processes and automatic tabulation of critical values for a functional capturing excessive fluctuations. Traditional significance tests are supplemented by graphical methods which do not only visualize the result of the testing procedure but also convey information about the nature and timing of the structural change and which component of the parametric model is affected by it. / Series: Research Report Series / Department of Statistics and Mathematics

Thesis advisor: Udayan Mohanty / In chapter one, two simple models are used to estimate the electrostatic contributions to the stiffness of short DNA fragments. The first model views DNA as two strands that are appropriately parameterized and are wrapped helically around a straight cylinder radius equal to the radius of the DNA molecule. The potential energy of the DNA due to phosphate-phosphate electrostatic interactions is evaluated assuming that the charges interact through Debye-Hückle potentials. This potential energy is compared with the potential energy as computed using our second model in which DNA is viewed as two helical strands wrapping around a curved tube whose cross-section is a disk of radius equal to the radius of the DNA. The results are compared with counterion condensation models and experimental data (Guo et al. J. Phys. Chem. B, 2008, 112, 16163-16169). In chapter two, the fidelity of translation selection begins with the base pairing of codon-anticodon complex between the mRNA and tRNAs. Binding of cognate and near-cognate tRNAs induces 30S subunit of the ribosome to wrap around the ternary complex, EF-Tu(GTP)aa-tRNA. We have proposed that large thermal fluctuations play a crucial role in the selection process. The binding energies of over a dozen unique site-bound magnesium structural motifs are investigated and provide insights into the nature of interaction of divalent metal ions with the ribosome (Guo et al. Proc. Nat. Acad. Sci. 2011, 108, 3947-3951). In chapter three, we use extensive molecular dynamics simulations to study a series of stapled alpha helical peptides over a range of temperatures in solution. The peptides are found to exhibit substantial variations in predicted helicities that are in good agreement with the experimental value. In addition, we find significant variation in local structural flexibility of the peptides with the position of the linker, which appears to be more closely related to the observed differences in activity than the absolute alpha helical stability (Guo et al. Chem. Biol. Drug. Des. 2010, 75, 348-359.). In chapter four, the alpha helical conformation and structural stability of single and double stapled all-hydrocarbon cross-linked p53 peptides in solution and when bound to MDM2 is investigated. We determined the effects of the peptide sequence, the stereochemistry of the cross-linker, the conformation of the double bond in the alkene bridge, the length of the bridge, on the relative stability of the alpha helix structure. The conformation population distribution indicates a fully helical state and several partially folded states. The distribution of dihedral pairs of the stapled peptides in the bound state indicates a significant population around the alpha helical region. Sequences over which the linker spans tend to have the highest helical occupancy. Significant helical content is observed for a double stapled p53 peptide at 575 K. The probability to form native contacts is increased when the stapled peptides are bound to MDM2. The distribution of the end-to-end distance of the peptides is bimodal. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Well reported problems around air quality and climate change, together with the energy crisis resulting from finite fossil fuel resources is motivating all the automotive manufacturers to develop new propulsion systems through electrification and hybridisation. The range extended electric vehicle (REEV) is one of these solutions that seeks a practical compromise between the on-board battery size and the one-charge driving range. The auxiliary power unit (APU) is the key component in a REEV and is designed to maintain the battery charge for long distance trips. Since the APU does not propel the vehicle, it only requires a small capacity engine with low-cylinder-count. This type of engine exhibits severe speed fluctuations due to its low firing frequency. As the engine and the M/G are isolated from the vehicle driving wheels, it is possible to use the electric machine to deliver a counteracting torque to the engine reducing the resultant torque spikes and thus the system speed oscillation but likely to increase the electric losses. This research work aims to minimise the speed fluctuation balanced against the extra losses introduced. A Dynamic Torque Control (DTC) strategy was designed and tested on an APU using a novel approach to achieve this target. The system components were modelled individually regarding to the prototype system specifications, which is developed within a collaborative R&D project. The empirical engine model was calibrated with extensive bench testing data to recreate the in-cycle torque waveforms. The motor/generator was modelled as a novel hybrid between an analytical model and an FEA model which allowed the winding inductance variation due to the current rise to be included in the model. This approach was designed to replicate the electric machine performance with high fidelity whilst keeping the computational time and cost low. With the help from the system model, the DTC torque demand patterns were designed based on detailed analysis of the contribution factors of the speed fluctuation and the electric machine losses. A unique Pareto Curve of the speed fluctuation reduction and the electrical loss was identified during the analysis and allowed the optimal demand pattern to be developed for a given torque capability electric machine. The simulation results showed that the system in-cycle speed fluctuations could be reduced by 16.4% and 19.11% at 2000rpm full load and 4500rpm full load condition respectively while the electric specific fuel consumption (ESFC) rose by 2.26% and 1.35% at the same operation points. The DTC strategy was implemented in the prototype APU and successfully tested on the rig at 2000rpm and 4500rpm. A reduction in the speed oscillation and the ESFC increase consistent with the simulation results were observed. The simulation estimates on ESFC was proved within an error of 2.19%. This research improves the insight into the mechanisms that are responsible for increased losses when dynamic torque control is used and develops an optimisation approach which takes account of these factors. When an electric machine, which does not have the same instantaneous peak torque capability as the engine, is used in an APU, a better compromise between speed fluctuation smoothing and system efficiency can be achieved.