>Magister Scientiae - MSc / The main aim of this study is to investigate theelectrochemical determination of two beneficial (selenium and zinc) and two toxic (chromium and vanadium) metals in the potable water within the City of Cape Town's distribution area. The Water Laboratory of the City's Scientific Services Branch analyses for these metals in their elemental state, using the Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). This is a standard method used for the detection of trace metals. The most sensitive voltammetric method for determining these metals is by adsorptive stripping voltammetry, using a thin mercury film electrode with a glassy carbon support. This voltammetric method is used for quantitative determination of specific ionic species. Because of mercury's toxicity it is not really favoured for trace metals anymore. Many other possibilities are under investigation, e.g. bismuth-film, modified glassy carbon and antimony electrodes. The boron-doped diamond (BDD) electrode has distinct advantages when used to determine metal concentrations. Advantages of BDD electrodes include lower detection limit, speciation and wider potential window. In this study cyclic voltammetry (CV) was used to determine the copper, cadmium and lead concentrations in potable water by means of square wave voltammetry (SWV) and a bare glassy carbon electrode (GCE). Furthermore, a boron-doped diamond electrode (BDDE) was used to investigate the possibilities of determining selenium, chromium and vanadium by SWV. Real samples (potable water samples) were analysed electrochemically to qualify and quantify these metals and determine whether they comply with the SANS 241:2006 drinking water guidelines.The copper, cadmium, lead and selenium peaks appear very close to the theoretical values, which indicate that these metals can be detected by SWV method, but further analysis with more samples is advised. Even though responses were observed for vanadium and chromium, it was not reliable and requires further investigation. Further studies into the analyses of zinc are also advised.

In this dissertation we first derive a new unified upper solution bound for the continuous coupled algebraic Riccati equation, which arises from the optimal control of a Markovian jump linear system. In particular, we address the issue of rank deficiency with the control matrices. In the case of rank deficiency the existing matrix upper bounds are inapplicable. Moreover, our new result is not restricted to rank deficiency cases only. It now contains the existing results as special cases. Next, an iterative refinement is presented to improve our new unified matrix upper solution bounds. In particular, this iterative refinement determines a monotonically decreasing sequence of upper bounds for the solution of the continuous coupled algebraic Riccati equation. We formulate a new iterative algorithm by modifying this iterative refinement. We also prove that this new algorithm generates a monotonically decreasing sequence of matrix upper solution bounds that converges to the maximal solution of the continuous coupled algebraic Riccati equation. Furthermore, we prove the convergence of an accelerated Riccati iteration which computes a positive semidefinite solution of the continuous coupled algebraic Riccati equation. In particular, we establish sufficient conditions for the convergence of this algorithm. We also prove that for particular initial values this algorithm determines a monotonically increasing sequence of positive semidefinite matrices that converge to the minimal solution of the continuous coupled algebraic Riccati equation. Additionally, we show that for specific initial values this algorithm generates a monotonically decreasing sequence that converges to the maximal solution of the continuous coupled algebraic Riccati equation. In addition, we prove that this accelerated Riccati iteration converges faster than the Riccati iteration. Finally, we formulate a weighted modified accelerated Riccati iteration which is a more generalized Riccati type iteration. All of the existing Riccati iterations are now the special cases of this algorithm. Furthermore, we establish sufficient conditions for the convergence of this algorithm and we prove the monotonic convergence of the sequence generated by this algorithm. We also discuss how the weight and other quantities affect the rate of convergence of this algorithm. Illustrative numerical examples are also presented.

Circular air-coupled ultrasonic testing (ACUT) setup for the inspection of commercial carbon-carbon composite aircraft brake disks was developed in Intelligent Measurement and Evaluation Laboratory (IMEL) at Southern Illinois University Carbondale (SIUC). The developed test setup utilizes Airstar single channel air-coupled equipment and has only manual A-scan and B-scan capability. The developed ACUT technique is unique compared to the commercial C-scan ultrasonic systems and is proficient, fast, economically feasible, and easy to implement method particularly for the inspection of carbon-carbon (C/C) composites aircraft brake disks. Prior to conducting air-coupled measurements, wobble analysis was carried out. This was important because significant wobbling in the test setup can lead to the interference of the reflected and the incident beam which would result to inaccurate ultrasonic measurements. The measured deviation due to wobbling, surface profile of the disk, design, and experimental error were relatively small. Therefore, these errors were neglected while performing ACUT measurements. For ACUT measurements, several through-transmitted amplitude signals were recorded within the C/C brake disks manually. The images were then reconstructed using Matlab based on the through-transmitted amplitude signals. Finally, a comparison was drawn between the reconstructed images and the C-scan images of the C/C brake disks obtained from the commercial Airstar C-scan ACUT system. Like commercial C-scan ACUT image results, reconstructed images were also able to detect all defects in the commercial C/C brake disks which served for the system verification and validation. In addition, defect, non-defect, and suspected areas within the C/C brake disks were quantified with air-coupled measurement. For this, light microscopy was conducted for every sample made from each C/C brake disks at lower magnification of 10X. It was concluded that it is very difficult to assess the crack or delamination situation based on a 2D micrograph of one depth. Also, it was concluded that an internal porosity and micro-cracks may not be only factors that can be related to defects. Finally, an intelligent systems approach, specifically, fuzzy logic and artificial neural network (ANN) methodologies were implemented for the automatic defect detection in commercial C/C aircraft brake disks by using air-coupled ultrasonic results. For this, a multi-layer perceptron (MLP) with two hidden layers and a scaled conjugate gradient back-propagation (BP) learning algorithm was used for the ANN training. The network training process was performed in an off-line mode using the ANN toolbox in Matlab. The network training was repeated until a steady state was reached, where there was no further change in the synaptic weights. The ANN provided plausible results in detecting the defect areas for different C/C brake disks. It was also demonstrated that the system was able to learn the rules without knowing any algorithm for automatic defect detection.

In this paper we develop new and improved results in the numerical solution of the coupled algebraic Riccati equations. First we provide improved matrix upper bounds on the positive semidefinite solution of the unified coupled algebraic Riccati equations. Our approach is largely inspired by recent results established by Liu and Zhang. Our main results tighten the estimates of the relevant dominant eigenvalues. Also by relaxing the key restriction our upper bound applies to a larger number of situations. We also present an iterative algorithm to refine the new upper bounds and the lower bounds and numerically compute the solutions of the unified coupled algebraic Riccati equations. This construction follows the approach of Gao, Xue and Sun but we use different bounds. This leads to different analysis on convergence. Besides, we provide new matrix upper bounds for the positive semidefinite solution of the continuous coupled algebraic Riccati equations. By using an alternative primary assumption we present a new upper bound. We follow the idea of Davies, Shi and Wiltshire for the non-coupled equation and extend their results to the coupled case. We also present an iterative algorithm to improve our upper bounds. Finally we improve the classical Newton's method by the line search technique to compute the solutions of the continuous coupled algebraic Riccati equations. The Newton's method for couple Riccati equations is attributed to Salama and Gourishanar, but we construct the algorithm in a different way using the Fr\'echet derivative and we include line search too. Our algorithm leads to a faster convergence compared with the classical scheme. Numerical evidence is also provided to illustrate the performance of our algorithm.

We study different phenomena associated with single-photon propagation in optical cavities coupled through optical fibers. We first address the issue of storing and delaying single-photon wavepackets in an array of microcavities. This has possible applications in developing reliable and efficient quantum repeaters that will be utilized in building long distance quantum networks. Second, we investigate a Hong-Ou-Mandel (HOM) type of interference between two photons that are produced in two coupled atom-cavity systems. The HOM effect in this setup can test the degree of indistinguishability between photons when they are stored inside cavities. This part of the dissertation also includes the study of entanglement between atoms, cavities and atom-cavity systems induced by the photons. Finally, we focus on single-photon interactions with a tiny movable mirror in the context of quantum optomechanics. We investigate how the mechanical motion of the mirror leaves its imprints on the optical spectrum of the photon This dissertation includes previously published and unpublished co-authored material. / 10000-01-01

L’écoulement de Taylor-Couette entre deux cylindres concentriques (cylindre interne en rotation et cylindre externe fixe) est actuellement mis à profit au CEA pour étudier les performances d’extraction d’une colonne liquide/liquide pour le retraitement du combustible nucléaire. Ces performances étant fortement liées au mélange, il est important de le quantifier. En monophasique, les propriétés de mélange ont été étudiées dans une thèse précédente, à la fois expérimentalement et numériquement, et ont été reliées aux paramètres hydrodynamiques de l’écoulement. L’effet du nombre de Reynolds, du régime d’écoulement et de la taille des rouleaux (longueur d’onde axiale) ont notamment été prouvés. Le but de ce travail est d’étendre les précédentes études aux écoulements de Taylor-Couette diphasiques. Pour des raisons pratiques et afin de s’affranchir des phénomènes de coalescence et de rupture, des billes de PMMA de diamètres 800 µm à 3 mm sont choisies pour simuler la phase dispersée, en suspension dans une solution aqueuse de Dimethylsulfoxyde (DMSO) et de Thiocyanate de Potassium (KSCN). Le montage expérimental couple les méthodes de PIV et de PLIF afin d’obtenir en simultané les informations concernant l’hydrodynamique de l’écoulement et le mélange. Cependant la mise en place du diphasique impose un certain nombre de contraintes qui doivent être prises en compte. Bien que les deux phases soient soigneusement choisies afin d’être adaptées en indice et en densité, le recours à une deuxième chaine d’acquisition PLIF est nécessaire afin d’améliorer la qualité des mesures. Ainsi, une première voie de PLIF classique suit l’évolution au cours du temps de la concentration de Rhodamine WT, injectée au centre de la colonne au début de l’expérience. La voie supplémentaire visualise un autre fluorophore, de la Fluorescéine répartie de manière homogène dans la colonne, permettant ainsi de créer un masque dynamique des billes. Grâce à ce montage expérimental, une étude paramétrique (taille, rétention des billes) a été menée. Un double effet des billes sur le mélange a ainsi été observé. D’une part, la présence d’une phase dispersée modifie les propriétés hydrodynamiques de l’écoulement : les régimes (Couette, Taylor Vortex Flow et Wavy Vortex Flow) sont d’autant plus déstabilisés que la rétention ou la taille des billes augmente. De plus un régime supplémentaire, inhabituel dans le cas du cylindre externe fixe, apparait, forcé par la phase dispersée : le régime Spiral Vortex Flow, dans lequel le mélange est très efficace. D’autre part, une influence propre des billes sur le mélange a été mise en évidence, en fonction de leur taille et de leur concentration. Ces deux effets se combinent pour expliquer une forte augmentation du mélange en présence de la phase dispersée. Les mécanismes physiques liés à ces résultats sont ensuite discutés, et leur influence relative est comparée. Enfin, le rôle du mélange local sur le coefficient de dispersion global, paramètre classiquement utilisé en génie chimique afin de prédire les performances des colonnes d’extraction, est discuté. / In the scope of the nuclear fuel reprocessing, Taylor-Couette flows between two concentric cylinders (the inner one in rotation and the outer one at rest) are used at laboratory scale to study the performances of new liquid/liquid extraction processes. Separation performances are strongly related to the mixing efficiency, the quantification of the latter is therefore of prime importance. A previous Ph.D. work has related the mixing properties to the hydrodynamics parameters in single-phase flow, using both experimental and numerical investigations. The Reynolds number, flow state and vortices height (axial wavelength) impacts were thus highlighted. This Ph.D. work extends the previous study to two-phase configurations. For experimental simplification, and to avoid droplets coalescence or breakage, spherical solid particles of PMMA from 800 µm to 1500 µm diameter are used to model rigid droplets. These beads are suspended in an aqueous solution of dimethyl sulfoxide (DMSO) and potassium Thiocyanate (KSCN). The experimental setup uses coupled Particle Image Velocimetry (PIV) and Planar Laser-Induced Fluorescence (PLIF) to access simultaneously the hydrodynamic and the mixing properties. Although the two phases are carefully chosen to match in density and refractive index, these precautions are not sufficient to ensure a good measurement quality, and a second PLIF channel is added to increase the precision of the mixing quantification. The classical PLIF channel monitors the evolution of Rhodamine WT concentration, while the additional PLIF channel is used to map a Fluorescein dye, which is homogeneously concentrated inside the gap. This way, a dynamic mask of the bead positions can be created and used to correct the Rhodamine WT raw images. Thanks to this experimental setup, a parametric study of the particles size and concentration is achieved. A double effect of the dispersed phase is evidenced. On one hand, the particles affect the flow hydrodynamic properties : the more the particles size and concentration grows, the more the studied flow regimes (Couette, Taylor Vortex Flow and Wavy Vortex Flow) are destabilized. In addition, a new flow state appears in presence of a dispersed phase, that is unusual in the configuration we use where the outer cylinder is at rest. This Spiral Vortex Flow is characterized by an enhanced mixing. On the other hand, for given hydrodynamic properties and depending on the particles size and concentration, a specific effect of the particles on mixing is highlighted. Both the “hydrodynamic” and “intrinsic“ effects are responsible for the significant increase of the global mixing observed in two-phase configuration. Possible physical mechanisms are proposed to analyze these results, and their relative influence is compared. At last, an attempt is made to relate the local mixing properties to a global dispersion coefficient of the flow, data commonly used in chemical engineering to predict the performances of extraction columns.

La conception des moteurs aéronautiques est soumise à de nombreuses contraintes telles que les gains de performance ou les normes environnementales de plus en plus exigeantes. Face à ces objectifs souvent contradictoires, les nouvelles technologies de moteur tendent vers une augmentation de la température locale et globale dans les étages chauds. En conséquence, les parties solides comme les parois du brûleur sont soumises à des niveaux de température élevés ainsi que d’importants gradients de température, tous deux critiques pour la durée de vie du moteur. Il est donc essentiel pour les concepteurs de caractériser précisément la thermique locale de ces systèmes. Aujourd’hui, la température de paroi est évaluée par des essais de coloration. Pour limiter ces essais relativement chers et complexes, des outils numériques haute fidélité capables de prédire la température de paroi des chambres de combustion sont actuellement développés. Cet exercice nécessite de considérer tous les modes de transfert de chaleur (convection, conduction et rayonnement) ainsi que la combustion au sein du brûleur. Ce problème multi-physique peut être résolu numériquement à l’aide de différentes approches numériques. La méthode utilisée dans ce travail repose sur une approche partitionnée qui inclut la résolution de l’écoulement turbulent réactif par un code de simulation aux grandes échelles (LES), un solveur radiatif basé sur la méthode aux ordonnées discrètes ainsi qu’ un code de conduction solide.Les diverses questions et difficultés liées à la répartition des ressources informatiques ainsi qu’à la méthodologie de couplage employée pour traiter les disparités d’échelles de temps et d’ espace présentes dans chacun des modes de transfert de chaleur sont discutées. La performance informatique des applications couplées est étudiée à travers un modèle très simplifié ainsi que sur une application industrielle. Les paramètres importants sont identifiés et des pistes potentielles d’amélioration sont proposées. La méthodologie de couplage thermique est ensuite étudiée du point de vue physique sur deux configurations distinctes. Pour commencer, l’équilibre thermique entre un fluide réactif et un solide est étudié pour une configuration académique d’accroche flamme. L’influence de la température de paroi de l’accroche flamme sur la stabilisation de flamme est mise en évidence sur des simulations fluideseul. Ces résultats indiquent trois états d’équilibre théorique différents. La pertinence physique de ces trois états est ensuite évaluée à l’aide de diverses simulations de transfert de chaleur conjugué réalisées pour différentes solutions initiales et conductivités solides. Les résultats indiquent que seulement deux états d’équilibre ont un sens physique et que la bifurcation entre les deux états possibles dépend à la fois de la condition initiale et de la conductivité solide. De plus, pour la gamme de paramètres testés, la méthodologie de couplage n’a pas d’effet sur les solutions obtenues. Une méthodologie similaire est ensuite appliquée à une chambre de combustion d’hélicoptère pour laquelle le rayonnement est de plus pris en compte. Diverses simulations sont présentées afin d’évaluer l’impact de chacun des processus de transfert de chaleur sur le champ de température : une simulation fluide-seul adiabatique de référence, de transfert de chaleur conjugué, d’interaction thermique fluide-rayonnement ainsi qu’une simulation incluant toutes les physiques. Ces calculs montrent la faisabilité d’un couplage LES/conduction solide dans un contexte industriel et fournissent de bonnes tendances de distribution de température. Pour finir, pour cette géométrie de brûleur et la condition d’opération simulée, les divers résultats montrent que le rayonnement joue un rôle important dans la distribution des températures de paroi. De ce fait, les comparaisons aux essais de coloration sont globalement en meilleur accord quand les trois modes de transfert sont pris en compte / The design of aeronautical engines is subject to many constraints that cover performance gain as well as increasingly sensitive environmental issues. These often contradicting objectives are currently being answered through an increase in the local and global temperature in the hot stages of the engine. As a result, the solid parts encounter very high temperature levels and gradients that are critical for the engine lifespan. Combustion chamber walls in particular are subject to large thermal constraints. It is thus essential for designers to characterize accurately the local thermal state of such devices. Today, wall temperature evaluation is obtained experimentally by complex thermocolor tests. To limit such expensive experiments, efforts are currently performed to provide high fidelity numerical tools able to predict the combustion chamber wall temperature. This specific thermal field however requires the consideration of all the modes of heat transfer (convection, conduction and radiation) and the heat production (through the chemical reaction) within the burner. The resolution of such a multi-physic problem can be done numerically through the use of several dedicated numerical and algorithmic approaches. In this manuscript, the methodology relies on a partitioned coupling approach, based on a Large Eddy Simulation (LES) solver to resolve the flow motion and the chemical reactions, a Discrete Ordinate Method (DOM) radiation solver and an unsteady solid conduction code. The various issues related to computer resources distribution as well as the coupling methodology employed to deal with disparity of time and space scales present in each mode of heat transfer are addressed in this manuscript. Coupled application high performance studies, carried out both on a toy model and an industrial burner configuration evidence parameters of importance as well as potential path of improvements. The thermal coupling approach is then considered from a physical point of view on two distinct configurations. First, one addresses the impact of the methodology and the thermal equilibrium state between a reacting fluid and a solid for a simple flame holder academic case. The effect of the flame holder wall temperature on the flame stabilization pattern is addressed through fluid-only predictions. These simulations highlight interestingly three different theoretical equilibrium states. The physical relevance of these three states is then assessed through the computation of several CHT simulations for different initial solutions and solid conductivities. It is shown that only two equilibrium states are physical and that bifurcation between the two possible physical states depends both on solid conductivity and initial condition.Furthermore, the coupling methodology is shown to have no impact on the solutions within the range of parameters tested. A similar methodology is then applied to a helicopter combustor for which radiative heat transfer is additionally considered. Different computations are presented to assess the role of each heat transfer process on the temperature field: a reference adiabatic fluid-only simulation, Conjugate Heat Transfer, RadiationFluid Thermal Interaction and fully coupled simulations are performed. It is shown that coupling LES with conduction in walls is feasible in an industrial context with acceptable CPU costs and gives good trends of temperature repartition. Then, for the combustor geometry and operating point studied, computations illustrate that radiation plays an important role in the wall temperature distribution. Comparisons with thermocolor tests are globally in a better agreement when the three solvers are coupled.

Master of Science / Mechanical and Nuclear Engineering / Hitesh Bindra / This thesis extends the application of Lattice Boltzmann Methods (LBM) to radiation transport problems in thermal sciences and nuclear engineering. LBM is used to solve the linear Boltzmann transport equation through discretization into Lattice Boltzmann Equations (LBE). The application of weighted summations for the scattering integral as set forth by Bindra and Patil are used in this work. Simplicity and localized discretization are the main advantages of using LBM with fixed lattice configurations for radiation transport problems. Coupled solutions to radiation transport and material energy transport are obtained using a single framework LBM. The resulting radiation field of a one dimensional participating and conducting media are in very good agreement with benchmark results using spherical harmonics, the P₁ method. Grid convergence studies were performed for this coupled conduction-radiation problem and results are found to be first-order accurate in space. In two dimensions, angular discretization for LBM is extended to higher resolution schemes such as D₂Q₈ and a generic formulation is adopted to derive the weights for Radiation Transport Equations (RTEs). Radiation transport in a two dimensional media is solved with LBM and the results are compared to those obtained from the commercial software COMSOL, which uses the Discrete Ordinates Method (DOM) with different angular resolution schemes. Results obtained from different lattice Boltzmann configurations such as D₂Q₄ and D₂Q₈ are compared with DOM and are found to be in good agreement. The verified LBM based radiation transport models are extended for their application into coupled multi-physics problems. A porous radiative burner is modeled as a homogeneous media with an analytical velocity field. Coupling is performed between the convection-diffusion energy transport equation with the analytical velocity field. Results show that radiative transport heats the participating media prior to its entering into the combustion chamber. The limitations of homogeneous models led to the development of a fully coupled LBM multi-physics model for a heterogeneous porous media. This multi-physics code solves three physics: fluid flow, conduction-convection and radiation transport in a single framework. The LBE models in one dimension are applied to solve one-group and two-group eigenvalue problems in bare and reflected slab geometries. The results are compared with existing criticality benchmark reports for different problems. It is found that results agree with benchmark reports for thick slabs (>4 mfp) but they tend to disagree when the critical slab dimensions are less than 3 mfp. The reason for this disagreement can be attributed to having only two angular directions in the one dimensional problems.

abstract: Sunlight, the most abundant source of energy available, is diffuse and intermittent; therefore it needs to be stored in chemicals bonds in order to be used any time. Photosynthesis converts sunlight into useful chemical energy that organisms can use for their functions. Artificial photosynthesis aims to use the essential chemistry of natural photosynthesis to harvest solar energy and convert it into fuels such as hydrogen gas. By splitting water, tandem photoelectrochemical solar cells (PESC) can produce hydrogen gas, which can be stored and used as fuel. Understanding the mechanisms of photosynthesis, such as photoinduced electron transfer, proton-coupled electron transfer (PCET) and energy transfer (singlet-singlet and triplet-triplet) can provide a detailed knowledge of those processes which can later be applied to the design of artificial photosynthetic systems. This dissertation has three main research projects. The first part focuses on design, synthesis and characterization of suitable photosensitizers for tandem cells. Different factors that can influence the performance of the photosensitizers in PESC and the attachment and use of a biomimetic electron relay to a water oxidation catalyst are explored. The second part studies PCET, using Nuclear Magnetic Resonance and computational chemistry to elucidate the structure and stability of tautomers that comprise biomimetic electron relays, focusing on the formation of intramolecular hydrogen bonds. The third part of this dissertation uses computational calculations to understand triplet-triplet energy transfer and the mechanism of quenching of the excited singlet state of phthalocyanines in antenna models by covalently attached carotenoids. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

abstract: This study explores the possibility of two matrices containing metallic particulates to act as smart materials by sensing of strain due to the presence of the conducting particles in the matrix. The first matrix is a regular Portland cement-based one while the second is a novel iron-based, carbonated binder developed at ASU. Four different iron replacement percentages by volume (10%, 20%, 30% and 40%) in a Portland cement matrix were selected, whereas the best performing iron carbonate matrix developed was used. Electrical impedance spectroscopy was used to obtain the characteristic Nyquist plot before and after application of flexural load. Electrical circuit models were used to extract the changes in electrical properties under application of load. Strain sensing behavior was evaluated with respect to application of different stress levels and varying replacement levels of the inclusion. A similar approach was used to study the strain sensing capabilities of novel iron carbonate binder. It was observed that the strain sensing efficiency increased with increasing iron percentage and the resistivity increased with increase in load (or applied stress) for both the matrices. It is also found that the iron carbonate binder is more efficient in strain sensing as it had a higher gage factor when compared to the OPC matrix containing metallic inclusions. Analytical equations (Maxwell) were used to extract frequency dependent electrical conductivity and permittivity of the cement paste (or the host matrix), interface, inclusion (iron) and voids to develop a generic electro-mechanical coupling model to for the strain sensing behavior. COMSOL Multiphysics 5.2a was used as finite element analysis software to develop the model. A MATLAB formulation was used to generate the microstructure with different volume fractions of inclusions. Material properties were assigned (the frequency dependent electrical parameters) and the coupled structural and electrical physics interface in COMSOL was used to model the strain sensing response. The experimental change in resistance matched well with the simulated values, indicating the applicability of the model to predict the strain sensing response of particulate composite systems. / Dissertation/Thesis / Masters Thesis Civil and Environmental Engineering 2017