La rationalisation des processus chimiques élémentaires aux surfacesest d'intérêt primordial pour de nombreux phénomènes naturels ou d'intérêttechnologique. D'un point de vue fondamental, la façon dont l'énergie, concomitanteà toute réaction chimique, est distribuée parmi les degrés de liberté des moléculesformées et/ou transférée à la surface est loin d'être systématisée. Dans ce travail,des simulations, reposant sur la méthode des trajectoires quasi-classiques (QCT),sont réalisées pour examiner cette problématique lors de recombinaisons demolécules d'hydrogène (H2) et d'azote (N2) résultant de l'abstraction d'atomesadsorbés via collision par un atome provenant de la phase gazeuse sur des surfacesde Tungstène - W(100) et W(110) - à taux de couverture non nul. Ces processussont ici étudiés pour leur intérêt en physique des interactions plasma-paroi. Dessurfaces d'énergie potentielle, construites à partir de calculs de structure électroniquebasés sur la théorie de la fonctionnelle densité (DFT), sont utilisées pour simuler,dans le cadre de la mécanique classique - incluant les corrections semi-classiquespertinentes - les processus ultrarapides dit de "Eley-Rideal" et par "atomes-chauds"(sub-picoseconde). La mise en place de modèle effectifs, pour tenir compte de ladissipation de l'énergie aux phonons de la surface et aux excitations électroniques(paires électron-trou), permet de rationaliser la dynamique non-adiabatique del'abstraction atomique aux surfaces métalliques. / The rationalization of elementary processes at surfaces is of prime importance for numerous natural and technological areas. From a fundamental pointof view, the way the energy concomitant to any chemical reaction is distributed among the desorbing molecules degrees-of-freedom and the surface is far frombeing fully pictured. In this work, quasiclassical molecular dynamics (QCT)simulations have been carried out to investigate this issue for the recombination ofH2 and N2 resulting from atomic adsorbate abstraction by atom scattering off theW(100) and W(110) covered surfaces, these processes being of relevance inplasma-wall interactions. Potential energy surfaces, built from density functional(DFT) theory calculations, have been used to simulate, within the framework ofclassical dynamics (including semi-classical corrections), the subpicosecond Eley-Rideal and Hot-Atom processes. The implementation of effective models to accountfor energy dissipation to surface phonons and electron-hole pair excitations, have allowed to rationalize the non-adidabatic dynamics of atom abstraction at metalsurfaces.

<p>Impressive examples of the generation of hierarchically-patterned, three-dimensional (3-D) structures for the control of light can be found throughout nature. <i>Morpho rhetenor</i> butterflies, for example, possess scales with periodic parallel ridges, each of which consists of a stack of thin (nanoscale) layers (lamellae). The bright blue color of <i>Morpho</i> butterflies has been attributed to controlled scattering of the incident light by the lamellae of the wing scales. Another stunning example is the frustule (microshell) of the <i>Coscinodiscus wailesii</i> diatom, which is capable of focusing red light without possessing a traditional lens morphology. The photonic structures and the optical behaviors of <i>Morpho</i> butterflies and <i>Coscinodiscus wailesii</i> diatoms have been extensively studied. However, no work has been conducted to shift such light manipulation from the visible to the infrared (IR) range via shape-preserving conversion of such biogenic structures. Controlling IR radiation (i.e., heat) utilizing biogenic or biomimetic structures can be of significant utility for the development of energy-harvesting devices. In order to enhance the optical interaction in the IR range, inorganic replicas of biogenic structures comprised of high-refractive-index materials have been generated in this work. Such replicas of <i>Morpho</i> <i>rhetenor</i> scales were fabricated via a combination of sol-gel solution coating, organic pyrolysis, and gas/solid reaction methods. Diatomimetic structures have also been generated via sol-gel coating, gas/solid reaction, and then patterning of pore arrays using focused ion beam (FIB) milling.</p> Throughout the sol-gel solution coating and chemical conversion steps of the processes developed in this study, attention was paid to preserve the starting shapes of the nanopatterned, microscale biogenic or biomimetic structures. Factors affecting such shape preservation included the thicknesses and uniformities of coatings applied to the biogenic or biomimetic templates, nano/microstructural evolution during thermal treatment, and reaction-induced volume changes. A conformal surface sol-gel (SSG) coating process was developed in this work to generate oxide replicas of <i>Morpho rhetenor</i> butterfly scales with precisely-controlled coating thicknesses. The adsorption kinetics and relevant adsorption isotherm of the SSG process were investigated utilizing a quartz crystal microbalance. Analyses of thermodynamic driving forces, rate-limiting kinetic steps, and volume changes associated with various chemical reactions were used to tailor processing parameters for optimized shape preservation.

Over the past decades, attention has been brought to the importance of indoor air quality and the serious threat of bio-aerosol contamination towards human health. A novel idea to transport hazardous particles away from sensitive areas is to automatically control bio-aerosol concentrations, by utilising airflows from ventilation systems. Regarding this, computational fluid dynamics (CFD) may be employed to investigate the dynamical behaviour of airborne particles, and data-driven methods may be used to estimate and control the complex flow simulations. This thesis presents a methodology for machine-learning based control of particle concentrations in turbulent gas-solid flow. The aim is to reduce concentration levels at a 90 degree corner, through systematic manipulation of underlying two-phase flow dynamics, where an energy constrained inlet airflow rate is used as control variable. A CFD experiment of turbulent gas-solid flow in a two-dimensional corner geometry is simulated using the SST k-omega turbulence model for the gas phase, and drag force based discrete random walk for the solid phase. Validation of the two-phase methodology is performed against a backwards facing step experiment, with a 12.2% error correspondence in maximum negative particle velocity downstream the step. Based on simulation data from the CFD experiment, a linear auto-regressive with exogenous inputs (ARX) model and a non-linear ARX based neural network (NN) is used to identify the temporal relationship between inlet flow rate and corner particle concentration. The results suggest that NN is the preferred approach for output predictions of the two-phase system, with roughly four times higher simulation accuracy compared to ARX. The identified NN model is used in a model predictive control (MPC) framework with linearisation in each time step. It is found that the output concentration can be minimised together with the input energy consumption, by means of tracking specified target trajectories. Control signals from NN-MPC also show good performance in controlling the full CFD model, with improved particle removal capabilities, compared to randomly generated signals. In terms of maximal reduction of particle concentration, the NN-MPC scheme is however outperformed by a manually constructed sine signal. In conclusion, CFD based NN-MPC is a feasible methodology for efficient reduction of particle concentrations in a corner area; particularly, a novel application for removal of indoor bio-aerosols is presented. More generally, the results show that NN-MPC may be a promising approach to turbulent multi-phase flow control.

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No presente trabalho desenvolve-se um estudo de modelagem matemática e simulação numérica do escoamento bifásico gás-sólido na coluna ascendente de um leito fluidizado circulante. Utiliza-se o modelo euleriano de duas fases separadas considerando dois procedimentos diferentes para a modelagem do tensor das tensões da fase sólida: modelo tradicional e a teoria cinética dos escoamentos granulares (TCEG). As simulações numéricas são conduzidas com a utilização do código MFIX que é um software livre e disponível na rede (Internet). Os resultados da simulação numérica são avaliados por meio da análise da influência dos seguintes parâmetros: malha computacional, correlações para o computo do tensor das tensões da fase sólida e esquemas de discretização dos termos advectivos. Também se desenvolve estudo de caracterização de estruturas coerentes - \"clusters\". De forma complementar foram realizadas duas análises teóricas compreendendo: uma análise da influência das diversas correlações utilizadas na TCEG para o computo da viscosidade dinâmica do sólido; e uma análise enfocando o emprego de diversos esquemas de discretização para os termos advectivos presentes nas equações de conservação (Foup, Muscl, Van Leer, Minmod e Superbee). De todos os estudos e resultados apresentados no trabalho conclui-se que os escoamentos gás-sólido em leitos fluidizados circulantes são muito complexos, sendo necessário a realização de futuras pesquisas para uma melhor compreensão dos fenômenos físicos inerentes a esses escoamentos. / In the present work is described a mathematical model and numerical study simulation of the gas-solid flow in the riser of a circulating fluidized bed. It is used the two fluids eulerian model considering two different procedures for the solid phase stress tensor modeling: the traditional model and the kinetic theory of granular flows (KTGF). The numerical simulation results are evaluated through the influence analysis of the following parameters: computational mesh, correlations for computing the solid phase stress tensor and the discretization of the advective terms. It is also presented a study concerning the characterization coherent structures - \"clusters\". Complementing the above studies were accomplished two theoretical analyses comprehending: an influence analysis of several correlations used in the KTGF for computing the dynamic viscosity of the solid phase; and an analysis concerning several discretization schemes for the advective terms present in the conservative equations. Considering the developed studies and the obtained results it is concluded that the gas-solid flows in circulating fluidized beds are very complex, being necessary future research works for a better comprehension of the inherent physical phenomena to these flows.

No presente trabalho desenvolve-se um estudo de modelagem matemática e simulação numérica do escoamento bifásico gás-sólido na coluna ascendente de um leito fluidizado circulante. Utiliza-se o modelo euleriano de duas fases separadas considerando dois procedimentos diferentes para a modelagem do tensor das tensões da fase sólida: modelo tradicional e a teoria cinética dos escoamentos granulares (TCEG). As simulações numéricas são conduzidas com a utilização do código MFIX que é um software livre e disponível na rede (Internet). Os resultados da simulação numérica são avaliados por meio da análise da influência dos seguintes parâmetros: malha computacional, correlações para o computo do tensor das tensões da fase sólida e esquemas de discretização dos termos advectivos. Também se desenvolve estudo de caracterização de estruturas coerentes - \"clusters\". De forma complementar foram realizadas duas análises teóricas compreendendo: uma análise da influência das diversas correlações utilizadas na TCEG para o computo da viscosidade dinâmica do sólido; e uma análise enfocando o emprego de diversos esquemas de discretização para os termos advectivos presentes nas equações de conservação (Foup, Muscl, Van Leer, Minmod e Superbee). De todos os estudos e resultados apresentados no trabalho conclui-se que os escoamentos gás-sólido em leitos fluidizados circulantes são muito complexos, sendo necessário a realização de futuras pesquisas para uma melhor compreensão dos fenômenos físicos inerentes a esses escoamentos. / In the present work is described a mathematical model and numerical study simulation of the gas-solid flow in the riser of a circulating fluidized bed. It is used the two fluids eulerian model considering two different procedures for the solid phase stress tensor modeling: the traditional model and the kinetic theory of granular flows (KTGF). The numerical simulation results are evaluated through the influence analysis of the following parameters: computational mesh, correlations for computing the solid phase stress tensor and the discretization of the advective terms. It is also presented a study concerning the characterization coherent structures - \"clusters\". Complementing the above studies were accomplished two theoretical analyses comprehending: an influence analysis of several correlations used in the KTGF for computing the dynamic viscosity of the solid phase; and an analysis concerning several discretization schemes for the advective terms present in the conservative equations. Considering the developed studies and the obtained results it is concluded that the gas-solid flows in circulating fluidized beds are very complex, being necessary future research works for a better comprehension of the inherent physical phenomena to these flows.