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<p dir="ltr">The demand for sustainable and renewable energy sources has prompted significant research and development efforts in the field of biomass gasification. Biomass gasification technology holds significant promise for sustainable energy production, offering a renewable alternative to fossil fuels while mitigating environmental impact. This thesis presents a detailed study on the design, development, and implementation of a Plug-Flow Reactor Biomass Gasifier integrated with an Automated Auger Jam Detection System and a Blower Algorithm to maintain constant reactor pressure by varying blower speed with respect to changes in reactor pressure. The system is based on indirectly- heated pyrolytic gasification technology and is developed using Simulink™.</p><p dir="ltr">The proposed gasification system use the principles of pyrolysis and gasification to convert biomass feedstock into syngas efficiently. An innovative plug-flow reactor configuration ensures uniform heat distribution and residence time, optimizing gasification performance and product quality. Additionally, the system incorporates an automated auger jam detection system, which utilizes sensor data to detect and mitigate auger jams in real-time, thereby enhancing operational reliability and efficiency. By monitoring these parameters, the system detects deviations from normal operating conditions indicative of auger jams and initiates corrective actions automatically. The detection algorithm is trained using test cases and validated through detailed testing to ensure accurate and reliable performance.</p><p dir="ltr">The MATLAB™-based implementation offers flexibility, scalability, and ease of integration with existing gasifier control systems. The graphical user interface (GUI) provides operators with real-time monitoring and visualization of system status, auger performance, and detected jam events. Additionally, the system generates alerts and notifications to inform operators of detected jams, enabling timely intervention and preventive maintenance. </p><p dir="ltr">To maintain consistent gasification conditions, a blower algorithm is developed to regulate airflow and maintain constant reactor pressure within the gasifier. The blower algorithm dynamically adjusts blower speed based on feedback from differential pressure sensors, ensuring optimal gasification performance under varying operating conditions. The integration of the blower algorithm into the gasification system contributes to stable syngas production and improved process control. The development of the Plug-Flow Reactor Biomass Gasifier, Automated Auger Jam Detection System, and Blower Algorithm is accompanied by rigorous simulation studies and experimental validation.</p><p dir="ltr">Overall, this thesis contributes to the advancement of biomass gasification technology by presenting a detailed study on a plug flow reactor biomass gasifier with indirectly- heated pyrolytic gasification technology with an Automated Auger Jam Detection System and Blower Algorithm. The findings offer valuable insights for researchers, engineers, policymakers, and industry stakeholders supporting the transition towards cleaner and more renewable energy systems.</p>

<p>In this thesis we have performed core-electron spectroscopy studies of gas phase molecular systems starting with smaller diatomic, continuing with triatomic and extending our research to more complex polyatomic ones. We can subdivide the results presented here into two categories: the first one focusing on electronic fine structure and effect of the chemical bonds on molecular core-levels and the other one dealing with nuclear dynamics induced by creation of a core hole. In our research we have mostly used synchrotron radiation based techniques such as X-ray Photoelectron (XPS), X-ray Absorption (XAS), normal and Resonant Auger (AES and RAS, respectively) and Energy-Selected Auger Electron PhotoIon COincidence (ES-AEPICO) spectroscopies.</p><p>We have demonstrated that resonant Auger spectroscopy can be used to aid interpretation of the features observed in XAS for Rydberg structures in the case of Cl₂ and C1s⁻¹π*¹ states of allene molecules. The combined use of high-resolution spectroscopy with <i>ab initio</i> calculations can help the interpretation of strongly overlapped spectral features and disentangle their complex profiles. This approach enabled us to determine the differences in the lifetimes for core-hole 2p sublevels of Cl₂ which are caused by the presence of the chemical bond. We have shown that contribution in terms of the Mulliken population of valence molecular orbitals is a determining factor for resonant enhancement of different final states and fragmentation patterns reached after resonant Auger decays in N₂O.</p><p>We have also performed a systematic study of the dependence of the C1s resonant Auger kinetic energies on the presence of different substituents in CH₃X compounds. For the first time we have studied possible isomerization reaction induced by core excitation of acetylacetone. We could observe a new spectral feature in the resonant Auger decay spectra which we interpreted as a signature of core-excitation-induced keto-enol tautomerism.</p>

In this thesis we have performed core-electron spectroscopy studies of gas phase molecular systems starting with smaller diatomic, continuing with triatomic and extending our research to more complex polyatomic ones. We can subdivide the results presented here into two categories: the first one focusing on electronic fine structure and effect of the chemical bonds on molecular core-levels and the other one dealing with nuclear dynamics induced by creation of a core hole. In our research we have mostly used synchrotron radiation based techniques such as X-ray Photoelectron (XPS), X-ray Absorption (XAS), normal and Resonant Auger (AES and RAS, respectively) and Energy-Selected Auger Electron PhotoIon COincidence (ES-AEPICO) spectroscopies. We have demonstrated that resonant Auger spectroscopy can be used to aid interpretation of the features observed in XAS for Rydberg structures in the case of Cl2 and C1s−1π*1 states of allene molecules. The combined use of high-resolution spectroscopy with ab initio calculations can help the interpretation of strongly overlapped spectral features and disentangle their complex profiles. This approach enabled us to determine the differences in the lifetimes for core-hole 2p sublevels of Cl2 which are caused by the presence of the chemical bond. We have shown that contribution in terms of the Mulliken population of valence molecular orbitals is a determining factor for resonant enhancement of different final states and fragmentation patterns reached after resonant Auger decays in N2O. We have also performed a systematic study of the dependence of the C1s resonant Auger kinetic energies on the presence of different substituents in CH3X compounds. For the first time we have studied possible isomerization reaction induced by core excitation of acetylacetone. We could observe a new spectral feature in the resonant Auger decay spectra which we interpreted as a signature of core-excitation-induced keto-enol tautomerism.

<p>This thesis contains two parts. The first part concerns the research work on free molecules using synchrotron-radiation-related techniques. Auger electron spectra of two free open-shell molecules, O₂ and NO, were studied experimentally and theoretically. Photoionization experimental technique with tunable synchrotron radiation source was used to induce core-level electron ionization and obtain the <i>KVV</i> normal Auger electron spectra. A quantitative assignment of O₂ normal Auger spectrum was obtained by applying <i>ab initio</i> CI calculations and LVI Auger line shape simulations including the bond length dependence of Auger transition rates. The photon energy dependence of normal Auger electron spectra was focused on with photon energies in the vicinities of core-ionization threshold energies. Consequently, the MAPCI (Molecular Auger Post Collision Interaction) theory was developed. Taking the near-threshold O₂ normal Auger spectrum as an example, the two extreme cases of MAPCI effect, “atomic-like PCI” and “molecular PCI”, were discovered and discussed. The effect of shape resonance on near-threshold molecular normal Auger spectrum was discussed taking NO near threshold normal Auger spectra as example.</p><p>The second part deals with research work on the chemisorption of small epoxy organic molecules, ethylene oxide, methyl oxirane, on Si (100) surfaces. Synchrotron radiation related techniques, UPS, XPS and NEXAFS, were applied. Based on the valence photoemission spectra, C 1<i>s</i> and Si 2<i>p</i> XPS spectra, the epoxy ring opening reactions of these molecules in chemisorption process were proved. Further tentative search for the surface-adsorbate CDAD effect was performed, and no evident circular dichroism was confirmed.</p>

Ce manuscrit présente différentes études expérimentales des collisions en incidence rasante (< 3 degrés) sur LiF(001) d'ions simplement chargés tels que le néon et le fluor de basses énergies (< 3 keV). Le faisceau incident est pulsé. Le produit de la diffusion après une analyse en charge entre des plaques électrostatiques est détecté sur un détecteur sensible en position. Les particules secondaires (électrons ou ions) sont recueillies sur un détecteur composé de 16 unités de détection (2 galettes microcanaux) couvrant 2p stéradian au dessus de la surface. La technique de mesure de perte d'énergie (spectroscopie de translation) associée à la détection des particules diffusées en coïncidence avec les électrons émis de la surface lors de la collision d'ions néons simplement chargés, a permis de mettre en évidence des états excités de la surface. Ces états excités, localisés sur les ions fluors négatifs de la surface, sont soit centrés autour d'une seule lacune (les excitons), soit autour de 2 lacunes, ce dernier, complexe à 3 corps est connu dans la littérature sous le nom de trion. On trouvera dans ce manuscrit la première caractérisation de ces états par impact d'ions. Dans le cas du néon la capture correspond à une neutralisation Auger Les collisions d'atomes de fluors ont confirmé l'existence d'un seuil en vitesse, lors de la formation des ions négatifs. La formation de ces ions à partir d'ions positifs sous ce seuil, donne une preuve expérimentale d'une double capture simultanée. La valeur de la perte d'énergie s'explique correctement si l'on tient compte de l'interaction entre les deux lacunes voisines. La corrélation statistique se double donc d'une corrélation spatiale où les captures d'électrons s'effectuent sur deux sites halogènes voisins. Dans ce cas l'expérience ne permet pas de différencier un processus di-électronique d'un processus mono-électronique du second ordre alors que la théorie semble indiquer qu'il s'agit de processus du second ordre.

Les matériaux de couverture des réacteurs à fusion nucléaire par confinement magnétique subissent un environnement agressif ; le flux intense de particules extraites du plasma attaque les parois du réacteur, engendrant la pulvérisation de la matière en surface. Cette pulvérisation est à l'origine de l'érosion des parois mais aussi de la pollution du plasma, ainsi, afin de maitriser la réaction de fusion dans des réacteurs de plus en plus complexes, il est impératif de bien comprendre les phénomènes d'interaction plasma-paroi. Cette thèse a pour but l'étude de la pulvérisation des matériaux des réacteurs de fusion nucléaire (carbone et tungstène), pour cela nous proposons de simuler le flux de particules chargées du plasma par des faisceaux d'ions monochargés d'énergies inférieures à la dizaine de keV. Cette étude est basée sur la méthode du collecteur, aussi afin de s'affranchir des problèmes liés aux polluants (notamment pour l'étude du carbone), nous avons conçu et réalisé un nouveau dispositif permettant l'analyse des collecteurs in situ par spectroscopie des électrons Auger. Les résultats obtenus donnent accès à l'évolution de la distribution angulaire en fonction des paramètres d'irradiation comme la masse du projectile (de hélium au xénon) ou l'énergie (de 3 keV à 9 keV).

Esta dissertação apresenta uma avaliação do comportamento de estacas hélice contínua quanto à capacidade de carga, ao recalque e à segurança e confiabilidade, a partir de um cenário de análise em que foi considerado um banco de dados de 58 provas de carga estáticas, realizadas em estacas hélice contínua de 13 obras distintas. Esta pesquisa está focada principalmente no comportamento carga-recalque e confiabilidade de fundações em estacas hélice contínua. Nesta análise foi também verificada a aplicabilidade do método proposto por Aoki (1989) para determinação da curva carga-recalque destas provas de carga. Os valores de capacidade de carga medidos foram comparados com os previstos pelos método Aoki & Velloso (1975), o método Decourt & Quaresma (1978), o método de Cabral (1996), e o método Alonso (1996). Estes métodos também foram utilizados para previsão de transferência de carga nas estacas, necessária para a previsão da curva carga-recalque pelos método de Aoki (1989). Adicionalmente, com os resultados das provas de carga foram estimadas para cada obra a probabilidade de ruína da fundação, e de ocorrência de recalques superiores a um valor limite. / This dissertation presents an evaluation of the behavior of continuous flight auger piles on ultimate capacity, settlments, safety and reliability, from a scenario analysis in which we considered a database of 58 static load tests, performed on piles of 13 distinct sites. However, this research is focused on the loaddisplacement behavior and reliability of this type of foundation. This analysis also verified the applicability of the method proposed by Aoki (1989) to determine the load-displacement curve of these pile load tests. The values of measured pile capacity were compared with those provided by the method Aoki & Velloso (1975), the method Decourt & Quaresma (1978), the method Cabral (1996), and the method Alonso (1996). These methods were also used to predict the load transfer along the piles, necessary to predict the load-displacement curve by the method of Aoki (1989). Additionally, the results of these load tests were used to estimate the probability of failure of the foundations tested, and the occurrence of settlements exceeding a threshold value.

In the nanoscale metrology industry, there is a need for low-cost instruments, which have the ability to probe the structrure and elemental composition of thin films. This dissertation, describes the research performed to design and simulate a miniature Cylindrical Mirror Analyzer, (CMA), and Auger Electron Spectrometer, (AES). The CMA includes an integrated coaxial thermionic electron source. Electron optics simulations were performed using the Finite Element Method, (FEM), software COMSOL. To address the large Secondary Electron, (SE), noise, inherent in AES spectra, this research also included experiments to create structures in materials, which were intended to suppress SE backgound noise in the CMA. Laser Beam Machining, (LBM), of copper substrates was used to create copper pillars with very high surface areas, which were designed to supress SE’s. The LBM was performed with a Lumera SUPER RAPID‐HE model Neodymium Vanadate laser. The laser has a peak output power of 30 megawatts, has a 5x lens and a spot size of 16 μm. The laser wavelength is in the infrared at 1064 nm, a pulse width of 15 picoseconds, and pulse repetition rate up to 100 kHz. The spectrometer used in this research is intended for use when performing chemical analysis of the surface of bulk materials and thin films. It is applicable for metrology of thin films, as low as 0.4 nm in thickness, without the need to perform destructive sample thinning, which is required in Scanning Tranmission Electron Microscopy, (STEM). The spectrometer design is based on the well known and widely used coaxial cylinder capacitor design known as the Cylindrical Mirror Analyzer, (CMA). The coaxial tube arrangement of the CMA allows for placing an electron source,which is mounted in the center of the inner cylinder of the spectrometer. Simulation of the electron source with an Einzel Lens was also performed. In addtion, experiments with thin film coatings and Laser Beam Machining to supress Secondary Electron emission noise within the Auger electron spectrum were completed. Design geometry for the miniature CMA were modeled using Computer Aided Design, (CAD). Fixed Boundary Conditions, (BC), were applied and the geometry was then meshed for FEM. The electrostatic potential was then solved using the Poisson equation at each point. Having found the solution to the electrostatic potentials, electron flight simulations were performed and compared with the analytical solution. From several commercially available FEM modeling packages, COMSOL Multiphysics was chosen as the research platform for modeling of the spectrometer design. The CMA in this design was reduced in size by a factor of 4 to 5. This enabled mounting the CMA on a 2 ¾ in flange compared to the commercial PHI model 660 CMA which mounts onto a 10 in flange. Results from the Scanning Electron Microscopy measurements of the Secondary Electron emission characteristics of the LBM electron suppressor will also be presented.

Cette thèse a porté principalement sur la caractérisation de nanocristaux dont la structure permet de réduire de façon drastique leur scintillement. La caractéristique essentielle de ces nanocristaux de CdSe est qu'ils sont entourés d'une coquille épitaxiée très épaisse de CdS qui les préserve d'interactions trop importantes avec l'extérieur. La réalisation d'une coquille très épaisse permet de supprimer les longues périodes d'extinction. De plus, on a pu vérifier que si le trou reste localisé dans le coeur du nanocristal, l'électron est délocalisé dans l'ensemble de la structure. Cet effet de délocalisation provoque une réduction de l'efficacité des processus Auger. À bas taux de pompage, cette propriété implique que les nanocristaux ne présentent plus d'états réellement éteints. Ce résultat, associé aux mesures des durées de vie correspondant aux périodes d'extinction et d'émission, nous a permis de calculer les taux de recombinaisons des différents processus en jeu dans un nanocristal faiblement excité, qu'il soit neutre ou ionisé. A plus fort taux de pompage, nous montrons la possibilité d'observer des cascades radiatives consécutives à des recombinaisons d'états multiexcitoniques. La dernière partie a été consacrée à des premiers résultats concernant le contrôle de l'émission de nanocristaux par leur insertion dans des cavités photoniques à miroirs de Bragg. Nous observons l'émission de photons uniques et nous démontrons l'effet de la cavité sur la durée de vie radiative des nanocristaux.