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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
261

Membrane Electrochemical Treatment of Landfill Leachate: Processes, Performance and Challenges

Liu, Xingjian 13 April 2020 (has links)
Landfilling is the most common approach to dispose of municipal solid wastes but inevitably leads to leachate formation. Persistent UV quenching substances (UVQS) in landfill leachate can affect the effectiveness of UV disinfection in municipal wastewater treatment systems when leachate co-treatment is applied. Membrane electrochemical reactor (MER) treatment was investigated to reduce the UV quenching capability and simultaneously recover resources in the leachate as an effective onsite pre-treatment. Ion-selective membranes were used in this MER to create two different conditions: a low-pH anolyte for organic oxidation and a high-pH catholyte for ammonia recovery. The MER achieved significantly higher removals of both dissolved organic carbon and UV254nm absorbance than membrane-less electrochemical treatment. The MER was able to remove a large percentage of total nitrogen from the leachate while recovering about half of the influent ammonia in the catholyte with less specific energy consumption. The second study coupled MER with Fenton oxidation through providing synergistic benefits with the low solution pH, reduced organics, and ammonia removal. This two-stage coupled system reduced the more leachate COD than the standalone Fenton process treating raw leachate. Also, the usage of chemicals as Fenton reagents has been greatly reduced: FeSO4 and H2O2 by 39%, H2SO4 by 100%, and NaOH by 55%. Consequently, the sludge production was reduced by 51% in weight and 12% in volume. Despite electricity consumption by the MER, the coupled system cost $4.76 per m3 leachate less than the standalone Fenton treatment. More notably, direct Fenton oxidation removed only 21% of ammonia; in comparison, the MER-Fenton system removed ammonia by 98% with the possibility for recovery at a rate of 30.6 -55.2 kg N m-3 reactor d-1. Those results demonstrated that coupling MER with the Fenton process could mitigate some inherent drawbacks of Fenton oxidation such as ineffective ammonia removal, high acid and chemical reagents dose requirements, and a large amount of sludge generation. The third study investigated the formation of total halogenated organics (DBP) and the associated toxicity as the side effect of leachate treatment in the MER. Compared to the 4538±100 µg L-1 from the control membrane-less electrochemical oxidation reactor, the amount of DBP generated in the MER only accounted for 19.1±4.5 % after the same treatment period. The total toxicity value (26.6 ×10-3 ) was low for MER effluent, only 15.1% of that in the control group. Both high pH and high ammonia concentration introduced more DBP mass and toxicity production after MER treatment. DBP concentrations were shown to increase with applied current density and possible temperature raise. With 67.5% of DBP mass concentration and 74.4% of the additive toxicity removal, the granular activated carbon (GAC) electrode system was shown more effective than GAC adsorption alone in remediating DBP harmful effects. This dissertation introduced MER as a promising technology for the treatment of leachate through performance demonstration, process integration and by-product remediation. / Doctor of Philosophy / Municipal solid waste is often disposed of in landfills because of the most economics and convenience. However, one of the most challenging problems is the leachate formation and treatment. In the US, leachate is currently often diluted in domestic wastewater treatment systems; meanwhile, the persistent contaminants in landfill leachate can lower the effectiveness of UV disinfection and result in high cost and permit violation. In this study, the membrane electrochemical reactor (MER) using electricity as the driving force was applied to solve the issue and simultaneously recover valuable resources in the leachate. Membranes as a barrier for selective ions were used in this MER to create two different conditions with different purposes: a low-pH anolyte for organic oxidation and a high-pH catholyte for ammonia recovery. The MER achieved significantly higher contaminants removals than membrane-less electrochemical treatment. The second study coupled MER with one of the established advanced oxidation processes, also known as Fenton oxidation through providing mutual benefits with the low solution pH, reduced organics, and ammonia removal/recovery. This two-stage coupled system reduced the leachate contaminants effectively towards the direct discharge standard. In addition, the usage of chemical reagents, as well as the amount of process residual, has significantly been reduced. The third study investigated the formation of by-products as the side effect of leachate treatment in the MER. Compared to the membrane-less reactor, the undesirable by-products generated in the MER only accounted for one fifth after the same treatment period. A granular activated carbon electrode system was shown effective in remediating the harmful effects. This dissertation introduced MER as a promising technology for the treatment of leachate as one of the toughest wastewaters.
262

Modeling of Nonlinear Unsteady Aerodynamics, Dynamics and Fluid Structure Interactions

Yan, Zhimiao 29 January 2015 (has links)
We model different nonlinear systems, analyze their nonlinear aspects and discuss their applications. First, we present a semi-analytical, geometrically-exact, unsteady potential flow model is developed for airfoils undergoing large amplitude maneuvers. Towards this objective, the classical unsteady theory of Theodorsen is revisited by relaxing some of the major assumptions such as (1) flat wake, (2) small angle of attack, (3) small disturbances to the mean flow components, and (4) time-invariant free-stream. The kinematics of the wake vortices is simulated numerically while the wake and bound circulation distribution and, consequently, the associated pressure distribution are determined analytically. The steady and unsteady behaviors of the developed model are validated against experimental and computational results. The model is then used to determine the lift frequency response at different mean angles of attack. Second, we investigate the nonlinear characteristics of an autoparametric vibration system. This system consists of a base structure and a cantilever beam with a tip mass. The dynamic equations for the system are derived using the extended Hamilton's principle. The method of multiple scales is then used to analytically determine the stability and bifurcation of the system. The effects of the amplitude and frequency of the external force, the damping coefficient and frequency of the attached cantilever beam and the tip mass on the nonlinear responses of the system are determined. As an application, the concept of energy harvesting based on the autoparametric vibration system consisting of a base structure subjected to the external force and a cantilever beam with a tip mass is evaluated. Piezoelectric sheets are attached to the cantilever beam to convert the vibrations of the base structure into electrical energy. The coupled nonlinear distributed-parameter model is developed and analyzed. The effects of the electrical load resistance on the global frequency and damping ratio of the cantilever beam are analyzed by linearizion of the governing equations and perturbation method. Nonlinear analysis is performed to investigate the impacts of external force and load resistance on the response of the harvester. Finally, the concept of harvesting energy from ambient and galloping vibrations of a bluff body is investigated. A piezoelectric transducer is attached to the transverse degree of freedom of the body in order to convert the vibration energy to electrical power. A coupled nonlinear distributed-parameter model is developed that takes into consideration the galloping force and moment nonlinearities and the base excitation effects. The aerodynamic loads are modeled using the quasi-steady approximation. Linear analysis is performed to determine the effects of the electrical load resistance and wind speed on the global damping and frequency of the harvester as well as on the onset of instability. Then, nonlinear analysis is performed to investigate the impact of the base acceleration, wind speed, and electrical load resistance on the performance of the harvester and the associated nonlinear phenomena. Short- and open-circuit configurations for different wind speeds and base accelerations are assessed. / Ph. D.
263

Membrane binding properties of Disabled-2

Alajlouni, Ruba 10 May 2011 (has links)
Disabled-2 (Dab2) is an adapter protein that interacts with cell membranes and it is involved in several biological processes including endocytosis and platelet aggregation. During endocytosis, the Dab2 phosphotyrosine-binding (PTB) domain mediates protein binding to phosphatidylinositol 4,5-bisphosphate (PIP2) at the inner leaflet of the plasma membrane and helps co-localization with clathrin coats. Dab2, released from platelet alpha granules, inhibits platelet aggregation by binding to the °IIb? integrin receptor on the platelet surface through an Arg-Gly-Asp (RGD) motif located within the PTB domain. Alternatively, Dab2 binds sulfatides on the platelets surface, and this binding partition Dab2 in two pools (sulfatide and integrin receptor-bound states), but the biological consequences of lipid binding remain unclear. Dab2 binds sulfatides through two basic motifs located on its N-terminal region including the PTB domain (N-PTB). We have characterized the binding of Dab2 to micelles, which are widely used to mimic biological membranes. These micellar interactions were studied in the absence and presence of Dab2 lipid ligands, sulfatides and PIP2. By applying multiple biochemical, biophysical, and structural techniques, we found that whereas Dab2 N-PTB binding to PIP2 stabilized the protein but did not contribute to the penetration of the protein into micelles, sulfatides induced conformational changes and facilitated penetration of Dab2 N-PTB into micelles. This is in agreement with previous observation that sulfatides, but not PIP2, protect Dab2 N-PTB from thrombin cleavage. By studying the mechanism by which Dab2 targets membranes, we will have the opportunity to manipulate its function in different lipid-dependent biological processes. / Master of Science
264

Nutzung der Photolumineszenz von Quantenpunkten für die Belastungsdetektion an Leichtbaumaterialien

Möbius, Martin 17 February 2021 (has links)
Die vorliegende Arbeit beschäftigt sich mit der Entwicklung eines neuartigen, autarken, folienbasierten Sensorsystems für die Belastungsdetektion an Leichtbaumaterialien. Das integrierte Sensorsystem ist in der Lage mechanische Belastungen über die Photolumineszenz von Quantum Dots visuell darzustellen, wodurch strukturelle Defekte in Leichtbaumaterialien frühzeitig erkannt und ein Totalausfall einer gesamten Leichtbaukonstruktion verhindert werden kann. Dies führt neben einer erhöhten Sicherheit einzelner Komponenten und kompletter Konstruktionen auch zu Gewichts-, Kosten- und Rohstoffersparnissen. Die gezielte Beeinflussung der Photolumineszenz von Quantum Dots durch Ladungsträgerinjektion als Hauptmechanismus des Sensorsystems erfordert spezielle Lagenaufbauten von Dünnschichtsystemen. Durch die Kombination dieser Dünnschichtsysteme mit piezoelektrischen Materialien entsteht ein autarkes Sensorsystem, wodurch eine Auswertung, Visualisierung und Speicherung der Information über eine stattgefundene mechanische Belastung an Leichtbaumaterialien auf kleinsten Raum erreicht wird.:Inhaltsverzeichnis Formelverzeichnis Abkürzungsverzeichnis Vorwort 1 Einleitung 1.1 Motivation 1.2 Zielstellung 2 Autarker Sensor für mechanische Beanspruchungen 2.1 Sensorkonzept, -aufbau und Funktionsweise 2.2 Anforderungen an die Funktionalität 2.3 Stand der Technik 3 Theoretische Grundlagen 3.1 Quantum Dots 3.1.1 Größenquantisierungseffekt 3.1.2 Photolumineszenz 3.1.3 Aufbau und Materialien 3.1.4 Kommerziell erhältliche Quantum Dots 3.2 Mechanismen zur Beeinflussung der Photolumineszenz 3.2.1 Ladungsträgerinjektion in den QD Kern 3.2.2 Feldinduzierte Ionisation des Exzitons 3.2.3 Weitere Mechanismen 3.3 Ladungsträgertransportschichten 3.3.1 Poly(N-vinylkarbazol) 3.3.2 N,N,N´,N´-Tetrakis(3-methylphenyl)-3,3´-dimethylbenzidin 3.3.3 Poly(3,4-ethylendioxythiophen)-poly(styrolsulfonat) 3.4 Lithiumfluorid als elektrischer Isolator 3.5 Modellsysteme 3.5.1 Einbettung der QDs in organische Lochtransportschichten 3.5.2 QDs zwischen Elektrode und organischer Lochtransportschicht 3.5.3 QDs zwischen Elektrode und Nichtleiter 4 Experimentelle Vorgehensweise 4.1 Layout und Kontaktierung von Teststrukturen 4.2 Verfahren zur Herstellung dünner Schichten 4.2.1 Physikalische Gasphasenabscheidung 4.2.2 Rotationsbeschichtung 4.2.3 Weitere Verfahren 4.3 Charakterisierung der Schichten und der Gesamtfunktionalität 4.3.1 Mikrospektroskopieaufbau 4.3.2 Weitere Messverfahren 4.4 Integration der Schichtstapel in Faserkunststoffverbund 5 Experimentelle Untersuchungen 5.1 Einordnung der einzelnen Schichten der Modellsysteme 5.1.1 Elektroden 5.1.2 Matrixmaterial und Quantum Dots 5.2 Einordnung des elektrischen Verhaltens der Modellsysteme 5.2.1 Modellsystem I 5.2.2 Modellsystem II 5.2.3 Modellsystem III 5.3 Einfluss externer Beleuchtung am Modellsystem II und III 5.3.1 Modellsystem II 5.3.2 Modellsystem III 5.4 Wiederholbarkeit der elektrischen Beanspruchung am Modellsystem III 5.4.1 Photolumineszenzintensität 5.4.2 Stromdichte 5.4.3 Gesamtwiderstand im Schichtstapel 5.5 Einfluss des elektrischen Feldes am Modellsystem III 5.5.1 Photolumineszenzintensität 5.5.2 Stromdichte 5.5.3 Widerstand 5.6 Einfluss der Integration auf das Verhalten von Modellsystem III 5.6.1 Optisches Verhalten der Laminiertasche und des Harzsystems 5.6.2 Funktionalität des Schichtstapels nach der Integration 5.7 Temperaturwechseltest am integrierten Schichtstapel 5.8 Speicherzeit elektrischer Ladungsträger am Modellsystem III 5.8.1 Stabilität des Lasers und der PL Intensität 5.8.2 Reproduzierbarkeit 5.8.3 Langzeitmessung 5.9 Kopplung des Schichtsystems mit piezoelektrischem Element 6 Zusammenfassung und Ausblick 6.1 Zusammenfassung 6.2 Ausblick Anhang A : Layouts für untere Elektrode E1 und obere Elektrode E2 Anhang B : Halter für die Kontaktierung der Teststrukturen Anhang C : Frontpanel zur Aufnahme der Photolumineszenz Anhang D : Messdaten Profilometer Veeco Dektak 150 Literaturverzeichnis Abbildungsverzeichnis Tabellenverzeichnis Lebenslauf / This work focuses on the development of a novel, self-sufficient, film-based sensor system for load detection on lightweight materials. The integrated sensor system is capable to visualize mechanical loads on lightweight structures by quenching the photoluminescence of quantum dots. Structural defects in lightweight materials can thus be detected at an early stage and total failure of an entire lightweight structure can be prevented. In addition to increased safety of individual components and complete structures, this also leads to weight, cost and raw material savings. The quenching of the photoluminescence of quantum dots by charge carrier injection as the main mechanism of the sensor system requires special thin-film layer stacks. By combining these thin-film layer stacks with piezoelectric materials, a self-sufficient sensor system is created. An evaluation, visualization and storage of the information about a mechanical load that has taken place on lightweight materials is thus achieved in a very small space.:Inhaltsverzeichnis Formelverzeichnis Abkürzungsverzeichnis Vorwort 1 Einleitung 1.1 Motivation 1.2 Zielstellung 2 Autarker Sensor für mechanische Beanspruchungen 2.1 Sensorkonzept, -aufbau und Funktionsweise 2.2 Anforderungen an die Funktionalität 2.3 Stand der Technik 3 Theoretische Grundlagen 3.1 Quantum Dots 3.1.1 Größenquantisierungseffekt 3.1.2 Photolumineszenz 3.1.3 Aufbau und Materialien 3.1.4 Kommerziell erhältliche Quantum Dots 3.2 Mechanismen zur Beeinflussung der Photolumineszenz 3.2.1 Ladungsträgerinjektion in den QD Kern 3.2.2 Feldinduzierte Ionisation des Exzitons 3.2.3 Weitere Mechanismen 3.3 Ladungsträgertransportschichten 3.3.1 Poly(N-vinylkarbazol) 3.3.2 N,N,N´,N´-Tetrakis(3-methylphenyl)-3,3´-dimethylbenzidin 3.3.3 Poly(3,4-ethylendioxythiophen)-poly(styrolsulfonat) 3.4 Lithiumfluorid als elektrischer Isolator 3.5 Modellsysteme 3.5.1 Einbettung der QDs in organische Lochtransportschichten 3.5.2 QDs zwischen Elektrode und organischer Lochtransportschicht 3.5.3 QDs zwischen Elektrode und Nichtleiter 4 Experimentelle Vorgehensweise 4.1 Layout und Kontaktierung von Teststrukturen 4.2 Verfahren zur Herstellung dünner Schichten 4.2.1 Physikalische Gasphasenabscheidung 4.2.2 Rotationsbeschichtung 4.2.3 Weitere Verfahren 4.3 Charakterisierung der Schichten und der Gesamtfunktionalität 4.3.1 Mikrospektroskopieaufbau 4.3.2 Weitere Messverfahren 4.4 Integration der Schichtstapel in Faserkunststoffverbund 5 Experimentelle Untersuchungen 5.1 Einordnung der einzelnen Schichten der Modellsysteme 5.1.1 Elektroden 5.1.2 Matrixmaterial und Quantum Dots 5.2 Einordnung des elektrischen Verhaltens der Modellsysteme 5.2.1 Modellsystem I 5.2.2 Modellsystem II 5.2.3 Modellsystem III 5.3 Einfluss externer Beleuchtung am Modellsystem II und III 5.3.1 Modellsystem II 5.3.2 Modellsystem III 5.4 Wiederholbarkeit der elektrischen Beanspruchung am Modellsystem III 5.4.1 Photolumineszenzintensität 5.4.2 Stromdichte 5.4.3 Gesamtwiderstand im Schichtstapel 5.5 Einfluss des elektrischen Feldes am Modellsystem III 5.5.1 Photolumineszenzintensität 5.5.2 Stromdichte 5.5.3 Widerstand 5.6 Einfluss der Integration auf das Verhalten von Modellsystem III 5.6.1 Optisches Verhalten der Laminiertasche und des Harzsystems 5.6.2 Funktionalität des Schichtstapels nach der Integration 5.7 Temperaturwechseltest am integrierten Schichtstapel 5.8 Speicherzeit elektrischer Ladungsträger am Modellsystem III 5.8.1 Stabilität des Lasers und der PL Intensität 5.8.2 Reproduzierbarkeit 5.8.3 Langzeitmessung 5.9 Kopplung des Schichtsystems mit piezoelektrischem Element 6 Zusammenfassung und Ausblick 6.1 Zusammenfassung 6.2 Ausblick Anhang A : Layouts für untere Elektrode E1 und obere Elektrode E2 Anhang B : Halter für die Kontaktierung der Teststrukturen Anhang C : Frontpanel zur Aufnahme der Photolumineszenz Anhang D : Messdaten Profilometer Veeco Dektak 150 Literaturverzeichnis Abbildungsverzeichnis Tabellenverzeichnis Lebenslauf
265

Conception d'un circuit d'étouffement de photodiodes avalanches monophotoniques pour une intégration matricielle dans un module de comptage monophotonique

Nolet, Frédéric January 2016 (has links)
De nombreuses applications en sciences nucléaires bénéficieraient d’un détecteur possédant une précision temporelle de 10 ps largeur à mi-hauteur à la mesure d’un photon unique. Par exemple, le projet de Time-Imaging Calorimeter en cours de conception au CERN requiert un détecteur possédant une telle précision temporelle afin de mesurer le temps de vol (TDV) et la trajectoire des particules émises lors des collisions dans les expériences du Large Hadron Collider (LHC), ce qui permet d’identifier ces dites particules. De plus, un détecteur possédant une précision temporelle de l’ordre de 10 ps permettra la mitigation de l’empilement des événements. Un second exemple est la tomographie d’émission par positrons (TEP), une modalité d’imagerie médicale non-invasive qui mesure la distribution d’un traceur radioactif afin d’étudier et détecter le cancer. Dans le but de développer un scanner TEP temps réel, le groupe de recherche en appareillage médical de Sherbrooke (GRAMS) travaille sur l’intégration de la mesure du TDV de l’interaction TEP. Les meilleures performances actuelles des détecteurs TEP se situent aux alentours de 150 ps, ce qui n’est pas suffisant pour intégrer le TDV dans un scanner TEP préclinique. Cette mesure exige une résolution temporelle TEP de l’ordre de 10 ps. La solution proposée par le GRAMS est de développer un module de comptage monophotonique (MCMP) 3D qui est composé d’une matrice de photodiodes avalanches monophotoniques (PAMP) reliée par des interconnexions verticales (TSV) à une matrice de circuits de lecture composée d’un circuit d’étouffement et d’un convertisseur temps-numérique. Ce détecteur permet donc de mesurer précisément le temps d’arrivée de chaque photon détecté. Ce document présente la conception du circuit d’étouffement réalisé en technologie CMOS 65 nm de TSMC (Taiwan Semiconductor Manufacturing Company) intégré à chaque pixel de 50 × 50 µm2 dans un MCMP 3D. Afin de répondre au besoin de précision temporelle de 10 ps dans un détecteur 3D, le circuit proposé est un circuit d’étouffement passif avec une recharge active possédant un amplificateur opérationnel en boucle ouverte à titre de comparateur de tension. L’amplificateur opérationnel utilisé possède un seuil ajustable de 0 à 2,5 V afin d’être en mesure d’évaluer le seuil optimal pour la mesure de gigue temporelle avec une PAMP. La taille finale du circuit d’étouffement est de 18 × 30 µm2 incluant l’amplificateur qui est d’une taille de 13 × 8 µm2, ce qui représente respectivement environ 22% et 4% de la taille totale du pixel. Le circuit d’étouffement possède une gigue temporelle de 4 ps largeur à mi-hauteur (LMH). Les résultats obtenus prouvent qu’il est possible d’intégrer de l’électronique de lecture de PAMP dans un MCMP 3D possédant des performances temporelles sous les 10 ps.
266

FTIR studies of chemical processes

Few, Julian William January 2013 (has links)
This thesis presents the study of a selection of gas phase chemical processes using time-resolved Fourier transform infrared (FTIR) emission spectroscopy. Such processes include molecular energy transfer, chemical reaction and photodissociation. The major focus of this thesis was the investigation of collisional energy transfer from the electronically excited states of NO and OH, with particular attention paid to the fate of the electronic energy. NO A<sup>2</sup>&Sigma;<sup>+</sup>(v = 0) is prepared by laser excitation, pumping the overlapped Q<sub>1</sub> and P<sub>21</sub> band heads of the NO A-X (0,0) transition at 226.257 nm. The quenching of this state by O<sub>2</sub> and CO<sub>2</sub> was studied. Experiments were performed to investigate what channels contribute to the quenching process, the branching ratio of these different channels and the partitioning of energy among the various products. Quenching by O<sub>2</sub> was found to proceed mostly through non-reactive channels. High vibrational excitation of NO X <sup>2</sup>&Pi; was observed, with population detected in v = 22, representing 79% of the available energy. The O<sub>2</sub> product was found to be formed in more than one electronic state: the ground state, X <sup>3</sup>&Sigma;<sup>-</sup><sub style='position: relative; left: -.3em;'>g</sub>, and a high-lying electronically excited state, such as the A <sup>3</sup>&Sigma;<sup>+</sup><sub style='position: relative; left: -.5em;'>u</sub>, A' <sup>3</sup>&Delta;<sub>u</sub> or c <sup>1</sup>&Sigma;<sup>-</sup><sub style='position: relative; left: -.5em;'>u</sub> states. A reactive channel producing vibrationally excited NO<sub>2</sub> was observed, but was found to be a minor process with an upper limit of 18% for the branching ratio. In contrast the quenching of NO A <sup>2</sup>&Sigma;<sup>+</sup>(v = 0) by CO<sub>2</sub> was found to proceed predominately by reaction, with a branching ratio of 76 %. While emission from NO<sub>2</sub> was observed, it was weak, and therefore it was concluded that the main reaction products were CO, O(<sup>3</sup>P) and NO X <sup>2</sup>&Pi;(v = 0). The nascent strong CO<sub>2</sub> v3 emission band from the non-reactive channel exhibited a large red-shift from its fundamental position. This indicates that the CO<sub>2</sub> vibrational distribution is significantly hotter than statistical. Investigations were then performed studying the quenching of NO A <sup>2</sup>&Sigma;<sup>+</sup>(v = 1) by NO and CO<sub>2</sub>, with both systems exhibiting similar characteristics to the quenching of the ground vibrational level of NO A <sup>2</sup>&Sigma;<sup>+</sup>. From comparison of the emission intensity of the CO fundamental and CO<sub>2</sub> v3 mode following quenching of the v = 0 and 1 levels of the NO A <sup>2</sup>&Sigma;<sup>+</sup> state, it was concluded that the branching ratio for reactive quenching was larger in the latter case. Secondly, experiments were performed to measure the rate constants for the quenching of NO A <sup>2</sup>&Sigma;<sup>+</sup>(v = 0) by the noble gases. The noble gases are inefficient quenchers of electronically excited NO and therefore careful experimental design was required to minimise the influence of impurities on the results. All the rate constants were found to be of the order of 10<sup>-14</sup> cm<sup>3</sup> molecule<sup>-1</sup> s<sup>-1</sup>. The value for Xe was 50 times smaller than reported previously in the literature. In light of this new measurement, a re-analysis of experiments, performed previously in the group, on the electronic quenching of NO A <sup>2</sup>&Sigma;<sup>+</sup>(v = 0) by Xe was performed. A very hot vibrational distribution of NO X <sup>2</sup>&Pi; was obtained. Next, the collisional quenching of OH A <sup>2</sup>&Sigma;<sup>+</sup>(v = 0) by H<sub>2</sub> was investigated. OH radicals were generated in situ by the photolysis of HNO<sub>3</sub> at 193 nm, which were excited to the A <sup>2</sup>&Sigma;<sup>+</sup>(v = 0) state on the overlapped Q<sub>1</sub>(1) and P<sub>21</sub>(1) rotational lines at 307.935 nm. Reactive quenching was found to be the major pathway, in agreement with the literature. Copious emission from vibrationally excited water was observed. Comparison of this emission with theoretical calculations revealed a hotter distribution than predicted. It was concluded that the energy channelled into the vibrational modes of H<sub>2</sub>O is in excess of 60% of the available energy. Experiments performed with D<sub>2</sub> allowed the non-reactive channel to be studied; a cold vibrational distribution of the OH X <sup>2</sup>&Pi; was observed. Finally the reaction between CN radicals and cyclohexane was studied. CN was generated by the photolysis of ICN at 266 nm. Prompt emission from HCN in the C-H stretching region was observed meaning the new bond was formed in a vibrationally excited state. Analysis of the emission revealed HCN was populated up to v3 = 2. Excellent agreement with the results of a theoretical study of the system was found.
267

Field Dependence of Optical Properties in Quantum Well Heterostructures Within the Wentzel, Kramers, and Brillouin Approximation

Wallace, Andrew B. 08 1900 (has links)
This dissertation is a theoretical treatment of the electric field dependence of optical properties such as Quantum Confined Stark (QCS) shifts, Photoluminescence Quenching (PLQ), and Excitonic Mixing in quantum well heterostructures. The reduced spatial dimensionality in heterostructures greatly enhances these optical properties, more than in three dimensional semiconductors. Charge presence in the quantum well from doping causes the potential to bend and deviate from the ideal square well potential. A potential bending that varies as the square of distance measured from the heterostructure interfaces is derived self-consistently. This potential is used to solve the time-independent Schrodinger equation for bound state energies and wave functions within the framework of the Wentzel, Kramers, and Brillouin (WKB) approximation. The theoretical results obtained from the WKB approximation are limited to wide gap semiconductors with large split off bands such as gallium arsenide-gallium aluminum arsenide and indium gallium arsenide—indium phosphide. Quantum wells with finite confinement heights give rise to an energy dependent WKB phase. External electric and magnetic fields are incorporated into the theory for two different geometries. For electric fields applied perpendicular to the heterostructure multilayers, QCS shifts and PLQ are found to be in excellent agreement with the WKB calculations. Orthogonality between electrons and holes gives rise to interband mixing in the presence of an external electric field. On the contrary, intraband mixing between light and heavy holes is not sufficiently accounted for in the WKB approximation.
268

Étude de dépendance des dynamiques de Polarons avec microstructures des semi-conducteurs polymériques

Berteli Cardoso, Carine 08 1900 (has links)
Cet ouvrage présente une étude portant sur le polymère P3EHT (poly(3-(20-ethyl)hexyl-thiophene)). Parmi les nombreuses caractéristiques de la dynamique des polarons pouvant être étudiées, seules celles liées aux changement de morphologie le seront dans ce travail. De plus, la vérification du modèle HJ permet d’expliquer la photophysique des polymères conjugués, grâce à l’étude des spectres de photoluminescence. L’étude de la dynamique des polarons à travers l’absorption photo-induite en fonction de la fréquence a permis de trouver les durées de vie pour un même échantillon avec des morphologies différentes. Les résultats ont démontré que la morphologie est non seulement fondamentale pour l’étude des polarons, mais consiste aussi en une caractéristique essentielle pour comprendre le nouveau modèle HJ. / This work presents a study of the polymer P3EHT (poly (3 - (20-ethyl) hexyl-thiophene)). Among the many features of the dynamics of polarons that could be studied further, we chose those related to changes in morphology. In addition, the verification of the model HJ can explain the photophysics of conjugated polymers, through the study of photoluminescence spectra. The study of the dynamics of polarons through photoinduced absorption as a function of frequency allowed us to find the lifetimes of our sample with different morphologies. Our results demonstrate that the morphology is not only to the study of polarons, but is also an essential feature to understand the new model HJ.
269

Modélisation de la trempe gazeuse haute pression : application aux aciers de cémentation et de trempe / High pressure gas quenching modelling : application to carburizing and quenching steels

Douce, Jean-François 14 November 2008 (has links)
L’utilisation de fluides non vaporisables tels que les gaz pour tremper différentes pièces d’acier rend possible, avec les outils numériques actuels, la simulation de l’ensemble des phénomènes physiques mis en jeu dans ce traitement thermique et ainsi de prédire les comportements thermique, métallurgique et mécanique des pièces. Plusieurs auteurs s’intéressent à la construction de ce type de modèles dont les enjeux sont de promouvoir l’utilisation de la trempe gazeuse haute pression, en cherchant à remplacer les trempes à l’huile plus polluantes et/ou à maîtriser les déformations pendant ou après la trempe. Lors de notre travail, un modèle décrivant ces phénomènes physiques, de l’écoulement gazeux aux déformations, et leurs couplages a été construit par étapes en couplant les deux codes de calcul commerciaux Fluent et Sysweld. Les résultats de simulations ont ensuite été confrontés à des mesures de vitesses d’écoulements de gaz (par PIV), de températures et de déformations in situ (détection de contours). Malgré quelques écarts dont les origines ont été analysées, la comparaison a révélé une très bonne concordance des résultats de calculs et expérimentaux, validant ainsi la démarche de calcul. Le modèle pourrait maintenant être testé pour des refroidissements plus rapides que ceux considérés mais son utilisation pour des applications industrielles (pièces de géométrie plus complexe, refroidissement de charges entières, …) peut d’ores et déjà être envisagée avec confiance / The use of non vaporizable fluids such as gas to quench steel bodies makes the simulation of all the coupled physical phenomena involved in this heat treatment possible thanks to current numerical simulation tools. It gives access to the prediction of thermal, metallurgical and mechanical behaviour of steel pieces during quenching operation. Several authors have tried and build such kind of models in order to promote gas quenching use either by trying to replace less environmental friendly oil treatments or by trying to control distortions during or after quenching. In our work a model describing the physical coupled phenomena, from gas flow to distortion has been built step by step by coupling both commercial numerical codes Fluent and Sysweld. Simulation results have then been compared to gas flow velocities measurements (by PIV), temperature measurements and in situ distortions measurements (contour’s detection method). This confrontation revealed a very good agreement between calculated and experimental data despite some slight differences, which have been analysed in detail. This validated the calculation method used in the model. One of the perspectives of this work could be the validation of the model for higher quenching rate. However, some industrial applications (tridimensional more complex bodies quenching simulation, quenching of full loads, …) can be run from now on with confidence
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Modélisation et mesure des facteurs de modification nucléaire des jets issus de quarks beaux dans les collisions p-Pb à 5.02 TeV avec l'expérience ALICE auprès du LHC / Modeling and measurement of the b-jet nuclear modification factor in p-Pb collisions at 5.02 Tev with ALICE at the LHC

Hassan, Hadi 19 February 2019 (has links)
Dans les collisions Pb-Pb au LHC, un milieu chaud et dense formé de quarks et de gluons déconfinés est formé, communément appelé Plasma de Quarks et de Gluons (PQG). Le PQG est l’état hypothétique de l’univers primordial quelques microsecondes après le Big Bang et constituerait encore à ce jour le cœur des étoiles à neutrons. Une des signatures les plus frappantes de l’occurrence du PQG lors de collisions d’ions lourds est la suppression des jets. Ce phénomène appelé étouffement des jets est attribué au mécanisme de perte d’énergie du parton à l’origine du jet lors de son trajet au travers du milieu formé par le PQG.Les deux dernières décennies ont vu l’émergence d’une formulation théorique du phénomène d’étouffement des jets dans le cadre de la Chromo Dynamique Quantique. La perte d’énergie étant le plus fréquemment attribuée dans la littérature à des processus radiatifs et collisionnels. Un nouveau mécanisme de perte d’énergie à été étudié dans ce travail de thèse qui outre la description des effets de diffusions multiples, met en œuvre une perte d’énergie radiative induite par un champ chromomagnétique, de sorte qu’un parton rapide se propageant au travers du milieu ressentira l’effet des champs magnétique et de couleur tout en subissant des diffusions multiples avec les particules du milieu.De plus, les modèles théoriques prédisent une dépendance de la perte d’énergie avec la charge de couleur et la masse du parton issu d’une diffusion à grand transfert d’impulsion lors de sa traversée du milieu.Une telle dépendance en masse peut être étudiée en mesurant la production de hadrons et de jets contenant des quarks lourds dans les collisions pp, p-Pb et Pb-Pb au LHC. Dans cette thèse, un modèle original du milieu est présenté, décrit comme un ensemble de centres de diffusion statiques colorés en présence d’un champ chromomagnétique, de même qu’une description du mécanisme de perte d’énergie associé. Enfin, la mesure de la production de jets issus de quarks beaux avec le détecteur ALICE dans les colllsions pp et p-Pb à l’énergie de 5.02 TeV au LHC à l’aide d’une méthode d’étiquetage utilisant le paramètre d’impact des traces est présenté dans cette thèse. / In Pb-Pb collisions at the LHC, a hot and dense medium of deconfined quarks and gluons is formed, the so-called Quark-Gluon Plasma (QGP).The QGP is conjectured to be the state of matter of the early Universe up to few microseconds after the Big Bang and may still exist in the core of neutron stars. One of the most striking signatures of the QGP formation in heavy-ion collisions is the suppression of jet production. This phenomenon, called jet quenching, is ascribed to the energy lost by the initial parton while traveling through the QGP medium.In the last two decades, many theoretical developments of the theory of jet quenching have been formulated within pQCD.The main energy loss mechanisms proposed in the literature are attributed to radiative and collisional processes. Another kind of energy loss is developed in this work comprises a background field induced radiative energy loss which besides that besides scattering effects. Under the suggested model, a fast parton propagating through the medium will feel the effect of the color magnetic and the color electric fields while undergoing multiple scatterings with the particles in the medium.Besides, theoretical models predict that energy loss depends on the color charge and mass of the hard-scattered parton traversing the medium. Such mass dependence can be studied by measuring the production of hadrons and jets containing heavy-quarks in pp, p-Pb and Pb-Pb collisions at the LHC.In this thesis report, a new model for the medium is presented, which is described as a collection of static colored scattering centers in the presence of a chromomagnetic field, together with the description of the related energy loss mechanism. The ALICE measurement of b-jet production in pp and p-Pb collisions at $sqrt{s_{mathrm{NN}}}=5.02$ TeV using an impact parameter based tagger is also presented.

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