As ligações entre a termodinâmica e a mecânica quântica mostram-se interessantes tópicos de pesquisa desde os anos 50 e tem atraído cada vez mais atenção nos últimos anos, tanto por suas possíveis aplicações tecnológicas, quanto pelo aspecto teórico - como, por exemplo, as relações de sistemas quânticos com a segunda lei da termodinâmica. Para sistemas quânticos mesoscópicos, restritos apenas a um número relativamente pequeno de estados energéticos, torna-se necessária uma generalização da termodinâmica usual. Neste trabalho mostramos como construir uma máquina de Stirling no contexto de íons aprisionados. Para isso, faz-se necessária a engenharia de frequências dependentes do tempo do modo vibracional do íon, além da engenharia de reservatórios térmicos com temperaturas controladas. Após a construção da máquina de Stirling e do cálculo do trabalho e da eficiência associados apresentamos um protocolo para a medida da função de distribuição do trabalho que recorre às medidas dos níveis de energia eletrônicos do íon para, a partir dessas, extrair-se informação sobre o seu estado vibracional. / The connections between quantum mechanics and thermodynamics have been an interesting research topic since the 1950´s and began attracting more and more attention recently, not only for the technological applications, but also from a theoretical point of view - as, for instance, when dealing with the relations between quantum systems and the second law of thermodynamics. For mesoscopic (or even macroscopic) quantum systems, restricted to relatively few energy states, a generalization of the usual thermodynamics becomes necessary. In the present work we show how to engeneer a Stirling engine in an ionic trap. To achieve this we have to engeneer an ionic vibrational mode with a time dependent frequency, and simutaneously engeneer a thermal reservoir with controled temperatures. After the construction of the Stirling machine and the calculation of the associated work and efficiency, we show a protocol that allows the measurement of the work distribution function which call on the measurement of the electronic energy levels of the ion and, from them, extract information about the vibrational state of the trap.

Les micro-instabilités ioniques et électroniques présentes dans les plasmas de fusion sont à l’origine de la turbulence. Le transport anormal de particules et d’énergie, induit par cette turbulence, joue un rôle néfaste pour les performances des machines à fusion nucléaire comme le tokamak. C’est dans ce cadre général que s’inscrit ce travail visant à une meilleure compréhension de la turbulence et des phénomènes de transport sous-jacents. On sait que la dynamique des particules piégées joue un rôle très important dans l’établissement de la turbulence au travers des instabilités ioniques TIM (Trapped Ion Modes) et électroniques TEM (Trapped Electron Modes). Nous nous attachons donc dans ce travail au développement d’un modèle décrivant ces particules piégées (ions et électrons) de manière cinétique. L’échelle de temps à laquelle nous nous plaçons est de l’ordre de la période de précession toroïdale des particules piégées, période typique de la turbulence TIM/TEM. L’originalité de ce modèle réside dans la réduction de la dimension du problème (de 6D à 4D) par la moyenne sur les deux échelles de temps rapides associées aux particules piégées, respectivement le mouvement cyclotronique et le mouvement de rebond. De plus, l’utilisation des variables d’angle et d’action permet de transformer deux variables en paramètres. Le modèle final ainsi obtenu est 4D, dont deux dimensions interviennent sous la forme de paramètres. L’analyse linéaire du modèle nous permet de connaître les gradients de température et de densité permettant le déclenchement des instabilités TIM et TEM. Il nous permet également de connaître les taux de croissance et les pulsations associés à ces deux instabilités. Ensuite, nous nous appuyons sur le code global TERESA 4D décrivant les ions piégés cinétiques pour y inclure la résolution non-linéaire du modèle décrivant les ions et les électrons piégés cinétiques. Les échelles spatio-temporelles de la turbulence induite par les électrons et celle induite par les ions étant du même ordre de grandeur, cela nous permet d’intégrer à ce code une réponse cinétique des électrons avec un très faible coût numérique supplémentaire par rapport à la version existante. A l’aide de ce nouveau code nous pouvons observer une turbulence générée à la fois par les TIM et les TEM, ceci avec peu de ressources numériques. Nous pouvons obtenir des turbulences présentant différentes structures typiques observées dans les tokamak. C’est le cas des écoulements zonaux et des streamers ayant un rôle majeur dans le transport de particules et d’énergie. En vue d’une meilleure compréhension, voire d’un meilleur contrôle du transport, l’influence de différents paramètres, comme la largeur banane ou le rapport de température ionique sur la température électronique, est étudiée. / In tokamak plasmas, it is recognized that ion and electron micro- instabilities are held responsible for turbulence giving rise to anomalous transport. These limit particle and energy confinements in tokamak devices. This is the context of this work. The main objective is to have a better understanding of turbulence and thus of anomalous transport. It is known that the behaviour of trapped particles plays a major role in the development of turbulence via trapped ion mode (TIM) instability and trapped electron mode (TEM) instability. This work focus on the development of a model describing kinetic trapped particles (ions and electrons). The involved time scale is of the order of the trapped particle precession frequency which corresponds to characteristic frequency of TIM/TEM turbulence. The originality of this model is the reduction of the dimension from6D to 4D. This reduction is made by averaging over both the fast cyclotron motion and the bounce motion. In addition, using a set of action-angle variables allows one to deal with two parameters instead of two variables. The final model is 4D, dealing with two parameters and 2D space coordinates. The temperature and density gradients which trigger TIM and TEM instabilities are given by the linear analysis of the model. This analysis allows us to calculate the growth rates and frequencies associated with these instabilities. In order to solve the non-linear model describing both trapped kinetic ions and trapped kinetic electrons, we use the existing global code TERESA 4D including only trapped kinetic ions. The spatial and temporal scales associated to TIM and TEM turbulence are of the same order of magnitude. It allows us to include trapped electron kinetic response with very low numerical cost compared to the existing version. The TIM/TEM turbulence can be generated by this new code with low computational resources. Different typical structures observed in tokamak can be studied. This is the case of zonal flow and streamer structures which play a major role in anomalous transport. Finally, the influence of different parameters, such as banana width or electron to ion temperature ratio, is considered.

A new Trapped Vortex Combustor (TVC) concept has been studied for applications such as those in Unmanned Aerial Vehicles (UAVs) as it offers potential for superior flame stability and low pressure loss. Flame stability is ensured by a strong vortex in a physical cavity attached to the combustor wall, and low pressure loss is due to the absence of swirl. Earlier studies on a compact combustor concept showed that there are issues with ensuring stable combustion over a range of operating conditions. The present work focuses on experimental studies and numerical simulations to study the stability issues and performance optimization in this compact single-cavity TVC configuration. For performing numerical simulations, an accurate and yet computationally affordable Modified Eddy Dissipation Concept combustion model is built upon the KIVA-3V platform to account for turbulence-chemistry interactions. Detailed validation with a turbulent non-premixed CH4/H2/N2 flame from literature showed that the model is sufficiently accurate and the effect of various simulation strategies is assessed. Transient flame simulation capabilities are assessed by comparison with experimental data from an acoustically excited oscillatory H2-air diffusion flame reported in literature. Subsequent to successful validation of the model, studies on basic TVC flow oscillations are performed. Frequencies of flow oscillations are found to be independent of flow velocities and cavity length, but dependent on the cavity depth. Cavity injection and combustion individually affect the magnitude of flow oscillations but do not significantly alter the resonant frequencies. Reacting flow experiments and flow visualization studies in an existing experimental TVC rig with optical access and variable cavity L/D ratio show that TVC flame stability depends strongly on the cavity air velocity. A detailed set of numerical simulations also confirms this and helps to identify three basic modes of TVC flame stabilization. A clockwise cavity vortex stabilized flame is formed at low cavity air velocities relative to the mainstream, while a strong anticlockwise cavity vortex is formed at high cavity air velocities and low L/Ds. At intermediate conditions, the cavity vortex structure is found to be in a transition state which leads to large scale flame instabilities and flame blow-out. For solving the flame instability problem, a novel strategy of incorporating a flow guide vane is proposed to establish the advantageous anticlockwise vortex without the use of cavity air. Experimental results with the modified configuration are quite encouraging for TVC flame stability at laboratory conditions, while numerical results show good stability even at extreme operating conditions. Further design optimization studies are performed in a multi-parameter space using detailed simulations. From the results, a strategy of using inclined struts in the main flow path along with the flow guide vane seems most promising. This configuration is tested experimentally and results pertaining to pressure drop, pattern factor and flame stability are found to be satisfactory.

Cette thèse porte sur deux sujets principaux: l'évaluation de la stabilité d'une horloge sur microcircuit utilisant des atomes piégés (Trapped Atom Clock on a Chip - TACC) et l'extension de cette technologie vers la réalisation d'un interféromètre atomique sur la même puce. Cette combinaison constitue la base pour la réalisation de capteurs inertiels intégrés pour la navigation. Des travaux antérieurs ont installé l'horloge et ont découvert, entre autres, des temps de cohérence très longs, qui permettent une interrogation Ramsey jusqu'à 5 s, une condition préalable pour le fonctionnement à grande stabilité. Je présente ici la première évaluation approfondie de la stabilité de l'horloge. Avec mon prédécesseur, nous avons démontré les fluctuations de fréquences relatives de 5.8 10-13 à 1 s intégrant jusqu'à 6 10-15 à 30000 s.La deuxième partie de cette thèse vise à étendre la polyvalence de notre puce atomique pour créer un interféromètre. J'ai étudié divers régimes d'interféromètres en utilisant des potentiels habillés par microondes. Le premier régime consiste à déplacer l'un des états d'horloge verticalement pendant une séquence d'horloge Ramsey. Ceci permet la mesure de gradients de potentiel en exploitant la différence de fréquences entre les deux états. Le second régime utilise des champs microondes pour générer un potentiel de double puits dans l'un des états d'horloge et un seul puits dans l'autre.À partir du seul puits, un pulse-π sur la transition d'horloge constitue la séparatrice de l'interféromètre et conduit une séparation spatiale tout en préservant le même état interne pour les deux bras de l'interféromètre. / This thesis covers two main subjects: the evaluation of the stability of a Trapped Atom Clock on a Chip (TACC) and the expansion of this technology towards creating an atom interferometer on the same chip. The combination of a clock and an interferometer on the same chip constitutes the basis for the realization of atom-based integrated inertial navigation units. Previous work installed the clock operation and discovered, among others, very long coherence times, which allow Ramsey interrogations of up to 5 s, a prerequisite for high stability operation. I present the first thorough evaluation of the clock stability. Together with my predecessor we have demonstrated relative frequency fluctuations of 5.8 10-13 at 1 s integrating down to 6 10-15 at 30,000 s. The second part of this thesis aims to expand the versatility of our atom chip to create an atom interferometer. I have studied various interferometer schemes using microwave dressed potentials and implemented these to the set-up. The first scheme, following work by P. Treutlein et al., involves displacing one of the clock states vertically during a Ramsey clock sequence thereby allowing the measurement of potential gradients by exploiting the differential frequency shift accumulated between the two states. Ramsey fringes where recorded for different durations of the splitting, resulting in a clear signal of the wavepacket separation. The second scheme uses microwave dressing to generate a double well potential in one of the clock states and a single well in the other. Starting in the single well, a π-pulse on the clock transition constitutes the beam splitter and leads to a spatial separation for the same internal state.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2015-12-14T12:27:47Z No. of bitstreams: 1 williamcezargoncalves.pdf: 1779253 bytes, checksum: 71d9278fc91b4107a17474769011469a (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2015-12-14T15:50:34Z (GMT) No. of bitstreams: 1 williamcezargoncalves.pdf: 1779253 bytes, checksum: 71d9278fc91b4107a17474769011469a (MD5) / Made available in DSpace on 2015-12-14T15:50:34Z (GMT). No. of bitstreams: 1 williamcezargoncalves.pdf: 1779253 bytes, checksum: 71d9278fc91b4107a17474769011469a (MD5) Previous issue date: 2015-02-26 / Nosso trabalho parte de um apanhado histórico sobre o processo de implantação e formação da televisão e da telenovela no Brasil. Posteriormente, discorremos sobre a importância da mídia televisiva e do gênero ficcional na formação das identidades, tanto coletiva como individualmente. A partir desta conceituação, discutimos o processo de constituição das identidades na modernidade, tendo por base os estudos de autores filiados aos Estudos Culturais, Interacionismo Simbólico e à Psicologia Social. Este debate é afunilado quando abordamos a prisão como uma instituição que reformula as identidades dos indivíduos que nela se inserem. Consequente a esta discussão, tecemos considerações sobre a estrutura da telenovela “Insensato Coração” e as características do seu autor, Gilberto Braga, que implanta em suas histórias a crítica social. Tendo este panorama, apresentamos a metodologia utilizada, a Análise de Conteúdo de Laurence Bardin. Explicitamos os objetivos, hipóteses e categorias que balizam nossa análise, que pauta-se na trajetória de personagem Norma Pimentel (Glória Pires), uma mulher que é enganada e presa injustamente. Ainda dentro do cárcere, ela trama uma vingança nos moldes do romance francês “O Conde de Monte Cristo”, de Alexandre Dumas, colocando-a em prática no momento em que deixa a prisão. Neste percurso ficcional, Norma descortina diversas mazelas encontradas no claustro, revela o estigma que é anexado ao indivíduo preso e como sua identidade é modificada. / Our work begins with a historical overview on the process of implementation and development of television and telenovela in Brazil. Later, carry on about the importance of television media and the fictional genre in the formation of identities, both collectively and individually. From this concept, we discussed the process of constitution of identity in modernity, based on the studies of authors affiliated to Cultural Studies, Symbolic Interaction and Social Psychology. This debate is tapered when we approached the prison as an institution recasting the identities of individuals who fall into it. Consequent to this discussion, we consider the structure of the telenovela "Insensato Coração" and the characteristics of its author, Gilberto Braga, which deploys in his stories social criticism. Having this background, we explain the methodology used, the Laurence Bardin Content Analysis. We underline our objectives, assumptions and categories that guide our analysis, which is guided in character trajectory Norma Pimentel (Gloria Pires), a woman who is blinded and imprisoned unjustly. Still within the prison, she plot revenge along the lines of the French novel "The Count of Monte Cristo" by Alexandre Dumas, putting it into practice when leaving prison. In this fictional route, Norma reveals a variety of illnesses found in the cloister, reveals the stigma that is attached to the individual arrested and how their identity is modified.

Consistent charge or defect control in oxide grown on silicon carbide (SiC) continues to be difficult to achieve and directly impacts the electrical performance of SiC-based metal oxide semiconductor (MOS) devices. This research applied non-contact Corona-Kelvin metrology to investigate the charge transport in oxides grown on n-type 4H-SiC epitaxial substrates. The cost and engineering science impact of this metrology are significant as device fabrication is avoided leading to quick determination of electrical characteristics from as-grown oxide films. Non-contact current-voltage (I-V) measurements of oxide on SiC were first demonstrated within this work and revealed that Fowler-Nordheim (F-N) current emission was the dominant conduction mechanism at high electric fields. Oxides on SiC were grown at atmospheric pressure (thermal oxides) or at a reduced pressure (afterglow oxides) ambient and examined using non-contact charge-voltage (Q-V), capacitance-voltage (C-V), equivalent oxide thickness (EOT), and I-V methods. The F-N conduction model was modified to address charge trapping and effective barrier effects obtained from experimental oxide films. Trap densities determined with this metrology were used to show that the F-N model including their density and position was adequate for thermal oxides on SiC but not for afterglow films. Data from the latter films required further modification of the theory to include a chemical effect of the oxide growth process on the effective conduction band offset or barrier. This work showed that afterglow chemistry was able to vary the effective conduction band offset from 2.9 eV, typical of thermal oxidation of SiC, up to 3.2 eV. Stress induced leakage current (SILC), an excess above the F-N base current resulting from prolonged current through the dielectric films, was also investigated. Multiple point SILC testing was used to identify statistical effects of process variations and defects in as-grown oxide films on SiC. These results open the possibility to improve oxide manufacture on SiC using methods common in the silicon IC industry. This work demonstrated the first non-contact F-N current determination in oxides on SiC and showed both charge trapping and chemical dependencies of as-grown films. Future studies may extend the findings of this work to further improve this important dielectric-semiconductor system.

This dissertation focuses on the development of analytical methods based on Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and their applications for separation and structural characterization of oligosaccharides. Porous graphitized carbon liquid chromatography (PGC-LC), gated-trapped ion mobility spectrometry (Gated-TIMS), and electronic excitation dissociation tandem mass spectrometry (EED MS/MS) are three essential techniques employed here. First, the EED method was optimized to generate more informative glycan tandem mass spectra for accurate structural analysis. Glycans were reduced and permethylated or labeled with a reducing-end fixed charge to increase sensitivity, avoid gas-phase structural rearrangement, and facilitate spectral interpretation. EED of glycans produced nearly complete series of Z-, Y- and 1,5X-ions, that appear in the spectra as triplets with characteristic spacing, thus facilitating accurate determination of the glycan topology. Additional radical-driven dissociation pathways were identified, from which different types of linkage-diagnostic ions (cross-ring, secondary, or internal fragments) were generated. The results demonstrated that linkage analysis can be accomplished by utilizing one or a combination of several linkage-diagnostic fragments. EED MS/MS was then implemented, in conjunction with PGC-LC or Gated-TIMS, for on-line separation and characterization of complex mixtures of glycans. These two methods were successfully applied for high-throughput and detailed structural analysis of N-glycans released from human serum, O-glycans released from bovine submaxillary mucin and free oligosaccharides. The performance of these methods was tested and improved through analysis of different types of glycans from a variety of biological sources. Finally, in collaboration with bioinformaticians, a spectral interpretation algorithm, GlycoDeNovo, has been developed for automated and de novo glycan topology reconstruction from their tandem mass spectra. A large number of EED tandem spectra of glycan standards generated in house were used as the training dataset to establish appropriate IonClassifiers for candidate ranking. GlycoDeNovo is capable of identifying correct topologies from MS/MS spectra of glycans in different derivatized forms. Several aspects of this collaborative project were covered in this thesis, including glycan derivatization, data acquisition and manual spectral interpretation to guide the development and evaluate the performance of the automated approach. In this thesis research, integrated approaches utilizing PGC-LC–EED-MS/MS and Gated-TIMS–EED-MS/MS, and the appropriate bioinformatics software, have been established for structural analysis of glycan mixtures. They hold great potential for comprehensive, automated, and de novo glycome characterization.

Within this thesis, photo-induced mechanisms of the light-matter interaction are investigated in tailored and photofunctional materials that differ significantly in their optical and structural properties. The individual coupling mechanisms in congruently melted, nominally undoped or iron doped lithium niobate crystals as well as in structurally disordered photoswitchable molecules embedded into a solid state polymer are examined in particular by the principle of holographic grating recording and transient absorption spectroscopy which provide new insight into a variety of material response properties. In case of photoswitchable ruthenium sulfoxide compounds, the underlying mechanism can be unambiguously assigned to a photochromic material response evoked by a photochemical reaction, i.e., a non-instantaneous, local ligand isomerisation. Comparable results are obtained for iron-doped, oxidized lithium niobate where holographic grating recording is related to the photophysical generation of transient excitonic states whose photochromic properties are characterized by targeted ns-pump, supercontinuum probe spectroscopy. In the event of nominally undoped lithium niobate, the holographic amplification of two sub-picosecond pulses is attached to the phenomenon of two-beam coupling on a self-induced dynamic grating. By correlating the individually obtained mechanisms of the light-matter interaction and the light-induced material response, generally accepted conclusions on a microscopic level can be achieved. A major influence of the internal structure and orientation of the excited states, i.e., an appropriate threedimensional structural arrangement, is deduced as a prerequisite for the formation of light-induced, macroscopic refractive index changes while absorption and microscopic refractive index alterations linked via the Kramers-Kronig relation are unaffected. In systems featuring a random distribution of excited states, an orientational order might be achieved as a consequence of linear polarized light, i.e., by polarization structuring. Moreover, if the photorefractive effect can be ruled out, the material response in lithium niobate can be solely assigned to a local alteration of the transient electronic states, i.e., to the photochromic properties of polarons and/or excitonic states, which is in particular comparable to the linkage isomerism of molecular photoswitchable molecules. In addition, the influence of structural parameters on the light-matter/surface interaction is studied on the μm-scale by analyzing the diffraction phenomenon arising from a relief grating. A considerable impact on the surface grating assisted coupling is determined by the transition from cw-lasers to ultrashort laser pulses which enables interference quenching. However, this phenomenon is of no consequence in case of selfinduced holographic gratings.

One of the most intriguing properties of light-matter interaction is the ability of an electromagnetic field to exert mechanical forces on polarizable objects. This phenomenon is a direct consequence of the fact that light carries momentum, which in turn can be transferred to matter. Mediated by scattering, this interaction usually manifests itself as a “pushing force” in the direction of beam propagation. However, it is possible to judiciously engineer these optical forces, either by tailoring particle polarizability, and/or by structuring the incident light field. As a simple example, a tightly focused laser beam demonstrates strong gradient forces, which may attract and even trap particles with positive polarizability in the focal volume. The opposite occurs in the regime of negative polarizability, where particles are expelled from the regions of highest intensity. Based on this fundamental principle, one can actively shape the beam using spatial light modulators to manipulate individual objects as well as ensembles of particles suspended in a liquid. In the latter case, a modulation of the local particle concentration is associated with changes of the effective refractive index. The result is an artificial nonlinear medium, whose Kerr-type response can be readily tuned by the parameters of its constituent particles. In the course of this work, we introduce a new class of synthetic colloidal suspensions exhibiting negative polarizabilities, and observe for the first time robust propagation and enhanced transmission of self-trapped light over long distances. Such light penetration in strongly scattering environments is enabled by the interplay between optical forces and self-activated transparency effects. We explore various approaches to the design of negative-polarizability arrangements, including purely dielectric as well as metallic and hybrid nanoparticles. In particular, we find that plasmonic resonances allow for extremely high and spectrally tunable polarizabilities, leading to unique nonlinear light-matter interactions. Here, for the first time we were able to observe plasmonic resonant solitons over more than 25 diffraction lengths, in colloidal nanosuspensions.

Here the nature of gas phase processes and their implications for flow and transport were examined using a pilot-scale, 2-dimensional, laboratory tank instrumented for direct, in situ trapped gas measurements. Experimental conditions mimicked an unconfined, homogeneous sand aquifer with horizontal flow. Key areas of investigation included i) trapped gas dissolution following a water table fluctuation; and ii) gas phase dynamics within a hydrocarbon plume experiencing dissolved gas production via biodegradation. In the first experiment, dissolution occurred as a diffuse, wedge-shaped front propagating down-gradient in the tank over time, with enhanced dissolution at depth. Front advancement at the deepest monitoring point was 4.1 - 5.7x faster. This dynamic, depth-dependent pattern was mainly attributed to increased dissolved gas solubility. An estimated 12% increase in quasi-saturated hydraulic conductivity (Kqs) also contributed to greater dissolution at depth. Overall, the dissolution front near the water table advanced 1 m down-gradient in 344 days, suggesting that gas trapped shallowly will likely persist for significant periods of time. The utility of total dissolved gas pressure sensors for simple in-well measurements to detect trapped gas and monitor its dissolution were also demonstrated. During the second experiment, biodegradation occurred under variable redox conditions, ranging from denitrification to methanogenesis. Significant in situ increases in trapped gas were observed within the tank over 330 days. Maximum gas saturations never exceeded 27% of pore volume even during continued dissolved gas production, indicating ebullition upon reaching a gas phase mobilization threshold. Consequently, associated reductions in Kqs were restricted to a factor of 2 or less, but still appeared to alter the groundwater flow field. While trapped gas increases within the biodegradation plume were expected, declines in gas saturations were also observed. Thus, the overall pattern of trapped gas growth exhibited high spatial and temporal variability. Influencing factors included changes in hydrocarbon inputs and microbial controls on redox zonation, in addition to ebullition and changes in groundwater flow; emphasizing that gas phase growth in contaminant plumes will be highly complex and dynamic in the natural systems. Given the impacts on hydraulic conductivity, and the fate and transport of volatile compounds, an improved understanding of quasi-saturated conditions will be beneficial for various groundwater applications, from recharge and paleoclimate studies to site characterizations and remediation strategies. / Dissertation / Doctor of Philosophy (PhD)