Doctor of Philosophy / Department of Chemistry / Daniel A. Higgins / This dissertation describes the application of wide-field single-molecule fluorescence microscopy techniques to investigations of DNA-surface interactions on chemically graded organosilane surfaces. The adsorption and desorption behaviors of double-stranded (ds) plasmid DNA along the amino-trimethoxysilane and octyl-trichlorosilane gradients were explored as a function of solution pH, solution ionic strength and surface properties. The results provide an improved fundamental understanding of DNA interactions with different surfaces and are certain to aid in the development and advancement of DNA-based biological and biomedical devices. Three distinct experiments were performed in completion of the work for this dissertation. In the first study, total internal reflection fluorescence (TIRF) microscopy was employed to study DNA interactions with aminosilane gradient surfaces under relatively acidic and basic environments. Electrical potentials were applied to assist DNA adsorption and desorption. The single-molecule data clearly showed that DNA capture and release was achieved on the monolayer and submonolayer coated regions of the aminosilane gradient surface under relatively basic pH conditions, with the help of an electrical potential. Meanwhile, DNA adsorption was found to be quasi-reversible on the multilayers at the high aminosilane end of the gradient in the relatively acidic solution. The results of these studies demonstrate the importance of manipulating the electrostatic interactions of DNA with charged surfaces in order to achieve DNA capture and release. The fundamental knowledge of the DNA-surface interactions gained in these studies will be helpful in diverse fields ranging from the layer-by-layer assembly of polyelectrolyte-based thin films to the selective electronic sensing of charged biomolecules. In the second study, the local dielectric properties of the least polar environments in dsDNA were assessed by using the solvatochromic dye, nile red, as a polarity-sensitive probe. TIRF spectroscopic imaging methods were employed in these studies. Although the dielectric constant within the least polar regions of dsDNA was previously predicted by theoretical and computational methods, no experimental measurements of its value had been reported to date. The results provide important knowledge of the factors governing the polarity of DNA microenvironments to which intercalators bind, and provide vital experimental support for the values determined in computational studies. In the third study, TIRF microscopy and single molecule tracking methods were employed to study DNA interactions with an opposed two-component C8-silane and aminosilane gradient surface as a function of solution pH. The mobility of surface-adsorbed DNA molecules was explored and quantified in these studies. The preliminary results further demonstrated the importance of electrostatic interactions over hydrophobic interactions in governing the adsorption of DNA to surfaces. The mobility of surface-adsorbed DNA was found to be largely independent of position along the two-component gradient. These studies were originally undertaken as a route to observation of cooperative effects that are believed to govern DNA-surface binding. Unfortunately, no clear evidence of cooperative effects was observed at the mixed regions of the two-component gradient surface.

In this thesis, we focused on understanding the synthesis of titanium dioxide (TiO2) films and nitrogen doped TiO2 films using an atmospheric pressure Dielectric Barrier Discharge (DBD). The first part of the work was dedicated to the deposition of TiO2 films by cold plasma DBD with titanium tetraisopropoxide as precursor in a single-step process at room temperature. The deposition rate was about 70 nm·min-1. The photocatalytic degradation rate for the degradation of methylene blue (MB) under ultra violet (UV) irradiation of the TiO2 film after annealing was close to a reference anatase TiO2 spin coated film. Moreover, the TiO2 films showed a good photocatalytic stability. The second part of the study focused on the optimization and the understanding of the effect of the plasma parameters (gas flow rate and power) on the morphology of the TiO2 films and on the investigation of the deposition mechanisms. The morphology of the film changed from granular to compact film by either increasing the total flow rate or decreasing the plasma power. In other words, adapting the energy density in the plasma allowed the control of the morphology of the TiO2 films. To our knowledge, it was the first time that the energy density parameters of the plasma were used to control the morphology of TiO2 films. The photocatalytic degradation rate for the degradation of MB under UV irradiation of the annealed TiO2 film turned out to be about 2 and 15 times higher than the one of the commercial TiO2 film and the as-deposited TiO2 films, respectively. In order to extend the light utilization to the visible light range, TiO2 films were doped with nitrogen using a room temperature argon/ammonia plasma discharge. XPS and SIMS results confirmed that the nitrogen has been incorporated in the TiO2 lattice mostly in Ti-N state. This was further confirmed by Raman spectroscopy and XRD. The plasma properties and the doping mechanism were studied by Optical Emission Spectroscopy. It is suggested that the NH radicals played a key role in the doping of TiO2. The concentration of nitrogen in the N-TiO2 coatings could be tuned by adapting the ratio of NH3 in the plasma or the plasma power. The band gap of our N-TiO2 coatings is lower than the one of undoped TiO2 coating. The photocatalytic degradation rate for N-TiO2 coating was more than 4 times higher than the one of the undoped TiO2 coating. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

La connaissance et la compréhension des propriétés électrocinétiques des cellulesapportent de multiples applications en recherche biomédicale, comme le diagnostic et le suivi del'évolution d'un cancer. L'application de champs électriques alternatifs non-uniformes dans desmicrosystèmes, et plus particulièrement la force de diélectrophorèse, permet de caractériser despopulations de cellules sans marqueur spécifique.Nous avons tout d'abord mené une étude fondamentale pour décrire de la réponse des celluleshumaines dans telles conditions. La compétition entre les forces diélectrophorétique et électro-hydrodynamiques (effets électrothermiques, électro-osmose) a été modélisée. La confrontation dumodèle à l'observation expérimentale du mouvement de telles cellules dans des canaux micro-fluidiques comportant des électrodes micro structurées a été effectuée. À partir de cette étude,une nouvelle méthode de détermination de la fréquence de coupure de cellules humaines sur unnombre statistique de cellules représentant une population a été élaborée.Ensuite, nous avons étudié les fréquences de coupure entre des lignées issues de différents tissusépithéliaux (rein et prostate) ou de cellules circulantes. Il a été démontré que les fréquences decoupure sont statistiquement différentes entre les lignées. Les méthodes développées ont ainsipermis de mesurer les différentes signatures électriques de cellules cancéreuses de prostates àchaque stade d'évolution du cancer.Enfin, nous nous sommes intéressés à comprendre les mécanismes de polarisation des cellulessous champ électrique alternatif. Nous avons modifié la membrane des cellules chimiquement oubiologiquement pour comprendre l'origine moléculaire de la fréquence de coupure. Il a été mis enévidence que la concentration en protéines et l'activité de certains canaux ioniques augmententsignificativement la fréquence de coupure des cellules.En exploitant les effets de la diélectrophorèse sur les cellules, il devient possible de caractériserfinement leurs propriétés diélectriques, et de proposer à plus long terme de nouvelles technologiesde détection et de diagnostic / Measuring and understanding cells' electrokinetic properties bring several appli-cations in the biomedical field, like the diagnosis and the monitoring of cancer diseases. Theapplication of alternative non uniform electric fields in microsystems, in particular the dielec-trophoretic force, allows a label-free characterization of cell populations.In this Thesis, a comprehensive study has been established to describe the response of humancells in non-uniform AC fields. We have modeled the competition between dielectrophoresisand electro-hydrodynamical forces (electrothermal effects, AC electro-osmosis). This model wascompared to the observation of cell motions in microfluidic channels with structured electrodes.We have established a new method to determine the crossover frequencies of human cells on astatistically relevant number of cells, which represents a population.Then, the Clausius-Mossotti factor of cell lines has been measured, from different epithelial tis-sues (kidney, prostate) or circulating cells. We have demonstrated that the crossover frequenciesare statistically different between these lines. This method has been used to monitor the differentelectrical signatures of prostate cancer cells at each grade of cancer.Finally, we have focused on the polarization process of cells regarding the electric field. We havemodified chemically and biologically cell membranes to understand the molecular origin of thecrossover frequency. The membrane proteins depletion and the activity of some ion channelssignificantly increase the cell crossover frequency.By taking advantage of the dielectrophoretic response of cells, it becomes possible to characte-rize their dielectric properties and to develop new technologies for cancer detection and diagnosis

L'augmentation des besoins en énergie électrique et l'éloignement croissant des lieux de production par rapport aux centres de consommation impulsent le développement du transport d'énergie en courant continu. Dans le cas des câbles haute tension à courant continue (HTCC) à isolation polymère, la problématique de la fiabilité est liée à l'établissement, sous l'effet des fortes contraintes électrothermiques, de zones de charges électriques dans le diélectrique et au niveau des interfaces isolant/compound semi-conducteur. De telles accumulations de charges (dites charges « d'espace » car reparties dans un espace isolant) peuvent faire vieillir prématurément les isolations, voire les faire claquer de manière intempestive. La mise en œuvre de nouveaux matériaux et l’optimisation des structures isolantes pour câbles HTCC nécessitent ainsi le suivi des zones de charges d’espace avec la plus grande précision. Il est alors nécessaire de développer des techniques de mesure non destructives, telle que la méthode de l’onde thermique (MOT), basée sur l’application d’un faible échelon de température à une structure isolante et sur la mesure d’un courant transitoire provoqué par la redistribution des charges d’influence aux électrodes.Ce travail porte sur la faisabilité et la mise en œuvre expérimentale d’une installation, basée sur le principe de la MOT, visant à mesurer les charges d’espace dans des échantillons isolants comportant des couches semi-conductrices, avec une résolution la plus proche possible du degré d’homogénéité des interfaces (de l’ordre du micromètre).Après avoir passé en revue les problématiques des diélectriques soumis à des forts champs continus et les méthodes de mesure de charges d’espace existantes, le mémoire présente divers aspects et grandeurs liés au principe de la MOT, ainsi qu’à la définition et à l’estimation des résolutions spatiales. Des simulations analytiques et numériques sont par la suite menées pour étudier les apports d’une mise en œuvre de la MOT sur des structures isolantes de polyéthylène réticulé chimiquement de 100 µm d’épaisseur avec des électrodes semi-conductrices de 30 µm. Elles montrent que l’application d’échelons de température d’amplitudes n’affectant pas les états électrique et de surface des matériaux se traduit par des signaux de mesure de plusieurs nano ampères pour des variations de champ résiduel de l’ordre du kV/mm par micron. La génération de ces signaux, nécessaires à des mesures ayant une dynamique suffisante et à des résolutions s’approchant du micron, requière des échanges thermiques hautement efficaces entre la source de chaleur (liquide caloporteur) et l’isolant. Une étude par simulation multi-physique bidimensionnelle est réalisée afin d’analyser le transfert de chaleur par contact direct entre un liquide caloporteur et un échantillon-type. Elle permet de définir et d’optimiser une structure innovante de diffuseur thermique et dans laquelle l’échange de chaleur entre le fluide et l’échantillon s’opère par contact direct, assurant ainsi une efficacité bien supérieure aux structures existantes.Le développement d’un outil de mesure par la MOT, basé sur les conclusions des travaux de simulation, est par la suite présentée. Il associe un système hydropneumatique, un diffuseur haute efficacité favorisant la dynamique du transfert thermique et un système de capteurs, en augmentant ainsi l’amplitude des signaux, la reproductibilité et la précision de la mesure. Des mesures d’étalonnage sur des échantillons cibles montrent, par rapport aux résolutions disponibles sur ce type de structure (autour de 10 µm), des améliorations d’un facteur 2 à 5 pour la résolution de positionnement et une résolution de discernement proche de l’état de l’art. L’analyse critique du banc développé, corroborée aux prédictions des simulations, met également en évidence la marge de progression sensible de l’outil, dont les évolutions proposées permettront d’accroître les performances. / The increasing needs of electric power and the placement of power plants at more and more remote locations with respect to the users promote the development of electric power transport by DC submarine or terrestrial links. In the case of high voltage direct current (HVDC) cables with polymeric insulation, reliability is strongly affected by the development, under high electrical and thermal stress, of electric charges in the bulk of the dielectric and at the insulator/semiconductor interfaces. These accumulations of charges (called space charges as they are distributed in an insulating space) may lead to premature ageing and breakdown. The setup of new materials and the optimization of insulating structures for HVDC cables require a precise follow-up of the space charge zones. It is therefore necessary to develop non-destructive space charge measurement techniques, as the thermal step method (TSM), which is based on the application of a low temperature step to an insulating structure and on the measurement of a transient current due to the redistribution of influence charges at electrodes.The present work concerns the feasibility and the experimental set up of a device, based on the principle of the TSM, aiming to measure the space charges in insulating samples with semi-conducting electrodes, with a resolution approaching the degree of homogeneity of the interfaces (i.e., of micrometric order).After having reviewed the problematic of the dielectrics subjected to high dc fields and the existing space charge measurement methods, this dissertation presents several aspects and parameters related to the principle of the TSM, as well as to the definition and to the estimation of spatial resolutions. Analytical and numerical simulations are then carried out to study the contributions of a TSM-based setup on insulating structures composed of 100 µm-thick cross-linked polyethylene slabs provided with 30 µm-thick semiconducting electrodes. They show that the application of temperature steps, with amplitudes that do not affect the electrical and surface states of the materials, leads to measurement signals of several nano amperes for variations of the remnant electric field of the order of the kV/mm per micron. Highly effective thermal exchanges between the heat source (heating or coolant liquid) and the insulator are required to generate such signals, needed for measurements of sufficient dynamics and for resolutions approaching the micrometer. A bi-dimensional multi-physics simulation study is made, in order to analyze the heat transfer through a direct contact between the coolant liquid and a sample of the aimed type. The study allows to define and to optimize an innovating structure of thermal diffuser, where the heat exchanges operates by direct contact, thus providing a much better efficiency than the existing structures.The development of a TSM-based measurement tool, using the fallouts of the simulations, is then presented. It associates a hydro pneumatic system, a high efficiency diffuser favoring the dynamics of the thermal transfer and a sensor system, thus increasing the amplitude of the signals, the reproducibility and the accuracy of the measurements. Calibration measurements on the aimed samples show, with respect to the resolutions available on this type of structures (close to 10 µm), enhancements by a factor of 2 to 5 for the positioning resolution an a discerning resolution close to the state of the art. The critical analysis of the developed bench, corroborated to the predictions of the simulations, also puts into focus a significant room for improvement of the tool, for which evolutions proposed in this work would allow to enhance the performance.

SILVA, Roger Ribeiro. Estudo das propriedades dielétricas do Niobato de Bismuto e Titânio dopado com PbO e Bi2O3 para aplicações em antenas. 2009. 93 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2009. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-06-16T21:40:35Z No. of bitstreams: 1 2009_dis_rrsilva.pdf: 3731493 bytes, checksum: ea1e0ca9dd5b082cce643034649ad572 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-06-18T18:22:11Z (GMT) No. of bitstreams: 1 2009_dis_rrsilva.pdf: 3731493 bytes, checksum: ea1e0ca9dd5b082cce643034649ad572 (MD5) / Made available in DSpace on 2015-06-18T18:22:11Z (GMT). No. of bitstreams: 1 2009_dis_rrsilva.pdf: 3731493 bytes, checksum: ea1e0ca9dd5b082cce643034649ad572 (MD5) Previous issue date: 2009 / Dielectric resonators based on type structure compound Bi3TiNbO9 show singular characteristics for microwave applications, including high dielectric constants, low dissipation losses and low temperature coefficients. Single phase of the Bi3TiNbO9 powder was obtained by x-ray diffraction technique. The ceramics doped during manufacture, with lead oxide and bismuth oxide, were synthesized by solid state reaction at 950°C for two hours. Samples were analysed by Archimedes method and exhibited good levels of density for doped ceramics with bismuth and lead oxide. Grain morphology and stoichiometry of ceramics were investigated by scanning electron microscopy and energy dispersive spectroscopy technique. Far infrared spectroscopy identified large bands on the Bi3TiNbO9 structure by attenuated total reflection technique. Radiofrequency measurements showed that doped ceramics exhibited higher dielectric constants than pure phase. Microwave measurements were investigated by Hakki-Coleman and resonant cylindrical cavity. The ceramics called as BTNO3BiP, BTNO5BiP, BTNO10BiP, BTNO3PbG e BTNO5PbG, showed high dielectric constants and high quality factors demonstrating that they can be applied in dielectric antennas on microwave range. / Ressoadores dielétricos baseados na estrutura do composto Bi3TiNbO9 apresentam características singulares para aplicações em microondas, incluindo altas constantes dielétricas, baixos fatores de dissipação e baixos coeficientes de temperatura. Obteve-se a fase pura da amostra em pó de Bi3TiNbO9 pela técnica de difração de raios X. As amostras cerâmicas dopadas durante a fabricação, com óxido de chumbo e óxido de bismuto, foram sintetizadas pelo método de reação do estado sólido a 950°C por 2 horas. As amostras foram analisadas pelo método de Arquimedes e apresentaram bons níveis de densidade nas dopagens com os óxidos de bismuto e chumbo. A morfologia dos grãos e a estequiometria das amostras cerâmicas foram investigadas pelas técnicas de microscopia eletrônica de varredura e análise por energia dispersiva de raios X. A espectroscopia no infravermelho distante identificou bandas largas na estrutura do Bi3TiNbO9 pela técnica de reflexão total atenuada. As medidas de constante dielétrica e perda dielétrica em radiofreqüência demonstraram que as dopagens com chumbo e bismuto exibiram maiores constantes dielétricas em relação à cerâmica pura. As medidas em microondas foram estudadas pelos métodos Hakki-Coleman e a cavidade ressonante metálica. As cerâmicas denominadas como BTNO3BiP, BTNO5BiP, BTNO10BiP, BTNO3PbG e BTNO5PbG, apresentaram altas constantes dielétricas e altos fatores de qualidade, demonstrando que podem ser aplicadas em antenas dielétricas na faixa de micro-ondas.

CAMPOS FILHO, Múcio Costa. Estudo das propriedades dielétricas e ópticas na matriz cerâmica CaBi4Ti4O15 com adição de V2O5, Er2O3 e Yb2O3. 2015. 169 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2015. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-10-26T21:58:54Z No. of bitstreams: 1 2015_tese_mccamposfilho.pdf: 9304166 bytes, checksum: 0448bdd2063e3fc697dee9f5c6efb532 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-10-26T21:59:04Z (GMT) No. of bitstreams: 1 2015_tese_mccamposfilho.pdf: 9304166 bytes, checksum: 0448bdd2063e3fc697dee9f5c6efb532 (MD5) / Made available in DSpace on 2015-10-26T21:59:04Z (GMT). No. of bitstreams: 1 2015_tese_mccamposfilho.pdf: 9304166 bytes, checksum: 0448bdd2063e3fc697dee9f5c6efb532 (MD5) Previous issue date: 2015 / A strong demand for compressed materials, low cost and easy to manufacture are needed for various technological applications, in this sense many ceramics are candidates for its dielectric and optical properties .In this work, structural, dielectric and optical phase of the orthorhombic ferroelectric ceramic matrixCaBi4Ti4O15were investigated, one pseudo-perovskite bismuth layer structure (BLSFs) of space group A21am of the aurivillius family, prepared by the solid state method and sintered in low temperatures. Sample preparation for structural analysis and dielectric, had the addition of vanadium pentóxido (V2O5) to the phase CaBi4Ti4O15 calcined in ratios of 0.5, 1.0, 1.5, 2.0 and 5.0% by mass. To obtain optical properties of the ceramic matrix doped with rare earth ions erbiumIII (Er2O3) and III ytterbium oxide (Yb2O3). The study of the structure and composition of the samples was done by X-ray diffraction and confirmation was made by single stage rietveld refinement. The vibrational characteristics was obtained by Raman spectroscopy (RS). The morphology study off or analysis of grain and grain boundary, was performed by scanning electron microscopy. The dielectric characterization of radio frequency spectroscopy was performed in impedance which occurred two conductivity mechanisms for all samples, one at low frequency and the on the rat high frequency. Models of dielectric relaxation approach the Cole-Cole type model. Measures in the microwave range were obtained using the hakki-coleman method and monopole, which gave a temperature coefficient of resonant frequency (f) close to zero with the addition of V2O5. The dielectric permittivity measurements in radiofrequency and microwave, performe dat room temperature, had a high constant value (εr≈150) with the addition of 1%V2O5, and a value of relatively low loss tangent for family aurivillus (tan[δ]≈10-2) at 2 GHz. A numerical simulation was performed with each sample verifying approach with the experimental data. In rare earth doped samples was checked energy up-conversion phenomenon with the presence of intense bands samples of visible light emission in the green region and a less intense bands in thered region.The investigated material has potential for application in volatile memories, capacitive filters and optical components such as sensors, solar cells and LEDs. / Uma forte demanda por materiais mais compactados, de baixo custo e de fácil fabricação são necessários para diversas aplicações tecnológicas, neste sentido diversos materiais cerâmicos são candidatos por suas propriedades dielétricas e ópticas. Neste presente trabalho, foram investigadas as propriedades estruturais, dielétricas e ópticas da fase ortorrômbica da matriz cerâmica ferroelétrica CaBi4Ti4O15, uma pseudo-perosviskita de estrutura de camada de bismuto (BLSFs) do grupo espacial A21am da família aurivillius, preparada pelo método do estado sólido e sinterizada em baixas temperaturas. A preparação das amostras para análise estrutural e dielétrica, tiveram a adição de pentóxido de vanádio (V2O5) à fase CaBi4Ti4O15 calcinada, em proporções de 0.5, 1.0, 1.5, 2.0 e 5.0 % em massa. Para obtenção das propriedades ópticas, a matriz cerâmica pura foi dopada com os íons terras raras érbio III (Er2O3) e óxido de itérbio III (Yb2O3). O estudo da estrutura e composição das amostras foi feito através de difração de raios-X e a confirmação da fase única foi feita pelo Refinamento Rietveld. A caracterização vibracional foi obtida através da Espectroscopia Raman (SR). O estudo da morfologia, para análise de grão e contorno de grão, foi realizado através de Microscopia Eletrônica de Varredura. A caracterização dielétrica em radio freqüência foi realizada por Espectroscopia em Impedância a qual se verificou dois mecanismos de condutividade para todas as amostras analisadas, um em baixa freqüência e outro em alta freqüência. Os modelos de relaxação dielétrica se aproximam do modelo do tipo Cole-Cole. As medidas na faixa de microondas foram obtidas utilizando-se o método hakki-coleman e monopolo, chegou-se a um coeficiente de temperatura da frequência de ressonância (tAU f) próximo de zero com adição de V2O5. As medidas de permissividade dielétrica em radiofreqüência e microondas, realizadas em temperatura ambiente, tiveram um alto valor constante (εr ≈ 150) com a adição de 1% de V2O5, e um valor da tangente de perda relativamente baixa em relação à família de Aurivillus (tan[δ] ≈10-2 ) em 2 GHz.. Uma simulação numérica foi realizada com cada amostra verificando-se aproximação com os dados experimentais. Nas amostras dopadas com terras raras foi verificado o fenômeno de conversão ascendente de energia com a presença de bandas intensas amostras de emissão de luz visível na região do verde e de bandas de menor intensidade na região do vermelho. O Material investigado tem potencial para aplicação em memórias voláteis, filtros capacitivos e componentes ópticos, como sensores, células fotoelétricas e leds.

Les matériaux diélectriques sont utilisés dans le domaine de l'aérospatial pour assurer la régulation thermique des engins spatiaux. Ils sont soumis à un environnement chargeant composé de rayonnements ionisants tels que les électrons ou les protons. Un stockage de ces charges se produit dans le volume du matériau et engendre des dégradations et un vieillissement prématuré amenant à une perte de fiabilité globale du système qui doit être anticipée. Le but de ce travail de thèse a été d'évaluer la densité de charges d'espace injectées au sein d'un matériau diélectrique pendant une irradiation électronique afin de recréer partiellement l'environnement radiatif auquel il peut être soumis. Pour mener à bien ce projet, nous avons utilisé un dispositif expérimental basé sur la méthode Electro-Acoustique Pulsée (PEA) couramment utilisé dans le domaine du génie électrique. Nous avons développé une électrode de mesure innovante sans contact et circulaire permettant la mesure pendant irradiation électronique car les dispositifs expérimentaux précédents ne le permettaient pas. Ce type de mesures n'avait jamais été réalisé ailleurs auparavant, ce qui un vrai apport pour ce domaine d'étude car il permet de conserver l'échantillon dans une configuration proche de son utilisation finale. L'électrode est basé sur une ligne de transmission de type microstrip. Dont les caractéristiques géométriques ont été déterminées d'une part avec le logiciel Orcad PCB Editor, mais aussi avec le logiciel COMSOL Multiphysics. La validation expérimentale a été menée et les premières mesures réalisées dans l'enceinte d'irradiation MATSPACE du laboratoire ont permis de mettre en évidence le bon fonctionnement de l'électrode et de valider les résultats de simulation obtenus précédemment. Le traitement du signal a également été adapté pour cette nouvelle configuration. Une étude a ensuite été menée avec différentes énergies cinétiques (comprises entre 50 et 100 keV) et différentes densités de flux électronique (0.5 à 2 nA/cm2) pour la phase d'irradiation suivi d'une phase de relaxation (maintien de l'échantillon sous vide) afin de suivre la dynamique des charges d'espace implantées au sein du diélectrique. La représentation par cartographie de la quantité de charges injectées en volume permet de suivre aisément l'évolution de cette dernière en fonction du temps. Ce travail de thèse a permis d'atteindre les objectifs fixés concernant la réalisation de mesures pendant une irradiation électronique. Ce dispositif de caractérisation peut également être utilisé sur des films polymères issus du domaine du génie électrique, les conditions d'irradiation étant contrôlées. Dans un futur proche, ce prototype d'électrode pourra être associé à un capteur à haute résolution spatiale développé dans l'équipe pour un système encore plus performant. / Dielectric materials are widely used in space industries to ensure the spacecrafts thermal regulation. Spacecrafts are submitted to charging environment made of ionizing rays as electrons and protons. These charges are trapped in the material bulk and cause degradations and premature ageing and a global loss of reliability which had to be anticipated. The aim of this work was to evaluate the injected space charges density in a dielectric material during an electronic irradiation in order to partially reproduce the radiative environment. To lead this study, we used an experimental set up based on Pulsed Electro Acoustic (PEA) Method commonly used in electrical engineering. We have developed a new ring and contactless excitation electrode allowing to perform measurements during an electronic irradiation because the previous experimental setups don't allow to realize measurements during an electronic irradiation. This kind of measurements are performed for the first time ever in scientific research which is a real innovation for this research field because it is possible to keep the dielectric sample under vacuum and to be near the space environment. The new electrode is based on a signal transmission line (microstrip). Its geometric characteristics have been determined with two softwares as Orcad PCB Editor and COMSOL Multiphysics. The experimental validation has been led and the first measurements are performed in the irradiation chamber called MATSPACE allowing to highlight the good working of this new electrode and to validate the simulation results previously obtained. Moreover, the signal treatment has been adapted for this new configuration. A study has been also led with several kinetic energies ( 50 to 10 keV) and with several electronic flux density ( 0.5 to 2 nA/cm2) for the irradiation step followed by a relaxation step ( the sample is kept under vacuum) in order to to follow the injection dynamic of the injected electrons in the sample bulk. The space charge cartography representation allow to easily follow the dynamic injection. This work enabled to reach the differents objectives concerning the realizatiion of the space charges measurements during an electronic irradiation. This characterization setup can be used with several dielectric material used in electrical engineering, irradiation conditions being controlled. In next futur, this electrode prototype could be coupled with a very thin piezoelectric sensor to improve the spatial resolution to lead to a high temporal and spatial measurements system.

Nesta pesquisa é feita uma análise da interação do campo eletromagnético gerado por microcomputadores portáteis com o corpo humano, operando na faixa de radiocomunicações WI-FI, através da avaliação da taxa de absorção especifica (SAR). Os modelos de corpo humano heterogêneos utilizados são de um adulto de 34 anos e duas crianças de 6 e 11 anos os quais foram analisados em varias situações típicas de exposição à presença de um microcomputador portátil. Nas simulações dos cenários para avaliar a dosimetria foi utilizada a versão comercial do programa chamado SEMCAD X que é baseado no Método das Diferenças Finitas no Domínio no Tempo (FDTD). Da análise das simulações do modelo de corpo inteiro, o único resultado que ultrapassou a recomendação do (FCC, 1997) para 1 g de tecido foi na situação em que o microcomputador portátil, com a antena dipolo na parte posterior do teclado, está no colo do modelo de 34 anos. Numa segunda etapa, é feito um estudo teórico experimental da intensidade do campo elétrico gerado por dispositivos geradores de sinais Wi-Fi comerciais. Analisa-se à propagação de ondas eletromagnéticas através de paredes, utilizando uma antena monocone não ressonante e de banda larga, mediante o estudo e análise da sua taxa de onda estacionária. As medidas visam avaliar que projetando uma parede com uma espessura determinada consegue a propagação dos campos eletromagnéticos evitando reflexões e pontos quentes que possam produzir uma taxa de absorção maior no corpo humano presente nestes ambientes, além de caracterizar as propriedades dielétricas destas paredes. / This research analyses the interaction of the electromagnetic field generated by portable computers with the human body, operating in the range of radio Wi-Fi, by evaluating the specific absorption rate (SAR). The heterogeneous human body models used were those of a 34 years old adult and two children aged 6 and 11, were analyzed under various standard conditions of exposure to the presence of a portable microcomputer. The commercial version of SEMCAD X which is based on the Finite Difference Method in the Time Domain (FDTD) method was used in the simulations of the scenarios, to evaluate the dosimetry. The analysis of the simulation of the whole body model, the only result that exceeded the recommendation of the (FCC, 1997) for 1g of tissue was the simulation in which the dipole antenna on the back of the keyboard of the laptop resting on the lap of the 34-year old model. In the second stage, a theoretical experimental study was made of the intensity of the electric field created from Wi-Fi band signals generating devices. Subsequently, an analysis is made of the propagation of the electromagnetic waves through walls, using a non-resonant broadband monocone antenna by analyzing its voltage standing wave ratio (VSWR). The measures aim to assess that designing a wall with a given thickness, propagation of electromagnetic waves can be achieved, thus avoiding reflections and hot spots that can lead to higher SAR in the human body present in these environments, moreover to characterize the dielectric properties of these walls.

Made available in DSpace on 2014-06-11T19:25:32Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-03-28Bitstream added on 2014-06-13T19:53:24Z : No. of bitstreams: 1 santos_afs_me_ilha.pdf: 529659 bytes, checksum: add7c6495e005e9cdef13e0ca3baf349 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Na caracterização das propriedades ópticas em materiais, a determinação dos parâmetros ópticos como o índice de refração (n) e o coeficiente de extinção (k) são fundamentais. A análise da dispersão dos parâmetros ópticos com a freqüência fornece informações do comportamento da polarização do material com a radiação e as relações de Kramers-Kronig representam uma ferramenta básica de estudo. Neste trabalho, o principal objetivo é determinar parâmetros ópticos (n e k) e dielétricos do sistema vítreo telureto ((20-x)Li2O-xWO3-80TeO2) através da análise de espectro infravermelho pelas relações de Kramers-Kronig. Para tanto, amostras de vidro na composição x = 0, 5, 10 e 15 %mol foram sintetizadas no laboratório do grupo Vidros e Cerâmicas. As amostras foram polidas opticamente e seus espectros de refletância foram obtidos nos espectrômetros Bomem DA8 e Nexus 670 da Nicolet, na região entre 40 e 4000 cm-1. Os espectros obtidos apresentam picos de reflexão característicos observados em outros sistemas vítreos telureto, o que permitiu identificar as bandas vibracionais. As constantes ópticas foram obtidas utilizando as relações de Kramers-Kronig. Para todas as composições estudadas foi observado um aumento no índice de refração quando se aumentou a quantidade de WO3. Do espectro obtido para a constante dielétrica foi possível determinar as freqüências correspondentes aos modos ópticos transversais e longitudinais. As freqüências obtidas se ajustam com aquelas obtidas pelo modelo analítico dos quatro parâmetros semi-quânticos da constante dielétrica, principalmente para a região acima de 500 cm-1. / In the study of optical and dielectric properties of materials, the determination of complex indices of refraction and complex dielectric function is fundamental. The analysis of the dispersion of the optical parameters with the frequency provides information about the behavior of the polarization of the material with the radiation, and the Kramers-Kronig relations represent a basic tool of the study. In this work, the main objective was to determine the optical (n and k) and dielectric parameters of a tellurite glasses system ((20-x)Li2O-xWO3-80TeO2) through the infrared spectrum analysis by Kramers-Kronig dispersion relations. For this, glass samples with x=0, 5, 10, and 15 %mol were prepared at the laboratory of Glasses and Ceramics group. The glass samples were polished and their reflectance spectra were obtained in the Bomem DA8 and Nicolet Nexus 670 spectrometers, in the spectral range of 40 to 4000 cm-1. The obtained spectra present allowed us to assign the vibrational bands. The optical and dielectric constants were obtained by the Kramers-Kronig method. For all studied glass compositions an increase was observed in the real part of refractive index when the WO3 content is increased. From de obtained dielectric function it was possible to extract transversal and longitudinal optical phonons frequencies. The frequencies agree with those obtained by the four-parameter semiquantum model, mainly for the region above 500 cm-1.

abstract: Broadband dielectric spectroscopy is a powerful technique for understanding the dynamics in supercooled liquids. It generates information about the timescale of the orientational motions of molecular dipoles within the liquid. However, dynamics of liquids measured in the non-linear response regime has recently become an area of significant interest, because additional information can be obtained compared with linear response measurements. The first part of this thesis describes nonlinear dielectric relaxation experiments performed on various molecular glass forming-liquids, with an emphasis on the response at high frequencies (excess wing). A significant nonlinear dielectric effect (NDE) was found to persist in these modes, and the magnitude of this NDE traces the temperature dependence of the activation energy. A time resolved measurement technique monitoring the dielectric loss revealed that for the steady state NDE to develop it would take a very large number of high amplitude alternating current (ac) field cycles. High frequency modes were found to be ‘slaved’ to the average structural relaxation time, contrary to the standard picture of heterogeneity. Nonlinear measurements were also performed on the Johari-Goldstein β-relaxation process. High ac fields were found to modify the amplitudes of these secondary modes. The nonlinear features of this secondary process are reminiscent of those found for the excess wing regime, suggesting that these two contributions to dynamics have common origins. The second part of this thesis describes the nonlinear effects observed from the application of high direct current (dc) bias fields superposed with a small amplitude sinusoidal ac field. For several molecular glass formers, the application of a dc field was found to slow down the system via reduction in configurational entropy (Adam-Gibbs relation). Time resolved measurements indicated that the rise of the non-linear effect is slower than its decay, as observed in the electro-optical Kerr effect. A model was discussed which quantitatively captures the observed magnitudes and time dependencies of the NDE. Asymmetry in these rise and decay times was demonstrated as a consequence of the quadratic field dependence of the entropy change. It was demonstrated that the high bias field modifies the polarization response to the field, even including the zero field limit. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016