The objective of this work was to analyze the relationship of the sea level pressure (SLP) of Tahiti and some meteorological variables over Brazil, with emphasis in the eastern coast of Northeastern Brazil (ENE). For this purpose, NCEP/NCAR reanalysis data sets of SLP, rainfall rate, outgoing longwave (OLR), zonal and meridional wind components at 850 mb level, for a period that includes two phases of Pacific Decadal Oscillation (PDO), a cold phase (1948-1976) and a warm phase (1977-1998), were used. Firstly, the variables anomaly fields were elaborated. Then, a Tahiti SLP standardized index time series (IPT) was constructed and used for correlating with the above mentioned variables anomalies over Brazil. The software GrADS was employed to constructing the variables anomaly fields and the IPT linear correlation coefficient maps. The IPT spatial correlation was performed for each variable anomalies of the cold and the warm PDO phases separately. IPT and rainfall rate correlation coefficients values, ranging from 0,3 to 0,5 , with statistically significance level up to 99%, were found over the northeastern Amazon (Trombetas river watershed) and ENE. In general, the correlation coefficients presented higher values in the PDO warm phase and the IPT performed better than other climatic indices, such as SOI, MEI and Niño 3.4, with respect to rainfall rate over Brazil. Lag correlations were performed, with the meteorological variables lagging up to 5 months the IPT. The results suggested that the IPT is a good predictor of the rainfall rate 5 months in advance, particularly in northeastern Amazon. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo deste trabalho foi analisar a relação da pressão atmosférica ao nível do mar (PNM) de Tahiti com algumas variáveis meteorológicas sobre o Brasil, com ênfase na costa leste de Nordeste Brasileiro (ENE). Para esse propósito, foram utilizados conjuntos de dados de reanálises do NCEP/NCAR das variáveis PNM, taxa de precipitação, radiação de onda longa emergente (ROLE) e componentes zonal e meridional do vento ao nível de 850 mb para um período que compreende duas fases da Oscilação Decadal do Pacífico (ODP), suas fases fria (1948-1976) e quente (1977-1998). Primeiramente, foram elaborados os campos de anomalias dessas variáveis. Em seguida, foi construída uma série temporal do índice de PNM de Tahiti padronizado (IPT), que foi correlacionado com as variáveis acima mencionadas sobre o Brasil. O software GrADS foi usado para construir os mapas de coeficientes de correlação entre o IPT e as anomalias das variáveis. A correlação espacial foi feita para cada variável nas fases fria e quente da ODP separadamente. Foram encontrados valores dos coeficientes de correlação entre o IPT e a taxa de precipitação variando de 0,3 a 0,5, com nível de significância de até 99%, para o nordeste da Amazônia (bacia do rio Trombetas) e o ENE. De maneira geral, os coeficientes de correlação apresentaram valores maiores durante a fase quente da ODP e o IPT teve um desempenho melhor que os outros índices climáticos, como o IOS, IME e Niño 3.4 com relação à taxa de precipitação sobre o Brasil. Correlações atrasadas ( lag ) foram feitas, com as variáveis meteorológicas atrasadas de até 5 meses com relação ao IPT. Os resultados sugeriram que o IPT é um bom previsor da taxa de precipitação com até 5 meses de antecedência, particularmente sobre o nordeste da Amazônia.

Le manuscrit porte sur l'élaboration de couches minces ayant des propriétés barrières aux liquides, aux gaz et aux ultra-violets. Pour réaliser nos différents systèmes, la technologie plasma à décharge à barrière diélectrique à la pression atmosphérique (DBD) a été utilisée. Dans la première partie, des films polymère plasma à base de 1H, 1H, 2H, 2H, Perfluorodecyl acrylate ont été développé. En fonction des paramètres plasma une surface dîtes superhydrophobe en une étape a été obtenue grâce à l'obtention d'un film composé de nanoparticules fluorés. La seconde partie des travaux a consisté à développer des films barrières aux gaz à partir de l'hexamethyldisiloxane. Ainsi, des films minces SiOx et multicouches SiOxHyCz/SiOx ont pu être obtenue afin d'améliorer les performances barrières de substrat PET et PEN. Enfin, l'obtention de film barrière aux UV a consisté à une croissance in-situ de nanoparticules de dioxyde de titane (TiO2) à partir du film polymère plasma. La matrice polymère constitué d'une structure siloxane et aminée plasma joue le rôle de nano-réacteur pour la croissance de cristaux de TiO2. / This works presents the development of plasma-polymrized surfaces for superhydrophobic, gas barrier and UV attenuation properties. These functional coatings have been deposited by means of atmospheric pressure dielectric barrier discharge (DBD). The first part deals on the plasma polymerization of the de 1H, 1H, 2H, 2H, Perfluorodecyl acrylate. According to the plasma parameters, surperhydrophobic coatings have obtained on several substrates. Morphologies analysis have shown the formation of fluorinate nanoparticles. The second part of the work was to develop gas barrier films from hexamethyldisiloxane. Thus, SiOx thin films and SiOxHyCz / SiOx multilayers have been obtained in order to improve the barrier performance of PET and PEN substrate. Finally, obtaining UV barrier film was to an in-situ growth of nanoparticles of titanium (TiO2) dioxide from the plasma polymer filin. The plasma polymer acts as a nano-reactor for the growth of TiO2 nanoparticles

Submitted by DIEGO GLAUCO AZARIAS DOS REIS null (diego.dgadr@gmail.com) on 2017-04-19T18:15:44Z No. of bitstreams: 1 Dissertação-Diego_Reis_2017.pdf: 2518961 bytes, checksum: a16c2b4a218332cdf0587afa47cadbff (MD5) / Rejected by Luiz Galeffi (luizgaleffi@gmail.com), reason: Solicitamos que realize uma nova submissão seguindo a orientação abaixo: O arquivo submetido está sem a ficha catalográfica. A versão submetida por você é considerada a versão final da dissertação/tese, portanto não poderá ocorrer qualquer alteração em seu conteúdo após a aprovação. Corrija esta informação e realize uma nova submissão com o arquivo correto. Agradecemos a compreensão. on 2017-04-19T19:55:04Z (GMT) / Submitted by DIEGO GLAUCO AZARIAS REIS (diego.dgadr@gmail.com) on 2017-04-20T13:12:56Z No. of bitstreams: 1 Dissertação-Diego_Reis_2017.pdf: 2653651 bytes, checksum: af70d0852f1dbed4cb80ba89720797f4 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-04-25T17:14:34Z (GMT) No. of bitstreams: 1 azarias_dga_me_guara.pdf: 2653651 bytes, checksum: af70d0852f1dbed4cb80ba89720797f4 (MD5) / Made available in DSpace on 2017-04-25T17:14:34Z (GMT). No. of bitstreams: 1 azarias_dga_me_guara.pdf: 2653651 bytes, checksum: af70d0852f1dbed4cb80ba89720797f4 (MD5) Previous issue date: 2017-02-20 / O tratamento de materiais utilizando plasma tem sido utilizado amplamente nos dias atuais com o desenvolvimento de novas tecnologias baseadas em descargas elétricas a pressão atmosférica. Dentre os diversos métodos para produzir plasmas nestas condições destaca-se a descarga por microplasmas. No presente trabalho, um novo dispositivo foi desenvolvido e utilizado para deposição de filmes finos. Em estudos de arrasto de vapores no dispositivo foi verificado a relação linear entre a vazão do gás e a massa arrastada. Deposições poliméricas foram obtidas pela mistura de gás argônio com o monômero hexametildissiloxano (HMDSO) em substratos de vidro. A deposição de filmes ocorreu com a vazão de gás entre 0,07 L/min e 0,4 L/min para potências entre 100 mW e 650 mW. Para outras vazões, ocorreu a formação de material sólido em forma de grânulos submilimétricos. A caracterização dos filmes por espectroscopia infravermelha com transformada de Fourier (FTIR) mostrou a presença de grupos moleculares como trimetilsilil Si(CH3)3, siloxano SiOSi e metino CHx. Os testes de adesão realizados no padrão D3359 ASTM com fita Scotch 3M mostraram boa adesão dos filmes aos substratos. Medições de ângulo de contato mostraram a diminuição da hidrofilicidade da superfície dos substratos com valores variando de 40° sem tratamento para quase 90° com o filme fino. Os resultados mostraram que dispositivo desenvolvido foi utilizado com sucesso na deposição em pressão atmosférica de filmes de HMDSO indicando que pode ser empregado também com outros monômeros. / The treatment of materials using plasma has been used widely nowadays with the development of new technologies based on electrical discharges at atmospheric pressure. Among the various methods of producing plasma in these conditions, we gave attention to microplasmas. In this study, a new device was developed and applied to the deposition of polymeric thin films. The dragging of the vapour in the device was investigated for various organic compounds and gas flow rate. It was observed a linear relation between these parameters. The polymeric depositions were obtained with the mixture of argon gas and hexamethyldisiloxane (HMDSO) on glass slides. The thin film deposition occurred with gas flow rate between 0.07 L/min and 0.4 L/min with potencies around 100 mW and 650 mW. The formation of solid submilimeter grains was observed at others gas glow rates. The regular thin films was analysed by Fourier transform infrared spectroscopy (FTIR) and showed the molecular groups of trimethylsilyl Si(CH3)3, siloxane SiOSi and methyne CHx. The films had a good adhesion when subjected to the D3359 ASTM standard test using adhesive tape Scotch 3M. Contact angle characterization has shown a decrease of the hydrophilicity surface property with values changing from 40o without treatment up to 90o with thin film. The results has shown that the developed device was successfully used for deposition of HMDSO films at atmospheric pressure indicating that can be used with other monomers as well.

Water droplets tend to bead up on rough or textured hydrophobic surfaces by trapping air on the crevices underneath resulting in “Cassie” state of wetting. When a textured hydrophobic surface is immersed in water, the resulting underwater “Cassie” state can lead to significant drag reduction. The entrapped air pockets act as shear free regions and the composite interface consisting of alternate no slip and no shear regions thus formed can deliver substantial drag reduction during flow. The magnitude of drag reduction depends not only on the fractional coverage of air on the surface, but also on the size of the air pockets, with larger sized air pockets facilitating larger drag reduction. It is a common observance that Lotus leaf when kept immersed in water for a few minutes loses its water repellency due to the loss of entrapped air on the surface. Underwater Cassie state on textured hydrophobic surfaces is also not sustainable because of the depletion of air pockets caused by the diffusion of trapped air into water. This causes the drag reduction to diminish with time. Rate of diffusion of air across the water–air interface depends on the concentration gradient of air across the interface. Under flow conditions, removal of entrapped air is further enhanced by convection, leading to more rapid shrinkage of the air pockets. In order to sustain the Cassie state, it is thus necessary to continuously supply air to these air pockets. In this work, we explore the possibility of supplying air to the cavities on the textured surface inside a microchannel by controlling the solubility of air in water close to the surface. The solubility is varied by i) Controlling the absolute pressure inside the channel and ii) Localized heating of the surface To trap uniform air pockets, a textured surface containing a regular array of blind holes is used. The textured surface is generated by photo etching of brass and is rendered hydrophobic through a self-assembled monolayer. The sustainability of the underwater Cassie state of wetting on the surface is studied at various flow conditions. The air trapped on the textured surface is visualized using total internal reflection based technique, with the pressure drop (or drag) being simultaneously measured. Water which is initially saturated with air at atmospheric conditions, when subjected to sub-atmospheric pressures within the channel becomes supersaturated causing the air bubbles to grow in size. Further growth causes the bubbles to merge and eventually detach from the surface. The growth and subsequent merging of the air bubbles leads to a substantial increase in the pressure drop because as the air pockets grow in size, they project into the flow and start obstructing the flow. On the other hand, a pressure above the atmospheric pressure within the channel makes the water undersaturated with air, leading to gradual shrinkage and eventual disappearance of air bubbles. In this case, the air bubbles do cause reduction in the pressure drop with the minimum pressure drop (or maximum drag reduction) occurring when the bubbles are flush with the surface. The rate of growth or decay of air bubbles is found to be significantly dependent on the absolute pressure in the channel. Hence by carefully controlling the absolute pressure, the Cassie state of wetting can be sustained for extended periods of time. A drag reduction of up to 15% was achieved and sustained for a period of over 5 hours. Temperature of water also influences the solubility of air in water with higher temperatures resulting in reduced solubility. Thus locally heating the textured hydrophobic surface causes the air bubbles to grow, with the rate of growth being dependent on the heat input. The effect of trapped air bubbles on thermal transport is also determined by measuring the heat transfer rate through the surface in the presence and absence of trapped air bubbles. Even though the trapped air bubbles do cause a reduction in the heat transfer coefficient by about 10%, a large pressure drop reduction of up to 15% obtained during the experiments helps in circumventing this disadvantage. Hence for the same pressure drop across the channel, the textured hydrophobic surface helps to augment the heat transfer rate. The experiments show that, by varying the solubility of air in water either by controlling the pressure or by local heating, underwater Cassie state of wetting can be sustained on textured hydrophobic surfaces, thus delivering up to 15% drag reduction in both cases for extended periods of time. The results obtained hold important implications towards achieving sustained drag reduction in microfluidic applications.

L’utilisation de plasmas, qu’ils soient thermiques ou basse pression, dans le domaine biomédical remonte aux années 1970. Au cours de ces dernières années, les développements concernant des jets de plasma froid à pression atmosphérique, ont permis un élargissement des domaines d’applications biomédicales des plasmas. Au sein du GREMI, un type de jet de plasma a été développé : le Plasma Gun. Le plasma généré par le Plasma Gun se propage sur de longues distances à l’intérieur de capillaires. L’optimisation des traitements visés nécessite une étude approfondie des décharges créées par le Plasma Gun. La caractérisation du Plasma Gun a mis en évidence la génération de Pulsed Atmospheric pressure Plasma Streams ou PAPS, ces derniers se propageant du réacteur jusque dans l’air ambiant où ils génèrent une plume plasma. Ces PAPS présentent deux modes de propagation, au cours desquels une connexion entre le front d’ionisation et le réacteur est présente en permanence. Ces deux modes nommés respectivement Wall-hugging et Homogène, diffèrent principalement par la morphologie et la vitesse de propagation des PAPS qui leur sont associés. Chacun de ces modes présentent donc des caractéristiques qui leur sont propres mais certaines propriétés de propagation leur sont communes, telles que la possibilité de division ou de réunion de PAPS, ainsi que du transfert de PAPS à travers une barrière diélectrique ou via un capillaire métallique creux. L’étude de la plume plasma, propagation des PAPS dans l’air ambiant, a souligné l’importance de la longueur des capillaires sur la longueur du jet plasma. De plus, la génération du plasma a une très forte influence sur l’écoulement du gaz et la structuration du jet lors de son expansion dans l’air. / The use of plasmas, thermic or low pressure, in biomedical goes back up to 1970s. During these last years, atmospheric pressure cold plasma jets have been developed, allowed an increase of biomedical applications of plasmas. In GREMI, a plasma jet was developed : the Plasma Gun (PG). The plasma generated by the PG propagates on long distances inside capillaries. The optimization of the aimed treatments requires a detailed study of the discharges created by the PG. The characterization of the PG highlights the generation of Pulsed Atmospheric pressure Plasma Streams or PAPS, these last ones propagating from the reactor to the capillary outlet (ambient air) where they generate a plasma plume. These PAPS present two propagation modes, during which a connection between the ionization front and the reactor is present permanently. These two modes named respectively Wall-hugging and Homogeneous, differ mainly by the morphology and their propagation velocity. These modes have common characteristics, such as the possibility of division or meeting of PAPS, as well as the transfer of PAPS through a dielectric barrier or via a hollow metal capillary. The study of the plasma plume underlined the importance of the length of capillaries on the length of the plasma jet. Furthermore, the generation of the plasma has a very strong influence on the gas flow and the jet structuration during air expansion.

Le développement de procédé évoluant à la pression atmosphérique représente un enjeu majeur dans le dépôt de couches minces nanocomposites. Parmi ces procédés, les Décharges à Barrières Diélectriques présentent l'avantage d'être un procédé vert sans effluent gazeux, pouvant facilement être intégrées dans une chaine de production industrielle. L'approche choisie pour la réalisation de couches minces nanocomposites repose sur l'injection sous forme d'aérosol d'une suspension colloïdale dans la DBD. Les nanoparticules semi-conductrices de TiO2 sont choisies et mise en suspension dans un alcool polymérisable tel que l'isopropanol. L’objectif de ce travail est de contrôler le transport des nanoparticules et la croissance de la matrice dans la DBD en vue de réaliser une couche mince nanocomposite.Différentes méthodes de formation de l'aérosol et de filtration sont évaluées, ainsi que différents gaz vecteur (Ar, N2). Dans tous les cas considérés, la décharge est filamentaire.L'estimation des valeurs des différentes forces s'exerçant sur une nanoparticule dans une DBD confortée par un modèle numérique à permis d'orienter les expérimentations. Il est ainsi possible, à partir des paramètres permettant de générer le plasma, d'influencer le dépôt des nanoparticules et la croissance de la matrice. Les dépôts obtenus sont analysés ex situ par microscopie électronique à balayage, spectroscopie infrarouge, Raman et à rayon X et in situ avec la diffusion laser.Dans le régime filamentaire considéré, nous montrons que le flux de gaz et la fréquence de la tension joue des rôles prépondérants sur le dépôt des couches minces nanocomposites. Cette étude a permis de mettre en évidence qu’une simple fréquence n’est pas suffisante pour déposer la couche mince nanocomposite. Cependant l’utilisation d’une double fréquence semble être la meilleure approche pour séparer le transport des nanoparticules de celui de la croissance de la matrice. / Development of an atmospheric pressure process presents a major concern in the deposition of nanocomposites thin films. Among these processes, Dielectrics Barrier Discharges takes advantages to be green processes without gas effluent, which can be easily integrate in an industrial line production. The chosen approach for the nanocomposite thin film deposition is based on the injection of an aerosol of a colloidal suspension in the DBD. Semi-conductive TiO2 nanoparticles are chosen and put in suspension in a polymerizable alcohol as isopropanol. The objective of the present work is to control the transport of the nanoparticles as well as the matrix growth in the DBD in order to realize the nanocomposites thin film Different methods of the aerosol formation and filtration are evaluated, as well as the carrier gas (Ar, N2). In each case considered, the discharge works in filamentary. Estimating values of the different forces acting on the nanoparticles in a DBD comforted by a numerical model allowed to guide the experimentations. Thanks to the parameter which generated the plasma, it is possible to influence the nanoparticles deposition and the matrix growth. Depositions are ex situ analyzed by scanning electron microscopy, Infra-red, Raman, and X-ray spectroscopy and in situ by laser scattering. In the filamentary regime considered, we show that the gas flow rate and the frequency of the voltage play a dominant role on the deposition of nanocomposites thin films. This study allowed to highlight that a simple frequency is not enough to deposit the nanocomposite thin film. However, the use of a double frequencies seems to be the best way to separate the nanoparticles transport to the surface from that of the matrix growth.

The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.

No description available.

This diploma thesis deals with the design of an autonomous system for the measurement of the concentration of atmospheric ions. This is a new version of the already asembled Iontmeter by UTEE FEKT. Unlike the previous version, this new one should be completely independent of electrical network and configurable even without a PC. The design includes increased water and dust resistance, wireless transmission from the weather station and its own temperature, atmospheric pressure and relative humidity sensor.

<p>High resolution tandem mass spectrometry (MSⁿ) coupled with various separation techniques, such as high-performance liquid chromatography (HPLC) and gas chromatography (GC), is widely used to analyze mixtures of unknown organic compounds. In a mass spectrometric analysis, analytes of interest are at first transferred into the gas phase, ionized (protonated or deprotonated) and introduced into the instrument. Tandem mass spectrometric experiments may then be used to gain insights into structure and reactivity of the analyte ions in the gas phase. The tandem mass spectral data are often compared to those reported in external databases. However, the tandem mass spectra obtained for protonated analytes may be markedly different from those in external databases because protonation site manifested during a mass spectrometric experiment can be affected by the ionization technique, ionization solvents and condition of the ion source. This thesis focuses on investigating the effects of instrumental conditions and analyte concentrations on the protonation sites of 4-aminobenzoic acid. Reactivities of radical species were also investigated. A modified bracketing method was developed and proton affinities of a series of mono- and biradicals of pyridine were measured. In another study, a <i>para</i>-benzyne analog was generated in both solution and the gas phase and its reactivities towards various neutral reagents in the gas phase were compared to those in solution.</p> <p> Chapter 2 discusses the fundamental aspects of the instruments used in this research. In chapter 3, the effects of residual moisture in linear quadrupole ion trap on the protonation sites of 4-aminobenzoic acid are considered. Chapter 4 focuses on the use of gas-phase ion-molecule reactions with trimethoxymethylsilane (TMMS) for the identification of the protonation sites of 4-aminobenzoic acid. Further, the effects of analyte concentration on the protonation sites of 4-aminobenzoic acid are considered. Chapter 5 introduces a modified bracketing method for the experimental determination of proton affinities of a series of pyridine-based mono- and biradicals. In chapter 6, successful generation of <i>para</i>-benzynes in solution is discussed. The reactivity of a <i>para</i>-benzyne analog, 1,4-didehydrophenazine, is compared to its reactivity in the gas phase.</p>