Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T11:09:13Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T11:09:13Z (GMT). No. of bitstreams: 0 / Neste trabalho foi desenvolvido uma metodologia para a determinação de metais (Cr, Cu, Fe, Mg, Mo, Pb), em óleos lubrificantes e estes quantificados pela técnica de espectrometria de emissão optica com plasma induzido por laser (LIBS). As amostras de óleo usadas foram coletadas em oficina de troca de óleo, variando-se a quilometragem, ano, marca do carro e a marca do óleo, com o preenchimento de formulários contendo as informações necessárias à pesquisa. A preparação de amostras foi realizada com o depósito ds mesmas em substrato de papel e sequente otimização dos parâmetros instrumentais. Para a calibração, foi utilizado o padrão de óleo S-21 multielementar da Conostan (SCP Science, Champlain, NY). Para a avaliação da exatidão do método desenvolvido foi utilizado o padrão de óleos lubrificantes (SRM 1084a) obtidos junto ao Instituto Nacional de Padrões e Tecnologia (NIST, Gaithersburg, MD). O método proposto apresentou as seguintes vantagens quando comparado com métodos de análise tradicionais (espectrometria de absorção atômica ou espectrometria de emissão optica acoplado ao plasma indutivo com diluição da amostra): mais rápida, sem desgaste do equipamento (em função da não introdução de solvente), geração de resíduo praticamente nula e menor consumo de reagentes. O método desenvolvido foi aplicado em amostras reais e o tratamento de dados realizado por análise estatística (equação de Stuarges, teste não paramétrico de Kruskalwallis). / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-08-26T11:26:18Z No. of bitstreams: 0 / Made available in DSpace on 2016-08-26T11:26:18Z (GMT). No. of bitstreams: 0 / A água é um recurso essencial à vida, logo deve estar presente em quantidade e qualidade adequada para seu consumo. O presente estudo teve como objetivo avaliar a qualidade ambiental da represa Guarapiranga, Localizado em partes dos municípios de Cotia, Embu, Itapecerica da Serra, Juquitiba, São Lourenço da Serra e São Paulo e na área total do município de Embu Guaçu, este sistema tem significativa degradação em sua qualidade de água devido ao aporte de efluente doméstico e industrial aumentando o custo do tratamento e dificultando o acesso a água potável. Foram apresentados os resultados de 26 metais, 7 ânions, parâmetros limnológicos: pH, condutividade, temperatura, oxigênio dissolvido, transparência da água, obtidos a partir das amostras das coletas realizadas entre os anos de 2011 a 2013, em amostras de água na superfície, meio e fundo em 14 pontos e de sedimento de fundo nestes mesmos pontos sendo avaliando 26 metais. Os resultados de sedimento foram comparados com os valores de TEL e PEL e os resultados de água foram com os limites de estabelecidos pela resolução COMANA 357/2005. Os parâmetros limnológicos, condutividade, pH e oxigênio dissolvido ficaram fora do enquadramento da resolução do COMANA 357/05. Todas as espécies iônicas atenderam ao estabelecido pelo CONAMA 357/05, no entanto é observado um aumento das concentrações no decorrer das coletas. A serie nitrogenada assim com a relação Fe:P mostraram ser importantes parâmetros de controle do aporte da carga orgânica no reservatório. Dos 26 elementos analisados somente Al, Cu, Mn apresentaram concentrações fora do estabelecido pela resolução COMANA 357/05. Os sedimentos analisados os elementos químicos Cu, Cr, Zn apresentaram valores acima do TEL e do PEL. A partir dos resultados obtidos infere-se que o reservatório do Guarapiranga apresenta dois compartimentos distintos, um mais degradado que vai do ponto 05 a 14 que sofre os impactos da ocupação do seu entorno e um mais preservado que vai do ponto 01 a 05, sem tanta influência de ocupação urbana no seu entorno. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

La technique laser-induced breakdown spectroscopy (LIBS), qui consiste à exploiter le spectre du plasma induit par laser sur la surface de l'échantillon pour déterminer sa composition élémentaire, a été inventée il y a plus de 50 ans. Récemment, elle connaît un développement rapide, poussée par des besoins d'application dans différents domaines, citons par exemple, exploration océanique, détection de pollution environnementale, ou contrôle de procédés industriels. Cette technique utilise le plasma généré par ablation laser comme la source spectroscopique. La particularité de LIBS est que le plasma induit par laser présente un comportement transitoire et une distribution spatiale qui ne soit pas uniforme en général. Bien que la détection résolue en temps puisse améliorer considérablement la performance de LIBS, surtout pour le procédé de LIBS autocalibration avec une meilleure détermination de température, l'évolution temporelle du plasma est souvent corrélée avec sa morphologie et son inhomogénéité spatiale. L'étude de la morphologie ainsi que la structure interne du plasma avec l'évolution pendant l'expansion de celui-ci dans un gaz ambiant, représente donc un point crucial pour l'optimisation du plasma entant qu'une source spectroscopique. Suite à la thèse de Qianli Ma réalisée dans notre équipe et soutenue en décembre 2012, qui a été notamment consacrée à l'étude de l'effet de la longueur d'onde du laser d'ablation sur les propriétés et l'évolution du plasma dans un gaz ambiant d'argon, la présente thèse s'intéresse aux effets des autres paramètres, la fluence du laser d'ablation, la durée de l'impulsion, et les différents gaz ambiants (argon ou air), sur la morphologie et la structure du plasma. Par ailleurs, les mécanismes microscopiques conduisant à l'onde de détonation soutenue par laser dans argon ou dans l'air sont aussi étudiés. Lors du refroidissant du plasma dans l'air, des oxydes métalliques peuvent se former. L'étude de la formation de molécules, au-delà de l'intérêt pratique pour la LIBS, fournit également un aperçu de la cinétique chimique dans le plasma, ce qui est intéressant pour l'étude de la transformation du plasma en phase gazeuse à une phase recondensée de nanoparticules / Laser-induced breakdown spectroscopy (LIBS) has been invented for more than 50 years, which analyzes the spectrum of the laser-induced plasma to determine the elemental composition of the ablated sample. Recently, LIBS technique has been well developed and applied in different domains, for example oceanic exploration, pollution monitoring in the environment. LIBS uses the ablation plasma as a light source that contains the elemental composition information of the sample. However, the laser-induced plasma exhibits a transient behavior. Although time-resolved and gated detection can greatly improve the performance of the LIBS technique especially that of calibration-free LIBS (CF-LIBS) with a better determination of plasma temperature, the temporal evolution of the plasma is correlated to its morphology and its spatial inhomogeneity. The determination of the morphology as well as the internal structure of the plasma together with their evolution during plasma expansion into the ambient gas is therefore crucial for the optimization of the use of ablation plasma as a spectroscopic emission source. Evolutions of the morphology and the internal structure of the ablation plasma are considered as the consequence of its hydrodynamic expansion into the ambient gas. Following the thesis of Qianli Ma which has studied the effect of laser wavelength on the behavior of the plasma induced in an ambient gas of argon, the present thesis has used the same diagnostic techniques (time- and space-resolved emission spectroscopy and fast spectroscopic images) together with 1064 nm ns laser pulse ablation of a target of aluminum to investigate the effects of other parameters, such as the fluence and the duration of laser pulse, the effect of different ambient gases (argon and air), on the morphology and internal structure of the plasma. Furthermore, in order to understand the effects of these parameters on the properties of the plasma, the microscopic mechanisms during post ablation and the propagation of the plasma are also studied. While the plasma cools down in air, molecules are formed, AlO for instance. So the thesis also studied the condition for the formation of the molecules in the plasma. Beyond the practical interest of this study for LIBS, it provides also insights to the kinetics of the AlO molecule formation in laserinduced plasma

Les nanocristaux de CdSe font l'objet d'applications émergentes dans les domaines de la nano-électronique, des technologies laser ou du marquage fluorescent de biomolécules. Pour ces applications, la détermination de la structure fine de l'exciton de bord de bande et des mécanismes de relaxation entre sous-niveaux est d'un intérêt majeur. Cette thèse a été consacrée à l'étude spectroscopique à basse température et sous champ magnétique de nanocristaux individuels de CdSe/ZnS. La remarquable photostabilité des nanocristaux étudiés a permis de caractériser les propriétés optiques des deux états excitoniques de plus basse énergie: l'état excitonique fondamental "noir", et l'état excitonique "brillant" situé quelques meV plus haut en énergie. Ces études ont aussi permis d'identifier un état excitonique chargé (trion) et de caractériser ses propriétés photophysiques. La possibilité de générer une cascade radiative biexciton-exciton a également été démontrée dans ces systèmes. / CdSe nanocrystals are attractive for many applications such as nanoscale electronics, laser technology, and biological fluorescent labelling. A detailed understanding of the band-edge exciton fine structure and the relaxations pathways between sub-levels are crucial for these applications. During this project we have studied the optical properties of single CdSe/ZnS nanocrystals at cryogenical temperature and under magnetic field. The dramatic photostability of the nanocrystals' emission has allowed the optical study of the two lowest exciton states: the "dark" excitonic state and the "bright" excitonic state, lying few meV above. These studies have also enabled us to identify a charged excitonic state (negative trion) and to characterize its photophysical properties. Besides we have demonstrated that in these nanocrystals, radiative cascade biexciton-exciton might be generated.

Magister Scientiae - MSc / The spectroscopic, SEM and Raman measurements on carbon nanotubes under the exact conditions of which OES analysis were made showed that at a pressure of 400 Torr and a flow rate of 200 sccm, the quality and quantity of single-walled carbon nanotubes was the highest. / South Africa

Le soudage à l’arc avec fil fusible est un procédé très utilisé, mais la compréhension des mécanismes régissant son fonctionnement comporte toujours quelques interrogations compte tenu de sa complexité. La composition du gaz de protection a une très forte influence sur le procédé : l’ajout de gaz actif modifie, par exemple, le courant nécessaire à la transition entre les différents régimes et est responsable de l’apparition d’oxyde de fer (gangue) à l’extrémité du fil fusible. Pour mener à bien l’étude du soudage MIG-MAG sous mélanges Ar-CO₂-O₂, plusieurs études sont réalisées pour caractériser et mieux comprendre les phénomènes physico-chimiques qui gouvernent le soudage MIG-MAG afin d’optimiser à terme le procédé. Un diagnostic spectroscopique, avec la mise en place d’un système d’acquisition composé de deux spectromètres qui permet d’enregistrer simultanément les raies spectrales de fer et d’argon, permet d’évaluer les distributions radiales de température et densité électronique dans la colonne de plasma. Une étude par cinématographie rapide est également menée pour tenter d’évaluer la formation et l’écoulement de la couche d’oxyde apparaissant en régime globulaire à la surface de l’anode fusible. Et enfin, des analyses micrographiques des électrodes sont réalisées pour étudier l’influence des modifications chimiques et structurales sur le comportement général du procédé pour différents types de paramètres utilisés. Les conséquences d’un changement de gaz de protection sont également appréhendées : Ar-CO₂, Ar-O₂ et Ar-CO₂-O₂. Il s’avère que la température électronique de l’arc évolue en présence d’oxygène dans le gaz de protection et que la modification du gaz actif modifie le type d’oxyde de fer formé. / The arc welding with consumable wire is a process widely used, but understanding the mechanisms governing its operation still has some questions given its complexity. The composition of the shielding gas has a very strong influence on the process: the addition of active gas changes, for example, the current necessary for the transition between the different metal transfers and is responsible for the appearance of an iron oxide (gangue) at the end of the consumable wire. To carry out the study of MIG-MAG welding under mixtures Ar-CO₂-O₂, several studies are performed to characterize and understand the physical and chemical phenomena that govern the MIG-MAG welding to optimize the process. A spectroscopic diagnosis, with the establishment of an acquisition system consisting of two spectrometers to record simultaneously the iron and argon spectral lines, allows to estimate the radial distributions of temperature and electron density in the plasma column. A study by rapid cinematography is also conducted to try to estimate the formation and flow of the iron oxide layer appearing in globular regime on the surface of the anode consumable. And finally, micrographic analyzes of the electrodes are made to study the influence of chemical and structural changes on the general behavior of the process for different types of parameters used. The consequences of a shielding gas change are also apprehended: Ar-CO₂, Ar-O₂ and Ar-CO₂-O₂. It turns out that the electron temperature of the arc changes in the presence of oxygen in the shielding gas and the change of the active gas modifies the type of iron oxide formed.

Incineration is an attractive solution to the problems of disposing of municipal solid wastes and supplying energy. Because up to 25 percent of the waste in refuse-derived-fuel systems is ash, the physical and chemical characteristics of ash become more and more important for its potential impacts and methods suitable for their disposal. Trace elements concentration in ash is of great interest because of its relationship to regulatory criteria under the Resource Conservation and Recovery Act (RCRA) regarding toxicity and hazards. The applications of a microwave oven sample dissolution method has been tested on a variety of standard reference materials, with reproducible and accurate results. Fourteen trace elements, As, Ba, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Tl, V, and Zn, from the dissolved ash samples were determined by inductively coupled plasma atomic emission spectrometry.

Transition-metal oxides (TMOs) display numerous fascinating and complex properties, such as mixed-valency, low dimensionality, lattice distortion, and phase transition, etc. These properties arise from the partially filled d- or f-electron shells of TM cations and are often accompanied by the intriguing interplay between degrees of freedom. To understand the complexity of d-electron TMOs, this thesis is primarily focused on studying their underlying electronic structure using X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES), X-ray photoemission spectroscopy (XPS), and resonant inelastic X-ray scattering (RIXS). The measurements at the O K- and TM L-edges are achieved by taking advantage of high-flux and high-resolution synchrotron radiation light with tunable monochromatic photon energy. Four electronically and structurally distinctive oxides are selected as representative TMOs for investigation in this thesis. To begin with, through a comparative study of WO3 and Na0.67WO3 crystals, the narrowing of the conduction band is observed with Na doping and the core-hole energy shift in the O K-edge XAS process is experimentally determined. Indirect and direct band gaps of photoanode WO3 are measured from the resonant XES with polarization-dependent experimental geometry. The other sodium bronze studied is quasi-one-dimensional β-Na0.33V2O5 polycrystalline film. The film stoichiometry, preferential orientation, and orbital anisotropy are well characterized by a variety of photon and electron techniques and compared to density-functional theory (DFT) calculation. The V 3d orbital splitting of β-Na0.33V2O5 is surveyed by the V L-edge RIXS and compared with isoelectronic β-Sr0.17V2O5 regarding distortions to VO6 octahedra. Furthermore, the complex electronic structure of Mott insulators La1-xLuxVO3 is investigated to understand their spin-orbital phase diagram. The effects of rare-earth size on the O 2p hybridization states and the local crystal field of VO6 octahedron are found to agree with the prediction of DFT calculation and the evolution of crystal structure. The changes of experimental spectra with temperature are associated with Jahn-Teller distortion and orbital ordering due to structural phase transition. Lastly, the band structure and low-energy excitations of spinel MnV2O4 are explored using soft x-ray spectroscopies and theoretical calculations. The presence of Hubbard bands and the mixing between V and Mn 3d states are suggested both experimentally and theoretically.

Ce travail de thèse est une étude expérimentale, basée sur la spectroscopie d’émission et d’absorption de plasmas chauds et denses créés par une impulsion laser nanoseconde. La physique atomique au sein de ce type de plasmas représente un sujet complexe et de grand intérêt, notamment dans les domaines de l’astrophysique ou de la fusion par confinement inertiel. Du point de vue de la physique atomique, cela revient à déterminer des paramètres tels que l’ionisation moyenne ou l’opacité en fonction de la température électronique et de la densité de matière du milieu. Les codes de physique atomique ont alors besoin de données expérimentales pour se développer et être validés afin qu’ils soient prédictifs sur une large gamme de plasmas. Dans ce travail nous nous concentrons sur des plasmas dont la température électronique varie de 10 eV à plus d’une centaine d’électron-volts pour des densités de matière allant de 10⁻⁵ à 10⁻² g/cm³. Dans ce manuscrit on distingue deux types de données spectroscopiques qui sont toutes les deux utiles et nécessaires au développement des codes de physique atomique car elles sont caractéristiques de l’état du plasma étudié : 1) des spectres d’absorption obtenus avec des plasmas proche de l’équilibre thermodynamique local de Cu, de Ni et d’Al ; 2) des spectres d’émission obtenus avec des plasmas hors équilibre thermodynamique local de C, d’Al et de Cu. Ce travail met en lumière différentes techniques expérimentales ainsi que diverses comparaisons avec des codes de physique atomique et d’hydrodynamique. / This PhD work is an experimental study, based on emission and absorption spectroscopy of hot and dense nanosecond laser-produced plasmas. Atomic physics in such plasmas is a complex subject and of great interest especially in the fields of astrophysics or inertial confinement fusion. On the atomic physics point of view, this means determining parameters such as the average ionization or opacity in plasmas at given electronic temperature and density. Atomic physics codes then need of experimental data to improve themself and be validated so that they can be predictive for a wide range of plasmas. With this work we focus on plasmas whose electronic temperature varies from 10 eV to more than a hundred and whose density range goes from 10⁻⁵ à 10⁻² g/cm³. In this thesis, there are two types of spectroscopic data presented which are both useful and necessary to the development of atomic physics codes because they are both characteristic of the state of the studied plasma: 1) some absorption spectra from Cu, Ni and Al plasmas close to local thermodynamic equilibrium; 2) some emission spectra from non local thermodynamic equilibrium plasmas of C, Al and Cu. This work highlights the different experimental techniques and various comparisons with atomic physics codes and hydrodynamics codes.

The aim of this master thesis is the preparation and characterization of plasma activated water (PAW) prepared by dielectric barrier discharge at atmospheric pressure in air for the future applications in agriculture and medicine. The theoretical part is focused on plasma activated water and its effects on seeds and plants. The work also deals with the preparation and application of PAW in the world. Various types of plasma discharge configurations suitable for its preparation are described here. In the experimental part of the master thesis, distilled and tap water were chosen for activation. The concentrations of active particles in PAW generated by DBD such as nitrites, nitrates and hydrogen peroxide were determined. The value of the concentration of active particles changes probably due to mutual interactions when nitrites are oxidized by hydrogen peroxide to nitrates. Physical properties of PAW such as conductivity and pH were also characterized. After the preparation of PAW, the conductivity increases due to the increase in the concentration of active particles formed by dissociation and ionization of water molecules by plasma. The particles presented in the air, which are dissociated and ionized by plasma, also diffuse into the liquid, and contribute to this increase. The decrease in pH also corresponds to an increase in the concentration of hydrogen ions and the formation of nitric acids. Another aspect of this work was to study plasma activated water during the first eight hours after its preparation and to determine its properties. We have found that PAW prepared from tap water retains its characteristic properties for at least 8 hours and distilled water for 6 hours. In the master thesis, the analysis of plasma discharge was performed using optical emission spectroscopy. OES measurements were performed in the wavelength range 300 to 800 nm. The second positive nitrogen system (N2 (C 3u) N2 (B 3g)) and the first positive nitrogen system (N2 (B 3g) N2 (A 3+u)) were identified in the overview spectrum. Molecular nitrogen ions, OH· radicals, atomic oxygen and atomic hydrogen can be observed in the spectrum, too. The dielectric barrier discharge was also captured using a high-speed camera, and the recording shows the occurrence of multiple discharges that are spatially as well as temporary unstable.