Submitted by Maike Costa (maiksebas@gmail.com) on 2016-05-16T13:29:45Z No. of bitstreams: 1 arquivo total.pdf: 3062751 bytes, checksum: 5355db4f5e8fd0c5ecd86a23e5d0ad77 (MD5) / Made available in DSpace on 2016-05-16T13:29:45Z (GMT). No. of bitstreams: 1 arquivo total.pdf: 3062751 bytes, checksum: 5355db4f5e8fd0c5ecd86a23e5d0ad77 (MD5) Previous issue date: 2016-02-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The single-phase extraction is based on the formation of a homogeneous mixture formed ideally between two immiscible phases (aqueous and organic) and a third component in the two immiscible phases, is added to achieve opalescence. In this mixture the complexation reactions occur and the subsequent extraction is performed by breaking the phase equilibrium by addition of an excess of the components of the mixture. However, the automation of this method by analyzing flow injection requires a device with a significant degree of complexity and difficult to control operating parameters. The objective of this study was to develop an automatic method of extracting single phase using flow-batch in question applied to the quantification of chromium in water and in commercial samples of vinegar by atomic absorption spectrometry graphite furnace. To this end, modifications have been made both in the mixing chamber (two outputs) as the extraction method, in which more suited to this proposal chemical systems were studied. The performance of the method was attested by statistical tests, in terms of precision (RSD <12%), accuracy (recovery between 82 and 108%), (m0 = 0.32 pg L-1 and LOQ = 0.86 μgL -1) and analytical frequency (26h-1). In this new strategy, the whole process of extraction was performed in mixing chamber quickly, simply and with adequate sensitivity to GF AAS technique. Moreover, it was possible to analyze samples of different matrices using the same method / A extração em fase única baseia-se na formação de uma mistura homogênea entre duas fases idealmente imiscíveis (uma aquosa e uma orgânica) e um terceiro componente miscível em ambas as fases, que é adicionado até atingir a opalescência. Nesta mistura ocorrem as reações de complexação e, a subsequente extração é realizada pela quebra do equilíbrio de fases através da adição de excesso de um dos componentes da mistura. Entretanto, a automação deste método através da análise por injeção em fluxo exige um aparato com significativo grau de complexidade e de difícil controle dos parâmetros operacionais. Assim, o objetivo deste trabalho foi desenvolver uma metodologia automática de extração em fase única utilizando análise em fluxo-batelada aplicada à quantificação de cromo em águas e amostras comerciais de vinagre por espectrometria de absorção atômica em forno de grafite. Para isto, foram feitas modificações tanto na câmara de mistura (duas saídas) como na técnica de extração, na qual foram estudados sistemas químicos mais adequados a esta proposta. O desempenho do método foi atestado através de testes estatísticos, em termos de precisão (RSD < 12%), exatidão (recuperação entre 82 e 108%), (m0 = 0,32 pg L-1 e LOQ = 0,86 μgL-1), e frequência analítica (26 h-1). Nesta nova estratégia, todo o processo de extração foi realizado na câmara de mistura de forma rápida, simples e com sensibilidade adequada para a técnica GF AAS. Além disso, foi possível analisar amostras de diferentes matrizes usando o mesmo método.

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Bi12GeO20 (BGO) belongs to the family of sillenite crystals BMO, where M = Ge, Si, Ti. These compounds exhibit remarkable photorefractive e ect and therefore are used in the development of information and image storage technologies, holography, ampli cation of luminous signals and dynamic interferometry. One of the strategies used to enhance the properties of interest of these sillenites is doping. The defects can create photorefractive centers in the matrix, introducing energy levels within the gap, in uencing the electronic and optical properties of the selenites. Experimental work reported a curious behavior when using transition metal ions (TMI) as dopants. Most of the TMIs, including Cr ions, are allocated at the high symmetry site Ge4+, with the exception of Cu2+ which enters into the matrix at the low symmetry site of Bi3+. This is a surprising fact due to the di erence between ionic radii and charge states of the dopants and the substitution ion Ge4+. In this work the LAPW method, based on the DFT theory and implemented in the WIEN2k program, was used to study the electronic, structural and energetic properties of pure BGO and doped BGO with chromium ions. In the study of doped cases, Cr ions were inserted at the substitutional sites of Ge4+ and Bi3+ The calculations were performed for neutral and charged systems. The approximations for correlation and exchange e ects were made through GGA-PBE and mBJ potentials. Were performed calculations of lattice parameter optimization, relaxation of atomic positions, state density, Bader charge and formation energies of defects. It was possible to nd the lattice parameter, and the band gap energy os the BGO pure, to analyse the way how the neighbourhood of the substitutional site behaves with the presence of the defect and nd the states that populate the valence and conduction bands of the studies cases. These data were taking into account to measure the ions valence. The results of the modeling showed that Cr prefers to accommodate in the BGO matrix with Cr3+/4+ valences. The preferential accommodation site of Cr3+ is Bi3+, which didn't meet with what has been reported experimentally in the literature. / O Bi12GeO20 (BGO) pertence a fam lia de cristais silenitas do tipo BMO, onde M = Ge, Si, Ti. Tais compostos apresentam um not avel efeito fotorrefrativo e por isso s~ao utilizados no desenvolvimento de tecnologias de armazenamento de informa c~oes e imagens, hologra a, amplia c~ao de sinais luminosos e interferometria din^amica. Uma das estrat egias utilizadas para potencializar as propriedades de interesse dessas silenitas e a dopagem. Os defeitos podem criar centros fotorrefrativos na matriz, introduzindo n veis de energias dentro do gap e in uenciar nas propriedades eletr^onicas e opticas das silenitas. Trabalhos experimentais relataram um comportamento curioso ao se utilizar ons de metais de transi c~ao (TMI) como dopantes. A maior parte dos TMIs, incluindo os ons de Cr, s~ao alocados no s tio de alta simetria Ge4+, com exce c~ao do Cu2+ que se insere na matriz no s tio de baixa simetria do Bi3+. Esse e um fato surpreendente devido a diferen ca entre raios i^onicos e estados de carga dos dopantes e do on substitucional Ge4+. Neste trabalho foi utilizado o m etodo LAPW, baseado na teoria DFT e implementado no programa WIEN2k, para estudar as propriedades eletr^onicas, estruturais e energ eticas do BGO puro e dopado com ons de cromo. No estudo de casos dopados, os ons de Cr foram inseridos nos s tios substitucionais Ge4+ e Bi3+. Os c alculos foram executados para sistemas neutros e carregados. As aproxima c~oes para os efeitos de correla c~ao e troca foram feitas atrav es do funcional GGA-PBE e do potencial mBJ. Foram realizados c alculos de otimiza c~ao de par^ametro de rede, relaxa c~ao de posi c~oes at^omicas, densidade de estados, carga de Bader e energias de forma c~ao de defeito. Foi poss vel encontrar o par^ametro de rede, a energia de gap do BGO puro, analisar a forma como a vizinhan ca do s tio substitucional se comporta com a presen ca do defeito e encontrar os estados que populam as bandas de val^encia e condu c~ao dos casos estudados. Esses dados foram levados em conta para aferir a val^encia dos ons. Os resultados das modelagens mostraram que o Cr prefere se acomodar na matriz do BGO com val^encias Cr3+/4+. O s tio de acomoda c~ao preferencial do Cr3+ e o Bi3+, o que vai de encontro ao que foi relatado experimentalmente na literatura. / São Cristóvão, SE

In the last decade, web browsers have seen a remarkable increase of performance, especially in the JavaScript engines. JavaScript has over the years gone from being a slow and rather limited language, to today have become feature-rich and fast. It’s speed can be around the same or half of comparable code written in C++, but this speed is directly dependent on the choice of the web browser, and the best performance is seen in browsers using JIT compilation techniques. Even though the language has seen a dramatic increase in performance, there’s still major problems regarding memory usage. JavaScript applications typically consume 3-4 times more memory than similar applications written in C++. Many browser vendors, like Opera Software, acknowledge this and are currently trying to optimize their memory usage. This issue is hopefully non-existent within a near future. Because the majority of scientific papers written about JavaScript only compare performance using the industry benchmarks SunSpider and V8, this thesis have chosen to widen the scope. The benchmarks really give no information about how JavaScript stands in comparison to C#, C++ and other popular languages. To be able to compare that, I’ve implemented a GIF decoder, an XML parser and various elementary tests in both JavaScript and C++ to compare how far apart the languages are in terms of speed, memory usage and responsiveness.

La détection sensible et sélective des métaux lourds, en particulier les métaux detransition, est d’une grande importance pour la santé publique ainsi que pour la surveillancede l’environnement. Les méthodes actuelles de référence, de par leur non portabilité, limitentla possibilité de disposer de mesures à haute résolution spatiale et temporelle. Lesmicrocapteurs optiques offrent un moyen attrayant et pratique pour surmonter ces limitationsde coût global et de temps d’analyse, en permettant la mesure en temps réel sur site.Pour démontrer ce potentiel, ces travaux de thèse sont orientés sur la détermination duchrome hexavalent Cr(VI) en solution à l’aide d’une réaction colorimétrique avec le 1,5-diphénylcarbazide (DPC), permettant de créer un complexe présentant un maximumd’absorption dans le domaine du visible. Ces travaux s’inscrivent dans la volonté dedévelopper un véritable laboratoire sur puce, intégrant la fonction fluidique parélectromouillage sur diélectrique pour créer la réaction colorimétrique, ainsi que la fonctionde mesure par intégration d’un capteur optique dédié à la mesure d’absorption dans desmicrovolumes (< μL). Pour la mesure d'absorption sur de si faibles volumes, l'utilisation demicrorésonateurs vise à augmenter de façon importante le chemin optique effectif et ainsi lasensibilité du capteur.Nous décrivons nos travaux sur la conception, la fabrication de la plateformemicrofluidique digitale ainsi que du résonateur optique en anneaux à des dimensionssubmicroniques par photolithographie par projection. Les matériaux polymères sontprivilégiés pour une intégration totale bas coût à terme, ainsi qu’un substrat verre, dont lespropriétés sont particulièrement adaptées aux applications optiques dans le domaine duvisible. / The selective and sensitive detection of heavy metals, such as transition metals, is ofparamount importance for health and safety an environmental monitoring. Current referencemethods, due to their lack of portability, are limiting factors to obtain high-resolution spatialand temporal data. Optical sensors offer an attractive and convenient way to overcome theselimitations of cost and time per analysis by offering real time, on-site measurementcapabilities.In order to demonstrate this potential, this thesis is focused on the detection and quantificationof hexavalent chromium Cr(VI) in water samples by a colorimetric reaction based on areaction with the 1,5-diphenylcarbazide (DPC), that produces a complex possessing anabsorption maximum in the visible range. This works endorse the goal of creating a true labon-chip, integrating both the fluidic function based on ElectroWetting on Dielectric (EWOD)to create the colorimetric reaction, and the sensing function based on the integration of anoptical sensor able to measure absorption variations in micro-volumes (< μL). In order toobtain sufficient sensitivity on such small volumes, optical microring resonators are used inthis work, due to their ability to enhance the effective optical path length by constructiveinterferences.This thesis describes the conception and fabrication of the EWOD microfluidic platform, aswell as the conception, simulation and fabrication of submicronic microring resonators usingstepper lithography. Polymer materials and glass substrates are selected, due to their greatoptical properties in the visible range, their compatibility with the EWOD platform, and theirintegrability at a reasonable cost.

Notre étude porte sur des matériaux à effets relativistes importants. L'hamiltonien semi-relativiste, couplé aux équations de Maxwell (EM), permet de déduire les sources de courant et de densité, incluant des termes de second ordre (polarisations de spin et de Darwin). Différents modèles sont développés par expansion des EM. L'étude ab initio montre que (1) le désordre atomique peut produire le ferrimagnétisme (FM) dans GaFeO3 (GFO) multiferroïque, (2) les états 3d Fe des octaèdres déformés ont une levée de dégénérescence tétraédrique (théorie du champ cristallin), (3) la polarisation électrique concorde avec l'expérience, (4) le mécanisme magnétoélectrique (ME) direct est insuffisant pour expliquer le ME observé. Pour Cr2O3, le calcul de l'état massif sous contraintes biaxiales n'explique pas son FM, la taille de l'échantillon ou l'excès d'oxygène pourrait de fait être important. Enfin, nous avons développé le XAS et le XMCD dans le code VASP et calculé ces spectres pour GFO. / We studied the physics of materials where relativistic effects are important. We first coupled the semi-relativistic Hamiltonian with the Maxwell's equations, and derived the current and density sources, which included second-order terms like the spin and Darwin polarizations. Different models were developed, by expanding the Maxwell's equations. We then performed ab initio studies to explain (1) site disorders as the origin of ferrimagnetism in multiferroic GaFeO3 (GFO), (2) crystal-field theory where the Fe 3d states at the deformed octahedra have tetrahedral splittings, (3) the electric polarization as a function of temperature, and (4) the insufficiency of the direct magnetoelectric (ME) mechanism to explain observed ME behavior. For Cr2O3, bulk calculations for different biaxial strains failed to explain its ferromagnetism, indicating that size or excess-O effects might be important. Finally, we implemented XAS and XMCD in VASP and computed these spectra for GFO.

This report has investigated the ethical issues associated with mining or processing of materials that make them considered as controversial. For each material, the main areas of use and the top producing countries are analysed, followed by social and/or environmental issues as well as potential problems in the future. In total, 13 materials are discussed, of which most are minerals. The overall issues, that are recurring throughout the report and are important to be aware of are: child labor, low safety standards, mining activity resulting in deforestation or harming biodiversity, mining processes that affect communities (e.g. because of large water consumption) and the risks associated with widespread illegal mining. The report also provides research about organisations and initiatives that aim to affect the problems, and gives a brief view over tools that can be used to increase awareness of these issues.

L’efficacité des cellules solaires peut être améliorée en exploitant pleinement la partie UV-bleue du spectre solaire, par un mécanisme de conversion de fréquence de type down-conversion. Ce processus utilisant des transferts d’énergie entre ions de terre rare (TR) ou métal de transition 3d (paires TR3+/Yb3+ avec TR = Pr, Tm,… et Cr3+/Yb3+) requiert des matrices à basse énergie de phonon pour réduire les relaxations non radiatives.Jusqu’à présent, les matériaux étudiés sont principalement sous forme de poudre polycristalline, ce qui limite leur utilisation à cause de la diffusion, ou de monocristaux dont le coût de fabrication est élevé.Dans le cadre de cette thèse, les verres fluorés à base de fluorozirconate ZLAG (ZrF4-LaF3-AlF3-GaF3) et ZBLA (ZrF4-BaF2-LaF3-AlF3) ont été préparés par la technique de fusion-coulée. Ces derniers sont adaptés du fait de leurs propriétés intrinsèques de transparence et de leur faible énergie de phonon. Les matériaux obtenus ont ensuite été caractérisés par, analyse thermique, diffraction des rayons X, microscopie électronique à transmission et luminescence.Des études par dynamique moléculaire et fluorescence par affinement de raies ont été effectuées sur la matrice ZLAG afin de suivre les modifications structurales lors du passage du verre à la vitrocéramique.La luminescence de l’ion Yb3+ a été observée dans l’infra-rouge à 980 nm sous excitation bleue dans toutes les séries étudiées, signature d’un transfert d’énergie. ans le verre ZLAG, l’efficacité atteint 92% pour le transfert d’énergie Pr3+ → Yb3+ et 65% pour le transfert d’énergie Tm3+ → Yb3+. L’efficacité est plus faible dans le verre ZBLA et la vitrocéramisation du verre ZLAG n’améliore pas les performances. / The efficiency of solar cells can be improved by fully exploiting the UV-blue portion of the solar spectrum, through a frequency converting mechanism of type downconversion. This process using energy transfer between rare earth ions (RE) or 3d transition metal (pairs RE3+/Yb3+ with TR = Pr, Tm,… and Cr3+/Yb3+) requires a matrix with low phonon energy to reduce non radiative relaxation.So far, the studied materials are mainly in the form of polycristalline powder, which limits their use due to diffusion or single crystals which manufacturing cost is high.As part of this thesis, fluoride glasses based on fluorozirconate ZLAG (ZrF4-LaF3-AlF3-GaF3) and ZBLA (ZrF4-LaF2-LaF3-AlF3) have been prepared by the melting-casting technique. These are suitable because of their intrinsic properties of transparency and low phonon energy. The resulting materials were then characterized by thermal analysis, X-ray diffraction, transmission electron microscopy and luminescence.Molecular Dynamics simulation and Fluorescence line narrowing of ZLAG matrix have been performed in order to investigate the structural modification during the transformation of the glass into the glass-ceramic.Luminescence of Yb3+ ion was observed in the near IR at 980 nm under blue excitation in all studied series, which is the signature of energy transfer. In the ZLAG glass, the efficiency reaches 92% for Pr3+ → Yb3+ energy transfer and 65% for Tm3+ → Yb3+ energy transfer. The efficiency is lower in the ZBLA glass and the ZLAG ceramisation does not improve the performances.

This diploma thesis deals with measuring touches problems in industrial metrology. Thesis describes adhesive wear and tear which is caused by measuring probes when dynamical measuring is being concluded. Measuring of damaged component made of silumin and its different changes of texture by different measuring probes are evaluated. Measuring touches are made of titanium nitride, silicon nitride, zirconium, bearing chrome steel, ruby, experimental composite material and nanocrystalline diamond.

In this thesis, the structural and mechanical changes, which took place in flake graphite cast iron after electron beam surface melting and chrome-nickel surface alloying, were studied. Furthermore, the effect of set parameters on properties and depth of the melted and alloyed region is also analyzed. In the experimental part, the analyzed microstructures, micro-hardness and the distribution of elements after melting and alloying, were presented. Structural differences of material regions caused by melting were described based on microstructures. In the end of diploma thesis, the conclusions of using EB technology for surface melting and alloying were discussed.

No description available.