This thesis presents a study of the inner plasma disk of Saturn. The results are derived from measurements by the instruments on board the Cassini spacecraft, mainly the Cassini Langmuir probe (LP), which has been in orbit around Saturn since 2004. One of the great discoveries of the Cassini spacecraft is that the Saturnian moon Enceladus, located at 3.95 Saturn radii (1 RS = 60,268 km), constantly expels water vapor and condensed water from ridges and troughs located in its south polar region. Impact ionization and photoionization of the water molecules, and subsequent transport, creates a plasma disk around the orbit of Enceladus. The plasma disk ion components are mainly hydrogen ions H+ and water group ions W+ (O+, OH+, H2O+, and H3O+). The Cassini LP is used to measure the properties of the plasma. A new method to derive ion density and ion velocity from Langmuir probe measurements has been developed. The estimated LP statistics are used to derive the extension of the plasma disk, which show plasma densities above ~20 cm-3 in between 2.7 and 8.8 RS. The densities also show a very variable plasma disk, varying with one order of magnitude at the inner part of the disk. We show that the density variation could partly be explained by a dayside/nightside asymmetry in both equatorial ion densities and azimuthal ion velocities. The asymmetry is suggested to be due to the particle orbits being shifted towards the Sun that in turn would cause the whole plasma disk to be shifted. We also investigate the ion loss processes of the inner plasma disk and conclude that loss by transport dominates loss by recombination in the entire region. However, loss by recombination is still important in the region closest to Enceladus (~±0.5 RS) where it differs with only a factor of two from ion transport loss.

Surface-assisted directed assembly allows ultrasoft and replusive functional polymeric “colloids” to assemble into the organized supramolecular ultrathin films on a monomolecular level. This study aims at achieving a fundamental understanding of molecular morphology and responsive behavior of major classes of branched star-shaped polymers (star amphiphilic block copolymers and star polyelectrolytes) and their aggregation into precisely engineered functional ultrathin nanofilms. Thus, we focus on elucidating the role of molecular architecture, chemical composition, and intra/intermolecular interactions on the assembly behavior of highly-branched entities under variable environmental and confined interfacial conditions. The inherent molecular complexity of branched architectures facilitates rich molecular conformations and phase states from the combination of responsive dynamics of flexible polymer chains (amphiphilic, ionizable arms, multiple segments, and free chain ends) and extened molecular design parameters (number of arms, arm length, and segment composition/sequence). These marcromolecular building components can be affected by external conditions (pH, salinity, solvent polarity, concentration, surface pressure, and substrate nature) and transformed into a variety of complex nanostructures, such as two-dimensional circular micelles, core/shell unimicelles, nanogel particles, pancake & brush micelles, Janus-like nanoparticles, and highly nanoporous fractal networks. The fine balance between repulsive mulitarm interactions and surface energetic effects in the various confined surfaces and interfaces enables the ability to fabricate and tailor well-organized ultrathin nanofilms. The most critical findings in this study include: (1) densely packed circular unimicelle monolayers from amphiphilic and amphoteric multiblock stars controlled by arm number, end blocks, and pH/pressure induced aggregation, (2) monolayer polymer-metal nanocomposites by in-situ nanoparticle growth at confined interfaces, (3) on-demand control of exponentially or linearly grown heterogeneous stratified multilayers from self-diffusive pH-sensitive star polyelectrolyte nanogels, (4) core/shell umimicelle based microcapsules with a fractal nanoporous multidomain shell morphology, and (5) preferential binding and ordering of Janus-like unimicelles on chemically heterogeneous graphene oxide surfaces for biphasic hybrid assembly. The advanced branched molecular design coupled with stimuli responsive conformational and compositional behavior presents an opportunity to control the lateral diffusion and phase segregation of branched compact supermolecules on the surface resulting in the generation of well-controllable monolayers with tunable ordering and complex morphology, as well as to tailor their stratified layered nanostructures with switchable morphological heterogeneity and multicompartmental architectures. These surface-driven star polymer supramolecular assemblies and interfaces will enable the design of multifunctional nanofilms as hierarchical responsive polymer materials.

Die vorliegende Dissertation behandelt Charakterisierung, Modellbildung sowie Anwendung einer magnetfeldgestützten Hohlkathoden-Bogenentladung. Hohlkathoden sind seit den 1960er Jahren Gegenstand grundlagen- sowie anwendungsorientierter Forschung und werden seit 20 Jahren am Fraunhofer-Institut für Elektronenstrahl- und Plasmatechnik für die Anwendung auf dem Gebiet der Vakuumbeschichtung weiterentwickelt. Ziel dieser Arbeit ist es, die technologischen Fortschritte physikalisch zu verstehen und gezielte Weiterentwicklungen für spezifische Einsatzgebiete zu ermöglichen. In der untersuchten Hohlkathodenbauform ist das aus Tantal bestehende, vom Arbeitsgas Argon durchströmte Kathodenröhrchen koaxial von einer Ringanode sowie von einer Magnetfeldspule umgeben. Die Entladung wird durch Hochspannungspulse gezündet, worauf sich ein diffuser Bogen im Röhrchen (internes Plasma) ausbildet. Das Röhrchen wird von Plasmaionen auf hohe Temperaturen geheizt, die eine thermionische Emission von Elektronen ermöglichen, welche das Plasma speisen. Das technologisch nutzbare externe Plasma wird im Vakuumrezipienten durch Wechselwirkung der Gasteilchen mit Strahlelektronen aus der Kathode erzeugt. Bei starker Reduktion des Arbeitsgasflusses wird die Entladung durch das Magnetfeld der Spule stabilisiert. Der experimentelle Befund, dass dadurch Plasmadichte und -reichweite sowie ggf. die Ladungsträgerenergien im Rezipienten aufgrund des intensiveren Elektronenstrahls wesentlich gesteigert werden können, wird durch ortsaufgelöste Langmuir-Sondenmessung, optische Emissionsspektroskopie und energieaufgelöste Massenspektrometrie ausführlich belegt und nach der Lösung von Strom- und Wärmebilanzgleichungen durch die Verhältnisse im Kathodenröhrchen begründet. Neben Argon werden auch typische Reaktivgase der Vakuumbeschichtung im Hohlkathodenplasma betrachtet: zum einen Stickstoff und Sauerstoff, die in reaktiven PVD-Prozessen (physikalische Dampfphasenabscheidung) zur Beschichtung mit Oxid- bzw. Nitridschichten zum Einsatz kommen und durch Ionisation, Dissoziation und Anregung im Hohlkathodenplasma verbesserte Schichteigenschaften ermöglichen; zum anderen Azetylen, das bei PECVD (plasmagestützte chemische Dampfphasenabscheidung) von amorphen wasserstoffhaltigen Kohlenstoffschichten z. B. für tribologische oder biokompatible Beschichtungen genutzt wird. Azetylen wird durch Streuprozesse mit Elektronen und Ionen im Plasma aufgespalten, wodurch schichtbildende Spezies erzeugt werden, die am Substrat kondensieren. Durch die Wahl der Plasmaparameter sowie durch abgestimmte Substratbiasspannung und Substratkühlung lassen sich die Beschichtungsrate einstellen sowie polymer-, graphit- oder diamantartige Eigenschaften erzielen. Neben der Plasmadiagnostik mittels energieaufgelöster Massenspektrometrie werden die erzeugten Kohlenstoffschichten vorgestellt und hinsichtlich Härte, Zusammensetzung und Morphologie analysiert. / In the present thesis, characterization, modeling and application of a magnetically enhanced hollow cathode arc discharge are presented. Since the 1960s, hollow cathodes are being studied in basic and applied research. At Fraunhofer Institute for Electron Beam and Plasma Technology, further development concerning the application in vacuum coating technology has been carried out for about twenty years. The present work targets on physically understanding the technological progress in order to enable specific further development and application. In the investigated hollow cathode device, a ring-shaped anode and a magnetic field coil are arranged coaxially around the tantalum cathode tube, which is flown through by argon as the working gas. The discharge is ignited by high voltage pulses establishing a diffuse arc within the cathode tube (internal plasma). The cathode is being heated by the plasma ions to high temperatures, which leads to thermionic emission of electrons sustaining the plasma. The external plasma in the vacuum chamber, which can be used for technological applications, is generated by collisions of gas atoms with beam electrons originating from the cathode. In the case of strongly reduced working gas flow, the discharge is stabilized by the magnetic field of the coil; the related experimental findings such as significantly increased plasma density and range as well as higher charge carrier energies in the external plasma are extensively proved by spatially resolved Langmuir probe measurements, optical emission spectroscopy, and energy-resolved ion mass spectrometry. Furthermore, the results are correlated to the conditions within the cathode tube by solving the current and heat balance equations. Besides argon, typical reactive gases used in vacuum coating are examined in the hollow cathode plasma, too. First, nitrogen and oxygen, which are applied in PVD (physical vapor deposition) processes for the deposition of oxide and nitride layers, are ionized, dissociated, and excited by plasma processes. In the case of practical application, this plasma activation leads to improved film properties. Second, acetylene is used as a precursor for PECVD (plasma-enhanced chemical vapor deposition) of amorphous hydrogenated carbon films, e.g. for tribological or biocompatible applications. Acetylene is cracked by electron and ion scattering in the plasma providing film-forming species to be deposited on the substrate. The deposition rate as well as the polymeric, graphitic, or diamond-like properties can be controlled by plasma parameters, a defined substrate bias, and substrate cooling. The hollow cathode-generated acetylene plasma has been characterized by energy-resolved ion mass spectrometry, and the carbon films obtained are analyzed regarding hardness, film composition, and morphology.

The non-uniform dc glow discharge plasma system is studied by using isolated computer controlled three couples of double probe system (TCDP) in argon gas, simultaneously. TCDP system has been developed to use for magnetized, unmagnetized, and for low oscillating plasma systems by using low pass filter with optically isolated circuitry to minimize the measurement errors with higher resolution and accuracy. Difference in the shapes and diameters of the discharge tube from region to region leads to change in the positive column glow discharge properties. This is because the positive column inhomogeneities, rising from the increase in the electron densities at the small tube radius region than the large one. Therefore, the axial electric field and the electron temperature have been diverted from their normal behavior in the positive column. However, at the large radius regions, the axial electric field seams to stay approximately constant at higher discharge currents. On the other hand, In this work the radial dependence of the electron temperature, density, floating potential, and the normalized probe radius (&amp / #958 / =rp&amp / #955 / D) has been investigated. Since, the probe radius is smaller than Debye length, the orbital motion limited (OML) theory has been used. As a result, the electron temperature (at the center) decreased and density increased with decreasing tube radius, and they have maximum values at the first probe (near the cathode). The electron density ne was observed to decrease and electron temperature Te to increase with increasing the discharge current. The floating potential has less negative value with decreasing tube radius except at the higher currents. Finally, it has been found that the &amp / #958 / is proportional with electron density, but it remains constant depending on the value of Te and ne.

Two designs of inorganic/organic hybrid micro-structures are discussed: (1) silver nanowire reinforced layer-by-layer (LbL) polyelectrolyte composite film and (2) bimetallic silver-gold core-shell nanoparticles. In this work, zero-dimensional spherical gold nanoparticles (AuNPs), one-dimensional silver nanowires (AgNWs), and two-dimensional silver nanoplates (AgNPls) represent the inorganic component. Three-arm star polymer and polyelectrolytes represent the organic component. In the first design, the one-dimensional AgNWs serves as a mechanical reinforcement for the fabrication of mechanically isotropic and anisotropic polyelectrolyte composite films. The composite film is mechanically isotropic when the AgNWs are randomly oriented, and it is anisotropic when the AgNWs are unidirectionally oriented within the LbL polyelectrolyte matrix. Furthermore, above the AgNWs percolation threshold, the AgNWs reinforced LbL composite film is electrically conductive. Therefore, it can find application in ultrathin LbL film-based sensor. In the second design, the zero-dmensional AuNPs were assembled onto one-dimensional AgNWs and two-dimensional AgNPls by means of star polymer linker, or alternatively using polyelectrolytes via electrostatics interaction. The unique feature of these bimetallic silver-gold core-shell nanoparticles is their ability to greatly enhance electric field, due to the silver-gold intra-particle interaction. This allows it to serve as a single-nanoparticle surface enhanced Raman scattering (SERS) substrate for chemical sensing.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-16T18:41:45Z No. of bitstreams: 1 JOSÉ VANDERLEY DO NASCIMENTO SILVA - TESE PPGEQ 2015..pdf: 2308601 bytes, checksum: 9f12a4c2a7b8abc9470ef017ee29755e (MD5) / Made available in DSpace on 2018-03-16T18:41:45Z (GMT). No. of bitstreams: 1 JOSÉ VANDERLEY DO NASCIMENTO SILVA - TESE PPGEQ 2015..pdf: 2308601 bytes, checksum: 9f12a4c2a7b8abc9470ef017ee29755e (MD5) Previous issue date: 2015-02 / Capes / O aumento da produção industrial tem proporcionado à geração de efluentes aquosos contaminados com íons de metais pesados. Esses devem ser tratados antes de serem descartados no meio ambiente. Por este motivo é muito importante à utilização de processos para reduzir ou eliminar metais pesados presentes em efluentes industriais. Dentre os vários processos existentes, a adsorção apresenta grande eficiência na remoção de metais presentes em baixas concentrações. As argilas têm apresentado ótimos resultados em processos de adsorção de metais pesados, o que motiva a busca por argilas que possuam maior afinidade com cada tipo de metal. Neste trabalho as argilas naturais esmectiticas Chocobofe e Chocolate B proveniente do estado da Paraíba foram investigadas com o objetivo de avaliar sua afinidade e capacidade para remoção de cádmio, chumbo e zinco. Realizou-se, inicialmente, a caracterização das argilas pelas técnicas: Difração de Raios X; Análises químicas; Análises térmicas (diferencial e gravimétrica); Espectroscopia na região do infravermelho; Adsorção Física de Nitrogênio; Microscopia eletrônica de varredura e capacidade de troca de cátions. Depois de caracterizadas, as argilas foram avaliadas quanto a sua capacidade de remoção (qeq) e seu percentual de remoção (%Rem) para os metais (Cádmio, Chumbo e Zinco), presentes em efluente sintético, através de sistema de banho finito. De forma a se obter uma maior eficiência na remoção dos metais, foi realizado um planejamento fatorial 22 avaliando duas variáveis de entrada: concentração inicial de metais pesados (10, 30 e 50 ppm) e pH (3, 4 e 5), para determinar as melhores condições de trabalho, no qual se verificou que o pH= 5 e concentração inicial de 50 mg/g foram as condições que apresentaram melhores resultados alcançando Valores de 88,54-99,44% de percentagem de remoção e 3,36-4,43 mg/g de capacidade de remoção. A partir desses dados foram desenvolvidos estudos cinéticos e isotermas de equilíbrio que serviram de dados para avaliar a capacidade de adsorção das argilas com ajustes feitos através dos modelos de Langmuir, Freundlich e Redlich-Peterson. Os resultados dos testes cinéticos indicaram que o processo de remoção dos íons Cd2+, Pb2+ e Zn2+ pelas argilas se aplicam ao mecanismo do modelo de velocidade de pseudo-segunda ordem, sendo necessário um tempo de 10 minutos para alcançar o equilíbrio. Os modelos matemáticos adotados para a modelagem dos dados experimentais descreveram adequadamente a dinâmica da adsorção, produzindo isotermas teóricas com comportamento bastante próximos daqueles encontrados com as isotermas experimentais e que dos modelos utilizados, verifica-se que os modelos de Langmuir e Redlich-Peterson apresentaram melhor ajuste aos dados experimentais. A capacidade máxima de adsorção obtida pelas argilas Chocobofe e Chocolate B foram: 18,35 -21,88 mg. g-1 para o Pb2+; 10,0-11,20 mg. g-1 para o Cd2; 8,64-8,69 mg.g-1 para o Zn2, indicando uma seletividade das argilas em relação aos metais em estudo uma sequência de afinidade: Pb2+ > Cd2 > Zn2. Assim, os resultados experimentais indicaram que as argilas bentonitas podem ser utilizadas como adsorventes para a eliminação dos metais Cádmio, Chumbo e Zinco de aguas e efluentes contaminados por meio do mecanismo de adsorção. / The increase in industrial production has provided the generation of wastewater contaminated with heavy metal ions. These must be treated before disposal into the environment. For this reason it is very important to the use of processes to reduce or eliminate heavy metals from industrial effluents. Among the many existing processes, adsorption has great efficiency in the removal of metals present in low concentrations. Clays have shown excellent results in heavy metal adsorption processes, which motivates the search for clays having higher affinity with each type of metal. In this work the smectite clays natural Chocobofe and Chocolate B from the state of Paraíba were investigated in order to evaluate their affinity and capacity for the removal of cadmium, lead and zinc. Held, initially, the characterization of clays by techniques: X-ray diffraction; Chemical analysis; Thermal analysis (differential and gravimetric); Spectroscopy in the infrared region; Adsorption Nitrogen Physics; Scanning electron microscopy and capacity of cation exchange. After characterized the clays were evaluated for removal capacity (q and q) and its removal percentage (% Rem) to metals (cadmium, lead and zinc) present in synthetic wastewater through finite bath system. In order to achieve greater efficiency in the removal of metals a 22 factorial experimental design was conducted to evaluate two input variables: initial concentration of heavy metals (10, 30 and 50 ppm) and pH (3, 4 and 5) to determine the best working conditions, which revealed that the pH = 5 and initial concentration of 50 mg/g were the conditions that showed better results from 88.54 to 99.44% reaching values of percentage removal and 3,36- 4.43 mg/g of removability. From these data were developed kinetic and equilibrium isotherms that served data to evaluate the adsorption capacity of clays with adjustments made through the Langmuir, Freundlich and Redlich-Peterson. The results of the kinetic tests indicated that the removal of Cd2+ ions, Pb2+ and Zn2+ the clay are applied to the mechanism of the pseudo-second-order rate model, a time of 10 minutes is required to reach equilibrium. The mathematical models used to model the experimental data adequately describe the dynamics of adsorption, producing theoretical isotherms quite close to those found behavior with experimental isotherms and that of the models used, it appears that the Langmuir and Redlich-Peterson showed better fit to the experimental data. The maximum adsorption capacity obtained by clays Chocobofe and Chocolate B were 18.35 -21.88 mg. g-1 for Pb2+; 10.0 to 11.20 mg. g-1 for Cd2+; 8.64 to 8.69 mg.g-1 for Zn2+, indicating a selectivity of clays in relation to studying a metal affinity sequence: Pb2+> Cd2+> Zn2+. Thus, the experimental results indicate that the bentonite clays can be used as adsorbents for the removal of metals cadmium, lead and zinc contaminated water and effluent by adsorption mechanism.

Submitted by Deyse Queiroz (deysequeirozz@hotmail.com) on 2018-06-13T13:49:19Z No. of bitstreams: 1 GILVANISE ALVES TITO - TESE PPGEA 2009..pdf: 11064945 bytes, checksum: bac5edce5a2a3875418ba29344312d3e (MD5) / Made available in DSpace on 2018-06-13T13:49:19Z (GMT). No. of bitstreams: 1 GILVANISE ALVES TITO - TESE PPGEA 2009..pdf: 11064945 bytes, checksum: bac5edce5a2a3875418ba29344312d3e (MD5) Previous issue date: 2009-09 / A contaminação dos solos por metais pesados tem sido um problema crescente ao meio ambiente e à saúde das pessoas em função da alta toxicidade, razão por que a ciência busca alternativas que possam impedir ou pelo menos minimizar os efeitos poluidores desses metais ou, ainda, remediar os ambientes já contaminados. Assim, vários estudos utilizando matérias adsorventes estão sendo conduzidos como forma de reduzir os efeitos poluidores desses metais. E importante conhecer o processo de adsorção de metais pesados por minerais de argila, uma vez que estes são capazes de imobilizar referidos metais. No presente trabalho avaliou-se, através de três experimentos, a capacidade da bentonita na remediação de solos contaminados com zinco e cobre. O primeiro experimento consistiu no estudo da adsorção desses metais pela bentonita, em pH 4; 5 e 6, utilizando-se os modelos matemáticos de Langmuir e Freundlich. A partir de experimentos tipo "batch" foram elaboradas isotermas de adsorção com quantidades crescentes de zinco e cobre (5; 10; 20; 30; 50; 100; 150 e 200 mg L"1); o segundo experimento consistiu no estudo da mobilidade de zinco e cobre em colunas de lixiviação, preparadas com solo e doses crescentes de bentonita (0; 30 e 60 t ha"1). Os parâmetros de transporte foram calculados através do modelo computacional DISP. No último experimento avaliou-se, em casa de vegetação, o efeito das doses de zinco e cobre (50; 250 e 450 mg kg"1) e de bentonita (0; 30 e 60 t ha"1), adicionados ao solo, na produção de fitomassa e composição mineral do feijoeiro. Terminado o experimento (65 dias), foram determinadas as concentrações do zinco e do cobre nas partes aéreas e nas raízes das plantas e no solo das unidades experimentais, cujos resultados permitiram concluir que a incorporação de bentonita ao solo aumentou a adsorção do zinco e do cobre e que esta adsorção é dependente do pH da solução; que os modelos de Langmuir e Freundlich se apresentaram adequados para descrever a adsorção desses metais; que o tamanho das partículas da bentonita não influenciou na adsorção e a incorporação de bentonita ao solo contribuiu para diminuir a concentração e o acúmulo dos metais zinco e cobre, nas plantas de feijão-macassar. / The contamination of soil by heavy metais has been a growing problem to the environment and to the people's health in function of their toxicity, that has induced the science to search alternatives to prevent, or at least, minimize the pollutant effects of those metais or still, remediate the already polluted environment. Thus, several studies using sorbent materiais are conducted aiming to reduce the pollution problems produced by the excess of heavy metais. It is important to know the process of adsorption of heavy metais by clay minerais, because these are capable to immobilize such metais. The present study was carried out aiming, through three experiments, to evaluate the ability of the bentonite clay on the remediation of soils contaminated with zinc and copper. The fírst experiment consisted in studying the adsorption of these metais by bentonite at pH 4; 5 and 6, using the mathematical models of Langmuir and Freundlich. Adsorption isotherms were elaborated from batch adsorption assays, with increasing zinc and copper concentrations (5; 10; 20; 30; 50; 100; 150 and 200 mg L"1); the second experiment consisted in studying the zinc and copper mobility through leaching columns, prepared with soil and increasing bentonite leveis (0; 30 and 601 ha"1). The transport parameters were calculated using the computer model DISP. Finally, a greenhouse experiment was conducted to evaluate the effects of zinc and copper (50; 250 and 450mg kg"1) and bentonite (0; 30 and 60 t ha"1) added to the soil, on the phytomass production and mineral composition of a bean plant (Vigna unguiculata.h). At the end of the experiment (65 days) the phytomass and the content of zinc and copper in the aerial part, in the roots and in the soil were determined. It was observed that the adsorption of the elements increased with the bentonite application being dependent of the pH of the solution; the two studied models are appropriate to describe the zinc and copper adsorption for the bentonite; the granulometric size of the bentonite does not influence the metais adsorption and that the application of bentonite to the soil contributed to the decrease the concentration and accumulation of the heavy metais in the bean plant.

Diagnosing the temperatures and densities of plasmas is critical to the understanding of a wide variety of phenomena. Everything from equations of state for warm dense matter (WDM) found in Jovian planets and inertial confinement fusion (ICF) to turbulent and dissipative processes in laser-produced plasmas, rely on accurate and precise measurements of temperature and density. This work presents improvements on two distinct techniques for measuring temperatures and densities in plasmas: x-ray Thomson scattering (XRTS), and Langmuir probes (LPs). At the OMEGA laser facility, experiments on warm dense matter were performed by firing lasers at an ablator foil and driving a planar shock into cryogenically cooled liquid deuterium. XRTS in the collective scattering regime was implemented to probe the matter, measuring densities of n_e ~ 4.3 x 10²³ cm^-3, temperatures of T_e ~ 12 eV and ionizations of Z ~ 1.0. Through an extension to XRTS theory for inhomogeneous systems, it was possible to extract an additional parameter, the length scale of the shock, whose value of ? ~ 1.33 nm was consistent with the predicted mean free path, and therefore the thickness of the shock. A unique triple Langmuir probe prototype was designed and tested at the Gregori group's lab at the University of Oxford. This probe was designed for a high temporal resolution of ~ 200 MHz for probing laser-produced shocks. The probes were used to measure the shock formed from ablating carbon rods in an argon gas fill. The probe yielded plasma parameters of n_e ~ 1.0 x 10¹⁷ cm^-3 , and T^e ~ 1.5 eV, consistent with measurements from interferometry and emission spectroscopy.

Submitted by EDILENE ASSUNÇÃO DA SILVA (edileneass@gmail.com) on 2018-10-15T12:58:45Z No. of bitstreams: 1 Thesis final corrected version_Silva.pdf: 5038032 bytes, checksum: 096e39873786dd29f13d8faedd460bb8 (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-10-15T17:17:09Z (GMT) No. of bitstreams: 1 silva_ea_dr_bauru.pdf: 5038032 bytes, checksum: 096e39873786dd29f13d8faedd460bb8 (MD5) / Made available in DSpace on 2018-10-15T17:17:09Z (GMT). No. of bitstreams: 1 silva_ea_dr_bauru.pdf: 5038032 bytes, checksum: 096e39873786dd29f13d8faedd460bb8 (MD5) Previous issue date: 2018-07-05 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Les cellules solaires polymériques attirent un grand intérêt dans ce domaine de recherche, en raison du faible coût, du procédé de fabrication de grandes surfaces, des matériaux de manutention légers et de la possibilité de leur fabrication par diverses techniques. Pour une bonne efficacité des dispositifs photovoltaïques, la couche active doit contenir une bonne absorption de la lumière du soleil. En termes de bandgap,cela signifie que plus le bandgap est petit, plus le flux de photons absorbés est grand. Une manière d'accomplir ceci avec les matériaux polymères est la synthèse d'un copolymère alterné dans lequel le bandgap optique est diminué, ce que l'on appelle des polymères low-bandgap. L'organisation structurelle de la couche active joue un rôle important dans la performance des dispositifs, y compris les dispositifs photovoltaïques, et la technique Langmuir-Schaefer (LS) permet de fabriquer des films nanostructurés avec contrôle de l'épaisseur, qui peuvent servir de base pour construire de meilleurs dispositifs. Dans ce contexte, l'objectif de ce travail était de synthétiser des polymères low-bandgap et ensuite de fabriquer et caractériser des films LS de ces polymères et leurs mélanges avec un dérivé de fullerène, le PCBM, pour leur application en tant que couche active de cellules solaires. Les films LS des polymères et leurs mélanges avec PCBM ont été fabriqués et des mesures de caractérisation ont été effectuées. Ces films ont été caractérisés par des mesures électriques (courant vs tension, spectroscopie d'impédance et voltampérométrie cyclique), morphologiques (microscopie à force atomique) et optiques (UV-visible, diffusion Raman et transmission infrarouge). Par les films de Langmuir et les mesures morphologiques, il a été possible d'observer les caractéristiques spécifiques concernant la conformation de chaque polymère sous forme de film. Des mesures optiques confirment l'absorption aux longueurs d'onde élevées attendues pour ces polymères. Dans les mesures électriques, les résultats ont montré des conductivités différentes pour les mêmes matériaux lorsque les types d'électrodes ont été changés. Les dispositifs photovoltaïques des films LS fabriqués n'ont pas atteint de bonnes valeurs d'efficicacité. Les films spincoating de ces polymères testés en tant que couche active des dispositifs, sous atmosphère contrôlée, ont montré un’efficacité allant jusqu'à 0,6%. / Células solares poliméricas atraem grande interesse nessa área de pesquisa, devido ao baixo custo, processo de fabricação de grandes áreas, materiais de manuseio leves e a possibilidade de sua fabricação por diversas técnicas. Para uma boa eficiência dos dispositivos fotovoltaicos, a camada ativa deve conter uma boa absorção da luz solar. Em termos de bandgap, isto quer dizer que quanto menor o bandgap maior o fluxo de fótons absorvidos. Uma maneira de realizar isto com os materiais poliméricos é a síntese de um polímero no qual o bandgap óptico tem a capacidade de aumentar a captura da luz solar, os chamados polímeros low-bandgap. A organização estrutural da camada ativa possui um papel importante na performance de dispositivos, inclusive dos fotovoltaicos, e a técnica Langmuir-Schaefer (LS) proporciona a capacidade de fabricar filmes nanoestruturados e com controle de espessura, podendo servir de base para construção de melhores dispositivos. Dentro deste contexto, o objetivo deste trabalho foi sintetizar polímeros low-bandgap e, posteriormente fabricar e caracterizar filmes LS destes polímeros e de suas blendas com um derivado de fulereno, o PCBM, para a aplicação dos mesmos como camada ativa de células solares. Foram fabricados filmes LS dos polímeros e de suas misturas com PCBM e realizadas medidas de caracterização. Estes filmes foram caracterizados por meio de medidas elétricas (corrente vs. Tensão, espectroscopia de impedância e voltametria cíclica), morfológica (microscopia de força atômica) e óptica (Ultravioleta-Visível, Espalhamento Raman e transmissão no infravermelho). Com os filmes de Langmuir e as medidas morfológicas foi possível observar as características específicas de como é a conformação de cada polímero na forma de filme. As medidas ópticas confirmam a absorção em altos comprimentos de onda esperados para estes polímeros. Nas medidas elétricas os resultados mostraram diferentes condutividades para os mesmos materiais quando mudado os tipos de eletrodos. Os dispositivos fotovoltaicos dos filmes LS fabricados não alcançaram bons valores de eficiência. Filmes spin-coating destes polímeros testados como camada ativa dos dispositivos, em atmosfera controlada, revelaram eficiência de até 0.6%. / Polymeric solar cells attract great interest in this area of research due to the potential low cost, large area fabrication process, lightweight physical feature and the possibility of fabricating these cells by several techniques. To achieve good efficiency in the photovoltaic devices the active layer must have an efficient absorption of sunlight. In terms of bandgap, this means that the smaller the bandgap the greater the flux of photons absorbed. One way to accomplish this, with the polymeric materials, is the synthesis of a polymer in which the optical bandgap has the ability to increase the capture of sunlight, the so-called low-bandgap polymers. The structural organization of the active layer plays an important role in the performance of devices, including in photovoltaic devices, and the Langmuir-Schaefer (LS) technique provides the ability to manufacture nanostructured films with thickness control, which can serve as a basis for building better devices. In this context, the aim of this work was to synthesize low-bandgap polymers for later manufacturing and characterization of LS films of these polymers and their blends with a fullerene derivative, PCBM, and test them as active layer of solar cells. LS films of such polymers and their blends with PCBM were made and characterization measurements were performed. These films were characterized by electrical (current vs. voltage, impedance spectroscopy and cyclic voltammetry), morphology (atomic force microscopy) and optical (ultraviolet-visible, Raman scattering and infrared) measurements. Through the Langmuir films and the morphological measurements, it was possible to observe the specific characteristics of how it is the conformation of each polymer in film form. Optical measurements confirmed the absorption at high wavelengths expected for these polymers. In the electrical measurements, the results showed different conductivities for the same materials when the types of electrodes were changed. The photovoltaic devices manufactured from LS technique have not reached good efficiency values. When spin-coated active layers were tested as OPV devices in a controlled atmosphere the efficiency achieved up to 0.6% / CAPES DS / CNPq SWE 205489/2014-1

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-10-27T12:25:12Z No. of bitstreams: 0 / Made available in DSpace on 2017-10-27T12:25:12Z (GMT). No. of bitstreams: 0 / Nas ultimas décadas o processo de biossorção tem alcançado grande relevância no tratamento de efluentes contendo metais potencialmente tóxicos. O uso de bactérias nesse processo tem obtido destaque, uma vez que possuem inúmeras vantagens. O presente estudo pretendeu avaliar o mecanismo envolvido no processo de biossorção dos íons Pb(II) e Hg(II) por meio das linhagens Cupriavidus metallidurans (CH34) e Cupriavidus metallidurans (CH34/pCM3). Dentre os modelos estudados a isoterma de Langmuir foi a que melhor se ajusta ao processo de adsorção, apresentando uma capacidade máxima de adsorção (qmax) de 0,98 mg.g-1 para o Hg(II) e 86,2 mg.g-1 para o Pb(II), para a linhagem selvagem. Já para a linhagem recombinante o qmax obtido foi 3,4 mg.g-1 para o mercúrio e 172,4mg g-1 para o chumbo. Baseado nos valores referentes à energia livre de Gibbs (ΔG) o processo de retenção ocorreu de forma química e espontânea. A influencia do pH foi avaliada por meio de estudo competitivo entre os íons metálicos, em níveis equimolares. O valor que melhor contemplou a adsorção para ambos os íons foi o pH 7,0, tendo o Pb(II) demonstrado maior capacidade de retenção. Em pH 2,0 houve maior retenção do Hg (II), já em pH 10,0 o Pb(II) obteve maior retenção. Indicando que o meio influencia diretamente na competição dos íons metálicos pelos sítios ativos. Constatou-se que a retenção do metal é robusta e estável ao longo de 6 meses. Os resultados indicam que a Cupriavidus metallidurans (CH34/pCM3) pode ser uma boa opção para biossorção de íons metálicos por meio de biorreator. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP