Nas últimas décadas diversos tipos de meio suporte têm sido propostos para a melhoria da eficiência e/ou aumento da compacidade de reatores biológicos tratando esgoto sanitário. No presente trabalho de doutorado são apresentados os resultados obtidos com a aplicação de um novo tipo de reator biológico anaeróbio de fluxo ascendente com leito de fibras flexíveis aplicado ao tratamento de esgoto sintético. Sua concepção foi motivada pelas dificuldades verificadas em alguns tipos de reatores de leito expandido, os quais ao longo do tempo de operação podem perder suas características hidrodinâmicas iniciais, devido ao acúmulo de biomassa, passando a apresentar expansão não homogênea do leito. A proposta de uso da fibra de nylon como meio suporte se deveu a sua capacidade de atuar como leito flexível - quando fixo em apenas uma de suas extremidades - que, devido á sua flexibilidade, apresenta também características parecidas às de leito móvel. Nesse novo tipo de concepção de leito, a biomassa aderida às fibras flexíveis adquirem forma de longos filamentos, os quais, devido ao próprio escoamento do esgoto e à rotação do eixo em que as fibras são fixadas, permanecem estendidos de modo a proporcionar elevada relação volume/superfície. Essa biomassa na forma de finos filamentos permanece firmemente aderida ás fibras flexíveis, reduzindo o potencial de perda de biomassa juntamente com o efluente e também de possíveis obstruções de poros, comum em leitos granulares. Para o estudo, foi projetada, construída, operada e avaliada durante 458 dias, uma instalação piloto constituída de seis reatores na forma de colunas verticais com escoamento contínuo e ascendente, operando em paralelo. Nesses reatores foram variados parâmetros de configuração e operação, como: i) a densidade de fibras flexíveis que compuseram o leito de fibras flexíveis; ii) a rotação do eixo vertical onde foram fixadas as fibras do leito; iii) o tempo de detenção hidráulica (nas etapas de 1 a 4 foram testados TDH de 9; 6; 4 e 3 horas, respectivamente); iv) a interrupção da rotação em reator em andamento. Foram analisadas as eficiências de remoção de carga orgânica e do perfil vertical dos reatores, assim como foi realizada a avaliação da composição da biomassa encontrada no biofilme, com análise de imagem e microscopia. Os resultados demonstram que a configuração dos reatores forneceram excelentes resultados de remoção de carga orgânica e também se mostraram aptos para se adaptar as variações de vazões aplicadas ao longo do trabalho, sendo observados os melhores resultados na Etapa 1 da fase 1, onde o Reator 2 apresentou eficiência de remoção de 91% de DQO total, 96% de DQO filtrada, 86% de DBO e 60% de SST. Também foi possível observar que os reatores com maiores densidades de fibras apresentaram melhores eficiências e permaneceram mais estáveis em face às características investigadas. Quanto à aplicação de rotação foi possível observar sua interferência positiva sobre a eficiência de remoção dos reatores, principalmente para as densidades de fibras inferiores e que o aumento de sua rotação também trazia melhorias na remoção de carga orgânica. Já para a avaliação da interrupção da rotação foi possível observar a redução de eficiência para os parâmetros avaliados. Também foram analisados três pós-tratamentos do efluente do reator anaeróbio por flotação, sedimentação (com e sem coagulante) e filtração em filtro de fibras flexíveis. O pós-tratamento mais adequado para ser aplicado em conjunto ao reator anaeróbio de fibras flexíveis foi a flotação, por separação (sem adição de coagulante), que apresentou remoção de 71%de turbidez, 51% de cor aparente, 40% de DQO, 25% de DQO filtrada, 34% de fósforo total e 52% de SST. Na avaliação do pós-tratamentos físico-químico mais adequado, a flotação por ar dissolvido apresentou melhores resultados utilizando o coagulante PAC em dosagem de 14 mg.L-1 do princípio ativo de Al2O3, com eficiência de remoção do sistema de 84% de turbidez, 73% de cor aparente, 50% de DQO total e 31% de DQO filtrada, 45% de fosforo total e 62% SST. / In the last decades, many different types of support media have been proposed for improving the efficiency and / or increasing the compactness of biological reactors treating domestic sewage. The results obtained in the application of a new type of up flow anaerobic bioreactor with flexible fibers bed applied to synthetic wastewater treatment are presented in this PhD thesis. Its design was motivated by the difficulties observed in some types of expanded bed reactors, which may lose their initial hydrodynamic characteristics during operation time, due to the biomass accumulation, leading to inhomogeneous bed expansion. The proposed nylon fiber is used as the support media due to its ability to operate as flexible bed - when it is fixed at only one end - which, due to its flexibility, also has characteristics similar to the moving bed. In this new type of bed design, the biomass attached to the flexible fibers acquire the form of long filaments, which, due to the sewage flow and the rotation axis in which the fibers are fixed, remain extended in order to provide high volume /surface ratio. This biomass in the form of fine filament remains firmly attached to the flexible fibers, thereby reducing the potential loss of biomass along with the effluent, as well as possible pore clogging, which are common in granular beds. For this study, a pilot installation consisted of six parallel reactors in the form of vertical columns with continuous upflow was designed, constructed, operated and evaluated for 458 days. In these reactors were varied configuration settings and operation as: i) the density of flexible fibers that composed the bed of flexible fibers; ii) the rotation of the vertical axis where the bed fibers were fixed; iii) the hydraulic retention time (in steps 1 to 4, HDTs of 9, 6, 4 and 3 hours were tested, respectively); iv) interruption of the rotation in the reactor in progress. The organic load removal and the reactors vertical profile efficiencies were analyzed, as well as the biomass composition found in biofilm, with image analysis and microscopy. The results demonstrate that the configuration of reactors provided excellent results of organic load removal and also proved to be able to adapt to variations in flow rates applied during the tests. The best results were observed in Step 1 in phase 1, where the reactor 2 presented removal efficiency of 91% of total COD, 96% of filtered COD, 86% of BOD and 60% of SST. Reactors with higher fiber density presented improved efficiencies and remained more stable, considering the investigated characteristics. The application of rotation was proved to cause a positive interference on the efficiency of the reactors removal, mainly for lower fiber density, and the increase of this rotation also brought improvements in the organic load removal. The rotation interruption caused en efficiency reduction for the evaluated parameters. Three post-treatments of the effluent of anaerobic reactor were analyzed: flotation, sedimentation (with and without coagulant) and filtration on flexible fibers filter in phase 2. The most suitable post-treatment to be applied along with the anaerobic reactor with flexible fibers was the flotation by separation (without addition of coagulant), which presented removal of 71% of turbidity, 51% of apparent color, 40% of COD, 25% of filtered COD, 34% of total phosphorus and 52% of SST. In the evaluation of the most appropriate chemical-physical post-treatment, the dissolved air flotation presented better results when using the PAC coagulant in the dosage of 14 mg.L-1 of the active principle of Al2O3, with removal efficiency of 84% of turbidity, 73% of apparent color, 50% of total COD, 31% of filtered COD, 45% of total phosphorus and 62% of TSS.

O presente trabalho teve como objetivo principal a avaliação da eficiência de remoção de carga orgânica, fósforo e sólidos em suspensão de sistema de flotação tratando esgoto sanitário pré-tratado em reatores UASB, da ETE Monjolinho da cidade de São Carlos/SP, e coagulado com tanino associado ou não a polímeros sintéticos. Os ensaios com variação de dosagem de coagulante Tanino e polímeros (polímero catiônico, polímero não-iônico e polímero aniônico) foram realizados em escala de laboratório, com o uso do equipamento flotateste. Em todos os ensaios foram fixados os valores de gradiente de velocidade na mistura rápida (800/s) e na floculação (90/s), ao tempos de detenção na mistura rápida (20 s) e na floculação (15 min) e, a pressão de saturação 5 Bar e a razão de recirculação (17%). Durante os ensaios com unidade de flotação em escala de bancada foram avaliados três valores de velocidades de flotação: 12,0 cm/min, 16,0 cm/min e 20,0 cm/min. Os ensaios foram divididos em duas fases: a fase 1 teve como objetivo analisar a resposta do sistema de flotação com o emprego do coagulante Tanino no tratamento do efluente do reator UASB da ETE Monjolinho (fase 1A) e também determinar as duas dosagens do coagulante Tanino mais adequadas para o tratamento do efluente de UASB da ETE Monjolinho para cada polímero testado (fase 1B). As fases 1A e 1B foram realizadas com efluente coletado às 8:00 h e 14:00 h, respectivamente. A fase 2 teve como objetivo a busca da dosagem ótima de tanino dentro de uma faixa mais estreita de valores, assim como a verificação do melhor tipo e dosagem de polímero sintético (não-iônico, aniônico e catiônico) para ser associado ao coagulante tanino. Na fase 1A, verificou-se que a flotação foi efetiva para remoção de cor aparente mesmo para dosagem nula de coagulante Tanino. Quanto à turbidez, verificou-se efeito marcante da adição de dosagem crescente de coagulante no aumento da eficiência de remoção desse parâmetro. Após a obtenção dos resultados da fase 1B, foram escolhidas para a fase 2 as duas menores dosagens de coagulante capazes de promover redução da turbidez em pelo menos 85%. Além destas duas dosagens, foram avaliados na fase 2 outras 3 dosagens compreendidas entre elas. Sendo assim, na fase 2 foram estudadas as doses de 65, 75, 85, 95 e 105 mg/L de coagulante, cada qual associada a seis dosagens de cada um dos polímeros estudados. Entre os tratamentos empregados, pôde-se verificar maior eficácia do polímero não-iônico e do polímero catiônico para o tratamento por flotação, associado ao coagulante tanino. O conjunto de dosagem de coagulante tanino e polímero mais vantajoso, ou seja, menor dosagem de tanino que, associada a polímero, apresentou remoção satisfatória dos parâmetros estudados, foi 65 mg/L de Tanino e 2,0 mg/L de polímero catiônico, atingindo remoções de 95,2% de turbidez (Residual de 3,65 NTU), 82,1% de cor aparente (Residual de 98 mgPT/L), 49,2% de fósforo total (Residual de 3,2 mg/L), 80,7% de DQO (Residual de 25 mg/L) e 87,9 % de SST (Residual de 13 mg/L) nas condições encontradas na época dos ensaios, para o pós-tratamento por flotação de efluente de reator UASB da ETE Monjolinho, São Carlos/SP. / The main objective of this work is the evaluation of the efficiency of removal of organic load, phosphorus and suspended solids in the flotation system treating domestic wastewater pretreated in UASB reactors, of the Monjolinho Wastewater Treatment Plant (WWTP) of Sao Carlos, SP and clotted with tannin alone or combined with synthetic polymers. Tests varying tannin dosage of coagulant and polymer (cationic polymer, nonionic polymer and anionic polymer) were performed on a batch scale, using flotatest. In all the tests were fixed the values of rapid mix (800/s) and flocculation (90/s) velocity gradients, the rapid mix (20 s) and flocculation (15 min) times, saturation pressure (5 Bar) and recycle rate (17%). During the test in the flotation bench scale unity three values of flotation velocities were evaluated: 12.0 cm/min, 16.0 cm/min and 20.0 cm/min. The tests were divided in two phases: the objective of phase 1 was to examine the response of the flotation system with the use of tannin coagulant in the treatment of Monjolinho WWTP UASB effluent (Phase 1A) and also determine the two most suitable dosages of tannin coagulant for the treatment of wastewater from the Monjolinho WWTP UASB tested for each polymer (phase 1B). Phases 1A and 1B were performed with wastewater collected at 8:00 h and 14:00 h, respectively. The objective of phase 2 was to find the optimum dosage of tannin within a narrower range of values, as well as verification of the optimal type and dosage of synthetic polymer (non-ionic, anionic and cationic) to be associated with the tannin coagulant. In phase 1A, it was found that flotation was effective for apparent color removal even to zero coagulant dosage tannin. As for turbidity, there is a marked effect when increasing the coagulant dose, which increased the removal efficiency of this parameter. After obtaining the results of Phase 1B, were chosen for phase 2 two low coagulant dosages which can promote reduction of turbidity by 85%. Besides the two dosages obtained in phase 1B, in phase 2 were evaluated other three between them. Thus, in phase 2 were studied coagulant doses of 65, 75, 85, 95 and 105 mg/L, each one associated with six doses of each one of the studied polymers. Among the treatments employed, it could be seen that the non-ionic polymer and the cationic polymer were the most efficient for treatment by coagulation associated with tannin in flotation. The set of tannin coagulant dosage and polymer which showed satisfactory removal of parameters was 65 mg/L of Tannin with 2.0 mg/L of cationic polymer, reaching 95.2% removal of turbidity, 83% of color apparent, 49.2% of total phosphorus, COD 80.7% and 87.9% of TSS under the conditions found at the time of testing, for post-treatment of Monjolinho WWTP UASB effluent by flotation.

With the advancements in the field of wireless sensor networks (WSNs), more and more applications require the sensor nodes to have long lifetime. Energy harvesting sources, e.g. thermoelectric generators (TEGs), can be used to increase the lifetime and capability of the WSNs. Integration of energy harvesters into sensor nodes of WSNs can realize self powered systems, providing the possibility for maintenance free WSNs. TEGs can convert the existing temperature differences into electricity. The efficiency of TEGs is directly related to the dimensionless figure of merit (ZT) of materials, which is given as ZT=σS^2 T/k, where σ is the electrical conductivity, S is the Seebeck coefficient, k is the thermal conductivity, T is the temperature and σS^2 is the power factor. Traditional thermoelectric (TE) materials are based on inorganic materials, of which the thermal conductivity is high. Over the past decade, the use of nanostructuring technology, e.g. superlattice, could decrease the thermal conductivity in order to enhance the efficiency of TE materials. However, the high cost and the rigidity of inorganic TE materials are limiting factors. As alternatives, polymer based materials have become the research focus due to their intrinsic low thermal conductivity, high flexibility and high electrical conductivity. Moreover, polymer based materials could be fabricated in solution form, giving the possibility for employing printing techniques hence a decrease in the production cost. Unlike the typical approach, in which secondary dopants are added into PEDOT:PSS solutions to modify the power factor of polymer films, this thesis is focused on a more efficient method to improve TE properties. This thesis demonstrates for the first time that post treatment of PEDOT:PSS films with the secondary dopant DMSO as the medium results in a much larger power factor than the traditional addition method. The post treatment method also avoids the usually required mixing step involved in the addition method. Different solvents were selected to discuss the impact factors in the modification of the power factor by this post treatment approach. The post treatment of PEDOT:PSS films was then extended to utilize a green solvent EMIMBF_4 (an ionic liquid) as the medium. EMIMBF_4 is found to exchange ions with PEDOT:PSS films. As a result, the EMIM^+ cations remain in the films and reduce the oxidation level of PEDOT chains, which affects the Seebeck coefficient and the electrical conductivity. Furthermore, TE materials based on hybrid composites with polymer as the matrix and Te nanostructures as the nanoinclusions were investigated. This thesis successfully developed a green synthesis method to obtain Te nanostructures, in which a non toxic reductant and a non toxic Te sources were used. Well controlled Te nanostructures including nanorods, nanowires and nanotubes were synthesized by wet chemical and hydrothermal synthesis. Those as synthesized Te nanowires were then integrated into PEDOT:PSS solution for composite films fabrication. A high Seebeck coefficient up to 200 μV/K was observed in the composite film. / Mit den Weiterentwicklungen der Drahtlosen Sensornetzwerke (engl. WSN, wireless sensor networks) stellen immer mehr Anwendungen die Forderung einer langen Lebensdauer der Sensorknoten. Energiegewinnungssysteme (engl. Energy Harvesters) wie z.B. thermoelektrische Generatoren (TEGs) können genutzt werden, um die Lebensdauer und Leistungsfähigkeit der WSN zu steigern. Mit der Integration von Energy Harvesters können WSN ohne äußere Stromversorgung realisiert und somit die Möglichkeit zur Wartungsfreiheit geschaffen werden. TEGs liefern Energie durch die Umwandlung einer Temperaturdifferenz in Elektrizität. Die Effektivität der TEG ist direkt verbunden mit der Material-Kennzahl ZT und ist gegeben durch ZT=σS^2 T/k, wobei σ die elektrische Leitfähigkeit ist, S der Seebeck Koeffizient, k die thermische Leifähigkeit, T die Temperatur und σS^2 der Leistungsfaktor. Herkömmliche thermoelektrische (TE) Materialien basieren auf anorganischen Materialien, von denen die thermische Leitfähigkeit hoch ist. Im Laufe des letzten Jahrzehnts konnte durch den Einsatz der Nanostrukturierung die thermische Leitfähigkeit verringern werden um damit die Effizienz von TE-Materialien zu steigern. Die Steifigkeit dieser Materialien ist ein anderer Aspekt. Als Alternative für anorganische TE Materialien sind Polymer basierte TE Materialien zum Fokus der Forschung geworden aufgrund einer intrinsisch niedrigen thermischen Leitfähigkeit, hohen Flexibilität und hohen elektrischen Leitfähigkeit. Des Weiteren können diese Polymere in gelöster Form verarbeitet werden, was die Möglichkeit für den Einsatz von Drucktechnologien und damit geringeren Produktionskosten gibt. Anders als der herkömmliche Ansatz den Leistungsfaktor der Polymerfilme durch die Ergänzung von sekundären Dotanten in PEDOT:PSS Lösungen zu verändern, wurde in dieser Arbeit eine effizientere Methode zur Verbesserung der TE Eigenschaften gesucht. In dieser Arbeit wird zum ersten Mal gezeigt, dass die Nachbehandlung von PEDOT:PSS Schichten mit sekundären Dotanten Dimethylsulfoxid (DMSO) als Medium der Nachbehandlung zu einem viel höheren Leistungsfaktor führt als bei der Zugabemethode und außerdem die sonst erforderliche Mischprocedur vermeidet. Es wurden verschiedene Lösungsmittel ausgewählt um die Einflussfaktoren bei der Modifikation des Leistungsfaktors durch die Nachbehandlung von Polymerschichten zu diskutieren. Die Nachbehandlung von PEDOT:PSS Schichten wurde nachfolgend erweitert um das umweltfreundliche Lösungsmittel EMIMBF4 (eine ionische Flüssigkeit) als das Medium einzusetzen. EMIMBF4 ist bekannt für den Austausch von Ionen mit PEDOT:PSS Schichten, so dass EMIM Kationen in der Schicht verbleiben, die Oxidationsstufe der PEDOT-Ketten senken und damit den Seebeck-Koeffizient und die elektrische Leitfähigkeit beeinflussen. Des Weiteren konzentriert sich diese Arbeit auf TE Materialien basierend auf Kompositen aus Polymeren mit Nanoeinlagerungen. Erfolgreiche Syntheseansätze wurden für Tellur-Nanostrukturen entwickelt, bei denen keine giftigen Reduktionsmittel und keine giftigen Tellur-Quellen zur Verwendung kamen. Es erfolgte die Erzeugung von kontrollierten Tellur-Nanostrukturen, einschließlich Nanostäben, Nanodrähten und Nanoröhren, mit nass-chemischer und hydrothermaler Synthese. Die so hergestellten Nanodrähte wurden dann in PEDOT:PSS Lösungen integriert für die Herstellung von Komposite-Schichten. Dabei konnte ein hoher Seebeck-Koeffizienten, bis zu 200 μV/K, festgestellt werden.

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