The self-assembly of polystyrene-stabilized cadmium sulfide nanoparticles (PS-CdS) with amphiphilic stabilizing chains of polystyrene-block-poly(acrylic acid) (PS-b-PAA) into colloidal quantum dot compound micelles (QDCMs) is studied on two-phase gas-liquid segmented microfluidic reactors. The resulting particle sizes are found to arise from the interplay of shear-induced coalescence and particle breakup, depending on a combination of chemical and flow conditions. Variation of water content, gas-to-liquid ratio, and total flow rate, enable control of QDCM sizes in the range of 140 – 40 nm. The flow-variable shear effect on similar microfluidic reactors is then applied to direct the solution self-assembly of a PS-b-PAA block copolymer into various micelle morphologies. The difference between off-chip and on-chip morphologies under identical chemical conditions is explained by a mechanism of shear-induced coalescence enabled by strong and localized on-chip shear fields, followed by intraparticle chain rearrangements to minimize local free energies. Time-dependent studies of these nanostructures reveal that on-chip kinetic structures will relax to global equilibrium given sufficient time off-chip. Further investigations into the effect of chemical variables on on-chip shear-induced morphologies reveal a combination of thermodynamic and kinetic effects, opening avenues for morphology control via combined chemical (bottom-up) and shear (top-down) forces. An equilibrium phase diagram of off-chip micelle morphologies is constructed and used in conjunction with kinetic considerations to rationalize on-chip mechanisms and morphologies, including cylinders and vesicles, under different chemical conditions. Finally, we extend our strategy of two-phase microfluidic self-assembly of PS-b-PAA to the loading of fluorescent hydrophobic probes (pyrene and naphthalene) with different affinities for the PS core. The on-chip loading approach provides a fast alternate to the slow off-chip method, with implications for the potential development for point-of-care devices for drug loading. On-chip loading results indicate that loading efficiencies are dependent on water content and, to a lesser extent, on flow rate; the results also suggest that the on-chip morphologies of the PS-b-PAA micelles are an important factor in the loading efficiencies. / Graduate

Thermal nanoimprint lithography (T-NIL) is a cheap and fast technique to produce nanopatterns in polymeric materials. It creates these patterns by pressing a stamp down into a polymer film that has been heated above its glass transition temperature. These nanopatterned polymer films can be used in a wide variety of scientific fields, not the least the organic semiconductor industry. There the nanopatterned films have, among else, been used to improve the efficiency of organic light-emitting diodes (OLEDs). The light-emitting electrochemical cell (LEC), which is similar in structure to an OLED, also uses polymer films in their device structure but the light emitting layer also contains an electrolyte. However, it has not been shown if nanopatterns can improve LECs as well or if it is even possible to make an imprint in their polymer films that are mixed with an electrolyte. This thesis shows that T-NIL can be used to imprint nanopatterns in films made of poly(ethylene oxide) and the conjugated polymer Super Yellow. The best nanopatterns were produced by setting the imprint parameters to  85 °C, 10 bar, 1800 s for poly(ethylene oxide) and 115 °C, 20 bar, 1800 s for Super Yellow. Imprints were also performed on polystyrene but no nanopatterns could be produced. This was most likely because the stamp could not handle the high temperature that is required to make a nanopattern in polystyrene. The best imprint parameters of Super Yellow were then used to produce a pattern in a film made of Super Yellow mixed with the salt tetrahexylammonium tetrafluoroborate (THABF4) in order to be able to produce one imprinted and one reference LEC. The imprinted LEC had a luminosity of 139 cd/m2, an improvement of 20% compared to the reference’s 115 cd/m2 when operated under identical conditions.  The forward direction and the angular dependent electroluminescence spectrum of the imprinted LEC clearly showed an effect not observed in the reference. These findings show that the polymer films used in a LEC can be imprinted with a nanopattern by using T-NIL. The imprinted films can be used to create functional LECs that show different behavior and a higher luminosity compared to a non-imprinted reference. If these results can be repeated it might be the starting point of a brighter future.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-25T20:43:17Z No. of bitstreams: 1 DIVÂNIA FERREIRA DA SILVA – TESE (UAEMa) 2015.pdf: 6209897 bytes, checksum: dff0cafabba0ab449d69fdaef6faf3af (MD5) / Made available in DSpace on 2018-06-25T20:43:17Z (GMT). No. of bitstreams: 1 DIVÂNIA FERREIRA DA SILVA – TESE (UAEMa) 2015.pdf: 6209897 bytes, checksum: dff0cafabba0ab449d69fdaef6faf3af (MD5) Previous issue date: 2018-06-25 / Capes / O objetivo deste trabalho foi desenvolver blendas de poliestireno/composto de resíduo de borracha de estireno-co-butadieno (PS/SBRr) da indústria calçadista visando tenacificar o PS e reaproveitar o SBRr. As blendas foram preparadas nas composições (70/30; 60/40 e 50/50%) em massa e com 5% do compatibilizante estireno-butadieno-estireno (SBS). A fim de se estudar o efeito da sequência de mistura, escolheu-se a composição 50/50% que apresentou o melhor resultado de resistência ao impacto. As sequências realizadas foram: PS/SBRr/SBS 47,5/47,5/5%; PS/SBRr + SBS 47,5/47,5 + 5% e PS/SBS + SBRr 47,5/5 + 47,5% em massa. As blendas foram preparadas por extrusão seguida de injeção e caracterizadas por reometria de torque, tração, impacto, flexão, temperatura de deflexão térmica (HDT), análise térmica dinâmico-mecânica (DMTA), calorimetria exploratória diferencial (DSC), microscopia eletrônica de varredura (MEV) e microscopia eletrônica de transmissão (MET). Observou-se nos resultados dos ensaios mecânicos redução no módulo de elasticidade e na resistência à tração e um aumento significativo na resistência ao impacto quando comparados ao PS para todas as composições. A HDT das misturas reduziu pouco em relação ao PS. A sequência de mistura proporcionou bons resultados das propriedades mecânicas, principalmente na composição PS/SBS + SBRr 47,5/5 + 47,5% em massa. Por MEV e MET, pôde-se observar que as blendas compatibilizadas obtiveram uma melhor distribuição das partículas de borracha com uma morfologia mais estável que as não compatibilizadas. Estes resultados foram confirmados por meio dos maiores valores de resistência ao impacto, o que indica a ação do compatibilizante melhorando a adesão entre os componentes desta blenda. Por DMTA constatou-se que estas blendas são imiscíveis. Portanto, fica evidenciada a importância da reutilização dos resíduos de borracha tanto para a tenacificação do PS como também para a redução dos problemas causados ao meio ambiente, quando estes são descartados de forma indevida. / The aim of this study was to develop blends of polystyrene/compound of rubber waste (PS/SBRr) of the shoes industry aiming to tough the PS and to reuse the SBRr. The blends were prepared in the compositions (70/30; 60/40 and 50/50 wt.%) and with 5 wt.% of styrene-butadiene-styrene compatibilizer (SBS). In order to study the effect of mixing sequence, the 50/50 wt.% composition, which presented the best result in impact strength, was selected. The sequences were PS/SBRr/SBS 47.5/47.5/5%; PS/SBRr + SBS 47.5/47.5 + 5% and PS/SBS + SBRr 47.5/5 + 47.5 wt.%. The blends were prepared by co-rotational twin screw extruder and molded by injection and characterized by torque rheometer, mechanical properties, heat deflection temperature (HDT), dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). From the mechanical tests, a reduction in elastic modulus and tensile strength and a significant increase in impact strength were observed in relation to PS. The HDT for all blends was reduced compared to the PS. The mixing sequence showed good results in mechanical properties, especially in composition PS/SBS + SBRr 47.5/ 5 + 47.5 wt.%. By SEM and TEM it can be seen that the compatibilized blends presented a better distribution of the rubber particles with a morphology that was more stable than the one that was not compatibilized. These results were confirmed by the highest impact strength values, indicating the compatibiliz er action that improves adhesion among the components of the blend. By DMTA it was possible to state that these blends are immiscible. Hence, the importance of the reusing of rubber wastes is evidenced both for toughening of the PS and for the reduction of problems caused to the environment, when they are discharged improperly.

AquaVillas CasaBona väggsystem innehåller i dagsläget isoleringsmaterialet EPS, vilket har visat svagheter vid brand. Målet med denna studie var att föreslå ett alternativt isoleringsmaterial till EPS med hänsyn till brand, energianvändning och U-värde, samt energiåtgång och koldioxidutsläpp vid tillverkning. Syftet var att det föreslagna alternativa isoleringsmaterialet skall kunna användas av tillverkare i väggprodukter som ett alternativ till EPS. I denna studie undersöktes fyra olika isoleringsmaterial genom kritisk granskning av vetenskapliga artiklar och litteratur, samt genom fältstudie och beräkningar i energiberäkningsprogrammet VIP-energy. De isoleringsmaterial som undersöktes var expanderad polystyren, polyuretan, polyisocyanurat och stenull. Resultaten visade att EPS, PUR och PIR är avsevärt sämre ur brandsynpunkt än stenull. Vid tillverkning av de olika isoleringsmaterialen fick EPS bäst resultat när det gäller koldioxidutsläpp. För energiåtgång vid tillverkning fick EPS bäst resultat då isoleringsskiktet i det undersökta väggsystemet var 200 mm tjockt, men då utgångspunkten istället var att väggen skulle ha ett U-värde på 0,112 W/m2K, fick stenull bäst resultat i denna kategori. PUR och PIR fick sämst resultat gällande både energiåtgång och koldioxidutsläpp vid tillverkning. Stenull gav väggen den bästa energianvändningen men samtliga material klarade kraven i Boverkets Byggregler. Vid sammanvägning av samtliga undersökta egenskaper för de olika isoleringsmaterialen anses det mest lämpliga materialet för en vägg vara stenull. / The AquaVilla CasaBona wall system currently contains the insulation material EPS, which has shown weaknesses while exposed to fire. The aim for this study was to suggest an alternative insulation material to EPS regarding fire, energy use and U-vale as well as energy use and carbon dioxide emissions for manufacturing. The purpose was that the suggested alternative insulation material should be able to be used by manufacturers in wall products as an alternative to EPS. In this study, four different insulation materials were examined by critically reviewing scientific articles and literature, as well as field studies and calculations with the energy calculation program VIP-energy. The insulation materials investigated were expanded polystyrene, polyurethane, polyisocyanurate and rockwool. The findings showed that EPS, PUR and PIR were not nearly as good as rockwool regarding fire. When manufacturing the various insulation materials, EPS gives the best results in terms of carbon dioxide emissions. EPS gives the best results regarding energy use for manufacturing when the insulation layer in the investigated wall system was 200 mm thick, but when the wall was given a U-value of 0,112 W/m2K, rockwool got the best results in this category. PUR and PIR gave the worst results regarding both energy use and carbon dioxide emissions at manufacturing. Rockwool generated the best results regarding energy use, but all of the materials met the requirements from Boverkets Byggregler. When comparing all the investigated characteristics of the various insulation materials, the most suitable material for an external wall was considered to be rockwool.

Submitted by ROBSON ROSA DA SILVA (robsilva31@gmail.com) on 2016-07-04T18:50:31Z No. of bitstreams: 1 Silva_2016_New photonic structures_Self assembly of 1D Te structures_Multifunctional biopolymers and reused plastics.pdf: 40718449 bytes, checksum: 9c299b328a4a54c169de6647b0225f34 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-07-07T17:57:07Z (GMT) No. of bitstreams: 1 silva_rr_dr_araiq_par.pdf: 1063262 bytes, checksum: cc72dc79773da734cac767490756f56e (MD5) / Made available in DSpace on 2016-07-07T17:57:07Z (GMT). No. of bitstreams: 1 silva_rr_dr_araiq_par.pdf: 1063262 bytes, checksum: cc72dc79773da734cac767490756f56e (MD5) Previous issue date: 2016-05-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Nanoestruturas unidimensionais de telúrio (Te1D) na forma de whiskers, fios e hélices foram preparados com facilidade por uma síntese em etapa única na presença de solução aquosa de Pluronic® F68 à baixas temperaturas (< 100 °C) e pressão ambiente. A forma das nanoestruturas puderam ser controladas de acordo com a cinética da reação. Estruturas empacotadas de nanowhiskers e nanofios de Te foram obtidas via auto-organização em interface líquido-líquido e pela técnica de drop-cast em substrato de Si/SiO2. Estruturas híbridas 1D foram obtidas utilizando nanoestruturas Te1D como molde de sacrifício para anexar nanopartículas metálicas ou mesmo produzir nanoestruturas 1D metálicas. Por exemplo, nanoestruturas híbridas 1D foram preparadas decorando nanofios de Te com nanopartículas de Ag em solução aquosa de poli(vinilpirrolidona). Nanoestruturas 1D de Au com forma de nódulos foram preparados por deslocamento galvânico de íons Au3+ em uma mistura de nanohélices de Te, ácido ascórbico e solução aquosa de poli(vinilpirrolidona). Além disso, nanohélices de Te foram funcionalizadas com uma camada resina resorcinol-formaldeído em condições brandas de síntese. A resina de resorcinol-formaldeído é uma via intermédia para explorar a deposição de compostos opticamente ativos tais como nanopartículas de hidroxicarbonato de Tb3+ ou nanopartículas de Au. Para aplicações práticas é essencial que estas nanoestruturas possam ser suportadas em filmes rígidos ou flexíveis de alta qualidade óptica. Filmes de polímeros naturais puros e filmes híbridos de sol-gel epóxi foram avaliados como potenciais matrizes hospedeiras para luminóforos. A fabricação de híbridos é baseada na incorporação de 3-glicidoxipropiltrimetoxissilano na solução homogênea de polímero natural com posterior secagem sobre uma superfície plana. Particularmente, filmes flexíveis de fibroína da seda e acetato de celulose e os seus híbridos derivados exibiram excelentes propriedades ópticas para hospedar compostos opticamente ativos. Por exemplo, compostos de Eu3+ emissores na região do vermelho e corantes fluorescentes foram incorporados em matriz pura de polímero e híbridos epóxi e suas propriedades ópticas foram investigadas. Laser de corantes por feedback distribuído (DFB) foram fabricados dopando grades de difração de fibroína de seda com Rodamina 6G. Devido a sua capacidade de replicar superfícies padronizadas com resolução nanométrica, grades de fibroina da seda dopadas com corante foram depositadas contra a grade de difração de uma mídia de disco compacto comercial. Lasers modificados de DFB baseados em filmes de fibroina contendo nanopartículas espalhadoras de luz de SiO2 e Ag aleatoriamente distribuídas na grade de fibroina demonstraram aumento da intensidade do laser, além de estreitamento da largura do pico de emissão. Filmes híbridos flexíveis e transparentes (> 85%) de fibroina da seda e acetato de celulose modificados com função epóxi e contendo compostos fluorescentes na região do vermelho como complexos β-dicetonato de Eu3+ e nanopartículas de YVO4:Eu3+ em baixa proporção relativa mássica (<5%) foram preparados. De maneira geral, o resultado são filmes homogêneos com funções epoxi e/ou alcoxissilano não hidrolisados disponíveis para outras modificações químicas. Devido a matéria-prima limitada de polímeros naturais para uma alta demanda de fabricação de dispositivos ópticos, é igualmente importante desenvolver materiais com base na reutilização de polímeros sintéticos. Filmes finos de poliestireno foram concebidos por dissolução de poliestireno expandido (EPS) recuperado de resíduos em D-limoneno, um solvente verde proveniente de óleos cítricos. Filmes transparentes dopados com complexos β-dicetonato de Eu3+ demonstraram excelente transparência e aptos para uso em guias de luz. Estes resultados são motivadores para a) a engenharia de nanoestruturas 1D com propriedades ópticas sintonizáveis bem como, b) desenvolvimento de híbridos flexíveis e transparentes baseados em híbridos de polímeros naturais com alta funcionalidade química ou polímeros sintéticos reciclados como potenciais matrizes hospedeiras ópticas almejadas em aplicações fotônicas. / One-dimensional Te nanostructures (Te1D) in the shape of whiskers, wires and helices were prepared by a facile one-pot synthesis in the presence of aqueous Pluronic® F68 solution at low temperatures (< 100 ºC) and ambient pressure. The shape of Te1D nanostructures could be manuvered according with the reaction kinectics. We evaluate some techniques to assemble Te1D nanostructures on the pursuit for complex nanoarchitectures. Bundles of Te nanowhiskers and nanowires were achieved by self-assembly in liquid-liquid interface or by drop-cast technique in Si/SiO2 substrates. 1D hybrid structures have been conceived by using Te1D nanostructures as sacrificial template to attach metallic nanoparticles or even produce metallic 1D nanostructures. For example, 1D hybrid nanostructures were easily prepared by decorating Te nanowires with Ag nanoparticles in aqueous solution of poly(vinylpyrrolidone). Au 1D nanostructures with nodular-like shape were prepared by galvanic displacement of Au3+ ions in a mixture of Te nanohelices, ascorbic acid and an aqueous solution of poly(vinylpyrrolidone). Furthermore, Te1D nanohelices were functionalized with a layer of resorcinol-formaldehyde resin at mild synthesis conditions. The RF resin allowed us to fashion an intermediate pathway to explore the deposition of optically active compounds like Tb3+ hydroxylcarbonate or Au nanoparticles. Seeking practical applications, these nanostructures should be hosted over rigid or flexible films possessing excellent optical properties. Pure natural polymers and epoxy sol-gel hybrids films were evaluated as potential host for luminophors. The fabrication of epoxy hybrids is based on the incorporation of 3-glycidoxypropyltrimethoxysiloxane on the homogenous solution of natural polymer with subsequent casting over flat surface. Particularly, flexible silk fibroin and cellulose acetate films and their derivative hybrids displayed excellent optical properties to host optically active compounds. For instance, red emitting Eu3+ compounds and fluorescent dyes were hosted on pure natural polymer and hybrid films and the optical features of the luminescent films were investigated thoroughly. Distributed feedback dye-lasers were fabricated by doping silk fibroin diffraction gratings with Rhodamine 6G. Owing its ability to mimic patterned surfaces at nanoscale resolution, dye-doped SF gratings were fabricated using replica-casting patterning against a commercial blank digital versatile disc as template. A modified DFB Laser based on SF films with Ag or SiO2 light scattering particles randomly distributed on the grating unveiled an enhancement of laser intensity withal narrowing of emission peak linewidth. Flexible and highly transparent SF- and CA-epoxy hybrids (> 85%) containing red fluorescent Eu3+ b-diketonate complex and YVO4:Eu3+ nanoparticles at low relative content (< 5 wt%) were tailored. In general, the outcome is homogeneous films with epoxy and/or unhydrolized alkoxysilane functions available for further chemical modification. Owing the limited feedstock of natural polymers for high demanding production of optical devices, it is equally important develop materials based on the reuse of synthetic polymers. Thin films of polystyrene were conceived by dissolving waste-recovered expanded-polystyrene (EPS) in D-limonene, a green solvent from citrus oil. Transparent EPS films doped with Eu3+ b-diketonate complex displayed excellent transparency and light waveguiding, These assertions provide a framework that motivates the research on a) engineering of 1D hybrids nanostructures with tunable optical properties and b) flexible natural polymer/epoxy hybrid with enhanced functionality or plastic recycled as potential optical hosts sought in photonic applications. / FAPESP: 2013/12367-6

Made available in DSpace on 2016-06-02T19:55:33Z (GMT). No. of bitstreams: 1 4623.pdf: 1933289 bytes, checksum: 2fe0862970018a5264c75880e4d507f8 (MD5) Previous issue date: 2012-03-09 / Universidade Federal de Sao Carlos / Hydrogen and ethanol production using microorganisms is a promising area of technological development from a wide variety of renewable and alternative to this production is the use of anaerobic fluidized bed reactor (AFBR). One of the factors that most influence the performance of the AFBR is the material support, which must provide abrasion resistance, porous surface conducive to colonization by microorganisms, easy to achieve fluidization and ability to promote mass transfer between the medium and biofilm. Thus, the objective of this study was to evaluate the influence of different support materials (polystyrene - R1, grounded tire - R2 and polyethylene terephthalate (PET) - R3) on producing hydrogen and ethanol using three anaerobic fluidized bed reactors. Each reactor had a total volume of 4192 cm3 and was fed with media containing glucose as the carbon source (4000 mg L-1) with an influent pH around 5.0 and an effluent pH of about 3.5, a hydraulic retention time (HRT) of 8 1 h at a temperature of 23 &#61617;&#61472;2 ºC, with thermal treatment of the inoculum. For hydrogen production, the best performance was achieved with R2 (2.11 mol H2 mol-1 glucose), providing the highest H2 content in biogas (60%). In all reactors, the predominant soluble metabolites were acetic acid, butyric acid, lactic acid and ethanol, with small amounts of propionic acid. The reactor R2 produced more acetic and butyric acid (434.74 and 1013.61 mg L-1, respectively). However, reactor R3 showed a better performance for ethanol production (1941.78 mg L-1). / A produção de hidrogênio e etanol usando microrganismos é uma promissora área de desenvolvimento tecnológico a partir de uma ampla variedade de fontes renováveis e uma das alternativas para esta produção é a utilização do reator anaeróbio de leito fluidizado (RALF). Desta maneira, o objetivo deste trabalho foi avaliar a influência de diferentes materiais suporte (poliestireno - R1, pneu inservível triturado - R2 e PET - R3) visando à produção de hidrogênio e etanol utilizando três reatores anaeróbios de leito fluidizado. Cada reator possuía um volume total de 4192 cm3, alimentado com meio contendo glicose como fonte de carbono (4000 mg.L-1), com tempo de detenção hidráulica (TDH) entre 8 e 1 h a uma temperatura entre 20 e 25ºC, com tratamento térmico do inóculo, utilizando culturas mistas. Para produção de hidrogênio, o melhor desempenho foi do R2, apresentando melhor rendimento de H2 (2,11 mol-H2.mol-1-glicose) e melhor conteúdo de H2 no biogás (60%). Os metabólitos solúveis predominantes em todos os reatores foram ácidos acético e butírico e etanol, havendo uma pequena produção de ácido propiônico, sendo o R2 o que mais produziu ácidos acético e butírico (434,74 e 1013,61 mg/L, respectivamente). Entretanto, o R3 apresentou um melhor desempenho para produção de etanol (2,43 mol-EtOH.mol-1-glicose). Assim, pode-se afirmar que foi possível produzir simultaneamente hidrogênio e etanol como biocombustíveis.

Made available in DSpace on 2016-06-02T19:56:35Z (GMT). No. of bitstreams: 1 2404.pdf: 4034212 bytes, checksum: 2913adf06c11c92402ccb17ed7a97fa8 (MD5) Previous issue date: 2009-02-27 / Universidade Federal de Sao Carlos / Hydrogen is a clean and renewable source of energy and it is considered the "fuel of the future", because it produces only water during combustion and when it is used as fuel and hydrogen has a high energy yield of 122 kJ/g, which is 2.75 times greater than hydrocarbon fuels. The hydrogen production using microorganisms is a promising area of technological development from a wide variety of renewable and a alternative for this production is to use the anaerobic fluidized bed reactor (AFBR), a promising reactor for hydrogen production. One of the factors that most influence the performance of AFBR is the support material, which should provide resistance to abrasion, porous surface conducive to colonization by microorganisms, easy fluidization to reach and ability to facilitate the transfer of mass between the middle and biofilm. Thus, the objective of this study was to evaluate the influence of different support materials (polystyrene - R1, ground tire - R2 and PET - R3) for the hydrogen production, using three AFBR. Each reactor had a total volume of 4192 cm3, which was used as carbon source 4000 mg.L-1 of glucose, with pH influent around 7.0 and pH effluent of around 5.5, with hydraulic retention time (HRT) between 8 and 0.5 h, with temperature of 30 o C } 1, with heat treatment of the inoculum. The best performance was R2, giving better hydrogen yield production (HY) (2.15 mol-H2.mol-1-glucose), best H2 content in the biogas (52.97%) and showed a higher glucose conversion (90%). However, the R3 was better in the hydrogen production rate (HPR), 1.07 lh-1.L-1, a secondary parameter in the analysis of performance of the reactors. In all reactors, the production volume of hydrogen and H2 content in biogas increased with the reduction of the TDH, 8 pm to 1 HEO yield of hydrogen production increased with the reduction of the TDH, 8 h for 2 h. The major soluble metabolites during H2 fermentation were acetic acid (HAc), butyric acid (HBu), lactic acid (HLa) and ethanol (EtOH), and a small production of propionic acid and R2 was the reactor that more produced HAc and HBu (42.0% e 36.5%, respectively) . The better performance of R2 can be explained by the roughness of ground tire is larger than the other materials used, accumulating a large quantity of attached biomass, and a greater quantity of bacteria hydrogen producing. There was a predominance of bacilli like Clostridium sp. in the biofilm of all support materials. / O hidrogenio e uma fonte de energia limpa e renovavel e e considerado o combustivel do futuro , pois gera somente agua durante sua combustao e apresenta calor de combustao de 122 kJ.g-1, o que representa 2,75 vezes mais conteudo de energia do que qualquer hidrocarboneto. A producao de hidrogenio usando microrganismos e uma promissora area de desenvolvimento tecnologico a partir de uma ampla variedade de fontes renovaveis e uma das alternativas para esta producao e a utilizacao do reator anaerobio de leito fluidizado (RALF). Um dos fatores que mais influenciam o desempenho do RALF e o material suporte, que deve apresentar resistencia a abrasao, superficie porosa favoravel a colonizacao de microrganismos, facilidade para alcancar a fluidizacao e capacidade de favorecer a transferencia de massa entre o meio e o biofilme. Desta maneira, o objetivo deste trabalho foi avaliar a influencia de diferentes materiais suporte (poliestireno - R1, pneu inservivel triturado - R2 e PET - R3) na producao de hidrogenio utilizando tres reatores anaerobios de leito fluidizado. Cada reator possuia um volume total de 4192 cm3, alimentado com meio contendo glicose como fonte de carbono (4000 mg.L-1), com pH afluente em torno de 7,0 e efluente em torno de 5,5, com tempo de detencao hidraulica (TDH) entre 8 e 0,5 h a uma temperatura de 30oC } 1oC, com tratamento termico do inoculo. O melhor desempenho foi do R2, apresentando melhor rendimento de H2 (2,15 mol-H2.mol-1-glicose), melhor conteudo de H2 no biogas (52,97%) e maior conversao de glicose (90%). Entretanto, o R3 foi melhor na producao volumetrica de H2, 1,07 L.h-1.L-1, um parametro secundario na analise de desempenho dos reatores. Em todos os reatores, a producao volumetrica de hidrogenio e o conteudo de H2 no biogas aumentaram com a reducao do TDH de 8 h para 1 h e o rendimento de producao de hidrogenio aumentou com a reducao do TDH de 8 h para 2 h. Os metabolitos soluveis predominantes em todos os reatores foram acidos acetico, butirico, latico e etanol, havendo uma pequena producao de acido propionico, sendo o R2 o que mais produziu acidos acetico e butirico (42,0% e 36,5%, respectivamente). O melhor desempenho do R2 pode ser explicado pela rugosidade do pneu triturado ser maior do que a dos demais materiais empregados, acumulando uma maior quantidade de biomassa aderida e uma maior quantidade de bacterias acidogenicas produtoras de hidrogenio. Houve predominancia de bacilos semelhantes a Clostridium sp. no biofilme de todos os materiais suporte.

Determinações de tensão superficial (&#947;) na interface ar-água e espessuras médias elipsométricas in situ (d), foram usadas para estudar as interações entre dispersões de lípides (em forma de bicamadas) e filmes de poliestireno sulfato produzidos por revestimento rotacional sobre placas de óxido de silício. A adição de NaCl para uma concentração final de 50 mM em uma dispersão de 0.2 mM de lípide catiônico sintético produziu instantaneamente uma camada de 6 nm de espessura que permaneceu estável com o tempo, indicando uma cinética de adsorção muito rápida, determinada possivelmente, pela atração hidrofóbica entre defeitos sobre a bicamada, induzidos pelo sal, e a superfície do filme. Contudo, em água a adsorção de DODAB cresceu monotonicamente alcançando no máximo uma espessura de 1.6-1.8 nm (após 15 horas de interação) em função do tempo, a qual não foi consistente com deposição de bicamada. Nos estágios iniciais em água pura, a adsorção do anfifílico aumentou linearmente com a raiz quadrada do tempo, mostrando um processo controlado por difusão de vesículas, com coeficiente de difusão(D), aproximadamente igual a 1.0 x 10-11 m22s-1 em boa aproximação com valores determinados para vesículas de outros lípides por outros autores. Medidas elipsométricas sob o ar (ex- situ) de adsorção de DODAB, DHP e PC foram difíceis de realizar devido ao aumento da espessura média do filme polimérico durante o ciclo de lavagem e secagem. Na faixa de concentração de 0.1- 1.0 mM o filme adsorvido de DODAB em ar foi mais hidrofóbico (ângulo de contato de avanço &#920;A= 84° &#177; 3°) do que aquele para o filme puro de polímero (&#920;A=71 ° &#177; 4°). Nenhum efeito do filme de DHP sobre a molhabilidade do filme de PSA foi observado, apenas um aumento de rugosidade revelado pela mudança em &#916;&#920; de 2° para 11° (tabela 3). Filmes planos de PSA são hidrofóbicos(&#920;A= 86° &#177; 5°). Após interação com PC, as superfícies tornam-se menos hidrofóbicas (&#920;A= 75° &#177; 3°). A tensão superficial em ar-água para uma dispersão lipídica em água pura diminuiu rapidamente sob adição de sal (7-50 mM de NaCl), sugerindo a ocorrência de fusão de vesículas, induzida por sal, com a interface ar-água.O estudo da interação entre sais de DODA e partículas poliméricas por medidas de tamanho e potencial-zeta das partículas permitiu observar deposição de bicamadas optimizada por adição de sal a baixas concentrações (0.05-5.0 mM NaCl). / Determinations of surface tension (&#947;) at the air--water interface, contact angles (&#920;), and in and ex-situ ellipsometric mean thickness (d) were used to study the interaction between dioctadecyldimethylammonium bromide (DODAB) small vesicles and spin-coated polystyrene sulfate (PSS) films on silicon wafers. Upon the adition of NaCl (50 mM final concentration) to a 0.2 mM DODAB dispersion, adsorption from vesicles on PSS films immediatly yielded a DODAB layer 6.0 nm thick which remained stable as a function of time. However, in water, in situ DODAB adsorption monotonically increased reaching at most 1.6--1.8 nm as a function of time (from 15 mm of interaction), which were not values consistent with bilayer deposition. At early stages in pure water, DODAB adsorption linearly increased with the square root of time, indicating a vesicle difision controlled process with ca. 1.0 x 10-11 m2s-1 as the vesicle diffusion coeficient (D) in nice agreement with reported D for similar vesicles. In contrast, adding 50 mM salt, resulted in a very fast adsorption kinetics determined by the hydrophobic atraction between salt-induced defects on lhe bilayer and the film surface. Ex situ measurements of DODAB, DHP e PC adsorption were difficult because wetting/drying cycles of the polimeric fiIms increased its mean thickness. From 0.1 up to 1.0 mM DODAB, the adsorbed film in air was more hydrophobic (advancing contact angle, &#920;A = 84 &#177; 3°) than the bare PSS film (&#920;A = 71 &#177; 4°). No effect of DHP film on the wettability of PSA film could be observed, just a increase of rougness revealed by the change of &#916;&#920; from2° to 11°( table 3). Pure PSA films are hydrophobic, as revealed by the mean advancing angle &#920;A = 86 &#177; 5°. After interaction with PC, the surfaces turn less hydrophobic with a mean &#920;A = 75 &#177; 3°. Air-water surface tension for a DODAB dispersion in pure water rapidly decreased upon salt addition (7-50 mM NaCI), suggesting salt-induced vesicle fusion wilh the air--water interface occurred, in nice agreement with saIt-induced vesicle fusion at the hydrophobic polymer-water surface.The investigation of the interaction between DODA salts and polymeric particles from diameter and zeta- potential measurements, allowed us to detect bilayer deposition optimized by salt adition in low concentration(0.05-5.0 mM NaCl).

O crescimento na geração de rejeitos de equipamentos elétricos e eletrônicos (REEE), legislações mais rigorosas e o valor agregado destes materiais incentivam o desenvolvimento de tecnologias de reciclagem. Contudo, a reciclagem dos componentes poliméricos dos REEE (CP-REEE) precisa superar desafios como a degradação durante o uso e reprocessamento, a presença de diferentes aditivos nos rejeitos e a depreciação de propriedades causada pela mistura não controlada de polímeros. Assim, o objetivo deste trabalho foi desenvolver um estudo sobre a reciclagem mecânica na forma de blendas poliméricas de rejeitos do copolímero acrilonitrila-butadieno-estireno (ABS) e do poliestireno de alto impacto (HIPS), empregando agentes compatibilizantes. No desenvolvimento do trabalho foram realizadas a caracterização dos CP-REEE, análise das propriedades mecânicas, químicas, térmicas e morfológicas dos polímeros e das blendas de ABS/HIPS nas proporções de 1:3, 1:1 e 3:1 com variações na composição dos polímeros reciclados e virgens e por fim, realizado um estudo do envelhecimento foto-oxidativo acelerado de uma blenda ABS/HIPS. Os resultados mostraram que os polímeros ABS e HIPS reciclados ainda apresentam boas propriedades mecânicas e que a presença de agentes compatibilizantes provoca o aumento da tenacidade nas blendas ABS/HIPS. A incorporação de polímeros virgens nos materiais reciclados não promove ganho significativo nas propriedades mecânicas das blendas. Blendas com até 50% de ABS demonstraram ter propriedades próximas às do HIPS, enquanto as blendas com altos teores de ABS não alcançaram valores de propriedades mecânicas similares aos do ABS virgem. O comportamento das propriedades das blendas virgens e recicladas frente ao envelhecimento fotoquímico foi similar, indicando que o material reciclado apresenta grande potencial para aplicações. O estudo de blendas ABS/HIPS de CP-REEE demonstra que o controle da composição das blendas definem a sua aplicação. / The growth in waste electrical and electronic equipment (WEEE) generation, directives more stringent and the aggregate value presents in these waste are encouraging the development of recycling technologies. However, recycling of polymeric components from WEEE (PC-WEEE) must overcome challenges such as degradation during use and reprocessing, the presence of various additives in the waste and the depreciation of properties caused by uncontrolled polymers mixture. The aim of this work was to develop a study of the mechanical recycling in the form blends with of polymeric waste of acrylonitrile-butadiene-styrene copolymer blends (ABS) and high impact polystyrene (HIPS) using compatibilizers. During the study was carried out the characterization of the PCWEEE and mechanical, chemical, thermal and morphological analysis of the polymers and the ABS / HIPS blends in proportions of 1:3, 1:1 and 3:1 with recycled and virgin polymers, as well as a study of the accelerated photo-oxidative aging of the ABS/HIPS blends. The results showed that ABS and HIPS recycled polymers still have good mechanical properties and the presence of compatibilization agents leads to increased toughness in ABS/HIPS blends. The incorporation of virgin polymers in recycled materials does not promote significant gain in the mechanical properties of the blends. Blends with up to 50% ABS have demonstrated to be closer to the HIPS, while blends with high content of ABS did not reach values of mechanical properties similar to the virgin ABS. The mechanical properties of virgin and recycled blends during the photochemical aging were similar, indicating that the recycled material has great potential for applications. The study of ABS/HIPS blends from PC-WEEE demonstrated that control of the blend composition establish their applications.

Les cellules solaires organiques ont longtemps été qualifiées de cellules solaires« polymères ». Cette appellation découle du fait que la couche active de telles cellules solaires a majoritairement été réalisée avec un polymère donneur d’électrons. L’utilisation d’un polymère au sein de la couche active a permis d’envisager la production de cellules solaires organiques par voie liquide avec des procédés d’impression à grande vitesse. Il existe cependant un autre type de matériau donneur d’électrons : les petites molécules. Ces dernières déposées par évaporation thermique permettent d’obtenir des cellules à haut rendement. A cause de leur faible propriété filmogène, les petites molécules n’ont cependant pas été envisagées pour un procédé d’impression industrielle. Or, en 2012 plusieurs petites molécules déposables par voie liquide font leur apparition et permettent d’obtenir des rendements suffisamment élevés à l’échelle laboratoire, pour envisager leur à l’échelle industrielle. Ces travaux de thèse ont été conduits en collaboration avec ARMOR, une entreprise visant à commercialiser les cellules solaires organiques, dans le but d’évaluer le potentiel d’industrialisation des petites molécules donneuses d’électrons. Le p-DTS(FBTTh2)2 a été choisi pour cette étude. Il a été montré qu’il était possible d’atteindre des rendements de 2% avec ce matériau à l’air, avec des solvants non toxiques en utilisant un procédé d’enduction à racle. L’industrialisation du p-DTS(FBTTh2)2 n’a cependant pas été poursuivie car ce dernier est très instable à l’air. Ces travaux présentent une méthodologie pouvant être utilisée pour évaluer l’industrialisation d’autres matériaux de ce type. / Organic solar cells are often called “polymer” solar cells. This term comes from the fact that the active layer of such solar cells have been widely made with a donor polymer. The use of polymer inthe active layer gives interesting filming properties that can be used to produce these solar cells industrially with a high speed printing process. Yet, another type of donor materials exists: the small molecules. Deposited by thermal evaporation, this type of materials can allow to reach high efficiency solar cells. Because of their poor filming properties, small molecules were not a good candidate for an industrialization using high speed printing. However, in 2012 several solution processable small molecules were proven particularly promising by demonstrating high efficiency at a laboratory scale.These encouraging results let imagine that it could be possible to produce organic solar cells with such materials. This PhD work has been done in collaboration with ARMOR, a company highly implied in the commercialization of organic solar cells, in order to evaluate if small molecules materials could be use dindustrially with a high speed printing process. The p-DTS(FBTTh2)2 has been chosen for this study. It has been shown that it is possible to reach efficiencies as high as 2 % with such a material, using non toxicsolvents and by making the solar cell in the air with a Doctor Blade. Nevertheless, the industrialization ofthe p-DTS(FBTTh2)2 has not been pursued due to the rapid degradation of this molecule in the air. This work presents a method that can be used to evaluate the industrialization of other efficient small molecules.