Proton Exchange Membrane Fuel Cell has the potential to become an important energy conversion technigne. Lots of efforts oriented toward the electrochemical conversion of energy using proton exchange membrane (PEM) fuel cells have been enormously accelerated with the hope to promote as an alternative power source for transport and portable purposes. However, they still suffer from such disadvantages as limited operation temperature, high cost, insufficient durability and high methanol permeability.Good membranes should meet several strict requirements as follows; reasonable proton conductivity, high stability and durny the performance of a fuel cell environment,outstanding mechanical toughness, high heat endurance, and impermeability to fuel gas or liquid. Presently,a lot of references have mentioned some sulfonatied polymer sulfonated of poly(ether ether ketone) (SPEEK), sulfonatedpolysulfone (SPSF), sulfonated polysulfide sulfone(SPSS), and polybenzimidazole(PBI) and so on.To achieve high proton conductivity usually match with a high degree of sulfonation that means owning a large Ion Exchange Capacity, IEC.But which in turn leads to a decrease in the electrochemical¡Bdimensional stability¡Bwater uptake¡Boxidative stability. Therefore they suffer from such disadvantages as limited operation range of temperature.Three aromatic poly(arylene ether)s P4b¡BP4c¡BP4d were synthesized from the polymer consists nine of polyaromatic groups with bisfluoride monomer at studying long time in our laboratory with S1¡BS2¡BS3 diol monomer.The molecular weight of the polymer (Mw:1.49¡Ñ105~5.3¡Ñ105 g/mol ,PDI: 1.82~2)This polymer has high strength,thermal stability and all of polymers own very high Td ,which are over than 500oC.We sulfonatied the polymer in order to apply as the proton exchange membrane of a fuel cell.The results showed after sulfonation of P4b¡BP4c¡BP4d.All IEC reaches 3.9~1(meq/g).According to above result, we propose the aromatic poly(arylene ether)s is good matenal can be used on all application as a proton exchange membrane.

Polycondensation reaction was carried out for synthesizing rigid-rod polymer hPBI. Various molar ratios (50:1, 25:1, and 15:1) of 2-hydroterephthalic acid and 5-hydroisophthalic acid were also introduced in the synthesis for articulated rigid-rod polymer a-hPBI. The polymers were further derivatized with 1,3-propanesulton for pendants of lithium ionomer to become water soluble polyelectrolytes hPBI-PS(Li+) and a-hPBI-PS(Li+), respectively. Lithium salt doped cast film of the rigid-rod polyelectrolyte hPBI-PS(Li+) showed a room-temperature DC conductivity parallel to film surface as high as 4.02¡Ñ10-3 S/cm. Molecular weight of the rigid-rod polyelectrolyte was low indicating a small molecular aspect ratio. In cast film, the molecules were randomly distributed and highly isotropic facilitated Li cations mobility for a high film conductivity. The conductivity was also insensitive to the anion of lithium salt. No apparent layered structure was revealed by scanning electron microscope suggesting that the cast films had near three-dimensionally isotropic structure and conductivity.

Atualmente, a preocupação com a redução da poluição industrial tem motivado os pesquisadores na busca de novas tecnologias para o tratamento de resíduos industriais. Tecnologias limpas, como a eletrodiálise, são capazes de tratar alguns destes resíduos, como por exemplo o efluente da indústria de galvanoplastia, minimizando os impactos que ocorreriam caso eles fossem descartados diretamente no meio ambiente. O componente principal desta técnica é a membrana na qual ocorre a etapa de retirada dos íons da solução. Atualmente estas membranas são importadas e caras, o que justifica o desenvolvimento de membranas eficientes e acessíveis. Neste sentido, no presente trabalho membranas de poliestireno sulfonado/ poliestireno de alto impacto (SPS/HIPS), polianilina dopada com ácido canforsulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniCSA/SPS/HIPS), polianilina sulfonada/ poliestireno sulfonado/ poliestireno de alto impacto (SPAN/SPS/HIPS), e polianilina dopada com ácido p-tolueno sulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniTSA/SPS/HIPS) foram desenvolvidas usando o método de mistura química. As membranas foram caracterizadas utilizando as técnicas Análise termogravimétrica (TGA), Análise dinâmico Mecânica (DMA), e Microscopia Eletrônica de Varredura (MEV). Membranas foram submetidas a curvas corrente-potencial e ensaios de eletrodiálise em soluções de NaCl e KCl, a fim de determinar o transporte iônico através das mesmas. Os resultados foram comparados com uma membrana comercial Selemion CMT. A extração percentual média para íons de Na+ obtidos pelas membranas desenvolvidas foi superior a 20%. / Nowadays the concern with the reduction of industrial pollution has motivated researchers to found out new technologies for treatment of industrial waste. The clean technologies, as electrodialysis, are capable of treating some these residues, as for example the galvanoplasty’s waste, minimizing the impacts that would happen to them if they were discarded directly on the environment. The main component of this technique is the membrane on which occurs the ions removal stage of the solution. The membranes are imported and expensive what justifies the development of efficient and accessible membranes. In this sense, in the present work membranes of sulfonated polystyrene / high impact polystyrene (SPS/HIPS), polyaniline doped with camphorsulfonic acid / sulfonated polystyrene / high impact polystyrene (PAniCSA/SPS/HIPS), sulfonated polyaniline/ sulfonated polystyrene / high impact polystyrene (SPAN/SPS/HIPS), and polyaniline doped with p-toluenesulfonic acid / sulfonated polystyrene / high impact polystyrene (PAniTSA/SPS/HIPS) were developed using chemical mixture method. Membranes were characterized by Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Dynamic Mechanical Analysis (DMA) and Scanning Electronic Microscopy (SEM). Membranes were submitted to current-voltage curves and electrodialysis experiments with NaCl and KCl solutions, in order to determine ionic transport through them. Results were compared with a commercial membrane, Selemion CMT. The average percent extraction for Na+ ions obtained by membranes developed were beyond 20%.

Atualmente, a preocupação com a redução da poluição industrial tem motivado os pesquisadores na busca de novas tecnologias para o tratamento de resíduos industriais. Tecnologias limpas, como a eletrodiálise, são capazes de tratar alguns destes resíduos, como por exemplo o efluente da indústria de galvanoplastia, minimizando os impactos que ocorreriam caso eles fossem descartados diretamente no meio ambiente. O componente principal desta técnica é a membrana na qual ocorre a etapa de retirada dos íons da solução. Atualmente estas membranas são importadas e caras, o que justifica o desenvolvimento de membranas eficientes e acessíveis. Neste sentido, no presente trabalho membranas de poliestireno sulfonado/ poliestireno de alto impacto (SPS/HIPS), polianilina dopada com ácido canforsulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniCSA/SPS/HIPS), polianilina sulfonada/ poliestireno sulfonado/ poliestireno de alto impacto (SPAN/SPS/HIPS), e polianilina dopada com ácido p-tolueno sulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniTSA/SPS/HIPS) foram desenvolvidas usando o método de mistura química. As membranas foram caracterizadas utilizando as técnicas Análise termogravimétrica (TGA), Análise dinâmico Mecânica (DMA), e Microscopia Eletrônica de Varredura (MEV). Membranas foram submetidas a curvas corrente-potencial e ensaios de eletrodiálise em soluções de NaCl e KCl, a fim de determinar o transporte iônico através das mesmas. Os resultados foram comparados com uma membrana comercial Selemion CMT. A extração percentual média para íons de Na+ obtidos pelas membranas desenvolvidas foi superior a 20%. / Nowadays the concern with the reduction of industrial pollution has motivated researchers to found out new technologies for treatment of industrial waste. The clean technologies, as electrodialysis, are capable of treating some these residues, as for example the galvanoplasty’s waste, minimizing the impacts that would happen to them if they were discarded directly on the environment. The main component of this technique is the membrane on which occurs the ions removal stage of the solution. The membranes are imported and expensive what justifies the development of efficient and accessible membranes. In this sense, in the present work membranes of sulfonated polystyrene / high impact polystyrene (SPS/HIPS), polyaniline doped with camphorsulfonic acid / sulfonated polystyrene / high impact polystyrene (PAniCSA/SPS/HIPS), sulfonated polyaniline/ sulfonated polystyrene / high impact polystyrene (SPAN/SPS/HIPS), and polyaniline doped with p-toluenesulfonic acid / sulfonated polystyrene / high impact polystyrene (PAniTSA/SPS/HIPS) were developed using chemical mixture method. Membranes were characterized by Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Dynamic Mechanical Analysis (DMA) and Scanning Electronic Microscopy (SEM). Membranes were submitted to current-voltage curves and electrodialysis experiments with NaCl and KCl solutions, in order to determine ionic transport through them. Results were compared with a commercial membrane, Selemion CMT. The average percent extraction for Na+ ions obtained by membranes developed were beyond 20%.

Atualmente, a preocupação com a redução da poluição industrial tem motivado os pesquisadores na busca de novas tecnologias para o tratamento de resíduos industriais. Tecnologias limpas, como a eletrodiálise, são capazes de tratar alguns destes resíduos, como por exemplo o efluente da indústria de galvanoplastia, minimizando os impactos que ocorreriam caso eles fossem descartados diretamente no meio ambiente. O componente principal desta técnica é a membrana na qual ocorre a etapa de retirada dos íons da solução. Atualmente estas membranas são importadas e caras, o que justifica o desenvolvimento de membranas eficientes e acessíveis. Neste sentido, no presente trabalho membranas de poliestireno sulfonado/ poliestireno de alto impacto (SPS/HIPS), polianilina dopada com ácido canforsulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniCSA/SPS/HIPS), polianilina sulfonada/ poliestireno sulfonado/ poliestireno de alto impacto (SPAN/SPS/HIPS), e polianilina dopada com ácido p-tolueno sulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniTSA/SPS/HIPS) foram desenvolvidas usando o método de mistura química. As membranas foram caracterizadas utilizando as técnicas Análise termogravimétrica (TGA), Análise dinâmico Mecânica (DMA), e Microscopia Eletrônica de Varredura (MEV). Membranas foram submetidas a curvas corrente-potencial e ensaios de eletrodiálise em soluções de NaCl e KCl, a fim de determinar o transporte iônico através das mesmas. Os resultados foram comparados com uma membrana comercial Selemion CMT. A extração percentual média para íons de Na+ obtidos pelas membranas desenvolvidas foi superior a 20%. / Nowadays the concern with the reduction of industrial pollution has motivated researchers to found out new technologies for treatment of industrial waste. The clean technologies, as electrodialysis, are capable of treating some these residues, as for example the galvanoplasty’s waste, minimizing the impacts that would happen to them if they were discarded directly on the environment. The main component of this technique is the membrane on which occurs the ions removal stage of the solution. The membranes are imported and expensive what justifies the development of efficient and accessible membranes. In this sense, in the present work membranes of sulfonated polystyrene / high impact polystyrene (SPS/HIPS), polyaniline doped with camphorsulfonic acid / sulfonated polystyrene / high impact polystyrene (PAniCSA/SPS/HIPS), sulfonated polyaniline/ sulfonated polystyrene / high impact polystyrene (SPAN/SPS/HIPS), and polyaniline doped with p-toluenesulfonic acid / sulfonated polystyrene / high impact polystyrene (PAniTSA/SPS/HIPS) were developed using chemical mixture method. Membranes were characterized by Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Dynamic Mechanical Analysis (DMA) and Scanning Electronic Microscopy (SEM). Membranes were submitted to current-voltage curves and electrodialysis experiments with NaCl and KCl solutions, in order to determine ionic transport through them. Results were compared with a commercial membrane, Selemion CMT. The average percent extraction for Na+ ions obtained by membranes developed were beyond 20%.

High resolution solid state 1H NMR is used to investigate proton mobility of Nafion, Sulfonated Polyether Ether Ketones(S-PEEK) and their composites, which provides better understanding of their proton conductivities. Proton exchange between sulfonic acid groups and water was observed in these materials. The proton mobility is dependent on both the temperature and the water content. Variable temperature experiments were used to determine the activation energy for proton transportation which generally increases with decrease in hydration level. The preparation of Nafion/SiO2 composites can cause large difference in proton diffusion coefficients and proton conductivities in dried states. This indicates that the amount of dopants needs to be optimized to minimize the blocking of proton diffusion pathways by dopant particles. Detailed information on the control of surface hydroxyl groups in Nafion/SiO2 is obtained through the combination of 29Si and 1H NMR. Although hydrated Nafion/ZrP composites show reduced proton activation energy, they present lower proton conductivity at 35°C than unmodified Nafion. For composites dried at 160°C, both the conversion of monohydrogen phosphate into pyrophosphate and the protonation of monohydrogen phosphate have been observed, which could be one of reasons for the decreased proton conductivity after rehydration. Under high humidification, a single or multiple sulfonic acid proton environments was observed in S-PEEKs, which explains the small proton conductivity difference between some of S-PEEKs. However, the observed conductivity difference for S-PEEKs cast from different solvents was attributed to distinct mobilities of polymer chains. In the crosslinked S-PEEK, not all the crosslinkers of ethylene glycol are fully crosslinked. Proton exchange between residual sulfonic acid and hydroxyls of the crosslinker was observed, which is the primary reason that the crosslinked S-PEEK, with very low residual degree of sulfonation (13 %), still shows proton conductivity comparable to those of S-PEEKs. / Thesis / Doctor of Philosophy (PhD)

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