This study deals with poly(ether block amide) (PEBA) (type 2533) membranes for gas separation. A new method was developed to prepare flat thin film PEBA membranes by spontaneous spreading of a solution of the block copolymer on water surface. The membrane formation is featured with simultaneous solvent evaporation and solvent exchange with the support liquid, i.e. water. The formation of a uniform and defect-free membrane was affected by the solvent system, polymer concentration in the casting solution and temperature. Propylene separation from nitrogen, which is relevant to the recovery of propylene from the de-gassing off-gas during polypropylene manufacturing, was carried out using flat PEBA composite membranes formed by laminating the aforementioned PEBA on a microporous substrate. The propylene permeance was affected by the presence of nitrogen, and vice versa, due to interactions between the permeating components. Semi-empirical correlations were developed to relate the permeance of a component in the mixture to the pressures and compositions of the gas on both sides of the membrane, and the separation performance at different operating conditions was analyzed in terms of product purity, recovery and productivity on the basis of a cross flow model. To further understand gas permeation behavior and transport mechanism in the membranes, sorption, diffusion, and permeation of three olefins (i.e., C2H4, C3H6, and C4H8) in dense PEBA membranes were investigated. The relative contribution of solubility and diffusivity to the preferential permeability of olefins over nitrogen was elucidated. It was revealed that the favorable olefin/nitrogen permselectivity was primarily attributed to the solubility selectivity, whereas the diffusivity selectivity may affect the permselectivity negatively or positively, depending on the operating temperature and pressure. At a given temperature, the pressure dependence of solubility and permeability could be described empirically by an exponential function. The limiting solubility at infinite dilution was correlated with the reduced temperature of the permeant. The separation of volatile organic compounds (VOCs), which are more condensable than olefin gases, from nitrogen stream by the thin film PEBA composite membranes for potential use in gasoline or other organic vapour emission control was also studied. The membranes exhibited good separation performance for both binary VOC/N2 and multi-component VOCs/N2 gas mixtures. The permeance of N2 in the VOC/N2 mixtures was shown to be higher than pure N2 permeance due to membrane swelling induced by the VOCs dissolved in the membrane. The effects of feed VOC concentration, temperature, stage cut, and permeate pressure on the separation performance were investigated. Additionally, hollow fiber PEBA/polysulfone composite membranes were prepared by the dip coating technique. The effects of parameters involved in the procedure of polysulfone hollow fiber spinning and PEBA layer deposition on the permselectivity of the resulting composite membranes were investigated. Lab scale PEBA hollow fiber membrane modules were assembled and tested for CO2/N2 separation with various flow configurations using a simulated flue gas (15.3% carbon dioxide, balance N2) as the feed. The shell side feed with counter-current flow was shown to perform better than other configurations over a wide range of stage cuts in terms of product purity, recovery and productivity.

The current reverse osmosis desalination membrane market is dominated by aromatic polyamide thin film composite (TFC) membranes. However, these polyamide membranes suffer from poor resistance to continual exposure to oxidizing agents such as chlorine in desalination applications. To overcome these problems, we have synthesized and characterized a new generation of materials, disulfonated poly(arylene ether sulfone) (BPS) random copolymer, for desalination membranes. A key technical feature of these new materials is their high tolerance to chlorine in feed water and their excellent reproducibility in synthesis. In this study, water and sodium chloride solubility, diffusivity and permeability in BPS copolymers were measured for both acid and salt form samples at sulfonation levels from 20 to 40 mol percent. The hydrophilicity of these materials, based on water uptake, increased significantly as sulfonation level increased. The water and salt diffusivity and permeability were correlated with water uptake, consistent with expectations from free volume theory. In addition, a tradeoff was observed between water/salt solubility, diffusivity, and permeability selectivity and water solubility, diffusivity and permeability, respectively. The influence of cation form and degree of sulfonation on free volume, as probed via positron annihilation lifetime spectroscopy (PALS), was determined in BPS random copolymers in both the dry and hydrated states. PALS-based free volume data for hydrated polymers were correlated with water and salt transport properties. The influence of processing history on transport properties of BPS films was also studied. Potassium form BPS films having a 32 mol% sulfonation level were acidified using solid state and solution routes. Additionally, several films were subjected to various thermal treatments in the solid state. The influence of acidification, thermal treatment, and counter-ion form on transport properties was investigated. Finally, the influence of synthesis methods of polyamide TFC membranes from m-phenylenediamine (MPD) and trimesoyl chloride (TMC) via interfacial polymerization on transport properties is reported. Then, a disulfonated diamine monomer (S-BAPS) was used instead of MPD to prepare TFC membranes. The resulting membranes exhibited reduced chlorine tolerance than those prepared from MPD. However, introduction of S-BAPS to the MPD/TMC polymerization system increased the fouling resistance of the resulting polyamide TFC membranes. / text

Membrane processes have received growing attention due to their low energy consumption and ease of operation. Thin-film composite reverse osmosis membranes based on polyamides are the most widely applied commercial membranes, because of their high flux and selectivity. However, their application for gas separation processes is still limited. This is the due to the presence of defects in the membrane when in the dry state. Traditionally, thin-film composite membranes are made by interfacial polymerization between a polar (aqueous) phase and a non-polar (organic) phase. The most commonly applied thin-film composite membranes are made by dissolving m-phenylene diamine in the aqueous phase and trimesoyl chloride in the organic phase. This work investigated the possibility of fabricating thin-film composite membranes when an aliphatic alcohol (methanol, ethanol or isopropanol) is used as the polar phase. This is further extended to examining the ability of a PDMS coating to plug the defects in such layers. The effects of temperature and support type on the membrane performance were also studied. Solubility tests were conducted to determine the solubility limit of commercial and in-house fabricated amine monomers in water, methanol, ethanol and isopropanol. Water-insoluble monomers were found to be soluble in ethanol and methanol. Gas permeation tests were conducted on membranes made using water, methanol, ethanol and isopropanol as the polar phase. The results showed that the membranes produced by aliphatic alcohols had higher selectivities. The highest H2/CO2 selectivity of ~ 26 was observed in the ethanol-based membranes when they were coated with PDMS and tested at 80 C. It was confirmed that PDMS is able to plug the defects in the membrane. Membranes made on the polysulfone support were found to have higher permeance and comparable selectivity relative to the membranes made on the polyacrylonitrile supports. It was also found that a change in the polar phase solvent is able to alter the morphology of the membranes. SEM micrographs showed clear differences in the surface structure of each membrane. The average thickness values obtained from ellipsometry measurements showed a correlation with the interface miscibility. The thickest membrane corresponded to the most miscible interface (IPA/Isopar).

No description available.

Membrane technology has been used in water purification for decades. However, membrane fouling remains a limiting factor. One way to control fouling is through surface modification. Several studies report that increasing surface hydrophilicity can reduce membrane fouling. Surface modification via physical coating (i.e., thin-film composite membrane) was explored in this research to prevent membrane fouling. Before making thin-film composite membranes, it was important to study structure/property relations in a series of potential coating materials. This research aims to contribute to a better fundamental understanding of the structure/property relations which govern water transport, rejection of model foulants (i.e., emulsified oil droplet or protein), and fouling characteristics in hydrogels based on poly(ethylene glycol) diacrylate (PEGDA) and N-vinyl-2-pyrrolidone (NVP). Crosslinked poly(ethylene glycol) (PEG) free-standing films were prepared by UV-induced photopolymerization of PEGDA crosslinker in the presence of varying amounts of water or monofunctional poly(ethylene glycol) acrylate (PEGA). The crosslinked PEGDA films exhibited polymerization induced phase separation (PIPS) when the water content of the prepolymerization mixture was greater than 60 wt%. Visible light absorbance measurements, water uptake, water permeability, and salt kinetic desorption experiments were used to characterize the structure of these phase-separated, crosslinked hydrogels. The films with PIPS exhibited a porous morphology in cryogenic scanning electron microscope (CryoSEM) studies. Dead-end filtration experiments using deionized water and bovine serum albumin (BSA) solutions were performed to explore the fundamental transport and fouling properties of these materials. The total flux of pure water through the films after prior exposure to BSA solution was nearly equal to that of the as-prepared material, indicating that these PEGDA films resist fouling by BSA under the conditions studied. Crosslinked NVP free-standing films were prepared by UV-induced photopolymerization in the presence of water, with NVP as the monomer and N,N’-methylenebisacrylamide (MBAA) as the crosslinker. A series of crosslinked films were polymerized at various prepolymerization water contents, NVP/MBAA ratios and at various levels of UV light intensity in the polymerization. Like PEGDA, the NVP films also underwent phase-separation during polymerization. The influence of monomer/ crosslinker ratio, prepolymerization water content, and UV intensities on membrane morphology and water transport was characterized with CryoSEM, bio-atomic force microscope (Bio-AFM) and dead-end filtration. Molecular weight cutoff (MWCO) measurements were used to characterize the sieving property of crosslinked NVP films polymerized at different UV intensities. UV intensity was found to have an impact on the interconnectivity of crosslinked membranes. Finally, tests of fouling resistance to protein solution (bovine serum albumin) and oily water emulsion were performed. The NVP crosslinked films had good protein and oily water fouling resistance. Overall, both crosslinked PEGDA and NVP films exhibit fouling resistance to oily water emulsions or protein solution. NVP films had more porous structure and higher water permeability than did PEGDA films, while the more compact structure of PEGDA films led to better rejection of model foulants (e.g., protein) than in NVP films. Based on different applications (e.g., oil/water separation, protein filtration), different coating materials must be chosen according to the membrane morphology, transport property, and rejection of model foulants to achieve the highest water flux and foulant rejection in membranes used for water purification. / text

Um grande obstáculo a ser vencido para que se tenha uma maior utilização da tecnologia de membranas na purificação de líquidos é o fenômeno do fouling. Como consequência, o desenvolvimento de membranas menos propensas ao fouling é hoje objeto de inúmeras pesquisas. Dentre os processos estudados, tem-se o desenvolvimento de membranas de filme fino composto, que possui como vantagem a possibilidade de se melhorar cada camada de maneira independente, de forma a se aperfeiçoar o desempenho da membrana como um todo. O projeto de pesquisa foi desenvolvido no laboratório do Centro Internacional de Referência em Reúso de Água (CIRRA/IRCWR), uma entidade sem fins lucrativos, vinculado ao Departamento de Engenharia Hidráulica e Ambiental da Escola Politécnica da Universidade de São Paulo (USP). Este teve como objetivo a síntese e a caracterização de membranas de filme fino composto de polissulfona e quitosana reticulada com glutaraldeído. Embora o objetivo principal desse trabalho tenha sido o desenvolvimento de membranas menos propensa ao fouling, a susceptibilidade ao fouling das membranas produzidas foi avaliada de maneira indireta, através da avaliação de propriedades como hidrofilicidade e rugosidade da superfície. Membranas de ultrafiltração a base de polissulfona (PSF) foram produzidas, através do método de separação de fases via imersão-precipitação, para serem usadas como suporte poroso para a camada de quitosana. Nessa etapa, a influência da concentração de PSF na solução polimérica; da temperatura de síntese; da umidade relativa do ar; e do suporte (não-tecido) nas características da membrana foram estudadas. O efeito da aplicação de uma camada de álcool polivinílico, reticulada com glutaraldeído, entre as camadas de PSF e quitosana, como forma de melhorar a estabilidade estrutural da membrana, foi avaliado. Adicionalmente, analisou-se a influência da introdução do glutaraldeído como agente reticulante na solução de quitosana na seletividade; na taxa de permeação; na estabilidade química; e na toxicidade da membrana. Os resultados obtidos mostraram que o aumento da concentração de PSF na solução polimérica, a diminuição da temperatura de síntese e o aumento da umidade do ar levaram à formação de membranas menos porosas. Os suportes de poliéster avaliados, CU414 e CU424 (Crane Nonwovens), embora apresentem características adequadas à produção de membranas, não se mostraram adequados para a síntese de membranas de PSF nas condições avaliadas devido a sua alta porosidade. A solução de reticulação da camada de álcool polivinílico (PVA), composta de glutaraldeído em solução aquosa de acetona, atacou quimicamente o suporte de poliéster e a membrana de polissulfona, inviabilizando a aplicação da camada de PVA entre as camadas de PSF e quitosana. A introdução do glutaraldeído tornou a camada de quitosana menos rugosa e mais hidrofílica. Adicionalmente, o aumento da concentração de glutaraldeído na solução de quitosana levou a um decréscimo na permeabilidade da membrana, o qual foi atribuído à compactação da estrutura da membrana. A reticulação da quitosana com glutaraldeído não levou a uma melhora significativa da capacidade de separação das membranas. A rejeição de ions bivalentes (Mg2+ e SO4 2-) e monovalentes (Na+ e Cl-) não ultrapassou 25% e 12%, respectivamente. Análises de microscopia de eletrônica de varredura realizadas com as membranas reticuladas com glutaraldeído, antes e após sua imersão em solução de HCl, indicaram que a superfície das membranas reticuladas com 3% de glutaraldeído aparentemente não foi afetada pelo ácido, ao contrário das membranas reticuladas com 1% e 5% de glutaraldeído, que apresentaram aumento no tamanho de seus poros. Não foi observada toxicidade aguda e/ou crônica, em relação aos organismos teste Daphinia similis e Ceriodaphinia dubia, respectivamente, em amostras de água que permaneceram em contato com as membranas reticuladas com glutaraldeído. / A major obstacle to be overcome in order to have a greater use of membrane technology in liquids purification is the phenomenon of fouling. As a consequence, the development of membranes less prone to fouling is now the objective of numerous studies. Among the processes evaluated, the development of thin film composite membranes has been the focus of many researches since it is possible to improve each layer independently, in order to improve the membrane performance as a whole. This work aimed to study the synthesis and characterization of thin film composite chitosan, crosslinked with glutaraldehyde, and polysulfone (PSF) membranes. PSF ultrafiltration membranes were produced by phase inversion via immersion precipitation to be used as porous support for the chitosan layer. The influence of PSF concentration in the polymeric solution; temperature of synthesis; air humidity, and membrane nonwoven support, CU414 and CU424 (Crane Nonwovens), on the membrane characteristics and performance were studied. The effect polyvinyl alcohol (PVA), crosslinked with glutaraldehyde, between PSF and chitosan layers, on the cast membrane structural stability was investigated. The influence of glutaraldehyde as a chitosan crosslinking agent on membrane selectivity, permeability, chemical stability, and toxicity was also evaluated. The results showed that increasing PSF concentration, decreasing temperature and increasing air humidity resulted in less porous membranes. The support media used were not suitable for the production of PSF membranes under the conditions used in this work due to its high porosity. The solution used to crosslink the PVA layer, composed of glutaraldehyde in aqueous solution of acetone, attacked the support media and the PSF membrane, preventing the application of the PVA layer between the PSF and chitosan layers. The use of glutaraldehyde as a chitosan crosslinking agent made the membrane less rough and more hydrophilic. Additionally, increasing glutaraldehyde concentration in the chitosan solution led to a decrease in membrane permeability, which was attributed to a compaction of the membrane structure, leading to a decreased mobility of polymer chains and a decrease in the membrane void volume. Membranes separation capacity was evaluated using two different ionic solutions, magnesium sulphate (MgSO4 1,000 mg/L), and sodium chloride (NaCl 2,000 mg/L). Rejection of bivalent and monovalent ions did not exceed 25% and 12%, respectively. Scanning electron microscopy images showed that the membrane surface crosslinked with 3% glutaraldehyde apparently was not affected by immersion into HCl solution. However, the membranes crosslinked with 1% and 5% glutaraldehyde showed an increase in pore size after immersion, compared to the untreated membrane, suggesting an increased susceptibility to acid attack of the membrane. The potential for glutaraldehyde membrane releasing was evaluated through acute and chronic toxicity assays using Daphnia similis and Ceriodaphnia dubia, respectively. None of tested membranes induced acute or chronic toxicity to the water at which they remained in contact, under tested conditions.

Um grande obstáculo a ser vencido para que se tenha uma maior utilização da tecnologia de membranas na purificação de líquidos é o fenômeno do fouling. Como consequência, o desenvolvimento de membranas menos propensas ao fouling é hoje objeto de inúmeras pesquisas. Dentre os processos estudados, tem-se o desenvolvimento de membranas de filme fino composto, que possui como vantagem a possibilidade de se melhorar cada camada de maneira independente, de forma a se aperfeiçoar o desempenho da membrana como um todo. O projeto de pesquisa foi desenvolvido no laboratório do Centro Internacional de Referência em Reúso de Água (CIRRA/IRCWR), uma entidade sem fins lucrativos, vinculado ao Departamento de Engenharia Hidráulica e Ambiental da Escola Politécnica da Universidade de São Paulo (USP). Este teve como objetivo a síntese e a caracterização de membranas de filme fino composto de polissulfona e quitosana reticulada com glutaraldeído. Embora o objetivo principal desse trabalho tenha sido o desenvolvimento de membranas menos propensa ao fouling, a susceptibilidade ao fouling das membranas produzidas foi avaliada de maneira indireta, através da avaliação de propriedades como hidrofilicidade e rugosidade da superfície. Membranas de ultrafiltração a base de polissulfona (PSF) foram produzidas, através do método de separação de fases via imersão-precipitação, para serem usadas como suporte poroso para a camada de quitosana. Nessa etapa, a influência da concentração de PSF na solução polimérica; da temperatura de síntese; da umidade relativa do ar; e do suporte (não-tecido) nas características da membrana foram estudadas. O efeito da aplicação de uma camada de álcool polivinílico, reticulada com glutaraldeído, entre as camadas de PSF e quitosana, como forma de melhorar a estabilidade estrutural da membrana, foi avaliado. Adicionalmente, analisou-se a influência da introdução do glutaraldeído como agente reticulante na solução de quitosana na seletividade; na taxa de permeação; na estabilidade química; e na toxicidade da membrana. Os resultados obtidos mostraram que o aumento da concentração de PSF na solução polimérica, a diminuição da temperatura de síntese e o aumento da umidade do ar levaram à formação de membranas menos porosas. Os suportes de poliéster avaliados, CU414 e CU424 (Crane Nonwovens), embora apresentem características adequadas à produção de membranas, não se mostraram adequados para a síntese de membranas de PSF nas condições avaliadas devido a sua alta porosidade. A solução de reticulação da camada de álcool polivinílico (PVA), composta de glutaraldeído em solução aquosa de acetona, atacou quimicamente o suporte de poliéster e a membrana de polissulfona, inviabilizando a aplicação da camada de PVA entre as camadas de PSF e quitosana. A introdução do glutaraldeído tornou a camada de quitosana menos rugosa e mais hidrofílica. Adicionalmente, o aumento da concentração de glutaraldeído na solução de quitosana levou a um decréscimo na permeabilidade da membrana, o qual foi atribuído à compactação da estrutura da membrana. A reticulação da quitosana com glutaraldeído não levou a uma melhora significativa da capacidade de separação das membranas. A rejeição de ions bivalentes (Mg2+ e SO4 2-) e monovalentes (Na+ e Cl-) não ultrapassou 25% e 12%, respectivamente. Análises de microscopia de eletrônica de varredura realizadas com as membranas reticuladas com glutaraldeído, antes e após sua imersão em solução de HCl, indicaram que a superfície das membranas reticuladas com 3% de glutaraldeído aparentemente não foi afetada pelo ácido, ao contrário das membranas reticuladas com 1% e 5% de glutaraldeído, que apresentaram aumento no tamanho de seus poros. Não foi observada toxicidade aguda e/ou crônica, em relação aos organismos teste Daphinia similis e Ceriodaphinia dubia, respectivamente, em amostras de água que permaneceram em contato com as membranas reticuladas com glutaraldeído. / A major obstacle to be overcome in order to have a greater use of membrane technology in liquids purification is the phenomenon of fouling. As a consequence, the development of membranes less prone to fouling is now the objective of numerous studies. Among the processes evaluated, the development of thin film composite membranes has been the focus of many researches since it is possible to improve each layer independently, in order to improve the membrane performance as a whole. This work aimed to study the synthesis and characterization of thin film composite chitosan, crosslinked with glutaraldehyde, and polysulfone (PSF) membranes. PSF ultrafiltration membranes were produced by phase inversion via immersion precipitation to be used as porous support for the chitosan layer. The influence of PSF concentration in the polymeric solution; temperature of synthesis; air humidity, and membrane nonwoven support, CU414 and CU424 (Crane Nonwovens), on the membrane characteristics and performance were studied. The effect polyvinyl alcohol (PVA), crosslinked with glutaraldehyde, between PSF and chitosan layers, on the cast membrane structural stability was investigated. The influence of glutaraldehyde as a chitosan crosslinking agent on membrane selectivity, permeability, chemical stability, and toxicity was also evaluated. The results showed that increasing PSF concentration, decreasing temperature and increasing air humidity resulted in less porous membranes. The support media used were not suitable for the production of PSF membranes under the conditions used in this work due to its high porosity. The solution used to crosslink the PVA layer, composed of glutaraldehyde in aqueous solution of acetone, attacked the support media and the PSF membrane, preventing the application of the PVA layer between the PSF and chitosan layers. The use of glutaraldehyde as a chitosan crosslinking agent made the membrane less rough and more hydrophilic. Additionally, increasing glutaraldehyde concentration in the chitosan solution led to a decrease in membrane permeability, which was attributed to a compaction of the membrane structure, leading to a decreased mobility of polymer chains and a decrease in the membrane void volume. Membranes separation capacity was evaluated using two different ionic solutions, magnesium sulphate (MgSO4 1,000 mg/L), and sodium chloride (NaCl 2,000 mg/L). Rejection of bivalent and monovalent ions did not exceed 25% and 12%, respectively. Scanning electron microscopy images showed that the membrane surface crosslinked with 3% glutaraldehyde apparently was not affected by immersion into HCl solution. However, the membranes crosslinked with 1% and 5% glutaraldehyde showed an increase in pore size after immersion, compared to the untreated membrane, suggesting an increased susceptibility to acid attack of the membrane. The potential for glutaraldehyde membrane releasing was evaluated through acute and chronic toxicity assays using Daphnia similis and Ceriodaphnia dubia, respectively. None of tested membranes induced acute or chronic toxicity to the water at which they remained in contact, under tested conditions.

Hydrogen is considered to be the most promising energy carrier of the 21st century due to its high energy density and sustainability. The chemical energy of hydrogen can be directly converted into electricity by means of electrochemical devices called fuel cells. Proton exchange membrane fuel cells (PEMFC) are the most preferred type of fuel cells due to their low operating temperatures enabling fast and easy start-ups and quick responses to load changes. One of the most important components of a PEMFC is the proton conducting membrane. The current membrane technology is based on perfluorosulfonic acid membranes and the most common one being Nafion. Although these membranes have good thermal and chemical stability, mechanical strength and high proton conductivities, they tend to dehydrate very fast at high temperatures and low relative humidity leading to poor fuel cell performances. Moreover, the high manufacturing cost of these membranes limits the mass-production of PEMFC&amp / #8217 / s in near future. The aim of this study is to develop alternative PEMFC membranes that have sufficient thermal and chemical stability, mechanical strength and comparable proton conductivity and fuel cell performances with Nafion membranes at relatively low cost. In this context, organic-inorganic composite membranes and blends were developed. A relatively cheap and commercially available polymer, polyether ether ketone, (PEEK), was chosen as the membrane matrix for its high thermal and mechanical stability and improvable proton conductivity via post-sulfonation. The proton conductivity of SPEEK membrane (at DS 68%) was 0.06 S/cm at 60&deg / C, and this conductivity was further increased to 0.13 S/cm with the introduction of zeolite beta crystals as inorganic fillers. The conductivity of a SPEEK blend (25wt% SPES-75wt% SPEEK) membrane was 0.08 S/cm at 90&deg / C. In PEMFC performance tests, 397 mA/cm2 was obtained for SPEEK membrane (DS 56%) at 0.6V for a H2/O2 PEMFC working at 1 atm and 80&deg / C. This result is promising when compared to the performance of Nafion 112&reg / of 660mA/cm2 under same conditions. These results are welcomed since the target for commercially viable alternate membranes are reached.

Intensive research on development of alternative low cost, high temperature membranes for proton exchange membrane (PEM) fuel cells is going on because of the well-known limitations of industry standard perfluoro-sulfonic acid (PFSA) membranes. To overcome these limitations such as the decrease in performance at high temperatures (&gt / 80 0C) and high cost, non-fluorinated aromatic hydrocarbon based polymers are attractive. The objective of this study is to develop alternative membranes that possess comparable properties with PFSA membranes at a lower cost. For this purpose post-sulfonation studies of commercially available engineering thermoplastics, polyether-ether ketone (PEEK) and polyether-sulfone (PES), were performed by using suitable sulfonating agents and conditions. Post sulfonated polymers were characterized with proton nuclear magnetic resonance spectroscopy (H+-NMR), sulfur elemental analysis and titration to calculate the degree of sulfonation (DS) values and with TGA and DSC for thermal stability and glass transition temperature (Tg). Chemical stabilities were evaluated by hydrogen v peroxide tests. Proton conductivities of sulfonated PEEK (SPEEK) measured by electrochemical impedance spectroscopy (EIS) were observed to increase linearly with degree of sulfonation (DS). However, above a certain DS SPEEK loses its mechanical stability significantly with excessive swelling which leads to deteriorations in mechanical stability. Therefore, DS of 50-70% were used for the fabrication of composite membranes. To improve mechanical stability, SPEEK polymers were blended with more stable polymers, polyether-sulfone (PES) or in its sulfonated form (SPES) or with polybenzimidazole (PBI). In addition, the composite approach, which involves the incorporation of various inorganic fillers such as zeolite beta, TiO2, montmorrilonite (MMT), heteropolyacids (HPA), was used for further improvement of proton conductivity. Among the composite membranes 20% TPA/SPEEK (DS=68) composites conductivity value exceeded that of Nafion&lsquo / s at room temperature. Effects of various parameters during the fabrication process such as the filler type and loading, DS of sulfonated polymer, casting solvents, and thermal and chemical treatment were also investigated and optimized. Various blend/composite membranes were fabricated with solvent casting method, and characterized for their proton conductivity, chemical/thermal stability and for evaluating their voltage/current performance at various temperatures in a single cell setup. Chemically and thermo-hydrolytically stable composite/blend membranes such as 25% tungstophosphoric acid (TPA)/PBI(5%)/SPEEK (DS=68) with good single cell performances at 800C were developed (~450 mA/cm2 at 0.5 V). The performance of the hydrolytically stable composite/blend membrane prepared with SPEEK (DS=59) / 5% PBI / and 10% TiO2 increased appreciably when the temperature was raised from 80 0C to 90 0C while the performance of Nafion decreases sharply after 80 0C. Methanol permeability studies were also performed for investigating the potential of fabricated blend/composite membranes for direct methanol fuel cell (DMFC) use. Selectivities (conductivity/methanol permeability) vi greater than Nafion 112 (S=7.3x107) for DMFC were observed for composite/blend membranes such as 10% TiO2/10% PES blend with SPEEK (DS=68) with a selectivity of 9.3x107. The factors that affect proton conductivity measurements were investigated and equivalent circuit analysis was performed with results obtained by electrochemical impedance spectroscopy (EIS). The choice of the conductivity cell (electrodes, cell geometry) and the method (2-probe vs 4-probe) were shown to affect the conductivity analysis. A systematic development and characterization route was established and it was shown that by optimizing proton conductivity and thermal/chemical stability with blending/composite approaches it is possible to produce novel high performance proton exchange membranes for fuel cell applications.

This dissertation presents the development of novel nano-composite membranes as introduction systems for mass spectrometers. These nano-composite membranes incorporate anodic aluminum oxide (AAO) membranes as templates that can be used by themselves or modified by a variety of chemical deposition processes. Two types of nano-composite membranes are presented. The first nano-composite membrane has carbon deposited within the pores of an AAO membrane. The second nano-composite membrane is made by coating an AAO membrane with a thin polymer film. The following chapters describe the transmission properties these nano-composite membranes and compare them to conventional mass spectrometry introduction systems. The nano- composite membranes were finally coupled to the inlet system of an underwater mass spectrometer revealing their utility in field deployments.