• Macromolecular Research
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• v.14 no.4
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• pp.449-455
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• 2006

Ionic cluster mimic, polymer electrolyte membranes were prepared using polymer composites of crosslinked poly(vinyl alcohol) (PVA) with sulfated-${\beta}$-cyclodextrins (${\beta}-CDSO_3H$) or phosphated-${\beta}$-cyclodextrins (${\beta}-CDPO(OH)_2$). When Nafion, developed for a fuel cell using low temperature, polymer electrolyte membranes, is used in a direct methanol fuel cell, it has a methanol crossover problem. The ionic inverted micellar structure formed by micro-segregation in Nafion, known as ionic cluster, is distorted in methanol aqueous solution, resulting in the significant transport of methanol through the membrane. While the ionic structure formed by the ionic sites in either ${\beta}-CDSO_3H$ or ${\beta}-CDPO(OH)_2$ in this composite membrane is maintained in methanol solution, it is expected to reduce methanol transport. Proton conductivity was found to increase in PVA membranes upon addition of ionized cyclodextrins. Methanol permeability through the PVA composite membrane containing cyclodextrins was lower than that of Nafion. It is thus concluded that the structure and fixation of ionic clusters are significant barriers to methanol crossover in direct methanol fuel cells.

• Journal of the Semiconductor & Display Technology
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• v.8 no.2
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• pp.49-53
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• 2009

The oxygen barrier films were formed on poly(ethylene terephthalate) (PET) substrate by a sol-gel process using 3-aminoproprytrimethoxysilane (APTMOS). The effects of solvent type, coating times and incorporation of fumed silica on oxygen permeability coefficient were investigated. The APTMOS coating film prepared from methanol as a solvent exhibited higher oxygen barrier properties than that using THF. The oxygen permeability coefficient of coated film with APTMOS/methanol by coating 7 times was measured to be $2.28{\times}10^{-6}$, while that of PET film was $1.16{\times}10^{-4}$ GPU. The addition of fumed silica does not affect the oxygen barrier properties. It may be explained that silica particles disrupt chain packing, which leads to an increase in free volume for permeation.

• Macromolecular Research
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• v.17 no.10
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• pp.729-733
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• 2009

Solution casting films of sulfonated poly[styrene-b-(ethylene-r-butylene)-b-styrene] copolymer (sSEBS)-based composite membranes that contained different amounts of organic, nanorod-shaped polyrotaxane were annealed at various temperatures for 1 h. The films' properties were characterized with respect to their use as polymer electrolyte membranes in direct methanol fuel cells (DMFCs). Different aspect ratios of polyrotaxane were prepared using the inclusion-complex reaction between $\alpha$-cyclodextrin and poly(ethylene glycol). The presence of the organic polyrotaxane inside the membrane changed the morphology during the membrane preparation and reduced the transport of methanol. The conductivity and methanol permeability of the composite membranes decreased with increasing polyrotaxane content, while the annealing temperature increased. All of the sSEBS-based, polyrotaxane composite membranes annealed at $140^{\circ}C$ showed a higher selectivity parameter, suggesting their potential usage for DMFCs.

• Macromolecular Research
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• v.14 no.2
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• pp.214-219
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• 2006

Cast Nafion-based composite membranes containing different amounts of organic, nanorod-shaped polyrotaxane were prepared and characterized, with the aim of improving the properties of polymer electrolyte membranes for direct methanol fuel cell applications. Polyrotaxane was prepared using the inclusion-complex reaction between ${\alpha}$-cyclodextrin and poly(ethylene glycol) (PEG) of different molecular weights. The addition of polyrotaxane to Nafion changed the morphology and reduced the crystallinity. The conductivity of the composite membranes increased with increasing polyrotaxane content up to 5 wt%, but then decreased at higher polyrotaxane contents. Well-dispersed, organic polyrotaxane inside the membrane can provide a tortuous path for the transport of methanol, as the methanol permeability depends on the aspect ratio of polyrotaxane, which is controlled by the molecular weight of PEG. All of the Nafion-based, polyrotaxane composite membranes showed a higher selectivity parameter than the commercial Nafion films did.

• Polymer(Korea)
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• v.34 no.6
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• pp.540-546
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• 2010

In this manuscript, in order to reduce methanol permeability and, at the same time, to increase proton conductivity THS-PSA containing silica compound, responsible for methanol permeability reduction, and sulfonic acid, responsible for proton conductivity enhancement, was applied onto PVA/PSSA-MA membranes. And in order to improve durability, the resulting membranes, PVA/PSSAMA/THS-PSA, were exposed to 500ppm F2 gas at varying reaction times. The surface-fluorinated membranes were characterized through the measurement of contact angles, thermo-gravimetric analysis, and X-ray photoelectron spectroscopy to observe the physico-chemical changes. For the evaluation of the electro-chemical changes in the resulting membranes, its water contents, ion exchange capacity, proton conductivity, and methanol permeability were measured and then compared with the commercial membrane, Nafion 115. Finally, the membran electrode assembly(MEA) was prepared and the cell voltage against the current density was measured. As fluorination time increased, the contents of F2 increased up to maximum 4.3% and to depth of 50 nm. At 60 min of fluorination, the proton conductivity was 0.036 S/cm, larger than Nafion 115 at 0.024 S/cm, and the methanol permeability was $9.26E-08cm^2/s$, less than Nafion 115 at $1.17E-06cm^2/s$.

• Proceedings of the Membrane Society of Korea Conference
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• 2003.05a
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• pp.61-63
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• 2003

• Journal of the Korean Electrochemical Society
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• v.12 no.3
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• pp.219-233
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• 2009

Mobile devices in the next generation such as camera, cell phone, network, Note PC, etc. require higher power and energy sources due to convergences of various functions. Direct methanol fuel cell (DMFC) has been focused as an attractive power source, but there are critical issues involved in its commercialization with regard to the core technologies of materials, components, and system. The requirements of key technologies are differentiated from applications and fuel supply methods. Here, the roles of the proton-conducting membrane are discussed and the current status of DMFC systems is discussed in terms of proton conductivity, methanol permeability, and water management. Materials such as perfluorinated and partially fluorinated membranes, hydrocarbon membranes, composite membranes, and other modified ionomers have been studied. These would explain the critical issues of DMFC and the role of membranes for commercialization.

• Korean Membrane Journal
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• v.5 no.1
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• pp.18-24
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• 2003

In order to improve the mechanical properties of the sulfonated polysulfone (SPSf) membranes previously synthesized in our laboratory, poly(vinyl alcohol) (PVA) was blended which is well known as the excellent physical and chemical properties. The resulting membranes blended with several molecular weight of PVA varying from 13,000 to 124,000 have been characterized to investigate the effect of PVA molecular weight in terms of ion conductivities, methanol permeabilities, water contents and ion exchange capacities for both heat treated and untreated membranes at 150$^{\circ}C$. The proton conductivity is decreased as the molecular weight of PVA increases. The plain SPSf-6.0 showed the proton conductivity of 0.078 S/cm whereas the blended membrane with M.W. 31,000 PVA indicated 0.04 S/cm. For methanol permeabilities, when PVA is added to SPAf-6.0, methanol crossover is increased because of the gain of the hydrophilicity from 3.4 to 6.5${\times}$10$\^$-6/ $\textrm{cm}^2$/s. For the annealed blended membranes (with M.W. 31,000 PVA), both the methanol corssover and proton conductivity showed very consistent values, about 2.3${\times}$10$\^$-6/ $\textrm{cm}^2$/s and 0.036 S/cm, respectively.

• Proceedings of the Membrane Society of Korea Conference
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• 2003.11a
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• pp.61-63
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• 2003

A major research objective related to proton exchange membrane(PEM) for DMFC is to achieve high proton conductivity over 10$^{-2}$ S/cm, high hydrolytic stability and low methanol permeability with low cost base materials. for the purpose, a lot of thermoplastic polymers such as polysulfones, polyethersulfone, polyetherketones, polyimides, polyoxadiazole, polyphosphazene and polybenzimidazol have been investigated. Amongst those polymers, polyimides have been suggested as a potential PEM due to their excellent thermal, chemical stability and good mechanical properties. Generally, polyimides are synthesized by polycondensation with numerious diamines and dianhydriedes. In our study, polyimide was prepared using non-sulfonated diamine, sulfonated diamine directly synthesized by fuming sulfuric acid, and naphthalenic dianhydride to improve the hydrolysis stability under acidic condition. Through monomer sulfonation-subsequent polymerization method, the high proton conducting capability and the desired sulfonation level were effectively controlled at the same time. To reduce severe methanol transport through the membrane, the chemical crosslinking among polymer chains was introduced using various crosslinking agents with different chain lengths. The crosslinked sulfonated polyimide membranes showed high proton conductivity up to 8.09$\times$10$^{-2}$ S/cm and from crosslinking effect methanol transport through the membranes was considerably reduced as compared with unmodified membranes. For increase of chain length of crosslinker, methanol permeability was adversely reduced to 10$^{-8}$ $\textrm{cm}^2$/s due to decrease of IEC and increase of crosslinking desity.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.1
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• pp.42-50
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• 2011

The Montmorillonite (MMT) in the polymer matrix is expected to reduce methanol permeability due to the tortous path formed by dispersed silicate layers. However, the polymer composite membranes containing non-proton conducting inorganic particle tend to show low proton conductivity. To solve this problem, we used an ion exchange method to prepare functionalized MMT with various silane coupling agents. The modified MMT was randomly dispersed in sulfonated poly (arylene ether sulfone) (SPAES) matrix to prepare SPAES/modified MMT composite membranes. The performances of hybrid membranes for DMFCs application were investigated. The SPAES/modified composite membrane showed increased proton conductivity compared with the non-modified MMT composite membrane. However, the methanol permeability of the SPAES/modified membrane was higher than that of the non-modified MMT.