• Macromolecular Research
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• v.13 no.6
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• pp.514-520
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• 2005

Composite membranes of Nafion and sulfonated poly(arylene ether sulfone) were prepared. Sulfonated poly(arylene ether sulfone)s with different degrees of sulfonation were blended with Nafion to reduce the methanol crossover. The morphology, proton conductivity and methanol permeability of the resulting composite membranes were investigated by SEM, EDAX, AC impedance spectroscopy and permeability measuring instrument. The cross­sections of the composite membranes showed a phase separated morphology. The morphology and phase separation mechanism could be controlled by varying the blend ratio and the degree of sulfonation of poly(arylene ether sulfone). These complex morphologies can be applied for reducing methanol crossover. The methanol permeability and proton conductivity of the composite membranes were lower than those of Nafion 117 membrane since the development of an ionic pathway in the blend membrane was more difficult than that in Nafion itself.

• Macromolecular Research
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• v.15 no.2
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• pp.160-166
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• 2007

Novel multiblock copolymers, based on segmented sulfonated hydrophilic-hydrophobic blocks, were synthesized and investigated for their application as proton exchange membranes. A series of segmented sulfonated poly(arylene ether sulfone)-b-polyimide multiblock copolymers, with various block lengths, were synthesized via the coupling reaction between the terminal amine moieties on the hydrophilic blocks and naphthalene anhydride functionalized hydrophobic blocks. Successful imidization reactions required a mixed solvent system, comprised of NMP and m-cresol, in the presence of catalysts. Proton conductivity measurements revealed that the proton conductivity improved with increasing hydrophilic and hydrophobic block lengths. The morphological structure of the multiblock copolymers was investigated using tapping mode atomic force microscopy (TM-AFM). The AFM images of the copolymers demonstrated well-defined nanophase separated morphologies, with the changes in the block length having a pronounced effect on the phase separated morphologies of the system. The self diffusion coefficient of water, as measured by $^1H$ NMR, provided a better understanding of the transport process. Thus, the block copolymers showed higher values than Nafion, and comparable proton conductivities in liquid water, as well as under partially hydrated conditions at $80^{\circ}C$. The new materials are strong candidates for use in PEM systems.

• Membrane Journal
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• v.22 no.3
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• pp.191-200
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• 2012

New composite membranes were manufactured by impregnating post-sulfonated poly(arylene ether sulfone)s containing perfluorocyclobutane (PFCB) groups into porous polytetrafluoroethylene (PTFE) films. Two kinds of post-sulfonated poly(arylene ether sulfone)s with two different monomer ratios (sulfonable biphenylene monomer : non-sulfonable sulfonyl monomer = 6 : 4, 4 : 6) were first prepared through three synthetic steps: synthesis of trifluorovinylether-terminated monomers, thermal cycloaddition polymerization and post-sulfonation using chlorosulfonic acid (CSA). The composite membranes were then prepared by adjusting the concentrations (5~20 wt%) of the resulting copolymers impregnated in the PTFE films. The water uptake, ion exchange capacity (IEC) and ion conductivity of the composite membranes were characterized and compared with their unreinforced dense membranes and Nafion. All the synthesized compounds, monomers and polymers were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR and the composite membranes were observed with scanning electron micrographs (SEM).

• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.75-80
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• 2015

Multi-block sulfonated poly(arylene ether sulfone) (SPAES) copolymer was synthesized via nucleophilic aromatic substitution reaction for proton exchange membrane fuel cell application. After synthesizing the hydrophilic and hydrophobic precursor oligomers having different end-groups (F-terminated or OH-terminated), the effect of end group on the molecular weight was investigated. Hydrophilic oligomers with hydroquinone showed better performance as fuel cell membranes. SPAES membranes showed comparable proton conductivity to that of Nafion at $80^{\circ}C$ and above 70% RH. In particular, SPAES 9 with hydroquinone showed higher proton conductivity than SPAES 10 in the whole RH range studied. Increased local concentration of sulfonic acids within hydrophilic block might develop the hydrophilic-hydrophobic phase separation in the block copolymers.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.426-426
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• 2008

Blend membranes were prepared by solvent casting method from sulfonated fluorinated poly(arylene ether)s (SDFF) and chemically modified polyvinylidene fluoride (mPVdF) in isopropanol and were evaluated as proton exchange membrane electrolytes in PEMFC. $^1H$-NMR, differential scanning calorimeter and thermogravimetric analysis was utilized to characterize the structure of the blend membranes (SDFF/mPVDF) and effects of mPVDF content on the properties of the membrane such as water uptake and proton conductivity were also investigated.

• Proceedings of the Membrane Society of Korea Conference
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• 2004.11a
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• pp.165-166
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• 2004

• Proceedings of the Membrane Society of Korea Conference
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• 2008.05a
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• pp.163-163
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• 2008

• Korean Chemical Engineering Research
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• v.53 no.6
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• pp.690-694
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• 2015

Recently, direct formic acid fuel cells (DFAFC) among direct liquid fuel cells is studied actively. Economical hydrocarbon membranes alternative to fluorinated membranes for DFAFC's membrane are receiving attention. In this study, characteristics of sulfonated poly(ether ether ketone, sPEEK) and sulfonated poly(arylene ether sulfone, PAES) membranes were compared with Nafion membrane at DFAFC operation condition. Formic acid crossover current density of hydrocarbon membranes were lower than that of Nafion 211 fluorinated membrane. I-V performance of sPEEK MEA(Membrane and Electrode Assembly) was similar to that of Nafion 211 MEA due to similar membrane resistance each other. sPEEK MEA with low formic acid crossover showed higher stability compared with Nafion 211 MEA.

• Transactions of the Korean hydrogen and new energy society
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• v.29 no.4
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• pp.331-338
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• 2018

In this study, sulfonated PAES block copolymers have been synthesized via nucleophilic substitution reaction. Hydrophobic oligomer was prepared using 2,6-dihydroxynaphthalene and bis(4-chlorophenyl) sulfone, whereas hydrophilic oligomer was prepared using sulfonated bis(4-chlorophenyl) sulfone and bis(4-hydroxyphenyl) sulfone. The chemical structure of polymers was analyzed by $^1H$ NMR, FT-IR and GPC. The thermal properties of polymers were measured by TGA and DSC. The oxidative stability of membranes was investigated by Fenton's test. Furthermore, the proton conductivity of membrane was found to be 26 mS/cm at $90^{\circ}C$. All physiochemical properties suggest that fabricated membrane have a great potential for applications in PEMFC.

• Membrane Journal
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• v.21 no.1
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• pp.1-12
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• 2011

Partially fluorinated poly(arylene ether sulfone) block ionomer membranes with different branch degree for fuel cell applications were investigated. A sulfonable monomer, a non-sulfonable monomer and a trifunctional branching agent were synthesized and the sulfonable monomer was oligomerized to obtain block structures. The oligomer was then further polymerized with the non-sulfonable monomer and the branching agent. The mole ratio of oligomer : non-sulfonable monomer was fixed at 4:6 and the content of the branching agent was varied from 0 to 2 mol% (BBC-40Bx). Post-sulfonation of BBC-40Bx was carried out using chlorosulfonic acid (CSA) (SBBC-40Bx). All the synthesized compounds were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR. It was confirmed that the ion exchange capacity (IEC), water uptake and ion conductivity of SBBC-40Bx increased with the increment of branching agent content.