• Membrane Journal
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• v.27 no.5
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• pp.389-398
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• 2017

The most important characteristic of the polymer electrolyte membranes (PEMs) for fuel cells, the proton conducting ability is mainly influenced by the distribution and morphology of the water channels inside the PEMs. Non-perfluorinated hydrocarbon PEMs are known to have weaker water channels than perfluorinated PEM, Nafion, and thus relatively low proton conducting ability. In this study, we used a mesoscale simulation technique to observe the water channel formation and phase separation behavior of hydrocarbon PEM, sulfonated polyimides, under the humidification condition. It was observed that the water molecules were distributed evenly through the entire hydrophilic region, and clear water clusters were formed only in the sulfonated polyimide having high sulfonation degree. In addition, it was observed that sulfonated polyimides have a difficulty in forming water channel under the low hydrated condition. These results clearly support the theories of the formation of water channels in non-perfluorinated hydrocarbon PEMs, and also well explain the tendency of proton conducting abilities of sulfonated polyimides. Thus, it is confirmed that mesoscale simulation techniques can be very effective in analyzing phase separation behavior and water channel formation in PEMs for fuel cells and elucidating the ion conducting abilities.

• Applied Chemistry for Engineering
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• v.7 no.2
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• pp.215-220
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• 1996

Nine kinds of amphoteric surfactants were derived from 1-(2-hydroxyethyl)-2-undecyl-2-imidazoline. Their surface activities including surface tension and isoelectric points were measured in aqueous solution and critical micelle concentration(cmc) was also evaluated by the measurement of surface tension. From the measurement of surface tension, carboxylated amides revealed to be 26~40dyne/cm at $4.0{\times}10^{-4}{\sim}1.0{\times}10^{-3}mol/{\ell}$, sulfonated or sulfated imidazolines, 30~35 dyne/cm at $1.5{\times}10^{-3}{\sim}2.5{\times}10^{-3}mol/{\ell}$ and sulfonated amides, 25~33 dyne/cm at $5.8{\times}10^{-4}{\sim}8.0{\times}10^{-4}mol/{\ell}$ concentration range. It was found that isoelectric points of carboxylated amides were pH 7.2~7.9 and those of sulfonated or sulfated imidazolines and sulfonated amides were pH 4.5~5.5.

• Applied Chemistry for Engineering
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• v.9 no.4
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• pp.595-602
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• 1998

${\alpha}$-sulfonated fatty acid methyl esters[$C_mH_{2m+1}CH(SO_3Na)COOC_nH_{2n+1}$], where hydrophobic group has carbon number of 12~18, were prepard by sulfonation of fatty acid methylester. The mole ratio of $SO_3$ to ester used was 1.3 and the reaction temperature was $70{\sim}90^{\circ}C$. The yield was found to be 97% by mixed gas reaction of inactive gas/gaseous $SO_3$. Studies on bleaching and neutralization processes in the pilot scale provided conditions applicable to industrial synthesis process.

• Membrane Journal
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• v.13 no.2
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• pp.110-117
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• 2003

Sulfonated polyimides had been utilized and studied widely as available materials in chloro-alkali electrolysis, cationic exchange resins, and so on. However, a slow decrease in performance during experiments had been reported, which could be attributed to a loss of ionic conductivity related to either a continuous dehydration or polymer degradation. One of main reasons to account for the degradation of sulfonated polymers is the hydrolysis leading to polymer chain scission and decrement of molecular weight. Therefore, the objective of our study was to investigate possible imide cycle and additional ester bond cleavage connected with $SO_3$H presence under hydrated condition. In order to confirm and obtain as clear information as possible about breakages of bonds via $^1H\; and \;^{13}C$ NMR and IR spectroscopic analyses, our study was performed by model compound. Consequently, model compounds with both phthalic and naphthalenic imide ring and ester bonds were synthesized to evaluate the hydrolysis stability of sulfonated polyimide. The experiments were performed for prepared model compounds before and after aging in deionized water at $80^{\circ}C$ and were terminated by lyophilization technique. The aging products were finally analyzed by NMR and IR spectroscopy.

• Journal of Adhesion and Interface
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• v.15 no.1
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• pp.1-8
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• 2014

Ion exchange membrane is widely used in various fields such as electro dialysis, diffusion dialysis, redox flow battery, fuel cell. PVC cation exchange membrane using ultrasonic modification was prepared by sulfonation reaction in various sulfonation times. Sulfuric acid was used as a sulfonating agent with ultrasonic condition. We've characterized basic structure of sulfonated PVC cation exchange membrane by FT-IR, EDX, water uptake, ion exchange capacity (IEC), electrical resistance (ER), conductivity, ion transport number and surface morphology (SEM). The presence of sulfonic groups in the sulfonated PVC cation exchange membrane was confirmed by FT-IR. The maximum values of water uptake, IEC, electrical resistance and ion transport number were 40.2%, 0.87 meq/g, $35.2{\Omega}{\cdot}cm^2$ and 0.88, respectively.

• Journal of the Korean Chemical Society
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• v.53 no.3
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• pp.345-354
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• 2009

Sulfonated poly(ether sulfone)s (PESs) with a network structure were prepared by heat-induced crosslinking of the allyl-terminated telechelic sulfone polymers using a bisazide and their structure was analyzed by $^1H$ NMR. Having both uniform distribution of the hydrophilic conductive sites and controlled hydrophobic nature by minimized crosslinking, the crosslinked polymer (PES-60) membrane offered excellent proton conductivity at high temperature with a good thermal stability. In addition, selectivity of the crosslinked membrane (PES-60) was more than three times than that of Nafion$^{(R)}$.

• Membrane Journal
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• v.14 no.2
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• pp.173-184
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• 2004

For the application of direct methanol fuel cell (DMFC), sulfonated polystyrene/teflon (PS/PTFE) composite membranes were developed by changing monomer ratio of styrene and DVB. The composite membranes were prepared as follows: first, the monomer mixtures consisting of styrene, divinyl benzene and AIBN were impregnated in porous PTFE film and then, polymerized under 8$0^{\circ}C$ to give PS/PTFE membranes. Finally, the membranes were reacted with chlorosulfonic acid in 1,2-dichloroethane to give the sulfonated composite membranes. The measurements of ATR-FTIR, SEM, solvent uptake test and ion exchange capacity (IEC) were done for the resulting membranes before or after sulfonation, respectively, which showed the composite membranes with proper crosslinking degree and sulfonic acid content were prepared well as a function of styrene/DVB ratio. ion conductivity and methanol permeability were studied for the sulfonated membranes. It was found that with decreasing the ratio of styrene/DVB, methanol permeability decreased from $6.6{\times}10^{-7}∼1.3{\timas}10^{-7}$ $\textrm{cm}^2$/s, which are much lower values than that of Nafion$^{(R)}$117($1.02{\times}10^{-6}$ $\textrm{cm}^2$/s). Under the same monomer condition, ion conductivity decreased from 0.11 S/cm ($25^{\circ}C$) to 0.08 S/cm ($25^{\circ}C$), which are similar or a little higher values compared with $Nafion^{(R)}117 (1.02{\times}10^{-6}$ $\textrm{cm}^2$/s, 0.0824 S/cm). These two results confirmed the composite membranes prepared could be applied successfully to DMFC.C.

• Membrane Journal
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• v.18 no.4
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• pp.282-293
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• 2008

Partially sulfonated poly(aryl ether sulfone) membranes were prepared from the sulfonated sulfone monomer, which was synthesized by a nucleophilic substitution, non-sulfonated monomers and potassium carbonate by a direct polymerization method and a subsequent solution casting technique with mixed solvents of N-methyl-2-pyrrolidone (NMP) and dimethylacetamide (DMAc). To investigate the effect of mixed solvent, the volume ratios of NMP and DMAc were varied in the range of $0{\sim}100%$ and the degrees of sulfonation of the copolymers were fixed as 50%. The surface properties of the resulting membranes were examined by scanning electron microscope (SEM) and atomic force microscope (AFM), and a comparative study of the morphology changes and the physicochemical properties such as proton conductivity and methanol permeability was achieved. It was found that proton conductivities depend on the volume ratio of NMP-DMAc mixed solvents, and the proton conductivity determined at the condition of $25^{\circ}C$ and 100% relative humidity was $1.38{\times}10^{-1}\;S/cm$ for the membrane prepared in the 50:50 v/v-% of NMP : DMAc mixed solvent.

• Membrane Journal
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• v.16 no.3
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• pp.221-229
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• 2006

This study is about the preparation and characterization of sulfonated random copolymer membranes containing perfluorocyclobutane (PFCB), fluorenyl, and sulfonyl units. The polymers were prepared through three synthetic steps, that is, the synthesis of a trofluorovinylether-terminated monomer, its thermal polymerization, and post-sulfonation using chlorosulfonic acid. A series of sulfonated random copolymers with different ion exchange capacity (IEC) were prepared by changing contents of fluorenyl uints in polymers with fixed molar ratio of chlorosulfonic acid during the post-sulfonation reaction. All the synthesized compounds were characterized by FT-lR, $^1H-NMR$, $^{19}F-NMR$, and Mass spectroscopy. As the content of sulfonated fluorenyl units increased, the IEC, water uptake, and ion conductivity of the sulfonated random copolymer membranes increased. The sulfonated random copolymer S-1 and S-2 showed higher values of ion conductivity than the Nafion-115 in a wide range of temperatures ($25{\sim}80^{\circ}C$).

• Membrane Journal
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• v.19 no.4
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• pp.291-301
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• 2009

Double-layered polymer electrolyte membranes were prepared from two different sulfonated poly(aryl ether sulfone) copolymers by the two-step solution casting method for direct methanol fuel cells (DMFC). Sulfonation degrees were adjusted 10% (SPAES-10) and 50% (SPAES-50) by controlling monomer ratios, and the weight ratios of SPAES-10 copolymer were varied in the range of 5~20% to investigate the effect of thickness of coating layers on the membranes. Proton conducting layers were fabricated from SPAES-50 solutions of N-methyl-2-pyrrolidone (NMP) by a solution casting technique, and coating layers formed on the semiliquid surface of the conducting layer by pouring of SPAES-10-NMP solutions onto. It was found that double-layered polymer electrolyte membrane could significantly reduce the methanol crossover through the membrane and maintain high proton conductivities being comparable to single-layered SPAES-50 membrane. The maximum power density of membrane-electrolyte assembly (MEA) at the condition of $60^{\circ}C$ and 2 M methanol-air was $134.01\;mW/cm^2$ for the membrane prepared in the 5 wt-% of SPAES-10 copolymer, and it was corresponding to the 105.5% of the performance of the commercial Nafion 115 membrane.