• Journal of the Korean Chemical Society
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• v.59 no.5
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• pp.413-422
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• 2015

Proton exchange membrane (PEM), which transfers proton from the anode to the cathode, is the key component of the proton exchange membrane fuel cell (PEMFC). Nafion is widely used as PEM due to its high proton conductivity as well as excellent chemical and physical stabilities. However, its high cost and the environmental hazards limit the commercial application in PEMFCs. To overcome these disadvantages, various alternative polymer electrolytes have been investigated for fuel cell applications. We used densely sulfonated polymers to maximize the ion conductivity of the corresponding membrane. To overcome high swelling, dipole-dipole interaction was used by introducing nitrile groups into the polymer backbone. As a result, physically-crosslinked membranes showed improved swelling ratio despite of high water uptake. All the membranes with different hydrophilic-hydrophobic compositions showed higher conductivity, despite their lower IEC, than that of Nafion-117.

• Polymer(Korea)
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• v.37 no.5
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• pp.587-591
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• 2013

Poly(3,4-ethylenedioxythiophene) (PEDOT) has good properties such as high conductivity, optical transmittance, and chemical stability, while offering relatively weak physicochemical properties. The main purpose of this paper is the improvement of physicochemical properties such as solvent resistance and pencil hardness of PEDOT. Carboxyl groups in the anionic type waterborne polyurethane (WPU) chains can effectively crosslink each other in the presence of aziridine, resulting in physicochemically robust PEDOT/WPU organic-organic hybrid conductive thin films. The electrical conductivity, optical properties, and physicochemical properties of the hybrid conductive film were compared by varying the solid content and WPU portion in the coating precursor solution. From the results, the transparency and surface resistance of the hybrid film show a decreasing tendency with increasing solid content in the coating precursor. Moreover, solvent resistance and hardness were dramatically enhanced by hybridization of PEDOT and crosslinked WPU due to curing reactions between carboxyl groups.

• Membrane Journal
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• v.16 no.4
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• pp.241-251
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• 2006

In this study, crosslinked copolyimides with random (r-) and block (b-) structure were fabricated using N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid and pentanediol as crosslinkers. Linear r- and b-sulfonated copolyimides were also fabricated for comparison. Ion exchange capacities of r- and b-copolyimides were very similar to each other owing to their strong dependence of sulfonic acid content. The physical crosslinking via dimerization of carboxylic acid groups induced a reduced average interchain distance in b-copolyimide without crosslinkers. Consequently, its water uptake and methanol permeability were lower than those of r-sulfonated copolyimides. Simultaneously, the reduced interchain distance increased the content of fixed-charged ions per unit volume. The high fixed-charged ion density contributed to an enhancement of proton conductivity In the b-sulfonated copolyimide. Crosslinking caused the reduction of average interchain distance between polymer chains irrespective of types of crosslinker and polymer structure, leading to low methanol permeability. On the contrary, their proton conductivity was improved owing to formation of effective hydrophilic channels responsible for proton conduction. In particular, this trend was observed in r-copolyimide containing a fixed charged ion.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.65-70
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• 2014

In this study, crosslinked poly(POEM-co-AMPSLi-co-GMA)s were prepared by epoxy coupling of GMA after radical copolymerization of AMPS, POEM and GMA followed by acid-base titration reaction between sulfonic acid of AMPS and $Li_2CO_3$. It was observed that the crystalline melting temperature of POEM was effected by mol% of components and shifted to lower value by lithiation of AMPS group. The ionic conductivity of crosslinked polymer electrolyte was decreased by addition of GMA but maintained over $1.0{\times}10^{-6}S\;cm^{-1}$ until 16 mol%. Particularly, the self-doped polymer electrolyte with 2 mol% of GMA showed its ionic conductivity as high as $4.08{\times}10^{-6}S\;cm^{-1}$ at room temperature and electrochemical stability up to 6 V. In addition, 0.11 MPa of modulus and 270% of elongation were obtained from the free standing film of crosslinked polymer electrolyte.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.17 no.1
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• pp.433-440
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• 2016

Composite membranes were prepared by the solution casting method from sulfonated poly(etheretherketone)(sPEEK) and imidazole and phosphotungstic acid(PWA) to enhance the electrolytic properties of the membrane. TGA measurements showed that physical crosslinking due to acid-base interactions improved the thermal resistance to the desulfonation of sulfonic acid groups of the composite membrane and the addition of PWA enhanced the resistance to thermal decomposition of the composite membrane. The acid-base interaction decreased the water uptake, proton conductivity and methanol permeability of the sPEEK/imidazole composite membranes. The addition of PWA increased the proton conductivities while it decreased the water uptake and methanol permeability of sPEEK/imidazole/PWA composite membranes. Therefore, the selectivity of the composite membranes was enhanced by the addition of PWA.

• Membrane Journal
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• v.33 no.2
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• pp.77-86
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• 2023

In this study, pore-filled ion exchange membranes with low membrane resistance and high hydroxide ion conductivity was developed. To improve alkali durability, a porous substrate made of polytetrafluoroethylene was used, and a copolymer was prepared using monomers 2-(dimethyl amino) ethyl methacrylate (DMAEMA) and vinyl benzyl chloride (VBC) for pores. divinyl benzene (DVB) was used as the cross-linker, and ion exchange membranes were prepared for each cross-linking agent content to study the effect of the cross-linker content on DMAEMA-DVB and VBC-DMAEMA-DVB copolymers. As a result, chemical stability is improved by using a PTFE material substrate, and productivity can be increased by enabling fast photo polymerization at a low temperature by using a low-pressure UV lamp. To confirm the physical and chemical stability of the ion exchange membrane required for an anion exchange membrane fuel cell, tensile strength, and alkali resistance tests were conducted. As a result, as the cross-linking degree increased, the tensile strength increased by approximately 40 MPa, and finally, through the silver conductivity and alkali resistance tests, it was confirmed that the alkaline stability increased as the cross-linking agent increased.

• 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.30 no.6
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• pp.395-408
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• 2020

Polymer electrolyte membrane fuel cells (PEMFCs) have gained much attention as eco-friendly energy conversion devices without emission of environmental pollutant. Polymer electrolyte membrane (PEM) that can transfer proton from anode to cathode and also prevent fuel cross-over has been regarded as a key component of PEMFCs. Although perfluorinated polymer membranes such as Nafion® were already commercialized in PEMFCs, their high cost and toxic byproduct generated by degradation have still limited the wide spread of PEMFCs. To overcome these issues, development of hydrocarbon based PEMs have been studied. Incorporation of cross-linked structure into the hydrocarbon based PEM system has been reported to fabricate the PEMs showing both high proton conductivity and outstanding physicochemical stability. This study focused on the various cross-linking strategies to the preparation of cross-linked PEMs based on hydrocarbon polymers with ion conducting groups for application in PEMFCs.

• Polymer(Korea)
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• v.27 no.1
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• pp.40-45
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• 2003

In this work, the effect of different contents of $Fe_3O_4$ and temperature variation on the electrical conductivity ($\sigma$) in the polar acrylonitrile butadiene rubber (NBR)/$Fe_3O_4$ (magnetite) mixture system was investigated. It was found that the percolation threshold concept holds true for the conductive particle-filled composites where $\sigma$ indicates a nearly sharp increase when the concentration of magnetite in the mixture exceeds 22%. The temperature dependence of $\sigma$ was thermally activated below and at the percolation threshold ($P_c$). Magnetite acted as reinforcing and conductive filler for NBR. At room temperature and higher voltages, the electrical current was proportional to the square of voltage ($I{\propto}V^2$) for the composites which contain 30 phr of magnetite. Moreover, it was shown that the composites with magnetite of 50 phr showed the highest tensile strength and elongation at break, which was due to the formation of optimal physical interlock and crosslinking. The results of 100%, 200%, and 300% Young moduli said that the moduli are largely correlated with reinforcement effect of magnetite and viscosity of the blends from torque curve.

• Elastomers and Composites
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• v.38 no.1
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• pp.81-87
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• 2003

In this work, $Fe_3O_4$ (magnetite), conductive filler was prepared from $FeCl_2{\cdot}4H_2O,\;(CH_2)_6N_4$ (hexamethylene tetramine), and $NaNO_2$, followed by mixing with crystallizable chloroprene rubber(CR). The influence of conductive filler content on the properties of the conductive composite was studied and temperature dependence of the electrical conductivity (${\sigma}$) was also investigated. It is found that the percolation threshold concept holds true for the conductive particle-filled composite where ${\sigma}$ indicates a nearly sharp increase when the fraction of magnetite in the mixture exceeds 27%. The temperature dependence of ${\sigma}$ is thermally activated blelow or at the $P_c$. Magnetite acts as reinforcement and conductive filler for CR rubber. Moreover, it is shown that the composite with magnetite of 50 phr gives the most significant mechanical properties for tensile strength and elongation at break, which is due to the formation of optimum physical interlock and crosslinking. The results of 100%, 200%, and 300% moduli suggest that the moduli are related with reinforcement effect of magnetite and viscosity of the blend.