• Proceedings of the Membrane Society of Korea Conference
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• 1997.10a
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• pp.69-70
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• 1997

Polyimides and related polymers, when synthesized from aromatic monomers, have generally rigid chain structures resulting in a low gas permeability. The rigidity of polymer chains reduces the segmental motion of chains and works as a good barrier against gas transport. To overcome the limit of use as materials of gas separation membranes due to low gas permeability, block copolymers with the incorporation of flexible segments like siloxane linkage and ether linkage have been studied. These block copolymers have microphase-separated structures composed of microdomains of flexible poly(dimethylsiloxane) or polyether segments and of rigid polyimides segments. In case of rigid-flexible block copolymers, the characteristics of both phases for gas permeation are of great difference. The permeation of gas molecules occurs favorably through microdomains of flexible segments, whereas those of rigid segments hinder the permeation of gas molecules. Accordingly the increase of content of flexible segments in a rigid polymer matrix will increase the gas permeability of the membrane linearly. However, this prediction does not satisfy enough many experimental results and in particular the drastic increase of the permeability is observed in a certain volume fraction. It was proposed that the gas transport mechanism is dominated by diffusion rather than gas solubility in a certain content of flexible phase if solution-diffusion mechanism is adopted. However, the transition from solubility-dependent to diffusion-dependent cannot be explained by the understanding of mechanism itself. Therefore, we consider an effective chemical path which permeable phase can form in a microheterogenous medium, and percolation concept is introduced to describe the permeability transition at near threshold where for the first time a percolation path occurs. The volume fraction of both phases is defined as V$_{\alpha}$ and V$_{\beta}$ in block copolymers, and the volume of $\beta$ phase in the threshold forming geometrically a traversing channel is defined as V$_{\betac}$. The formation mechanism of shortest chemical channel is schematically depicted in Fig. 1.

• Membrane Journal
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• v.18 no.3
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• pp.234-240
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• 2008

This work demonstrates the preparation of proton conducting crosslinked polymer electrolyte membranes by blending polystrene-b-poly(hydroxyethyl acrylate) (PS-b-PHEA) and poly(vinyl alcohol) (PVA) at 1 : 1 wt ratio. The PHEA block of the diblock copolymer was crosslinked with PVA using sulfosuccinic acid (SA) via the esterification reaction between -OH of membrane and -COOH of SA, as confirmed by FT-IR spectroscopy. Ion exchange capacity (IEC) continuously increased from 0.14 to 0.91 meq/g with increasing concentrations of SA, due to the increasing portion of charged groups in the membrane. In contrast, the water uptake increased up to 20.0 wt% of SA concentration above which it decreased monotonically. The membrane also exhibited a maximum proton conductivity of 0.024 S/cm at 20.0 wt% of SA concentration. The maximum behavior of water uptake and proton conductivity is considered to be due to competitive effect between the increase of ionic sites and the crosslinking reaction according to the SA concentration.

• New & Renewable Energy
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• v.2 no.4 s.8
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• pp.46-55
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• 2006

본 연구는 불소그룹을 함유한 술폰화된 아릴렌에테르계 블록 공중합체 고분자 전해질막의 제조 및 연료전지 특성에 관한 것이다. 이러한 불소그룹을 함유한 술폰화된 아랄렌에테르계 블록 공중합체를 제조하기 위하여 양말단에 불소계 비닐기를 가지면서, 고분자 전환시 상온에서 술폰화 가능한 biphenyl계 단량체와 술폰화가 불가능한 sulfonyl계 단량체를 각각 합성하였다. Biphenyl계 단량체로 부터 올리고머를 합성한 후 sulfonyl계 단량체와 열적 고리화 부가중합을 하여 다양한 몰조성을 갖는 일련의 perfluorocyclobutane(PFCB)기를 포함하는 블록 공중합체를 제조하였다. 제조된 블록 공중합체를 상온에서 술폰화제인 chlorosulfonic acid(CSA)를 이용하여 후술폰화시켜 강산 이온기인 sulfonic acid를 biphenyl계 올리고머 부분에 선택적으로 도입하였다. 이렇게 제조된 술폰화된 고분자를 제막한 후 연료전지 특성을 Nafion-115와 비교하였다. 술폰화가 되는 올리고머 블록의 비율 증가에 따라 이온교환능력 (IEC)이 증가하였고 , 그에 따른 팽윤도 역시 증가하는 것을 보였다. 술폰화된 고분자들은 건조 및 습윤 상태에서도 기계적 강도가 우수하였다. 최적화된 술폰화 블록 고분자(S-2) 를 대상으로 membrane electrolyte assembly(MEA) 를 제조하여 연료전지 초기성능을 측정한 결과 Nafion-112와 유사한 전기화학적 성능을 나타내었다.

• Journal of Hydrogen and New Energy
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• v.28 no.2
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• pp.144-149
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• 2017

A proton-conducting bisphenylpropaned sulfonated fluorinated blockcopolymer (BPSFBC) was synthesized. Five kinds of polymer electrolyted composite membranes were preparated by incorporating silica ($SiO_2$) with various weight ratio. And their characteristics were investigated by FT-IR (fourier transform infrared), $^1H-NMR$ ($^1H$ nuclear magnetic resonance), TGA (thermogravimetric analysis), water uptake, FE-SEM (field emission scanning electron microscopes), and ion conductivity properties. The water uptake and ion conductivity were increased until 9 wt% $SiO_2$, and then decreased. The maximum proton conductivity equal to $52mScm^{-1}$ was measured for the BPSFBC/$SiO_2$-9 composite membrane at $90^{\circ}C$ and 100% relative humidity. From the measured results, it is distinct that the manufactured composite membrane BPSFBC/$SiO_2$-9 can be considered as a polymer membrane suitable for a fuel cell electrolyte.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.313-313
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• 2006

In this study, we describe a new double layered nanoporous membrane suitable for virus filtration. One layer is an 80 nm thick film having cylindrical pores with diameters of 15 nm and a narrow pore size distribution. This layer is prepared by using a thin film of the mixture of a block copolymer and a homopolymer, and mainly acts to separate viruses. The support layer (${\sim}150\;microns\;thick$) is a conventional micro-filtration membrane with a broad pore size distribution. This asymmetric membrane showed very high selectivity and flux for the separation of human rhinovirus type 14 (HRV 14) which has a diameter of ${\sim}30\;nm$ and is a major pathogen of the common cold in humans.

• 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.7 no.3
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• pp.131-135
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• 1997

Polymeric micellar enhanced ultrafiltration method using a new type of polyrmer, $\alpha$-allyl-$\omega$-methoxy polyoxyethlene and maleic anhydride copolymer (AKM-0531, Mw 15, 000), has been proposed to separate 1-naphthylamine as a weak cationic toxic organic solubilizate. Enhancement effect of polymeric micelle was identified by the ultrafiltration runs using polyacryronitrile(PAN) holow fiber membrane with molecular weight cut off 6, 000. The linear dependance of flux on the pressure difference is shown to be valid up to 0.6kg/${cm}^2$ and the rate of flux increase in response to change in the pressure is gradually reduced under the pressure difference. Rejection of 0.96 was observed for f mM of 1-naphthylamine with 2 wt.% polymer solution at the conditions of 0.4kg/${cm}^2$, natural pH. and $25^{\circ}C$ Solubilization of 1-naphthylamine into the polymeric micelle enhanced the separation efficiency.

• Membrane Journal
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• v.33 no.4
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• pp.211-221
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• 2023

This study presents a comprehensive study on the synthesis and characterization of PVI-PGMA/LiTFSI polymeric membrane electrolytes and CxNy-C flexible electrodes for energy storage applications. The dual-functional PVI-PGMA copolymer exhibited excellent ionic conductivity, with the PVI-PGMA73/LiTFSI200 membrane electrolyte achieving the highest conductivity of 1.0 × 10^-3 S cm^-1. The electrochemical performance of the CxNy-C electrodes was systematically investigated, with C3N2-C demonstrating superior performance, achieving the highest specific capacitance of 958 F g^-1 and lowest charge transfer resistance (R_ct) due to its highly interconnected hybrid structure comprising nanowires and polyhedrons, along with binary Co/Ni oxides, which provided abundant redox-active sites and facilitated ion diffusion. The presence of a graphitic carbon shell further contributed to the enhanced electrochemical stability during charge-discharge cycles. These results highlight the potential of PVI-PGMA/LiTFSI polymeric membrane electrolytes and CxNy-C electrodes for advanced energy storage devices, such as supercapacitors and lithium-ion batteries, paving the way for further advancements in sustainable and high-performance energy storage technologies.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.269-269
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• 2006

The molecular structure of poly(2,6-dimethyl-4,4' -phenylene oxide)-g-poly (styrenesulfonic acid) (PPO-g-PSSA) graft copolymer was designed, and synthesized via living radical polymerization. Obtained graft copolymers were transformed into proton exchange membranes for direct methanol fuel cell (DMFC) application. The performance of the membranes was measured in terms of water uptake, proton conductivity, methanol permeability, and thermal stability. Very low methanol permeability and good proton conductivity were observed by adjusting grafting frequency and PSSA block content.

• Journal of Hydrogen and New Energy
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• v.23 no.5
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• pp.461-467
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• 2012

Multi-block sulfonated poly (arylene ether sulfone) (SPES) membranes were synthesized by post-sulfonation and its properties characterized. Two types of oligomers, F-terminated and OH-terminated telechelic oligomers, were synthesized by controlling the feed ratio of dihydroxyl- and difluoro-monomers. Their number of repeating unit (X and Y) was analyzed by GPC and $^1H$ NMR. Copolymerization with F-terminated and OH-terminated telechelic oligomers via nucleophilic aromatic substitution, gave high-molecular-weight multi-block PESs. Each block length was controlled to have different values with X5Y10, X10Y10, X20Y10 and X20Y20. Successful polymerization and its successful sulfonation was confirmed by GPC and $^1H$ NMR. RH dependence of proton conductivity of multi-block SPES membranes was comparable to that of Nafion 212 at high RH conditions.