• Membrane Journal
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• v.27 no.2
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• pp.182-188
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• 2017

Sulfonated poly(arylene ether sulfone) (SPAES)-3-mercaptopropyl silica gel (3MPTSG) composite membranes with improved oxidative stability were prepared for polymer electrolyte fuel cell application. It has been reported that ether part of main chain of aromatic hydrocarbon based membranes were weak to radical attack to decrease membrane durability. In this study, the hydrophilic inorganic particles were introduced by minimizing a decrease in ion conductivity and increasing an oxidative stability. The composite membranes were investigated in terms of ionic conductivity, ion exchange capacity (IEC), FT-IR, TGA and contact angle, etc. As a result, increasing amount of the 3MPTSG resulted in decrease in proton conductivities and water uptakes at 100% R.H. but enhanced thermal and oxidative stabilities.

• Proceedings of the Korean Society for Noise and Vibration Engineering Conference
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• 2009.10a
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• pp.316-317
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• 2009

The ion-exchange membrane, Nafion, remains as the benchmark for a majority of research and development in IPMC technology. In this research, we employed a novel ionomer named by sulfonated poly(styrene-ran-ethylene) (SPSE) that is crosslinked by UV irradiation. The sulfonic acid groups were stable during the UV irradiation crosslinking process. Water uptake, ion exchange capacity, and proton conductivity are characterized for both pure SPSE and crosslinked SPSE membrane. The bending responses of SPSE actuators under both direct current (DC) and alternating current (AC) excitations were investigated. The voltage-current behaviors of the actuators under AC excitations are also measured. Results showed the crosslinked SPSE actuators have better electromechanical performance than that of pure SPSE actuator with regard to tip displacement as a novel smart material.

• Macromolecular Research
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• v.15 no.6
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• pp.587-594
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• 2007

Well defined amphiphilic diblock copolymers of poly(styrene-b-vinylbenzylphosphonic acid) (PS-b-PVBPA) were prepared by controlled radical polymerization technique, two-step hydrolysis reactions using trime-thylsilyl bromide from the corresponding phosphonic ethyl ester. By indirect, backward pH titration of the block copolymer, a good titration curve of a dibasic acid was observed. The IEC values obtained from both backward pH titration and volumetric back titration were almost identical. Thermal gravimetric analysis (TGA) of the phosphonic acid containing block copolymer showed a high thermal stability up to $400^{\circ}C$.

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.2
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• pp.103-110
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• 2005

Proton conducting solid polymer electrolyte (SPE) membranes have been used in many energy technological applications such as water electolysis, fuel cells, redox-flow battery, and other electrochemical devices. The availability of stable membranes with good electrochemical characteristics as proton conductivity at high temperatures above 80 $^{\circ}C$ and low cost are very important for its applications. However, the presently available perfluorinated ionomers are not applicable because of high manufacturing cost and high temperature use to the decrease in the proton conductivity and mechanical strength. In order to make up for the weak points, the block copolymer (BPSf) of polysulfone and poly (phenylene sulfide sulfone) were synthesized and sulfonated. The electrolyte membranes were prepared with phosphotungstic acid (HPA)/sulfonated BPSf via solution blending. This study would be desirable to investigate the interaction between the HPA and sulfonated polysulfone. The results showed that the characteristics of SPSf/HPA blend membrane was a better than Nafion at high temperature, 100 $^{\circ}C$. These membranes proved to have a high proton conductivity, $6.29{\times}10-2$ S/cm, a water content, 23.9%, and a ion exchange capacity, 1.97 meq./g dry membrane. Moreover, some of the membranes kept their high thermal and mechanical stability.

• Macromolecular Research
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• v.16 no.6
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• pp.549-554
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• 2008

Proton conducting crosslinked membranes were prepared using polymer blends of polystyrene-b-poly(hydroxyethyl acrylate)-b-poly(styrene sulfonic acid) (PS-b-PHEA-b-PSSA) and poly(vinyl alcohol) (PVA). PS-b-PHEA-b-PSSA triblock copolymer at 28:21:51 wt% was synthesized sequentially using atom transfer radical polymerization (ATRP). FT-IR spectroscopy showed that after thermal ($120^{\circ}C$, 2 h) and chemical (sulfosuccinic acid, SA) treatments of the membranes, the middle PHEA block of the triblock copolymer was crosslinked with PVA through an esterification reaction between the -OH group of the membrane and the -COOH group of SA. The ion exchange capacity (IEC) decreased from 1.56 to 0.61 meq/g with increasing amount of PVA. Therefore, the proton conductivity at room temperature decreased from 0.044 to 0.018 S/cm. However, the introduction of PVA resulted in a decrease in water uptake from 87.0 to 44.3%, providing good mechanical properties applicable to the membrane electrode assembly (MEA) of fuel cells. Transmission electron microscopy (TEM) showed that the membrane was microphase-separated with a nanometer range with good connectivity of the $SO_3H$ ionic aggregates. The power density of a single $H_2/O_2$ fuel cell system using the membrane with 50 wt% PVA was $230\;mW/cm^2$ at $70^{\circ}C$ with a relative humidity of 100%. Thermogravimetric analysis (TGA) also showed a decrease in the thermal stability of the membranes with increasing PVA concentration.

• Membrane Journal
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• v.15 no.1
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• pp.1-7
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• 2005

Polymer electrolyte membranes containing polysilsesquioxane (PSQ) spheres were prepared with the blend of sulfonated poly(ether ether ketone) (SPEEK) (60%) and poly(ether sulfone) (PES) (40%). The amount of PSQ spheres was fixed at 10 wt%. The prepared polymer electrolyte membranes were characterized in terms of methanol permeability, proton conductivity, and ion exchange capacity. In all cases, both methanol permeability and proton conductivity of the polymer electrolyte membranes containing PSQ spheres were lower than the values of Nafion 117 and higher than those of SPEEK/PES (6:4) blend without PSQ spheres. The experimental results indicated that the polymer electrolyte membranes containing MS64 and VTMOS spheres were the best choice in terms of the ratio of proton conductivity to methanol permeability.

• Korean Membrane Journal
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• v.11 no.1
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• pp.8-14
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• 2009

The sulfonated poly(styrene-divinylbenzene-acrylonitrile) (ST-DVB-AN) composite polymer electrolyte membrane based on the original PVC film was successfully synthesized to improve oxidative stability using semi-interpenetrated polymer network (semi-IPN). Weight gain ratio after copolymerization was enhanced by the DVB and AN contents, and the sulfonated membranes were characterized in terms of proton conductivity (k), ion exchange capacity (IEC), and water uptake ($W_U$). The effect of DVB content and AN addition were thoroughly investigated by comparing the resulted properties including oxidative stability. The obtained ST-DVB-AN composited semi-IPN membranes showed relatively high proton conductivity and IEC compared with Nafion117, and greatly improved oxidative stability of the synthesized membrane was obtained. This study demonstrated that a semi-interpenetrated sulfonated ST-DVB-AN composited membrane reinforced by PVC polymer network is a promising candidate as an inexpensive polymer electrolyte membrane for fuel cell applications.

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.1
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• pp.40-48
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• 2005

Until recently, only perfluorinated ionomer membrane such as Nation and Aciflex practically could be successfully used in water splitting. However, these membrane are limited by high cost and loss of membrane performance such as proton conductivity at elevated temperature above 80$^{\circ}C$. The sulfonated aromatic polymers such as PEEK and PSf, polyimides, and polybenzimidazoles are expected to have lower production cost as well as satisfactory chemical and electrochemical properties. HPAs and sulfonated polymers could have a significant influence on water electrolysis performance at elevated temperatures above 80$^{\circ}C$, but these phenomena have received relatively little attention until now. Therefore, it would be desirable to investigate the interrelation between the HPA and sulfonated polymer, such as SPEEK. The SPEEK membrane were prepared by the sulfonation of PEEK, and HPA was blended with SPEEK to increase the mechanical strength and electrochemical characteristics. As a results, electrochemical characteristics such as proton conductivity and ion exchange capacity were improved with the addion of 0.5 g HPA. And the properties of polymer electrolyte, SPEEK/HPA were better than Nation membrane at elevated temperature above 80$^{\circ}C$.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.4
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• pp.391-398
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• 2007

The covalently cross-linked sulfonated polyetheretherketone (CL-SPEEK) membrane was prepared by four-step synthesis of sulfonation-sulfochlorination, partial reduction, lithiation, and cross-linking, and its electrochemical and mechanical properties were investigated for water electrolysis application. The prepared ion exchange membranes showed good electrochemical and mechanical properties; proton conductivity of 0.116 S/cm at $80^{\circ}C$, water uptake of 44.6%, ion exchange capacity of 1.75 meq/g-dry-memb., tensile strength of 64.25 MPa and elongation of 61.11%. The membrane electrode assembly (MEA) with homemade membranes were prepared by non-equilibrium impregnation-reduction (I-R) method. Especially, the electrochemical surface area (ESA) and roughness factor of CL-SPEEK electrolyte by cyclic voltammetry method were 23.46 $m^2/g$ and 307.3 $cm^2-Pt/cm^2$, respectively. The prepared MEA was used in the unit cell of water electrolysis and the cell voltage was 1.81 V at 1 A/$cm^2$ and $80^{\circ}C$, with platinum loadings of 1.31 mg/$cm^2$.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.1
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• pp.60-68
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• 2011

[ $ZrO_2-TiO_2$ ]binary oxides with various Zr:Ti molar ratios were prepared by sol-gel method and Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membranes were fabricated for proton exchange membrane fuel cells (PEMFCs) at high temperature and low humidity. Water uptake, Ion exchange capacity (IEC), and proton conductivity of Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membranes were characterized and these composite membranes were tested in a single cell at $120^{\circ}C$ with various relative humidity (R.H.) conditions. The obtained results were compared with the unmodified membranes (Nafion$^{(R)}$ 112 and Recast Nafion$^{(R)}$). A Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membrane with 1:3 of Zr:Ti molar ratio showed the highest performance. The performance showed 500 mW/$cm^2$ (0.499V) at $120^{\circ}C$, 50% R. H., and 2 atm.