• Transactions of the Korean hydrogen and new energy society
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• v.33 no.2
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• pp.164-175
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• 2022

In this work, sulfonated poly (ether ether ketone) (SPEEK) composite membranes including strontium zirconate (SrZrO₃) were fabricated by the electrospinning method. Fourier-transform infrared spectroscopic analysis and X-ray diffraction analysis were used to identify the chemical structure and the crystallinity of SrZrO₃ and electrospun composite membranes. The thermal stability of the pure SPEEK and SPEEK/SrZrO₃ electrospun composite membranes were investigated by using thermogravimetric analysis. The physicochemical properties and proton conductivity were enhanced with the addition of different weight ratio of SrZrO₃ nanofiller (2, 4 and 6 wt%) in SPEEK polymer. The optimized SPEEK/SrZrO₃-4 electrospun membrane containing 4 wt% of SrZrO₃ showed a high proton conductivity compared to other electrospun SPEEK/SrZrO₃ composite membranes. The results indicate that electrospun composite membranes incorporating these perovskite nanofillers should be explored as potential candidates for use in proton exchange membrane fuel cells.

• Transactions of the Korean hydrogen and new energy society
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• v.34 no.6
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• pp.673-681
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• 2023

Hydrocarbon-based polymer membranes to replace perfluorinated polymer membranes are being continuously researched. However, hydrocarbon-based membranes have a problem in that they are less durable than fluorine-based membranes. In this study, we sought to compare the annealing effect to improve the durability of sulfonated poly(ether ether ketone) (SPEEK). After membranes formation, thermogravimetric analysis and tensile strength were measured to compare changes in membranes properties due to annealing. After manufacturing the membrane and electrode assembly (MEA), the initial performance and chemical durability was compared with unit cell operation. During the 24-hour annealing process, the strength increased due to the increase in-S-O-S-crosslinking, and the sulfonic acid group decreased, leading to a decrease in I-V performance. By annealing, the hydrogen permeability was reduced to less than 1/10 of that of the nafion membrane, and as a result, open circuit voltage (OCV) and durability was improved. The SPEEK membranes annealed for 24 hours showed higher durability than the nafion 211 membranes of the same thickness.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.135.1-135.1
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• 2010

최근 고온에서 사용 가능한 PEMFC용 고분자전해질 막 개발에 대한 연구가 활발히 진행되고 있다. PEMFC가 고온에서 작동하게 되면 높은 성능과 많은 장점을 갖게 된다. PEMFC를 $100^{\circ}C$ 이상에서 운전하게 될 경우 백금 전극 반응을 향상시켜 고가의 백금 촉매 양을 줄일 수 있게 되고, 수소연료 속에 미량 포함된 CO에 의한 촉매표면 피독현상에 대한 내구성을 높일 수 있어 저 순도 수소연료 사용이 가능해 진다. 또한 가습장치와 수소 연료 개질장치의 부피를 줄일 수 있게 되어 전체적인 PEMFC 시스템이 단순화 된다. 현재 연료전지용 고분자 전해질막으로 DuPont사의 과-불소계 고분자 전해질막인 Nafion$^{(R)}$이 가장 널리 사용되고 있다. Nafion$^{(R)}$은 유연한 분자구조 안에 소수성이 강한 주사슬과 친수성을 나타내는 술폰산이 결합된 곁사슬이 존재하여 술폰화 곁사슬의 클러스터 둘레에는 친수성 영역이 형성이 되기때문에 소수/친수 상 분리가 잘되어 이온 클러스터 형성이 용이하지만 제조비용이 높은 단점을 갖고 있다. 특히, 전해질 막내에서 Bronsted base 역할을 하는 물에 의해 이온전도가 이루어지기 때문에 고온에서는 수분증발로 인해 성능이 급격히 감소된다. 따라서, 본 연구에서는 고온 저가습 조건에서 운전이 가능하고 Nafion이 갖는 문제점을 해결하고자, 내열특성이 뛰어나며 높은 수소이온 전도도 학보가 용이한 Sulfonated Poly(aryl ether)sulfone(SPAES) 고분자 전해질에, 고온에서도 수화성이 유지될 수 있도록 지르코니아를 황산화한 sulfated zirconia(s-$ZrO_2$)를 함침하여 복합 고분자전해질막을 제조하여 고온 저가습 조건에서의 수소이온 전도 특성에 관한 연구를 수행하였다. 개발된 막의 물리/화학적 특성은 water content(Wup%), 이온교환 용량(IEC, meq $g^{-1}$), 수소이온전도도(s $cm^{-1}$) 열 중량 분석(TGA), X선 회절분석(XRD) 등을 통하여 분석 및 관찰하였다. 내화학 및 열적 특성분석 결과, 황산화 반응공정으로 $ZrO_2$에 술폰산기가 안정적으로 결합하고 있음이 관찰되었으며, 본 연구에서 개발된 유 무기 복합막이 $250^{\circ}C$이상 열적안정성을 확보하고 있는 것으로 판단되었다. $100^{\circ}C$ 이하의 저온 영역에서, 일정 비율의 s-$ZrO_2$/SPAES막에서 이온교환용량(IEC)이 순수 SPAES 막보다 낮음에도 불구하고, water uptake가 증가함과 동시에 수소이온 전도도가 향상된 것을 관찰하였다. 또한, 고온에서는 수소이온이 자유롭게 이동할 수 있는 water channel을 형성하는 free water는 증발 하지만 s-$ZrO_2$와 SPAES의 술폰산기 사이에 강력하게 결합하고 있는 bound Water는 $100^{\circ}C$ 이상의 고온 영역에서도 존재하여, 비록 무가습 조건에서도 일정 비율의 s-$ZrO_2$/SPAES50 전해질 막의 경우, 높은 전도도를 나타냄을 관찰할 수 있었다. 따라서 본 연구를 통해 저가습 고온 적용을 목적으로 개발된 s-$ZrO_2$/SPAES50막은 우수한 내열 특성을 나타냄과 동시에 저가습 고온 영역($120^{\circ}C$, $50RH{\downarrow}$)에서 높은 수소이온 전도도를 유지하여, 고온 저가습 연료전지 운전에 적합할 것으로 사료된다.

• Journal of Marine Bioscience and Biotechnology
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• v.9 no.1
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• pp.14-21
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• 2017

The purpose of this study was to inhibit biofouling on a selectively permeable membrane (SPM) and increase biomass productivity in marine photobioreactors (PBRs) for microalgal cultivation by chemical treatment. Surfaces of a SPM, composed of polyethylene terephthalate (PET), was sulfonated to decrease hydrophobicity through attaching negatively charged sulfonic groups. Reaction time of sulfonation was varied from 0 min to 60 min. As the reaction time increased, the water contact angle value of SPM surface was decreased from $75.5^{\circ}$ to $44.5^{\circ}$, indicating decrease of surface hydrophobicity. Furthermore, the water permeability of sulfonated SPM was increased from $5.42mL/m^2/s$ to $10.58mL/m^2/s$, which reflects higher nutrients transfer rates through the membranes, due to decreased hydrophobicity. When cultivating Tetraselmis sp. using 100-mL floating PBRs with sulfonated SPMs, biomass productivity was improved by 34% compared with the control group (non-reacted SPMs). In addition, scanning electron microscopic observation of SPMs used for cultivation clearly revealed lower degree of cell attachment on the sulfonated SPMs. These results suggest that sulfornation of a PET SPM could improve microalgal biomass productivity by increasing nutrients transfer rates and inhibiting biofouling by algal cells.

• Journal of Energy Engineering
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• v.25 no.4
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• pp.176-183
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• 2016

This study relates to a polymer electrolyte membrane for improved performance fuel cell, were researched with respect to properties required for driving a fuel cell. The bis(4-fluorophenyl)phenyl phosphine oxide was sulfonated using fuming sulfuric acid. Synthetic hydrophilic oligomer and the hydrophobic oligomer and the block copolymers were prepared via aromatic nucleophilic substitution polycondensation. A block copolymer structure and degree of sulfonation was analyzed by $^1H$-NMR and gel permeation chromatography(GPC) analysis. Thermal stability was confirmed by thermogravimetric analysis(TGA), block copolymer was stable at high temperature(>$200^{\circ}C$), The ion conductivity was measured in order to demonstrate the performance of fuel cell. Synthesis membrane was the increase of temperature was improved conductivity up to 58 mS/cm due to the influence of the developed ion clusters. The phase separation of the polymer was observed to make AFM analysis.

• Membrane Journal
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• v.24 no.4
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• pp.301-310
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• 2014

In this study, the silica nanoparticles were considerably chosen to improve a dimensional stability, proton transport and electrochemical performance of the resulting inorganic-organic nanocomposite membranes. For this purpose, hydrophobic silica (Aerosil$^{(R)}$ 812, Degussa) and hydrophilic silica (Aerosil$^{(R)}$ 380, Degussa) nanoparticles were, respectively, introduced into a Sulfonated poly(arylene ether sulfone) (SPAES) polymer matrix. The $SiO_2$ particles are evenly dispersed in a SPAES matrix by the aid of a non-ionic surfactant (Pluronics$^{(R)}$ L64). A $SiO_2$ content plays an important role in membrane microstructures and membrane properties such as proton conductivity and water uptake. Therefore, to study nanocomposite membranes with excessive amount of silica, the content of silica nanoparticles were increased up to 5 wt%. Interestingly, a hydrophobic $SiO_2$ containing nanocomposite membrane showed better electrochemical performance (29% higher than pristine SPAES) despite of low proton conductivity due to its adhesive properties with a catalyst layer in a single cell test. All the silica-SPAES membranes exhibited better performance than a pristine SPAES membrane.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.1
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• pp.1-12
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• 2011

To improve the mechanical properties, such as durabilities and antioxidative characteristics, the covalently cross-linked (CL-) SPEEK (sulfonated polyether ether ketone)/Cs-substituted HPA (heteropoly acid) organic-inorganic composite membranes (CL-SPEEK/Cs-HPAs), have been intensively investigated. The composite membrane were prepared by blending cesium-substituted HPAs (Cs-HPAs), including tungstophosphoric acid (TPA), molybdophosphoric acid (MoPA), and tungstosilicic acid (TSiA) with cross-linking agent content of 0.01 mL. And composite electrolytes composed of Cs-HPAs, prepared by immersion (imm.) and titration (titr.) methods to increase the stability of HPAs in water, were applied to polymer electrolyte membrane electrolysis (PEME). As a result, the proton conductivity of Cs-substituted composite membranes increased rapidly over $60^{\circ}C$ but mechanical properties, such as tensile strength, decreased in accordance with added Cs content. The bleeding-out of Cs-TPA membranes by titration method (50 vol.% Cs) decreased steadily to 2.15%. In the oxidative stability test by Fenton solution, the durability of membranes with Cs-HPA significantly increased. In case of CL-SPEEK/ Cs-TPA membrane, duration time increased more than 1200 hours. It is expected that even though CL-SPEEK/Cs-MoPA membrane shows the high proton conductivity, electrocatalytic activity and cell voltage of 1.80 V for water electrolysis, the CL-SPEEK/Cs-TPA (imm.) is more suitable as an alternative membrane in real system with the satisfactory proton conductivity, mechanical properties, anti-oxidative stability and cell voltage of 1.89 V.

• Membrane Journal
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• v.21 no.4
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• pp.389-397
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• 2011

In this study, polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) were prepared using a solution casting method with different amount of vermiculite (VMT) content. The dispersion of VMT particles in the SPAES matrix was confirmed by means of a scanning electron microscopy observation. The composite membrane containing less than 1 wt% of VMT has a smooth skin on the top and bottom, which means there is a good dispersion of VMT in the matrix. The water uptake of the composite membranes gradually increases as the temperature increases, and the results confirm that all the adsorbed water is bound water because VMT has a strong water affinity on account of its high cation exchange value. A composite membrane with a VMT content of less than 1 wt% increases the proton conductivity and reduces the methanol permeability. Of all the composite membranes, the membrane SPAES/VMT 1.0 has the best fuel cell performance in terms of membrane selectivity. The performance value of SPAES/VMT 1.0 is double that of Nafion 112, which suggests that SPAES/VMT1.0 could be an excellent candidate for direct methanol fuel cells.

• Journal of the Korean Society of Radiology
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• v.16 no.2
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• pp.141-150
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• 2022

The initial co-transport and counter-transport permeate transport characteristics of calcium ion at epithelial cell membrane model in parathyroid which irradiated by high energy x-ray(linac 6 MV) was investigated. The epithelial cell membrane model used in this experiment was a polysulfonated copolymerized membrane of poly(PS-DVB: polystyrene-divinylbenzene). The difference of sorbed water in membrane, fixed carrier concentration(SO₃^2-), initial pH value, OH^- concentration were occurred at difference of Ca²⁺concentration and quantity of parathyroid hormone, respectively. The initial co-transport and counter-transport permeate flux of Cl^-, OH^-, Ca²⁺ on fixed carrier concentration(SO₃^2-) and initial pH value of irradiated membrane was found to be decreased than non-irradiated membrane. The initial co-transport and counter-transport permeate flux of Ca²⁺ on fixed carrier concentration (SO₃^2-), initial pH value, OH^- concentration in irradiated membrane were found to be decreased about 2.68 ~ 6.87 times, about 1.42 ~ 1.63 times, about 2.07 ~ 1.672 times than non-irradiated membrane, respectively. As a result, the quantity of parathyroid hormone was decreased at irradiated membrane than non-irradiated membrane. The decrease of parathyroid hormone was occurred at hypoparathyroidism and osteoporosis, parathyroiditis, and so on. As the parathyroid hormone in epithelial cell membrane model were abnormal, cell damages were appeared at cell.