• Membrane Journal
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• v.17 no.4
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• pp.311-317
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• 2007

Proton conducting crosslinked membranes have been prepared by polymer blending, which consist of poly(vinyl alcohol-co-ethylene) (PVA-co-PE) and poly(styrene sulfonic acid-co-maleic acid) (PSSA-co-PMA) at 50 : 50 wt ratio. Two kinds of PSSA-co-PMA copolymer with 3 : 1 and 1 : 1 the molar ratio of PSSA to PMA wereused as a proton conducting source. The ethylene content of PVA-co-PE was also changed as 0, 27 and 44 mol%. The membranes were thermally crosslinked via the esterification reaction between -OH of PVA and -COOH of PMA, as demonstrated by FT-IR spectroscopy (PVA-co-PE)/(PSSA-co-PMA) membranes with 3 : 1 the molar ratio of PSSA to PMA showed higher ion exchange capacity (IEC), lower water uptake and higher proton conductivity than those with 1 : 1 molar ratio. As the PE concentration increased, the IEC values, water uptake and proton conductivities decreased continuously. These properties were elucidated in terms of competitive effect between the concentration of sulfonic acid, hydrophilicity and the crosslinked structure of membranes.

• Membrane Journal
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• v.19 no.2
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• pp.89-95
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• 2009

A comb-like copolymer consisting of a poly(vinyl chloride) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. PVC-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP). This comb-like copolymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA in the graft copolymer and the -COOH groups of IDA. Upon doping with phosphoric acid (PA, $H_3PO_4$) to form imidazole-PA complexes, the proton conductivity of the membranes continuously increased with increasing PA content. A maximum proton conductivity of 0.011 S/cm was achieved at $100^{\circ}C$ under anhydrous conditions. The PVC-g-PHEA/IDA/PA complex membranes exhibited good mechanical properties, i.e. 575 MPa of Young's modulus, as determined by a universal testing machine (UTM). Thermal gravimetric analysis (TGA) shows that the membranes were thermally stable up to $200^{\circ}C$.

• Polymer(Korea)
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• v.29 no.1
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• pp.87-90
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• 2005

In this study, we have examined the exfoliation behavior of layered clay during in-situ polymeriztion with styrene by using real-time XRD analysis. The 4C1 beam line at the Pohang Accelerator Laboratory (PAL) was used for this study. Different exfoliation behaviors have been shown to depend on the cation exchange capacity (CEC) of clay and the chemical structure of organic modifiers. For 10A-MMT and 15A-MMT having high CEC, no peak shifts were observed on real-time XRD analysis during polymerization. However, 2$\theta$ for 25A-MMT and VDAC-MMT, each having low CEC’s as well as aromatic benzene moieties and vinyl groups, respectively, decreased as polymerization time increased.

• 한국신재생에너지학회:학술대회논문집
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• 2006.11a
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• pp.329-331
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• 2006

연료전지용으로 많이 사용되는 전불소계 고분자인 Nafion은 좋은 기계적, 화학적 안정성 및 높은 이온전도도에도 불구하고 고가의 생산단가, 높은 메탄올 투과도, 그리고 MEA 재활용 문제 등으로 인해 상업적 응용에 제한이 있다. 본 연구는 불소그룹을 함유한 술폰화된 아릴렌이서계 블록 공중합체 고분자 전해질막의 제조 및 연료전지 특성에 관한 것이다. 이러한 고분자를 제조하기 위하여 양말단에 불소계 비닐기를 가지면서, 상온에서 술폰화 가능한 biphenyl계 단량체와 술폰화가 불가능한 sulfonyl계 단량체를 각각 합성하였으며, 이들로부터 다양한 몰조성과 분자량을 갖는 올리고머를 포함한 일련의 perfluorocyclobutane기를 포함하는 블록 공중합체를 열적 고리화 부가중합을 사용하여 합성하였다. 제조된 블록 공중합체를 상온에서 술폰화제인 chlorosulfonic acid를 이용하여 선택적으로 후술폰화시켜 강산 이온기인 sulfonic acid를 블록 올리고머에 도입하였다. 합성된 고분자들의 연료전지 특성을 Nafion-115와 비교하였다. 술폰화가 되는 올리고머 블록의 비율 증가에 따라 이온교환능력이 증가하였고, 그에 따라 높은 함수율과 이온 전도도를 나타내었으며 건조 및 습윤 상태에서도 기계적 강도가 우수하였다. 최적화된 블록공중합체를 대상으로 MEA를 제조하여 연료전지 초기성능을 측정한 결과 Nafion과 유사한 전기화학적 성능을 나타내었다.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.44-48
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• 2014

Sulfonated poly(arylene ether sulfone)-cerium composite membranes with improved oxidative stability were prepared for proton exchange membrane fuel cell application. Oxidative stability of the composite membranes changed depending on the amount of incorporated metal. Their water uptake, IEC and proton conductivity were also affected. ICP analysis confirmed trace of cerium ion in the composite membranes and $^1H$-NMR indicated successful coordination of sulfonic acid groups with the metal ions. Increasing amount of the cerium ion resulted in decrease in proton conductivities and water uptake, but enhanced oxidative stabilities. A hydrogen peroxide exposure equipment was used for the test of oxidative stability of the composite membranes, which enabled to mimic fuel cell operating condition compared with conventional Fenton's test.

• Applied Chemistry for Engineering
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• v.19 no.1
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• pp.111-116
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• 2008

Collapsed perflurostearic acid (PFS) films were prepared on the different pH and the various metal ion ($Na^+$, $Ca^{2+}$, $La^{3+}$) containing subphase using Langmuir-Blodgett (LB) trough. The degree of ionization of collapsed PFS film formed from floating monolayer has been determined by Fourier transform infrared (FTIR) spectroscopy. The intensity of C = O of -COOH peaks of collapsed PFS decreased with increasing pH of subphase. The order of ionization of collapsed PFS on the subphase of the same pH was $La^{3+}$ > $Ca^{2+}$ > $Na^+$. The degree of ionization of collapsed PFS on the Deionized (D.I.) water subphase is above 50% even at subpahse pH 3, which is much higher degree of ionization than that of stearic acid.

• Korean Journal of Agricultural and Forest Meteorology
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• v.13 no.3
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• pp.140-147
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• 2011

We studied the influence of livestock waste leachate on oxidative damage and antioxidative responses in poplar clones in August which increase the demand of antioxidants because of high temperature and high light during this period. We measured ion leakage, antioxidant enzyme activities (APX, GR), and carotenoid contents. Oxidative damage and antioxidative responses by treated livestock waste leachate in poplar clones showed various results. We divided poplar clones into three groups using the criteria based on ion leakage which represent cell damage induced oxidative stress. Eco 28, 62-10, Bonghwa1 and Dorskamp belonged to the first group in which the cell damaged level was lower than that of the control. The results suggest that this group augmented for demand of antioxidative in summer because high concentration of nitrogen induced by treatment of live stock wastes acted as environmental stress. Consequently, they failed to keep up the homeostasis of reactive oxygen species. The second group in which the cell damaged level was similar to that of the control was Suwon, 72-30 and 72-31 clones. Finally, 97-18 clone belonged to the third group in which the cell damaged level was lower than that of the control group. In this case, nitrogen treated by livestock waste leakage decreased oxidative stress. 97-18 clone was the clones with the least damage in summer oxidative stresses treated by livestock waste leakage. These results suggest that the high concentration nitrogen due to the livestock waste leakage can act differently upon the clones. We speculate that the added oxidation damage in the summer (growing season) may have an effect on the total fresh weight and also influence the purification ability for livestock waste leakage. However, further studies are needed for the confirmation.

• Journal of the Korean Vacuum Society
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• v.18 no.6
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• pp.435-439
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• 2009

The reason of lowering the dielectric constant of SiOC film was studied using parameters obtained from C-V measurement and refractive index. SiOC film was formed by the force of ionic bonding during the recombination of dissociated gases. Generally, the dielectric constant was obtained from the square of the refractive index or C-V measurement using the metal/insulator/Si structure. The dielectric constant consists of the ionic and electronic elements. It was researched about the dielectric constant of SiOC film using the average of the ionic and electronic elements. The dielectric constant decreased after annealing process. As deposited films trended toward the dielectric constant consisted of most ionic elements, on the other hand, annealed films mostly consisted of electronic elements. Because the effect of ionic elements reduced after annealing. Consequently, it was found that the electronic effect of SiOC film increased and the ionic effect of SiOC film decreased by the after-annealing.

• Proceedings of the Korean Vacuum Society Conference
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• 1999.07a
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• pp.112-112
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• 1999

고분자 표면에 MeV급 이온을 주입하게 되면 화학적, 광학적, 물리적, 전기적 특성 등 기존의 재래식 공정으로는 불가능한 다양한 특성변화가 일어나게 된다. 본 실험에서는 이온 조사에 따른 micro-hardness의 변화에 중점을 두어 관찰하였다. 수 MeV로 가속시킨 Cl과 C 이온을 Kapton, Teflon, PMMA에 조사량을 바꾸어가며 조사하였다. 이때 조사 전후 고분자 시료의 표면 경도는 depth-sensing nanoindentation technique (Nano Indenter II, USA)을 이용하여 측정하였다. 측정깊이는 극표면 효과와 기측효과의 영향을 무시할 수 없는 100nm로 결정하였다. 또한 이와 같은 경도변화를 규명하기 위하여 각각의 시료에 대해 FTIR, Raman, UV-VIS, RBS, XPS 스펙트럼을 측정하였으며, 조사중에 발생되는 가스상 분자들을 RGA를 이용하여 측정하였다. 1 MeV Cl 이온을 Kato에 4x1015ions/cm2 조사하면 경도가 0.35 GPa에서 7.1GPa로 약 20배 정도 증가하게 되며, 이 경도는 stainless steel 경도 2~3 GPa, martensite steel 8~12와 비교하여 보면 상당히 높은 수준임을 알 수 있다. Teflon과 PMMA 시료의 경우 1MeV Cl 이온 4X1015ions/cm2를 조사시키면 각각 경도가 0.31GPa에서 4.1a, 0.30 GPa에서 3.9GPa로 변화하였으며 Kapton에 비하여 상대적으로 경도의 변화가 적음을 알 수 있었다. 이온 주입된 Kapton의 경우 FT-IR측정에 의하여 이온 조사량이 증가함에 따라 C=O 진동, 이미드그룹의 CONH, tertiary amine의 C-N 흡수 피크가 감소되며, 1X1014ions/cm2 이상의 양이 조사되어야 개질변화가 일어남을 알 수 있었다. XPS 측정 결과 Kapton에 조사되는 이온양이 증가할수록 C=O, C-O 및 C-N의 탄소는 감소하고 페닐고리 탄소가 증가함을 알 수 있었다. 또한 이온 조사 중 측정한 RGA에서도 CO 가스가 대량 방출되는 현상을 관찰하였으며 FTIR 및 XPS에서의 C=O 결합의 감소와도 일치하였다. RBS에 의한 CNO 원소의 변화에서도 다른 원소보다 O의 감소가 현저하게 나타남을 확인하였다. UV-VIS 측정을 통해 조사 이온량에 따라 에너지 준위가 변동하여 흡수스펙트럼이 장파장으로 확대됨을 알 수 있었으며, 이는 공액 2중 결합의 형성에 의한 $\pi$-전자 및 기타 결함에 기인한다. PMMA 및 Teflon의 경우 FTIR 측정에 의하여 이온 조사됨에 따라 function group 들의 peak가 세기가 감소되면서 완만해지는 경향을 보이며 원래의 구조를 상실하게 된다. PMMA와 Teflon은 이온 조사가 되면 가교형서보다는 사슬절단이 주로 일어나므로 가교형성이 잘 일어나는 Kapton보다는 상대적으로 경도의 증가가 적음을 알 수 있었다.

• Journal of the Korean Chemical Society
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• v.21 no.5
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• pp.320-329
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• 1977

p-Phenylenediamine dihydroperchlorate, $C_6H_4N_2H_4{\cdot}2HC1O_4$, crystallizes in space group $P\={1}$ with $a=4.79{\pm}0.02,\;b=9.03{\pm}0.02,\;c=7.12{\pm}0.03{\AA},\;{\alpha}=109.4{\pm}0.2,\;{\beta}=79.6{\pm}0.2,\;r=104.6{\pm}0.2^{\circ},\;Z=1$. The structure has been solved by the Patterson and Fourier methods. The refinement by block-diagonal least-squares cycles gives R = 0.13 for 387 observed reflexions collected on equi-inclination Weissenberg photographs with CuK${\alpha}$ radiation. There are two different types of five hydrogen bonds. The first type consists of one trifurcated N${\cdot}{\cdot}{\cdot}$O hydrogen bond and the second of two normal N${\cdot}{\cdot}{\cdot}$O hydrogen bonds, both of which exist between the amino group and the perchlorate, groups. A p-phenylenediamine group is approximately planar within an experimental error and bonded to twelve perchlorates: ten perchlorates forming hydrogen bonds and two being contacted with the van der Waals forces. A perchlorate group is surrounded by six p-phenylenediamines and four perchlorates; among the six p-phenylenediamines, five of them are hydrogen-bonded, and the rest contacted with the van der Waals force.ce anaysis of our samples and investigated the variarions in the values of parameters obtained through fitting the theoretical impedance to the experimental impedance. The characters of the dielectric constant and the impedance showed abnormal variations for the 0.2 at K-doped NSBN ceramics, which we were able to interpret in terms of the variations in the number A-site vacancies with the K doping ratio. From these results, A-site vacancies are thought to be space charges that influence the ferroelectric properties of NSBN ceramics.