• Membrane Journal
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• v.33 no.6
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• pp.325-343
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• 2023

Direct methanol fuel cells (DMFCs) have been attracting attention as energy conversion devices that can directly supply methanol liquid fuel without a fuel reforming process. The commercial polymer electrolyte membranes (PEMs) currently applied to DMFC are perfluorosulfonic acid ionomer-based PEMs, which exhibit high proton conductivity and physicochemical stability during the operation. However, problems such as high methanol permeability and environmental pollutants generated during decomposition require the development of PEMs for DMFCs using novel ionomers. Recently, studies have been reported to develop PEMs using hydrocarbon-based ionomers that exhibit low fuel permeability and high physicochemical stability. This review introduces the following studies on hydrocarbon-based PEMs for DMFC applications: 1) synthesis of grafting copolymers that exhibit distinct hydrophilic/hydrophobic phase-separated structure to improve both proton conductivity and methanol selectivity, 2) introduction of cross-linked structure during PEM fabrication to reduce the methanol permeability and improve dimensional stability, and 3) incorporation of organic/inorganic composites or reinforcing substrates to develop reinforced composite membranes showing improved PEM performances and durability.

• Journal of Adhesion and Interface
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• v.7 no.1
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• pp.3-9
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• 2006

Three isocyanate groups of IP-$75^{(R)}$ and one hydroxyl group of various amino alcohols were applied for preparing cationic type water-borne polyurthane (PU) having ionic center onto flexible side chains. Average particle size, dispersion stability, viscosity, contact angle, surface energy, glass transition temperature ($T_g$), and adhesion strength of prepared water-borne PUs were measured and analyzed with different NCO/OH mol ratios, ionomers, and neutralizing agents. It was characterized that the prepared PU has a smaller particle size and a better dispersion stability than the conventional cationic water-borne PU containing ionic centers onto main chains.

• Proceedings of the Membrane Society of Korea Conference
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• 1993.10a
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• pp.58-58
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• 1993

Pervaporation has become important as a method to separate liquid mixtures, sepecially azeotropic and close boiling-point mixtures. Especially, water-alcohol separations have been carried out a lot because of the practical interests in the industries. However, outstanding membranes with high selectivity and high permeability have not been available in common use yet. In order to separate selectively out the water mixed with alcohols with an aim of the purification of the alcohols, a membrane has tO have excellent affinity to water. Among the hydrophilic polymers, polyacrylic acid and poly(vinyl alcohol) are used widely. In recent years, ionomers and polyion complexes, better hydrophitic materials, start to be used. The polyion complex membranes, consisting of polyacrylic acid (PAA) and polycation, showed excellent permeation rates and selectivities. It was known that among the polycations, ioneries, which have quaternary ammonium groups in the backbone chain, were more effective in giving membranes of higher permselectivities. On this base, syntheses and characterizations of the polycations, with different chemical structures from the published ones, for the polyion complex membrane formation were studied in this paper.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.93-96
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• 2007

Recently, much attentions have been paid on the commercialization of PEMFC, especially for the applications of residential and portable. In order to achieve the early commercialization of PEMFC, thee are two hurdles to overcome. One is cost down and the other is improvement of durability of the system components. Numerous companies have tried to reduce the production cost and the main research topics have been changed from performance to durability improvement. In this work, acceleration test were performed to find and evaluate the main reason of degradation of the MEA(membrane-electrode assembly) which is one of the core component of the PEMFC system. Based upon the test results, a way to make durable MEA was suggested. Acceleration tests were made by applying high voltage of 1.2V to the several kinds of single cells to increase the growth of catalyst particles. Cell performance, ac-impedance and electrochemically active area measurements were made atfter every 8 hours of acceleration test. Degradations of catalyst and membrane were examined by SEM, TEM and XRD. Obtained results were discussed in terms of structural stability and loss of catalyt and ionomers in the electrode layer. In addition, the way to make highly durable MEA was suggested.

• Elastomers and Composites
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• v.31 no.5
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• pp.341-346
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• 1996

The fracture mechanics investigation of the thermoplastic vulcanizates(TPV) from EPDM and PP/Ionomer ternary blends was performed in terms of the J-integral by measuring fracture energy via the locus method. The TPV from ternary blends consisting of EPDM, PP and ionomer were prepared in a laboratory integral mixer by blending and vulcanizing simultaneously. Vulcanization was performed with dicumyl peroxide (DCP) and the composition of EPDM and PP was fixed at 50/50 by weight. Two kinds of poly(ethylene-co-methacrylic acid) (EMA) lonomers were used. The J-integral values at crack initiation, Jc, of the dynamically vulcanized EPDM and PP/EMA Ionomer ternary blends were affected by the cation types $(Na^+\;or\;Zn^{2+})$ and contents(5-20wt%) of the added EMA Ionomers. The ternary blend containing 20wt% zinc-neutralized EMA Ionomer and 1.0phr DCP showed the highest Jc values of the blends.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.58-59
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• 2006

Less than a decade ago, most alternate membrane materials for fuel cells relied upon a post-sulfonation process to generate ionic groups capable of transporting protons from the anode to the cathode. These random post sulfonations showed some promise, but in general they produced materials that were not sufficiently stable or protonically conductive at ion exchange capacities where aqueous swelling could be restricted. Our group began to synthesize disulfonated monomers that could be used to incorporate into random copolymer proton exchange membranes. The expected limitation was that the aromatic polymers might not be stable enough to withstand fuel cell conditions. However, this was mostly based upon an accelerated test known was the Fenton's Reagent Test, which did not seem to this author as being a reliable predictor of performance. A much better approach has been to evaluate the open circuit voltage (OCV) for alternate membranes, as well as the benchmark perfluorosulfonic acid systems. When this is done, the aromatic ionomers of this study, primarily based upon disulfonated polyarylene ether sulfones, show up quite well. Real time 3000 hours DMFC results have also been generated. Obtaining conductive materials at low humidities is another major issue where alternate membranes have not been particularly successful. In order to address this problem, multiblock copolymers with relatively high water diffusion coefficients have been designed, which show promise for conductivity at lowered humidity.

• Applied Chemistry for Engineering
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• v.3 no.4
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• pp.614-619
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• 1992

Two types of polyurethane(PU) ionomer dispersion having different type of soft segment, viz. Poly (tetramethylene adipate) glycol(PTAd), and polypropylene glycol(PPG) were emulsion blended. Viscosity of emulsion blend, mechanical, and surface properties of the emulsion cast films were determined as a function of blend composition. Mechanical properties showed a large scatter of data or negative deviation from the additivity rule, and this was attributed to the incompatibility of soft segments. Contact angle measurement indicated that air facing surface of emulsion cast film contained more of PPG PU, due probably to its smaller particle diameter compared to PTAd PU.

• Fibers and Polymers
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• v.3 no.3
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• pp.97-102
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• 2002

A series of waterbome poly(urethane-urea) anionomers were prepared from isophorone diisocyanate (IPDI), polycaprolactone diol (PCL), dimethylol propionic acid (DMPA), ethylene diamine (EDA), and triethylamine (TEA), NaOH, or Cu($(COOCH_3)_2$) as neutralizing agent. This study was performed to decide the effect of neutralizing agent type on the particle size viscosity, hydrogen bonding index, adhesive strength, antistaticity, antibacterial and mechanical properties. The particle size of the dispersions decreased in the following order: TEA based samples (T-sample), NaOH based samples (N-sample), and Cu($(COOCH_3)_2$) based sample (C-sample). The viscosity of the dispersions increased in the order of C-sample, N-sample, and T-sample. Metal salt based film samples Of and C-sample) had much higher antistaticity than TEA based sample. By infrared spectroscopy, it was found that the hydrogen bonding index (or fraction) of samples decreased in the order of T-sam-pie, N-sample, and C-sample. The adhesive strength and tensile modulus/strength decreased in the order of T-sample, N-sam-pie, and C-sample. The C-sample had strong antibacterial halo, however, T- and N-samples did not

• Restorative Dentistry and Endodontics
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• v.22 no.2
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• pp.792-800
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• 1997

The purpose of this study was to evaluate the adaptation of self-cured glass ionomer cement and resin-modified glass ionomer cement and polyacid-modified resin composite, which are light-cured giass ionomer cements, to dentin surface. Twelve extracted human maxillary and mandibular molar teeth were used in this study. The entire occlusal dentin surfaces of teeth were exposed with Diamond Wheel Saw and smoothed with sand papers (300, 600, 1200grits). They were randomly assigned into 3 groups according to glass ionomer cements used; Control group- Fuji II, Expeimental group 1 - Fuji II LC, Expeimental group 2 - Dyract. According to the manufacturer's directions, three glass ionomer cements were bonded to exposed dentin surfaces of the tooth crown and cured. Crowns and glass ionomers were trimmed after 24hrs and sectioned horizontally and vertically with diamond saw. The interface of glass ionomer cements and dentin was examined under SEM. The results were as follows : 1. Good adatation between glass ionomer cement and dentin on the horizontal section was showed in control and experimental group 1, but the gap of $20{\mu}m$, which was observed distinct separation between glass ionomer cement and dentin, was showed in experimental group 2. 2. Good adatation between glass ionomer cements and dentin on the vertical section was showed in control and experimental group 1, but the gap of 80-$100{\mu}m$ was showed in experimental group 2. 3. Cohesive fracture within glass ionomer cements in control and experimental group 1 was showed, but no cohesive fracture was showed in experimental group 2.

• Restorative Dentistry and Endodontics
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• v.26 no.1
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• pp.64-76
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• 2001

Despite the improvements in bond strengths of dentin adhesives and resin-modified glass ionomers, the marginal seal of cervical restorations remains a concern. Microleakage at poorly sealed margins can result in staining, post-operative sensitivity, pulpal irritation, and recurrent caries. The objective of this study was to evaluate the effect of surface penetrating sealant(SPS) on the microleakage of cervical restorations. 45 extracted human teeth were selected, and Class V preparations were prepared on the both buccal and lingual surface of the teeth to the following dimensions : 1.5mm axially, 3mm mesiodistally, and 3mm incisogingivally. After cervical restoration with composite resin, compomer, glass ionomer each restoration was treated as three methods: No Tx., Scotchbond Multipurpose Adhesive$^{\circledR}$, Fortify$^{\circledR}$. The sections were examined with a stereomicroscope to determine the extent of microleakage at enamel and dentin margins. The results of this study were as follows. 1. All groups showed some microleakage. 2. Gingival cavity wall with cementum margin showed significantly higher leakage value than occlusal cavity wall with enamel margin. 3. The group treated with SPS showed significantly lower leakage value than no treated group(p<0.05). But there is no difference between Fortify$^{\circledR}$ and Scotchbond Multipurpose adhesive$^{\circledR}$. The results of this study suggest that SPS are effective in reducing microleakage of class V restorations. But it is certain that some microleakage still occurred despite the application of SPS.