• Proceedings of the Membrane Society of Korea Conference
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• 2003.07a
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• pp.29-32
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• 2003

Polymer electrolyte membranes are developed for the applications to facilitated transport membranes, fuel cells and solar cells. The polymer electrolyte membranes containing silver salt show the remarkably high separation performance for olefin/paraffin mixture in the solid state; the propylene permeance is 45 GPU and the ideal selectivity of propylene/propane is 15,000. For fuel cell membranes, the effects of the presence and size of the proton transport channels on the proton conductivity and methanol permeability were investigated. The cell performance for dye-sensitized solar cells employing polymer electrolytes are measured under light illumination. The overall energy conversion efficiency reaches 5.44 % at 10 ㎽/$\textrm{cm}^2$, to our knowledge the highest value ever reported in the polymer electrolytes.

• Macromolecular Research
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• v.16 no.8
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• pp.676-681
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• 2008

The $\pi$-complex membranes of poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) of two silver salts of $AgBF_4$ and $AgCF_3SO_3$ were prepared and tested for the separation of the propylene/propane mixtures. The Fourier-transform infrared (FT-IR) spectra of these complexes showed that the silver salts were dissolved in SEBS up to a silver mole fraction of 0.14, due to $\pi$-complexation between the aromatic C=C bonds of styrene blocks and silver ions. Above this solubility limit, ion pairs and high-order ionic aggregates began to form, so that silver salts were distributed unselectively in both the EB and PS blocks. The domain size of the PS blocks was enlarged up to this critical concentration with increasing silver concentration without structural transitions, as confirmed by small angle x-ray scattering (SAXS). These structural properties of the SEBS/silver salt complexes may explain the lower separation properties for propylene/propane mixtures compared to poly(styrene-b-butadiene-b-styrene)(SBS)/silver salt complex membranes.

• Korean Membrane Journal
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• v.8 no.1
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• pp.43-49
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• 2006

Complex membranes consisting of silver salt ($AgBF_4,\;AgCF_3SO_3,\;AgSbF_6,\;AgNO_3$) and poly(vinyl alcohol) (PVA) or crosslinked PVA (CPVA) were prepared and tested for the separation of propylene/propane mixtures. For the tested membranes, the complex membranes containing $AgBF_4$ exhibited the highest separation properties, i.e., approximately 20 GPU ($1 GPU=10^{-6}cm^3 (STP)/(cm^2 sec cmHg)$) and 100 of selectivity at 0.2 of silver mole fraction. The CPVA membranes containing silver salt always showed higher selectivity than PVA membranes, presenting silver ions coordinated to -CHO are more effective than those to -OH groups. The threshold silver concentration of CPVA membranes was lower than that of PVA membranes, which might be due to stronger interaction of silver ions with -CHO than that with -OH. The composition at which the selectivity is the highest did not significantly depend on the crosslinking, but did on the kind of silver salt.

• Membrane Journal
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• v.24 no.6
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• pp.417-422
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• 2014

The poly(ethylene oxide) (PEO)/Ag Nanoparticles (NPs)/7,7,8,8-Tetracyanoquinodimethane (TCNQ) membrane was fabricated to obtain highly permeable facilitated olefin transport nanocomposite membrane, compared with PEO/Ag NPs/p-Benzoquinone (p-BQ) membrane. Polymer matrix, PEO and silver nanoparticle precursor $AgBF_4$ were fixed at 1 : 0.4 mole ratio and electron acceptor TCNQ content was controlled variously. And the best olefin separation performance was obtained at 1/0.4/0.004 mole ratio, and long-term separation performance was measured at this ratio. As a result, mixed-gas permeance decreased from 23 to 6 GPU, and selectivity decreased from 6 to 2 (propylene/propane) after 32 hours.

• Membrane Journal
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• v.25 no.5
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• pp.398-405
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• 2015

Facilitated transport is considered to be a possible solution to simultaneously improve permeability and selectivity, which is challenging in normal polymeric membranes based on solution-diffusion transport only. We investigated the effect of adding mesoporous $TiO_2$ ($m-TiO_2$) upon the separation performance of facilitated olefin transport membranes comprising poly(vinyl pyrrolidone), Ag nanoparticles, and 7,7,8,8-tetracyanoquinodimethane as the polymer matrix, olefin carrier, and electron acceptor, respectively. In particular, $m-TiO_2$ was prepared by means of a facile, mass-producible method using poly(vinyl chloride)-g-poly(oxyethylene methacrylate) graft copolymer as the template. The crystal phase of $m-TiO_2$ consisted of an anatase/rutile mixture, of crystallite size approximately 16 nm as determined by X-ray diffraction. The introduction of $m-TiO_2$ increased the membrane diffusivity, thereby increasing the mixed-gas permeance from 1.6 to 16.0 GPU ($1GPU=10^{-6}cm^3$(STP)/($s{\times}cm^2{\times}cmHg$), and slightly decreased the propylene/propane selectivity from 45 to 37. However, both the mixed-gas permeance and selectivity of the membrane containing $m-TiO_2$ rapidly decreased over time, whereas the membrane without $m-TiO_2$ had more stable long-term performance. This difference might be attributed to specific chemical interactions between $TiO_2$ and Ag nanoparticles, causing Ag to lose activity as an olefin carrier.

• Membrane Journal
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• v.25 no.6
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• pp.496-502
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• 2015

Facilitated transport is one of the possible solutions to simultaneously improve permeability and selectivity, which is challenging in conventional polymer-based membranes. Olefin/paraffin separation using facilitated transport membrane has received much attention as an alternative solution to the conventional distillation process. Herein, we report olefin separation composite membranes based on the polymer blends containing $AgBF_4/Al(NO_3)_3$ mixed salts. Free radical polymerization process was used to synthesize an amphiphilic graft copolymer of poly(dimethyl siloxane)-graft- poly(ethylene glycol) methyl ether methacrylate (PDMS-g-POEM). In addition, poly(ethylene oxide) (PEO) was introduced to the PDMS-g-POEM graft copolymer to form polymer blends with various ratios. The propylene/propane mixed-gas selectivity and permeance reached up to 5.6 and 10.05 GPU, respectively, when the PEO loading was 70 wt% in polymer blend. The improvement of olefin separation performance was attributed to the olefin facilitating silver ions as well as the highly permeable blend matrix. The stabilization of silver ions in the composite membrane was achieved through the introduction of $Al(NO_3)_3$ which suppressed the reduction of silver ions to silver particles.

• Membrane Journal
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• v.16 no.4
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• pp.294-302
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• 2006

Silver polymer electrolytes are very promising membrane materials for the separation of olefin/paraffn mixtures. Olefin molecules are known to be transported through reversible complex formation with silver ions entrapped iii polymer matrix. However, they have poor long-term stability, which is very important fur the industrial application; the selectivity through the membrane decreases gradually with time mostly due to the reduction of silver ions ($Ag^+$) into silver nanoparticles ($Ag^0$). In this study, the stability of silver polymer electrolyte was investigated for poly(vinyl pyrrolidone) (PVP) and $AgBF_4$ system containing a surfactant, i.e. $C_{18}H_{35}(OCH_2CH_2)_{20}OH$ (Brij98) as a stabilizer. The reduction behavior of silver ions to silver nanoparticles in PVP was also investigated by atomic force microscopy (AFM) and UV-visible spectroscopy. It was found that the growth of silver nanoparticles was slower and selectivity of polymer electrolyte for propylene in propylene/propane was maintained longer time when Brij98 was added as a stabilizer.