• Macromolecular Research
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• v.17 no.2
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• pp.104-109
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• 2009

Solid-state facilitated, olefin transport membranes were prepared by complexation of poly(styrene-b-iso-prene-b-styrene) (SIS) block copolymer and silver salt. Facilitated olefin transport was not observed up to a silver mole fraction of 0.14, representing a threshold concentration, above which transport increased almost linearly with increasing silver salt concentration. This was because firstly the silver ions were selectively coordinated with the C=C bonds of PI blocks up to a silver mole fraction of 0.20, and secondly the coordinative interaction of the silver ions with the aliphatic C=C bond was stronger than that with the aromatic C=C bond, as confirmed by FT-Raman spectroscopy. Small angle X-ray scattering (SAXS) analysis showed that the cylindrical morphology of the neat SIS block copolymer was changed to a disordered structure at low silver concentrations ($0.01{\sim}0.02$). However, at intermediate silver concentrations ($0.15{\sim}0.20$), disordered-ordered structural changes occurred and finally returned to a disordered structure again at higher silver concentrations (>0.33). These results demonstrated that the facilitated olefin transport of SIS/silver salt complex membrancs was significantly affected by their coordinative interactions and nano-structural morphology.

• Macromolecular Research
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• v.10 no.2
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• pp.80-84
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• 2002

Silver species other than the silver ion were formed by UV irradiation on polymer electrolyte membranes containing silver salts and their effect on complexation behavior between the silver and olefin was investigated through the separation performance of olefin/paraffin mixtures. The ideal propylene/propane separation factor reached 350 and the separation coefficient was ca.15 due to the high loading amount of silver ions into poly(2-ethyl-2-oxazoline) (POZ) without UV irradiation. On UV irradiation either in air or under nitrogen, the silver-POZ membranes became yellow-brown initially due to the formation of colloidal silver particles, and finally black and metal-like luster. Even when Ag$^{+}$ was converted, to some extent, to Ag$^{\circ}$ by UV irradiation in air at the early stage, the separation coefficient of olefin/paraffin mixtures was maintained. This suggests that silver species other than the silver ion is active for olefin carrier for facilitated transport. Meanwhile the steady decrease of the separation coefficient was observed in the silver/POZ membranes irradiated under $N_2$. It is suggested that the reduction of silver ions in POZ goes through a different photoreduction mechanism with UV irradiation depending on the environment.t.

• Macromolecular Research
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• v.11 no.5
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• pp.375-381
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• 2003

Silver salt complex membranes with glassy poly(methyl methacrylate) (PMMA) unexpectedly showed higher propylene permeance than those with rubbery poly(butyl methacrylate) (PBMA) where as neat PMMA is much less permeable to propylene than that of neat PBMA. Such unusual facilitated olefin transport has been systematically investigated by changing the side chain length of polymethacrylates (PMAs) from methyl, ethyl to butyl. The ab initio calculation showed almost the same electron densities of the carbonyl oxygens in the three PMAs, expecting very similar intensity of the interaction between carbonyl oxygen and silver ion. However, the interaction intensity decreases with the length of the alkyl side chain: PMMA > PEMA > PBMA according to wide angle X-ray scattering and FT-Raman spectroscopy. The difference in the interaction intensity may arise from the difference in the hydrophilicity of the three PMAs, as confirmed by the contact angle of water, which determines the concentrations of the ionic constituents of silver salts: free ion, contact ion pair and higher order ionic aggregate. However, propylene solubilities and facilitated propylene transport vary with the side chain length significantly even at the same concentration of the free ion, the most active olefin carrier, suggesting possible difference in the prohibition of the molecular access of propylene to silver ion by the side chains: the steric hindrance. Therefore, it may be concluded that both the hydrophilicity and the steric hindrance associated with the side chain length in the three PMAs are of pivotal importance in determining facilitated olefin transport through polymer/silver salt complex membranes.

• Proceedings of the Membrane Society of Korea Conference
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• 2004.05a
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• pp.136-139
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• 2004

Olefin/paraffin separation by the facilitated transport membrane using silver salts as carriers has been considered as a promising alternative to the conventional energy intensive distillation process. The basis for the separation is the ability of silver ions to react reversibly with olefin forming silver-olefin complexes.(omitted)

• Macromolecular Research
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• v.12 no.2
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• pp.145-155
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• 2004

Facilitated transport membranes for the separation of olefin/paraffin mixtures have long been of interest in separation membrane science because olefins, such as propylene and ethylene, which are important chemicals in petrochemical industries, are currently separated by energy-intensive cryogenic distillation processes. Recently, solid polymer electrolyte membranes containing silver ions have demonstrated remarkable performance in the separation of olefin/paraffin mixtures in the solid state and, thus, they can be considered as alternatives to cryogenic distillation. Here, we review recent progress, and critical issues affecting in the use of facilitated olefin transport membranes; in particular, we provide a general overview with reference to carrier properties, transport mechanisms, and separation performance.

• Membrane Journal
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• v.13 no.2
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• pp.125-129
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• 2003

A remarkable separation performance of olefin/paraffin mixtures has been observed through facilitated olefin transport membranes consisting of silver ions dissolved in polymer matrices. In this research, valine, an amino acid, was introduced in poly (2-ethyl-2-oxazoline) (POZ)/$AgBF_4$ membranes to increase the separation performance. FT-IR spectra show that the cationic sites ($-NH_3^+$) of valine interact with the counter anion of the silver salt, resulting in the enhanced activity of the silver ions and consequently improved separation perfornance. Therefore, the $POZ/AgBF_4$ membranes containing valines exhibit the higher permeance as well as the higher selectivity of propylene/propane than those without valine.

• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.489-493
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• 2003

2-Mercaptobenzothiazole was used as a highly selective and efficient carrier for the uphill transport of silver ion through a chloroform bulk liquid membrane. In the presence of thiosulfate ion as a suitable metal ion acceptor in the receiving phase, the amount of silver transported across the liquid membrane after 180 min was 90 ± 3.0%. The selectivity and efficiency of silver ion transported from aqueous solutions containing equimolar mixtures of $Zn^{2+}, Cu^{2+}, Co^{2+}, Ni^{2+}, Cd^{2+}, Pb^{2+}, Bi^{3+}, Fe^{2+}, Fe^{3+}, Pd^{2+}, Mn^{2+}, Hg^{2+}, Sn^{2+}, Ca^{2+}, Mg^{2+}, K^+, Na^+ and Li^+$ were investigated.

• 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.

• Journal of Soil and Groundwater Environment
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• v.21 no.1
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• pp.104-110
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• 2016

The transport of silver nanoparticles (AgNPs) was investigated through a column packed with sand. A series of column experiments were carried out to evaluate the effect of ionic strength (IS), pH, electrolyte type and clay mineral on mobility of polyvinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs). The deposition of PVP-AgNPs was increased with increasing solution ionic strength and decreasing pH. Furthermore, the depositon of PVP-AgNPs was affected by the electrolyte type (NaCl vs. NaNO₃) and was shown to be greater at NaNO₃ solution. Also, the transport of PVP-AgNPs was greatly increased after the pre-deposition of clay particles on sand. Our results suggest that various environmental factors can influence the mobility of PVP-AgNPs in soil-groundwater systems and should be carefully considered in assessing their environmental risks.