• Applied Microscopy
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• v.31 no.2
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• pp.117-128
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• 2001

DMF is not a good solvent for PVA. There is no solvent-PVA interaction such as H-bonding. DMF/PVA makes a UCST system. DMF/PVA makes a gel through crystallization-induced gelation. X-ray, thermal analysis, and other experimental proofs are presented. The gelation rate was faster at low temperature. Small addition of PEG increased the rate of gelation, but urea decreased the rate. SEM showed the phase demixing process very clearly. In the early stage of gelation, only phase demixing was occurring at a low rate. Hence, no holes appear in the early stage photographs. As demixing proceeded further, the holes began to appear and the sizes became bigger. DMF phase remains many holes after vaporization and PVA phase constitute the matrix phase.

• Proceedings of the Membrane Society of Korea Conference
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• 1995.04a
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• pp.11-15
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• 1995

Polysulfone (PS) membranes were prepared by the phase inversion process using water or isopropanol as nonsolvent. The Flory-Huggins theory for a ternary system nonsolvent/solvent/polymer is applied to describe the thermodynamic equilibria of the components. The calculated ternary phase equilibria show that demixing of a PS binary solution with n-methylpyrrolidone (NMP) will be fast in a water coagulation bath and will be delayed in an isopropanol bath. The prepared membranes were characterized by SEM, gas adsorption-desorption measurement, and permeability test. The membrane, which is precipitated by fast demixing in a water bath, has nodular structures in the skin region and includes finger-like cavities in the sublayer. The membrane coagulated by isopropanol has a very dense and thick skin structure, which is formed by delayed demixing. The membrane coagulated by isopropanol showed considerably lower pore volume and surface area compared to that observed with water coagulation method. With dimethylformamide (DMF) as solvent and 2-3 wt% of water, the solution can show the liquid-liquid phase separation due to agglomation of the polymer-lean phase from the homogeneous solution. The membranes, which were coagulated near an equilibrium state, show the large (micron size) round pores in the whole membranes. The pores do not contribute the permeation characteristics.

• Membrane Journal
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• v.5 no.3
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• pp.119-128
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• 1995

The effects of coarsening on microstructure formation in polystyrene-cyclohexane solutions and membranes made from them were studied by scanning electron miccoscopy(SEM). Thermal analysis of the polymer solutions was carried out with a differential scanning calorimeter and the binodal curve was determined from the onset temperature of the heat of demixing peak. Using thermally induced phase separation(TIPS) and a freeze drying technique, it was demonstrated that polymer membrane microstructure can be changed significantly by controlling coarsening time and quench route. For systems undergoing phase separation by spinodal decomposition, resulting in a well interconnecmd, microporous structure with nearly uniform pore sizes, it was found that extending the phase separation time prior m freezing and solvent removal can result in a significant increase in pore or cell size which is highly dependent on both quench depth and coarsening time. Also this study has revealed the important role of polymer concentration in dictating the material continuity of the membranes.

• Korean Membrane Journal
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• v.6 no.1
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• pp.61-69
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• 2004

Small angle light scattering (SALS) and field emission scanning electron microscope (FE-SEM) have been used to investigate the effects of alcohol on phase separation of chlorinated poly(vinyl chloride) (CPVC)/tetrahydrofuran (THF)/alcohol (9/61/30 wt%) solution during water vapor induced phase separation. A typical scattering pattern of nucleation & growth (NG) was observed for all casting solutions of CPVC/THF/alcohol. In the case of the phase separation of CPVC dope solution containing 30 wt% ethanol or n-propanol, the demixing with NG was observed to be heterogeneous. Meanwhile, the phase separation of CPVC dope solution with 30 wt% n-butanol was found to be predominantly homogeneous NG. Although the different phase separation behavior of NG was observed with types of alcohol additives, the resultant surface morphology had no remarkable differences. That is, even though the NG process by water vapor is either homogeneous or heterogeneous, this difference does not play a main role on the final surface morphology. However, it was estimated from the result of hydraulic flux that the phase separation by homogeneous NG provided the membrane geometry with lower resistance in comparison with that by heterogeneous one.

• Membrane Journal
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• v.8 no.3
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• pp.157-169
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• 1998

The effects of solvents (DMAc, NMP, 1,4-dioxane) and nonsolvents ($H_2O$, Methanol, n-hexane) on the morphology of 6FDA-p-TeMPD polyimide membrane, prepared by the wet phase inversion method, were studied. In the polymer/solvent/nonsolvent ternary system, the binodal curve, the coagulation value and the relative light transmission were measured, and the solubility parameter difference was calculated. The onset state and rate of liquid-liquid alemixing were predicted and the morphology of membrane was analyzed. It is found that the finger-like pores are formed within discontinuous polymer nodules when the binoclal curve is close to the polymer-solvent (P-S) axis, the coagulation value is small, the reduction of light transmission is easy to occur and the order of solubility parameter difference ($\Delta \delta_{i-j}$) is $\Delta \delta_{S-NS} > \Delta \delta_{P-NS} > \Delta \delta_{P-S}$. The dense skin with small nodules and the sponge type sublayer with macrovoid are formed in the case that the binodal curve is distant from the P-S axis, the onset time of liquid-liquid demixing is long and the order of $\Delta \delta_{i-j}$ is $\Delta \delta_{P-NS} >(\Delta \delta_{S-NS} < > \Delta \delta_{P-S})$. The thick layer of fine nodule coagulation and loosely grown sublayer of nodules appear when the binodal curve is distant from the P-S axis, the onset time of liquid-liquid demixing is very long and the order of $\Delta \delta_{i-j}$가 $\Delta \delta_{S-NS} > (\Delta \delta_{P-NS}$\lessgtr$ > (\Delta \delta_{P-NS} < >)\Delta \delta_{P-S}$ ).

• Membrane Journal
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• v.19 no.1
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• pp.25-33
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• 2009

PES (polyethersulfone) membranes with highly enhanced their asymmetry were prepared by phase inversion process. The membranes were prepared by using PES/DMF (N,N-dimethylformamide)/TSA (p-toluenesulfonic acid)/PVP (polyvinylpyrrolidone) casting solution and water coagulant. The pre-coagulation of membrane surface which was induced by an addition of TSA as a demixing agent and PVP as a swelling polymer in the PES solution and humid exposure time, played a crucial role in determining morphological properties and the PWP (pure water permeation) performance. The PES solution was coated on polyester film under condition of 80% humidity for a while ($72{\sim}144$ sec) before immersing in a coagulation bath. The characterization of membranes was carried out by a capillary flow porometer, a FE-SEM and a permeation test apparatus. As the thickness of the smallest pore size layer (SPL) decreased, the asymmetry of membrane increased under conditions of 20 wt% of TSA and 10 wt% of PVP in 11 wt% of PES solution during longer humid contact time. As a result, the membranes showed a remarkable increase of PWP.

• Membrane and Water Treatment
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• v.6 no.3
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• pp.205-224
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• 2015

A novel hydrophilic poly (vinylidene fluoride)/poly (p-phenylene terephthalamide) (PVDF/PPTA) blend membrane was prepared by in situ polycondensation of p-phenylene diamine (PPD) and terephthaloyl chloride (TPC) in PVDF solution with subsequent nonsolvent induced phase separation (NIPS) process. For comparison, conventional solution blend membrane was prepared directly by adding PVDF powder into PPTA polycondensation solution. Blend membranes were characterized by means of viscometry, X-ray photoelectron spectroscopy (XPS), Field Emission Scanning Electron Microscopy (FESEM). The effects of different blending methods on membrane performance including water contact angle (WCA), mechanical strength, anti-fouling and anti-compression properties were investigated and compared. Stronger interactions between PVDF and PPTA in in situ blend membranes were verified by viscosity and XPS analysis. The incorporation of PPTA accelerated the demixing rate and caused the formation of a more porous structure in blend membranes. In situ blend membranes exhibited better hydrophilicity and higher tensile strength. The optimal values of WCA and tensile strength were $65^{\circ}$ and 34.1 MPa, which were reduced by 26.1% and increased by 26.3% compared with pure PVDF membrane. Additionally, antifouling properties of in situ blend membranes were greatly improved than pure PVDF membrane with an increasing of flux recovery ratio by 25%. Excellent anti-compression properties were obtained in in situ blend membranes with a stable pore morphology. The correlations among membrane formation mechanism, structure and performance were also discussed.

• Membrane Journal
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• v.15 no.4
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• pp.272-280
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• 2005

In this study, asymmetric polysulfone membranes were prepared by the phase inversion method and the casting solutions were containing N-methyl-2-pyrrolidone (NMP) as a solvent. Deionized water and various alcohols(methanol, ethanol, and propanol) were used as a coagulation medium in preparing asymmetric polysulfone membranes. This study investigates the effect of alcohol coagulants having different solubility parameters as a pore-former on the construction of porous structures and their pure water permeation properties. Asymmetric polysulfone membranes immersed in the pure alcohol coagulation bath solution showed the typical sponge-like structures and the reduced water permeability as compared with those of polysulfone membranes precipitated in the pure water coagulation bath solution. In the water/alcohol mixtures, asymmetric polysulfone membranes showed the finger-like structures with the sponge-like structures. Therefore, the sponge-like structure of polysulfone membrane was formed under the delayed demixing systems while the porosity of membrane was decreased significantly. The water permeability of polysulfone membrane precipitated in the pure water coagulant showed 164 [$L/m^2hr$] at 14.7 psi. In case of polysulfone membranes prepared in the pure methanol and ethanol coagulant, they showed the water permeability of 56 and 30 [$L/m^2hr$], respectively.

• Membrane Journal
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• v.17 no.3
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• pp.219-232
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• 2007

The polyethersulfone(PES)-titanium oxide($TiO_2$) hybrid membranes were prepared by immersion precipitation phase inversion method. The casting solution for the preparation of $PES-TiO_2$ hybrid membrane was provided by adding $TiO_2$ nano particles into the basis polymer solution of 14 wt% and 20 wt% PES/N-methyl-2-pyrrolidone(NMP). The $TiO_2$ loading [wt% ($TiO_2/NMP$)] in eating solution was varied from 0 to 60 wt%. Membrane performance and morphological change of the resulting $PES-TiO_2$ hybrid membranes were discussed in aspect of $TiO_2$ loading, by viscosity, coagulation value and light transmittance of the casting solution, measurement of tensile strength, pore size and contact angle, surface and cross sectional SEM images of the hybrid membrane, and ultrafiltration experiments using the hybrid membrane. According as increase of $TiO_2$ loading in the casting solution, viscosity is increased and coagulation value becomes lower, therefore the thermodynamic instability of the casting solution is increased. It is found that when $TiO_2$ loading is increased, 1) precipitation rate becomes faster while instantaneous demixing is maintained, 2) pure water flux, membrane pore size and compaction stability of the resulting membranes are increased, 3) tensile strength and contact angle are decreased. Dead-end ultrafiltration of bovine serum albumin(BSA) solution using the hybrid membrane shows that membrane performance(flux of BSA solution) enhanced up to 7 times compared with the results obtained using the pure PES membrane(not containing $TiO_2$ particle), due to the increase of hydrophilicity.

• Membrane Journal
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• v.12 no.2
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• pp.75-89
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• 2002

The effect of addition of inorganic salts in polyethersulfone (PES) polymer solution on the membrane formation and ultrafiltartion performance was studied through the thermodynamic and kinetic properties of casting solution. To control the thermodynamic and kinetic properties of casting solution, various inorganic salts $[CaC1_2, LiCl, LiClO_4, ZnC1_2 $and Mg(ClO_4)_2]$ were added in the PES/NMP solution. Variation of membrane morphology and performance of the resulting membranes with change of the salt type and content added in tasting solution were discussed using viscosity, coagulation value, light transmittance measurement, overall membrane porosity, ultrafiltration experiment and cross-sectional SEM image. For all kind of inorganic salts, according as increase of the salt content in casting solution, viscosity is increased, coagulation value becomes lower, top layer thickness below the skin surface is increased, bovine serum albumin(BSA) rejection decreased and pure water flux is increased except $CaC1_2$ and LiCl. In case of $CaC1_2$ and LiCl, it is found that when the salt content is increased, the formation of macrovoids is suppressed and the precipitation rate becomes slow while instantaneous demixing of precipitation type is maintained. However, in case of $LiClO_4$ and $Mg(ClO_4)_2,$ it is found that precipitation rate becomes faster.