• Fibers and Polymers
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• v.4 no.4
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• pp.188-194
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• 2003

Phase behavior and spinodal phase separation kinetics in binary blends of a random copolymer of vinylidene fluoride and trifluoroethylene (75/25) [P(VDF/TrFE)] and poly(l,4-butylene adipate) (PBA) have been investigated by means of optical microscopic observation and time-resolved light scattering. The blends exhibited a typical lower critical solution temperature (LCST)∼${34}^{\circ}C$ above the melting temperature of the P(VDF/TrFE) crystals over the entire blend composition range. P(VDF/TrFE) and PBA were totally miscible in the temperature gap between the melting point of P(VDF/TrFE) and the LCST. Temperature jump experiments of the 3/7 P(VDF/TrFE)/PBA blend were carried out on a light-scattering apparatus from a single-phase melt state (${180}^{\circ}C$) to a two-phase region (205∼${215}^{\circ}C$). Since the late stage of spinodal decomposition (SD) is prevalent in the 3/7 blend, SD was analyzed using a power law scheme. Self-similarity was preserved well in the late stage of SD in the 3/7 blend.

• Proceedings of the Membrane Society of Korea Conference
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• 1995.04a
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• pp.1-4
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• 1995

The microstructure of polymer membranes produced via thermally induced phase separation (TIPS) of polymer solutions is a strong function of both the early-stage (by spinodal decomposition or nucleation & growth) and the late-stage phase separation (referred to in general as coarsening). In the case of early stage effects, the membrane morphology resulting from a nucleation & growth mechanism is either a poorly interconnecsed, stringy, beady structure which is mechanically fragile or a well interconnected structure with highly nonuniform pore sizes. In contrast, spinodal decomposition results in a well interconnected, mechanically strong membrane with highly uniform pore sizes. Here I describe recent quantitative studies of the coarsening effects on the microstructure of membranes produced via TIPS process. The dependence of microstructure on coarsening time, quench depth, solution viscosity, and polymer molecular weight was investigated in order to distinguish among three possible coarsening mechanisms, Ostwald ripening, coalescence, and hydrodynamic flow, which may be responsible for structural evolution after the early-stage phase Separation (spinodal decomposition or nucleation & growth).

• Polymer(Korea)
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• v.26 no.6
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• pp.821-828
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• 2002

Regular and highly interconnected macroporous poly(L-lactic acid) (PLLA) scaffolds with pore size of 10∼300 ㎛ were fabricated through thermally induced phase separation of a PLLA-dioxane-water ternary system in the presence of a small amount of Pluronics. Addition of Pluronics to the ternary system raised the cloud-point temperature curve in the order of P-123< F-68< F-127. The Pluronics act as nuclei for the phase separation. This assistance is enhanced with increasing length of the hydrophilic PEO blocks in the Pluronics molecules. Liquid-liquid spinodal phase separation was induced at higher temperatures in the systems containing Pluronics because the spinodal region is raised to higher temperature. The absorption of Pluronics onto the interface stabilizes a macro scale structure and increases the interconnection of pores.

• Proceedings of the Membrane Society of Korea Conference
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• 2002.05a
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• pp.81-85
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• 2002

Small angle light scattering and field emission scanning electron microscope have been used to quantify the kinetics of liquid-liquid separation behavior during water vapor(RH52%[$\pm$3%] at 27$^{\circ}C$) quenching (non-solvent induced phase separation, NIPS) of polysulfone/NMP/Alcohol and CPVC/THF/Alcohol, respectively. Time dependence of the position of the light scattering maximum was observed at polysufone dope solutions, confirming spinodal secomposition (SD). while CPVC dope solutions showed a decreased scattered light intensity with a increased q-valuel, indicating nucleation & growth (NG). For the each system, domain growth rate in the intermediate and late stage of phase separation decreased with increasing the number of carbon of alcohol used as additive (non-solvent). Also, in the early stage for SD, the scattering intensity with time was in accordance with Cahns linear theory of spinodal decomposition,[1-3] regardless of types of non-solvent additive.

• Membrane Journal
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• v.7 no.2
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• pp.49-56
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• 1997

In order to understand the formation of polymeric membranes or microcellular foams, phase separation phenomena in polymer solutions should be understood. The present review examines the progress made in the understanding of these phenomena, with emphasis on selected polymer-solvent systems. In the case of polymer-solvent systems, coarsening is of particular importance as it may come to dominate or overshadow spinodal decomposition effects within the first minute or few minutes of phase separation. In this article, some of the most important theoretical models of late stage of phase separation are reviewed, and recent experimental studies on coarsening in polymer-solvent systems are studied.

• Proceedings of the Membrane Society of Korea Conference
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• 1998.10a
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• pp.103-105
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• 1998

Asymmetric polymeric membranes prepared by the phase transition technique usually have either a top layer consisting of closely packed nodules or pores dispersed throughout the membrane surfaces. In this study, we present AFM image of a polysulfone membrane which show a clear evidence for the nodular structure and porous structure resulted from different phase separation mechanisms; spinodal decomposition and nucleation and growth. The surface morphology obtained by SEM and AFM was also compared.

• Proceedings of the Membrane Society of Korea Conference
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• 2004.05a
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• pp.74-77
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• 2004

Porous membranes were prepared via thermally induced phase separation (TIPS) of (ethylene-co-vinyl alcohol) (EVOH)/glycerol mixtures. The liquid-liquid (L-L) phase boundaries are shifted to higher temperature when the ethylene contents in EVOH increase. Moreover, the kinetic study proved that the growth of droplets formed by the general liquid-liquid (L-L) phase separation obeyed a power-law scaling relationship in the later stage of spinodal decomposition (SD). A new phase separation mechanism was presented, in which the L-L phase separation could be resulted from the crystallization. The hollow fiber membranes were prepared. The membranes showed asymmetric structures with skin layer near the outer surface, the larger pores just below the skin layer and the smaller pores near the inner surface. The effect of ethylene content (EC) in EVOH, cooling water bath temperature and take-up speed on membrane performance was investigated.

• Proceedings of the Membrane Society of Korea Conference
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• 1997.10a
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• pp.11-15
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• 1997

Liquid-liquid phase separation에는 nucleation and growth와 spinodal decomposition의 2가지 경로가 있다. 상온에서 고농도의 고분자 용액과 저량의 비용매의 조성의 근처에는 용해도 갭으로 들어가게 되면 비용매에 아주 미량의 고분자가 있는 조성을 갖는 핵이 고분자 용액 내에서 형성되고 이러한 핵은 여러게가 액적의 형태로 주위의 고분자 용액의 gelation에 의해서 성장이 멈출 때까지 커지게 된다. 여기서 어떤 고분자 상이 nucleation되는지가 매우 중요하게 된다. 실제 우리가 상전이 막을 제조할 경우는 대부분 10wt% 이상의 고분자 농도이므로 polymer-poor상이 nucleation이 된다. Spinodal decomposition의 경우는 용해도 갭을 빠르게 통과해서 nucleation이 일어나지 않고 spinodal line을 지나는 경우이다. 이러한 경우의 용액은 매우 불안정해서 약간의 농도 변화에도 자발적인 상분리가 일어나서 polymer-poor상과 polymer-rich상이 서로 얽혀져 있는 network구조를 형성하게 된다.

• 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.

• Proceedings of the Korean Fiber Society Conference
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• 2002.04a
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• pp.207-210
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• 2002

PVDF는 측쇄에 C=O기를 갖는 고분자인 PMMA와 PVAc와의 블렌드 및 주쇄에 C=O기를 갖는 poly(1,4-butylene adipate) (PBA)와의 블렌드에서 PVDF의 융점보다 상당히 높은 온도에서 LCST거동을 보이고 있음이 알려져 있다. 그런데 PVDF/PMMA와 PVDF/PVAC 블렌드계에서는 LCST가 고분자의 열분해온도와 유사하여 LCST거동을 실험적으로 관찰하기 어려웠다. 그런데 PVDF/PBA 블렌드계에서는 실험적으로 측정할 수 있을 정도로 LCST가 낮아지긴 하였지만 PBA의 열분해를 완전히 배제하기엔 아직도 높은 온도이다.[1] (중략)