Experimental Study and Theoretical Phase Diagram Calculation for Polystyrene Membranes Prepared by Supercritical CO2-induced Phase Inversion†

doi:10.7503/cjcu20160208

Abstract

Abstract:

Microporous asymmetric polystyrene(PSt) membranes were prepared by supercritical CO₂-induced phase inversion. The experiments were designed and conducted to investigate the effects of different process parameters, such as temperature, CO₂ pressure and PSt concentration in casting solution, on the membrane morphologies, pore size distribution and especially on the porosity of the membranes. The ternary phase diagrams of polystyrene/supercritical CO₂/toluene system were determined based on the extended Flory-Huggins theory of polymer solutions of Tompa. The prepared PSt membrane had a cellular structure. The porosity of the products was in the range of 53.54%—84.67%; and it showed a tendency of increasing to a peak and then decreasing with the increase of each parameter(temperature, pressure or PSt concentration). The theoretical phase diagrams indicated that pressure has more influence in changing the binodal curve location than that of temperature.

Key words: Supercritical CO2 phase inversion, Polystyrene, Microporous membrane, Porosity, Ternary phase diagram(Ed.: D, Z)

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LIU Xuewu,CHEN Shuhua,ZHAN Shiping. Experimental Study and Theoretical Phase Diagram Calculation for Polystyrene Membranes Prepared by Supercritical CO₂-induced Phase Inversion^†[J]. Chem. J. Chinese Universities, 2016, 37(8): 1573.

Figures/Tables 13

Fig.1 Schematic illustration of the ScCO2 setup P: Pressure gauge; TCI: temperature control indicator; 1. CO2 tank; 2,4,5. valve; 3. compressor; 6. polymer membrane;7. supporting block; 8. membranes formation vessel.

Fig.2 Effect of temperature on PSt(25%, mass fraction) membrane cross-section at 12 MPa Temperature/℃: (A) 35; (B) 55.

Fig.3 Cell size distribution of PSt(25%) membrane at 35 ℃(a) and 55 ℃(b) with 12 MPa

Fig.4 Porosity of PSt(25%) membrane at different temperature with 12 MPa

Fig.5 Effect of pressure on PSt(25%) membrane cross-section at 40 ℃ Pressure/MPa: (A) 9; (B) 16.

Fig.6 Cell size distribution of PSt(25%) membrane with 9 MPa(a) and 16 MPa(b) at 40 ℃

Fig.7 Porosity of PSt(25%) membrane with different pressure at 40 ℃

Fig.8 Effect of polymer concentration on PSt membrane cross-section at 40 ℃ and 10 MPa Mass fraction of PSt: (A) 15%; (B) 35%.

Fig.9 Cell size distribution of 15% PSt(a) and 35% PSt(b) membranes at 40 ℃ and 10 MPa

Fig.10 Porosity of PSt membrane with different mass fractions of PSt at 40 ℃ and 10 MPa

Table 1 Input parameters for calculating the ternary phase diagram of PSt/ScCO2/toluene system

Component	Hansen solubility parameter/MPa^1/2			Molar volume/(cm³·mol^-1)	Reference
Component	δ_d			δ_p	δ_h
PSt	21.28	5.75	4.30	40909	[21]
Toluene	18.00	1.40	2.00	107	[21]
ScCO₂(35 ℃, 12 MPa)	9.71	4.30	4.73	57	This paper
ScCO₂(55 ℃, 12 MPa)	5.79	3.50	3.75	86	This paper
ScCO₂(40 ℃, 9 MPa)	5.54	3.44	3.76	89	This pepar
ScCO₂(40 ℃, 16 MPa)	10.14	4.38	4.79	55	This pepar

Fig.11 Phase diagram of the PSt/ScCO2/toluene system with different temperatures

Fig.12 Phase diagram of the PSt/ScCO2/toluene system with different pressures

References 21

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Experimental Study and Theoretical Phase Diagram Calculation for Polystyrene Membranes Prepared by Supercritical CO₂-induced Phase Inversion^†

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