Abstract
In this study, variation in the thermodynamic and kinetic properties of the casting solution achieved by tailoring initial composition (IC) of the polymer–solvent-nonsolvent ternary mixture is investigated to engineer pores in a polymer film prepared by liquid–liquid phase separation (LLPS). The driving force for liquid–liquid phase separation, identified as thermodynamic enhancement factor (TE), is observed to influence the LLPS rate. At an IC closer to the phase boundary, the LLPS rate is higher. The kinetic restraint (KR), which is dictated by the viscosity of the casting solution, also alters the LLPS rate. The interplay of these two opposing factors determines the final film morphology. The higher LLPS rate obtained from a larger TE value leads to finger-like pore structure, while lowering LLPS rate by considering a casting solution with lower TE results in polymer film with spherical sponge-like pores irrespective of casting solution viscosity. On the other hand, when the concentration of both the polymer and nonsolvent is high, i.e., for high KR value, polymer film with interconnected pores and higher pore number density are obtained.
Similar content being viewed by others
Data availability
The data that supports the findings in this study are available within the article.
References
Fink Y, Urbas AM, Bawendi MG, Joannopoulos JD, Thomas EL (1999) Block copolymers as photonic bandgap materials. J Lightwave Technol 17(11):1963–1969
Beattie D, Wong KH, Williams C, Poole-Warren LA, Davis TP, Barner-Kowollik C, Stenzel MH (2006) Honeycomb-structured porous films from polypyrrole-containing block copolymers prepared via raft polymerization as a scaffold for cell growth. Biomacromol 7(4):1072–1082
Xiang Z, Cao D (2013) Porous covalent–organic materials: synthesis, clean energy application and design. J Mater Chem A 1(8):2691–2718
Prasanth R, Shubha N, Hng HH, Srinivasan M (2013) Effect of nano-clay on ionic conductivity and electrochemical properties of poly (vinylidene fluoride) based nanocomposite porous polymer membranes and their application as polymer electrolyte in lithium ion batteries. Eur Polymer J 49(2):307–318
Wang W, Zhou M, Yuan D (2017) Carbon dioxide capture in amorphous porous organic polymers. J Mater Chem A 5(4):1334–1347
Kim S, Lee YM (2015) Rigid and microporous polymers for gas separation membranes. Prog Polym Sci 43:1–32
Kaur P, Hupp JT, Nguyen ST (2011) Porous organic polymers in catalysis: opportunities and challenges. ACS Catal 1(7):819–835
Pervin R, Ghosh P, Basavaraj MG (2019) Tailoring pore distribution in polymer films via evaporation induced phase separation. RSC Adv 9(27):15593–15605
Kesting R (1973) Concerning the microstructure of dry-ro membranes. J Appl Polym Sci 17(6):1771–1785
Jansen J, Macchione M, Drioli E (2005) High flux asymmetric gas separation membranes of modified poly (ether ether ketone) prepared by the dry phase inversion technique. J Membr Sci 255(1–2):167–180
Matsuyama H, Teramoto M, Uesaka T (1997) Membrane formation and structure development by dry-cast process. J Membr Sci 135(2):271–288
Ulbricht M (2006) Advanced functional polymer membranes. Polymer 47(7):2217–2262
Loeb S (1981) The loeb-sourirajan membrane: How it came about, pp. 1–9. ACS Publications. Chap. 1
Reuvers A, Smolders C (1987) Formation of membranes by means of immersion precipitation: Part ii the mechanism of formation of membranes prepared from the system cellulose acetate-acetone-water. J Membr Sci 34(1):67–86
Buonomenna M, Macchi P, Davoli M, Drioli E (2007) Poly (vinylidene fluoride) membranes by phase inversion: the role the casting and coagulation conditions play in their morphology, crystalline structure and properties. Eur Polymer J 43(4):1557–1572
Guillen GR, Pan Y, Li M, Hoek EM (2011) Preparation and characterization of membranes formed by nonsolvent induced phase separation: a review. Ind Eng Chem Res 50(7):3798–3817
Young T-H, Huang J-H, Chuang W-Y (2002) Effect of evaporation temperature on the formation of particulate membranes from crystalline polymers by dry-cast process. Eur Polymer J 38(1):63–72
Nguyen QT, Alaoui OT, Yang H, Mbareck C (2010) Dry-cast process for synthetic microporous membranes: Physico-chemical analyses through morphological studies. J Membr Sci 358(1–2):13–25
Phong HQ, Wang S-L, Wang M-J (2010) Cell behaviors on micropatterned porous thin films. Mater Sci Eng, B 169(1–3):94–100
Wang Y, Liu Z, Huang Y, Han B, Yang G (2006) Micropatterned polymer surfaces induced by nonsolvent. Langmuir 22(4):1928–1931
Altinkaya SA, Yenal H, Ozbas B (2005) Membrane formation by drycast process: model validation through morphological studies. J Membr Sci 249(1–2):163–172
Pervin R, Ghosh P, Basavaraj MG (2021) Engineering polymer film porosity for solvent triggered actuation. Soft Matter 17(10):2900–2912
Kesting RE (1985) Phase inversion membranes, 131–164. Chap. 7
Van de Witte P, Dijkstra P, Van den Berg J, Feijen J (1996) Phase separation processes in polymer solutions in relation to membrane formation. J Membr Sci 117(1–2):1–31
Matsuyama H, Nishiguchi M, Kitamura Y (2000) Phase separation mechanism during membrane formation by dry-cast process. J Appl Polym Sci 77(4):776–783
Schuhmacher E, Soldi V, Pires ATN (2001) Pmma or peo in thf/h2o mixture: phase diagram, separation mechanism and application. J Membr Sci 184(2):187–196
Altinkaya SA, Ozbas B (2004) Modeling of asymmetric membrane formation by dry-casting method. J Membr Sci 230(1–2):71–89
Arya RK (2012) Drying induced phase separation. J Chem Eng 27:12–20
Shojaie SS, Krantz WB, Greenberg AR (1994) Dense polymer film and membrane formation via the dry-cast process. Part II. Model validation and morphological studies. J Membr Sci 94(1):281–298
Sadrzadeh M, Bhattacharjee S (2013) Rational design of phase inversion membranes by tailoring thermodynamics and kinetics of casting solution using polymer additives. J Membr Sci 441:31–44
Zheng Q-Z, Wang P, Yang Y-N (2006) Rheological and thermodynamic variation in polysulfone solution by peg introduction and its effect on kinetics of membrane formation via phase-inversion process. J Membr Sci 279(1–2):230–237
Han M-J, Nam S-T (2002) Thermodynamic and rheological variation in polysulfone solution by pvp and its effect in the preparation of phase inversion membrane. J Membr Sci 202(1–2):55–61
Lee K-W, Seo B-K, Nam S-T, Han M-J (2003) Trade-off between thermodynamic enhancement and kinetic hindrance during phase inversion in the preparation of polysulfone membranes. Desalination 159(3):289–296
Wang Z, Gao K, Kan Y, Zhang M, Qiu C, Zhu L, Zhao Z, Peng X, Feng W, Qian Z et al (2021) The coupling and competition of crystallization and phase separation, correlating thermodynamics and kinetics in opv morphology and performances. Nat Commun 12(1):1–14
Albrecht W, Weigel T, Schossig-Tiedemann M, Kneifel K, Peinemann K-V, Paul D (2001) Formation of hollow fiber membranes from poly (ether imide) at wet phase inversion using binary mixtures of solvents for the preparation of the dope. J Membr Sci 192(1–2):217–230
Shieh J-J, Chung TS (1998) Effect of liquid-liquid demixing on the membrane morphology, gas permeation, thermal and mechanical properties of cellulose acetate hollow fibers. J Membr Sci 140(1):67–79
Strathmann H, Kock K (1977) The formation mechanism of phase inversion membranes. Desalination 21(3):241–255
Strathmann H, Scheible P, Baker R (1971) A rationale for the preparation of loeb-sourirajan-type cellulose acetate membranes. J Appl Polym Sci 15(4):811–828
So M, Eirich F, Strathmann H, Baker R (1973) Preparation of asymmetric loeb-sourirajan membranes. J Polym Sci Polym Lett Ed 11(3):201–205
Smolders C, Reuvers A, Boom R, Wienk I (1992) Microstructures in phase-inversion membranes. Part 1. Formation of macrovoids. J Membr Sci 73(2–3):259–275
Van der Bruggen B (2018) Fundamental modelling of membrane systems, pp. 25–70. Elsevier. Chap. 2
Strathmann H, Kock K, Amar P, Baker R (1975) The formation mechanism of asymmetric membranes. Desalination 16(2):179–203
Xu H, Zheng X, Huang Y, Wang H, Du Q (2016) Interconnected porous polymers with tunable pore throat size prepared via pickering high internal phase emulsions. Langmuir 32(1):38–45
Silverstein MS (2014) Polyhipes: Recent advances in emulsion-templated porous polymers. Prog Polym Sci 39(1):199–234
Kim JH, Min BR, Won J, Park HC, Kang YS (2001) Phase behavior and mechanism of membrane formation for polyimide/dmso/water system. J Membr Sci 187(1–2):47–55
Yamamura M, Horiuchi K, Kajiwara T, Adachi K (2002) Decrease in solvent evaporation rate due to phase separation in polymer films. AIChE J 48(11):2711–2714
Patsis A, Henriques E, Frisch H (1990) Interdiffusion in complex polymer systems used in the formation of microporous coatings. J Polym Sci, Part B Polym Phys 28(13):2681–2689
Roesink HDW (1989) Microfiltration: membrane development and module design, phd thesis
Loeb S, Sourirajan S (1962) Sea water demineralization by means of an osmotic membrane, pp. 117–132. ACS Publications. Chap. 9
Rautenbach R, Vossenkaul K, Linn T, Katz T (1997) Waste water treatment by membrane processes—new development in ultrafiltration, nanofiltration and reverse osmosis. Desalination 108(1–3):247–253
Acknowledgements
We would like to acknowledge the high resolution scanning electron microscopy (HR-SEM) facility (procured through a DST-FIST grant) at the Department of Chemical Engineering, IIT-Madras.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflicts of interest
There are no conflicts to declare.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Pervin, R., Ghosh, P. & Basavaraj, M.G. Influence of initial composition of casting solution on morphology of porous thin polymer films produced via phase separation. J Polym Res 29, 486 (2022). https://doi.org/10.1007/s10965-022-03325-7
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10965-022-03325-7