Preparation and characterization of PVDF-PFSA flat sheet ultrafiltration membranes

Abstract

High performance polyvinylidene fluoride (PVDF) flat sheet ultrafiltration (UF) membranes have been prepared by an immersion precipitation phase inversion method using perfluorosulfonic acid (PFSA) as a pore former and as a hydrophilic component of the membranes and polyethylene glycol (M_w = 400) (PEG400) as a pore forming agent. The effects of the presence of PEG and the concentration of the PFSA on the phase separation of the casting solutions and on the morphologies and performance of UF membranes including their porosity, water flux, rejection of bovine serum albumin (BSA) protein, and anti-fouling property were investigated. Phase diagrams, viscosities and the phase separations upon exposure to water vapor showed that both PEG400 and PFSA promoted demixing of the casting solution. Scanning electron microscopy measurements showed that the PVDF-PFSA blend membranes had more macropores and finger-like structures than the native PVDF membranes. The PVDF-PFSA membrane (5 wt-% PEG400+ 5 wt-% PFSA) had a pure water flux of 141.7 L/m²·h, a BSA rejection of 90.1% and a relative pure water flux reduction (RFR) of 15.28%. These properties were greatly superior to those of the native PVDF membrane (pure water flux of 5.6 L/m²·h, BSA rejection of 96.3% and RFR of 42.86%).

Keywords

polyvinylidene fluoride / perfluorosulfonic acid / polyethylene glycol / flat sheet membrane / ultrafiltration

References

[1] Yeow M, Liu Y, Li K. Preparation of porous PVDF hollow fibre membrane via a phase inversion method using lithium perchlorate (LiClO) as an additive. Journal of Membrane Science, 2005, 258(1-2): 16-22

[2] Liu F, Hashim N A, Liu Y, Abed M R M, Li K. Progress in the production and modification of PVDF membranes. Journal of Membrane Science, 2011, 375(1-2): 1-27

[3] Du J R, Peldszus S, Huck P M, Feng X. Modification of poly(vinylidene fluoride) ultrafiltration membranes with poly(vinyl alcohol) for fouling control in drinking water treatment. Water Research, 2009, 43(18): 4559-4568

[4] Chanachai A, Meksup K, Jiraratananon R. Coating of hydrophobic hollow fiber PVDF membrane with chitosan for protection against wetting and flavor loss in osmotic distillation process. Separation and Purification Technology, 2010, 72(2): 217-224

[5] Qiu G M, Zhu L P, Zhu B K, Xu Y Y, Qiu G L. Grafting of styrene/maleic anhydride copolymer onto PVDF membrane by supercritical carbon dioxide: preparation, characterization and biocompatibility. Journal of Supercritical Fluids, 2008, 45(3): 374-383

[6] Rahimpour A, Madaeni S S, Zereshki S, Mansourpanah Y. Preparation and characterization of modified nano-porous PVDF membrane with high antifouling property using UV photo-grafting. Applied Surface Science, 2009, 255(16): 7455-7461

[7] Yuan Z, Danli X. Porous PVDF/TPU blends asymmetric hollow fiber membranes prepared with the use of hydrophilic additive PVP (K30). Desalination, 2008, 223(1-3): 438-447

[8] Rajabzadeh S, Maruyama T, Ohmukai Y, Sotani T, Matsuyama H. Preparation of PVDF/PMMA blend hollow fiber membrane via thermally induced phase separation (TIPS) method. Separation and Purification Technology, 2009, 66(1): 76-83

[9] Liu F, Xu Y Y, Zhu B K, Zhang F, Zhu L P. Preparation of hydrophilic and fouling resistant poly(vinylidene fluoride) hollow fiber membranes. Journal of Membrane Science, 2009, 345(1-2): 331-339

[10] Yuliwati E, Ismail A F. Effect of additives concentration on the surface properties and performance of PVDF ultrafiltration membranes for refinery produced wastewater treatment. Desalination, 2011, 273(1): 226-234

[11] Yan L, Hong S, Li M L, Li Y S. Application of the Al₂O₃-PVDF nanocomposite tubular ultrafiltration (UF) membrane for oily wastewater treatment and its antifouling research. Separation and Purification Technology, 2009, 66(2): 347-352

[12] Cho K, Jung H, Choi N, Sung S, Park J, Choi J, Sung Y. A coated Nafion membrane with a PVdF copolymer/Nafion blend for direct methanol fuel cells (DMFCs). Solid State Ionics, 2005, 176(39-40): 3027-3030

[13] Song M K, Kim Y T, Fenton J M, Kunz H R, Rhee H W. Chemically-modified Nafion®/poly(vinylidene fluoride) blend ionomers for proton exchange membrane fuel cells. Journal of Power Sources, 2003, 117(1-2): 14-21

[14] Mai Z, Zhang H, Li X, Xiao S, Zhang H. Nafion/polyvinylidene fluoride blend membranes with improved ion selectivity for vanadium redox flow battery application. Journal of Power Sources, 2011, 196(13): 5737-5741

[15] Peighambardoust S J, Rowshanzamir S, Amjadi M. Review of the proton exchange membranes for fuel cell applications. International Journal of Hydrogen Energy, 2010, 35(17): 9349-9384

[16] Cho K, Eom J, Jung H, Choi N, Lee Y, Park J, Choi J, Park K, Sung Y. Characteristics of PVdF copolymer/Nafion blend membrane for direct methanol fuel cell (DMFC). Electrochimica Acta, 2004, 50(2-3): 583-588

[17] Cho K Y, Jung H Y, Sung K A, Kim W K, Sung S J, Park J K, Choi J H, Sung Y E. Preparation and charateristics of Nafion membrane coated with a PVdF copolymer/recast Nafion blend for direct methanol fuel cell. Journal of Power Sources, 2006, 159(1): 524-528

[18] Lang W Z, Xu Z L, Yang H, Tong W. Preparation and characterization of PVDF-PFSA blend hollow fiber UF membrane. Journal of Membrane Science, 2007, 288(1-2): 123-131

[19] Yuan G L, Xu Z L, Wei Y M. Characterization of PVDF-PFSA hollow fiber UF blend membrane with low-molecular weight cut-off. Separation and Purification Technology, 2009, 69(2): 141-148

[20] Li L, Shang F, Wang L, Pei S, Zhang Y. Transport properties of PFSA membranes with various ion exchange capacities for direct methanol fuel cell application. Energy & Environmental Science, 2010, 3(1): 114

[21] Luan Y, Zhang H, Zhang Y, Li L, Li H, Liu Y. Study on structural evolution of perfluorosulfonic ionomer from concentrated DMF-based solution to membranes. Journal of Membrane Science, 2008, 319(1-2): 91-101

[22] Shang F, Li L, Zhang Y, Li H. PWA/silica/PFSA composite membrane for direct methanol fuel cells. Journal of Materials Science, 2009, 44(16): 4383-4388

[23] Ai F, Yuan W Z, Wang Q, Li H, Zhang Y, Pei S. Enhancing the anti-cracking performance of perfluorosulfonic acid membranes for implantable biosensors through supercritical CO₂ treatment. Journal of Materials Science, 2012, 47(8): 3602-3606

[24] Ai F, Wang Q, Yuan W Z, Li H, Chen X, Yang L, Zhang Y, Pei S. Biocompatibility and anti-cracking performance of perfluorocarboxylic acid ionomer membranes for implantable biosensors. Journal of Materials Science, 2012, 47(13): 5181-5189

[25] Luan Y, Zhang Y, Li L, Zhang H, Zhang Q, Huang Z, Liu Y. Perfluorosulfonic ionomer solution in N,N-dimethylformamide. Journal of Applied Polymer Science, 2008, 107(5): 2892-2898

[26] Idris A, Mat Zain N, Noordin M Y. Synthesis, characterization and performance of asymmetric polyethersulfone (PES) ultrafiltration membranes with polyethylene glycol of different molecular weights as additives. Desalination, 2007, 207(1-3): 324-339

[27] Mansourizadeh A, Ismail A F. Effect of additives on the structure and performance of polysulfone hollow fiber membranes for CO₂ absorption. Journal of Membrane Science, 2010, 348(1-2): 260-267

[28] Han M J, Nam S T. Thermodynamic and rheological variation in polysulfone solution by PVP and its effect in the preparation of phase inversion membrane. Journal of Membrane Science, 2002, 202(1-2): 55-61

[29] Krishnamoorthy L, Arif P M, Ahmedkhan R. Separation of proteins from aqueous solution using cellulose acetate/poly (vinyl chloride) blend ultrafiltration membrane. Journal of Materials Science, 2011, 46(9): 2914-2921

[30] Susanto H, Feng Y, Ulbricht M. Fouling behavior of aqueous solutions of polyphenolic compounds during ultrafiltration. Journal of Food Engineering, 2009, 91(2): 333-340

[31] Lee K W, Seo B K, Nam S T, Han M J. Trade-off between thermodynamic enhancement and kinetic hindrance during phase inversion in the preparation of polysulfone membranes. Desalination, 2003, 159(3): 289-296

[32] Rahimpour A, Madaeni S S, Mehdipour-Ataei S. Synthesis of a novel poly(amide-imide) (PAI) and preparation and characterization of PAI blended polyethersulfone (PES) membranes. Journal of Membrane Science, 2008, 311(1-2): 349-359

[33] Susanto H, Ulbricht M. Characteristics, performance and stability of polyethersulfone ultrafiltration membranes prepared by phase separation method using different macromolecular additives. Journal of Membrane Science, 2009, 327(1-2): 125-135

[34] Bormashenko Y, Pogreb R, Stanevsky O, Bormashenko E. Vibrational spectrum of PVDF and its interpretation. Polymer Testing, 2004, 23(7): 791-796

[35] Gruger A, Régis A, Schmatko T, Colomban P. Nanostructure of Nafion® membranes at different states of hydration: An IR and Raman study. Vibrational Spectroscopy, 2001, 26(2): 215-225

[36] Boributh S, Chanachai A, Jiraratananon R. Modification of PVDF membrane by chitosan solution for reducing protein fouling. Journal of Membrane Science, 2009, 342(1-2): 97-104

Acknowledgements

The work was supported by the National Natural Science Foundation of China (Grant No. 20904031) and the Shanghai Leading Academic Discipline Project (No. B202). Thanks for Instrumental Analysis Center of Shanghai Jiao Tong University.

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg