Langmuir, 23 (26), 13085 -13092, 2007. 10.1021/la701329r S0743-7463(70)01329-X
Web Release Date: November 16, 2007

Copyright © 2007 American Chemical Society

Plasma-Induced Graft Copolymerization of Poly(methacrylic acid) on Electrospun Poly(vinylidene fluoride) Nanofiber Membrane

Satinderpal Kaur,* Zuwei Ma, Renuga Gopal, Gurdev Singh, Seeram Ramakrishna,* and Takeshi Matsuura

Nanoscience and Nanotechnology Initiative, Faculty of Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore, Department of Mechanical Engineering, Faculty of Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore, Division of Bioengineering, Faculty of Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore, and Industrial Membrane Research Institute, Department of Chemical Engineering, University of Ottawa, 161 Louis Pasteur Street, P.O. Box 450, Station A, Ottawa, Ontario K1N 6N5, Canada

Received May 10, 2007

In Final Form: August 30, 2007

Abstract:

Electrospun nanofibrous membranes (ENM) which have a porous structure have a huge potential for various liquid filtration applications. In this paper, we explore the viability of using plasma-induced graft copolymerization to reduce the pore sizes of ENMs. Poly(vinylidene) fluoride (PVDF) was electrospun to produce a nonwoven membrane, comprised of nanofibers with diameters in the range of 200-600 nm. The surface of the ENM was exposed to argon plasma and subsequently graft-copolymerized with methacrylic acid. The effect of plasma exposure time on grafting was studied for both the ENM and a commercial hydrophobic PVDF (HVHP) membrane. The grafting density was quantitatively measured with toluidine blue-O. The degree of grafting increased steeply with an increase in plasma exposure time for the ENM, attaining a maximum of 180 nmol/mg after 120 s of plasma treatment. However, the increase in the grafting density on the surface of the HVHP membrane was not as drastic, reaching a plateau of 65 nmol/mg after 60 s. The liquid entry permeation of water dropped extensively for both membranes, indicating a change in surface properties. Field emission scanning electron microscopy micrographs revealed an alteration in the surface pore structure for both membranes after grafting. Bubble point measurements of the ENM reduced from 3.6 to 0.9 um after grafting. The pore-size distribution obtained using the capillary flow porometer for the grafted ENM revealed that it had a similar profile to that of a commercial hydrophilic commercial PVDF (HVLP) membrane. More significantly, water filtration studies revealed that the grafted ENM had a better flux throughput than the HVLP membrane. This suggests that ENMs can be successfully engineered through surface modification to achieve smaller pores while retaining their high flux performance.


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