Membrane separations are simple to operate, scalable, versatile, and energy efficient, but their broader use is curtailed by fouling or performance decline due to feed component depositing on the membrane surface. Surface functionalization with groups such as zwitterions can mitigate the adsorption of organic compounds, thus limiting fouling. This can be achieved by using surface-segregating copolymer additives during membrane manufacture, but there is a need for better understanding of how the polymer structure and architecture affect the effectiveness of these additives in improving membrane performance. In this study, we aim to explore the impact of the architecture of zwitterionic copolymer additives for polyvinylidene fluoride (PVDF)-based membranes in fouling mitigation and ionic strength response. We prepared membranes from blends of PVDF with zwitterionic (ZI) copolymers with two different architectures, random and comb-shaped. As the random copolymer, we used poly(methyl methacrylate- random- sulfobetaine-2-vinyl pyridine) (PMMA- r -SB2VP) synthesized by free radical polymerization. The comb-shaped copolymer was synthesized by grafting SB2VP side-chains from a PVDF backbone by controlled radical polymerization. Membranes were fabricated from PVDF-copolymer blends containing up to 5 wt% ZI copolymer. Compared to the additive-free PVDF membrane, water permeance increased five-fold with 5 wt% addition of either copolymer. The comb copolymer additive led to better resistance to fouling by a saline oil-in-water emulsion and to simulated protein adsorption in Atomic Force Microscopy (AFM) force measurements. The additive architecture had a significant influence on how membranes respond to changes in feed salinity, which is known to affect intra- and inter-molecular interactions in zwitterionic polymers. The random copolymer containing membrane showed a small and mostly reversible decrease in its permeance with salinity. In contrast, the comb copolymer-containing membrane underwent a conformational reorganization in saline solutions that leads to an irreversible permeance decrease, increased zwitterionic group content on the membrane surface, and smoother surface topography. The higher mobility of the zwitterionic groups in the comb-shaped architecture facilitates reorganization of the zwitterionic side-chains in response to ionic strength. Overall, this study establishes a new approach for developing highly fouling resistant membranes and defines how the architecture of a zwitterionic copolymer additive impacts the ionic strength response and fouling resistance of the membrane.
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Electrospun fiber membranes from blends of poly(vinylidene fluoride) with fouling‐resistant zwitterionic copolymers
Nonwoven super‐hydrophobic fiber membranes have potential applications in oil–water separation and membrane distillation, but fouling negatively impacts both applications. Membranes were prepared from blends comprising poly(vinylidene fluoride) (PVDF) and random zwitterionic copolymers of poly(methyl methacrylate) (PMMA) with sulfobetaine methacrylate (SBMA) or with sulfobetaine‐2‐vinylpyridine (SB2VP). PVDF imparts mechanical strength to the membrane, while the copolymers enhance fouling resistance. Blend composition was varied by controlling the PVDF‐to‐copolymer ratio. Nonwoven fiber membranes were obtained by electrospinning solutions of PVDF and the copolymers in a mixed solvent of
- NSF-PAR ID:
- 10056588
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Polymer International
- Volume:
- 68
- Issue:
- 2
- ISSN:
- 0959-8103
- Page Range / eLocation ID:
- p. 231-239
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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As wastewater reclamation and reuse technologies become more critical to meeting the growing demand for water, a need has emerged for separation platforms that can be tailored to accommodate the highly varied feed water compositions and treatment demands of these technologies. Nanofiltration (NF) membranes based on copolymer materials are a promising platform in this regard because they can be engineered at the molecular scale to address an array of separation process needs. Here, for example, a resilient NF membrane is developed through the design of a poly(trifluoroethyl methacrylate- co -oligo(ethylene glycol) methyl ether methacrylate- co -glycidyl methacrylate) [P(TFEMA-OEGMA-GMA)] copolymer that can be dip-coated onto hollow fiber supports. By exploiting the microphase separation of the oligomeric ethylene glycol side chains from the copolymer backbone and by elucidating the processing–structure–property relationships for the dip-coating process, membranes with pores 2 nm-in-diameter that exhibit a hydraulic permeability of 15.6 L m −2 h −1 bar −1 were generated. The GMA repeat units were functionalized post-coating with hexamethylene diamine to incorporate positively-charged moieties along the pore walls. This functionality resulted in membranes that rejected 98% of the MgCl 2 from a 1 mM feed solution. Moreover, the reaction with the diamine crosslinked the copolymer such that the membranes operated stably in ethanol, an organic solvent that damaged the unreacted parent membranes irreparably. Finally, the stability of the crosslinked P(TFEMA-OEGMA-GMA) copolymer resulted in membranes that could operate continuously for a 24 hour period in aqueous solutions containing 500 ppm chlorine without exhibiting signs of structural degradation as evidenced by consistent rejection of neutral probe solutes. These results demonstrate how resilient, charge-selective NF membranes can be fabricated from microphase separated copolymers by engineering each of the constituent repeat units for a directed purpose.more » « less
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ABSTRACT Relaxation dynamics of PVDF blended with a random zwitterionic copolymer (
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