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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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This content will become publicly available on June 1, 2026
Fouling Resistant Liquid-Infused membranes for oil separations
Bioinspired membranes offer an alternative approach to improving the fouling resistance of commercial membranes for oil separations. Here, two perfluoropolyether oils, a lower viscosity Krytox 103 (K103) and a higher viscosity Krytox 107 (K107), were infused into commercial polyvinylidene fluoride (PVDF) ultrafiltration membranes to mimic the Nepenthes pitcher plant. The transmembrane pressure required to perform long-term oil permeance tests was optimized by testing the liquid-infused membranes at different applied pressures. Crystal violet staining and variable pressure scanning electron microscopy qualitatively suggest that the oil layer remained on the membranes after the oil separation experiments were conducted. Over 5 cycles, K103- and K107- liquid-infused membranes exhibited a consistent permeance of ∼ 30000 L m-2h−1 bar−1 at 1.0 bar and ∼ 14500 L m-2h−1 bar−1 at 0.5 bar, respectively. The steady performance further supports a long-lasting oil layer persists on the membrane surface and inside membrane’s pores. Next, experiments were conducted to determine the stability of the Krytox oil post accelerated cleaning tests using bleach. No structural changes to the Krytox oils were detected by thermogravimetric analysis or nuclear magnetic resonance spectroscopy. Dynamic fouling experiments using Escherichia coli K12 revealed that the liquid-infused membranes had higher flux recovery ratios (∼95 %) than the bare PVDF control membranes (∼55 %). Our results demonstrate that liquid-infused membranes exhibit chlorine stability and superior fouling resistance, presenting a promising bioinspired membrane that can be used in pressure-driven oil separation applications.
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- Award ID(s):
- 1930610
- PAR ID:
- 10555503
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Separation and Purification Technology
- Volume:
- 358
- Issue:
- PA
- ISSN:
- 1383-5866
- Page Range / eLocation ID:
- 130253
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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