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In this manuscript, we report the facile fabrication of large-area model membranes with highly uniform and high aspect ratio pores with diameters <20 nm. These membranes are useful for fundamental investigations of separation by size exclusion in the ultrafiltration regime, where species to be separated from solution have dimensions of 1–100 nm. Such investigations require membranes with narrow pores and high aspect ratios such that the Hagen–Poiseuille equation is followed, enabling well-known models such as the hindered transport model to be evaluated and other affecting factors to be ignored. We demonstrate that the sub-20 nm pores in the membrane are of sufficiently high aspect ratio such that water flux through the membrane is consistent with the Hagen–Poiseuille equation. The fabrication relies on self-assembling block copolymers to form uniform, densely packed patterns with sub-20 nm resolution, sequential infiltration synthesis to convert the block copolymer in situ into a mask with adequate contrast to etch pores with an aspect ratio >5, and low-resolution photolithography to transfer the pattern over a large area into a silicon nitride membrane. Model membranes with narrow pore-size distribution fabricated in this way provide the means to investigate parameters that impact size-selective ultrafiltration separations such as the relationships between solute or particle size and pore size, their distributions, and rejection profiles, and, therefore, test the validity or limits of separation models.
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Current status and future directions of self-assembled block copolymer membranes for molecular separations
One of the most efficient and promising separation alternatives to thermal methods such as distillation is the use of polymeric membranes that separate mixtures based on molecular size or chemical affinity. Self-assembled block copolymer membranes have gained considerable attention within the membrane field due to precise control over nanoscale structure, pore size, and chemical versatility. Despite the rapid progress and excitement, a significant hurdle in using block copolymer membranes for nanometer and sub-nanometer separations such as nanofiltration and reverse osmosis is the lower limit on domain size features. Strategies such as polymer post-functionalization, self-assembly of oligomers, liquid crystals, and random copolymers, or incorporation of artificial/natural channels within block copolymer materials are future directions with the potential to overcome current limitations with respect to separation size.
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- PAR ID:
- 10352943
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 17
- Issue:
- 46
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 10405 to 10415
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1SM01368H
