Reverse Osmosis and Ultrafiltration Membrane Surface Nano-Structuring with Tethered Hydrophilic Polymer Layers for Seawater Desalination
- Author(s): Kim, Soomin
- Advisor(s): Cohen, Yoram
- et al.
A systematic investigation of membrane surface nano-structuring (SNS) with surface tethered hydrophilic polymer layers was conducted in order to mitigate fouling of reverse osmosis (RO) and ultrafiltration (UF) membranes and tune membrane performance in seawater desalination. Surface tethered hydrophilic polymer (i.e., polyacrylic acid (PAA)) layers were synthesized onto base polysulfone (PSf) UF and polyamide (PA) thin film composite (TFC) RO membranes via membrane surface activation with an atmospheric pressure plasma (APP), followed by graft polymerization (GP) of acrylic acid. Both APP surface activation and GP conditions impacted the structure of the synthesized tethered PAA layers and RO membrane desalination performance. Detailed characterization of tethered PAA chain extension length via atomic force microscopy (AFM) based force spectroscopy (FS) revealed that the number average molecular weight of the synthesized tethered PAA chains was estimated to be in the range of ∼13,000–35,000 with chain-chain separation of 1.5–2.4 nm. Extension of the tethered PAA chains in DI water was significantly greater in DI water than in high salinity aqueous environment. UF fouling stress tests with alginic acid in high salinity water and post-cleaning with non-saline water demonstrated permeability restoration of up to 90–100% for a surface nano-structured (SNS)-PAA-PSf membrane relative to 50–70% for the native PSf membrane. Synthesized SNS-PAA-PA BWRO and SWRO membranes having water and salt permeability coefficient in the range of 2.3 – 3.4 L�m-2�h-1�bar-1 and 0.15 – 0.54 L�m-2�h-1 revealed that membrane surface structuring with a tethered PAA layer enabled tuning membrane performance (in terms of Lp and B) to achieve water/salt selectivity (evaluated as Lp:B ratio) that was significantly higher (by up to 56%) relative to the base PA membranes. It was demonstrated that, depending on APP surface activation and GP conditions, PA TFC membranes could be tuned to have essentially the same salt rejection over a wide permeability range or a given permeability over a range of salt rejection. It was also shown that membrane performance could be achieved that overcomes the permeability-selectivity trade-off. Lastly, the present study developed an approach to scale up the APP surface activation and GP process by performing membrane surface nano-structuring for large PA TFC flat sheet membranes that are suitable for fabricating 2.5” x 21” spiral wound RO elements.