Characterization of morphology controlled polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to the dope and bore liquid solution

The preparation of polyethersulfone (PES) hollow fiber membranes has been studied using N-methylpyrrolidone (NMP) as solvent, polyethylene glycol 400 (PEG 400) as weak nonsolvent and water as strong nonsolvent. When PEG 400 is used as polymeric additive to the spinning dope the viscosity of the PES solution is strongly enhanced. Furthermore, it was observed that PEG 400 could be added to the solution in large amounts without causing phase separation (NMP/PEG ratio 1:9, PES concentration approximately 11 wt.%). Membranes prepared from a solution containing a NMP/PEG ratio of 1:1 results in higher fluxes than when a ratio of 1:4 is used. Similar fluxes were obtained for PES concentrations of 16 and 20 wt.%. Looking at the fiber cross-section it became clear that macrovoid formation could not be suppressed by the addition of PEG 400 alone, not even at concentrations as high as 38 wt.%. Only when relatively large amounts of water were added to the dope solution macrovoids disappeared and nice spongy structures were obtained. Variation of the bore liquid composition using the components NMP, PEG 400 and water showed to be a powerful method to control the pore size of the bore surface. Pores of 5–28 nm were obtained in combination with high pure water fluxes; e.g. a membrane with pores of 7 nm had a pure water flux of 940 l/(m2 h bar) and showed 100% BSA retention. When an air gap larger than 10 mm was applied the shell surface contained relatively large pores. Spinning directly in water (airgap=0) resulted in shell side pores of 8–10 nm, while an air gap of 10 mm resulted in pore sizes of 40–54 nm.