Effect of polyethylene glycol (PEG) as an additive on the fabrication of polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) asymmetric microporous hollow fiber membranes

Polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) has received much attention recently as a promising membrane material for membrane contactor application. A systematic study has been carried out to investigate the effects of polyethylene glycol (PEG) with different molecular weights and different loadings as an additive on the fabrication of PVDF-HFP asymmetric microporous hollow fiber membranes. Moreover, the synergetic effects of coagulation temperature and the second additive (lithium chloride: LiCl) with PEG are also evaluated. Experiments revealed that the addition of PEG into the PVDF-HFP/NMP solution resulted in the system thermodynamically less stable in reaction with water, promoting rapid phase demixing in the phase inversion process. When the same 3 wt% PEG was added into the dope solution, the dimension of finger-like macrovoids of the resultant membrane increased in parallel with the increase of PEG molecular weight from 200 to 600 and 6000 kDa, and pure water permeability (PWP) also increased accordingly. An increase in PWP was also observed when PEG-200 loading in the dope solution was increased from 3 to 5 and 10 wt%, corresponding to the morphology change of resultant membranes. As a synergetic effect of coagulation temperature with PEG, the finger-like pores occurred in the membrane at room temperature expanded to much larger macrovoids using 10 °C water as the coagulant, and the big finger-like pores almost disappeared when the coagulation bath temperature was increased to 40 °C because of delayed phase demixing. The big macrovoid size can also be suppressed by adding the second small molecule additive, LiCl, due to its strong interactions with NMP and PVDF-HFP to delay the dope precipitation. The irregular inner contour of the membrane can be eliminated by the increase of coagulation bath temperature to 40 °C. The hollow fiber membrane made by a dope of PVDF-HFP/PEG-6000/LiCl/NMP (15/3/3/79 in weight) using 40 °C water as the coagulant exhibited a high PWP of 117 L/m2 h atm and reasonably good MWCO of 150 kDa. An improvement has been made in the current work as compared to previous PVDF-HFP hollow fiber membranes reported in literatures.