Effect of chitosan crosslinking time on the structure and antifouling performance of polyvinylidene fluoride membrane by surface gelation‐immersion precipitation phase inversion

Abstract

Polyvinylidene fluoride (PVDF) porous membrane was prepared by a two‐step method of surface gelation‐immersion precipitation phase inversion. Chitosan/acetic acid solution and glutaraldehyde aqueous solution were sequentially sprayed onto the surface of the PVDF solution film, with chitosan crosslinking and gelation occurring simultaneously on the film surface. The solution film was then immersed in a coagulation bath to obtain a modified PVDF porous membrane. The effect of the crosslinking time of chitosan and glutaraldehyde on the structure and properties of the PVDF porous membrane was discussed. The results showed that with the prolongation of crosslinking time, the surface structure of the membrane changed from a dense skin layer to a porous structure; the porosity and the mean pore size of the modified PVDF membranes increased first and then decreased, and the contact angle gradually decreased. When the crosslinking time extended to 15 min, the water flux of modified membrane (M153) reached a maximum value. BSA dynamic cyclic filtration experiment showed that the retention rate (R) of the modified membrane was significantly improved, compared to 68.3% retention rate of the blank membrane (M000), but the crosslinking time had little effect on the retention rates of the four modified membranes. The antifouling data showed that the flux recovery rate of the blank membrane was 73.0%, while the flux recovery rate of the modified membrane can reach as high as 84.40%, and the irreversible pollution rate of the blank membrane was 27.7%, while the irreversible pollution rate of the modified membrane reduced to 15.6%. These results indicated that, after surface chitosan crosslinking, the hydrophilicity and antifouling properties of PVDF membranes were improved.Practitioner Points Modified PVDF membranes with crosslinking CS coating were prepared by a two‐step method of surface gelation‐immersion precipitation phase inversion. ‐OH groups and ‐NH2 groups of CS coating improve the hydrophilicity and the antifouling property of modified PVDF membranes. Modified PVDF membranes had larger mean pore size and higher porosity than unmodified membrane. Flux recovery rates of the modified membranes were higher than that of unmodified membrane. Pollution degree, reversible pollution rate, and irreversible pollution rate of modified membranes were lower than those of unmodified membrane.