Composite PVDF-TiO₂ membranes are studied extensively in literature as effective anti-fouling membranes with photocatalytic properties. Yet, a full understanding of how preparation parameters affect the final membrane structure, properties and performance has not been realized. In this study, PVDF-TiO₂ membranes (20 wt% TiO₂/PVDF) were fabricated via the non-solvent-induced phase separation (NIPS) method with an emphasis on the preparation temperature. Then, a systematic approach was employed to study the evolution of the membrane formation process and membrane properties when the preparation temperature changed, as well as to establish a link between them. Typical asymmetric membranes with a high porosity were obtained, along with a vast improvement in the permeate flux compared to the neat PVDF membranes, but a reduction in mechanical strength was also observed. Interestingly, upon the increase in preparation temperature, a significant transition in membrane morphology was observed, notably the gradual diminution of the finger-like macrovoids. Other membrane properties such as permeability, porosity, thermal and mechanical properties, and compression behavior were also influenced accordingly. Together, the establishment of the ternary phase diagrams, the study of solvent–nonsolvent exchange rate, and the direct microscopic observation of membrane formation during phase separation, helped explain such evolution in membrane properties.

In this study, the anti-fouling performance of PVDF-TiO₂ composite membranes, indicated by their permeate flux, was studied with different types of synthetic feed solutions. Photo-filtration (filtration under continuous UV irradiation) of solutions containing inorganic and organic components, which are ubiquitous in drinking/natural water, was performed to evaluate their influence on the photo-induced properties and performance of the membranes. The results indicated that inorganic fouling was unlikely to occur on PVDF-TiO₂ membranes, and the presence of common inorganic ions in drinking water did not hinder their performance. However, in the particular case where a small amount of Cu²⁺ coexisted alongside HCO₃⁻ in the feed solution, inorganic fouling occurred, causing severe flux decline and prohibiting the photo-induced properties of the membranes. On the other hand, when used to filter organic fouling solutions, the membranes showed strong resistance to sodium alginate fouling, and less so for humic acids. In terms of separation efficiency, the membranes showed no advantages when operated in photo-filtration mode, as the rejection rate of both foulants under photo-filtration was not higher than that under normal filtration. In the case of humic acids, the photodegradation of humic substances into smaller compounds that were able to enter the permeate stream led to a lower rejection rate. Nevertheless, photo-filtration of these organic foulants still offered a higher permeate flux than normal filtration, up to a certain concentration level (5 mg/L for humic acids and 50 mg/L for sodium alginate).