In this study, the pullulan/ethyl cellulose composite nanofiber films with tunable physical properties were fabricated by blend electrospinning process. The solution properties of polysaccharide polymers were investigated and related with the morphology of the nanofiber films, and the results showed that the addition of ethyl cellulose caused decreasing viscosity and conductivity of solutions, which gave rise to the smaller fiber diameter. The Fourier transform infrared spectroscopy indicated that pullulan and ethyl cellulose chains interacted with each other through hydrogen bonding. X-ray diffraction analysis showed that electrospinning process retarded the crystallization of polysaccharide molecules. Thermal analysis showed that the composite nanofiber films possessed higher melting temperature and degradation temperature than the pure pullulan nanofiber film. Water contact angle and water stability test proved that the composite nanofiber films possessed tunable surface wettability (94.6°–120.1°) and improved water stability. The mechanical test showed that the composite nanofiber films had enhanced mechanical strength.
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