Nonwoven fibrous mats of poly(ethylene‐co‐vinyl alcohol) (EVOH) and thermoplastic starch (TPS) blends were successfully prepared through the electrospinning technique using a mixed solvent system of isopropyl alcohol and water. The influence of TPS on the morphology and structure of the fibrous mats was investigated using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy. The addition of TPS to EVOH resulted in beaded electrospun fibers. The SEM images revealed decreasing average width of the blend fibers and increasing quantity of beads with an increased TPS content. EVOH/TPS fibers mats irradiated under ultraviolet light using sodium benzoate as a photosensitizer were also prepared. The size and number of beads were diminished in the photocrosslinked EVOH/TPS fiber mats. The as‐spun and crosslinked EVOH/TPS fiber mats exhibit a superior fluid uptake ability (with 20 wt% of TPS) and superior barrier properties (with 20 and 40 wt% of TPS) in comparison to those observed in neat electrospun EVOH mats. These properties are of particular interest for use in dressing materials for the medical industry and for use in multilayer plastic fuel tanks for the automotive industry, respectively. POLYM. ENG. SCI., 60:474–480, 2020.
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