Confined crystallization and chain conformational change in electrospun poly(ethylene oxide) nanofibers

This study focused on understanding the confined crystallization of poly(ethylene oxide) (PEO) in electrospun nanofibers. The effect of thermal treatment on PEO crystallization was also studied. An electrospinning process with a rotating drum collector enabled stretching and aligning of polymer chains, which resulted in the formation of a planar zigzag conformation. The confined environment in nanofibers facilitated an ordered crystal arrangement, resulting in an increase in the degree of crystallinity with a decrease in the fiber diameter. By contrast, large fibers extended solvent evaporation, which resulted in large crystallite sizes. The confined geometry and mechanical force provided by a rotating collector induced the preferred crystal orientation parallel to the fiber axis. Upon thermal annealing, the stretched PEO chains relaxed, resulting in a change from the metastable zigzag conformation to a stable helical conformation. Thermal treatment monotonically increased the melting temperature, degree of crystallinity, and crystallite size of PEO nanofibers regardless of the fiber diameter but did not influence the orientation of the organized crystals.