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Poly(l-lactide)/polyacrylonitrile (PLLA/PAN) core-sheath composite fibers were fabricated by coaxial electrospinning. The crystallization behavior of PLLA within the coaxial electrospun fibers was studied by differential scanning calorimetry (DSC). The PLLA/PAN coaxial electrospun fiber with a PLLA diameter of ∼32 nm (C1) exhibits a crystallization temperature (Tc) of 22.5 °C higher but a cold-crystallization temperature (Tcc) of 10 °C lower than bulk PLLA. The crystallinity of C1 fiber is also higher than bulk PLLA. In both isothermal melt- and cold-crystallization, PLLA in C1 fiber crystallizes faster than the bulk PLLA, as revealed by the smaller half crystallization times (t1/2). The enhanced crystallizability of PLLA in the C1 fiber may be attributed to the increased nuclei number and crystal growth rate induced by the PAN surface, i.e., surface-induction effect. However, PLLA also suffers a nano-confinement effect exerted by PAN sheath in the coaxial electrospun fiber, which can suppress PLLA crystallization. When the diameter of PLLA is too small (< 32 nm), the nano-confinement effect may prevail over the surface-induction effect, leading to a slower crystallization rate and smaller crystallinity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 135, 45980.

Glassy polymer nanofibers with spatially confined poly(ethylene oxide) (PEO) were fabricated by coaxial electrospinning of PEO with polyacrylonitrile (PAN) or polystyrene. The effect of melt-annealing on the crystallization behavior of the confined PEOs was studied using differential scanning calorimetry. It is found that the crystallization behavior of the confined PEOs varies with annealing temperature (Ta), annealing time (ta), and molecular weight of PEO. Notably, it is observed that the crystallization temperature (Tc) and melting temperature (Tm) of PEO increase with prolongation of ta, for PEO600K/PAN and PEO2K/PAN coaxial electrospun fibers. This phenomenon can be interpreted by the annealing-induced demixing at the core-sheath interface. After the coaxial electrospinning, the core and sheath of the PEO/PAN coaxial fibers are partially compatible due to the miscible solvents used for the core and sheath polymers. Upon annealing, demixing occurs at the core-sheath interface, leading to improved crystallizability of PEO. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45760.