Confinement Effects on the Crystallization of Poly(ethylene oxide) Nanotubes

In this work, we show the effects of nanoconfinement on the crystallization of poly(ethylene oxide) (PEO) nanotubes embedded in anodized aluminum oxide (AAO) templates. The morphological characteristics of the hollow ID PEO nanostructures were evaluated by scanning electron microscopy (SEM). The crystallization of the PEO nanostructures and bulk was studied with differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). The crystallization of PEO nanotubes studied by DSC is strongly influenced by the confinement showing a strong reduction in the crystallization temperature of the polymer. X-ray diffraction (XRD) experiments confirmed the isothermal crystallization results obtained by DSC, and studies carried out at low temperatures showed the absence of crystallites oriented with the extended chains perpendicular to the pore wall within the PEO nanotubes, which has been shown to be the typical crystal orientation for one-dimensional polymer nanostructures. In contrast, only planes oriented 33, 45, and 90 degrees with respect to the plane (120) are arranged parallel to the pore's main axis, indicating preferential crystal growth in the direction of the radial component. Calculations based on classical nucleation theory suggest that heterogeneous nucleation prevails in the bulk PEO whereas for the PEO nanotubes a surface nucleation mechanism is more consistent with the obtained results.