Electrospinning of Polyvinylidene Difluoride with Carbon Nanotubes: Synergistic Effects of Extensional Force and Interfacial Interaction on Crystalline Structures

Polyvinylidene difluoride (PVDF) solutions containing a very low concentration of single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs) of similar surface chemistry, respectively, were electrospun, and the nanofibers formed were collected using a modified rotating disk collector. The polymorphic behavior and crystal orientation of the nanofibers were studied using wide-angle X-ray diffraction and infrared spectroscopy, while the nanotube alignment and interfacial interactions in the nanofibers were probed by transmission electron microscopy and Raman spectroscopy. It is shown that the interfacial interaction between the SWCNTs and PVDF and the extensional force experienced by the nanofibers in the electrospinning and collection processes can work synergistically to induce highly oriented β-form crystallites extensively. In contrast, the MWCNTs could not be well aligned along the nanofiber axis, which leads to a lower degree of crystal orientation.