Enhanced Piezoelectric Properties of Electrospun Poly(vinylidene fluoride)/Multiwalled Carbon Nanotube Composites Due to High β‑Phase Formation in Poly(vinylidene fluoride)

We prepared poly(vinylidene fluoride) (PVDF)/multiwalled carbon nanotube (MWCNT) nanocomposites using the electrospinning process and investigated the effects of varying the MWCNT content, as well as the additional use of drawing and poling on the polymorphic behavior and electroactive (piezoelectric) properties of the membranes obtained. Fourier transform infrared spectroscopy and wide-angle X-ray diffraction revealed that dramatic changes occurred in the β-phase crystal formation with the MWCNT loading. This was attributed to the nucleation effects of the MWCNTs as well as the intense stretching of the PVDF jets in the electrospinning process. The remanent polarization and piezoelectric response increased with the amount of MWCNTs and piezoelectric β-phase crystals. A further mechanical stretching and electric poling process induced not only highly oriented β-phase crystallites, but also very good ferroelectric and piezoelectric performances. In the drawn samples, the interfacial interaction between the functional groups on the MWCNTs and the CF2 dipole of PVDF chains produced a large amount of β-phase content. In the poled samples, the incorporation of the MWCNTs made it easy to obtain efficient charge accumulation in the PVDF matrix, resulting in the conversion of the α-phase into the β-phase as well as the enhancement of remanent polarization and mechanical displacement.