Nanomanufacturing and analysis of novel continuous ferroelectric PVDF and P(VDF-TrFE) nanofibers

Poly(vinylidene fluoride) (PVDF) and PVDF copolymers are well known for their ferroelectric and piezoelectric properties. Currently, they are mainly used in applications in the form of films. Thin PVDF films have been shown to possess unique ferroelectric properties in the nanoscale range. However, their two-dimensional nature limits their applicability in active engineering materials and structures. One-dimensional PVDF nanofibers can be expected to combine ferroelectric behavior with enhanced mechanical properties and ultrahigh flexibility providing critical advantages for applications. In this work, novel continuous PVDF nanofibers were nanomanufactured and systematically studied for the first time. Nanofibers from PVDF and P(VDF-TrFE) copolymer with several molecular weights and co-polymer compositions were manufactured by electrospinning. The method consists of spinning polymer solutions in high electric fields. Effects of process parameters on nanofiber diameters and morphology were studied. Resulting nanofibers were characterized by FE-SEM, TEM, XRD, FTIR, DSC and TGA. Effects of annealing on copolymer nanofibers were analyzed. Nanofiber-reinforced composites were manufactured and their polarization behavior studied using a specially designed experimental device. A number of pioneering observations and discoveries were made as a result of this analysis. For example, analysis of crystalline structure of PVDF nanofibers showed that the initial a phase of the PVDF raw material was converted to β phase during electrospinning. This result is very encouraging as the β phase is primarily responsible for the piezo- and ferroelectric behavior of PVDF polymers. It was also shown for the first time that nanofabricated P(VDF-TrFE) nanofibers exhibited distinct Curie points and different structures than their raw materials. Annealing was shown to be an effective way to modify properties of P(VDF-TrFE) co-polymer nanofibers. Overall, the results demonstrated for the first time flexible nanomanufacturing of continuous PVDF and co-polymer nanofibers exhibiting a number of unusual ferroelectric properties. The developed continuous nanofibers can be used in a broad range of applications spanning smart and active composites, multifunctional coatings, functional textiles, ultrafast/sensitive sensors, tailorable miniature actuators, MEMS/NEMS, energy conversion devices, and many others