Crystallization and mechanical behavior of the ferroelectric polymer nonwoven fiber fabrics for highly durable wearable sensor applications

•Performance of the hollow cylindrical near-field electrospinning (HCNFES).•Well-aligned self-assembled PVDF nonwoven fiber fabrics.•Highly durable wearable sensors.•The mechanical characterization of HCNFES piezoelectric NFFs.•The formation of β-form extended-chain crystallites in the PVDF nanofibers. The mechanical characterization of the electrospinning polyvinylidene fluoride (PVDF) nonwoven fiber fabrics (NFFs) doped with multi-walled carbon nanotubes (MWCNTs) was investigated. Piezoelectric composite nanofibers of the PVDF/MWCNTs were directly electrospun by the hollow cylindrical near-field electrospinning (HCNFES) without any post-poling treatment. We have made the HCNFES NFFs consisted of high-orderly arranged nanofiber assemblies for further characterizing the effect of MWCNTs filling PVDF nanofibers. An in situ electrical poling and high uniaxial stretching imparted on the polymer jet during the HCNFES process, which naturally align the dipoles in the PVDF crystals and promote the formation of the polar β-crystalline phase within the fibers. Moreover, the reinforcement of the HCNFES PVDF nanofibers indicated the improvement in mechanical properties and the degree of high oriented extended-chain crystallites through adding adequate contents of MWCNTs. In the case of alignment of the all-trans polymer chains in the vicinity of MWCNTs along the fiber axis, X-ray diffraction (XRD) patterns showed the strongest diffraction peak of the β-crystalline phase. In the comparison of the near-field electrospinning (NFES), the HCNFES nanofibers with smooth surface and smaller diameter can easily form high density structural NFFs. After nano-indentation and tensile strength measurements, the results indicated that the mechanical properties of the HCNFES NFFs are better than the NFES ones. When 16wt% PVDF solution doped with 0.03wt% MWCNTs, the results reveal that Young's modulus, hardness, yield stress, yield strain, ultimate tensile strength, and strain at break of the HCNFES composite NFFs are obviously enhanced to 1.39GPa, 39.6MPa, 28MPa, 48.17MPa, 3.3%, and 32.5%, respectively. Finally, a flexible wearable sensor made of three-dimensional piezoelectric NFFs was actually experimented. Outstanding mechanical properties with highly deformable of PVDF/MWCNTs composite nanofibers would maintain it to represent great challenges during practical implementation.