One-step production of 3D printed ferroelectric polymer forms using fused deposition modeling

This Letter presents the possibility of 3D print polymer forms with a ferroelectric crystal structure in a one-step process by using the fused deposition modeling method. The approach does not require any additional equipment, other than an extruder for filament production and a commercial 3D printer to fabricate ferroelectric polymer forms. By using the copolymer of vinylidene fluoride and tetrafluoroethylene as a filament for 3D printing, complex spatial structures, such as the gyroid form, are accessible. Compared to polyvinylidene fluoride, the copolymer of vinylidene fluoride and tetrafluoroethylene retains its ferroelectric properties even after melting in the 3D printing process and soldification. The x-ray diffraction investigation shows that the 3D forms are having a planar zigzag conformation on macromolecule scales, which relates to a crystal structure with ferroelectric properties. Annealing the 3D forms at a temperature of 110 °C for 12 h does not cause any changes to the spatial polymer structures but leads to an increase in the degree of crystallinity by more than 20%. This result contributes to an increase in the ferroelectric crystalline phase content by ∼17% and the Curie temperature by ∼7 °C in contrast to non-annealed 3D forms.