ß-Phase Crystallinity, Printability, and Piezoelectric Characteristics of Polyvinylidene Fluoride (PVDF)/Poly(methyl methacrylate) (PMMA)/Cyclopentyl-Polyhedral Oligomeric Silsesquioxane (Cp-POSS) Melt-Compounded Blends.

ABSTRACT

Poly(vinylidene fluoride) (PVDF) is a semicrystalline polymer that exhibits unique piezoelectric characteristics along with good chemical resistance and high thermal stability. Layer-based material extrusion (MEX) 3D printing of PVDF is desired to create complex structures with piezoelectric properties; however, the melt processing of PVDF typically directs the formation of the α crystalline allomorph, which does not contribute to the piezoelectric response. In this work, PVDF was compounded with poly(methyl methacrylate) (PMMA) and cyclopentyl-polyhedral oligomeric silsesquioxane (Cp-POSS) nanostructured additives in binary and ternary blends to improve MEX printability while maintaining piezoelectric performance. Overall crystallinity and ß phase content were evaluated and quantified using a combination of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and differential scanning calorimetry (DSC). Enhancement of MEX printability was measured by quantifying the interlayer adhesion and warpage of printed parts. All blends studied contained a significant percentage of ß allomorph, but it could be detected by ATR-FTIR only after the removal of a thin surface layer. Inclusion of 1% Cp-POSS and up to 10% PMMA in blends with PVDF improved interlayer adhesion (2.3-3.6x) and lowered warpage of MEX printed parts compared to neat PVDF. The blend of 1% Cp-POSS/1% PMMA/PVDF was demonstrated to significantly improve the quality of MEX printed parts while showing similar piezoelectric performance to that of neat PVDF (average piezoelectric coefficient 24 pC/N). MEX printing of PVDF blends directly into usable parts with significant piezoelectric performance while reducing the challenges of printing the semicrystalline polymer opens the potential for application in a number of high value sectors.