Challenges and opportunities in piezoelectric polymers: Effect of oriented amorphous fraction in ferroelectric semicrystalline polymers

TL;DR

This paper investigates the role of oriented amorphous fractions in ferroelectric semicrystalline polymers, revealing that they significantly influence piezoelectricity through electrostrictive mechanisms and can be enhanced via ultrasonication.

Contribution

It uncovers the dominant contribution of oriented amorphous fractions to piezoelectricity and demonstrates a novel ultrasonication method to improve performance in PVDF polymers.

Findings

Oriented amorphous fraction (OAF) significantly affects piezoelectricity.

Electrostrictive conformation transformation induces polarization changes.

Ultrasonication effectively induces secondary crystals to enhance piezoelectricity.

Abstract

Despite extensive research on piezoelectric polymers since the discovery of piezoelectric poly(vinylidene fluoride) (PVDF) in 1969, the fundamental physics of polymer piezoelectricity has remained elusive. Based on the classic principle of piezoelectricity, polymer piezoelectricity should originate from the polar crystalline phase. Surprisingly, the crystal contribution to the piezoelectric strain coefficient d31 is determined to be less than 10%, primarily owing to the difficulty in changing the molecular bond lengths and bond angles. Instead, >85% contribution is from Poisson's ratio, which is closely related to the oriented amorphous fraction (OAF) in uniaxially stretched films of semicrystalline ferroelectric (FE) polymers. In this perspective, the semicrystalline structure-piezoelectric property relationship is revealed using PVDF-based FE polymers as a model system. In melt-processed FE polymers, the OAF is often present and links the crystalline lamellae to the isotropic amorphous fraction. Molecular dynamics simulations demonstrate that the electrostrictive conformation transformation of the OAF chains induces a polarization change upon the application of either a stress (the direct piezoelectric effect) or an electric field (the converse piezoelectric effect). Meanwhile, relaxor-like secondary crystals in OAF (SCOAF), which are favored to grow in the extended-chain crystal (ECC) structure, can further enhance the piezoelectricity. However, the ECC structure is difficult to achieve in PVDF homopolymers without high-pressure crystallization. We have discovered that high-power ultrasonication can effectively induce SCOAF in PVDF homopolymers to improve its piezoelectric performance. Finally, we envision that the electrostrictive OAF mechanism should also be applicable for other FE polymers such as odd-numbered nylons and piezoelectric biopolymers.