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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 coefficientd31is 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 SCOAFin 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.
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Double Yielding in Deformation of Semicrystalline Polymers
Abstract Different semicrystalline polymers including poly(l‐lactic acid), poly(ethylene terephthalate), syndiotactic polystyrene, and polyamide 12 are studied in terms of their mechanical response to uniaxial compression deformation. Apparent decoupling of yielding of amorphous and crystalline phases is identified as separate peaks in the stress–strain curve in the vicinity of the glass transition temperature. The same feature is also observed for the uniaxial extension of predrawn semicrystalline poly(ethylene terephthalate). It is indicated that in absence of a strong amorphous phase a semicrystalline polymer is unable to yield and undergo plastic deformation and it fails in a brittle manner in the uniaxial compression. Treating a semicrystalline polymer as a composite of amorphous and crystalline phases, putting emphasis on the crucial role of amorphous phase in acting as connectors between crystalline domains and indicating that the yielding of amorphous phase is a prerequisite for yielding of crystalline phase, work toward a better understanding of the mechanical properties of semicrystalline polymers at the molecular level is done.
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- Award ID(s):
- 1905870
- PAR ID:
- 10456823
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Macromolecular Chemistry and Physics
- Volume:
- 221
- Issue:
- 19
- ISSN:
- 1022-1352
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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