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Review
. 2025 Mar 28;16(4):386.
doi: 10.3390/mi16040386.

A Comprehensive Review of Piezoelectric PVDF Polymer Fabrications and Characteristics

Nadia Ahbab  1 , Sidra Naz  1 , Tian-Bing Xu  1 , Shihai Zhang  2
Affiliations
Review

A Comprehensive Review of Piezoelectric PVDF Polymer Fabrications and Characteristics

Nadia Ahbab et al. Micromachines (Basel). .

Abstract

Polyvinylidene fluoride (PVDF) polymer films, renowned for their exceptional piezoelectric, pyroelectric, and ferroelectric properties, offer a versatile platform for the development of cutting-edge micro-scale functional devices, enabling innovative applications ranging from energy harvesting and sensing to medical diagnostics and actuation. This paper presents an in-depth review of the material properties, fabrication methodologies, and characterization of PVDF films. Initially, a comprehensive description of the physical, mechanical, chemical, thermal, electrical, and electromechanical properties is provided. The unique combination of piezoelectric, pyroelectric, and ferroelectric properties, coupled with its excellent chemical resistance and mechanical strength, makes PVDF a highly valuable material for a wide range of applications. Subsequently, the fabrication techniques, phase transitions and their achievement methods, and copolymerization and composites employed to improve and optimize the PVDF properties were elaborated. Enhancing the phase transition in PVDF films, especially promoting the high-performance β-phase, can be achieved through various processing techniques, leading to significantly enhanced piezoelectric and pyroelectric properties, which are essential for diverse applications. This concludes the discussion of PVDF material characterization and its associated techniques for thermal, crystal structure, mechanical, electrical, ferroelectric, piezoelectric, electromechanical, and pyroelectric properties, which provide crucial insights into the material properties of PVDF films, directly impacting their performance in applications. By understanding these aspects, researchers and engineers can gain valuable insights into optimizing PVDF-based devices for various applications, including energy-harvesting, sensing, and biomedical devices, thereby driving advancements in these fields.

Keywords: characterizations; fabrication; material properties; piezoelectric; poly(vinylidene fluoride).

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Conflict of interest statement

Author Shihai Zhang was employed by the company PolyK Technologies, LLC. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Figures

Figure 1
Figure 1
Different properties of PVDF.
Figure 2
Figure 2
Different phases of PVDF and their properties. (a) α-phase, (b) β-phase, and (c) γ-phase. Redrawn from reference [11,74].
Figure 3
Figure 3
Different methods of improving PVDF properties.
Figure 4
Figure 4
A 3D printing mechanism for PVDF films.
Figure 5
Figure 5
The PVDF polymer’s crystalline phase transformation diagram [140].
Figure 6
Figure 6
Phase transition by temperature stretching method. The 1D WAXS profiles during stretching at (A) 60 °C and (B) 140 °C [142].
Figure 7
Figure 7
Diagrammatic representation of PVDF films’ uniaxial stretching process and structure formation phase change, crystalline orientation, and crystalline shape as the stretch ratio increases [145].
Figure 8
Figure 8
Various stretching conditions of PVDF films for structure evolution. (a1) FTIR spectra. (a2) PVDF films’ phase composition changes when the stretch ratio rises. (b1) DSC traces. (b2) Crystallinity and melting temperatures in relation to stretch ratios. (c1) The 1D WAXD patterns. (c2) The (110)/(200)β-phase’s crystallite size and 2θ as a function of stretch ratio, determined by 1D XRD [145].
Figure 9
Figure 9
Experimental setup for biaxial stretching of PVDF [104].
Figure 10
Figure 10
Test setup for measurement of piezoelectric coefficient: (a) d33 and (b) d31 [104].
Figure 11
Figure 11
FTIR spectra of stretched PVDF: (a) uniaxial and (b–d) biaxial [104].
Figure 12
Figure 12
Schematic diagram of in situ polarization for PVDF film [156].
Figure 13
Figure 13
Piezoelectric coefficient corresponding to different polarization voltage [156].
Figure 14
Figure 14
XRD patterns of PVDF-TrFE films after poling [9].
Figure 15
Figure 15
Schematic of setup for stretching and corona poling experiment [157].
Figure 16
Figure 16
(a) XRD patterns of PVDF after corona polarization. (b) FTIR spectra of PVDF [157].
Figure 17
Figure 17
PVDF copolymers: (a) poly(vinylidene fluoride-hexafluoropropylene), (b) poly(vinylidene fluoride-co-trifluoroethylene), and (c) poly(vinylidene fluoride-co-chlorotrifluoroethylene).
Figure 18
Figure 18
Effects of various nanofillers on PVDF properties and their applications.
Figure 19
Figure 19
The classification of thermoplastics blending criteria [189].
Figure 20
Figure 20
Different methods used for PVDF characterization. (a) Crystalline and amorphous regions measured with DSC. (b) Crystallin phases, measured with FTIR, XRD, and Raman. (c) Net polarization P-E hysteresis measured with a ferroelectric test station [204].
Figure 21
Figure 21
PVDF’s engineering stress–strain curves at various temperatures under uniaxial tensile deformation [142].
Figure 22
Figure 22
Yield stress and yield strain at various temperatures [142].
Figure 23
Figure 23
Structural characterizations by WAXD and FTIR. (a) BOPVDF films at room temperature are profiled using 1D WAXD. (b) The FTIR spectra analysis for the poled and fresh BOPVDF films in the transmission mode [205].
Figure 24
Figure 24
Tensile stress versus tensile strain curves of specimens printed with various crystalline patterns by using (a) PVDF-homopolymer and (b) PVDF-copolymer [208].
Figure 25
Figure 25
Tensile test for highly poled PVDF film. (a) The compression modulus (Y3) is obtained by nanoindentation. (b) Tensile moduli (Y1 and Y2) are obtained from the stress–strain curves [205].
Figure 26
Figure 26
The elastic modulus for both stretched and unstretched materials as a function of temperature. The data recorded at 1 and 10 Hz are represented by the dots and solid lines, respectively [209].
Figure 27
Figure 27
Dielectric constant for various temperature of PVDF-TrFE-CFE [57].
Figure 28
Figure 28
P-E loop for commercial piezoelectric PVDF polymer provided by PolyK Technologies [57].
Figure 29
Figure 29
Several piezoelectric coefficients for highly poled BOPVDF film: (a) d33 and (b) d31 and d32 as a function of dynamic stress [205]. The red star in (a) indicates the d33 value measured by the d33 piezo meter with a static force of 2.5 N.
Figure 30
Figure 30
Pure PVDF piezoelectric film’s transverse strain at room temperature under various electric fields of 1 Hz [216].
Figure 31
Figure 31
Frequency dependence of the transverse strain caused by an electric field in a PVDF piezoelectric film [216].
Figure 32
Figure 32
Load effect on the electric field induced transverse strain response measured for PVDF-TrFE copolymer film. (a) Strain response as function of electric field for films under different loads. (b) Strain response and static load for films at various electric field strengths [216].
Figure 33
Figure 33
The impedance as a function of frequency: (a) the capacitance and (b) the dielectric loss [217].
Figure 34
Figure 34
Electromechanical coupling coefficient vs. dc-bias fields for the copolymer [217].
Figure 35
Figure 35
The pyroelectricities of PVDF film with various wt% GO-doping [122].
Figure 36
Figure 36
The pyroelectric currents of PVDF film with various wt% GO-doping [122].
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