Understanding nonlinear dielectric behavior in polar polymers is crucial to their potential application as next generation high energy density and low loss dielectrics. In this work, we studied nonlinear dielectric properties of a biaxially oriented poly(vinylidene fluoride) (BOPVDF) film under both low and high electric fields. For fundamental nonlinear dielectric constants at low fields (<30 MV/m), Novocontrol high-voltage broadband dielectric spectroscopy (HVBDS) was accurate enough to measure up to the third harmonics. It was observed that the low-field dielectric nonlinearity for the BOPVDF disappeared above 10 Hz at room temperature, suggesting that the low-field dielectric nonlinearity originated from ionic migration of impurity ions rather than dipolar relaxation of the amorphous segments. Above the coercive field (EC ≈ 70 MV/m), bipolar electric displacement-electric field (D-E) loop tests were used to extract the nonlinear behavior for pure PVDF crystals, which had a clear origin of ferroelectric switching of polar crystalline dipoles and domains and nonpolar-to-polar (α → δ → β) phase transformations. By using HVBDS, it was observed that the ferroelectric switching of polar crystalline dipoles and domains in BOPVDF above the EC always took place between 20 and 500 Hz regardless of a broad range of temperature from -30 to 100 °C. This behavior was drastically different from that of the amorphous PVDF dipoles, which had a strong dependence on frequency over orders of magnitude.
Keywords: dipolar relaxation; ferroelectric; high-voltage broadband dielectric spectroscopy; nonlinear dielectric property; poly(vinylidene fluoride).