Modern material science often makes use of polyvinylidene fluoride thin films because of various properties, like a high thermal and chemical stability, or a ferroelectric, pyroelectric and piezoelectric activity. Fibers of this polymer material are, on the other hand, much less explored due to various issues presented by the fibrous form. By introducing carbon nanotubes via electrospinning, it is possible to affect the chemical and electrical properties of the resulting composite. In the case of this paper, the focus was on the further improvement of interesting polyvinylidene fluoride properties by incorporating carbon nanotubes, such as changing the concentration of crystalline phases and the resulting increase of the dielectric constant and conductivity. These changes in properties have been explored by several methods that focused on a structural, chemical and electrical point of view. The resulting obtained data have been documented to create a basis for further research and to increase the overall understanding of the properties and usability of polyvinylidene fluoride fiber composites.
Polyvinylidene fluoride (PVDF) is a modern polymer material used in a wide variety of ways. Thanks to its excellent resistance to chemical or thermal degradation and low reactivity, it finds use in biology, chemistry, and electronics as well. By enriching the polymer with an easily accessible and cheap variant of graphite, it is possible to affect the ratio of crystalline phases. A correlation between the ratios of crystalline phases and different properties, like dielectric constant as well as piezo- and triboelectric properties, has been found, but the relationship between them is highly complex. These changes have been observed by a number of methods from structural, chemical and electrical points of view. Results of these methods have been documented to create a basis for further research and experimentation on the usability of this combined material in more complex structures and devices.
Electrospinning as a versatile technique producing nanofibers was employed to study the influence of the processing parameters and chemical and physical parameters of solutions on poly(vinylidene fluoride) (PVDF) fibers’ morphology, crystallinity, phase composition and dielectric and piezoelectric characteristics. PVDF fibrous layers with nano- and micro-sized fiber diameters were prepared by a controlled and reliable electrospinning process. The fibers with diameters from 276 nm to 1392 nm were spun at a voltage of 25 kV–50 kV from the pure PVDF solutions or in the presence of a surfactant—Hexadecyltrimethylammonium bromide (CTAB). Although the presence of the CTAB decreased the fibers’ diameter and increased the electroactive phase content, the piezoelectric performance of the PVDF material was evidently deteriorated. The maximum piezoelectric activity was achieved in the fibrous PVDF material without the use of the surfactant, when a piezoelectric charge of 33 pC N−1 was measured in the transversal direction on a mean fiber diameter of 649 nm. In this direction, the material showed a higher piezoelectric activity than in the longitudinal direction.
The method of inclusion of various additives into a polymer depends highly on the material in question and the desired effect. In the case of this paper, nitride salts were introduced into polyvinylidene fluoride fibers prepared by electrospinning. The resulting changes in the structural, chemical and electrical properties of the samples were observed and compared using SEM-EDX, DSC, XPS, FTIR, Raman spectroscopy and electrical measurements. The observed results displayed a grouping of parameters by electronegativity and possibly the molecular mass of the additive salts. We virtually demonstrated elimination of the presence of the γ-phase by addition of Mg(NO3)2, Ca(NO3)2, and Zn(NO3)2 salts. The trend of electrical properties to follow the electronegativity of the nitrate salt cation is demonstrated. The performed measurements of nitrate salt inclusions into PVDF offer a new insight into effects of previously unstudied structures of PVDF composites, opening new potential possibilities of crystalline phase control of the composite and use in further research and component design.
8 May 2015 in Journal of the American Ceramic Society
Creating stimulus-sensitive smart catalysts capable of decomposing organic dyes with high efficiency is a critical task in ecology. Combining the advantages of photoactive piezoelectric nanomaterials and ferroelectric polymers can effectively solve this problem by collecting mechanical vibrations and light energy. Using the electrospinning method, we synthesized hybrid polymer-inorganic nanocomposite fiber membranes based on polyvinylidene fluoride (PVDF) and bismuth ferrite (BFO). The samples were studied by scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), total transmittance and diffuse reflectance, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), vibrating-sample magnetometer (VSM), and piezopotential measurements. It has been demonstrated that the addition of BFO leads to an increase in the proportion of the polar phase from 86.5% to 96.1% due to the surface ion–dipole interaction. It is shown that the composite exhibits anisotropy of magnetic properties depending on the orientation of the magnetic field. The results of piezo-photocatalytic experiments showed that under the combined action of ultrasonic treatment and irradiation with both visible and UV light, the reaction rate increased in comparison with photolysis, sonolysis, and piezocatalysis. Moreover, for PVDF/BFO, which does not exhibit photocatalytic activity, under the combined action of light and ultrasound, the reaction rate increases by about 3× under UV irradiation and by about 6× under visible light irradiation. This behavior is explained by the piezoelectric potential and the narrowing of the band gap of the composite due to mechanical stress caused by the ultrasound.