Piezoelectric and Electrostatic Properties of Electrospun PVDF‐TrFE Nanofibers and their Role in Electromechanical Transduction in Nanogenerators and Strain Sensors

Piezo‐ and ferroelectric nanofibers of the polymer poly(vinylidenefluoride) (PVDF) have been widely employed in strain and pressure sensors as well as nanogenerators for energy harvesting. Despite this interest, the mechanism of electromechanical transduction is under debate and a deeper knowledge about relevant piezoelectric or electrostatic properties of nanofibers is crucial to optimize transduction efficiency. Here poly(vinylidenefluoride‐trifluoroethylene) nanofibers at different electrospinning conditions are prepared. Macroscopic electromechanical response of fiber mats with microscopic analysis of single nanofibers performed by piezoelectric and electrostatic force microscopy are compared. The results show that electrospinning favors the formation of the piezoelectric β‐phase in the polymer and leads directly to piezoelectric properties that are comparable to annealed thin films. However, during electrospinning the electric field is not strong enough to induce direct ferroelectric domain polarization. Instead accumulation of triboelectric surface charges and trapped space charge is observed in the polymer that explain the electret like macroscopic electromechanical response.     

Coaxial electrospun nanofibers of poly(vinylidene fluoride)/polyaniline filled with multi‐walled carbon nanotubes

Core‐shell nanofibers of poly (vinylidene fluoride)/polyaniline/multi‐walled carbon nanotubes (PVDF/PANi/MWCNTs) have been produced using the coaxial electrospinning technique. The nanofibers were semiconductive and had better piezoelectric properties than pure PVDF nanofibers. Piezoelectric PVDF nanofibers are capable of converting mechanical energy into electrical energy, which can be stored in charge storage devices. However, PVDF is not conductive and therefore, a conductive associate material is needed to transfer accumulated static charges into the capacitor. Fourier Transform Infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) were carried out to study the crystalline β‐phase of PVDF. There was an increase in β‐phase in the electrospun PVDF nanofibers filled with MWCNTs as compared with compression molded samples of neat PVDF. Incorporation of PANi as an intrinsically conductive polymer (ICP) and MWCNTs as conductive nanofiller helps the movement of static charges. Core‐shell nanofibers had conductivities of about seven orders of magnitude higher than simple electrospun nanofibers. POLYM. COMPOS., 35:1198–1203, 2014. © 2013 Society of Plastics Engineers     

Investigation of β phase formation in piezoelectric response of electrospun polyvinylidene fluoride nanofibers: LiCl additive and increasing fibers tension

As a piezoelectric polymer, poly (vinylidene fluoride) (PVDF) is attractive in energy conversion applications between electrical and mechanical forms because of its low cost, high flexibility, and biocompatibility. The piezoelectricity of electrospun PVDF polymer is due to changes in the crystalline structure (e.g., creating the β‐phase) during the electrospinning process. This research focuses on two approaches for investigation of β Phase formation: (1) addition of LiCl in different concentrations (0.001, 0.00133, 0.002, 0.004 wt%) as inorganic salt to the polymer solution, (2) increasing tension along the fiber axis by increasing the collector drum speed during the aligning process. Performances of these structures were evaluated by using X‐ray diffraction (XRD), Fourier Transform Infrared (FTIR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). A one‐step nano‐generator and cost‐effective package based on electrospun nanofibers was presented to measure output voltages as a performance factor. Results show that the addition of LiCl leads to β Phase formation in the crystalline structure, decreasing fiber diameter to 65 nm, and increment in the work of rupture and piezoelectric output. Moreover, the results show that increasing collector drum speed causes the alignment of β‐crystallites along the fiber axis and subsequently no considerable effect on the formation of β‐phases and output voltage. POLYM. ENG. SCI., 56:61–70, 2016. © 2015 Society of Plastics Engineers     

Melt spinning of β‐phase poly(vinylidene fluoride) yarns with and without a conductive core

When poly(vinylidene fluoride) (PVDF) is to be used as a piezoelectric material, the processing must include the formation of polar β‐phase crystallites, as well as the application of electrically conducting charge collectors, that is, electrodes. In this article, results from the melt spinning of PVDF yarns and a novel bicomponent PVDF‐yarn with a conductive carbon black/polypropylene (CB/PP) core are presented. Melt spinning has been done under conditions typical for industrial large‐scale fiber production. The effects on the resulting crystalline structure of varying the spinning velocity, draw rate, and draw temperature are discussed. The results show that, for maximum α‐to‐β phase transformation, cold drawing should take place at a temperature between 70 and 90°C, and both the draw ratio and the draw rate should be as high as possible. It was observed that the cold drawing necessary to form β‐phase crystallinity simultaneously leads to a decrease in the core conductivity of the bicomponent yarns. In this work, the melt spinning of bicomponent fibers with high‐β‐phase PVDF in the sheath and a CB/PP core was successfully accomplished. The core material remained electrically conductive, paving the way for the use of a CB‐polymer compound as inner electrode in the melt spinning of piezoelectric bicomponent fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Sensitivity of polyvinylidene fluoride films to mechanical vibration modes and impact after optimizing stretching conditions

The β‐phase of polyvinylidene fluoride (PVDF) is well known for its piezoelectric properties. PVDF films have been developed using solvent cast method. The films thus produced are in α‐phase. The α‐phase is transformed to piezoelectric β‐phase when the film is hot‐stretched with various different stretching factors at various different temperatures. The films are then characterized in terms of their mechanical properties and surface morphological changes during the transformation from α‐ to β‐phases by using X‐ray diffraction, differential scanning calorimeter, Raman spectra, Infrared spectra, tensile testing, and scanning electron microscopy. The films showed increased crystallinity with stretching at temperature up to 80°C. The optimum conditions to achieve β‐phase have been discussed in detail. The fabricated PVDF sensors have been tested for free vibration and impact on plate structure, and its response is compared with conventional piezoelectric wafer type sensor. The resonant and antiresonant peaks in the frequency response of PVDF sensor match well with that of lead zirconate titanate wafer sensors. Effective piezoelectric properties and the variations in the frequency response spectra due to free vibration and impact loading conditions are reported. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Nanocomposite films of poly(vinylidene fluoride) filled with polyvinylpyrrolidone‐coated multiwalled carbon nanotubes: Enhancement of β‐polymorph formation and tensile properties

To improve interactions between carbon nanotubes (CNTs) and poly(vinylidene fluoride) (PVDF) matrix, multiwalled CNTs (MWCNTs) were successfully coated with amphiphilic polyvinylpyrrolidone (PVP) using an ultrasonication treatment performed in aqueous solution. It was found that PVP chains could be attached noncovalently onto the nanotubes' surface, enabling a stable dispersion of MWCNTs in both water and N,N‐dimethylformamide. PVP‐coated MWCNTs/PVDF nanocomposite films were prepared by a solution casting method. The strong specific dipolar interaction between the PVP's carbonyl group (C?O) and the PVDF's fluorine group C?F₂ results in high compatibility between PVP and PVDF, helping PVP‐coated MWCNTs to be homogenously dispersed within PVDF. Fourier transform infrared and X‐ray diffraction characterization revealed that the as‐prepared nanocomposite PVDF films exhibit a purely β‐polymorph even at a very low content of PVP‐wrapped MWCNTs (0.1 wt%) while this phase is totally absent in the corresponding unmodified MWCNTs/PVDF nanocomposites. A possible mechanism of β‐phase formation in PVP‐coated MWCNTs/PVDF nanocomposites has been discussed. Furthermore, the tensile properties of PVDF nanocomposites as function of the content in PVP‐coated MWCNTs were also studied. Results shows that the addition of 2.0 wt% of PVP‐coated MWCNTs lead to a 168% increase in Young's modulus and a 120% in tensile strength. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Electrospun composite nanofibers of poly (vinylidene fluoride‐trifluoroethylene)/polyaniline‐polystyrene sulfonic acid

Nanofibers of poly(vinylidene fluoride‐trifluoroethylene)/polyaniline‐polystyrene sulfonic acid (PVDF‐TrFE/PANi‐PSSA) were fabricated in air at room temperature using electrospinning, with the thinnest fiber having a diameter of ～ 6 nm. This is a cheap, fast, and reliable process for generating PVDF‐TrFE/PANi‐PSSA composite nanofibers. The presence of conducting PANi‐PSSA increased the charge density of the solution and assisted in the fabrication of PVDF‐TrFE nanofibers at low polymer concentrations in dimethylformamide without the beading effect. Ultraviolet and visible spectroscopy showed that PANi‐PSSA was well incorporated into the PVDF‐TrFE solution with no polymer segregation or degradation. A scanning electron microscope was used for morphological characterization of the fibers and a profilometer used to determine the fiber diameter. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Enhanced airborne sound absorption effect in poly(vinylidene fluoride)/(K0.5Na0.5)NbO3-nanofiber composite foams

Introducing electrical conductive function to discharge local piezoelectric effect is found effective for improving airborne sound absorption performance. In this work, instead of conductive fillers, a composite with two piezoelectric materials with opposite piezoelectric responses was explored aiming at enhanced sound absorption effect. Open-cell poly(vinylidene fluoride)/(K_0.5Na_0.5)NbO₃ (PVDF/KNN)-nanofiber composite foams were proposed and investigated for airborne sound absorption purpose. Structural and thermal analyses showed that the KNN nanofibers were well dispersed in the PVDF matrix and enhanced the degree of crystallinity of polar phase of PVDF. Significantly enhanced airborne sound absorption over a broad frequency range was observed in the PVDF/KNN-nanofiber composite foams, with increasing KNN nanofibers. One possible mechanism for the improved sound absorption with the piezoelectric KNN nanofibers with positive piezoelectric coefficient added in the PVDF matrix with negative piezoelectric coefficient is that electrical discharge could be facilitated for energy dissipation with the opposite charges generated through the piezoelectric effects in the two phases with opposite polarity. The experimental results show that the open-cell PVDF/KNN-nanofiber composite foams are promising for broadband airborne sound absorption application, and our analysis shed a light on the strategy in designing piezoelectric composite foam with high sound absorption performance.     

Efficient wound odor removal by β‐cyclodextrin functionalized poly (ε‐caprolactone) nanofibers

Polymer‐cyclodextrin (CD) composite nanofibers, by virtue of the hollow cavities and abundant hydroxyl groups present in CDs, have tremendous potential in a variety of biomedical applications. However, in most cases, especially in aliphatic polyesters, polymer chains thread readily into CD cavities, therefore its potential has not yet been fully realized. Herein, we report the formation of poly(ε‐caprolactone) (PCL)/β‐CD functional nanofibers by electrospinning their mixture from chloroform/N,N‐dimethylformamide (60 : 40). The fiber diameters of the neat PCL and β‐CD functionalized fibers were measured from the images obtained from a scanning electron microscope and were found to be about 500 nm. The efficiency of wound odor absorbance by these composite fibers was studied using a simulated wound odor solution, consisting of butyric and propionic acids in ethanol. Immersion tests indicated that even under less than ideal test conditions, the nanofibers containing β‐CDs were very efficient in masking the odor. The odor masking capability of the β‐CD functionalized PCL nanofibers were further confirmed by thermogravimetric analyses and GC observations, with the former method showing unique degradation patterns. The PCL/β‐CD nanocomposites, by virtue of having their β‐CD cavities free and unthreaded by PCL, could potentially be an ideal substrate for removing wound odors through formation of inclusion compounds with odorants, while providing an ideal environment for the wound to heal. These results suggest tailoring polymer‐CD nanostructures for specific applications in wound odor absorbance, surface grafting of chemical moieties, and vehicles for drug delivery, as examples. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42782.     

Increasing solvent polarity and addition of salts promote β‐phase poly(vinylidene fluoride) formation

This article investigates the effects of solvent polarity and salt addition on β‐phase poly(vinylidene fluoride) (PVDF) formation. Films were solvent cast in aprotic solvents of varying polarities with or without salt addition. Characterization was done by Fourier transformed infra‐red spectroscopy, differential scanning calorimetry, and scanning electron microscopy. Decreasing fractions of β‐phase PVDF was observed with increasing drying temperature when less polar solvents were used. The most polar solvent (hexamethylphosphoramide) consistently produced films with at least 90.0% β‐phase PVDF within the crystalline regions. Melting temperatures increased in correlation to absolute proportions of β‐phase PVDF. Salt addition increased the formation of β‐phase PVDF by 30%, with salts of higher valencies and smaller ionic radii resulting in more significant increases. Taken collectively, using solvents of higher polarities and addition of salts with high cationic valencies and small ionic radii will maximize β‐phase formation in solvent cast PVDF films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crystal phase transition dependence of the energy storage performance of poly(vinylidene fluoride) and poly(vinylidene fluoride‐hexafluoropropene) copolymers

Large‐scale mechanical stretching has been performed to modify the crystal phase structures of the pristine poly(vinylidene fluoride) (PVDF) and its copolymer poly(vinylidene fluoride‐hexafluoropropylene) [P(VDF‐HFP)] with various molar contents HFP in an attempt to improve their energy storage performances. It is found that the physical stretched PVDF and P(VDF‐HFP) 95.5/4.5 mol % films have a phase transition from the nopolar α‐phase to highly polar β‐phase, which is different from the P(VDF‐HFP) films with relative high HFP molar contents (α to γ phases). The following results show that the phase transition in these PVDF‐based polymers has a significant effect on their dielectric and energy storage performances. On account of the reformation of the crystalline property and elimination of the impurity defects, an ultra‐high breakdown electric field of ∼900 MV/m has been obtained in all the stretched samples. Consequently, the higher discharged energy densities of 27.1 and 27.7 J/cm³ are calculated from the D–E loops of the β‐PVDF and β‐P(VDF‐HFP) 95.5/4.5 mol % films, respectively. Regarding their excellent discharging energy density of ∼10 J/cm³ under 600 MV/m for thousands of times, the stretched PVDF and its copolymer P(VDF‐HFP)s are promising candidates for high power capacitors applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46306.     

3D Printing of BaTiO3/PVDF Composites with Electric In Situ Poling for Pressure Sensor Applications

This paper presents 3D printing of piezoelectric sensors using BaTiO₃ (BTO) filler in a poly(vinylidene) fluoride (PVDF) matrix through electric in situ poling during the 3D printing process. Several conventional methods require complicated and time‐consuming procedures. Recently developed electric poling‐assisted additive manufacturing (EPAM) process paves the way for printing of piezoelectric filaments by incorporating polarizing processes that include mechanical stretching, heat press, and electric field poling simultaneously. However, this process is limited to fabrication of a single PVDF layer and quantitative material characterizations such as piezoelectric coefficient and β‐phase percentage are not investigated. In this paper, an enhanced EPAM process is proposed that applies a higher electric field during 3D printing. To further increase piezoelectric response, BTO ceramic filler is used in the PVDF matrix. It is found that a 55.91% PVDF β‐phase content is nucleated at 15 wt% of BTO. The output current and β‐phase content gradually increase as the BTO weight percentage increases. Scanning electron microscopy analysis demonstrates that larger agglomerates are formulated as the increase of BTO filler contents and results in increase of toughness and decrease of tensile strength. The highest fatigue strength is observed at 3 wt% BTO and the fatigue strength gradually decreases as the BTO filler contents increases.     

Temperature‐dependent transition of crystal phases in the electrospinning process of poly(vinylidene fluoride‐co‐hexafluoropropylene)

The temperature‐dependent transition of the crystal phases of poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) was investigated in the electrospinning process. A solution of PVDF‐HFP in N,N‐dimethyl acetamide (DMAc) produced only the β‐phase‐dominant crystal up to 70 °C, irrespective of the spinneret temperature. In a mixed solvent of DMAc and acetone, however, the crystal phase of the electrospun fibers was dependent on temperature: β‐phase‐dominant at 30 and 50 °C and α‐phase‐dominant at 70 °C. The transition was related to a change of the coagulation rate during electrospinning, because the less perfect α phase is preferable to the β phase at a higher coagulation rate. The temperature‐dependent increase of the coagulation rate was more drastic in the presence of acetone, so the transition took place only in the mixed solvent. At elevated temperature, acetone not only raised the evaporation rate of the solvent but promoted the phase separation of the polymer resulting from the lower critical solution temperature behavior, which was rheologically traced. © 2019 Society of Chemical Industry     

Influence of additive on structure of PVDF nanofibers electrospun via new spinneret design

Surface morphology and internal structure of polyvinylidene fluoride (PVDF) nanofibers were investigated in this study. PVDF nanofibers were electrospun by two types of spinnerets, nozzle and channel spinneret, with different contents of tetrabutylammonium chloride (TBAC) and at various take‐up velocities. The new spinneret design, channel spinneret, resulted in thicker fibers while high β‐phase content and small d‐spacing were obtained, especially in the case of low TBAC content. And high TBAC content led to finer PVDF nanofibers with high β‐phase content and small d‐spacing compared to low TBAC content regardless of spinneret types, while an increase in take‐up velocity did not have significant effect on both morphology and internal structure of PVDF nanofibers regardless of TBAC content. It suggests that electrostatic drawing acted dominantly rather than mechanically drawing in the system cooperating TBAC. However, the decreasing difference between two types of spinnerets was observed in terms of β‐phase content with an increase in TBAC content. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1752–1758, 2013     

Pre‐thermal treatment in binary solvent systems promoting β crystalline phase of electrospun poly(vinylidene fluoride) nanofibers

Poly(vinylidene fluoride) (PVDF) nanofibers were fabricated via electrospinning with an investigation of various ratios of binary solvents at different temperatures. The amount of acetone influenced the morphology. Scanning electron microscopy showed a PVDF membrane composed of smooth and unblemished fibers without beads and dark spots with small diameters of 201 ± 54 nm at a dimethylformamide‐to‐acetone ratio of 4:6. The temperature of pre‐thermal treatment from room temperature to 120 °C was investigated to promote the β crystalline phase in electrospun PVDF nanofibers. The result was characterized using Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD). PVDF solution prepared at 80 °C was used to increase the β crystalline phase of the electrospun PVDF nanofibers due to the transformation of α to β phase occurring during the spinning process and also bead‐free PVDF nanofibers were obtained. Differential scanning calorimetry revealed crystallization behavior corresponding with that determined using FTIR spectroscopy and XRD. Therefore, the solvent proportion and pretreatment temperature were observed to affect ultrafine nanofiber and crystalline structure of PVDF, respectively. © 2020 Society of Chemical Industry     

Electrospun Antimicrobial PVDF‐DTAB Nanofibrous Membrane for Air Filtration: Effect of DTAB on Structure,Morphology, Adhesion,and Antibacterial Properties

Antimicrobial polyvinylidene fluoride (PVDF) membrane modified by dodecyltrimethyl ammonium bromide (DTAB) has been electrospun using simple one‐step technology, where the modifying agent DTAB is dissolved in spinning solution. X‐ray photoelectron spectroscopy and electrokinetic analysis confirm reliably the presence of DTAB on the nanofibers surfaces; electrokinetic analysis shows the changes of zeta potential due to modification by DTAB. X‐ray diffraction shows that electrospinning converts the part of α phase (≈40%) present in PVDF powder into β phase with all trans (TTT) zigzag chains conformation in PVDF electrospun membrane. Surface modification does not affect the phase composition of PVDF nanofibers, just only leads to lower crystallinity (smaller size of crystallites) in PVDF nanofibers. DTAB causes the curling of fibers and their aggregation, what completely changed the membrane structure. DTAB‐modified membrane exhibits antibacterial properties against Staphylococcus aureus subsp. Aureus. Concentration of 0.5 wt% DTAB in spinning solution causes partial inhibition of bacterial growth only, while 1.0 wt% concentration leads to complete inhibition.     

复合工艺对压电复合材料性能的影响

采用直接混合和溶液混合两种不同的复合工艺,将铌锌锆钛酸铅（PZN—PZT）压电陶瓷粉体分散于有机聚偏二氟乙烯（PVDF）基体中,制备了0—3型PZN—PZT／PVDF压电复合材料。研究了复合工艺对压电复合材料性能的影响。结果表明,采用溶液混合法能有效地改善陶瓷的分散性及复合材料的压电性,当陶瓷质量分数为90％时,压电复合材料的压电常数d33达到33．4pC·N^-1。     

Improving the dielectric performance of poly(vinylidene fluoride)/polyaniline nanorod composites by stretch‐induced crystal transition

The introduction of conductive polyaniline (PANI) can significantly improve the dielectric constant of polymer‐based materials. However, there is a drawback of high dielectric loss. Herein, a simple and efficient stretching process was applied to improve the dielectric performance of poly(vinylidene fluoride)/PANI (PVDF/PANI) nanorod films through the stretch‐induced crystal transition from non‐polar α‐crystal to polar β‐crystal in PVDF and the oriented distribution of PANI nanorods. XRD, DSC and Fourier transform IR analyses indicate that the stretched PVDF and stretched PVDF/PANI films possess a high content of β‐crystal at the stretching temperature of 135 °C under a stretching ratio of 200%–400%. Furthermore, the stretched PVDF/PANI film with 10 wt% PANI displays a high dielectric constant of 338 at 100 Hz, which is increased by 20% compared to non‐stretched PVDF/PANI film (281). More importantly, the corresponding dielectric loss is reduced from 0.31 for the non‐stretched film to 0.17 for the stretched film. © 2018 Society of Chemical Industry     

Enhanced Piezoelectric Performance of Electrospun Polyvinylidene Fluoride Doped with Inorganic Salts

A novel approach to preparing electrospun polyvinylidene fluoride (PVDF) nanofibers is proposed, with high piezoelectric performance. PVDF nanofibers are doped with inorganic salts without the use of any postpolarization treatment. Twenty‐six salts are doped into the nanofibers and their piezoelectric properties are studied. The salts are classified into three groups based on their differing piezoelectric enhancement effects. A piezoelectric nanogenerator fabricated with an optimized electrospun PVDF nanofiber mat shows a piezovoltage seven times greater than that of a device based on undoped nanofibers. The simple and low‐cost approach to fabricate these piezoelectric nanofiber mats may broaden the range of industrial applications of these materials in energy‐harvesting devices and portable sensors.     

Morphology,polymorphism, and metal ion adsorption studies of electrospun nanofibers based on PVDF and organically modified layered double hydroxide

Nonwoven nanofiber mats of polyvinylidene fluoride (PVDF) with modified layered double hydroxide (MLDH) were prepared by electrospinning. The fiber morphology was studied using scanning electron microscopy. X‐ray diffraction and FTIR spectroscopy was used to characterize the polymorphism in electrospun mats. Fibers of diameter in the range 80–800 nm with beads of about 2–3 µm size were observed for pure PVDF, while in case of PVDF/MLDH nanocomposites the number and size of beads were found to be significantly reduced. Uniform and fine nanofibers were obtained at lower content of MLDH, but slightly rough surface was seen for higher content. FTIR and X‐ray diffraction patterns signify various crystalline forms of electrospun PVDF. The content of polar β‐crystalline phase of PVDF, which exhibit piezo and ferroelectric properties was found to be enhanced significantly due to reinforcement of MLDH. Use of these nanofiber mats for heavy metal Cu (II) removal was explored. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4508–4515, 2013