Dielectric behavior characterization of a fibrous‐ZnO/PVDF nanocomposite

This study is focused on forming a fibrous‐zinc oxide/polyvinylidine fluoride (ZnO/PVDF) nanocomposite and characterizing its dielectric behavior. The nanocomposite is prepared in two steps. First, a network of nanoscale diameter ZnO fibers is produced by sintering electrospun PVA/Zinc Acetate fibers. Second, the ZnO fibrous nonwoven mat is sandwiched between two PVDF thermoplastic polymer films by hot‐press casting. Scanning electron microscope images of the nanocomposite show that hot‐press casting of the fibrous‐ZnO network breaks the network up into short fibers. The in‐plane distribution of the ZnO fillers (i.e., the short fibers) in the PVDF matrix appears to comply with that of the pristine ZnO fibers before hot‐pressing, indicating that the fillers remain well‐dispersed in the polymer matrix. To the authors' knowledge, the work reported herein is the first demonstration of the use of electrospinning to secure the dispersion and distribution of a network of inorganic fillers. Moreover, processing a fibrous‐ZnO/PVDF flexible composite as described in this report would facilitate material handling and enable dielectric property measurement, in contrast to that on a fibrous mat of pure ZnO. Because of the high surface area of the short ZnO fibers and their polycrystalline structure, interfacial polarization is pronounced in the nanocomposite film. The dielectric constant is enhanced significantly‐up to a factor of 10 at low frequencies compared to the dielectric constant of constituent materials (both bulk ZnO and PVDF), and up to a factor of two compared to a bulk‐ZnO/PVDF composite. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Dielectric properties of Ag@C/PVDF composites

The core–shell Ag@C nanoparticles were prepared by hydrothermal method. The silver cores with diameters from 100 to 120 nm are each covered with a carbon shell about 60–80‐nm thick. Ag@C/poly(vinylidene fluoride) (PVDF) composites were prepared by the solution cast method. Transmission electron microscopy showed that the Ag@C core–shell nanoparticles were dispersed homogenously in the PVDF matrix with little agglomeration. The crystallization behavior and dielectric properties of the Ag@C/PVDF composites as a function of frequency and temperature were studied. The differential scanning calorimeter measurements showed that the crystallinity of the Ag@C/PVDF composites decreased with the increasing content of the Ag@C nanoparticles. The dielectric tests showed that the permittivity of the Ag@C/PVDF composites increased obviously over that of the pure PVDF with increasing content of Ag@C particles because of the enhanced interfacial polarization. The tan δ of the composites remained at a low level (～0.08 at 1000 Hz). Furthermore, the permittivity and the tan δ of the composites increased with increasing temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Core‐shell structured Al/PVDF nanocomposites with high dielectric permittivity but low loss and enhanced thermal conductivity

Surface modification of core‐shell structured Al (Al@Al₂O₃) nanoparticles was performed using γ‐(Aminopropyl)‐triethoxysilane (APS) and dopamine (DA), respectively, and the microstructures, dielectric properties and thermal conductivities of the Al/poly(vinylidene fluoride) (PVDF) nanocomposites were investigated. Both DA and APS enhance the interfacial bonding strength between the fillers and the matrix, leading to homogeneous dispersion of Al nanoparticles in PVDF matrix. Compared with raw Al nanoparticles, surface‐treated Al/PVDF exhibit much higher dielectric permittivity due to the enhanced interfacial interactions between the two components, whereas, the dielectric loss and electric conductivity of the nanocomposites still remain at rather low levels owing to the insulating alumina shell preventing effectively core Al from direct contact. The dynamic dielectric properties results reveal that dielectric constant and loss increase with temperature due to the gradually enhanced mobility of molecular chain segments of PVDF for the raw Al/PVDF and treated Al/PVDF nanocomposites. Additionally, the PVDF nanocomposites with Al treated with APS and DA show enhanced thermal conductivities compared with raw Al/PVDF under the same filler loading because of reduced thermal interfacial resistance promoting phonon transfer across the interfaces. POLYM. ENG. SCI., 59:103–111, 2019. © 2018 Society of Plastics Engineers     

PVDF/BaTiO3/carbon nanotubes ternary nanocomposites prepared by ball milling: Piezo and dielectric responses

Nanocomposites based on poly(vinylidene fluoride) (PVDF) filled with barium titanate, BaTiO₃, (BT) particles, and multiwalled carbon nanotubes (MWCNTs) were prepared by high-energy ball milling (HEBM) and subsequent hot pressing. This method of materials preparation allowed obtaining uniform dispersions of the nanofillers. The influence of the particles on the polymer structure and morphology was studied. To understand the origin of changes in the PVDF properties, thermal and electrical behaviors of the PVDF/BT/MWCNT nanocomposites were studied as a function of composition. The addition of BT, MWCNT, or its mixture had not any influence on the PVDF polymorphism. However, calorimetric results pointed out that the presence of the nanofillers exerted nucleation mainly ascribed to the surface to volume ratio of the nanoparticles. The capacitance of the composites increased as the nanofiller content increased, being the effect mainly dependent on the surface to volume ratio of the nanoparticles. The dielectric behavior of the materials as a function of frequency was modeled by a Debye equivalent circuit only below the percolation threshold respect to the amount of MWCNT. The piezoelectric behavior of the ternary nanocomposites was highly affected by the incorporation of the nanofillers only when high dielectric losses occurred above the percolation threshold. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47788.     

CdS impregnated cellulose nanocrystals/PVDF composite flexible and freestanding films: Impedance spectroscopic studies

Nanocrystalline CdS impregnated cellulose nanocrystals (CdS‐Cellulose) were embedded in polyvinylidene fluoride (PVDF) matrix and free‐standing flexible films of CdS‐cellulose/PVDF nanocomposite were made by sol‐gel technique. Effect of CdS loadings in cellulose embedded in the host matrix (PVDF) on the impedance properties was studied critically for the above samples. Dielectric constants were studied as a function of frequencies (1–100 kHz) at room temperatures. The dielectric constant increased significantly in CdS‐cellulose/PVDF nanocomposite than that for pristine PVDF film. The higher values of dielectric constant as well as dielectric loss were obtained at lower frequencies. This may be caused due to contributions arising out of space charge, dipole, and electronic polarizations. At higher frequencies, only dipole and electronic polarization were seen to contribute significantly. The nature of the Cole‐Cole plots could be seen to deviate significantly from one impedance semicircular arc before diverging after a frequency of 3,158, 2,147, and 1,925 Hz for CdS‐cellulose/PVDF nanocomposite with increased loading of CdS. POLYM. ENG. SCI., 58:1419–1427, 2018. © 2017 Society of Plastics Engineers     

Novel composites of copper nanowire/PVDF with superior dielectric properties

Novel copper nanowires (CuNWs)/poly(vinylidene fluoride) (PVDF) nanocomposites with high dielectric permittivity (ε′) and low dielectric loss (ε″) were prepared by a precipitation technique followed by melt compression. Their dielectric properties over the broadband frequency range, i.e. 10¹–10⁶ Hz, were compared with multi-walled carbon nanotubes (MWCNT)/PVDF nanocomposites prepared by the same technique. It was observed that the CuNWs/PVDF nanocomposites had higher dielectric permittivity, lower dielectric loss and thus significantly lower dissipation factor (tan δ) than the MWCNT/PVDF nanocomposites at room temperature. This behavior was ascribed to a higher conductivity of the fresh core of the CuNWs relative to the MWCNT, which provided the composites with a higher amount of mobile charge carriers participating in the interfacial polarization. Moreover, the presence of oxide layers on the CuNWs surfaces diminished the conductive network formation leading to a low dielectric loss.     

陶瓷粉体粒度对PZN—PZT／PVDF压电复合材料性能的影响

将铌锌锆钛酸铅（PZN—PZT）压电陶瓷粉体分散于聚偏二氟乙烯（PVDF）基体中,制备出0-3型PZN—PZT／PVDF压电复合材料。文中研究了PZN—PZT陶瓷不同粒度对复合材料的压电性、介电性、铁电性的影响。结果表明,当陶瓷粒度为100～150目时,压电复合材料的综合性能最佳,压电常数d33达到23．10pC／N,剩余极化强度Pr达到5．131μC·era2,矫顽场Ec为45．7lkV·cm^-1,介电常数ε。为192．86,介电损耗tanδ为0．10。     

Preparation and Dielectric Properties of AGS@CuPc/PVDF Composites

GNS/PVDF, AGS/PVDF and AGS@CuPc/PVDF composites were prepared using hot press molding technique. The micromorphologies showed that the dispersion degree of the GNS in the matrix decreases in the following order: AGS@CuPc/PVDF > AGS/PVDF > GNS/PVDF. It could be attributed to AGS treated with copper phthalocyanine (CuPc) exhibit strongest interface bonding with PVDF, and acidification GNS (AGS) have stronger interface bonding with PVDF than GNS. GNS/PVDF composites showed a slight increase in dielectric constant and dielectric loss with the growing content of fillers. AGS/PVDF composites presented a better performance in dielectric constant than that of GNS/PVDF but with a much higher dielectric loss. Especially AGS@CuPc/PVDF three-phase composite displayed better dielectric properties than GNS/PVDF and AGS/PVDF composites, with a dielectric constant 327 and a dielectric loss 0.63 at 10 kHz. It could be attributed to the cooperation of well dispersion of conductive fillers and the electric barrier effects of CuPc.     

Smart,lightweight, flexible NiO/poly(vinylidene flouride) nanocomposites film with significantly enhanced dielectric,piezoelectric and EMI shielding properties

We report a facile technique to fabricate flexible and self-standing NiO/PVDF nanocomposite films. Detail structural and thermal characterizations of nanocomposite films show the gradual increase of electroactive β-phase of PVDF with increasing NiO nanoparticles content. The enhancement of β phase in the NiO/PVDF nanocomposites has been explained from physicochemical point of view. Electrical properties of the nanocomposites indicate fair improvement in dielectric properties at low filler loading with less dielectric loss. The value of dielectric constant of 0.75 wt% NiO/PVDF films at 100 Hz is five times higher than that of neat PVDF. Series-parallel model was used to describe the filler concentration dependence of the dielectric constant of the nanocomposites. These nanocomposites also exhibit excellent ferroelectric properties. Nanocomposite films having thickness 300 μm were also successfully employed for microwave shielding application. This work suggests that these films would be very useful for thinner, lighter energy harvesting storage and EMI shielding applications.     

COOHMWCNTs‐induced BiFeO3‐poly(vinylidene fluoride) (PVDF) composites with enhanced dielectric and ferroelectric properties

In this work, flexible three phase composite films were prepared with surface functionalized multi‐walled carbon nanotubes (f‐MWCNTs) and bismuth ferrite (BiFeO₃;BFO) particles embedded into the poly(vinylidene fluoride) (PVDF) matrix via solution casting technique. The properties and the microstructure of prepared composites were investigated using an impedance analyzer and field emission scanning electron microscope. The micro‐structural study showed that the f‐MWCNTs and BFO particles were dispersed homogeneously within the PVDF matrix, nicely seated on the floor of the f‐MWCNTs separately. The dielectric measurement result shows that the resultant composites with excellent dielectric constant (≈96) and relatively lower dielectric loss (<0.23 at 100 Hz). Furthermore, the percolation theory is explored to explain the dielectric properties of the resultant composites. It says that the percolation threshold of f_MWCNTs = 0.9 wt % and the enhancement of the dielectric constant of the composite was also discussed. In addition, the remnant polarization of the un‐poled PVDF‐BFO‐f‐MWCNTs composites (2P_r ～1.34 µC/cm² for 1.1 wt % of f‐MWCNTs) is also improved. These three phase composites provide a new insight to fabricate flexible and enhanced dielectric properties as a promising application in modern electrical and electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46002.     

Electroactive PVDF thin films fabricated via cooperative stretching process

Ferroelectric polymers have obtained much attention in low cost and flexible electronics. As one representative ferroelectric polymer, poly(vinylidene fluoride) (PVDF) has been comprehensively studied. Due to its complicated phase composition, fabrication of electroactive phases has been an open question especially for PVDF thin films deposited on solid substrates. Here cooperative stretching process is introduced for the fabrication of electroactive PVDF thin films. PVDF thin films are coated on stretchable poly(vinyl alcohol) substrates and mechanically stretched under optimized stretching parameters. Structural, spectral, and electrical measurements indicate that cooperative stretching process can effectively convert the nonpolar α phase to the electroactive β and γ phases companied by an enhancement of film crystallinity. Stretched PVDF films present a reverse piezoelectric coefficient of ?37 pm/V, comparable with the results from films fabricated by the other techniques. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46324.     

GO@TA-Fe/PVDF纳米复合材料制备与介电性能

为降低氧化石墨烯（GO）/聚偏氟乙烯（PVDF）体系的介电损耗，本文采用单宁酸-铁配合物（TA-Fe）修饰GO表面，将改性GO和PVDF复合后制得了GO@TA-Fe/PVDF纳米复合电介质材料，研究了GO@TA-Fe对PVDF复合材料的微观形貌及介电性能影响。研究结果表明，TA-Fe包覆层强化了GO与PVDF基体间界面相容性及界面作用力，促进了GO在基体中均匀分散；TA-Fe界面层的存在显著降低了GO/PVDF漏导电流及损耗，归因于绝缘界面层有效阻止了GO之间直接接触，抑制漏导电流；TA-Fe用量对体系介电性能有明显影响，随TA-Fe用量增大，体系的介电损耗和电导率显著降低。与GO/PVDF相比，质量分数2%的GO@TA-Fe/PVDF在100Hz下介电常数为1000，而介电损耗由19.8降低为0.08。本研究制备的高介电常数及低损耗的柔性GO@TA-Fe/PVDF纳米电介质材料在电子器件及电力设备领域具有潜在应用。     

Enhanced dielectric properties of three phase dielectric MWCNTs/BaTiO3/PVDF nanocomposites for energy storage using fused deposition modeling 3D printing

This research studied the effect of fused deposition modeling (FDM) 3D printing on three phase dielectric nanocomposites using poly(vinylidene) fluoride (PVDF), BaTiO₃ (BT), and multiwall carbon nanotubes (CNTs). PVDF polymer and BT ceramics are piezo-, pyro- and di-electric materials extensively used for sensor and energy storage/harvesting applications due to their unique characteristic of dipole polarization. To increase dielectric property, CNTs have been recently utilized for uniform dispersion of BT nanoparticles, ultrahigh polarization density, and local micro-capacitor among matrix. It was proved that 3D printing process provides homogeneous dispersion of nanoparticles, alleviating agglomeration of nanoparticles and reducing micro-crack/voids in matrix which can potentially enhance their dielectric property than traditional methods. In this research, these three-phase nanocomposites are fabricated through FDM 3D printing process and characterized for dielectric property. Increasing both BT and CNT nanoparticles improves dielectric properties, while CNTs have a percolation threshold near 1.7?wt%. The most desirable combination of dielectric constant and loss properties (118 and 0.11 at 1?kHz) is achieved with nanocomposites containing 1.7?wt%-CNT/45?wt%-BT/PVDF. These results provide not only a technique to 3D print dielectric nanocomposites with improved dielectric property but also large-scale electronic device manufacturing possibility with freedom of design, low cost, and faster process.     

Mixed Matrix PVDF/Graphene and Composite‐Skin PVDF/Graphene Oxide Membranes Applied in Membrane Distillation

This work elucidates the influence of graphene (G) and graphene oxide (GO) content on the desalination performance and scaling characteristics of G/polyvinylidene fluoride (G/PVDF) mixed matrix and GO/PVDF composite‐skin membranes, applied in a direct contact membrane distillation process (DCMD). Inclusion of high quality, nonoxidized, monolayered graphene sheets as polymer membrane filler, and application of a novel GO/water‐bath coagulation method for the preparation of the GO/PVDF composite films, took place. Water permeability and desalination tests via DCMD, revealed that the optimal G content was 0.87 wt%. At such concentration the water vapor flux of the G/PVDF membrane was 1.7 times that of the nonmodified reference, while the salt rejection efficiency was significantly improved (99.8%) as compared to the neat PVDF. Similarly the GO/PVDF surface‐modified membrane, prepared using a GO dispersion with low concentration (0.5 g/L), exhibited twofold higher water vapor permeate flux as compared to the neat PVDF, but however, its salt rejection efficiency was moderate (80%), probably due to pore wetting during DCMD. The relatively low scaling tendency observed for both G and GO modified membranes is primarily attributed to their smoother surface texture as compared to neat PVDF, while scaling is caused by the deposition of calcite crystals, identified by XRPD analysis. POLYM. ENG. SCI., 59:E262–E278, 2019. © 2018 Society of Plastics Engineers     

PDMS/PVDF microporous membrane with semi‐interpenetrating polymer networks for vacuum membrane distillation

In this article, using the non‐solvent induced phase separation process, a new microporous membrane with the semi‐interpenetrating polymer network (semi‐IPN) structure was produced. For this membrane, polydimethylsiloxane (PDMS) polymer is crosslinking and poly(vinylidene fluoride) (PVDF) polymer is linear, by changing the mass ratio of PDMS/PVDF, the structure and the performance of the prepared membranes were studied. The membranes were also investigated by attenuated total reflection‐Fourier transform infrared (ATR‐FTIR), scanning electron microscopy–energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, thermogravimetric analysis, and water contact angle, etc. ATR‐FTIR spectroscopy confirmed the formation of semi‐IPN; compared with the PDMS/PVDF polymer without semi‐IPNs structure, the viscosity of the semi‐IPNs structured casting solution increased, membrane mechanical property increased but its hydrophobicity decreased. Using the resulting membranes for the vacuum membrane distillation desalt of the NaCl solution (30 g/L), 99.9% salt rejection and reasonable flux were obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45792.     

Enhanced dielectric properties of poly(vinylidene fluoride)–surface functionalized BiFeO3 composites using sodium dodecyl sulfate as a modulating agent for device applications

In this work, we prepared a series of poly(vinylidene fluoride) (PVDF)–surface functionalized BiFeO₃ (h‐BFO)–Sodium dodecyl sulfate (SDS) composite films by solvent casting method to investigate the effect of SDS in the composites. The X‐ray diffraction confirmed that the structure of h‐BFO significantly changed in the PVDF‐(h‐BFO)‐SDS composite in comparison with the rhombohedral structure of pure BiFeO₃. The microscopic study illustrated that the composite with a higher percentage of SDS content facilitated the dispersion as well as proper distribution of ceramic particles in the polymer matrix. The presence of different functionalities of respective polymer and the modified fillers was confirmed by FTIR Spectrophotometer. The dielectric and electrical study done by Impedance Analyzer revealed that the SDS treated surface functionalized composites showed relatively higher dielectric properties than that of two phase composites and pure polymer. Finally, the ferroelectric properties of the composite films done by P‐E loop tracer revealed that the SDS‐treated composites showed an enhanced remanent polarization. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45040.     

In situ electrical resistance and X‐ray tomography study of copper–tin polymer composites during thermal annealing

In situ electrical conductivity and X‐ray tomography experiments are conducted on a conductive polymer composite containing polyvinylidene fluoride (PVDF) copolymer, copper (Cu), and tin (Sn) during thermal annealing. During annealing, the electrical resistivity drops by an order of magnitude, while X‐ray tomography, electron microscopy, and spectroscopy results show increasingly homogeneous dispersion of Sn in the conductive filler network, accompanied by the formation of Cu–Sn intermetallic around Cu and Sn particles. This study provides detailed insight into the morphological origins of the beneficial effect of thermal annealing on the electrical properties of conductive composites containing low melting metal fillers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45399.     

Effect of heat treatment on the electrical properties of lead zirconate titanate/poly (vinylidene fluoride) composites

Ceramic/polymer composites are attracting increasing interest in materials research and practical applications due to the combination of excellent electric properties of piezoelectric ceramics and good flexibility of polymer matrices. In this case, the crystallization of the polymer has a significant effect on the electric properties of ceramic/polymer composites. Based on different heat treatment methods, the crystallization of poly(vinylidene fluoride) (PVDF) in composites of lead zirconate titanate (PZT) and PVDF can be controlled effectively. PZT/PVDF composites with various PVDF crystallizations exhibit distinctive dielectric and piezoelectric properties. When the crystallization of PVDF is 21%, the PZT/PVDF composites show a high dielectric constant (ε) of 165 and a low dielectric loss (tan δ) of 0.03 at 10³ Hz, and when the crystallization of PVDF reaches 34%, the piezoelectric coefficient (d₃₃) of PZT/PVDF composites can be up to ca 100 pC N^?1. By controlling the crystallization of PVDF, PZT/PVDF composites with excellent dielectric and piezoelectric properties were obtained, which can be employed as promising candidates in high‐efficiency capacitors and as novel piezoelectric materials. Copyright © 2010 Society of Chemical Industry     

PVDF based all-organic composite with high dielectric constant

High dielectric constant copper phthalocyanine oligomer (o-CuPc) was chemically grafted to poly(p-chloromethyl styrene) (PCMS) to improve its dispersibility in PVDF. From SEM results, the size of o-CuPc-g-PCMS particles in the blend of poly(vinylidene fluoride) (PVDF) and o-CuPc-g-PCMS (o-CuPc-g-PCMS/PVDF) was about 70nm, less than 1/7 the size of o-CuPc in o-CuPc/PVDF. In addition, o-CuPc-g-PCMS in o-CuPc-g-PCMS/PVDF showed much improved dispersibility. Both of the improvements obviously enhanced the electric properties of the composite. The dielectric constant of o-CuPc-g-PCMS/PVDF was more than 325 (100Hz), which was about 7 times higher than that of o-CuPc/PVDF. The dielectric constant at high frequencies (∼1MHz) was also high (∼130).     

Visualization of PVDF nanofibers coated on filter paper using fluorescein silica nanoparticles

Fluorescein silica nanoparticles (NPs) were prepared using a silane compound bound between fluorescein‐N‐hydroxysuccinimide (NHS‐Fluorescein) and 3‐aminopropylorthosilicate by a sol–gel method. The fluorescein‐silica NPs were mixed with a poly(vinylidene fluoride) (PVDF) solution, and the solution loaded with the NPs was electrospun on a filter paper. Scanning electron microscopy and transmission electron microscopy images confirmed the encapsulation of the fluorescein silica NPs in the PVDF nanofibers. Laser scanning confocal microscopy (LSCM) images showed fluorescein silica NPs as dots, and photoluminescence (PL) images obtained using a fluoroanalyzer indicated the emission of uniform PL from filter papers coated with fluorescein‐silica‐NP‐encapsulated PVDF nanofibers. It was demonstrated that the fluorescein silica NPs enabled PVDF nanofibers coated on a filter paper to be easily visualized. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45125.