Enhanced electrical properties of multiwalled carbon nanotube/poly(vinylidenefluoride) films through a rolling process

Poly(vinylidene fluoride) (PVDF) films containing multiwalled carbon nanotubes (MWCNTs) were prepared by solution casting method, followed by a rolling process. With the presence of MWCNTs (up to 0.3 wt%), the influence of rolling process on the crystal structure and the electrical properties of PVDF was studied. It is shown that rolling can induce phase transition as well as increase in the crystallinity of PVDF, leading to enhancement of ferroelectric and dielectric properties. In addition, MWCNTs may promote the phase transition of PVDF, while impeding the increase of crystallinity during the rolling process. With a higher breakdown field and a lower coercive electric field in comparison with the original films, the rolled films can be efficiently poled to obtain good piezoelectricity. Moreover, with the presence of MWCNTs, electric field-induced changes in crystallinity can be obviously observed in the poled MWCNTs/PVDF films. With the highest crystallinity of β-phase, the rolled films containing 0.075 wt% MWCNTs possess the highest piezoelectric coefficient d₃₃ of ~33 pC/N while that of pure PVDF films is only ~22 pC/N.     

Multi-walled CNT-induced phase behaviour of poly(vinylidene fluoride) and its electro-mechanical properties

A simple two-step process was used to disperse acid functionalized multi-walled carbon nanotubes (CNTs) in poly(vinylidene fluoride) (PVDF). While the neat solvent-cast PVDF showed coexistence of α- and β-phases; the composite films exhibited only β-phase crystals. Further studies on the crystalline behaviour, using differential scanning calorimetry and small-angle X-ray scattering techniques showed an increase in the percentage of crystalline phase with CNT. The network formed by CNTs in the matrix reduced the macroscopic electrical resistivity of composite films. The dielectric constant increased with CNT loading. Further, these composites were investigated for its electromagnetic wave absorbance (EWA) and strain sensing properties. The EWA properties were studied in the X-band (6–12 GHz) region. A maximum of ~37 dB reflectivity loss at ~9.0 GHz was obtained in a ~25 μm thick PVDF film containing only 0.25 wt% of functionalized CNT. Preliminary studies showed a systematic change in electrical resistance by the application of dynamic bending strain in nanocomposite film. The film also showed a significant improvement in mechanical stiffness owing to efficient stress transfer from matrix to filler, the property desirable for a good strain sensor. In view of the unique combination of EWA and electro-mechanical properties, the nanocomposite films are expected to serve as a multifunctional material for strain sensing in health monitoring as well as in radar absorption.     

Piezoelectric formation mechanisms and phase transformation of poly(vinylidene fluoride)/graphite nanosheets nanocomposites

The β-phase of poly(vinylidene fluoride) (PVDF) is of great technical importance because of its high dielectric constant and piezoelectric effect. In this work, we exfoliated and dispersed natural graphite to prepare 2D-graphite nanosheets (GNS) and prepared PVDF/GNS nanocomposites with different GNS volumes from 1 to 7 ml as film via solution casting method. The concentration of the supernatant was about 0.3 mg/mL. The effect of GNS on the β-phase formation and mechanisms of piezoelectric formation in the PVDF/GNS nanocomposites were investigated. The results showed that with the varying amounts of GNS, the crystalline structure, the morphology, and the dielectric and piezoelectric properties of PVDF/GNS nanocomposites changed. GNS acts as an effective nucleation agent with the orientation almost parallel to the surface of the film meanwhile increasing the amount of beta phase in the PVDF matrix with increasing amount of GNS, also the relative dielectric constant and dielectric loss of the nanocomposites increased with increasing amount of GNS. The value d₃₃ also increased with increasing amount of GNS, and reached a maximum (6.7 pC/N) with 6 ml GNS. The mechanism of piezoelectric formation was proposed based on experiment results of PVDF/GNS nanocomposites.     

High Performance Flexible Actuator of Urchin‐Like ZnO Nanostructure/Polyvinylenefluoride Hybrid Thin Film with Graphene Electrodes for Acoustic Generator and Analyzer

A bass frequency response enhanced flexible polyvinylidene fluoride (PVDF) based thin film acoustic actuator is successfully fabricated. High concentrations of various zinc oxide (ZnO) is embedded in PVDF matrix, enhancing the β phase content and the dielectric property of the composite thin film. ZnO acts as a nucleation agent for the crystallization of PVDF. A chemical vapor deposition grown graphene is used as electrodes, enabling high electron mobility for the distortion free acoustic signals. The frequency response of the fabricated acoustic actuator is studied as a function of the film thickness and filler content. The optimized film has a thickness of 80 μm with 30 wt% filler content and shows 72% and 42% frequency response enhancement in bass and midrange compared to the commercial PVDF, respectively. Also, the total harmonic distortion decreases to 82% and 74% in the bass and midrange regions, respectively. Furthermore, the composite film shows a promising potential for microphone applications. Most of all, it is demonstrated that acoustic actuator performance is strongly influenced by degree of PVDF crystalline.     

Improved zinc oxide film for gas sensor applications

Zinc oxide (ZnO) is a versatile material for different commercial applications such as transparent electrodes, piezoelectric devices, varistors, SAW devices etc because of its high piezoelectric coupling, greater stability of its hexagonal phase and its pyroelectric property. In fact, ZnO is a potential material for gas sensor applications. Good quality ZnO films were deposited on glass and quartz substrates by a novel CVD technique using zinc acetate as the starting solution. X-ray diffraction confirmed the crystallinity of the zinc oxide film and SEM study revealed uniform deposition of fine grains. Undoped ZnO films were used for detection of dimethylamine (DMA) and H₂ at different temperatures by recording the change in resistivity of the film in presence of the test gases. The response was faster and the sensitivity was higher compared to the earlier reported ZnO based sensors developed in our laboratory. The main objective of this work was to study the selectivity of the ZnO film for a particular gas in presence of the others. The operating temperature was found to play a key role in the selectivity of such sensors.     

Dielectric and magnetic properties of ferrite/poly(vinylidene fluoride) nanocomposites

Particulate composite films of poly(vinylidene fluoride) and CoFe₂O₄ and NiFe₂O₄ were prepared by solvent casting and melt processing. The well-dispersed ferrite nanoparticles nucleate the piezoelectric β-phase of the polymer, but the different ferrites nucleate the whole polymer crystalline phase at different filler concentrations. The macroscopic magnetic and dielectric response of the composites demonstrates a strong dependence on the volume fraction of ferrite nanoparticles, with both magnetization and dielectric constant increasing for increasing filler content. The β-relaxation in the composite samples is similar to the one observed for β-PVDF obtained by stretching. A superparamagnetic behavior was observed for NiFe₂O₄/PVDF composites, whereas CoFe₂O₄/PVDF samples developed a hysteresis cycle with coercivity of 0.3 T.     

Flexible ZnO-cellulose nanocomposite for multisource energy conversion

Materials with the ability to harness multiple sources of energy from the ambient environment could lead to new types of energy-harvesting systems. It is demonstrated that nanocomposite films consisting of zinc oxide nanostructures embedded in a common paper matrix can be directly used as energy-conversion devices to transform mechanical and thermal energies to electric power. These mechanically robust and flexible devices can be fabricated over large areas and are capable of producing an output voltage and power up to 80 mV and 50 nW cm(-2) , respectively. Furthermore, it is shown that by integrating a certain number of devices (in series and parallel) the output voltage and the concomitant output power can be significantly increased. Also, the output voltage and power can be enhanced by scaling the size of the device. This multisource energy-harvesting system based on ZnO nanostructures embedded in a flexible paper matrix provides a simplified and cost-effective platform for capturing trace amounts of energy for practical applications.     

Multilayered flexible nanocomposite for hybrid nanogenerator enabled by conjunction of piezoelectricity and triboelectricity

We fabricate a flexible hybrid nanogenerator (HNG),based on multilayered nanocomposite materials,which integrates a piezoelectric nanogenerator (PENG) and a triboelectric nanogenerator (TENG) into a single structure with only two electrodes.The HNG enables enhancement of the electrical output of the nanogenerators.An open-circuit voltage of 280 V and a short-circuit current of 25 μA are achieved by a HNG of 2.5 cmx 2.5 cm in size,superior to the performance of previously reported HNGs.In addition,the energy-conversion process of the HNG relies on the working mechanism of both the PENG and TENG.The polarization direction and doping content of BTO are the two major factors that affect the electrical output.Biomechanical energy harvesting from walking motion or the bending of an arm is also demonstrated.     

聚偏氟乙烯基复合材料的制备及介电性能

为有效改善聚合物基复合材料的介电性能,兼顾高介电常数和低填料量同时并存,采用以聚偏氟乙烯(PVDF)为基体树脂,钛酸钡(BT)和石墨烯(GNP)分别为介电填料和导电填料,在BT-GNP/PVDF复合体系内部构建微电容器结构。采用溶液法和热压法制备GNP/PVDF薄膜和BT-GNP/PVDF复合薄膜。结果表明,BT和GNP填料在BT-GNP/PVDF复合薄膜中能够均匀分散,在薄膜内能形成明显的微电容器结构。陶瓷填料BT的引入,使微电容器结构更有利于提高BT-GNP/PVDF复合薄膜的介电常数。BT含量大于50wt%的BT-GNP/PVDF复合薄膜介电常数均不低于GNP/PVDF薄膜。BT含量为50wt%的BT-GNP/PVDF复合薄膜的介电常数高于BT含量分别为35wt%、60wt%和70wt%的BT-GNP/PVDF复合薄膜,最大值约为43,相当于GNP含量为0.8wt%的GNP/PVDF薄膜的1.5倍;BT含量为50wt%的BT-GNP/PVDF复合薄膜损耗角正切均小于其他体系薄膜,最大不超过0.09,最小约为0.02。BT-GNP/PVDF复合薄膜的电导率变化趋势基本一致,没有明显差异。      

Performance enhancements in poly(vinylidene fluoride)-based piezoelectric films prepared by the extrusion-casting process

The extrusion-casting process can realize large-area and continuous preparation of polymer-based films. In this paper, five different types of polyvinylidene fluoride (PVDF)-based piezoelectric films: PVDF, PVDF/PZT, PVDF/PZT@105, PVDF/PZT/BNNS and PVDF/PZT@105/BNNS were prepared by the extrusion-casting process. The mechanical, dielectric, thermal conductivity and piezoelectric properties were studied. It is found that PZT particles can well improve the dielectric performance and also the mechanical stability under variable temperature conditions. PZT powders modified by titanate coupling reagent (UP-105) can further improve the performance of the PVDF/PZT@105 films by improving the combination and dispersion of organic and inorganic phases. The addition of boron nitride nanosheets (BNNS) can improve the thermal conductivity of the films and the breakdown strength. The piezoelectric coefficient (d₃₃) of PVDF/PZT@105/BNNS composite film can reach 21pC/N, compared with the neat PVDF film (4pC/N) and PZT/PVDF (9pC/N) film realizing great improvement.

     

固相剪切碾磨对聚偏氟乙烯结构和介电性能的影响

利用固相剪切碾磨技术(S~3M)制备了高β晶含量的聚偏氟乙烯(PVDF)微米级粉体,研究了PVDF粉体的结构形态、粒径及粒径分布,碾磨遍数对粉体结晶结构和介电性能的影响。结果表明,固相力化学反应器强大的挤压和剪切作用可使PVDF中α晶转变为晶,从而有效提高PVDF粉体中β晶相对含量;随碾磨遍数增加,PVDF粉体β晶含量逐渐提高,未碾磨PVDF中的β晶相对含量为37%,碾磨15遍后β晶相对含量达90%以上;同时,介电常数则由1.20增加至10.77,提高约1个数量级。固相剪切碾磨技术为高介电性能材料的制备提供了新途径。     

Polydopamine coating layer on graphene for suppressing loss tangent and enhancing dielectric constant of poly(vinylidene fluoride)/graphene composites

Graphene with polydopamine (PDA) coating layer which displays promoted dispersibility in organic solvent was prepared through self-polymerization of dopamine onto graphene oxide (GO) and subsequent chemical reduction. The PDA coated reduced GO (RDGO) is homogeneously incorporated into poly(vinylidene fluoride) (PVDF) matrix, which exhibit a percolation threshold at 0.643 wt%. The dielectric constant of PVDF with 0.70 wt% RDGO increases to 176, about 17 times of neat PVDF. Importantly, the loss tangent is suppressed to 0.337 due to reduction of the concentration and mobility of ionizable carboxylic groups by PDA. The enhancement of dielectric constant probably rises from duplex interfacial polarization induced by graphene–semiconductor interface, and semiconductor–insulator interface. The composites displays advantages in excellent dielectric properties and good flexibility and processability guaranteed by low loading of RDGO, which is suitable for the development of dielectric materials for energy storage.     

PVDF/PZNZT压电复合材料的结构与性能

为了扩展压电复合材料的应用领域,首先,通过固相合成法制备了0-3型聚偏氟乙烯(PVDF)/Pb(Zn_1/3Nb_2/3)_0.05Zr_0.47Ti_0.48O₃ (PZNZT)压电复合材料;然后,研究了PVDF含量对PVDF/PZNZT复合材料物相、显微结构及性能的影响。结果表明:PZNZT陶瓷粉料与PVDF粉料混合后,其平均粒度接近于纯PVDF粉料的。于220℃下烧结后, PVDF/PZNZT复合材料在XRD谱图中主要显现出PZNZT钙钛矿结构的衍射峰。当PVDF含量较低时, PZNZT陶瓷晶粒间的结合较松散;随着PVDF含量的增加,陶瓷晶粒几乎都被PVDF相包围。因显微结构不同,不同PVDF含量的PVDF/PZNZT复合材料在极化电场中呈现出不同的串、并联电路。极化后, 5wt% PVDF/PZNZT复合材料的电性能最佳,其介电常数为116、介电损耗tan δ为0.04、压电常数为48 pC/N且机电耦合系数为0.28。随PVDF含量的增加, PVDF/PZNZT复合材料的居里温度降低,维氏硬度有所增加,但仍小于纯PZNZT压电陶瓷的硬度。所得结论显示PVDF/PZNZT压电复合材料的性能可以满足水声、电声及超声换能器等的要求。      

改性PZT/PVDF体系压电复合材料的介电和压电性能

采用复合材料模压工艺,制备了体积分数不同的改性PZT(含铌的钛锆酸铅)/PVDF(聚偏二氟乙烯)压电复合材料。采用扫描电镜对材料的形貌进行了分析,并利用HP4294A,Z-3A型准静态测试仪等系统地研究了改性PZT体积分数对材料介电、压电性能的影响。结果显示,在改性PZT体积分数为70%时,获得了性能优良的压电复合材料。在压电陶瓷高含量区(>0.5),部分压电陶瓷颗粒相互联接,形成了类似0-3(3-3)型复合连通形式,是复合材料获得优良压电、介电性能的主要原因。     

Effect of CoCl<Subscript>2</Subscript>–BaCl<Subscript>2</Subscript> fillers on morphology,dielectric constant and conductivity of PVDF composite for pressure sensing application

This present study focuses on the effect of addition of CoCl₂–BaCl₂ fillers on the β phase formation and dielectric constant in the PVDF composite films. The pristine and filler based PVDF films were prepared using solution casting technique. XRD analysis were carried out to investigate the crystalline structure in the prepared composite films. The surface morphology of the films were observed using SEM indicating the formation of agglormated structures. The UV–Vis absorption spectrum was obtained to investigate the effect of filler concentration on the optical band gap. The decrease in optical band gap with increase in filler concentration was confirmed from Tauc plot. The incorporation of filler significantly improved the ac conductivity. The dielectric study reveals the increase in value of dielectric constant from 10.8 to 42.3 as the filler content increased from 0 to 12 wt%. A pressure measurement set up was developed and voltage output was measured from the PVDF thin film sensor for variation in applied pressure.     

Impedance studies of free-standing,flexible thin films of PVDF filled with gallium nitride nanoparticles

Flexible, free-standing composite films of poly(vinylidene fluoride) (PVDF) with Gallium Nitride (GaN) as fillers, in varying concentrations, were synthesized by sol–gel method. Modulations in the microstructural, morphological and dielectric properties, due to the addition of fillers, were investigated. Modifications in the spherocrystal structure, their dimensions and their number density were observed. Microstructural studies confirmed the presence of GaN nanoparticles in the matrix. FTIR and Raman spectroscopy revealed the presence of the three polymorphs of PVDF in the composite films. The dielectric constant of the composite films were found to increase with the increase in the filler concentration, to almost?~?6 times that of the value for the pristine film due to the interfacial polarization playing between the polymer chains and the filler nanoparticles. Low values of dielectric constant at higher frequencies were observed due to the contribution of dipolar polarization. A peak-to-peak voltage of ~?5.4?V, from a triboelectric nanogenerator fabricated using a 1 wt% composite films, was obtained.

     

Interface characterization and thermal degradation of ferrite/poly(vinylidene fluoride) multiferroic nanocomposites

Flexible multiferroic 0–3 composite films, with CoFe₂O₄, Ni_0.5Zn_0.5Fe₂O₄ or NiFe₂O₄ ferrite nanoparticles as filler and polyvinylidene fluoride (PVDF) as the polymer matrix, have been prepared by solvent casting and melt crystallization. The inclusion of ferrite nanoparticles in the polymer allows to obtain magnetoelectric nanocomposites through the nucleation of the piezoelectric β-phase of the polymer by the ferrite fillers. Since the interface between PVDF and the nanoparticles has an important role in the nucleation of the polymer phase, thermogravimetric analysis was used in order to identify and quantify the interface region and to correlate it with the β-phase content. It is found that an intimate relation exists between the size of the interface region and the piezoelectric β-phase formation that depends on the content and type of ferrite nanoparticles. The interface value and the β-phase content increase with increasing ferrite loading and they are higher for CoFe₂O₄ and Ni_0.5Zn_0.5Fe₂O₄ ferrite nanoparticles. The composites shows lower thermal stability than the pure polymer due to the existence of mass loss processes at lower temperature than the main degradation of the polymer. The main degradation of the polymer matrix, nevertheless, shows increased degradation temperature with increasing ferrite content.     

多巴胺改性聚苯硫脲与聚偏氟乙烯共混复合材料的制备与性能

聚苯硫脲（ArPTU）是一种新型高击穿、低损耗的材料,为提高其储能密度,在与聚偏氟乙烯（PVDF）共混的过程中,如何提高其溶解性,降低界面问题,成为研究热点之一。利用多巴胺（DA）对其进行改性可以有效地改善其与PVDF的界面问题。采用溶液流延热压的方法制备出不同共混比的多巴胺改性聚苯硫脲共混聚偏氟乙烯（DA/ArPTU-PVDF）复合薄膜。并采用X射线衍射仪、扫描电子显微镜、核磁共振、凝胶渗透色谱、阻抗分析仪等对其进行表征。结果表明:当DA/ArPTU-PVDF中DA/ArPTU质量分数为10wt%~15wt%时,PVDF的β晶型相对含量显著增加,这是其介电性能增加的主要原因之一;100 Hz时,介电常数最大可以达到10.3（10wt% DA/ArPTU）,同时介电损耗降低,最低达到了0.008（25wt% DA/ArPTU）。复合材料的储能密度也有明显提高,最大可以达3.0 J/cm3（10wt% DA/ArPTU）,相对于纯PVDF提高了63.3%。此外,复合材料的击穿特性相比于纯PVDF具有很大的提高,最大可达556.4MV/m（15wt% DA/ArPTU）。而且,改性后的复合材料力学性能也有了很大的提高。最大断裂伸长率可以达到196.7%（5wt% DA/ArPTU）,展现出了柔性高击穿储能材料的潜力。      

Influence of annealing on dielectric and polarization behavior of PVDF thick films

The polyvinylidene fluoride (PVDF) thick film has been fabricated by a solution casting method. The fabricated film is subjected to annealing at 50, 90, 100, 110 and 130?°C for 5 h. The effect of annealing on structural, crystalline, dielectric and polarization behavior is investigated. The β-phase PVDF is found to coexist with α-phase for annealing temperature upto 100?°C, after that β-phase is converted to α-phase. The film annealed at 100?°C, exhibits enhanced permittivity, reduced tangent loss and enhanced polarization. The dielectric permittivity and tangent loss of film annealed at 100?°C are ~11 and ~0.025 respectively for the frequency range of 10³–10⁵ Hz. The saturation polarization for this film is ~1.27 µC/cm². The enhanced dielectric permittivity and polarization for the film annealed at 100?°C might be attributed to increase in crystalline α and β-phase interface as well as crystalline amorphous interface. The thick film of PVDF with improved dielectric and polarization behavior could be useful for high power electronics application.     

Electrospun poly(vinylidene fluoride-trifluoroethylene)/zinc oxide nanocomposite tissue engineering scaffolds with enhanced cell adhesion and blood vessel formation

Piezoelectric materials that generate electrical signals in response to mechanical strain can be used in tissue engineering to stimulate cell proliferation.Poly (vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)),a piezoelectric polymer,is widely used in biomaterial applications.We hypothesized that incorporation of zinc oxide (ZnO) nanoparticles into the P(VDF-TrFE) matrix could promote adhesion,migration,and proliferation of cells,as well as blood vessel formation (angiogenesis).In this study,we fabricated and comprehensively characterized a novel electrospun P(VDF-TrFE)/ZnO nanocomposite tissue engineering scaffold.We analyzed the morphological features of the polymeric matrix by scanning electron microscopy,and utilized Fourier transform infrared spectroscopy,X-ray diffraction,and differential scanning calorimetry to examine changes in the crystalline phases of the copolymer due to addition of the nanoparticles.We detected no or minimal adverse effects of the biomaterials with regard to blood compatibility in vitro,biocompatibility,and cytotoxicity,indicating that P(VDF-TrFE)/ZnO nanocomposite scaffolds are suitable for tissue engineering applications.Interestingly,human mesenchymal stem cells (hMSCs) and human umbilical vein endothelial cells cultured on the nanocomposite scaffolds exhibited higher cell viability,adhesion,and proliferation compared to cells cultured on tissue culture plates or neat P(VDF-TrFE) scaffolds.Nanocomposite scaffolds implanted into rats with or without hMSCs did not elicit immunological responses,as assessed by macroscopic analysis and histology.Importantly,nanocomposite scaffolds promoted angiogenesis,which was increased in scaffolds pre-seeded with hMSCs.Overall,our results highlight the potential of these novel P(VDF-TrFE)/ZnO nanocomposites for use in tissue engineering,due to their biocompatibility and ability to promote cell adhesion and angiogenesis.