All‐polymer electromechanical systems consisting of electrostrictive poly(vinylidene fluoride‐trifluoroethylene) and conductive polyaniline

The low elastic modulus and the ability to withstand high strain without failure make the conducting polymer attractive for a wide range of acoustic applications based on high‐strain electroactive polymers. In this article, we examine the electric and electromechanical performance of all‐polymer electromechanical systems, fabricated by painting conductive polyaniline (PANI) doped with camphor sulfonic acid (HCSA) on both sides of electrostrictive Poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) copolymer films, and compare them with those from the same copolymers with gold electrodes. The all‐polymer composite films are flexible, with strong coherent interfaces between the electrostrictive polymer layer and the conductive polymer layer. The electric performance such as dielectric properties and polarization hysteresis loops from P(VDF‐TrFE)/PANI film is nearly identical to those of P(VDF‐TrFE)/gold films in a wide temperature (from −50 to 120°C), and frequency range (from 1 Hz to 1 MHz). The all‐polymer systems also show a similar or even larger electric field induced strain response than that of films with electrodes under identical measurement conditions. The results demonstrate that the polyaniline/HCSA is good candidate material as the electrodes for electroactive polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 945–951, 2000     

聚偏氟乙烯的宽频介电谱特征研究

采用熔融法制备了聚偏氟乙烯（PVDF）样品,通过X射线衍射仪、傅里叶变换红外光谱仪和宽频介电谱分析仪对PVDF样品的结构及介电性能进行了测试分析。结果表明,熔融法获得的PVDF主要含α相;在40～100℃范围内出现由玻璃化转变引起的α-PVDF的松弛现象, 在-100～-50 ℃范围内出现的δ-PVDF松弛,是由非晶区分子运动产生的极化现象。     

聚偏氟乙烯共混隔膜的制备与性能

以乙二醇二甲基丙烯酸酯和丙烯腈为单体,合成了聚合物poly(AN-co-PEGDMA),然后与聚偏氟乙烯(PVDF)共混,制备了不同poly(AN-co-PEGDMA)含量的PVDF/poly(AN-co-PEGDMA)共混隔膜,利用X射线衍射、扫描电子显微镜(SEM)、差示扫描量热对共混隔膜的性能进行表征。结果表明,随着poly(AN-co-PEGDMA)含量的增加,PVDF/poly(AN-co-PEGDMA)的玻璃化转变温度逐渐提高,衍射峰的谱峰强度逐渐降低,隔膜的结晶度降低。SEM结果显示,随着poly(AN-co-PEGDMA)含量的增加共混隔膜的孔隙变大,有利于电解液的有效吸收。通过对PVDF/poly(AN-co-PEGDMA)共混隔膜电导率、吸液率的测定,表明在poly(AN-co-PEGDMA)质量分数为30%时,制得的共混隔膜的性能较佳。在此基础上,对共混隔膜构建的聚合物锂离子电池的电化学稳定窗口、电池容量和循环性能进行测试,其电化学稳定窗口为0～4.7 V(vs Li+/Li),放电电容为1.433～1.151 mAh,可以满足商业使用要求,具有广阔的应用前景。     

锂离子电池用胶粘剂

重点介绍了用作液态锂离子电池胶粘剂的偏氟乙烯均聚物和共聚物的结构与性能,介绍了对此类胶粘剂的要求和近年来有关的改性方法与开发动向。     

Heat capacities of polyethylene and linear fluoropolymers

Heat capacities at constant pressure, C_p, and at constant volume C_v, were calculated with the help of normal mode frequency spectra and compared to experimental data for crystalline or semicrystalline polyethylene, poly(vinyl fluoride), poly(vinylidene fluoride), polytrifluooroethylene and poly(tetrafluoroethylene). A calculation scheme using a Tarasov function for 2N skeletal vibrational modes and an approximation of the residual 7N normal modes from known data on polyethylene and polytetrafluoroethylene is developed for all homologous, linear fluoropolymers. N is the number of carbon backbone atoms of the repeating unit. Calculations can be carried out over the whole temperature range 0 K to melting. For the two theta temperatures and the constant A₀ used for C_v to C_p conversion, fluorine-concentration dependent curves are given. The relations are expected to hold also for copolymers and blends of intermediate fluorine contents. Recommended experimental (data bank) heat capacities agree to ±2.5% with the calculations.     

熔融模压制备PVDF/石墨烯复合材料及其性能研究

以聚偏二氟乙烯(PVDF)树脂为基体、石墨烯为填料,通过高速混合机混合作用,经分散剂、润湿剂、表面活性剂、相容剂等组分协同作用,使石墨烯在PVDF中分散均匀,然后经熔融模压成型,制得PVDF/石墨烯复合材料。利用扫描电子显微镜和透射电子显微镜研究了复合材料的微观形貌,并研究了石墨烯含量、制备工艺、助剂及PVDF树脂牌号对复合材料介电性能、导电性能和导热性能的影响。结果表明,采用的助剂体系和高速混合、熔融模压的制备方法能使石墨烯以微片的形态均匀地分散在PVDF树脂基体中,形成良好的功能网络结构;复合材料介电常数、电导率、介电损耗、体积电阻率和导热系数均随石墨烯含量增加而增大;当石墨烯质量分数达到2.0%左右时,复合材料的介电和导电特性均发生突变,向高介电、高导电材料转变,而当石墨烯质量分数达到5.0%左右时,复合材料开始向高导热材料转变;制备工艺和PVDF树脂牌号对复合材料热、电性能的影响则相对较小。     

Grafting of silicon phthalocyanine dichloride onto poly(vinylidene fluoride) film surfaces by ultrasound

Two procedures allowing grafting of an axially functionalized silicon phthalocyanine dichloride across the surface of a dehydrofluorinated polyvinylidene fluoride (PVDF) film surface are presented. In the first method, a PDVF surface was initially dehydrofluorinated by an alkaline degradation process, followed by grafting of a phthalocyanine moiety across the conjugated surface in the presence of a platinic acid catalyst. In the second, one-step sonication method, the use of a lithium coupling agent was employed. UV-VIS, ATR FT-IR, and XPS spectroscopies was used to characterize the nature of surface bonding and the extent of surface reactions.     

A large enhancement in dielectric properties of poly(vinylidene fluoride) based all-organic nanocomposite

A nanocomposite was fabricated using poly(vinylidene fluoride) (PVDF) as matrix and poly(p-chloromethyl styrene) (PCMS) grafted with high dielectric constant copper phthalocyanine oligomer (CuPc) (PCMS-g-CuPc) as filler. Transmission electron microscopic morphologies reveal that the PCMS-g-CuPc particle size of ca. 80 nm in average are dispersed in PVDF matrix, while in PCMS-g-CuPc particles the PCMS acts as “matrix” which contains dispersed CuPc balls with a average size of ca. 25 nm [1/20 of that of CuPc in simple blend of PVDF and CuPc (PVDF/CuPc)]. The nanocomposite with only 15 wt% CuPc can realize a dielectric constant of 325 at 100 Hz, about 7 times larger than that of PVDF/CuPc, and nearly 40-fold enhancement with respect to that of the pure PVDF. The significant enhancement of dielectric response can be attributed to the remarkably strengthened exchange coupling effect as well as the Maxwell-Wagner-Sillars polarization mechanism.     

聚偏氟乙烯-b-聚乙烯基吡咯烷酮嵌段共聚物的制备和结构

以C₆F₁₃I为链转移剂,通过碘转移乳液聚合制得碘封端的聚偏氟乙烯（PVDF-I）,再以PVDF-I为大分子链转移剂进行N-乙烯基吡咯烷酮碘转移溶液聚合,得到聚偏氟乙烯-b-聚乙烯基吡咯烷酮（PVDF-b-PVP）两亲性嵌段共聚物;采用NMR、IR、XRD、DSC和AFM等对PVDF-b-PVP嵌段共聚物的分子和相态结构进行了表征。发现PVP能有效嵌入PVDF与末端碘之间,PVDF嵌段PVP后,PVDF分子链的有序度明显降低,产生γ晶型PVDF,同时结晶温度和结晶度降低。PVDF-b-PVP嵌段共聚物表现微相分离结构,相分离尺寸约20 nm,其亲水性也优于PVDF均聚物。     

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.     

Thermal transitions,microstructure and miscibility in ternary polyblends based on poly(vinylidene fluoride)

The morphology, microstructure and compatibility of binary and ternary polyblends based on poly(vinylidene fluoride) have been studied by means of glass transition temperature, isothermal crystallization kinetics analysis and scanning electron microscopy in order to determine the possibilities offered by poly(vinyl acetate) for compatibilizing poly(vinylidene fluoride) and polystyrene. Calorimetric and dynamic mechanical analyses demonstrate that poly(vinyl acetate) tends to ‘compatibilize’ blends of PVF₂/PS, although the results of the two analyses do not agree with each other; we presume that this is due to differences in the techniques employed.     

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.