聚偏氟乙烯/聚氯乙烯相容性研究

采用溶解度参数法和混合焓变理论预测聚偏氟乙烯(PVDF)／聚氯乙烯(PVC)共混体系为部分相容体系,并用共溶剂法、黏度法、微分扫描量热法判断聚偏氟乙烯／聚氯乙烯的相容性．结果表明:两者属于部分相容体系,与理论预测相符,为后续制备聚偏氟乙烯／聚氯乙烯纤维膜奠定理论基础．     

聚偏氟乙烯共聚物薄膜铁电性能和电容特性研究

制备了以聚苯乙烯磺酸(PSSH)为上下界面层的聚(偏氟乙烯)(PVDF)二元共聚物聚(偏氟乙烯-三氟乙烯)[P(VDF-TrFE)]及聚(偏氟乙烯-氯氟乙烯)[P(VDF-CTFE)]的三明治结构电容器,研究了P(VDF-TrFE)和P(VDF-CTFE)2两种共聚物薄膜的铁电性能和电容特性。结果表明,厚度为60nm的Ti/PSSH/P(VDF-TrFE)/PSSH/Ti超薄薄膜表现出优异的铁电性能;而厚度为100nm的Ti/PSSH/P(VDF-CTFE)/PSSH/Ti薄膜表现出较好的电容特性,存储能量密度高达60J/cm3。研究结果为其在电子器件上的应用提供理论指导。     

聚偏氟乙烯/碳纳米管复合材料的形态结构及性能

通过超声分散方法制备了聚偏氟乙烯/多壁碳纳米管复合材料,研究了复合材料的形态结构、导电性和热膨胀性质。扫描电镜观察表明碳纳米管被均匀地分散在聚偏氟乙烯基体中。虽然碳纳米管和聚偏氟乙烯之间存在相互作用,但超声并没有引起聚偏氟乙烯的化学交联。同时还研究了复合材料的导电性和正温度系数效应,发现这些复合材料具有较低的逾渗阈值,掺入少量碳纳米管就可使聚偏氟乙烯/碳纳米管复合材料的导电性获得明显改善。此外,碳纳米管的添加能够明显降低聚偏氟乙烯/碳纳米管复合材料的热膨胀系数。     

PVDF／PAn纳米复合材料的制备及介电性能的研究

以N—N二甲基甲酰胺为溶剂、十二烷基苯磺酸钠为表面活性剂、过硫酸铵为氧化剂,利用聚偏氟乙烯（PVDF）中氟原子与苯胺分子中胺基氢原子之间的氢键作用,将苯胺小分子吸附于聚偏氟乙烯表面,然后经过乳液聚合反应,使聚苯胺（PAn）纳米颗粒均匀地包覆在聚偏氟乙烯表面,通过分子自组装过程制备出了具有核壳结构的聚苯胺包覆型PVDF／PAn纳米复合材料,用FT—IR、XRD、SEM、TH2818分析仪分析了材料的结构、形貌以及介电性能。     

CNTs/Ferrite/PVDF复合材料的电磁波吸收特性

本文采用水热合成法在碳纳米管(CNTs)表面包覆了一层组分为Ni0.2Cu0.2Zn0.6Fe.1.96O4的尖晶石型纳米铁氧体(Ferrite)颗粒,并应用共混法制备了碳纳米管/铁氧体/聚偏二氟乙烯(PVDF)三相复合材料.使用矢量网络分析仪在8-18GHz的频率范围内对复合材料的复介电常数和复磁导率进行了测试,并由此计算出复合材料的反射损失率.测试结果表明,复合材料在宽约为几个GHz的频段内反射损失超过了10dB,碳纳米管/铁氧体/聚偏二氟乙烯复合材料呈现出非常良好的电磁波吸收性能.     

纳米ZnS/PVDF复合膜的制备及其光学性能

以醋酸锌(ZnAC₂ ·2H₂O)和聚偏氟乙烯(PVDF)为原料, N-N-二甲基甲酰胺为溶剂, 采用溶胶-凝胶原位复合的方法制备纳米硫化锌/聚偏氟乙烯复合膜。X射线衍射和透射电镜分析表明, 复合膜中的ZnS晶粒分布均匀, 平均尺寸在3~7nm之间, 具有明显的立方相结构。紫外-可见吸收光谱和荧光光谱分析表明, 随着ZnS晶粒度的减小, 复合膜的吸收边出现从310→270nm的蓝移, 该复合膜中同时存在368nm的激子复合发光和429nm自激活发光。分散剂的加入不会对复合膜的荧光性能产生本质的影响, 但可以使ZnS生长速度减慢, 分散更均匀。      

纳米Fe2O3对聚氨酯/聚偏氟乙烯复合涂层摩擦学性能的影响

利用M-2000型摩擦磨损试验机考察了干滑动下纳米Fe2O3改性的聚氨酯/聚偏氟乙烯(PU/PVDF)复合涂层的摩擦磨损性能。采用扫描电子显微镜分析了纳米Fe2O3在复合涂层中的分布以及涂层的磨损表面。结果显示纳米Fe2O3在涂层中分布比较均匀,少量的纳米Fe2O3的加入不仅降低了聚氨酯/聚偏氟乙烯复合涂层的摩擦系数,而且还提高了聚氨酯/聚偏氟乙烯复合涂层的抗磨性。负载对复合涂层的摩擦磨损性能有较大的影响,随着负载的增加,涂层的磨损率升高。     

全氟磺酸树脂/PVDF共混膜的研究

为了降低质子交换膜的成本,选用聚偏氟乙烯和全氟磺酸树脂为原料,采用溶液-浇铸法制备了全氟磺酸树脂/聚偏氟乙烯的共混膜.通过XPS测试发现共混膜在制备过程中不同接触面元素含量不同;这些不同的元素含量对共混膜的发电性能产生了一定程度的影响.在相同条件下,O2通往空气成膜一方时的发电性能比通往玻璃一方的发电性能要好.     

PT/P(VDF-TrFE)/多孔氧化硅衬底热释电传感器研制

用电化学方法制备多孔化率约６９％的多孔硅，在湿氧中氧化成多孔氧化硅，作热释电传感器的衬底。将用溶胶凝胶法制备的钛酸铅（ＰＴ）纳米粉粒掺入聚偏氟乙烯／三氟乙烯共聚物中形成ＰＴ／Ｐ（ＶＤＦＴｒＦＥ）热释电复合敏感膜。ＰＴ粉粒的掺入体积比为０１２时，与成膜条件相同的Ｐ（ＶＤＦＴｒＦＥ）膜相比，热释电优值提高２０％，探测优值提高３５％。多孔氧化硅结构降低了衬底的热导率和元件热容，使多孔硅衬底传感器的电流灵敏度比结构相同的体硅衬底传感器样品高约２倍。     

1996年日本氟树脂工业一瞥

１９９６年日本氟树脂工业一瞥在日本的氟树脂应用中，作为密封材料广泛使用的聚四氟乙烯（ＰＴＦＥ）约占７０％，其它的有可热熔融成型的可熔性聚四氟乙烯（ＰＦＡ）、聚全氟乙丙烯（ＦＥＰ）、高机械强度的聚偏氟乙烯（ＰＶＤＦ）和乙烯一四氟乙烯共聚物（ＥＴＦＥ）等...     

Organic thin film transistors with polymer high-k dielectric insulator

With the soluble copolymer poly(vinylidene fluoride–trifluoroethylene) (P(VDF–TrFE)) for the dielectric layer, we fabricate organic field effect transistors with enhanced gate effects, if we use P(VDF–TrFE) layers with a thickness of 2 μm. No hysteresis is observed. We obtain a relative dielectric constant of about 11 (at 1 kHz), which enables operation voltages smaller than for the organic insulator polymethylmetacrylate (PMMA, ε = 3.3 at 1 kHz). In contrast, for thinner films of P(VDF–TrFE) (250 nm), we find the typical ferroelectric hysteresis of the copolymer. This gives opportunities for building up organic transistors with a thin P(VDF–TrFE) ferroelectric layer as nonvolatile memory element.     

陶瓷型铁电复合物厚片介电系数的电场依赖性

建立起高压介电测试装置和相应的数据处理方法。研究了PZT/P (VDF-T rFE) 和PT/P (VDF- rFE) 0-3型铁电复合物厚片介电系数的电场依赖性。对于陶瓷体积分数U> 0.3 的复合物, 介电系数随测试场强的升高明显增大。在U< 0.1 时, 可用M axw ell-Garnet t 方程拟合试验结果。B ruggeman 方程适合于低电场(< 1MV/m ) 下复合物介电系数的预测。通过L z 的变化, 用Yamada 模型可拟合复合物介电系数随电场变化的关系, 说明L z 是由复合物的组分维数、粒子形状以及粒子间静电相互作用所决定的参数。      

The effect of local polarized domains of ferroelectric P(VDF/TrFE) copolymer thin film on a carbon nanotube field-effect transistor

We produced local polarized domains of ferroelectric P(VDF/TrFE) copolymer thin films on a carbon nanotube field-effect transistor (CN-FET) channel by atomic force microscopy (AFM). The drain current versus gate voltage (I(d)-V(g)) curves measured after forming the local polarized domains showed a shift in the threshold voltages. We also found that the amount of the shifts in the threshold voltages gradually decreased during the measurement of this characteristic over 100?h after forming the polarized domains. The mechanisms of the shifts in the threshold voltages and their decreasing behaviour were explained in terms of the excessive charges that were induced upon the formation of the polarized domains.     

An application of polarized domains in ferroelectric thin films using scanning probe microscope

The feasibility of utilizing PZT films as future data storage media was investigated using a modified AFM. Applying voltages between a conductive AFM tip and the PZT films causes the switching of ferroelectric domains. The domains are observed using an EFM imaging technique. The experimental results and calculations revealed that the electrostatic force generated between the polarized area and the tip is a main contributor for the imaging of the polarized domains. The written features on ferroelectric films were less than 100 nm in diameter, implying the possibility of realizing data storage devices with ultra-high area density. The disappearance of the polarized images without any applied voltage was observed, which is a drawback in this application of PZT thin films.     

High‐Performance Piezoelectric Nanogenerators with Imprinted P(VDF‐TrFE)/BaTiO3 Nanocomposite Micropillars for Self‐Powered Flexible Sensors

Piezoelectric nanogenerators with large output, high sensitivity, and good flexibility have attracted extensive interest in wearable electronics and personal healthcare. In this paper, the authors propose a high‐performance flexible piezoelectric nanogenerator based on piezoelectrically enhanced nanocomposite micropillar array of polyvinylidene fluoride‐trifluoroethylene (P(VDF‐TrFE))/barium titanate (BaTiO₃) for energy harvesting and highly sensitive self‐powered sensing. By a reliable and scalable nanoimprinting process, the piezoelectrically enhanced vertically aligned P(VDF‐TrFE)/BaTiO₃ nanocomposite micropillar arrays are fabricated. The piezoelectric device exhibits enhanced voltage of 13.2 V and a current density of 0.33 µA cm^?2, which an enhancement by a factor of 7.3 relatives to the pristine P(VDF‐TrFE) bulk film. The mechanisms of high performance are mainly attributed to the enhanced piezoelectricity of the P(VDF‐TrFE)/BaTiO₃ nanocomposite materials and the improved mechanical flexibility of the micropillar array. Under mechanical impact, stable electricity is stably generated from the nanogenerator and used to drive various electronic devices to work continuously, implying its significance in the field of consumer electronic devices. Furthermore, it can be applied as self‐powered flexible sensor work in a noncontact mode for detecting air pressure and wearable sensors for detecting some human vital signs including different modes of breath and heartbeat pulse, which shows its potential applications in flexible electronics and medical sciences.     

Dielectric response of polymer relaxors

Dielectric response of vinylidene fluoride type ferroelectric polymers is dominated by that of segmental motions in the amorphous phase in temperature range 200–300 K and contributions related to the local mode and ferroelectric–paraelectric transition in the crystalline phase of the polymer at higher temperatures. Diffuse and frequency-dependent dielectric anomaly observed in fast electron irradiated polyvinylidene fluoride-trifluoroethylene P(VDF/TrFE) has been related to relaxor-like behavior induced in the semicrystalline ferroelectric copolymers. As random field and the response of polar nanosize clusters determine the relaxor behavior the effects of disorder and fast electron irradiation (below and above T _C) on the three contributions to the dielectric response of PVDF, P(VDF/TrFE)(75/25) and P(VDF/TrFE)(50/50) are shown. The processes involved in radiation-induced functionalization of PVDF-type polymers are discussed on the basis of results of ESR, IR and Raman spectroscopy studies.     

Electrical and thermal properties of vinylidene fluoride–trifluoroethylene-based polymer system with coexisting ferroelectric and relaxor states

Dielectric, thermal, and electrocaloric investigations of poly(vinylidene fluoride–trifluoroethylene) P(VDF–TrFE) copolymer, irradiated with high-energy electrons, are reported. While the ferroelectric copolymer is transformed into a relaxor system at high irradiation doses, dielectric investigations, particularly nonlinear dielectric experiments, i.e., temperature dependences of the second and the third harmonic dielectric response, clearly evidence that at lower doses ferroelectric and relaxor states coexist in the P(VDF–TrFE). This is confirmed by the differential scanning calorimetry, which further reveals the influence of irradiation on the copolymer crystallinity and melting point. Finally, it is shown that large electrocaloric response of VDF–TrFE-based polymers is further enhanced in systems with coexisting relaxor and normal ferroelectric states.     

电子辐照的P(VDF/TrFE)共聚物的铁电弛豫异常现象

本文研究了聚偏氟乙烯和三氟乙烯的铁电共聚物P(VDF/TrFE)的铁电弛豫现象,并讨论了铁电弛豫异常想象.比较了VDF不同含量的共聚物在辐照前后铁电性能的改变,电子辐照大大改变了聚合物样品的性能,使VDF含量52%和70%的样品出现了明显的铁电弛豫现象,但发现在VDF含量为80%的样品中存在一种铁电弛豫异常现象:铁电居里峰随着频率的升高而向低温端移动.研究样品的二氟乙烯(VDF)的摩尔含量在52%～80%之间.     

Solution-processed Ni–CNTs filled ferroelectric P(VDF–TrFE) composites with improved dielectric properties and thermal conductivity

Dielectric composites made using two kinds of poly(vinylidene fluoride–trifluoroethylene) [P(VDF–TrFE)] (70/30 and 80/20 mol%) as polymer matrices and nickel particles coated carbon nanotubes (Ni–CNTs) as filler were developed via solution-processed method. The scanning electron microscopy (SEM) indicated good compatibility and dispersion of Ni–CNTs in the P(VDF–TrFE) matrix. Ni–CNTs/P(VDF–TrFE) composites exhibited high dielectric constants with low dielectric losses. The maximum dielectric constants of Ni–CNTs/P(VDF–TrFE) composites of 198 and 185 at 100 Hz were obtained at 18.0 wt% Ni–CNTs loading, respectively. The incorporation of Ni–CNTs in the P(VDF–TrFE) matrix resulted in enhanced thermal conductivity. The highest values, obtained at 18.0 wt% Ni–CNTs loading, were 1.05 and 1.03 W/m K, respectively. Although there were no very obvious difference, the dielectric properties and thermal conductivity of Ni–CNTs/P(VDF–TrFE) 70/30 mol% composites were slightly better to those of Ni–CNTs/P(VDF–TrFE) 80/20 mol% composites in many cases. The aforementioned results suggest that these high-performance composites hold great promise for application in electrical and electronic field.     

The "millipede" - nanotechnology entering data storage

Present a new scanning-probe-based data-storage concept called the "millipede" that combines ultrahigh density, terabit capacity, small form factor, and high data rate. Ultrahigh storage density has been demonstrated by a new thermomechanical local-probe technique to store, read back, and erase data in very thin polymer films. With this new technique, nanometer-sized bit indentations and pitch sizes have been made by a single cantilever/tip into thin polymer layers, resulting in a data storage densities of up to 1 Tb/in². High data rates are achieved by parallel operation of large two-dimensional (2-D) atomic force microscope (AFM) arrays that have been batch-fabricated by silicon surface-micromachining techniques. The very large-scale integration (VLSI) of micro/nanomechanical devices (cantilevers/tips) on a single chip leads to the largest and densest 2-D array of 32×32 (1024) AFM cantilevers with integrated write/read/erase storage functionality ever built. Time-multiplexed electronics control the functional storage cycles for parallel operation of the millipede array chip. Initial areal densities of 100-200 Gb/in² have been achieved with the 32×32 array chip