聚四氟乙烯和氟化乙丙烯共聚物复合膜的压电性

以多孔PTFE膜为骨架,而以致密（非多孔）FEP膜为储电介质层的孔洞结构复合压电驻极体膜的制备方法.利用正压电效应,测量了复合膜的准静态压电系数d₃₃;研究了压电系数的热稳定性和复合膜中空间电荷的动态特性;并通过介电谐振谱的分析,比较了这类复合膜的准静态和动态压电系数.结果表明：FEP和PTFE复合膜压电驻极体的准静态压电系数d₃₃可以达到300 pC/N.经90℃老化20 h 后的d₃₃仍保持在初 关键词： 压电驻极体 压电性 多孔聚四氟乙烯 致密氟化乙丙烯共聚物     

氟聚合物压电驻极体的压电性及其电荷的动态行为

描述了一种可控微结构的多孔聚合物压电功能膜的制备方法,讨论了采用该工艺制备的聚四氟乙烯(PTFE)和全氟乙丙烯共聚物(FEP)复合膜压电驻极体的压电性能及其热稳定性.通过等温压电系数衰减和短路热刺激放电(TSD)方法,研究了氟聚合物复合膜压电活性热稳定性改善的根源,以及脱阱电荷输运和复合的特性.结果表明,这类氟聚合物压电驻极体膜的准静态压电系数d₃₃可高达2200pC/N;压电系数d₃₃的压强特性在直到20kPa的压强范围内呈现良好的 关键词： 氟聚合物 压电驻极体 热稳定性 电荷动态特性     

多孔聚四氟乙烯/氟代乙烯丙烯共聚物复合驻极体材料的压电效应研究

采用高温熔融和电晕充电方法制备了由聚四氟乙烯/氟代乙烯丙烯共聚物复合而成的空间电荷驻极体压电膜.借助准静态压电系数测量，研究了制备工艺对复合膜压电活性的影响.根据Kacprzyk等提出的复合驻极体膜的压电模型，结合等温表面电位衰减和压电系数衰减测量结果，讨论了驻极体复合膜系统中的压电性产生机制.结果表明，压电效应的大小不仅取决于俘获在材料中的电荷密度的大小，还与被俘获电荷在材料中的存在形式和分布有关. 关键词： 空间电荷驻极体 压电效应 聚合物复合膜     

聚四氟乙烯多孔薄膜驻极体的电荷储存稳定性

利用在室温和高温下的栅控恒压电晕充电,常温电晕充电后经不同温度老化处理后的表面电位衰减测量,及开路热刺激放电(ThermallyStimulatedDischarge,TSD)研究了正负充电后PTFE(Polytetrafluoroethylene)多孔薄膜驻极体的电荷储存稳定性.PTFE多孔膜,PTFE非多孔膜(TeflonPTFE)和FEP(TetrafluoroethylenehexafluoropropyleneCopolymer)非多孔膜(TeflonFEP)间的电荷储存稳定性的比较研究也已进行.通过等温退极化程序,对上述三种薄膜驻极体的电荷储存寿命(有效时间常数)τ进行了定量估算.结果指出:在有机驻极体材料中,对正负充电后两种极性驻极体样品的PTFE多孔薄膜驻极体均呈现最优异的电荷储存稳定性,尤其是在高温条件下.通过扫描电镜(SEM)对这种新结构的氟聚合物驻极体材料的突出电荷储存能力和结构根源也已初步讨论. 关键词： 聚四氟乙烯 多孔膜 驻极体 电荷稳定性     

电晕充电多孔PTFE/PP复合驻极体过滤材料的电荷存储特性

报道采用电晕充电方法，对用高温熔融粘合工艺制备得到的双向拉伸多孔PTFE与PP复合过滤材料进行驻极体改性，并采用热刺激放电和表面电位测量等方法研究了材料的电荷存储稳定性,根据驻极体相关理论，对实验结果进行了解释. 结果表明，电晕充电的多孔PTFE/熔喷或纺粘PP覆膜材料中，既存在空间电荷又存在极化电荷，复合膜的界面是电荷陷阱的主要来源. 从不同面对复合膜材料进行充电时，材料具有完全不同的电荷存储特性. 由于材料体内空间电荷和极化电荷的极性相反、相互补偿，表面电位测定并不能真正反映材料内部电荷的存储状态. 关键词： 驻极体 电晕充电 聚合物复合膜 热刺激放电     

交联聚丙烯压电驻极体的压电性能及振动能量采集研究

以电子束辐照交联聚丙烯(IXPP)泡沫薄板为原材料, 首先利用热压工艺对微观结构进行改性, 然后采用电晕充电方法对样品实施极化处理, 使之具有压电效应, 成为压电驻极体. 通过准静态和动态压电系数d₃₃、复电容谱, 以及等温衰减的测量, 研究了IXPP压电驻极体膜的机电耦合性能; 同时考察了基于IXPP压电驻极体膜的振动能量采集器在{3-3}模式下对环境振动能的俘获. 结果表明, IXPP压电驻极体的准静态压电系数d₃₃可高达620 pC/N; 厚度方向的杨氏模量和品质因数(FOM, d₃₃·g₃₃)分别是0.7 MPa和11.2 GPa^-1; 在50, 70和90℃下进行等温老化, 经过24 h后, IXPP压电驻极体膜的准静态压电系数d₃₃分别降低到初始值的54%, 43%和29%; 采用面积为3.14 cm²的IXPP压电驻极体膜为换能元件, 当振子质量为25.6 g, 振动频率为820 Hz时, 振动能量采集器在匹配负载附近可以输出高达65 μW/g²的功率.     

厚度对非极性聚合物薄膜驻极体电荷储存及电荷动态特性的影响

以Du Pont公司的商用Teflon FEP A型薄膜为例，通过热脉冲技术、等温表面电位衰减测量和开路热刺激放电电流谱分析等实验结果，讨论了经常温和高温电晕充电后样品厚度对薄膜驻极体的沉积电荷密度、薄膜驻极体的内电场、体电导率以及电荷储存稳定性的影响.通过热脉冲技术组合电导率温度曲线的测量，研究了在不同温度条件下样品厚度对沉积电荷层的平均电荷重心移动的影响.结果表明：在充电参数一定的条件下，随着膜厚的降低，储存电荷密度上升，但电荷稳定性有所下降.因此，合理地调控薄膜厚度，可以有效地优化驻极体的电荷储存能 关键词： 厚度 驻极体 电荷储存能力 电荷稳定性     

Si基Si3N4/SiO2双层膜驻极体的电荷储存与输运

利用等温表面电位衰减及热刺激放电(thermally stimulated discharge,TSD)方法探讨了恒栅压电晕充电经常压化学气相沉积(APCVD)的Si基Si3N4和热生长SiO₂双层薄膜驻极体电荷的存储特性.结果表明:在常温环境中,300℃高温下,以及95%相对湿度时的60℃条件下,所有试样表现出极好的电荷储存稳定性.对于负电晕充电试样,其电荷输运受慢再捕获效应(slow retrapping effect)控制;用热离子发射模型来描述了正电晕充电Si₃N₄/SiO₂驻极体的正电荷输运特性. 关键词： 驻极体 薄膜 电荷储存 热离子发射     

聚丙烯孔洞驻极体膜的化学表面处理及电荷稳定性

利用热刺激放电(Thermally Stimulated Discharge, TSD)电流谱、在线电荷TSD、电荷等温衰减测量和衰减全反射(Attenuated Total Reflection, ATR)红外光谱分析，本文系统地研究了经化学表面处理(萃取、氧化及氢氟酸)的聚丙烯(PP)孔洞驻极体膜的电荷储存稳定性及电荷稳定性提高的原因.结果表明：经适当地氧化和氢氟酸室温处理试样的TSD电流谱中在温位约为184℃处出现原膜所没有的非常强的新峰，电荷热稳定性得到显著的提高，这一电荷热稳定性通过高温充电工艺得到进一步地改善；适当延长室温下氢氟酸处理的时间或延长氧化时间，都会使处理膜的电荷稳定性得到提高.理论分析表明在线电荷TSD测量法可给出线性升温过程中电荷重心及驻极体电荷量变化的综合信息，结合TSD电流谱和初始电荷重心位置的测量，可精确地考察线性升温过程中电荷重心的在线变化. 关键词： 聚丙烯孔洞膜 表面氧化 氢氟酸处理 电荷稳定性 在线电荷TSD     

有序结构氟聚合物压电驻极体的制备和压电性研究

描述了一种有序微孔结构压电聚合物功能膜的制备方法,利用模板的高度有序实现薄膜微孔结构的精确控制.将此制备方法用于氟聚合物压电驻极体薄膜的制备,通过扫描电子显微镜(SEM)对其微观结构的观察表明薄膜具有理想的有序结构.对氟聚合物压电驻极体压电性的研究则是利用正压电效应测量准静态压电系数d₃₃,通过等温衰减和压强依赖性的测量考察其压电性能.结果表明:有序结构氟聚合物压电驻极体的准静态压电系数d₃₃可高达300 pC/N;与无序结构氟聚合物     

Polarization and piezoelectricity in polymer films with artificial void structure

Laminated polymer-film systems with well-defined void structures were prepared from fluoroethylenepropylene (FEP) and polytetrafluoroethylene (PTFE) layers. First the PTFE films were patterned and then fusion-bonded with the FEP films. The laminates were subjected to either corona or contact charging in order to obtain the desired piezoelectricity. The build-up of the “macro-dipoles” in the laminated films was studied by recording the electric hysteresis loops. The resulting electro-mechanical properties were investigated by means of dielectric resonance spectroscopy (DRS) and direct measurements of the stress-strain relationship. Moreover, the thermal stability of the piezoelectric d ₃₃ coefficient was investigated at elevated temperatures and via thermally stimulated discharge (TSD) current measurements in short circuit. For 150 μm thick laminated films, consisting of one 25 μm thick PTFE layer, two 12.5 μm thick FEP layers, and a void of 100 μm height, the critical voltage necessary for the build-up of the “macro-dipoles” in the inner voids was approximately 1400 V, which agrees with the value calculated from the Paschen Law. A quasi-static piezoelectric d ₃₃ coefficient up to 300 pC/N was observed after corona charging. The mechanical properties of the film systems are highly anisotropic. At room temperature, the Young’s moduli of the laminated film system are around 0.37 MPa in the thickness direction and 274 MPa in the lateral direction, respectively. Using these values, the theoretical shape anisotropy ratio of the void was calculated, which agrees well with experimental observation. Compared with films that do not exhibit structural regularity, the laminates showed improved thermal stability of the d ₃₃ coefficients. The thermal stability of d ₃₃ can be further improved by pre-aging. E.g., the reduction of the d ₃₃ value in the sample pre-aged at 150°C for 5 h was less than 5% after annealing for 30 h at a temperature of 90°C.     

Polytetrafluoroethylene piezoelectrets prepared by sintering process

Polytetrafluoroethylene (PTFE) films with a void structure are prepared by a sintering process. Such void PTFE films are piezoelectric after proper corona charging. The quasi-static piezoelectric d ₃₃ coefficients up to 250 pC/N are achieved for the samples which were made of compact and biaxial-tension porous PTFE layers. Pre-ageing treatment is an effective method to further improve the thermal stability. For the samples with pre-ageing treatment, the reduction of the d ₃₃ coefficients is around 2% per day when exposed to 120 °C.     

Three-layer piezoelectrets from fluorinated ethylene-propylene (FEP) copolymer films

A process for preparing three-layer piezoelectrets from fluorinated ethylene-propylene (FEP) copolymer films is introduced. Samples are made from commercial FEP films by means of laser cutting, laser bonding, electrode evaporation, and high-field poling. The observed dielectric-resonance spectra demonstrate the piezoelectricity of the FEP sandwiches. Piezoelectric d ₃₃ coefficients up to a few hundred pC/N are achieved. Charging at elevated temperatures can increase the thermal stability of the piezoelectrets. Isothermal experiments for approximately 15 min demonstrate that samples charged at 140°C keep their piezoelectric activity up to at least 120°C and retain 70% of their initial d ₃₃ even at 130°C. Acoustical measurements show a relatively flat frequency response in the range between 300 Hz and 20 kHz.     

Physical foaming of fluorinated ethylene-propylene (FEP) copolymers in supercritical carbon dioxide: single-film fluoropolymer piezoelectrets

Cellular polymer foams with significant piezoelectric activity were prepared from fluorinated ethylene-propylene (FEP) copolymers. The required void structure is obtained by saturation of FEP films with supercritical carbon dioxide and a subsequent heat treatment for controlled inflation. After bipolar electric charging of the voids and evaporation of electrodes, the FEP films show piezoelectric d₃₃ coefficients up to 50 pC/N. The present physical foaming process generates cellular fluoropolymer piezoelectret films with usually only one single void across the film thickness. PACS 81.05.Rm; 77.65.-j; 77.84.Jd; 61.41.+e     

聚四氟乙烯多孔膜的压电活性及其稳定性

研究了经单向机械拉伸形成的非极性空间电荷型薄膜驻极体聚四氟乙烯(PTFE)多孔膜的压电性.讨论了由PTFE多孔膜和非多孔的聚合物薄膜（PTFE，聚酰亚胺PI，氟化乙丙烯共聚物FEP 和聚三氟氯乙烯PCTFE）组成的双层膜的突出压电活性.初步研究结果指出：在优化的极化条 件下形成的上述双层压电膜以外电极测量的准静态压电d₃₃常数可达186 pC/N， 这个数值与压电陶瓷锆钛酸铅PZT的相应常数接近，而比铁电聚合物聚偏氟乙烯(PVDF)的相 应常数约高出一个数量级.还研究了这类柔性多孔膜 关键词： 聚四氟乙烯多孔膜 压电性 空间电荷驻极体 充电参数 压电活性的热稳定性     

Fluoropolymer piezoelectrets with tubular channels: resonance behavior controlled by channel geometry

Ferro- or piezoelectrets are dielectric materials with two elastically very different macroscopic phases and electrically charged interfaces between them. One of the newer piezoelectret variants is a system of two fluoroethylenepropylene (FEP) films that are first laminated around a polytetrafluoroethylene (PTFE) template. Then, by removing the PTFE template, a two-layer FEP structure with open tubular channels is obtained. After electrical charging, the channels form easily deformable macroscopic electric dipoles whose changes under mechanical or electrical stress lead to significant direct or inverse piezoelectricity, respectively. Here, different PTFE templates are employed to generate channel geometries that vary in height or width. It is shown that the control of the channel geometry allows a direct adjustment of the resonance frequencies in the tubular-channel piezoelectrets. By combining several different channel widths in a single ferroelectret, it is possible to obtain multiple resonance peaks that may lead to a rather flat frequency-response region of the transducer material. A phenomenological relation between the resonance frequency and the geometrical parameters of a tubular channel is also presented. This relation may help to design piezoelectrets with a specific frequency response.     

Piezoelectric performance of fluor polymer sandwiches with different void structures

Film sandwiches, consisting of two outer layers of fluoroethylenepropylene and one middle layer of patterned porous polytetrafluoroethylene, were prepared by patterning and fusion bonding. Contact charging was conducted to render the films piezoelectric. The critical voltage to trigger air breakdown in the inner voids in the fabricated films was investigated. The piezoelectric d ₃₃ coefficients were measured employing the quasistatic method and dielectric resonance spectrum. The results show that the critical voltage for air breakdown in the inner voids is associated with the void microstructure of the films. For the films with patterning factors of?0%, 25% and?44%, the critical values are?300, 230?and 230?kV/cm, respectively. With an increase in the patterning factor, both the piezoelectric d ₃₃ coefficients determined from the dielectric resonance spectra and those determined from quasistatic measurements increase, which might be due to a decrease in Young??s modulus for the films. The nonlinearity of d ₃₃ becomes increasingly obvious as the patterning factor increases.