人工调控微结构压电驻极体的热稳定性和电荷动态特性

利用表面带有周期性结构的硬质模板,通过冷压工艺将周期结构图案复制到多孔聚四氟乙烯(PTFE)薄膜表面,再经过热黏合工艺与致密氟化乙丙烯共聚物(FEP)薄膜复合,制备出了高度有序的微孔结构复合膜,并用电晕充电的方法对复合膜进行极化处理,最终获得氟聚合物复合膜压电驻极体.借助对这类复合膜压电驻极体介电谐振谱的测量,得到了材料的杨氏模量.并利用等温热老化工艺对它们的压电系数d33的热稳定性进行了考察.最后通过短路热刺激放电谱的测量和分析,讨论了该复合膜在热老化处理后的电荷动态 关键词： 有序结构 压电驻极体 压电性 电荷动态特性     

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     

PT-PEK-c电光聚合物薄膜的厚度和介电性质

研制了新的PT-PEK-c电光聚合物薄膜材料,用准波导耦合m线方法测量了PT-PEK-c电光聚合物薄膜的厚度,并测量了该聚合物薄膜在1×10²Hz到1×10⁷Hz频率范围内的室温介电常数.测量结果为:厚度d=2.328±0.315μm,在10KHz下,介电常数ε_r＝4023±0.063,介电损耗tanδ＝0.003.     

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     

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     

极化电压对聚丙烯压电驻极体膜压电性能的影响

压电驻极体是具有压电效应的微孔结构空间电荷驻极体材料,其压电性能与材料的微结构和空间电荷密切相关.本文首先利用压缩气体膨化工艺对聚丙烯(PP)的微结构进行改性,然后利用接触极化方法,研究了极化电压与PP膜空间电荷密度之间的关系,及其对压电性能的影响.结果表明对于极化前厚度为100μm的PP膜,其内部建立有序空间电荷分布的阈值极化电压为2 kV;一旦有序空间电荷建立起来,PP膜即具有压电效应.随着极化电压的提高,PP膜的空间电荷密度逐步增大,压电效应显著增强.当峰值电压为8 kV时,PP膜电极上的电荷密度、准静态压电系数和品质因数FOMv(d33·g33)分别为0.56 mC/m2,379 pC/N和8.6(GPa)-1.PP压电驻极体膜的FOMv比聚偏氟乙烯(PVDF)铁电聚合物膜高2个量级以上,且声阻抗非常低(～0.025 MRayl),因此该压电膜在超声波发射-接收系统或脉冲-回波系统中具有明显的优势.     

不同氮流量制备Mn3CuNx薄膜及其电、磁输运性质的研究

采用对靶磁控溅射方法在单晶Si(100)基片上制备了反钙钛矿结构的Mn₃CuN_x薄膜.通过控制制备过程中的反应气体氮气(N₂) 流量(N₂/Ar+N₂), 研究了氮含量对Mn₃CuN_x薄膜结构及物理性能的影响.分别利用X射线衍射仪、俄歇电子能谱、 原子力显微镜、X射线光电子能谱、物理性能测试系统和超导量子干涉仪, 对所制备薄膜的晶体结构、成分、表面形貌和电、磁输运性质进行了测试.结果表明:制备的薄膜均为反钙钛矿立方结构,且沿 (200) 晶面择优生长.随着氮含量的增大,薄膜表面粗糙度和颗粒度尺寸逐渐增大, 导致电阻率增加.氮含量对薄膜的电输运性质没有影响,所有薄膜电阻率均随着温度的降低逐渐增大, 呈现半导体型导电行为,这与对应的块体材料结果相反.Mn₃CuN_x薄膜随着测试温度的增大发生了 亚铁磁到顺磁的磁转变,且N含量的增大降低了磁有序转变温度,主要是由于N缺陷对Mn₆N八面体结构中 磁交换作用的影响所致.     

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.     

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     

用CARS技术确定拉曼退偏比的一种数据处理新方法

Yuika等人利用偏振CARS技术可以准确地确定分子的拉曼退偏比.其方法是，首先对不同检偏角_d所对应CARS谱峰的频率分布进行数学模拟，然后由所得系数随检偏角φ_d的变化求得使CARS信号中共振项消失的偏振角φ^０_d，最后由消失条件ρ＝-1/(tanθtanφ⁰_d)求出退偏比ρ，θ为产生CARS光的Pump光与Stokes光偏振方向的夹角.本文提出的数据处理方法，即交点法.同Yuika等人处理数据的方法相比，交点法毋需关于谱峰频率分布的知识，做法也更为简便.     

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     

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.     

Improved piezoelectric properties of cellular polypropylene ferroelectrets by chemical modification

To improve the thermal stability of piezoelectricity of polypropylene (PP) ferroelectrets, chemical modification of the cellular PP film was performed via chromic acid oxidation and then hydrofluoric acid treatment. Deep chemical modification is achieved as indicated by the energy-dispersive X-ray analyses on the cross-section of the modified cellular PP film. The results of the isothermal decay for piezoelectric d ₃₃-coefficient at 70°C indicate the improved thermal stability of piezoelectricity and the enhanced piezoelectric activity of the modified PP ferroelectrets. The former is attributed to the improvement of thermal stability of the charges trapped in the internal void surface layers as indicated by the thermally stimulated discharge measurements, while the latter results not only from the improved thermal stability of the charges but also from the reduction in Young’s modulus of the PP ferroelectrets due to the chemical modification as revealed by the dielectric resonance analyses.     

Piezoelectric property of hot pressed electrospun poly(γ-benzyl-α, L-glutamate) fibers

Since the 1960s, the piezoelectricity in biopolymers (e.g. proteins and polynucleotides) has attracted considerable scientific attention. In particular, poly(glutamate)s have been one of the most popular targets for this research due to their well-defined helical structure and permanent polarity along the helical axis. To date, films of poly(glutamate)s have been shown to exhibit piezoelectricity only in shear mode (d₁₄), mainly due to the limitation in fabricating electrically poled polymer samples. This paper describes a combined electrospinning and hot press method that allows production of poled poly(??-benzyl-??,L-glutamate) (PBLG) films with piezoelectricity in all d₃₃, d₃₁ and d₁₄ modes for the first time. It is found that this PBLG film belongs to the matrix structure of C_??v group, which is the same as that of poled PVDF film. The moderately high piezoelectric coefficients in both d₃₃ and d₁₄ modes as well as their thermal stability make the poled PBLG film an excellent candidate for use in flexible transducers and small energy harvesting devices.     

Preparation and optical constants of the nano-crystal and polymer composite Bi4Ti3O12/PMMA thin films

Bismuth titanate, Bi₄Ti₃O₁₂ (BTO), is a typical ferroelectric material with useful properties for optical memory, piezoelectric and electro-optic devices. Its nano-crystals were compounded by the chemical solution decomposition technique. Its structure and size were analyzed by X-ray diffraction and transmissive electron microscopy. The composite thin film of BTO nano-crystals and high transparency polymethylmethacrylate (PMMA) polymer was prepared by spin coating. The transmitted spectrum of BTO/PMMA composite thin film in 300–1500 nm was measured. The film thickness d and the optical constants of the film, such as the refractive index n, the absorption coefficient α, and the extinction coefficient κ were obtained using the data from the transmitted spectrum.     

The influence of different doping elements on microstructure, piezoelectric coefficient and resistivity of sputtered ZnO film

ZnO film is attractive for high frequency surface acoustic wave device application when it is coupled with diamond. In order to get good performance and reduce insertion loss of the device, it demands the ZnO film possessing high electrical resistivity and piezoelectric coefficient d₃₃. Doping ZnO film with some elements may be a desirable method. In this paper, the ZnO films undoped and doped with Cu, Ni, Co and Fe, respectively (doping concentration is 2.0 at.%) are prepared by magnetron sputtering. The effect of different dopants on the microstructure, piezoelectric coefficient d₃₃, and electrical resistivity of the film are investigated. The results indicate that Cu dopant can enhance the c-axis orientation and piezoelectric coefficient d₃₃, the Cu and Ni dopant can increase electrical resistivity of the ZnO film up to 10⁹ Ω cm. It is promising to fabricate the ZnO films doped with Cu for SAW device applications.