PZT/PVDF压电复合材料的制备及其性能研究
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摘要
压电复合材料一般是由压电陶瓷和聚合物基体按照一定的连接方式，一定比例和一定的空间几何分布复合而成。由于这种复合材料兼有组成复合材料各组分的性能，克服了陶瓷和聚合物两者的不足，具有强压电性、脆性低、密度和介电系数低、易制得大面积薄片以及复杂形状制品，制造工艺简单等优点。论文首先利用Banno Unit Cell模型，计算了PZT／PVDF压电复合材料的组成、结构、与其压电和介电等性能之间的关系；针对压电复合材料存在的均匀分散性差的缺点，选用水热法制备的粒度均匀的PZT陶瓷粉末，并采用溶液混和法与聚合物PVDF进行分散复合，重点研究了不同工艺条件下陶瓷的均匀分散性及其与材料微观结构之间的关系。制备了少量PAn添加的PVDF／PZT复合材料，对其微观结构就压电和介电性能作了较为系统的分析。最后依据性能测试结果对计算模型进行了完善，使复合材料具备一定的可设计性。
论文研究表明，在适当的工艺条件下，水热法制备的PZ-T陶瓷粉纯度高，粒度分布窄，平均粒度为0.5μm，适合于溶液复合。通过陶瓷颗粒对PVDF吸附量的大小的比较确定乙醇为分散溶剂，同时以超声震荡来提高陶瓷颗粒分散的均匀性。实验发现在100Mpa下成型的样品的致密度比无压热处理的要高出近10个百分点。在此基础上，发现在PVDF／PZT体系中引入少量导电聚合物PAn并使其均匀分布于材料内部时提高了陶瓷相的极化率和压电复合材料的压电性能，并且根据介电常数介电损耗及与温度关系的分析可知，添加少量PAn的PZT／PVDF压电复合材料具有更宽的温度使用范围，温度依赖性小。性能测试结果表明，当PZT、PVDF、PAn三相体积比的含量为55％、0.45％、5％时，材料的压电常数最高，达到68pc／N。而且经过理论计算与比较，当以下三个参量取下列值时，即陶瓷颗粒形状因子n=5、极化率α=0.6、结构因子q=0.3时，实验数据与理论计算吻合较好。
PVDF/PZT piezocomposite consisting of piezoelectric ceramic and polymer was made according the connection mode, volume fraction ratio or geometric distribution mode. This kind piezocomposite not only possesses properties of the piezoelectric ceramic and the polymer, but also overcomes the disadvantage of each single material. It contains many fine properties such as the high piezoelectricity, low brittleness, density and dielectric constant. And it also can be easy made into various shape products and thin slice. But the disperse degree of PZT ceramic particle in the PVDF is an exigent problem to be solved. The disperse degree of the ceramic can greatly affect uniformity of the composite, which limit the poling voltage and affect the piezoelectricity. In this paper, the relationships among constitutes, microstructures, dielectric and piezoelectric properties were calculated by employing the Banno Unit Cell mode; PZT ceramic were synthesized by the hydrothermal method and the appropriate solution was selected
according the adsorption of PVDF on the ceramic particle surface; Then, relationships between the disperse degree and the fabrication process were studied. Base on these, the PZT/PVDF composites intermingled some PAn were prepared and the microstructures were investigated. At last, the Banno Unit Cell mode was proved and improved by the experimental data in order that the design of piezocomposite was more scientific and accurate.
The research results show that the PZT ceramic particle with high purity, narrow granularity disperse, so this kind PZT ceramic particle is suitable to prepare the piezocomposite. Then the ethanol was selected to mix the PZT and PVDF. The mixed solution was ultrasonically dispersed to improve the dispersion degree. After that, the sample was pressed into shape and annealed. And it also found that the relative densities of the samples annealed under lOOMpa were 10 percent above those of the samples annealed without pressure. Based on this fabrication process, the PAn was introduced to enhance the uniformity of the composite, thus the piezoelectricity was greatly improved and the poling voltage can be lowered. At the same time, the dielectric properties
under different temperature were investigated, it was found that the dielectric properties of PZT/PVDF piezocomposite with some PAn changed slowly from 25C to 250C. The maximum of the piezoelectric constant d33 is 68pc/N when the volume fraction of PZT, PVDF, PAn is 0.55, 0.45, and 0.05 respectively. Finally, ,when the n , a , p are 6, 0.6, 0.3 respectively, the calculation value can agree well with the experimental data.
论文研究表明，在适当的工艺条件下，水热法制备的PZ-T陶瓷粉纯度高，粒度分布窄，平均粒度为0.5μm，适合于溶液复合。通过陶瓷颗粒对PVDF吸附量的大小的比较确定乙醇为分散溶剂，同时以超声震荡来提高陶瓷颗粒分散的均匀性。实验发现在100Mpa下成型的样品的致密度比无压热处理的要高出近10个百分点。在此基础上，发现在PVDF／PZT体系中引入少量导电聚合物PAn并使其均匀分布于材料内部时提高了陶瓷相的极化率和压电复合材料的压电性能，并且根据介电常数介电损耗及与温度关系的分析可知，添加少量PAn的PZT／PVDF压电复合材料具有更宽的温度使用范围，温度依赖性小。性能测试结果表明，当PZT、PVDF、PAn三相体积比的含量为55％、0.45％、5％时，材料的压电常数最高，达到68pc／N。而且经过理论计算与比较，当以下三个参量取下列值时，即陶瓷颗粒形状因子n=5、极化率α=0.6、结构因子q=0.3时，实验数据与理论计算吻合较好。
PVDF/PZT piezocomposite consisting of piezoelectric ceramic and polymer was made according the connection mode, volume fraction ratio or geometric distribution mode. This kind piezocomposite not only possesses properties of the piezoelectric ceramic and the polymer, but also overcomes the disadvantage of each single material. It contains many fine properties such as the high piezoelectricity, low brittleness, density and dielectric constant. And it also can be easy made into various shape products and thin slice. But the disperse degree of PZT ceramic particle in the PVDF is an exigent problem to be solved. The disperse degree of the ceramic can greatly affect uniformity of the composite, which limit the poling voltage and affect the piezoelectricity. In this paper, the relationships among constitutes, microstructures, dielectric and piezoelectric properties were calculated by employing the Banno Unit Cell mode; PZT ceramic were synthesized by the hydrothermal method and the appropriate solution was selected
according the adsorption of PVDF on the ceramic particle surface; Then, relationships between the disperse degree and the fabrication process were studied. Base on these, the PZT/PVDF composites intermingled some PAn were prepared and the microstructures were investigated. At last, the Banno Unit Cell mode was proved and improved by the experimental data in order that the design of piezocomposite was more scientific and accurate.
The research results show that the PZT ceramic particle with high purity, narrow granularity disperse, so this kind PZT ceramic particle is suitable to prepare the piezocomposite. Then the ethanol was selected to mix the PZT and PVDF. The mixed solution was ultrasonically dispersed to improve the dispersion degree. After that, the sample was pressed into shape and annealed. And it also found that the relative densities of the samples annealed under lOOMpa were 10 percent above those of the samples annealed without pressure. Based on this fabrication process, the PAn was introduced to enhance the uniformity of the composite, thus the piezoelectricity was greatly improved and the poling voltage can be lowered. At the same time, the dielectric properties
under different temperature were investigated, it was found that the dielectric properties of PZT/PVDF piezocomposite with some PAn changed slowly from 25C to 250C. The maximum of the piezoelectric constant d33 is 68pc/N when the volume fraction of PZT, PVDF, PAn is 0.55, 0.45, and 0.05 respectively. Finally, ,when the n , a , p are 6, 0.6, 0.3 respectively, the calculation value can agree well with the experimental data.
引文
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[3] 徐红星、骆英，柳侏，等．PVDF压电薄膜的应用进展．江苏理工学学报(自然科学版)1999 Vol．20(5)：88
[4] 邹小平、王丽坤、张福学．复合材料PZT-PVDF和PT-P(VDF／TeFE)的压电性 仪表技术与传感器 1997 7：18
[5] 扬大本，许萍PVDF／PMN-PZT复合驻体薄膜及其特性 电子元件与材料 1997 Vol．16(5)：17-20
[6] 裴柳近，唐风，石孝进．PVDF-PZT纤维薄膜压电传感器的研究 压电与声光 1996 Vol．18(3)：24-28
[7] 熊兆贤，材料物理导论．北京：科学出版社，2001．124-135
[8] 关振铎，张中太，焦金生．无机材料物理性能，北京：清华大学出版社 1992：247-259
[9] 钟维烈 铁电物理学．北京：科学出版社，1996：268-287
[10] 冯亚军，井晓天．PVDF及其共聚物地压电性和制备．传感器技术 1996 NO．4：36-41
[11] 汪济奎，徐廷钒．聚偏二氟乙烯压电薄膜及其应用．塑料技术 1997．1：14-16
[12] 方俊鑫，陆栋．上海：固体物理学，上海科学技术出版社，1981．12
[13] 殷敬华 莫志深 现代高分子物理学．北京：科学出版社，3．2001
[14] Dage Liu, Hongxi Zhang, Wei Cai. Synthesis of PZTnanocrystalline powder by a modified sol-gel process using zirconium wxynitrate as zirconium source Materials Chemistry physics 1997 (51). 186-189
[15] B.Su, C.B.Ponton, T.W. Button Hydrothermal and electrophoretic deposition of lead zirconate titanate(PZT) films. Journal of the European Ceramic Ceramic Society 21(2001). 1539-1542
[16] Ce-Wen Nan, Fu-Sheng Jin Multiple-scattering approach to effective properties of piezoelectric composites Phys. Rev. B 48(1993)8578-8582
[17] Ce-Wen Nan, Effective-medium theory of piezoelectric composites Phys. Rew. B 49(1994).3256-3260
[18]. J.F. Tressler, S.Alkoy, A.Dogan, R.E.Newnham. Functional composites for sensors, actuators and transducers, Composites, 1999(38).477-482
[19] 朱嘉林，王丽坤，张福学．0-3型压电复合材料的硬球无规堆积模型．压电与声光 Aug．2000 Vol．22．35-39
[20] Franck Levassort, Mare Lethiecq, Member, Effective Electroelectric Moduli of 3-3(0-3) Piezocomposites IEEE TRANSACTIONS ON ULTRASONICS, FERROELECTRICS, AND FREQUENCY CONTROL, Vol.46, 1998.256-264
[21]. DAI-NING FANG, AL.KAH.SOH, CHANG-QING LI, BING JIANG. Nonlinear behavior of 0-3 type ferroelectric composites with polymer matrices, JOURNAL OF MATERLALS SCIENCE, 2001.5281-5288
[22]. C.R.Bowen, H.Kara. Pore anisotropy in 3-3 piezoelectric composites, Journal of the European Ceramic Society, 2001.1463-1467
[23]. C.R.Bowen, A.Perry, H.Kara, S.W. Mahon. Analytical modeling of 3-3 piezoelectric composites, Journal of the European Ceramic Society. 2001.1463-1467
[24] T.E Gomez, F. Montero de Espinosa, F. Levassort, etc, Ceramic powder-polymer piezo-composite for electroacoustic-transduction: modeling and design. Ultrasonic 369 (1998)' 907-923
[25] Takeshi Yamada, Toshinobu Ueda, Toyoki Kitayama piezoelectricity of a high-content lead zirconate titanate/polymer composite. J.Appl. Phys.53(6), (1982):4382-4332
[26] 惠春，徐爱兰，梁瑞林 水热合成PZT热电体结晶粉末工艺及相关性能的研究 功能材料 1995 26(4)．332-335
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