碳纳米管/高分子复合材料的制备及其性能研究
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摘要
本文主要研究了碳纳米管/聚偏氟乙烯复合材料的电学性能和温度系数效应。为了充分利用碳纳米管的优异性能,提高碳纳米管与聚偏氟乙烯基体的相容性,我们对碳纳米管进行了化学修饰,制备了羧基修饰和酯基修饰的碳纳米管。利用溶液混合法、冷压、热处理技术,制备了未修饰、羧基修饰和酯基修饰碳纳米管/聚偏氟乙烯复合材料。研究表明:三类碳纳米管复合材料的渗流阈值大致相等,大约都为3.8 vol%。但是,未修饰碳纳米管/聚偏氟乙烯复合材料表现出明显的绝缘体-导体转变性质,而化学修饰碳纳米管复合材料的电导率随着碳管含量的增加缓慢上升。在达到复合材料渗流阈值时,复合材料的介电常数迅速增大。三种复合材料在室温下、1 KHz时所达到的最大介电常数和所需的碳管含量不同,分别为:未修饰碳纳米管/聚偏氟乙烯复合材料的最大介电常数为1700,碳管体积分数为6%;羧基修饰碳纳米管/聚偏氟乙烯复合材料的最大介电常数为3600,碳管体积分数为8%;酯基修饰碳纳米管/聚偏氟乙烯复合材料的最大介电常数为2400,碳管体积分数为6.5%。利用渗流阈值理论对复合材料的电学性质进行了解释。三种复合材料的温度系数效应都比较弱。但是,化学修饰碳纳米管/聚偏氟乙烯复合材料的熔融转变温度提高大约40度。复合材料的介电常数随温度变化关系一致,在1 KHz下表现为先增大后减小,后来又增大的变化趋势,这可能与基体的膨胀以及导电网络的改变有关。这类高介电高分子基复合材料有望在电活性高分子、电致伸缩等功能材料领域得到应用。
In this paper, the electrical properties and temperature coefficient effects of the multi-walled carbon nanotube/poly(vinylidene fluoride) (MWCNT/PVDF) composites were investigated. The carboxylic and ester functionalized MWCNT were prepared and the pristine, carboxylic, ester functionalized MWCNT/PVDF composites were fabricated by simple physical blending, cold-press, and heat treatment technology. The percolation thresholds of the three kinds of composites are approximately equal, about 3.8 vol%. The conductivity of the pristine MWCNT/PVDF composites increases remarkably near the percolation threshold, and exhibits a typical insulator-conductor transition. However, the conductivity of the chemically functionalized MWCNT/PVDF composites increases slowly with increasing the MWCNT volume fraction. The dielectric constants increase remarkably after the percolation threshold. However, the largest dielectric constant of these three kinds of composites is different. The largest dielectric constant of the pristine MWCNT/PVDF composites is 1700 with 6 vol% MWCNTs, while it reaches 3600 for carboxylic functionalized MWCNT/PVDF composites with about 8 vol% MWCNTs, and 2400 for ester functionalized MWCNT/PVDF composites with about 6.5 vol% MWCNTs. The positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects of these three kinds of composites are all small. However, the melting point of the chemically functionalized MWCNT/PVDF composites is larger than that of the pristine MWCNT/PVDF composites. The temperature dependence of the dielectric properties of these three kinds of MWCNT/PVDF composites is basically coincident. The dielectric constants of these composites increase with increasing temperature at low frequency, and then decrease when the temperature further increases up to about 140℃. However, the dielectric constants increase again at 180℃, which all can be attributed to the thermal expansion of the matrix and the change of the conduct net in these composites.
In this paper, the electrical properties and temperature coefficient effects of the multi-walled carbon nanotube/poly(vinylidene fluoride) (MWCNT/PVDF) composites were investigated. The carboxylic and ester functionalized MWCNT were prepared and the pristine, carboxylic, ester functionalized MWCNT/PVDF composites were fabricated by simple physical blending, cold-press, and heat treatment technology. The percolation thresholds of the three kinds of composites are approximately equal, about 3.8 vol%. The conductivity of the pristine MWCNT/PVDF composites increases remarkably near the percolation threshold, and exhibits a typical insulator-conductor transition. However, the conductivity of the chemically functionalized MWCNT/PVDF composites increases slowly with increasing the MWCNT volume fraction. The dielectric constants increase remarkably after the percolation threshold. However, the largest dielectric constant of these three kinds of composites is different. The largest dielectric constant of the pristine MWCNT/PVDF composites is 1700 with 6 vol% MWCNTs, while it reaches 3600 for carboxylic functionalized MWCNT/PVDF composites with about 8 vol% MWCNTs, and 2400 for ester functionalized MWCNT/PVDF composites with about 6.5 vol% MWCNTs. The positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects of these three kinds of composites are all small. However, the melting point of the chemically functionalized MWCNT/PVDF composites is larger than that of the pristine MWCNT/PVDF composites. The temperature dependence of the dielectric properties of these three kinds of MWCNT/PVDF composites is basically coincident. The dielectric constants of these composites increase with increasing temperature at low frequency, and then decrease when the temperature further increases up to about 140℃. However, the dielectric constants increase again at 180℃, which all can be attributed to the thermal expansion of the matrix and the change of the conduct net in these composites.
引文
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[15] Wang Z. L., Poncharal P., Heer W. A .de. Measuring physical and mechanical properties of individual carbon nanotubes by in situ TEM[J]. Journal of Physics and Chemistry of Solids, 2000,61(7):1025-1030
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[18] Bandow S., Asaka S., Zhao X., et al. Purificatin and magnetic properties of carbon nanotubes[J]. Applied Physics Letters, 1998,67(1):23-27
[19] Hou P. X., Bai S., Yang Q. H., et al. Multi-step purification of carbon nanotubes[J]. Carbon, 2002,409(1):81-85
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[21] Hamon M. A., Chen J., Hu H., et al. Dissolution of single-walled carbon nanotubes[J]. Advanced Materials, 1999,11(10):834-840
[22] ChenY., Chen J., Hu H., et al. Solution-phase ERP studies of single-walled carbon nanotubes[J]. Chemical Physics Letters, 1999,299(6):532-535
[23] Mickelson E. T., Huffman C. B., Rinzler A. G., et al. Fluorination of single-wall carbon nanotubes[J]. Chemical Physics Letters, 1998,296(1-2):188-194
[24] Boul K. A., Liu J., Mickelson E. T., et al. Reversible sidewall functionalization of buckytubes[J]. Chemical Physical Letters, 1999,310(3-4):367-372
[25] Mickelson E. T., Chiang I. W., Zimmerman J. L., et al. Solvation of fluorinated single-wall carbon nanotubes in alcohol solvents[J]. Journal of Physical Chemistry B, 1999,103(21):4318-4322
[26] Qin Y., Shi J., Wu W., et al. Concise route to functionalized carbon nanotubes[J]. Journal of Physical Chemistry B, 2003,107(47):12899-12901
[27] Qin Y., Liu L., Shi J., et al. Large-scale preparation of solubilized carbon nanotubes[J]. Chemistry of Materials, 2003,15(17):3256-3260
[28] Li S., Qin Y. Shi J., et al. Electrical properties of soluble carbon nanotube/polymer composite films[J]. Chemistry of Materials, 2005,17(1):130-135
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