聚苯胺及其衍生物/无机物复合材料制备及其导电性研究
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摘要
纳米材料的研究及其制备技术引起了世界各国的普遍重视。近年来纳米材料的发展朝着功能互补、性能优化的趋势发展。有机-无机纳米复合材料因其兼具有机聚合物和无机材料的优良特性,在电学、光学、力学和磁学等方面赋予材料许多优异的特性,已成为当今材料科学、物理化学、有机化学和高分子化学等多学科交叉的前沿领域。
聚苯胺因其原料廉价易得、合成方法简单、电导率较高且可调、环境稳定性好,以及独特的化学和电化学性能,成为最有应用前景的导电高分子材料。但聚苯胺难溶解、难熔融、难于加工等特性极大地阻碍了聚苯胺的实用化进程。由于纳米材料尺度极小,使之表面原子数、表面能急剧增加,产生了宏观物体所不具有的表面效应、量子效应和宏观量子隧道效应等新的性能。因此将纳米技术引入导电聚苯胺的合成工艺中,可以使其集导电性和纳米颗粒功能于一体,能极大地改善导电聚苯胺的加工性。本课题主要研究了以下几方面的内容:
1.本章主要介绍了纳米结构聚苯胺的研究进展并对可溶性聚苯胺的研究进行了简要概述。碳纳米管具有优异的力学性能,优良的化学稳定性和热稳定性,良好的电性能,并具有独特的一维纳米结构所特有的纳米效应,使其成为聚合物材料理想的增强体,并能赋予聚合物材料许多新的功能。本章也综述了碳纳米管/聚合物复合材料研究的新进展。
2.本章首次报道了以纳米石墨薄片为导电填料,用超声法成功的制备了纳米石墨薄片/聚苯胺(NanoGs/PAN)复合棒状材料。研究了掺杂剂的种类、掺杂剂的浓度以及纳米石墨薄片的用量对材料导电性能影响。并利用红外光谱(FTIR)、扫描电镜(SEM)表征了材料的组成和结构。结果表明超声法可抑制苯胺聚合时的团聚,形成均匀的棒状纳米复合材料。纳米石墨薄片加入量在1.3%时达到渗域滤值,材料的导电率由4.8S/cm达到22S/cm。热重分析说明纳米石墨薄片/聚苯胺复合棒状材料的热稳定性优于单纯的聚苯胺。
3.本章首次介绍了以纳米石墨薄片为导电填料,成功的制备了纳米石墨薄片/聚苯胺-g-聚乙二醇(NanoGs/PANI-PEG-PANI)复合材料。研究了掺杂剂的种类、掺杂剂的浓度以及纳米石墨薄片的用量对材料导电性能影响。利用红外光谱(FTIR)、扫描电镜(SEM)表征了材料的组成和结构,结果表明盐酸掺杂的在1.6mol/L左右,而对甲苯磺酸掺杂的在0.75mol/L左右,纳米石墨薄片加入量在2.3%时达到渗域滤值,电导率达到16.9S/cm。热重分析说明纳米石墨薄片/聚苯胺-g-聚乙二醇复合材料的热稳定性优于单纯的聚苯胺,而共聚物中PEG链段的引入使得NanoGs/PANI-PEG-PANI复合材料的热稳定性降低。。
4.本章运用超声法成功的制备了碳纳米管/PANI-PEG-PANI复合材料。研究了碳纳米管的用量对材料导电性能影响。利用红外光谱(FTIR)、原子力(AFM)表征了材料的组成和结构,电导率测试结果表明:纯嵌段共聚物的导电率为3.4S/cm,加入碳纳米管的含量为1.2%时,导电率为下降至最低点;碳纳米管的含量大于1.2%时,材料的导电率呈现出增加的趋势。热重分析说明由于耐热的碳纳米管的引入使得复合材料的热稳定性优于单纯的嵌段共聚物。
Research and preparation of nanomaterials is causing an extensive concern of all over the world. Recently, the developing direction of materials is the functional complementarity and the property optimization. Nowadays, organic-inorganic nanocomposites have become full-subject crossed leading field across material science, physical chemistry, organic chemistry and polymeric chemistry, because they combine the merits of the organic polymers and inorganic material, exhibiting good electrical, optical, mechanical and magnetic properties.
Polyaniline (PANI) is one of the most promising conducting polymers due to its lower cost, higher and tunable conductivity, environmental stability and unique chemical and electrochemical properties. However, the properties of infusibility, insolubility and poor processability have greatly prevented its application. Nanomaterial has the special physical and chemical properties. Introducing nanotechnology into the synthetical technology of polyaniline will remarkably improve its processability; moreover it has conductivity and nanopartical function together. The research contains four parts, as follows:
1. In this chapter, we mainly describe the development of the nano structure and of soluble PANI. CNTs have excellent mechanical properties, good chemical and thermal stabilities predominant nano-effects electrical and microwave absorption properties, and have the unique of one dimensional nano-structure which makes CNTs be reinforcen for polymer materials, and give polymer materials many new the perfect functions, we describe the development of the CNTs/polymer composite.
2. The graphite nanosheets/polypaniline (NanoGs/PANI) nanorod composites were fabricated via ultrasonic polymerization of aniline monomer in the presence of NanoGs which was used as electric filling. The kind of doped acids, the concentration, and the content of the graphite nanosheets as impact factor to the conductivity of the material was investigated. The structure of nanocomposites was characterized by FT-IR, SEM. The results show that ultrasonic can effectively restrain the agglomerate of the aniline and come to uniformity nanorods composite. The conductivity reached to 4.8S/cm and 22S/cm respectively.
3. The NanoGs/PANI-PEG-PANI composites were fabricated via polymerization of aniline monomer and BAPPEG in the presence of NanoGs which was used as electric filling. The kind of doped acids, the concentration, and the content of the graphite nanosheets as impact factors to the conductivity of the material was investigated. The structure of composites was characterized by FT-IR, SEM. The results showed the materials with even film structure have excellent conductivity. The conductivity reached to 3.4 S/cm and 16.9 S/cm respectively.
4. The CNTs/PANI-PEG-PANI composites were fabricated via ultrasonic polymerization of PANI-PEG-PANI in the presence of CNTs which was used as electric filling. The structure of nanocomposites was characterized by FT-IR, AFM. The conductivity of pure PANI-PEG-PANI is 3.4S/cm, the conductivity of composite cut down to minimum when the CNTs is 1.2%, but after the piont the conductivity are increase.
聚苯胺因其原料廉价易得、合成方法简单、电导率较高且可调、环境稳定性好,以及独特的化学和电化学性能,成为最有应用前景的导电高分子材料。但聚苯胺难溶解、难熔融、难于加工等特性极大地阻碍了聚苯胺的实用化进程。由于纳米材料尺度极小,使之表面原子数、表面能急剧增加,产生了宏观物体所不具有的表面效应、量子效应和宏观量子隧道效应等新的性能。因此将纳米技术引入导电聚苯胺的合成工艺中,可以使其集导电性和纳米颗粒功能于一体,能极大地改善导电聚苯胺的加工性。本课题主要研究了以下几方面的内容:
1.本章主要介绍了纳米结构聚苯胺的研究进展并对可溶性聚苯胺的研究进行了简要概述。碳纳米管具有优异的力学性能,优良的化学稳定性和热稳定性,良好的电性能,并具有独特的一维纳米结构所特有的纳米效应,使其成为聚合物材料理想的增强体,并能赋予聚合物材料许多新的功能。本章也综述了碳纳米管/聚合物复合材料研究的新进展。
2.本章首次报道了以纳米石墨薄片为导电填料,用超声法成功的制备了纳米石墨薄片/聚苯胺(NanoGs/PAN)复合棒状材料。研究了掺杂剂的种类、掺杂剂的浓度以及纳米石墨薄片的用量对材料导电性能影响。并利用红外光谱(FTIR)、扫描电镜(SEM)表征了材料的组成和结构。结果表明超声法可抑制苯胺聚合时的团聚,形成均匀的棒状纳米复合材料。纳米石墨薄片加入量在1.3%时达到渗域滤值,材料的导电率由4.8S/cm达到22S/cm。热重分析说明纳米石墨薄片/聚苯胺复合棒状材料的热稳定性优于单纯的聚苯胺。
3.本章首次介绍了以纳米石墨薄片为导电填料,成功的制备了纳米石墨薄片/聚苯胺-g-聚乙二醇(NanoGs/PANI-PEG-PANI)复合材料。研究了掺杂剂的种类、掺杂剂的浓度以及纳米石墨薄片的用量对材料导电性能影响。利用红外光谱(FTIR)、扫描电镜(SEM)表征了材料的组成和结构,结果表明盐酸掺杂的在1.6mol/L左右,而对甲苯磺酸掺杂的在0.75mol/L左右,纳米石墨薄片加入量在2.3%时达到渗域滤值,电导率达到16.9S/cm。热重分析说明纳米石墨薄片/聚苯胺-g-聚乙二醇复合材料的热稳定性优于单纯的聚苯胺,而共聚物中PEG链段的引入使得NanoGs/PANI-PEG-PANI复合材料的热稳定性降低。。
4.本章运用超声法成功的制备了碳纳米管/PANI-PEG-PANI复合材料。研究了碳纳米管的用量对材料导电性能影响。利用红外光谱(FTIR)、原子力(AFM)表征了材料的组成和结构,电导率测试结果表明:纯嵌段共聚物的导电率为3.4S/cm,加入碳纳米管的含量为1.2%时,导电率为下降至最低点;碳纳米管的含量大于1.2%时,材料的导电率呈现出增加的趋势。热重分析说明由于耐热的碳纳米管的引入使得复合材料的热稳定性优于单纯的嵌段共聚物。
Research and preparation of nanomaterials is causing an extensive concern of all over the world. Recently, the developing direction of materials is the functional complementarity and the property optimization. Nowadays, organic-inorganic nanocomposites have become full-subject crossed leading field across material science, physical chemistry, organic chemistry and polymeric chemistry, because they combine the merits of the organic polymers and inorganic material, exhibiting good electrical, optical, mechanical and magnetic properties.
Polyaniline (PANI) is one of the most promising conducting polymers due to its lower cost, higher and tunable conductivity, environmental stability and unique chemical and electrochemical properties. However, the properties of infusibility, insolubility and poor processability have greatly prevented its application. Nanomaterial has the special physical and chemical properties. Introducing nanotechnology into the synthetical technology of polyaniline will remarkably improve its processability; moreover it has conductivity and nanopartical function together. The research contains four parts, as follows:
1. In this chapter, we mainly describe the development of the nano structure and of soluble PANI. CNTs have excellent mechanical properties, good chemical and thermal stabilities predominant nano-effects electrical and microwave absorption properties, and have the unique of one dimensional nano-structure which makes CNTs be reinforcen for polymer materials, and give polymer materials many new the perfect functions, we describe the development of the CNTs/polymer composite.
2. The graphite nanosheets/polypaniline (NanoGs/PANI) nanorod composites were fabricated via ultrasonic polymerization of aniline monomer in the presence of NanoGs which was used as electric filling. The kind of doped acids, the concentration, and the content of the graphite nanosheets as impact factor to the conductivity of the material was investigated. The structure of nanocomposites was characterized by FT-IR, SEM. The results show that ultrasonic can effectively restrain the agglomerate of the aniline and come to uniformity nanorods composite. The conductivity reached to 4.8S/cm and 22S/cm respectively.
3. The NanoGs/PANI-PEG-PANI composites were fabricated via polymerization of aniline monomer and BAPPEG in the presence of NanoGs which was used as electric filling. The kind of doped acids, the concentration, and the content of the graphite nanosheets as impact factors to the conductivity of the material was investigated. The structure of composites was characterized by FT-IR, SEM. The results showed the materials with even film structure have excellent conductivity. The conductivity reached to 3.4 S/cm and 16.9 S/cm respectively.
4. The CNTs/PANI-PEG-PANI composites were fabricated via ultrasonic polymerization of PANI-PEG-PANI in the presence of CNTs which was used as electric filling. The structure of nanocomposites was characterized by FT-IR, AFM. The conductivity of pure PANI-PEG-PANI is 3.4S/cm, the conductivity of composite cut down to minimum when the CNTs is 1.2%, but after the piont the conductivity are increase.
引文
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