垂直有序CNTs 聚苯胺纳米复合膜的抽滤-电场法制备及性能研究

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摘要

碳纳米管（CNTs）具有优异的电学、力学、热学、磁学及气体吸附等性能。

以CNTs 为基材的 CNTs/聚合物复合膜不仅具备 CNTs 的诸多优势，聚合物填充

在CNTs 中不仅能起到支撑作用，并且使得复合膜拥有聚合物所具备的特点，近

年来已被广泛研究。其中，垂直有序 CNTs/聚合物复合膜在力学、电学、选择性

透过、热性能等方面能够展现出各向异性，可以直接加工成很多功能器件如电容

器、导热薄膜材料、选择性分离膜等，具有较好的研究和应用前景。

聚苯胺（PANi）纳米纤维具有原料易得、合成简单、导电率高、抗腐蚀及热

稳定性高等优点。此外，PANi 纳米纤维是一种特殊的光致发热材料，在一定强

度闪光照射下，PANi 纳米纤维将光源转化成热源，即具有闪焊效应而将 PANi 纳

米纤维熔连成致密的薄膜。本论文鉴于 CNTs、PANi 纳米纤维的优势，以及

PANi 能够与 CNTs 较好地分散在溶剂中的特点，制备了 PANi 均匀填充的

CNTs/PANi 复合膜。

本论文首先采用化学氧化聚合法合成了尺寸均匀的 PANi 纳米纤维，并使用

抽滤法制备了 PANi 纳米纤维膜。闪焊实验表明，闪光强度增加、膜厚减小及闪

焊距离减小时，PANi 纳米纤维膜表面熔融程度越大，表面变得致密光滑。TG 分

析也表明，闪焊能够提高 PANi 纳米纤维膜的热稳定性。采用抽滤法制备了

CNTs/PANi 复合膜，抽滤过程中 CNTs 能够在溶剂流形成的剪切力作用下沿着力

的方向排列，并与 PANi 纳米纤维沉积在滤纸上成膜，但抽滤法制备出的复合膜

中CNTs 的有序度不高。通过闪焊效应制备获得的 CNTs/PANi 复合膜表面，随着

闪焊次数的增加而变得更加致密光滑，复合膜的水接触角值也明显提高。

在抽滤法的基础上，本论文提出了采用抽滤 /电场协同法制备垂直有序

CNTs/PANi 复合膜的新方法，并设计制造了相关的抽滤/电场装置。在抽滤作用的

同时，将 CNTs 和PANi 的纳米分散液置于与抽滤剪切方向一致的交流电场中，

CNTs 除了在抽滤形成的剪切力作用下沿着溶剂流方向有序排列，还由于 CNTs 的

介电泳效应使其沿着电场的方向定向排列，最终在滤纸上形成 CNTs 垂直有序排

列的 CNTs/PANi 复合膜。协同法结合了静电场法能够制备出有序度较高的 CNTs

及抽滤法可以简单地通过混合抽滤分散液制备复合膜的优势，一步制备获得垂直

有序度较高的 CNTs/PANi 复合膜。本论文研究了抽滤/电场协同作用时间、电极

间距及电压大小对复合膜中 CNTs 有序度的影响。利用 SEM 观察不同工艺参数下

制备的复合膜断面，发现协同作用时间越长、电极间距越小、电压越大，复合膜

中CNTs 的有序度越高。通过偏振拉曼定量检测发现，当电压为 250 V、电极间

距为 16 mm、电极作用时间为 24 h 时，表明复合膜中 SWNTs 取向程度的 IP/IV值

为8.586，是纯抽滤法（即电压为 0 V）制备的复合膜 IP/IV值的 3倍。将协同法

制备的 CNTs/PANi 复合膜进行闪焊，复合膜表面变得更加致密光滑，其水接触角

值由未闪焊的 52°上升到闪焊强度 100%时的 66.4°。但是，当闪焊强度过大时，

CNTs 有序度有所降低。

本论文还进一步探究了 PANi 包覆 CNTs 分散液及 CNTs 和PANi 共混分散液

对协同法制备的 CNTs/PANi 复合膜形貌的影响。实验发现，CNTs 和PANi 共混

分散液制备出的复合膜有序度更高，且闪焊后所制备的复合膜表面闪焊熔融程度

明显较强，表面更加致密光滑。

关键词：碳纳米管聚苯胺纳米纤维垂直有序抽滤法静电场法闪

焊

ABSTRACT

Carbon nanotubes (CNTs) possess excellent electrical, mechanical, thermal,

magnetic and gas adsorption property. Recently, CNTs/polymer composite membranes

which not only have the advantages of CNTs but also possess the characteristics of

polymer have been widely researched. Meanwhile the polymer filled in the CNTs can

play a supporting role. Vertical aligned CNTs/polymer composite membranes can

exhibit anisotropy in mechanical, electrical, thermal, selective permeability aspects, and

it can be directly processed into multifunctional devices such as capacitors, the heat

conducting film, selective separation membrane, thus making vertical aligned

CNTs/polymer composite membranes have good prospects for research and application.

Polyaniline (PANi) nanofibers stand out in its low-cost, facile synthesis, high

electrical conductivity, extraordinary chemical and environmental stability. Furthermore,

PANi nanofiber is a special kind of light-induced heating material. At a certain intensity

of the flash, PANi nanofibers convert light source to thermal energy to make them

molten. PANi nanofibers have great water dispersibility so that they can be filled into

CNTs solutions uniformly. According to the advantages of CNTs and PANi nanofibers,

this paper prepare CNTs/PANi composite membranes filled with PANi uniformly.

In this paper, PANi nanofibers with the uniform size were prepared by chemical

polymerization, and the PANi nanofibers membranes were produced by the filtration

method. According to the flash process, when the flash intensity increased, or the film

thickness or flash welding distance reduced, the surface of PANi nanofibers membrane

exhibited greater degree of melting with denser and smoother surface. And TG analysis

showed that flash welding can improve the thermostability of PANi nanofibers

membranes. CNTs/PANi composite membranes were prepared by filtration method.

Shear force produced by solvent stream made the CNTs align, and then they deposited

together with the PANi nanofibers on the filter; while the vertical order degree of CNTs

in the composite membrane was not very high. Denser and smoother CNTs/PANi

composite membraned could be acquired after flash welding. Water contact angle

values of the composite membranes were improved by different times of flash welding.

Based on filtration method, this paper proposes a filtration/electric synergy method

for producing vertical aligned CNTs/PANi composite membrane, and the

filtration/electric device is designed and fit. Except for filtration, the CNTs and the

PANi nanofibers dispersions were placed in an alternating electric field with the same

direction of the filtration force. CNTs can not only be aligned under the shear force

formed by filtration, but also be ordered in the direction of electric field due to the

dielectrophoresis effect of CNTs. Filtration/electric field method can get vertical aligned

CNTs/PANi composite membrane in one step by combining the advantages of electric

field method which can obtain high vertical aligned CNTs, and the filtration method

which can obtain composite membrane simply by filtrating the dispersion liquid. This

paper researches the effect of acting time, electrode spacing and voltage on the vertical

order degree of CNTs in composite membrane. The morphology of the composite

membrane’s cross section shows that longer acting time, smaller electrode spacing and

higher voltage will improve the vertical order degree of CNTs. Polarization Raman

analysis presents that the value of IP/IV(8.586) in composite membrane prepared by 250

V of voltage is 3 times higher than composite membrane prepared by 0 V (i.e. prepared

by filtration method) with 16 mm of electrode spacing and 24 h of acting time. The

surface of composite membrane becomes denser and smoother after flash in different

intensity. Compared to the raw composite membrane, the value of water contact angle

increases from 52oto 66.4oafter flash in 100% intensity. However, SEM pictures reveal

that the ordered degree decreases with an intense flash welding.

This paper also researches the difference between the composite membranes

prepared by two kinds of CNT/PANi dispersion liquid. One is CNTs coated with PANi

aqueous dispersion, the other is the mixing aqueous dispersion of CNTs and PANi

nanofibers. Experiments have showed that the vertical ordered degree of CNTs in

composite membrane prepared by the mixing aqueous dispersion is higher and the

melting degree of surface becomes more obvious after flash.

Key word: carbon nanotube, polyaniline nanofiber, vertical aligned,

filtration, electric field, flash welding

中文摘要

ABSTRACT

第一章绪论...................................................................................................................... 1

1.1 引言......................................................................................................................1

1.2 CNTs 巴基纸....................................................................................................... 1

1.3 CNTs/聚合物复合膜及研究进展....................................................................... 3

1.3.1 CNTs/聚合物复合膜.................................................................................3

1.3.2 垂直有序 CNTs/聚合物复合膜及制备方法............................................3

1.3.3 PANi 纳米纤维..........................................................................................8

1.4 研究意义、研究内容及创新点........................................................................10

第二章实验部分............................................................................................................ 12

2.1 实验原料与仪器设备........................................................................................12

2.2 实验步骤............................................................................................................13

2.2.1 CNTs 酸化处理....................................................................................... 13

2.2.2 PANi 纳米纤维制备................................................................................14

2.2.3 抽滤分散液的制备................................................................................. 14

2.2.4 抽滤法制备 PANi 纳米纤维膜及 CNTs/PANi 复合膜......................... 15

2.2.5 抽滤/电场协同法制备垂直有序 CNTs/PANi 复合膜...........................16

2.3 实验分析测试....................................................................................................17

第三章结果与讨论........................................................................................................ 19

3.1 CNTs 酸化处理................................................................................................. 19

3.2 PANi 纳米纤维..................................................................................................24

3.3 抽滤法制备的 PANi 纳米纤维膜及闪焊性能.................................................25

3.4 抽滤法制备 CNTs/PANi 复合膜...................................................................... 31

3.4.1 抽滤法制备的 MWNTs/PANi 复合膜的结构及形貌........................... 31

3.4.2 闪焊对抽滤法制备的 MWNTs/PANi 复合膜的影响........................... 32

3.4.3 抽滤法制备的 SWNTs/PANi 复合膜的形貌.........................................34

3.4.4 小结......................................................................................................... 35

3.5 抽滤/电场协同法制备垂直有序 CNTs/PANi 复合膜..................................... 35

3.5.1 抽滤/电场协同法装置............................................................................ 35

3.5.2 抽滤分散液制备方法对协同法制备的复合膜的影响......................... 38

3.5.3 抽滤/电场协同法制备的复合膜断面形貌............................................ 46

3.5.4 协同法制备复合膜的影响因素..............................................................47

3.5.5 偏振拉曼定量表征复合膜有序度......................................................... 52

3.5.6 闪焊对复合膜的影响..............................................................................54

3.5.7 小结......................................................................................................... 57

第四章结论与展望........................................................................................................ 59

4.1 结论....................................................................................................................59

4.2 展望....................................................................................................................60

参考文献......................................................................................................................... 61

在读期间公开发表的论文和承担科研项目及取得成果............................................. 67

致谢................................................................................................................................. 68

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摘要：

摘要碳纳米管（CNTs）具有优异的电学、力学、热学、磁学及气体吸附等性能。以CNTs为基材的CNTs/聚合物复合膜不仅具备CNTs的诸多优势，聚合物填充在CNTs中不仅能起到支撑作用，并且使得复合膜拥有聚合物所具备的特点，近年来已被广泛研究。其中，垂直有序CNTs/聚合物复合膜在力学、电学、选择性透过、热性能等方面能够展现出各向异性，可以直接加工成很多功能器件如电容器、导热薄膜材料、选择性分离膜等，具有较好的研究和应用前景。聚苯胺（PANi）纳米纤维具有原料易得、合成简单、导电率高、抗腐蚀及热稳定性高等优点。此外，PANi纳米纤维是一种特殊的光致发热材料，在一定强度闪光照射下，PANi纳米纤维...

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