Preparation and study of polyaniline-and multiwall-carbon-nanotube-based composite materials

Polyaniline (PANI)-based composite materials containing 5 to 65 wt % of multi-wall carbon nanotubes (MCNT) are prepared. Their electrochemical characteristics are studied, in particular, the effect of the MCNT content in the composite on the composite and PANI specific capacitance. The increase in the composite capacitance, as well as the capacitance of the PANI being part of the composite, varies over the range from 5 to 25 wt %. This MCNT content is optimal for the preparing of a new MCNT-and PANI-based composite material. Over the above-given range, the increase in capacitance and the improving of conductivity are compromised at best. For a set of samples with varying MCNT content, the conductivity curve practically replicates the capacitance curve. The critical conductivity changes fall practically into the same range (5–30 wt %).     

The new composites,polyacetylene-carbon nanotubes: Electrochemical properties

Polyacetylene- and carbon-nanotube-based composite materials are prepared by the method of polymerization filling for the first time. It is shown that the acetylene polymerization mainly occurs at catalytic centers attached to the carbon nanotubes. It follows from TEM data that in the case of single-wall nanotubes the polyacetylene fibriles are wound up onto the nanotubes. In the case of multi-wall nanotubes, polyacetylene can form separate bodies that are connected to the multi-wall nanotubes. The specific electrochemical capacity of the novel composite materials is nearly twice as large as compared with that of the composite prepared by mechanical mixing; it is by two orders of magnitude larger than the pure polyacetylene capacity. The reversibility of the Li⁺ intercalation-deintercalation electrode reaction appears significantly improved at the polyacetylene-carbon nanotubes composites.     

Effects of processing conditions on rheological,thermal, and electrical properties of multiwall carbon nanotube/epoxy resin composites

We report on the effect of processing conditions on rheology, thermal and electrical properties of nanocomposites containing 0.02–0.3 wt % multiwall carbon nanotubes in an epoxy resin. The influence of the sonication, the surface functionalization during mixing, as well as the application of external magnetic field (EMF) throughout the curing process was examined. Rheological tests combined with optical microscopy visualization are proved as a very useful methodology to determine the optimal processing conditions for the preparation of the nanocomposites. The Raman spectra provide evidence for more pronounced effect on the functionalized with hardener compositions, particularly by curing upon application of EMF. Different chain morphology of CNTs is created depending of the preparation conditions, which induced different effects on the thermal and electrical properties of the nanocomposites. The thermal degradation peak is significantly shifted towards higher temperatures by increasing the nanotube content, this confirming that even the small amount of carbon nanotubes produces a strong barrier effect for the volatile products during the degradation. The ac conductivity measurements revealed lower values of the percolation threshold (pc) in the range of 0.03–0.05 wt %. CNTs for the nanocomposites produced by preliminary dispersing of nanotubes in the epoxy resin, compared to those prepared by preliminary functionalization of the nanotubes in the amine hardener. This is attributed to the higher viscosity and stronger interfacial interactions of the amine hardener/CNT dispersion which restricts the reorganization of the nanotubes. The application of the EMF does not influence the pc value but the dc conductivity values (σ_dc) of the nanocomposites increased at about one order of magnitude due to the development of the aforementioned chain structure. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

聚苯胺/分级碳纳米管复合材料的制备与性能研究

在众多的导电高分子中，聚苯胺具有原料易得、合成简便、能进行快速与可逆的氧化还原反应、可储存高密度的电荷等优点，在能源、光电子器件、电容器、传感器、分子导线和分子器件，以及电磁屏蔽、金属防腐和隐身技术等领域有着诱人的应用前景．近年来，将导电聚苯胺用于超电容器，倍受人们的广泛关注．     

ZnO纳米线基MWNTs/PVDF复合热电材料的制备及特性研究

将不同比例的多壁碳管(MWNTs)与聚偏二氟乙烯(PVDF)聚合物混合后,喷涂于n型ZnO半导体纳米线阵列上,制备了一种新型ZnO纳米线基MWNTs/PVDF热电复合材料.与以往采用价格昂贵的p型与n型单壁碳纳米管(SWNTs)与聚合物混合制备的复合热电材料特性相比,这种新型热电复合材料在降低制造成本的同时,利用分散于聚合物中MWNTs的一维电子传输特性及形成的大量界面势垒,加上ZnO半导体纳米线具有的较高载流子密度与迁移率,提高了复合热电材料中电子的输运特性,增加了材料对声子的散射强度.测试发现,在一定的温度梯度下,随着MWNTs添加质量百分比的增加,热电材料的温差电动势和电导率也随之增加,但其Seebeck系数变化量不大.研究表明,这种热电材料有望替代采用p型与n型SWNTs构建的SWNTs/PVDF复合热电材料.研究结果对开发超轻、无毒、廉价、可应用于各种微纳电子领域的新型电源具有重要的参考价值.     

Influence of multiwall carbon nanotubes on morphology and electrical conductivity of PP/ABS blends

Polypropylene (PP) and acrylonitrile‐butadiene‐styrene (ABS) blends with multiwall carbon nanotubes (MWNT) were prepared by melt mixing. PP/ABS blends without MWNT revealed coarse co continuous structures on varying the ABS content from 40 to 70 wt %. Bulk electrical conductivity of the blends showed lower percolation threshold (0.4–0.5 wt %) in the 45/55 co continuous blends whereas the percolation threshold was between 2 and 3 wt % in matrix‐particle dispersed morphology of 80/20 blends. Interestingly, droplet size was observed to decrease with addition of MWNT above percolation threshold in 80/20 blends. Further, the bulk electrical conductivity was found to be dependent on the melt flow index of PP. The non‐polar or weakly polar nature of blends constituents resulted in the temperature independent dielectric constant, dielectric loss, and DC electrical conductivity. Rheological analysis revealed the formation of 3D network‐like structure in 80/20 PP/ABS blends at 3 wt % MWNT. An attempt was made to understand the relationship between rheology, morphology, and electrical conductivity of these blends. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2286–2295, 2008     

Synthesis and characterization of single‐wall‐carbon‐nanotube‐doped emeraldine salt and base polyaniline nanocomposites

Nanocomposites of polyaniline (PANI) and single‐wall carbon nanotubes (SWNTs) were prepared and characterized via resonance Raman and electronic absorption spectroscopy (ultraviolet–visible/near‐infrared). The chemical synthesis of PANI was performed in the presence of SWNTs in concentrations ranging from 10 to 50 wt % (SWNT/PANI). The obtained materials were hydrophilic, homogeneous composite compounds. The chemical interaction between PANI (in the conducting emeraldine salt form and in the insulating emeraldine base form) and metallic and semiconducting nanotubes was investigated. The emeraldine salt form of the polymer was significantly stabilized in the composite in comparison with plain PANI. A selective electronic interaction process between PANI and metallic SWNTs was found. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 815–822, 2005     

聚苯胺/纳米二氧化锰复合材料Ⅰ.原位氧化合成制备

用固相合成法制备了纳米二氧化锰(nm-MnO2),并通过原位聚合法制备了聚苯胺／纳米二氧化锰复合材料。研究结果表明：在苯胺／nm-MnO2的盐酸反应体系中,nm-MnO2可以使苯胺氧化聚合。在一定的nm-MnO2用量下,聚苯胺的产率随苯胺添加量的增加而下降,nm-MnO2在产物中的含量也随之下降,且含量很低。在苯胺：／nm-MnO2／过硫酸铵的反应体系中,研究了Nm-MnO2通过两种不同的加料方式原位制备PA-NI／nm-MnO2复合材料的合成条件。第一种方式为nm-MnO2和过硫酸铵同时与苯胺混合,一起参与苯胺的氧化聚合。第二种方法是先将过硫酸铵和苯胺混合,3min后再将nm-MnO2加入反应体系中。研究表明：第一种加料方式得到的队NI／nm-MnO2中nm-MnO2的含量很低;第二种加料方式可以得到高nm-MnO2含量(w=0．14-0．73)的产物,其电导率约10^-4S／cm。     

Composites based on polyaniline and aligned carbon nanotubes

Composites based on aligned carbon nanotubes and polyaniline are prepared via the electrochemical polycondensation of aniline in a sulf uric acid solution. The structure of the composites and the character of interaction of polyaniline and the surface of carbon nanotubes are studied by scanning and transmission electron microscopy, X-ray diffraction, and IR and X-ra y photoelectron spectroscopy. It is shown that in the composites, electron density is transferred from the carbon nanotube to the polyaniline film. The occurrence of polyaniline on the surface of nanotubes increases the mean current in cyclic voltammograms of the composite material and leads to a marked increase in the calculated specific capacity of electrodes formed on its basis.     

Effects of the reduction of PAni-coated oxidized multiwall carbon nanotubes on the positive temperature coefficient behaviors of their carbon black/high density polyethylene composites

Polyaniline (PAni)-coated reduced multiwall carbon nanotubes (PRMWNTs) and carbon black (CB)-filled high-density polyethylene (HDPE) composites (PRMWNTs/CB/HDPE) were prepared through a melt mixing method. Oxidized MWNTs (OMWNTs) were prepared by treating pristine multiwall carbon nanotubes (MWNTs) with an acid mixture (HNO₃:H₂SO₄), and PAni-coated OMWNTs (POMWNTs) were synthesized via in-situ polymerization of aniline monomer in the presence of OMWNTs. POMWNTs were further reduced using hydrazine monohydrate to obtain the PRMWNTs. Fourier transform infrared (FT-IR) spectra and thermogravimetric analysis (TGA) confirmed the formation of PRMWNTs. PRMWNTs showed significantly improved thermal stability and electrical conductivity comparing to POMWNTs. The positive temperature coefficient (PTC) behavior of PRMWNTs/CB/HDPE composites revealed enhanced PTC intensity and electrical conductivity at room temperature compared to POMWNTs/CB/HDPE composites. The PRMWNTs-10/CB/HDPE composite showed high peak resistivity (301.99 MΩ-cm) and low room temperature resistivity compared to the POMWNTs/CB/HDPE composite, and thus showed the highest PTC intensity value of 6.693 as well as very excellent cyclic stability.     

Composite materials based on polyaniline and multiwalled carbon nanotubes: Morphology and electrochemical behavior

Composites based on polyaniline are prepared via the chemical oxidative polymerization of aniline in the presence of multiwalled carbon nanotubes modified by the sorption of the co-oxidants IrC ₆ ^2? and 2,2′-azino-bis(3-ethyl-benzthiazolin-6-sulfonate). The approach used here, in combination with corresponding conditions of polymerization, ensures the synthesis of composite materials with a high morphological homogeneity of the polymer phase. The study of the electrochemical properties of composites (the reversibility of redox transitions and the stability of capacity parameters) indicates that that they are strongly influenced by the morphological features of the polymer coating. The composite prepared with the use of nanotubes modified by 2,2′-azino-bis(3-ethyl-benzthiazolin-6-sulfonate) possesses better electrochemical characteristics. This effect is associated with a closer to perfect morphology of the polymer coating, a coaxial polyaniline shell highly uniform in thickness along the entire length of nanotubes.     

超级电容器石墨烯-聚苯胺复合材料的研究进展

超级电容器具有功率密度高、充放电速度快、循环寿命长和维护成本低的特点,在电动车动力电池领域具有潜在的应用前景。超级电容器性能主要由其电极材料所决定。聚苯胺易合成、理论比容量高,而且导电性能优异,作为超级电容器电极材料有很高的应用价值。但是,在长期使用过程中,它的体积容易发生膨胀或收缩,循环寿命差。为了解决这个问题,将聚苯胺与石墨烯复合可以扬长避短,充分利用两者之间的协同效应,赋予复合材料优异电化学电容性能。本文综述了超级电容器用石墨烯-聚苯胺复合材料的制备方法,包括原位聚合法、油水界面合成法、电化学合成法、层层自组装法等;提出了三维网状石墨烯和对石墨烯-聚苯胺复合材料进行改性来提高复合材料的电化学电容性能的思路。     

多壁碳纳米管/溴/聚苯乙炔三元复合材料导电性能的研究

通过机械共混和溶液共混制备了多壁碳纳米管(MWNTs)/溴/聚苯乙炔(PPA)三元复合材料, 复合材料表现出良好的导电性能, 电导率为10 S/m, 达到掺溴MWNTs的导电水平. 通过固体紫外光谱、XPS和SEM分析了复合材料中MWNTs、溴与PPA三者之间的相互作用, 研究了独立导电单元的形成, 以及导电单元对电导率提高所起的作用. 结果表明, 当MWNTs含量较低时, MWNTs和PPA之间的溴转移导致复合材料电导率降低; MWNTs含量较高时, 独立导电单元的数目增多, 复合材料的电导率随之大幅提高.     

铂纳米粒子和锰卟啉修饰的聚苯胺新材料的制备及表征

借助循环伏安电化学聚合制备了聚苯胺(PANi)/MnT1239卟啉复合材料,再利用还原恒电位沉积法负载铂纳米粒子(Pt NP),最终制备了聚苯胺/MnT1239卟啉/铂纳米粒子复合材料.电沉积铂之后聚苯胺/MnT1239卟啉材料发生明显样貌变化,棒状结构平均直径从90 nm增加到200 nm,材料具有较大的表面积,空间可负载性好.铂纳米粒子平均尺寸在20 nm,附着均匀,氧化峰电流在0.2 V处达到7.4 mA,电化学性能优良.     

链珠状氢氧化亚镍的准电容特性及其在复合型超电容器中的应用(英)

本文采用溶胶凝聚方法制备了超细氢氧化亚镍电极材料并通过在其中掺加适量碳纳米管的方法大大提高了电极的比容量并有效改善了电极材料的阻抗特性。掺有20%碳纳米管的氢氧化亚镍复合电极材料的单电极比容量可达到320 F·g^-1。本文分别采用氢氧化亚镍/碳纳米管复合电极作为正极，活性炭作为负极，6 mol·L^-1 KOH作为电解液制备了复合型电化学电容器。采用上述方法制备的复合型电容器工作电压达到1.6 V，电容器质量比容量达到60 F·g^-1。复合型电容器能量密度达到20.11 Wh·kg^-1，最大功率密度达到8.6 kW·kg^-1,兼具高能量特性和优良的大电流放电特性。     

聚丙烯/石墨导电纳米复合材料的制备与性能

用溶液插层及其与熔体混合相结合的母料熔体混合 (MMM)方法制备了聚丙烯 (PP) 马来酸酐接枝聚丙烯 (gPP) 膨胀石墨 (EG) (gPP EG =3 2wt)导电纳米复合材料 ,其室温逾渗阀值 (c)分别为 6wt%和 8wt % ,明显低于直接熔体混合制得复合材料和PP EG对照材料的c=11wt%和 12wt% .增加gPP含量 (Cg)能提高复合材料的电导率 (σ) ,例如对于MMM法制备的复合材料 ,固定PP gPP =1 1wt时 ,c 降为 7wt% ;保持EG含量 =9wt%时 ,σ在Cg>30wt %后跃升 7个数量级以上 .通过TEM、SEM和OM观察 ,从制备方法、EG和gPP含量影响复合材料形态和微结构的角度 ,分析说明了出现上述差异和现象的原因 .     

Polyanine and its composites as sorbents of influenza viruses

Polyaniline and its composites with carbon nanotubes or silver nanoparticles are prepared and characterized via electron microscopy, spectroscopy, conductometry, and BET analysis. The in vitro and in vivo toxicities of the materials are studied, and then the materials are used as sorbents of the influenza A and B viruses. It is shown that the best sorption capacity with respect to all of the virus strains is exhibited by the polyaniline composite with silver, which provides for almost complete removal of viruses from aqueous solutions.     

聚吡咯/聚苯胺二元复合纳米管及其热电性能

以甲基橙为软模板, 六水合三氯化铁为催化剂, 在水溶液中通过沉淀聚合法制备了管径为20~180 nm的聚吡咯(PPy)纳米管; 以聚吡咯纳米管为基体, 通过原位聚合制备了聚吡咯/聚苯胺(PPy/PANi)二元复合纳米管. 研究发现, 在PPy/PANi二元复合纳米管中, PANi均匀地包覆在PPy纳米管表面, 并形成有序堆积, PPy与PANi间存在强烈的π-π共轭作用与氢键作用, 当PPy与PANi单体摩尔比为1∶2时, PPy/PANi二元复合纳米管的功率因子在363 K时达到0.74 μW/(m·K ²).     

Current trends in spinel based modified polymer composite materials for electromagnetic shielding

The present article deals with current trends in spinel based modified polymer composite materials for applications in the field of electromagnetic shielding. The interaction between the various spinel based materials and polymers is an emerging field of studies among various researchers. The thermal stability, electrical conductivity, the bonding between the metal ferrites and the polymer plays an important role in the interaction of electromagnetic radiation. These properties also effect the mechanism of the EM waves for the shielding applications. Considering these all properties, polyaniline appears to be an suitable polymer for electromagnetic shielding applications. Polyaniline composites not only reinforced the properties of spinel materials but also enhanced the dielectric properties of the composite material. When carbon based materials such as graphene, graphene oxide and CNT was added along with spinel material in polyaniline based composite, they accelerate the electrical properties and enhances the shielding applications. In this paper the various synthesis methods, fabrication methods of polyaniline, and the properties of polyaniline based composites have been discussed. In addition, the various salient features and futuristic challenges of polyaniline based composite materials for EMI shielding applications were attempted to make a well equipped material for radar absorption.     

Properties of Film Materials Based on Composite Nanofibers from Aliphatic Copolyamide and Carbon Nanotubes for Tissue Engineering

The investigation of the dependence of effective viscosity on shear rate for a water-alcohol solution of an aliphatic copolyamide and its mixtures with single-wall carbon nanotubes reveals that additives of the nanoparticles in the amount of 0.5 wt % lead to a substantial reduction in the effective viscosity as the shear rate rises. The measurement of the surface tension and electrical conductivity of the solutions bearing 0.1–2.0 wt % of the nanotubes allows one to choose an optimal mode for electrospinning of the composite nanofibers based on the aliphatic copolyamide. The introduction of carbon nanofibers reduces the specific resistance of the material to 8.9 × 10⁹ Ω m, but increases the elastic modulus. The lack of cytotoxicity of the resulting materials and the high proliferative activity of human dermal fibroblasts on their surface allow one to use the film materials based on the composite nanofibers in cell technologies and as matrices for tissue engineering.