水溶性导电聚苯胺的制备*

水溶性聚苯胺在防腐涂料、电磁屏蔽、生物医学等领域有重要应用前景。该文结合本研究组在水溶性聚苯胺自支撑膜方面的研究进展,总结了水溶性聚苯胺的制备方法,并重点综述了用嵌段和接枝等共聚法制备的水溶性聚苯胺及其共聚机理,提出水溶性导电聚苯胺今后的研究方向。     

聚(3,4-乙烯二氧噻吩)在电磁屏蔽领域的应用

随着现代电子信息技术的迅猛发展,电磁干扰问题日益严重,发展综合性能优异的电磁屏蔽材料具有重要意义.聚(3,4-乙烯二氧噻吩)(poly(3,4-ethylenedioxythiophene),PEDOT)具有分子结构简单、能隙小、电导率高等特点,为高性能电磁屏蔽材料的实现提供了新途径.同时,随着对材料电磁屏蔽性能研究的深入以及制备技术的进步,将PEDOT与其他材料复合,通过合理的组分选择与结构设计,可以协同发挥各组分间电磁匹配特性,从而使PEDOT更好地满足柔性显示、智能可穿戴设备、高频器件、高精密电子设备等应用领域对电磁屏蔽材料"厚度薄、密度低、屏蔽强、屏蔽带宽宽"的具体要求.近年来,较多的研究致力于此并取得重要的成果.本文对以PEDOT为功能组分的电磁屏蔽材料的最新研究进展进行了综述,将近年来PEDOT及其与不同功能组分复合(包括导电组分、磁性组分及无电磁特性组分)构筑的电磁屏蔽材料体系的制备及电磁性能进行归纳总结,重点讨论电磁组分、微观结构与电磁屏蔽特性的联系,及其电磁屏蔽机理与性能优化方式,并对PEDOT在电磁屏蔽研究领域的机遇与挑战进行了展望.     

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．     

原位溶液聚合聚苯胺与聚苯乙烯溶液共混复合材料的制备及表征

以DNSA掺杂剂,在醇(或酮)-水介质中采用原位溶液聚合法制备出了聚苯胺,以溶液共混法制备出了聚苯胺/聚苯乙烯复合材料,采用红外光谱、热失重、元素分析、扫描电镜对产物进行了表征。结果显示：掺杂的聚苯胺电导率最高为0.65 S/cm,优于常用的DBSA,具有一定实用价值和理论意义。该复合材料表面电阻率最低为101Ω/□数量级,并在一定范围内可调,可用于电磁屏蔽,适合于聚合物表面使用。     

导电聚苯胺/橡胶复合材料的研究进展

聚苯胺是一种结构型导电高分子,因其特殊的结构和优异的物理化学性能,使它在二次电池、金属防腐、传感器、电容器、电磁屏蔽及抗静电等领域有着广泛而深入的应用前景。本文概述了导电聚苯胺的结构和特性,主要综述了聚苯胺/橡胶基复合材料的制备方法。其制备方法主要有共混法和聚合法,共混法主要有机械熔融共混法、溶液共混法和乳液共混法;聚合法主要包括电化学聚合、原位乳液聚合法、吸附聚合法等,总结了聚苯胺/橡胶基复合材料的研究情况及发展应用。     

一维聚苯胺纳米材料的制备方法研究进展

一维聚苯胺纳米材料具有电导率高、环境稳定性好、分散性好、比表面积大、扩散路径短等独特性能以及易于大量生产和成本相对低廉等优点,在传感器与传动器、防腐涂料、电磁屏蔽等领域应用潜力大,成为目前研究最为广泛的导电聚合物纳米材料之一,其制备方法也日益成为研究的热点。综述了近年来一维聚苯胺纳米材料制备方法的最新研究进展,介绍了模板法、非模板法和电纺法等制备方法,并对各种不同制备方法的优缺点进行了比较分析。     

碳纳米管/聚合物基柔性电磁干扰屏蔽复合材料研究进展

当今,柔性可穿戴电子设备、航空航天等领域的快速发展对柔性、轻质电磁干扰(electromagnetic interference,EMI)屏蔽材料的需求不断增加,碳纳米管/聚合物基复合材料因具有柔性好、质量轻、导电性和机械稳定性优异、EMI屏蔽效能可调等优点而备受关注。本文介绍了电磁屏蔽机理,对碳纳米管的分散方法和碳纳米管/聚合物基柔性EMI屏蔽复合材料的制备方法进行了对比总结,综述了碳纳米管/聚合物基柔性EMI屏蔽复合材料的研究进展。最后,提出了碳纳米管/聚合物基柔性EMI屏蔽复合材料亟待解决的关键科学问题,并对其未来发展趋势进行了展望。     

电磁屏蔽材料的研究进展

介绍了电磁屏蔽材料在军用和民用领域的重要性;简要阐述了电磁屏蔽的机理;综述了4种不同电磁屏蔽材料的优缺点以及研究现状,分别为金属型、表面导电型、填充复合型和本征型导电聚合物电磁屏蔽材料;分析并提出了3种提高电磁屏蔽效能的方式,分别为多孔结构设计、多层结构设计、复合填料优化.     

电磁屏蔽材料的研究进展

介绍了电磁屏蔽材料在军用和民用领域的重要性;简要阐述了电磁屏蔽的机理;综述了4种不同电磁屏蔽材料的优缺点以及研究现状,分别为金属型、表面导电型、填充复合型和本征型导电聚合物电磁屏蔽材料;分析并提出了3种提高电磁屏蔽效能的方式,分别为多孔结构设计、多层结构设计、复合填料优化。     

聚苯胺纳米复合材料的优良性能

聚苯胺纳米复合材料因结合了聚苯胺和纳米粒子的特殊性能,从而改善了基体的物理化学性能,赋予了材料前所未有的独特的性能,成为目前研究最为广泛的导电高分子纳米复合材料之一.本文基于国内外最新研究文献,结合典型事列详细综述了聚苯胺纳米复合材料在生物传感、催化、电磁、微波吸收和光电等方面呈现出的独特性能,简单评述了其在生物传感、催化、电磁、微波吸收、防腐等领域的应用前景.     

Effect of oxyfluorination on electromagnetic interference shielding of polyaniline-coated multi-walled carbon nanotubes

Highly conducting polyaniline (PANi)-coated multi-walled carbon nanotubes (MWCNTs) were prepared by in situ polymerization method for electromagnetic interference shielding. The thickness of the PANi coatings was controlled by the oxyfluorination treatment on the multi-walled carbon nanotubes and analyzed with both SEM and TEM. The oxyfluorination with higher oxygen content produced more hydrophilic functional groups on the surface of multi-walled carbon nanotubes. The functional groups led to the well distribution and coating of PANi on the multi-walled carbon nanotubes resulting in the higher interfacial affinity between them. The uniform coating of PANi on MWCNTs by controlling the oxyfluorination conditions also played a crucial role in increasing the electrical conductivity of nanocomposites. The improved interfacial affinity resulted in the higher electromagnetic interference (EMI) SE of 47.03?dB based on the synergistic combination of the conductive components. The EMI shielding mechanism of PANi on MWCNTs suggested that EMI was mainly shielded by adsorption to avoid secondary EMI.     

Conducting polystyrene/polyaniline blend through template-assisted emulsion polymerization

Electrically conducting polystyrene (PS)/polyaniline blends have been prepared through a one-step “anilinium-surfactant template”-assisted emulsion polymerization at room temperature. The self-assembled cylindrical An⁺PDPSA^? micelle formed inside the PS matrix can act as a structure directing template cum dopant. Morphological observation under scanning electron microscopic studies revealed that during the progress of polymerization, the initially formed nanostructured conducting polyaniline was changed into cubic/hexagonal/lamellar particles and finally transformed into a percolated structure inside the PS matrix. Blend was further characterized by UV-Vis spectroscopy, FTIR spectroscopy, X-ray diffraction, electrical conductivity, thermal stability, dielectric property, rheological property, and electromagnetic shielding efficiency. The key finding of this work is that the conductive blend prepared through micelle-guided polymerization exhibited superior electrical conductivity (9.6 S/m) with low percolation threshold concentration (5 wt%), excellent thermal stability, electromagnetic interference (EMI) SE of 1–10 dB which makes it a promising candidate for EMI shielding and antistatic discharge matrix for the encapsulation of microelectronic devices.     

Asymmetric Ni/PVC films for high-performance electromagnetic interference shielding

A novel asymmetric Ni/PVC film has been developed by solution casting method. The structure, electrical conductivity, electromagnetic interference(EMI) shielding, and impact resistance were investigated. The results showed that the Ni particles were asymmetrically distributed along the thickness direction in the film. The top surface resistivity increased with film thickness, while the bottom surface exhibited the different trend. EMI shielding effectiveness(SE) depended on formation of closed packed conductive Ni network, which was influenced by both Ni content and film thickness. A linear relationship was observed between EMI SE and film thickness. The films with lower Ni content showed the faster increasing rate of EMI SE with film thickness. Some of the films show appreciably high EMI SE( 40 d B), indicating the promising application in EMI shielding field. Moreover, the films exhibit different impact performance under different impacting directions. All the experimental facts demonstrate that the asymmetric structure endows the film achieving high-performance EMI shielding function.     

Electromagnetic interference shielding effectiveness and microwave absorption properties of thermoplastic polyurethane/montmorillonite‐polypyrrole nanocomposites

In this work, thermoplastic polyurethane‐filled montmorillonite‐polypyrrole (TPU/Mt‐PPy) was prepared through melt mixing process for using in electromagnetic shielding applications. The effect of conducting filler content and type, sample thickness, and X‐band frequency range on the electromagnetic interference shielding effectiveness (EMI SE) and EMI attenuation mechanism was investigated. A comparative study of electrical and microwave absorption properties of TPU/Mt‐PPy nanocomposites and TPU/PPy blends was also reported. The total EMI SE average and electrical conductivity of all Mt‐PPy.Cl or Mt‐PPy.DBSA nanocomposites are higher than those found for TPU/PPy.Cl and TPU/PPy.DBSA blends. This behavior was attributed to the higher aspect ratio and better dispersion of the nanostructured Mt‐PPy when compared with neat PPy. Moreover, the presence of Mt‐PPy into TPU matrix increases absorption loss (SE_A) mechanism, contributing to increase EMI SE. The total EMI SE values of nanocomposites containing 30 wt% of Mt‐PPy.DBSA with 2 and 5 mm thickness were approximately 16.6 and approximately 36.5 dB, respectively, corresponding to the total EMI of 98% (75% by absorption) and 99.9% (88% by absorption). These results highlight that the nanocomposites studied are promising materials for electromagnetic shielding applications.     

Intrinsically conducting polymers for electromagnetic interference shielding

This paper summarizes and reviews the research on electromagnetic interference (EMI) shielding with intrinsically conducting polymers (ICPs), mainly polyaniline (PANI) and polypyrrole (PPY), and their composites in various frequency ranges. ICPs are new alternative candidates for EMI shielding applications due to their lightweight, corrosion resistance, ease of processing, and tunable conductivities as compared with typical metals. More importantly, the dominant shielding characteristic of absorption other than that of reflection for metals render ICPs more promising materials in applications requiring not only high EMI shielding effectiveness but also shielding by absorption, such as in stealth technology. Copyright © 2005 John Wiley & Sons, Ltd.     

Nanoscale measurements of conducting domains and current-voltage characteristics of chemically deposited polyaniline films

Spatial variations in electric conductivity and evolutions of band structures of polyaniline (PANI) films have been studied by use of a so-called current-sensing atomic force microscope (CS-AFM) or atomic force microscope current image tunneling spectroscopy (AFM-CITS). PANI films were deposited chemically onto indium-tin oxide- (ITO-) glass substrates, and their thickness and doping levels were controlled by polymerization and acid-doping conditions. The conducting uniformity of the PANI films depends on their doping level and thickness. Conducting domains were observed in fully doped PANI film, even when the bias voltage was reduced to as small as 30 mV. High current flowing regions gradually disappeared when conducting PANI films were partially dedoped. The point-contact current-voltage (I-V) characteristics of conducting tip-polymer/ITO systems were investigated on PANI films with different thickness and degree of doping. Various types of I-V curves representing metallic, semiconducting, and insulating states were obtained depending on the aggregation of polymer chains and doping level of the polymer film. The band gap energies (estimated from the I-V or dI/dV-V curves) of emeraldine base (EB) (undoped polyaniline) films are all higher than 3.8 eV, and a wide distribution of the band gap energies (0-1.1 eV and 0.75-1.8 eV for fully and partially doped PANI thin films, respectively) was found in a single polymer film.     

Multi-layered graphene-Fe3O4/poly (vinylidene fluoride) hybrid composite films for high-efficient electromagnetic shielding

A flexible and multi-layered graphene nanosheets (GNSs)-Fe₃O₄/poly (vinylidene fluoride) hybrid composite film with high-efficient electromagnetic interference (EMI) shielding was fabricated via a facile layer-by-layer coating. The well-designed multi-layered and hybrid electromagnetic fillers endow the prepared film with good surface impedance matching and prominent internal multiple absorption, which forms “absorb-reflect-reabsorb” electromagnetic transmission pattern and results in highly efficient electromagnetic shielding effectiveness (EMI SE). The resultant composite film exhibits an exceptional EMI SE of 52.0 dB at a thickness of 0.3 mm. What is more important is that the prepared film exhibits excellent flexibility and EMI stability, and the retention rate of efficient EMI SE is high as 91.9% after 1000 bending-release cycles. This study provides a feasible strategy for designing high-efficient EMI shielding film with excellent flexibility and ultra-thin thickness that suitable for next-generation intelligent protection devices.     

Lightweight electromagnetic shields using optimized polyaniline composites in the microwave band

A genetic algorithm (GA) was used to optimize a multilayer electromagnetic shield of polyaniline (PANI)–polyurethane (PU) conducting composites in the microwave band. First, the electronic properties of freestanding films with different mass fractions of polyaniline were studied. A very low percolation threshold (0.2%) was found, with a maximum of conductivity of 10⁴ S/m. Second, the electromagnetic shielding effectiveness of the films were investigated in the X and Ku bands (8.2–18 GHz), showing an attenuation increase of 1–40 dB with the mass fraction of polyaniline in the blends. Then, the electromagnetic shielding properties of multi‐layered PAni–PU composites were investigated in order to obtain an attenuation superior to 40 or 80 dB, depending on the application. To improve the performances of the electromagnetic shields, three‐layered PAni–PU composites were made, using an optimization method. The intrinsic physical parameters of the composites were used as a database for the optimization calculation. The optimization results showed that materials with a thickness of <500 µm could answer many industrial or military shielding applications. As the electronic properties can be tuned easily with the mass fraction of polyaniline in the blends, conducting multi‐layered composite materials can be made following the results of the optimization. Their electromagnetic shielding effectiveness was measured, showing good agreement between the measurements and modeling. These results demonstrated that the genetic algorithm allows us to conceive lightweight and high performance electromagnetic shields using intrinsically conducting polymers. The mass per unit of surface of the shield was <200 g/m², giving potential applications in the aeronautics domain. Copyright © 2007 John Wiley & Sons, Ltd.     

电化学组装法制备对-巯基苯胺/聚苯胺纳米有序导电聚合物膜

提出了制备二维纳米有序有机导电聚合物膜的新方法--电化学组装法,应用该方法在电位脉冲的作用下使苯胺聚合到对-巯基苯胺修饰的金电极上,获得了致密、有序的对-巯基苯胺/聚苯胺(p-aminothiolphenol/polyaniline,PATP/PANI)导电寡聚物薄膜.用STM研究了Au(111)/PATP、Au(111)/PATP/PANI膜表面的二维有序性,用SERS谱表征了Au(粗糙表面)/PATP、Au(粗糙表面)/PATP/PANI膜的结构和成分,并以[Fe(CN)₆]^3-/[Fe(CN)₆]^4-为探针研究了其电子传递性能.结果表明用电化学组装法制备的PATP/PANI膜在纳米尺度上是二维有序的,且具有良好的电子传递性能.     

Polymerization and characterization of high conductivity and good adhension polypyrrole films for electromagnetic interference shielding

<正>Polypyrrole(PPy) shows a favorable application in the electromagnetic interference(EMI) shielding due to its good electrical conductivity and outstanding air stability.Conducting PPy films with high conductivity and good adhesion were successfully polymerized on the surface of insulating epoxy resin substrates using chemical polymerization.The factors affecting the properties of PPy films,such as the surface morphology,adhesion between PPy film and substrate,electrical conductivity,EMI shielding effectiveness(SE),were investigated.The adhesion was improved significantly through a three-step surface pretreatment of epoxy resin substrates including removing impurities,roughening,and surface modification with silane coupling agent.An enhancement in the conductivity of PPy films of about one order of magnitude was achieved by adding dopant in FeCl_3 solution.The higher the conductivity,the better the shielding effectiveness.Taking sodium p-toluenesulfonate doped PPy film as example,EMI SE was in the practically useful range of about 30 dB over a wide frequency range from 30 MHz to 1500 MHz.The PPy film samples were characterized by scanning electron microscopy (SEM),infrared spectra(IR),X-ray photoelectron spectroscopy(XPS) and the flange coaxial transmission device.The fourpoint probe method was used to measure conductivity of PPy films.