The influence of single-walled carbon nanotube functionalization on the electronic properties of their polyaniline composites

The “in situ” preparation and characterization of composites of polyaniline (PANI) and single-walled carbon nanotubes (SWCNTs) are reported. To improve the dispersion and compatibility with the polymer matrix the raw SWCNTs were modified following different routes. SWCNTs oxidized by chemical or thermal treatments (nitric acid and air oxidation, respectively) were subjected to covalent functionalization with octadecylamine (ODA). SWCNT/PANI composites were prepared either from just oxidized SWCNTs, or from ODA functionalized SWCNTs. Temperature-programmed desorption, elemental analyses, ultraviolet-visible (UV-vis), UV-vis with near infrared and Raman spectroscopy, X-ray diffraction, scanning and transmission electron microscopy and conductivity measurements were used to characterize the functionalized SWCNT materials, dispersions and composites. The PANI composite prepared from air oxidized SWCNTs showed the best electrical conductivity indicating a better interaction with polyaniline than ODA functionalised SWCNTs. The improvement of conductivity is attributed to the doping effect or charge transfer of quinoide rings from PANI to SWCNTs.     

Mechanical,dielectric and EMI shielding response of styrene acrylonitrile,styrene acrylonitrile/polyaniline polymer blends,upon incorporation of few layer graphene at low filler loadings

The malfunction of electronic devices and many health-related issues may be caused due to electromagnetic interference (EMI) pollution. To overcome this problem a new set of material SAN/PANI/FLG hybrid composite with better EMI shielding properties is prepared using solution casting technique. Conductive polyaniline (PANI) is added (5 wt% and 10 wt%) to otherwise, an insulative polymer styrene acrylonitrile (SAN). Furthermore, few layer graphene (FLG) is added (0.1–1 wt%) to SAN/PANI polymer blends for preparation of SAN/PANI/FLG hybrid composites. The incorporation of PANI in SAN produces a phase separated morphology, whereas graphene appears in sheet like structure. For 0.1 wt% FLG/SAN/PANI-10 composite, total shielding effectiveness (SE_T) is enhanced from 1.1 to 24.3 dB (100 Hz), mainly due to enhanced dielectric characteristics. However, the maximum increase in tensile strength (49.6 MPa) and modulus (1.5 GPa) is observed for 0.5 wt% FLG/SAN/PANI-5.0 hybrid composite. The increase in dielectric properties and shielding efficiency of SAN/PANI/FLG may be credited to the accumulation of space charges or electric dipoles at the insulator conductor-interface.     

一维有序聚苯胺纳米阵列在超级电容器中的研究进展

从聚苯胺（polyaniline, PANI）的结构特征和导电机理出发,详细叙述了一维有序PANI纳米阵列的优点及各种制备方法,指出了PANI纳米阵列作为超级电容器电极材料的优势。根据电极材料分类,重点综述了PANI阵列结构基与导电高分子材料、碳材料、金属氧化物复合作为超级电容器电极材料的应用情况;讨论了这些电极材料的结构特点、制备方法、提高电化学储能性的机理及上述研究中存在的问题;最后根据存在的问题,提出进一步优化PANI阵列结构基电极材料电化学性能的制备方法与策略,并对未来PANI阵列结构基电极材料在超级电容器的发展前景进行了展望。     

Transforming polymer blends into composites: a pathway towards nanostructured materials

Polymer blends and polymer‐based composites are two of the most rapidly developing groups of materials being of industrial, as well as of academic, interest. More than a decade ago a new group of polymer materials was introduced, which became known under the name ‘microfibrilar composites’ (MFCs). They were obtained by the transformation of blends of thermoplastic polymers into micro‐ or nanostructured systems by combination of appropriate mechanical and thermal treatments. Since then, the importance of these novel materials, both for theory and for engineering practice, has increased significantly. It is an objective of this review to outline the place of MFCs within the whole variety of polymer‐based composites. Furthermore, the methods of their preparation, the ways of investigating their structure and the relation of the structure and mechanical properties are discussed. Ultimately, an evaluation of the future trends in this exiting interdisciplinary research field is attempted. Copyright © 2007 Society of Chemical Industry     

Preparation and Characterization of Conductive Polyaniline/Silver Nanocomposite Films and Their Antimicrobial Studies

Silver (Ag) nanoparticles are known to hold an important place in nanotechnology, and studies herein present the preparation and characterization of Ag metallic nanoparticles bearing antibacterial properties. In situ polymerization was used to prepare the conductive polymer polyaniline (PANI) and polyaniline/silver (PANI/Ag) nanocomposites. Increases in electrical conductivities of the nanocomposite films were observed compared to neat PANI, whereby these increases may be a result of the Ag doping effect or its complex formation. Spectroscopic techniques, such as, UV–Vis, FTIR, and photoluminescence were used for the characterizations of PANI and PANI/Ag nanocomposites. UV–Vis and FTIR data showed the quinoid units along the polymer chain being affected, such that strong interactions between Ag nanoparticles and quinoidal sites of PANI were presumed. The PANI/Ag nanocomposites showed higher photoluminescence intensities than neat PANI. TGA analyzes were used to determine weight losses and thermostabilities of PANI and PANI/Ag nanocomposites. Scanning electron microscopy was used for morphological evaluations of the nanoparticles and films, where the micrographs revealed that Ag nanoparticles were well dispersed and isolated in nanocomposite films. The presence and distribution of the Ag nanoparticles in PANI film matrix were analyzed by EDX. Antimicrobial properties of the nanocomposite films obtained were also explored. POLYM. ENG. SCI., 59:E182–E194, 2019. © 2018 Society of Plastics Engineers     

大分子相容剂在填充PP基复合材料中的应用

大分子相容剂在共混高分子材料中有着广泛的应用，并获得明显的效果。近年来，国内外关于大分子相容剂用于填充PP基塑料中以促进填料在高分子基体中的分散，改善填料和基体间的界面粘结，提高填充复合材料的物理与力学性能的研究越来越多。本文结合自己的研究工作，综述了大分子相容剂在填充PP基复合材料中的应用和研究进展，介绍了大分子相容剂的主要类型、制备方法及其改性填充PP基复合材料的物理与力学性能。     

Effect of carbon black and nanoclay on mechanical and thermal properties of ABS–PANI/ABS–PPy blends

Acrylonitrile butadiene styrene (ABS)–polyaniline (PANI) and ABS–polypyrrole (PPy) blends exhibit poor mechanical and thermal properties due to their weak interfacial adhesion and inhomogeneous mixing. The properties have been improved by addition of carbon black (CB) and nanoclay (NC). Composites are prepared by mixing CB and NC with ABS–PANI and ABS–PPY blends. The morphology and crystalline characteristics are studied using field emission scanning electron spectroscopy (FESEM) and X‐ray diffraction, respectively. In addition, all the composites have been analyzed for their mechanical and thermal performance. The tensile strength of ABS–PANI has been increased by 7.18% and 65.83% with addition of CB and a combination of CB–NC, respectively. FESEM images are found supportive with these trends and show homogeneous dispersion of CB in the polymer matrix, assisted by NC. Dynamic mechanical analysis results also show slight improvement of glass transition temperature (T_g) with addition of fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42577.     

DBSA参杂聚丙烯接枝苯乙烯磺酸聚苯胺抗静电剂的制备与应用

以聚丙烯 (PP) 为基体,聚苯胺（SPSS）为接枝物,十二烷基苯磺酸（DBSA）为掺杂剂,采用溶液接枝法制备了高分子永久型抗静电剂聚丙烯接枝苯乙烯磺酸聚苯胺 (PP g SPS PANI)。探讨了DBSA及引发剂用量对该高分子抗静电剂性能的影响,利用红外光谱对该高分子抗静电剂进行了表征,通过扫描电子显微镜分析了PP/ PP g SPS PANI共混物的断面。结果表明,PP g SPS PANI可使PP体积电阻率降低到1.0×1012 Ω·cm,且二者有很好的相容性。     

Progress on the morphological control of conductive network in conductive polymer composites and the use as electroactive multifunctional materials

Since the emergence of large aspect ratio and multifunctional conductive fillers, such as carbon nanotubes, graphene nanoplates, etc., conductive polymer composites (CPCs) have attracted increasing attention. Although the morphological control of conductive networks in CPCs has been extensively investigated as an important issue for the preparation of high performance CPCs, recent extensive progress has not been systematically addressed in any review. It has been observed that the morphological control of conductive networks during the preparation of CPCs has crucial influence on the electrical properties of these composites. Several methods have been shown to be able to control the network structure, and thus, tune the electrical properties of CPCs, including the use of shear, polymer blends, thermal annealing, mixed filler, latex particle etc. Moreover, many novel and exciting applications have been extensively investigated for CPCs, such as stretchable conductor, electroactive sensors, shape memory materials and thermoelectric materials, etc. Therefore, the morphological control of conductive network in CPCs is reviewed here. Issues regarding morphology characterization methods, morphological control methods, resulted network morphology and electrical properties are discussed. Furthermore, the use of CPCs as electroactive multifunctional materials is also reviewed.     

Properties and Degradation of Novel Fully Biodegradable PLA/PHB Blends Filled with Keratin

The utilization of keratin waste in new materials formulations can prevent its environmental disposal problem. Here, novel composites based on biodegradable blends consisting of poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB), and filled with hydrolyzed keratin with loading from 1 to 20 wt % were prepared and their properties were investigated. Mechanical and viscoelastic properties were characterized by tensile test, dynamic mechanical thermal analysis (DMTA) and rheology measurements. The addition of acetyltributyl citrate (ATBC) significantly affected the mechanical properties of the materials. It was found that the filled PLA/PHB/ATBC composite at the highest keratin loading exhibited similar shear moduli compared to the un-plasticized blend as a result of the much stronger interactions between the keratin and polymer matrix compared to composites with lower keratin content. The differences in dynamic moduli for PLA/PHB/ATBC blend filled with keratin depended extensively on the keratin content while loss the factor values progressively decreased with keratin loading. Softening interactions between the keratin and polymer matrix resulted in lower glass transitions temperature and reduced polymer chain mobility. The addition of keratin did not affect the extent of degradation of the PLA/PHB blend during melt blending. Fast hydrolysis at 60 °C was observed for composites with all keratin loadings. The developed keratin-based composites possess properties comparable to commonly used thermoplastics applicable for example as packaging materials.     

Modified continuous carbon fiber‐reinforced poly(phthalazinone ether sulfone ketone) composites by blending polyetherimide and polyethersulfone

Poly(phthalazinone ether sulfone ketone) (PPESK) is a novel high performance thermoplastic with outstanding high temperature resistance and excellent mechanical properties and therefore, it is a very ideal candidate matrix for advanced composites. However, its high melting viscosity makes the melting process difficult. In this article, two well‐known high performance thermoplastics, polyetherimide (PEI) and polyethersulfone (PES) were introduced to PPESK in order to reduce the melting viscosity of PPESK and to improve the properties of composites. The effect of addition of PEI and PES on the resultant composites was studied. A series of unidirectional composites were made of PPESK and its PEI and PES blends as matrix and continuous carbon fiber (T700) as reinforcement. The solution prepregging method and hot‐press molding method were used in preparation of composites. The effects of polymer blends matrix on mechanical properties, interfacial adhesion, and fracture mode were studied by three points bending, interlaminar shearing, porosity, and scanning electron microscope test. The results show that the mechanical properties and interfacial adhesion increases, and the porosity decrease after blending PEI or PES in the matrix. Addition of PEI and PES to PPESK results in an obvious transition of fracture mode. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

微孔炭/聚苯胺纳米线复合材料的制备及其电化学电容性能

纳米线型导电聚合物是一种具有良好应用前景的超级电容器电极材料,该文用简易的原位化学氧化法制备了微孔炭/聚苯胺纳米线(MC/PANI)复合材料,并以此复合材料为活性物质制备工作电极,在1 mol/L H2SO4中,通过循环伏安、交流阻抗和恒流充放电技术考察了其电化学电容性能,结果表明,在0.2 A/g的电流密度下,MC/PANI电极首次充放电比电容可达到329 F/g,高于PANI电极的259 F/g,且MC/PANI电极电荷传递电阻(Rct)小于MC和PANI,可见纳米线型PANI可加强电极材料的电化学性能。     

Enhanced microwave absorbing properties of lightweight films based on polyaniline/aliphatic polyurethane composites in X band

Polymer blends based on nanostructured polyaniline (PANI) doped with hydrochloric acid (HCl) and para‐toluene sulfonic acid (PTSA) introduced into aliphatic polyurethane matrix (PU) are synthesized to produce flexible thin composite films for microwave absorbers. The effects of dopant type, PANI content and film thickness on morphologies, dielectric and microwave absorption properties in the X‐band are studied. It reveals that real and imaginary parts of the complex permittivity are proportional to filler concentrations and type of doped PANI. The PANI‐PTSA/PU films show higher permittivity and better microwave absorbing properties than PANI‐HCl/PU for the same weight fraction of PANI. The minimum reflection loss RL_(dB) values for the PANI‐PTSA/PU are ?37 dB at (20% PANI and 11.6 GHz) and ?30 dB at (15% PANI and 11.3 GHz) for thicknesses of 1.2 and 1.6 mm, respectively. These high values of reflection losses make the obtained lightweight and flexible composites promising radar absorbing materials (RAM). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40961.     

High dielectric constant polyaniline/epoxy composites via in situ polymerization for embedded capacitor applications

Polyaniline (PANI)/epoxy composites with different polyaniline (PANI) contents were successfully developed by in situ polymerization of aniline salt protonated with camphorsulfonic acid within epoxy matrices and fully characterized. The influence of PANI loading levels on various properties was also explored. Dielectric and electrical properties of PANI/epoxy composites were studied for samples in parallel plate configuration. A PANI/epoxy composite prepared in this fashion reached a high dielectric constant close to 3000, a dielectric loss tangent less than 0.5 at room temperature and 10 kHz. The hardener type was also found as a critical parameter for the dielectric properties of PANI/epoxy composites. The distribution of the conductive element clusters within the polymer matrix was studied by SEM and correlated to the dielectric behavior of the composite films.     

纳米粒子改性丙烯酸酯制备复合材料

作为分散相的纳米粒子以独立的相态形式通过改性,分散到作为连续相的丙烯酸酯聚合物基体中形成一种既保留无机材料的热稳定性与硬度,又兼具聚合物韧性与介电性能的复合材料,该过程不是无机相与有机相的简单混合,而是在纳米尺度内两相的有机复合。综述了近年来纳米粒子改性丙烯酸酯复合材料,重点介绍了纳米粒子种类、纳米粒子表面改性、复合材料制备方法及其工业应用等方面的研究成果,并对其发展方向进行了分析和展望。     

Fluorescent thermostable crosslinked poly(dodecylmethacrylate) composites based on porous polyethylene and CdSe/ZnS quantum dots

Hybrid fluorescent polymer–inorganic nanoparticle composites have a broad set of valuable properties that allow them to be considered promising materials for photonics and photovoltaics. The design and methods of preparation of these composites are among the most critical topics of modern materials science. In this work, we have developed an approach to the preparation of composite polymer films with bright fluorescence and high thermostability. These composite films are based on a porous polyethylene (PE) matrix, the pores of which are filled by crosslinked poly(dodecylmethacrylate) and CdSe/ZnS core/shell quantum dots (QDs). The composites obtained are transparent in the visible spectral region and are able to withstand heating to high temperature and a considerable mechanical stress without loss of this property. These QD–PE composite films contain QDs in a high concentration and display very bright fluorescence, while they retain the mechanical properties of the initial porous PE film. Thus, the developed approach makes it possible to obtain composite materials combining the advantageous properties of PE and QDs without appreciable loss of individual component characteristics. A novel approach to the preparation of fluorescence composite polymer films, which have transparency, dimensional thermostability and resistance to mechanical stress, has been developed. © 2018 Society of Chemical Industry     

高强度碳纳米管/聚合物复合材料的制备和应用

介绍了碳纳米管的结构和碳纳米管/聚合物复合材料的制备方法——溶液共混法、熔融法、原位聚合法和化学修饰法等。结合碳纳米管的特性,综述了碳纳米管/聚合物复合材料在力学性能的增强、电极材料、生物医学材料等方面的应用。     

Mechanical,thermal, and conductivity performances of novel thermoplastic natural rubber/graphene nanoplates/polyaniline composites

Conventional polymer blending has a shortcoming in conductivity characteristic. This research addresses the preparation of conductive thermoplastic natural rubber (TPNR) blends with graphene nanoplates (GNPs)/polyaniline (PANI) through melt blending using an internal mixer. The effect of PANI content (10, 20, 30, and 40 wt %) on the mechanical and thermal properties, thermal and electrical conductivities, and morphology observation of the TPNR/GNPs/PANI nanocomposites was investigated. The results showed that the tensile and impact properties as well as thermal conductivity of nanocomposite had improved with the incorporation of 3 wt % of GNPs and 20 wt % of PANI as compared to neat TPNR and reduced with further increase of the PANI content. It was observed that the GNPs and PANI acted as a critical component to improve the thermal stability and electrical conductivity of the TPNR/GNPs/PANI nanocomposites. The most improved conductivity of 5.22 E-5 S/cm was observed at 3 wt % GNPs and 40 wt % PANI. Variable-pressure scanning electron microscopy micrograph revealed the good interaction and distribution of GNPs and PANI within TPNR matrix at PANI loadings lower than 30 wt %. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48873.     

Carboxymethylcellulose/polyaniline blends. Synthesis and properties

Summary Polyaniline (PANI) as one of the conducting polymers focuses intensive research on both scientific and practical field. There are quite a lot of known hybrid materials of PANI and other polymer systems with various synthetic polymers, which results in blends with various properties. The presented research covers the blends of polyaniline with semisynthetic (carboxymethyl) cellulose (CMC). The system could lead to a new antielectrostatic material with interesting properties and seems to be applicable as an additive for packaging in both food and non-food industry. The final material was obtained using both protonated (HCl) and deprotonated form of polyaniline in its semi-oxidized form of leucoemeraldine. Blending consisted in obtaining of thin layer by slow evaporation of the solvent from a mixture of PANI and CMC. For the main investigation atomic force microscopy (AFM) in non-contact mode was used, which gave the topological information about the surface and also some structural information about the material. The described process seems to be very interesting as a route for obtaining a new hybrid natural/synthetic material with very interesting properties and a potential for application.     

Incorporation of 4‐aminobenzene functionalized multi‐walled carbon nanotubes in polyaniline for application in formic acid electrooxidation

Incorporation of carbon nanotubes (CNTs) in conducting polymer can lead to new composites with enhanced electrical and mechanical properties. However, the development of such composites has been hampered by the inability to disperse CNTs in polymer matrix due to the lack of chemical compatibility between polymers and CNTs. Covalent sidewall functionalization of carbon nanotube provides a feasible route to incorporate carbon nanotube in polymer. In this work, 4‐aminobenzene groups were grafted onto the surface of multi‐walled carbon nanotube (MWNT) via C? C covalent bond. Polyaniline (PANI)/MWNT composites were fabricated by electrochemical polymerization of aniline containing well‐dissolved functionalized MWNTs. The obtained composites can be used as catalyst supports for electrooxidation of formic acid. Cyclic voltammogram results show that platinum particles deposited in PANI/MWNT composite films exhibit higher electrocatalytic activity and better long‐term stability towards formic acid oxidation than that deposited in pure PANI films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010