碳纳米管/聚合物复合材料

本文简要介绍了碳纳米管的纯化和表面改性方法,着重对碳纳米管/聚合物复合材料的制备方法、微观结构表征及其力学、电学、光学等性能的研究进行了综述;简述了此类复合材料在电学、电磁屏蔽材料及吸波隐身材料、纤维材料以及航天工业等领域的应用,探讨了该研究领域所面临的一些问题及今后的发展方向。     

石墨烯/聚苯胺复合材料的制备及应用

石墨烯/聚苯胺复合材料由于其优异的电学、热学、电化学性能和机械性能等特点,吸引了研究者们的广泛关注。本文对近几年来石墨烯/聚苯胺复合材料的发展状况进行了简单介绍,首先总结了原位聚合法、界面聚合法、自组装法、溶液共混法等不同制备方法对石墨烯/聚苯胺复合材料结构和性能的影响。由于石墨烯/聚苯胺复合材料结合了石墨烯和聚苯胺两者的优点,展现出更加优异的性能,因此本文还对其在超级电容器、传感器、燃料电池、太阳能电池等方面的应用进行了详细介绍。     

Graphene and MnO2 decorated graphene filled composites for electromagnetic shielding applications having excellent dielectric properties

Graphene nanoplatelets (GnP) and α-MnO₂ decorated GnP were integrated into an ethylene vinyl acetate (EVA) matrix using the dual mixing method (solution followed by melt mixing). GnP was added in 1, 3, 5, 8, 10 and 15 phr loadings into an EVA matrix to obtain composites and evaluate their various properties suitable for mechanical and electrical applications. The graphene nanoplatelets were further decorated with α-MnO₂ which was subsequently integrated into EVA at an 8 phr loading to form composites. It was observed in the GnP-EVA composites, that with an increasing GnP content, a substantial increase in the tensile strength (188%) over the neat polymer was observed at a 10 phr loading but reduced thereafter at a 15 phr loading. Dielectric permittivity of the composites were observed to increase with an increasing filler loading, the addition of α-MnO₂ also having a beneficial effect. Conductivity as well as the electromagnetic interference shielding performance were improved with increasing GnP concentrations. A maximum 28 dB of shielding was observed in the 15 phr loaded GnP-EVA composite whereas the α-MnO₂ decorated GnP-EVA composite showed a shielding efficiency of 22 dB at a concentration of 8 phr for a thickness of 2 mm with excellent thermal and mechanical properties. Overall, the composite material will find its application as a flexible EMI shielding material.     

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.     

EMI shielding and dynamic mechanical analysis of graphene oxide-carbon nanotube-acrylonitrile butadiene styrene hybrid composites

Carbon nanomaterials such as carbon nanotubes (CNTs), graphene and their hybrid have been studied extensively. Despite having excellent properties of CNTs and graphene have not yet been fully realized in the polymer composites. During fabrication agglomeration of CNTs and restacking of graphene is a serious concern that results in the degradation of properties of nanomaterials into the final composites. To improve the dispersion of CNTs and restacking graphene, in the present research work, we focused on the hybridization of graphene oxide and CNTs. Multiwalled carbon nanotubes (MWCNTs), functionalized carbon nanotubes (FCNTs), and graphene oxide-carbon nanotubes (GCNTs) reinforced acrylonitrile butadiene styrene (ABS) composites were prepared separately by vacuum filtration followed by hot compression molding. Further, dynamic mechanical analysis (DMA), and electromagnetic interference (EMI) shielding properties of ABS composites reinforced carbon nanofillers were investigated. The dynamic mechanical properties of polymers strongly depend on the adhesion of fillers and polymer, entanglement density of polymer chains in the presence of carbon fillers. The dynamic mechanical characteristics such as storage, loss modulus, and damping factor of prepared composites were significantly affected by the incorporation of MWCNTs, FCNTs, and GCNTs. Maximum EMI shielding effectiveness of −49.6 dB was achieved for GCNT-ABS composites which were highest compared to MWCNTs-ABS composites (−38.6 dB) and FCNTs-ABS composites (−36.7 dB) in the Ku band (12.4–18 GHz). These results depict the great potential of GCNTs-ABS composites to be used in various applications of efficient heat dissipative EMI shielding materials for electronic devices.     

Recent progress in MXene and graphene based nanocomposites for microwave absorption and electromagnetic interference shielding

There is widespread use of telecommunication and microwave technology in modern society, and raised the electromagnetic interference (EMI) issue to alarming situation due to apprehensive demand and growth of 5G technology undesirably disturbing the human health. The two dimensional (2D) materials including graphene and MXenes are already been used for variety of electronic devices due to their exceptional electrical, mechanical, optical, chemical, and thermal properties. MXene is composed of metal carbides, in which mainly metals are the building blocks for dielectrics, semiconductors, or semimetals. However, the strong interfaces with electromagnetic waves (EM) are variable from terahertz (THz) to gigahertz (GHz) frequency levels and are widely used in EMI and Microwave absorption (MA) for mobile networks and communication technologies. The use of different organic materials with metal, organic, inorganic fillers, polymers nanocomposite and MXene as a novel material has been studied to address the recent advancement and challenges in the microwave absorption mechanism of 2D materials and their nanocomposites. In this concern, various techniques and materials has been reported for the improvement of shielding effectiveness (SE), and theoretical aspects of EMI shielding performance, as well stability of 2D materials particularly MXene, graphene and its nanocomposites. Consequently, various materials including polymers, conducting polymers, and metal–organic frameworks (MOF) have also been discussed by introducing various strategies for improved MA and control of EMI shieling. Here in this comprehensive review, we summarized the recent developments on material synthesis and fabrication of MXene based nanocomposites for EMI shielding and MA. This research work is a comprehensive review majorly focuses on the fundamentals of EMI/MA.  The recent developments and challenges of the MXene and graphene based various structures with different polymeric composites are described in a broader perspective.     

Segregated reduced graphene oxide polymer composite as a high performance electromagnetic interference shield

Herein, we report the synthesis of a graphene/polymer composite via a facile and straightforward approach for electromagnetic interference (EMI) shielding applications. Polystyrene (PS) beads were added in graphene oxide (GO)/water solution followed by the addition of hydroiodic acid (HI) for in situ reduction of GO. The composite solution (rGO/PS) was filtered, hot compressed and tested for EMI shielding and dielectric measurements. A 2-mm thick segregated rGO/PS sample with 10 wt% filler loading delivered a high EMI shielding effectiveness (SE) of 29.7 dB and an AC electrical conductivity of 21.8 S m^?1, which is well above the commercial requirement for EMI shielding applications. For comparison with the segregated rGO/PS composite, a control polymer composite sample utilizing a thermally reduced graphene oxide was synthesized by following a conventional coagulation approach. The as-synthesized conventional rGO/PS yield an EMI SE of 14.2 dB and electrical conductivity of 12.5 S m^?1. The high EMI shielding of segregated rGO/PS is attributed to the better filler-to-filler contact among graphene layers surrounded by PS beads and also to the better reduction and preservation of graphene structure during reduction process that makes the low temperature chemically reduced segregated rGO/PS approach a viable route compared to high temperature thermally reduced conventional rGO/PS approach.     

Chemically modified polyaniline nanocomposites by poly(2-acrylamido-2-methyl-1-propanesulfonicacid)/graphene nanoplatelet

New conducting polyaniline (PANI) nanocomposites that were chemically modified by poly(2-acrylamido-2-methyl-1-propanesulfonicacid) (PMP) and graphene nanoplatelets (GNPs) were prepared via in situ deposition. PMP was first synthesized using GNPs, and aniline hydrochloride monomer was then polymerized in the presence of PMP-GNPs. The nanopolymer composites were characterized, and its structural morphology was analyzed via transmission electron microscopy and scanning electron microscopy. Fourier transformation infrared spectroscopy results indicate a strong interaction between PANI, PMP, and GNPs. To understand the conduction behavior of the composites, temperature-dependent DC electrical conductivity was measured between 295 K and 503 K, and the mechanism of transport properties of the new composites was analyzed by Mott’s variable range of hopping model. The PANI/PMP-GNP showed higher conductivity than pure PANI polymer. The high electrical conductivity of the nanocomposites may be useful in fabricating multifunctional materials in bulk for future technological applications.     

Electromagnetic Interference Shielding Polymers and Nanocomposites - A Review

Intrinsically conducting polymers (ICP) and conductive fillers incorporated conductive polymer-based composites (CPC) greatly facilitate the research in electromagnetic interference (EMI) shielding because they not only provide excellent EMI shielding but also have advantages of electromagnetic wave absorption rather than reflection. In this review, the latest developments in ICP and CPC based EMI shielding materials are highlighted. In particular, existing methods for adjusting the morphological structure, electric and magnetic properties of EMI shielding materials are discussed along with the future opportunities and challenges in developing ICP and CPC for EMI shielding applications.     

Thermomechanical behaviors and dielectric properties of polyaniline‐doped para‐toluene sulfonic acid/epoxy resin composites

Composites based on conductive organic/inorganic fillers dispersed in insulating matrix have been widely investigated because of their widespread applications such as electromagnetic shielding, electrostatic discharge, and sensors. In this context, novel composite materials based on epoxy resin matrix charged with polyaniline (PANI)‐doped para‐toluene sulfonic acid were elaborated. Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy were used to check the structure and the morphology of the samples. Viscoelastic behavior and thermal stability of the composites were explored by dynamic mechanical thermal analysis and thermogravimetric analysis. It was shown that the PANI particles exhibited a partial crystalline structure and were homogeneously dispersed in epoxy matrix. Consequently, this structure affected the thermal stability and viscoelastic properties of the composites. Furthermore, the dielectric and electrical properties were investigated up to 1 MHz. Measurements of dielectric properties revealed that with loading fillers in matrix, the dielectric parameters increased to high values at low frequency then decreased at values around 40 and 32 of real and imaginary parts, respectively, at 1 MHz with 15% of PANI content. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

Graphene‐polymer nanocomposites for biomedical applications

Despite the significant efforts in the synthesis of new polymers, the mechanical properties of polymer matrices can be considered modest in most cases, which limits their application in demanding areas. The isolation of graphene and evaluation of its outstanding properties, such as high thermal conductivity, superior mechanical properties, and high electronic transport, have attracted academic and industrial interest, and opened good perspectives for the integration of graphene as a filler in polymer matrices to form advanced multifunctional composites. Graphene‐based nanomaterials have prompted the development of flexible nanocomposites for emerging applications that require superior mechanical, thermal, electrical, optical, and chemical performance. These multifunctional nanocomposites may be tailored to synergistically combine the characteristics of both components if proper structural and interfacial organization is achieved. The investigations carried out in this aim have combined graphene with different polymers, leading to a variety of graphene‐based nanocomposites. The extensive research on graphene and its functionalization, as well as polymer graphene composites, aiming at applications in the biomedical field, are reviewed in this paper. An overview of the polymer matrices adequate for the biomedical area and the production techniques of graphene composites is presented. Finally, the applications of such nanocomposites in the biomedical field, particularly in drug delivery, wound healing, and biosensing, are discussed.     

聚苯胺复合材料的制备方法及应用进展

复合材料是由两种或多种性质不同的物质组成的多元材料,具有比各组分材料更优异的或原来不具备的性能。聚苯胺(PANI)作为最具应用前景的导电高分子材料,国内外对基于PANI的复合材料的研究也愈加关注。本文对PANI复合材料制备方法的研究成果进行了综述,主要包括原位化学法、共混法、电化学法、层层自组装法等。探讨了PANI复合材料在电极、导电、防腐、传感、分离、催化等方面的应用性能,并展望了PANI复合材料今后研究与应用的发展方向。     

Towards efficient electromagnetic interference shielding performance for polyethylene composites by structuring segregated carbon black/graphite networks

An electromagnetic interference (EMI) shielding composite based on ultrahigh molecular weight polyethylene (UHMWPE) loaded with economical graphite-carbon black (CB) hybrid fillers was prepared via a green and facile methodology, i.e., high-speed mechanical mixing combined with hot compression thus avoiding the assistance of the intensive ultrasound dispersion in volatile organic solvents. In this composite, the graphite-CB hybrid fillers were selectively distributed in the interfacial regions of UHMWPE domains resulting a typical segregated structure. Thanks to the specific morphology of segregated conductive networks along with the synergetic effect of large-sized graphite flakes and small-sized CB nanoparticles, a low filler loading of 7.7 vol% (15 wt%) yielded the graphite-CB/UHMWPE composites with a satisfactory electrical conductivity of 33.9 S/m and a superior shielding effectiveness of 40.2 dB, manifesting the comparable value of the pricey large-aspect-ratio carbon nanofillers (e.g., carbon nanotubes and graphene nanosheets) based polymer composites. More interestingly, with the addition of 15 wt% graphite-CB (1/3, W/W) hybrid fillers, the tensile strength and elongation at break of the composite reached 25.3 MPa and 126%, respectively; with a remarkable increase of 58.1% and 2420% over the conventional segregated graphite/UHMWPE composites. The mechanical reinforcement could be attributed to the favor of the small-sized CB particles in the polymer molecular diffusion between UHMWPE domains which in turn provided a stronger interfacial adhesion. This work provides a facile, green and affordable strategy to obtain the polymer composites with high electrical conductivity, efficient EMI shielding, and balanced mechanical performance.     

A Review Featuring Fabrication,Properties and Applications of Carbon Nanotubes (CNTs) Reinforced Polymer and Epoxy Nanocomposites

Carbon nanotubes (CNTs) have long been recognized as the stiffest and strongest man-made material known to date.In addition,their high electrical conductivity has roused interest in the areas of electrical appliances and communication related applications.However,due to their miniature size,the excellent properties of these nanostructures can only be exploited if they are homogeneously embedded into light-weight matrices as those offered by a whole series of engineering polymers.In order to enhance their chemical affinity to engineering polymer matrices,chemical modification of the graphitic sidewalls and tips is necessary.The mechanical and electrical properties to date of a whole range of nanocomposites of various carbon nanotube contents are also reviewed in this attempt to facilitate progress in this emerging area.Recently,carbonaceous nano-fillers such as graphene and carbon nanotubes (CNTs) play a promising role due to their better structural and functional properties and broad range of applications in every field.Since CNTs usually form stabilized bundles due to van der Waals interactions,they are extremely difficult to disperse and align in a polymer matrix.The biggest issues in the preparation of CNTs reinforced composites reside in efficient dispersion of CNTs into a polymer matrix,the assessment of the dispersion,and the alignment and control of the CNTs in the matrix.An overview of various CNT functionalization methods is given.In particular,CNT functionalization using click chemistry and the preparation of CNT composites employing hyperbranched polymers are stressed as potential techniques to achieve good CNT dispersion.In addition,discussions on mechanical,thermal,electrical,electrochemical and applications ofpolymer/CNT composites are also included.     

Monolithic polyimine vitrimer/graphene aerogel composites

Graphene-polymer composites have attracted great attention as sensing materials due to their tailorable electrical conductivity, physicochemical properties, and sensitivity to geometric and functional changes. Herein, we report the first example of cylindrical monolithic polyimine vitrimer/graphene composites with excellent mechanical, compressive, rehealable and recyclable, and piezoresistive properties via simple infiltration of polymer monomers into the pores of graphene aerogel followed by thermal curing. The composites exhibit excellent durable compressibility (negligible reduction in the compression properties even after 3000 consecutive compression cycles), rapid recovery to the original size upon stress released, high compressive strength (up to 1.2 MPa), and high conductivity (up to 79 S/m). Excellent piezoresistive properties were observed, displaying consistent and reliable change of the electrical resistance with the compression ratio. Furthermore, rehealing with ～100% recovery of the compressive strength and electric conductivity was achieved under mild rehealing conditions, which is highly desired but has rarely been reported for electronic materials. The facile strategy for fabrication of rehealable monolithic polymer/GAs can open new possibilities for the sustainable development of composites with high electrical conductivity for various applications such as sensing, health monitoring, and movement detection.     

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。     

Cement Composites with Carbon-Based Nanomaterials for 3D Concrete Printing Applications – A Review

3D concrete printing (3DCP) is an emerging additive manufacturing technology in the construction industry. Its challenges lie in the development of high-performance printable materials and printing processes. Recently developed carbon-based nanomaterials (CBNs) such as graphene, graphene oxide, graphene nanoplatelets, and carbon nanotubes, have various applications due to their exceptional mechanical, chemical, thermal, and electrical characteristics. CBNs also have found potential applications as a concrete ingredient as they enhance the microstructure and modify concrete properties at the molecular level. This paper focuses on state-of-the-art studies on CBNs, 3DCP technology, and CBNs in conventional and 3D printable cement-based composites including CBN dispersion techniques, concrete mixing methods, and fresh and hardened properties of concrete. Furthermore, the current limitations and future perspectives of 3DCP using CBNs to produce high-quality composite mixtures are discussed.     

Inorganic semiconductors-graphene composites in photo(electro)catalysis: Synthetic strategies,interaction mechanisms and applications

The remarkable physicochemical properties of graphene (GR) and derivatives can be leveraged in the photocatalytic activity of GR-semiconductor photocatalysts. The hitherto state of knowledge on the role of GR in these composite materials is insufficient and leaves many questions unanswered, thus it is imperative to fully understand the interaction mechanisms between GR and inorganic semiconductors. Detailed study and optimization of the features related to the interface are still very much sought to efficiently design photocatalysts targeting their eventual commercialization. This review shows that photocatalytic activity of such composites depends not only on high GR electron mobility and charge transfer, but also on the properties of the interface (such as interface morphology, size, crystal phases and facet, dimensionality of composites, etc.). Focusing on the last advancements in this field, this review analyses the challenges involved in the synthetic strategies of GR-semiconductor photo(electro)catalysts in various applications including pollutant degradation, organic synthesis, hydrogen evolution and photoreduction of carbon dioxide (CO₂). Mechanism of interaction between GR and semiconductors are thoroughly discussed by examining the proposed mechanism in the diverse areas where the composite materials are employed in photo(electro)catalytic processes. In addition, various synthetic and characterization technique available hitherto are presented, since they are pivotal to the understanding of the composites properties (such as morphology, crystal phases and exposed facets, degree of crystallinity, dimensionality etc.), and even to shed more light on interaction mechanisms of the photocatalyst constituents. As a future outlook, it is envisaged that research will not only focus on optimizing GR electrical and chemical properties, yet in the synthesis of GR-semiconductor photocatalysts attention needs also be placed on the properties of the resulting composites, using suitable synthetic methods and proper characterizations to assess their performance.