Synergistic effects of micro-/nano-fillers on conductive and electromagnetic shielding properties of polypropylene nanocomposites

This study presents the synergistic effects of graphene nanosheets (GNSs) and carbon fibers (CFs) additions on the electrical and electromagnetic shielding properties of GNS/CF/polypropylene (PP) composites. These composites were fabricated by the melt blending of different ratios of GNSs and CFs (20:0, 15:5, 10:10, 5:15 and 0:20 wt/wt%) into a PP polymer matrix using a Brabender mixer. Besides, the chemical and crystalline structures and the thermal stability of the resultant GNS/CF/PP composites were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). FT-IR and XRD showed that with the addition of GNSs content, transmittances at 1373.4?cm^?1 and 1454.4?cm^?1 became smaller and the characteristic peak at 26.82° became stronger. TGA showed that the GNS/CF/PP composite can be used at high temperature below 456°C. Blending 10?wt% CFs and 10?wt% GNSs into the PP polymer resulted in excellent conductivity (0.397 S/cm), which indicated the occurrence of the critical percolation threshold phenomenon, and also reached the maximum electromagnetic shielding effectiveness (EMSE) of 20?dB at 1.28–2.00?GHz. Laminated with five layers of composites, its EMSE achieved 25–38?dB at 0.3–3.0?GHz, corresponding to blocking of 94.38–98.74% electromagnetic waves.     

Electrical conductivity and shielding effectiveness of poly(trimethylene terephthalate)/multiwalled carbon nanotube composites

Poly(trimethylene terephthalate) (PTT)/multiwalled carbon nanotube (MWCNT) composites have been fabricated to evaluate the potential of PTT composites as electromagnetic interference (EMI) shielding material. The room temperature electrical conductivity, complex permittivity, and shielding effectiveness (SE) of PTT/MWCNT composites were studied in the frequency range of 8.2–12.4 GHz (X-band). The dc conductivity (σ) of composites increased with increasing MWCNT loading and a typical percolation behavior was observed at 0.48 vol% MWCNT loading. The highest EMI SE of PTT/MWCNT composites was ~23 decibel (dB) at 4.76 vol% MWCNT loading which suggest that these composites can be used as light weight EMI shielding materials. The correlation among the SE, complex permittivity, and electrical conductivity was also studied. The EMI shielding mechanism of PTT/MWCNT composites was studied by resolving the total EMI SE into absorption and reflection loss.     

Carbon Nanotube–Multilayered Graphene Edge Plane Core–Shell Hybrid Foams for Ultrahigh‐Performance Electromagnetic‐Interference Shielding

Materials with an ultralow density and ultrahigh electromagnetic‐interference (EMI)‐shielding performance are highly desirable in fields of aerospace, portable electronics, and so on. Theoretical work predicts that 3D carbon nanotube (CNT)/graphene hybrids are one of the most promising lightweight EMI shielding materials, owing to their unique nanostructures and extraordinary electronic properties. Herein, for the first time, a lightweight, flexible, and conductive CNT–multilayered graphene edge plane (MLGEP) core–shell hybrid foam is fabricated using chemical vapor deposition. MLGEPs are seamlessly grown on the CNTs, and the hybrid foam exhibits excellent EMI shielding effectiveness which exceeds 38.4 or 47.5 dB in X‐band at 1.6 mm, while the density is merely 0.0058 or 0.0089 g cm^?3, respectively, which far surpasses the best values of reported carbon‐based composite materials. The grafted MLGEPs on CNTs can obviously enhance the penetration losses of microwaves in foams, leading to a greatly improved EMI shielding performance. In addition, the CNT–MLGEP hybrids also exhibit a great potential as nano‐reinforcements for fabricating high‐strength polymer‐based composites. The results provide an alternative approach to fully explore the potentials of CNT and graphene, for developing advanced multifunctional materials.     

石墨烯多壁碳纳米管/超高分子量聚乙烯导电复合材料的制备及性能

为了比较超高分子量聚乙烯(UHMWPE)在单一填充和混合填充时, 复合材料导电性的差别。在超声和肼的作用下, 通过对氧化石墨烯(GO)、 多壁碳纳米管(MWCNTs)和超高分子量聚乙烯水/乙醇分散液减压蒸馏及热压制备了隔离型MWCNTs/UHMWPE、 石墨烯(GNS)/UHMWPE和MWCNTs-GNS/UHMWPE导电复合材料。经SEM、 TEM测试发现, 导电填料分散于UHMWPE颗粒表面, 热压后形成隔离结构。隔离型的MWCNTs/UHMWPE和GNS/UHMWPE复合材料均表现出较低的导电逾渗(0.148%和0.059%, 体积分数,下同), 但MWCNTs/UHMWPE复合材料的电导率(2.0×10^-2 S/m, 1.0%, 质量分数, 下同)明显高于相同填料含量下的GNS/UHMWPE复合材料。 MWCNTs-GNS/UHMWPE复合材料表现出了更低的逾渗(0.039%) 和较高导电性能(1.0×10^-2 S/m, 1.0%), 其拉伸强度和断裂伸长率随填充剂含量的增加呈现出先上升后下降的趋势。     

Pickering乳液技术制备纤维素纳米纤丝-还原氧化石墨烯/聚甲基丙烯酸甲酯电磁屏蔽复合材料

利用纤维素纳米纤丝（CNF）和氧化石墨烯（GO）共稳定的含有聚甲基丙烯酸甲酯（PMMA）的Pickering乳液法,并经抽滤、还原、热压等工艺制备高性能的纤维素纳米纤丝-还原氧化石墨烯/聚甲基丙烯酸甲酯（CNF-rGO/PMMA）电磁屏蔽复合材料。通过调节油相中聚合物的质量浓度、水油体积比,从而调控GO在复合材料中的质量分数。研究GO还原方式、质量分数及热压过程对所制备的CNF-rGO/PMMA电磁屏蔽复合材料的形貌结构与性能的影响。CNF-rGO/PMMA电磁屏蔽复合材料中GO经水合肼处理后有效还原为rGO,热压工艺使包裹在PMMA颗粒外的CNF-rGO片层与PMMA颗粒紧密堆积并形成交联的三维导电网络从而具有优异的导电率,在X波段不同频率（8.2~12.4 GHz）下具有良好的电磁屏蔽效能及稳定性,电磁屏蔽效能可达20 dB以上,可用于民用电磁屏蔽材料。      

Effect of carbon nanotube type and functionalization on the electrical,thermal, mechanical and electromechanical properties of carbon nanotube/styrene–butadiene–styrene composites for large strain sensor applications

Thermoplastic elastomer tri-block copolymer, namely styrene–butadiene–styrene (SBS) composites filled with carbon nanotubes (CNT) are characterized with the main goal of obtaining electro-mechanical composites suitable for large deformation sensor applications. CNT/SBS composites with different filler contents and filler functionalizations are studied by morphological, thermal, mechanical and electrical analyses. It is shown that the different dispersion levels of CNT in the SBS matrix are achieved for pristine or functionalized CNT with strong influence in the electrical properties of the composites. In particular covalently functionalized CNTs show percolation thresholds higher than 8 weight percentage (wt%) whereas pristine CNT show percolation threshold smaller than 1 wt%. On the other hand, CNT functionalization does not alter the conduction mechanism which is related to hopping between the CNT for concentrations higher than the percolation threshold.Pristine single and multiwall CNT within the SBS matrix allow the preparation of composites with electro-mechanical properties appropriate for strain sensors for deformations up to 5% of strain, the gauge factor varying between 2 and 8. Composites close to the percolation threshold show larger values of the gauge factor.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

Complementary percolation characteristics of carbon fillers based electrically percolative thermoplastic elastomer composites

Electrically percolative composites of thermoplastic elastomers (TPE) filled with different concentrations of carbon nanotubes (CNT), carbon black (CB) and (CNT–CB) hybrid fillers were fabricated by melt blending. The effects of filler type and composition on the electrical properties of the percolative TPE composites were studied. Percolation threshold for CB-, CNT- and (CNT–CB)-based composites was found to be 0.06, 0.07 and 0.07 volume fraction respectively. Compared to CB-based composites and earlier reported results, CNT- and (CNT–CB)-based ones revealed an unexpectedly high percolation threshold, which otherwise considered an unwelcome phenomenon, lead to distinct and rare percolation characteristics of CNT filled percolative composites like per-percolation conductivity and a relatively steep percolation curves. CB-based composites showed a comparatively sharp insulator–conductor transition curve complementing the percolation characteristics CNT- and (CNT–CB)-based composites. Percolation threshold conductivity of the fillers was in the order of CB > CNT > (CNT–CB), while maximum attained conductivities followed the order of CNT > (CNT–CB) > CB. Conductivity order of fillers not only denied much reported synergic effect in (CNT–CB) filler but also highlighted the effect of percolation characteristics on the outcome of conductivity values. Results obtained were of theoretical as well as practical importance and were explained in the context of filler morphology and different dispersion characteristics of the carbon based fillers.     

Graphene foam/carbon nanotube/poly(dimethyl siloxane) composites for exceptional microwave shielding

Highly porous poly(dimethyl siloxane) (PDMS) composites containing cellular-structured microscale graphene foams (GFs) and conductive nanoscale carbon nanotubes (CNTs) are fabricated. The unique three-dimensional, multi-scale hybrid composites with inherent percolation and a high porosity of 90.8% present a remarkable electromagnetic interference shielding effectiveness (EMI SE) of ∼75 dB, a 200% enhancement against 25 dB of the composites made from GFs alone with the same graphene content and porosity. The corresponding specific EMI SE measured against the composite density is 833 dB cm³/g. These values are among the highest for all carbon filler/polymer composites reported thus far. Significant synergy arises from the hybrid reinforcement structure of the composites: the GFs drive the incident microwaves to be attenuated by dissipation of the currents induced by electromagnetic fields, while the CNTs greatly enhance the dissipation of surface currents by expanding the conductive networks and introducing numerous interfaces with the matrix.     

Comparing carbon nanotubes and graphene nanoplatelets as reinforcements in polyamide 12 composites

We investigate the influence of nanofillers including carbon nanotubes (CNTs) and graphene nanoplatelets on a thermoplastic engineering polymer, polyamide 12 (PA12). The comparison between these two important nanofillers as to how they influence the structure and properties of the polymer is systematically studied. The polymer-nanofiller composites were prepared using a twin-screw micro-extruder and the composite was thereafter hot pressed into thin films. The structure (using wide angle x-ray diffraction and differential scanning calorimetry) and properties (through tensile testing and conductivity measurement) of the thin films have been investigated. The composites incorporating surfactant showed the best CNT distribution and dispersion, causing an improvement of up to 80% in the toughness modulus over pure PA12. Electrical percolation could also be achieved at nanofiller concentrations of 1 to 2?wt%. In this study we observed that CNT fillers bring about more pronounced improvements in PA12 compared to graphene nanoplatelets, as far as mechanical and electrical properties are concerned.     

Effects of hybrid fillers on the electromagnetic interference shielding effectiveness of polyamide 6/conductive filler composites

The effects of hybrid conductive fillers on the electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE) of polyamide 6 (PA6)/conductive filler composites were investigated. Nickel-coated carbon fiber (NCCF) was used as the main filler and multi-walled carbon nanotube (MWCNT), nickel-coated graphite, carbon black, and titanium dioxide (TiO₂) were used as the second fillers in this study. From the results of morphological studies of the PA6/NCCF/second filler composites, NCCF easily formed an electrical pathway since it has a high aspect ratio and random orientation, and the second fillers seemed to disperse evenly in the PA6 matrix. The electrical conductivity and EMI SE of the PA6/NCCF composites were increased with the increase of NCCF content. Among the second fillers used in this study, TiO₂ appeared to be the most effective second filler with regard to increasing the EMI SE and electrical conductivity of the PA6/NCCF composite. This was probably because TiO₂ has a high dielectric constant with dominant dipolar polarization, consequently leading to greater shielding effectiveness due to the absorption of electromagnetic waves. From the above results of EMI SE and electrical conductivity, it was suggested that the TiO₂ produced a synergistic effect when it was hybridized with the NCCF of the PA6/NCCF/TiO₂ composites.     

Advanced elastomer nano-composites based on CNT-hybrid filler systems

Different techniques to disperse multiwalled carbon nanotubes (CNT) in elastomers using an internal mixer are applied and physical properties of the composites are evaluated: stress–strain behavior, dynamic-mechanical, thermal diffusivity, dielectric and fracture mechanical properties. The electrical percolation threshold is found to decrease by using ethanol as dispersion agent, compared to “dry” mixing, correlating with improved optical dispersion. The effect of nanoscopic gaps between adjacent CNTs on the electrical and thermal conductivity of the composites and the missing percolation behavior of the thermal conductivity are discussed. We have found some technically promising synergetic effects of the hybrid filler systems. For all systems one observes significantly steeper stress–strain curves by addition of 1.6 vol.% CNT to the systems with conventional fillers. In natural rubber the fatigue crack propagation resistance, tensile strength and electrical conductivity is found to be improved also for dry mixed CNT-silica hybrid systems.     

Enhanced thermal conductivity in polymer composites with aligned graphene nanosheets

We developed highly aligned graphene nanosheets (GNSs) in epoxy composites with incorporating magnetic GNS–Fe₃O₄ hybrids under a magnetic field with the aim to take full advantage of the high inplane thermal conductivity of graphene. GNS–Fe₃O₄ hybrids were fabricated by a simple coprecipitation method, and their morphology, chemistry, and structure were characterized. GNS–Fe₃O₄ hybrids were found to be homogenously dispersed and well aligned through the direction of the magnetic field in the epoxy matrix, as confirmed by SEM observation and Raman spectra analysis. The resulting epoxy/GNS–Fe₃O₄ composites possessed high thermal conductivity in a parallel magnetic-alignment direction at low GNS–Fe₃O₄ loadings, which greatly outperformed the composites with randomly dispersed bare GNSs. The obtained results indicated that the magnetic alignment of magnetic-functionalized GNSs is an effective way for greatly improving the thermal conductivity of the graphene-based composites.     

Graphene/thermoplastic polyurethane nanocomposites: Surface modification of graphene through oxidation,polyvinyl pyrrolidone coating and reduction

Herein, oxidation, polyvinyl pyrrolidone (PVP) coating and reduction are used to modify the surface of graphene in thermoplastic polyurethane (TPU)/graphene nanocomposites. It is demonstrated that graphene could be easily dispersed in TPU with PVP absorbed on reduced graphene oxide (RGO) as stabilizer during reduction. In the stress–strain curves for these composites containing GO, PVP coated GO (GO/PVP) and reduced GO/PVP (RGO/PVP) as filler, PVP coating and reduction can largely enhance the stress in low modulus region. It is thought to largely related with enhanced interfacial interaction between filler and matrix and healing of graphene structure during reduction. Consequently, the modulus of TPU/GO/PVP and TPU/RGO/PVP is significantly increased. Meanwhile, an electrical percolation threshold of 0.35 wt.% is obtained for TPU/RGO/PVP. Comparing with the results in literature, the filler surface modification used in this study has created nanocomposites with a good balance between electrical conductivity and mechanical properties.     

不同形貌纳米炭/聚苯胺复合材料对超级电容器电化学性能的影响

通过原位化学聚合制备了不同形貌的纳米炭材料(炭黑,碳纳米管及石墨烯纳米片)/聚苯胺复合电极材料.分析表明:石墨烯/聚苯胺复合材料相比于炭黑/聚苯胺、碳纳米管/聚苯胺复合物及纯聚苯胺,具有产率和比容量高,内阻低及明显提高的循环稳定性和倍率性能.石墨烯/聚苯胺复合材料更好的电化学性能归因于:(a)二维平面结构石墨烯有利于大量聚苯胺在其表面均匀沉积及更多的活性位使聚苯胺和电解液离子接触,从而有利于聚苯胺得失电子促使氧化还原反应的顺利进行;(b)石墨烯间的面接触有利于构建电子的快速传输网络使电极材料具有更低的电阻;(c)石墨烯及聚苯胺层层堆叠结构具有柔性包覆限制作用,可有效防止聚苯胺在充放电过程中因膨胀和收缩而从石墨烯表面脱离.     

The electrical properties of polymer nanocomposites with carbon nanotube fillers

The electrical properties of polymer nanocomposites containing a small amount of carbon nanotube (CNT) are remarkably superior to those of conventional electronic composites. Based on three-dimensional (3D) statistical percolation and 3D resistor network modeling, the electrical properties of CNT nanocomposites, at and after percolation, were successfully predicted in this work. The numerical analysis was also extended to investigate the effects of the aspect ratio, the electrical conductivity, the aggregation and the shape of CNTs on the electrical properties of the nanocomposites. A simple empirical model was also established based on present numerical simulations to predict the electrical conductivity in several electronic composites with various fillers. This investigation further highlighted the importance of theoretical and numerical analyses in the exploration of basic physical phenomena, such as percolation and conductivity in novel nanocomposites.     

New alignment procedure of magnetite–CNT hybrid nanofillers on epoxy bulk resin with permanent magnets

The main properties of epoxy composites reinforced with aligned carbon nanotubes (CNTs) have been studied. The alignment was carried out in a specific designed device applying a weak magnetic field (0.3 T) with permanent magnets. CNTs were modified with magnetite nanoparticles (Fe₃O₄) functionalized, in a one-stage-process which does not require use of strong acids or aggressive treatments which could affect the structural integrity of CNTs. The study by transmission electron microscopy confirmed that the Fe₃O₄ nanoparticles were closely bonded over CNT surfaces. The thermo-mechanical and tensile properties of composites measured were higher than neat epoxy resin and were similar for both composites: reinforced with neat CNTs and magnetite–CNT hybrid nanofillers. The electrical behaviour indicates a high anisotropy for aligned composites, showing an increase of one order of magnitude for the electrical conductivity in the direction of aligned nanotubes.     

Hybrid network structure and thermal conductive properties in poly(vinylidene fluoride) composites based on carbon nanotubes and graphene nanoplatelets

A small quantity of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) were introduced into the poly(vinylidene fluoride) (PVDF)/GNP and PVDF/CNT composites, respectively, to prepare the corresponding ternary PVDF/CNT/GNP and PVDF/GNP/CNT composites. The results demonstrated that adding CNTs into the PVDF/GNP composites greatly promoted the formation of the hybrid network structure of fillers. This was much different from the scenario that adding GNPs into the PVDF/CNT composites. GNPs and CNTs exhibited excellent nucleation effects for the crystallization of PVDF matrix; however, the variation of the PVDF crystallinity was small. Adding CNTs into the PVDF/GNP composites greatly enhanced the electrical conductivity of the PVDF/CNT/GNP composites. This was also different from the scenario of the PVDF/GNP/CNT composites. Furthermore, the PVDF/CNT/GNP composites exhibit higher thermal conductivity and higher synergistic efficiency compared with the PVDF/GNP/CNT composites. The conductive mechanisms and the synergistic effects of the ternary composites were then analyzed.     

Properties of synthetic diamond and graphene nanoplatelet-filled epoxy thin film composites for electronic applications

Epoxy thin film composites filled with particulate nanofillers; synthetic diamond and graphene nanoplatelets were prepared and characterized based on tensile, thermal, and electrical properties. The influences of these two types of fillers, especially in terms of their loading, sizes and shapes, were discussed. It was found that the epoxy thin film composites incorporating synthetic diamond displayed optimum properties where the addition of synthetic diamond from 0 to 2 vol.% results in higher elastic modulus, tensile strength, elongation at break, thermal conductivity and storage modulus if compared to those of graphene nanoplatelets composites. Both thin film composites showed improvement in the glass transition temperature with increasing filler loadings. Results on the electrical conductivity of both systems showed that higher conductivity is observed in graphene nanoplatelets composites if compared to synthetic diamond composites.     

Micromechanics modeling of the electrical conductivity of carbon nanotube (CNT)–polymer nanocomposites

A mixed micromechanics model was developed to predict the overall electrical conductivity of carbon nanotube (CNT)–polymer nanocomposites. Two electrical conductivity mechanisms, electron hopping and conductive networks, were incorporated into the model by introducing an interphase layer and considering the effective aspect ratio of CNTs. It was found that the modeling results agree well with the experimental data for both single-wall carbon nanotube and multi-wall carbon nanotube based nanocomposites. Simulation results suggest that both electron hopping and conductive networks contribute to the electrical conductivity of the nanocomposites, while conductive networks become dominant as CNT volume fraction increases. It was also indicated that the sizes of CNTs have significant effects on the percolation threshold and the overall electrical conductivity of the nanocomposites. This developed model is expected to provide a more accurate prediction on the electrical conductivity of CNT–polymer nanocomposites and useful guidelines for the design and optimization of conductive polymer nanocomposites.