Effect of Different Hybrid Method on Properties of Carbon Nanotubes/Dolomite Hybrid Filled Phenolic Composites

Hybridization of multi wall carbon nanotubes (MWCNTs) with other filler in polymer matrix composites (PMC) is one of the techniques for combining different properties of fillers for making more unique composites. In this work, the hybrid filler (CNTs–dolomite) are prepared via chemical vapour deposition (CVD hybrid) and the milling method (physically hybrid). The effect of different hybrid method on properties of multi wall carbon nanotubes/dolomite hybrid filled phenolic composites were studied. Phenolic/CVD hybrid composites and phenolic/physically hybrid composites with different filler loadings were prepared using hot mounting press. The prepared samples were characterized for their thermal conductivity and hardness. The thermal conductivity was measured using the Transient Plane Source (TPS) method, using a Hot-DiskTM Thermal Constant Analyzer and the hardness was measured using Rockwell micro-hardness. The results showed that at 5% filler loading, the phenolic/CVD hybrid composites were capable of increasing the thermal conductivity and micro-hardness up to 7.22% and 101.6% respectively compared to pure phenolic.     

具有隔离结构的聚丙烯/碳纳米管复合材料的制备及电磁屏蔽性能

通过共挤出包覆-热压法制备了具有隔离结构的聚丙烯(PP)/碳纳米管(CNTs)电磁屏蔽复合材料。 其中,CNTs随机分布于PP基体中形成导电相,该导电复合物作为包覆层包敷在纯PP颗粒表面,形成包覆复合粒子,经热压后形成隔离导电网络。 结果表明,所制备的隔离结构复合材料呈现良好的导电性能,可获得较低的导电逾渗值0.28%(体积分数);在CNTs质量分数为5.6%时,该复合材料电磁屏蔽性能达到25.6 dB,同时具有良好的力学性能。 本文结果表明,共挤出包覆-热压法制备隔离结构导电复合材料方法简单可控、绿色环保,对开发高性能电磁屏蔽复合材料具有重要指导意义。     

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.     

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.     

导热膨胀石墨/聚醚酰亚胺复合材料的制备与性能

利用膨胀石墨(EG)经高温处理后比表面积大的特点, 以膨胀石墨作为导热填料, 通过球磨和热模压方法制备了膨胀石墨/聚醚酰亚胺(PEI)导热复合材料, 并对其加工过程、 微观形貌、 热性能和导热性能进行了研究. 结果表明, 球磨处理可以打破膨胀石墨的“泡沫”状态并减少石墨纳米片间的间隙, 热压可以诱使和促进石墨纳米片沿着水平方向排列和取向, 从而显著提升了复合材料的平面内导热性能. 当膨胀石墨在复合材料中的质量分数为20%时, EG/PEI复合材料的面内导热系数为2.38 W?m^?1?K^?1. 与PEI相比, 复合材料导热系数的增幅约为12倍. 所制备的EG/PEI复合材料均具有良好的散热能力、 较好的热稳定性和较高的储能模量, 是一种综合性能优异的导热材料.     

An Electroconductive Filler for Shielding Plastics

A well characterised grade of mica was used to prepare nickel-coated mica fillers by an electroless coating technique. These fillers were incorporated into polypropylene (PP) and acrylonitrile-butadiene-styrene (ABS) using a Haake Internal mixer and a two-roll mill to produce conducting composites suitable for EMI shielding applications. Compounded polymers were fabricated into sheets of different thickness by compression moulding. The dependence of conductivity on sample thickness was studied and samples were tested for electrical resistivity, shielding efficiency, and thermal and mechanical properties. Reduced sample thickness during compression moulding decreased the electrical resistance of the polymer composites due to orientation and the formation of a good conducting network. Volume resistivity of PP composites was lower than for ABS composites with 50% Ni coating and equivalent filler weight fracions, showing that better conductivity could be achieved in a semi crystalline polymer than in an amorphous polymer. 0.6 weight fraction of 50 wt.% nickel coated mica in ABS showed a shielding efficiency of 16dB compared with 27.8dB in PP.     

形状记忆聚偏氟乙烯/丙烯酸酯/碳纳米管纳米复合材料的导电及导热性能

利用聚偏氟乙烯（PVDF）微小结晶的物理交联点作用,制备了形状记忆性能优异的聚偏氟乙烯/丙烯酸酯聚合物（PVDF/ACM）共混材料,为提高其导电及导热性能,于其中引入了碳纳米管（CNT）,系统研究了PVDF/ACM/CNT三元体系纳米复合材料的导热及导电性能。 结果表明,碳纳米管在PVDF/ACM体系中分散均匀;在基本保持其形状记忆性能的前提下,碳纳米管的加入使材料导热性能及导电性能有较大程度的提高：质量分数为4%的CNT使材料25 ℃的电阻值降低至5000 Ω/square,导热系数提高至0.157 W/(m·K)。     

Fabrication of thermoplastic polyurethane composites with a high dielectric constant and thermal conductivity using a hybrid filler of CNT@BaTiO3

Thermoplastic polyurethane composites with an excellent dielectric constant and high thermal conductivity were obtained using CNT@BaTiO₃ as a filler through a low-speed melt extrusion method. Before preparing the hybrid filler for the composite, the filler particles were surface modified to ensure that the outer surfaces could facilitate the reaction among particles to form the hybrid and ensure complete dispersion in the thermoplastic polyurethane matrix. After confirming the proper surface treatment of the filler particles using infrared spectroscopy, thermal degradation analysis and field emission scanning electron microscopy, they were used to prepare the composite materials at a processing temperature of 200 °C. The thermal stability, thermomechanical properties, mechanical properties, thermal conductivity, and dielectric properties of the composites were investigated. Compared to the neat thermoplastic polyurethane matrix, the prepared composite exhibited a higher thermal stability, approximately 300% higher storage modulus, higher tensile strength and elongation at break values, approximately three times higher thermal conductivity (improved from 0.19 W/(m.K) to 0.38 W/(m.K), and approximately five times larger dielectric constant at high frequencies (at 1 MHz a dielectric constant of 19.2 was obtained).     

马来酸酐接枝聚丙烯/石墨导电纳米复合材料的研究

用溶液插层 (SI)法制备了马来酸酐接枝聚丙烯 (gPP) 膨胀石墨 (EG)导电纳米复合材料 ,以熔体混合(MM)法作对照 ,通过室温体积电导率 (σ)测试和OM、SEM、TEM观察 ,研究了复合材料的制备方法、微观结构和导电性能关系 .结果表明 ,SI法制得纳米复合材料的室温逾渗阈值c=0 6 7vol% ,远低于MM法制得复合材料的c=2 96vol% ;3 90vol%EG含量下 ,前者的σ达 2 4 9× 10 - 3S cm ,而后者的σ仅 6 85× 10 - 9S cm .产生上述差异的原因 ,与两种方法制得复合材料中EG分散相的形态及其内部微结构直接相关 .     

Study on insulating thermal conductive BN/HDPE composites

Thermal conductivity of boron nitride (BN) reinforced high density polyethylene (HDPE) composites was investigated under a special dispersion state of BN particles in HDPE, i.e., BN particles surrounding HDPE matrix particles. The results indicated that the special dispersion of BN in matrix gives the composites high thermal conductivity at low filler content; moreover, the smaller BN particles can more easily form conductive chains of filler compared to the larger filler particles. Examining the dependence of electrical insulation and mechanical properties of the composites on BN content demonstrated that the reinforced composites containing 30% by volume of filler has good electrical insulation and mechanical properties.     

Enhanced thermal conductivity of epoxy–matrix composites with hybrid fillers

The results of thermal conductivity study of epoxy–matrix composites filled with different type of powders are reported. Boron nitride and aluminum nitride micro‐powders with different size distribution and surface modification were used. A representative set of samples has been prepared with different contents of the fillers. The microstructure was investigated by SEM observations. Thermal conductivity measurements have been performed at room temperature and for selected samples it was also measured as a function of temperature from 300 K down to liquid helium temperatures. The most spectacular enhancement of the thermal conductivity was obtained for composites filled with hybrid fillers of boron nitride–silica and aluminum nitride–silica. In the case of sample with 31 vol.% of boron nitride–silica hybrid filler it amounts to 114% and for the sample with 45 vol.% of hybrid filler by 65% as compared with the reference composite with silica filler. However, in the case of small aluminum nitride grains application, large interfacial areas were introduced, promoting creation of thermal resistance barriers and causing phonon scattering more effective. As a result, no thermal conductivity improvement was obtained. Different characters of temperature dependencies are observed for hybrid filler composites which allowed identifying the component filler of the dominant contribution to the thermal conductivity in each case. The data show a good agreement with predictions of Agari‐Uno model, indicating the importance of conductive paths forming effect already at low filler contents. Copyright © 2014 John Wiley & Sons, Ltd.     

碳纳米管/高分子复合导电材料的研究进展

从碳纳米管的电性质出发,对以它为填料的导电性复合材料的制备方法和研究进展进行了综述,同时简单介绍了导电性复合材料电性质转变现象的理论分析模型,最后对碳纳米管/高分子复合导电材料的研究前景作了一定探讨。     

iPP/HDPE/CB三元导电复合材料的导电与流变行为

利用界面能原理使CB选择性分布于HDPE中成为复合导电相,固定CB在HDPE中的质量分数(20 wt％),控制CB/HDPE导电相在iPP中的含量,制备出一系列三元(iPP/HDPE/CB)导电复合材料,并研究其导电逾渗和流变逾渗行为.结果表明,在复合导电相含量为20 wt％时复合材料内即形成导电网络,在复合导电相含量30 wt％时出现流变网络.只有当复合导电相在材料中形成连续相时(60 wt％),损耗因子在频率扫描中才出现峰值.     

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.     

Thermally conductive cyanate ester nanocomposites filled with graphene nanosheets and multiwalled carbon nanotubes

In this work, dodecylamine‐modified graphene nanosheets (DA‐GNSs) and γ‐aminopropyl‐triethoxysilane‐treated multiwalled carbon nanotubes (f‐MWCNTs) are employed to prepare cyanate ester (CE) thermally conductive composites. By adding 5 wt% DA‐GNSs or f‐MWCNTs to the CE resin, the thermal conductivities of the composites became 3.2 and 2.5 times that of the CE resin, respectively. To further improve the thermal conductivity, a mixture of the two fillers was utilized. A remarkable synergetic effect between the DA‐GNSs and f‐MWCNTs on improving the thermal conductivity of CE resin composites was demonstrated. The composite containing 3 wt% hybrid filler exhibited a 185% increase in thermal conductivity compared with pure CE resin, whereas composites with individual DA‐GNSs and f‐MWCNTs exhibited increases of 158 and 108%, respectively. Moreover, the composite with hybrid filler retained high electrical resistivity. Scanning electron microscopy images of the composite morphologies showed that the modified graphene nanosheets (GNSs) and multiwalled carbon nanotubes (MWCNTs) were uniformly dispersed in the CE matrix, and a number of junction points among MWCNTs and between MWCNTs and GNSs formed in the composites with hybrid fillers. Generally, we can conclude that these composites filled with hybrid fillers may be promising materials of further improving the thermal conductivity of CE composites. Copyright © 2014 John Wiley & Sons, Ltd.     

Simultaneous enhancement of electrical conductivity and impact strength via formation of carbon black‐filler network in PP/EPDM Blends

The electrical conductivity and impact strength of polypropylene(PP)/EPDM/carbon black ternary composites were investigated in this paper. Two processing methods were employed to prepare these ternary composites. One was called one‐step processing method, in which the elastomer and the filler directly melt blended with PP matrix. Another one was called two‐step processing method, in which the elastomer and the filler were mixed first, and then melt blended with pure PP. To get an optimal phase morphology that favors the electrical conductivity and impact strength, controlling the distribution of CB in PP/EPDM blend was a crucial factor. Thus the interfacial tension and the work of adhesion were first calculated based on the measurement of contact angle, and the results showed that CB tended to be accumulated around EPDM phases to form filler‐network structure. Expectably, the filler‐network structure was observed in PP/EPDM/CB(80/20/3) composite prepared by two‐step processing method. The formation of this filler‐network structure decreased the percolation threshold of CB particles in polymer matrix, and the electrical conductivity as well as Izod impact strength of the composite increased dramatically. This work provided a new way to prepare polymer composites with both improved conductivity and impact strength. Copyright © 2009 John Wiley & Sons, Ltd.     

Carbon Papers from Tall Goldenrod Cellulose Fibers and Carbon Nanotubes for Application as Electromagnetic Interference Shielding Materials

To transform tall goldenrods, which are invasive alien plant that destroy the ecosystem of South Korea, into useful materials, cellulose fibers isolated from tall goldenrods are applied as EMI shielding materials in this study. The obtained cellulose fibers were blended with CNTs, which were used as additives, to improve the electrical conductivity. TGCF/CNT papers prepared using a facile paper manufacturing process with various weight percent ratios and thickness were carbonized at high temperatures and investigated as EMI shielding materials. The increase in the carbonization temperature, thickness, and CNT content enhanced the electrical conductivity and EMI SE of TGCF/CNT carbon papers. TGCF/CNT-15 papers, with approximately 4.5 mm of thickness, carbonized at 1300 °C exhibited the highest electrical conductivity of 6.35 S cm⁻¹, indicating an EMI SE of approximately 62 dB at 1.6 GHz of the low frequency band. Additionally, the obtained TGCF/CNT carbon papers were flexible and could be bent and wound without breaking.     

聚吡咯/多壁碳纳米管及其聚氨酯导电复合材料的制备和性能

以羧基化多壁碳纳米管(MWCNTs)做模版剂,采用化学氧化法将吡咯(Py)在羧基化MWCNTs表面聚合制备PPy/MWCNTs导电材料,将其添加到溶剂型聚氨酯(PU)溶液中制备了PPy/MWCNTs/PU导电复合材料,研究了Py用量对PPy/MWCNTs及其PU复合材料性能的影响.研究表明,随Py用量的增加,PPy/MWCNTs的长度不变,管径增大,sp~2和sp~3杂化C含量先提高后减少,N的掺杂梯度降低,PPy/MWCNTs的导电率高于羧基化MWCNTs和PPy.当Py用量为羧基化MWCNTs的20%时,其导电率最大.PPy/MWCNTs中N元素的掺杂程度及其管径变化是引起PPy/MWCNTs/PU复合材料的性能不同的主要原因.增加Py用量,MWCNTs中亲水的羧基因对PPy掺杂而消耗,相同导电材料用量时纳米导电粒子数目相对减少,PPy/MWCNTs/PU复合材料的耐水性能提高,定向应力、储能模量和玻璃化温度降低,导电率先增加后减小.当Py用量为羧基化MWCNTs的15%时,导电率最大.     

聚苯乙烯/碳纳米管复合材料研究进展

聚苯乙烯/碳纳米管复合材料是近年来开发的新型聚合物基复合材料,具有独特的一维纳米管分散微结构,往往表现出比纯聚苯乙烯更好的机械力学性能、电学性能和热性能等,在诸多领域具有广泛的应用前景.本文首先简要介绍了碳纳米管的结构特点、制备与纯化和性能,然后重点阐述了聚苯乙烯/碳纳米管复合材料的几种制备方法、结构表征以及力学、电学和热性能等方面的研究进展,并对聚苯乙烯共聚物/碳纳米管复合材料的研究现状进行介绍.     

Isothermal crystallization kinetics,morphology, and thermal conductivity of graphene nanoplatelets/polyphenylene sulfide composites

Graphene nanoplatelets (GNP) and polyphenylene sulfide (PPS) were used as filler and matrix, respectively, to produce composites. The PPS/GNP thermal composites were prepared via a melt blending method. The effects of GNP on crystallization behavior and kinetics, morphology, and thermal properties of PPS/GNP composites were investigated. To determine the isothermal crystallization kinetics parameters and isothermal crystallization activation energy, the Avrami model was used to comparatively analyze the relevant DSC experimental data. The results show that GNP provides an obvious heterogeneous nucleation effect on PPS to accelerate the crystallization and decrease isothermal crystallization activation energy. Thermal conductivity values of PPS/GNP composites with various GNP contents revealed that GNP remarkably increases thermal conductivity of composites mainly via a layered dispersion in PPS matrix. Thermal conductivity also increased with increasing GNP content, which was further improved at elevated temperatures. The thermal conductivities of PPS composite containing 30 mass% of GNP were 1.156 and 1.350 W m^?1 K^?1 at 30 and 110 °C, respectively, indicating an increase of more than 3 times compared with the neat PPS.