低逾渗MWCNTs-CB/UHMWPE导电复合材料的制备及性能

采用溶液法及机械共混法分别制备了均匀结构的炭黑(CB)/超高分子量聚乙烯(UHMWPE)及隔离结构的多壁碳纳米管(MWCNTs)-CB/UHMWPE复合薄膜。扫描电镜分析显示,虽然大部分CB均匀分散于UHMWPE基体中,但依然存在明显的局部团聚,而隔离结构中的MWCNTs-CB分布于UHMWPE界面间,更易形成导电通道。导电测试结果表明,复合材料的导电逾渗值由均匀分布的4.91%(体积分数)下降到隔离结构的0.42%。MWCNTs的加入完善了CB间的导电网络,使复合材料的逾渗值进一步下降,当CB∶MWCNTs=15∶1时,复合薄膜的逾渗值由0.42%(体积分数)下降到0.24%,然而混合填料中MWCNTs含量的进一步增加几乎对逾渗值没有影响。力学性能研究表明,隔离型复合材料的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。     

隔离结构石墨烯-多壁碳纳米管/超高分子量聚乙烯导电复合材料阻温特性

以多壁碳纳米管(MWCNTs)及石墨烯(GNS)为填料,超高分子量聚乙烯(UHMWPE)为基体,采用溶液共混及模压工艺制备了具有隔离结构的混合填充导电复合材料。扫描电镜(SEM)和电阻率测试发现,MWCNTs、GNS形成的导电通路相互协作,填料的含量比对复合材料导电网络有明显的影响。复合材料的阻温特性曲线随填料含量比的变化而发生改变,当MWCNTs含量较高时(MWCNTs:GNS=3:1和1:1),复合材料的电阻率随温度升高而升高,在之后的降温过程中电阻率也逐渐升高;当GNS含量较高时(MWCNTs:GNS=1:3),复合材料的电阻率随温度升高而降低,降温过程中电阻率逐渐升高;经过热循环后复合材料的导电性能降低,此时复合材料中的隔离结构被破坏。     

石墨烯/超高分子量聚乙烯导电复合材料的电性能

通过两步法制备了纳米石墨烯(GNS)/超高分子量聚乙烯(UHMWPE)分离结构导电复合材料,通过扫描电子显微镜和透射偏光显微镜研究了导电复合材料的形态结构与电性能的关系。研究表明,GNS粒子能够均匀地涂覆在UHMWPE粒子表面。当GNS的体积分数为0.4%时,复合材料电导率提升了15个量级,渗流阀值为0.028%(体积分数,下同)。GNS/UHMWPE分离结构导电复合材料的正温度系数效应(PTC)研究表明,由于填料分布形态及含量的变化,导致复合材料PTC转变温度发生改变。     

具有隔离结构的超高分子量聚乙烯/镍高导电复合材料

采用化学镀手段制备金属镍包覆的超高分子量聚乙烯复合粒子,通过热压成型方法制得具有隔离结构的超高分子量聚乙烯(UHMWPE)/镍(Ni)高导电复合材料。通过调节金属(镍)镀层厚度及加工温度考察不同Ni含量及加工温度对复合材料导电性能的影响。结果表明,复合材料具有明显的导电逾渗行为;通过化学镀工艺可有效提高金属填料与基体的结合力,同时实现金属镍在聚合物基体中的选择性稳定分布,构建具有隔离结构的导电网络,使得复合材料的逾渗值降低至1.02%(体积分数)。基于金属填料优异的导电性能,在Ni体积分数仅为2.53%时,复合材料的电导率达到2648S/m。此外,降低复合材料的加工成型温度有助于减少加工过程对导电网络的破坏作用,从而有效降低复合材料的导电逾渗值,对提高复合材料导电性能具有重要意义。     

石墨烯/超高分子量聚乙烯复合材料的导电性能

采用氧化还原法制备了石墨烯(GNS),用X射线衍射(XRD)、红外光谱、透射电子显微镜对所得GNS进行了分析和表征。采用溶液混合、超声波分散的方法,制备了GNS/超高分子量聚乙烯(UHMWPE)导电复合材料,研究了材料的导电渗流行为和阻-温特性。结果表明,溶液混合法可使GNS较好地分散于UHMWPE基体中,复合材料表现出典型的导电渗流行为,其渗流阈值为3.6%(质量分数)。在大于渗流阈值的情况下,复合材料的正温度系数效应(PTC)强度随GNS含量的增加而提高;热循环使得复合材料的PTC强度有所降低。     

超高分子量聚乙烯／石墨包覆铜纳米粒子摩擦磨损性能

在超高分子量聚乙烯(UHMWPE)中填充石墨包覆铜纳米粒子(GECNP),利用扫描电子显微镜观察了复合材料的断面形貌,用XP销-盘摩擦磨损试验机研究了其摩擦磨损性能,并用铜粉(Copper)、纳米石墨粉(GNS)作对比添加荆进行了同等试验.结果表明,GECNP均匀分散在UHMWPE中,当线速度为0.25m·s-1,GECNP填充量不高于3%时,UHMWPE/GECNP复合材料与空白UHMWPE相比磨损率降低,摩擦系数保持不变,综合性能优于UHMWPE/Copper和UHMWPE/GNS.当GECNP填充量为1%时,磨损率最低,与空白样相比降低了53.9 %,摩擦系数也略有降低.     

CB/UHMWPE复合材料的制备及导电性能

通过高速机械混磨方法制备了具有分离结构的炭黑(CB)/超高分子量聚乙烯(UHMWPE)复合材料,研究了复合材料的形态结构和导电性。结果表明,炭黑粒子可在较短的时间内涂覆在UHMWPE粒子表面。当CB的体积分数为0.6%时,复合材料的电导率提高了14个数量级,而渗流阈值仅为0.4%(体积分数,下同)。研究了热压工艺对导电复合材料电性能的影响,随热压时间的延长,复合材料的电导率出现下降趋势。     

UHMWPE/CNTs导电复合体系的电性能

制备了低逾渗值的超高分子量聚乙烯(UHMWPE)/多壁碳纳米管(CNTs)导电复合材料,CNTs分布于UHMWPE粒子的表面和界面处。研究了UHMWPE/CNTs复合材料的温度电阻行为,发现在基体熔点附近,电阻急剧增加,并达到一最大值,然后电阻开始下降,体现负温度电阻效应(NTC)。分析了复合材料电阻松弛时间的升温速率的依赖性,结果表明,升温速率越快,电阻的松弛时间越短。     

纳米ZnO和SiO2共混填充UHMWPE复合材料的摩擦磨损行为

以纳米ZnO和纳米SiO2作为复合填料,通过热压成型工艺制备了纳米ZnO-SiO2复合填充超高分子量聚乙烯(UHMWPE)复合材料;采用销-盘式摩擦磨损试验机考察了复合材料在干摩擦条件下与45#钢配副时的摩擦磨损行为;采用扫描电子显微镜观察了复合材料磨损表面形貌。结果表明,适量的纳米ZnO-SiO2作为复合填料可有效地改善UHMWPE的摩擦磨损性能,其中填充2%ZnO 2%SiO2的UHMWPE基复合材料改性效果最为明显。与纯UHMWPE材料相比,其磨损率下降了84.7%。纯UHMWPE的磨损机制主要表现为粘着磨损和疲劳磨损,而不同含量的无机纳米微粒共混填充UHMWPE基复合材料的磨损机制主要表现为不同程度的粘着磨损、犁沟效应和塑性变形特征。     

三元层状陶瓷Ti_3AlC_2/超高分子量聚乙烯复合材料的制备及性能

为了增强超高分子量聚乙烯(UHMWPE)的性能,研究采用表面改性的Ti_3AlC_2填充UHMWPE,通过热压成型制备了Ti_3AlC_2/UHMWPE复合材料。采用SEM观察复合材料的微观结构,表明Ti_3AlC_2均匀分散在UHMWPE基体中,表面处理后的填料与基体界面熔合较好;热分析结果表明,Ti_3AlC_2的添加降低了UHMWPE的结晶度和结晶热焓,同时提高了聚合物的热传导性;DMA分析结果表明,添加Ti_3AlC_2有效地提高了Ti_3AlC_2/UHMWPE复合材料的抗蠕变性能,得益于无机粒子改善了复合材料的硬度和刚性,提高了复合材料抗外界应力变形能力;摩擦学性能分析表明,适量的Ti_3AlC_2(质量分数≤15wt%)填充UHMWPE能有效提高复合材料的减磨抗摩性能,同时磨痕表面形貌分析结果表明,Ti_3AlC_2/UHMWPE复合材料的摩擦磨损机制由粘着磨损向磨粒磨损转变。     

The effect of geometric factor of carbon nanofillers on the electrical conductivity and electromagnetic interference shielding properties of poly(trimethylene terephthalate) composites: a comparative study

In this study, the effects of filler geometry on the electrical conductivity and electromagnetic interference (EMI) shielding properties of poly(trimethylene terephthalate) (PTT) composites filled with graphene nanosheets (GNSs), carbon nanotubes (CNTs), and GNS–CNT hybrid nanofillers have been investigated. The GNSs, CNTs, and hybrid GNS–CNT were well dispersed in the PTT matrix using a simple coagulation process. GNSs were prepared from graphene oxide (GO) through hydrazine reduction, and thermal reduction of GO at two different temperatures of 1050 and 1500 °C. PTT filled with different aspect ratios and oxygen functional groups of GNS were also prepared in order to compare the electrical conductivity and EMI shielding properties. The aspect ratios of GNSs and CNTs were estimated by using an ellipsoid model. Percolation scaling laws were applied to the magnitudes of conductivity to reveal the percolation network and filler dispersion. The percolation exponent of the PTT/GNS composites was larger than that of the PTT/CNT composites. The percolated filler–filler network at which the percolation exponent changed was correlated with the filler geometric structure. GNS–CNT hybrid nanofillers formed a complex double brush structure in the PTT/GNS–CNT composites. The geometric structure, aspect ratio, and intrinsic conductivity of carbon nanofillers affected the electrical percolation threshold and EMI shielding efficiency of the composites.     

Properties of poly(lactic acid)/montmorillonite/carbon nanotubes nanocomposites: determination of percolation threshold

Incorporation of rigid nanoparticles is the most effective means of improving polymer properties. Montmorillonite (MMT) and multi-walled carbon nanotubes (MWCNTs) are legendary in this field for their individual exceptional properties. A synergistic phenomenon is induced between these two particles when they are simultaneously incorporated into polymers. At a definite nanofillers concentration, called the percolation threshold, there is a sudden change in nanocomposite properties due to the formation of a 3D-structured network of the nanoparticles within the matrix. In this work, the properties of poly(lactic acid) (PLA) nanocomposites filled with different fractions of MMT/MWCNTs hybrid (0.5–2.0 wt%) were analyzed. In particular, the percolation threshold of the MMT/MWCNTs hybrid was uniquely identified by differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical thermal analysis. The structural studies by X-ray diffraction and Fourier-transform infrared spectroscopy were also associated with the percolation threshold of MMT/MWCNTs in PLA. At 1.0 wt% MMT/MWCNTs concentration, the complete exfoliation of the particles was maintained, and the thermal characteristics such as glass transition, crystallization and melting temperatures reached their plateau at this hybrid concentration. Moreover, the thermal degradation and viscoelastic parameters showed their peak values at this critical point, which is correlated with the formation of the percolation threshold within the matrix. The morphological studies confirmed the homogeneous dispersion of MMT/MWCNTs in PLA up to a concentration of 1.0 wt%. At 2.0 wt% MMT/MWCNTs, few aggregations occurred in the PLA-based composite, confirming that the percolation threshold was formed at a lower concentration of MMT/MWCNTs nanoparticles.

     

Percolation model of reinforcement efficiency for carbon nanotubes dispersed in thermoplastics

Considerable experimental work on carbon nanotube-reinforced composites has shown that the reinforcement efficiency of carbon nanotubes (CNTs) becomes lower than the theoretical expectation when CNT content reaches a critical value. This critical volume fraction (percolation threshold) is considered related to the formation of percolating network. In this work, a percolation model is proposed to describe the observed sharp decrease in the reinforcement efficiency of multiwalled CNTs (MWCNTs) dispersed in thermoplastics when the CNT content exceeds the percolation threshold. The percolation threshold is estimated via a numerical simulation of randomly curved CNTs according to the statistics on geometrical features of real CNTs. The percolation model, integrated into the Halpin–Tsai equations, is verified using the experimental data of various thermoplastic composites reinforced with MWCNTs. The developed mechanical model achieves a good agreement with the measured moduli of nanocomposites, and demonstrates an excellent prediction capability over a wide range of CNT content.     

Preparation and properties of carbon black/polymer composites with segregated and double-percolated network structures

A carbon black (CB)/low-density polyethylene (LDPE)/ultrahigh-molecular-weight polyethylene (UHMWPE) composite with a segregated and double-percolated structure has been fabricated using the solution mixing and high-speed mechanical mixing method. Structural observations show that the conducting CB/LDPE layers were only dispersed at the interface of UHMWPE granules and formed a well-developed CB conductive network with a percolation threshold of 0.26 vol%. The low percolation threshold in CB/LDPE/UHMWPE composites can be explained by the segregated and double-percolated networks of CB within the polymer matrix. A noticeable double positive temperature coefficient of resistivity can be observed around the melting temperature of LDPE and UHMWPE followed by a negative temperature coefficient of resistivity. The microstructure evolution of CB/LDPE/UHMWPE composites can be observed and explained by in situ optical micrographs.     

抗静电PET/ATO纤维的制备及材料的性能

采用原位聚合的方法制备了抗静电涤纶(PET)/锑掺杂二氧化锡(ATO)纳米复合材料。结果显示,ATO在PET中分散良好,团聚体尺寸小于200 nm;加入ATO没有影响PET的流动曲线类型,随着ATO含量的增加,在相同的剪切频率下,熔体黏度均呈先增加后减小的趋势;加入ATO提高了材料的热性能,利于熔融纺丝。采用熔融纺丝法制备了抗静电纳米复合纤维。ATO含量为1.0%(质量分数,下同)时纤维的比电阻由2.7×1013Ω.cm下降到4.9×108Ω.cm。抗静电纤维的渗滤阈值为1.05%,低于传统抗静电填料。     

不同沉积物无溶剂纳米石墨烯流体/环氧树脂复合材料阻燃性能对比

分别以沉积碳纳米管(MWCNTs)和羟基锡酸锌的石墨烯片层(GNS)纳米粒子为核、表面活性剂KH560为颈状层、聚醚胺M2070为冠状层,制备了无溶剂(GNS-MWCNTs)@M2070流体及无溶剂(GNS-ZHS)@M2070流体。将质量分数为2.0wt%的两种无溶剂纳米流体分别加入环氧树脂(EP)中,制备了无溶剂(GNS-MWCNTs)@M2070/EP和(GNS-ZHS)@M2070/EP复合材料,并对其热性能和阻燃性能进行研究。锥形量热测试结果表明,纯EP、(GNS-MWCNTs)@M2070/EP、(GNS-ZHS)@M2070/EP的火焰增长速率(FIGRA)值分别为3.682,3.118和4.391kW(m~2·s)~(-1),同时,相比(GNS-MWCNTs)@M2070/EP,含有(GNS-ZHS)@M2070的EP基复合材料较纯环氧树脂具有更低的生烟速率(SPR)、生烟总量(TSR)和一氧化碳释放量(COP)值,说明沉积有羟基锡酸锌的石墨烯片层纳米粒子为核的无溶剂纳米流体对提高环氧树脂阻燃性能更为有效。     

CNTs/ UHMWPE composites with a two-dimensional conductive network

A low percolation threshold can be achieved for the conductive polymer composites(CPC) materials having a segregated structure in which the conductive particles like carbon black (CB), carbon nanotubes (CNTs), etc. are only located on the interface of the polymer matrix particles instead of being randomly distributed in the whole system. Multiwalled carbon nanotubes (MWNTs) were experienced alcohol-assisted dispersion under ultrasonication and intense mechanical mixing, and only located on the interfaces of the ultrahigh molecular weight polyethylene (UHMWPE) matrix particles to form a segregated structure. The morphological observation and the critical exponent t value obtained from the classical threshold mechanism indicate that the MWNTs/UHMWPE composites form a 2-dimension conductive network, which leads to a very low percolation of 0.072vol%.     

ABS/石墨复合材料的交直流导电特性及流变性能

研究了石墨填充丙烯腈-丁二烯-苯乙烯共聚物(ABS)复合材料的直流(DC)和交流(AC)导电特性和线性粘弹行为。电性能测试结果表明,石墨体积分数为13.21%~16.36%时,ABS/石墨复合材料的DC电阻率突降6个数量级,说明发生电学逾渗;同时,AC电阻率在低频区不随频率而变化,且AC阻抗复平面图中阻抗实部与阻抗虚部呈现半圆弧,进一步证明导电网络的形成。流变性能测试结果表明石墨体积分数为10.24%~13.21%时复合体系的储能模量和复数黏度出现跳跃,损耗因子(tanδ)的峰值减小且逐渐向高频移动,说明复合体系从"类液态"转变为"类固态",发生流变逾渗现象。流变逾渗阈值小于导电逾渗阈值是因为传递电子时石墨之间的距离比阻碍聚合物分子链运动时石墨之间的距离小。     

Electrical conductivity enhancement of polymer/multiwalled carbon nanotube (MWCNT) composites by thermally-induced defunctionalization of MWCNTs

We report a thermally-induced increase of electrical conductivity of polymer/multiwalled carbon nanotube (MWCNT) composites using Diels-Alder-adduct-modified MWCNTs as additives. Thermal treatments of the composites induce the defunctionalization of the modified MWCNTs through retro-DA reaction, consequently to recover the electrical conductivity of MWCNTs and to increase the conductivity of PVDF/MWCNT composites. For the composites possessing 0.5 wt % of MWCNTs, thermal treatment increases the electrical conductivity from 2 × 10(-12) S cm(-1) to 4 × 10(-8) S cm(-1) and significantly reduces the value of percolation threshold. Meanwhile, the thermal treatment does not alter the mechanical properties of the composites.